CN112778598A - Polyolefin composition and preparation method and application thereof - Google Patents

Polyolefin composition and preparation method and application thereof Download PDF

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Publication number
CN112778598A
CN112778598A CN201911090156.2A CN201911090156A CN112778598A CN 112778598 A CN112778598 A CN 112778598A CN 201911090156 A CN201911090156 A CN 201911090156A CN 112778598 A CN112778598 A CN 112778598A
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molecular weight
polyethylene
polyolefin composition
ultra
mixture
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CN112778598B (en
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孙婧元
冷家厂
黄正梁
吴斌斌
田思航
王靖岱
阳永荣
崔宇辉
刘焕毅
蒋斌波
孙侨
杨遥
廖祖维
历伟
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China Petroleum and Chemical Corp
Zhejiang University ZJU
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China Petroleum and Chemical Corp
Zhejiang University ZJU
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    • 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
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethylene
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
    • D01F8/06—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyolefin as constituent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/06—Properties of polyethylene
    • C08L2207/062—HDPE
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/06—Properties of polyethylene
    • C08L2207/068—Ultra high molecular weight polyethylene

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Artificial Filaments (AREA)

Abstract

The present invention provides a polyolefin composition comprising: polyalphaolefins, ultra high molecular weight polyethylene, polyethylene waxes, and high density polyethylene. The mechanical property and the processing property of the prepared polyolefin composition are greatly improved by matching the poly-alpha olefin oil, the ultra-high molecular weight polyethylene, the polyethylene wax and the high density polyethylene.

Description

Polyolefin composition and preparation method and application thereof
Technical Field
The invention relates to the technical field of high polymer materials, and particularly relates to a polyolefin composition, and a preparation method and application thereof.
Background
High density polyethylene has good properties such as wear resistance, electrical insulation, toughness, cold resistance, and mechanical strength, and is widely used in the fields of construction, industry, medicine, and daily product manufacture. However, high density polyethylene also has certain disadvantages: poor mechanical properties, easy stress cracking, low surface hardness and the like, and seriously influences the use of the high-density polyethylene. The ultra-high molecular weight polyethylene has various excellent properties such as ultra-light weight, high strength, wear resistance, corrosion resistance, impact resistance, self-sliding property and the like, so the ultra-high molecular weight polyethylene is widely applied to the fields of aerospace, military, sports equipment, medicine, industry and the like. The blending of the high-density polyethylene and the ultrahigh molecular weight polyethylene can improve the performance of the high-density polyethylene, enhance the mechanical property, the surface hardness, the processing performance and the like, and simultaneously solve the problem of serious entanglement of the ultrahigh molecular weight polyethylene.
The Chinese invention patent CN101003651A uses 50-90 wt% of ultra-high molecular weight polyethylene and 50-10 wt% of composite dispersant to blend, and then mixes with elastomer and high density polyethylene in a double screw extruder to granulate, thus achieving the purpose of modification. However, the ultra-high molecular weight polyethylene is seriously entangled, and the blending effect of the ultra-high molecular weight polyethylene and the high density polyethylene can be influenced.
The Chinese patent CN103305954A uses poly-alpha olefin oil and ultra-high molecular weight polyethylene to blend, and prepares high-quality fiber under the conditions of low spinning temperature, low shearing speed and low energy consumption, and overcomes the defect that ultra-high molecular weight polyethylene is difficult to process. However, this patent is only directed to the modification of ultra-high molecular weight polyethylene.
In view of the above, there is a need to develop a new material to overcome the problems of poor mechanical properties and easy stress cracking of the existing high density polyethylene, and to improve the problems of serious entanglement of the ultrahigh molecular weight polyethylene.
Disclosure of Invention
In view of the problems in the prior art, the present invention aims to provide a polyolefin composition, and a preparation method and applications thereof, wherein the mechanical properties and the processability of the prepared polyolefin composition are greatly improved by combining and using poly-alpha-olefin oil, ultra-high molecular weight polyethylene, polyethylene wax and high density polyethylene.
In one aspect, the present invention provides a polyolefin composition comprising: polyalphaolefins, ultra high molecular weight polyethylene, polyethylene waxes, and high density polyethylene.
