WO2022083659A1 - 基于丙烯聚合物的复合薄膜及其制备方法和应用 - Google Patents

基于丙烯聚合物的复合薄膜及其制备方法和应用 Download PDF

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Publication number
WO2022083659A1
WO2022083659A1 PCT/CN2021/125096 CN2021125096W WO2022083659A1 WO 2022083659 A1 WO2022083659 A1 WO 2022083659A1 CN 2021125096 W CN2021125096 W CN 2021125096W WO 2022083659 A1 WO2022083659 A1 WO 2022083659A1
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Prior art keywords
weight
layer
propylene
composite film
component
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/CN2021/125096
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English (en)
French (fr)
Inventor
徐萌
张师军
高达利
白弈青
徐凯
任月明
刘建叶
权慧
董穆
张琦
侴白舸
吕芸
邵静波
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
Original Assignee
Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from CN202011125599.3A external-priority patent/CN114434913B/zh
Priority claimed from CN202011126164.0A external-priority patent/CN114434914B/zh
Application filed by Sinopec Beijing Research Institute of Chemical Industry, China Petroleum and Chemical Corp filed Critical Sinopec Beijing Research Institute of Chemical Industry
Priority to KR1020237017082A priority Critical patent/KR20230090352A/ko
Priority to CN202180064273.0A priority patent/CN116261518B/zh
Priority to US18/249,794 priority patent/US20240017533A1/en
Priority to JP2023524150A priority patent/JP7778143B2/ja
Priority to EP21882074.4A priority patent/EP4234238B1/en
Publication of WO2022083659A1 publication Critical patent/WO2022083659A1/zh
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • B32B2264/102—Oxide or hydroxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/10—Inorganic particles
    • B32B2264/107—Ceramic
    • B32B2264/108—Carbon, e.g. graphite particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/30—Particles characterised by physical dimension
    • B32B2264/303—Average diameter greater than 1µm
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2270/00—Resin or rubber layer containing a blend of at least two different polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2274/00—Thermoplastic elastomer material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/31—Heat sealable
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/412—Transparent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/514—Oriented
    • B32B2307/518—Oriented bi-axially
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/54—Yield strength; Tensile strength
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/558—Impact strength, toughness
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/732—Dimensional properties
    • B32B2307/737—Dimensions, e.g. volume or area
    • B32B2307/7375—Linear, e.g. length, distance or width
    • B32B2307/7376—Thickness
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2439/00—Containers; Receptacles
    • B32B2439/40—Closed containers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2439/00—Containers; Receptacles
    • B32B2439/70—Food packaging
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/10—Batteries
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J151/06—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond

