WO2020091621A1 - Composition à base de polypropylène présentant une transparence, une dureté et une viscosité d'impact améliorées pour des articles moulés par injection à paroi mince, procédé de préparation d'une telle composition et articles fabriqués à partir de celle-ci - Google Patents

Composition à base de polypropylène présentant une transparence, une dureté et une viscosité d'impact améliorées pour des articles moulés par injection à paroi mince, procédé de préparation d'une telle composition et articles fabriqués à partir de celle-ci Download PDF

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WO2020091621A1
WO2020091621A1 PCT/RU2018/000720 RU2018000720W WO2020091621A1 WO 2020091621 A1 WO2020091621 A1 WO 2020091621A1 RU 2018000720 W RU2018000720 W RU 2018000720W WO 2020091621 A1 WO2020091621 A1 WO 2020091621A1
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composition
elastomer
preparing
ethylene
density
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Alexey Mikhailovich VOLKOV
Irina Gennadievna RYZHIKOVA
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Sibur Holding PJSC
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Sibur Holding PJSC
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Priority to PCT/RU2018/000720 priority Critical patent/WO2020091621A1/fr
Priority to RU2021108825A priority patent/RU2770368C1/ru
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/005—Processes for mixing polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
    • C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
    • C08F255/08—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having four or more carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
    • C08L23/30—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment by oxidation
    • C—CHEMISTRY; METALLURGY
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/08—Homopolymers or copolymers of acrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/10—Homopolymers or copolymers of propene
    • C08J2323/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2423/04—Homopolymers or copolymers of ethene
    • C08J2423/06—Polyethene
    • C—CHEMISTRY; METALLURGY
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    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2423/04—Homopolymers or copolymers of ethene
    • C08J2423/08—Copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2423/10—Homopolymers or copolymers of propene
    • C08J2423/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2423/16—Ethene-propene or ethene-propene-diene copolymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/10—Transparent films; Clear coatings; Transparent materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2310/00—Masterbatches

Definitions

  • the present invention is related to polypropylene (PP) based compositions that possess an optimal balance of properties, in particular, improved flowability, improved impact resistance and hardness and also transparency.
  • the polypropylene-based composition obtained according to the claimed method is meant for injection molding of thin-walled articles used as packages and for storage of various materials including at temperatures below freezing point, for manufacture of thin-walled vessels for liquid and bulk materials, and also for lamination of various surfaces.
  • the important characteristics for the polypropylene-based composition used for injection molding of thin-walled articles are: high flowability and good mechanical properties, in particular, hardness and impact resistance.
  • the flowability requirement is important for providing high processability of the manufacture of articles based on the polypropylene composition.
  • the mechanical properties of the composition such as hardness and impact resistance provide the articles with resistance to damage, e.g. at mechanical compression or fall.
  • an important requirement for a polypropylene-based composition is optical characteristics, namely, transparency.
  • improvement of the optical properties of a polypropylene-based composition often leads to deterioration of mechanical properties and vice versa.
  • High degree of crystallinity of the polypropylene comprised in the composition provides good mechanical properties to the articles based thereon, in particular, hardness; however, it thus adversely affects transparency.
  • Decrease in the degree of crystallinity due to, e.g. increase in the amount of comonomer contained in the propylene copolymer facilitates improvement of optical properties of the compositions and articles based thereon; however, a significant deterioration of hardness thus occurs.
  • compositions the articles made of which are characterized by transparency are known from the art.
  • patent CN 103709518 discloses a composition based on the polypropylene random copolymer with propylene unit content from 87 to 99 wt.%.
  • Ethylene and a-olefm containing 4 to 8 carbon atoms are used as comonomers in this composition, they are introduced into the copolymer in an amount from 0.5 to 3.5 wt.% and from 0.5 to 9.5 wt.%, respectively.
  • the composition also comprises a nucleating agent, which is represented by sorbitol derivatives or aromatic phosphates.
  • the melt flow index (MFI) of the composition varies in the range from 0.5 to 20 g/10 min.
  • the composition is characterized by good transparency: the haze value is less than 10%; however, it does not possess the required level of impact strength characteristics required in the number of cases, especially at low temperatures and at high MFI value.
  • a number of patents described further discloses formulation and technological solutions allowing to increase the impact resistance of the polypropylene-based composition, including at low temperatures with maintaining of the optical properties (transparency).
  • the said balance of the mechanical and optical properties is achievable due to the composition based on the binary mixture of highly crystalline (co)polymer of propylene with an elastomer, wherein the elastomer has good compatibility with the propylene (co)polymer and is preferably an amorphous copolymer of propylene with relatively high contents of ethylene comonomer or a-olefm with 4 to 8 carbon atoms. Production of such copolymers is often carried out using metallocene catalytic systems according to two- or multi-stage reactor technology.
  • compositions based on propylene copolymers for the production of fibers, films or molded articles are disclosed.
  • the composition consists of A and B components obtained in separate reactors in the presence of metallocene catalytic system.
  • the component A is a propylene homopolymer with isotactic structure.
  • the component B is a propylene copolymer comprising from 12 to 18 wt.% ethylene.
  • the composition may also optionally comprise other additives, such as stabilizers, lubricants, nucleating agents, antistatic agents, dyes and pigments. It is noted that A and B components are present in the form of separate phases, and the weight ratio of A to B is from 80:20 to 60:40.
  • the composition described above is characterized by high transparency (haze is at most 30%) and Charpy notched impact resistance at room temperature (23°C) from 41.3 to 49.4 kJ/m 2 , and from 12.6 to 28.9 kJ/m 2 at 0°C.
  • the impact resistance drastically decreases to the values of 2.1 to 2.6 kJ/m 2 .
  • Another drawback of the composition is low tension modulus of from 602 to 609 MPa.
  • a binary composition that is characterized by increased flexural modulus value is represented.
  • the said composition consists of the propylene homopolymer (A), propylene copolymer (B) comprising from 10 to 35 wt.% of olefin other than propylene and, optionally, additives.
  • the increase in flexural modulus is achieved due to broadening of the content variation ranges for the component B and olefin in the propylene copolymer.
  • the propylene homopolymer and propylene copolymer are obtained using Ziegler-Natta catalytic system.
  • Patent RU 2528425 also describes a binary composition based on polypropylene with improved transparency, and also a method for preparing such composition by polymerization in reactor or via extrusion technology.
  • the said composition comprises: (A) from 60 to 90 wt.% of crystalline propylene copolymer comprising 3.5 to 10.0 wt.% units formed by ethylene, and (B) from 10 to 40 wt.% of propylene copolymer comprising from 18.5 to 23.5 wt.% units formed by ethylene.