The inventor of the application finds that the viscosity of the ultra-high molecular weight polyethylene is high, the viscosity of the high density polyethylene is low, the chain section of the ultra-high molecular weight polyethylene is long, and the entanglement between the chain interior and the chain section is serious. If the ultra-high molecular weight polyethylene and the high density polyethylene are directly blended, better dispersion and mixing are difficult to realize. When the ultra-high molecular weight polyethylene is mixed with the poly-alpha-olefin, the ultra-high molecular weight polyethylene swells, meanwhile, the poly-alpha-olefin props up gaps among platelets, the distance between chain segments is increased, the entanglement phenomenon inside the chain and among the chain segments is relieved, and a semi-dilute solution or a non-solution mixture is formed after mixing and dissolving. The added polyethylene wax plays a role in lubrication. After the high-density polyethylene is added and mixed, the molecular chain of the ultra-high molecular weight polyethylene can penetrate through the inside of the high-density polyethylene to form a 'string crystal structure', and the blending of the molecular layer is carried out. The mechanical property and the processing property of the modified mixture containing the ultra-high molecular weight polyethylene and the high density polyethylene are greatly improved.
In accordance with the present invention, polyalphaolefins may also be referred to as polyalphaolefin oils.
In some preferred embodiments of the present invention, the polyalphaolefin is present in an amount of 1 to 10 parts, the ultra high molecular weight polyethylene is present in an amount of 0.1 to 1000 parts, the polyethylene wax is present in an amount of 0.1 to 1000 parts, and the high density polyethylene is present in an amount of 1 to 1000 parts, by weight.
According to the invention, the content of the poly-alpha olefin is 1 to 10 parts, the content of the ultra-high molecular weight polyethylene is 1 to 100 parts, the content of the polyethylene wax is 1 to 100 parts, and the content of the high density polyethylene is 10 to 100 parts by weight.
In some preferred embodiments of the invention, the polyalphaolefin is selected from the group consisting of poly-C3-C19Preferably the polyalphaolefin is selected from the group consisting of poly C2nWherein n is 2 to 9, more preferably the polyalphaolefin is selected from at least one of polybutene-1, polyhexene-1, polyoctene-1, polydecene-1, and dodecene-1.
According to the invention, the polyalphaolefin is selected from the group consisting of poly C3-C9Preferably the polyalphaolefin is selected from the group consisting of poly C2nWherein n is 2 to 4.
In some preferred embodiments of the invention, the polyalphaolefin has a molecular weight in the range of 150-1000 and a density in the range of 0.74g/cm3-0.9g/cm3。
According to the invention, the molecular weight of the polyalphaolefin can be listed as 150, 200, 250, 300, 350, 400, 450, 500, 550, 600, 650, 700, 750, 800, 850, 900, 950 and 1000.
According to the invention, the polyalphaolefin may be enumerated as having a density of 0.74g/cm3、0.75g/cm3、0.76g/cm3、0.77g/cm3、0.78g/cm3、0.79g/cm3、0.80g/cm3、0.81g/cm3、0.82g/cm3、0.83g/cm3、0.84g/cm3、0.85g/cm3、0.86g/cm3、0.87g/cm3、0.88g/cm3、0.89g/cm3And 0.9g/cm3。
In some preferred embodiments of the present invention, the ultra high molecular weight polyethylene has a molecular weight in the range of 1000000-10000000 and a density in the range of 0.925g/cm3-0.945g/cm3。
According to the invention, the molecular weight of the ultra-high molecular weight polyethylene may be enumerated as 1000000, 1500000, 2000000, 2500000, 3000000, 3500000, 4000000, 4500000, 5000000, 5500000, 6000000, 6500000, 7000000, 7500000, 8000000, 8500000, 9000000, 9500000 and 10000000.
According to the invention, the density of the ultra-high molecular weight polyethylene is listed as 0.925g/cm3、0.930g/cm3、0.935g/cm3、0.940g/cm3And 0.945g/cm3。
In some preferred embodiments of the present invention, the polyethylene wax has a molecular weight in the range of 2000-5000 and a density in the range of 0.93g/cm3-0.98g/cm3。
According to the invention, the molecular weights of the polyethylene waxes may be cited as 2000, 2500, 3000, 3500, 4000, 4500 and 5000.
According to the invention, the density of the polyethylene wax may be cited as 0.93g/cm3、0.935g/cm3、0.94g/cm3、0.945g/cm3、0.95g/cm3、0.955g/cm3、0.96g/cm3、0.965g/cm3、0.97g/cm3、0.975g/cm3And 0.98g/cm3。
In some preferred embodiments of the inventionIn an embodiment of (1), the high-density polyethylene has a molecular weight in the range of 50000-3-0.955g/cm3。
According to the invention, the molecular weight of the high-density polyethylene can be cited as 50000, 60000, 70000, 80000, 90000, 100000, 110000, 120000, 130000, 140000, 150000, 160000, 170000, 180000, 190000 and 200000.