Definitions

  • the present invention relates to the field of polymer films, in particular to a propylene polymer-based composite film, a preparation method and application thereof, and a packaging material comprising the composite film.
  • Polypropylene films are usually prepared by methods such as casting and biaxial stretching, but polypropylene films prepared from homopolypropylene raw materials usually have low impact strength. Polypropylene films are often used in packaging applications, which require high impact properties, as well as good optical properties for content visualization and aesthetics.
  • impact-resistant polypropylene can be used to prepare films, or polyolefin elastomers can be added to polypropylene, but the films prepared by the above methods usually have high haze, poor transparency and other optical properties . It is also possible to add nucleating agents to the film at the same time to reduce the haze of the film by refining the crystals in the film, but this method leads to a decrease in impact performance.
  • the film can also be prepared by a multi-layer co-extrusion method.
  • CN101913279A adopts a three-layer co-extrusion method to prepare a composite film.
  • the layers in the film contain 1:10-1:3 Elastomer and PP are blended in proportion, and the elastomer provides better impact resistance.
  • the elastomer will also lead to a large difference in the flow properties of the core surface layer, further aggravating the problem of uneven film surface, and may lead to uneven performance of the film everywhere;
  • the difference in properties also affects the uniformity of the film and can affect the optical and mechanical properties of the film.
  • propylene polymer-based films It is difficult for existing propylene polymer-based films to have good optical properties and impact resistance at the same time; in addition, when propylene polymer films are used in packaging applications, it is generally desirable to have better performance at lower heat sealing temperatures. Good heat sealing performance, the propylene polymer films in the prior art cannot meet such performance requirements. In addition, existing composite films have poor uniformity in thickness and properties.
  • the object of the present invention is to provide a low haze high impact film based on propylene polymer and a preparation method thereof.
  • Such films can have both good impact resistance and optical properties.
  • Another object of the present invention is to provide a film as described above which may additionally have good mechanical properties (eg tensile properties) and/or good heat seal strength at lower heat seal temperatures.
  • Another object of the present invention is to provide a transparent impact-resistant composite film based on propylene polymers, which has good impact resistance and optical properties at the same time, and has good film thickness and uniformity of properties.
  • Another object of the present invention is to provide a preparation method of the composite film, which has a stable preparation process and good uniformity of the obtained film.
  • a propylene impact copolymer containing a specific elastic moiety as a raw material in at least one layer of a composite film, through extrusion casting, a specific microstructure containing a uniformly dispersed strip-like rubber phase is prepared.
  • the composite film thus achieves the purpose.
  • a first aspect of the present invention provides a propylene polymer-based composite film comprising at least two distinct layers: layer a and layer b;
  • layer a and layer b each comprise at least one propylene polymer
  • layer a and layer b comprises a propylene impact copolymer
  • the propylene impact copolymer comprises elastic moieties which form a dispersed strip-like rubber phase in the composite film.
  • a second aspect of the present invention provides a method for preparing the composite film of the present invention, which comprises extrusion casting the raw material composition for forming each layer to form the composite film.
  • the third aspect of the present invention provides the application of the composite film of the present invention in the field of packaging materials.
  • a fourth aspect of the present invention provides a packaging material comprising the composite film of the present invention.
  • Fig. 1a and Fig. 1b are schematic diagrams of the sampling point selection of the thin film of the present invention.
  • Example A1 is a scanning electron microscope (SEM) photograph of a cross-section of the raw propylene impact copolymer spline used in Example A1 according to the present invention.
  • FIG. 3 is an atomic force microscope photograph of a section of the thin film of Example A1 according to the present invention.
  • FIG. 4 is an atomic force microscope photograph of a section of a thin film of Comparative Example A3 according to the present invention.
  • FIG. 5 is an atomic force microscope photograph of a section of a thin film of Example C1 according to the present invention.
  • Figure 6a is a SEM photograph of a cross-section of the raw propylene impact copolymer spline used in Example E1 according to the present invention.
  • Figure 6b is a SEM photograph of a cross-section of the raw propylene impact copolymer spline used in Comparative Example E1 according to the present invention.
  • FIG. 7 is an atomic force microscope photograph of a section of a thin film of Example E1 according to the present invention.
  • a first aspect of the present invention provides a propylene polymer-based composite film comprising at least two distinct layers: layer a and layer b;
  • layer a and layer b each comprise at least one propylene polymer
  • layer a and layer b comprises a propylene impact copolymer
  • the propylene impact copolymer comprises elastic moieties which form a dispersed strip-like rubber phase in the composite film.
  • Dispersed as used herein means that the rubber phase is not continuously distributed in the composite film.
  • AFM atomic force microscope
  • TD transverse direction
  • stripe refers to a shape with an aspect ratio generally greater than 2.
  • aspect ratio refers to the ratio of the vertical axis to the horizontal axis of an object.
  • the longitudinal axis refers to the longest dimension of the object (here, the rubber phase), ie the distance between two points on the contour of the object that are farthest apart.
  • the horizontal axis refers to the length of the straight line perpendicular to the vertical axis between the intersection points with the object outline and the longest distance between the intersection points.
  • the average size of the lateral axis of the rubber phase may be 20-200 nm, more preferably 20-150 nm.
  • the average value of the aspect ratio of the rubber phase may be 5-20, preferably 5-15.
  • the transverse dimension and aspect ratio are measured by atomic force microscopy, observing a cross section of the composite film cut in the transverse direction (TD). Based on 200 sample points, the average value of the horizontal axis size of the rubber phase was calculated as the average size of the horizontal axis of the rubber phase, and the average value of the aspect ratio of the rubber phase was calculated as the average value of the aspect ratio of the rubber phase.
  • the machine direction refers to the machine direction.
  • the transverse direction refers to the direction perpendicular to the machining direction.
  • the rubber phases are advantageously arranged parallel to each other.
  • parallel alignment means that the transverse cross-sections of the rubber phases are aligned parallel to each other along a certain direction. Excluded here are a small amount of rubber phase particles arranged in different directions in local areas that are inconsistent with the overall arrangement direction of the rubber phase particles in the entire composite film due to the preparation process, and those that cannot be clearly observed due to the preparation process or AFM method. Rubber phase particles.
  • parallel arrangement includes substantially parallel conditions.
  • the transverse cross-sections of the rubber phase are at an angle of no greater than about 10 degrees to each other, preferably less than about 5 degrees.
  • Both layer a and layer b in the present invention comprise at least one propylene polymer, both consist of a propylene polymer-based composition, but differ in their specific composition and/or thickness.
  • the entire composite film is a propylene polymer-based composite film, which can also be called a polypropylene composite film.
  • layer a is intended to serve as the core layer of the composite film, ie a layer relatively remote from the medium to which the composite film is to be in contact during use of the composite film.
  • Layer b is intended to serve as the skin layer of the composite film, ie the layer close to the medium to which the composite film is to be in contact during use of the composite film, such as the electrolyte to which the battery packaging material comes into contact.
  • At least one of the layers a and b comprises the propylene impact copolymer having a specific elastic portion, so that the entire composite film contains a specific dispersed rubber phase.
  • the elastic portion may appear as a spherical or near-spherical rubber phase in scanning electron micrographs of impact bars of the propylene impact copolymer.
  • the propylene impact copolymer is preferably a propylene impact copolymer containing ethylene units, wherein the elastic part is a copolymerized part containing ethylene units, preferably selected from ethylene-propylene copolymerized parts and ethylene-butene copolymerized parts.
  • the propylene impact copolymer comprises a propylene homopolymeric portion and the copolymerized portion containing ethylene units.
  • the propylene homopolymeric portion may comprise an isotactic polymeric structure.
  • the content of the copolymerized moiety containing ethylene units in the propylene impact copolymer is preferably 3-15% by weight, more preferably 7-12% by weight, as determined by13C NMR.
  • the ethylene unit content of the propylene impact copolymer is preferably 1-14% by weight, preferably 3-12% by weight, based on the total weight of the propylene impact copolymer.
  • the ethylene unit content preferably does not exceed 40% by weight.
  • the ethylene unit group [EEE] content preferably does not exceed 20% by weight, determined by 13 C NMR.
  • the propylene impact copolymer may have a block structure or comprise a propylene block copolymer.
  • the melt mass flow rate (MFR) of the propylene impact copolymer at 230° C. and a load of 2.16kg can be 1-10g/10min, preferably 1-8g/10min, determined according to the standard GB/T 3682-2000, test The temperature was 230°C and the load was 2.16kg.
  • Useful propylene impact copolymers are commercially available, such as propylene impact copolymers of Zhongsha Petrochemical under the brand name EP200K, propylene impact copolymers of Shanghai Petrochemical under the brand names of F200R and M180R, and propylene impact copolymers of Maoming Petrochemical under the brand name PPB-M02D. Impact copolymer, Korea Hyosung brand J410F propylene impact copolymer.
  • the propylene impact copolymers can also be prepared by continuous polymerization in the presence of Ziegler-Natta catalysts with high stereoselectivity.
  • the continuous polymerization method means that the preparation process includes at least two sequential steps, wherein the elastic part and the non-elastic part are each prepared in a separate step, and, in addition to the first step, the latter step has been The resulting polymer is carried out in the presence of the catalyst used in the previous step.
  • Layer a may comprise homopolypropylene and/or propylene random copolymer.
  • the melt mass flow rate of the homopolypropylene at 230°C under a load of 2.16kg is preferably 2-15g/10min, measured according to the standard GB/T 3682-2000, the test temperature is 230°C, and the load is 2.16kg.
  • the isotacticity of the homopolypropylene is preferably greater than 97%, as determined by13C NMR.
  • the molecular weight distribution Mw/Mn of the homopolypropylene is preferably 4.5-7.0, as determined by gel permeation chromatography (GPC).
  • the propylene random copolymer may be a copolymer of propylene and ethylene and/or butene, such as ethylene-propylene-butene ternary random copolymer, propylene-ethylene binary random copolymer, propylene-butene di- Elemental random copolymers.
  • the melt mass flow rate of the propylene random copolymer at 230° C. and a load of 2.16kg can be 2-15g/10min, preferably 2-10g/10min, determined according to the standard GB/T 3682-2000.
  • the molecular weight distribution Mw/Mn of the random copolymer is preferably 4.5-7.0, as determined by GPC.
  • Useful propylene random polymers are commercially available, for example, random propylene copolymers of Yanshan Petrochemical's grade F5006, Shanghai Petrochemical's random propylene copolymers of grades F500EPS, F800EDF or F800EPS; or by methods conventional in the art preparation.
  • Layer b may comprise a propylene random copolymer.
  • the propylene random copolymer is as described above.
  • the propylene random copolymers in layer b and layer a may be the same or different.
  • layer b may comprise 60-100 wt% propylene random copolymer.
  • At least one of layer a and layer b may comprise a polyolefin elastomer, thereby advantageously further enhancing the impact resistance of the composite film.
  • the polyolefin elastomer may be an elastomeric copolymer of ethylene and an alpha olefin.
  • the alpha olefin is preferably a C 3 -C 12 alpha olefin, more preferably at least one selected from the group consisting of propylene, 1-butene, 1-hexene and 1-octene.
  • Useful polyolefin elastomers are commercially available, for example, Dow's polyolefin elastomer 8200, Dow's 8411 polyolefin elastomer, Mitsui's DF640 or DF840 polyolefin elastomers, Exxon's polyolefin elastomers are 6102, VM3980 or EXACT3139; or can be prepared by conventional methods in the art.
  • the elastic portion in the propylene impact copolymer and the polyolefin elastomer form a dispersed rubber phase in the composite film, which also takes the form of strips and is parallel to each other arrangement.
  • the average size of the transverse axis of such a rubber phase may also be 20 to 200 nm, preferably 20 to 150 nm.
  • the average aspect ratio of the rubber phase may be 5-20, preferably 5-15.
  • the dimensions are determined by AFM as described above.
  • the presence of the polyolefin elastomer advantageously compensates for possible uneven distribution of the rubber phase in the propylene impact copolymer, thereby improving the uniformity of impact properties throughout the film.
  • the polyolefin elastomer has a shear viscosity ratio ⁇ 160 / ⁇ 640 of 1.2-3, preferably 1.7-2.3 at 230° C. and shear rates of 160r ⁇ 1 and 640r ⁇ 1 .
  • the shear viscosity ⁇ 640 of the polyolefin elastomer at 230° C. and a shear rate of 640r ⁇ 1 is preferably 100-500 Pa ⁇ s, more preferably 140-400 Pa ⁇ s.
  • Shear viscosity ⁇ 160 and ⁇ 640 were determined according to ISO 11443:2014 using a capillary rheometer.
  • the material constituting layer a may have a melt mass flow rate at 230°C under a load of 2.16kg of 2-10g/10min, preferably 2-8g/10min, more preferably 3-7g /10min, measured according to the standard GB/T3682-2000, the test temperature is 230°C, and the load is 2.16kg.
  • the material constituting layer b may have a melt mass flow rate at 230°C under a load of 2.16kg of 2-10g/10min, preferably 3-10g/10min, more preferably 3-9g/ 10min, more preferably 4-8g/10min, measured according to the standard GB/T 3682-2000, the test temperature is 230°C, and the load is 2.16kg.
  • melt mass flow rate can advantageously make the film preparation process smoother, resulting in better uniformity, mechanical properties and optical properties of the film.
  • Layer a and layer b may both comprise the propylene impact copolymer, wherein the propylene impact copolymer in layer a and layer b may be the same or different. It is also possible that only one of the layers a and b contains the propylene impact copolymer.
  • Layer a and layer b may also both comprise the polyolefin elastomer, wherein the polyolefin elastomers in layer a and layer b may be the same or different.
  • the ratio between the weight ratio of the polyolefin elastomer in the layer a and the weight ratio of the polyolefin elastomer in the layer b is 6:1-1:6. It is also possible that only one of the layers a and b contains the polyolefin elastomer.
  • Layer a and layer b may also both comprise said propylene impact copolymer and said polyolefin elastomer, wherein the propylene impact copolymer in layer a and layer b may be the same or different, and layer a and layer b
  • the polyolefin elastomers in can also be the same or different.
  • layers a and b contains the propylene impact copolymer and one or both of the layers a and b contain the polyolefin elastomer; alternatively, layers a and b contain the polyolefin elastomer Only one layer of b contains the polyolefin elastomer, and one or both of layers a and b contain the propylene impact copolymer.
  • layer a comprises the homopolypropylene, the propylene impact copolymer and the polyolefin elastomer
  • layer b comprises the random propylene copolymer and the polyolefin elastomer
  • the ratio between the weight ratio of the polyolefin elastomer in layer a and the weight ratio of the polyolefin elastomer in layer b is 2:1-1:4, for example, it can be It is 1.5:1, 1:1, 1:1.5, 1:2, 1:2.5, 1:3, 1:3.5 and any value therebetween, more preferably 1:1-1:2.
  • the ratio of the weight proportion of the polyolefin elastomer in the above layer a to the weight proportion of the polyolefin elastomer in the layer b can further improve the impact resistance and impact resistance of the composite film. Optical performance, while making the extrusion process smoother.
  • layer a may comprise 40-90% by weight, preferably 50-90% by weight, more preferably 55-75% by weight of said homopolypropylene, 5-40% by weight, preferably 10 - 30% by weight of said propylene impact copolymer and 2 to 30% by weight, preferably 5 to 20% by weight of said polyolefin elastomer, each based on the total weight of layer a.
  • Layer b may comprise 40-95% by weight, preferably 60-95% by weight, more preferably 75-90% by weight of said random propylene copolymer, and 5-60% by weight, preferably 5-40% by weight, more preferably 10 - 25% by weight of said polyolefin elastomer, each based on the total weight of layer b.
  • Composite films comprising such skin layers and core layers may advantageously have not only excellent optical properties, but also enhanced heat seal strength.
  • the thickness uniformity and property uniformity of the film can be greatly improved when the polyolefin elastomers in both layer a and layer b meet the following conditions: at 230°C, shear rates 160r -1 and 640r
  • the ratio of shear viscosity ⁇ 160 / ⁇ 640 under -1 is 1.2-3, preferably 1.7-2.3, and the shear viscosity ⁇ 640 at 230°C and shear rate 640r -1 is 100-500Pa ⁇ s, It is preferably 140-400 Pa ⁇ s.
  • the difference in shear viscosity ( ⁇ A 160 - ⁇ B at 230°C and shear rate 160r ⁇ 1 of the propylene polymer composition constituting the layer a and the propylene polymer composition constituting the layer b) 160 ) and the difference ( ⁇ A 640 - ⁇ B 640 ) of the shear viscosity at 230 ° C and shear rate 640r -1 are all ⁇ 0, and the ratio of the two ( ⁇ A 160 - ⁇ B 160 )/( ⁇ A 640 - ⁇ B 640 ) is 1-2.6, preferably 1.4-2.5, more preferably 1.5-2.2, so that the uniformity of film thickness and performance can be further improved by adjusting the fluidity compatibility of each layer of raw materials.
  • layer a comprises a propylene polymer and the polyolefin elastomer
  • layer b comprises the random propylene copolymer, the polyolefin elastomer and the propylene impact copolymer.
  • the propylene polymer in layer a may be selected from homopolypropylene and/or the propylene impact copolymer.
  • layer a may comprise 70-100% by weight of propylene polymer.
  • the ratio between the weight ratio of the polyolefin elastomer in layer a and the weight ratio of the polyolefin elastomer in layer b is 10:1-1:6, preferably 6 :1-1:4, more preferably 4:1-1:4, such as 3.5:1, 3:1, 2.5:1, 2:1, 1.5:1, 1:1, 1:1.5, 1 :2, 1:2.5, 1:3, 1:3.5 and any value in between.
  • the ratio of the weight proportion of the polyolefin elastomer in the above layer a to the weight proportion of the polyolefin elastomer in the layer b can further improve the impact resistance and impact resistance of the composite film. Optical performance, while making the extrusion process smoother.
  • layer a may comprise 50-95% by weight, preferably 70-95% by weight, more preferably 80-95% by weight of said propylene polymer and 5-50% by weight, preferably 5- 30% by weight, more preferably 5-20% by weight of said polyolefin elastomer, each based on the total weight of layer a;
  • layer b may comprise 40-90% by weight, preferably 50-90% by weight, more preferably 60-85% by weight % by weight of said random propylene copolymer, 5-40% by weight, preferably 5-30% by weight, more preferably 5-20% by weight of said polyolefin elastomer and 2-30% by weight, preferably 5-20% by weight % of the propylene impact copolymer, each based on the total weight of layer b.
  • a composite film comprising such a skin layer and a core layer can not only have improved impact resistance and improved optical and mechanical properties, but also due to the fact that the skin layer (heat seal layer) contains a specific rubber phase of the propylene impact copolymer and other components.
  • the synergistic effect between the components can effectively improve the heat sealing strength while reducing the heat sealing temperature.
  • layer a comprises the polyolefin elastomer, the propylene impact copolymer and other types of propylene polymers, which may be selected from the homopolypropylene and/or propylene random copolymer; and layer b comprises said random propylene copolymer and said polyolefin elastomer.
  • layer a may comprise 40-90 wt% propylene impact copolymer, 5-40 wt% other types of propylene polymers and 2-30 wt% polyolefin elastomer, Preferably 55-75% by weight of propylene impact copolymer, 10-30% by weight of other types of propylene polymers and 5-20% by weight of polyolefin elastomer, each based on the total weight of layer a; layer b may comprise 40-95% by weight of propylene random copolymer and 5-60% by weight of polyolefin elastomer, preferably 75-90% by weight of propylene random copolymer and 10-25% by weight of polyolefin elastomer, each based on the layer total weight of b.
  • the composite film can have good impact resistance, optical properties and tensile properties at the same time, and can have good heat-sealing strength at a lower heat-sealing temperature.
  • the sum of the wt % of all components of each layer is 100 wt %.
  • Layer a and/or layer b may also contain additives conventionally used in polymer films, such as antioxidants, lubricants, antihalogens, light stabilizers, heat stabilizers, colorants, fillers, slip agents, surface adhesives At least one of adhesive, electromagnetic shielding aid, flame retardant, insulating additive, anti-sticking agent and antistatic agent, etc.
  • additives conventionally used in polymer films such as antioxidants, lubricants, antihalogens, light stabilizers, heat stabilizers, colorants, fillers, slip agents, surface adhesives At least one of adhesive, electromagnetic shielding aid, flame retardant, insulating additive, anti-sticking agent and antistatic agent, etc.
  • antioxidants can be used to improve the oxidation resistance of the composite film during processing.
  • the antioxidant can be various antioxidants commonly used in the art, such as at least one of antioxidant 1076, antioxidant 1010, antioxidant 168, and thioester antioxidants (such as DLTP, DSTP), etc. kind.
  • the content of the antioxidant may be 0.1-0.8 parts by weight, preferably 0.2-0.4 parts by weight.
  • the composite film may also contain other film auxiliaries commonly used in the art, such as selected from lubricants, anti-halogen agents, light stabilizers, heat stabilizers, colorants, fillers, slip agents, surface adhesives At least one of adhesive, electromagnetic shielding aid, flame retardant, insulating additive, anti-sticking agent and antistatic agent.
  • film auxiliaries can be used in conventional amounts.
  • the content of each of the other film auxiliaries can be 0.01-0.5 parts by weight, preferably 0.05-0.3 parts by weight, more preferably 0.01-0.5 parts by weight. 0.05-0.15 parts by weight unless otherwise specified.
  • lubricants can be added to the composite film.
  • the lubricant may be a PEG-based lubricant and/or a monoglyceride-based lubricant. Based on the total weight of the layer being 100 parts by weight, the content of the lubricant may be 0.01-0.5 part by weight, preferably 0.05-0.2 part by weight.
  • polar monomer modified polypropylene can be added as a surface adhesive, thereby enhancing the bonding between the composite film and the interface of other materials, and obtaining a high-adhesion and high-impact propylene polymer composite film .
  • the polar monomer-modified polypropylene is especially added in layer b.
  • layer a may comprise 40-90% by weight, preferably 50-85% by weight of homopolypropylene, 5-45% by weight, preferably 10-30% by weight % by weight of propylene impact copolymer and 2-40% by weight, preferably 5-20% by weight of polyolefin elastomer; and based on the total weight of layer b, layer b comprises 40-99% by weight, preferably 70-90% by weight % by weight of propylene random copolymer, 0-30% by weight, preferably 5-15% by weight of polyolefin elastomer and 1-30% by weight, preferably 5-15% by weight of polar monomer modified polypropylene.
  • layer a may comprise 50-100% by weight, preferably 75-95% by weight polypropylene and 0-50% by weight, preferably 5-25% by weight, based on the total weight of layer a % of polyolefin elastomer; and based on the total weight of layer b, layer b may comprise 30-90% by weight, preferably 60-85% by weight of propylene random copolymer, 5-40% by weight, preferably 5-20% by weight % by weight of polyolefin elastomer, 2.5-20% by weight, preferably 5-10% by weight of propylene impact copolymer and 2.5-20% by weight, preferably 5-10% by weight of polar monomer modified polypropylene.
  • the polar monomer in the polar monomer-modified polypropylene may be selected from at least one of hydroxyl group-containing comonomers, cyano group-containing comonomers and acid anhydride monomers.
  • the hydroxyl-containing comonomer is preferably a hydroxy acid and/or vinyl alcohol.
  • the cyano group-containing comonomer is preferably a cyanoacrylate.
  • the acid anhydride monomer is preferably maleic anhydride and/or itaconic anhydride, more preferably maleic anhydride.
  • Maleic anhydride grafted polypropylene (PP-g-MAH) has both polar groups and olefin non-polar segments, and it has the basic physical properties of the original polypropylene, such as high crystallinity, high strength, high impact, etc. properties and improved adhesion to other materials.
  • the polar monomer-modified polypropylene is commercially available, for example, maleic anhydride-modified polypropylene with the brand name of QF551A from Mitsui, maleic anhydride-modified polypropylene with the brand name of CMG9801 from Jiayirong, Exxon The company's grade is PO1015 maleic anhydride modified polypropylene.
  • a conductive filler can also be added to the composite film of the present invention, thereby improving the antistatic property of the composite film.
  • the conductive filler is preferably added in layer b.
  • the conductive filler may be added in an amount of 0.1-10 parts by weight, preferably 0.5-4.5 parts by weight, based on 100 parts by weight of the total weight of the matrix polymer in layer b.
  • the conductive filler may be, for example, at least one of carbon black, graphite, carbon nanotubes, carbon fibers, conductive metal particles, conductive metal fibers, and metal oxides.
  • the carbon black-based conductive filler includes, but is not limited to, at least one of acetylene carbon black, superconducting carbon black, and special conducting carbon black.
  • the graphite-based conductive filler includes, but is not limited to, at least one of natural graphite, expandable graphite, expanded graphite and graphene.
  • the carbon nanotube-based conductive fillers include, but are not limited to, unsurface-modified or surface-modified single-wall carbon nanotubes and/or multi-wall carbon nanotubes.
  • the conductive metal in the conductive metal particles and the conductive metal fibers may each independently be at least one of silver, aluminum, copper, iron, nickel and stainless steel.
  • the conductive metal-coated filler may be selected from at least one of lead-plated, nickel-plated, silver-plated glass balls, glass fibers and mica flakes.
  • the metal oxide includes, but is not limited to, at least one of titanium oxide, zinc oxide, tin oxide, indium oxide, and cadmium oxide.
  • Antistatic propylene polymer films can be prepared by adding conductive fillers, and their surface resistivity can be 10 2 -10 8 ⁇ , preferably 10 2 -10 4 ⁇ , as measured by Keithley 6517B Electrometer. The antistatic properties of the films are durable and less affected by ambient humidity.
  • an electromagnetic shielding aid can be added to the composite film to prepare an electromagnetic shielding film.
  • the electromagnetic shielding aid is preferably added in layer b.
  • the electromagnetic shielding aids may be conductive metal fillers and/or carbon materials.
  • the conductive metal filler is preferably conductive metal particles and/or conductive metal fibers.
  • the metals in the conductive metal particles and the conductive metal fibers may each be independently selected from one or more of silver, aluminum, copper, iron, nickel, and stainless steel.
  • the carbon material is preferably one or more of carbon black, graphite, graphene and carbon nanotubes.
  • the electromagnetic shielding aid can be added in an amount of 5-30 parts by weight, preferably 15-25 parts by weight, based on 100 parts by weight of the matrix polymer in layer b.
  • the electromagnetic shielding effectiveness of the obtained composite film can reach ⁇ 25dB, preferably ⁇ 28dB.
  • the electromagnetic wave band is in the frequency range of 50MHz to 1GHz when tested with a flange coaxial test equipment.
  • the electromagnetic shielding aid can also be used in combination with a coupling agent.
  • the coupling agent can improve the compatibility between the matrix polymer component (resin component) of the propylene polymer composition and the electromagnetic shielding aid, and the type, usage and amount of the coupling agent can be conventionally selected in the field,
  • the coupling agent may be selected from titanate type coupling agents, and the titanate type coupling agent may be selected from monoalkoxy type titanate, monoalkyl pyrophosphate type titanate, One or more of coordination titanate and chelate titanate; preferably, the titanate coupling agent is selected from tetrabutyl titanate and/or tetraisopropyl titanate.
  • the content of the coupling agent may be 1-6 parts by weight, preferably 4-6 parts by weight, based on 100 parts by weight of the total weight of the base polymer components.
  • Flame retardants can also be added to the composite film to improve the flame retardant properties.
  • it can be added in layers a and/or b, and can also be added in another layer c, in which case layer c is a flame retardant functional layer.
  • layer c may comprise 30-80% by weight, preferably 40-70% by weight of propylene polymer and 20-70% by weight, preferably 30-60% by weight of flame retardant, based on the total weight of layer c.
  • the oxygen index ⁇ 21% can be achieved, preferably the oxygen index ⁇ 23%, measured according to the method specified in GB/T 2406-2008.
  • the flame retardant can be selected from the hydrates of metal or non-metal hydroxides and/or oxides, phosphorus-based flame retardants, boron-based flame retardants, antimony-based flame retardants and intumescent flame retardants. at least one.
  • the metal or non-metal hydroxide and/or oxide hydrate may be at least one of aluminum, magnesium, boron, zinc hydroxide and layered double metal hydroxide;
  • the phosphorus-based flame retardant The agent can be at least one of red phosphorus, phosphate, polyphosphate and phosphate ester;
  • the boron-based flame retardant can be boric acid and/or borate, and the borate is preferably ammonium borate and/or Zinc borate;
  • the antimony flame retardant can be at least one of antimony trioxide, antimony pentoxide and sodium antimonate;
  • the intumescent flame retardant is sulfuric acid, pentaerythritol or its dimer or trimer , butaneerythritol, cyclohexanol, sorbitol, glucose, maltose, starch, resorcinol, ammonium polyphosphate, dicyandiamide, melamine, urea, mel
  • the flame retardant is an intumescent flame retardant, preferably a mixture of ammonium polyphosphate and pentaerythritol, and specifically, the weight ratio of ammonium polyphosphate and pentaerythritol is 0.5-5:1.
  • the flame retardant is a mixture of magnesium hydroxide and aluminum hydroxide, and specifically, the weight ratio of magnesium hydroxide and aluminum hydroxide is 0.5-2:1.
  • the flame retardant polypropylene film prepared by adding flame retardant has the advantages of easy processing and good performance.
  • colorants can be added to the composite film.
  • the colorant may be a conventional choice in the art, including but not limited to at least one of azo pigments, phthalocyanine pigments, heterocyclic pigments, lake pigments, dyes, optical brighteners, and fluorescent pigments.
  • the colorants described above are all commercially available.
  • the colorant is preferably added in layer a. Based on 100 parts by weight of the matrix polymer in the layer a, the content of the colorant may be 0.1-1 part by weight, preferably 0.3-0.8 part by weight.
  • Layer a may also include a dispersant.
  • the dispersant can improve the processability and uniformity between the matrix polymer component of the layer a and the colorant, and the type, usage and amount of the dispersant can be conventionally selected in the art.
  • the dispersant can be For low molecular weight polyethylene wax, the weight content of the dispersant may be 20-30% by weight of the colorant.
  • a slip agent can also be added to the composite film of the present invention.
  • the slip agent can be an amide slip agent, preferably at least one of erucamide, oleic acid amide, stearic acid amide, behenic acid amide, stearyl erucic acid amide and ethylene bis-stearamide. kind.
  • the slip agent may be a mixture of an amide type slip agent and a migration-resistant slip agent, wherein the amide type slip agent is preferably erucamide, oleic acid amide, stearic acid amide, At least one of behenamide, stearyl erucamide and ethylene bisstearamide.
  • the migration-resistant slip agent is preferably at least one of polytetrafluoroethylene particles, polyimide particles, polyamide particles, polycarbonate particles, organic silicon, nano-calcium carbonate, mica and nano-silica.
  • the weight ratio of the amide-based slip agent and the migration-resistant slip agent is 1:20-1:1, preferably 1:10-1:2.
  • the particle size range of the migration-resistant slip agent contained in the slip agent may be 0.1-5 ⁇ m, preferably 0.3-2 ⁇ m.
  • the slip agent can be added in the layer a and/or the layer b, and its addition amount can be 0.01-1.5% by weight, preferably 0.08-0.6% by weight, based on the total weight of the layer.
  • slip agents are added in both layer a and layer b.
  • the molecular weight of the amide type slip agent in the slip agent in the layer b is not less than the molecular weight of the amide type slip agent in the slip agent in the layer a.
  • an amide-based slip agent is added to layer a, and a mixture of an amide-type slip agent and a migration-resistant slip agent is added to layer b.
  • the initial slip performance of the film is improved.
  • the migration-resistant slip agent in the composite slip agent can provide a part of the slip performance without the need for precipitation.
  • the particle size range can ensure that the heat sealing performance and optical properties of the film will not change; in addition, the amide-type slip agent in the surface layer can also provide a certain slip performance, further reduce the friction coefficient of the film, and improve the initial smoothness of the film. slip performance.
  • better high-temperature slip and heat-sealing performance retention can be provided through the use of the composite slip agent and the combination of the slip agent in the core surface layer.
  • the obtained composite film may have a surface friction coefficient of ⁇ 0.3, preferably ⁇ 0.23; after heating at 60°C for 24 hours, the change of the film surface friction coefficient is ⁇ 0.02, preferably the change of the film surface friction coefficient ⁇ 0.01.
  • insulating additives can be added to the composite film of the present invention, so that the electrical insulating properties of the propylene polymer composite film can be improved.
  • propylene graft polymers can be used as insulating additives.
  • a propylene graft polymer can be added in layer a and/or layer b.
  • the propylene graft polymer can be added in an amount of 5 to 45% by weight, based on the total weight of the layer.
  • layer a comprises 50-90% by weight, preferably 55-75% by weight of homopolypropylene, 5-45% by weight, preferably 10-30% by weight of propylene, based on the total weight of layer a
  • layer a comprises 50-100% by weight, preferably 75-95% by weight of propylene polymer and 0-50% by weight, preferably 5-25% by weight of polymer, based on the total weight of layer a olefin elastomer; and layer b comprising 50-90% by weight, 60-85% by weight of propylene random copolymer, 5-40% by weight, preferably 5-20% by weight of polyolefin elastomer, based on the total weight of layer b body and 2-40% by weight, preferably 5-20% by weight of the propylene graft polymer.
  • the propylene graft polymer may include structural units derived from copolymerized polypropylene and structural units derived from grafted monomers grafted thereto.
  • the grafting monomers can be selected from acrylates; acrylics; styrenes; alkenyl-containing silanes; alkenyl-containing heterocyclic monomers; acid anhydrides with at least one olefinic unsaturation and alkenyl-containing A combination of polymerized monomers.
  • the melt mass flow rate of the propylene graft polymer at 230°C under a load of 2.16kg can be 0.01-30g/10min, preferably 0.05-20g/10min, more preferably 0.1-10g/10min, more preferably 0.2 -8g/10min.
  • the copolymerized polypropylene may be a propylene copolymer containing ethylene or higher alpha-olefins or a mixture thereof.
  • the comonomer of the copolymerized polypropylene is selected from at least one of ethylene and C 4 -C 8 ⁇ -olefin.
  • the C 4 -C 8 alpha-olefins include but are not limited to: 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene and 1-octene at least one of them.
  • the comonomer is preferably ethylene and/or 1-butene, and further preferably, the copolymerized polypropylene consists of propylene and ethylene.
  • the copolymerized polypropylene also has at least one of the following features: the comonomer content is 0.5-30 mol%, preferably 4-25 mol%; the xylene soluble content is 2-80 wt% , preferably 18-75% by weight, more preferably 30-70% by weight; comonomer content in the soluble matter is 10-70% by weight, preferably 10-50% by weight, more preferably 20-35% by weight;
  • the intrinsic viscosity ratio of the soluble matter to polypropylene is 0.3-5, preferably 0.5-3, more preferably 0.8-1.3; the melt mass flow rate at 230° C.
  • under a load of 2.16kg is 0.01-60g/10min, Preferably it is 0.05-35g/10min, more preferably 0.5-15g/10min; melting temperature Tm is above 100°C, preferably 110-180°C, more preferably 120-170°C; weight average molecular weight is 20 ⁇ 10 4 -60 ⁇ 10 4 g/mol.
  • the copolymerized polypropylene can be any suitable polypropylene powder that is commercially available, and can also be produced by a common polymerization process described in the literature. For example, refer to the methods described in CN101679557A and CN101058654A.
  • the propylene graft polymer may include structural units derived from copolymerized polypropylene and grafted thereto structural units derived from acrylic monomers and optionally acrylic monomers. Based on the weight of the propylene graft polymer, the content of the grafted structural units derived from acrylic monomers and optional acrylic monomers may be 0.3-7% by weight, preferably 0.8-5% by weight . In the propylene graft polymer, the molar ratio of the structural unit derived from the acrylate monomer to the structural unit derived from the acrylic monomer may be 1:0-2, preferably 1:0.125-1.
  • the acrylate-based monomer used as the grafting monomer can be any monomeric acrylate-based compound that can be polymerized by free radicals, and can be selected from at least one of the monomers having the structure shown in formula I;
  • R 1 , R 2 , R 3 are each independently selected from H, C 1 -C 6 straight-chain alkyl, C 3 -C 6 branched-chain alkyl;
  • R 4 is selected from substituted or unsubstituted following groups: C 1 -C 20 straight chain alkyl, C 3 -C 20 branched chain alkyl, C 3 -C 12 cycloalkyl, C 3 -C 12 epoxy alkyl, C 3 -C 12 epoxy alkyl alkyl , the substituted group is selected from at least one of halogen, amino and hydroxyl.
  • the acrylate monomer is selected from methyl (meth)acrylate, sec-butyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, (meth)acrylate Isobutyl acrylate, tert-butyl (meth)acrylate, isooctyl (meth)acrylate, dodecyl (meth)acrylate, cocoate (meth)acrylate, ten (meth)acrylate At least one of octaalkyl ester, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, dimethylaminopropyl (meth)acrylate and glycidyl (meth)acrylate kind.
  • the acrylic monomer can be any monomeric acrylic compound that can be polymerized by free radicals, and can be selected from at least one of the monomers having the structure shown in formula II;
  • R 1 , R 2 , and R 3 are each independently selected from H, C 1 -C 6 straight-chain alkyl, and C 3 -C 6 branched-chain alkyl.
  • the acrylic monomer is selected from at least one of acrylic acid, methacrylic acid and 2-ethylacrylic acid.
  • C 3 -C 12 epoxyalkylalkyl refers to an alkylene oxide substituted alkyl group having 3 to 12 carbon atoms, eg, oxiranylmethyl.
  • structural units derived from acrylic monomers may not exist, or may coexist with structural units derived from acrylic monomers, preferably, structural units derived from acrylic monomers and acrylic monomers
  • the molar ratio of the structural units of the monomer is 1:0-2, preferably 1:0.125-1.
  • the ratio of the total mass of the acrylic monomer and optional acrylic monomer to the mass of the copolymerized polypropylene is 0.1-10:100, preferably 0.5-8:100, more preferably 0.8-7: 100.
  • the molar ratio of the acrylate monomer to the acrylic monomer is 1:0-2, preferably 1:0.125-1.
  • the propylene graft polymer may include structural units derived from copolymerized polypropylene and structural units derived from styrene-based monomers. Based on the weight of the propylene graft polymer, the content of the grafted structural units derived from the styrene-based monomer in the propylene graft polymer may be 0.5-14% by weight, preferably 1-7.5% by weight, More preferably, it is 1.5 to 5% by weight.
  • the styrene-based monomer used as the grafting monomer can be any monomeric styrene-based compound that can be polymerized by free radicals, and can be selected from monomers with the structure shown in formula III, monomers with the structure shown in formula IV at least one of the monomer and the monomer having the structure shown in formula V;
  • R 1 , R 2 , R 3 are each independently selected from H, substituted or unsubstituted C 1 -C 6 alkyl;
  • R 4 -R 8 are each independently selected from H, halogen, hydroxyl, amino , phosphoric acid group, sulfonic acid group, substituted or unsubstituted C 1 -C 12 alkyl, substituted or unsubstituted C 3 -C 12 cycloalkyl, substituted or unsubstituted C 1 -C 12 alkoxy group, substituted or unsubstituted C 1 -C 12 ester group, substituted or unsubstituted C 1 -C 12 amine group, the substituent group is selected from halogen, hydroxyl, amino, phosphoric acid group, sulfonic acid group, C 1 -C 12 alkyl group, C 3 -C 12 cycloalkyl group, C 1 -C 12 alkoxy group, C 1 -C 12 ester group, C
  • R 1 , R 2 , R 3 are each independently selected from H, substituted or unsubstituted C 1 -C 6 alkyl;
  • R 4 -R 10 are each independently selected from H, halogen, hydroxyl, amino , phosphoric acid group, sulfonic acid group, substituted or unsubstituted C 1 -C 12 alkyl, substituted or unsubstituted C 3 -C 12 cycloalkyl, substituted or unsubstituted C 1 -C 12 alkoxy group, substituted or unsubstituted C 1 -C 12 ester group, substituted or unsubstituted C 1 -C 12 amine group, the substituent group is selected from halogen, hydroxyl, amino, phosphoric acid group, sulfonic acid group, C 1 -C 12 alkyl group, C 3 -C 12 cycloalkyl group, C 1 -C 12 alkoxy group, C 1 -C 12 ester group, C
  • R 1 ', R 2 ', R 3 ' are each independently selected from H, substituted or unsubstituted C 1 -C 6 alkyl;
  • R 4 '-R 10 ' are each independently selected from H, Halogen, hydroxyl, amino, phosphoric acid, sulfonic acid, substituted or unsubstituted C 1 -C 12 alkyl, substituted or unsubstituted C 3 -C 12 cycloalkyl, substituted or unsubstituted C 1 - C 12 alkoxy group, substituted or unsubstituted C 1 -C 12 ester group, substituted or unsubstituted C 1 -C 12 amine group, the substituted group is selected from halogen, hydroxyl, amino, phosphoric acid group , sulfonic acid group, C 1 -C 12 alkyl group, C 3 -C 12 cycloalkyl group, C 1 -C 12 alkoxy group, C 1 -C 12 este
  • the styrene-based monomer can be selected from styrene, ⁇ -methylstyrene, 1-vinylnaphthalene, 2-vinylnaphthalene, mono- or poly-substituted styrene, mono- or poly-substituted styrene At least one of ⁇ -methylstyrene, monosubstituted or polysubstituted 1-vinylnaphthalene and monosubstituted or polysubstituted 2-vinylnaphthalene; the substituent group is preferably selected from halogen, hydroxyl, amino, Phosphoric acid group, sulfonic acid group, C 1 -C 8 straight-chain alkyl, C 3 -C 8 branched or cycloalkyl, C 1 -C 6 straight-chain alkoxy, C 3 -C 8 branched alkoxy or cyclic alkoxy, C 1 -C 8 straight chain este
  • the styrene-based monomer is selected from at least one of styrene, ⁇ -methylstyrene, 2-methylstyrene, 3-methylstyrene and 4-methylstyrene.
  • the mass ratio of the styrene-based monomer to the copolymerized polypropylene may be 0.5-16:100, preferably 1-12:100, more preferably 2-10:100.
  • the propylene graft polymer includes a structural unit derived from a copolymerized polypropylene and a structural unit derived from an alkenyl group-containing silane-based monomer. Based on the weight of the propylene graft polymer, the content of the grafted structural unit derived from the alkenyl group-containing silane monomer in the propylene graft polymer b may be 0.2-6% by weight, preferably 0.2% -2.5 wt%.
  • the alkenyl-containing silane-based monomer used as the grafting monomer can be any monomeric silane-based compound that can be polymerized by free radicals, and can be selected from the alkenyl-containing silane-based monomer selected from the group having the formula VI at least one of the monomers showing the structure,
  • R 1 is a C 2 -C 12 alkenyl group, preferably a monounsaturated alkenyl group;
  • R 2 , R 3 , R 4 are each independently selected from substituted or unsubstituted C 1 -C 12 straight chain Alkyl, substituted or unsubstituted C 3 -C 12 branched alkyl, substituted or unsubstituted C 1 -C 12 alkoxy, substituted or unsubstituted C 1 -C 12 acyloxy; preferably R 1 is a C 2 -C 6 alkenyl group, preferably a monounsaturated alkenyl group;
  • R 2 , R 3 , R 4 are each independently selected from substituted or unsubstituted C 1 -C 6 straight-chain alkyl groups , substituted or unsubstituted C 3 -C 6 branched alkyl, substituted or unsubstituted C 1 -C 6 alkoxy, substituted or unsubstit
  • the alkenyl-containing silane-based monomer is selected from vinyltriethoxysilane, vinyltrimethoxysilane, vinyltriisopropoxysilane, vinyltri-tert-butoxysilane, vinyl triacetoxysilane, methylvinyldimethoxysilane, ethylvinyldiethoxysilane, allyltriethoxysilane, allyltrimethoxysilane, allyltriisopropyl Oxysilane, vinyl tris ( ⁇ -methoxyethoxy) silane, allyl tris ( ⁇ -methoxyethoxy) silane, allyl tri-tert-butoxy silane, allyl triacetoxy At least one of silane, methallyldimethoxysilane, and ethylallyldiethoxysilane.
  • the mass ratio of the alkenyl-containing silane-based monomer to the copolymerized polypropylene may be 0.5-12:100, preferably 0.8-9:100, more preferably 1-6:100.
  • the propylene graft polymer includes structural units derived from copolymerized polypropylene, structural units derived from acid anhydride monomers, and structural units derived from alkenyl-containing polymerized monomers.
  • the alkenyl group-containing polymerizable monomer may be selected from vinyl acetate, styrene, ⁇ -methylstyrene, (meth)acrylate, vinyl alkyl ether, vinyl pyrrolidone, vinyl pyridine, vinyl imidazole and At least one of acrylonitrile.
  • the acid anhydride is preferably selected from maleic anhydride and/or itaconic anhydride.
  • the content of the graft-on structural unit derived from the acid anhydride monomer and the alkenyl group-containing polymerized monomer may be 0.1-5 wt %, preferably 0.4-3 wt %.
  • the content of the grafted structural units derived from acid anhydride monomers may be 0.05 to 2% by weight, preferably 0.2 to 0.7% by weight.
  • the molar ratio of the structural unit derived from the acid anhydride monomer to the structural unit derived from the alkenyl group-containing polymerized monomer may be 1:1-20, preferably 1:1-10.
  • the alkenyl group-containing polymerizable monomer used as the grafting monomer is preferably at least one selected from the monomers having the structure represented by formula 1,
  • R 1 , R 2 , R 3 are each independently selected from H, substituted or unsubstituted alkyl;
  • R 4 is selected from substituted or unsubstituted alkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted Unsubstituted aryl, substituted or unsubstituted ester, substituted or unsubstituted carboxyl, substituted or unsubstituted cycloalkyl or heterocyclyl, cyano.
  • R 1 , R 2 , R 3 are each independently selected from H, substituted or unsubstituted C 1 -C 6 alkyl, more preferably, R 1 , R 2 , R 3 are each independently selected from H, Substituted or unsubstituted C 1 -C 3 alkyl;
  • R 4 is selected from substituted or unsubstituted C 1 -C 20 alkyl, substituted or unsubstituted C 1 -C 20 alkoxy, substituted or unsubstituted C 6 -C 20 aryl group, substituted or unsubstituted C 1 -C 20 ester group, substituted or unsubstituted C 1 -C 20 carboxyl group, substituted or unsubstituted C 3 -C 20 cycloalkyl group or heterocyclic group, cyano, the substituted group is halogen, hydroxyl, amino, C 1 -C 6 alkyl, C 3 -C 6 cycloalkyl;
  • the heterocyclic group is selected from imidazolyl, pyrazolyl, carbazolyl, pyrrolidone, pyridyl, piperidinyl, caprolactam, pyrazinyl, thiazolyl, purinyl, morpholinyl, oxa oxazoline.
  • R 1 , R 2 , R 3 are each independently selected from H, substituted or unsubstituted C 1 -C 6 alkyl;
  • R 4 is selected from a group represented by formula 2, a group represented by formula 3, a group represented by formula 4, a group represented by formula 5, a combination of a group represented by formula 5 and a group represented by formula 6, a heterocyclic ring group;
  • R 4 -R 8 are each independently selected from H, halogen, hydroxyl, amino, phosphoric acid group, sulfonic acid group, substituted or unsubstituted C 1 -C 12 alkyl, substituted or unsubstituted C 3 -C 12 cycloalkyl, substituted or unsubstituted C 1 -C 12 alkoxy, substituted or unsubstituted C 1 -C 12 ester group, substituted or unsubstituted C 1 -C 12 amine group , the substituted group is selected from halogen, hydroxyl, amino, phosphoric acid group, sulfonic acid group, C 1 -C 12 alkyl group, C 3 -C 12 cycloalkyl group, C 1 -C 12 alkoxy group , C 1 -C 12 ester group, C 1 -C 12 amine group; preferably, R 4 -R 8 are each independently selected from H, halogen, hydroxyl, amino, substituted
  • R 4 -R 10 are each independently selected from H, halogen, hydroxyl, amino, phosphoric acid group, sulfonic acid group, substituted or unsubstituted C 1 -C 12 alkyl, substituted or unsubstituted C 3 -C 12 cycloalkyl, substituted or unsubstituted C 1 -C 12 alkoxy, substituted or unsubstituted C 1 -C 12 ester group, substituted or unsubstituted C 1 -C 12 amine group , the substituted group is selected from halogen, hydroxyl, amino, phosphoric acid group, sulfonic acid group, C 1 -C 12 alkyl group, C 3 -C 12 cycloalkyl group, C 1 -C 12 alkoxy group , C 1 -C 12 ester group, C 1 -C 12 amine group; preferably, R 4 -R 10 are each independently selected from H, halogen, hydroxyl, amino, substituted
  • R 4 '-R 10 ' are each independently selected from H, halogen, hydroxyl, amino, phosphoric acid, sulfonic acid, substituted or unsubstituted C 1 -C 12 alkyl, substituted or unsubstituted C 3 -C 12 cycloalkyl, substituted or unsubstituted C 1 -C 12 alkoxy, substituted or unsubstituted C 1 -C 12 ester group, substituted or unsubstituted C 1 -C 12 Amine group, the substituted group is selected from halogen, hydroxyl, amino, phosphoric acid group, sulfonic acid group, C 1 -C 12 alkyl, C 3 -C 12 cycloalkyl, C 1 -C 12 alkane Oxy group, C 1 -C 12 ester group, C 1 -C 12 amine group; preferably, R 4 '-R 10 ' are each independently selected from H, halogen, hydroxyl, amino, amino
  • R m is selected from the following substituted or unsubstituted groups: C 1 -C 20 straight chain alkyl, C 3 -C 20 branched chain alkyl, C 3 -C 12 cycloalkyl, C 3 -C 12 epoxyalkyl, C3 - C12 epoxyalkylalkyl , the substituted group is selected from at least one of halogen, amino and hydroxyl.
  • the alkenyl group-containing polymerized monomer is selected from vinyl acetate, styrene, ⁇ -methylstyrene, (meth)acrylate, vinyl alkyl ether, vinyl pyrrolidone, vinyl pyridine, vinyl At least one of imidazole and acrylonitrile; the (meth)acrylate is preferably at least one of methyl (meth)acrylate, ethyl (meth)acrylate and glycidyl (meth)acrylate .
  • the ethylenic group-containing polymerized monomer is selected from vinyl acetate, styrene, and ⁇ -methylstyrene.
  • the ethylenic group-containing polymerizable monomer is styrene.
  • the molar ratio of the structural unit derived from the (maleic) anhydride monomer to the structural unit derived from the alkenyl group-containing polymerized monomer in the acid anhydride group-containing propylene graft polymer may be 1:1-20, preferably 1:1-20. 1:1-10.
  • the acid anhydride may be selected from acid anhydrides having at least one olefinic unsaturation; more preferably, the acid anhydride is selected from maleic anhydride and/or itaconic anhydride; further preferably, the acid anhydride is maleic anhydride.
  • the mass ratio of the total mass of the acid anhydride monomer and the ethylenic group-containing polymerized monomer to the copolymerized polypropylene may be 0.1-8:100, preferably 0.3-5:100.
  • the mass amount of the acid anhydride monomer may be 5-100 wt % of the mass amount of the ethylenic group-containing polymerized monomer, preferably 10-100 wt %.
  • the propylene graft polymer includes structural units derived from copolymerized polypropylene and structural units derived from alkenyl-containing heterocyclic monomers. Based on the weight of the propylene graft polymer, the content of the grafted structural unit derived from the alkenyl group-containing heterocyclic monomer may be 0.5-6 wt %, preferably 0.5-4 wt %.
  • the alkenyl-containing heterocyclic monomer as the grafting monomer can be any alkenyl-containing heterocyclic compound that can be polymerized by free radicals, and can be selected from alkenyl-substituted imidazole, alkenyl-containing Substituted pyrazole, alkenyl substituted carbazole, alkenyl substituted pyrrolidone, alkenyl substituted pyridine or pyridine salt, alkenyl substituted piperidine, alkenyl substituted caprolactam , at least one of pyrazine containing alkenyl substituent, thiazole containing alkenyl substituent, purine containing alkenyl substituent, morpholine containing alkenyl substituent and oxazoline containing alkenyl substituent;
  • the alkenyl-containing heterocyclic monomer is a monoalkenyl-containing heterocyclic monomer.
  • the alkenyl-containing heterocyclic monomer can be selected from: 1-vinylimidazole, 2-methyl-1-vinylimidazole, N-allylimidazole, 1-vinylpyrazole, 3 -Methyl-1-vinylpyrazole, vinylcarbazole, N-vinylpyrrolidone, 2-vinylpyridine, 3-vinylpyridine, 4-vinylpyridine, 2-methyl-5-vinylpyridine , vinylpyridine N oxide, vinylpyridine salt, vinylpiperidine, N-vinylcaprolactam, 2-vinylpyrazine, N-vinylpiperazine, 4-methyl-5-vinylthiazole, N - at least one of vinylpurine, vinylmorpholine and vinyloxazoline.
  • the mass ratio of the alkenyl-containing heterocyclic monomer to the copolymerized polypropylene may be 0.3-12:100, preferably 0.5-10:100.
  • the grafting reaction described herein is a free radical polymerization reaction. Upon free radical polymerization, the grafted monomers form covalent linkages (grafts) to the copolymerized polypropylene.
  • the propylene graft polymer can be prepared by solid-phase grafting reaction of copolymerized polypropylene and graft monomers, for example, according to Chinese patent applications with application numbers 202011195771.2, 202011191001.0, 202011195799.6, 202011190917.4, and 202011195819.X prepared by the method described.
  • it can be prepared by a method comprising the following steps: in the presence of an inert gas, a solid-phase grafting reaction is performed on a reaction mixture comprising a copolymerized polypropylene and a grafting monomer to obtain the propylene graft polymer.
  • the solid-phase grafting reaction can be carried out with reference to various conventional methods in the art, for example, forming active grafting points on the copolymerized polypropylene in the presence of a grafting monomer, or forming active grafting on the copolymerized polypropylene first
  • the dots are then treated with monomers for grafting.
