WO2020177241A1 - 一种耐切割、耐蠕变uhmwpe纤维及其制备方法 - Google Patents

一种耐切割、耐蠕变uhmwpe纤维及其制备方法 Download PDF

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WO2020177241A1
WO2020177241A1 PCT/CN2019/092224 CN2019092224W WO2020177241A1 WO 2020177241 A1 WO2020177241 A1 WO 2020177241A1 CN 2019092224 W CN2019092224 W CN 2019092224W WO 2020177241 A1 WO2020177241 A1 WO 2020177241A1
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silicon carbide
molecular weight
ultra
modified
high molecular
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French (fr)
Inventor
沈文东
陈清清
曹海建
陈小林
车俊豪
张玲丽
宋兴印
喻峰
曹亚峰
朱宸宇
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JIANGSU JONNYMA NEW MATERIALS Co Ltd
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JIANGSU JONNYMA NEW MATERIALS Co Ltd
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Priority to US17/042,944 priority Critical patent/US11859071B2/en
Priority to EP19917735.3A priority patent/EP3778754B1/en
Publication of WO2020177241A1 publication Critical patent/WO2020177241A1/zh
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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
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/04—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyolefins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C08K3/042—Graphene or derivatives, e.g. graphene oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/10—Metal compounds
    • C08K3/14—Carbides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/10—Silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
    • 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
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/46—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polyolefins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/12—Applications used for fibers
    • 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

Definitions

  • the present invention belongs to the field of polymer material manufacturing. More specifically, the present invention relates to a cut-resistant, creep-resistant UHMWPE fiber and a preparation method thereof.
  • Ultra-high molecular weight polyethylene fiber refers to a molecular weight of 1 to 6 million. Because of its high crystallinity and strong intermolecular force, it has many excellent properties such as wear resistance, Extremely high impact resistance, chemical corrosion resistance, high noise elimination performance, self-lubrication, low friction coefficient, safety, health and non-toxicity, etc. Excellent performance, known as "magic plastic", widely used in Chemicals, machinery, textiles, papermaking, packaging, mining, construction, sports, military, medical and many other fields.
  • UHMWPE is a high-performance fiber made by spinning-extraction-drying-super-stretching in turn.
  • Fiber-reinforced composite materials made of ultra-high molecular weight polyethylene have the advantages of light weight, impact resistance, and high dielectric properties. They are widely used in aerospace, maritime defense, weaponry and daily industry.
  • the present invention provides an inorganic filler filled UHMWPE to modify it, and at the same time, the present invention can solve the problem of poor dispersibility of inorganic filler under the condition of high viscoelasticity of ultra-high molecular weight polyethylene.
  • the first aspect of the present invention provides an ultra-high molecular weight polyethylene composition, which includes the following components: modified graphene, modified silicon carbide whiskers, and ultra-high molecular weight polyethylene.
  • the content of the modified graphene is 0.5-5 wt% of the ultra-high molecular weight polyethylene.
  • the content of the modified silicon carbide whiskers is 0.5-5 wt% of the ultra-high molecular weight polyethylene.
  • the weight average molecular weight of the ultra-high molecular weight polyethylene is 2 to 2.4 million.
  • the modified graphene is aminated graphene.
  • the aminated graphene includes piperazine modified graphene and stearylamine modified graphene.
  • the modified silicon carbide whiskers are silicon carbide whiskers modified by a silane coupling agent.
  • the weight ratio of the silicon carbide whiskers to the silane coupling agent in the silicon carbide whiskers modified by the silane coupling agent is 1:(0.1-0.5).
  • the second aspect of the present invention provides a cut-resistant and creep-resistant fiber prepared from the above-mentioned ultra-high molecular weight polyethylene composition.
  • the third aspect of the present invention provides a method for preparing a cut-resistant and creep-resistant fiber.
  • the steps include:
  • step (1) The mixture in step (1) is sheared and stirred by an emulsifier at high speed to obtain a spinning solution;
  • the fiber provided by the present invention has excellent cut resistance, high strength and high modulus.
  • By adjusting the shape of silicon carbide, coupling agent type, ratio, etc. it can not only solve the problem of cutting resistance, high strength and high modulus, but also improve creep resistance.
  • the addition of coupling agent in the formula makes the silicon carbide coated to avoid It is in direct contact with the human body to improve product performance while ensuring safety and no toxic side effects.
  • the above-mentioned range is regarded as continuous and includes the minimum and maximum values of the range, and every value between such minimum and maximum values. Further, when the range refers to an integer, it includes every integer between the minimum value and the maximum value of the range.
  • the ranges can be combined. In other words, unless otherwise specified, all ranges disclosed herein should be understood to include any and all sub-ranges subsumed therein. For example, a specified range from "1 to 10" should be regarded as including any and all sub-ranges between the minimum value of 1 and the maximum value of 10. Exemplary sub-ranges of the range 1 to 10 include, but are not limited to, 1 to 6.1, 3.5 to 7.8, 5.5 to 10, and the like.
  • the first aspect of the present invention provides an ultra-high molecular weight polyethylene composition, which includes the following components: modified graphene, modified silicon carbide whiskers, and ultra-high molecular weight polyethylene.
  • the graphene of the present invention is a two-dimensional crystal of a monoatomic layer formed by sp 2 hybrid connection of carbon atoms, and the carbon atoms are regularly arranged in the honeycomb lattice structure unit. Each carbon atom is connected to the other three carbon atoms with a ⁇ bond, and the remaining ⁇ electrons form a large delocalized ⁇ bond with the ⁇ electrons of other carbon atoms. The electrons can move freely in this region, so that the graphene has Excellent electrical conductivity. At the same time, this densely packed honeycomb structure is also the basic unit for constructing other carbon materials.
  • a single atomic layer of graphene can be wrapped to form zero-dimensional fullerene, and single or multilayer graphene can be rolled to form a single wall or multiple layers. Wall of carbon nanotubes.
  • Graphene is also an excellent thermal conductor. Its thermal conductivity is as high as 5000W/(m ⁇ K), which is better than carbon nanotubes and more than 10 times higher than some common metals, such as gold, silver, and copper.
  • Graphene preparation methods mechanical peeling method, epitaxial growth method, chemical vapor deposition method, chemical synthesis method, graphene oxide reduction method and longitudinal cutting carbon tube method.
  • Epitaxial growth method Use high temperature (1200-1500°C) sublimation to remove silicon atoms from the surface of single crystal silicon carbide (SiC), thereby obtaining epitaxially grown graphene.
  • Chemical vapor deposition method refers to cracking carbon source (such as hydrocarbon) at high temperature and depositing it on the surface of a solid substrate, which is usually Ni, Ru and other transition metals.
  • Graphene oxide reduction method At present, the most widely used and the most promising method for the preparation of graphene on a large scale is to use graphene oxide as a precursor to heat or chemically reduce the surface of graphene oxide. The oxygen-containing groups are removed. Although this method cannot obtain perfect graphene, it can restore the intrinsic properties of graphene to a large extent. At the same time, compared with other graphene preparation methods, the graphene oxide reduction method has abundant raw materials, simple equipment and operation process, and the prepared graphene has good workability, so it has attracted much attention.
  • the graphene oxide reduction method includes thermal expansion reduction method and chemical reduction method.
  • the preparation method of the graphene can be prepared by any method known in the art, and the method of reducing graphene oxide is preferred in the present invention.
  • Graphene oxide is a derivative of graphene.
  • Graphene treated with a strong oxidant contains three elements: C, H, and O. Similar to graphite, graphite oxide also has a two-dimensional layered structure, and graphene oxide is stacked layer by layer through interlayer hydrogen bonding and other forces. However, the surface of graphene oxide contains a large number of oxygen-containing groups, which makes it exhibit strong hydrophilicity and can be dispersed in water.
  • Preparation method of graphene oxide The three commonly used methods for preparing graphite oxide at present, namely Brodie method, Staudenmaier method and Hummers method, all use a combination of strong acid-enhanced oxidant to treat graphite. Strong protic acid enters between graphite layers to form graphite intercalation compounds, and then a strong oxidant oxidizes the graphite and introduces a large number of hydrophilic oxygen-containing functional groups to the surface and edges of graphene to form graphene oxide. Due to the strong hydrophilicity of oxygen-containing groups, graphene oxide can be completely exfoliated and dispersed in the aqueous solution.
  • the graphene oxide is the product of graphite powder after chemical oxidation and exfoliation.
  • Graphene oxide is a single atomic layer and can be expanded to tens of micrometers in the lateral dimension at any time. Therefore, its structure exceeds the general chemical And the typical scale of materials science.
  • Graphene oxide can be regarded as an unconventional type of soft material, with the characteristics of polymers, colloids, films, and amphiphilic molecules. After oxidation treatment, graphite oxide still maintains the layered structure of graphite, but many oxygen functional groups are introduced on each layer of graphene monolithic sheet.
  • the Hummers method has relatively good timeliness and is relatively safe during the preparation process, and is currently the most commonly used one.
  • the idea of the former is to split graphite flakes to prepare graphene oxide, represented by an improved method of the traditional three methods, and also include splitting (breaking) carbon nanotubes and so on.
  • the latter is a synthesis method using various carbon sources, and the specific methods are diverse and diverse.
  • the oxygen content of the oxidized graphene is 15at%-20at%.
  • the oxygen content is 16at%-18at%, more preferably 17at% %.
  • the analysis of the oxygen content can be obtained by any method known to those skilled in the art; in the present invention, the method of element analysis is mainly used for testing.
  • the graphene is often processed to have amino groups on the surface.
  • the method of the functionalization treatment is not specifically limited in the present invention, and can be prepared by any method known to those skilled in the art, or can be commercially available.
  • the modified graphene of the present invention is aminated graphene.
  • the aminated graphene of the present invention includes piperazine modified graphene and stearylamine modified graphene.
  • the weight ratio of the piperazine-modified graphene and the stearylamine-modified graphene of the present invention is 1:(2-3).
  • the piperazine-modified graphene of the present invention is purchased from Nanjing Xianfeng Nanomaterials Technology Co., Ltd., and the brand is XF005-1; the octadecylamine-modified graphene is purchased from Nanjing Xianfeng Nano Material Technology Co., Ltd., brand name is XF005-3.
  • modifying graphene can form a film on its surface, avoiding adsorption and agglomeration between graphene molecules or between silicon carbide molecules, and improving the dispersion effect between materials.
  • an anchor point is formed inside the fiber to absorb the transferred energy and avoid local crack expansion, thereby improving the effect of tearing resistance.
  • the inventors unexpectedly discovered that the creep resistance and high temperature resistance of UHMWPE fiber can be improved by adjusting the ratio of piperazine-modified graphene and stearylamine-modified graphene.
  • the flexible aliphatic alkane chain on the octamine and the cyclic structure on the piperazine form a protective film on the surface of the graphene to prevent agglomeration, and at the same time, it is beneficial to form an interpenetrating network structure inside the UHMWPE segment, thereby changing the strength of the fiber And cutting resistance.
  • the silicon carbide (SiC) of the present invention is a binary compound of group IV-IV, which is the only and extremely stable compound among group IV elements. It is formed by covalent bonding of carbon atoms and silicon atoms. It has a hexahedral crystal structure similar to diamond.
  • the SiC crystal structure consists of two densely arranged sublattices, the Si atom sublattice and the C atom sublattice, and the displacement of the latter along the main symmetry axis is a quarter of the distance between two adjacent layers of Si atoms .
  • the silicon carbide group is centered on one carbon atom, and four Si atoms are connected by covalent bonds.
  • Si atoms are shared with adjacent groups, that is, one Si atom belongs to 4 such groups at the same time. Therefore, the simplest ratio of atoms of each group is 1:1, so the chemical formula is SiC.
  • the minimum distance between Si atoms and C atoms is 0.189 nm, and each Si (or C) atom is surrounded by four C (or Si) atoms, and is bonded together by directed strong tetrahedral sp 3 bonds.
  • This structure determines the good chemical and thermal stability of SiC, as well as its wide band gap, excellent corrosion resistance, excellent mechanical properties and heat transfer performance.
  • Silicon carbide is a hard material, and its Mohs hardness can reach 9.2-9.5.
  • the typical structure of SiC can be divided into two categories: one is the cubic SiC crystal form of zinc blende structure, collectively referred to as ⁇ -SiC; the other is the large periodic structure of hexagonal or rhombic structure, typically 6H, 4H , Qiao R, etc., collectively referred to as ⁇ -SiC.
  • the silicon carbide powder of the present invention includes hexagonal or rhombohedral ⁇ -SiC, cubic ⁇ -SiC and ⁇ -SiC whiskers.
  • the composite materials composed of silicon carbide powder and plastics, metals, and ceramics can significantly improve its various characteristics. Due to its high thermal stability, high strength, high thermal conductivity and other characteristics, it is widely used in atomic energy materials, chemical devices, high temperature processing, electrical and electronics Materials, semiconductors, electric heating elements and resistors can also be used in abrasives, abrasive tools, advanced refractory materials, and fine ceramics.