According to the invention, the density of the high-density polyethylene may be cited as 0.935g/cm3、0.940g/cm3、0.945g/cm3、0.950g/cm3And 0.955g/cm3。
In some preferred embodiments of the invention, the ratio of the molecular weight of the polyalphaolefin to the ultra high molecular weight polyethylene is from 1:100 to 1: 10000.
According to the invention, the ratio of the molecular weight of the polyalphaolefin to the ultra high molecular weight polyethylene is given as 1:100, 1:200, 1:300, 1:400, 1:500, 1:600, 1:700, 1:800, 1:900, 1:1000, 1:1500, 1:2000, 1:2500, 1:3000, 1:3500, 1:4000, 1:4500, 1:5000, 1:5500, 1:6000, 1:6500, 1:7000, 1:7500, 1:8000, 1:8500, 1:9000, 1:9500, 1: 10000.
In some preferred embodiments of the present invention, the ratio of the molecular weight of the polyethylene wax to the molecular weight of the ultra-high molecular weight polyethylene is from 1:200 to 1: 5000.
According to the invention, the molecular weight ratio of the polyethylene wax to the ultra-high molecular weight polyethylene may be enumerated as 1:200, 1:300, 1:400, 1:500, 1:600, 1:700, 1:800, 1:900, 1:1000, 1:1100, 1:1200, 1:1300, 1:1400, 1:1500, 1:1600, 1:1700, 1:1800, 1:1900, 1:2000, 1:2100, 1:2200, 1:2300, 1:2400, 1:2500, 1:2600, 1:2700, 1:2800, 1:2900, 1:3000, 1:3100, 1:3200, 1:3300, 1:3400, 1:3500, 1:3600, 1:3700, 1:3900, 1:4000, 1:4100, 1:4300, 1:4400, 1:4500, 1:4600, 1:4700, 5000: 4800, 491: 38000, and 4938000.
In some preferred embodiments of the invention, the ratio of the molecular weight of the high density polyethylene to the molecular weight of the ultra high molecular weight polyethylene is from 1:2 to 1: 50.
According to the invention, the ratio of the molecular weight of the high density polyethylene to the molecular weight of the ultra high molecular weight polyethylene is 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, 1:10, 1:11, 1:12, 1:13, 1:14, 1:15, 1:16, 1:17, 1:18, 1:19, 1:20, 1:21, 1:22, 1:23, 1:24, 1:25, 1:26, 1:27, 1:28, 1:29, 1:30, 1:31, 1:32, 1:33, 1:34, 1:35, 1:36, 1:37, 1:38, 1:39, 1:40, 1:41, 1:42, 1:43, 1:44, 1:45, 1:46, 1:47, 1:48, 1:49 and 1: 50.
In some preferred embodiments of the invention, the polyolefin composition has a tensile strength of greater than 40MPa, preferably greater than 60 MPa.
In another aspect, the present invention provides a method for preparing a polyolefin composition, comprising:
a) providing a semi-dilute solution or non-solution mixture comprising a polyalphaolefin and an ultra-high molecular weight polyethylene;
b) adding polyethylene wax to the semi-dilute solution or non-solution mixture to form a first mixture;
c) carrying out extrusion molding treatment on the first mixture to obtain a second mixture; and
d) blending high density polyethylene with said obtained second mixture to obtain a polyolefin composition.
The inventor of the present application finds that by the above steps, the mechanical properties and processability of the prepared polyolefin composition can be improved by sequentially introducing the ultra-high molecular weight polyethylene, the polyalphaolefin oil, the polyethylene wax and the high density polyethylene into the system.
In some preferred embodiments of the present invention, the weight ratio of the polyalphaolefin to the ultra high molecular weight polyethylene is from 1:1 to 1: 100.
According to the present invention, the mass ratio of the polyalphaolefin to the ultrahigh molecular weight polyethylene is exemplified by 1:1, 1:5, 1:10, 1:15, 1:20, 1:25, 1:30, 1:35, 1:40, 1:45, 1:50, 1:55, 1:60, 1:65, 1:70, 1:75, 1:80, 1:85, 1:90, 1:95 and 1: 100.
In some preferred embodiments of the present invention, the mass ratio of the polyethylene wax to the semi-dilute solution or non-solution mixture is from 1:0.1 to 1: 100.
According to the invention, the mass ratio of the polyethylene wax to the semi-dilute solution or the mixture of non-solutions may be listed as 1:0.1, 1:0.5, 1:1, 1:5, 1:10, 1:15, 1:20, 1:25, 1:30, 1:35, 1:40, 1:45, 1:50, 1:55, 1:60, 1:65, 1:70, 1:75, 1:80, 1:85, 1:90, 1:95 and 1: 100.
