CN112778598B - Polyolefin composition and preparation method and application thereof - Google Patents
Polyolefin composition and preparation method and application thereof Download PDFInfo
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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—Polyethene
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- 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
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- 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
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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
- 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
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- C—CHEMISTRY; METALLURGY
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- 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
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- C—CHEMISTRY; METALLURGY
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/06—Properties of polyethylene
- C08L2207/062—HDPE
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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
- 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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Abstract
The present invention provides a polyolefin composition comprising: poly alpha olefins, ultra high molecular weight polyethylene, polyethylene wax, 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
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 50-90wt% of ultra-high molecular weight polyethylene and 50-10wt% of composite dispersant to mix, and then mixes with elastomer and high density polyethylene in a double screw extruder to granulate, so as to achieve 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 invention patent CN103305954A uses poly-alpha-olefin oil and ultra-high molecular weight polyethylene to blend, and prepares high quality fiber under low energy consumption conditions of low spinning temperature, low shearing speed, etc., which improves the defect that ultra-high molecular weight polyethylene is not easy 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: poly alpha olefins, ultra high molecular weight polyethylene, polyethylene wax, and high density polyethylene.
The inventor of the present application found that the viscosity of the ultra-high molecular weight polyethylene is high, the viscosity of the high density polyethylene is low, the chain segment of the ultra-high molecular weight polyethylene is long, and the entanglement between the chain interior and the chain segment is severe. 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.
Polyalphaolefins, according to the present invention, 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-C 3 -C 19 Preferably the polyalphaolefin is selected from the group consisting of poly C 2n 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, and dodecene-1.
According to the invention, the polyalphaolefin is selected from the group consisting of poly C 3 -C 9 Preferably the polyalphaolefin is selected from the group consisting of poly C 2n Wherein n is 2 to 4.
In some preferred embodiments of the invention, the polyalphaolefin has a molecular weight in the range of 150 to 1000 and a density in the range of 0.74g/cm 3 -0.9g/cm 3 。
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/cm 3 、0.75g/cm 3 、0.76g/cm 3 、0.77g/cm 3 、0.78g/cm 3 、0.79g/cm 3 、0.80g/cm 3 、0.81g/cm 3 、0.82g/cm 3 、0.83g/cm 3 、0.84g/cm 3 、0.85g/cm 3 、0.86g/cm 3 、0.87g/cm 3 、0.88g/cm 3 、0.89g/cm 3 And 0.9g/cm 3 。
In some preferred embodiments of the invention, the ultra high molecular weight polyethylene has a molecular weight in the range of 1000000 to 10000000 and a density in the range of 0.925g/cm 3 -0.945g/cm 3 。
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/cm 3 、0.930g/cm 3 、0.935g/cm 3 、0.940g/cm 3 And 0.945g/cm 3 。
In some preferred embodiments of the present invention, the polyethylene wax has a molecular weight in the range of 2000 to 5000 and a density in the range of 0.93g/cm 3 -0.98g/cm 3 。
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/cm 3 、0.935g/cm 3 、0.94g/cm 3 、0.945g/cm 3 、0.95g/cm 3 、0.955g/cm 3 、0.96g/cm 3 、0.965g/cm 3 、0.97g/cm 3 、0.975g/cm 3 And 0.98g/cm 3 。
In some preferred embodiments of the invention, the high density polyethylene has a molecular weight in the range of 50000 to 200000 and a density in the range of 0.935g/cm 3 -0.955g/cm 3 。
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/cm 3 、0.940g/cm 3 、0.945g/cm 3 、0.950g/cm 3 And 0.955g/cm 3 。
In some preferred embodiments of the invention, the ratio of the molecular weight of the polyalphaolefin to the ultra high molecular weight polyethylene is 1.
According to the invention, the ratio of the molecular weight of the polyalphaolefin to the ultrahigh molecular weight polyethylene can be listed as 1.