  • the crystalline phase is that the raw material SiO 2 and C continuously precipitate SiC crystal nuclei through gas-liquid-solid superposition at high temperature, and finally grow continuously along the ab axis and the reverse c axis of the SiC six-section ring plane.
  • a hexagonal crystal system is formed, and SiC nanowires or rods or nanosheets can be formed according to the reaction conditions.
  • Carbothermal reduction method The mixed powder of SiO 2 and Si powder is heated at high temperature to release SiO gas and react with activated carbon to prepare ⁇ -SiC.
  • Sol-gel method using tetraethoxysilane and methyltriethoxysilane as silicon source, phenolic resin, starch, etc. as carbon source, the formed gel is carbonized in nitrogen at 800°C to obtain SiC precursor, Then heated at 1550°C in hydrogen to obtain 5-20nm SiC.
  • Polymer thermal decomposition method Using low-molecular polycarbosilane (LPS) as raw material, SiC ultrafine powder was prepared by gas-phase thermal cracking process.
  • LPS low-molecular polycarbosilane
  • the silicon carbide whisker of the present invention is a cubic whisker, which belongs to the same crystal type as diamond. It is the crystal with the highest hardness, the highest modulus, the highest tensile strength and the highest heat-resistant temperature among the whiskers synthesized so far. Whisker products are divided into two forms: ⁇ type and ⁇ type. The performance of ⁇ type is better than that of ⁇ type and has higher hardness (Mohs hardness above 9.5), better toughness and conductivity.
  • the modified silicon carbide whiskers of the present invention often process silicon carbide to improve self-dispersibility.
  • the silicon carbide whiskers in the modified silicon carbide whiskers of the present invention are of ⁇ crystal form.
  • the silicon carbide whiskers in the modified silicon carbide whiskers of the present invention have a diameter of 100-600 nm and a length of 10-50 ⁇ m.
  • the silicon carbide whisker of the present invention is a product purchased from Qinhuangdao Yinuo High-tech Materials Development Co., Ltd. with a brand name of SiCW-80. Other preferable ones include but are not limited to those purchased from this company.
  • the product brand is SiCW-90.
  • the modified silicon carbide whiskers of the present invention are silicon carbide whiskers modified by a silane coupling agent.
  • the silane coupling agent of the present invention is an organosilicon compound containing two groups of different chemical properties in the molecule.
  • the common silane coupling agent is a hydrolyzable Y-functional silane coupling agent. Its general structural formula is Y-CH 2 SiR n X (3-n) , where X is a hydrolyzable organic functional group, such as chlorine, acetoxy Group, methoxy and ethoxy, etc. X is easy to be hydrolyzed, and the silanol groups produced are easy to bond with the hydroxyl groups on the surface of inorganic substances.
  • Y is a non-hydrolyzable, reactive organic functional group that can react with organic matter, or an inert organic functional group that does not react with organic matter, such as hexenyl, epoxy, amino, sulfydryl, thiocyano, phenyl or Long chain alkyl and so on.
  • the Y is preferably an alkyl group or an amino group, that is, the silane coupling agent is selected from one or more of alkyl silane coupling agents and amino silane coupling agents.
  • the silane coupling agent of the present invention is selected from one or more of alkyl silane coupling agents and amino silane coupling agents.
  • the general formula of the alkylsilane coupling agent in the present invention is: Y-CH 2 Si n X (3-n) , and Y is an alkyl group.
  • Y is an alkyl group. Examples that may be cited include but are not limited to: 1,2-bis(triethoxysilyl)ethane, 1,2-bis(trimethoxysilyl)ethane, methyltriethoxysilane, methyl Trimethoxysilane, propyltriethoxysilane, propyltrimethoxysilane, octyltriethoxysilane, octyltrimethoxysilane, dodecyltriethoxysilane, dodecyl Trimethoxysilane, hexadecyltrimethoxysilane, octadecyltrimethoxysilane, dimethyldiethoxysilane, dimethyldimethoxysilane, isooc
  • the general formula of the aminosilane coupling agent in the present invention is: Y-CH 2 Si n X (3-n) , and Y is an amino group.
  • Y is an amino group. Examples that may be mentioned include but are not limited to: ⁇ -aminopropyltrimethoxysilane, ⁇ -aminopropyltriethoxysilane, ⁇ -aminopropyltriethoxysilane, N-( ⁇ -aminoethyl )- ⁇ -Aminopropylmethyldimethoxysilane, N- ⁇ (aminoethyl)- ⁇ -aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltri Ethoxysilane, ⁇ -aminopropylmethyldiethoxysilane, 3-aminopropylmethyldimethoxysilane, N-n-butyl-3-aminopropyltrimeth
  • the silane coupling agent of the present invention is a mixture of an alkyl silane coupling agent and an amino silane coupling agent.
  • the weight ratio of the alkylsilane coupling agent and the aminosilane coupling agent of the present invention is (2:3)-(3:2).
  • the number of alkyl groups in the alkylsilane coupling agent of the present invention is 12.
  • the silane coupling agent of the present invention is a mixture of dodecylsilane coupling agent and 3-aminopropyltrimethoxysilane.
  • the dodecyl silane coupling agent of the present invention is purchased from Nanjing Youpu Chemical Co., Ltd., the brand is UP-312, and other preferred ones include UP-313; the 3- Aminopropyltrimethoxysilane was purchased from Qingdao Hengda Zhongcheng Technology Co., Ltd., with the brand name KH-540.
  • the silicon carbide whiskers modified by the silane coupling agent of the present invention are prepared through functional group coupling.
  • the reaction conditions can be prepared by any method known to those skilled in the art.
  • the silicon carbide whiskers are ultrasonically dispersed in a solvent for 30 minutes and then the silane coupling agent is added, the temperature is controlled at 60-80°C, and after stirring for 2-6 hours, it is dried to obtain the silane coupling agent Modified silicon carbide whiskers.
  • the solvent can be respectively taken from water, methanol, ethyl acetate, acetone, N,N-dimethylformamide, N,N-dimethylacetamide, N,N-diethylformamide, tetrahydrofuran, two One or a combination of methyl sulfoxide.
  • the weight ratio of the silicon carbide whiskers and the silane coupling agent in the silicon carbide whiskers modified by the silane coupling agent of the present invention is 1:(0.1-0.5).
  • the weight ratio of the silicon carbide whiskers and the silane coupling agent in the silicon carbide whiskers modified by the silane coupling agent of the present invention is 1:(0.2-0.4).
  • nano-silicon carbide is added to improve the cutting resistance of UHMWPE fiber, but nano-silicon carbide tends to agglomerate during the gel spinning process, resulting in poor dispersion. Therefore, the inventor adopts Silicon carbide whiskers modified by silane coupling agent have hydroxyl groups because the surface of nano-silicon carbide easily interacts with water in the air.
  • Modified silicon carbide material can not only weaken the force between the silicon carbide whiskers and avoid the agglomeration of the whiskers, thereby improving the dispersibility of silicon carbide in UHMWPE; on the other hand, it can be dispersed in the UHMWPE.
  • the silicon carbide whiskers in UHMWPE can absorb the energy transferred from the outside, increase the strength and modulus, and improve the strength, anti-cutting performance and safety performance of UHMWPE fiber.
  • the inventors adjusted the silicon carbide whiskers and unexpectedly discovered that when the silicon carbide whiskers have a diameter of 100-600nm and a length of 10-50 ⁇ m, the fiber strength and cutting resistance are greatly improved.
  • the inventor speculates that the possible reason is that under the premise of good dispersibility, nano-silicon carbide with a certain diameter and length can easily form uniform and regular fibrous crystal nuclei during the extraction, stretching and heat treatment of UHMPWE fibers.
  • the fibrous crystal nucleus can effectively promote the UHMWPE segment along its orientation and grow into an ordered crystal structure on its surface, which not only improves the heat resistance, modulus and strength of UHMWPE fiber, but also helps to improve the fiber The cutting resistance performance.
  • the product of the present invention is not only excellent in strength and cutting resistance, but also excellent in creep resistance. More importantly, the silicon carbide in the product is coated to avoid direct contact with the human body, thereby making it safer .
  • the inventor speculates that when the long-chain alkyl silane coupling agent is used in the present invention, the difference between the polarity and cohesive energy density between the long aliphatic chain and the UHMWPE molecular chain is small, and it is easy to interpenetrate and entangle each other, which improves The force between silicon carbide and UHMWPE. Because the molecular chains of UHMWPE fiber materials are all non-polar alkyl chains, the interaction between the segments mainly depends on molecular entanglement and cohesive energy.
  • silane coupling agent containing amino groups can not only form a "protective layer" on the surface of silicon carbide, improve dispersibility, avoid direct contact with the human body, and be safe, but also can generate hydrogen bonds between amino groups on the surface of silicon carbide, which improves
  • the force between UHMWPE molecular chains increases the energy required for untangling and stress relaxation, and improves the creep resistance of the fiber.
  • Modified graphene and modified silicon carbide are uniformly dispersed in the UHMWPE molecular chain, forming an interpenetrating network structure through intermolecular hydrogen bonds and other forces, thereby further improving the comprehensive performance of UHMWPE fibers.
  • the ultra-high molecular weight polyethylene used in the present invention uses ethylene as the main component (the largest mole% of all copolymerization components), such as ethylene monomers, ethylene and energy and ethylene with ethylene as the main component. Copolymers of other monomers, etc. As other monomers copolymerizable with the ethylene, there are, for example, ⁇ -olefins having 3 or more carbon atoms. Examples of such ⁇ -olefins having 3 or more carbon atoms include propylene, 1-butene, isobutene, 1-pentene, 2-methyl-1-butene, and 3-methyl-1-butene.
  • 1-hexene 3-methyl-1-pentene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-decene, 1-dodecene, 1- Tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, etc.
  • ethylene accounts for 80 mol% or more of the total polymer, and preferably 90 mol% or more. , More preferably 99 mol% or more.
  • Ultra-high molecular weight polyethylene is a thermoplastic engineering plastic with a linear structure. It has a series of excellent properties that general high-density polyethylene can’t match. It has tensile strength, abrasion resistance, impact resistance, self-lubrication, and noise reduction. Performance and excellent chemical resistance, thermal performance, non-stick characteristics.
  • the weight average molecular weight of the ultra-high molecular weight polyethylene of the present invention is 1 to 4 million.
  • the weight average molecular weight of the ultra-high molecular weight polyethylene of the present invention is 2 to 2.4 million.
  • the weight average molecular weight is a value measured in terms of polystyrene based on gel permeation chromatography (hereinafter referred to as "GPC").
  • the measurement condition of GPC adopts the conventional condition test in this field, for example, it can be obtained by the following method test.
  • Detector RI (differential refractometer); column temperature: 40°C; eluent: tetrahydrofuran (THF); flow rate: 1.0 mL/min; injection volume: 100 ⁇ L (a tetrahydrofuran solution with a sample concentration of 4 mg/mL).
  • the ultra-high molecular weight polyethylene may be commercially available, or may be a preparation method known to those skilled in the art.
  • a synthetic ultra-high molecular weight polyethylene its preparation method is as follows: the raw materials (ethylene and/or ⁇ -olefin), hydrogen, and catalyst are continuously added to the polymerization reactor, and the slurry is carried out at 80°C and 0.98MPa. After 4 hours of polymerization, the heat of polymerization was removed by jacket cooling of the polymerization vessel and external gas circulation.
  • the present invention provides a cut-resistant and creep-resistant fiber prepared from the above-mentioned ultra-high molecular weight polyethylene composition.
  • the method for preparing the cut-resistant and creep-resistant fiber of the present invention includes:
  • step (1) The mixture in step (1) is sheared and stirred by an emulsifier at high speed to obtain a spinning solution;
  • the silicon carbide whiskers were ultrasonically dispersed in deionized water for 30 minutes, and then the silane coupling agent was added. The temperature was controlled at 60-80°C. After stirring for 2-6 hours, the silane coupling agent modified was obtained by drying. Silicon carbide whiskers;
  • Silicon carbide whiskers modified by silane coupling agent are dispersed in ultra-high molecular weight polyethylene powder by high-speed shear blending, and the prepared powder premix is uniformly dispersed in mineral oil under ultrasonic conditions , And then slowly heat the mineral oil solution in a reaction kettle with stirring and shearing effect until the solution is evenly mixed; spinning the uniformly mixed solution, and then extracting and drawing to obtain the composite fiber of the present invention.
  • the preparation method of ultra-high molecular weight polyethylene spinning can be melt spinning method, solid state extrusion method, super drawing or partial drawing method, surface crystal growth method, gel spinning method.
  • the gel spinning process has great adaptability. In addition to the size and number of filaments, its mechanical properties can be adjusted in a larger range as needed. Other properties such as conductivity, bonding strength and flame retardancy are available Controlled by additives, dyes or other carriers can also be added.