  • the MFI value of the composition varies in the range from 3 to 20 g/10 min.
  • the Izod notched impact resistance are relatively low and are as follows: from 33.8 to 51.0 J/m at 23°C, from 9.9 to 45 J/m at 0°C, and from 3.3 to 4.9 J/m at 20°C.
  • the composition is characterized by low values of the flexural modulus from 500 to 700 MPa.
  • This composition comprises: (A) from 70 to 98 wt.% of crystalline homopolypropylene or propylene copolymer with 0.5 to 10.0 wt.% contents of units of ethylene or other olefin other than propylene; and (B) from 2 to 30 wt.% elastomer based on copolymer of ethylene with a- olefin comprising from 4 to 10 carbon atoms. It is noted that ethylene content in the copolymer (B) may vary from 60 to 85 wt.%. Thereby, the xylene- soluble fraction should possess intrinsic viscosity in the range from 0.8 to 1.1 dl/g.
  • the technical solution of a similar essence is known from patent RU 2043373 where a composition and a method for preparing a polypropylene composition with improved transparency and impact resistance, is disclosed.
  • the known composition comprises: (A) from 87.0 to 92.5 wt.% of crystalline copolymer of propylene and ethylene, and (B) from 7.5 to 13.0 wt.% of the elastomer based on copolymer of ethylene and C 3 -C 4 -a-olefin.
  • the composition is made by two-stage copolymerization. The content of ethylene units introduced at second stage of copolymerization using titanium-magnesium catalysts varies from 25 to 68.5 wt.%.
  • the additional conditions are certain values of intrinsic viscosities of xylene-soluble fractions of components A and B and also certain ratio of ethylene units in elastomeric, xylene-soluble ethylene copolymer.
  • a nucleating agent is further added to the composition.
  • the composition properties are not so good: the Izod notched impact resistance is 118 J/m at 23°C and from 30.4 to 45.0 J/m at 0°C, flexural modulus is from 780 to 880 MPa.
  • the solution directed to producing a composition with optimal balance of mechanical and optical properties is disclosed in the patent RU 2315069.
  • the content of elastomer in the composition is increased to the values from 30 to 45 wt.%, the xylene- soluble fraction content being at most 35 wt.%, preferably at most 30 wt.%.
  • the obtained composition is characterized by combination of high flowability and impact resistance, expressed via the ductile-to-brittle transition temperature and Izod notched impact resistance.
  • the ductile-to-brittle transition temperature is at most - 35°C.
  • the MFI value of the composition is > 15 g/10 min.
  • a drawback of the composition is the low value of the flexural modulus: from 600 to 770 MPa.
  • Patent EP 2471858 represents a composition of a more complex content, comprising: (A) from 30 to 60 wt.% of homopolypropylene; (B) from 30 to 60 wt.% of random copolymer of propylene with a-olefms comprising 4 to 8 carbon atoms; (C) from 2 to 15 wt.% of the elastomer based on copolymer of ethylene with a-oleflns comprising 4 to 8 carbon atoms; (D) homo- or copolymer of ethylene with the density from 0.905 to 0.920 g/cm 3 and (D) from 0.001 to 1.0 wt.% nucleating agent.
  • compositions is made according to multi-stage technology in several reactors.
  • the obtained composition has a tension modulus from 100 to 1600 MPa.
  • a drawback of this composition is low Charpy notched impact resistance that is from 4 to 7 kJ/m 2 at room temperature and from 2.5 to 3.0 kJ/m 2 at 0°C.
  • patent US 8779064 proposes contents and method for making polypropylene compositions with good impact resistance and transparency.
  • the composition contains a mixture of three components of different structure and properties.
  • the main component (A) comprised in the composition in an amount of from 50 to 95 wt.% is a random copolymer of propylene comprising from 0.5 to 10 wt.% of ethylene or other a-olefm. Its production is carried out in a reactor according to suspension technology using Ziegler-Natta catalytic systems or metallocene catalysts.
  • the reaction mass obtained in the said reactor is fed to another reactor wherein at the second stage the B component is obtained, the content of which in the final composition may vary from 5 to 49 wt.%.
  • the B component is an elastomer based on copolymer of propylene comprising from 20 to 70 wt.% of ethylene and/or butene units.
  • the obtained product (A + B) is mixed with component (C) via extrusion processing.
  • the component (C) is a copolymer of ethylene with a-olefin comprising 4 to 10 carbon atoms, and its content in the composition is from 1 to 45 wt.%.
  • the density of the component C may be varied in the range from 0.870 to 0.955 g/cm 3 ; therefore, both amorphous elastomers and plastomers and more crystalline (co)polymers of ethylene (LLDPE, MDPE and HDPE) may be used.
  • the composition may also comprise nucleating agents and other standard additives. The required properties of the composition are achievable by varying the amount of the components (A + B + C) in the mixture, ratio of their viscosities, and also nature of each component.
  • compositions outlined in the specific invention embodiment examples are varied in the following ranges: MFI is from 2.4 to 2.6 g/10 min, flexural modulus is from 930 to 1000 MPa, Izod notched impact resistance is from 550 to 570 J/m at 23°C and from 28 to 30 J/m at -20°C.
  • a drawback of the composition is a sophisticated method for making thereof and also low flowability and insufficiently high impact resistance at low temperatures.
  • the composition comprises (A) a highly crystalline random copolymer of propylene with ethylene and/or a-olefin with 4 to 8 carbon atoms.
  • the said copolymer comprises from 85 to 99 wt.% of propylene, from 1 to 5 wt.% of ethylene, from 1 to 6 wt.% of a-olefin.
  • the density of the copolymer (A) can be varied in the range from 0.885 to 0.910 g/cm 3 .
  • the B component content of which in the composition is from 40 to 75 wt.%, is a binary mixture of elastomer (Bl) based on copolymer of ethylene with a-olefin comprising 3 to 8 carbon atoms, with a density from 0.855 to 0.865 g/cm 3 (Mooney ML(1+4) 125 o from 10 to 100 relative units) and component (B2) which is a polyethylene thermoplast (LDPE, LLDPE or HDPE or mixture thereof) with a density from 0.910 to 0.965 g/cm 3 .
  • a drawback of the proposed composition is an insufficiently good balance of impact resistance and flexural modulus.
  • the flexural modulus is from 200 to 600 MPa.
  • the ductile-to-brittle transition temperature drastically increases to - 15°C.