In some preferred embodiments of the present invention, the ratio of the molecular weight of the polyethylene wax to the ultra-high molecular weight polyethylene is 1.
According to the present invention, the ratio of the polyethylene wax to the ultrahigh molecular weight polyethylene can be listed as 1.
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 1.
According to the present invention, the ratio of the high-density polyethylene to the ultrahigh-molecular-weight polyethylene is 1.
In some preferred embodiments of the invention, the polyolefin composition has a tensile strength of greater than 40MPa, preferably greater than 60MPa.
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 1 to 1.
According to the present invention, the mass ratio of the polyalphaolefin and the ultrahigh molecular weight polyethylene can be listed as 1, 5, 1, 15, 1, 20, 1, 25, 1, 35, 1, 40, 1, 45, 1, 50, 1.
In some preferred embodiments of the invention, the mass ratio of the polyethylene wax to the semi-dilute solution or non-solution mixture is from 1.
According to the present invention, the mass ratio of the polyethylene wax to the semi-dilute solution or non-solution mixture can be listed as 1.
In some preferred embodiments of the present invention, the mass ratio of the high density polyethylene to the second mixture is 1.
According to the invention, the mass ratio of the high-density polyethylene to the second mixture can be listed as 1.
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 poly-alpha-olefin and ultra-high molecular weight polyethylene in a container according to the mass ratio of 1.1-1.
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 container according to the mass ratio of 1.1-1;
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;
3) Feeding the mixture obtained in step 2) into a screw extruder, and extruding at 100-400 ℃ to obtain a blend, wherein the screw shear rate is 70-350rpm, and the ratio of the screw length to the screw diameter (L/D) 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.
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 multistage drawing device and are subjected to super-doubling and multistage 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.
Adding polyethylene wax (molecular weight 3000, density 0.95 g/cm) into the semi-dilute solution according to the mass ratio of the polyethylene wax to the semi-dilute solution mixture of 1 3 ) 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 thus obtained, high-density polyethylene (molecular weight 100000, density 0.945 g/cm) was added in a mass ratio of 1 3 ) And blended at 100 ℃ to obtain polyolefin composition 1.
The resulting polyolefin composition 1 was tested to have a tensile strength of 70MPa.
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 multistage traction device, and performing super-power and multistage drawing to obtain a final product.
The fiber breaking strength is 35.9 Ren/dtex, and the bending modulus is 3500MPa.
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.
Adding polyethylene wax (with the molecular weight of 3000 and the density of 0.95 g/cm) into the semi-dilute solution according to the mass ratio of the polyethylene wax to the mixture of the semi-dilute solution being 1 3 ) 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 thus obtained, high-density polyethylene (molecular weight 100000, density 0.945 g/cm) was added in a mass ratio of 1 3 ) And blended at 100 ℃ to obtain the polyolefin composition 2.
The resulting polyolefin composition 2 was found to have a tensile strength of 46MPa.
Pressurizing the polyolefin composition 2 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 multistage traction device, and performing super-power and multistage drawing to obtain a final product.
The fiber breaking strength is 30.5 Ren/dtex, and the flexural modulus is 2700MPa.
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 in a mixing kettle according to the mass ratio of 1.
Adding polyethylene wax (molecular weight 3000, density 0.95 g/cm) into the semi-dilute solution according to the mass ratio of the polyethylene wax to the semi-dilute solution mixture of 1 3 ) 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 high density polyethylene to second mixture of 1 3 ) And blended at 100 ℃ to obtain polyolefin composition 3.
The resulting polyolefin composition 3 was found to have a tensile strength of 42MPa.
Pressurizing the polyolefin composition 3 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 multistage traction device, and performing super-power and multistage drawing to obtain a final product.
The fiber breaking strength is 29.6 Ren/dtex and the bending modulus is 2500MPa.