  • Grafting sites can be formed by treatment with free radical initiators, or by treatment with high energy ionizing radiation or microwaves. Free radicals generated in the polymer as a result of chemical or radiation treatment form grafting points on the polymer and initiate polymerization of the monomers at these points.
  • the grafting point is initiated by a free-radical initiator and the grafting reaction further proceeds.
  • the reaction mixture further includes a radical initiator; further preferably, the radical initiator is selected from peroxide-based radical initiators and/or azo-based radical initiators.
  • the peroxide-based free radical initiator is preferably selected from dibenzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, lauroyl peroxide, lauroyl peroxide, peroxide At least one of tert-butyl benzoate, diisopropyl peroxydicarbonate, tert-butyl peroxy(2-ethylhexanoate) and dicyclohexyl peroxydicarbonate; the azo is free
  • the base initiator is preferably azobisisobutyronitrile and/or azobisisoheptanenitrile.
  • the grafting point is initiated by a peroxide-based radical initiator and the grafting reaction is further carried out.
  • the grafting reaction can also be carried out by the methods described in CN106543369A, CN104499281A, CN102108112A, CN109251270A, CN1884326A and CN101492517B.
  • the ratio of the mass of the free radical initiator to the total mass of the grafting monomer may be 0.1-10:100, preferably 0.5-5:100.
  • the temperature of the grafting reaction can be 30-130°C, preferably 60-120°C; the time can be 0.5-10h, preferably 1-5h.
  • reaction mixture includes all the materials added to the grafting reaction system, and the materials can be added at one time or at different stages of the reaction.
  • the reaction mixture may also include a dispersant, and the dispersant is preferably water or an aqueous solution of sodium chloride.
  • the mass amount of the dispersant is preferably 50-300% of the mass of the copolymerized polypropylene.
  • the reaction mixture may also include an interface agent, which is an organic solvent that has a swelling effect on polyolefins, preferably at least one of the following organic solvents that have a swelling effect on copolymerized polypropylene: ether solvents, Ketone-based solvent, aromatic hydrocarbon-based solvent, alkane-based solvent; more preferably at least one of the following organic solvents: chlorinated benzene, polychlorinated benzene, alkanes above C 6 or naphthenic hydrocarbons, benzene, C 1 -C 4 Alkyl-substituted benzene, C 2 -C 6 aliphatic ether, C 3 -C 6 aliphatic ketone, decalin; more preferably at least one of the following organic solvents: benzene, toluene, xylene, chlorobenzene, tetrahydrofuran, Diethyl ether, acetone, hexane, cyclohexane,
  • the reaction mixture may also include an organic solvent as a solvent for dissolving the solid radical initiator, and the organic solvent preferably includes C 2 -C 5 alcohols, C 2 -C 4 ethers and C 3 -C 5 ketones At least one of, more preferably at least one of C 2 -C 4 alcohols, C 2 -C 3 ethers and C 3 -C 5 ketones, most preferably at least one of ethanol, ether and acetone kind.
  • the mass content of the organic solvent is preferably 1-35% of the mass of the copolymerized polypropylene.
  • the grafted monomers can be polymerized individually or with each other to form a certain amount of ungrafted polymer, so the propylene grafted polymer can include both the copolymerized polypropylene and the grafted monomers through the grafting reaction
  • the directly prepared product also includes the graft-modified polypropylene pure product obtained by further purifying the product. Therefore, the preparation method may optionally include a step of purifying the crude product. The purification can be carried out by various methods conventional in the art, such as extraction methods.
  • the grafting efficiency of the grafting reaction is controlled to be 5-100%, preferably 30-100%, more preferably 25-80%, or 35-60%.
  • the concept of the grafting efficiency is well known to those skilled in the art, and refers to the amount of grafted monomers on the graft/total amount of the grafted monomers fed into the reaction.
  • the inert gas can be various inert gases commonly used in the art, including but not limited to nitrogen and argon.
  • the composite film of the present invention may consist of only layer a and layer b, that is, a bilayer film.
  • the composite film of the present invention may comprise, in addition to layer a and layer b, one or more additional layers, ie three or more layers, thereby forming three layers layer film or more than three-layer film, where layer b is the surface layer of the composite film.
  • the composition of this additional layer may be the same as or different from that of layer a or layer b.
  • the layer may also be a mixture of the components of layer a and the components of layer b.
  • the additional layer is called layer c
  • layer b and layer c are located on both sides of layer a, that is, layer c is located on the opposite side of layer a from layer b, this Time layer c is also the surface layer.
  • the composite film has five layers, it is possible that two layers b serve as upper and lower layers, respectively, two layers c serve as intermediate layers, and one layer a serves as a core layer.
  • the thicknesses of layer a, layer b and optional layer c and further layers in the present invention are not particularly limited.
  • the ratio of the sum of the thicknesses of the other layers except the layer a to the thickness of the layer a may be 1:6-2:1, for example, it may be 1:5.5, 1:5, 1:4.5, 1:4, 1:4. 3.5, 1:3, 1:2.5, 1:2, 1:1.5, 1:1, 1.5:1, and any value between them, preferably 1:4-2:1, more preferably 1:2- 1:1.
  • Such composite films can advantageously have better mechanical properties (eg, tensile strength) and performance stability.
  • the composite film of the present invention can have excellent impact resistance and optical properties at the same time because the composite film of the present invention contains the rubber phase derived from the propylene impact copolymer in the form of dispersed strips arranged in parallel with each other, It even has excellent mechanical properties (such as tensile strength) and/or excellent heat-sealing properties, and can have good heat-sealing strength at lower heat-sealing temperatures.
  • the rubber phase and the non-elastic portion in the propylene impact copolymer are associated with the homopolymer
  • the synergistic interaction between the polymer spherulites formed by propylene and the rubber phase of the polyolefin elastomer can further improve the impact resistance and optical properties of the composite film at the same time, and even improve its mechanical properties.
  • the composite film according to the invention may advantageously have one or more, preferably all of the following properties:
  • the pendulum impact strength is ⁇ 0.4J, such as ⁇ 0.5J, 0.6J or 0.7J, preferably ⁇ 0.9J, more preferably ⁇ 1.1J, such as ⁇ 1.5J, or even ⁇ 1.8J;
  • the haze of the film is less than 7%, preferably ⁇ 5%, more preferably ⁇ 3%, for example ⁇ 2.5%, even more preferably ⁇ 2%;
  • the longitudinal (MD) tensile strength is ⁇ 40MPa, preferably ⁇ 50MPa;
  • the heat sealing strength at 150°C is ⁇ 12N/15mm, preferably ⁇ 15N/15mm, preferably ⁇ 17N/15mm, more preferably ⁇ 18N/15mm, even ⁇ 19N/15mm, such as ⁇ 20N/15mm;
  • the thickness deviation in the MD direction is not more than 1.3, for example, not more than 1.0, preferably not more than 0.5;
  • the thickness deviation in the TD direction is not more than 1.5, for example, not more than 1.3, preferably not more than 0.75 or not more than 0.8;
  • the deviation of impact resistance in MD direction is not more than 0.05, preferably not more than 0.03;
  • the deviation of impact resistance in TD direction is not more than 0.07, preferably not more than 0.05, more preferably not more than 0.04;
  • Volume resistivity ⁇ 1.5 ⁇ 10 15 ⁇ m, preferably rate ⁇ 2.0 ⁇ 10 15 ⁇ m.
  • Pendulum impact strength according to the standard GB/T 8809-2015;
  • Heat-sealing strength According to the standard QB/T 2358, the heat-sealing temperature is 150°C, the heat-sealing pressure is 0.2MPa, and the heat-sealing time is 3s during sample preparation.
  • Thickness deviation in the MD direction The thickness of the film was tested with a thickness gauge of Mitutoyo Japan, model 7301. As shown in Figure 1a, after the film is trimmed, on the center line of the film, take a point every 1 meter along the MD direction, take a total of 10 points, and test each point according to the method specified in GB/T 8809-2015. Thickness, the average value is the thickness (MD) of the film. And based on the above data, the standard deviation of the thickness is calculated as the thickness deviation in the MD direction.
  • Thickness deviation in the TD direction as shown in Figure 1b, along the TD direction of any part of the film, take 10 points uniformly, test the thickness of each point according to the method specified in GB/T 8809-2015, and take the average value as the film thickness (TD). And based on the above data, the standard deviation of the thickness is calculated as the thickness deviation in the TD direction.
  • Impact strength deviation in MD direction as shown in Figure 1a, after the film is trimmed, take a point every 1 meter along the MD direction on the center line of the film, taking a total of 10 points, according to GB/T 8809-2015 The impact strength of each point is tested by the specified method, and the average value is taken as the impact strength (MD) of the film; and the standard deviation of the impact strength is calculated according to the above data as the impact strength deviation in the MD direction.
  • MD impact strength
  • Impact strength deviation in TD direction as shown in Figure 1b, along the TD direction of any part of the film, take 10 points uniformly, test the impact strength of each point according to the method specified in GB/T 8809-2015, and take the average value is the impact strength (TD) of the film; and according to the above data, the standard deviation of the impact strength is calculated as the impact strength deviation in the TD direction.
  • Film surface energy measured according to the method specified in GB/T 14216-2008.
  • Volume resistivity measured according to the method specified in GB/T 1410-2006.
  • the second aspect of the present invention provides a method for preparing the composite film of the present invention.
  • the method of the present invention comprises extrusion casting the feedstock composition for forming each layer to form the composite film.
  • the elastic part of the propylene impact copolymer used in the raw material composition can form a granular rubber phase
  • the average particle size of the rubber phase is less than or equal to 1.8 ⁇ m, preferably less than or equal to 1.8 ⁇ m. It is equal to 1.5 ⁇ m, and the maximum particle size is not more than 2.5 ⁇ m, preferably not more than 2 ⁇ m, measured by SEM observation of the spline section.
  • the rubber phase is generally spherical or nearly spherical.
  • the spherical and sub-spherical shape means that the aspect ratio of the particles is substantially in the range of 1-2. “Substantially” means that at least 90% of the rubber phase particles have an aspect ratio in the range of 1-2.
  • the average particle size and the maximum particle size of the rubber phase in the propylene impact copolymer in the raw material were determined by observing the cross section of the impact strip by the scanning electron microscope (SEM) method, and the impact strip was determined according to the method specified in the standard GB/T 8809-2015 preparation.
  • SEM scanning electron microscope
  • the diameter of the particle is determined; for nearly spherical particles, the longitudinal axis of the particle (the distance between the two most distant points on the particle profile) is measured.
  • the average value of the above-mentioned dimensions of 50 sample points was obtained by SEM photograph observation as the average particle diameter, and the maximum value of the above-mentioned dimensions in the above-mentioned sample points was taken as the maximum particle diameter.
  • the size of the rubber phase in the raw propylene impact copolymer by controlling the size of the rubber phase in the raw propylene impact copolymer, the size of the rubber phase in the composite film can be made within the specific range according to the present invention.
  • the components of the polymer composition used to prepare the layers may be mixed or blended prior to the extrusion process, and optionally granulated.
  • the pelletizing process can be carried out as follows: the propylene polymer composition A used to make up layer a and the propylene polymer composition B used to make up layer b and optionally the polymer composition used to make up additional layers
  • the components and optional additives are mixed uniformly in a high-speed mixer, and the uniformly mixed materials are added to a twin-screw extruder, melted and mixed, uniformly extruded and pelletized, and dried to obtain pellets.
  • the processing temperature of the twin-screw extruder can be controlled to be 170-230°C.
  • the extrusion casting process of the pellets can be carried out in a conventional manner and using conventional equipment.
  • the extrusion casting method may include sending the pellets of the polymer composition for preparing each layer to a plurality of extruders respectively, and after the pellets are co-extruded and compounded out through the die of the extruder, the pellets are sequentially casted. Roll, pulling roll, and then trimming and winding, so as to prepare the composite film.
  • the temperature of extrusion casting can be controlled to 170-230°C.
  • the temperature of the casting roll may be 10-50°C.
  • the rubber phase contained in the propylene impact copolymer as the raw material is deformed during the preparation process of the composite film, and is transformed from spherical or nearly spherical to strip-like, and is oriented in a certain direction, that is, are arranged in parallel and maintain such a microstructure in the final composite film product, thereby obtaining a composite film with good impact resistance and optical properties according to the present invention.
  • the polyolefin elastomer used is also deformed during the preparation of the composite film, becoming a strip-like rubber phase, and is oriented in a certain direction, i.e. parallel, and remains so in the final composite film product.
  • the microstructure of the composite film simultaneously interacts synergistically with the rubber phase derived from the propylene impact copolymer, thereby further improving the impact resistance and optical properties of the composite film as well as other properties (mechanical properties, heat sealing properties, film uniformity, etc.).
  • the obtained composite film can be stretched in a subsequent process, such as biaxial stretching, so that the mechanical properties of the composite film can be advantageously further improved.
  • the preparation method of the composite film includes pelletizing the propylene polymer composition A and the propylene polymer composition B, extrusion casting, and stretching to prepare the composite film.
  • the third aspect of the present invention provides the application of the composite film of the present invention in the field of packaging materials.
  • the composite film of the present invention can have good impact resistance and optical properties at the same time, even good tensile properties and/or good heat sealing strength at lower heat sealing temperature, and even good thickness and/or performance uniformity, so the composite film of the present invention is particularly useful in high-end packaging fields, such as fields where both film impact resistance and optical properties are required to be high, such as battery packaging materials, electronic product packaging and high-end food packaging. and other fields.
  • the packaging materials may be, for example, those comprising aluminum-plastic composite films.
  • layer a serves as the core layer, ie, the layer relatively far from the medium to which the composite film is to be contacted
  • layer b serves as the skin layer, ie, the layer close to the medium to which the composite film is to be contacted.
  • the medium is, for example, the electrolyte that the battery packaging material contacts.
  • a fourth aspect of the present invention provides a packaging material comprising the composite film of the present invention.
  • the packaging material may be, for example, battery packaging material, electronic product packaging material or food packaging material, especially high-end food packaging material.
  • the packaging materials may be, for example, those comprising aluminum-plastic composite films.
  • the film casting equipment was purchased from Labtech, Sweden, model LCR400.
  • MFR Melt mass flow rate
  • Film heat sealing strength measured according to the method specified in QB/T 2358. During sample preparation, the heat-sealing temperature was 150°C, the heat-sealing pressure was 0.2MPa, and the heat-sealing time was 3s.
  • Isotacticity measured by 13 C NMR, using a nuclear magnetic resonance spectrometer (NMR) of AVANCE III from Bruker, Switzerland to measure the carbon nuclear magnetic spectrum ( 13 C-NMR) of the propylene polymer at 400 MHz, wherein the solvent For deuterated o-dichlorobenzene, the sample concentration is 250mg sample/2.5mL solvent.
  • NMR nuclear magnetic resonance spectrometer
  • BHT 2,6-di-tert-butyl-4-methylphenol antioxidant
  • the isotacticity is taken as the content of diad isotactic [mm].
  • molecular weight distribution measure by gel permeation chromatography (GPC), adopt the gel permeation chromatograph of PL-GPC 220 produced by British Polymer Laboratories company to measure in combination with IR5 type infrared detector, wherein , the chromatographic column in the gel permeation chromatograph is 3 Plgel 10 ⁇ m MIXED-B columns connected in series, the solvent and mobile phase are 1,2,4-trichlorobenzene (containing 0.3g/1000mL of antioxidant 2,6 -di-tert-butyl-p-cresol), the column temperature was 150 °C, the flow rate was 1.0 mL/min, and the EasiCal PS-1 narrow-distribution polystyrene standard produced by PL Company was used for universal calibration.
  • GPC gel permeation chromatography
  • Test of film thickness and thickness deviation The thickness of the film was tested with a thickness gauge of Japan Mitutoyo, model 7301. As shown in Figure 1a, after the film is trimmed, on the center line of the film, take a point every 1 meter along the MD direction, take a total of 10 points, and test each point according to the method specified in GB/T 8809-2015. Thickness, the average value is the thickness (MD) of the film. And based on the above data, the standard deviation of the thickness is calculated as the thickness deviation in the MD direction.
  • the shear viscosities of the propylene polymer composition A in the examples and comparative examples at shear rates of 160 s -1 and 640 s -1 are denoted as ⁇ A 160 and ⁇ A 640 , respectively, and the propylene polymer composition B at shear rates of The shear viscosities at 160s -1 and 640s -1 are denoted as ⁇ B 160 and ⁇ B 640 , respectively, and P represents the shear viscosity of propylene polymer composition A and propylene polymer composition B at a shear rate of 160r -1 .
  • Atomic force microscope (AFM) photo The Dimension FastScan Icon type atomic force microscope of Bruker Company in the United States was used to scan and observe the cross section of the film sample cut along the transverse direction using the quantitative nanomechanical scanning mode.
  • the transverse axis size and aspect ratio of the rubber phase in the film was scanned and observed.
  • the horizontal axis of the phase (the length of the straight line with the longest distance between the intersection points intersecting with the outline of the object among the lines perpendicular to the vertical axis), and the vertical axis (the distance between the two points on the outline of the object that are farthest apart) distance) and aspect ratio were measured, calculated and counted, and the average size of the horizontal axis and the average of the aspect ratio were obtained based on 200 sample points.
  • the average particle size and maximum particle size of the rubber phase of the propylene impact copolymer in the raw material Using the scanning electron microscope of EM-30AX from Korea COXEM, the cross section of the impact spline after the gold spray treatment was scanned by gold spray treatment. Observe, measure and count the particle size of the rubber phase to obtain the average particle size and the maximum particle size.
  • For spherical particles measure the diameter of the particle; for nearly spherical particles, measure the longitudinal axis of the particle (the distance between the two farthest points on the outline of the object), and obtain the largest of the above dimensions based on 50 sample points The value was taken as the maximum particle diameter, and the average value of the above-mentioned dimensions was calculated as the average particle diameter.
  • 13 C NMR was measured using a 400 MHz nuclear magnetic resonance spectrometer (NMR) from Bruker, Switzerland, with the instrument model AVANCE III.
  • the solvent was deuterated o-dichlorobenzene, 250 mg of sample/2.5 ml of solvent.
  • 2 mg of BHT antioxidant was added to the samples. Dissolve the sample at 140°C, collect 13 C-NMR, the test temperature is 125°C, the probe size is 10 mm, the 90° pulse, the sampling time AQ is 5 seconds, the delay time D1 is 1 second, and the number of scans is 6000 times.
  • Comonomer content of polypropylene copolymerized in the propylene graft polymer was determined by quantitative Fourier transform infrared (FTIR) spectroscopy. The correlation of the determined comonomer content was calibrated by quantitative nuclear magnetic resonance (NMR) spectroscopy. The calibration method based on the results obtained from the quantitative 13 C-NMR spectrum is carried out according to conventional methods in the art.
  • FTIR quantitative Fourier transform infrared
  • NMR nuclear magnetic resonance
  • the weight average molecular weight of the copolymerized polypropylene in the propylene graft polymer measured by high temperature GPC, using PL-GPC 220 gel permeation chromatography of Polymer Laboratory Company, the sample is dissolved in 1,2,4-trichlorobenzene , the concentration is 1.0mg/ml.
  • the test temperature was 150°C, and the solution flow rate was 1.0ml/min.
  • the molecular weight of polystyrene was used as an internal reference to formulate a standard curve, and the molecular weight and molecular weight distribution of the samples were calculated according to the elution time.
  • Melting temperature Tm Differential scanning calorimeter was used to analyze the melting process and crystallization process of the material. The specific operation is as follows: under nitrogen protection, the 5-10 mg sample is measured from 20 °C to 200 °C using a three-stage temperature rise and fall measurement method, and the change of heat flow reflects the melting and crystallization process of the material, so as to calculate the melting temperature Tm.
  • Grafting efficiency GE, parameter M1 put 2-4 g of the grafted product into a Soxhlet extractor, use ethyl acetate (for the case of alkenyl-containing silane monomers as grafting monomers, use acetone ) extraction for 24 hours to remove unreacted monomers and their homopolymers to obtain pure grafted products, oven-dried and weighed to calculate parameters M1 and grafting efficiency GE.
  • the parameter M1 represents the total content of structural units derived from graft monomers in the propylene graft polymer.
  • the formulas for calculating M1 and GE are as follows:
  • w 0 is the mass of the PP matrix
  • w 1 is the mass of the graft product before extraction
  • w 2 is the mass of the graft product after extraction
  • w 3 is the total mass of the grafted monomer.
  • the parameter M2 represents the content of grafted structural units derived from maleic anhydride monomers in the propylene graft polymer.
  • the formula for calculating M2 is as follows:
  • w 1 is the mass of the graft product before extraction
  • w 2 is the mass of the graft product after extraction
  • %G MAH is the mass content of maleic anhydride.
  • Component a is a homopolymerized polypropylene with a grade of PPH-FA03 (purchased from Qingdao Refinery, with a melt mass flow rate of 3.1 g/10min, an isotacticity of 98%, and a molecular weight distribution of Mw/Mn of 4.7);
  • b is a propylene impact copolymer with a trade name of EP200K (purchased from Zhongsha Petrochemical, with an ethylene content of 8 wt %, an ethylene-propylene copolymer content of 13 wt %, and a melt mass flow rate of 3.2 g/10min);
  • components c is a polyolefin elastomer with the grade of 6102 (purchased from Exxon Company, obtained by copolymerizing propylene and ethylene, and the content of ethylene structural unit is 16% by weight).
  • the above-mentioned components are weighed and mixed according to the proportions, wherein the parts by mass Wa of component a are 75 parts by weight, the parts by mass Wb of component b are 10 parts by weight, and the parts by mass of component c are 10 parts by weight Wc is 15 parts by weight.
  • lubricant PEG lubricant produced by Swiss Clariant company, molecular weight is 10000, and the sum of the mass of above-mentioned component a, component b and component c is 100 parts by weight, the amount of lubricant added is 0.1 weight part parts
  • lubricant PEG lubricant produced by Swiss Clariant company, molecular weight is 10000, and the sum of the mass of above-mentioned component a, component b and component c is 100 parts by weight, the amount of lubricant added is 0.1 weight part parts
  • Component x is the random propylene copolymer with trade mark F5006 (purchased from Yanshan Petrochemical, ethylene-propylene-butene terpolymer, and the melt mass flow rate is 5.2g/10min); component y is the grade of 6102 Polyolefin elastomer (purchased from Exxon).
  • the components prepared above are weighed and mixed according to the proportions, wherein the mass fraction Wx of the component x is 75 weight parts, and the mass fraction Wy of the component y is 25 weight parts. Wc:Wy is 3:5.
  • the other operations are the same as those in step (1), and finally the pellets of the propylene polymer composition B are obtained.
  • the melt mass flow rate MFR B 3.2 g/10min.
  • the pellets of the propylene polymer composition A and the propylene polymer composition B obtained in the above steps (1) and (2) are dried, and then the propylene polymer composition A is added to the multi-layer extrusion casting machine.
  • the propylene polymer composition B is added to the upper surface layer extruder of the multi-layer extrusion casting machine, wherein the upper surface layer extruder also needs to be added with an inorganic antiblocking agent (silicon dioxide). , Japan Mizusawa, brand JC-50, the same below), the weight ratio of anti-blocking agent and propylene polymer composition pellets is 0.02:1.
  • the temperature of the casting chill roll was set to 30° C., and then it was wound up to form a composite film, which consisted of an upper skin layer (layer b) and a core layer (layer a).
  • the film thickness was 50 ⁇ m with a thickness ratio of layer b to layer a of 1:2.
  • the atomic force microscope photograph of the section of the composite film is shown in FIG. 3 .
  • the black part is the rubber phase, and the rubber phase is dispersed, strip-like, and arranged parallel to each other.
  • the rubber phase had an average size on the horizontal axis of 56 nm and an average aspect ratio of 10.3.
  • Component a is a homopolymerized polypropylene with a grade of PPH-FA03 (purchased from Qingdao Refinery, with a melt mass flow rate of 3.1 g/10min, an isotacticity of 98%, and a molecular weight distribution of Mw/Mn of 4.7);
  • b is a propylene impact copolymer with a brand name of M180R (purchased from Shanghai Petrochemical, with an ethylene content of 11% by weight, an ethylene-propylene copolymerization content of 15% by weight, and a melt mass flow rate of 2.0g/10min);
  • component c It is a polyolefin elastomer with the trade name of DF640 (obtained by copolymerization of ethylene and butene, the content of butene structural unit is 32% by weight, purchased from Mitsui Corporation).
  • the above-mentioned components are weighed and mixed according to the proportions, wherein the parts by mass Wa of component a are 65 parts by weight, the parts by mass Wb of component b are 30 parts by weight, and the parts by mass of component c are 30 parts by weight Wc is 5 parts by weight.
  • lubricant PEG lubricant produced by Swiss Clariant company, molecular weight is 10000, and the sum of the mass of above-mentioned component a, component b and component c is 100 parts by weight, the amount of lubricant added is 0.1 weight part parts
  • lubricant PEG lubricant produced by Swiss Clariant company, molecular weight is 10000, and the sum of the mass of above-mentioned component a, component b and component c is 100 parts by weight, the amount of lubricant added is 0.1 weight part parts
  • Component x is a random propylene copolymer with trade name F500EPS (purchased from Shanghai Petrochemical, ethylene-propylene-butene terpolymer, melt mass flow rate is 5.3g/10min); component y is a DF640 Polyolefin elastomer (purchased from Mitsui Corporation).
  • the components prepared above are weighed and mixed according to the proportions, wherein the mass fraction Wx of the component x is 90 weight parts, and the mass fraction Wy of the component y is 10 weight parts. Wc:Wy is 1:2.
  • the pellets of the propylene polymer composition A and the propylene polymer composition B obtained in the above steps (1) and (2) are dried, and then the propylene polymer composition A is added to the multi-layer extrusion casting machine.
  • the propylene polymer composition B is added to the upper surface layer extruder and the lower layer extruder of the multi-layer extrusion casting machine, wherein the upper and lower layer extruders also need to be added.
  • Inorganic release agent (silica, same as above), the weight ratio of release agent to propylene polymer composition pellets was all 0.02:1.
  • the temperature of the casting quench roll was set to 30°C, and then wound up to make a composite film, which consists of upper and lower layers (layer b; the composition of layer c and layer b is the same) and the core layer (layer a) constitutes.
  • the thickness of the film is 50 ⁇ m, and the ratio of the sum of the thickness of the upper and lower layers to the thickness of the core layer is 1:1.
  • Component a is a homopolypropylene with a trade mark of FC801 (purchased from Shanghai Petrochemical, the melt mass flow rate is 7.8 g/10min, the isotacticity is 98%, and the molecular weight distribution Mw/Mn is 4.8); component b is a trade mark It is a propylene impact copolymer of PPB-M02D (purchased from Maoming Petrochemical, with an ethylene content of 8 wt %, an ethylene-propylene copolymerized part content of 10 wt %, an ethylene-propylene copolymerized part content of 10 wt %, and its room temperature xylene can be The ethylene unit content in the solution is 36.3% by weight, the ethylene unit group [EEE] content is 18.5% by weight, and the melt mass flow rate is 1.5g/10min); It is obtained by copolymerization with octene, and the content of octene structural unit is 14% by weight, which is purchased
  • the above-mentioned components are weighed and mixed according to the proportions, wherein the parts by mass Wa of component a are 55 parts by weight, the parts by mass Wb of component b are 25 parts by weight, and the parts by mass of component c are 25 parts by weight Wc is 20 parts by weight.
  • lubricant PEG lubricant produced by Swiss Clariant company, molecular weight is 10000, and the sum of the mass of above-mentioned component a, component b and component c is 100 parts by weight, the amount of lubricant added is 0.1 weight part parts
  • lubricant PEG lubricant produced by Swiss Clariant company, molecular weight is 10000, and the sum of the mass of above-mentioned component a, component b and component c is 100 parts by weight, the amount of lubricant added is 0.1 weight part parts
  • Component x is a random propylene copolymer with the trade name of F800EPS (purchased from Shanghai Petrochemical, which is an ethylene-propylene-butene terpolymer, and the melt mass flow rate is 8.2g/10min); component y is the trade mark of EXACT3139 The polyolefin elastomer (purchased from Exxon).
  • the components prepared above are weighed and mixed according to the proportions, wherein the mass fraction Wx of the component x is 80 weight parts, and the mass fraction Wy of the component y is 20 weight parts. Wc:Wy is 1:1.
  • the other operations are the same as those in step (1), and finally the pellets of the propylene polymer composition B are obtained.
  • the melt mass flow rate MFR B 7.9 g/10min.
  • the preparation process is the same as the step (3) of Example A1.
  • the operation is the same as the step (3) of Example A1.
  • the film thickness was 50 ⁇ m, where the thickness ratio of layer b and layer a was 1:3.
  • the operation is the same as the step (3) of Example A2.
  • the thickness of the film is 50 ⁇ m, and the ratio of the sum of the thickness of the upper and lower layers to the thickness of the core layer is 2:1.
  • the operation is the same as the step (3) of Example A3.
  • the film thickness is 50 ⁇ m, and the ratio of the thickness of the upper surface layer to the thickness of the core layer is 1:4.
  • the operation is the same as the step (3) of Example A1.
  • the film thickness was 50 ⁇ m, where the thickness ratio of layer b and layer a was 1:3.
  • the composite film was prepared according to the method of Example A1. Only the propylene polymer composition B contains only component x.
  • a composite film was prepared according to the operation of Example A1, except that only the propylene polymer composition A was used for extrusion casting into a single-layer film, and the film thickness was 50 ⁇ m.
  • a composite film was prepared according to the operation of Example A2, except that only the propylene polymer composition B was used for extrusion casting into a single-layer film, and the film thickness was 50 ⁇ m.
  • a composite film was prepared as in Example A1, except that the propylene polymer composition A contained only component b. As shown in FIG. 4 , according to AFM observation, the rubber phase had an average size of 380 nm on the horizontal axis and an average aspect ratio of 23.4.
  • the composite film was prepared according to the operation of Example A1, except that the propylene polymer composition A only contained component a and component b, wherein the mass fraction Wa of component a was 75 parts by weight, and the mass fraction Wb of component b 25 parts by weight.
  • the composite film was prepared according to the operation of Example A1, except that the propylene polymer composition A only contained component a and component c, wherein the mass fraction Wa of component a was 75 parts by weight, and the mass fraction Wc of component c 25 parts by weight.
  • the composite film according to the present invention can have good impact resistance and optical properties at the same time, and even have good tensile strength and good heat-sealing strength.
  • the composite film of the present invention can achieve a better balance of the above-mentioned various properties, and during extrusion casting, the stability of the film surface and the thickness uniformity. better.
  • Component a is a homopolymerized polypropylene with a grade of PPH-FA03 (purchased from Qingdao Refinery, with a melt mass flow rate of 3.1 g/10min, an isotacticity of 98%, and a molecular weight distribution of Mw/Mn of 4.7);
  • b is a polyolefin elastomer with the grade of 6102 (purchased from Exxon).
  • the components prepared above are weighed and mixed according to the proportions, wherein the mass fraction Wa of the component a is 80 weight parts, and the mass fraction Wb of the component b is 20 weight parts.
  • lubricant PEG lubricant produced by Clariant, Switzerland, molecular weight is 10,000, and based on the sum of the mass of the above-mentioned component a and component b as 100 parts by weight, the amount of lubricant added is 0.1 part by weight
  • the mixture is added to the high-speed mixer and mixed evenly, and then the mixed material is added to the feeder of the twin-screw extruder manufactured by W&P Company.
  • the material enters the twin-screw through the feeder.
  • Component x is the random propylene copolymer with trade mark F5006 (purchased from Yanshan Petrochemical, ethylene-propylene-butene terpolymer, and the melt mass flow rate is 5.2g/10min); component y is the grade of 6102 Polyolefin elastomer (purchased from Exxon); component z is a propylene impact copolymer (purchased from Zhongsha Petrochemical Co., Ltd.) with a trade name of EP200K, with an ethylene content of 8 wt % and an ethylene-propylene copolymer content of 13 wt % , the melt mass flow rate is 3.2g/10min).
  • the pellets of the propylene polymer composition A and the propylene polymer composition B obtained in the above steps (1) and (2) are dried, and then the propylene polymer composition A is added to the multi-layer extrusion casting machine.
  • the propylene polymer composition B is added to the upper surface layer extruder of the multi-layer extrusion casting machine, wherein the upper surface layer extruder also needs to be added with an inorganic antiblocking agent (silicon dioxide). , the same as above), the weight ratio of release agent to propylene polymer composition pellets is 0.02:1.
  • the temperature of the casting chill roll was set to 30° C., and the film was wound to form a composite film, which consisted of an upper surface layer (layer b) and a core layer (layer a).
  • the film thickness was 50 ⁇ m, where the thickness ratio of layer b and layer a was 1:2.
  • Component a is a propylene impact copolymer with a trade mark of M180R (purchased from Shanghai Petrochemical, with an ethylene content of 11% by weight, an ethylene-propylene copolymerization content of 15% by weight, and a melt mass flow rate of 2.0g/10min);
  • Item b is a polyolefin elastomer with the grade of DF640 (purchased from Mitsui Company). The components prepared above are weighed and mixed according to the proportions, wherein the mass fraction Wa of the component a is 95 weight parts, and the mass fraction Wb of the component b is 5 weight parts.
  • lubricant PEG lubricant produced by Clariant, Switzerland, molecular weight is 10,000, and based on the sum of the mass of the above-mentioned component a and component b as 100 parts by weight, the amount of lubricant added is 0.1 part by weight
  • the mixture is added to the high-speed mixer and mixed evenly, and then the mixed material is added to the feeder of the twin-screw extruder manufactured by W&P Company.
  • the material enters the twin-screw through the feeder.
  • Component x is a random propylene copolymer with trade name F500EPS (purchased from Shanghai Petrochemical, ethylene-propylene-butene terpolymer, melt mass flow rate is 5.3g/10min); component y is a DF640 Polyolefin elastomer (purchased from Mitsui Co., Ltd.); component z is a propylene impact copolymer with trade name M180R (purchased from Shanghai Petrochemical, ethylene content is 11% by weight, ethylene-propylene copolymer content is 15% by weight, melt The mass flow rate was 2.0 g/10 min).
  • F500EPS purchasedd from Shanghai Petrochemical, ethylene-propylene-butene terpolymer, melt mass flow rate is 5.3g/10min
  • component y is a DF640 Polyolefin elastomer (purchased from Mitsui Co., Ltd.)
  • component z is a propylene impact copolymer with trade name M180R (purchased from Shanghai
  • the pellets of the propylene polymer composition A and the propylene polymer composition B obtained in the above steps (1) and (2) are dried, and then the propylene polymer composition A is added to the multi-layer extrusion casting machine.
  • the propylene polymer composition B is added to the upper surface layer extruder and the lower layer extruder of the multi-layer extrusion casting machine, wherein the upper and lower layer extruders also need to be added.
  • Inorganic release agent (silica, same as above), the weight ratio of release agent to propylene polymer composition pellets was all 0.02:1.
  • the temperature of the casting quench roll is set to 30°C, and the roll is wound to make a composite film, which consists of upper and lower layers (layer b; the composition of layer c and layer b is the same) and a core layer (Layer a) constitutes.
  • the thickness of the film is 50 ⁇ m, and the ratio of the thickness of the upper and lower layers to the core layer is 1:1.
  • Component a is a homopolypropylene with a trade mark of FC801 (purchased from Shanghai Petrochemical, the melt mass flow rate is 7.8 g/10min, the isotacticity is 98%, and the molecular weight distribution Mw/Mn is 4.8);
  • component b is a trade mark Polyolefin elastomer (purchased from Exxon Corporation) of EXACT3139. The components prepared above are weighed and mixed according to the proportions, wherein the mass fraction Wa of the component a is 85 weight parts, and the mass fraction Wb of the component b is 15 weight parts.
  • lubricant PEG lubricant produced by Clariant, Switzerland, molecular weight is 10,000, and based on the sum of the mass of the above-mentioned component a and component b as 100 parts by weight, the amount of lubricant added is 0.1 part by weight
  • the mixture is added to the high-speed mixer and mixed evenly, and then the mixed material is added to the feeder of the twin-screw extruder manufactured by W&P Company.
  • the material enters the twin-screw through the feeder.
  • Component x is a random propylene copolymer with a trade name of F800EPS (purchased from Shanghai Petrochemical); component y is a polyolefin elastomer with a trade mark of EXACT3139 (purchased from Exxon); component z is a trade mark of PPB-M02D
  • the polypropylene impact copolymer (purchased from Maoming Petrochemical).
  • the above-mentioned components are weighed and mixed according to the proportions, wherein the mass fraction Wx of the component x is 85 parts by weight, the mass fraction Wy of the component y is 10 weight parts, and the mass fraction of the component z is 10 weight parts. Wz is 5 parts by weight.
  • Wb:Wy is 3:2.
  • the other operations are the same as those in step (1), and finally the pellets of the propylene polymer composition B are obtained.
  • the melt mass flow rate MFR B 7.4 g/10min.
  • the preparation process is the same as the step (3) of Example B1.
  • step (2) of embodiment B1 Operation is the same as the step (2) of embodiment B1, except wherein the mass fraction Wx of component x is 90 weight parts, the mass fraction Wy of component y is 5 weight parts, and the mass fraction Wz of component z is 5 weight parts share. Wb:Wy is 6:1.
  • the operation is the same as step (3) of Example B1.
  • the film thickness was 50 ⁇ m, where the thickness ratio of layer b and layer a was 1:3.
  • the operation is the same as step (3) in Example B2.
  • the thickness of the film is 50 ⁇ m, and the ratio of the sum of the thickness of the upper and lower layers to the thickness of the core layer is 2:1.
  • the operation is the same as the step (3) of Embodiment B3.
  • the film thickness is 50 ⁇ m, and the ratio of the thickness of the upper surface layer to the thickness of the core layer is 1:4.
  • the operation is the same as step (1) of Example B1.
  • the mass fraction Wa of component a is 100 parts by weight.
  • step (2) of Example B1 The operation is the same as the step (2) of Example B1, except that the mass fraction Wx of component x is 50 weight parts, the mass fraction Wy of component y is 20 weight parts, and the mass fraction Wz of component z is 30 weight parts share.
  • the other operations are the same as those in step (1), and finally the pellets of the propylene polymer composition B are obtained.
  • the melt mass flow rate MFR B 3.5 g/10min.
  • the operation is the same as step (3) of Example B1.
  • the film thickness was 50 ⁇ m, where the thickness ratio of layer b and layer a was 1:3.
  • the composite film was prepared according to the method of Example B1, except that in the preparation of the propylene polymer composition B, the mass fraction Wx of the component x was 40 parts by weight, the mass fraction Wy of the component y was 30 parts by weight, and the component The mass fraction Wz of z is 30 parts by weight.
  • a composite film was prepared according to the method of Example B1, except that only the propylene polymer composition A was used for extrusion casting into a single-layer film, and the film thickness was 50 ⁇ m.
  • a composite film was prepared according to the method of Example B2, except that only the propylene polymer composition B was used for extrusion casting into a single-layer film, and the film thickness was 50 ⁇ m.
  • a composite film was prepared according to the method of Example B1, except that the propylene polymer composition B contained only component x.
  • the composite film was prepared according to the method of Example B1, except that the propylene polymer composition B only contained component x and component y, wherein the mass fraction Wx of component x was 85 parts by weight, and the mass fraction Wy of component y 15 parts by weight.
  • the composite film was prepared according to the method of Example B2, except that the propylene polymer composition B only contained component x and component z, wherein the mass fraction Wx of component x was 70 parts by weight, and the mass fraction Wz of component z 30 parts by weight.
  • the composite film according to the present invention has good impact resistance and optical properties at the same time, and even has good tensile properties and good heat-sealing strength.
  • the composite film of the present invention can achieve a good balance of various properties, and during extrusion casting, the stability of the film surface and the thickness uniformity are better. .
  • Example A1 The operation of Example A1 was basically repeated, except that the polyolefin elastomer used in the steps (1) and (2) was replaced by a polyolefin elastomer with a grade of 8200 (purchased from Dow Company, which is ethylene-1-octene copolymerization).
  • the content of octene structural unit is 38% by weight
  • shear rates 160r -1 and 640r -1 is 2.18
  • the elastomer The shear viscosity ⁇ 640 at 230° C.
  • step (3) the weight ratio of release agent to propylene polymer composition pellets is both 0.2:100.
  • melt mass flow rate MFR A 3.8g/10min
  • MFR B 4.2g/10min.
  • the atomic force microscope photograph of the section of the composite film is shown in FIG. 5 .
  • the black part is the rubber phase, and the rubber phase is dispersed, strip-like, and arranged parallel to each other.
  • the rubber phase had an average size on the horizontal axis of 84 nm, and an average aspect ratio of 8.8.
  • the composite film was observed under an atomic force microscope, and a dispersed, strip-like, mutually parallel rubber phase was seen, the average size of the rubber phase was 105 nm on the transverse axis, and the average aspect ratio was 8.5.
  • Component a is a homopolypropylene with a trade mark of FC801 (purchased from Shanghai Petrochemical, the melt mass flow rate is 7.8 g/10min, the isotacticity is 98%, and the molecular weight distribution Mw/Mn is 4.8);
  • component b is a trade mark It is the propylene impact copolymer of PPB-M02D (purchased from Maoming Petrochemical Company, the ethylene content is 8% by weight, the content of the ethylene-propylene copolymerization part is 10% by weight, and the ethylene unit content in the room temperature xylene soluble is 36.3% by weight, The ethylene unit group [EEE] content is 18.5% by weight, and the melt mass flow rate is 1.5 g/10min);
  • component c is a polyolefin elastomer with the trade name VM3980 (purchased from Exxon, propylene-ethylene copolymer, The ethylene structural unit content is 9% by weight, the shear visco
  • the above-mentioned components are weighed and mixed according to the proportions, wherein the parts by mass Wa of component a are 55 parts by weight, the parts by mass Wb of component b are 25 parts by weight, and the parts by mass of component c are 25 parts by weight Wc is 20 parts by weight.
  • lubricant PEG lubricant produced by Swiss Clariant company, molecular weight is 10000, and the sum of the mass of above-mentioned component a, component b and component c is 100 parts by weight, the amount of lubricant added is 0.1 weight part
  • the mixture is added to the high-speed mixer and mixed evenly, and then the mixed material is added to the feeder of the twin-screw extruder manufactured by W&P Company, and the material enters the twin-screw through the feeder.
  • Component x is a random propylene copolymer with trade mark F800EDF (purchased from Shanghai Petrochemical, propylene-ethylene binary copolymer, melt mass flow rate is 7.8g/10min); component y is a polyolefin elastic with trade mark VM3980 (purchased from Exxon Company, propylene-ethylene copolymer, the content of ethylene structural unit is 9% by weight, the ratio of shear viscosity of this polyolefin elastomer at 230 ° C, shear rate 160r -1 and 640r -1 ⁇ 160 / ⁇ 640 was 2.26, and the shear viscosity ⁇ 640 of the elastomer at 230° C.
  • F800EDF trade mark
  • component y is a polyolefin elastic with trade mark VM3980 (purchased from Exxon Company, propylene-ethylene copolymer, the content of ethylene structural unit is 9% by weight, the ratio of shear viscosity of this poly
  • the pellets of the propylene polymer composition A and the propylene polymer composition B obtained in the above steps (1) and (2) are dried, and then the propylene polymer composition A is added to the multi-layer extrusion casting machine.
  • the propylene polymer composition B is added to the upper surface layer extruder and the lower layer extruder of the multi-layer extrusion casting machine, wherein inorganic inorganic compounds are added to the upper and lower layer extruders.
  • Antiblocking agent (silica, same as above), the weight ratio of antiblocking agent to propylene polymer composition pellets was all 0.2:100.
  • the temperature of the casting quench roll is set to 30°C, and the roll is wound to make a composite film, which consists of upper and lower layers (layer b; the composition of layer c and layer b is the same) and a core layer (Layer a) constitutes.
  • the thickness of the film is 50 ⁇ m, and the ratio of the sum of the thickness of the upper and lower layers to the thickness of the core layer is 1:4.
  • the composite film was observed under an atomic force microscope, and a dispersed, strip-like, mutually parallel rubber phase could be seen, the average size of the rubber phase was 88 nm in the transverse axis, and the average aspect ratio was 9.6.
  • component c is a polyolefin elastomer with the brand name of 8411 (purchased from Dow Company, it is an ethylene-1-octene copolymer, and the content of octene structural unit is 36% by weight).
  • the shear viscosity ratio ⁇ 160 / ⁇ 640 of the polyolefin elastomer at 230°C, shear rate 160r -1 and 640r -1 is 1.80, and the shear viscosity of the elastomer at 230°C and shear rate 640r -1 is 1.80.
  • step (2) of Example C1 The operation is the same as the step (2) of Example C1, except that the mass fraction Wx of the component x is 92 parts by weight, and the mass fraction Wy of the component y is 8 parts by weight.
  • the other operations are the same as those in step (1), and finally the pellets of the propylene polymer composition B are obtained.
  • the melt mass flow rate MFR B 7.5g/10min.
  • the operation is the same as the step (3) of Example C1.
  • the film thickness was 50 ⁇ m, where the thickness ratio of layer b and layer a was 1:6.
  • the composite film was observed under an atomic force microscope, and a dispersed, strip-shaped, mutually parallel rubber phase was seen, the average size of the lateral axis of the rubber phase was 196 nm, and the average aspect ratio was 5.3.
  • the operation is the same as the step (3) of Example C2.
  • the thickness of the film is 50 ⁇ m, and the ratio of the sum of the thickness of the upper and lower layers to the thickness of the core layer is 2:1.
  • the composite film was observed under an atomic force microscope, and a dispersed, strip-shaped, mutually parallel rubber phase was seen, the average size of the lateral axis of the rubber phase was 23 nm, and the average aspect ratio was 19.8.
  • step (2) of Example C1 The operation is the same as the step (2) of Example C1, except that the mass fraction Wx of the component x is 85 weight parts, and the mass fraction Wy of the component y is 15 weight parts.
  • the other operations are the same as those in step (1), and finally the pellets of the propylene polymer composition B are obtained.
  • the melt mass flow rate MFR B 4.3 g/10min.
  • Example C1 The operation is the same as in Example C1.
  • the film thickness was 50 ⁇ m, where the thickness ratio of layer b and layer a was 1:3.
  • the composite film was observed under an atomic force microscope, and a dispersed, strip-shaped, mutually parallel rubber phase was seen, the average size of the lateral axis of the rubber phase was 145 nm, and the average aspect ratio was 12.1.
  • the composite film was observed under an atomic force microscope, and a dispersed, strip-like, mutually parallel rubber phase was seen, the average size of the lateral axis of the rubber phase was 88 nm, and the average aspect ratio was 17.0.
  • the propylene polymer composition A was prepared according to the method of Example C3, and the propylene polymer composition B was prepared according to the method of Example C2, so that both ( ⁇ A 160 - ⁇ B 160 ) and ( ⁇ A 640 - ⁇ B 640 ) were less than 0.
  • the composite film was prepared according to the method of Example C3.
  • the propylene polymer film was prepared according to the method of Example C1, except that in the preparation process of the propylene polymer composition A, the polyolefin elastomer c was replaced with a polyolefin elastomer (purchased from Mitsui Company, DF740)
  • the butene structural unit content is 28% by weight
  • shear rates 160r -1 and 640r -1 is 1.63
  • the elastomer is at 230°C
  • the shear viscosity ⁇ 640 under shear rate 640r -1 is 554Pa ⁇ s).
  • the propylene polymer film was prepared according to the method of Example C2, the difference was that in the preparation process of the propylene polymer composition B, the polyolefin elastomer y was replaced with a polyolefin elastomer with a grade of 8400 (purchased from The Dow Company).
  • propylene-octene copolymer the content of octene structural unit is 35%.
  • the ratio of shear viscosity ⁇ 160 / ⁇ 640 of the polyolefin elastomer at 230 ° C, shear rate 160r -1 and 640r -1 is 2.45
  • the shear viscosity ⁇ 640 of the elastomer at 230°C and shear rate 640r -1 is 84Pa ⁇ s).
  • a composite film was prepared according to the method of Example C1, except that the propylene polymer composition B contained only component x.
  • the composite film was prepared according to the method of Example C1, except that the propylene polymer composition A only contained component a and component b, wherein the mass fraction Wa of component a was 75 parts by weight, and the mass of component b was 75 parts by weight.
  • the number of parts Wb is 25 parts by weight.
  • the composite film was prepared according to the method of Example C1, except that the propylene polymer composition A only contained component a and component c, wherein the mass fraction Wa of component a was 75 parts by weight, and the mass of component c was 75 parts by weight.
  • the number of parts Wc is 25 parts by weight.
  • the composite films according to the present invention have both good impact resistance and optical properties, and even good film uniformity, especially when polyolefins with specific shear viscosities are used In the case of elastomers, the film surface is stable during extrusion casting, and the uniformity of film thickness and impact resistance is greatly improved.
  • Example B1 The operation of Example B1 is basically repeated, except:
  • the polyolefin elastomer used in the step (2) was replaced with a polyolefin elastomer with a trade mark of 8200 (purchased from Dow Company, ethylene-1-octene copolymer, the octene structural unit content was 38% by weight, and the polymer was The shear viscosity ratio ⁇ 160 / ⁇ 640 of the olefin elastomer at 230°C, shear rate 160r -1 and 640r -1 is 2.18, and the shear rate of the elastomer at 230°C and shear rate 640r -1 The viscosity ⁇ 640 is 185 Pa ⁇ s).
  • step (3) the weight ratio of the release agent to the propylene polymer composition pellets is both 0.2:100.
  • the composite film was observed under an atomic force microscope, and a dispersed, strip-shaped, mutually parallel rubber phase was seen, the average size of the rubber phase was 72 nm in the transverse axis, and the average aspect ratio was 5.5.
  • Example B2 The operation of Example B2 was basically repeated, except that the polyolefin elastomer used in steps (1) and (2) was replaced by a polyolefin elastomer of DF840 (purchased from Mitsui, ethylene-1-butene copolymer). , the butene structural unit content is 25% by weight, the shear viscosity ratio ⁇ 160 / ⁇ 640 of the polyolefin elastomer at 230 ° C, shear rates 160r -1 and 640r -1 is 1.75, and the elastomer is 230 r -1 .
  • the shear viscosity ⁇ 640 at °C and shear rate of 640r -1 is 398 Pa ⁇ s); in step (3), the weight ratio of the antiblocking agent to the propylene polymer composition pellets is both 0.2:100.
  • the composite film was observed under an atomic force microscope, and a dispersed, strip-like and mutually parallel rubber phase was seen, the average size of the rubber phase was 130 nm in the transverse axis, and the average aspect ratio was 6.4.
  • Component a is a homopolypropylene with a trade mark of FC801 (purchased from Shanghai Petrochemical, the melt mass flow rate is 7.8 g/10min, the isotacticity is 98%, and the molecular weight distribution Mw/Mn is 4.8);
  • component b is a trade mark Polyolefin elastomer of VM3980 (purchased from Exxon, propylene-ethylene copolymer, ethylene structural unit content of 9% by weight, the polyolefin elastomer at 230° C., shear rates 160r -1 and 640r -1
  • the shear viscosity ratio ⁇ 160 / ⁇ 640 of the elastomer is 2.26, and the shear viscosity of the elastomer at 230°C and shear rate 640r ⁇ 1 is 205Pa ⁇ s).
