CN109610028B

CN109610028B - Graphene composite ultra-high molecular weight polyethylene fiber and preparation method thereof

Info

Publication number: CN109610028B
Application number: CN201810014978.1A
Authority: CN
Inventors: 王咸华; 欧崇华; 任申东; 张明
Original assignee: Jiangsu Hanvo Safety Product Co ltd
Current assignee: Jiangsu Hanvo Safety Product Co ltd
Priority date: 2018-01-08
Filing date: 2018-01-08
Publication date: 2021-12-21
Anticipated expiration: 2038-01-08
Also published as: CN109610028A

Abstract

The invention provides a preparation method of a graphene composite ultra-high molecular weight polyethylene fiber, which comprises the following steps: preparing a glass fiber premix: dispersing glass fibers in first white oil to obtain glass fiber premix; preparing graphene slurry: dispersing graphene in second white oil to obtain graphene slurry; preparing a spinning mixed solution: mixing the glass fiber premixed solution, the graphene slurry, UHMWPE powder and the antioxidant in third white oil to obtain a spinning mixed solution; swelling and mixing the spinning mixed solution to form a molten state, and extruding the spinning mixed solution in the molten state; cooling to form gel silk; and preparing the gel silk into the graphene composite ultra-high molecular weight polyethylene fiber. The method disclosed by the invention not only can solve the problem of poor glass fiber dispersibility under the condition of high viscoelasticity of the ultra-high molecular weight polyethylene, but also effectively improves the cutting resistance of the UHMWPE fibers on the basis of ensuring the flexibility of the yarns.

Description

Graphene composite ultra-high molecular weight polyethylene fiber and preparation method thereof

Technical Field

The invention relates to an ultra-high molecular weight polyethylene fiber and a preparation method thereof, belonging to the technical field of high-performance fibers.

Background

Ultrahigh molecular weight polyethylene (UHMWPE) fibers, also known as ultra-high strength polyethylene (UHMWPE) fibers, ultra-high modulus polyethylene (UHMWPE) fibers. Due to the fact that UHMWPE has incomparable ultrahigh tensile strength, the fiber with ultrahigh elastic modulus and strength can be prepared through a gel spinning method, the tensile strength is 3-3.5 GPa, and the tensile elastic modulus is 100-125 GPa; the fiber strength is the highest of all the fibers commercialized so far, and is 4 times greater than that of carbon fiber, 10 times greater than that of steel wire and 50% greater than that of aramid fiber. It is widely applied to the fields of military equipment, aerospace, marine operation, sports equipment and the like.

Patents for improving the cut resistance of the fiber include CN102828312A, JP2004-19050, WO2008/046476, and CN102037169A, in which a high-strength fiber such as high-molecular-weight polyethylene or highly symmetric polyamide is coated with an inorganic metal or glass fiber, but the addition of a hard material such as an inorganic metal or glass fiber makes the body feel hard and uncomfortable to wear. The graphene has good mechanical property and self-lubricating property, can be coated on the surface of a hard material, increases the lubricating property and makes up the deficiency. Through tests, if graphene powder is directly added in the spinning mixed solution process, a large amount of graphene can be agglomerated, the particle size distribution of graphene particles is wide, the size is large, the agglomeration is serious, effective interface combination is difficult to form with white oil, the spinning mixed solution with poor dispersibility is obtained, the graphene in the spinning mixed solution is uniform in dispersion and poor in stability, and the shelf life is short. In the composite material, the dispersion of the reinforcing phase in the matrix has a crucial influence on the performance of the material.

The technical contents listed in the prior art merely represent the techniques mastered by the inventor and are not of course considered as the prior art for evaluating the novelty and inventive step of the present invention.

Disclosure of Invention

The invention aims to provide an ultra-high molecular weight polyethylene fiber with uniformly dispersed graphene aiming at the defects of the prior art.

The invention also aims to provide a preparation method of the graphene composite ultra-high molecular weight polyethylene fiber.

The purpose of the invention is realized by the following technical scheme:

a preparation method of graphene composite ultra-high molecular weight polyethylene fibers comprises the following steps:

preparing a glass fiber premix: dispersing glass fibers in first white oil to obtain glass fiber premix;

preparing graphene slurry: dispersing graphene in second white oil to obtain graphene slurry;

preparing a spinning mixed solution: mixing the glass fiber premixed solution, the graphene slurry, UHMWPE powder and the antioxidant in third white oil to obtain a spinning mixed solution;

swelling and mixing the spinning mixed solution to form a molten state, and extruding the spinning mixed solution in the molten state;

cooling to form gel silk; and

and preparing the gel silk into the graphene composite ultra-high molecular weight polyethylene fiber.