  • a multi-component composition comprising a mixture of highly crystalline components: (A) from 30 to 60 wt.% of homopolypropylene; (B) from 10 to 50 wt.% of random copolymer with comonomer content of up to 5 wt.%; (C) from 10 to 20 wt.% of a mixture of two different elastomers based on ethylene copolymers differing in content of ethylene units and viscosity, (D) from 5 to 25 wt.% of homo- or random thermoplastic ethylene copolymer with a density of from 0.905 to 0.925 g/cm 3 . Mixing of all said components is carried out in a melt.
  • the obtained composition is characterized by the following properties: MFI > 20 g/10 min, Charpy notched impact resistance from 7.0 to 12.0 kJ/m 2 (from -70 to -120 J/m) at 23°C, from 1.8 to 4.0 kJ/m 2 (from -18 to -40 J/m) at -20°C, the haze of 2 mm thick injection molded samples is from 70 to 80%.
  • Drawbacks of this composition include sophisticated contents, insufficiently high impact resistance both at room and at decreased temperatures.
  • the main problem of the proposed solutions remains an infeasibility of optimal balance of the main characteristic of the polypropylene-based compositions used for producing packaging films, containers and other injection molded thin-walled articles. Therefore, there is a need to produce a polypropylene-based composition, which, retaining good impact resistance, including at low temperature, has improved flowability, namely a high melt flow index and high hardness and transparency.
  • the aim of the present invention is to provide a polypropylene-based composition that is characterized by high flowability and optimal combination of mechanical and optical properties, in particular, hardness, impact resistance and transparency.
  • the technical result of the present invention consists in increasing impact strength and physical and mechanical properties of the polypropylene-based composition, while maintaining optimal optical properties, namely, transparency.
  • the Izod notched impact resistance of the polypropylene-based composition is increased to the values from 150 to 517 J/m at 23°C and from 41 to 52 J/m at -20°C.
  • the composition has increased hardness, expressed via flexural modulus, which is from 910 to 1200 MPa.
  • the melt flow index of the composition is at the level of at least 20 g/10 min.
  • the additional technical result is simplifying the contents of the composition with respect to the prototype, which makes a method for making the composition more efficient.
  • the said technical result consisting in achieving the best transparency, is achievable at using an elastomer and a thermoplastic polymer at such weight ratio to each other, wherein the density of their mixture would be close or equal to the density of isotactic polypropylene; thereby, the elastomer content in the composition should be at least 10 wt.%.
  • high values of the composition transparency are provided at using the nucleating agent, preferably, a“brightener”.
  • the required flowability parameters and, simultaneously, high impact resistance and hardness parameters are achievable due to the use of crystalline isotactic polypropylene and also due to chemical modification of polymer components by modifying system comprising an organic peroxide and a co-agent, a vinyl monomer with three or more acrylate functional groups.
  • a claimed composition comprises, based on the total weight of the composition:
  • (C) from 10 to 25 wt.% of one or more copolymers of ethylene and/or random thermoplastic copolymers of ethylene with a-olefins comprising 3 to 10 carbon atoms, and also
  • (D) a modifying system comprising (Dl) from 0.04 to 0.64 wt.% of organic peroxide, (D2) from 0.04 to 0.64 wt.% of co-agent, which is represented by a vinyl monomer with three or more acrylate functional groups, and
  • the crystalline isotactic polypropylene (A) is a mixture of polypropylenes (A’) and (A”) differing in the values of melt flow indices.
  • two crystalline isotactic polypropylenes (A’) and (A”) with melt flow indices (MFI 230/2.16 ) of (A’) from 2.0 to 4.0 g/10 min, preferably from 2.5 to 3.5 g/ 10 min, and that of (A”) from 20 to 40 g/10 min, preferably from 25 to 35 g/10 min are used.
  • elastomer (B) a copolymer of ethylene with a-olefm comprising 4 to 10 carbon atoms is used, preferably the one obtained using metallocene catalytic systems.
  • a copolymer of ethylene with octene-l is used.
  • the said elastomer is characterized by density from 0.855 to 0.890 g/cm 3 , preferably from 0.857 to 0.885 g/cm 3 , and also a melt flow index (MFI190/2.16) from 1 to 30 g/10 min.
  • the content of the elastomer (B) based on 100 wt.% of the composition is from 10 to 20 wt.%, preferably from 10 to 17 wt.%, most preferably from 10 to 15 wt.%.
  • the component (C) in the claimed composition comprises one or several homopolymers of ethylene and/or random thermoplastic copolymers of ethylene with a- olefins comprising from 3 to 10 carbon atoms.
  • the density of the said homo- or copolymer of ethylene is from 0.910 to 0.965 g/cm 3 , preferably from 0.915 to 0.960 g/cm 3
  • MFI190/216 value is from 0.1 to 10 g/10 min, preferably from 0.3 to 8 g/10 min.
  • any basic grades of industrial polyethylene compliant with the aforesaid requirements selected from low density polyethylene (LDPE), linear low density polyethylene (LLDPE), linear medium density polyethylene (LMDPE) and high density polyethylene(HDPE) may be used as the component (C).
  • LDPE low density polyethylene
  • LLDPE linear low density polyethylene
  • LMDPE linear medium density polyethylene
  • HDPE high density polyethylene
  • LDPE polyethylene obtained according to the mechanism of radical-chain initiation of ethylene polymerization at high pressure (up to 2000 atm and more) in tubular- or autoclave-type reactors is used as LDPE.
  • the LDPE comprised in the claimed composition is characterized by melt flow index (MFI 190°c/2.16kg ) from 0.1 to 10 g/10 min, preferably from 0.2 to 10 g/10 min, more preferably from 0.3 to 5 g/10 min and has a density from 0.910 to 0.935 g/cm 3 , preferably from 0.910 to 0.930 g/cm 3 , more preferably from 0.915 to 0.925 g/cm 3 .
  • the polyethylene obtained by a method of anionic and coordination copolymerization of ethylene with a-olefins comprising 4 to 10 carbon atoms at low pressure using Ziegler-Natta catalysts or using metallocene catalytic systems according to standard industrial technologies is used as LLDPE and LMDPE according to the present invention.
  • the LLDPE comprised in the claimed composition is characterized by melt flow index (MFI 190°c/2.16kg ) from 0.1 to 10 g/10 min, preferably from 0.3 to 10 g/10 min, more preferably from 0.5 to 5 g/10 min and has a density from 0.910 to 0.927 g/cm 3 , preferably from 0.915 to 0.925 g/cm 3 .
  • the melt flow index (MFI 190°c/2.16kg ) of LMDPE is from 0.1 to 10 g/10 min, preferably from 0.3 to 10 g/10 min, more preferably from 0.5 to 5 g/10 min and has a density from 0.930 to 0.940 g/cm 3 , preferably from 0.930 to 0.935 g/cm 3 .