  • melt spinning and gel spinning have been industrialized, and the gel spinning method is the most promising, and the fiber strength and modulus obtained are the highest.
  • the steps of the gel spinning method are to dissolve the ultra-high molecular weight polyethylene composition in a solvent, cool and solidify, to obtain a gel strand of an undrawn filament containing a solvent; then perform further extraction to obtain an undrawn filament containing an extractant.
  • the stretched gel strands are then subjected to the final heating and drawing.
  • Solvents commonly used to dissolve ultra-high molecular weight polyethylene include kerosene, paraffin, paraffin oil-based alkane solvents, and decalin.
  • the ultra-high molecular weight polyethylene is dissolved in a solvent to prepare a semiene solution, wherein the concentration of the semiene solution is 0.5-10%, and the more suitable concentration is 3-5%.
  • the removal of the solvent in the gel strands is very necessary to remove the solvent contained in the frozen collagen filaments before stretching. It is not only beneficial to the stability of the stretching process, but also improves the effectiveness of the stretching. If the frozen collagen filament contains a large amount of solvent, during the stretching process, due to the plasticizing effect of the solvent, the relative slippage between the macromolecules will be caused, thereby reducing the effectiveness of stretching; at the same time, the presence of solvent will freeze the collagen filament
  • the stretching ratio of the film is greatly affected by the solvent content, resulting in a decrease in stretching stability. For solvents with lower boiling points, drying is mainly used to remove the solvent; for solvents with higher boiling points, extraction is used to remove them.
  • the super-stretching multiples of the gel strands are all above 20 times.
  • the content of the modified graphene of the present invention is 0.5-5 wt% of the ultra-high molecular weight polyethylene.
  • the content of the modified graphene of the present invention is 1-3 wt% of the ultra-high molecular weight polyethylene.
  • the content of the modified graphene of the present invention is 2.2 wt% of the ultra-high molecular weight polyethylene.
  • the content of the modified silicon carbide whiskers of the present invention is 0.5-5 wt% of the ultra-high molecular weight polyethylene.
  • the content of the modified silicon carbide whiskers of the present invention is 2-4 wt% of the ultra-high molecular weight polyethylene.
  • the content of the modified silicon carbide whiskers of the present invention is 3 wt% of the ultra-high molecular weight polyethylene.
  • the wt% is a percentage by weight.
  • the preparation process of the cut-resistant and creep-resistant fiber of the present invention specifically includes:
  • silane coupling agent-modified silicon carbide whiskers prepared above are dispersed in ultra-high molecular weight polyethylene powder by high-speed shear blending, and the prepared powder premix is subjected to ultrasonic waves Evenly dispersed in mineral oil;
  • Another aspect of the present invention provides a finished product made of cut-resistant and creep-resistant fibers made of the ultra-high molecular weight polyethylene composition.
  • the finished product may be a fabric, such as cut-resistant gloves, clothing, Cloth etc.
  • Example 1 provides a cut-resistant and creep-resistant fiber, which is prepared from an ultra-high molecular weight polyethylene composition and includes the following components: modified graphene, modified silicon carbide whiskers, and ultra-high molecular weight polyethylene.
  • the modified graphene is a mixture of piperazine-modified graphene and stearylamine-modified graphene; the weight ratio of the piperazine-modified graphene and the stearylamine-modified graphene is 1:2; The content of modified graphene is 0.5 wt% of the ultra-high molecular weight polyethylene.
  • the modified silicon carbide whiskers are silicon carbide whiskers modified by a silane coupling agent; the content of the modified silicon carbide whiskers is 5 wt% of the ultra-high molecular weight polyethylene.
  • the ultra-high molecular weight polyethylene has a weight average molecular weight of 2 million and was purchased from Yuyao Jiuding Chemical Materials Co., Ltd.
  • the preparation method of the silicon carbide whiskers modified by the silane coupling agent includes: first dispersing the silicon carbide whiskers in deionized water for 30 minutes, then adding the silane coupling agent, controlling the temperature at 70°C, and stirring After 5h, dry to obtain silicon carbide whiskers modified by silane coupling agent.
  • the weight ratio of the silicon carbide whiskers and the silane coupling agent in the silicon carbide whiskers modified by the silane coupling agent is 1:0.1;
  • the silane coupling agent is a dodecyl silane coupling agent and A mixture of 3-aminopropyltrimethoxysilane, and the weight ratio of the dodecylsilane coupling agent and 3-aminopropyltrimethoxysilane is 2:3;
  • the dodecylsilane coupling The agent was purchased from Nanjing Youpu Chemical Co., Ltd., and the brand was UP-312;
  • the 3-aminopropyltrimethoxysilane was purchased from Qingdao Hengda Zhongcheng Technology Co., Ltd., and the brand was KH-540.
  • the silicon carbide whiskers in the silicon carbide whiskers modified by the silane coupling agent have a diameter of 200-500 nm and a length of 10-50 ⁇ m, ⁇ -type, purchased from Qinhuangdao Yinuo High-tech Material Development Co., Ltd., and the brand is SiCW- 80.
  • the preparation process of the cut-resistant and creep-resistant fiber is specifically:
  • silane coupling agent-modified silicon carbide whiskers prepared above are dispersed in ultra-high molecular weight polyethylene powder by high-speed shear blending, and the prepared powder premix is subjected to ultrasonic waves Evenly dispersed in mineral oil;
  • Example 2 provides a cut-resistant and creep-resistant fiber, which is prepared from an ultra-high molecular weight polyethylene composition and includes the following components: modified graphene, modified silicon carbide whiskers, and ultra-high molecular weight polyethylene.
  • the modified graphene is a mixture of piperazine-modified graphene and stearylamine-modified graphene; the weight ratio of the piperazine-modified graphene and the stearylamine-modified graphene is 1:3; The content of modified graphene is 5 wt% of the ultra-high molecular weight polyethylene.
  • the modified silicon carbide whiskers are silicon carbide whiskers modified by a silane coupling agent; the content of the modified silicon carbide whiskers is 0.5 wt% of the ultra-high molecular weight polyethylene.
  • the UHMWPE has a weight average molecular weight of 2.1 million and was purchased from Shanghai Chuhao Import and Export Co., Ltd.
  • the preparation method of the silicon carbide whiskers modified by the silane coupling agent includes: first dispersing the silicon carbide whiskers in deionized water for 30 minutes, then adding the silane coupling agent, controlling the temperature at 70°C, and stirring After 5h, dry to obtain silicon carbide whiskers modified by silane coupling agent.
  • the weight ratio of the silicon carbide whiskers and the silane coupling agent in the silicon carbide whiskers modified by the silane coupling agent is 1:0.3;
  • the silane coupling agent is a dodecyl silane coupling agent and A mixture of 3-aminopropyltrimethoxysilane, and the weight ratio of the dodecylsilane coupling agent and 3-aminopropyltrimethoxysilane is 3:2;
  • the dodecylsilane coupling The agent was purchased from Nanjing Youpu Chemical Co., Ltd., and the brand was UP-313;
  • the 3-aminopropyltrimethoxysilane was purchased from Qingdao Hengda Zhongcheng Technology Co., Ltd., and the brand was KH-540.
  • the silicon carbide whiskers in the silicon carbide whiskers modified by the silane coupling agent have a diameter of 200-500 nm and a length of 10-50 ⁇ m, ⁇ -type, purchased from Qinhuangdao Yinuo High-tech Material Development Co., Ltd., and the brand is SiCW- 80.
  • the preparation process of the cut-resistant and creep-resistant fiber is specifically:
  • silane coupling agent-modified silicon carbide whiskers prepared above are dispersed in ultra-high molecular weight polyethylene powder by high-speed shear blending, and the prepared powder premix is subjected to ultrasonic waves Evenly dispersed in mineral oil;
  • Example 3 provides a cut-resistant and creep-resistant fiber, which is prepared from an ultra-high molecular weight polyethylene composition and includes the following components: modified graphene, modified silicon carbide whiskers, and ultra-high molecular weight polyethylene.
  • the modified graphene is a mixture of piperazine-modified graphene and stearylamine-modified graphene; the weight ratio of the piperazine-modified graphene and the stearylamine-modified graphene is 1:2.2; The content of modified graphene is 1 wt% of the ultra-high molecular weight polyethylene.
  • the modified silicon carbide whiskers are silicon carbide whiskers modified by a silane coupling agent; the content of the modified silicon carbide whiskers is 4 wt% of the ultra-high molecular weight polyethylene.
  • the ultra-high molecular weight polyethylene has a weight average molecular weight of 2.4 million and was purchased from Shanghai Chuhao Import and Export Co., Ltd.
  • the preparation method of the silicon carbide whiskers modified by the silane coupling agent includes: first dispersing the silicon carbide whiskers in deionized water for 30 minutes, then adding the silane coupling agent, controlling the temperature at 70°C, and stirring After 5h, dry to obtain silicon carbide whiskers modified by silane coupling agent.
  • the weight ratio of the silicon carbide whiskers to the silane coupling agent in the silicon carbide whiskers modified by the silane coupling agent is 1:0.2;
  • the silane coupling agent is a dodecyl silane coupling agent and A mixture of 3-aminopropyltrimethoxysilane, and the weight ratio of the dodecylsilane coupling agent and 3-aminopropyltrimethoxysilane is 1:1;
  • the dodecylsilane coupling The agent was purchased from Nanjing Youpu Chemical Co., Ltd., and the brand was UP-312;
  • the 3-aminopropyltrimethoxysilane was purchased from Qingdao Hengda Zhongcheng Technology Co., Ltd., and the brand was KH-540.
  • the silicon carbide whiskers in the silicon carbide whiskers modified by the silane coupling agent have a diameter of 100-600 nm and a length of 10-50 ⁇ m, ⁇ -type, purchased from Qinhuangdao Yinuo High-tech Materials Development Co., Ltd., and the brand is SiCW- 90.
  • the preparation process of the cut-resistant and creep-resistant fiber is specifically:
  • silane coupling agent-modified silicon carbide whiskers prepared above are dispersed in ultra-high molecular weight polyethylene powder by high-speed shear blending, and the prepared powder premix is subjected to ultrasonic waves Evenly dispersed in mineral oil;
  • Example 4 provides a cut-resistant and creep-resistant fiber, which is prepared from an ultra-high molecular weight polyethylene composition and includes the following components: modified graphene, modified silicon carbide whiskers, and ultra-high molecular weight polyethylene.
  • the modified graphene is a mixture of piperazine-modified graphene and stearylamine-modified graphene; the weight ratio of the piperazine-modified graphene and the stearylamine-modified graphene is 1:2.8; The content of modified graphene is 3wt% of the UHMWPE.
  • the modified silicon carbide whiskers are silicon carbide whiskers modified by a silane coupling agent; the content of the modified silicon carbide whiskers is 2wt% of the ultra-high molecular weight polyethylene.
  • the UHMWPE has a weight average molecular weight of 2.1 million and was purchased from Shanghai Chuhao Import and Export Co., Ltd.
  • the preparation method of the silicon carbide whiskers modified by the silane coupling agent includes: first dispersing the silicon carbide whiskers in deionized water for 30 minutes, then adding the silane coupling agent, controlling the temperature at 70°C, and stirring After 5h, dry to obtain silicon carbide whiskers modified by silane coupling agent.
  • the weight ratio of the silicon carbide whiskers and the silane coupling agent in the silicon carbide whiskers modified by the silane coupling agent is 1:0.4;
  • the silane coupling agent is a dodecyl silane coupling agent and A mixture of 3-aminopropyltrimethoxysilane, and the weight ratio of the dodecylsilane coupling agent and 3-aminopropyltrimethoxysilane is 1:1.2;
  • the dodecylsilane coupling The agent was purchased from Nanjing Youpu Chemical Co., Ltd., and the brand was UP-312;
  • the 3-aminopropyltrimethoxysilane was purchased from Qingdao Hengda Zhongcheng Technology Co., Ltd., and the brand was KH-540.
  • the silicon carbide whiskers in the silicon carbide whiskers modified by the silane coupling agent have a diameter of 100-600 nm and a length of 10-50 ⁇ m, ⁇ -type, purchased from Qinhuangdao Yinuo High-tech Materials Development Co., Ltd., and the brand is SiCW- 90.
  • Example 5 provides a cut-resistant and creep-resistant fiber, which is prepared from an ultra-high molecular weight polyethylene composition and includes the following components: modified graphene, modified silicon carbide whiskers, and ultra-high molecular weight polyethylene.
  • the modified graphene is a mixture of piperazine-modified graphene and stearylamine-modified graphene; the weight ratio of the piperazine-modified graphene and the stearylamine-modified graphene is 1:2.5; The content of modified graphene is 2.2 wt% of the ultra-high molecular weight polyethylene.
  • the modified silicon carbide whiskers are silicon carbide whiskers modified with a silane coupling agent; the content of the modified silicon carbide whiskers is 3 wt% of the ultra-high molecular weight polyethylene.