In some preferred embodiments of the present invention, the mass ratio of the high density polyethylene to the second mixture is 1:1 to 1: 100.
According to the invention, the mass ratio of the high-density polyethylene to the second mixture may be enumerated by 1:1, 1:5, 1:10, 1:15, 1:20, 1:25, 1:30, 1:35, 1:40, 1:45, 1:50, 1:55, 1:60, 1:65, 1:70, 1:75, 1:80, 1:85, 1:90, 1:95 and 1: 100.
According to the invention, the semi-dilute solution or non-solution mixture comprising poly-alpha-olefin and ultra-high molecular weight polyethylene can be prepared by:
heating and mixing the poly-alpha-olefin and the ultra-high molecular weight polyethylene in a mass ratio of 1:0.1-1:100 in a container, and performing pre-swelling at 90-150 ℃ and dissolving at 100-400 ℃ to form a semi-dilute solution or a non-solution mixture.
In some preferred embodiments of the invention, said step b) is carried out at a temperature of from 90 ℃ to 200 ℃, preferably from 120 ℃ to 180 ℃.
In some preferred embodiments of the invention, the temperature of the extrusion process is from 100 ℃ to 400 ℃; preferably, the extrusion process is carried out in a screw extruder, more preferably, the screw shear rate is from 70rpm to 350rpm and the ratio of screw length to diameter is from 40 to 100.
In some preferred embodiments of the invention, said step d) is carried out at a temperature of from 90 ℃ to 200 ℃, preferably from 120 ℃ to 180 ℃.
In one embodiment of the present invention, a method of preparing a polyolefin composition comprises:
1) heating and mixing poly-alpha-olefin and ultra-high molecular weight polyethylene in a mass ratio of 1:0.1-1:100 in a container, pre-swelling at 90-150 ℃, and dissolving at 100-40 ℃ to form a semi-dilute solution or a non-solution mixture;
2) adding polyethylene wax into the semi-dilute solution or the non-solution mixture according to the mass ratio of the polyethylene wax to the mixture of 1:0.1-1:100, and mixing at 90-200 ℃;
3) feeding the mixture obtained in the step 2) into a screw extruder, and extruding at 100-400 ℃ to obtain a blend, wherein the screw shear speed is 70-350rpm, and the ratio (L/D) of the length to the diameter of the screw is 40-100.
4) In the extrusion blend, adding the high-density polyethylene according to the mass ratio of the high-density polyethylene to the extrusion blend of 1:1-1:100, and blending at 90-200 ℃ to obtain the polyolefin composition.
The invention also provides, in a further aspect, the use of a polyolefin composition according to the above or a polyolefin composition obtained according to the above preparation process in the field of spinning.
In still another aspect, the present invention provides a method for spinning using the above polyolefin composition or the polyolefin composition prepared according to the above preparation method, comprising:
the polyolefin composition is fed to a spinning die plate and is spun at a speed of 2 to 5m/min to produce filaments.
According to the invention, the polyolefin composition is conveyed through a filter to a spinning die plate, pressurized by a melt booster pump.
According to the invention, the prepared filaments are cooled to 0-50 ℃ by air or water and dried, and then a plurality of cooled and dried filaments are drawn by a roller multi-stage drawing device and are subjected to super-doubling and multi-stage drawing to obtain the final product.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the invention adopts four substances of poly-alpha-olefin-ultra-high molecular weight polyethylene-polyethylene wax-high density polyethylene to blend and modify. Wherein, the poly-alpha olefin enters into the space between the ultra-high molecular weight polyethylene platelets to open the gap, the distance between chain segments is increased, and the problem of serious entanglement of the ultra-high molecular weight polyethylene chain segments is solved. The polyethylene wax is added for lubrication. Then adding high-density polyethylene for blending, and allowing the ultrahigh molecular weight polyethylene chain section to pass through the high-density polyethylene to realize the blending of molecular scales, thereby forming a 'string crystal' structure.
(2) The strength of the prepared polyolefin composition is increased, and the problem of serious entanglement of ultrahigh molecular weight polyethylene chain segments is effectively improved.
Detailed Description
The present invention will be described in detail below with reference to examples, but the scope of the present invention is not limited to the following description.
The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
The molecular weight, density and other parameters of each substance in the invention are measured by conventional methods and techniques.
Example 1
Polyhexene-1 (molecular weight 500, density 0.8 g/cm)3) With ultra-high molecular weight polyethylene (molecular weight 5000000, density 0.935 g/cm)3) Heating and mixing in a mixing kettle according to the mass ratio of 1:50, pre-swelling at 95 ℃, and dissolving at 150 ℃ to form a semi-dilute solution mixture.