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/cm) 3 ) Heating and mixing in a mixing kettle according to the mass ratio of 1 to 50, pre-swelling at 95 ℃, and dissolving at 150 ℃ to form a semi-dilute solution mixture.
Adding polyethylene wax (with the molecular weight of 3000 and the density of 0.95 g/cm) into the semi-dilute solution according to the mass ratio of the polyethylene wax to the mixture of the semi-dilute solution of 1 3 ) 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 thus obtained, high-density polyethylene (molecular weight 100000, density 0.945 g/cm) was added in a mass ratio of 1 3 ) At 100 ℃ inAnd blended to produce polyolefin composition 4.
The resulting polyolefin composition 4 was found to have a tensile strength of 23MPa.
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 multistage traction device, and performing super-power and multistage drawing to obtain a final product.
The fiber breaking strength is 19.5 Ren/dtex, and the flexural modulus is 1700MPa.
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 according to the mass ratio of the polyethylene wax to the semi-dilute solution mixture of 1 3 ) 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 thus obtained, high-density polyethylene (molecular weight 100000, density 0.945 g/cm) was added in a mass ratio of 1 3 ) Blending was conducted at 100 ℃ to obtain polyolefin composition 5.
The resulting polyolefin composition 5 was found to have a tensile strength of 35MPa.
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 950MPa.
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.
Adding polyethylene wax (with the molecular weight of 3000 and the density of 0.95 g/cm) into the semi-dilute solution according to the mass ratio of the polyethylene wax to the mixture of the semi-dilute solution of 1 3 ) Mixing was carried out to obtain a first mixture, the temperature of the mixing operation being 200 ℃.
The first mixture was fed to a screw extruder and extruded at 150 ℃ to give a polyolefin composition 6 having a screw shear rate of 150rpm and a ratio of screw length to screw diameter (L/D) of 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 found to have a tensile strength of 30MPa.
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 800MPa through detection.
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 in a mixing kettle according to the mass ratio of 1 to 50, pre-swelling at 95 ℃, and dissolving 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;
to the resulting blend, high density polyethylene (molecular weight 100000, density 0.945 g/cm) was added in a mass ratio of 1 3 ) And blended at 100 ℃ to obtain polyolefin composition 7.
The resulting polyolefin composition 7 was tested to have a tensile strength of 40MPa.
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 2300MPa.
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 in relation to an exemplary embodiment, and it is understood that 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 (18)
1. A polyolefin composition, the polyolefin composition comprising: polyalphaolefins, ultra high molecular weight polyethylene, polyethylene waxes, and high density polyethylene;
the polyethylene composition comprises, by weight, 1-10 parts of poly-alpha-olefin, 1-100 parts of ultra-high molecular weight polyethylene, 1-100 parts of polyethylene wax and 10-100 parts of high density polyethylene.
2. Polyolefin composition according to claim 1, wherein the polyalphaolefin is selected from the group consisting of poly-C 3 -C 19 The alpha olefin of (a); and/or
The ultra-high molecular weight polyethylene has a molecular weight range of 1000000-10000000 and a density range of 0.925g/cm 3 -0.945g/cm 3 (ii) a And/or
The polyethylene wax has a molecular weight in the range of 2000-5000 and a density in the range of 0.93g/cm 3 -0.98g/cm 3 (ii) a And/or
The high density polyethylene has a molecular weight range of 50000-200000 and a density range of 0.935g/cm 3 -0.955 g/cm 3 。
3. Polyolefin composition according to claim 2, wherein the polyalphaolefin is selected from the group consisting of poly-C 2n Wherein n is 2 to 9.
4. Polyolefin composition according to any one of claims 1 to 3, wherein the polyalphaolefin is selected from at least one of polybutene-1, polyhexene-1, polyoctene-1, polydecene-1, and polydodecene-1.