  • Copolymers of ethylene with a-olefin comprising 4 to 10 carbon atoms for example with a-olefin selected from the group comprising butene- 1, hexene- 1, octene-l and other a-olefms are used as LLDPE and LMDPE according to the present invention.
  • the most preferable is the polymer of ethylene with octene-l.
  • the content of the a- olefin comonomer in LLDPE and LMDPE is from 2.5 to 8 wt.%, preferably from 3 to 6 wt.%, most preferably from 3.5 to 5 wt.%.
  • the HDPE comprised in the claimed composition is characterized by values melt flow index (MFI 190°c/5kg ) from 0.1 to 5 g/10 min, preferably from 0.3 to 5 g/10 min, more preferably from 0.5 to 5 g/10 min and has a density from 0.945 to 0.965 g/cm 3 , preferably from 0.950 to 0.960 g/cm 3 .
  • the content of the component (C) in the composition is from 10 to 25 wt.%, preferably from 10 to 23 wt.%, most preferably from 10 to 20 wt.% based on total weight of the composition.
  • the concentration of the elastomer (B) in the claimed composition is at least 10 wt.%
  • the density of the mixture of elastomer (B) and homopolymer of ethylene and/or its random thermoplastic copolymer with a-olefm comprising 4 to 10 carbon atoms (C) is close or equal to the density of isotactic polypropylene (A), i.e. so that the density of (B + C) is at least 0.995, preferably at least 0.997 of the density of the polypropylene (A) and at most 1.007, preferably at most 1.005 of the density of the polypropylene (A).
  • the claimed composition necessarily comprises a modifying system (D) comprising, based on the total weight of the composition, from 0.04 to 0.64 wt.% of organic peroxide (Dl), from 0.04 to 0.64 wt.% of co-agent (D2), which is a vinyl monomer with three or more acrylate functional groups.
  • D modifying system
  • the organic peroxide (Dl) is selected from tert-butyl hydroperoxide, cumyl hydroperoxide, diisopropyl benzoyl hydroperoxide, di-tert-butyl peroxide, tert- butylcumyl peroxide, dicumyl peroxide, l,3-l,4-bis(tert-butylperoxyisopropyl)benzene, acetyl peroxide, benzoyl peroxide, isobutyryl peroxide, bis-3,5,5-trimethylhexanoyl peroxide, methyl ethyl ketone peroxide and other peroxides.
  • organic peroxides are used as individual components, because peroxide concentrates on inorganic and polymer carriers may decrease transparency of the obtained composition.
  • the content of the organic peroxide based on total weight of the composition is from 0.04 to 0.64 wt.%, preferably from 0.08 to 0.48 wt.%, most preferably from 0.1 to 0.40 wt.%.
  • the co-agent (D2) is a vinyl monomer with three or more acrylate functional groups. Pentaerythritol tetraacrylate, sorbitol hexaacrylate, xylitol pentaacrylate, glycerol triacrylate, trimethylolpropane triacrylate, preferably, trimethylolpropane triacrylate (TMPTA) are used as such monomers. Mono- and bifunctional esters, amides and other derivatives of acrylic monomers do not allow to achieve the desired technical result, as well as polyfunctional monomers of other nature, for example such as triallyl isocyanurate (TAIC), l,3,5-trivinylcyclohexane and the like.
  • TAIC triallyl isocyanurate
  • the content of the D2 co-agent based on total weight of the composition is from 0.04 to 0.64 wt.%, preferably from 0.08 to 0.48 wt.%, most preferably from 0.1 to 0.40 wt.%.
  • the claimed composition comprises (E) a nucleating agent in an amount from 0.05 to 1.0 wt.%, preferably from 0.1 to 0.8 wt.%, most preferably from 0.2 to 0.5 wt.% and also other optional additives.
  • a nucleating agent in an amount from 0.05 to 1.0 wt.%, preferably from 0.1 to 0.8 wt.%, most preferably from 0.2 to 0.5 wt.% and also other optional additives.
  • the nucleating agent of organic origin is used. It is also possible to use mixtures of nucleating agents.
  • nucleating agents are derivatives of dibenzylidene sorbitol that are also known as“brighteners”.
  • nucleating agent is selected from
  • composition of the present invention may also comprise optional additives other than nucleating agents, such as e.g. antioxidants, heat stabilizers, stabilizers and also mixtures thereof.
  • optional additives other than nucleating agents such as e.g. antioxidants, heat stabilizers, stabilizers and also mixtures thereof.
  • the content of such additives in the composition is preferably from 0 to 0.3 wt.%.
  • antioxidants examples include 2,6-di-tert-butyl-p-cresol, tetrakis[methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]methane and also 3,5- di-tert-butyl-4-hydroxy-phenylpropionic acid pentaerythritol ester of Irganox 1010 trademark.
  • Suitable heat stabilizers and light stabilizers comprise tri(phenyl-
  • Irgafos 168 trademark and/or analogous heat stabilizers of other trademarks and also light stabilizers like sterically hindered amines and mixture systems of stabilizers known under such trademarks as Irganox B225, Irganox B215.
  • composition according to the invention is obtained by mixing all components using known techniques for mixing thermoplastic materials, e.g. extrusion or mixing in mixers of various designs. Closed mixers with blades or rotors, single screw extruders, extruders with two screws rotating in the same or opposite directions are used.
  • the composition is obtained by mixing the components and subsequently compounding the obtained mixture in the melt using equipment known from the art, e.g. mixing equipment (Banbury mixers, Brabender mixer), single screw, double screw extruders and other similar mixers.
  • mixing is carried out in a mixing equipment and further compounding of the obtained mixture is carried out in an extruder.
  • the present inventors have unexpectedly found that mixing of all components in a single stage adversely affects the performance of the modifying system and nucleating agent (brightener), which does not lead to achievement of the required level of transparency of the obtained compositions. Therefore, use of the modifying system and nucleating agent in one stage is undesirable; therefore, the composition according to the present invention is obtained by a two-stage method comprising a stage of providing a modified concentrate composition as described below.
  • elastomer (B) based on copolymer of ethylene with a-olefin comprising 4 to 10 carbon atoms and (C) one or several homopolymers of ethylene and/or random thermoplastic copolymers of ethylene with a-olefins comprising 3 to 10 carbon atoms with (A ) a crystalline isotactic polypropylene, is carried out.
  • the mixing of said components (A’ + B + C) is carried out in the presence of the modifying system (D) comprising (D1) an organic peroxide in an amount from 0.1 to 0.8 wt.% and (D2) a co-agent in an amount from 0.1 to 0.8 wt.%, as which a vinyl monomer with three or more acrylate functional groups is used.