Adding polyethylene wax (molecular weight 3000, density 0.95 g/cm) into the semi-dilute solution at a mass ratio of 1:13) Mixing was carried out to obtain a first mixture, the temperature of the mixing operation being 150 ℃.
The first mixture was fed to a screw extruder and extruded at 150 ℃ to give a second mixture, the screw shear rate was 150rpm and the ratio of the screw length to the diameter (L/D) was 60. Cooling to 40 ℃ by adopting air; xylene is used as an extracting agent, and the extracting agent is removed by heating and drying to extract polyhexene-1 in the mixture;
to the second mixture obtained, high density polyethylene (molecular weight 100000, density 0.945 g/cm) was added in a mass ratio of 1:53) And blended at 100 ℃ to obtain the polyolefin composition 1.
The resulting polyolefin composition 1 was tested to have a tensile strength of 70 MPa.
Pressurizing the polyolefin composition 1 by a melt booster pump, conveying the polyolefin composition to a spinning template through a filter, spraying the polyolefin composition from holes of the spinning template at a speed of 3m/min, cooling the polyolefin composition to room temperature by using air or water, and drying the polyolefin composition; and then drawing the cooled and dried multiple spinning yarns by adopting a roller multi-stage traction device, and performing super-doubling and multi-stage stretching to obtain a final product.
The fiber breaking strength is 35.9 Ren/dtex, and the bending modulus is 3500 MPa.
Example 2
Polyhexene-1 (molecular weight 500, density 0.8 g/cm)3) With ultra-high molecular weight polyethylene (molecular weight 5000000, density 0.935 g/cm)3) Heating and mixing the materials in a mixing kettle according to the mass ratio of 1:80, pre-swelling the materials at 95 ℃, and dissolving the materials at 150 ℃ to form a semi-dilute solution mixture.
Adding polyethylene wax (molecular weight 3000, density 0.95 g/cm) into the semi-dilute solution at a mass ratio of 1:0.53) Mixing was carried out to obtain a first mixture, the temperature of the mixing operation being 150 ℃.
The first mixture was fed to a screw extruder and extruded at 150 ℃ to give a second mixture, the screw shear rate was 150rpm and the ratio of the screw length to the diameter (L/D) was 60. Cooling to 40 ℃ by adopting air; xylene is used as an extracting agent, and the extracting agent is removed by heating and drying;
to the second mixture obtained, high density polyethylene (molecular weight 100000, density 0.945 g/cm) was added in a mass ratio of 1:23) And blended at 100 ℃ to obtain the polyolefin composition 2.
The resulting polyolefin composition 2 was found to have a tensile strength of 46 MPa.
Pressurizing the polyolefin composition 2 by a melt booster pump, conveying the polyolefin composition to a spinning template through a filter, spraying the polyolefin composition from holes of the spinning template at the speed of 3m/min, cooling the polyolefin composition to room temperature by using air or water, and drying the polyolefin composition; and then drawing the cooled and dried multiple spinning yarns by adopting a roller multi-stage traction device, and performing super-doubling and multi-stage stretching to obtain a final product.
The fiber breaking strength is 30.5 Ren/dtex, and the flexural modulus is 2700 MPa.
Example 3
Polyhexene-1 (molecular weight 500, density 0.8 g/cm)3) With ultra-high molecular weight polyethylene (molecular weight 5000000, density 0.935 g/cm)3) Heating and mixing the materials in a mixing kettle according to the mass ratio of 1:30, pre-swelling the materials at 95 ℃, and dissolving the materials at 150 ℃ to form a semi-dilute solution mixture.
Adding polyethylene wax (molecular weight 3000, density 0.95 g/cm) into the semi-dilute solution at a mass ratio of 1:23) Mixing was carried out to obtain a first mixture, the temperature of the mixing operation being 150 ℃.
The first mixture was fed to a screw extruder and extruded at 150 ℃ to give a second mixture, the screw shear rate was 150rpm and the ratio of the screw length to the diameter (L/D) was 60. Cooling to 40 ℃ by adopting air; xylene is used as an extracting agent, and the extracting agent is removed by heating and drying;
to the second mixture obtained, high density polyethylene (molecular weight 100000, density 0.945 g/cm) was added in a mass ratio of 1:23) And blended at 100 ℃ to obtain polyolefin composition 3.
The resulting polyolefin composition 3 was found to have a tensile strength of 42 MPa.