In the disclosure of the present invention, the first white oil, the second white oil and the third white oil are white oils, and the terms "first", "second" and "third" are not intended to limit the white oils themselves, and are used to distinguish different applications in the preparation method of the present invention.

According to one aspect of the invention, the glass fiber premix contains 5 to 30 wt%, preferably 10 to 25 wt%, and most preferably 25 wt% of glass fibers.

According to one aspect of the invention, the glass fiber is dispersed in the first white oil by pouring the glass fiber into the first white oil for premixing, and then stirring at a high speed by using an emulsifying machine until a uniform slurry is formed. The mixed material of glass fiber and white oil is forced to pass through a narrow gap at a high speed by mechanical action, under the action of fluid mechanics effect, a high tangential linear velocity generated by high-speed rotation of a rotor forms a great speed gradient in the narrow gap between the rotor and a stator, and strong kinetic energy is brought by high-frequency mechanical effect, so that the material is subjected to comprehensive actions of strong hydraulic shearing, centrifugal extrusion, liquid layer friction, impact tearing, turbulent flow and the like in the gap between the stator and the rotor, incompatible solid phase and liquid phase are instantly, uniformly and finely dispersed and homogenized under the function of adding an auxiliary agent, and dispersed phase particles or liquid drops are broken to achieve the purpose of homogeneous emulsification through high-frequency circulation reciprocation.

According to an aspect of the present invention, in the above method, the stirring medium speed of the high-speed stirring is 3000-10000rpm, preferably 3500 rpm; the stirring time of the high-speed stirring is 5-60min, preferably 10-30min, and most preferably 15 min.

According to one aspect of the invention, the diameter of the glass fiber is 3-10um, preferably 5-7 um.

According to one aspect of the invention, the average length of the glass fibers is 30-100um, preferably 50-70 um.

According to one aspect of the invention, the glass fibers have a length in the range of 10-600um, preferably 50-400 um.

According to one aspect of the invention, the glass fiber is modified by the coupling agent in advance, and then the glass fiber premix is prepared. The specific treatment method comprises the following steps: dissolving the coupling agent in absolute ethyl alcohol, adding glass fiber, mixing uniformly, soaking, drying, grinding, and filtering with 100 meshes.

According to one aspect of the invention, the coupling agent is added in an amount of 0.1 to 3%, preferably 0.2% to 2%, by mass of the glass fibers.

According to one aspect of the invention, the immersion time of the glass fiber in the coupling agent ethanol solution is 10min to 5h, preferably 30min to 2 h.

According to one aspect of the invention, the drying temperature is between 50 ℃ and 180 ℃, preferably between 80 ℃ and 130 ℃; the drying time is 1h-6h, preferably 2h-3 h.

According to an aspect of the present invention, in the method for modifying a glass fiber, the coupling agent is one or a mixture of two or more silane coupling agents.

The silane coupling agent is preferably one or a mixture of more than two of A-150, A-151, A-171, KH-550, KH-560, KH-570, KH-580, KH-590, KH-902 or KH-792.

A-150, A-151, A-171, KH-550, KH-560, KH-570, KH-580, KH-590, KH-902, or KH-792 are grades of silane coupling agents, and the properties of different grades of coupling agents are different, these grades being internationally recognized grades.

The silane coupling agent is a low molecular organosilicon compound with a special structure, the general formula of which is RSiX3, wherein R represents an active functional group with affinity or reaction capability with polymer molecules, such as oxy, vinyl, epoxy, amido, aminopropyl and the like; x represents an alkoxy group capable of hydrolysis, such as a halogen, an alkoxy group, an acyloxy group, or the like. In the coupling process, firstly, the X group forms silanol, and then reacts with hydroxyl on the surface of the inorganic powder particles to form hydrogen bonds and condense into-SiO-M covalent bonds (M represents the surface of the inorganic powder particles). Meanwhile, silanol of each molecule of silane is mutually associated and oligomerized to form a film with a net structure to cover the surfaces of the powder particles, so that the surfaces of the inorganic powder are organized.