  • D the modifying system
  • Mixing of components is carried out in a mixing equipment for a period of time from 1 to 20 minutes, preferably from 2 to 10 minutes, at a temperature from 10 to 50°C, preferably from 20 to 40°C. Further, the obtained mixture is compounded in a melt, preferably in an extruder, at a temperature from 190 to 240 °C, preferably from 220 to 230°C. Thereby, the number of screw rotations is about 250 min 1 .
  • Mixing of the components is carried out in a mixing equipment for a period of time from 1 to 20 minutes, preferably from 2 to 10 minutes, at a temperature from 10 to 50°C, preferably from 20 to 40°C. Further, the obtained mixture is compounded in a melt, preferably in an extruder, at a temperature from 190 to 240°C, preferably from 220 to 230°C. The number of screw rotations is equal to about 250 min 1 .
  • polypropylene A’ in the first stage and A” in the second stage that differ in the values of melt flow indices as isotactic crystalline polypropylene is preferable.
  • a polypropylene with a melt flow index from 2.0 to 4.0 g/10 min, preferably from 2.5 to 3.5 g/10 min is used.
  • a polypropylene is used with a melt flow index from 20 to 40 g/10 min, preferably from 25 to 35 g/10 min.
  • the authors of the present invention believe that the use of the polypropylenes differing in the melt flow indices provides the formation of an interphase layer of certain morphology during modification of the dispersion heterophase mixture of (A) and (B) components.
  • the modified products comprising polypropylene-co-agent-elastomer thus formed are necessarily characterized by a high level of molecular mass characteristics in order to provide stability, uniformity and high density of the entangled polymer chains network of the macrochains in the dispersion system of polypropylene (A’) and elastomer (B) at the first stage of obtaining the composition.
  • the compounds described above are used as components (A), (B), (C), (D), (E) at producing the composition.
  • the content of the said components during producing the composition is varied in such a way, so the obtained composition complies with the claimed quantitative content; namely, comprises:
  • (C) from 10 to 25 wt.% of one or more copolymers of ethylene and/or random thermoplastic copolymers of ethylene with a-olefms comprising 3 to 10 carbon atoms, and also
  • (D) a modifying system comprising (Dl) from 0.04 to 0.64 wt.% of an organic peroxide, (D2) from 0.04 to 0.64 wt.% of a co-agent, as which a vinyl monomer with three or more acrylate functional groups is used, and
  • the ratios of the components (B) and (C) are varied in such a way, so that the density of the mixture of elastomer (B) and homopolymer (C) of ethylene and/or its thermoplastic copolymer with a-olefin comprising 4 to 10 carbon atoms , is close or equal to the density of isotactic polypropylene (A), i.e. it is required that the density of (B + C) is at least 0.995, preferably at least 0.997 of the density of the polypropylene (A) and at most 1.007, preferably at most 1.005 of the density of the polypropylene (A).
  • the concentration of the elastomer (B) in the composition should be at least 10 wt.%.
  • compositions of the present invention are preferably used as a material for manufacturing injection-molded articles, preferably, articles obtained by injection molding. It is even more preferable to use the compositions of the present invention for making thin-walled containers and packaging articles such as plastic cups, household items and food packaging.
  • the present invention also concerns articles made of the composition according to the invention; preferably, such articles are produced by injection molding.
  • melt flow index (MFI) at the temperature of 230°C and load of 2.16 kg is carried out according to ASTM D 1238-04C.
  • the samples for mechanical tests are prepared by injection molding according to ASTM D 4101.
  • the modes for injection molding on the injection molding machine Engel Victory 200/50 are as follows:
  • the determination of the Izod notched impact resistance at a temperature of 23 °C and -10°C is carried out according to ASTM D 256 (testing type A).
  • the determination of the flexural modulus is carried out according to ASTM D 790, testing type: three point bending, testing rate is 1.3 mm/min.
  • suitable polypropylenes (A’) comprise commercially available products known under the following trademarks: PPH 030 GP made by OOO “Tomskneftekhim”, OOO“Tobol'sk-Polymer”, OOO“Poliom”, NPO“Neftekhimija”, Balen 01030 made by OAO “Ufaorgsintez”, PP 1500J made by OOO
  • Suitable polypropylenes (A”) are the products known under the following trademarks: PPH 270 GP made by OOO “Tomskneftekhim”, OOO“Tobol'sk-Polymer”, OOO“Poliom”, NPO“Neftehimija”, Balen 01270 made by OAO “Ufaorgsintez”, PP 1300R made by OOO
  • Suitable elastomers (B) are commercially available products known under such trademarks as, for example, Engage 8452, Engage 8842, Engage 8137, Exact 8210. In particular, the following are used as the elastomer (B) in the present invention:
  • Engage 8452, 8842, 8137 - a copolymer of ethylene and octene made by Dow Chemical
  • Exact 8210 - a copolymer of ethylene and octene made by ExxonMobil
  • EPDM R563 - a triple copolymer of ethylene, propylene and diene.
  • LDPE low density polyethylene
  • thermoplastic copolymers of ethylene with a-olefms comprise low density polyethylenes (LDPE), for example such as PE 15303-003, PE 15803-020, PE 10803-020, PE 11503-070, PE 16803-070, Novex 20P730, LDPE 19N430, CA 8200, MA 8200, or mixtures thereof, linear low density polyethylenes (LLDPE), for example such as XP 9400, XP 9200, XP 9100, 3306WC4, PE 5118Q, UF414C4, 3840, SABIC LLDPE 318B, SABIC LLDPE 6318 BE, SABIC LLDPE R500035, or mixtures thereof, or linear medium density polyethylenes (LMDPE) such as e.g.
  • LDPE low density polyethylenes
  • LLDPE linear low density polyethylenes
  • LLDPE linear low density polyethylenes
  • SABIC LLDPE 318B SABIC LLDPE 6318 BE
  • DOWLEX 5066 Lumicene M3410 EP, or mixtures thereof, and also high density polyethylenes (HDPE), e.g. PE 6948C, PND-276-73, PND 273-83, SABIC HDPE B5205, SABIC HDPE B5429, SABIC HDPE F04660, PND PE30T-49, or mixture thereof.
  • HDPE high density polyethylenes
  • LDPE 15303-003 low density polyethylene made by OOO“Tomskneftekhim”,
  • HDPE 276-73 high density polyethylene made by OOO“Kazanorgsintez”.
  • Trigonox 301 examples of suitable peroxides are products known under the following trademarks: Trigonox 301, Luperox DCP, Luperox DI, Luperox DTA, Luperox F, Luperox 101, Luperox 801.
  • organic peroxide (Dl) the Trigonox 301, a cyclic peroxide made by AkzoNobel.