  • the components prepared above are weighed and mixed according to the proportions, wherein the mass fraction Wa of the component a is 85 weight parts, and the mass fraction Wb of the component b is 15 weight parts. Then add lubricant (PEG lubricant produced by Clariant, Switzerland, molecular weight is 10,000, and based on the sum of the mass of the above-mentioned component a and component b as 100 parts by weight, the amount of lubricant added is 0.1 part by weight), then The mixture is added to the high-speed mixer and mixed evenly, and then the mixed material is added to the feeder of the twin-screw extruder manufactured by W&P Company. The material enters the twin-screw through the feeder.
  • lubricant PEG lubricant produced by Clariant, Switzerland, molecular weight is 10,000, and based on the sum of the mass of the above-mentioned component a and component b as 100 parts by weight, the amount of lubricant added is 0.1 part by weight
  • Component x is the propylene random copolymer with trade mark F800EDF (purchased from Shanghai Petrochemical, is an ethylene-propylene binary copolymer, and the melt mass flow rate is 7.8g/10min);
  • component y is the polyolefin with trade mark VM3980 Elastomer (purchased from Exxon Company, propylene-ethylene copolymer, the content of ethylene structural unit is 9% by weight, the shear viscosity of the polyolefin elastomer at 230 ° C, shear rate 160r -1 and 640r -1 is between The ratio ⁇ 160 / ⁇ 640 is 2.26, and the shear viscosity of the elastomer at 230 ° C and shear rate 640r -1 is 205Pa s);
  • component z is a propylene impact copolymer with a trade mark of PPB-M02D (purchased From Maoming Petrochemical, the content of ethylene is 8% by weight,
  • the above-mentioned components are weighed and mixed according to the proportions, wherein the mass fraction Wx of the component x is 85 parts by weight, the mass fraction Wy of the component y is 10 weight parts, and the mass fraction of the component z is 10 weight parts. Wz is 5 parts by weight.
  • the preparation process is the same as the step (3) of Example D1.
  • the composite film was observed under an atomic force microscope, and a dispersed, strip-like, mutually parallel rubber phase was seen, the average size of the lateral axis of the rubber phase was 72 nm, and the average aspect ratio was 13.2.
  • the operation is the same as the step (2) of Example D1, except that the mass fraction Wx of component x is 90 parts by weight, the mass fraction Wy of component y is 5 weight parts, and the mass fraction Wz of component z is 5 parts by weight.
  • the other operations are the same as the operations in step (1), and finally the pellets of the propylene polymer composition B are obtained.
  • the melt mass flow rate MFR B 5.2 g/10min.
  • the operation is the same as step (3) of Example D1.
  • the film thickness was 50 ⁇ m, where the thickness ratio of layer b and layer a was 1:3.
  • the steps are the same as in Example D2.
  • the thickness of the film is 50 ⁇ m, and the ratio of the sum of the thickness of the upper and lower layers to the thickness of the core layer is 2:1.
  • the mass fraction Wx of component x is 50 parts by weight
  • the mass fraction Wy of component y is 30 parts by weight
  • component y is a polystyrene with a trade mark of 8411.
  • Olefin elastomer ethylene-1-octene copolymer, octene structural unit content of 36% by weight, purchased from Dow Company, the polyolefin elastomer at 230 ° C, shear rate 160r -1 and 640r -1 under the The ratio of shear viscosity ⁇ 160 / ⁇ 640 was 1.80, and the shear viscosity of the elastomer at 230° C.
  • the operation is the same as the step (3) of Example D3.
  • the film thickness is 50 ⁇ m, and the ratio of the thickness of the upper surface layer to the thickness of the core layer is 1:4.
  • the composite film was observed under an atomic force microscope, and a dispersed, strip-shaped, mutually parallel rubber phase was seen, the average size of the lateral axis of the rubber phase was 25 nm, and the average aspect ratio was 19.7.
  • the operation is the same as the step (2) of Example D1, except that the mass fraction Wx of component x is 50 parts by weight, the mass fraction Wy of component y is 20 weight parts, and the mass fraction Wz of component z is 30 parts by weight.
  • the other operations are the same as the operations in step (1), and finally the pellets of the propylene polymer composition B are obtained.
  • the melt mass flow rate MFR B 3.7 g/10min.
  • the operation is the same as step (3) of Example D1.
  • the film thickness was 50 ⁇ m, where the thickness ratio of layer b and layer a was 1:3.
  • the composite film was observed under an atomic force microscope, and a dispersed, strip-shaped, mutually parallel rubber phase was seen, the average size of the lateral axis of the rubber phase was 67 nm, and the average aspect ratio was 17.5.
  • the composite film was observed under an atomic force microscope, and a dispersed, strip-shaped, mutually parallel rubber phase was seen, the average size of the lateral axis of the rubber phase was 190 nm, and the average aspect ratio was 5.1.
  • the composite film was observed under an atomic force microscope, and a dispersed, strip-like, mutually parallel rubber phase was seen, the average size of the lateral axis of the rubber phase was 145 nm, and the average aspect ratio was 7.8.
  • the composite film was observed under an atomic force microscope, and a dispersed, strip-like, mutually parallel rubber phase was seen, the average size of the lateral axis of the rubber phase was 85 nm, and the average aspect ratio was 18.3.
  • the propylene polymer composition A was prepared according to the method of Example D3, and the propylene polymer composition B was prepared according to the method of Example D2, so that both ( ⁇ A 160 - ⁇ B 160 ) and ( ⁇ A 640 - ⁇ B 640 ) were less than 0.
  • the composite film was prepared according to the method of Example D3.
  • the composite film was prepared according to the method of Example D1, the difference was that the polyolefin elastomer b was replaced with a polyolefin elastomer with a trade mark of DF740 (purchased from Mitsui Company, and the polyolefin elastomer was heated at 230°C and a shear rate of 160r-
  • the ratio ⁇ 160 / ⁇ 640 of shear viscosity at 1 and 640r -1 was 1.63, and the shear viscosity of the elastomer at 230°C and shear rate 640r -1 was 554 Pa ⁇ s).
  • Melt mass flow rate MFR A of propylene polymer composition A 2.6 g/10 min.
  • the film thickness was 50 ⁇ m.
  • a composite film was prepared according to the method of Example D1, except that the propylene polymer composition B contained only component x.
  • the composite film was prepared according to the method of Example D1, except that the propylene polymer composition B only contained component x and component y, wherein the mass fraction Wx of component x was 85 parts by weight, and the mass of component y was 85 parts by weight.
  • the number of parts Wy is 15 parts by weight.
  • the composite film was prepared according to the method of Example D2, except that the propylene polymer composition B only contained component x and component z, wherein the mass fraction Wx of component x was 70 parts by weight, and the mass of component z was 70 parts by weight.
  • the number of parts Wz is 30 parts by weight.
  • the composite film was prepared according to the method of Example D2. The difference is that propylene polymer composition A contains only component a.
  • the composite film according to the present invention has both good impact resistance and optical properties.
  • the composite film of the present invention has better comprehensive properties, especially when a polyolefin elastomer with a specific shear viscosity is used, the film surface is stable and the film thickness is stable during extrusion casting. The uniformity and the uniformity of the impact resistance properties are greatly improved.
  • Component a is a propylene impact copolymer with a trade name of J410F (purchased from Hyosung, South Korea, the average particle size of the rubber phase is 600 nm, the maximum particle size of the rubber phase is 800 nm, the ethylene unit content is 5.3% by weight, and the ethylene-propylene copolymer content is 5.3% by weight. It is 7.2 wt %. In its room temperature xylene soluble, the ethylene unit content is 26.0 wt %. The ethylene unit group [EEE] content is 6.9 wt %. The melt mass flow rate is 4.6 g/10min.
  • Figure 6a shows the propylene SEM photo of the cross section of the impact copolymer spline); component b is a homopolypropylene with a grade of PPH-FA03 (purchased from Qingdao Refinery, the melt mass flow rate is 3.0g/10min, and the molecular weight distribution Mw/Mn is 4.6); Component c is a polyolefin elastomer with the trade name of DF840 (purchased from Mitsui Corporation, which is an ethylene-1-butene copolymer).
  • the above-mentioned components are weighed and mixed according to the proportions, wherein the parts by mass Wa of component a are 65 parts by weight, the parts by mass Wb of component b are 30 parts by weight, and the parts by mass of component c are 30 parts by weight Wc is 5 parts by weight.
  • lubricant PEG lubricant produced by Swiss Clariant company, molecular weight is 10000, and the sum of the mass of above-mentioned component a, component b and component c is 100 parts by weight, the amount of lubricant added is 0.1 weight part parts
  • lubricant PEG lubricant produced by Swiss Clariant company, molecular weight is 10000, and the sum of the mass of above-mentioned component a, component b and component c is 100 parts by weight, the amount of lubricant added is 0.1 weight part parts
  • Component x is a propylene random copolymer with the trade name of F500EPS (purchased from Shanghai Petrochemical, which is an ethylene-propylene-butene terpolymer, and the melt mass flow rate is 5.3g/10min); component y is the trade mark of DF840 The polyolefin elastomer (purchased from Mitsui, as ethylene-1-butene copolymer).
  • the components prepared above are weighed and mixed according to the proportions, wherein the mass fraction Wx of the component x is 90 weight parts, and the mass fraction Wy of the component y is 10 weight parts.
  • the other operations are the same as those in step (1), and finally the pellets of the propylene polymer composition B are obtained.
  • the melt mass flow rate MFR B 5.6 g/10min.
  • the pellets of the propylene polymer composition A and the propylene polymer composition B obtained in the above steps (1) and (2) are dried, and then the propylene polymer composition A is added to the multi-layer extrusion casting machine.
  • the propylene polymer composition B is added to the upper surface layer extruder and the lower layer extruder of the multi-layer extrusion casting machine, wherein inorganic inorganic compounds are added to the upper and lower layer extruders.
  • the antiblocking agent (silica, ibid.), the weight ratio of the antiblocking agent to the pellets of the propylene polymer composition was all 0.2:100.
  • the temperature of the casting quench roll was set to 30°C, and the film was wound to form a composite film, which consisted of upper and lower layers (layer b) and a core layer (layer a).
  • the thickness of the film is 50 ⁇ m, and the ratio of the sum of the thickness of the upper and lower layers to the thickness of the core layer is 1:1.
  • the atomic force microscope photo of the cut surface of the composite film is shown in Figure 7, wherein the black part is the rubber phase, and it can be seen that the rubber phase is dispersed, strip-shaped, and arranged parallel to each other.
  • the average size of the lateral axis of the rubber phase was 53 nm, and the average value of the aspect ratio was 5.2.
  • Component a is the propylene impact copolymer (purchased from Shanghai Petrochemical Co., Ltd.) whose trade mark is F200R, and the ethylene unit content is 9.1% by weight, and the content of the ethylene-propylene copolymerized part is 12.2% by weight.
  • the average particle size of the rubber phase is 800 nm, and the maximum particle size is 800 nm. is 1 ⁇ m, the content of ethylene units in the room temperature xylene soluble is 38.1% by weight.
  • the content of ethylene unit group [EEE] is 13.6% by weight.
  • the melt mass flow rate is 2.1g/10min); -FA03 homopolypropylene (purchased from Qingdao Refinery, with a melt mass flow rate of 3.1g/10min and a molecular weight distribution of Mw/Mn of 4.7); component c is a polyolefin elastomer with a grade of 8200 (purchased from Taobao Company, ethylene-1-octene copolymer).
  • the above-mentioned components are weighed and mixed according to the proportions, wherein the parts by mass Wa of component a are 75 parts by weight, the parts by mass Wb of component b are 10 parts by weight, and the parts by mass of component c are 10 parts by weight Wc is 15 parts by weight.
  • lubricant PEG lubricant produced by Swiss Clariant company, molecular weight is 10000, and the sum of the mass of above-mentioned component a, component b and component c is 100 parts by weight, the amount of lubricant added is 0.1 weight part parts
  • lubricant PEG lubricant produced by Swiss Clariant company, molecular weight is 10000, and the sum of the mass of above-mentioned component a, component b and component c is 100 parts by weight, the amount of lubricant added is 0.1 weight part parts
  • Component x is a propylene random copolymer with trade mark F5006 (purchased from Yanshan Petrochemical, ethylene-propylene-butene terpolymer, melt mass flow rate is 5.2g/10min); component y is a 8200 grade Polyolefin elastomer (available from The Dow Company, ethylene-1-octene copolymer).
  • the components prepared above are weighed and mixed according to the proportions, wherein the mass fraction Wx of the component x is 75 weight parts, and the mass fraction Wy of the component y is 25 weight parts.
  • the other operations are the same as those in step (1), and finally the pellets of the propylene polymer composition B are obtained.
  • the melt mass flow rate MFR B 4.2 g/10min.
  • the pellets of the propylene polymer composition A and the propylene polymer composition B obtained in the above steps (1) and (2) are dried, and then the propylene polymer composition A is added to the multi-layer extrusion casting machine.
  • the propylene polymer composition B is added to the upper surface layer extruder of the multi-layer extrusion casting machine, wherein the upper surface layer extruder is added with an inorganic anti-blocking agent (silicon dioxide, Ibid), the weight ratio of release agent to pellets of the propylene polymer composition was 0.2:100.
  • the temperature of the casting chill roll was set to 30° C., and the film was wound to form a composite film, which consisted of an upper surface layer (layer b) and a core layer (layer a).
  • the film thickness was 50 ⁇ m, where the thickness ratio of layer b and layer a was 1:2.
  • the composite film was observed under an atomic force microscope, and a dispersed, striped, and parallel to each other rubber phase was seen, the average size of the lateral axis of the rubber phase was 62 nm, and the average aspect ratio was 11.2.
  • Component a is a propylene impact copolymer with a trade name of PPB-M02D (the average particle size of the rubber phase is 1.4 ⁇ m, the maximum particle size of the rubber phase is 1.9 ⁇ m, purchased from Maoming Petrochemical, ethylene content is 8% by weight, ethylene-propylene copolymerization The partial content is 10% by weight, and in the room temperature xylene soluble, the content of ethylene units is 36.3% by weight.
  • PPB-M02D the average particle size of the rubber phase is 1.4 ⁇ m, the maximum particle size of the rubber phase is 1.9 ⁇ m, purchased from Maoming Petrochemical, ethylene content is 8% by weight, ethylene-propylene copolymerization The partial content is 10% by weight, and in the room temperature xylene soluble, the content of ethylene units is 36.3% by weight.
  • the content of ethylene unit group [EEE] is 18.5% by weight, and the melt mass flow rate is 1.5g/10min);
  • b is the propylene-ethylene binary random copolymer polypropylene with the trade mark F800EDF (purchased from Shanghai Petrochemical, the melt mass flow rate is 7.8g/10min);
  • component c is the polyolefin elastomer with the trade mark VM3980 (purchased from Angstrom Kesen Company, for propylene-ethylene copolymer).
  • the above-mentioned components are weighed and mixed according to the proportions, wherein the parts by mass Wa of component a are 55 parts by weight, the parts by mass Wb of component b are 25 parts by weight, and the parts by mass of component c are 25 parts by weight Wc is 20 parts by weight.
  • lubricant PEG lubricant produced by Swiss Clariant company, molecular weight is 10000, and the sum of the mass of above-mentioned component a, component b and component c is 100 parts by weight, the amount of lubricant added is 0.1 weight part parts
  • lubricant PEG lubricant produced by Swiss Clariant company, molecular weight is 10000, and the sum of the mass of above-mentioned component a, component b and component c is 100 parts by weight, the amount of lubricant added is 0.1 weight part parts
  • Component x is a propylene random copolymer with trade mark F800EDF (purchased from Shanghai Petrochemical, is a propylene-ethylene binary copolymer, and the melt mass flow rate is 7.8g/10min); component y is a polyolefin with trade mark VM3980 Elastomer (purchased from Exxon as a propylene-ethylene copolymer).
  • the components prepared above are weighed and mixed according to the proportions, wherein the mass fraction Wx of the component x is 80 weight parts, and the mass fraction Wy of the component y is 20 weight parts.
  • the other operations are the same as those in step (1), and finally the pellets of the propylene polymer composition B are obtained.
  • the melt mass flow rate MFR B 8.3 g/10min.
  • the thickness of the obtained film is 50 ⁇ m, and the ratio of the sum of the thickness of the upper and lower layers to the thickness of the core layer is 1:4.
  • Example E2 The operation is the same as the step (1) of Example E2, except that the mass fraction Wa of component a is 80 parts by weight, the mass fraction Wb of component b is 18 weight parts, and the mass fraction Wc of component c is 2 parts by weight.
  • step (2) of Example E2 The operation is the same as the step (2) of Example E2, except that the mass fraction Wx of the component x is 92 parts by weight, and the mass fraction Wy of the component y is 8 parts by weight.
  • the other operations are the same as those in step (1), and finally the pellets of the propylene polymer composition B are obtained.
  • the melt mass flow rate MFR B 7.5g/10min.
  • the operation is the same as step (3) of Example E2.
  • the film thickness was 50 ⁇ m, where the thickness ratio of layer b and layer a was 1:6.
  • the composite film was observed under an atomic force microscope, and the rubber phases were dispersed, striped, and arranged in parallel with each other.
  • the average size of the lateral axis of the rubber phases was 77 nm, and the average aspect ratio was 5.6.
  • the operation is the same as step (3) of Example E1.
  • the thickness of the film is 50 ⁇ m, and the ratio of the sum of the thickness of the upper and lower layers to the thickness of the core layer is 2:1.
  • the composite film was observed under an atomic force microscope, and the rubber phases were dispersed, striped and arranged parallel to each other, the average size of the transverse axis of the rubber phases was 25 nm, and the average aspect ratio was 14.6.
  • the composite film was observed under an atomic force microscope, and the rubber phases were dispersed, striped, and arranged parallel to each other.
  • the average size of the lateral axis of the rubber phases was 138 nm, and the average aspect ratio was 6.3.
  • step (2) of Example E2 The operation is the same as the step (2) of Example E2, except that the mass fraction Wx of the component x is 85 parts by weight, and the mass fraction Wy of the component y is 15 parts by weight.
  • the other operations are the same as those in step (1), and finally the pellets of the propylene polymer composition B are obtained.
  • the melt mass flow rate MFR B 4.3 g/10min.
  • the operation is the same as step (3) of Example E2.
  • the film thickness was 50 ⁇ m, where the thickness ratio of layer b and layer a was 1:3.
  • the composite film was observed under an atomic force microscope, and the rubber phases were dispersed, striped and arranged parallel to each other, the average size of the lateral axis of the rubber phases was 106 nm, and the average aspect ratio was 8.6.
  • the composite film was prepared according to the method of Example E2, the difference was that in the preparation process of the propylene polymer composition A, the propylene impact copolymer was replaced with a propylene impact copolymer with a trade mark of F780R (purchased from Shanghai Petrochemical, rubber).
  • the average particle size of the phase is 2.0 ⁇ m
  • the maximum particle size of the rubber phase is 3.0 ⁇ m
  • the content of ethylene units is 9.0% by weight
  • the content of ethylene-propylene copolymerized part is 17.1% by weight.
  • the melt mass flow rate is 7.3 g/10min.
  • Figure 6b is a SEM photograph of the cross section of the propylene impact copolymer spline).
  • the composite film was prepared according to the method of Example E2, except that the propylene polymer composition A only contained component a and component b, wherein the mass fraction Wa of component a was 75 parts by weight, and the mass of component b was 75 parts by weight.
  • the number of parts Wb is 25 parts by weight.
  • the composite film was prepared according to the method of Example E2, except that the propylene polymer composition A only contained component a and component c, wherein the mass fraction Wa of component a was 75 parts by weight, and the mass of component c was 75 parts by weight.
  • the number of parts Wc is 25 parts by weight.
  • the composite film with the microstructure according to the present invention has both good impact resistance and optical properties, and even good heat seal strength.
  • composite films made with propylene impact copolymers not according to the present invention without the microstructures according to the present invention have poor optical properties or impact properties, and the film surface does not appear to be well after extrusion casting. Stable, it is difficult to obtain a film of uniform thickness.
  • Component a is a homopolymerized polypropylene with a grade of PPH-FA03 (purchased from Qingdao Refinery, with a melt mass flow rate of 3.1 g/10min, an isotacticity of 98%, and a molecular weight distribution of Mw/Mn of 4.7);
  • b is a polyolefin elastomer with the grade of 8411 (purchased from Dow Company, which is an ethylene-1-octene copolymer).
  • the components prepared above are weighed and mixed according to the proportions, wherein the mass fraction Wa of the component a is 80 weight parts, and the mass fraction Wb of the component b is 20 weight parts.
  • lubricant PEG lubricant produced by Clariant, Switzerland, molecular weight is 10,000, and based on the sum of the mass of the above-mentioned component a and component b as 100 parts by weight, the amount of lubricant added is 0.1 part by weight
  • the mixture is added to the high-speed mixer and mixed evenly, and then the mixed material is added to the feeder of the twin-screw extruder manufactured by W&P Company. The material enters the twin-screw through the feeder.
  • Component x is a propylene random copolymer with trade mark F5006 (purchased from Yanshan Petrochemical, is an ethylene-propylene-butene terpolymer, and the melt mass flow rate is 5.2g/10min); component y is a trade mark of 8200 The polyolefin elastomer (purchased from Dow, which is ethylene-1-octene copolymer); component z is polypropylene impact copolymer with the grade of PPB-M02D, the average particle size of the rubber phase is 1.4 ⁇ m, and the rubber The phase maximum particle size is 1.9 ⁇ m, purchased from Maoming Petrochemical, the ethylene content is 8 wt %, and the melt mass flow rate is 1.5 g/10 min).
  • trade mark F5006 purchased from Yanshan Petrochemical, is an ethylene-propylene-butene terpolymer, and the melt mass flow rate is 5.2g/10min
  • component y is a trade mark of 8200
  • the above-mentioned components are weighed and mixed according to the proportions, wherein the mass fraction Wx of the component x is 85 parts by weight, the mass fraction Wy of the component y is 5 weight parts, and the mass fraction of the component z is 5 weight parts. Wz is 10 parts by weight.
  • the pellets of the propylene polymer composition A and the propylene polymer composition B obtained in the above steps (1) and (2) are dried, and then the propylene polymer composition A is added to the multi-layer extrusion casting machine.
  • the propylene polymer composition B is added to the upper surface layer extruder of the multi-layer extrusion casting machine, wherein the upper surface layer extruder is added with an inorganic anti-blocking agent (silicon dioxide, Ibid), the weight ratio of release agent to propylene polymer composition pellets was 0.2:100.
  • the temperature of the casting chill roll was set to 30° C., and the film was wound to form a composite film, which consisted of an upper surface layer (layer b) and a core layer (layer a).
  • the film thickness was 50 ⁇ m, where the thickness ratio of layer b and layer a was 1:2.
  • the atomic force microscope photo of the cross section of the composite film shows that there is a rubber phase in the film, the rubber phase is uniformly dispersed, strip-shaped, and arranged parallel to each other, and the average size of the transverse axis of the rubber phase is 128nm, The average aspect ratio is 5.2.
  • Component a is the propylene impact copolymer of F200R (purchased from Shanghai Petrochemical, the rubber phase average particle size is 800nm, the rubber phase maximum particle size is 1 ⁇ m, the ethylene content is 9.1% by weight, and the ethylene-propylene copolymerization part content is 12.2 % by weight, in its room temperature xylene solubles, the ethylene unit content is 38.1 wt %, the ethylene unit group [EEE] content is 13.6 wt %, and the melt mass flow rate is 2.1 g/10min); component b is the grade of Polyolefin elastomer of DF840 (purchased from Mitsui, as ethylene-1-butene copolymer).
  • the components prepared above are weighed and mixed according to the proportions, wherein the mass fraction Wa of the component a is 95 weight parts, and the mass fraction Wb of the component b is 5 weight parts. Then add a lubricant (the lubricant is a PEG lubricant produced by Clariant, Switzerland, with a molecular weight of 10,000, and the sum of the mass of the above-mentioned component a and component b is 100 parts by weight, and the added amount of the lubricant is 0.1 parts by weight), then add the mixture into a high-speed mixer to mix evenly, and then add the mixed material to the feeder of the twin-screw extruder manufactured by W&P Company, and the material enters the twin-screw via the feeder for processing.
  • a lubricant is a PEG lubricant produced by Clariant, Switzerland, with a molecular weight of 10,000, and the sum of the mass of the above-mentioned component a and component b is 100 parts by weight, and
  • the temperature of the screw is maintained between 160-230 ° C, and the screw is melted and mixed uniformly, extruded, granulated and dried to obtain propylene polymer composition A pellets.
  • the melt mass flow rate MFR A 3.6g/10min.
  • Component x is a propylene random copolymer with the trade name of F500EPS (purchased from Shanghai Petrochemical, which is an ethylene-propylene-butene terpolymer, and the melt mass flow rate is 5.3g/10min); component y is the trade mark of DF840 The polyolefin elastomer (purchased from Mitsui Co., Ltd.); component z is a polypropylene impact copolymer with the grade of F200R.
  • the above-mentioned components are weighed and mixed according to the proportions, wherein the mass fraction Wx of the component x is 60 parts by weight, the mass fraction Wy of the component y is 20 weight parts, and the mass fraction of the component z is 20 parts by weight. Wz is 20 parts by weight.
  • the pellets of the propylene polymer composition A and the propylene polymer composition B obtained in the above steps (1) and (2) are dried, and then the propylene polymer composition A is added to the multi-layer extrusion casting machine.
  • the propylene polymer composition B is added to the upper surface layer extruder and the lower layer extruder of the multi-layer extrusion casting machine, wherein inorganic inorganic compounds are added to the upper and lower layer extruders.
  • Antiblocking agent (silica, same as above), the weight ratio of antiblocking agent to propylene polymer composition pellets was all 0.2:100.
  • the temperature of the casting quench roll was set to 30°C, and the film was wound to form a composite film, which consisted of upper and lower layers (layer b) and a core layer (layer a).
  • the thickness of the film is 50 ⁇ m, and the ratio of the sum of the thickness of the upper and lower layers to the thickness of the core layer is 1:1.
  • the composite film was observed under an atomic force microscope, and a dispersed, striped, and parallel to each other rubber phase was seen, the average size of the lateral axis of the rubber phase was 88 nm, and the average aspect ratio was 7.5.
  • Component a is a homopolypropylene with a trade mark of FC801 (purchased from Shanghai Petrochemical, the melt mass flow rate is 7.8 g/10min, the isotacticity is 98%, and the molecular weight distribution Mw/Mn is 4.8); component b is a trade mark It is a polyolefin elastomer of VM3980 (purchased from Exxon Company, it is a propylene-ethylene copolymer, the content of ethylene structural unit is 9% by weight).
  • the components prepared above are weighed and mixed according to the proportions, wherein the mass fraction Wa of the component a is 85 weight parts, and the mass fraction Wb of the component b is 15 weight parts.
  • the lubricant is a PEG lubricant produced by Clariant, Switzerland, with a molecular weight of 10,000, and the sum of the mass of the above-mentioned component a and component b is 100 parts by weight, and the added amount of the lubricant is 0.1 parts by weight
  • the mixture was added to a high-speed mixer to mix evenly, and then the mixed material was added to the feeder of the twin-screw extruder manufactured by W&P Company, and the material entered the twin-screw through the feeder for processing.
  • the temperature of the screw is kept between 160-230 ° C, and the screw is melted and mixed uniformly, extruded, granulated and dried to obtain propylene polymer composition A pellets.
  • the melt mass flow rate MFR A 7.4g/10min.
  • Component x is a propylene random copolymer with a trade mark of F800EPS (purchased from Shanghai Petrochemical, is an ethylene-propylene-butene terpolymer, and the melt mass flow rate is 8.2g/10min); component y is a trade mark of VM3980 The polyolefin elastomer (purchased from Exxon Corporation, is a propylene-ethylene copolymer, and the content of ethylene structural units is 9% by weight; component z is a polypropylene impact copolymer with a trade name of J410F (purchased from Hyosung, South Korea, The average particle size of the rubber phase is 600 nm, the maximum particle size of the rubber phase is 800 nm, the ethylene content is 5.3% by weight, the content of the ethylene-propylene copolymer part is 7.2% by weight, and the room temperature xylene soluble The content of ethylene units is 26.0% by weight , the ethylene unit group [EEE] content is 6.
  • the preparation process is the same as the step (3) of Example F1.
  • the composite film was observed under an atomic force microscope, and a dispersed, strip-like, and parallel to each other rubber phase was seen, the average size of the lateral axis of the rubber phase was 54 nm, and the average aspect ratio was 9.8.
  • the step is the same as the step (2) of Embodiment F1, except that the mass fraction Wx of component x is 90 parts by weight, the mass fraction Wy of component y is 5 weight parts, and the mass fraction Wz of component z is 5 parts by weight.
  • Other operations are the same as the operations in step (1), and finally the pellets of the propylene polymer composition B are obtained.
  • the melt mass flow rate MFR B 5.5g/10min.
  • Example F1 The steps are the same as in Example F1.
  • the film thickness was 50 ⁇ m with a thickness ratio of layer B to layer A of 1:3.
  • the operation is the same as that of Example F2.
  • the thickness of the film is 50 ⁇ m, and the ratio of the sum of the thickness of the upper and lower layers to the thickness of the core layer is 2:1.
  • the operation is the same as step (3) of Example F3.
  • the film thickness is 50 ⁇ m, and the ratio of the thickness of the upper surface layer to the thickness of the core layer is 1:4.
  • the composite film was observed under an atomic force microscope, and a dispersed, striped, and parallel to each other rubber phase was seen, the average size of the lateral axis of the rubber phase was 28 nm, and the average aspect ratio was 14.5.
  • the operation is the same as the step (2) of Example F1, except that the mass fraction Wx of component x is 50 parts by weight, the mass fraction Wy of component y is 20 weight parts, and the mass fraction Wz of component z is 30 parts by weight.
  • Other operations are the same as the operations in step (1), and finally the pellets of the propylene polymer composition B are obtained.
  • the melt mass flow rate MFR B 4.3 g/10min.
  • the operation is the same as step (3) of Example F1.
  • the film thickness was 50 ⁇ m with a thickness ratio of layer B to layer A of 1:3.
  • the composite film was observed under an atomic force microscope, and a dispersed, striped, and parallel to each other rubber phase was seen, the average size of the lateral axis of the rubber phase was 120 nm, and the average aspect ratio was 5.5.
  • the composite film was observed under an atomic force microscope, and a dispersed, striped, and parallel to each other rubber phase was seen, the average size of the lateral axis of the rubber phase was 145 nm, and the average aspect ratio was 7.4.
  • the composite film was observed under an atomic force microscope, and a dispersed, striped, and parallel to each other rubber phase was seen, the average size of the lateral axis of the rubber phase was 102 nm, and the average aspect ratio was 9.3.
  • the composite film was prepared according to the method of Example F1, except that in the preparation process of the propylene polymer composition B, the polypropylene impact copolymer z was replaced with a polypropylene impact copolymer with a trade mark of F780R (purchased from Shanghai Petrochemical Co., Ltd.).
  • the average particle size of the rubber phase is 2.0 ⁇ m
  • the maximum particle size is 3.0 ⁇ m
  • the ethylene unit content is 9.0 wt %
  • the ethylene-propylene copolymer content is 17.1 wt %
  • the melt mass flow rate is 7.3g/10min).
  • the film thickness was 50 ⁇ m.
  • the film thickness was 50 ⁇ m.
  • a composite film was prepared according to the method of Example F1, except that the propylene polymer composition B contained only component x.
  • the composite film was prepared according to the method of Example F1, except that the propylene polymer composition B only contained component x and component y, wherein the mass fraction Wx of component x was 85 parts by weight, and the mass of component y was 85 parts by weight.
  • the number of parts Wy is 15 parts by weight.
  • the composite film was prepared according to the method of Example F2, except that the propylene polymer composition B only contained component x and component z, wherein the mass fraction Wx of component x was 70 parts by weight, and the mass of component z was 70 parts by weight.
  • the number of parts Wz is 30 parts by weight.
  • the composite film with the microstructure according to the present invention prepared by using the propylene impact copolymer according to the present invention has both good impact resistance and optical properties, as well as good tensile properties. performance and good heat seal strength.
  • composite films not having the microstructures according to the present invention prepared using the propylene impact copolymers not according to the present invention have poor optical properties or impact properties, and at the same time poor tensile properties or heat seal strength;
  • the film surface is unstable, and it is difficult to obtain a film with a uniform thickness.
  • Example G1 (using maleic anhydride modified polypropylene)
  • Component a is a homopolymerized polypropylene with a grade of PPH-FA03 (purchased from Qingdao Refinery, with a melt mass flow rate of 3.1 g/10min, an isotacticity of 98%, and a molecular weight distribution of Mw/Mn of 4.7);
  • b is a propylene impact copolymer with a trade mark of EP200K (purchased from Zhongsha Petrochemical, with an ethylene content of 8% by weight and a melt mass flow rate of 3.2 g/10min);
  • component c is a polyolefin elastomer with a trade mark of 6102 ( Available from Exxon as an ethylene-propylene copolymer).
  • the above-mentioned components are weighed and mixed according to the proportions, wherein the parts by mass Wa of component a are 75 parts by weight, the parts by mass Wb of component b are 10 parts by weight, and the parts by mass of component c are 10 parts by weight Wc is 15 parts by weight.
  • lubricant the PEG lubricant produced by Clariant, Switzerland, FL7540L, the molecular weight is 10000, and the sum of the mass of the above-mentioned component a, component b and component c is 100 parts by weight, and the amount of lubricant added is 0.1 parts by weight
  • the mixture was added to a high-speed mixer to mix evenly, and then the mixed material was added to the feeder of the twin-screw extruder manufactured by W&P Company, and the material entered the twin-screw through the feeder for processing.
  • the temperature of the screw is maintained between 160-230 ° C, and the screw is melted and mixed evenly, extruded, pelletized and dried to obtain pellets of the propylene polymer composition A.
  • Component x is a propylene random copolymer with trade mark F5006 (purchased from Yanshan Petrochemical, is an ethylene-propylene-butene terpolymer, and the melt mass flow rate is 5.2g/10min); component y is a trade mark of 6102 The polyolefin elastomer (purchased from Exxon, which is an ethylene-propylene copolymer); component z is maleic anhydride modified polypropylene (purchased from Mitsui Co., Ltd.) with the brand name QF551A.
  • the above-mentioned components are weighed and mixed according to the proportions, wherein the mass fraction Wx of the component x is 70 weight parts, the mass fraction Wy of the component y is 15 weight parts, and the mass fraction of the component z is 15 weight parts. Wz is 15 parts by weight. Wc:Wy is 1:1.
  • the pellets of the propylene polymer composition A and the propylene polymer composition B obtained in the above steps (1) and (2) are dried, and then the propylene polymer composition A is added to the multi-layer extrusion casting machine.
  • the propylene polymer composition B is added to the upper surface layer extruder of the multi-layer extrusion casting machine, wherein the upper surface layer extruder is added with an inorganic anti-blocking agent (silicon dioxide, Ibid), the weight ratio of release agent to propylene polymer composition pellets was 0.2:100.
  • the temperature of the casting chill roll was set to 30° C., and the film was wound to form a composite film, which consisted of an upper surface layer (layer b) and a core layer (layer a).
  • the thickness of the composite film is 50 ⁇ m, and the thickness ratio of layer b and layer a is 1:2.
  • the composite film was observed under an atomic force microscope, and a rubber phase was seen, the average size of the rubber phase was 65 nm on the horizontal axis, and the average value of the aspect ratio was 10.9.
  • Example G2 (using polypropylene-g-glycidyl methacrylate)
  • the basic copolymerized polypropylene powder with the following characteristics was selected: ethylene content of comonomer 18.1 wt%, xylene soluble content 48.7 wt%, soluble comonomer content 31.9 wt%, soluble content/copolymerized polypropylene
  • the intrinsic viscosity ratio is 0.89
  • the weight average molecular weight is 34.3 ⁇ 10 4 g/mol
  • the MFR at 230°C under a load of 2.16kg is 1.21g/10min
  • Tm 143.4°C
  • the fine powder less than 40 meshes is removed by sieving.
  • Component a is a homopolymerized polypropylene with a grade of PPH-FA03 (purchased from Qingdao Refinery, with a melt mass flow rate of 3.1 g/10min, an isotacticity of 98%, and a molecular weight distribution of Mw/Mn of 4.7);
  • b is polypropylene-g-glycidyl methacrylate prepared as above;
  • component c is a polyolefin elastomer with a trade name of 6102 (purchased from Exxon, which is an ethylene-propylene copolymer).
  • the above-mentioned components are weighed and mixed according to the proportions, wherein the parts by mass Wa of component a are 75 parts by weight, the parts by mass Wb of component b are 10 parts by weight, and the parts by mass of component c are 10 parts by weight Wc is 15 parts by weight.
  • a lubricant is a PEG lubricant produced by Clariant, Switzerland, with a molecular weight of 10,000, and the sum of the mass of the above-mentioned component a, component b and component c is 100 parts by weight, and the amount of the lubricant is 100 parts by weight.
  • the addition amount is 0.1 parts by weight), then the mixture is added to the high-speed mixer and mixed evenly, and then the mixed material is added to the feeder of the twin-screw extruder manufactured by W&P Company, and the material enters the twin-screw extruder through the feeder.
  • the temperature of the screw is maintained between 160-230 ° C during the processing, and the screw is melted and mixed uniformly, extruded, pelletized and dried to obtain pellets of the propylene polymer composition A, and the melt quality is tested.
  • Flow rate MFR A 2.8 g/10 min.
  • Component x is a propylene random copolymer with trade mark F5006 (purchased from Yanshan Petrochemical, is an ethylene-propylene-butene terpolymer, and the melt mass flow rate is 5.2g/10min); component y is a trade mark of 6102 The polyolefin elastomer (purchased from Exxon, as ethylene-propylene copolymer).
  • the components prepared above are weighed and mixed according to the proportions, wherein the mass fraction Wx of the component x is 75 weight parts, and the mass fraction Wy of the component y is 25 weight parts. Wc:Wy is 3:5.
  • the pellets of the propylene polymer composition A and the propylene polymer composition B obtained in the above steps (1) and (2) are dried, and then the propylene polymer composition A is added to the multi-layer extrusion casting machine.
  • the propylene polymer composition B is added to the upper surface layer extruder of the multi-layer extrusion casting machine, wherein the upper surface layer extruder is added with an inorganic anti-blocking agent (silicon dioxide, Ibid), the weight ratio of release agent to propylene polymer composition pellets was 0.2:100.
  • the temperature of the casting chill roll was set to 30° C., and the film was wound to form a composite film, which consisted of an upper surface layer (layer b) and a core layer (layer a).
  • the film thickness was 50 ⁇ m, where the thickness ratio of layer b and layer a was 1:2.
  • Example G3 (using polypropylene-g-styrene)
  • the basic copolymerized polypropylene powder with the following characteristics was selected: ethylene content of comonomer 18.1 wt%, xylene soluble content 48.7 wt%, soluble comonomer content 31.9 wt%, soluble content/copolymerized polypropylene
  • the intrinsic viscosity ratio is 0.89
  • the weight average molecular weight is 34.3 ⁇ 10 4 g/mol
  • the MFR at 230°C under a load of 2.16kg is 1.21g/10min
  • Tm 143.4°C
  • the fine powder less than 40 meshes is removed by sieving.
  • Component a is a homopolymerized polypropylene with a grade of PPH-FA03 (purchased from Qingdao Refinery, the melt mass flow rate is 3.1 g/10min, the isotacticity is 98%, and the molecular weight distribution Mw/Mn is 4.7);
  • b is polypropylene-g-styrene prepared as above;
  • component c is polyolefin elastomer with trade name 6102 (purchased from Exxon, which is an ethylene-propylene copolymer).
  • the above-mentioned components are weighed and mixed according to the proportions, wherein the parts by mass Wa of component a are 75 parts by weight, the parts by mass Wb of component b are 10 parts by weight, and the parts by mass of component c are 10 parts by weight Wc is 15 parts by weight.
  • lubricant PEG lubricant produced by Swiss Clariant company, molecular weight is 10000, and the sum of the mass of above-mentioned component a, component b and component c is 100 parts by weight, the amount of lubricant added is 0.1 weight part
  • the mixture is added to the high-speed mixer and mixed evenly, and then the mixed material is added to the feeder of the twin-screw extruder manufactured by W&P Company, and the material enters the twin-screw through the feeder.
  • the temperature of the middle screw is kept between 160-230 ° C, and the screw is melted and mixed uniformly, extruded, pelletized and dried to obtain pellets of the propylene polymer composition A.
  • the melt mass flow rate MFR A 2.9g/10min.
  • Component x is a propylene random copolymer with trade mark F5006 (purchased from Yanshan Petrochemical, is an ethylene-propylene-butene terpolymer, and the melt mass flow rate is 5.2g/10min); component y is a trade mark of 6102 The polyolefin elastomer (purchased from Exxon, as ethylene-propylene copolymer).
  • the components prepared above are weighed and mixed according to the proportions, wherein the mass fraction Wx of the component x is 75 weight parts, and the mass fraction Wy of the component y is 25 weight parts. Wc:Wy is 3:5.
  • the pellets of the propylene polymer composition A and the propylene polymer composition B obtained in the above steps (1) and (2) are dried, and then the propylene polymer composition A is added to the multi-layer extrusion casting machine.
  • the propylene polymer composition B is added to the upper surface layer extruder of the multi-layer extrusion casting machine, wherein the upper surface layer extruder is added with an inorganic anti-blocking agent (silicon dioxide, Ibid), the weight ratio of release agent to propylene polymer composition pellets was 0.2:100.
  • the temperature of the casting chill roll was set to 30° C., and the film was wound to form a composite film, which consisted of an upper surface layer (layer b) and a core layer (layer a).
  • the film thickness was 50 ⁇ m, where the thickness ratio of layer b and layer a was 1:2.
  • Example G4 (using polypropylene-g-vinyltriethoxysilane)
  • the basic copolymerized polypropylene powder with the following characteristics was selected: ethylene content of comonomer 18.1 wt%, xylene soluble content 48.7 wt%, soluble comonomer content 31.9 wt%, soluble content/copolymerized polypropylene
  • the intrinsic viscosity ratio is 0.89
  • the weight average molecular weight is 34.3 ⁇ 10 4 g/mol
  • the MFR at 230°C under a load of 2.16kg is 1.21g/10min
  • Tm 143.4°C
  • the fine powder less than 40 meshes is removed by sieving.
  • Component a is a homopolymerized polypropylene with a grade of PPH-FA03 (purchased from Qingdao Refinery, with a melt mass flow rate of 3.1 g/10min, an isotacticity of 98%, and a molecular weight distribution of Mw/Mn of 4.7);
  • b is polypropylene-g-vinyltriethoxysilane prepared as above;
  • component c is polyolefin elastomer with trade name 6102 (purchased from Exxon, which is an ethylene-propylene copolymer).
  • the above-mentioned components are weighed and mixed according to the proportions, wherein the parts by mass Wa of component a are 75 parts by weight, the parts by mass Wb of component b are 10 parts by weight, and the parts by mass of component c are 10 parts by weight Wc is 15 parts by weight.
  • lubricant PEG lubricant produced by Swiss Clariant company, molecular weight is 10000, and the sum of the mass of above-mentioned component a, component b and component c is 100 parts by weight, the amount of lubricant added is 0.1 weight part parts
  • lubricant PEG lubricant produced by Swiss Clariant company, molecular weight is 10000, and the sum of the mass of above-mentioned component a, component b and component c is 100 parts by weight, the amount of lubricant added is 0.1 weight part parts
  • the temperature of the middle screw is kept between 160-230 ° C, and the screw is melted and mixed uniformly, extruded, pelletized and dried to obtain pellets of the propylene polymer composition A.
  • the melt mass flow rate MFR A 3.0g/10min.
  • Component x is a propylene random copolymer with trade mark F5006 (purchased from Yanshan Petrochemical, is an ethylene-propylene-butene terpolymer, and the melt mass flow rate is 5.2g/10min); component y is a trade mark of 6102 The polyolefin elastomer (purchased from Exxon, as ethylene-propylene copolymer).
  • the components prepared above are weighed and mixed according to the proportions, wherein the mass fraction Wx of the component x is 75 weight parts, and the mass fraction Wy of the component y is 25 weight parts. Wc:Wy is 3:5.
  • the pellets of the propylene polymer composition A and the propylene polymer composition B obtained in the above steps (1) and (2) are dried, and then the propylene polymer composition A is added to the multi-layer extrusion casting machine.
  • the propylene polymer composition B is added to the upper surface layer extruder of the multi-layer extrusion casting machine, wherein the upper surface layer extruder is added with an inorganic anti-blocking agent (silicon dioxide, Ibid), the weight ratio of release agent to propylene polymer composition pellets was 0.2:100.
  • the temperature of the casting chill roll was set to 30° C., and the film was wound to form a composite film, which consisted of an upper surface layer (layer b) and a core layer (layer a).
  • the film thickness was 50 ⁇ m, where the thickness ratio of layer b and layer a was 1:2.
  • the basic copolymerized polypropylene powder with the following characteristics was selected: ethylene content of comonomer 18.1 wt%, xylene soluble content 48.7 wt%, soluble comonomer content 31.9 wt%, soluble content/copolymerized polypropylene
  • the intrinsic viscosity ratio is 0.89
  • the weight average molecular weight is 34.3 ⁇ 10 4 g/mol
  • the MFR at 230°C under a load of 2.16kg is 1.21g/10min
  • Tm 143.4°C
  • the fine powder less than 40 meshes is removed by sieving.
  • Component a is a homopolymerized polypropylene with a grade of PPH-FA03 (purchased from Qingdao Refinery, with a melt mass flow rate of 3.1 g/10min, an isotacticity of 98%, and a molecular weight distribution of Mw/Mn of 4.7);
  • b is polypropylene-g-4-vinylpyridine prepared as above;
  • component c is a polyolefin elastomer with the brand name of 6102 (purchased from Exxon, which is an ethylene-propylene copolymer).
  • the above-mentioned components are weighed and mixed according to the proportions, wherein the parts by mass Wa of component a are 75 parts by weight, the parts by mass Wb of component b are 10 parts by weight, and the parts by mass of component c are 10 parts by weight Wc is 15 parts by weight.
  • lubricant PEG lubricant produced by Swiss Clariant company, molecular weight is 10000, and the sum of the mass of above-mentioned component a, component b and component c is 100 parts by weight, the amount of lubricant added is 0.1 weight part parts
  • lubricant PEG lubricant produced by Swiss Clariant company, molecular weight is 10000, and the sum of the mass of above-mentioned component a, component b and component c is 100 parts by weight, the amount of lubricant added is 0.1 weight part parts
  • the temperature of the middle screw is kept between 160-230 ° C, and the screw is melted and mixed uniformly, extruded, pelletized and dried to obtain pellets of the propylene polymer composition A.
  • the melt mass flow rate MFR A 3.1g/10min.
  • Component x is a propylene random copolymer with trade mark F5006 (purchased from Yanshan Petrochemical, is an ethylene-propylene-butene terpolymer, and the melt mass flow rate is 5.2g/10min); component y is a trade mark of 6102 The polyolefin elastomer (purchased from Exxon, as ethylene-propylene copolymer).
  • the components prepared above are weighed and mixed according to the proportions, wherein the mass fraction Wx of the component x is 75 weight parts, and the mass fraction Wy of the component y is 25 weight parts. Wc:Wy is 3:5.
  • the propylene polymer composition A and propylene polymer composition B pellets obtained in the above steps (1) and (2) are dried, and then the propylene polymer composition A is added to the core of the multi-layer extrusion casting machine
  • the propylene polymer composition B was added to the upper surface layer extruder of the multi-layer extrusion casting machine, wherein an inorganic antiblocking agent (silica, ibid.) was added to the upper surface layer extruder. ), the weight ratio of release agent to propylene polymer composition pellets was 0.2:100.
  • the temperature of the casting chill roll was set to 30° C., and the film was wound to form a composite film, which was composed of an upper surface layer (layer b) and a core layer (layer b).
  • the film thickness was 50 ⁇ m, where the thickness ratio of layer b and layer a was 1:2.
  • Example G6 (using polypropylene-g-styrene prepared in Example G3)
  • Component a is a homopolymerized polypropylene with a grade of PPH-FA03 (purchased from Qingdao Refinery, with a melt mass flow rate of 3.1 g/10min, an isotacticity of 98%, and a molecular weight distribution of Mw/Mn of 4.7);
  • b is a polyolefin elastomer with the grade of 6102 (purchased from Exxon, which is an ethylene-propylene copolymer).
  • the components prepared above are weighed and mixed according to the proportions, wherein the mass fraction Wa of the component a is 80 weight parts, and the mass fraction Wb of the component b is 20 weight parts.
  • the lubricant is a PEG lubricant produced by Clariant, Switzerland, with a molecular weight of 10,000, and the sum of the mass of the above-mentioned component a and component b is 100 parts by weight, and the added amount of the lubricant is 0.1 parts by weight
  • the mixture was added to a high-speed mixer to mix evenly, and then the mixed material was added to the feeder of the twin-screw extruder manufactured by W&P Company, and the material entered the twin-screw through the feeder for processing.
  • the temperature of the screw is maintained between 160-230 ° C, and the screw is melted and mixed evenly, extruded, pelletized and dried to obtain pellets of the propylene polymer composition A.
  • the propylene polymer composition A and propylene polymer composition B pellets obtained in the above steps (1) and (2) are dried, and then the propylene polymer composition A is added to the core of the multi-layer extrusion casting machine
  • the propylene polymer composition B was added to the upper surface layer extruder of the multi-layer extrusion casting machine, wherein an inorganic antiblocking agent (silica, ibid.) was added to the upper surface layer extruder. ), the weight ratio of release agent to propylene polymer composition pellets was 0.2:100.
  • the temperature of the casting chill roll was set to 30° C., and the film was wound to form a composite film, which consisted of an upper surface layer (layer b) and a core layer (layer a).
  • the film thickness was 50 ⁇ m, where the thickness ratio of layer b and layer a was 1:2.
  • Example G7 (using polypropylene-g-styrene/maleic anhydride)
  • Component a is a homopolypropylene with a trade name of PPH-FA03 (purchased from Qingdao Refinery, with a melt flow rate of 3.1 g/10min, an isotacticity of 98%, and a molecular weight distribution of Mw/Mn of 4.7); component b It is polypropylene-g-styrene/maleic anhydride prepared as above; component c is a polyolefin elastomer with the grade of 6102 (purchased from Exxon, which is an ethylene-propylene copolymer).
  • the above-mentioned components are weighed and mixed according to the proportions, wherein the parts by mass Wa of component a are 75 parts by weight, the parts by mass Wb of component b are 10 parts by weight, and the parts by mass of component c are 10 parts by weight Wc is 15 parts by weight.
  • lubricant PEG lubricant produced by Swiss Clariant company, molecular weight is 10000, and the sum of the mass of above-mentioned component a, component b and component c is 100 parts by weight, the amount of lubricant added is 0.1 weight part parts
  • lubricant PEG lubricant produced by Swiss Clariant company, molecular weight is 10000, and the sum of the mass of above-mentioned component a, component b and component c is 100 parts by weight, the amount of lubricant added is 0.1 weight part parts
  • the temperature of the middle screw is kept between 160-230 ° C, and the screw is melted and mixed uniformly, extruded, pelletized and dried to obtain pellets of the propylene polymer composition A.
  • the melt mass flow rate MFR A 2.9g/10min.
  • Component x is the random polypropylene with trade mark F5006 (purchased from Yanshan Petrochemical, which is ethylene-propylene-butene terpolymer, and the melt flow rate is 5.2g/10min); component y is the polypropylene with trade mark 6102. Olefin elastomer (available from Exxon as an ethylene-propylene copolymer).
  • the components prepared above are weighed and mixed according to the proportions, wherein the mass fraction Wx of the component x is 75 weight parts, and the mass fraction Wy of the component y is 25 weight parts. Wc:Wy is 3:5.
  • the pellets of the propylene polymer composition A and the propylene polymer composition B obtained in the above steps (1) and (2) are dried, and then the propylene polymer composition A is added to the multi-layer extrusion casting machine.
  • the propylene polymer composition B is added to the upper surface layer extruder of the multi-layer extrusion casting machine, wherein the upper surface layer extruder is added with an inorganic anti-blocking agent (silicon dioxide, The same below), the weight ratio of the release agent to the propylene polymer composition pellets was 0.2:100.
  • the temperature of the casting chill roll was set to 30° C., and the film was wound to form a composite film, which consisted of an upper surface layer (layer b) and a core layer (layer a).
  • the film thickness was 50 ⁇ m, where the thickness ratio of layer b and layer a was 1:2.