The coupling agent A-150 is vinyl trichlorosilane, colorless liquid is dissolved in an organic solvent, and hydrolysis and alcoholysis are easy. Molecular formula is CH₂＝CHSiCl₃Molecular weight 161.5, boiling point 90.6 deg.C, density 1.265g/cm³It is suitable for use as a surface treating agent for glass fiber and a treating agent for reinforced plastic laminates.

The coupling agent A-151 is vinyl triethoxysilane with a molecular formula of CH₂＝CHSi(OCH₂CH₃)₃. Soluble in organic solvents and insoluble in water at pH 7, and is suitable for polymer-based polyethylene, polypropylene, unsaturated polyester, etc., as well as glass fiber, plastic, glass, cable, ceramic, etc.

The coupling agent A-171 is vinyl trimethoxy silane with a molecular formula of CH₂＝CHSi(OCH₃)₃. Colorless transparent liquid with density of 0.95-0.99g/cm³The refractive index is 1.38-1.40, the boiling point is 123 ℃, the polymer has the functions of a coupling agent and a crosslinking agent, and suitable polymer types comprise polyethylene, polypropylene, unsaturated polyester and the like, and are commonly used for glass fibers, plastics, glass, cables, ceramics, rubber and the like.

The coupling agent KH-550 is gamma-aminopropyltriethoxysilane, corresponding to the trade name A-1100 (USA), and has a density of 0.942g/ml, a melting point of-70 deg.C, a boiling point of 217 deg.C, a refractive index of 1.42-1.422, and a flash point of 96 deg.C. The composite material is applied to mineral filled thermoplastic and thermosetting resins such as phenolic aldehyde, polyester, epoxy, PBT, polyamide, carbonate and the like, can greatly improve the physical and mechanical properties such as dry-wet bending strength, compressive strength, shear strength and the like and wet-state electrical properties of reinforced plastics, and improves the wettability and the dispersibility of the filler in polymers.

The coupling agent KH-560 is gamma-glycidoxypropyltrimethoxysilane with the corresponding mark of A-187(GE), is mainly used for caulking glue and sealant of polysulfide and polyurethane, and is used for adhesive of epoxy resin, filled or enhanced thermosetting resin, glass fiber or glass reinforced thermoplastic resin and the like.

The coupling agent KH-570 is methacryloxy silane, corresponds to the mark A-174(GE), is colorless or yellowish transparent liquid in appearance, is dissolved in acetone, benzene, ether and carbon tetrachloride, and reacts with water. Boiling point 255 deg.C, density 1.04g/ml, refractive index 1.429, flash point 88 deg.C. The product is mainly used for unsaturated polyester resin, and can also be used for polybutylene, polyethylene and ethylene propylene diene monomer.

The coupling agent KH-580 is gamma-mercaptopropyltriethoxysilane, corresponds to the mark A-1891 (USA), is colorless transparent liquid with slightly special odor, and is easily soluble in various solvents such as ethanol, acetone, benzene, toluene and the like. Is insoluble in water, but is susceptible to hydrolysis upon contact with water or moisture. Boiling point 82.5 deg.C, specific gravity 1.000(20 deg.C), flash point 87 deg.C, and molecular weight 238.

The coupling agent KH-590 is gamma-mercaptopropyltrimethoxysilane which corresponds to the mark A-189 (USA), has the molecular weight of 196.3399, the density of 1.057g/ml, the boiling point of 213-215 ℃, the refractive index of 1.441-1.443 and the flash point of 88 ℃, and is commonly used as a glass fiber treating agent and a crosslinking agent.

The coupling agent KH-792 is N-beta- (aminoethyl) -gamma-aminopropyl trimethoxy silane, and the molecular formula is NH₂(CH₂)₂NH(CH₂)₃Si(OCH₃)₃The molecular weight is 222, the density is 1.010-1.030g/ml, the boiling point is 259 ℃, the refractive index is 1.4425-1.4460, the flash point is 138 ℃, and the organic solvent is soluble.

The coupling agent KH-902 is gamma-aminopropyl methyl diethoxy silane, and the molecular formula is NH₂(CH₂)₃SiCH₃(OC₂H₅)₂The molecular weight is 191.34, the density is 0.9160 +/-0.0050 g/ml, the boiling point is 85-88 ℃/1.07KPa, and the refractive index is 1.4270 +/-0.0050, so that the material is suitable for most organic and inorganic materials.