  • the UHMWPE has a weight average molecular weight of 2.1 million and was purchased from Shanghai Chuhao Import and Export Co., Ltd.
  • the preparation method of the silicon carbide whiskers modified by the silane coupling agent includes: first dispersing the silicon carbide whiskers in deionized water for 30 minutes, then adding the silane coupling agent, controlling the temperature at 70°C, and stirring After 5h, dry to obtain silicon carbide whiskers modified by silane coupling agent.
  • the weight ratio of the silicon carbide whiskers and the silane coupling agent in the silicon carbide whiskers modified by the silane coupling agent is 1:0.3;
  • the silane coupling agent is a dodecyl silane coupling agent and A mixture of 3-aminopropyltrimethoxysilane, and the weight ratio of the dodecylsilane coupling agent and 3-aminopropyltrimethoxysilane is 1:1.6;
  • the dodecylsilane coupling The agent was purchased from Nanjing Youpu Chemical Co., Ltd., and the brand was UP-312;
  • the 3-aminopropyltrimethoxysilane was purchased from Qingdao Hengda Zhongcheng Technology Co., Ltd., and the brand was KH-540.
  • the silicon carbide whiskers in the silicon carbide whiskers modified by the silane coupling agent have a diameter of 200-500 nm and a length of 10-50 ⁇ m, ⁇ -type, purchased from Qinhuangdao Yinuo High-tech Material Development Co., Ltd., and the brand is SiCW- 80.
  • Comparative Example 1 provides a cut-resistant and creep-resistant fiber, which is prepared from an ultra-high molecular weight polyethylene composition and includes the following components: modified graphene, modified silicon carbide whiskers, and ultra-high molecular weight polyethylene.
  • Comparative Example 1 The difference between Comparative Example 1 and Example 5 is that the content of the modified graphene is 0.1 wt% of the UHMWPE.
  • Comparative Example 2 provides a cut-resistant and creep-resistant fiber, which is prepared from an ultra-high molecular weight polyethylene composition and includes the following components: modified graphene, modified silicon carbide whiskers, and ultra-high molecular weight polyethylene.
  • Comparative Example 2 The difference between Comparative Example 2 and Example 5 is that the content of the modified graphene is 20 wt% of the ultra-high molecular weight polyethylene.
  • Comparative Example 3 provides a cut-resistant and creep-resistant fiber, which is prepared from an ultra-high molecular weight polyethylene composition and includes the following components: modified graphene, modified silicon carbide whiskers, and ultra-high molecular weight polyethylene.
  • Comparative Example 3 The difference between Comparative Example 3 and Example 5 is that the weight ratio of the piperazine-modified graphene and the stearylamine-modified graphene is 1:0.2.
  • Comparative Example 4 provides a cut-resistant and creep-resistant fiber, which is prepared from an ultra-high molecular weight polyethylene composition and includes the following components: modified graphene, modified silicon carbide whiskers, and ultra-high molecular weight polyethylene.
  • Comparative Example 4 The difference between Comparative Example 4 and Example 5 is that the weight ratio of the piperazine-modified graphene and the stearylamine-modified graphene is 1:15.
  • Comparative Example 5 provides a cut-resistant and creep-resistant fiber, which is prepared from an ultra-high molecular weight polyethylene composition and includes the following components: modified graphene, modified silicon carbide whiskers, and ultra-high molecular weight polyethylene.
  • Comparative Example 5 The difference between Comparative Example 5 and Example 5 is that the content of the modified silicon carbide whiskers is 0.1% by weight of the ultra-high molecular weight polyethylene.
  • Comparative Example 6 provides a cut-resistant and creep-resistant fiber, which is prepared from an ultra-high molecular weight polyethylene composition and includes the following components: modified graphene, modified silicon carbide whiskers, and ultra-high molecular weight polyethylene.
  • Comparative Example 6 The difference between Comparative Example 6 and Example 5 is that the content of the modified silicon carbide whiskers is 20 wt% of the UHMWPE.
  • Comparative Example 7 provides a cut-resistant and creep-resistant fiber, which is prepared from an ultra-high molecular weight polyethylene composition and includes the following components: modified graphene, modified silicon carbide whiskers, and ultra-high molecular weight polyethylene.
  • Comparative Example 7 The difference between Comparative Example 7 and Example 5 is that the weight average molecular weight of the ultra-high molecular weight polyethylene is 900,000, which is purchased from Yuyao Jiuding Chemical Materials Co., Ltd.
  • Comparative Example 8 provides a cut-resistant and creep-resistant fiber, which is prepared from an ultra-high molecular weight polyethylene composition and includes the following components: modified graphene, modified silicon carbide whiskers, and ultra-high molecular weight polyethylene.
  • Comparative Example 8 The difference between Comparative Example 8 and Example 5 is that the weight average molecular weight of the ultra-high molecular weight polyethylene is 5 million, which is purchased from Yuyao Jiuding Chemical Materials Co., Ltd.
  • Comparative Example 9 provides a cut-resistant and creep-resistant fiber, which is prepared from an ultra-high molecular weight polyethylene composition and includes the following components: modified graphene, modified silicon carbide whiskers, and ultra-high molecular weight polyethylene.
  • Comparative Example 9 The difference between Comparative Example 9 and Example 5 is that the weight ratio of the silicon carbide whiskers and the silane coupling agent in the silicon carbide whiskers modified by the silane coupling agent is 1:0.02.
  • Comparative Example 10 provides a cut-resistant and creep-resistant fiber, which is prepared from an ultra-high molecular weight polyethylene composition and includes the following components: modified graphene, modified silicon carbide whiskers, and ultra-high molecular weight polyethylene.
  • Comparative Example 10 The difference between Comparative Example 10 and Example 5 is that the weight ratio of the silicon carbide whiskers and the silane coupling agent in the silicon carbide whiskers modified by the silane coupling agent is 1:2.
  • Comparative Example 11 provides a cut-resistant and creep-resistant fiber, which is prepared from an ultra-high molecular weight polyethylene composition and includes the following components: modified graphene, modified silicon carbide whiskers, and ultra-high molecular weight polyethylene.
  • Comparative Example 11 The difference between Comparative Example 11 and Example 5 is that the weight ratio of the dodecylsilane coupling agent and 3-aminopropyltrimethoxysilane is 1:5.
  • Comparative Example 12 provides a cut-resistant and creep-resistant fiber, which is prepared from an ultra-high molecular weight polyethylene composition and includes the following components: modified graphene, modified silicon carbide whiskers, and ultra-high molecular weight polyethylene.
  • Comparative Example 12 The difference between Comparative Example 12 and Example 5 is that the weight ratio of the dodecylsilane coupling agent and 3-aminopropyltrimethoxysilane is 5:1.
  • Comparative Example 13 provides a cut-resistant and creep-resistant fiber, which is prepared from an ultra-high molecular weight polyethylene composition and includes the following components: modified graphene, modified silicon carbide whiskers, and ultra-high molecular weight polyethylene.
  • Comparative Example 13 The difference between Comparative Example 13 and Example 5 is that the silicon carbide whiskers in the silicon carbide whiskers modified by the silane coupling agent have a diameter of 100-600 nm and a length of 100 ⁇ m, ⁇ -type, purchased from Qinhuangdao Yinuo High-tech Materials Development Co., Ltd., the brand name is SiCW-98.
  • Comparative Example 14 provides a cut-resistant and creep-resistant fiber, which is prepared from an ultra-high molecular weight polyethylene composition and includes the following components: modified graphene, modified silicon carbide whiskers, and ultra-high molecular weight polyethylene.
  • the difference between Comparative Example 14 and Example 5 is that the silane coupling agent is a mixture of octadecyl silane coupling agent and 3-aminopropyltrimethoxysilane; the octadecyl silane coupling agent Purchased from Nanjing Youpu Chemical Co., Ltd., brand name UP-318.
  • the silane coupling agent is a mixture of octadecyl silane coupling agent and 3-aminopropyltrimethoxysilane; the octadecyl silane coupling agent Purchased from Nanjing Youpu Chemical Co., Ltd., brand name UP-318.
  • Comparative Example 15 provides a cut-resistant and creep-resistant fiber, which is prepared from an ultra-high molecular weight polyethylene composition and includes the following components: modified graphene, modified silicon carbide whiskers, and ultra-high molecular weight polyethylene.
  • the difference between Comparative Example 15 and Example 5 is that the silane coupling agent is a mixture of methylsilane coupling agent and 3-aminopropyltrimethoxysilane; the methylsilane coupling agent is purchased from Nanjing You Pu Chemical Co., Ltd., brand name is UP-302.
  • the cutting resistance test machine is used to test the cutting resistance of the raw yarn.
  • the device is a testing machine produced by Sodemat manufacturer according to the European standard EN388.
  • On the cutting resistance testing machine device pad aluminum foil underneath and move it horizontally. Place the spare circular blade on the sample and rotate while rotating in the direction of the test movement. The two directions are reversed.
  • the circular blade is in contact with the aluminum foil to be energized.
  • the circuit informs the counter of the end of cutting. The counter is always in the record during the whole process, so the cutting resistance data of the sample can be obtained.
  • the cutting resistance level is according to and used
  • the standard sample (a flat cotton fabric of 200g/m 2 ) was evaluated by comparing the cutting level under the same conditions. The test starts from the standard sample, the test sample and the standard sample alternately perform the cutting test. After the test sample is performed 3 times, the standard sample is finally tested for the fourth time, and this round of testing is over.
  • the evaluation value calculated by the following formula is called the cutting resistance index:
  • N (the counter reading value of the standard sample of the test sample before the test + the counter reading of the standard sample of the test sample after the test)/2;
  • the circular blade used in the test is a rotary cutting-L type manufactured by OLFA, with a diameter of 45 mm, a material of SKS-7 tungsten steel, and a blade thickness of 0.3 mm.
  • Creep resistance test creep elongation test conditions: under the conditions of temperature 20 ⁇ 2°C and relative humidity 63 ⁇ 3%, the applied stress is 50% of the fiber breaking strength, and the creep time is 1d.