  • Trimethylolpropane triacrylate (TMPTA), 1 ,4-butanediol dimethacrylate (BDDMA), triallyl isocyanurate (TAIC) are used as co-agents (D2).
  • nucleating agents suitable for use in the compositions of the present invention comprise products known under the trademarks Millad 3988, Millad 8000, in particular, a brightener Millad 8000 made by Milliken is used as the nucleating agent (E).
  • Stage I A mixture is prepared in a blade mixer according to the formulation of the concentrate composition (K-l) shown in Table 1. Such a ratio of elastomer component (B) and polyethylene thermoplast (C) is selected that the density of the mixture (B + C) is equal to 0.900 g/cm 3 . Then the polymer components A + (B + C), organic peroxide (Dl) and co-agent (D2) are mixed for 2 to 10 minutes at room temperature. The obtained mixture is then processed in the LTE-20-44 double screw extruder at a maximum temperature in cylinder zone of 230°C and number of screw rotations equal to 250 min 1 . The granulate obtained at the line of this extruder is further used in stage II of the composition preparation.
  • Stage II A mixture is prepared in a blade mixer according to the formulation shown in Table 2 and mixing is carried out for 2 to 10 minutes at a temperature of 20 to 50°C.
  • additives nucleating agent and other possible additives
  • mineral oil in an amount of up to 0.2 wt.% may be optionally applied to the granules.
  • the obtained mixture of components is processed in the LTE-20-44 double screw extruder at a maximum temperature in cylinder zone of 210°C and number of screw rotations equal to 250 min -1 .
  • the second stage granulate obtained at the line of the LTE-20-44 extruder is further used in a dry form for determination of the MFI 230/2.16 values and for preparing samples by injection molding method for subsequent mechanical, optical, and physical tests.
  • Example 2 The example is carried out according to the Example 1 except that 60.0% of the modified concentrate K-l is dosed at stage II. The results of all tests are shown in Table 2.
  • the obtained composition is characterized by Izod notched impact resistance at +23°C and -20°C equal to 155 J/m and 42 J/m respectively.
  • the haze of the 2 mm-thick sample is 74.1%.
  • Example 2 The example is carried out according to the Example 1 except that 70.0% of the modified concentrate K-l is dosed at stage II. The results of all tests are shown in Table 2.
  • the obtained composition is characterized by Izod notched impact resistance at +23°C and -20°C equal to 486H J/m (H - hinge break) and 48 J/m respectively.
  • the haze of the 2 mm-thick sample is 75.4%.
  • Example 2 The example is carried out according to the Example 1 except that 80.0% of the modified concentrate K-l is dosed at stage II.
  • the results of all tests are outlined in Table 2.
  • the obtained composition is characterized by Izod notched impact resistance at +23 °C and -20 °C equal to 517H J/m and 52 J/m respectively.
  • the haze of the 2 mm sample is 79.4%.
  • Example 2 The example is carried out according to the Example 1 except that 85.0% of the modified concentrate K-l is dosed at stage II. The results of all tests are shown in Table 2.
  • the obtained composition is characterized by Izod notched impact resistance at +23°C and -20°C equal to 528H J/m and 56 J/m respectively.
  • the haze of the 2 mm- thick sample is 85.3%.
  • Example 6 (comparative). The example is carried out according to the Example 1 except that the modified K-2 concentrate formulation (Table 1) is used at stage I, and 80.0% of the modified concentrate K-2 is dosed at stage II. The results of all tests are shown in Table 2. The obtained composition is characterized by Izod notched impact resistance at +23 °C and - 20°C equal to 143 J/m and 40 J/m respectively. The haze of the 2 mm sample is 80.0%.
  • the example is carried out according to the Example 1 except that the modified K-3 concentrate formulation (Table 1) is used at stage I, and 80.0% of the modified concentrate K-3 is dosed at stage II.
  • Table 2 The results of all tests are shown in Table 2.
  • the obtained composition is characterized by Izod notched impact resistance at +23°C and - 20°C equal to 157 J/m and 41 J/m respectively.
  • the haze of the 2 mm-thick sample is 74.3%.
  • the example is carried out according to the Example 1 except that the modified K-4 concentrate formulation (Table 1) is used at stage I, and 60.0% of the modified concentrate K-4 is dosed at stage II.
  • Table 2 The results of all tests are shown in Table 2.
  • the obtained composition is characterized by Izod notched impact resistance at +23 °C and - 20°C equal to 208 J/m and 43 J/m respectively.
  • the haze of the 2 mm-thick sample is 65.1%.
  • the example is carried out according to the Example 1 except that the modified K-5 concentrate formulation (Table 1) is used at stage I, and 60.0% of the modified concentrate K-5 is dosed at stage II.
  • Table 2 The results of all tests are shown in Table 2.
  • the obtained composition is characterized by Izod notched impact resistance at +23 °C and - 20°C equal to 157 J/m and 43 J/m respectively.
  • the haze of the 2 mm-thick sample is 79.5%.
  • the example is carried out according to the Example 1 except that the modified K-6 concentrate formulation (Table 1) is used at stage I, and 60.0% of the modified concentrate K-6 is dosed at stage II.
  • Table 2 The results of all tests are shown in Table 2.
  • the obtained composition is characterized by Izod notched impact resistance at +23 °C and - 20°C equal to 355H J/m and 45 J/m respectively.
  • the haze of the 2 mm-thick sample is 75.1%.
  • the example is carried out according to the Example 1 except that the modified K-7 concentrate formulation (see Table 1) is used at stage I, and 40.0% of the modified concentrate K-7 is dosed at stage II.
  • the results of all tests are shown in Table 2.
  • the obtained composition is characterized by Izod notched impact resistance at +23 °C and - 20°C equal to 162 J/m and 42 J/m respectively.
  • the haze of the 2 mm-thick sample is 60.1%.
  • K-8 concentrate formulation (see Table 1) is used at stage I, and 60.0% of the modified concentrate K-8 is dosed at stage II.
  • the results of all tests are shown in Table 2.
  • the obtained composition is characterized by Izod notched impact resistance at +23 °C and - 20 °C equal to 151 J/m and 41 J/m respectively.
  • the haze of the 2 mm sample is 71.4%.
  • the example is carried out according to the Example 1 except that the modified K-9 concentrate formulation (see Table 1) is used at stage I, and 60.0% of the modified concentrate K-9 is dosed at stage II.
  • the results of all tests are shown in Table 2.
  • the obtained composition is characterized by Izod notched impact resistance at +23 °C and - 20°C equal to 178 J/m and 44 J/m respectively.