According to an aspect of the invention, the concentration of graphene in the graphene paste is 1 wt% to 8 wt%, preferably 2 to 5 wt%.

According to one aspect of the invention, the graphene slurry is prepared by the following method:

adding graphene and a dispersing agent into first white oil, stirring by a high-speed shearing machine, and then grinding by a sand mill until the particle size D99 of the graphene is less than 7 um.

Preferably, the high speed shears stir for 10 min.

Preferably, the grinding medium is zirconium oxide beads during grinding by the sand mill, and the particle size of the zirconium oxide beads is preferably 0.6-0.8 mm.

Preferably, the rotation speed of the sand mill during grinding is 1500-2800 rpm.

Further preferably, the dispersant is one or a combination of two or more of PSS, SDBS, SDS, a commercial BYK series, and a commercial AFCONA series.

PSS is sodium polystyrene sulfonate (PSS) with the molecular formula of (C)₈H₇NaO₃S)_x. Light amber liquid, no bad smell, easy to dissolve in water. The sodium polystyrene sulfonate solution is a water-soluble polymer with unique function, and is applied to the aspects of reactive emulsifier, water-soluble high polymer (coagulant, dispersant, container cleaning agent, cosmetics and the like), water treatment agent (dispersant and flocculant), sulfur exchange resin (film), portrait chemical (film), semiconductor, image film, heat conduction product and the like.

SDBS is sodium dodecyl benzene sulfonate for short, and the molecular formula is C₁₈H₂₉NaO₃And S. White or light yellow powder or flake solid, dissolving in water to obtain translucent solution. Mainly used as an anionic surfactant. The hydrophilic-lipophilic balance value (HLB value) is 10.638, the decomposition temperature is 450 ℃, and the weight loss rate is 60%. Is easy to dissolve in water and absorb moisture to form lumps.

SDS is the abbreviation of sodium dodecyl sulfate, and the molecular formula is C₁₂H₂₅SO₄And (4) Na. White or yellowish powdery substance, which is soluble in water and insensitive to alkali and hard water. Has the advantages of decontamination, emulsification and excellent foaming power. Is a little toxic to human bodyAn ionic surfactant. Degree of biodegradation thereof>90 percent. The current uses are: can be used as emulsifier, fire-extinguishing agent, foaming agent and textile auxiliary, and also can be used as foaming agent for toothpaste, paste, powder and shampoo.

The commercial AFCONA series preferably adopts AFCONA 4010, AFCONA 4700 or AFCONA 4701; the commercial BYK series preferably employs BYK-P104S.

Commercial BYK is a series of dispersants produced by BYK chemical auxiliaries, germany. For example, BYK-P104S is a solution of a copolymer of a low molecular weight unsaturated polycarboxylic acid polymer and a polysiloxane in a solvent xylene/diisobutyl ketone, a wetting and dispersing agent for improving pigment wetting and stabilizing pigment dispersion, and controlled flocculation of pigments and extender pigments, thereby preventing flooding/blooming and hard-set.

Commercial AFCONA is a high molecular weight dispersant including polyurethanes, polyacrylates, and polyesters. For example, AFCONA 4010 is a polyurethane dispersant, the molecular structure of the dispersant contains a special anchoring group with an elastic structure, the anchoring efficiency is much higher than that of a dispersant with a common rigid structure, the dispersant can be well wetted and dispersed on the surface of a pigment, and meanwhile, a high molecular chain of the dispersant can well prevent pigment particles from aggregating, so that an ideal anti-flocculation effect is achieved. AFCONA 4700 and AFCONA 4701 are both three-stage block polyacrylate type polymeric dispersants. The appearance is transparent to very slight turbid liquid, the density is 1.028-1.038g/cm3, the amine value is 25-31mg KOH/g, the flash point is 24 ℃, the color is not more than 18, the solvent is propylene glycol monomethyl ether acetate, and the activity content is 49-52%.

Further preferably, the amount of the dispersant is 0.1-5%, preferably 0.2-1% of the mass of the graphene slurry.