Pressurizing the polyolefin composition 3 by a melt booster pump, conveying the polyolefin composition to a spinning template through a filter, spraying the polyolefin composition from holes of the spinning template at a speed of 3m/min, cooling the polyolefin composition to room temperature by using air or water, and drying the polyolefin composition; and then drawing the cooled and dried multiple spinning yarns by adopting a roller multi-stage traction device, and performing super-doubling and multi-stage stretching to obtain a final product.
The fiber breaking strength is 29.6 Ren/dtex, and the bending modulus is 2500 MPa.
Example 4
Polyhexene-1 (molecular weight 500, density 0.8 g/cm)3) With ultra-high molecular weight polyethylene (molecular weight 5000000, density 0.935 g)/cm3) Heating and mixing in a mixing kettle according to the mass ratio of 1:50, pre-swelling at 95 ℃, and dissolving at 150 ℃ to form a semi-dilute solution mixture.
Adding polyethylene wax (molecular weight 3000, density 0.95 g/cm) into the semi-dilute solution at a mass ratio of 1:503) Mixing was carried out to obtain a first mixture, the temperature of the mixing operation being 150 ℃.
The first mixture was fed to a screw extruder and extruded at 150 ℃ to give a second mixture, the screw shear rate was 150rpm and the ratio of the screw length to the diameter (L/D) was 60. Cooling to 40 ℃ by adopting air; xylene is used as an extracting agent, and the extracting agent is removed by heating and drying;
to the second mixture obtained, high density polyethylene (molecular weight 100000, density 0.945 g/cm) was added in a mass ratio of 1:53) And blended at 100 ℃ to obtain polyolefin composition 4.
The resulting polyolefin composition 4 was tested to have a tensile strength of 23 MPa.
Pressurizing the polyolefin composition 4 by a melt booster pump, conveying the polyolefin composition to a spinning template through a filter, spraying the polyolefin composition from holes of the spinning template at the speed of 3m/min, cooling the polyolefin composition to room temperature by using air or water, and drying the polyolefin composition; and then drawing the cooled and dried multiple spinning yarns by adopting a roller multi-stage traction device, and performing super-doubling and multi-stage stretching to obtain a final product.
The fiber breaking strength is 19.5 Ren/dtex, and the flexural modulus is 1700 MPa.
Comparative example 1
Mixing ultra-high molecular weight polyethylene (molecular weight 5000000, density 0.935 g/cm)3) Heating in a mixing kettle, and dissolving at 150 ℃ to form a semi-dilute solution mixture.
Adding polyethylene wax (molecular weight 3000, density 0.95 g/cm) into the semi-dilute solution at a mass ratio of 1:13) Mixing was carried out to obtain a first mixture, the temperature of the mixing operation being 150 ℃.
The first mixture was fed to a screw extruder and extruded at 150 ℃ to give a second mixture, the screw shear rate was 150rpm and the ratio of the screw length to the diameter (L/D) was 60. Cooling to 40 ℃ by adopting air; xylene is used as an extracting agent, and the extracting agent is removed by heating and drying;
to the second mixture obtained, high density polyethylene (molecular weight 100000, density 0.945 g/cm) was added in a mass ratio of 1:53) And blended at 100 ℃ to obtain polyolefin composition 5.
The resulting polyolefin composition 5 was found to have a tensile strength of 35 MPa.
Pressurizing the polyolefin composition 5 by a melt booster pump, conveying the polyolefin composition to a spinning template through a filter, spraying the polyolefin composition from holes of the spinning template at the speed of 3m/min, cooling the polyolefin composition to room temperature by using air or water, and drying the polyolefin composition; and then drawing the cooled and dried multiple spinning yarns by adopting a roller multi-stage traction device, and performing super-doubling and multi-stage stretching to obtain a final product.
The fiber breaking strength is detected to be 16.9 Ren/dtex, and the flexural modulus is 950 MPa.
Comparative example 2
Polyhexene-1 (molecular weight 500, density 0.8 g/cm)3) With ultra-high molecular weight polyethylene (molecular weight 5000000, density 0.935 g/cm)3) Heating and mixing in a mixing kettle according to the mass ratio of 1:50, pre-swelling at 95 ℃, and dissolving at 150 ℃ to form a semi-dilute solution mixture.
Adding polyethylene wax (molecular weight 3000, density 0.95 g/cm) into the semi-dilute solution at a mass ratio of 1:13) Mixing was carried out to obtain a first mixture, the temperature of the mixing operation being 200 ℃.
The first mixture was fed into a screw extruder and extruded at 150 ℃ to give a polyolefin composition 6, the screw shear rate was 150rpm and the ratio of the screw length to the diameter (L/D) was 60. Cooling to 40 ℃ by adopting air; xylene is used as an extracting agent, and the extracting agent is removed by heating and drying;
the resulting polyolefin composition 6 was tested to have a tensile strength of 30 MPa.