5. Polyolefin composition according to any one of claims 1 to 3, wherein the polyalphaolefin has a molecular weight in the range of from 150 to 1000 and a density in the range of from 0.74g/cm 3 -0.9 g/cm 3 。
6. Polyolefin composition according to claim 1, characterized in that,
the ratio of the molecular weight of the polyalphaolefin to the ultra-high molecular weight polyethylene is 1 to 1; and/or
The molecular weight ratio of the polyethylene wax to the ultrahigh molecular weight polyethylene is 1; and/or
The ratio of the molecular weight of the high density polyethylene to the molecular weight of the ultra-high molecular weight polyethylene is 1.
7. Polyolefin composition according to any one of claims 1 to 3, wherein the polyolefin composition has a tensile strength of more than 40MPa.
8. Polyolefin composition according to claim 7, wherein the polyolefin composition has a tensile strength of more than 60MPa.
9. A process for the preparation of a polyolefin composition according to any of claims 1 to 8 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 a high density polyethylene with the second mixture to produce a polyolefin composition.
10. The production method according to claim 9, wherein the mass ratio of the polyalphaolefin to the ultrahigh molecular weight polyethylene is 1 to 1; and/or
The mass ratio of the polyethylene wax to the semi-dilute solution or non-solution mixture is 1; and/or
The mass ratio of the high-density polyethylene to the second mixture is 1.
11. The method of claim 9 or 10, wherein the step b) is performed at a temperature of 90 ℃ to 200 ℃.
12. The method of claim 11, wherein the step b) is performed at a temperature of 120 ℃ to 180 ℃.
13. The method of claim 9 or 10, wherein the temperature of the extrusion molding process is 100 ℃ to 400 ℃.
14. The method of claim 13, wherein the extrusion molding process is performed in a screw extruder.
15. The method of claim 14, wherein the screw shear rate is from 70rpm to 350rpm and the ratio of screw length to screw diameter is from 40 to 100.
16. The method of claim 9 or 10, wherein the step d) is performed at a temperature of 90 ℃ to 200 ℃.
17. The method of claim 16, wherein the step d) is performed at a temperature of 120 ℃ to 180 ℃.
18. Use of a polyolefin composition according to any of claims 1 to 8 or obtained by the preparation process according to any of claims 9 to 17 in the field of spinning.
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| CN103012907A (en) * | 2011-09-28 | 2013-04-03 | 深圳市冠力新材料有限公司 | Modification method of ultra-high-molecular-weight polyethylene (UHMWPE) |
| CN103305954A (en) * | 2013-07-01 | 2013-09-18 | 浙江大学 | Method for preparing ultra-high molecular weight polyethylene fiber |
| CN108774349A (en) * | 2018-06-22 | 2018-11-09 | 上海化工研究院有限公司 | A kind of UHMWPE melting extrusions level composite material and preparation method thereof, moulding process and application |
| CN109233062A (en) * | 2018-09-21 | 2019-01-18 | 上海化工研究院有限公司 | It is a kind of prepare in strong fiber composite material and its quick molding method and application |
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| DE602007008600D1 (en) * | 2006-11-08 | 2010-09-30 | Panpan Hu | METHOD FOR PRODUCING FIBERS FROM POLYETHYLENE WITH ULTRA-HIGH MOLECULAR WEIGHT |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103012907A (en) * | 2011-09-28 | 2013-04-03 | 深圳市冠力新材料有限公司 | Modification method of ultra-high-molecular-weight polyethylene (UHMWPE) |
| CN103305954A (en) * | 2013-07-01 | 2013-09-18 | 浙江大学 | Method for preparing ultra-high molecular weight polyethylene fiber |
| CN108774349A (en) * | 2018-06-22 | 2018-11-09 | 上海化工研究院有限公司 | A kind of UHMWPE melting extrusions level composite material and preparation method thereof, moulding process and application |
| CN109233062A (en) * | 2018-09-21 | 2019-01-18 | 上海化工研究院有限公司 | It is a kind of prepare in strong fiber composite material and its quick molding method and application |
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