  • the haze of the 2 mm-thick sample is
  • the example is carried out according to the Example 1 except that the modified K-10 (comp.) concentrate formulation (Table 1) is used at stage I, and 60.0% of the modified concentrate K-10 (comp.) is dosed at stage II.
  • Table 1 modified K-10 (comp.) concentrate formulation
  • Table 2 modified concentrate K-10 (comp.) is dosed at stage II.
  • the results of all tests are shown in Table 2.
  • the obtained composition is characterized by Izod notched impact resistance at +23°C and -20°C equal to 175 J/m and 42 J/m respectively.
  • the haze of the 2 mm-thick sample is 85.0%.
  • K-l l (comp.) concentrate formulation (Table 1) is used at stage I, and 60.0% of the modified concentrate K-l l (comp.) is dosed at stage II.
  • Table 2 The results of all tests are shown in Table 2.
  • the obtained composition is characterized by Izod notched impact resistance at +23°C and -20°C equal to 79 J/m and 33 J/m respectively.
  • the haze of the 2 mm-thick sample is 64.1%.
  • the example is carried out according to the Example 1 except that the modified K-12 concentrate formulation (Table 1) is used at stage I, and 50.0% of the modified concentrate K-12 is dosed at stage II.
  • Table 2 The results of all tests are shown in Table 2.
  • the obtained composition is characterized by Izod notched impact resistance at +23 °C and - 20°C equal to 168 J/m and 43 J/m respectively.
  • the haze of the 2 mm-thick sample is 75.3%.
  • the example is carried out according to the Example 1 except that the modified K-13 concentrate formulation (Table 1) is used at stage I, and 60.0% of the modified concentrate K-13 is dosed at stage II.
  • Table 2 The results of all tests are shown in Table 2.
  • the obtained composition is characterized by Izod notched impact resistance at +23 °C and - 20°C equal to 259 J/m and 48 J/m respectively.
  • the haze of the 2 mm-thick sample is 77.9%.
  • the example is carried out according to the Example 1 except that the modified K-14 (comp.) concentrate formulation (Table 1) is used at stage I, and 70.0% of the modified concentrate K-14 (comp.) is dosed at stage II.
  • Table 1 modified K-14 (comp.) concentrate formulation
  • Table 2 modified concentrate K-14 (comp.) is dosed at stage II.
  • the results of all tests are shown in Table 2.
  • the obtained composition is characterized by Izod notched impact resistance at +23°C and -20°C equal to 77 J/m and 35 J/m respectively.
  • the haze of the 2 mm-thick sample is 95.1%.
  • the example is carried out according to the Example 1 except that the modified K-15 (comp.) concentrate formulation (Table 1) is used at stage I, and 60.0% of the modified concentrate K-15 (comp.) is dosed at stage II.
  • Table 1 modified K-15 (comp.) concentrate formulation
  • Table 2 modified concentrate K-15 (comp.) is dosed at stage II.
  • the results of all tests are shown in Table 2.
  • the obtained composition is characterized by Izod notched impact resistance at +23 °C and -20°C equal to 116 J/m and 35 J/m relatively.
  • the haze of the 2 mm-thick sample is 70.1%.
  • Example 20 (comparative). The example is carried out according to the Example 1 except that the modified K-16 (comp.) concentrate formulation (Table 1) is used at stage I, and 60.0% of the modified concentrate K-16 (comp.) is dosed at stage II. The results of all tests are shown in Table 2. The obtained composition is characterized by Izod notched impact resistance at +23°C and -20°C equal to 1 11 J/m and 32 J/m respectively. The haze of the 2 mm-thick sample is 72.4%.
  • the example is carried out according to the Example 1 except that the modified K-17 (comp.) concentrate formulation (Table 1), wherein the ratio of elastomer (B) (Engage 8452) to component C (LLDPE Daelim XP9200) is altered so that the total density of the B + C mixture is the value of 0.891 g/cm 3 , is used at stage I, and 50.0% of the modified concentrate K-17 (comp.) is dosed at stage II.
  • Table 2 The obtained composition is characterized by Izod notched impact resistance at +23°C and -20°C equal to 198 J/m and 48 J/m respectively.
  • the haze of the 2 mm-thick sample is 87.6%.
  • Example 2 The example is carried out according to the Example 1 except that the non- modified K-18 (comp.) concentrate formulation (Table 1) is used at stage I, and 60.0% of the non-modified concentrate K-18 (comp.) is dosed at stage II.
  • Table 2 The results of all tests are outlined in Table 2.
  • the obtained composition is characterized by Izod notched impact resistance at +23°C and -20°C equal to 75 J/m and 29 J/m respectively.
  • the haze of the 2 mm-thick sample is 70.2%.
  • the example is carried out according to the Example 1 except that the modified K-13 concentrate formulation (Table 1) is used at stage I, and 60.0% of the modified concentrate K-13 is dosed at stage II without the use of nucleating agent.
  • Table 1 modified K-13 concentrate formulation
  • Table 2 modified concentrate K-13 is dosed at stage II without the use of nucleating agent.
  • the results of all tests are outlined in Table 2.
  • the obtained composition is characterized by Izod notched impact resistance at +23 °C and -20°C equal to 215 J/m and 47 J/m respectively.
  • the haze of the 2 mm-thick sample is 89.1 %.
  • the polypropylene (PP) composition with the content of the components analogous to Example 2 is prepared in one stage without preliminary making of the modified concentrate.
  • a mixture is prepared in a blade mixer according to the formulation outlined in Table 2, and mixing is carried out for 2 to 10 minutes at a temperature of 20 to 50°C.
  • the obtained mixture of components is processed in the LTE-20-44 double screw extruder at maximum temperature in cylinder zones of 230°C and a number of screw rotations of 250 min '1 .
  • the second stage granulate obtained on the line of the LTE-20-44 extruder is further used in dry form for determination of the MFI230/2.I6 values and for making samples by injection molding method for subsequent mechanical, optical, and physical tests (names of tests are shown in Table 2).
  • the molding modes in the injection molding machine are analogous to the Example 1.
  • the results of all tests are shown in Table 2.
  • the obtained composition is characterized by Izod notched impact resistance at +23°C and -20°C equal to 158 J/m and 42 J/m respectively.
  • the haze of the 2 mm-thick sample is 89.7%.
  • the example is carried out according to the Example 1 except that the modified K-7 concentrate formulation (Table 1) is used at stage I, and 80.0% of the modified concentrate K-7 is dosed at stage II.
  • Table 2 The results of all tests are shown in Table 2.
  • the obtained composition is characterized by Izod notched impact resistance at +23 °C and - 20°C equal to 162 J/m and 42 J/m respectively.
  • the haze of the 2 mm-thick sample is 60.1%.