Pressurizing the polyolefin composition 6 by a melt booster pump, conveying the pressurized polyolefin composition to a spinning template through a filter, spraying the polyolefin composition from holes of the spinning template at a speed of 3m/min, cooling the polyolefin composition to room temperature by using air or water, and drying the polyolefin composition; and then drawing the cooled and dried multiple spinning yarns by adopting a roller multi-stage traction device, and performing super-doubling and multi-stage stretching to obtain a final product.
The fiber breaking strength is 15.6 Ren/dtex, and the flexural modulus is 800 MPa.
Comparative example 3
Polyhexene-1 (molecular weight 500, density 0.8 g/cm)3) With ultra-high molecular weight polyethylene (molecular weight 5000000, density 0.935 g/cm)3) Heating and mixing the materials in a mixing kettle according to the mass ratio of 1:50, pre-swelling the materials at 95 ℃, and dissolving the materials at 150 ℃ to form a mixture.
The above mixture was fed into a screw extruder and extruded at 150 ℃ to give a blend, the screw shear rate was 150rpm and the ratio of the screw length to the diameter (L/D) was 60. Cooling to 40 ℃ by adopting air; xylene is used as an extracting agent, and the extracting agent is removed by heating and drying;
in the resulting blend, high density polyethylene (molecular weight 100000, density 0.945 g/cm) was added in a mass ratio of 1:53) And blended at 100 ℃ to obtain polyolefin composition 7.
The resulting polyolefin composition 7 was tested to have a tensile strength of 40 MPa.
Pressurizing the polyolefin composition 7 by a melt booster pump, conveying the polyolefin composition to a spinning template through a filter, spraying the polyolefin composition from holes of the spinning template at a speed of 3m/min, cooling the polyolefin composition to room temperature by using air or water, and drying the polyolefin composition; and then drawing the cooled and dried multiple spinning yarns by adopting a roller multi-stage traction device, and performing super-doubling and multi-stage stretching to obtain a final product.
The fiber breaking strength is 26.4 Ren/dtex, and the bending modulus is 2300 MPa.
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.

Claims (10)

1.一种聚烯烃组合物，所述聚烯烃组合物包括：聚α烯烃、超高分子量聚乙烯、聚乙烯蜡和高密度聚乙烯；1. A polyolefin composition comprising: polyalphaolefin, ultra-high molecular weight polyethylene, polyethylene wax and high density polyethylene; 优选地，以重量份数计，所述聚α烯烃的含量为1份～10份，所述超高分子量聚乙烯的含量为0.1份～1000份，所述聚乙烯蜡的含量为0.1份～1000份，所述高密度聚乙烯的含量为1份～1000份。Preferably, in parts by weight, the content of the polyalphaolefin is 1 part to 10 parts, the content of the ultra-high molecular weight polyethylene is 0.1 part to 1000 parts, and the content of the polyethylene wax is 0.1 part to 1000 parts. 1000 parts, the content of the high density polyethylene is 1 part to 1000 parts. 2.根据权利要求1所述的聚烯烃组合物，其特征在于，所述聚α烯烃选自聚C3-C19的α烯烃，优选所述聚α烯烃选自聚C2n的α烯烃，其中n为2至9，更优选所述聚α烯烃选自聚丁烯-1、聚己烯-1、聚辛烯-1、聚癸烯-1、聚十二烯-1中的至少一种，优选地，所述聚α烯烃的分子量范围是150-1000，密度范围是0.74g/cm3-0.9g/cm3；和/或2. The polyolefin composition according to claim 1, wherein the polyalphaolefin is selected from poly-C 3 -C 19 alpha olefins, preferably the polyalphaolefin is selected from poly-C 2n alpha olefins, wherein n is 2 to 9, more preferably the polyalphaolefin is selected from at least one of polybutene-1, polyhexene-1, polyoctene-1, polydecene-1, polydodecene-1 species, preferably, the polyalphaolefin has a molecular weight range of 150-1000 and a density range of 0.74g/cm 3 -0.9g/cm 3 ; and/or 所述超高分子量聚乙烯的分子量范围是1000000-10000000，密度范围是0.925g/cm3-0.945g/cm3；和/或The ultra-high molecular weight polyethylene has a molecular weight range of 1000000-10000000 and a density range of 0.925g/cm3-0.945g/ cm3 ; and/or 所述聚乙烯蜡的分子量范围是2000-5000，密度范围是0.93g/cm3-0.98g/cm3；和/或The polyethylene wax has a molecular weight range of 2000-5000 and a density range of 0.93g/cm 3 -0.98g/cm 3 ; and/or 所述高密度聚乙烯的分子量范围是50000-200000，密度范围是0.935g/cm3-0.955g/cm3。