According to an aspect of the present invention, the graphene employs a graphene powder having a single-layer or multi-layer structure. Preferably, the sheet diameter of the graphene with the single-layer or multi-layer structure is 0.5-5 um, and the thickness of the graphene is 0.5-30 nm. More preferably, the graphene with the single-layer or multi-layer structure has a specific surface area of 200-1000 m²/g。

According to one aspect of the invention, of said UHMWPEViscosity average molecular weight is (2-6) x 10⁶g/mol, preferably (4-5). times.10⁶g/mol。

According to one aspect of the invention, the antioxidant is one or a combination of more than two of antioxidant 1010, antioxidant 1076, antioxidant CA, antioxidant 164, antioxidant DNP, antioxidant DLTP or antioxidant TNP; one or a combination of two or more of antioxidant 1010, antioxidant 164, and antioxidant DNP is preferred.

The antioxidant 1010 is short for pentaerythrityl tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ]; white flowable powder with a melting point of 120-125 ℃ and low toxicity is a good antioxidant. The polypropylene resin is widely applied to polypropylene resin, is an auxiliary agent which has high thermal stability and is very suitable for being used under high temperature conditions, can prolong the service life of products, and can also be used for most other resins.

The antioxidant 1076 is short for beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid octadecyl ester; white or yellowish crystalline powder, which has a melting point of 50-55 ℃, is non-toxic, insoluble in water, and soluble in solvents such as benzene, ethane, esters, etc. Can be used as antioxidant for polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyamide, ABS, acrylic acid and other resins. Has the characteristics of good oxygen resistance, small volatility, washing resistance and the like.

The antioxidant CA is the abbreviation of 1,1, 3-tri (2-methyl-4-hydroxy-5-tert-butylphenyl) butane; white crystalline powder, melting point 180-188 ℃, low toxicity, soluble in ethanol, toluene and ethyl acetate. It is suitable for antioxidant assistant in polypropylene, polyethylene, polyvinyl chloride, ABS and polyamide resin, and may be used in wire and cable.

The antioxidant 164 is white or pale yellow crystalline powder or flakes. Its melting point is 70 deg.C, boiling point is about 260 deg.C, and it is non-toxic. The resin is used in various resins and has wide application. Is more suitable for food packaging molding materials (polypropylene, polyethylene, polyvinyl chloride, ABS, polyester and polystyrene) resin.

The antioxidant DNP is short for N, N' -di (beta-naphthyl) p-phenylenediamine; light gray powder, melting point of about 230 ℃, is easily dissolved in aniline and nitrobenzene, and is not dissolved in water. Is suitable for polyethylene and polypropylene. The impact resistant polystyrene and ABS resin not only have antioxidant effect, but also have better thermal stability and inhibit the influence of copper and lemon metal.

The antioxidant DLTP is the abbreviation of dilauryl thiodipropionate; white crystalline powder, melting point of about 40 deg.C, low toxicity, water-insoluble, and soluble in benzene, carbon tetrachloride. The auxiliary antioxidant used for polyethylene, polypropylene, ABS and polyvinyl chloride resin can change the heat resistance and the oxygen resistance of the product.

The antioxidant TNP is short for tris (nonylphenyl) phosphite ester; light yellow viscous liquid with freezing point lower than-5 deg.C and boiling point higher than 105 deg.C, no odor, no toxicity, water insolubility, and ethanol solubility. Benzene and carbon tetrachloride. It is suitable for polyvinyl chloride, polyethylene, polypropylene, impact resistant polystyrene, ABS, polyester and other resins.

According to one aspect of the invention, the implementation method for mixing the glass fiber premix, the graphene slurry, the UHMWPE powder and the antioxidant in the third white oil is as follows:

under high-speed stirring, adding the glass fiber premixed solution and the graphene slurry into third white oil, and adding UHMWPE powder and an antioxidant while stirring to obtain a spinning mixed solution.

According to one aspect of the invention, in the preparation of the spinning mixture, the UHMWPE powder: the mass ratio of the third white oil is 6: 94.

According to one aspect of the present invention, in the preparation of the spinning mixture,

the glass fiber is 0.2-10 wt% of the graphene composite ultra-high molecular weight polyethylene fiber, preferably 5-6.5 wt%.

The graphene is 0.02-1 wt%, preferably 0.05 wt% of the graphene composite ultra-high molecular weight polyethylene fiber.

According to one aspect of the invention, the antioxidant is 0.01 to 1 wt%, preferably 0.1 to 0.5 wt% of the graphene composite ultra-high molecular weight polyethylene fiber. According to one aspect of the invention, the swelling is carried out by heating to 100 ℃ and 140 ℃ in a swelling kettle and keeping the temperature for 1-3 h; preferably, the temperature is raised to 110 ℃ and the temperature is kept for 2 h.