  • Example 4 5 29.58 1.029 Example 5 5 31.67 0.916 Comparative example 1 2 19.82 2.646 Comparative example 2 4 30.15 2.429 Comparative example 3 2 25.35 1.525 Comparative example 4 3 23.55 5.518 Comparative example 5 2 19.43 6.543 Comparative example 6 4 28.22 1.416 Comparative example 7 2 25.91 1.517 Comparative example 8 3 24.61 5.587 Comparative example 9 2 21.38 4.942 Comparative example 10 3 26.48 6.514 Comparative example 11 2 24.61 1.548 Comparative example 12 2 26.18 9.624 Comparative example 13 3 22.31 2.056 Comparative example 14 3 19.67 6.314 Comparative example 15 2 22.46 8.464

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Abstract

本发明涉及高分子材料制造领域，具体涉及到一种UHMWPE组合物及其制备得到的耐切割、耐蠕变纤维。所述超高分子量聚乙烯组合物，包括如下组分：改性石墨烯、改性碳化硅晶须、超高分子量聚乙烯。本发明所提供的超高分子量聚乙烯组合物具有优异的防切割性、高强高模性。通过调控碳化硅形态、偶联剂类型、配比等在解决防切割、高强高模的同时，还能改善耐蠕变性能，同时配方中偶联剂的加入使碳化硅被包覆起来，避免其与人体直接接触，改善产品性能的同时，确保安全且无毒副作用。

Description

一种耐切割、耐蠕变UHMWPE纤维及其制备方法 技术领域
本发明属于高分子材料制造领域，更具体地，本发明涉及一种耐切割、耐蠕变UHMWPE纤维及其制备方法。
背景技术
超高分子量聚乙烯纤维(UHMWPE)，是指分子量为100-600万，因其内部结构有较高的结晶度和较强的分子间作用力，使其拥有许多优良的性能如耐磨性、极高的抗冲击性、抗化学药品腐蚀性能、较高的消除噪音性能、自润滑性、低摩擦系数以及安全卫生无毒等卓越的性能，被称为是“神奇的塑料”，广泛应用在化工、机械、纺织、造纸、包装、矿山、建筑、体育、军事、医疗等诸多领域。
超高分子量聚乙烯依次经过纺丝-萃取-干燥-超倍拉伸制成的高性能纤维。采用超高分子量聚乙烯制成的纤维增强复合材料具有质量轻、耐冲击、介电性能高等优点，被广泛用于航空航天领域、海域防御领域、武器装备领域和日常工业领域。
但在现有的超高分子量聚乙烯纤维生产和使用过程中，对于材料的性能，大多着眼于牵伸强度、牵伸模量、线密度等显而易见的方面，而对于材料的蠕变性能则关注不多。这主要是由于大家对该产品的了解还停留在比较浅显的阶段，而蠕变性能对制品的影响往往要在使用若干年后才能体现出来，对于一种商业应用时间才十来年的新兴产品来说，其重要性还未被大多数生产者和使用者所认可。
事实上，蠕变性能对于超高分子量聚乙烯纤维及其制品的使用寿命的影响还是十分重大的，特别是在一些需要持续受力的场合。常用的解决方式是不同填料填充对UHMWPE进行改性使之成为复合材料是材料发展的必然趋势之一。
本发明提供一种无机填料填充UHMWPE对其进行改性，同时本发明可以在解决超高分子量聚乙烯的粘弹性高的情况下，无机填料分散性不好的问题。
发明内容
为了解决上述问题，本发明的第一个方面提供了一种超高分子量聚乙烯组合物，包括如下组分：改性石墨烯、改性碳化硅晶须、超高分子量聚乙烯。
作为一种优选的技术方案，所述改性石墨烯的含量为超高分子量聚乙烯的0.5-5wt％。
作为一种优选的技术方案，所述改性碳化硅晶须的含量为超高分子量聚乙烯的0.5-5wt％。
作为一种优选的技术方案，所述超高分子量聚乙烯的重均分子量为200-240万。
作为一种优选的技术方案，所述改性石墨烯为氨基化石墨烯。
作为一种优选的技术方案，所述氨基化石墨烯包括哌嗪改性石墨烯和十八胺改性石墨烯。
作为一种优选的技术方案，所述改性碳化硅晶须为硅烷偶联剂改性的碳化硅晶须。
作为一种优选的技术方案，所述硅烷偶联剂改性的碳化硅晶须中所述碳化硅晶须和硅烷偶联剂的重量比1:(0.1-0.5)。
本发明的第二个方面提供了一种耐切割、耐蠕变纤维，由上述超高分子量聚乙烯组合物制备得到。
本发明的第三个方面提供了一种耐切割、耐蠕变纤维的制备方法，步骤包括：
(1)将改性石墨烯、改性碳化硅晶须和超高分子量聚乙烯混合均匀；
(2)将步骤(1)中的混合物经乳化机高速剪切搅拌，得到纺丝溶液；
(3)将纺丝溶液纺丝后，进行萃取和热牵伸得到纤维。
有益效果：本发明所提供的纤维具有优异的防切割性、高强高模性。通过调控碳化硅形态、偶联剂类型、配比等在解决防切割、高强高模的同时，还能改善耐蠕变性能，同时配方中偶联剂的加入使碳化硅被包覆起来，避免其与人体直接接触，改善产品性能的同时，确保安全且无毒副作用。
具体实施方式
下面结合具体实施方式对本发明提供技术方案中的技术特征作进一步清楚、完整的描述，并非对其保护范围的限制。
本发明中的词语“优选的”、“更优选的”等是指，在某些情况下可提供某些有益效果的本发明实施方案。然而，在相同的情况下或其他情况下，其他实施方案也可能是优选的。此外，对一个或多个优选实施方案的表述并不暗示其他实施方案不可用，也并非旨在将其他实施方案排除在本发明的范围之外。
当本文中公开一个数值范围时，上述范围视为连续，且包括该范围的最小值 及最大值，以及这种最小值与最大值之间的每一个值。进一步地，当范围是指整数时，包括该范围的最小值与最大值之间的每一个整数。此外，当提供多个范围描述特征或特性时，可以合并该范围。换言之，除非另有指明，否则本文中所公开之所有范围应理解为包括其中所归入的任何及所有的子范围。例如，从“1至10”的指定范围应视为包括最小值1与最大值10之间的任何及所有的子范围。范围1至10的示例性子范围包括但不限于1至6.1、3.5至7.8、5.5至10等。
为了解决上述问题，本发明的第一个方面提供了一种超高分子量聚乙烯组合物，包括如下组分：改性石墨烯、改性碳化硅晶须、超高分子量聚乙烯。
石墨烯
本发明所述石墨烯是一种由碳原子以sp 2杂化连接形成的单原子层二维晶体，碳原子规整的排列于蜂窝状点阵结构单元之中。每个碳原子除了以σ键与其他三个碳原子相连之外，剩余的π电子与其他碳原子的π电子形成离域大π键，电子可在此区域内自由移动，从而使石墨烯具有优异的导电性能。同时，这种紧密堆积的蜂窝状结构也是构造其他碳材料的基本单元，单原子层的石墨烯可以包裹形成零维的富勒烯，单层或者多层的石墨烯可以卷曲形成单壁或者多壁的碳纳米管。
由于石墨烯中的每个碳原子均与相邻的三个碳原子结合成很强的σ键，因此石墨烯同样表现出优异的力学性能。最近，哥伦比亚大学科学家利用原子力显微镜直接测试了单层石墨烯的力学性能，发现石墨烯的杨氏模量约为1100GPa，断裂强度更是达到了130GPa，比最好的钢铁还要高100倍。
石墨烯同样是一种优良的热导体，其导热系数高达5000W/(m·K)，优于碳纳米管，更是比一些常见金属，如金、银、铜等高10倍以上。
石墨烯的制备方法：机械剥离法、外延生长法、化学气相沉积法、化学合成法、氧化石墨烯还原法以及纵向切割碳管法等几种。
机械剥离法：利用微机械剥离法从石墨中分离出石墨烯，在液相中超声剥离石墨是另外一种常用的剥离石墨的方法。
外延生长法：从单晶碳化硅片(SiC)表面利用高温(1200～1500℃)升华去除硅原子，从而得到外延生长的石墨烯。
化学气相沉积法：化学气相沉积法是指在高温下裂解碳源(如碳氢化合物)并沉积在固态衬底表面，衬底通常为Ni、Ru等过渡金属。
氧化石墨烯还原法：目前使用最广泛，也是最有希望率先实现大规模工业化的制备石墨烯的一种方法是利用氧化石墨烯为前驱体，通过热还原或者化学还原，将氧化石墨烯表面的含氧基团除去。这种方法虽然不能得到完美的石墨烯，但是能在很大程度上恢复石墨烯的本征性能。同时，相对于其他石墨烯制备方法，氧化石墨烯还原法的原料丰富，设备及操作过程简单，制备出的石墨烯的可加工性好，因此备受关注。
氧化石墨烯还原法又包括热膨胀还原法、化学还原法。
纵向切割碳管法：以碳纳米管为原料制备石墨烯是近年来发展起来的一种新型的制备石墨烯的方法，与以石墨为原料制备的各向同性石墨烯片层不同，切割碳纳米管得到的是各向异性的带状石墨烯。
作为本发明人合成的石墨，所述石墨烯的制备方法可以采用本领域已知的任何一种方法制备得到，本发明中优选氧化石墨烯还原的方法。
氧化石墨烯是石墨烯的一种衍生物，用强氧化剂处理过后的石墨烯包含C、H、O三种元素。与石墨相似，氧化石墨同样为二维层状结构，氧化石墨烯通过层间的氢键等作用力层层堆叠在一起。不过氧化石墨烯表面含有大量的含氧基团，使其表现出较强的亲水性并能分散在水中。
氧化石墨烯的制备方法：目前常用的三种制备氧化石墨的方法，即Brodie法、Staudenmaier法和Hummers法，均是利用强酸加强氧化剂的组合对石墨进行处理。强质子酸进入到石墨层间形成石墨插层化合物(graphite intercalation compounds)，随后强氧化剂对石墨进行氧化引入大量亲水的含氧官能团到石墨烯表面及边缘形成氧化石墨烯。由于含氧基团较强的亲水性，氧化石墨烯能完全的剥离并分散在水溶液当中。
本发明中，所述氧化石墨烯是石墨粉末经化学氧化及剥离后的产物，氧化石墨烯是单一的原子层，可以随时在横向尺寸上扩展到数十微米，因此，其结构跨越了一般化学和材料科学的典型尺度。氧化石墨烯可视为一种非传统型态的软性材料，具有聚合物、胶体、薄膜，以及两性分子的特性。经过氧化处理后，氧化石墨仍保持石墨的层状结构，但在每一层的石墨烯单片上引入了许多氧基功能团。其中Hummers法的制备过程的时效性相对较好而且制备过程中也比较安全，是目前最常用的一种。它采用浓硫酸中的高锰酸钾与石墨粉末经氧化反应之后，得 到棕色的在边缘有衍生羧酸基及在平面上主要为酚羟基和环氧基团的石墨薄片，此石墨薄片层可以经超声或高剪切剧烈搅拌剥离为氧化石墨烯，并在水中形成稳定、浅棕黄色的单层氧化石墨烯悬浮液。由于共轭网络受到严重的官能化，氧化石墨烯薄片具有绝缘的特质。目前，制备氧化石墨烯新方法已经层出不穷了，大体上分为自顶向下方法和自底向上方法两大类。前者的思路是拆分鳞片石墨等制备氧化石墨烯，以传统三方法的改进方法为代表，还包括拆分(破开)碳纳米管的方法等等。后者是用各种碳源合成的方法，具体方法五花八门，种类繁多。
本发明中，通过氧化后的石墨烯，其氧元素的含量为15at％-20at％，作为本发明的一种优选方式，所述氧元素的含量为16at％-18at％，更加进一步优选为17at％。
本发明中，所述氧元素含量的分析可以是本领域技术人员已知的任何一种方法测试得到；本发明中，主要采用元素分析的方法进行测试。
改性石墨烯
本发明所述改性石墨烯，往往是对石墨烯进行处理，使其表面具有氨基基团。
所述功能化处理的方式，本发明中不做具体限定，可以采用本领域技术人员已知的任何一种方法制备得到，也可以市购得到。
在一种优选的实施方式中，本发明所述改性石墨烯为氨基化石墨烯。