The molecular weight range of the high density polyethylene is 50000-200000, and the density range is 0.935g/cm 3 -0.955g/cm 3 . 3.根据权利要求1或2所述的聚烯烃组合物，其特征在于，3. The polyolefin composition according to claim 1 or 2, characterized in that, 所述聚α烯烃与所述超高分子量聚乙烯的分子量之比为1:100-1:10000；和/或The molecular weight ratio of the polyalphaolefin to the ultra-high molecular weight polyethylene is 1:100-1:10000; and/or 所述聚乙烯蜡与所述超高分子量聚乙烯的分子量之比为1:200-1:5000；和/或The molecular weight ratio of the polyethylene wax to the ultra-high molecular weight polyethylene is 1:200-1:5000; and/or 所述高密度聚乙烯与所述超高分子量聚乙烯的分子量之比为1:2-1:50。The molecular weight ratio of the high-density polyethylene to the ultra-high molecular weight polyethylene is 1:2-1:50. 4.根据权利要求1-3中任一项所述的聚烯烃组合物，其特征在于，所述聚烯烃组合物的拉伸强度大于40MPa，优选为大于60MPa。4 . The polyolefin composition according to claim 1 , wherein the tensile strength of the polyolefin composition is greater than 40 MPa, preferably greater than 60 MPa. 5 . 5.一种聚烯烃组合物的制备方法，包括：5. a preparation method of polyolefin composition, comprising: a)提供包含聚α烯烃和超高分子量聚乙烯的半稀溶液或非溶液混合物；a) providing a semi-dilute solution or non-solution mixture comprising polyalphaolefin and ultra-high molecular weight polyethylene; b)将聚乙烯蜡加入到所述半稀溶液或非溶液混合物中，形成第一混合物；b) adding polyethylene wax to the semi-dilute solution or non-solution mixture to form a first mixture; c)对所述第一混合物进行挤出成型处理，得到第二混合物；以及c) subjecting the first mixture to extrusion molding to obtain a second mixture; and d)使高密度聚乙烯与所述第二混合物共混，制得聚烯烃组合物。d) Blending high density polyethylene with the second mixture to produce a polyolefin composition. 6.根据权利要求5所述的制备方法，其特征在于，所述聚α烯烃和所述超高分子量聚乙烯的质量比1:1-1:100；和/或6. The preparation method according to claim 5, wherein the mass ratio of the polyalphaolefin and the ultra-high molecular weight polyethylene is 1:1-1:100; and/or 所述聚乙烯蜡与所述半稀溶液或非溶液混合物的质量比1:0.1-1:100；和/或The mass ratio of the polyethylene wax to the semi-dilute solution or non-solution mixture is 1:0.1-1:100; and/or 所述高密度聚乙烯与所述第二混合物的质量比1:1-1:100。The mass ratio of the high density polyethylene to the second mixture is 1:1-1:100. 7.根据权利要求5或6所述的制备方法，其特征在于，在90℃-200℃、优选120℃-180℃的温度下进行所述步骤b)。7. The preparation method according to claim 5 or 6, wherein the step b) is carried out at a temperature of 90°C-200°C, preferably 120°C-180°C. 8.根据权利要求4-7中任一项所述的制备方法，其特征在于，所述挤出成型处理的温度为100℃-400℃；优选地，所述挤出成型处理在螺杆挤出机中进行，更优选地，螺杆剪切速度为70rpm-350rpm，螺杆长度与直径之比为40-100。8 . The preparation method according to claim 4 , wherein the temperature of the extrusion molding process is 100° C. to 400° C.; preferably, the extrusion molding process is performed in a screw extrusion process. 9 . It is carried out in the machine, more preferably, the shearing speed of the screw is 70rpm-350rpm, and the ratio of screw length to diameter is 40-100. 9.根据权利要求4-8中任一项所述的制备方法，其特征在于，在90℃-200℃、优选120℃-180℃的温度下进行所述步骤d)。9 . The preparation method according to claim 4 , wherein the step d) is carried out at a temperature of 90°C-200°C, preferably 120°C-180°C. 10 . 10.一种根据权利要求1-4中任一项所述的聚烯烃组合物或根据权利要求5-9中任一项所述的制备方法制得的聚烯烃组合物在纺丝领域中的应用。10. Use of the polyolefin composition according to any one of claims 1-4 or the polyolefin composition obtained by the preparation method according to any one of claims 5-9 in the field of spinning application.
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