  • the example is carried out according to the Example 1 except that the modified K-7-1 concentrate formulation (Table 1) is used at stage I, and 40.0% of the modified concentrate K-7-1 is dosed at stage II.
  • Table 2 The results of all tests are shown in Table 2.
  • the obtained composition is characterized by Izod notched impact resistance at +23 °C and - 20°C equal to 159 J/m and 42 J/m respectively.
  • the haze of the 2 mm-thick sample is 65.0%.
  • Example 2 The example is carried out according to the Example 1 except that the modified K-19 concentrate formulation (Table 1) is used at stage I, and 80.0% of the modified concentrate K-19 is dosed at stage II. The results of all tests are shown in Table 2.
  • Table 2 The obtained composition is characterized by Izod notched impact resistance at +23 °C and - 20°C equal to 505H J/m and 50 J/m respectively.
  • the haze of the 2 mm-thick sample is 79.7%.
  • the example is carried out according to the Example 11 except that 0.05% of the nucleating agent is used at stage II.
  • the results of all tests are shown in Table 2.
  • the obtained composition is characterized by Izod notched impact resistance at +23 °C and - 20°C equal to 157 J/m and 41 J/m respectively.
  • the haze of the 2 mm-thick sample is 71.4%.
  • the example is carried out according to the Example 11 except that 1.0% of the nucleating agent is used at stage II.
  • the results of all tests are shown in Table 2.
  • the obtained composition is characterized by Izod notched impact resistance at +23 °C and - 20°C equal to 168 J/m and 43 J/m respectively.
  • the haze of the 2 mm-thick sample is 64.5%.
  • the polypropylene-based composition obtained in accordance with the method of the present invention has an improved balance of properties compared to prototypes and analogues and has the following parameters (in accordance with the Examples 2-4, 7-13, 16-17, Table 2):
  • compositions wherein the contents of components and their ratios are outside the claimed ranges demonstrate a significant deterioration of strength, mechanical and optical properties, which is confirmed by experimental data according to Examples 1, 5, 6 and 22.

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Abstract

La présente invention concerne une composition à base de polypropylène pour la fabrication d'articles moulés par injection, comprenant, par rapport au poids total de la composition : (A) 53,8 à 79,8 % en poids de polypropylène isotactique cristallin, (B) 10 à 20 % en poids d'élastomère à base d'un copolymère éthylène-oléfine comprenant de 4 à 10 atomes de carbone et (C) 10 à 25 % en poids d'un ou plusieurs homopolymères d'éthylène et/ou copolymères thermoplastiques aléatoires éthylène-oléfines comprenant de 3 à 10 atomes de carbone ; et également (D) un système de modification comprenant 0,04 à 0,64 % en poids de peroxyde organique (D1) et 0,04 à 0,64 % en poids d'un co-agent (D2), qui est un monomère vinylique comportant au moins trois groupes fonctionnels acrylate et (E) 0,05 à 1,0 % en poids d'un agent de nucléation et d'additifs facultatifs. La composition est fabriquée par un procédé en deux étapes comprenant une étape consistant à produire une composition concentrée modifiée par combinaison et mélange des composants pour obtenir une masse fondue à l'aide d'un équipement de mélange et d'une extrudeuse. La composition à base de polypropylène obtenue présente un équilibre optimal de ses propriétés, en particulier une fluidité accrue, une résistance aux chocs et une dureté améliorées, ainsi qu'une belle transparence. L'invention concerne également l'utilisation de la composition à base de polypropylène pour fabriquer des articles moulés par injection et, également, un article à base de la composition obtenue.
PCT/RU2018/000720 2018-11-02 2018-11-02 Composition à base de polypropylène présentant une transparence, une dureté et une viscosité d'impact améliorées pour des articles moulés par injection à paroi mince, procédé de préparation d'une telle composition et articles fabriqués à partir de celle-ci Ceased WO2020091621A1 (fr)

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PCT/RU2018/000720 WO2020091621A1 (fr) 2018-11-02 2018-11-02 Composition à base de polypropylène présentant une transparence, une dureté et une viscosité d'impact améliorées pour des articles moulés par injection à paroi mince, procédé de préparation d'une telle composition et articles fabriqués à partir de celle-ci
RU2021108825A RU2770368C1 (ru) 2018-11-02 2018-11-02 Композиция на основе полипропилена с улучшенной прозрачностью, ударной вязкостью и жесткостью, предназначенная для литья тонкостенных изделий, способ получения такой композиции и изделия, изготовленные из нее

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WO2022122614A1 (fr) * 2020-12-07 2022-06-16 Sabic Global Technologies B.V. Composition de polypropylène présentant une performance améliorée de blanchiment sous contrainte
CN117004130A (zh) * 2023-08-17 2023-11-07 苏州旭光聚合物有限公司 一种高强度高韧性汽车扎带用聚丙烯材料及其制备方法

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US20030055179A1 (en) * 2000-01-21 2003-03-20 Seiji Ota Olefin block copolymers processes for producing the same and uses thereof
US20070004864A1 (en) * 2005-06-24 2007-01-04 University Of Florida Research Foundation Method to enhance impact strength properties of melt processed polypropylene resins
US20090118426A1 (en) * 2000-01-26 2009-05-07 Makoto Mitani Olefin polymer and process for preparing the same
US20100087602A1 (en) * 2008-10-08 2010-04-08 Fina Technology, Inc. Long chain branched polypropylene for cast film applications
US20120289620A1 (en) * 2010-01-06 2012-11-15 Damien Deheunynck Process For Forming Crosslinked and Branched Polymers

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030055179A1 (en) * 2000-01-21 2003-03-20 Seiji Ota Olefin block copolymers processes for producing the same and uses thereof
US20090118426A1 (en) * 2000-01-26 2009-05-07 Makoto Mitani Olefin polymer and process for preparing the same
US20070004864A1 (en) * 2005-06-24 2007-01-04 University Of Florida Research Foundation Method to enhance impact strength properties of melt processed polypropylene resins
US20100087602A1 (en) * 2008-10-08 2010-04-08 Fina Technology, Inc. Long chain branched polypropylene for cast film applications
US20120289620A1 (en) * 2010-01-06 2012-11-15 Damien Deheunynck Process For Forming Crosslinked and Branched Polymers

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022122614A1 (fr) * 2020-12-07 2022-06-16 Sabic Global Technologies B.V. Composition de polypropylène présentant une performance améliorée de blanchiment sous contrainte
CN117004130A (zh) * 2023-08-17 2023-11-07 苏州旭光聚合物有限公司 一种高强度高韧性汽车扎带用聚丙烯材料及其制备方法

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