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Abstract

本发明公开了一种基于丙烯聚合物的复合薄膜及其制备方法和应用。所述复合薄膜至少包括两个不同的层：层a和层b；其中层a和层b各自包含至少一种丙烯聚合物；并且层a和层b中的至少一个层包含丙烯抗冲共聚物；其中所述丙烯抗冲共聚物包含弹性部分，该弹性部分在复合薄膜中形成分散的呈条状的橡胶相，所述橡胶相彼此平行排列，并且所述橡胶相的橫轴的平均尺寸为20-200nm和纵横比的平均值为5-20。该复合薄膜同时具有优异的抗冲性能和光学性能，甚至具有很好的拉伸性能和/或可在较低的热封温度下具有很好的热封强度，甚至还具有良好的均匀性。该复合薄膜尤其可用于包装材料领域，尤其是电池包装材料、电子产品包装材料或食品包装材料中。

Description

基于丙烯聚合物的复合薄膜及其制备方法和应用 技术领域
本发明涉及聚合物薄膜领域，具体涉及基于丙烯聚合物的复合薄膜及其制备方法和应用，以及包含所述复合薄膜的包装材料。
背景技术
聚丙烯薄膜通常可由流延和双向拉伸等方法制得，但均聚聚丙烯原料制备的聚丙烯薄膜通常冲击强度较低。而聚丙烯薄膜常用于包装用途，需要薄膜有较高的冲击性能，同时为了内容物可视化和美观性，还希望薄膜具有很好的光学性能。
为了提高聚丙烯薄膜的冲击性能，可以使用抗冲聚丙烯制备薄膜，或向聚丙烯中加入聚烯烃弹性体，但以上方法制备的薄膜通常具有较高的雾度，透明性等光学性能较差。也可以同时向薄膜中添加成核剂，通过细化薄膜中的晶体来降低薄膜的雾度，但这种方法会导致冲击性能的下降。
为了提高薄膜的抗冲性能和韧性，还可通过多层共挤的方法制备薄膜，如CN101913279A就采用了三层共挤的方法制备复合薄膜，薄膜中的层含有按1:10-1:3比例共混的弹性体和PP，由弹性体提供较好的抗冲击性能。但是，这种方法在弹性体含量较高的情况下存在难以分散均匀的问题，而且弹性体通常流动性能较差，会导致膜面不均，沿机器方向(MD)和横向方向(TD)厚度差较大的问题，很难得到光学性能较好的薄膜；而且，对于弹性体添加量会有一定的限制，因为当添加量高至一定水平会发生分相的问题，从而限制了抗冲击性能的进一步提高。另外，在多层共挤的过程中，弹性体还会导致芯表层流动性能差距较大，进一步加重膜面不均的问题，并且可能导致薄膜各处性能的不均匀；各层间原料流变性能的不同也会影响薄膜的均匀度，并会影响到薄膜的光学和力学性能。
现有的基于丙烯聚合物的薄膜很难同时具备较好的光学性能和抗冲性能；另外，当丙烯聚合物薄膜用于包装应用时，通常希望其在较低的热封温度下就具有较好的热封性能，现有技术中的丙烯聚合物薄膜不能满足这样的性能要求。另外，现有复合薄膜的厚度和性能方面的均匀性也较差。
发明内容
发明概述
鉴于如上所述的现有技术，本发明的目的是，提供一种基于丙烯聚合物的低雾度高抗冲薄膜及其制备方法。这样的薄膜可同时具有很好的抗冲性能和光学性能。
本发明的另一目的是提供一种上述薄膜，其可另外具有很好的力学性能(例如拉伸性能)和/或在较低的热封温度下具有很好的热封强度。
本发明的另一目的是提供一种基于丙烯聚合物的透明抗冲复合薄膜，其同时具有良好的抗冲性能和光学性能并具有良好的薄膜厚度和性能的均匀性。
本发明的另一目的是提供所述复合薄膜的制备方法，该方法的制备过程稳定并且所得的薄膜的均匀性好。
根据本发明发现，通过在复合薄膜的至少一个层中使用包含特定弹性部分的丙烯抗冲共聚物作为原料，通过挤出流延，制备得到包含具有均匀分散的条状橡胶相的特定微结构的复合薄膜，从而实现了所述目的。
因此，本发明的第一方面提供一种基于丙烯聚合物的复合薄膜，至少包括两个不同的层：层a和层b；
其中层a和层b各自包含至少一种丙烯聚合物；并且
层a和层b中的至少一个层包含丙烯抗冲共聚物；
其中所述丙烯抗冲共聚物包含弹性部分，该弹性部分在复合薄膜中形成分散的呈条状的橡胶相。
本发明的第二方面提供本发明的复合薄膜的制备方法，包括将用于形成各层的原料组合物挤出流延而形成所述复合薄膜。
本发明的第三方面提供本发明的复合薄膜在包装材料领域中的应用。
本发明的第四方面提供包含本发明的复合薄膜的包装材料。
本发明的其它方面和有益效果将从随后结合附图对发明的详述和具体实施方式部分中可以清楚看出。
附图说明
通过结合附图对本发明示例性实施方式进行更详细的描述。
图1a和图1b为本发明薄膜取样点选择的示意图。
图2为根据本发明的实施例A1中使用的原料丙烯抗冲共聚物样条断面的扫描电子显微镜(SEM)照片。
图3为根据本发明的实施例A1的薄膜切面的原子力显微镜照片。
图4为根据本发明的对比例A3的薄膜切面的原子力显微镜照片。
图5为根据本发明的实施例C1的薄膜切面的原子力显微镜照片。
图6a为根据本发明的实施例E1中使用的原料丙烯抗冲共聚物样条断面的SEM照片。
图6b是根据本发明的对比例E1中使用的原料丙烯抗冲共聚物样条断面的SEM照片。
图7为根据本发明的实施例E1的薄膜切面的原子力显微镜照片。
发明详述
本发明的第一方面提供一种基于丙烯聚合物的复合薄膜，至少包括两个不同的层：层a和层b；
其中层a和层b各自包含至少一种丙烯聚合物；并且
层a和层b中的至少一个层包含丙烯抗冲共聚物；
其中所述丙烯抗冲共聚物包含弹性部分，该弹性部分在复合薄膜中形成分散的呈条状的橡胶相。
本文中所述“分散”是指橡胶相在复合薄膜中不是连续分布的。通过原子力显微镜(AFM)观察复合薄膜沿横向(TD)切割的断面可以看到橡胶相，如图3、5和7中黑色部分所示，其中的橡胶相为多个条状的形式均匀分散在薄膜基体中。
本文中，所述“条状”是指纵横比通常大于2的形状。
本文中，纵横比是指物体的纵轴与横轴的比值。所述纵轴是指物体(在此是指橡胶相)的最长尺寸，即物体的轮廓上相距最远的两个点之间的距离。橫轴是指与纵轴垂直的直线中与物体轮廓相交的交点之间距离最长的直线在交点之间的长度。
在本发明复合薄膜中，所述橡胶相的橫轴的平均尺寸可以为20-200nm，更优选20-150nm。所述橡胶相的纵横比的平均值可以为5-20，优选5-15。
所述横轴尺寸和纵横比通过原子力显微镜，观察复合薄膜沿横向(TD)切割的横截面测得。基于200个样品点，计算橡胶相的横轴尺寸的平均值作为橡胶相的横轴的平均尺寸，和计算橡胶相的纵横比的平均值作为橡胶相的纵横比的平均值。
纵向(MD)是指机械加工方向。橫向(TD)是指与机械加工方向垂直的方向。
在本发明的复合薄膜中，所述橡胶相有利地彼此平行排列。
本文中，术语“平行排列”是指橡胶相的横向截面沿着某一方向彼此平行排列。这里排除由于制备工艺导致的与整个复合薄膜中橡胶相粒子的总体排列方向不一致的少量的位于局部区域的沿不同方向排列的橡胶相粒子，以及由于制备工艺或AFM方法导致的不能 清晰观察到的橡胶相粒子。
本文中，“平行排列”包括基本平行的情况。橡胶相的横向截面彼此之间的夹角不大于约10度，优选小于约5度。
本发明中的层a和层b都包含至少一种丙烯聚合物，都由基于丙烯聚合物的组合物构成，但是它们的具体组成和/或厚度不同。整个复合薄膜是基于丙烯聚合物的复合薄膜，也可以称为聚丙烯复合薄膜。
本发明中，层a意于用作复合薄膜的芯层，即在复合薄膜的使用中相对远离复合薄膜要接触的介质的层。层b意于用作复合薄膜的表层，即在复合薄膜的使用中靠近复合薄膜所要接触的介质的层，所述介质例如电池包装材料接触的电解液。
根据本发明，层a和层b中至少一个层包含所述具有特定弹性部分的丙烯抗冲共聚物，从而使得整个复合薄膜中包含特定分散的橡胶相。
所述弹性部分可在丙烯抗冲共聚物的冲击样条的扫描电子显微镜照片中显现为球状或近球状橡胶相。
所述丙烯抗冲共聚物优选是含有乙烯单元的丙烯抗冲共聚物，其中所述弹性部分是含有乙烯单元的共聚部分，优选选自乙烯-丙烯共聚部分和乙烯-丁烯共聚部分。
优选地，所述丙烯抗冲共聚物包含丙烯均聚部分与所述含有乙烯单元的共聚部分。所述丙烯均聚部分可以包含等规聚合结构。
所述丙烯抗冲共聚物中的含有乙烯单元的共聚部分含量优选为3-15重量％，更优选7-12重量％，通过 13C NMR测定。
以所述丙烯抗冲共聚物的总重量计，所述丙烯抗冲共聚物的乙烯单元含量优选为1-14重量％，优选3-12重量％。在所述丙烯抗冲共聚物的室温二甲苯可溶物中，乙烯单元含量优选不超过40重量％。乙烯单元组[EEE]含量优选不超过20重量％，通过 13C NMR测定。
所述丙烯抗冲共聚物可以具有嵌段结构或包含丙烯嵌段共聚物。
所述丙烯抗冲共聚物在230℃、2.16kg载荷下的熔体质量流动速率(MFR)可以为1-10g/10min，优选1-8g/10min，按照标准GB/T 3682-2000测定，测试温度为230℃，载荷为2.16kg。
可用的丙烯抗冲共聚物可商购获得，如中沙石化牌号为EP200K的丙烯抗冲共聚物、上海石化牌号为F200R、M180R的丙烯抗冲共聚物、茂名石化牌号为PPB-M02D的丙烯抗冲共聚物、韩国晓星牌号为J410F的丙烯抗冲共聚物。
所述丙烯抗冲共聚物也可通过在具有高立构选择性的齐格勒-纳塔催化剂存在下的连 续聚合法制得。所述连续聚合法是指制备过程包括至少两个顺序进行的步骤，其中，弹性部分和非弹性部分各自在单独的步骤中制备，而且，除第一步以外，后一步骤在前一步骤已形成的聚合物和在前一步骤中使用的催化剂的存在下进行。
层a可包含均聚聚丙烯和/或丙烯无规共聚物。
所述均聚聚丙烯在230℃、2.16kg载荷下的熔体质量流动速率优选为2-15g/10min，按照标准GB/T 3682-2000测定，测试温度为230℃，载荷为2.16kg。所述均聚聚丙烯的等规度优选大于97％，通过 13C NMR测定。该均聚聚丙烯的分子量分布Mw/Mn优选为4.5-7.0，通过凝胶渗透色谱法(GPC)测定。可用的均聚聚丙烯可商购获得，例如青岛炼化牌号为PPH-FA03的均聚聚丙烯、中原石化牌号为PPH-FA03的均聚聚丙烯、上海石化牌号为FC801的均聚聚丙烯；或者可通过本领域常规的方法制备。
所述丙烯无规共聚物可以为丙烯与乙烯和/或丁烯的共聚物，例如乙烯-丙烯-丁烯三元无规共聚物、丙烯-乙烯二元无规共聚物、丙烯-丁烯二元无规共聚物。所述丙烯无规共聚物在230℃、2.16kg载荷下的熔体质量流动速率可以为2-15g/10min，优选2-10g/10min，按照标准GB/T 3682-2000测定。所述无规共聚物的分子量分布Mw/Mn优选为4.5-7.0，通过GPC测定。可用的丙烯无规聚合物可商购获得，例如，燕山石化牌号为F5006的无规丙烯共聚物、上海石化牌号为F500EPS、F800EDF或F800EPS的无规丙烯共聚物；或者可以通过本领域常规的方法制备。
层b可包含丙烯无规共聚物。所述丙烯无规共聚物如上文所描述。层b与层a中的丙烯无规共聚物可以相同或不同。例如，层b可包含60-100重量％的丙烯无规共聚物。
在优选的实施方式中，层a和层b中的至少一个层可包含聚烯烃弹性体，从而有利地进一步提高复合薄膜的抗冲击性能。
所述聚烯烃弹性体可以为乙烯与α烯烃的弹性体共聚物。所述α烯烃优选为C 3-C 12的α烯烃，更优选选自丙烯、1-丁烯、1-己烯和1-辛烯中的至少一种。可用的聚烯烃弹性体可商购获得，例如，陶氏公司牌号为8200的聚烯烃弹性体、陶氏公司牌号为8411的聚烯烃弹性体、三井公司牌号为DF640或DF840的聚烯烃弹性体、埃克森公司牌号为6102、VM3980或EXACT3139的聚烯烃弹性体；或者可以通过本领域常规的方法制备。
当复合薄膜中使用聚烯烃弹性体时，所述丙烯抗冲共聚物中的弹性部分和所述聚烯烃弹性体在复合薄膜中形成分散的橡胶相，该橡胶相也呈现条状形式并且彼此平行排列。这样的橡胶相的橫轴的平均尺寸也可以为20-200nm，优选20-150nm。该橡胶相的纵横比的平均值可以为5-20，优选5-15。所述尺寸如上所述通过AFM测定。
聚烯烃弹性体的存在可有利地弥补丙烯抗冲共聚物中的橡胶相可能存在的不均匀分布的问题，从而提高薄膜各处冲击性能的均匀性。
在优选的实施方式中，所述聚烯烃弹性体具有在230℃、剪切速率160r -1和640r -1下的剪切黏度之比η 160/η 640为1.2-3，优选为1.7-2.3。所述聚烯烃弹性体在230℃、剪切速率640r -1下的剪切黏度η 640优选为100-500Pa·s，更优选为140-400Pa·s。剪切黏度η 160和η 640根据ISO11443:2014，采用毛细管流变仪测定。
构成层a的材料(丙烯聚合物组合物)在230℃下、2.16kg载荷作用下的熔体质量流动速率可以为2-10g/10min，优选为2-8g/10min，更优选为3-7g/10min，按照标准GB/T3682-2000测定，测试温度为230℃，载荷为2.16kg。
构成层b的材料(丙烯聚合物组合物)在230℃下、2.16kg载荷作用下的熔体质量流动速率可以为2-10g/10min，优选为3-10g/10min，更优选3-9g/10min，更优选为4-8g/10min，按照标准GB/T 3682-2000测定，测试温度为230℃，载荷为2.16kg。
这样的熔体质量流动速率可以有利地使得薄膜制备过程更加平稳，从而使得薄膜具有更好的均匀性、力学性能和光学性能。
层a和层b可以都包含所述丙烯抗冲共聚物，其中层a和层b中的丙烯抗冲共聚物可以是相同或不同的。也可能的是，层a和层b中的仅一个层含有所述丙烯抗冲共聚物。
层a和层b也可以都包含所述聚烯烃弹性体，其中层a和层b中的聚烯烃弹性体可以是相同或不同的。优选地，层a中所述聚烯烃弹性体的重量比例与层b中所述聚烯烃弹性体的重量比例之间的比值为6:1-1:6。也可能的是，层a和层b中的仅一个层含有所述聚烯烃弹性体。
层a和层b也可以都包含所述丙烯抗冲共聚物和所述聚烯烃弹性体，其中层a和层b中的丙烯抗冲共聚物可以是相同或不同的，而层a和层b中的聚烯烃弹性体也可以是相同或不同的。
也可能的是，层a和层b中的仅一个层含有所述丙烯抗冲共聚物，层a和层b中的一个或两个层含有所述聚烯烃弹性体；或者，层a和层b中的仅一个层含有所述聚烯烃弹性体，层a和层b中的一个或两个层含有所述丙烯抗冲共聚物。
在一种实施方式中，层a包含所述均聚聚丙烯、所述丙烯抗冲共聚物和所述聚烯烃弹性体，并且层b包含所述无规丙烯共聚物和所述聚烯烃弹性体。
在这种实施方式中，优选地，层a中所述聚烯烃弹性体的重量比例与层b中所述聚烯烃弹性体的重量比例之间的比值为2:1-1:4，例如可以是1.5：1、1：1、1：1.5、1：2、1： 2.5、1：3、1：3.5以及它们之间的任意值，更优选为1:1-1:2。在进行双层或多层薄膜共挤时，上述层a中所述聚烯烃弹性体的重量比例与层b中所述聚烯烃弹性体的重量比例的比值可以进一步提高复合薄膜的抗冲击性能和光学性能，同时可以使得挤出过程更加平稳。
具体地，在这种实施方式中，层a可包含40-90重量％，优选50-90重量％，更优选55-75重量％的所述均聚聚丙烯，5-40重量％，优选10-30重量％的所述丙烯抗冲共聚物和2-30重量％，优选5-20重量％的所述聚烯烃弹性体，各自基于层a的总重量计。层b可包含40-95重量％，优选60-95重量％，更优选75-90重量％的所述无规丙烯共聚物，和5-60重量％，优选5-40重量％，更优选10-25重量％的所述聚烯烃弹性体，各自基于层b的总重量计。
包含这样的表层和芯层的复合薄膜可以有利地不仅具有优异的光学性能，还具有提高的热封强度。
在这样的实施方式中，当层a和层b中所述聚烯烃弹性体均满足以下条件时可大大提高薄膜的厚度均匀性和性能均匀性：在230℃、剪切速率160r -1和640r -1下的剪切黏度之比η 160/η 640为1.2-3，优选为1.7-2.3，且在230℃、剪切速率640r -1下的剪切黏度η 640为100-500Pa·s，优选为140-400Pa·s。
此外，优选地，控制用于构成层a的丙烯聚合物组合物和构成层b的丙烯聚合物组合物在230℃、剪切速率160r -1下的剪切黏度的差值(ηA 160-ηB 160)与在230℃、剪切速率640r -1下的剪切黏度的差值(ηA 640-ηB 640)均≥0，且二者的比值(ηA 160-ηB 160)/(ηA 640-ηB 640)为1-2.6，优选1.4-2.5，更优选为1.5-2.2，由此可通过调整各层原料流动性配合度，进一步提高薄膜厚度和性能的均匀性。
在另一种实施方式中，层a包含丙烯聚合物和所述聚烯烃弹性体，并且层b包含所述无规丙烯共聚物、所述聚烯烃弹性体和所述丙烯抗冲共聚物。层a中所述丙烯聚合物可选自均聚聚丙烯和/或所述丙烯抗冲共聚物。例如，层a可包含70-100重量％的丙烯聚合物。
在这种实施方式中，优选地，层a中所述聚烯烃弹性体的重量比例与层b中所述聚烯烃弹性体的重量比例之间的比值为10:1-1:6，优选6:1-1:4，更优选为4:1-1:4，例如可以是3.5:1、3:1、2.5:1、2:1、1.5:1、1:1、1:1.5、1:2、1:2.5、1:3、1:3.5以及它们之间的任意值。在进行双层或多层薄膜共挤时，上述层a中所述聚烯烃弹性体的重量比例与层b中所述聚烯烃弹性体的重量比例的比值可以进一步提高复合薄膜的抗冲击性能和光学性能，同时可以使得挤出过程更加平稳。
具体地，在这种实施方式中，层a可包含50-95重量％，优选70-95重量％，更优选80-95重量％的所述丙烯聚合物和5-50重量％，优选5-30重量％，更优选5-20重量％的所述聚烯烃弹性体，各自基于层a的总重量计；层b可包含40-90重量％，优选50-90重量％，更优选60-85重量％的所述无规丙烯共聚物，5-40重量％，优选5-30重量％，更优选5-20重量％的所述聚烯烃弹性体和2-30重量％，优选5-20重量％的所述丙烯抗冲共聚物，各自基于层b的总重量计。
包含这样的表层和芯层的复合薄膜不仅可具有提高的抗冲击性能和提高的光学性能和力学性能，同时还由于表层(热封层)中包含特定橡胶相的丙烯抗冲共聚物与其他组分之间的协同作用而可以在降低热封温度的同时，还能有效提高热封强度。
在另一种实施方式中，层a包含所述聚烯烃弹性体、所述丙烯抗冲共聚物和其他类型的丙烯聚合物，所述其他类型的丙烯聚合物可选自所述均聚聚丙烯和/或丙烯无规共聚物；并且层b包含所述无规丙烯共聚物和所述聚烯烃弹性体。
具体地，在这种实施方式中，层a可包含40-90重量％的丙烯抗冲共聚物、5-40重量％的其他类型的丙烯聚合物和2-30重量％的聚烯烃弹性体，优选55-75重量％的丙烯抗冲共聚物、10-30重量％的其他类型的丙烯聚合物和5-20重量％的聚烯烃弹性体，各自基于层a的总重量计；层b可包含40-95重量％的丙烯无规共聚物和5-60重量％的聚烯烃弹性体，优选75-90重量％的丙烯无规共聚物和10-25重量％的聚烯烃弹性体，各自基于层b的总重量计。
这种复合薄膜可同时具有很好的抗冲性能、光学性能和拉伸性能，而且可在较低的热封温度下具有很好的热封强度。
本文中，每个层各自所有组分的重量％之和为100重量％。
添加剂
层a和/或层b还可包含聚合物薄膜中常规使用的添加剂，例如抗氧剂、润滑剂、抗卤素剂、光稳定剂、热稳定剂、着色剂、填料、爽滑剂、表面粘接剂、电磁屏蔽助剂、阻燃剂、绝缘添加剂、防粘剂和抗静电剂等中的至少一种。
例如，可以使用抗氧剂来提高所述复合薄膜在加工时的抗氧化性。所述抗氧剂可以为本领域常用的各种抗氧剂，例如抗氧剂1076、抗氧剂1010、抗氧剂168和硫酯类抗氧剂(如DLTP、DSTP)等中的至少一种。以所在层的总重量为100重量份计，所述抗氧剂的含量可以为0.1-0.8重量份，优选为0.2-0.4重量份。
为了改善或赋予复合薄膜其他性能(如摩擦、稳定性、颜色、抗静电性、强度、导电性、绝缘性、爽滑、滑动性能、表面粘接性、电磁屏蔽性能、阻燃性能、抗粘连效果等)，所述复合薄膜还可含有本领域常规使用的其他薄膜助剂，例如选自润滑剂、抗卤素剂、光稳定剂、热稳定剂、着色剂、填料、爽滑剂、表面粘接剂、电磁屏蔽助剂、阻燃剂、绝缘添加剂、防粘剂和抗静电剂中的至少一种。这些薄膜助剂可以常规用量使用，例如以所在层的总重量为100重量份计，所述其他薄膜助剂各自的含量可以为0.01-0.5重量份，优选为0.05-0.3重量份，更优选为0.05-0.15重量份，除非另外明确指明。
例如，可以在复合薄膜中添加润滑剂。所述润滑剂可以为PEG类润滑剂和/或单甘酯类润滑剂。以所在层的总重量为100重量份计，润滑剂的含量可以为0.01-0.5重量份，优选为0.05-0.2重量份。
本发明的复合薄膜中可以添加极性单体改性聚丙烯作为表面粘接剂，由此增强复合薄膜与其他材料界面的粘结，得到一种高粘合性高抗冲丙烯聚合物复合薄膜。所述极性单体改性聚丙烯尤其添加在层b中。
在一种优选的实施方式中，以层a的总重量为基准，层a可包含40-90重量％，优选50-85重量％的均聚聚丙烯，5-45重量％，优选10-30重量％的丙烯抗冲共聚物和2-40重量％，优选5-20重量％的聚烯烃弹性体；并且以层b的总重量为基准，层b包含40-99重量％，优选70-90重量％的丙烯无规共聚物，0-30重量％，优选5-15重量％的聚烯烃弹性体和1-30重量％，优选5-15重量％的极性单体改性聚丙烯。
在另一种优选的实施方式中，以层a的总重量为基准，层a可包含50-100重量％，优选75-95重量％的聚丙烯和0-50重量％，优选5-25重量％的聚烯烃弹性体；并且以层b的总重量为基准，层b可包含30-90重量％，优选60-85重量％的丙烯无规共聚物，5-40重量％，优选5-20重量％的聚烯烃弹性体，2.5-20重量％，优选5-10重量％的丙烯抗冲共聚物和2.5-20重量％，优选5-10重量％的极性单体改性聚丙烯。
所述极性单体改性聚丙烯中的极性单体可选自含羟基共聚单体、含氰基共聚单体和酸酐单体中的至少一种。所述含羟基共聚单体优选为羟基酸和/或乙烯醇。所述含氰基共聚单体优选为氰基丙烯酸酯。所述酸酐单体优选为马来酸酐和/或衣康酸酐，更优选为马来酸酐。马来酸酐接枝聚丙烯(PP-g-MAH)兼具极性基团和烯烃非极性链段，其具有原聚丙烯的基本物理性能，如高结晶性、高强度、高抗冲等特性，而且与其他材料的附着力提高。
所述极性单体改性聚丙烯可商购获得，例如，三井公司牌号为QF551A的马来酸酐改性聚丙烯、佳易容公司牌号为CMG9801的马来酸酐改性聚丙烯、埃克森公司牌号为 PO1015的马来酸酐改性聚丙烯。
还可以在本发明复合薄膜中添加导电填料，从而提高复合薄膜的抗静电性。所述导电填料优选添加在层b中。以层b中基体聚合物的总重量为100重量份计，导电填料的添加量可以为0.1-10重量份，优选为0.5-4.5重量份。
所述导电填料例如可以为炭黑类、石墨类、碳纳米管类、碳纤维类、导电金属粒子、导电金属纤维和金属氧化物中的至少一种。所述炭黑类导电填料包括但不限于乙炔炭黑、超导炭黑、特导炭黑中的至少一种。所述石墨类导电填料包括但不限于天然石墨、可膨胀石墨、膨胀石墨和石墨烯中的至少一种。所述碳纳米管类导电填料包括但不限于未经表面改性的或者经表面改性的单壁碳纳米管和/或多壁碳纳米管。所述导电金属粒子和导电金属纤维中的导电金属可各自独立地为银、铝、铜、铁、镍和不锈钢中的至少一种。所述包覆有导电金属的填料可选自镀铅、镀镍、镀银的玻璃球、玻璃纤维和云母片中的至少一种。所述金属氧化物包括但不限于氧化钛、氧化锌、氧化锡、氧化铟和氧化镉中的至少一种。可通过添加导电填料制备抗静电丙烯聚合物薄膜，其表面电阻率可以为10 2-10 8Ω，优选为10 2-10 4Ω，通过Keithley 6517B Electrometer进行测试。所述薄膜的抗静电性持久且受环境湿度影响小。
另外，可以在复合薄膜中添加电磁屏蔽助剂，从而制备电磁屏蔽薄膜。所述电磁屏蔽助剂优选添加在层b中。所述电磁屏蔽助剂可以为导电金属填料和/或碳材料。所述导电金属填料优选为导电金属粒子和/或导电金属纤维。所述导电金属粒子和导电金属纤维中的金属可各自独立地选自银、铝、铜、铁、镍和不锈钢中的一种或多种。所述碳材料优选为炭黑、石墨、石墨烯和碳纳米管中的一种或多种。所述电磁屏蔽助剂的添加量可以为5-30重量份，优选15-25重量份，以层b中基体聚合物的重量为100重量份计。所得复合薄膜的电磁屏蔽效能可以达到≥25dB，优选≥28dB，按照SJ20524标准，用法兰同轴测试设备测试，电磁波波段为50MHz至1GHz频率范围。
所述电磁屏蔽助剂还可以与偶联剂组合使用。所述偶联剂能够改善丙烯聚合物组合物的基体聚合物组分(树脂组分)和电磁屏蔽助剂之间的相容性，其种类、用法和用量均可以为本领域的常规选择，例如，所述偶联剂可以选自钛酸酯类偶联剂，所述钛酸酯类偶联剂可以选自单烷氧基型钛酸酯、单烷基焦磷酸酯型钛酸酯、配位型钛酸酯和螯合型钛酸酯中的一种或多种；优选地，所述钛酸酯类偶联剂选自钛酸四丁酯和/或钛酸四异丙酯。以所述基体聚合物组分的总重量为100重量份计，所述偶联剂的含量可以为1-6重量份，优选为4-6重量份。
还可以在复合薄膜中添加阻燃剂来提高阻燃性能。例如，可以在层a和/或b中添加，也可以在另外的层c中添加，此时层c为阻燃功能层。例如，以层c的总重量计，所述层c可包含30-80重量％，优选40-70重量％的丙烯聚合物和20-70重量％，优选30-60重量％的阻燃剂。由此可以实现氧指数≥21％，优选氧指数≥23％，按照GB/T 2406-2008规定的方法测定。
所述阻燃剂可选自金属或非金属的氢氧化物和/或氧化物的水合物、磷系阻燃剂、硼系阻燃剂、锑系阻燃剂和膨胀型阻燃剂中的至少一种。所述金属或非金属的氢氧化物和/或氧化物的水合物可以为铝、镁、硼、锌的氢氧化物以及层状双金属氢氧化物的至少一种；所述磷系阻燃剂可以为红磷、磷酸盐、聚磷酸盐和磷酸酯中的至少一种；所述硼系阻燃剂可以为硼酸和/或硼酸盐，所述硼酸盐优选为硼酸铵和/或硼酸锌；所述锑系阻燃剂可以为三氧化二锑、五氧化二锑和锑酸钠的至少一种；所述膨胀型阻燃剂为硫酸、季戊四醇或其二聚物或三聚物、丁四醇、环己六醇、山梨醇、葡萄糖、麦芽糖、淀粉、间苯二酚、聚磷酸铵、双氰胺、三聚氰胺、尿素、密胺、甘氨酸、可膨胀石墨和碳纳米管中的至少两种。在一种实施方式中，所述阻燃剂为膨胀型阻燃剂，优选为聚磷酸铵和季戊四醇的混合物，具体地，聚磷酸铵和季戊四醇的重量比为0.5-5:1。在另一种实施方式中，所述阻燃剂为氢氧化镁和氢氧化铝的混合物，具体地，氢氧化镁和氢氧化铝的重量比为0.5-2:1。通过添加阻燃剂制备的阻燃聚丙烯薄膜具有易加工、性能好等优点。
为了赋予复合薄膜有色彩的外观，可以在复合薄膜中添加着色剂。所述着色剂可以为本领域的常规选择，包括但不限于偶氮颜料、酞菁颜料、杂环颜料、色淀颜料、染料、荧光增白剂和荧光颜料中的至少一种。上述着色剂均可商购获得。所述着色剂优选添加在层a中。以层a中基体聚合物的重量为100重量份计，所述着色剂的含量可以为0.1-1重量份，优选0.3-0.8重量份。层a还可包括分散剂。所述分散剂能够改善所述层a的基体聚合物组分和着色剂之间的加工性和均匀性，其种类、用法和用量均可以为本领域的常规选择，例如，所述分散剂可以为低分子量聚乙烯蜡，所述分散剂的重量含量可以为所述着色剂的20-30重量％。
本发明的复合薄膜中还可以添加爽滑剂。所述爽滑剂可以为酰胺类爽滑剂，优选为芥酸酰胺、油酸酰胺、硬脂酸酰胺、山嵛酸酰胺、硬脂基芥酸酰胺和乙撑双硬脂酰胺中的至少一种。另选地，所述爽滑剂可以为酰胺类爽滑剂和耐迁移型爽滑剂的混合物，其中，所述酰胺类爽滑剂优选为芥酸酰胺、油酸酰胺、硬脂酸酰胺、山嵛酸酰胺、硬脂基芥酸酰胺和乙撑双硬脂酰胺中的至少一种。所述耐迁移型爽滑剂优选为聚四氟乙烯微粒、聚酰亚胺 微粒、聚酰胺微粒、聚碳酸酯微粒、有机硅、纳米碳酸钙、云母和纳米二氧化硅中的至少一种。优选地，所述酰胺类爽滑剂和所述耐迁移型爽滑剂的重量比为1:20-1:1，优选为1:10-1:2。所述爽滑剂中包含的耐迁移型爽滑剂的粒径范围可以为0.1-5μm，优选为0.3-2μm。
所述爽滑剂可以添加在层a和/或层b中，其添加量可以为基于所在层总重量计的0.01-1.5重量％，优选0.08-0.6重量％。
优选地，在层a和层b中都添加爽滑剂。
优选地，所述层b中爽滑剂中的酰胺类爽滑剂的分子量不小于层a中爽滑剂中的酰胺类爽滑剂的分子量。
特别优选，层a中添加酰胺类爽滑剂，而层b中添加酰胺类爽滑剂和耐迁移型爽滑剂的混合物。
通过向表层中添加复合爽滑剂的方法，提高了薄膜的初始爽滑性能，复合爽滑剂中的耐迁移型爽滑剂部分能够提供一部分的爽滑性能，且不需析出过程，通过调控粒径范围，可保证薄膜的热封性能和光学性能不会发生变化；另外，表层中的酰胺类爽滑剂也可以提供一定的爽滑性能，进一步降低薄膜的摩擦系数，提高薄膜的初始爽滑性能。另一方面，通过复合爽滑剂的使用和芯表层爽滑剂的配合提供较好的高温爽滑性和热封性能保持性。
所得复合薄膜可以具有＜0.3，优选≤0.23的表面摩擦系数；在60℃下加热24小时后，薄膜表面摩擦系数变化≤0.02，优选薄膜表面摩擦系数变化≤0.01。
另外，可以在本发明复合薄膜中添加绝缘添加剂，从而可以提高丙烯聚合物复合薄膜的电绝缘性能。优选可以使用丙烯接枝聚合物作为绝缘添加剂。
可以将丙烯接枝聚合物添加在层a和/或层b中。丙烯接枝聚合物的添加量可以为5-45重量％，基于所在层的总重量计。
在一种优选实施方式，以层a的总重量计，层a包含50-90重量％，优选55-75重量％的均聚聚丙烯，5-45重量％，优选10-30重量％的丙烯接枝聚合物和2-40重量％，优选5-20重量％的聚烯烃弹性体；和以层b的总重量计，层b包含40-100重量％，优选70-90重量％的丙烯无规共聚物和0-60重量％，优选10-30重量％的聚烯烃弹性体。
在另一种实施方式中，以层a的总重量计，层a包括50-100重量％，优选75-95重量％的丙烯聚合物和0-50重量％，优选5-25重量％的聚烯烃弹性体；和以层b的总重量计，层b包括50-90重量％，60-85重量％的丙烯无规共聚物，5-40重量％，优选5-20重量％的聚烯烃弹性体和2-40重量％，优选5-20重量％的丙烯接枝聚合物。
所述丙烯接枝聚合物可包括衍生自共聚聚丙烯的结构单元和接枝到其上的衍生自接枝单体的结构单元。
所述接枝单体可选自丙烯酸酯类；丙烯酸类；苯乙烯类；含烯基的硅烷类；含烯基的杂环类单体；具有至少一个烯烃不饱和度的酸酐和含烯基聚合单体的组合。
所述丙烯接枝聚合物在230℃，2.16kg载荷下的熔体质量流动速率可以为0.01-30g/10min，优选为0.05-20g/10min，进一步优选为0.1-10g/10min，更优选为0.2-8g/10min。
所述共聚聚丙烯可以为含有乙烯或高级α-烯烃的丙烯共聚物或者其混合物。具体地，所述共聚聚丙烯的共聚单体选自乙烯和C 4-C 8的α-烯烃中的至少一种。所述C 4-C 8的α-烯烃包括但不限于：1-丁烯、1-戊烯、4-甲基-1-戊烯、1-己烯、1-庚烯和1-辛烯中的至少一种。所述共聚单体优选为乙烯和/或1-丁烯，进一步优选地，所述共聚聚丙烯由丙烯和乙烯组成。
除上述组成特征以外，所述共聚聚丙烯还具有以下特征中的至少一种：共聚单体含量为0.5-30mol％，优选为4-25mol％；二甲苯可溶物含量为2-80重量％，优选为18-75重量％，进一步优选为30-70重量％；可溶物中共聚单体含量为10-70重量％，优选为10-50重量％，进一步优选为20-35重量％；可溶物与聚丙烯的特性粘数比为0.3-5，优选为0.5-3，更优选为0.8-1.3；在230℃，2.16kg载荷下的熔体质量流动速率为0.01-60g/10min，优选为0.05-35g/10min，进一步优选为0.5-15g/10min；熔融温度Tm为100℃以上，优选为110-180℃，进一步优选为120-170℃；重均分子量为20×10 4-60×10 4g/mol。
所述共聚聚丙烯可以是任意可商业获得的合适的聚丙烯粉料，也可以通过文献中记载的常用聚合工艺生产得到。例如参考CN101679557A、CN101058654A所述方法制备。
在一种实施方式中，所述丙烯接枝聚合物可包括衍生自共聚聚丙烯的结构单元和接枝到其上的衍生自丙烯酸酯类单体以及任选的丙烯酸类单体的结构单元。以丙烯接枝聚合物的重量为基准，接枝上的衍生自丙烯酸酯类单体以及任选的丙烯酸类单体的结构单元的含量可以为0.3-7重量％，优选为0.8-5重量％。所述丙烯接枝聚合物中，衍生自丙烯酸酯类单体的结构单元与衍生自丙烯酸类单体的结构单元的摩尔比可以为1:0-2，优选为1:0.125-1。
作为接枝单体的所述丙烯酸酯类单体可以是任何能够通过自由基进行聚合的单体丙烯酸酯类化合物，可选自具有式I所示结构的单体中的至少一种；
Figure PCTCN2021125096-appb-000001
其中，R 1、R 2、R 3各自独立地选自H、C 1-C 6直链烷基、C 3-C 6支链烷基；R 4选自取代或未取代的以下基团：C 1-C 20直链烷基、C 3-C 20支链烷基、C 3-C 12环烷基、C 3-C 12环氧烷基、C 3-C 12环氧烷基烷基，所述取代的基团选自卤素、氨基和羟基中的至少一种。
优选地，所述丙烯酸酯类单体选自(甲基)丙烯酸甲酯、(甲基)丙烯酸仲丁酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸异丁酯、(甲基)丙烯酸叔丁酯、(甲基)丙烯酸异辛酯、(甲基)丙烯酸十二烷基酯、(甲基)丙烯酸椰子油酸酯、(甲基)丙烯酸十八烷基酯、(甲基)丙烯酸二甲氨基乙酯、(甲基)丙烯酸二乙氨基乙酯、(甲基)丙烯酸二甲氨基丙酯和(甲基)丙烯酸缩水甘油酯中的至少一种。
所述的丙烯酸类单体可以是任何能够通过自由基进行聚合的单体丙烯酸类化合物，可选自具有式II所示结构的单体中的至少一种；
Figure PCTCN2021125096-appb-000002
式II中，R 1、R 2、R 3各自独立地选自H、C 1-C 6直链烷基、C 3-C 6支链烷基。
优选地，所述丙烯酸类单体选自丙烯酸、甲基丙烯酸和2-乙基丙烯酸中的至少一种。
本发明中C 3-C 12环氧烷基烷基是指具有3-12个碳原子的环氧烷基取代的烷基，例如，环氧乙烷基甲基。
本发明中，衍生自丙烯酸类单体的结构单元可不存在，也可与衍生自丙烯酸酯类单体的结构单元共同存在，优选地，衍生自丙烯酸酯类单体的结构单元与衍生自丙烯酸类单体的结构单元的摩尔比为1:0-2，优选为1:0.125-1。
所述丙烯酸酯类单体以及任选的丙烯酸类单体的总质量与所述共聚聚丙烯的质量的比为0.1-10:100，优选为0.5-8:100，进一步优选为0.8-7:100。所述丙烯酸酯类单体与丙烯酸类单体的摩尔比为1:0-2，优选为1:0.125-1。
在另一种实施方式中，所述丙烯接枝聚合物可包括衍生自共聚聚丙烯的结构单元和衍生自苯乙烯类单体的结构单元。以丙烯接枝聚合物的重量计，所述丙烯接枝聚合物中衍生自苯乙烯类单体的接枝上的结构单元的含量可以为0.5-14重量％，优选为1-7.5重量％，更优选为1.5-5重量％。
作为接枝单体的所述的苯乙烯类单体可以是任何能够通过自由基进行聚合的单体苯乙烯类化合物，可选自具有式III所示结构的单体、具有式IV所示结构的单体和具有式V所示结构的单体中的至少一种；
Figure PCTCN2021125096-appb-000003
式III中，R 1、R 2、R 3各自独立地选自H、取代或未取代的C 1-C 6的烷基；R 4-R 8各自独立地选自H、卤素、羟基、氨基、磷酸基、磺酸基、取代或未取代的C 1-C 12的烷基、取代或未取代的C 3-C 12的环烷基、取代或未取代的C 1-C 12的烷氧基、取代或未取代的C 1-C 12的酯基、取代或未取代的C 1-C 12的胺基，所述取代基团选自卤素、羟基、氨基、磷酸基、磺酸基、C 1-C 12的烷基、C 3-C 12的环烷基、C 1-C 12的烷氧基、C 1-C 12的酯基、C 1-C 12的胺基；优选地，R 1、R 2、R 3各自独立地选自H、取代或未取代的C 1-C 3的烷基，R 4-R 8各自独立地选自H、卤素、羟基、氨基、取代或未取代的C 1-C 6的烷基、取代或未取代的C 1-C 6的烷氧基；
Figure PCTCN2021125096-appb-000004
式IV中，R 1、R 2、R 3各自独立地选自H、取代或未取代的C 1-C 6的烷基；R 4-R 10各自独立地选自H、卤素、羟基、氨基、磷酸基、磺酸基、取代或未取代的C 1-C 12的烷基、取代或未取代的C 3-C 12的环烷基、取代或未取代的C 1-C 12的烷氧基、取代或未取代的C 1-C 12的酯基、取代或未取代的C 1-C 12的胺基，所述取代基团选自卤素、羟基、氨基、磷酸基、磺酸基、C 1-C 12的烷基、C 3-C 12的环烷基、C 1-C 12的烷氧基、C 1-C 12的酯基、C 1-C 12的胺基；优选地，R 1、R 2、R 3各自独立地选自H、取代或未取代的C 1-C 3的烷基，R 4-R 10各自独立地选自H、卤素、羟基、氨基、取代或未取代的C 1-C 6的烷基、取代或未取代的C 1-C 6的烷氧基，所述取代基团选自卤素、羟基、氨基、C 1-C 6的烷基、C 1-C 6的烷氧基；
Figure PCTCN2021125096-appb-000005
式V中，R 1’、R 2’、R 3’各自独立地选自H、取代或未取代的C 1-C 6的烷基；R 4’-R 10’各自独立地选自H、卤素、羟基、氨基、磷酸基、磺酸基、取代或未取代的C 1-C 12的烷基、取代或未取代的C 3-C 12的环烷基、取代或未取代的C 1-C 12的烷氧基、取代或未取代的C 1-C 12的酯基、取代或未取代的C 1-C 12的胺基，所述取代基团选自卤素、羟基、氨基、磷酸基、磺酸基、C 1-C 12的烷基、C 3-C 12的环烷基、C 1-C 12的烷氧基、C 1-C 12的酯基、C 1-C 12的胺基；优选地，R 1’、R 2’、R 3’各自独立地选自H、取代或未取代的C 1-C 3的烷基，R 4’-R 10’各自独立地选自H、卤素、羟基、氨基、取代或未取代的C 1-C 6的烷基、取代或未取代的C 1-C 6的烷氧基，所述取代基团选自卤素、羟基、氨基、C 1-C 6的烷基、C 1-C 6的烷氧基。
优选地，所述苯乙烯类单体可选自苯乙烯、α-甲基苯乙烯、1-乙烯基萘、2-乙烯基萘、单取代或多取代的苯乙烯，单取代或多取代的α-甲基苯乙烯、单取代或多取代的1-乙烯基萘和单取代或多取代的2-乙烯基萘中的至少一种；所述取代基团优选选自卤素，羟基，氨基，磷酸基，磺酸基，C 1-C 8的直链烷基、C 3-C 8的支链烷基或环烷基、C 1-C 6的直链烷氧基，C 3-C 8的支链烷氧基或环状烷氧基、C 1-C 8的直链酯基、C 3-C 8的支链酯基或环状酯基、C 1-C 8的直链胺基以及C 3-C 8的支链胺基或环状胺基中的至少一种。
更优选地，所述苯乙烯类单体选自苯乙烯、α-甲基苯乙烯、2-甲基苯乙烯、3-甲基苯乙烯和4-甲基苯乙烯中的至少一种。
所述苯乙烯类单体与所述共聚聚丙烯的质量比可以为0.5-16:100，优选为1-12:100，进一步优选为2-10:100。
在另一种实施方式中，所述丙烯接枝聚合物包括衍生自共聚聚丙烯的结构单元和衍生自含烯基的硅烷类单体的结构单元。以丙烯接枝聚合物的重量为基准，所述丙烯接枝聚合物b中衍生自含烯基的硅烷类单体的接枝上的结构单元的含量可以为0.2-6重量％，优选为0.2-2.5重量％。
作为接枝单体的所述的含烯基的硅烷类单体可以是任何能够通过自由基进行聚合的单体硅烷类化合物，可选自含烯基的硅烷类单体选自具有式VI所示结构的单体中的至少 一种，
Figure PCTCN2021125096-appb-000006
式VI中，R 1为C 2-C 12的烯基，优选为单不饱和烯基；R 2、R 3、R 4各自独立地选自取代或未取代的C 1-C 12的直链烷基、取代或未取代的C 3-C 12的支链烷基、取代或未取代的C 1-C 12的烷氧基、取代或未取代的C 1-C 12的酰氧基；优选地，R 1为C 2-C 6的烯基，优选为单不饱和烯基；R 2、R 3、R 4各自独立地选自取代或未取代的C 1-C 6的直链烷基、取代或未取代的C 3-C 6的支链烷基、取代或未取代的C 1-C 6的烷氧基、取代或未取代的C 1-C 6的酰氧基。
更优选地，所述含烯基的硅烷类单体选自乙烯基三乙氧基硅烷、乙烯基三甲氧基硅烷、乙烯基三异丙氧基硅烷、乙烯基三叔丁氧基硅烷、乙烯基三乙酰氧基硅烷、甲基乙烯基二甲氧基硅烷、乙基乙烯基二乙氧基硅烷、烯丙基三乙氧基硅烷、烯丙基三甲氧基硅烷、烯丙基三异丙氧基硅烷、乙烯基三(β-甲氧乙氧基)硅烷、烯丙基三(β-甲氧乙氧基)硅烷、烯丙基三叔丁氧基硅烷、烯丙基三乙酰氧基硅烷、甲基烯丙基二甲氧基硅烷和乙基烯丙基二乙氧基硅烷中的至少一种。
所述含烯基的硅烷类单体与所述共聚聚丙烯的质量比可以为0.5-12:100，优选为0.8-9:100，进一步优选为1-6:100。
在另一种实施方式中，所述丙烯接枝聚合物包括衍生自共聚聚丙烯的结构单元、衍生自酸酐单体的结构单元和衍生自含烯基聚合单体的结构单元。所述含烯基聚合单体可选自乙酸乙烯酯、苯乙烯、α-甲基苯乙烯、(甲基)丙烯酸酯、乙烯基烷基醚、乙烯基吡咯烷酮、乙烯基吡啶、乙烯基咪唑和丙烯腈中的至少一种。所述酸酐优选选自马来酸酐和/或衣康酸酐。衍生自酸酐单体和含烯基聚合单体的接枝上的结构单元的含量可以为0.1-5重量％，优选为0.4-3重量％。接枝上的衍生自酸酐单体的结构单元的含量可以为0.05-2重量％，优选为0.2-0.7重量％。衍生自酸酐单体的结构单元与衍生自含烯基聚合单体的结构单元的摩尔比可以为1：1-20，优选为1：1-10。作为接枝单体的所述的含烯基聚合单体优选选自具有式1所示结构的单体中的至少一种，
Figure PCTCN2021125096-appb-000007
式1中，R 1、R 2、R 3各自独立地选自H、取代或未取代的烷基；R 4选自取代或未取 代的烷基、取代或未取代的烷氧基、取代或未取代的芳基、取代或未取代的酯基、取代或未取代的羧基、取代或未取代的环烷基或杂环基、氰基。
优选地，R 1、R 2、R 3各自独立地选自H、取代或未取代的C 1-C 6烷基，更优选地，R 1、R 2、R 3各自独立地选自H、取代或未取代的C 1-C 3烷基；R 4选自取代或未取代的C 1-C 20烷基、取代或未取代的C 1-C 20烷氧基、取代或未取代的C 6-C 20芳基、取代或未取代的C 1-C 20酯基、取代或未取代的C 1-C 20羧基、取代或未取代的C 3-C 20环烷基或杂环基、氰基，所述取代的基团为卤素、羟基、氨基、C 1-C 6烷基、C 3-C 6环烷基；优选地，R 4选自取代或未取代的C 1-C 12烷基、取代或未取代的C 1-C 18烷氧基、取代或未取代的C 6-C 12芳基、取代或未取代的C 1-C 12酯基、取代或未取代的C 1-C 12羧基、取代或未取代的C 3-C 12环烷基或杂环基、氰基，所述取代的基团为卤素、C 1-C 6烷基、C 3-C 6环烷基；更优选地，R 4选自取代或未取代的C 1-C 6烷基、取代或未取代的C 1-C 12烷氧基、取代或未取代的C 6-C 8芳基、取代或未取代的C 1-C 6酯基、取代或未取代的C 1-C 6羧基、取代或未取代的C 3-C 6环烷基或杂环基、氰基。具体优选地，所述杂环基选自咪唑基、吡唑基、咔唑基、吡咯烷酮基、吡啶基、哌啶基、己内酰胺基、吡嗪基、噻唑基、嘌呤基、吗啉基、噁唑啉基。
更优选地，R 1、R 2、R 3各自独立地选自H、取代或未取代的C 1-C 6烷基；
R 4选自式2所示基团、式3所示基团、式4所示基团、式5所示基团、式5所示基团和式6所示基团的组合、杂环基团；
Figure PCTCN2021125096-appb-000008
式2中，R 4-R 8各自独立地选自H、卤素、羟基、氨基、磷酸基、磺酸基、取代或未取代的C 1-C 12的烷基、取代或未取代的C 3-C 12的环烷基、取代或未取代的C 1-C 12的烷氧基、取代或未取代的C 1-C 12的酯基、取代或未取代的C 1-C 12的胺基，所述取代的基团选自卤素、羟基、氨基、磷酸基、磺酸基、C 1-C 12的烷基、C 3-C 12的环烷基、C 1-C 12的烷氧基、C 1-C 12的酯基、C 1-C 12的胺基；优选地，R 4-R 8各自独立地选自H、卤素、羟基、氨基、取代或未取代的C 1-C 6的烷基、取代或未取代的C 1-C 6的烷氧基；
Figure PCTCN2021125096-appb-000009
式3中，R 4-R 10各自独立地选自H、卤素、羟基、氨基、磷酸基、磺酸基、取代或未取代的C 1-C 12的烷基、取代或未取代的C 3-C 12的环烷基、取代或未取代的C 1-C 12的烷氧基、取代或未取代的C 1-C 12的酯基、取代或未取代的C 1-C 12的胺基，所述取代的基团选自卤素、羟基、氨基、磷酸基、磺酸基、C 1-C 12的烷基、C 3-C 12的环烷基、C 1-C 12的烷氧基、C 1-C 12的酯基、C 1-C 12的胺基；优选地，R 4-R 10各自独立地选自H、卤素、羟基、氨基、取代或未取代的C 1-C 6的烷基、取代或未取代的C 1-C 6的烷氧基，所述取代的基团选自卤素、羟基、氨基、C 1-C 6的烷基、C 1-C 6的烷氧基；
Figure PCTCN2021125096-appb-000010
式4中，R 4’-R 10’各自独立地选自H、卤素、羟基、氨基、磷酸基、磺酸基、取代或未取代的C 1-C 12的烷基、取代或未取代的C 3-C 12的环烷基、取代或未取代的C 1-C 12的烷氧基、取代或未取代的C 1-C 12的酯基、取代或未取代的C 1-C 12的胺基，所述取代的基团选自卤素、羟基、氨基、磷酸基、磺酸基、C 1-C 12的烷基、C 3-C 12的环烷基、C 1-C 12的烷氧基、C 1-C 12的酯基、C 1-C 12的胺基；优选地，R 4’-R 10’各自独立地选自H、卤素、羟基、氨基、取代或未取代的C 1-C 6的烷基、取代或未取代的C 1-C 6的烷氧基，所述取代的基团选自卤素、羟基、氨基、C 1-C 6的烷基、C 1-C 6的烷氧基；
Figure PCTCN2021125096-appb-000011
式5中，R m选自取代或未取代的以下基团：C 1-C 20直链烷基、C 3-C 20支链烷基、C 3-C 12环烷基、C 3-C 12环氧烷基、C 3-C 12环氧烷基烷基，所述取代的基团选自卤素、氨基和羟基中的至少一种。
进一步优选地，所述含烯基聚合单体选自乙酸乙烯酯、苯乙烯、α-甲基苯乙烯、(甲基)丙烯酸酯、乙烯基烷基醚、乙烯基吡咯烷酮、乙烯基吡啶、乙烯基咪唑和丙烯腈中的至少一种；所述(甲基)丙烯酸酯优选为(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯和(甲基)丙烯 酸缩水甘油酯中的至少一种。优选地，所述含烯基聚合单体选自乙酸乙烯酯、苯乙烯、α-甲基苯乙烯。进一步优选地，所述含烯基聚合单体为苯乙烯。
所述含有酸酐基团的丙烯接枝聚合物中衍生自(马来)酸酐单体的结构单元与衍生自含烯基聚合单体的结构单元的摩尔比可以为1：1-20，优选为1：1-10。
所述酸酐可选自具有至少一个烯烃不饱和度的酸酐；更优选地，所述酸酐选自马来酸酐和/或衣康酸酐；进一步优选地，所述酸酐为马来酸酐。
所述酸酐单体和所述含烯基聚合单体的总质量与所述共聚聚丙烯的质量比可以为0.1-8:100，优选为0.3-5:100。所述酸酐单体的质量用量可以为所述含烯基聚合单体的质量用量的5-100wt％，优选为10-100wt％。
在另一种实施方式中，所述丙烯接枝聚合物包括衍生自共聚聚丙烯的结构单元和衍生自含烯基的杂环类单体的结构单元。以丙烯接枝聚合物的重量为基准，接枝上的衍生自含烯基的杂环类单体的结构单元的含量可以为0.5-6重量％，优选为0.5-4重量％。
作为接枝单体的所述含烯基的杂环类单体可以是任何能够通过自由基进行聚合的含烯基的杂环类化合物，可选自含烯基取代基的咪唑、含烯基取代基的吡唑、含烯基取代基的咔唑、含烯基取代基的吡咯烷酮、含烯基取代基的吡啶或吡啶盐、含烯基取代基的哌啶、含烯基取代基的己内酰胺、含烯基取代基的吡嗪、含烯基取代基的噻唑、含烯基取代基的嘌呤、含烯基取代基的吗啉和含烯基取代基的噁唑啉中的至少一种；优选地，所述含烯基的杂环类单体为含单烯基的杂环类单体。
具体地，所述含烯基的杂环类单体可选自：1-乙烯基咪唑、2-甲基-1-乙烯基咪唑、N-烯丙基咪唑、1-乙烯基吡唑、3-甲基-1-乙烯基吡唑、乙烯基咔唑、N-乙烯基吡咯烷酮、2-乙烯基吡啶、3-乙烯基吡啶、4-乙烯基吡啶、2-甲基-5-乙烯基吡啶、乙烯基吡啶N氧化物、乙烯基吡啶盐、乙烯基哌啶、N-乙烯基己内酰胺、2-乙烯基吡嗪、N-乙烯基哌嗪、4-甲基-5-乙烯基噻唑、N-乙烯基嘌呤、乙烯基吗啉和乙烯基噁唑啉中的至少一种。
所述含烯基的杂环类单体与所述共聚聚丙烯的质量比可以为0.3-12:100，优选为0.5-10:100。
本文中所述接枝反应是自由基聚合反应。经自由基聚合，接枝单体与共聚聚丙烯形成共价连接(接枝)。
优选地，所述丙烯接枝聚合物可由共聚聚丙烯与接枝单体经固相接枝反应制得，例如根据申请号为202011195771.2、202011191001.0、202011195799.6、202011190917.4、202011195819.X的中国专利申请中所述的方法制备。
具体地，可通过包括以下步骤的方法制备得到：在惰性气体存在下，使包括共聚聚丙烯和接枝单体的反应混合物进行固相接枝反应，得到所述丙烯接枝聚合物。
所述固相接枝反应可参考本领域常规的各种方法进行，如，在接枝单体的存在下在共聚聚丙烯上形成活性接枝点，或者先在共聚聚丙烯上形成活性接枝点接着用接枝用单体进行处理。接枝点可通过自由基引发剂处理形成，或进行高能电离辐射或微波处理来形成。在聚合物中作为化学或辐射处理的结果而产生的自由基在聚合物上形成接枝点并在这些点上引发单体聚合。
优选地，通过自由基引发剂引发接枝点并进一步进行接枝反应。在这种情况下，所述反应混合物还包括自由基引发剂；进一步优选地，所述自由基引发剂选自过氧化物类自由基引发剂和/或偶氮类自由基引发剂。
其中，所述过氧化物类自由基引发剂优选选自过氧化二苯甲酰、过氧化二异丙苯、二叔丁基过氧化物、过氧化月桂酰、过氧化十二酰、过氧化苯甲酸叔丁酯、过氧化二碳酸二异丙基酯、过氧化(2-乙基己酸)叔丁酯和过氧化二碳酸二环己基酯中的至少一种；所述偶氮类自由基引发剂优选为偶氮二异丁腈和/或偶氮二异庚腈。
更优选地，通过过氧化物类自由基引发剂引发接枝点并进一步进行接枝反应。
此外，所述接枝反应也可以通过CN106543369A、CN104499281A、CN102108112A、CN109251270A、CN1884326A和CN101492517B中描述的方法进行。
所述自由基引发剂的质量与接枝用单体的总质量的比可以为0.1-10:100，优选为0.5-5:100。
所述接枝反应的温度可以为30-130℃，优选为60-120℃；时间可以为0.5-10h，优选为1-5h。
所述“反应混合物”包括加入到接枝反应体系中的所有物料，物料可以一次性加入，也可以在反应的不同阶段加入。
所述反应混合物中还可以包括分散剂，所述分散剂优选为水或氯化钠的水溶液。所述分散剂的质量用量优选为共聚聚丙烯质量的50-300％。
所述反应混合物中还可以包括界面剂，所述界面剂为对聚烯烃具有溶胀作用的有机溶剂，优选为对共聚聚丙烯具有溶胀作用的下述有机溶剂中的至少一种：醚类溶剂、酮类溶剂、芳烃类溶剂、烷烃类溶剂；更优选为下述有机溶剂中的至少一种：氯代苯、多氯代苯、C 6以上的烷烃或环烷烃、苯、C 1-C 4烷基取代苯、C 2-C 6脂肪醚、C 3-C 6脂肪酮、十氢萘；进一步优选为下述有机溶剂中的至少一种：苯、甲苯、二甲苯、氯苯、四氢呋喃、乙醚、 丙酮、己烷、环己烷、十氢萘、庚烷。所述界面剂的质量含量优选为共聚聚丙烯质量的1-35％，进一步优选为10-25％。
所述反应混合物中还可以包括有机溶剂，作为溶解固体自由基引发剂的溶剂，所述有机溶剂优选包括C 2-C 5醇类、C 2-C 4醚类和C 3-C 5酮类中的至少一种，更优选包括C 2-C 4醇类、C 2-C 3醚类和C 3-C 5酮类中的至少一种，最优选为乙醇、乙醚和丙酮中的至少一种。所述有机溶剂的质量含量优选为共聚聚丙烯质量的1-35％。
在接枝反应过程中，接枝单体可各自或相互聚合成一定量的未接枝的聚合物，因此所述丙烯接枝聚合物可既包括由共聚聚丙烯和接枝单体经接枝反应直接制得的产物(粗品)，也包括将该产物进行进一步纯化得到的接枝改性聚丙烯纯品，因此，所述制备方法中，可任选地包括对粗品进行纯化的步骤。所述纯化可采用本领域常规的各种方法，如抽提法。
优选控制所述接枝反应的接枝效率为5-100％，优选30-100％，进一步优选为25-80％，或者35-60％。所述接枝效率的概念为本领域技术人员公知，是指接枝上的接枝单体的量/反应投料的接枝单体的总量。
所述惰性气体可以为本领域常用的各种惰性气体，包括但不限于氮气、氩气。
复合薄膜的层结构和性能
本发明的复合薄膜可以仅由层a和层b组成，即是双层薄膜。
在另选的实施方式中，除了层a和层b之外，本发明的复合薄膜还可包含一个或多个另外的层，即包含三个层或多于三个的层，由此形成三层薄膜或多于三层的薄膜，在此层b为复合薄膜的表层。该另外的层的组成可与层a或层b的组成相同或不同。该层也可以由层a的组分和层b的组分混合而成。例如，当复合薄膜为三层薄膜时，该另外的层称为层c，层b与层c分别位于层a的两侧，即层c位于层a的与层b相对的那一侧，此时层c也是表层。当复合薄膜为五层时，可能的是，两个层b分别作为上下表层，两个层c作为中间层，一个层a作为芯层。
本发明中层a、层b和任选的层c和另外的层的厚度不受特别限制。除了层a之外的其他层的厚度之和与层a的厚度之比可以为1:6-2:1，例如可以是1:5.5、1:5、1:4.5、1:4、1:3.5、1:3、1:2.5、1:2、1:1.5、1:1、1.5:1，以及它们之间的任意值，优选1:4-2:1，更优选为1:2-1:1。这样的复合薄膜可以有利地具有更好的力学性能(例如拉伸强度)和性能稳定性。
预料不到地发现，由于本发明的复合薄膜中含有分散的彼此平行排列的条状的来自丙烯抗冲共聚物的橡胶相，本发明的复合薄膜可同时具有优异的抗冲性能和光学性能，甚至还具有优异的力学性能(例如拉伸强度)和/或优异的热封性能，可在较低的热封温度下具有很好的热封强度。
当除了上述来自丙烯抗冲共聚物的橡胶相以外，本发明的复合薄膜中另外存在均聚聚丙烯和聚烯烃弹性体时，丙烯抗冲共聚物中的橡胶相和非弹性部分与均聚聚丙烯形成的聚合物球晶以及聚烯烃弹性体橡胶相之间会发生协同相互作用，使得可以进一步同时提高复合薄膜的抗冲击性能和光学性能，甚至还提高其力学性能。
根据本发明的复合薄膜可有利地具有以下性能中的一种或多种，优选全部以下性能：
1)摆锤冲击强度为≥0.4J，例如≥0.5J、0.6J或0.7J，优选≥0.9J，更优选≥1.1J，例如≥1.5J，甚至≥1.8J；
2)薄膜雾度为小于7％，优选≤5％，更优选≤3％，例如≤2.5％，再更优选≤2％；
3)纵向(MD)拉伸强度为≥40MPa，优选≥50MPa；
4)在150℃下的热封强度为≥12N/15mm，优选≥15N/15mm，优选≥17N/15mm，更优选≥18N/15mm，甚至≥19N/15mm，例如≥20N/15mm；
5)MD方向厚度偏差不大于1.3，例如不大于1.0，优选不大于0.5；
6)TD方向厚度偏差不大于1.5，例如不大于1.3，优选不大于0.75或不大于0.8；
7)MD方向抗冲击性能偏差不大于0.05，优选不大于0.03；
8)TD方向抗冲击性能偏差不大于0.07，优选不大于0.05，更优选不大于0.04；
9)表面能≥29mN/m，例如≥33mN/m、≥34.5mN/m，优选≥35mN/m；
10)体积电阻率≥1.5×10 15Ω·m，优选率≥2.0×10 15Ω·m。
所述性能的测量方法和标准如下：
摆锤冲击强度：按照标准GB/T 8809-2015；
薄膜雾度：按照标准GB/T 2410-2008；
拉伸强度：按照标准GB/T 1040.3-2006，沿薄膜的纵向；
热封强度：按照标准QB/T 2358，制样时热封温度为150℃、热封压力为0.2MPa、热封时间3s。
MD方向的厚度偏差：采用日本三丰的型号为7301的厚度表测试薄膜厚度。如附图1a所示，薄膜切边后，在薄膜中心线上，沿MD方向每隔1米取一个点，共取10个点，按照GB/T 8809-2015中规定的方法测试每一点的厚度，取平均值为薄膜的厚度(MD)。 并依据以上数据计算厚度的标准偏差，作为MD方向的厚度偏差。
TD方向的厚度偏差：如附图1b所示，沿薄膜任一处的TD方向，均匀取10个点，按照GB/T 8809-2015中规定的方法测试每一点的厚度，取平均值为薄膜的厚度(TD)。并依据以上数据计算厚度的标准偏差，作为TD方向的厚度偏差。
MD方向的冲击强度偏差：如附图1a所示，薄膜切边后，在薄膜中心线上，沿MD方向每隔1米取一个点，共取10个点，按照GB/T 8809-2015中规定的方法测试每一点的冲击强度，取平均值为薄膜的冲击强度(MD)；并依据以上数据计算冲击强度的标准偏差，作为MD方向的冲击强度偏差。
TD方向的冲击强度偏差：如附图1b所示，沿薄膜任一处的TD方向，均匀取10个点，按照GB/T 8809-2015中规定的方法测试每一点的冲击强度，取平均值为薄膜的冲击强度(TD)；并依据以上数据计算冲击强度的标准偏差，作为TD方向的冲击强度偏差。
薄膜表面能：按照GB/T 14216-2008中规定的方法进行测定。
体积电阻率：按照GB/T 1410-2006中规定的方法进行测定。
复合薄膜的制备
本发明的第二方面提供本发明的复合薄膜的制备方法。本发明的方法包括将用于形成各层的原料组合物挤出流延而形成所述复合薄膜。
根据本发明，在挤出过程之前，原料组合物中使用的丙烯抗冲共聚物中的弹性部分可形成粒状橡胶相，所述橡胶相的平均粒径为小于或等于1.8μm，优选地小于或等于1.5μm，且最大粒径不超过2.5μm，优选不超过2μm，通过SEM观察样条断面测定。