在一种优选的实施方式中，本发明所述氨基化石墨烯包括哌嗪改性石墨烯和十八胺改性石墨烯。
在一种优选的实施方式中，本发明所述哌嗪改性石墨烯和十八胺改性石墨烯的重量比为1:(2-3)。
在一种优选的实施方式中，本发明所述哌嗪改性石墨烯购买自南京先丰纳米材料科技有限公司，牌号为XF005-1；所述十八胺改性石墨烯购买自南京先丰纳米材料科技有限公司，牌号为XF005-3。
发明人在研究的过程中发现对石墨烯进行改性可以在其表面形成一层膜，避免石墨烯分子之间或与碳化硅分子之间的吸附和团聚，提高物料之间的分散性效果。同时在纤维内部形成锚固点，吸收传递的能量，避免局部裂纹扩张，从而提高抗撕裂效果。同时，发明人人预料不到的发现，通过调控哌嗪改性石墨烯和十八胺改性石墨烯的使用比例可以提高UHMWPE纤维的耐蠕变性能和耐高温性 能，其可能的原因是十八胺上的柔性脂肪族烷烃链和哌嗪上的环状结构在石墨烯表面形成的保护膜使其避免团聚的同时，有利于在UHMWPE链段内部形成互穿网络结构，从而改变纤维的强度和耐切割性能。
碳化硅
本发明所述碳化硅(SiC)是Ⅳ-Ⅳ族二元化合物，是第Ⅳ族元素中唯一的、也是极稳定的化合物，是由碳原子和硅原子以共价键为主结合而成，具有类似金刚石的六面体晶体结构。SiC晶体结构由致密排列的两个亚晶格组成，Si原子亚晶格和C原子亚晶格，并且后者沿主对称轴的位移为Si原子相邻两层之间距离的四分之一。碳化硅基团是以一个碳原子作为中心，通过共价键形式连接四个Si原子。由于Si原子是与相邻基团相互共用，即一个Si原子同时属于4个这样的基团。所以，每个基团的原子最简比为l:1，所以构成的化学式为SiC。Si原子和C原子最小间距为0.189nm，每个Si(或者C)原子被四个C(或者Si)原子包围，并通过定向的强四面体sp 3键结合在一起。这一结构决定了SiC良好的化学稳定性和热稳定性，还决定了它的宽禁带，优良的抗腐蚀性，优良的力学性能和传热性能。碳化硅属于硬质材料，其莫氏硬度可达9.2-9.5。SiC的典型结构可分为两大类：一类是闪锌矿结构的立方SiC晶型，统称为β-SiC；另一类是六角型或菱形结构的大周期结构，典型的有6H、4H、巧R等，统称为α-SiC。
本发明所述碳化硅粉体，包括六方或菱面体的α-SiC和立方体的β-SiC以及β-SiC晶须。碳化硅粉体与塑料、金属、陶瓷构成复合材料可显著改善其各种特性，由于其高热稳定性及高强度、高热传导性等特性，广泛应用于原子能材料、化学装置、高温处理、电工电子材料、半导体领域、电加热原件及电阻器等中亦可用于磨料、磨具、高级耐火材料、精细陶瓷。
本发明所述SiC粉体，晶相是在高温下原料SiO 2与C通过气-液-固不断析出SiC晶核叠加，最后沿SiC六节环平面的ab轴垂直反向c轴不断生长，形成六方晶系，根据反应条件可以形成SiC纳米线或棒或纳米片等形貌。
近年来碳化硅纳米粉体的制备方法，主要归为三大类：固相法、液相法、气相法。
碳热还原法：利用SiO 2与Si粉的混合粉末高温受热释放出SiO气体，与活性炭反应制得β-SiC。
机械合金化法：将Si粉与C粉按照n(Si):n(C)＝1:l混合，磨球和磨粉按球粉质量比40:l封装在充满氢气的磨罐中，在WL-1行星式球磨机上进行机械球磨，球磨25h后得到平均晶粒尺寸约为6nm的SiC粉体。
溶胶-凝胶法：以四乙氧基硅烷、甲基三乙氧基硅烷作硅源，以酚醛树脂、淀粉等为碳源，形成的凝胶在氮气中于800℃炭化得到SiC前驱体，再于氢气中1550℃加热，得到了5～20nm的SiC。
聚合物热分解法：以低分子聚碳硅烷(LPS)为原料，用气相热裂解工艺制备了SiC超细微粉。
改性碳化硅晶须
本发明所述碳化硅晶须为立方晶须，和金刚石同属于一种晶型，是目前已经合成出的晶须中硬度最高，模量最大，抗拉伸强度最大，耐热温度最高的晶须产品，分为α型和β型两种形式，其中β型性能优于α型并具有更高的硬度(莫氏硬度达9.5以上)，更好的韧性和导电性能。
本发明所述改性碳化硅晶须往往是对碳化硅进行处理，改善自身分散性。
在一种优选的实施方式中，本发明所述改性碳化硅晶须中的碳化硅晶须为β晶型。
在一种优选的实施方式中，本发明所述改性碳化硅晶须中的碳化硅晶须直径为100-600nm，长度为10-50μm。
在一种优选的实施方式中，本发明所述碳化硅晶须为购买自秦皇岛一诺高新材料开发有限公司，牌号为SiCW-80的产品，其他可优选的，包括但不限于购买自该公司牌号为SiCW-90的产品。
在一种优选的实施方式中，本发明所述改性碳化硅晶须为硅烷偶联剂改性的碳化硅晶须。
硅烷偶联剂
本发明所述硅烷偶联剂是一类在分子中同时含有两种不同化学性质基团的有机硅化合物。常见的硅烷偶联剂为水解性Y-官能团硅烷偶联剂，其结构通式为Y-CH 2SiR nX (3-n)，其中X为水解性的有机官能团，如氯基、乙酰氧基、甲氧基和乙氧基等。X易水解，产生的硅羟基易与无机物表面的羟基键合。其中的Y为非水解性的，能与有机物反应的反应性有机官能团，或不与有机物反应的惰性 有机官能团，如己烯基、环氧基、氨基、琉基、硫氰基、苯基或长链烷基等。
本发明中，所述Y优选为烷基、氨基，即硅烷偶联剂选自烷基硅烷偶联剂、氨基硅烷偶联剂中的一种或多种。
在一种优选的实施方式中，本发明所述硅烷偶联剂选自烷基硅烷偶联剂、氨基硅烷偶联剂中的一种或多种。
例如，本发明中所述烷基硅烷偶联剂的通式为：Y-CH 2Si nX (3-n)，Y为烷基。可举出的实例包括但不限于：1,2-双(三乙氧基硅基)乙烷、1,2-双(三甲氧基硅基)乙烷、甲基三乙氧基硅烷、甲基三甲氧基硅烷、丙基三乙氧基硅烷、丙基三甲氧基硅烷、辛基三乙氧基硅烷、辛基三甲氧基硅烷、十二烷基三乙氧基硅烷、十二烷基三甲氧基硅烷、十六烷基三甲氧基硅烷、十八烷基三甲氧基硅烷、二甲基二乙氧基硅烷、二甲基二甲氧基硅烷、异辛基三乙氧基硅烷、甲基三乙酰氧基硅烷、甲基三丁酮肟基硅烷等。
例如，本发明中所述氨基硅烷偶联剂的通式为：Y-CH 2Si nX (3-n)，Y为氨基。可举出的实例包括但不限于：γ-氨丙基三甲氧基硅烷、γ-氨丙基三乙氧基硅烷、γ-氨丙基三乙氧基硅烷、N-(β-氨乙基)-γ-氨丙基甲基二甲氧基硅烷、N-β(氨乙基)-γ-氨丙基三甲氧基硅烷、N-(2-氨乙基)-3-氨丙基三乙氧基硅烷、γ-氨丙基甲基二乙氧基硅烷、3-氨丙基甲基二甲氧基硅烷、N-正丁基-3-氨丙基三甲氧基硅烷、3-脲丙基三甲氧基硅烷、双-[3-(三乙氧基硅)-丙基]-胺、3-苯胺基丙基三甲氧基硅烷、二乙烯三胺基丙基三甲氧基硅烷、N-(2-氨乙基)-3-氨丙基甲基二乙氧基硅烷、3-脲丙基三乙氧基硅烷、双-[3-(三甲氧基硅)-丙基]-胺等。
在一种优选的实施方式中，本发明所述硅烷偶联剂为烷基硅烷偶联剂和氨基硅烷偶联剂的混合物。
在一种优选的实施方式中，本发明所述烷基硅烷偶联剂和氨基硅烷偶联剂的重量比为(2:3)-(3:2)。
在一种优选的实施方式中，本发明所述烷基硅烷偶联剂中烷基数为12。
在一种优选的实施方式中，本发明所述硅烷偶联剂为十二烷基硅烷偶联剂和3-氨丙基三甲氧基硅烷的混合物。
在一种优选的实施方式中，本发明所述十二烷基硅烷偶联剂购买自南京优普化工有限公司，牌号为UP-312，其他可优选的还有UP-313；所述3-氨丙基三甲 氧基硅烷购买自青岛恒达众诚科技有限公司，牌号为KH-540。
本发明所述硅烷偶联剂改性的碳化硅晶须通过官能团偶联制得。所述反应条件可以采用本领域技术人员已知的任何一种方法制备得到。
例如可以是：将所述碳化硅晶须先在溶剂中超声分散30min后添加所述硅烷偶联剂，将温度控制在60-80℃，搅拌2-6h后，烘干即得到硅烷偶联剂改性的碳化硅晶须。
所述溶剂可以分别取自水、甲醇、乙酸乙酯、丙酮、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、N,N-二乙基甲酰胺、四氢呋喃、二甲亚砜中的一种或几种的混合。
在一种优选的实施方式中，本发明所述硅烷偶联剂改性的碳化硅晶须中所述碳化硅晶须和硅烷偶联剂的重量比1:(0.1-0.5)。
在一种优选的实施方式中，本发明所述硅烷偶联剂改性的碳化硅晶须中所述碳化硅晶须和硅烷偶联剂的重量比1:(0.2-0.4)。
本申请发明人在研究的过程中发现，加入纳米碳化硅用以改善UHMWPE纤维的耐切割性能，但纳米碳化硅在凝胶纺丝的过程中容易团聚，导致分散性不佳，因此发明人采用硅烷偶联剂改性的碳化硅晶须，由于纳米碳化硅表面容易与空气中的水作用而带有羟基，在上述反应过程中参与到硅烷偶联剂的水解，通过化学键结合到一起，得到改性的碳化硅材料，一方面经过改性之后可以其不仅能减弱碳化硅晶须之间的作用力，避免晶须的团聚，从而提高碳化硅在UHMWPE中的分散性；另一方面分散在UHMWPE中的碳化硅晶须能够吸收外界传递的能量，增加强度和模量，提高UHMWPE纤维的强度、防切割性能、安全性能。在研发的过程中，发明人通过调控碳化硅晶须，意外的发现当所述碳化硅晶须为直径为100-600nm，长度为10-50μm时，进一步使得纤维强度以及耐切割性能大大提高，发明人推测可能的原因是，在具有较好分散性的前提下，一定直径与长度的纳米碳化硅在UHMPWE纤维进行萃取、拉伸和热处理等过程中会较容易形成均匀规整的纤维状晶核，而该纤维状晶核能有效促进UHMWPE链段沿着其取向，在其表面生长成有序排列的晶体结构，从而不仅提高了UHMWPE纤维的耐热性、模量和强度，也有助于提高纤维的耐切割性能。此外，发明人还发现本发明产品不仅强度以及耐切割性能优异，且耐蠕变性能也较为优异，更为重要的是本产品中 碳化硅被包覆，能避免与人体直接接触，从而更加安全。发明人推测，可能是本发明采用烷基长链硅烷偶联剂时，由于长的脂肪链与UHMWPE分子链之间的极性、内聚能密度之间差异小，容易互相穿插和缠绕，提高碳化硅与UHMWPE之间的作用力。UHMWPE纤维材料由于分子链均是非极性烷基链，链段之间作用主要靠分子缠绕和内聚能，因此材料在使用过程中由于解缠结或应力松弛等原因引起发生蠕变，而加入一定量的含有氨基的硅烷偶联剂不仅可以达到在碳化硅表面形成“保护层”，提高分散性、避免直接与人体接触、安全，还可以因为碳化硅表面的氨基之间产生氢键，提高UHMWPE分子链之间的作用力，提高解缠结和应力松弛所需的能量，改善纤维的耐蠕变性能。改性石墨烯和改性碳化硅在UHMWPE分子链内部均匀分散，通过分子间氢键等作用力形成互穿网络结构，从而进一步提高UHMWPE纤维的综合性能。
超高分子量聚乙烯
本发明中使用的超高分子量聚乙烯是利用乙烯作为主要成分(全部共聚成分中，是最大的摩尔％)，例如有乙烯的单聚物、将乙烯作为主要成分的该乙烯与能和该乙烯共聚的其他单体的共聚物等。作为能与该乙烯共聚的其他单体，例如有碳原子数为3以上的α-烯烃等。作为这种碳原子数为3以上的α-烯烃，例如可列举丙烯、1-丁烯、异丁烯、1-戊烯、2-甲基-1-丁烯、3-甲基-1-丁烯、1-已烯、3-甲基-1-戊烯、4-甲基-1-戊烯、1-庚烯、1-辛烯、1-癸烯、1-十二碳烯、1-十四碳烯、1-十六碳烯、1-十八碳烯、1-二十碳烯等。
其中，从经济性等方面考虑，优选使用乙烯的单聚物或者将乙烯作为主体的与上述α-烯烃共聚的共聚物，优选乙烯占聚合物全体的80摩尔％以上，优选为90摩尔％以上，更优选为99摩尔％以上。
超高分子量聚乙烯是一种线型结构的热塑性工程塑料，具有一般高密度聚乙烯所不能比拟的一系列优异性能，其具有拉伸强度、耐磨性、耐冲击性、自润滑性、消音性能和优良的化学耐药性、热性能、不粘性的特性。
在一种优选的实施方式中，本发明所述超高分子量聚乙烯的重均分子量为100-400万。
在一种优选的实施方式中，本发明所述超高分子量聚乙烯的重均分子量为200-240万。