The purpose of swelling is to maximize the penetration and diffusion of the solvent into the polymer, which weakens the strong interactions between the macromolecular chains, the more complete this solvation is, the easier it is to go into the dissolution phase. And because the crystalline polymer is in a thermodynamically stable phase state, the molecular chain arrangement is compact and regular, the interaction force among the molecular chains is large, and solvent molecules can hardly enter a crystal region, enough energy must be absorbed firstly to dissolve the crystalline polymer, so that the molecular chain movement is enough to destroy the crystal lattice, and the regular arrangement of the molecular chains is broken. Therefore, UHMWPE needs to swell at a high temperature of more than 100 ℃, and is dissolved when the temperature is higher, white oil can more easily enter the UHMWPE at 100 ℃ and 140 ℃, and the effect is optimal at 110 ℃.

According to one aspect of the invention, the extrusion is carried out by adopting a double-screw extruder, the extrusion temperature is increased to 243 ℃ in a stepped manner, and preferably, the length-diameter ratio of the double-screw extruder is 68, and the double-screw extruder consists of a feeding section, a temperature increasing section, a dissolving section and a uniformly mixing section.

A certain number of instant entanglement points are still kept on the molecular chain of the swelled UHMWPE, and the UHMWPE is extruded at a stepped temperature, so that macromolecules are dispersed into a solution in an integral coil form, the entanglement points are removed, and the solvation effect of the solvent on the UHMWPE is enhanced.

According to one aspect of the invention, the cooling is by hydraulic cooling.

According to one aspect of the invention, the execution method for preparing the graphene composite ultra-high molecular weight polyethylene fiber from the gel silk comprises the following steps: and (3) carrying out primary drawing, extraction, drying and super-hot drawing on the gel silk to obtain the composite fiber.

In the execution method for preparing the graphene composite ultra-high molecular weight polyethylene fiber by using the gel silk, the 3-level ultra-high hot drawing is adopted for the ultra-high hot drawing, and the drawing temperature is 140-146 ℃; the extraction adopts a continuous multistage closed ultrasonic extractor and a hydrocarbon extraction high-power stretching device, and the extraction temperature is 40 ℃; preferably, the extraction adopts a multi-stage multi-groove quantitative liquid supplementing and draining process to control the oil content after gel silk extraction, an ultrasonic generator is additionally arranged for full extraction, a water circulation mold temperature controller is arranged to accurately control the temperature of the extraction liquid, the temperature difference is less than or equal to +/-1 ℃, and the extraction rate is more than or equal to 99%.

The graphene composite ultra-high molecular weight polyethylene fiber is mixed with glass fiber and graphene, wherein the content of the glass fiber is 0.2-10 wt%, and the content of the graphene is 0.02-1 wt%.

According to one aspect of the invention, the content of glass fibers in the fibers is 5-6.5 wt%, and the content of graphene is 0.05 wt%.

According to one aspect of the invention, the diameter of the glass fiber is 3-10um, preferably 5-7 um; and/or the glass fibers have an average length of 30 to 100um, preferably 50 to 70 um.

According to an aspect of the present invention, the graphene employs a graphene powder having a single-layer or multi-layer structure. Preferably, the sheet diameter of the graphene with the single-layer or multi-layer structure is 0.5-5 um, and the thickness of the graphene is 0.5-30 nm; more preferably, the graphene with the single-layer or multi-layer structure has a specific surface area of 200-1000 m²/g。

According to one aspect of the invention, the viscosity average molecular weight of the UHMWPE is (2-6). times.10⁶g/mol, preferably (4-5). times.10⁶g/mol。

According to one aspect of the invention, the graphene composite ultra-high molecular weight polyethylene fiber is prepared according to the method.