所述橡胶相通常为球状或近球状的。
本文中，所述球状和近球状是指粒子的纵横比基本上在1-2的范围内。“基本上”是指至少90％的橡胶相粒子的纵横比在1-2的范围内。
原料中丙烯抗冲共聚物中的橡胶相的平均粒径和最大粒径通过扫描电镜(SEM)方法观察冲击样条断面测定，所述冲击样条根据标准GB/T 8809-2015中规定的方法制备。对于球状粒子，测定粒子的直径；对于近球状的粒子，则测量粒子的纵轴(粒子轮廓上相距最远的两个点之间的距离)。通过SEM照片观察获取50个样品点的上述尺寸的平均值作为平均粒径，取上述样品点中上述尺寸的最大值作为最大粒径。
根据本发明，通过控制原料丙烯抗冲共聚物中的橡胶相尺寸，可以使复合薄膜中的橡胶相尺寸处于根据本发明所述的特定范围内。
在挤出过程之前，可将作为原料的用于制备各层的聚合物组合物的各组分(包括任选的添加剂，例如抗氧剂、润滑剂和其他薄膜助剂)混合或共混，并任选地造粒。
所述造粒过程可以如下进行：将用于构成层a的丙烯聚合物组合物A和用于构成层b的丙烯聚合物组合物B和任选的用于构成另外的层的聚合物组合物的各组分连同任选的添加剂在高速搅拌器中混合均匀，将混合均匀的物料加入至双螺杆挤出机中熔融混合并均匀挤出造粒，烘干，从而得到粒料。所述双螺杆挤出机的加工温度可以控制为170-230℃。
然后，将所得粒料挤出流延，从而制成复合薄膜。所述粒料的挤出流延过程可以通过常规方式、采用常用设备进行。所述挤出流延法可以包括将用于制备各层的聚合物组合物的粒料分别送至多台挤出机中，粒料经挤出机模口共挤复合流出后，依次经过流延辊、牵引辊，再经裁边和收卷，从而制得所述复合薄膜。挤出流延的温度可以控制为170-230℃。流延辊的温度可以为10-50℃。
通过根据本发明的制备方法，作为原料的丙烯抗冲共聚物中包含的橡胶相在复合薄膜的制备工艺过程中发生了变形，由球状或近球状转变为条状，并且沿一定方向取向，即平行排列，并在最后的复合薄膜产品中保持了这样的微结构，从而获得根据本发明的具有良好抗冲性能和光学性能的复合薄膜。
有利的是，使用的聚烯烃弹性体在复合薄膜的制备过程中也发生了变形，变为条状橡胶相，并且沿一定方向取向，即平行排列，并在最后的复合薄膜产品中保持了这样的微结构，同时与来自丙烯抗冲共聚物的橡胶相发生协同相互作用，从而进一步提高了复合薄膜的抗冲性能和光学性能以及其他性能(力学性能、热封性能、薄膜均匀性等)。
所得复合薄膜可以在后续工艺中进行拉伸，例如双向拉伸，从而可有利地进一步改进复合薄膜的力学性能。
根据本发明的一些实施方式，所述复合薄膜的制备方法包括将所述丙烯聚合物组合物A和丙烯聚合物组合物B造粒后挤出流延，拉伸，制得所述复合薄膜。
复合薄膜的应用
本发明的第三方面提供本发明的复合薄膜在包装材料领域中的应用。
由于本发明的复合薄膜可同时具有良好的抗冲性能和光学性能，甚至具有良好的拉伸性能和/或可在较低的热封温度下具有良好的热封强度，甚至还具有良好的厚度和/或性能均匀性，因此本发明的复合薄膜尤其可用于高端包装领域，例如对薄膜抗冲性能和光学性能两者都要求较高的领域，如电池包装材料、电子产品包装和高端食品包装等领域。所述 包装材料例如可以是包含铝塑复合膜的那些。
当使用本发明的复合薄膜时，层a用作芯层，即相对远离复合薄膜要接触的介质的层，层b用作表层，即靠近复合薄膜所要接触的介质的层。所述介质例如电池包装材料接触的电解液。
相应地，本发明的第四方面提供包含本发明的复合薄膜的包装材料。所述包装材料例如可以是电池包装材料、电子产品包装材料或食品包装材料，尤其是高端食品包装材料。所述包装材料例如可以是包含铝塑复合膜的那些。
具体实施方式
下面结合实施例对本发明作进一步例示阐述，但本发明的范围并不受到这些实施例的限制。
在以下实施例和对比例中：
薄膜流延设备购自瑞典Labtech公司，型号为LCR400。
原料、聚合物组合物和薄膜的性能按照以下方法进行测量：
(1)熔体质量流动速率(MFR)：按照GB/T 3682-2000中规定的方法进行测定，其中测试温度为230℃，载荷为2.16kg。
(2)薄膜拉伸强度：按照GB/T 1040.3-2006中规定的方法进行测定。
(3)薄膜摆锤冲击强度及冲击强度偏差计算：按照GB/T 8809-2015中规定的方法进行测定；具体地，
如附图1a所示，薄膜切边后，在薄膜中心线上，沿MD方向每隔1米取一个点，共取10个点，按照GB/T 8809-2015中规定的方法测试每一点的冲击强度，取平均值为薄膜的冲击强度(MD)；并依据以上数据计算冲击强度的标准偏差，作为MD方向的冲击强度偏差。
如附图1b所示，沿薄膜任一处的TD方向，均匀取10个点，按照GB/T 8809-2015中规定的方法测试每一点的冲击强度，取平均值为薄膜的冲击强度(TD)；并依据以上数据计算冲击强度的标准偏差，作为TD方向的冲击强度偏差。
(4)薄膜雾度：按照GB/T 2410-2008中规定的方法进行测定。
(5)薄膜热封强度：按照QB/T 2358中规定的方法进行测定。制样时，热封温度为150℃，热封压力为0.2MPa，热封时间3s。
(6)等规度：通过 13C NMR测定，采用瑞士Bruker公司的型号为AVANCE III的 核磁共振波谱仪(NMR)测定400MHz下丙烯聚合物的核磁碳谱( 13C-NMR)，其中，溶剂为氘代邻二氯苯，样品浓度为250mg样品/2.5mL溶剂。为防止样品在溶解及数据采集过程中氧化降解，在样品中加入2mg的2,6-二叔丁基-4-甲基苯酚抗氧剂(简称BHT)。140℃溶解试样，采集 13C-NMR，测试温度125℃，探测头规格10毫米，90°脉冲，采样时间AQ为5秒，延迟时间D1为1秒，扫描次数6000次。以二单元组等规[mm]的含量作为等规度。
(7)分子量分布(Mw/Mn):通过凝胶渗透色谱法(GPC)测定，采用英国Polymer Laboratories公司生产的型号为PL-GPC 220的凝胶渗透色谱仪结合IR5型红外检测器测定，其中，凝胶渗透色谱仪中的色谱柱为3根串联的Plgel 10μm MIXED-B柱，溶剂和流动相均为1,2,4-三氯苯(含0.3g/1000mL的抗氧剂2,6-二叔丁基对甲酚)，柱温为150℃，流速为1.0mL/min，采用PL公司生产EasiCal PS-1窄分布聚苯乙烯标样进行普适标定。
(8)薄膜厚度及厚度偏差测试：采用日本三丰的型号为7301的厚度表测试薄膜厚度。如附图1a所示，薄膜切边后，在薄膜中心线上，沿MD方向每隔1米取一个点，共取10个点，按照GB/T 8809-2015中规定的方法测试每一点的厚度，取平均值为薄膜的厚度(MD)。并依据以上数据计算厚度的标准偏差，作为MD方向的厚度偏差。
如附图1b所示，沿薄膜任一处的TD方向，均匀取10个点，按照GB/T 8809-2015中规定的方法测试每一点的厚度，取平均值为薄膜的厚度(TD)。并依据以上数据计算厚度的标准偏差，作为TD方向的厚度偏差。
(9)标准偏差(S)的计算：根据公式(a)计算。
Figure PCTCN2021125096-appb-000012
其中，
Figure PCTCN2021125096-appb-000013
代表所测得的数据X1、X2……Xn的平均值，N是所采用的数据总数量。
(10)剪切黏度的测定：根据ISO11443:2014中描述的方法，采用德国GOTTFERT公司的Rheograph 25型毛细管流变仪测定。设定毛细管流变仪温度为230℃，口模毛细管长度为30mm，毛细管长径比为30:1，预热时间为300秒，分别测定剪切速率
Figure PCTCN2021125096-appb-000014
为160s -1和640s -1下的剪切应力(δ)，并根据公式(b)分别计算相应剪切速率下的剪切黏度η 160和η 640。
Figure PCTCN2021125096-appb-000015
实施例和对比例中的丙烯聚合物组合物A在剪切速率为160s -1和640s -1下的剪切黏度 分别标记为ηA 160和ηA 640，丙烯聚合物组合物B在剪切速率为160s -1和640s -1下的剪切黏度分别标记为ηB 160和ηB 640，用P代表丙烯聚合物组合物A和丙烯聚合物组合物B在剪切速率160r -1下的剪切黏度的差值(ηA 160-ηB 160)与640r -1下的剪切黏度的差值(ηA 640-ηB 640)的比值(ηA 160-ηB 160)/(ηA 640-ηB 640)。
(11)原子力显微镜(AFM)照片：采用美国Bruker公司的Dimension FastScan Icon型原子力显微镜，使用定量纳米力学扫描模式，对薄膜样品的沿横向切割的横截面进行扫描观察。
(12)薄膜中橡胶相的横轴尺寸和纵横比：采用美国Bruker公司的Dimension FastScan Icon型原子力显微镜，使用定量纳米力学扫描模式，对薄膜样品的沿横向切割的横截面进行扫描观察，对橡胶相的横轴(与纵轴垂直的直线中与物体轮廓相交的交点之间距离最长的直线在交点之间的长度)、纵轴(物体的轮廓上相距最远的两个点之间的距离)和纵横比进行测量、计算和统计，基于200个样品点得到横轴的平均尺寸和纵横比的平均值。
(13)原料中丙烯抗冲共聚物的橡胶相的平均粒径和最大粒径：采用韩国COXEM的EM-30AX的扫描电子显微镜，对喷金处理后的冲击样条断面进行喷金处理进行扫描观察，对橡胶相的粒径进行测量和统计，得到平均粒径和最大粒径。对于球状粒子，测定粒子的直径；对于近球状的粒子，则测量粒子的纵轴(物体的轮廓上相距最远的两个点之间的距离)，基于50个样品点，获取上述尺寸的最大值作为最大粒径，并计算上述尺寸的平均值作为平均粒径。
(14)丙烯抗冲共聚物中含有乙烯单元的共聚部分含量、乙烯单元含量、乙烯单元组[EEE]含量：通过 13C NMR测定。
13C NMR采用瑞士Bruker公司的400MHz核磁共振波谱仪(NMR)测定，仪器型号为AVANCE III。溶剂为氘代邻二氯苯，250mg样品/2.5ml溶剂。为防止样品在溶解及数据采集过程中氧化降解，在样品中加入2mg的BHT抗氧剂。140℃溶解试样，采集 13C-NMR，测试温度125℃，探测头规格10毫米，90°脉冲，采样时间AQ为5秒，延迟时间D1为1秒，扫描次数6000次。
(15)薄膜表面能：按照GB/T 14216-2008中规定的方法进行测定。
(16)丙烯接枝聚合物中共聚聚丙烯的共聚单体含量：通过定量傅里叶变换红外(FTIR)光谱测定共聚单体的含量。通过定量核磁共振(NMR)光谱对确定的共聚单体含量的相关性进行校准。所述基于定量 13C-NMR光谱所得结果的校准方法按照本领域的 常规方法进行。
(17)丙烯接枝聚合物中共聚聚丙烯的二甲苯可溶物含量、可溶物中共聚单体含量及可溶物/共聚聚丙烯的特性粘数比：用Polymer Char公司的CRYST-EX仪器进行测试。使用三氯苯溶剂，升温至150℃进行溶解，恒温90min，取样测试，再降温至35℃，恒温70min，取样测试。
(18)丙烯接枝聚合物中共聚聚丙烯的重均分子量：用高温GPC测定，采用Polymer Laboratory公司的PL-GPC 220型凝胶渗透色谱，试样用1,2,4-三氯苯溶解，浓度为1.0mg/ml。测试温度150℃，溶液流速为1.0ml/min。以聚苯乙烯的分子量作为内参来制定标准曲线，根据流出时间计算样品的分子量及分子量分布。
(19)熔融温度Tm：采用差示扫描量热仪对材料的熔融过程和结晶过程进行分析。具体操作为：在氮气保护下，将5-10mg样品从20℃至200℃采用三段式升降温测量方法进行测量，以热流量的变化反映材料的熔融和结晶过程，从而计算熔融温度Tm。
(20)接枝效率GE、参数M1：将2-4g接枝产物放入索氏提取器中，用乙酸乙酯(对于含烯基的硅烷类单体作为接枝单体的情况，使用丙酮)抽提24小时，除去未反应的单体及其均聚物，得到纯的接枝产物，烘干称重，计算参数M1及接枝效率GE。
参数M1代表所述丙烯接枝聚合物中衍生自接枝单体的结构单元的总含量。M1和GE的计算公式如下：
Figure PCTCN2021125096-appb-000016
Figure PCTCN2021125096-appb-000017
以上公式中，w 0是PP基体的质量；w 1是接枝产物抽提前的质量；w 2是接枝产物抽提后的质量；w 3是加入接枝单体的总质量。
根据文献(张广平，螺带反应器中聚丙烯固相接枝马来酸酐，中国塑料，2002年2月第16卷第2期，69-71)中所描述的方法测试并计算马来酸酐的质量含量％G MAH。参数M2代表所述丙烯接枝聚合物中衍生自马来酸酐单体的接枝上的结构单元的含量。M2的计算公式如下：
Figure PCTCN2021125096-appb-000018
以上公式中，w 1是接枝产物抽提前的质量；w 2是接枝产物抽提后的质量；％G MAH是马来酸酐的质量含量。
(21)体积电阻率：按照GB/T 1410-2006中规定的方法进行测定。
实施例A1
(1)用于制备层a的丙烯聚合物组合物A的制备：
组分a为牌号为PPH-FA03的均聚聚丙烯(购自青岛炼化，熔体质量流动速率为3.1g/10min，等规度为98％，分子量分布Mw/Mn为4.7)；组分b为牌号为EP200K的丙烯抗冲共聚物(购自中沙石化，乙烯含量为8重量％，乙烯-丙烯共聚部分含量为13重量％，熔体质量流动速率为3.2g/10min)；组分c为牌号为6102的聚烯烃弹性体(购自埃克森公司，由丙烯和乙烯共聚得到，乙烯结构单元含量为16重量％)。将上述制得的各组分按配比进行称重并混合，其中组分a的质量份数Wa为75重量份，组分b的质量份数Wb为10重量份，组分c的质量份数Wc为15重量份。然后加入润滑剂(瑞士科莱恩公司生产的PEG润滑剂，分子量10000，且以上述组分a、组分b和组分c的质量之和为100重量份计，润滑剂的加入量为0.1重量份)，之后将混合物加入到高速搅拌器中混合均匀，再将混合好的物料加入到W&P公司制造的双螺杆挤出机的喂料器中，物料经由喂料器进入双螺杆中，加工过程中螺杆的温度保持在160-230℃之间，经螺杆熔融混合均匀、挤出、造粒并烘干。得到丙烯聚合物组合物A的粒料，经测量，其熔体质量流动速率MFR A＝3.6g/10min。
(2)用于制备层b的丙烯聚合物组合物B的制备：
组分x为牌号为F5006的无规丙烯共聚物(购自燕山石化，乙烯-丙烯-丁烯三元共聚物，熔体质量流动速率为5.2g/10min)；组分y为牌号为6102的聚烯烃弹性体(购自埃克森公司)。将上述制得的各组分按配比进行称重并混合，其中组分x的质量份数Wx为75重量份，组分y的质量份数Wy为25重量份。Wc：Wy为3:5。其他操作同步骤(1)中的操作，最后得到丙烯聚合物组合物B的粒料，经测量，其熔体质量流动速率MFR B＝3.2g/10min。
(3)复合薄膜的制备：
将上述步骤(1)和步骤(2)制得的丙烯聚合物组合物A和丙烯聚合物组合物B的粒料进行干燥，之后将丙烯聚合物组合物A加入多层挤出流延机的芯层挤出机中，将丙烯聚合物组合物B加入多层挤出流延机的上表层挤出机中，其中所述上表层挤出机中还需加入无机防粘剂(二氧化硅，日本水泽，牌号JC-50，下同)，防粘剂与丙烯聚合物组合物粒料的重量比均为0.02:1。在流延过程中，将流延急冷辊温度设定为30℃，然后收卷，制成复合薄膜，其由上表层(层b)和芯层(层a)构成。薄膜厚度为50μm，其中层b和层a 的厚度比为1:2。
所述复合薄膜切面的原子力显微镜照片如图3所示。其中黑色部分为橡胶相，橡胶相是分散的，条状的，彼此平行排列的。所述橡胶相的横轴平均尺寸为56nm，纵横比的平均值为10.3。
实施例A2
(1)用于制备层a的丙烯聚合物组合物A的制备：
组分a为牌号为PPH-FA03的均聚聚丙烯(购自青岛炼化，熔体质量流动速率为3.1g/10min，等规度为98％，分子量分布Mw/Mn为4.7)；组分b为牌号为M180R的丙烯抗冲共聚物(购自上海石化，乙烯含量为11重量％，乙烯-丙烯共聚部分含量为15重量％，熔体质量流动速率为2.0g/10min)；组分c为牌号为DF640的聚烯烃弹性体(由乙烯和丁烯共聚得到，丁烯结构单元含量为32重量％，购自三井公司)。将上述制得的各组分按配比进行称重并混合，其中组分a的质量份数Wa为65重量份，组分b的质量份数Wb为30重量份，组分c的质量份数Wc为5重量份。然后加入润滑剂(瑞士科莱恩公司生产的PEG润滑剂，分子量10000，且以上述组分a、组分b和组分c的质量之和为100重量份计，润滑剂的加入量为0.1重量份)，之后将混合物加入到高速搅拌器中混合均匀，再将混合好的物料加入到W&P公司制造的双螺杆挤出机的喂料器中，物料经由喂料器进入双螺杆中，加工过程中螺杆的温度保持在160-230℃之间，经螺杆熔融混合均匀、挤出、造粒并烘干，得到丙烯聚合物组合物A的粒料，经测量，其熔体质量流动速率MFR A＝3.2g/10min。
(2)用于制备层b的丙烯聚合物组合物B的制备：
组分x为牌号为F500EPS的无规丙烯共聚物(购自上海石化，乙烯-丙烯-丁烯三元共聚物，熔体质量流动速率为5.3g/10min)；组分y为牌号为DF640的聚烯烃弹性体(购自三井公司)。将上述制得的各组分按配比进行称重并混合，其中组分x的质量份数Wx为90重量份，组分y的质量份数Wy为10重量份。Wc：Wy为1:2。其他操作同步骤(1)中的操作，最后得到丙烯聚合物组合物B的粒料，经测量，其熔体质量流动速率MFR B＝5.2g/10min。
(3)复合薄膜的制备：
将上述步骤(1)和步骤(2)制得的丙烯聚合物组合物A和丙烯聚合物组合物B的粒料进行干燥，之后将丙烯聚合物组合物A加入多层挤出流延机的芯层挤出机中，将丙烯聚 合物组合物B加入多层挤出流延机的上表层挤出机和下表层挤出机中，其中所述上、下表层挤出机中还需加入无机防粘剂(二氧化硅，同上)，防粘剂与丙烯聚合物组合物粒料的重量比均为0.02:1。在流延铸膜过程中，将流延急冷辊温度设定为30℃，然后收卷，制成复合薄膜，其由上、下表层(层b；层c与层b的组成相同)和芯层(层a)构成。薄膜厚度为50μm，其中上、下表层厚度之和与芯层的厚度比为1:1。
实施例A3
(1)用于制备层a的丙烯聚合物组合物A的制备：
组分a为牌号为FC801的均聚聚丙烯(购自上海石化，熔体质量流动速率为7.8g/10min，等规度为98％，分子量分布Mw/Mn为4.8)；组分b为牌号为PPB-M02D的丙烯抗冲共聚物(购自茂名石化，乙烯含量为8重量％，乙烯-丙烯共聚部分含量为10重量％，乙烯-丙烯共聚部分含量为10重量％，其室温二甲苯可溶物中乙烯单元含量为36.3重量％，乙烯单元组[EEE]含量为18.5重量％，熔体质量流动速率为1.5g/10min)；组分c为牌号为EXACT3139的聚烯烃弹性体(由乙烯和辛烯共聚得到，辛烯结构单元含量为14重量％，购自埃克森公司)。将上述制得的各组分按配比进行称重并混合，其中组分a的质量份数Wa为55重量份，组分b的质量份数Wb为25重量份，组分c的质量份数Wc为20重量份。然后加入润滑剂(瑞士科莱恩公司生产的PEG润滑剂，分子量10000，且以上述组分a、组分b和组分c的质量之和为100重量份计，润滑剂的加入量为0.1重量份)，之后将混合物加入到高速搅拌器中混合均匀，再将混合好的物料加入到W&P公司制造的双螺杆挤出机的喂料器中，物料经由喂料器进入双螺杆中，加工过程中螺杆的温度保持在160-230℃之间，经螺杆熔融混合均匀、挤出、造粒并烘干，得到丙烯聚合物组合物A的粒料，经测量，其熔体质量流动速率MFR A＝6.6g/10min。
(2)用于制备层b的丙烯聚合物组合物B的制备：
组分x为牌号为F800EPS的无规丙烯共聚物(购自上海石化，为乙烯-丙烯-丁烯三元共聚物，熔体质量流动速率为8.2g/10min)；组分y为牌号为EXACT3139的聚烯烃弹性体(购自埃克森公司)。将上述制得的各组分按配比进行称重并混合，其中组分x的质量份数Wx为80重量份，组分y的质量份数Wy为20重量份。Wc：Wy为1:1。其他操作同步骤(1)中的操作，最后得到丙烯聚合物组合物B的粒料，经测量，其熔体质量流动速率MFR B＝7.9g/10min。
(3)复合薄膜的制备：
制备过程同实施例A1的步骤(3)。
实施例A4
(1)用于制备层a的丙烯聚合物组合物A的制备：
操作同实施例A1的步骤(1)，只是其中组分a的质量份数Wa为80重量份，组分b的质量份数Wb为18重量份，组分c的质量份数Wc为2重量份。最后得到丙烯聚合物组合物A的粒料，经测量，其熔体质量流动速率MFR A＝2.8g/10min。
(2)用于制备层b的丙烯聚合物组合物B的制备：
操作同实施例A1中的步骤(2)，只是其中组分x的质量份数Wx为92重量份，组分y的质量份数Wy为8重量份。Wc：Wy为1:4。最后得到丙烯聚合物组合物B的粒料，经测量，其熔体质量流动速率MFR B＝7.7g/10min。
(3)复合薄膜的制备：
操作同实施例A1的步骤(3)。薄膜厚度为50μm，其中层b和层a的厚度比为1:3。
实施例A5
(1)用于制备层a的丙烯聚合物组合物A的制备：
操作同实施例A3的步骤(1)，只是其中组分a的质量份数Wa为90重量份，组分b的质量份数Wb为5重量份，组分c的质量份数Wc为5重量份。得到丙烯聚合物组合物A的粒料，经测量，其熔体质量流动速率MFR A＝9.6g/10min。
(2)用于制备层b的丙烯聚合物组合物B的制备：
操作同实施例A3中的步骤(2)，其中组分x的质量份数Wx为80重量份，组分y的质量份数Wy为20重量份。Wc：Wy为1:4。最后得到丙烯聚合物组合物B的粒料，经测量，其熔体质量流动速率MFR B＝7.9g/10min。
(3)复合薄膜的制备：
操作同实施例A2的步骤(3)。薄膜厚度为50μm，其中上、下表层厚度之和与芯层的厚度比为2:1。
实施例A6
(1)用于制备层a的丙烯聚合物组合物A的制备：
操作同实施例A3的步骤(1)，只是其中组分a的质量份数Wa为50重量份，组分b 的质量份数Wb为40重量份，组分c的质量份数Wc为10重量份。得到丙烯聚合物组合物A的粒料，经测量，其熔体质量流动速率MFR A＝4.6g/10min。
(2)用于制备层b的丙烯聚合物组合物B的制备：
操作同实施例A3的步骤(2)，只是其中组分x的质量份数Wx为60重量份，组分y的质量份数Wy为40重量份。Wc：Wy为1:4。最后得到丙烯聚合物组合物B的粒料，经测量，其熔体质量流动速率MFR B＝9.8g/10min。
(3)复合薄膜的制备：
操作同实施例A3的步骤(3)。薄膜厚度为50μm，其中上表层厚度与芯层的厚度比为1:4。
实施例A7
(1)用于制备层a的丙烯聚合物组合物A的制备：
操作同实施例A1的步骤(1)，只是其中组分a的质量份数Wa为50重量份，组分b的质量份数Wb为20重量份，组分c的质量份数Wc为30重量份。得到丙烯聚合物组合物A的粒料，经测量，其熔体质量流动速率MFR A＝2.2g/10min。
(2)用于制备层b的丙烯聚合物组合物B的制备：
操作同实施例A1的步骤(2)，只是其中组分x的质量份数Wx为85重量份，组分y的质量份数Wy为15重量份。Wc：Wy为2:1。最后得到丙烯聚合物组合物B的粒料，经测量，其熔体质量流动速率MFR B＝4.5g/10min。
(3)复合薄膜的制备：
操作同实施例A1的步骤(3)。薄膜厚度为50μm，其中层b和层a的厚度比为1:3。
实施例A8
按照实施例A1的方法制备复合薄膜，只是在丙烯聚合物组合物A的制备中，组分a的质量份数Wa为40重量份，组分b的质量份数Wb为40重量份，组分c的质量份数Wc为20重量份。Wc：Wy为4:5。得到丙烯聚合物组合物A的粒料，经测量，其熔体质量流动速率MFR A＝2.8g/10min。
实施例A9
按照实施例A1的方法制备复合薄膜，只是在丙烯聚合物组合物A的制备中，组分a 的质量份数Wa为50重量份，组分b的质量份数Wb为45重量份，组分c的质量份数Wc为5重量份。Wc：Wy为1:5。得到丙烯聚合物组合物A的粒料，经测量，其熔体质量流动速率MFR A＝3.1g/10min。
实施例A10
按照实施例A1的方法制备复合薄膜。只是在丙烯聚合物组合物A的制备中，组分a的质量份数Wa为50重量份，组分b的质量份数Wb为10重量份，组分c的质量份数Wc为40重量份。Wc：Wy为8:5。得到丙烯聚合物组合物A的粒料，经测量，其熔体质量流动速率MFR A＝2.7g/10min。
实施例A11
按照实施例A1的方法制备复合薄膜。只是在丙烯聚合物组合物B的制备中，组分x的质量份数Wx为50重量份，组分y的质量份数Wy为50重量份。Wc：Wy为3:10。得到丙烯聚合物组合物B的粒料，经测量，其熔体质量流动速率MFR B＝4.7g/10min。
实施例A12
按照实施例A1的方法制备复合薄膜。只是丙烯聚合物组合物B仅含有组分x。
实施例A13
按照实施例A1的方法制备复合薄膜。只是在丙烯聚合物组合物B的制备中，组分x的质量份数Wx为92.5重量份，组分y的质量份数Wy为7.5重量份。Wc：Wy为2:1。最后得到丙烯聚合物组合物B的粒料，经测量，其熔体质量流动速率MFR B＝5.5g/10min。
实施例A14
按照实施例A1的方法制备复合薄膜。只是在丙烯聚合物组合物B的制备中，组分x的质量份数Wx为85重量份，组分y的质量份数Wy为15重量份。Wc：Wy为1:1。最后得到丙烯聚合物组合物B的粒料，经测量，其熔体质量流动速率MFR B＝5.1g/10min。
实施例A15
按照实施例A1的方法制备复合薄膜。只是在丙烯聚合物组合物B的制备中，组分x 的质量份数Wx为70重量份，组分y的质量份数Wy为30重量份。Wc：Wy为1:2。最后得到丙烯聚合物组合物B的粒料，经测量，其熔体质量流动速率MFR B＝4.4g/10min。
实施例A16
按照实施例A1的方法制备复合薄膜。只是在丙烯聚合物组合物B的制备中，组分x的质量份数Wx为40重量份，组分y的质量份数Wy为60重量份。Wc：Wy为1:4。最后得到丙烯聚合物组合物B的粒料，经测量，其熔体质量流动速率MFR B＝2.9g/10min。
实施例A17
按照实施例A1的方法制备复合薄膜，只是在丙烯聚合物组合物B的制备中，组分x的质量份数Wx为97重量份，组分y的质量份数Wy为3重量份。Wc：Wy为5:1。最后得到丙烯聚合物组合物B的粒料，经测量，其熔体质量流动速率MFR B＝6.0g/10min。
对比例A1
按照实施例A1的操作制备复合薄膜，只是仅使用丙烯聚合物组合物A挤出流延为单层薄膜，薄膜厚度为50μm。
对比例A2
按照实施例A2的操作制备复合薄膜，只是仅使用丙烯聚合物组合物B挤出流延为单层薄膜，薄膜厚度为50μm。
对比例A3
按照实施例A1的操作制备复合薄膜，只是丙烯聚合物组合物A中仅含有组分b。如图4所示，根据AFM观察，所述橡胶相的横轴平均尺寸为380nm，纵横比的平均值为23.4。
对比例A4
按照实施例A1的操作制备复合薄膜，只是丙烯聚合物组合物A中仅含有组分a和组分b，其中组分a的质量份数Wa为75重量份，组分b的质量份数Wb为25重量份。
对比例A5
按照实施例A1的操作制备复合薄膜，只是丙烯聚合物组合物A中仅含有组分a和组分c，其中组分a的质量份数Wa为75重量份，组分c的质量份数Wc为25重量份。
表1
Figure PCTCN2021125096-appb-000019
从表1中的结果可以得出，根据本发明的复合薄膜可同时具有很好的抗冲性能和光学性能，甚至具有很好的拉伸强度和很好的热封强度。与仅采用单层薄膜或者不是根据本发明的复合薄膜相比，本发明的复合薄膜可以达到上述各种性能的更好平衡，而且在挤出流延时，膜面的稳定性和厚度均匀性更好。
实施例B1
(1)用于制备层a的丙烯聚合物组合物A的制备：
组分a为牌号为PPH-FA03的均聚聚丙烯(购自青岛炼化，熔体质量流动速率为3.1g/10min，等规度为98％，分子量分布Mw/Mn为4.7)；组分b为牌号为6102的聚烯 烃弹性体(购自埃克森公司)。将上述制得的各组分按配比进行称重并混合，其中组分a的质量份数Wa为80重量份，组分b的质量份数Wb为20重量份。然后加入润滑剂(瑞士科莱恩公司生产的PEG润滑剂，分子量10000，且以上述组分a和组分b的质量之和为100重量份计，润滑剂的加入量为0.1重量份)，之后将混合物加入到高速搅拌器中混合均匀，再将混合好的物料加入到W&P公司制造的双螺杆挤出机的喂料器中，物料经由喂料器进入双螺杆中，加工过程中螺杆的温度保持在160-230℃之间，经螺杆熔融混合均匀、挤出、造粒并烘干，得到丙烯聚合物组合物A的粒料，经测量，其熔体质量流动速率MFR A＝3.5g/10min。
(2)用于制备层b的丙烯聚合物组合物B的制备：
组分x为牌号为F5006的无规丙烯共聚物(购自燕山石化，乙烯-丙烯-丁烯三元共聚物，熔体质量流动速率为5.2g/10min)；组分y为牌号为6102的聚烯烃弹性体(购自埃克森公司)；组分z为牌号为EP200K的丙烯抗冲共聚物(购自中沙石化，乙烯含量为8重量％，乙烯-丙烯共聚部分含量为13重量％，熔体质量流动速率为3.2g/10min)。将上述制得的各组分按配比进行称重并混合，其中组分x的质量份数Wx为85重量份，组分y的质量份数Wy为5重量份，组分z的质量份数Wz为10重量份。Wb：Wy为4:1。其他操作同步骤(1)中的操作，最后得到丙烯聚合物组合物B的粒料，经测量，其熔体质量流动速率MFR B＝4.7g/10min。
(3)复合薄膜的制备：
将上述步骤(1)和步骤(2)制得的丙烯聚合物组合物A和丙烯聚合物组合物B的粒料进行干燥，之后将丙烯聚合物组合物A加入多层挤出流延机的芯层挤出机中，将丙烯聚合物组合物B加入多层挤出流延机的上表层挤出机中，其中所述上表层挤出机中还需加入无机防粘剂(二氧化硅，同上)，防粘剂与丙烯聚合物组合物粒料的重量比均为0.02:1。在流延过程中，将流延急冷辊温度设定为30℃，收卷，制成复合薄膜，其由上表层(层b)和芯层(层a)构成。薄膜厚度为50μm，其中层b和层a的厚度比为1:2。
实施例B2
(1)用于制备层a的丙烯聚合物组合物A的制备：
组分a为牌号为M180R的丙烯抗冲共聚物(购自上海石化，乙烯含量为11重量％，乙烯-丙烯共聚部分含量为15重量％，熔体质量流动速率为2.0g/10min)；组分b为牌号为DF640的聚烯烃弹性体(购自三井公司)。将上述制得的各组分按配比进行称重并混合， 其中组分a的质量份数Wa为95重量份，组分b的质量份数Wb为5重量份。然后加入润滑剂(瑞士科莱恩公司生产的PEG润滑剂，分子量10000，且以上述组分a和组分b的质量之和为100重量份计，润滑剂的加入量为0.1重量份)，之后将混合物加入到高速搅拌器中混合均匀，再将混合好的物料加入到W&P公司制造的双螺杆挤出机的喂料器中，物料经由喂料器进入双螺杆中，加工过程中螺杆的温度保持在160-230℃之间，经螺杆熔融混合均匀、挤出、造粒并烘干，得到丙烯聚合物组合物A的粒料，经测量，其熔体质量流动速率MFR A＝3.1g/10min。
(2)用于制备层b的丙烯聚合物组合物B的制备：
组分x为牌号为F500EPS的无规丙烯共聚物(购自上海石化，乙烯-丙烯-丁烯三元共聚物，熔体质量流动速率为5.3g/10min)；组分y为牌号为DF640的聚烯烃弹性体(购自三井公司)；组分z为牌号为M180R的丙烯抗冲共聚物(购自上海石化，乙烯含量为11重量％，乙烯-丙烯共聚部分含量为15重量％，熔体质量流动速率为2.0g/10min)。将上述制得的各组分按配比进行称重并混合，其中组分x的质量份数Wx为60重量份，组分y的质量份数Wy为20重量份，组分z的质量份数Wz为20重量份。Wb：Wy为1:4。其他操作同步骤(1)中的操作，最后得到丙烯聚合物组合物B的粒料，经测量，其熔体质量流动速率MFR B＝4.4g/10min。
(3)复合薄膜的制备：
将上述步骤(1)和步骤(2)制得的丙烯聚合物组合物A和丙烯聚合物组合物B的粒料进行干燥，之后将丙烯聚合物组合物A加入多层挤出流延机的芯层挤出机中，将丙烯聚合物组合物B加入多层挤出流延机的上表层挤出机和下表层挤出机中，其中所述上、下表层挤出机中还需加入无机防粘剂(二氧化硅，同上)，防粘剂与丙烯聚合物组合物粒料的重量比均为0.02:1。在流延铸膜过程中，将流延急冷辊温度设定为30℃，收卷，制成复合薄膜，其由上、下表层(层b；层c与层b的组成相同)和芯层(层a)构成。薄膜厚度为50μm，其中上、下表层厚度和与芯层的厚度比为1:1。
实施例B3
(1)用于制备层a的丙烯聚合物组合物A的制备：
组分a为牌号为FC801的均聚聚丙烯(购自上海石化，熔体质量流动速率为7.8g/10min，等规度为98％，分子量分布Mw/Mn为4.8)；组分b为牌号为EXACT3139的聚烯烃弹性体(购自埃克森公司)。将上述制得的各组分按配比进行称重并混合，其中 组分a的质量份数Wa为85重量份，组分b的质量份数Wb为15重量份。然后加入润滑剂(瑞士科莱恩公司生产的PEG润滑剂，分子量10000，且以上述组分a和组分b的质量之和为100重量份计，润滑剂的加入量为0.1重量份)，之后将混合物加入到高速搅拌器中混合均匀，再将混合好的物料加入到W&P公司制造的双螺杆挤出机的喂料器中，物料经由喂料器进入双螺杆中，加工过程中螺杆的温度保持在160-230℃之间，经螺杆熔融混合均匀、挤出、造粒并烘干，得到丙烯聚合物组合物A的粒料，经测量，其熔体质量流动速率MFR A＝7.9g/10min。
(2)用于制备层b的丙烯聚合物组合物B的制备：
组分x为牌号为F800EPS的无规丙烯共聚物(购自上海石化)；组分y为牌号为EXACT3139的聚烯烃弹性体(购自埃克森公司)；组分z为牌号为PPB-M02D的聚丙烯抗冲共聚物(购自茂名石化)。将上述制得的各组分按配比进行称重并混合，其中组分x的质量份数Wx为85重量份，组分y的质量份数Wy为10重量份，组分z的质量份数Wz为5重量份。Wb：Wy为3:2。其他操作同步骤(1)中的操作，最后得到丙烯聚合物组合物B的粒料，经测量，其熔体质量流动速率MFR B＝7.4g/10min。
(3)复合薄膜的制备：
制备过程同实施例B1的步骤(3)。
实施例B4
(1)用于制备层a的丙烯聚合物组合物A的制备：
操作同实施例B1的步骤(1)，只是组分a的质量份数Wa为70重量份，组分b的质量份数Wb为30重量份。得到丙烯聚合物组合物A的粒料，经测量，其熔体质量流动速率MFR A＝3.2g/10min。
(2)用于制备层b的丙烯聚合物组合物B的制备：
操作同实施例B1的步骤(2)，只是其中组分x的质量份数Wx为90重量份，组分y的质量份数Wy为5重量份，组分z的质量份数Wz为5重量份。Wb：Wy为6:1。其他操作同步骤(1)中的操作，最后得到丙烯聚合物组合物B的粒料，经测量，其熔体质量流动速率MFR B＝8.2g/10min。
(3)复合薄膜的制备：
操作同实施例B1的步骤(3)。薄膜厚度为50μm，其中层b和层a的厚度比为1:3。
实施例B5
(1)用于制备层a的丙烯聚合物组合物A的制备：
操作同实施例B3的步骤(1)，只是其中组分a的质量份数Wa为75重量份，组分b的质量份数Wb为25重量份。得到丙烯聚合物组合物A的粒料，经测量，其熔体质量流动速率MFR A＝9.3g/10min。
(2)用于制备层b的丙烯聚合物组合物B的制备：
操作同实施例B3的步骤(2)，只是其中组分x的质量份数Wx为85重量份，组分y的质量份数Wy为13重量份，组分z的质量份数Wz为2重量份。Wb：Wy为25:13。最后得到丙烯聚合物组合物B的粒料，经测量，其熔体质量流动速率MFR B＝9.2g/10min。
(3)复合薄膜的制备：
操作同实施例B2额步骤(3)。薄膜厚度为50μm，其中上、下表层厚度之和与芯层的厚度比为2:1。
实施例B6
(1)用于制备层a的丙烯聚合物组合物A的制备：
操作同实施例B3的步骤(1)，只是其中组分a的质量份数Wa为100重量份。得到丙烯聚合物组合物A的粒料，经测量，其熔体质量流动速率MFR A＝7.8g/10min。
(2)用于制备层b的丙烯聚合物组合物B的制备：
操作同实施例B3的步骤(2)，只是其中组分x的质量份数Wx为50重量份，组分y的质量份数Wy为30重量份，组分z的质量份数Wz为20重量份。最后得到丙烯聚合物组合物B的粒料，经测量，其熔体质量流动速率MFR B＝6.8g/10min。
(3)复合薄膜的制备：
操作同实施例B3的步骤(3)。薄膜厚度为50μm，其中上表层厚度与芯层的厚度比为1:4。
实施例B7
(1)用于制备层a的丙烯聚合物组合物A的制备：
操作同实施例B1的步骤(1)。其中组分a的质量份数Wa为100重量份。得到丙烯聚合物组合物A的粒料，经测量，其熔体质量流动速率MFR A＝3.1g/10min。
(2)用于制备层b的丙烯聚合物组合物B的制备：
操作同实施例B1的步骤(2)，只是其中组分x的质量份数Wx为50重量份，组分y的质量份数Wy为20重量份，组分z的质量份数Wz为30重量份。其他操作同步骤(1)中的操作，最后得到丙烯聚合物组合物B的粒料，经测量，其熔体质量流动速率MFR B＝3.5g/10min。
(3)复合薄膜的制备：
操作同实施例B1的步骤(3)。薄膜厚度为50μm，其中层b和层a的厚度比为1:3。
实施例B8
按照实施例B1的方法制备复合薄膜，只是在丙烯聚合物组合物A的制备中，组分a的质量份数Wa为100重量份。最后得到丙烯聚合物组合物A的粒料，经测量，其熔体质量流动速率MFR A＝3.1g/10min。
实施例B9
按照实施例B1的方法制备复合薄膜，只是在丙烯聚合物组合物A的制备中，组分a的质量份数Wa为50重量份，组分b的质量份数Wb为50重量份。Wb：Wy为10:1。最后得到丙烯聚合物组合物A的粒料，经测量，其熔体质量流动速率MFR A＝3.5g/10min。
实施例B10
按照实施例B1的方法制备复合薄膜，只是在丙烯聚合物组合物B的制备中，组分x的质量份数Wx为40重量份，组分y的质量份数Wy为30重量份，组分z的质量份数Wz为30重量份。Wb：Wy为2:3。得到丙烯聚合物组合物B的粒料，经测量，其熔体质量流动速率MFR B＝4.5g/10min。
实施例B11
按照实施例B1的方法制备复合薄膜，只是在丙烯聚合物组合物B的制备中，组分x的质量份数Wx为50重量份，组分y的质量份数Wy为40重量份，组分z的质量份数Wz为10重量份。Wb：Wy为1:2。得到丙烯聚合物组合物B的粒料，经测量，其熔体质量流动速率MFR B＝5.0g/10min。
实施例B12
按照实施例B1的方法制备复合薄膜。只是在丙烯聚合物组合物B的制备中，组分x的质量份数Wx为50重量份，组分y的质量份数Wy为10重量份，组分z的质量份数Wz为40重量份。Wb：Wy为2:1。得到丙烯聚合物组合物B的粒料，经测量，其熔体质量流动速率MFR B＝4.8g/10min。
实施例B13
按照实施例B1的方法制备复合薄膜，只是在丙烯聚合物组合物A的制备中，组分a的质量份数Wa为99重量份，组分b的质量份数Wb为1重量份。Wb：Wy为1:5。最后得到丙烯聚合物组合物B的粒料，经测量，其熔体质量流动速率MFR A＝3.2g/10min。
实施例B14
按照实施例B1的方法制备复合薄膜，只是在丙烯聚合物组合物A的制备中，组分a的质量份数Wa为97.5重量份，组分b的质量份数Wb为2.5重量份。Wb：Wy为1:2。最后得到丙烯聚合物组合物B的粒料，经测量，其熔体质量流动速率MFR A＝3.1g/10min。
实施例B15
按照实施例B1的方法制备复合薄膜，只是在丙烯聚合物组合物A的制备中，组分a的质量份数Wa为95重量份，组分b的质量份数Wb为5重量份。Wb：Wy为1:1。最后得到丙烯聚合物组合物B的粒料，经测量，其熔体质量流动速率MFR A＝3.2g/10min。
实施例B16
按照实施例B1的方法制备复合薄膜。只是在丙烯聚合物组合物A的制备中，组分a的质量份数Wa为90重量份，组分b的质量份数Wb为10重量份。Wb：Wy为2:1。最后得到丙烯聚合物组合物B的粒料，经测量，其熔体质量流动速率MFR A＝3.3g/10min。
实施例B17
按照实施例B1的方法制备复合薄膜，只是在丙烯聚合物组合物A的制备中，组分a的质量份数Wa为75重量份，组分b的质量份数Wb为25重量份。Wb：Wy为5:1。最后得到丙烯聚合物组合物B的粒料，经测量，其熔体质量流动速率MFR A＝3.1g/10min。
对比例B1
按照实施例B1的方法制备复合薄膜，只是仅使用丙烯聚合物组合物A挤出流延为单层薄膜，薄膜厚度为50μm。
对比例B2
按照实施例B2的方法制备复合薄膜，只是仅使用丙烯聚合物组合物B挤出流延为单层薄膜，薄膜厚度为50μm。
对比例B3
按照实施例B1的方法制备复合薄膜，只是丙烯聚合物组合物B仅含有组分x。
对比例B4
按照实施例B1的方法制备复合薄膜，只是丙烯聚合物组合物B中仅含有组分x和组分y，其中组分x的质量份数Wx为85重量份，组分y的质量份数Wy为15重量份。
实施例B18
按照实施例B2的方法制备复合薄膜，只是丙烯聚合物组合物B中仅含有组分x和组分z，其中组分x的质量份数Wx为70重量份，组分z的质量份数Wz为30重量份。
表2
Figure PCTCN2021125096-appb-000020
从表2中的结果可以得出，根据本发明的复合薄膜同时具有很好的抗冲性能和光学性能，甚至具有很好的拉伸性能和很好的热封强度。与仅采用单层薄膜或者不是根据本发明的复合薄膜相比，本发明的复合薄膜可以达到各种性能的良好平衡，而且在挤出流延时，膜面的稳定性和厚度均匀性更好。
实施例C1
基本重复实施例A1的操作，只是将步骤(1)和(2)中使用的聚烯烃弹性体替换为牌号为8200的聚烯烃弹性体(购自陶氏公司，为乙烯-1-辛烯共聚物，辛烯结构单元含量为38重量％，该聚烯烃弹性体在230℃、剪切速率160r -1和640r -1下的剪切黏度之比η 160/η 640为2.18，且该弹性体在230℃、剪切速率640r -1下的剪切黏度η 640为185Pa·s)；步骤(3) 中防粘剂与丙烯聚合物组合物粒料的重量比均为0.2:100。其中熔体质量流动速率MFR A＝3.8g/10min，MFR B＝4.2g/10min。
所述复合薄膜切面的原子力显微镜照片如图5所示。其中黑色部分为橡胶相，橡胶相是分散的，条状的，彼此平行排列的。所述橡胶相的横轴平均尺寸为84nm，纵横比的平均值为8.8。
实施例C2
基本重复实施例A2的操作，只是将步骤(1)和(2)中使用的聚烯烃弹性体替换为DF840的聚烯烃弹性体(购自三井公司，为乙烯-1-丁烯共聚物，丁烯结构单元含量为25重量％，该聚烯烃弹性体在230℃、剪切速率160r -1和640r -1下的剪切黏度之比η 160/η 640为1.75，且弹性体在230℃、剪切速率640r -1下的剪切黏度η 640为398Pa·s)；步骤(3)中防粘剂与丙烯聚合物组合物粒料的重量比均为0.2:100。其中熔体质量流动速率MFR A＝3.4g/10min，MFR B＝5.6g/10min。
在原子力显微镜下观察该复合薄膜，可见分散的、条状、互相平行的橡胶相，所述橡胶相的横轴平均尺寸为105nm，纵横比的平均值为8.5。
实施例C3
(1)用于制备层a的丙烯聚合物组合物A的制备：
组分a为牌号为FC801的均聚聚丙烯(购自上海石化，熔体质量流动速率为7.8g/10min，等规度为98％，分子量分布Mw/Mn为4.8)；组分b为牌号为PPB-M02D的丙烯抗冲共聚物(购自茂名石化，乙烯含量为8重量％，乙烯-丙烯共聚部分含量为10重量％，其室温二甲苯可溶物中乙烯单元含量为36.3重量％，乙烯单元组[EEE]含量为18.5重量％，熔体质量流动速率为1.5g/10min)；组分c为牌号为VM3980的聚烯烃弹性体(购自埃克森公司，丙烯-乙烯共聚物，乙烯结构单元含量为9重量％，该聚烯烃弹性体在230℃、剪切速率160r -1和640r -1下的剪切黏度之比η 160/η 640为2.26，且该弹性体在230℃、剪切速率640r -1下的剪切黏度η 640为205Pa·s)。将上述制得的各组分按配比进行称重并混合，其中组分a的质量份数Wa为55重量份，组分b的质量份数Wb为25重量份，组分c的质量份数Wc为20重量份。然后加入润滑剂(瑞士科莱恩公司生产的PEG润滑剂，分子量10000，且以上述组分a、组分b和组分c的质量之和为100重量份计，润滑剂的加入量为0.1重量份)，之后将混合物加入到高速搅拌器中混合均匀，再将混合好的物料加入到 W&P公司制造的双螺杆挤出机的喂料器中，物料经由喂料器进入双螺杆中，加工过程中螺杆的温度保持在160-230℃之间，经螺杆熔融混合均匀、挤出、造粒并烘干，得到丙烯聚合物组合物A的粒料，经测量，其熔体质量流动速率MFR A＝7.0g/10min。
(2)用于制备层b的丙烯聚合物组合物B的制备：
组分x为牌号为F800EDF的无规丙烯共聚物(购自上海石化，丙烯-乙烯二元共聚物，熔体质量流动速率为7.8g/10min)；组分y为牌号为VM3980的聚烯烃弹性体(购自埃克森公司，丙烯-乙烯共聚物，乙烯结构单元含量为9重量％，该聚烯烃弹性体在230℃、剪切速率160r -1和640r -1下的剪切黏度之比η 160/η 640为2.26，且弹性体在230℃、剪切速率640r -1下的剪切黏度η 640为205Pa·s)。将上述制得的各组分按配比进行称重并混合，其中组分x的质量份数Wx为80重量份，组分y的质量份数Wy为20重量份。其他操作同步骤(1)中的操作，最后得到丙烯聚合物组合物B的粒料，经测量，其熔体质量流动速率MFR B＝8.3g/10min。
(3)复合薄膜的制备：
将上述步骤(1)和步骤(2)制得的丙烯聚合物组合物A和丙烯聚合物组合物B的粒料进行干燥，之后将丙烯聚合物组合物A加入多层挤出流延机的芯层挤出机中，将丙烯聚合物组合物B加入多层挤出流延机的上表层挤出机和下表层挤出机中，其中，所述上、下表层挤出机中加入无机防粘剂(二氧化硅，同上)，防粘剂与丙烯聚合物组合物粒料的重量比均为0.2:100。在流延铸膜过程中，将流延急冷辊温度设定为30℃，收卷，制成复合薄膜，其由上、下表层(层b；层c与层b的组成相同)和芯层(层a)构成。薄膜厚度为50μm，其中上、下表层厚度之和与芯层的厚度比为1:4。
在原子力显微镜下观察该复合薄膜，可见分散的、条状、互相平行的橡胶相，所述橡胶相的横轴平均尺寸为88nm，纵横比的平均值为9.6。
实施例C4
(1)用于制备层a的丙烯聚合物组合物A的制备：
操作同实施例C1的步骤(1)，只是组分a的质量份数Wa为80重量份，组分b的质量份数Wb为18重量份，组分c的质量份数Wc为2重量份。其中组分c为牌号为8411的聚烯烃弹性体(购自陶氏公司，为乙烯-1-辛烯共聚物，辛烯结构单元含量为36重量％)。该聚烯烃弹性体在230℃、剪切速率160r -1和640r -1下的剪切黏度之比η 160/η 640为1.80，且弹性体在230℃、剪切速率640r -1下的剪切黏度η 640为148Pa·s)。得到丙烯聚合物组合 物A的粒料，经测量，其熔体质量流动速率MFR A＝2.6g/10min。
(2)用于制备层b的丙烯聚合物组合物B的制备：
操作同实施例C1的步骤(2)，只是组分x的质量份数Wx为92重量份，组分y的质量份数Wy为8重量份。其他操作同步骤(1)中的操作，最后得到丙烯聚合物组合物B的粒料，经测量，其熔体质量流动速率MFR B＝7.5g/10min。
(3)复合薄膜的制备：
操作同实施例C1的步骤(3)。薄膜厚度为50μm，其中层b和层a的厚度比为1:6。
在原子力显微镜下观察该复合薄膜，可见分散的、条状、互相平行的橡胶相，所述橡胶相的横轴的平均尺寸为196nm，纵横比的平均值为5.3。
实施例C5
(1)用于制备层a的丙烯聚合物组合物A的制备：
操作同实施例C1的步骤(1)，只是组分a的质量份数Wa为90重量份，组分b的质量份数Wb为5重量份，组分c的质量份数Wc为5重量份。得到丙烯聚合物组合物A的粒料，经测量，其熔体质量流动速率MFR A＝3.0g/10min。
(2)用于制备层b的丙烯聚合物组合物B的制备：
操作同实施例C1的步骤(2)，只是组分x的质量份数Wx为80重量份，组分y的质量份数Wy为20重量份。最后得到丙烯聚合物组合物B的粒料，经测量，其熔体质量流动速率MFR B＝3.5g/10min。
(3)复合薄膜的制备：
操作同实施例C2的步骤(3)。薄膜厚度为50μm，其中上、下表层厚度之和与芯层的厚度比为2:1。
实施例C6
(1)用于制备层a的丙烯聚合物组合物A的制备：
操作同实施例C3的步骤(1)，只是组分a的质量份数Wa为50重量份，组分b的质量份数Wb为40重量份，组分c的质量份数Wc为10重量份。得到丙烯聚合物组合物A的粒料，经测量，其熔体质量流动速率MFR A＝4.8g/10min。
(2)用于制备层b的丙烯聚合物组合物B的制备：
操作同实施例C3的步骤(2)，只是组分x的质量份数Wx为60重量份，组分y的质 量份数Wy为40重量份。最后得到丙烯聚合物组合物B的粒料，经测量，其熔体质量流动速率MFR B＝9.6g/10min。
(3)复合薄膜的制备：操作同实施例C3的步骤(3)。
在原子力显微镜下观察该复合薄膜，可见分散的、条状、互相平行的橡胶相，所述橡胶相的横轴的平均尺寸为23nm，纵横比的平均值为19.8。
实施例C7
(1)用于制备层a的丙烯聚合物组合物A的制备：
操作同实施例C1，只是组分a的质量份数Wa为50重量份，组分b的质量份数Wb为20重量份，组分c的质量份数Wc为30重量份。得到丙烯聚合物组合物A的粒料，经测量，其熔体质量流动速率MFR A＝2.0g/10min。
(2)用于制备层b的丙烯聚合物组合物B的制备：
操作同实施例C1的步骤(2)，只是组分x的质量份数Wx为85重量份，组分y的质量份数Wy为15重量份。其他操作同步骤(1)中的操作，最后得到丙烯聚合物组合物B的粒料，经测量，其熔体质量流动速率MFR B＝4.3g/10min。
(3)复合薄膜的制备：
操作同实施例C1。薄膜厚度为50μm，其中层b和层a的厚度比为1:3。
在原子力显微镜下观察该复合薄膜，可见分散的、条状、互相平行的橡胶相，所述橡胶相的横轴的平均尺寸为145nm，纵横比的平均值为12.1。
实施例C8
按照实施例C1的方法制备丙烯聚合物薄膜。不同的是，在丙烯聚合物组合物A的制备中，组分a的质量份数Wa为40重量份，组分b的质量份数Wb为40重量份，组分c的质量份数Wc为20重量份。得到丙烯聚合物组合物A的粒料，经测量，其熔体质量流动速率MFR A＝3.1g/10min。
在原子力显微镜下观察该复合薄膜，可见分散的、条状、互相平行的橡胶相，所述橡胶相的横轴的平均尺寸为88nm，纵横比的平均值为17.0。
实施例C9
按照实施例C1的方法制备丙烯聚合物薄膜，不同的是，在丙烯聚合物组合物B的制 备中，组分x的质量份数Wx为95重量份，组分y的质量份数Wy为5重量份。最后得到丙烯聚合物组合物B的粒料，经测量，其熔体质量流动速率MFR B＝5.5g/10min。
实施例C10
按照实施例C1的方法制备丙烯聚合物薄膜，不同的是，在丙烯聚合物组合物B的制备中，组分x的质量份数Wx为70重量份，组分y的质量份数Wy为30重量份。最后得到丙烯聚合物组合物B的粒料，经测量，其熔体质量流动速率MFR B＝4.7g/10min。
实施例C11
按照实施例C1的方法制备丙烯聚合物薄膜，不同的是，在丙烯聚合物组合物B的制备中，组分x的质量份数Wx为40重量份，组分y的质量份数Wy为60重量份。最后得到丙烯聚合物组合物B的粒料，经测量，其熔体质量流动速率MFR B＝3.2g/10min。
实施例C12
按照实施例C3的方法制备丙烯聚合物组合物A，按照实施例C2的方法制备丙烯聚合物组合物B，使(ηA 160-ηB 160)和(ηA 640-ηB 640)均小于0。按照实施例C3的方法制备复合薄膜。
对比例C1
按照实施例C1的方法制备丙烯聚合物薄膜，不同的是，在丙烯聚合物组合物A的制备过程中，将聚烯烃弹性体c换为牌号为DF740的聚烯烃弹性体(购自三井公司，丁烯结构单元含量为28重量％，该聚烯烃弹性体在230℃、剪切速率160r -1和640r -1下的剪切黏度之比η 160/η 640为1.63，且弹性体在230℃、剪切速率640r -1下的剪切黏度η 640为554Pa·s)。最后得到丙烯聚合物组合物A的粒料，经测量，其熔体质量流动速率MFR A＝2.4g/10min。
对比例C2
按照实施例C2的方法制备丙烯聚合物薄膜，不同的是，在丙烯聚合物组合物B的制备过程中，将聚烯烃弹性体y换为牌号为8400的聚烯烃弹性体(购自陶氏公司，丙烯-辛烯共聚物，辛烯结构单元含量为35％。该聚烯烃弹性体在230℃、剪切速率160r -1和640r -1下的剪切黏度之比η 160/η 640为2.45，且弹性体在230℃、剪切速率640r -1下的剪切黏度η 640 为84Pa·s)。最后得到丙烯聚合物组合物B的粒料，经测量，其熔体质量流动速率MFR B＝8.4g/10min。
对比例C3
按照实施例C1的方法制备复合薄膜，不同的是，丙烯聚合物组合物B仅含有组分x。
对比例C4
按照实施例C1的方法制备复合薄膜，不同的是，丙烯聚合物组合物A中仅含有组分a和组分b，其中组分a的质量份数Wa为75重量份，组分b的质量份数Wb为25重量份。
对比例C5
按照实施例C1的方法制备复合薄膜，不同的是，丙烯聚合物组合物A中仅含有组分a和组分c，其中组分a的质量份数Wa为75重量份，组分c的质量份数Wc为25重量份。
表3
Figure PCTCN2021125096-appb-000021
表4
Figure PCTCN2021125096-appb-000022
从表3和表4中的结果可以得出，根据本发明的复合薄膜同时具有良好的抗冲性能和光学性能，甚至具有良好的薄膜均匀性，尤其是当采用具有特定剪切黏度的聚烯烃弹性体时，在挤出流延时，膜面稳定，薄膜厚度均匀性和抗冲击性能的均匀性大幅提高。
实施例D1
基本重复实施例B1的操作，不同的是：
将步骤(1)中使用的聚烯烃弹性体替换为牌号为8411的聚烯烃弹性体(购自陶氏公司，乙烯-1-辛烯共聚物，辛烯结构单元含量为36重量％，该聚烯烃弹性体在230℃、剪切速率160r -1和640r -1下的剪切黏度之比η 160/η 640为1.80，且弹性体在230℃、剪切速率640r -1下的剪切黏度为148Pa·s)，得到的丙烯聚合物组合物A的粒料的熔体质量流动速率MFR A＝3.4g/10min。
将步骤(2)中使用的聚烯烃弹性体替换为牌号为8200的聚烯烃弹性体(购自陶氏公司，乙烯-1-辛烯共聚物，辛烯结构单元含量为38重量％，该聚烯烃弹性体在230℃、剪切速率160r -1和640r -1下的剪切黏度之比η 160/η 640为2.18，且该弹性体在230℃、剪切速率640r -1下的剪切黏度η 640为185Pa·s)。得到的丙烯聚合物组合物B的粒料的熔体质量流动速率MFR B＝4.9g/10min。
步骤(3)中防粘剂与丙烯聚合物组合物粒料的重量比均为0.2:100。
在原子力显微镜下观察该复合薄膜，可见分散的、条状、互相平行的橡胶相，所述橡胶相的横轴平均尺寸为72nm，纵横比的平均值为5.5。
实施例D2
基本重复实施例B2的操作，不同的是，将步骤(1)和(2)中使用的聚烯烃弹性体替换为DF840的聚烯烃弹性体(购自三井公司，乙烯-1-丁烯共聚物，丁烯结构单元含量为25重量％，该聚烯烃弹性体在230℃、剪切速率160r -1和640r -1下的剪切黏度之比η 160/η 640为1.75，且弹性体在230℃、剪切速率640r -1下的剪切黏度η 640为398Pa·s)；步骤(3)中防粘剂与丙烯聚合物组合物粒料的重量比均为0.2:100。其中熔体质量流动速率MFR A＝3.3g/10min，MFR B＝4.5g/10min。
在原子力显微镜下观察该复合薄膜，可见分散的、条状、互相平行的橡胶相，所述橡胶相的横轴平均尺寸为130nm，纵横比的平均值为6.4。
实施例D3
(1)用于制备层a的丙烯聚合物组合物A的制备
组分a为牌号为FC801的均聚聚丙烯(购自上海石化，熔体质量流动速率为 7.8g/10min，等规度为98％，分子量分布Mw/Mn为4.8)；组分b为牌号为VM3980的聚烯烃弹性体(购自埃克森公司，丙烯-乙烯共聚物，乙烯结构单元含量为9重量％，该聚烯烃弹性体在230℃、剪切速率160r -1和640r -1下的剪切黏度之比η 160/η 640为2.26，且弹性体在230℃、剪切速率640r -1下的剪切黏度为205Pa·s)。将上述制得的各组分按配比进行称重并混合，其中组分a的质量份数Wa为85重量份，组分b的质量份数Wb为15重量份。然后加入润滑剂(瑞士科莱恩公司生产的PEG润滑剂，分子量10000，且以上述组分a和组分b的质量之和为100重量份计，润滑剂的加入量为0.1重量份)，之后将混合物加入到高速搅拌器中混合均匀，再将混合好的物料加入到W&P公司制造的双螺杆挤出机的喂料器中，物料经由喂料器进入双螺杆中，加工过程中螺杆的温度保持在160-230℃之间，经螺杆熔融混合均匀、挤出、造粒并烘干，得到丙烯聚合物组合物A的粒料，经测量，其熔体质量流动速率MFR A＝7.4g/10min。
(2)用于制备层b的丙烯聚合物组合物B的制备
组分x为牌号为F800EDF的丙烯无规共聚物(购自上海石化，为乙烯-丙烯二元共聚物，熔体质量流动速率为7.8g/10min)；组分y为牌号为VM3980的聚烯烃弹性体(购自埃克森公司，丙烯-乙烯共聚物，乙烯结构单元含量为9重量％，该聚烯烃弹性体在230℃、剪切速率160r -1和640r -1下的剪切黏度之比η 160/η 640为2.26，且弹性体在230℃、剪切速率640r -1下的剪切黏度为205Pa·s)；组分z为牌号为PPB-M02D的丙烯抗冲共聚物(购自茂名石化，乙烯含量为8重量％，乙烯-丙烯共聚部分含量为10重量％，其室温二甲苯可溶物中乙烯单元含量为36.3重量％，乙烯单元组[EEE]含量为18.5重量％，熔体质量流动速率为1.5g/10min)。将上述制得的各组分按配比进行称重并混合，其中组分x的质量份数Wx为85重量份，组分y的质量份数Wy为10重量份，组分z的质量份数Wz为5重量份。其他操作同步骤(1)的操作，最后得到丙烯聚合物组合物B的粒料，经测量，其熔体质量流动速率MFR B＝7.9g/10min。