重均分子量是基于凝胶渗透色谱法(以下，简称为“GPC”)测定而进行聚苯乙烯换算后的值。GPC的测定条件采用本领域常规的条件测试，例如，可采用下述的方式测试得到。
柱：将下述柱串联连接而使用。
“TSKgelG5000”(7.8mmI.D.×30cm)×1根
“TSKgelG4000”(7.8mmI.D.×30cm)×1根
“TSKgelG3000”(7.8mmI.D.×30cm)×1根
“TSKgelG2000”(7.8mmI.D.×30cm)×1根
检测器：RI(差示折射计)；柱温度：40℃；洗脱液：四氢呋喃(THF)；流速：1.0mL/分钟；注入量：100μL(试样浓度4mg/mL的四氢呋喃溶液)。
本发明中，所述超高分子量聚乙烯可以是市售，也可以是本领域技术人员已知的制备方法。
作为市售的超高分子量聚乙烯，其购买于余姚九鼎化工材料有限公司。
作为合成的超高分子量聚乙烯，其制备方法为：将制备原料(乙烯和/或α-烯烃)、氢气、催化剂连续不断地加入聚合反应器中，在80℃及0.98MPa条件下进行淤浆聚合4小时，聚合热采用聚合釜夹套冷却及气体外循环方式除去。
耐切割、耐蠕变纤维
本发明提供一种由上述超高分子量聚乙烯组合物制备得到的耐切割、耐蠕变纤维。
本发明所述耐切割、耐蠕变纤维的制备方法，步骤包括：
(1)将碳化硅和超高分子量聚乙烯混合均匀；
(2)将步骤(1)中的混合物经乳化机高速剪切搅拌，得到纺丝溶液；
(3)将纺丝溶液纺丝后，进行萃取和热牵伸得到纤维。
即将所述碳化硅晶须先在去离子水中超声分散30min后添加所述硅烷偶联剂，将温度控制在60-80℃，搅拌2-6h后，烘干即得到硅烷偶联剂改性的碳化硅晶须；
将硅烷偶联剂改性的碳化硅晶须采用高速剪切共混的方式，分散在超高分子量聚乙烯粉末中，将制得的粉末预混料在超声波状态下均匀地分散于矿物油中，然后在带有搅拌剪切作用的反应釜中缓慢加热矿物油溶液，至溶液混合均匀；将 混合均匀的溶液进行纺丝，再经过萃取、牵伸，得到本发明的复合纤维。
超高分子量聚乙烯纺丝的制备方法可以是熔融纺丝法、固态挤出法、超拉伸或局部拉伸法、表面结晶生长法、凝胶纺丝法。
凝胶纺丝工艺有很大的适应性，除了丝的纤度和根数外，其机械性能可根据需要在较大的范围内调节，其它性能，如导电性、粘接强度和阻燃性可用添加剂来控制，还可加入染料或其它载体。上述几种纺丝方法中，熔融纺丝和凝胶纺丝己工业化生产，且以凝胶纺丝法最有前途，制得的纤维强度和模量最高。
冻胶纺丝法(凝胶纺丝法)
凝胶纺丝法的步骤是将超高分子量聚乙烯组合物溶解在溶剂中，冷却固化，得到含有溶剂的未拉伸丝的凝胶丝条；再进行进一步的萃取，得到含萃取剂的未拉伸的凝胶丝条，再进行最后的加热、拉丝。
常用于溶解超高分子量聚乙烯的溶剂有煤油、石蜡、石蜡油为主的烷烃类溶剂以及十氢萘等。
将超高分子量聚乙烯溶解在溶剂中，制成半烯溶液，其中半烯溶液的浓度为0.5-10％，更加适应的浓度是3-5％。
凝胶丝条中溶剂的脱除，在拉伸前脱除冻胶原丝中所含的溶剂是十分必要的，它既有利于拉伸过程的稳定性，又能提高拉伸的有效性。冻胶原丝中若包含着大量溶剂，在其拉伸过程中，由于溶剂的增塑作用，致使大分子间产生相对滑移，从而使拉伸的有效性降低；同时溶剂的存在，冻胶原丝的拉伸比受溶剂含量多少影响极大，造成拉伸稳定性的降低。则对于沸点较低的溶剂时，则主要采用干燥的方式使得溶剂去除；而对于沸点较高的溶剂时，则采用萃取的方式去除。
凝胶丝条的超倍拉伸的倍数均在20倍以上。
在一种优选的实施方式中，本发明所述改性石墨烯的含量为超高分子量聚乙烯的0.5-5wt％。
在一种优选的实施方式中，本发明所述改性石墨烯的含量为超高分子量聚乙烯的1-3wt％。
在一种优选的实施方式中，本发明所述改性石墨烯的含量为超高分子量聚乙烯的2.2wt％。
在一种优选的实施方式中，本发明所述改性碳化硅晶须的含量为超高分子量 聚乙烯的0.5-5wt％。
在一种优选的实施方式中，本发明所述改性碳化硅晶须的含量为超高分子量聚乙烯的2-4wt％。
在一种优选的实施方式中，本发明所述改性碳化硅晶须的含量为超高分子量聚乙烯的3wt％。
其中，所述wt％为重量含量百分数。
在一种优选的实施方式中，本发明所述耐切割、耐蠕变纤维制备过程具体为：
(1)将上述制备得到的硅烷偶联剂改性的碳化硅晶须采用高速剪切共混的方式，分散在超高分子量聚乙烯粉末中，将制得的粉末预混料在超声波状态下均匀地分散于矿物油中；
(2)然后在带有搅拌剪切作用的反应釜中缓慢加热矿物油溶液，至溶液混合均匀，其中，高速剪切搅拌的速度为1000-3000r/min，搅拌时间为2-4小时，混合均匀后，得到质量浓度为3-5％的纺丝溶液；
(3)将纺丝溶液采用凝胶纺丝的纺丝进行纺丝、萃取、热牵伸得到复合纤维，其中纺丝温度为230-280℃。
本发明的另一方面提供一种用所述的超高分子量聚乙烯组合物制成的耐切割、耐蠕变纤维所制成的成品，所述成品可以是织物，例如防切割手套、衣物、布料等。
下面通过实施例对本发明进行具体描述，另外，如果没有其它说明，所用原料都是市售的。
实施例
实施例1
实施例1提供了一种耐切割、耐蠕变纤维，其由超高分子量聚乙烯组合物制备得到，包括如下组分：改性石墨烯、改性碳化硅晶须、超高分子量聚乙烯。
所述改性石墨烯为哌嗪改性石墨烯和十八胺改性石墨烯的混合物；所述哌嗪改性石墨烯和十八胺改性石墨烯的重量比为1:2；所述改性石墨烯的含量为超高分子量聚乙烯的0.5wt％。
所述改性碳化硅晶须为硅烷偶联剂改性的碳化硅晶须；所述改性碳化硅晶须的含量为超高分子量聚乙烯的5wt％。
所述超高分子量聚乙烯的重均分子量为200万，购买自余姚九鼎化工材料有限公司。
所述硅烷偶联剂改性的碳化硅晶须的制备方法包括：将所述碳化硅晶须先在去离子水中超声分散30min后添加所述硅烷偶联剂，将温度控制在70℃，搅拌5h后，烘干即得到硅烷偶联剂改性的碳化硅晶须。
其中，所述硅烷偶联剂改性的碳化硅晶须中所述碳化硅晶须和硅烷偶联剂的重量比1:0.1；所述硅烷偶联剂为十二烷基硅烷偶联剂和3-氨丙基三甲氧基硅烷的混合物，且所述十二烷基硅烷偶联剂和3-氨丙基三甲氧基硅烷的重量比为2:3；所述十二烷基硅烷偶联剂购买自南京优普化工有限公司，牌号为UP-312；所述3-氨丙基三甲氧基硅烷购买自青岛恒达众诚科技有限公司，牌号为KH-540。
所述硅烷偶联剂改性的碳化硅晶须中的碳化硅晶须的直径为200-500nm，长度为10-50μm，β型，购买自秦皇岛一诺高新材料开发有限公司，牌号为SiCW-80。
所述耐切割、耐蠕变纤维制备过程具体为：
(1)将上述制备得到的硅烷偶联剂改性的碳化硅晶须采用高速剪切共混的方式，分散在超高分子量聚乙烯粉末中，将制得的粉末预混料在超声波状态下均匀地分散于矿物油中；
(2)然后在带有搅拌剪切作用的反应釜中缓慢加热矿物油溶液，至溶液混合均匀，其中，高速剪切搅拌的速度为1000r/min，搅拌时间为4小时，混合均匀后，得到质量浓度为3％的纺丝溶液；
(3)将纺丝溶液采用凝胶纺丝的纺丝进行纺丝、萃取、热牵伸得到复合纤维，其中纺丝温度为230℃。
实施例2
实施例2提供了一种耐切割、耐蠕变纤维，其由超高分子量聚乙烯组合物制备得到，包括如下组分：改性石墨烯、改性碳化硅晶须、超高分子量聚乙烯。
所述改性石墨烯为哌嗪改性石墨烯和十八胺改性石墨烯的混合物；所述哌嗪改性石墨烯和十八胺改性石墨烯的重量比为1:3；所述改性石墨烯的含量为超高分子量聚乙烯的5wt％。
所述改性碳化硅晶须为硅烷偶联剂改性的碳化硅晶须；所述改性碳化硅晶须的含量为超高分子量聚乙烯的0.5wt％。
所述超高分子量聚乙烯的重均分子量为210万，购买自上海楚灏进出口有限公司。
所述硅烷偶联剂改性的碳化硅晶须的制备方法包括：将所述碳化硅晶须先在去离子水中超声分散30min后添加所述硅烷偶联剂，将温度控制在70℃，搅拌5h后，烘干即得到硅烷偶联剂改性的碳化硅晶须。
其中，所述硅烷偶联剂改性的碳化硅晶须中所述碳化硅晶须和硅烷偶联剂的重量比1:0.3；所述硅烷偶联剂为十二烷基硅烷偶联剂和3-氨丙基三甲氧基硅烷的混合物，且所述十二烷基硅烷偶联剂和3-氨丙基三甲氧基硅烷的重量比为3:2；所述十二烷基硅烷偶联剂购买自南京优普化工有限公司，牌号为UP-313；所述3-氨丙基三甲氧基硅烷购买自青岛恒达众诚科技有限公司，牌号为KH-540。
所述硅烷偶联剂改性的碳化硅晶须中的碳化硅晶须的直径为200-500nm，长度为10-50μm，β型，购买自秦皇岛一诺高新材料开发有限公司，牌号为SiCW-80。
所述耐切割、耐蠕变纤维制备过程具体为：
(1)将上述制备得到的硅烷偶联剂改性的碳化硅晶须采用高速剪切共混的方式，分散在超高分子量聚乙烯粉末中，将制得的粉末预混料在超声波状态下均匀地分散于矿物油中；
(2)然后在带有搅拌剪切作用的反应釜中缓慢加热矿物油溶液，至溶液混合均匀，其中，高速剪切搅拌的速度为3000r/min，搅拌时间为2小时，混合均匀后，得到质量浓度为5％的纺丝溶液；
(3)将纺丝溶液采用凝胶纺丝的纺丝进行纺丝、萃取、热牵伸得到复合纤维，其中纺丝温度为280℃。
实施例3
实施例3提供了一种耐切割、耐蠕变纤维，其由超高分子量聚乙烯组合物制备得到，包括如下组分：改性石墨烯、改性碳化硅晶须、超高分子量聚乙烯。
所述改性石墨烯为哌嗪改性石墨烯和十八胺改性石墨烯的混合物；所述哌嗪改性石墨烯和十八胺改性石墨烯的重量比为1:2.2；所述改性石墨烯的含量为超高分子量聚乙烯的1wt％。
所述改性碳化硅晶须为硅烷偶联剂改性的碳化硅晶须；所述改性碳化硅晶须的含量为超高分子量聚乙烯的4wt％。
所述超高分子量聚乙烯的重均分子量为240万，购买自上海楚灏进出口有限公司。
所述硅烷偶联剂改性的碳化硅晶须的制备方法包括：将所述碳化硅晶须先在去离子水中超声分散30min后添加所述硅烷偶联剂，将温度控制在70℃，搅拌5h后，烘干即得到硅烷偶联剂改性的碳化硅晶须。
其中，所述硅烷偶联剂改性的碳化硅晶须中所述碳化硅晶须和硅烷偶联剂的重量比1:0.2；所述硅烷偶联剂为十二烷基硅烷偶联剂和3-氨丙基三甲氧基硅烷的混合物，且所述十二烷基硅烷偶联剂和3-氨丙基三甲氧基硅烷的重量比为1:1；所述十二烷基硅烷偶联剂购买自南京优普化工有限公司，牌号为UP-312；所述3-氨丙基三甲氧基硅烷购买自青岛恒达众诚科技有限公司，牌号为KH-540。
所述硅烷偶联剂改性的碳化硅晶须中的碳化硅晶须的直径为100-600nm，长度为10-50μm，β型，购买自秦皇岛一诺高新材料开发有限公司，牌号为SiCW-90。
所述耐切割、耐蠕变纤维制备过程具体为：
(1)将上述制备得到的硅烷偶联剂改性的碳化硅晶须采用高速剪切共混的方式，分散在超高分子量聚乙烯粉末中，将制得的粉末预混料在超声波状态下均匀地分散于矿物油中；
(2)然后在带有搅拌剪切作用的反应釜中缓慢加热矿物油溶液，至溶液混合均匀，其中，高速剪切搅拌的速度为2000r/min，搅拌时间为3小时，混合均匀后，得到质量浓度为4％的纺丝溶液；
(3)将纺丝溶液采用凝胶纺丝的纺丝进行纺丝、萃取、热牵伸得到复合纤维，其中纺丝温度为250℃。
实施例4
实施例4提供了一种耐切割、耐蠕变纤维，其由超高分子量聚乙烯组合物制备得到，包括如下组分：改性石墨烯、改性碳化硅晶须、超高分子量聚乙烯。
所述改性石墨烯为哌嗪改性石墨烯和十八胺改性石墨烯的混合物；所述哌嗪改性石墨烯和十八胺改性石墨烯的重量比为1:2.8；所述改性石墨烯的含量为超高分子量聚乙烯的3wt％。
所述改性碳化硅晶须为硅烷偶联剂改性的碳化硅晶须；所述改性碳化硅晶须的含量为超高分子量聚乙烯的2wt％。
所述超高分子量聚乙烯的重均分子量为210万，购买自上海楚灏进出口有限公司。