Drawings

The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:

FIG. 1 is a graph of the wetting of a water droplet 5 seconds after the surface of a glass fiber is not treated with a coupling agent;

FIG. 2 is a graph showing the wetting of a water droplet 5 seconds after the surface of a glass fiber is treated with a coupling agent;

FIG. 3 is a graph showing the wetting of oil droplets 5 seconds after the surface of the glass fiber is not treated with the coupling agent;

FIG. 4 shows the wetting of oil droplets 5 seconds after the coupling agent treatment of the glass fiber surface;

fig. 5 is an optical microscope image (5 x magnification) of a jelly-silk in which the rod is glass fiber and the black particles are graphene;

fig. 6 is an optical microscope image (10 x magnification) of a jelly-roll in which the rod is glass fiber and the black particles are graphene;

FIG. 7 is an SEM microtopography of the outer surface of the composite fiber;

FIG. 8 is an SEM microtopography of the outer surface of the composite fiber;

FIG. 9 is a cross-sectional SEM microtopography of the composite fiber;

FIG. 10 is a cross-sectional SEM microtopography of the composite fiber;

FIG. 11 is a flow chart of one embodiment of a method of making the graphene composite ultra high molecular weight polyethylene fibers disclosed herein;

FIG. 12 is a flow chart of another embodiment of a method of making a graphene composite ultra high molecular weight polyethylene fiber according to the present disclosure;

FIG. 13 is a schematic diagram of a specific process in an embodiment of the invention;

FIG. 14 is another specific process scheme in an embodiment of the present invention.

Detailed Description

In the following, only certain exemplary embodiments are briefly described. As those skilled in the art will appreciate, the described embodiments may be modified in various different ways, including by addition, deletion, modification, etc., without departing from the spirit or scope of the invention. Accordingly, the drawings and description are to be regarded as illustrative in nature, and not as restrictive.

In the disclosure of the present invention, the terms "first white oil", "second white oil" and "third white oil" are all white oils, and the terms "first", "second" and "third" are not limiting to the white oil itself, and are used to distinguish different applications in the preparation method of the present invention.

In a specific embodiment of the present invention, a method 100 for preparing a graphene composite ultra-high molecular weight polyethylene fiber is provided, which includes:

101: dispersing glass fibers in first white oil to obtain glass fiber premix;

102: dispersing graphene in second white oil to obtain graphene slurry;

103: mixing the glass fiber premixed solution, the graphene slurry, UHMWPE powder and the antioxidant in third white oil to obtain a spinning mixed solution;

104: swelling and mixing the spinning mixed solution to form a molten state, extruding the spinning mixed solution in the molten state, and cooling to form gel yarns; and

105: and preparing the gel silk into the graphene composite ultra-high molecular weight polyethylene fiber.

Each process is described in detail below.

In 101:

the glass fiber premix may contain 5 to 30 wt% of glass fibers, for example: 5 wt%, 7 wt%, 8 wt%, 10 wt%, 11 wt%, 13 wt%, 15 wt%, 17 wt%, 18 wt%, 19 wt%, 20 wt%, 21 wt%, 22 wt%, 23 wt%, 25 wt%, 26 wt%, 27 wt%, 29 wt%, 30 wt%, etc. As a preferred embodiment, the glass fiber premix contains 10 to 25 wt% of glass fibers, such as: 10 wt%, 11 wt%, 12 wt%, 13.5 wt%, 14 wt%, 15 wt%, 16 wt%, 16.5 wt%, 17 wt%, 18 wt%, 19 wt%, 20 wt%, etc. As a best embodiment, the glass fiber premix comprises 25 wt% of glass fibers.

The dispersing method for dispersing the glass fiber in the first white oil comprises the steps of pouring the glass fiber into the first white oil for premixing, and then stirring at a high speed by using an emulsifying machine until uniform slurry is formed. The purpose of this is: the mixed material of glass fiber and white oil is forced to pass through a narrow gap at a high speed by mechanical action, under the action of fluid mechanics effect, a high tangential linear velocity generated by high-speed rotation of a rotor forms a great speed gradient in the narrow gap between the rotor and a stator, and strong kinetic energy is brought by high-frequency mechanical effect, so that the material is subjected to comprehensive actions of strong hydraulic shearing, centrifugal extrusion, liquid layer friction, impact tearing, turbulent flow and the like in the gap between the stator and the rotor, incompatible solid phase and liquid phase are instantly, uniformly and finely dispersed and homogenized under the function of adding an auxiliary agent, and dispersed phase particles or liquid drops are broken to achieve the purpose of homogeneous emulsification through high-frequency circulation reciprocation.

The stirring speed of the high-speed stirring may be 3000-10000rpm, such as 3000rpm, 3500rpm, 3800rpm, 4000rpm, 4300rpm, 4500rpm, 5000rpm, 5500rpm, 6000rpm, 6500rpm, 6700rpm, 7000rpm, 7200rpm, 7600rpm, 8000rpm, 8500rpm, 9000rpm, 10000rpm, and the like; preferably 3500 rpm.