(3)复合薄膜的制备
制备过程同实施例D1的步骤(3)。
在原子力显微镜下观察该复合薄膜，可见分散的、条状、互相平行的橡胶相，所述橡胶相的横轴的平均尺寸为72nm，纵横比的平均值为13.2。
实施例D4
(1)用于制备层a的丙烯聚合物组合物A的制备
操作同实施例D1的步骤(1)，不同的是，组分a的质量份数Wa为70重量份，组分b的质量份数Wb为30重量份。得到丙烯聚合物组合物A的粒料，经测量，其熔体质量流动速率MFR A＝3.5g/10min。
(2)用于制备层b的丙烯聚合物组合物B的制备
操作同实施例D1的步骤(2)，不同的是，组分x的质量份数Wx为90重量份，组分y的质量份数Wy为5重量份，组分z的质量份数Wz为5重量份。其他操作同步骤(1)的操作，最后得到丙烯聚合物组合物B的粒料，经测量，其熔体质量流动速率MFR B＝5.2g/10min。
(3)复合薄膜的制备：
操作同实施例D1的步骤(3)。薄膜厚度为50μm，其中层b和层a的厚度比为1:3。
实施例D5
(1)用于制备层a的丙烯聚合物组合物A的制备
操作同实施例D3的步骤(1)，不同的是，组分a的质量份数Wa为75重量份，组分b的质量份数Wb为25重量份。得到丙烯聚合物组合物A的粒料，经测量，其熔体质量流动速率MFR A＝9.0g/10min。
(2)用于制备层b的丙烯聚合物组合物B的制备
操作同实施例D3的步骤(2)，不同的是，组分x的质量份数Wx为85重量份，组分y的质量份数Wy为13重量份，组分z的质量份数Wz为2重量份。最后得到丙烯聚合物组合物B的粒料，经测量，其熔体质量流动速率MFR B＝9.3g/10min。
(3)复合薄膜的制备：
步骤同实施例D2。薄膜厚度为50μm，其中上、下表层厚度之和与芯层的厚度比为2:1。
实施例D6
(1)用于制备层a的丙烯聚合物组合物A的制备
操作同实施例D3的步骤(1)。
(2)用于制备层b的丙烯聚合物组合物B的制备
操作同实施例D3的步骤(2)，不同的是，组分x的质量份数Wx为50重量份，组分y的质量份数Wy为30重量份，组分y为牌号为8411的聚烯烃弹性体(乙烯-1-辛烯共聚物，辛烯结构单元含量为36重量％，购自陶氏公司，该聚烯烃弹性体在230℃、剪切速率 160r -1和640r -1下的剪切黏度之比η 160/η 640为1.80，且弹性体在230℃、剪切速率640r -1下的剪切黏度为148Pa·s)。组分z的质量份数Wz为20重量份。最后得到丙烯聚合物组合物B的粒料，经测量，其熔体质量流动速率MFR B＝9.0g/10min。
(3)复合薄膜的制备：
操作同实施例D3的步骤(3)。薄膜厚度为50μm，其中上表层厚度与芯层的厚度比为1:4。
在原子力显微镜下观察该复合薄膜，可见分散的、条状、互相平行的橡胶相，所述橡胶相的横轴的平均尺寸为25nm，纵横比的平均值为19.7。
实施例D7
(1)用于制备层a的丙烯聚合物组合物A的制备
操作同实施例D1的步骤(1)。
(2)用于制备层b的丙烯聚合物组合物B的制备
操作同实施例D1的步骤(2)，不同的是，组分x的质量份数Wx为50重量份，组分y的质量份数Wy为20重量份，组分z的质量份数Wz为30重量份。其他操作同步骤(1)的操作，最后得到丙烯聚合物组合物B的粒料，经测量，其熔体质量流动速率MFR B＝3.7g/10min。
(3)复合薄膜的制备：
操作同实施例D1的步骤(3)。薄膜厚度为50μm，其中层b和层a的厚度比为1:3。
在原子力显微镜下观察该复合薄膜，可见分散的、条状、互相平行的橡胶相，所述橡胶相的横轴的平均尺寸为67nm，纵横比的平均值为17.5。
实施例D8
按照实施例D1的方法制备复合薄膜，不同的是，在丙烯聚合物组合物A的制备中，组分a的质量份数Wa为50重量份，组分b的质量份数Wb为50重量份。最后得到丙烯聚合物组合物A的粒料，经测量，其熔体质量流动速率MFR A＝3.6g/10min。
在原子力显微镜下观察该复合薄膜，可见分散的、条状、互相平行的橡胶相，所述橡胶相的横轴的平均尺寸为190nm，纵横比的平均值为5.1。
实施例D9
按照实施例D1的方法制备复合薄膜，不同的是，在丙烯聚合物组合物B的制备中，组分x的质量份数Wx为40重量份，组分y的质量份数Wy为30重量份，组分z的质量份数Wz为30重量份。得到丙烯聚合物组合物B的粒料，经测量，其熔体质量流动速率MFR B＝4.4g/10min。
在原子力显微镜下观察该复合薄膜，可见分散的、条状、互相平行的橡胶相，所述橡胶相的横轴的平均尺寸为145nm，纵横比的平均值为7.8。
实施例D10
按照实施例D1的方法制备复合薄膜，不同的是，在丙烯聚合物组合物B的制备中，组分x的质量份数Wx为50重量份，组分y的质量份数Wy为40重量份，组分z的质量份数Wz为10重量份。得到丙烯聚合物组合物B的粒料，经测量，其熔体质量流动速率MFR B＝5.1g/10min。
在原子力显微镜下观察该复合薄膜，可见分散的、条状、互相平行的橡胶相，所述橡胶相的横轴的平均尺寸为85nm，纵横比的平均值为18.3。
实施例D11
按照实施例D3的方法制备丙烯聚合物组合物A，按照实施例D2的方法制备丙烯聚合物组合物B，使(ηA 160-ηB 160)和(ηA 640-ηB 640)均小于0。按照实施例D3的方法制备复合薄膜。
对比例D1
按照实施例D1的方法制备复合薄膜，不同的是，将聚烯烃弹性体b换为牌号为DF740的聚烯烃弹性体(购自三井公司，该聚烯烃弹性体在230℃、剪切速率160r -1和640r -1下的剪切黏度之比η 160/η 640为1.63，且弹性体在230℃、剪切速率640r -1下的剪切黏度为554Pa·s)。丙烯聚合物组合物A的熔体质量流动速率MFR A＝2.6g/10min。薄膜厚度为50μm。
对比例D2
按照实施例D2的方法制备复合薄膜，不同的是，将聚烯烃弹性体y换为牌号为DF740的聚烯烃弹性体(购自三井公司，该聚烯烃弹性体在230℃、剪切速率160r -1和640r -1下的剪切黏度之比η 160/η 640为1.63，且弹性体在230℃、剪切速率640r -1下的剪切黏度为 554Pa·s)。得到丙烯聚合物组合物B的粒料，经测量，其熔体质量流动速率MFR B＝4.2g/10min。薄膜厚度为50μm。
对比例D3
按照实施例D1的方法制备复合薄膜，不同的是，丙烯聚合物组合物B仅含有组分x。
对比例D4
按照实施例D1的方法制备复合薄膜，不同的是，丙烯聚合物组合物B中仅含有组分x和组分y，其中组分x的质量份数Wx为85重量份，组分y的质量份数Wy为15重量份。
实施例D12
按照实施例D2的方法制备复合薄膜，不同的是，丙烯聚合物组合物B中仅含有组分x和组分z，其中组分x的质量份数Wx为70重量份，组分z的质量份数Wz为30重量份。
对比例D5
按照实施例D2的方法制备复合薄膜。不同的是，丙烯聚合物组合物A仅含有组分a。
表5
Figure PCTCN2021125096-appb-000023
表6
Figure PCTCN2021125096-appb-000024
从表5和6中的结果可以得出，根据本发明的复合薄膜同时具有良好的抗冲性能和光学性能。与非根据本发明的复合薄膜相比，本发明复合薄膜的综合性能更好，尤其是当采用具有特定剪切黏度的聚烯烃弹性体时，在挤出流延时，膜面稳定，薄膜厚度均匀性和抗冲击性能的均匀性大幅提高。
实施例E1
(1)用于制备层a的丙烯聚合物组合物A的制备：
组分a为牌号为J410F的丙烯抗冲共聚物(购自韩国晓星，橡胶相平均粒径为600nm，橡胶相最大粒径为800nm，乙烯单元含量为5.3重量％，乙烯-丙烯共聚部分含量为7.2重量％。其室温二甲苯可溶物中，乙烯单元含量为26.0重量％。乙烯单元组[EEE]含量为6.9重量％。熔体质量流动速率为4.6g/10min，图6a显示该丙烯抗冲共聚物样条断面的SEM照片)；组分b为牌号为PPH-FA03的均聚聚丙烯(购自青岛炼化，熔体质量流动速率为3.0g/10min，分子量分布Mw/Mn为4.6)；组分c为牌号为DF840的聚烯烃弹性体(购自三井公司，为乙烯-1-丁烯共聚物)。将上述制得的各组分按配比进行称重并混合，其中组 分a的质量份数Wa为65重量份，组分b的质量份数Wb为30重量份，组分c的质量份数Wc为5重量份。然后加入润滑剂(瑞士科莱恩公司生产的PEG润滑剂，分子量10000，且以上述组分a、组分b和组分c的质量之和为100重量份计，润滑剂的加入量为0.1重量份)，之后将混合物加入到高速搅拌器中混合均匀，再将混合好的物料加入到W&P公司制造的双螺杆挤出机的喂料器中，物料经由喂料器进入双螺杆中，加工过程中螺杆的温度保持在160-230℃之间，经螺杆熔融混合均匀、挤出、造粒并烘干，得到丙烯聚合物组合物A的粒料，经测量，其熔体质量流动速率MFR A＝4.1g/10min。
(2)用于制备层b的丙烯聚合物组合物B的制备：
组分x为牌号为F500EPS的丙烯无规共聚物(购自上海石化，为乙烯-丙烯-丁烯三元共聚物，熔体质量流动速率为5.3g/10min)；组分y为牌号为DF840的聚烯烃弹性体(购自三井公司，为乙烯-1-丁烯共聚物)。将上述制得的各组分按配比进行称重并混合，其中组分x的质量份数Wx为90重量份，组分y的质量份数Wy为10重量份。其他操作同步骤(1)中的操作，最后得到丙烯聚合物组合物B的粒料，经测量，其熔体质量流动速率MFR B＝5.6g/10min。
(3)复合薄膜的制备：
将上述步骤(1)和步骤(2)制得的丙烯聚合物组合物A和丙烯聚合物组合物B的粒料进行干燥，之后将丙烯聚合物组合物A加入多层挤出流延机的芯层挤出机中，将丙烯聚合物组合物B加入多层挤出流延机的上表层挤出机和下表层挤出机中，其中，所述上、下表层挤出机中加入无机防粘剂(二氧化硅，同上)，防粘剂与丙烯聚合物组合物的粒料的重量比均为0.2:100。在流延铸膜过程中，将流延急冷辊温度设定为30℃，收卷，制成复合薄膜，其由上、下表层(层b)和芯层(层a)构成。薄膜厚度为50μm，其中上、下表层厚度之和与芯层的厚度比为1:1。
所述复合薄膜切面的原子力显微镜照片如图7所示，其中黑色部分为橡胶相，可以看出该橡胶相是分散的，条状的，并且彼此平行排列的。所述橡胶相的横轴的平均尺寸为53nm，纵横比的平均值为5.2。
实施例E2
(1)用于制备层a的丙烯聚合物组合物A的制备：
组分a为牌号为F200R的丙烯抗冲共聚物(购自上海石化，乙烯单元含量为9.1重量％，乙烯-丙烯共聚部分含量为12.2重量％。橡胶相的平均粒径为800nm，最大粒径为1μm， 其室温二甲苯可溶物中乙烯单元含量为38.1重量％。乙烯单元组[EEE]含量为13.6重量％。熔体质量流动速率为2.1g/10min)；组分b为牌号为PPH-FA03的均聚聚丙烯(购自青岛炼化，熔体质量流动速率为3.1g/10min，分子量分布Mw/Mn为4.7)；组分c为牌号为8200的聚烯烃弹性体(购自陶氏公司，乙烯-1-辛烯共聚物)。将上述制得的各组分按配比进行称重并混合，其中组分a的质量份数Wa为75重量份，组分b的质量份数Wb为10重量份，组分c的质量份数Wc为15重量份。然后加入润滑剂(瑞士科莱恩公司生产的PEG润滑剂，分子量10000，且以上述组分a、组分b和组分c的质量之和为100重量份计，润滑剂的加入量为0.1重量份)，之后将混合物加入到高速搅拌器中混合均匀，再将混合好的物料加入到W&P公司制造的双螺杆挤出机的喂料器中，物料经由喂料器进入双螺杆中，加工过程中螺杆的温度保持在160-230℃之间，经螺杆熔融混合均匀、挤出、造粒并烘干，得到丙烯聚合物组合物A的粒料，经测量，其熔体质量流动速率MFR A＝3.3g/10min)。
(2)用于制备层b的丙烯聚合物组合物B的制备：
组分x为牌号为F5006的丙烯无规共聚物(购自燕山石化，乙烯-丙烯-丁烯三元共聚物，熔体质量流动速率为5.2g/10min)；组分y为牌号为8200的聚烯烃弹性体(购自陶氏公司，乙烯-1-辛烯共聚物)。将上述制得的各组分按配比进行称重并混合，其中组分x的质量份数Wx为75重量份，组分y的质量份数Wy为25重量份。其他操作同步骤(1)中的操作，最后得到丙烯聚合物组合物B的粒料，经测量，其熔体质量流动速率MFR B＝4.2g/10min。
(3)复合薄膜的制备：
将上述步骤(1)和步骤(2)制得的丙烯聚合物组合物A和丙烯聚合物组合物B的粒料进行干燥，之后将丙烯聚合物组合物A加入多层挤出流延机的芯层挤出机中，将丙烯聚合物组合物B加入多层挤出流延机的上表层挤出机中，其中，所述上表层挤出机中加入无机防粘剂(二氧化硅，同上)，防粘剂与丙烯聚合物组合物的粒料的重量比为0.2:100。在流延过程中，将流延急冷辊温度设定为30℃，收卷，制成复合薄膜，其由上表层(层b)和芯层(层a)构成。薄膜厚度为50μm，其中层b和层a的厚度比为1:2。
在原子力显微镜下观察该复合薄膜，可见分散的、条状的、彼此平行排列的橡胶相，所述橡胶相的横轴的平均尺寸为62nm，纵横比的平均值为11.2。
实施例E3
组分a为牌号为PPB-M02D的丙烯抗冲共聚物(橡胶相平均粒径为1.4μm，橡胶相最 大粒径为1.9μm，购自茂名石化，乙烯含量为8重量％，乙烯-丙烯共聚部分含量为10重量％，其室温二甲苯可溶物中，乙烯单元含量为36.3重量％。乙烯单元组[EEE]含量为18.5重量％，熔体质量流动速率为1.5g/10min)；组分b为牌号为F800EDF的丙烯-乙烯二元无规共聚聚丙烯(购自上海石化，熔体质量流动速率为7.8g/10min)；组分c为牌号为VM3980的聚烯烃弹性体(购自埃克森公司，为丙烯-乙烯共聚物)。将上述制得的各组分按配比进行称重并混合，其中组分a的质量份数Wa为55重量份，组分b的质量份数Wb为25重量份，组分c的质量份数Wc为20重量份。然后加入润滑剂(瑞士科莱恩公司生产的PEG润滑剂，分子量10000，且以上述组分a、组分b和组分c的质量之和为100重量份计，润滑剂的加入量为0.1重量份)，之后将混合物加入到高速搅拌器中混合均匀，再将混合好的物料加入到W&P公司制造的双螺杆挤出机的喂料器中，物料经由喂料器进入双螺杆中，加工过程中螺杆的温度保持在160-230℃之间，经螺杆熔融混合均匀、挤出、造粒并烘干，得到丙烯聚合物组合物A的粒料，经测量，其熔体质量流动速率MFR A＝6.4g/10min。
(2)用于制备层b的丙烯聚合物组合物B的制备：
组分x为牌号为F800EDF的丙烯无规共聚物(购自上海石化，为丙烯-乙烯二元共聚物，熔体质量流动速率为7.8g/10min)；组分y为牌号为VM3980的聚烯烃弹性体(购自埃克森公司，为丙烯-乙烯共聚物)。将上述制得的各组分按配比进行称重并混合，其中组分x的质量份数Wx为80重量份，组分y的质量份数Wy为20重量份。其他操作同步骤(1)中的操作，最后得到丙烯聚合物组合物B的粒料，经测量，其熔体质量流动速率MFR B＝8.3g/10min。
(3)复合薄膜的制备：
操作同实施例E1的步骤(3)。最后制得薄膜厚度为50μm，其中上、下表层厚度之和与芯层的厚度比为1:4。
在原子力显微镜下观察该复合薄膜，可见分散的、条状的、彼此平行的橡胶相，所述橡胶相的横轴的平均尺寸为143nm，纵横比的平均值为8.7。
实施例E4
(1)用于制备层a的丙烯聚合物组合物A的制备：
操作同实施例E2的步骤(1)，不同的是，组分a的质量份数Wa为80重量份，组分b的质量份数Wb为18重量份，组分c的质量份数Wc为2重量份。其中组分c为牌号为8411的聚烯烃弹性体(购自陶氏公司，为乙烯-1-辛烯共聚物)。得到丙烯聚合物组合物A 的粒料，经测量，其熔体质量流动速率MFR A＝3.1g/10min。
(2)用于制备层b的丙烯聚合物组合物B的制备：
操作同实施例E2的步骤(2)，不同的是，组分x的质量份数Wx为92重量份，组分y的质量份数Wy为8重量份。其他操作同步骤(1)中的操作，最后得到丙烯聚合物组合物B的粒料，经测量，其熔体质量流动速率MFR B＝7.5g/10min。
(3)复合薄膜的制备：
操作同实施例E2的步骤(3)。薄膜厚度为50μm，其中层b和层a的厚度比为1:6。
在原子力显微镜下观察该复合薄膜，可见分散、条状、彼此平行排列的橡胶相，所述橡胶相的横轴的平均尺寸为77nm，纵横比的平均值为5.6。
实施例E5
(1)用于制备层a的丙烯聚合物组合物A的制备：
操作同实施例E1的步骤(1)，不同的是，组分a的质量份数Wa为90重量份，组分b的质量份数Wb为5重量份，组分c的质量份数Wc为5重量份。得到丙烯聚合物组合物A的粒料，经测量，其熔体质量流动速率MFR A＝5.1g/10min。
(2)丙烯聚合物组合物B的制备：
操作同实施例E2的步骤(2)，不同的是，组分x的质量份数Wx为80重量份，组分y的质量份数Wy为20重量份。最后得到丙烯聚合物组合物B的粒料，经测量，其熔体质量流动速率MFR B＝3.5g/10min。
(3)复合薄膜的制备：
操作同实施例E1的步骤(3)。薄膜厚度为50μm，其中上、下表层厚度之和与芯层的厚度比为2:1。
在原子力显微镜下观察该复合薄膜，可见分散、条状和彼此平行排列的橡胶相，所述橡胶相的横轴的平均尺寸为25nm，纵横比的平均值为14.6。
实施例E6
(1)用于制备层a的丙烯聚合物组合物A的制备：
操作同实施例E3的步骤(1)，不同的是，组分a的质量份数Wa为50重量份，组分b的质量份数Wb为40重量份，组分c的质量份数Wc为10重量份。得到丙烯聚合物组合物A的粒料，经测量，其熔体质量流动速率MFR A＝2.3g/10min。
(2)用于制备层b的丙烯聚合物组合物B的制备：
操作同实施例E3的步骤(2)，不同的是，组分x的质量份数Wx为60重量份，组分y的质量份数Wy为40重量份。最后得到丙烯聚合物组合物B的粒料，经测量，其熔体质量流动速率MFR B＝9.6g/10min。
(3)复合薄膜的制备：操作同实施例E3的步骤(3)。
在原子力显微镜下观察该复合薄膜，可见分散、条状、彼此平行排列的橡胶相，所述橡胶相的横轴的平均尺寸为138nm，纵横比的平均值为6.3。
实施例E7
(1)用于制备层a的丙烯聚合物组合物A的制备：
操作同实施例E2的步骤(1)，不同的是，组分a的质量份数Wa为50重量份，组分b的质量份数Wb为20重量份，组分c的质量份数Wc为30重量份。得到丙烯聚合物组合物A的粒料，经测量，其熔体质量流动速率MFR A＝3.6g/10min。
(2)用于制备层b的丙烯聚合物组合物B的制备：
操作同实施例E2的步骤(2)，不同的是，组分x的质量份数Wx为85重量份，组分y的质量份数Wy为15重量份。其他操作同步骤(1)中的操作，最后得到丙烯聚合物组合物B的粒料，经测量，其熔体质量流动速率MFR B＝4.3g/10min。
(3)复合薄膜的制备：
操作同实施例E2的步骤(3)。薄膜厚度为50μm，其中层b和层a的厚度比为1:3。
在原子力显微镜下观察该复合薄膜，可见分散、条状和彼此平行排列的橡胶相，所述橡胶相的横轴的平均尺寸为106nm，纵横比的平均值为8.6。
实施例E8
按照实施例E2的方法制备复合薄膜，不同的是，在丙烯聚合物组合物A的制备中，组分a的质量份数Wa为40重量份，组分b的质量份数Wb为40重量份，组分c的质量份数Wc为20重量份。得到丙烯聚合物组合物A的粒料，经测量，其熔体质量流动速率MFR A＝3.3g/10min。
在原子力显微镜下观察该复合薄膜，可见分散、条状和彼此平行排列的橡胶相，所述橡胶相的横轴的平均尺寸为94nm，纵横比的平均值为9.3。
实施例E9
按照实施例E2的方法制备复合薄膜，不同的是，在丙烯聚合物组合物B的制备中，组分x的质量份数Wx为95重量份，组分y的质量份数Wy为5重量份。最后得到丙烯聚合物组合物B的粒料，经测量，其熔体质量流动速率MFR B＝5.5g/10min。
实施例E10
按照实施例E2的方法制备复合薄膜，不同的是，在丙烯聚合物组合物B的制备中，组分x的质量份数Wx为70重量份，组分y的质量份数Wy为30重量份。最后得到丙烯聚合物组合物B的粒料，经测量，其熔体质量流动速率MFR B＝4.7g/10min。
实施例E11
按照实施例E2的方法制备复合薄膜，不同的是，在丙烯聚合物组合物B的制备中，组分x的质量份数Wx为40重量份，组分y的质量份数Wy为60重量份。最后得到丙烯聚合物组合物B的粒料，经测量，其熔体质量流动速率MFR B＝3.2g/10min。
对比例E1
按照实施例E2的方法制备复合薄膜，不同的是，在丙烯聚合物组合物A的制备过程中，将丙烯抗冲共聚物换为牌号为F780R的丙烯抗冲共聚物(购自上海石化，橡胶相平均粒径为2.0μm，橡胶相最大粒径为3.0μm，乙烯单元含量为9.0重量％，乙烯-丙烯共聚部分含量为17.1重量％。熔体质量流动速率为7.3g/10min。图6b是该丙烯抗冲共聚物样条断面的SEM照片)。最后得到丙烯聚合物组合物A的粒料，经测量，其熔体质量流动速率MFR A＝7.7g/10min。
实施例E12
按照实施例E2的方法制备复合薄膜，不同的是，丙烯聚合物组合物A中仅含有组分a和组分b，其中组分a的质量份数Wa为75重量份，组分b的质量份数Wb为25重量份。
对比例E2
按照实施例E2的方法制备复合薄膜，不同的是，丙烯聚合物组合物A中仅含有组分 a和组分c，其中组分a的质量份数Wa为75重量份，组分c的质量份数Wc为25重量份。
表7
Figure PCTCN2021125096-appb-000025
从表7中的结果可以得出，具有根据本发明的微结构的复合薄膜同时具有良好的抗冲性能和光学性能，甚至还具有良好的热封强度。对此相对照，采用不是根据本发明的丙烯抗冲共聚物制备的不具有根据本发明的微结构的复合薄膜的光学性能或抗冲性能较差，而且在挤出流延时，膜面不稳定，很难得到厚度均匀的薄膜。
实施例F1
(1)用于制备层a的丙烯聚合物组合物A的制备
组分a为牌号为PPH-FA03的均聚聚丙烯(购自青岛炼化，熔体质量流动速率为3.1g/10min，等规度为98％，分子量分布Mw/Mn为4.7)；组分b为牌号为8411的聚烯烃弹性体(购自陶氏公司，为乙烯-1-辛烯共聚物)。将上述制得的各组分按配比进行称重并混合，其中组分a的质量份数Wa为80重量份，组分b的质量份数Wb为20重量份。然后加入润滑剂(瑞士科莱恩公司生产的PEG润滑剂，分子量10000，且以上述组分a和组分b的质量之和为100重量份计，润滑剂的加入量为0.1重量份)，之后将混合物加入到高速搅拌器中混合均匀，再将混合好的物料加入到W&P公司制造的双螺杆挤出机的喂料器中，物料经由喂料器进入双螺杆中，加工过程中螺杆的温度保持在160-230℃之间，经螺 杆熔融混合均匀、挤出、造粒并烘干，得到丙烯聚合物组合物A的粒料，经检测其熔体质量流动速率MFR A＝3.4g/10min。
(2)用于制备层b的丙烯聚合物组合物B的制备
组分x为牌号为F5006的丙烯无规共聚物(购自燕山石化，为乙烯-丙烯-丁烯三元共聚物，熔体质量流动速率为5.2g/10min)；组分y为牌号为8200的聚烯烃弹性体(购自陶氏公司，为乙烯-1-辛烯共聚物)；组分z为牌号为PPB-M02D的聚丙烯抗冲共聚物，橡胶相平均粒径为1.4μm，橡胶相最大粒径为1.9μm，购自茂名石化，乙烯含量为8重量％，熔体质量流动速率为1.5g/10min)。将上述制得的各组分按配比进行称重并混合，其中组分x的质量份数Wx为85重量份，组分y的质量份数Wy为5重量份，组分z的质量份数Wz为10重量份。其他步骤同步骤(1)，最终得到丙烯聚合物组合物B的粒料，经检测其熔体质量流动速率MFRB＝4.8g/10min。
(3)复合薄膜的制备：
将上述步骤(1)和步骤(2)制得的丙烯聚合物组合物A和丙烯聚合物组合物B的粒料进行干燥，之后将丙烯聚合物组合物A加入多层挤出流延机的芯层挤出机中，将丙烯聚合物组合物B加入多层挤出流延机的上表层挤出机中，其中，所述上表层挤出机中加入无机防粘剂(二氧化硅，同上)，防粘剂与丙烯聚合物组合物粒料的重量比为0.2:100。在流延过程中，将流延急冷辊温度设定为30℃，收卷，制成复合薄膜，其由上表层(层b)和芯层(层a)构成。薄膜厚度为50μm，其中层b和层a的厚度比为1:2。
所述复合薄膜切面的原子力显微镜照片显示，存在该薄膜中存在橡胶相，所述橡胶相是均匀分散的，条状的，并且彼此平行排列，所述橡胶相的横轴的平均尺寸为128nm，纵横比的平均值为5.2。
实施例F2
(1)用于制备层a的丙烯聚合物组合物A的制备：
组分a为牌号为F200R的丙烯抗冲共聚物(购自上海石化，橡胶相平均粒径为800nm，橡胶相最大粒径为1μm，乙烯含量为9.1重量％，乙烯-丙烯共聚部分含量为12.2重量％，其室温二甲苯可溶物中，乙烯单元含量为38.1重量％，乙烯单元组[EEE]含量为13.6重量％，熔体质量流动速率为2.1g/10min)；组分b为牌号为DF840的聚烯烃弹性体(购自三井公司，为乙烯-1-丁烯共聚物)。将上述制得的各组分按配比进行称重并混合，其中组分a的质量份数Wa为95重量份，组分b的质量份数Wb为5重量份。然后加入润滑剂(所 述润滑剂为瑞士科莱恩公司生产的PEG润滑剂，分子量10000，且以上述组分a和组分b的质量之和为100重量份计，润滑剂的加入量为0.1重量份)，之后将混合物加入到高速搅拌器中混合均匀，再将混合好的物料加入到W&P公司制造的双螺杆挤出机的喂料器中，物料经由喂料器进入双螺杆中，加工过程中螺杆的温度保持在160-230℃之间，经螺杆熔融混合均匀、挤出、造粒并烘干，得到丙烯聚合物组合物A粒料，经检测其熔体质量流动速率MFR A＝3.6g/10min。
(2)用于制备层b的丙烯聚合物组合物B的制备：
组分x为牌号为F500EPS的丙烯无规共聚物(购自上海石化，为乙烯-丙烯-丁烯三元共聚物，熔体质量流动速率为5.3g/10min)；组分y为牌号为DF840的聚烯烃弹性体(购自三井公司)；组分z为牌号为F200R的聚丙烯抗冲共聚物。将上述制得的各组分按配比进行称重并混合，其中组分x的质量份数Wx为60重量份，组分y的质量份数Wy为20重量份，组分z的质量份数Wz为20重量份。其他步骤同步骤(1)，最终得到丙烯聚合物组合物B的粒料，经检测其熔体质量流动速率MFR B＝4.3g/10min。
(3)复合薄膜的制备：
将上述步骤(1)和步骤(2)制得的丙烯聚合物组合物A和丙烯聚合物组合物B的粒料进行干燥，之后将丙烯聚合物组合物A加入多层挤出流延机的芯层挤出机中，将丙烯聚合物组合物B加入多层挤出流延机的上表层挤出机和下表层挤出机中，其中，所述上、下表层挤出机中加入无机防粘剂(二氧化硅，同上)，防粘剂与丙烯聚合物组合物粒料的重量比均为0.2:100。在流延铸膜过程中，将流延急冷辊温度设定为30℃，收卷，制成复合薄膜，其由上、下表层(层b)和芯层(层a)构成。薄膜厚度为50μm，其中上、下表层厚度之和与芯层的厚度比为1:1。
在原子力显微镜下观察该复合薄膜，可见分散的、条状的、彼此平行排列的橡胶相，所述橡胶相的横轴的平均尺寸为88nm，纵横比的平均值为7.5。
实施例F3
(1)用于制备层a的丙烯聚合物组合物A的制备：
组分a为牌号为FC801的均聚聚丙烯(购自上海石化，熔体质量流动速率为7.8g/10min，等规度为98％，分子量分布Mw/Mn为4.8)；组分b为牌号为VM3980的聚烯烃弹性体(购自埃克森公司，为丙烯-乙烯共聚物，乙烯结构单元含量为9重量％)。将上述制得的各组分按配比进行称重并混合，其中组分a的质量份数Wa为85重量份，组分 b的质量份数Wb为15重量份。然后加入润滑剂(所述润滑剂为瑞士科莱恩公司生产的PEG润滑剂，分子量10000，且以上述组分a和组分b的质量之和为100重量份计，润滑剂的加入量为0.1重量份)，之后将混合物加入到高速搅拌器中混合均匀，再将混合好的物料加入到W&P公司制造的双螺杆挤出机的喂料器中，物料经由喂料器进入双螺杆中，加工过程中螺杆的温度保持在160-230℃之间，经螺杆熔融混合均匀、挤出、造粒并烘干，得到丙烯聚合物组合物A粒料，经检测其熔体质量流动速率MFR A＝7.4g/10min。
(2)用于制备层b的丙烯聚合物组合物B的制备：
组分x为牌号为F800EPS的丙烯无规共聚物(购自上海石化，为乙烯-丙烯-丁烯三元共聚物，熔体质量流动速率为8.2g/10min)；组分y为牌号为VM3980的聚烯烃弹性体(购自埃克森公司，为丙烯-乙烯共聚物，乙烯结构单元含量为9重量％；组分z为牌号为J410F的聚丙烯抗冲共聚物(购自韩国晓星，橡胶相平均粒径为600nm，橡胶相最大粒径为800nm，乙烯含量为5.3重量％，乙烯-丙烯共聚部分含量为7.2重量％，其室温二甲苯可溶物中，乙烯单元含量为26.0重量％，乙烯单元组[EEE]含量为6.9重量％，熔体质量流动速率为4.6g/10min)。将上述制得的各组分按配比进行称重并混合，其中组分x的质量份数Wx为85重量份，组分y的质量份数Wy为10重量份，组分z的质量份数Wz为5重量份。其他步骤同步骤(1)，最终得到丙烯聚合物组合物B的粒料，经检测其熔体质量流动速率MFR B＝8.4g/10min。
(3)复合薄膜的制备：
制备过程同实施例F1的步骤(3)。
在原子力显微镜下观察该复合薄膜，可见分散的、条状的、彼此平行排列的橡胶相，所述橡胶相的横轴的平均尺寸为54nm，纵横比的平均值为9.8。
实施例F4
(1)用于制备层a的丙烯聚合物组合物A的制备：
操作同实施例F1的步骤(1)，不同的是，组分a的质量份数Wa为70重量份，组分b的质量份数Wb为30重量份。得到丙烯聚合物组合物A的粒料，经测量，其熔体质量流动速率MFR A＝3.5g/10min。
(2)用于制备层b的丙烯聚合物组合物B的制备：
步骤同实施例F1的步骤(2)，不同的是，组分x的质量份数Wx为90重量份，组分y的质量份数Wy为5重量份，组分z的质量份数Wz为5重量份。其他操作同步骤(1) 的操作，最后得到丙烯聚合物组合物B的粒料，经测量，其熔体质量流动速率MFR B＝5.5g/10min。
(3)复合薄膜的制备：
步骤同实施例F1。薄膜厚度为50μm，其中层B和层A的厚度比为1:3。
实施例F5
(1)用于制备层a的丙烯聚合物组合物A的制备：
操作同实施例F2的步骤(1)，不同的是，组分a的质量份数Wa为75重量份，组分b的质量份数Wb为25重量份。得到丙烯聚合物组合物A的粒料，经测量，其熔体质量流动速率MFR A＝4.0g/10min。
(2)用于制备层b的丙烯聚合物组合物B的制备：
操作同实施例F3，不同的是，组分x的质量份数Wx为85重量份，组分y的质量份数Wy为13重量份，组分z的质量份数Wz为2重量份。最后得到丙烯聚合物组合物B的粒料，经测量，其熔体质量流动速率MFR B＝8.2g/10min。
(3)复合薄膜的制备：
操作同实施例F2。薄膜厚度为50μm，其中上、下表层厚度之和与芯层的厚度比为2:1。
实施例F6
(1)用于制备层a的丙烯聚合物组合物A的制备：
操作同实施例F3的步骤(1)。
(2)用于制备层a的丙烯聚合物组合物B的制备：
操作同实施例F3的步骤(2)，不同的是，组分x的质量份数Wx为50重量份，组分y的质量份数Wy为30重量份，组分y为牌号为8411的聚烯烃弹性体(乙烯-1-辛烯共聚物，购自陶氏公司)。组分z的质量份数Wz为20重量份。最后得到丙烯聚合物组合物B的粒料，经测量，其熔体质量流动速率MFR B＝8.6g/10min。
(3)复合薄膜的制备：
操作同实施例F3的步骤(3)。薄膜厚度为50μm，其中上表层厚度与芯层的厚度比为1:4。
在原子力显微镜下观察该复合薄膜，可见分散的、条状的、彼此平行排列的橡胶相，所述橡胶相的横轴的平均尺寸为28nm，纵横比的平均值为14.5。
实施例F7
(1)用于制备层a的丙烯聚合物组合物A的制备：
操作同实施例F1的步骤(1)。
(2)用于制备层b的丙烯聚合物组合物B的制备：
操作同实施例F1的步骤(2)，不同的是，组分x的质量份数Wx为50重量份，组分y的质量份数Wy为20重量份，组分z的质量份数Wz为30重量份。其他操作同步骤(1)的操作，最后得到丙烯聚合物组合物B的粒料，经测量，其熔体质量流动速率MFR B＝4.3g/10min。
(3)复合薄膜的制备：
操作同实施例F1的步骤(3)。薄膜厚度为50μm，其中层B和层A的厚度比为1:3。
在原子力显微镜下观察该复合薄膜，可见分散的、条状的、彼此平行排列的橡胶相，所述橡胶相的横轴的平均尺寸为147nm，纵横比的平均值为6.3。
实施例F8
按照实施例F1的方法制备复合薄膜，不同的是，在丙烯聚合物组合物A的制备中，组分a的质量份数Wa为50重量份，组分b的质量份数Wb为50重量份。最后得到丙烯聚合物组合物A的粒料，经测量，其熔体质量流动速率MFR A＝3.6g/10min。
在原子力显微镜下观察该复合薄膜，可见分散的、条状的、彼此平行排列的橡胶相，所述橡胶相的横轴的平均尺寸为120nm，纵横比的平均值为5.5。
实施例F9
按照实施例F1的方法制备复合薄膜，不同的是，在丙烯聚合物组合物B的制备中，组分x的质量份数Wx为40重量份，组分y的质量份数Wy为30重量份，组分z的质量份数Wz为30重量份。得到丙烯聚合物组合物B的粒料，经测量，其熔体质量流动速率MFR B＝4.2g/10min。
在原子力显微镜下观察该复合薄膜，可见分散的、条状的、彼此平行排列的橡胶相，所述橡胶相的横轴的平均尺寸为145nm，纵横比的平均值为7.4。
实施例F10
按照实施例F1的方法制备复合薄膜，不同的是，在丙烯聚合物组合物B的制备中，组分x的质量份数Wx为50重量份，组分y的质量份数Wy为40重量份，组分z的质量份数Wz为10重量份。得到丙烯聚合物组合物B的粒料，经测量，其熔体质量流动速率MFR B＝5.3g/10min。
在原子力显微镜下观察该复合薄膜，可见分散的、条状的、彼此平行排列的橡胶相，所述橡胶相的横轴的平均尺寸为102nm，纵横比的平均值为9.3。
对比例F1
按照实施例F1的方法制备复合薄膜，不同的是，丙烯聚合物组合物B的制备过程中，将聚丙烯抗冲共聚物z换为牌号为F780R的聚丙烯抗冲共聚物(购自上海石化，橡胶相的平均粒径为2.0μm，最大粒径为3.0μm，乙烯单元含量为9.0重量％，乙烯-丙烯共聚部分含量为17.1重量％，熔体质量流动速率为7.3g/10min)。最后得到丙烯聚合物组合物B的粒料，经测量，其熔体质量流动速率MFR B＝7.9g/10min。薄膜厚度为50μm。
对比例F2
按照实施例F2的方法制备复合薄膜，不同的是，将组合物A中的组分a和组合物B中的组分z换为牌号为F780R的丙烯抗冲共聚物，得到丙烯聚合物组合物A的粒料(熔体质量流动速率MFR A＝7.3g/10min)和丙烯聚合物组合物B的粒料(熔体质量流动速率MFR B＝6.5g/10min)。薄膜厚度为50μm。
对比例F3
按照实施例F1的方法制备复合薄膜，不同的是，丙烯聚合物组合物B仅含有组分x。
对比例F4
按照实施例F1的方法制备复合薄膜，不同的是，丙烯聚合物组合物B中仅含有组分x和组分y，其中组分x的质量份数Wx为85重量份，组分y的质量份数Wy为15重量份。
对比例F5
按照实施例F2的方法制备复合薄膜，不同的是，丙烯聚合物组合物B中仅含有组分x和组分z，其中组分x的质量份数Wx为70重量份，组分z的质量份数Wz为30重量份。
表8
Figure PCTCN2021125096-appb-000026
从表8中的结果可以得出，采用根据本发明的丙烯抗冲共聚物制备的具有根据本发明的微结构的复合薄膜同时具有很好的抗冲性能和光学性能，同时具有良好的拉伸性能和良好的热封强度。相对照而言，采用不是根据本发明的丙烯抗冲共聚物制备的不具有根据本发明的微结构的复合薄膜的光学性能或抗冲性能较差，同时拉伸性能或热封强度较差；而且，在挤出流延时，膜面不稳定，很难得到厚度均匀的薄膜。
实施例G1(使用马来酸酐改性聚丙烯)
(1)用于制备层a的丙烯聚合物组合物A的制备：
组分a为牌号为PPH-FA03的均聚聚丙烯(购自青岛炼化，熔体质量流动速率为3.1g/10min，等规度为98％，分子量分布Mw/Mn为4.7)；组分b为牌号为EP200K的丙烯抗冲共聚物(购自中沙石化，乙烯含量为8重量％，熔体质量流动速率为3.2g/10min)；组分c为牌号为6102的聚烯烃弹性体(购自埃克森公司，为乙烯-丙烯共聚物)。将上述制得的各组分按配比进行称重并混合，其中组分a的质量份数Wa为75重量份，组分b的质量份数Wb为10重量份，组分c的质量份数Wc为15重量份。然后加入润滑剂(瑞士科莱恩公司FL7540L生产的PEG润滑剂，分子量10000，且以上述组分a、组分b和组 分c的质量之和为100重量份计，润滑剂的加入量为0.1重量份)，之后将混合物加入到高速搅拌器中混合均匀，再将混合好的物料加入到W&P公司制造的双螺杆挤出机的喂料器中，物料经由喂料器进入双螺杆中，加工过程中螺杆的温度保持在160-230℃之间，经螺杆熔融混合均匀、挤出、造粒并烘干，得到丙烯聚合物组合物A的粒料，经检测其熔体质量流动速率MFR A＝3.6g/10min。
(2)用于制备层b的丙烯聚合物组合物B的制备：
组分x为牌号为F5006的丙烯无规共聚物(购自燕山石化，为乙烯-丙烯-丁烯三元共聚物，熔体质量流动速率为5.2g/10min)；组分y为牌号为6102的聚烯烃弹性体(购自埃克森公司，为乙烯-丙烯共聚物)；组分z为牌号为QF551A的马来酸酐改性聚丙烯(购自三井公司)。将上述制得的各组分按配比进行称重并混合，其中组分x的质量份数Wx为70重量份，组分y的质量份数Wy为15重量份，组分z的质量份数Wz为15重量份。Wc：Wy为1:1。其他步骤同步骤(1)，最终得到丙烯聚合物组合物B的粒料，经检测其熔体质量流动速率MFR B＝3.5g/10min。
(3)复合薄膜的制备：
将上述步骤(1)和步骤(2)制得的丙烯聚合物组合物A和丙烯聚合物组合物B的粒料进行干燥，之后将丙烯聚合物组合物A加入多层挤出流延机的芯层挤出机中，将丙烯聚合物组合物B加入多层挤出流延机的上表层挤出机中，其中，所述上表层挤出机中加入无机防粘剂(二氧化硅，同上)，防粘剂与丙烯聚合物组合物粒料的重量比为0.2:100。在流延过程中，将流延急冷辊温度设定为30℃，收卷，制成复合薄膜，其由上表层(层b)和芯层(层a)构成。复合薄膜厚度为50μm，其中层b和层a的厚度比为1:2。
在原子力显微镜下观察该复合薄膜，可见橡胶相，所述橡胶相的横轴平均尺寸为65nm，纵横比的平均值为10.9。
实施例G2(使用聚丙烯-g-甲基丙烯酸缩水甘油酯)
I.聚丙烯-g-甲基丙烯酸缩水甘油酯的制备
选取具有以下特征的基础共聚聚丙烯粉料：共聚单体乙烯含量18.1重量％，二甲苯可溶物含量48.7重量％，可溶物中共聚单体含量31.9重量％，可溶物/共聚聚丙烯特性粘数比0.89，重均分子量为34.3×10 4g/mol，在230℃，2.16kg载荷下的MFR为1.21g/10min，Tm＝143.4℃，筛分除去小于40目的细粉。称取上述基础共聚聚丙烯粉料2.0kg，加入到带有机械搅拌的10L反应釜中，密闭反应系统，氮气置换除氧。加入2.5g过氧化二苯甲 酰和80g甲基丙烯酸缩水甘油酯，搅拌混合30min，升温至90℃，反应4小时。反应结束后，氮气吹扫降温，得到聚丙烯-g-甲基丙烯酸缩水甘油酯，其熔体质量流动速率为0.49g/10min，M1为2.96％，接枝效率为77％。
II.复合薄膜的制备
(1)用于制备层a的丙烯聚合物组合物A的制备：
组分a为牌号为PPH-FA03的均聚聚丙烯(购自青岛炼化，熔体质量流动速率为3.1g/10min，等规度为98％，分子量分布Mw/Mn为4.7)；组分b为如上制备的聚丙烯-g-甲基丙烯酸缩水甘油酯；组分c为牌号为6102的聚烯烃弹性体(购自埃克森公司，为乙烯-丙烯共聚物)。将上述制得的各组分按配比进行称重并混合，其中组分a的质量份数Wa为75重量份，组分b的质量份数Wb为10重量份，组分c的质量份数Wc为15重量份。然后加入润滑剂(所述润滑剂为瑞士科莱恩公司生产的PEG润滑剂，分子量10000，且以上述组分a、组分b和组分c的质量之和为100重量份计，润滑剂的加入量为0.1重量份)，之后将混合物加入到高速搅拌器中混合均匀，再将混合好的物料加入到W&P公司制造的双螺杆挤出机的喂料器中，物料经由喂料器进入双螺杆中，加工过程中螺杆的温度保持在160-230℃之间，经螺杆熔融混合均匀、挤出、造粒并烘干，得到丙烯聚合物组合物A的粒料，经检测其熔体质量流动速率MFR A＝2.8g/10min。
(2)用于制备层b的丙烯聚合物组合物B的制备：
组分x为牌号为F5006的丙烯无规共聚物(购自燕山石化，为乙烯-丙烯-丁烯三元共聚物，熔体质量流动速率为5.2g/10min)；组分y为牌号为6102的聚烯烃弹性体(购自埃克森公司，为乙烯-丙烯共聚物)。将上述制得的各组分按配比进行称重并混合，其中组分x的质量份数Wx为75重量份，组分y的质量份数Wy为25重量份。Wc：Wy为3:5。其他步骤同步骤(1)，最终得到丙烯聚合物组合物B的粒料，经检测其熔体质量流动速率MFR B＝3.2g/10min。
(3)复合薄膜的制备：
将上述步骤(1)和步骤(2)制得的丙烯聚合物组合物A和丙烯聚合物组合物B的粒料进行干燥，之后将丙烯聚合物组合物A加入多层挤出流延机的芯层挤出机中，将丙烯聚合物组合物B加入多层挤出流延机的上表层挤出机中，其中，所述上表层挤出机中加入无机防粘剂(二氧化硅，同上)，防粘剂与丙烯聚合物组合物粒料的重量比为0.2:100。在流延过程中，将流延急冷辊温度设定为30℃，收卷，制成复合薄膜，其由上表层(层b)和芯层(层a)构成。薄膜厚度为50μm，其中层b和层a的厚度比为1:2。
实施例G3(使用聚丙烯-g-苯乙烯)
I.聚丙烯-g-苯乙烯的制备
选取具有以下特征的基础共聚聚丙烯粉料：共聚单体乙烯含量18.1重量％，二甲苯可溶物含量48.7重量％，可溶物中共聚单体含量31.9重量％，可溶物/共聚聚丙烯特性粘数比0.89，重均分子量为34.3×10 4g/mol，在230℃，2.16kg载荷下的MFR为1.21g/10min，Tm＝143.4℃，筛分除去小于40目的细粉。称取上述基础共聚聚丙烯粉料2.0kg，加入到带有机械搅拌的10L反应釜中，密闭反应系统，氮气置换除氧。加入2g过氧化二苯甲酰和100g苯乙烯，搅拌混合60min，40℃溶胀4小时，升温至95℃，反应4小时。反应结束后，氮气吹扫降温，得到聚丙烯-g-苯乙烯，其熔体质量流动速率为0.75g/10min，M1为2.91％，接枝效率为61％。
II.复合薄膜的制备
(1)用于制备层a的丙烯聚合物组合物A的制备：
组分a为牌号为PPH-FA03的均聚聚丙烯(购自青岛炼化，熔体质量流动速率为3.1g/10min，等规度为98％，分子量分布Mw/Mn为4.7)；组分b为如上制备的聚丙烯-g-苯乙烯；组分c为牌号为6102的聚烯烃弹性体(购自埃克森公司，为乙烯-丙烯共聚物)。将上述制得的各组分按配比进行称重并混合，其中组分a的质量份数Wa为75重量份，组分b的质量份数Wb为10重量份，组分c的质量份数Wc为15重量份。然后加入润滑剂(瑞士科莱恩公司生产的PEG润滑剂，分子量10000，且以上述组分a、组分b和组分c的质量之和为100重量份计，润滑剂的加入量为0.1重量份)，之后将混合物加入到高速搅拌器中混合均匀，再将混合好的物料加入到W&P公司制造的双螺杆挤出机的喂料器中，物料经由喂料器进入双螺杆中，加工过程中螺杆的温度保持在160-230℃之间，经螺杆熔融混合均匀、挤出、造粒并烘干，得到丙烯聚合物组合物A的粒料，经检测其熔体质量流动速率MFR A＝2.9g/10min。
(2)用于制备层b的丙烯聚合物组合物B的制备：
组分x为牌号为F5006的丙烯无规共聚物(购自燕山石化，为乙烯-丙烯-丁烯三元共聚物，熔体质量流动速率为5.2g/10min)；组分y为牌号为6102的聚烯烃弹性体(购自埃克森公司，为乙烯-丙烯共聚物)。将上述制得的各组分按配比进行称重并混合，其中组分x的质量份数Wx为75重量份，组分y的质量份数Wy为25重量份。Wc：Wy为3:5。其他步骤同步骤(1)，最终得到丙烯聚合物组合物B的粒料，经检测其熔体质量流动速率 MFR B＝3.2g/10min。
(3)复合薄膜的制备：
将上述步骤(1)和步骤(2)制得的丙烯聚合物组合物A和丙烯聚合物组合物B的粒料进行干燥，之后将丙烯聚合物组合物A加入多层挤出流延机的芯层挤出机中，将丙烯聚合物组合物B加入多层挤出流延机的上表层挤出机中，其中，所述上表层挤出机中加入无机防粘剂(二氧化硅，同上)，防粘剂与丙烯聚合物组合物粒料的重量比为0.2:100。在流延过程中，将流延急冷辊温度设定为30℃，收卷，制成复合薄膜，其由上表层(层b)和芯层(层a)构成。薄膜厚度为50μm，其中层b和层a的厚度比为1:2。
实施例G4(使用聚丙烯-g-乙烯基三乙氧基硅烷)
I.聚丙烯-g-乙烯基三乙氧基硅烷的制备
选取具有以下特征的基础共聚聚丙烯粉料：共聚单体乙烯含量18.1重量％，二甲苯可溶物含量48.7重量％，可溶物中共聚单体含量31.9重量％，可溶物/共聚聚丙烯特性粘数比0.89，重均分子量为34.3×10 4g/mol，在230℃，2.16kg载荷下的MFR为1.21g/10min，Tm＝143.4℃，筛分除去小于40目的细粉。称取上述基础共聚聚丙烯粉料2.0kg，加入到带有机械搅拌的10L反应釜中，密闭反应系统，氮气置换除氧。加入2.5g过氧化月桂酰和50g乙烯基三乙氧基硅烷，搅拌混合30min，40℃溶胀1小时，升温至90℃，反应4小时。反应结束后，氮气吹扫，冷却降温，得到聚丙烯-g-乙烯基三乙氧基硅烷，其熔体质量流动速率为1.15g/10min，M1为1.03％，接枝效率为42％。
II.复合薄膜的制备
(1)用于制备层a的丙烯聚合物组合物A的制备：
组分a为牌号为PPH-FA03的均聚聚丙烯(购自青岛炼化，熔体质量流动速率为3.1g/10min，等规度为98％，分子量分布Mw/Mn为4.7)；组分b为如上制备的聚丙烯-g-乙烯基三乙氧基硅烷；组分c为牌号为6102的聚烯烃弹性体(购自埃克森公司，为乙烯-丙烯共聚物)。将上述制得的各组分按配比进行称重并混合，其中组分a的质量份数Wa为75重量份，组分b的质量份数Wb为10重量份，组分c的质量份数Wc为15重量份。然后加入润滑剂(瑞士科莱恩公司生产的PEG润滑剂，分子量10000，且以上述组分a、组分b和组分c的质量之和为100重量份计，润滑剂的加入量为0.1重量份)，之后将混合物加入到高速搅拌器中混合均匀，再将混合好的物料加入到W&P公司制造的双螺杆挤出机的喂料器中，物料经由喂料器进入双螺杆中，加工过程中螺杆的温度保持在160-230℃ 之间，经螺杆熔融混合均匀、挤出、造粒并烘干，得到丙烯聚合物组合物A的粒料，经检测其熔体质量流动速率MFR A＝3.0g/10min。
(2)用于制备层b的丙烯聚合物组合物B的制备：
组分x为牌号为F5006的丙烯无规共聚物(购自燕山石化，为乙烯-丙烯-丁烯三元共聚物，熔体质量流动速率为5.2g/10min)；组分y为牌号为6102的聚烯烃弹性体(购自埃克森公司，为乙烯-丙烯共聚物)。将上述制得的各组分按配比进行称重并混合，其中组分x的质量份数Wx为75重量份，组分y的质量份数Wy为25重量份。Wc：Wy为3:5。其他步骤同步骤(1)，最终得到丙烯聚合物组合物B的粒料，经检测其熔体质量流动速率MFR B＝3.2g/10min。
(3)复合薄膜的制备：
将上述步骤(1)和步骤(2)制得的丙烯聚合物组合物A和丙烯聚合物组合物B的粒料进行干燥，之后将丙烯聚合物组合物A加入多层挤出流延机的芯层挤出机中，将丙烯聚合物组合物B加入多层挤出流延机的上表层挤出机中，其中，所述上表层挤出机中加入无机防粘剂(二氧化硅，同上)，防粘剂与丙烯聚合物组合物粒料的重量比为0.2:100。在流延过程中，将流延急冷辊温度设定为30℃，收卷，制成复合薄膜，其由上表层(层b)和芯层(层a)构成。薄膜厚度为50μm，其中层b和层a的厚度比为1:2。
实施例G5(使用聚丙烯-g-4-乙烯基吡啶)
I.聚丙烯-g-4-乙烯基吡啶的制备
选取具有以下特征的基础共聚聚丙烯粉料：共聚单体乙烯含量18.1重量％，二甲苯可溶物含量48.7重量％，可溶物中共聚单体含量31.9重量％，可溶物/共聚聚丙烯特性粘数比0.89，重均分子量为34.3×10 4g/mol，在230℃，2.16kg载荷下的MFR为1.21g/10min，Tm＝143.4℃，筛分除去小于40目的细粉。称取上述基础共聚聚丙烯粉料2.0kg，加入到带有机械搅拌的10L反应釜中，密闭反应系统，氮气置换除氧。加入1.2g过氧化二苯甲酰和40g 4-乙烯基吡啶，搅拌混合30min，50℃溶胀30min，升温至90℃，反应4小时。反应结束后，氮气吹扫降温，得到聚丙烯-g-4-乙烯基吡啶，其熔体质量流动速率为0.89g/10min，M1为0.92％，接枝效率为47％。
II.复合薄膜的制备
(1)用于丙烯聚合物组合物A的制备：
组分a为牌号为PPH-FA03的均聚聚丙烯(购自青岛炼化，熔体质量流动速率为 3.1g/10min，等规度为98％，分子量分布Mw/Mn为4.7)；组分b为如上制备的聚丙烯-g-4-乙烯基吡啶；组分c为牌号为6102的聚烯烃弹性体(购自埃克森公司，为乙烯-丙烯共聚物)。将上述制得的各组分按配比进行称重并混合，其中组分a的质量份数Wa为75重量份，组分b的质量份数Wb为10重量份，组分c的质量份数Wc为15重量份。然后加入润滑剂(瑞士科莱恩公司生产的PEG润滑剂，分子量10000，且以上述组分a、组分b和组分c的质量之和为100重量份计，润滑剂的加入量为0.1重量份)，之后将混合物加入到高速搅拌器中混合均匀，再将混合好的物料加入到W&P公司制造的双螺杆挤出机的喂料器中，物料经由喂料器进入双螺杆中，加工过程中螺杆的温度保持在160-230℃之间，经螺杆熔融混合均匀、挤出、造粒并烘干，得到丙烯聚合物组合物A的粒料，经检测其熔体质量流动速率MFR A＝3.1g/10min。
(2)丙烯聚合物组合物B的制备：
组分x为牌号为F5006的丙烯无规共聚物(购自燕山石化，为乙烯-丙烯-丁烯三元共聚物，熔体质量流动速率为5.2g/10min)；组分y为牌号为6102的聚烯烃弹性体(购自埃克森公司，为乙烯-丙烯共聚物)。将上述制得的各组分按配比进行称重并混合，其中组分x的质量份数Wx为75重量份，组分y的质量份数Wy为25重量份。Wc：Wy为3:5。其他步骤同步骤(1)，最终得到丙烯聚合物组合物B的粒料，经检测其熔体质量流动速率MFR B＝3.2g/10min。
(3)复合薄膜的制备：
将上述步骤(1)和步骤(2)制得的丙烯聚合物组合物A和丙烯聚合物组合物B粒料进行干燥，之后将丙烯聚合物组合物A加入多层挤出流延机的芯层挤出机中，将丙烯聚合物组合物B加入多层挤出流延机的上表层挤出机中，其中，所述上表层挤出机中加入无机防粘剂(二氧化硅，同上)，防粘剂与丙烯聚合物组合物粒料的重量比为0.2:100。在流延过程中，将流延急冷辊温度设定为30℃，收卷，制成复合薄膜，其由上表层(层b)和芯层(层b)构成。薄膜厚度为50μm，其中层b和层a的厚度比为1:2。
实施例G6(使用实施例G3中制备的聚丙烯-g-苯乙烯)
(1)用于制备层a的丙烯聚合物组合物A的制备：
组分a为牌号为PPH-FA03的均聚聚丙烯(购自青岛炼化，熔体质量流动速率为3.1g/10min，等规度为98％，分子量分布Mw/Mn为4.7)；组分b为牌号为6102的聚烯烃弹性体(购自埃克森公司，为乙烯-丙烯共聚物)。将上述制得的各组分按配比进行称重并 混合，其中组分a的质量份数Wa为80重量份，组分b的质量份数Wb为20重量份。然后加入润滑剂(所述润滑剂为瑞士科莱恩公司生产的PEG润滑剂，分子量10000，且以上述组分a和组分b的质量之和为100重量份计，润滑剂的加入量为0.1重量份)，之后将混合物加入到高速搅拌器中混合均匀，再将混合好的物料加入到W&P公司制造的双螺杆挤出机的喂料器中，物料经由喂料器进入双螺杆中，加工过程中螺杆的温度保持在160-230℃之间，经螺杆熔融混合均匀、挤出、造粒并烘干，得到丙烯聚合物组合物A的粒料，经检测其熔体质量流动速率MFR A＝3.5g/10min。
(2)用于制备层b的丙烯聚合物组合物B的制备：
组分x为牌号为F5006的丙烯无规共聚物(购自燕山石化，为乙烯-丙烯-丁烯三元共聚物，熔体质量流动速率为5.2g/10min)；组分y为牌号为6102的聚烯烃弹性体(购自埃克森公司，为乙烯-丙烯共聚物)；组分z为实施例G3中制备的聚丙烯-g-苯乙烯。将上述制得的各组分按配比进行称重并混合，其中组分x的质量份数Wx为85重量份，组分y的质量份数Wy为5重量份，组分z的质量份数Wz为10重量份。Wb：Wy为4:1。其他步骤同步骤(1)，最终得到丙烯聚合物组合物B的粒料，经检测其熔体质量流动速率MFR B＝4.64g/10min。
(3)复合薄膜的制备：
将上述步骤(1)和步骤(2)制得的丙烯聚合物组合物A和丙烯聚合物组合物B粒料进行干燥，之后将丙烯聚合物组合物A加入多层挤出流延机的芯层挤出机中，将丙烯聚合物组合物B加入多层挤出流延机的上表层挤出机中，其中，所述上表层挤出机中加入无机防粘剂(二氧化硅，同上)，防粘剂与丙烯聚合物组合物粒料的重量比为0.2:100。在流延过程中，将流延急冷辊温度设定为30℃，收卷，制成复合薄膜，其由上表层(层b)和芯层(层a)构成。薄膜厚度为50μm，其中层b和层a的厚度比为1:2。
实施例G7(使用聚丙烯-g-苯乙烯/马来酸酐)
I.聚丙烯-g-苯乙烯/马来酸酐的制备
选取具有以下特征的基础共聚聚丙烯粉料：共聚单体乙烯含量18.1wt％，二甲苯可溶物含量48.7wt％，可溶物中共聚单体含量31.9wt％，可溶物/共聚聚丙烯特性粘数比0.89，重均分子量为34.3×10 4g/mol，在230℃，2.16kg载荷下的MFR为1.21g/10min，Tm＝143.4℃，筛分除去小于40目的细粉。称取上述基础共聚聚丙烯粉料2.0kg，加入到带有机械搅拌的10L反应釜中，密闭反应系统，氮气置换除氧。加入1.3g过氧化二苯甲酰、10g马 来酸酐和40g苯乙烯的溶液，搅拌混合30min，40℃溶胀2小时，升温至90℃，反应4小时。反应结束后，氮气吹扫降温，得到聚丙烯-g-苯乙烯/马来酸酐，其熔体流动速率为0.71g/10min，M1为1.27％，M2为0.44％，接枝效率为52％。
II.复合薄膜的制备
(1)用于制备层a的丙烯聚合物组合物A的制备：
组分a为牌号为PPH-FA03的均聚聚丙烯(购自青岛炼化，熔体流动速率为3.1g/10min，等规度为98％，分子量分布Mw/Mn为4.7)；组分b为如上制备的聚丙烯-g-苯乙烯/马来酸酐；组分c为牌号为6102的聚烯烃弹性体(购自埃克森公司，为乙烯-丙烯共聚物)。将上述制得的各组分按配比进行称重并混合，其中组分a的质量份数Wa为75重量份，组分b的质量份数Wb为10重量份，组分c的质量份数Wc为15重量份。然后加入润滑剂(瑞士科莱恩公司生产的PEG润滑剂，分子量10000，且以上述组分a、组分b和组分c的质量之和为100重量份计，润滑剂的加入量为0.1重量份)，之后将混合物加入到高速搅拌器中混合均匀，再将混合好的物料加入到W&P公司制造的双螺杆挤出机的喂料器中，物料经由喂料器进入双螺杆中，加工过程中螺杆的温度保持在160-230℃之间，经螺杆熔融混合均匀、挤出、造粒并烘干，得到丙烯聚合物组合物A的粒料，经检测其熔体质量流动速率MFR A＝2.9g/10min。
(2)用于制备层b的丙烯聚合物组合物B的制备：
组分x为牌号为F5006的无规聚丙烯(购自燕山石化，为乙烯-丙烯-丁烯三元共聚物，熔体流动速率为5.2g/10min)；组分y为牌号为6102的聚烯烃弹性体(购自埃克森公司，为乙烯-丙烯共聚物)。将上述制得的各组分按配比进行称重并混合，其中组分x的质量份数Wx为75重量份，组分y的质量份数Wy为25重量份。Wc：Wy为3:5。其他步骤同步骤(1)，最终得到丙烯聚合物组合物B的粒料，经检测其熔体质量流动速率MFR B＝3.2g/10min。
(3)复合薄膜的制备：
将上述步骤(1)和步骤(2)制得的丙烯聚合物组合物A和丙烯聚合物组合物B的粒料进行干燥，之后将丙烯聚合物组合物A加入多层挤出流延机的芯层挤出机中，将丙烯聚合物组合物B加入多层挤出流延机的上表层挤出机中，其中，所述上表层挤出机中加入无机防粘剂(二氧化硅，下同)，防粘剂与丙烯聚合物组合物粒料的重量比为0.2:100。在流延过程中，将流延急冷辊温度设定为30℃，收卷，制成复合薄膜，其由上表层(层b)和芯层(层a)构成。薄膜厚度为50μm，其中层b和层a的厚度比为1:2。
表9
Figure PCTCN2021125096-appb-000027
注释：-表示未测定
从表9的结果可以看出，通过在本发明的复合薄膜中添加极性单体改性聚丙烯可实现较高的表面能，从而使得所得复合薄膜与其他材料具有较好的附着力。通过添加丙烯接枝聚合物可实现较高的体积电阻率，因此所得复合薄膜具有较好的电绝缘性能。
以上已经结合实施例对本发明进行了示例性说明，但是所示说明并非穷尽性的，不意于限制本发明的范围。在不偏离本发明的范围和主旨的情况下，许多修改和变更对于本领域技术人员来说都是显而易见的。
另外需要说明的是，在上述具体实施方式中所描述的各个具体技术特征，在不矛盾的情况下，可以通过任何合适的方式进行组合。此外，本发明的各种不同的实施方式之间也可以进行任意组合，只要其不违背本发明的主旨，其同样应当视为本发明所公开的内容。
在本文中所披露的范围的端点和任何值都不限于该精确的范围或值，这些范围或值应当理解为包含接近这些范围或值的值。对于数值范围来说，各个范围的端点值之间、各个范围的端点值和单独的点值之间，以及单独的点值之间可以彼此组合而得到一个或多个新的数值范围，这些数值范围应被视为在本文中具体公开。