所述硅烷偶联剂改性的碳化硅晶须的制备方法包括：将所述碳化硅晶须先在去离子水中超声分散30min后添加所述硅烷偶联剂，将温度控制在70℃，搅拌5h后，烘干即得到硅烷偶联剂改性的碳化硅晶须。
其中，所述硅烷偶联剂改性的碳化硅晶须中所述碳化硅晶须和硅烷偶联剂的重量比1:0.4；所述硅烷偶联剂为十二烷基硅烷偶联剂和3-氨丙基三甲氧基硅烷的混合物，且所述十二烷基硅烷偶联剂和3-氨丙基三甲氧基硅烷的重量比为1:1.2；所述十二烷基硅烷偶联剂购买自南京优普化工有限公司，牌号为UP-312；所述3-氨丙基三甲氧基硅烷购买自青岛恒达众诚科技有限公司，牌号为KH-540。
所述硅烷偶联剂改性的碳化硅晶须中的碳化硅晶须的直径为100-600nm，长度为10-50μm，β型，购买自秦皇岛一诺高新材料开发有限公司，牌号为SiCW-90。
所述耐切割、耐蠕变纤维制备过程同实施例3。
实施例5
实施例5提供了一种耐切割、耐蠕变纤维，其由超高分子量聚乙烯组合物制备得到，包括如下组分：改性石墨烯、改性碳化硅晶须、超高分子量聚乙烯。
所述改性石墨烯为哌嗪改性石墨烯和十八胺改性石墨烯的混合物；所述哌嗪改性石墨烯和十八胺改性石墨烯的重量比为1:2.5；所述改性石墨烯的含量为超高分子量聚乙烯的2.2wt％。
所述改性碳化硅晶须为硅烷偶联剂改性的碳化硅晶须；所述改性碳化硅晶须的含量为超高分子量聚乙烯的3wt％。
所述超高分子量聚乙烯的重均分子量为210万，购买自上海楚灏进出口有限公司。
所述硅烷偶联剂改性的碳化硅晶须的制备方法包括：将所述碳化硅晶须先在去离子水中超声分散30min后添加所述硅烷偶联剂，将温度控制在70℃，搅拌5h后，烘干即得到硅烷偶联剂改性的碳化硅晶须。
其中，所述硅烷偶联剂改性的碳化硅晶须中所述碳化硅晶须和硅烷偶联剂的重量比1:0.3；所述硅烷偶联剂为十二烷基硅烷偶联剂和3-氨丙基三甲氧基硅烷的混合物，且所述十二烷基硅烷偶联剂和3-氨丙基三甲氧基硅烷的重量比为 1:1.6；所述十二烷基硅烷偶联剂购买自南京优普化工有限公司，牌号为UP-312；所述3-氨丙基三甲氧基硅烷购买自青岛恒达众诚科技有限公司，牌号为KH-540。
所述硅烷偶联剂改性的碳化硅晶须中的碳化硅晶须的直径为200-500nm，长度为10-50μm，β型，购买自秦皇岛一诺高新材料开发有限公司，牌号为SiCW-80。
所述耐切割、耐蠕变纤维制备过程同实施例3。
对比例1
对比例1提供了一种耐切割、耐蠕变纤维，其由超高分子量聚乙烯组合物制备得到，包括如下组分：改性石墨烯、改性碳化硅晶须、超高分子量聚乙烯。
对比例1与实施例5不同之处在于，所述改性石墨烯的含量为超高分子量聚乙烯的0.1wt％。
对比例2
对比例2提供了一种耐切割、耐蠕变纤维，其由超高分子量聚乙烯组合物制备得到，包括如下组分：改性石墨烯、改性碳化硅晶须、超高分子量聚乙烯。
对比例2与实施例5不同之处在于，所述改性石墨烯的含量为超高分子量聚乙烯的20wt％。
对比例3
对比例3提供了一种耐切割、耐蠕变纤维，其由超高分子量聚乙烯组合物制备得到，包括如下组分：改性石墨烯、改性碳化硅晶须、超高分子量聚乙烯。
对比例3与实施例5不同之处在于，所述哌嗪改性石墨烯和十八胺改性石墨烯的重量比为1:0.2。
对比例4
对比例4提供了一种耐切割、耐蠕变纤维，其由超高分子量聚乙烯组合物制备得到，包括如下组分：改性石墨烯、改性碳化硅晶须、超高分子量聚乙烯。
对比例4与实施例5不同之处在于，所述哌嗪改性石墨烯和十八胺改性石墨烯的重量比为1:15。
对比例5
对比例5提供了一种耐切割、耐蠕变纤维，其由超高分子量聚乙烯组合物制备得到，包括如下组分：改性石墨烯、改性碳化硅晶须、超高分子量聚乙烯。
对比例5与实施例5不同之处在于，所述改性碳化硅晶须的含量为超高分子 量聚乙烯的0.1wt％。
对比例6
对比例6提供了一种耐切割、耐蠕变纤维，其由超高分子量聚乙烯组合物制备得到，包括如下组分：改性石墨烯、改性碳化硅晶须、超高分子量聚乙烯。
对比例6与实施例5不同之处在于，所述改性碳化硅晶须的含量为超高分子量聚乙烯的20wt％。
对比例7
对比例7提供了一种耐切割、耐蠕变纤维，其由超高分子量聚乙烯组合物制备得到，包括如下组分：改性石墨烯、改性碳化硅晶须、超高分子量聚乙烯。
对比例7与实施例5不同之处在于，所述超高分子量聚乙烯的重均分子量为90万，购买自余姚九鼎化工材料有限公司。
对比例8
对比例8提供了一种耐切割、耐蠕变纤维，其由超高分子量聚乙烯组合物制备得到，包括如下组分：改性石墨烯、改性碳化硅晶须、超高分子量聚乙烯。
对比例8与实施例5不同之处在于，所述超高分子量聚乙烯的重均分子量为500万，购买自余姚九鼎化工材料有限公司。
对比例9
对比例9提供了一种耐切割、耐蠕变纤维，其由超高分子量聚乙烯组合物制备得到，包括如下组分：改性石墨烯、改性碳化硅晶须、超高分子量聚乙烯。
对比例9与实施例5不同之处在于，所述硅烷偶联剂改性的碳化硅晶须中所述碳化硅晶须和硅烷偶联剂的重量比1:0.02。
对比例10
对比例10提供了一种耐切割、耐蠕变纤维，其由超高分子量聚乙烯组合物制备得到，包括如下组分：改性石墨烯、改性碳化硅晶须、超高分子量聚乙烯。
对比例10与实施例5不同之处在于，所述硅烷偶联剂改性的碳化硅晶须中所述碳化硅晶须和硅烷偶联剂的重量比1:2。
对比例11
对比例11提供了一种耐切割、耐蠕变纤维，其由超高分子量聚乙烯组合物制备得到，包括如下组分：改性石墨烯、改性碳化硅晶须、超高分子量聚乙烯。
对比例11与实施例5不同之处在于，所述十二烷基硅烷偶联剂和3-氨丙基三甲氧基硅烷的重量比为1:5。
对比例12
对比例12提供了一种耐切割、耐蠕变纤维，其由超高分子量聚乙烯组合物制备得到，包括如下组分：改性石墨烯、改性碳化硅晶须、超高分子量聚乙烯。
对比例12与实施例5不同之处在于，所述十二烷基硅烷偶联剂和3-氨丙基三甲氧基硅烷的重量比为5:1。
对比例13
对比例13提供了一种耐切割、耐蠕变纤维，其由超高分子量聚乙烯组合物制备得到，包括如下组分：改性石墨烯、改性碳化硅晶须、超高分子量聚乙烯。
对比例13与实施例5不同之处在于，所述硅烷偶联剂改性的碳化硅晶须中的碳化硅晶须的直径为100-600nm，长度为100μm，β型，购买自秦皇岛一诺高新材料开发有限公司，牌号为SiCW-98。
对比例14
对比例14提供了一种耐切割、耐蠕变纤维，其由超高分子量聚乙烯组合物制备得到，包括如下组分：改性石墨烯、改性碳化硅晶须、超高分子量聚乙烯。
对比例14与实施例5不同之处在于，所述硅烷偶联剂为十八烷基硅烷偶联剂和3-氨丙基三甲氧基硅烷的混合物；所述十八烷基硅烷偶联剂购买自南京优普化工有限公司，牌号为UP-318。
对比例15
对比例15提供了一种耐切割、耐蠕变纤维，其由超高分子量聚乙烯组合物制备得到，包括如下组分：改性石墨烯、改性碳化硅晶须、超高分子量聚乙烯。
对比例15与实施例5不同之处在于，所述硅烷偶联剂为甲基硅烷偶联剂和3-氨丙基三甲氧基硅烷的混合物；所述甲基硅烷偶联剂购买自南京优普化工有限公司，牌号为UP-302。
性能评价
1.产物防切割性测试：
可按国家标准GB24541-2009或欧标EN388测试，根据欧洲标准EN388，使用耐切割试验机，测试原丝的耐切割性，装置为Sodemat厂商按欧标EN388 出品的试验机，将试样置于耐切割试验机装置台上，下面垫铝箔并水平移动，将所备用的圆形刀片置于试样上旋转按与试验移动的方向边旋转边前进，两者方向逆向，当试验被完全切断瞬间，圆形刀片与所垫铝箔接触通电，此时电路通知计数器切割终结，在整个过程中计数器始终处于记录中，所以可以得到试样耐切割性数据，试验后，耐切割水平是按与使用的标准样(为200g/m 2的平面棉织布)在同条件下的切割水平相比较来评价。从标准样开始试验，试验样与标准样轮流交互进行切割试验，试验样进行3次后，最后标准样进行第四次试验，这一轮试验就结束。
可按下式算出评价值称作耐切割指数：
N＝(试验样在试验前标准样的计数器读数值+试验样在试验后标准样的计数器读数)/2；
指数＝(试验样的计数器读数值+N)/N
指数的分类
指数 耐切割级数
2.0-2.5 1
2.5-5.0 2
5.0-10 3
10.0-20.0 4
>20.0 5
此外，试验使用的圆形刀片是OLFA公司制旋转式切割-L型，直径为45mm，材料为SKS-7钨钢，刀片厚度0.3mm。
2.抗撕强度测试：依据JB/T 1040-92进行测定。
3.耐蠕变性能测试：蠕变伸长率测试条件：在温度20±2℃、相对湿度63±3％条件下，施加应力为纤维断裂强力的50％，蠕变时间1d。
表1
  防切割性 抗撕强度(MPa) 耐蠕变性(％)
实施例1 5 27.52 1.416
实施例2 5 28.35 1.432
实施例3 5 29.87 1.284
实施例4 5 29.58 1.029
实施例5 5 31.67 0.916
对比例1 2 19.82 2.646
对比例2 4 30.15 2.429
对比例3 2 25.35 1.525
对比例4 3 23.55 5.518
对比例5 2 19.43 6.543
对比例6 4 28.22 1.416
对比例7 2 25.91 1.517
对比例8 3 24.61 5.587
对比例9 2 21.38 4.942
对比例10 3 26.48 6.514
对比例11 2 24.61 1.548
对比例12 2 26.18 9.624
对比例13 3 22.31 2.056
对比例14 3 19.67 6.314
对比例15 2 22.46 8.464

Claims (10)

  1. 一种超高分子量聚乙烯组合物，其特征在于，包括如下组分：改性石墨烯、改性碳化硅晶须、超高分子量聚乙烯。
  2. 根据权利要求1所述的超高分子量聚乙烯组合物，其特征在于，所述改性石墨烯的含量为超高分子量聚乙烯的0.5-5wt％。
  3. 根据权利要求1所述的超高分子量聚乙烯组合物，其特征在于，所述改性碳化硅晶须的含量为超高分子量聚乙烯的0.5-5wt％。
  4. 根据权利要求1所述的超高分子量聚乙烯组合物，其特征在于，所述超高分子量聚乙烯的重均分子量为200-240万。
  5. 根据权利要求1所述的超高分子量聚乙烯组合物，其特征在于，所述改性石墨烯为氨基化石墨烯。
  6. 根据权利要求5所述的超高分子量聚乙烯组合物，其特征在于，所述氨基化石墨烯包括哌嗪改性石墨烯和十八胺改性石墨烯。
  7. 根据权利要求1所述的超高分子量聚乙烯组合物，其特征在于，所述改性碳化硅晶须为硅烷偶联剂改性的碳化硅晶须。
  8. 根据权利要求7所述的超高分子量聚乙烯组合物，其特征在于，所述硅烷偶联剂改性的碳化硅晶须中所述碳化硅晶须和硅烷偶联剂的重量比1:(0.1-0.5)。
  9. 一种耐切割、耐蠕变纤维，其特征在于，由权利要求1-8中任一项所述的超高分子量聚乙烯组合物制备得到。
  10. 一种根据权利要求9所述的耐切割、耐蠕变纤维的制备方法，其特征在于，步骤包括：
    (1)将改性石墨烯、改性碳化硅晶须和超高分子量聚乙烯混合均匀；
    (2)将步骤(1)中的混合物经乳化机高速剪切搅拌，得到纺丝溶液；
    (3)将纺丝溶液纺丝后，进行萃取和热牵伸得到纤维。
PCT/CN2019/092224 2019-03-01 2019-06-21 一种耐切割、耐蠕变uhmwpe纤维及其制备方法 Ceased WO2020177241A1 (zh)

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