Claims (30)

  1. 一种基于丙烯聚合物的复合薄膜，至少包括两个不同的层：层a和层b；
    其中层a和层b各自包含至少一种丙烯聚合物；并且
    层a和层b中的至少一个层包含丙烯抗冲共聚物；
    其中所述丙烯抗冲共聚物包含弹性部分，该弹性部分在复合薄膜中形成分散的呈条状的橡胶相，所述橡胶相彼此平行排列，并且所述橡胶相的橫轴的平均尺寸为20-200nm和纵横比的平均值为5-20，通过原子力显微镜观察复合薄膜沿橫向(TD)切割的横截面测定。
  2. 根据权利要求1所述的复合薄膜，其特征在于，所述橡胶相的橫轴的平均尺寸为20-150nm，和纵横比的平均值为5-15，通过原子力显微镜观察复合薄膜沿横向切割的横截面测定。
  3. 根据权利要求1或2所述的复合薄膜，其特征在于，所述橡胶相的横向截面彼此之间的夹角不大于10度，优选小于5度，通过原子力显微镜观察复合薄膜沿橫向切割的横截面测定。
  4. 根据权利要求1-3中任一项所述的复合薄膜，其特征在于，所述弹性部分在丙烯抗冲共聚物的冲击样条的扫描电子显微镜照片中显现为球状或近球状橡胶相。
  5. 根据权利要求1-4中任一项所述的复合薄膜，其特征在于，所述丙烯抗冲共聚物是含有乙烯单元的丙烯抗冲共聚物，其中所述弹性部分是含有乙烯单元的共聚部分，优选选自乙烯-丙烯共聚部分和乙烯-丁烯共聚部分；
    优选地，
    所述丙烯抗冲共聚物包含丙烯均聚部分与所述含有乙烯单元的共聚部分；和/或
    所述丙烯抗冲共聚物中的含有乙烯单元的共聚部分含量为3-15重量％，优选7-12重量％；和/或
    以所述丙烯抗冲共聚物的总重量计，所述丙烯抗冲共聚物的乙烯单元含量为1-14重量％，优选3-12重量％；和/或，
    在所述丙烯抗冲共聚物的室温二甲苯可溶物中，乙烯单元含量不超过40重量％，和/ 或，乙烯单元组[EEE]含量不超过20重量％，通过 13C NMR测定；和/或，
    所述丙烯抗冲共聚物在230℃、2.16kg载荷下的熔体质量流动速率为1-10g/10min，优选1-8g/10min。
  6. 根据权利要求1-5中任一项所述的复合薄膜，其特征在于，
    层a和层b中都包含所述丙烯抗冲共聚物，其中层a和层b中的丙烯抗冲共聚物是相同或不同的；或者，
    层a和层b中的仅一个层含有所述丙烯抗冲共聚物。
  7. 根据权利要求1-6中任一项所述的复合薄膜，其特征在于，层a和层b中的至少一个层包含聚烯烃弹性体；
    优选地，所述聚烯烃弹性体为乙烯与α烯烃的弹性体共聚物，其中所述α烯烃优选为C 3-C 12的α烯烃，更优选选自丙烯、1-丁烯、1-己烯和1-辛烯中的至少一种；
    优选地，所述聚烯烃弹性体在230℃、剪切速率160r -1和640r -1下的剪切黏度之比η 160/η 640为1.2-3，优选为1.7-2.3，和/或，所述聚烯烃弹性体在230℃、剪切速率640r -1下的剪切黏度η 640为100-500Pa·s，优选为140-400Pa·s，所述剪切黏度根据ISO11443:2014，采用毛细管流变仪测定。
  8. 根据权利要求7所述的复合薄膜，其特征在于所述丙烯抗冲共聚物中的弹性部分和所述聚烯烃弹性体在复合薄膜中形成分散的橡胶相，该橡胶相呈现条状形式，该橡胶相的橫轴的平均尺寸为20-200nm，优选20-150nm；并且该橡胶相的纵横比的平均值为5-20，优选5-15，通过原子力显微镜观察复合薄膜沿横向切割的横截面测定。
  9. 根据权利要求7所述的复合薄膜，其特征在于，
    层a和层b中都包含所述聚烯烃弹性体，其中层a和层b中的聚烯烃弹性体是相同或不同的；优选地，层a中所述聚烯烃弹性体的重量比例与层b中所述聚烯烃弹性体的重量比例之间的比值为6:1-1:6；或者，
    层a和层b中的仅一个层含有所述聚烯烃弹性体。
  10. 根据权利要求1-9中任一项所述的复合薄膜，其特征在于，层a包含均聚聚丙烯和/或 丙烯无规共聚物；
    优选地，所述均聚聚丙烯在230℃、2.16kg载荷下的熔体质量流动速率为2-15g/10min；和/或，所述均聚聚丙烯的等规度大于97％；和/或，所述均聚聚丙烯的分子量分布Mw/Mn为4.5-7.0；
    优选地，所述丙烯无规共聚物选自乙烯-丙烯-丁烯三元无规共聚物、丙烯-乙烯二元无规共聚物、丙烯-丁烯二元无规共聚物中的至少一种；和/或，所述丙烯无规共聚物在230℃、2.16kg载荷下的熔体质量流动速率为2-15g/10min，优选2-10g/10min；和/或，所述丙烯无规共聚物的分子量分布Mw/Mn为4.5-7.0。
  11. 根据权利要求1-10中任一项所述的复合薄膜，其特征在于，层b包含丙烯无规共聚物；
    优选地，所述丙烯无规共聚物选自乙烯-丙烯-丁烯三元无规共聚物、丙烯-乙烯二元无规共聚物、丙烯-丁烯二元无规共聚物中的至少一种；和/或，所述丙烯无规共聚物在230℃、2.16kg载荷下的熔体质量流动速率为2-15g/10min，优选2-10g/10min；和/或，所述丙烯无规共聚物的分子量分布Mw/Mn为4.5-7.0。
  12. 根据权利要求11所述的复合薄膜，其特征在于，层a包含所述聚烯烃弹性体、所述丙烯抗冲共聚物和其他类型的丙烯聚合物，所述其他类型的丙烯聚合物优选选自所述均聚聚丙烯和/或丙烯无规共聚物；并且层b包含所述无规丙烯共聚物和所述聚烯烃弹性体；
    优选地，层a包含40-90重量％的丙烯抗冲共聚物、5-40重量％的其他类型的丙烯聚合物和2-30重量％的聚烯烃弹性体，优选55-75重量％的丙烯抗冲共聚物、10-30重量％的其他类型的丙烯聚合物和5-20重量％的聚烯烃弹性体，各自基于层a的总重量计；和，层b包含40-95重量％的丙烯无规共聚物和5-60重量％的聚烯烃弹性体，优选75-90重量％的丙烯无规共聚物和10-25重量％的聚烯烃弹性体，各自基于层b的总重量计。
  13. 根据权利要求11所述的复合薄膜，其特征在于，层a包含所述均聚聚丙烯、所述丙烯抗冲共聚物和所述聚烯烃弹性体并且层b包含所述无规丙烯共聚物和所述聚烯烃弹性体；
    优选地，层a中所述聚烯烃弹性体的重量比例与层b中所述聚烯烃弹性体的重量比例之间的比值为2:1-1:4，优选为1:1-1:2；和/或
    优选地，层a包含40-90重量％，优选50-90重量％的所述均聚聚丙烯、5-40重量％ 的所述丙烯抗冲共聚物和2-30重量％的所述聚烯烃弹性体；更优选地，层a包含55-75重量％的所述均聚聚丙烯、10-30重量％的所述丙烯抗冲共聚物和5-20重量％的所述聚烯烃弹性体，各自基于层a的总重量计；和，层b包含40-95重量％，优选60-95重量％的无规丙烯共聚物和5-60重量％，优选5-40重量％的聚烯烃弹性体；优选地，层b包含75-90重量％的无规丙烯共聚物和10-25重量％的聚烯烃弹性体，各自基于层b的总重量计。
  14. 根据权利要求11所述的复合薄膜，其特征在于，层a包含丙烯聚合物和所述聚烯烃弹性体，所述丙烯聚合物优选选自均聚聚丙烯和/或所述丙烯抗冲共聚物；并且层b包含所述无规丙烯共聚物、所述聚烯烃弹性体和所述丙烯抗冲共聚物；
    优选地，层a中所述聚烯烃弹性体的重量比例与层b中所述聚烯烃弹性体的重量比例之间的比值为6:1-1:4，优选为4:1-1:4；和/或
    优选地，层a包含50-95重量％的所述丙烯聚合物和5-50重量％的所述聚烯烃弹性体；更优选地，层a包含70-95重量％的所述丙烯聚合物和5-30重量％的所述聚烯烃弹性体；再更优选地，层a包含80-95重量％的所述丙烯聚合物和5-20重量％的所述聚烯烃弹性体，各自基于层a的总重量计；和，层b包含40-90重量％的所述无规丙烯共聚物、5-40重量％的所述聚烯烃弹性体和2-30重量％的所述丙烯抗冲共聚物；更优选地，层b包含50-90重量％的所述无规丙烯共聚物、5-30重量％的所述聚烯烃弹性体和2-30重量％的所述丙烯抗冲共聚物；再优选地，层b包含60-85重量％的所述无规丙烯共聚物、5-20重量％的所述聚烯烃弹性体和5-20重量％的所述丙烯抗冲共聚物，各自基于层b的总重量计。
  15. 根据权利要求1-14中任一项所述的复合薄膜，其特征在于，层a和/或层b还包含添加剂，例如选自抗氧剂、润滑剂、抗卤素剂、光稳定剂、热稳定剂、着色剂、填料、爽滑剂、防粘剂、表面粘接剂、电磁屏蔽助剂、阻燃剂、绝缘添加剂和抗静电剂中的至少一种。
  16. 根据权利要求15所述的复合薄膜，其特征在于，
    所述抗氧剂选自抗氧剂1076、抗氧剂1010、抗氧剂168和硫酯类抗氧剂中的至少一种，优选地，以所在层的总重量为100重量份计，所述抗氧剂的含量为0.1-0.8重量份，优选为0.2-0.4重量份；和/或，
    所述润滑剂是PEG类润滑剂和/或单甘酯类润滑剂，优选地，以所在层的总重量为100重量份计，所述润滑剂的含量为0.01-0.5重量份，优选为0.05-0.2重量份；和/或，
    所述填料是导电填料，优选选自炭黑类、石墨类、碳纳米管类、碳纤维类、导电金属粒子、导电金属纤维、包覆有导电金属的填料和金属氧化物中的至少一种；导电填料优选添加在层b中，以层b中基体聚合物的总重量为100重量份计，导电填料添加量优选为0.1-10重量份；和/或，
    所述电磁屏蔽助剂为导电金属填料和/或碳材料；所述导电金属填料优选为导电金属粒子和/或导电金属纤维；所述碳材料优选为炭黑、石墨、石墨烯和碳纳米管中的一种或多种；优选地，所述电磁屏蔽助剂添加在层b中，优选添加量为5-30重量份，优选15-25重量份，以层b中基体聚合物的重量为100重量份计；优选地，所述电磁屏蔽助剂与钛酸酯类偶联剂组合使用；和/或，
    所述阻燃剂选自金属或非金属的氢氧化物和/或氧化物的水合物、磷系阻燃剂、硼系阻燃剂、锑系阻燃剂和膨胀型阻燃剂中的至少一种；优选添加在除了层a和层b之外的层中；和/或，
    所述着色剂选自偶氮颜料、酞菁颜料、杂环颜料、色淀颜料、染料、荧光增白剂和荧光颜料中的至少一种；优选添加在层a中；和/或
    所述爽滑剂选自酰胺类爽滑剂(优选芥酸酰胺、油酸酰胺、硬脂酸酰胺、山嵛酸酰胺、硬脂基芥酸酰胺和乙撑双硬脂酰胺中的至少一种)；或者酰胺类爽滑剂和耐迁移型爽滑剂(优选聚四氟乙烯微粒、聚酰亚胺微粒、聚酰胺微粒、聚碳酸酯微粒、有机硅、纳米碳酸钙、云母和纳米二氧化硅中的至少一种)的混合物；优选，在层a和层b中都添加爽滑剂，其中层a中添加酰胺类爽滑剂，而层b中添加酰胺类爽滑剂和耐迁移型爽滑剂的混合物。
  17. 根据权利要求15所述的复合薄膜，其特征在于，所述表面粘接剂是极性单体改性聚丙烯，其中优选地，所述极性单体选自含羟基共聚单体、含氰基共聚单体和酸酐单体中的至少一种，更优选选自羟基酸、乙烯醇、氰基丙烯酸酯、马来酸酐和衣康酸酐；极性单体改性聚丙烯优选添加在层b中，基于层b的总重量计，其添加量优选为1-30重量％，更优选5-15重量％。
  18. 根据权利要求15所述的复合薄膜，其特征在于，所述绝缘添加剂是丙烯接枝聚合物，例如添加在层a和/或层b中；基于所在层的总重量计，其添加量优选为5-45重量％；优选地，所述丙烯接枝聚合物包含衍生自共聚聚丙烯的结构单元和衍生自以下接枝单体的结构单元：丙烯酸酯类；丙烯酸类；苯乙烯类；含烯基的硅烷类；含烯基的杂环类单体；具 有至少一个烯烃不饱和度的酸酐和含烯基聚合单体的组合。
  19. 根据权利要求18所述的复合薄膜，其特征在于，所述丙烯接枝聚合物由共聚聚丙烯与接枝单体经固相接枝反应制得；和/或
    所述共聚聚丙烯中除丙烯外的共聚单体选自乙烯和C 4-C 8的α-烯烃中的至少一种；和/或，
    所述共聚聚丙烯具有以下特征中的至少一种：共聚单体含量为0.5-30mol％，优选为4-25mol％；二甲苯可溶物含量为2-80重量％，优选为18-75重量％，进一步优选为30-70重量％；可溶物中共聚单体含量为10-70重量％，优选为10-50重量％，进一步优选为20-35重量％；可溶物与共聚聚丙烯的特性粘数比为0.3-5，优选为0.5-3，更优选为0.8-1.3；在230℃，2.16kg载荷下的熔体质量流动速率为0.01-60g/10min，优选为0.05-35g/10min，进一步优选为0.5-15g/10min；熔融温度Tm为100℃以上，优选为110-180℃，进一步优选为120-170℃；重均分子量为20×10 4-60×10 4g/mol；和/或，
    所述丙烯接枝聚合物在230℃，2.16kg载荷下的熔体质量流动速率为0.01-30g/10min，优选为0.05-20g/10min，进一步优选为0.1-10g/10min，更优选为0.2-8g/10min。
  20. 根据权利要求18或19所述的复合薄膜，其特征在于，
    所述丙烯接枝聚合物包括衍生自共聚聚丙烯的结构单元和接枝到其上的衍生自丙烯酸酯类单体以及任选的丙烯酸类单体的结构单元；优选地，以丙烯接枝聚合物的重量为基准，接枝上的衍生自丙烯酸酯类单体以及任选的丙烯酸类单体的结构单元的含量为0.3-7重量％，优选为0.8-5重量％；优选地，所述丙烯接枝聚合物中，衍生自丙烯酸酯类单体的结构单元与衍生自丙烯酸类单体的结构单元的摩尔比为1:0-2，优选为1:0.125-1；或者，
    所述丙烯接枝聚合物包括衍生自共聚聚丙烯的结构单元和衍生自苯乙烯类单体的结构单元；以丙烯接枝聚合物的重量计，所述丙烯接枝聚合物中衍生自苯乙烯类单体的接枝上的结构单元的含量为0.5-14重量％，优选为1-7.5重量％，更优选为1.5-5重量％；或者，
    所述丙烯接枝聚合物包括衍生自共聚聚丙烯的结构单元和衍生自含烯基的硅烷类单体的结构单元；优选地，以丙烯接枝聚合物的重量为基准，所述丙烯接枝聚合物b中衍生 自含烯基的硅烷类单体的接枝上的结构单元的含量为0.2-6重量％，优选为0.2-2.5重量％；或者，
    所述丙烯接枝聚合物包括衍生自共聚聚丙烯的结构单元、衍生自酸酐单体的结构单元和衍生自含烯基聚合单体的结构单元；所述含烯基聚合单体优选选自乙酸乙烯酯、苯乙烯、α-甲基苯乙烯、(甲基)丙烯酸酯、乙烯基烷基醚、乙烯基吡咯烷酮、乙烯基吡啶、乙烯基咪唑和丙烯腈中的至少一种；所述酸酐优选选自马来酸酐和/或衣康酸酐；优选地，衍生自酸酐单体和含烯基聚合单体的接枝上的结构单元的含量为0.1-5重量％，优选为0.4-3重量％；和/或，接枝上的衍生自酸酐单体的结构单元的含量为0.05-2重量％，优选为0.2-0.7重量％；和/或，衍生自酸酐单体的结构单元与衍生自含烯基聚合单体的结构单元的摩尔比为1：1-20，优选为1：1-10；或者，
    所述丙烯接枝聚合物包括衍生自共聚聚丙烯的结构单元和衍生自含烯基的杂环类单体的结构单元；优选地，以丙烯接枝聚合物的重量为基准，接枝上的衍生自含烯基的杂环类单体的结构单元的含量为0.5-6重量％，优选为0.5-4重量％。
  21. 根据权利要求1-20中任一项所述的复合薄膜，其特征在于，
    层a的材料在230℃下、2.16kg载荷作用下的熔体质量流动速率为2-10g/10min，优选为2-8g/10min，更优选为3-7g/10min；和/或
    层b的材料在230℃下、2.16kg载荷作用下的熔体质量流动速率为2-10g/10min，优选为3-9g/10min，更优选为4-8g/10min。
  22. 根据权利要求1-21中任一项所述的复合薄膜，其特征在于，层a的材料和层b的材料在230℃、剪切速率160r -1下的剪切黏度的差值，即ηA 160-ηB 160，与在230℃、剪切速率640r -1下的剪切黏度的差值，即ηA 640-ηB 640，均≥0，且二者的比值(ηA 160-ηB 160)/(ηA 640-ηB 640)为1-2.6，优选为1.4-2.5，更优选为1.5-2.2，所述剪切黏度根据ISO11443:2014，采用毛细管流变仪测定。
  23. 根据权利要求1-21中任一项所述的复合薄膜，其特征在于，所述复合薄膜还包含一个或多个另外的层，在此层b为复合薄膜的表层，其中该另外的层的组成与层a或层b的组成相同或不同；当复合薄膜为三层薄膜时，该另外的层称为层c，层b与层c分别位于层a的两侧。
  24. 根据权利要求22所述的复合薄膜，其特征在于，复合薄膜中除了层a之外的其他层的厚度之和与层a的厚度之比为1:6-2:1，优选1:4-2:1，更优选为1:2-1:1。
  25. 根据权利要求1-24中任一项所述的复合薄膜，其特征在于，所述复合薄膜具有以下性能中的一种或多种：
    1)摆锤冲击强度为≥0.4J，更优选≥0.9J，再更优选≥1.1J，更优选≥1.5J；
    2)薄膜雾度为小于7％，优选≤5％，更优选≤2％；
    3)纵向拉伸强度为≥40MPa，优选≥50MPa；
    4)在150℃下的热封强度为≥12N/15mm，优选≥15N/15mm，更优选≥18N/15mm；
    5)MD方向厚度偏差不大于1.3，优选不大于1.0，更优选不大于0.5；
    6)TD方向厚度偏差不大于1.5，优选不大于1.3，更优选不大于0.75；
    7)MD方向抗冲击性能偏差不大于0.05，优选不大于0.03；
    8)TD方向抗冲击性能偏差不大于0.07，优选不大于0.05；
    9)表面能≥29mN/m，优选≥35mN/m；
    10)体积电阻率≥1.5×10 15Ω·m，优选率≥2.0×10 15Ω·m。
  26. 一种制备根据权利要求1-25中任一项所述的复合薄膜的方法，包括：
    将用于形成各层的原料组合物在任选的造粒过程后挤出流延形成所述复合薄膜，
    其中在挤出过程之前，原料组合物中使用的丙烯抗冲共聚物中的弹性部分形成粒状橡胶相，该橡胶相的平均粒径为小于或等于1.8μm，优选地小于或等于1.5μm，且最大粒径不超过2.5μm，优选不超过2μm，通过扫描电子显微镜观察冲击样条断面测定。
  27. 根据权利要求26所述的方法，其特征在于，原料组合物中使用的丙烯抗冲共聚物中的弹性部分形成球状或近球状橡胶相。
  28. 根据权利要求26或27所述的方法，其特征在于，该方法进一步包括将所得复合薄膜进行拉伸，优选双向拉伸。
  29. 根据权利要求1-25中任一项所述的复合薄膜或根据权利要求26-28中任一项所述的方 法得到的复合薄膜在包装材料领域，例如在电池包装材料、电子产品包装材料或食品包装材料中的应用。
  30. 包装材料，其包含根据权利要求1-25中任一项所述的复合薄膜或根据权利要求26-29中任一项所述的方法得到的复合薄膜，所述包装材料例如是电池包装材料、电子产品包装材料或食品包装材料，如包含铝塑复合膜的那些。
PCT/CN2021/125096 2020-10-20 2021-10-20 基于丙烯聚合物的复合薄膜及其制备方法和应用 Ceased WO2022083659A1 (zh)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114908477A (zh) * 2022-06-28 2022-08-16 甘肃农业大学 用于水果套袋的聚丙烯无纺布及其制备方法
CN117087280A (zh) * 2022-05-12 2023-11-21 中国石油化工股份有限公司 聚丙烯薄膜及其应用
CN118849575A (zh) * 2023-04-29 2024-10-29 中国石油化工股份有限公司 导电高强度聚丙烯片材及其织物、聚丙烯复合材料以及其制法和应用
CN118849572A (zh) * 2023-04-29 2024-10-29 中国石油化工股份有限公司 抗静电聚丙烯片材及其织物、高强度高抗冲抗静电聚丙烯复合材料以及其制法和应用
CN118906600A (zh) * 2023-05-07 2024-11-08 中国石油化工股份有限公司 阻燃高强度高抗冲聚丙烯片材及其织物、阻燃聚丙烯复合材料以及其制法和应用

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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CA3181555A1 (en) * 2020-04-29 2021-11-04 China Petroleum & Chemical Corporation Grafting-modified polypropylene material and preparation method thereof
JP7632733B1 (ja) 2024-06-20 2025-02-19 王子ホールディングス株式会社 延伸ポリオレフィンフィルム
CN119823495A (zh) * 2024-12-31 2025-04-15 金发科技股份有限公司 一种聚丙烯复合材料及其制备方法和应用

Citations (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101058654A (zh) 2006-04-20 2007-10-24 中国石油化工股份有限公司 高性能聚丙烯组合物的制备方法
CN101492517A (zh) 2009-02-20 2009-07-29 北京化工大学 聚丙烯接枝聚合物的制备方法
CN101679557A (zh) 2007-05-22 2010-03-24 巴塞尔聚烯烃意大利有限责任公司 用于制备软质丙烯聚合物组合物的方法
CN101913279A (zh) 2010-07-08 2010-12-15 福建凯达印务有限公司 增韧型三层共挤复合薄膜及其制备方法
CN102108112A (zh) 2011-01-18 2011-06-29 黑龙江省科学院技术物理研究所 预辐照聚丙烯接枝共聚物及其制备方法
CN104080874A (zh) * 2012-01-31 2014-10-01 艾利丹尼森公司 取向的抗冲共聚物聚丙烯膜
CN104499281A (zh) 2015-01-14 2015-04-08 深圳前海中盛环保科技有限公司 一种制备强酸性离子交换纤维的方法
CN105593012A (zh) * 2013-10-11 2016-05-18 宝洁公司 多层聚合物膜
CN106029771A (zh) * 2013-12-23 2016-10-12 布拉斯科美国有限公司 具有增强的外观和优良模塑流动性的基于丙烯的组合物
CN106366540A (zh) * 2016-08-29 2017-02-01 联泓新材料有限公司 一种可热封的绝缘材料及其制备方法和应用
CN106543369A (zh) 2015-09-18 2017-03-29 中国石油化工股份有限公司 一种丙烯聚合物接枝极性单体的方法
CN108943932A (zh) * 2018-08-01 2018-12-07 张家港康得新光电材料有限公司 热封层、cpp膜、其制备方法及铝塑膜
CN109251270A (zh) 2018-08-11 2019-01-22 洛阳和梦科技有限公司 顺酐接枝聚丙烯的制备方法
CN112041943A (zh) * 2018-07-03 2020-12-04 Ls电线有限公司 电力电缆

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4915067B2 (ja) * 2004-09-15 2012-04-11 住友化学株式会社 ポリプロピレン系樹脂組成物およびそれからなる射出成形体
US7754814B2 (en) * 2005-05-16 2010-07-13 Fina Technology, Inc. Polypropylene materials and method of preparing polypropylene materials
EP2504391B1 (en) * 2009-11-25 2018-07-25 Dow Global Technologies LLC Molded polymeric article with low haze and high clarity
US10486402B2 (en) * 2013-12-31 2019-11-26 Dow Global Technologies Llc Multilayered films, methods of manufacture thereof and articles comprising the same
WO2017040023A1 (en) * 2015-08-31 2017-03-09 E. I. Du Pont De Nemours And Company Adhesive compositions and multilayered structures comprising functionalized polypropylene
CN108909123A (zh) * 2018-07-12 2018-11-30 安徽迈高化工科技有限公司 一种易剥离耐高温蒸煮聚丙烯薄膜
CN111645374A (zh) * 2020-04-30 2020-09-11 乐凯胶片股份有限公司 太阳能电池背板用透明聚烯烃薄膜

Patent Citations (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101058654A (zh) 2006-04-20 2007-10-24 中国石油化工股份有限公司 高性能聚丙烯组合物的制备方法
CN101679557A (zh) 2007-05-22 2010-03-24 巴塞尔聚烯烃意大利有限责任公司 用于制备软质丙烯聚合物组合物的方法
CN101492517A (zh) 2009-02-20 2009-07-29 北京化工大学 聚丙烯接枝聚合物的制备方法
CN101913279A (zh) 2010-07-08 2010-12-15 福建凯达印务有限公司 增韧型三层共挤复合薄膜及其制备方法
CN102108112A (zh) 2011-01-18 2011-06-29 黑龙江省科学院技术物理研究所 预辐照聚丙烯接枝共聚物及其制备方法
CN104080874A (zh) * 2012-01-31 2014-10-01 艾利丹尼森公司 取向的抗冲共聚物聚丙烯膜
CN105593012A (zh) * 2013-10-11 2016-05-18 宝洁公司 多层聚合物膜
CN106029771A (zh) * 2013-12-23 2016-10-12 布拉斯科美国有限公司 具有增强的外观和优良模塑流动性的基于丙烯的组合物
CN104499281A (zh) 2015-01-14 2015-04-08 深圳前海中盛环保科技有限公司 一种制备强酸性离子交换纤维的方法
CN106543369A (zh) 2015-09-18 2017-03-29 中国石油化工股份有限公司 一种丙烯聚合物接枝极性单体的方法
CN106366540A (zh) * 2016-08-29 2017-02-01 联泓新材料有限公司 一种可热封的绝缘材料及其制备方法和应用
CN112041943A (zh) * 2018-07-03 2020-12-04 Ls电线有限公司 电力电缆
CN108943932A (zh) * 2018-08-01 2018-12-07 张家港康得新光电材料有限公司 热封层、cpp膜、其制备方法及铝塑膜
CN109251270A (zh) 2018-08-11 2019-01-22 洛阳和梦科技有限公司 顺酐接枝聚丙烯的制备方法

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
See also references of EP4234238A4
ZHANG GUANGPING: "Solid Phase Graft of Maleic Anhydride onto Polypropylene in Helical Ribbon Reactor", CHINA PLASTICS, vol. 16, no. 2, February 2002 (2002-02-01), pages 69 - 71

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117087280A (zh) * 2022-05-12 2023-11-21 中国石油化工股份有限公司 聚丙烯薄膜及其应用
CN114908477A (zh) * 2022-06-28 2022-08-16 甘肃农业大学 用于水果套袋的聚丙烯无纺布及其制备方法
CN118849575A (zh) * 2023-04-29 2024-10-29 中国石油化工股份有限公司 导电高强度聚丙烯片材及其织物、聚丙烯复合材料以及其制法和应用
CN118849572A (zh) * 2023-04-29 2024-10-29 中国石油化工股份有限公司 抗静电聚丙烯片材及其织物、高强度高抗冲抗静电聚丙烯复合材料以及其制法和应用
CN118906600A (zh) * 2023-05-07 2024-11-08 中国石油化工股份有限公司 阻燃高强度高抗冲聚丙烯片材及其织物、阻燃聚丙烯复合材料以及其制法和应用

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