The stirring time of the high-speed stirring is within the range of 5-60min, for example: stirring for 5min, 8min, 10min, 11min, 12min, 15min, 19min, 20min, 25min, 30min, 33min, 35min, 40min, 45min, 47min, 50min, 55min, 60min, etc.; the stirring time is preferably 10 to 30min, for example: 10min, 11min, 12min, 13min, 15min, 16min, 18min, 20min, 22min, 23min, 25min, 27min, 28min, 30min, etc.; optimally 15 min.

The glass fibers may have a diameter of 3-10um, for example: 3um, 4um, 5um, 6um, 7um, 8um, 9um, 10um, etc.; preferably 5-7um, for example: 5um, 5.5um, 5.7um, 6um, 6.2um, 6.5um, 6.8um, 7um, etc. The average length of the glass fibers may be 30-100um, for example: 30um, 32um, 35um, 40um, 45um, 48um, 50um, 55um, 59um, 60um, 65um, 70um, 75um, 80um, 82um, 85um, 88um, 90um, 95um, 100um, etc.; preferably 50-70um, for example: 50um, 52um, 53um, 55um, 57um, 59um, 60um, 61um, 63um, 65um, 66um, 68um, 70um, etc. The glass fibers may have a length in the range of 10-600um, for example: 10-500um, 20-550um, 50-200um, 30-60um, 35-150um, 40-400um, 60-300um, 55-350um, 80-150um, etc.; preferably 50-400um, for example: 50-300um, 60-200um, 60-400um, 50-100um, 70-150um, etc.

In 102:

the concentration of graphene in the graphene paste may be 1-8 wt%, for example: 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt%, etc.; preferably 2 to 5% by weight, for example: 2 wt%, 2.5 wt%, 3 wt%, 3.5 wt%, 4 wt%, 4.5 wt%, 5 wt%, etc.

The graphene slurry is prepared by the following method:

and adding the graphene and the dispersing agent into second white oil, stirring by using a high-speed shearing machine, and grinding by using a sand mill until the particle size D99 of the graphene is less than 7 um.

The high-speed shearing machine can stir for 10 min; the grinding medium can adopt zirconium oxide beads when the sand mill grinds, and preferably, the particle size of the zirconium oxide beads can be 0.6-0.8 mm; the rotation speed of the sand mill during grinding can be 1500 and 2800rpm, for example: 1500rpm, 1600rpm, 1700rpm, 1800rpm, 1900rpm, 2000rpm, 2100rpm, 2200rpm, 2300rpm, 2400rpm, 2500rpm, 2600rpm, 2700rpm, 2800rpm, and the like.

The dispersant can adopt one or more of PSS, SDBS, SDS, commercial BYK series and commercial AFCONA series, wherein the commercial AFCONA series preferably adopts AFCONA 4010, AFCONA 4700 or AFCONA 4701; the commercial BYK series preferably employs BYK-P104S.

The dispersant may be used in an amount of 0.1 to 5 wt% of the graphene slurry, for example: 0.1 wt%, 0.5 wt%, 1 wt%, 1.5 wt%, 2 wt%, 2.5 wt%, 3 wt%, 3.5 wt%, 4 wt%, 4.5 wt%, 5 wt%; preferably 0.2 to 1 wt%, for example: 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt%, 1 wt%, etc.

The graphene can adopt graphene powder with a single-layer or multi-layer structure; preferably, the sheet diameter of the graphene of the single-layer or multi-layer structure can be 0.5-5 um, for example: 0.5um, 1um, 1.5um, 2um, 2.5um, 3um, 3.5um, 4um, 4.5um, 5um, etc.; the thickness can be 0.5 to 30nm, for example: 0.5um, 5um, 10um, 15um, 20um, 25um, 30um, etc.; more preferably, the graphene with the single-layer or multi-layer structure has a specific surface area of 200-1000 m²G, for example: 200m²/g、300m²/g、400m²/g、500m²/g、600m²/g、700m²/g、800m²/g、900m²/g、1000m²,/g, etc.

In 103:

the execution method for mixing the glass fiber premixed liquid, the graphene slurry, the UHMWPE powder and the antioxidant in the third white oil comprises the following steps: under high-speed stirring, adding the glass fiber premixed solution and the graphene slurry into third white oil, and adding UHMWPE powder and an antioxidant while stirring to obtain a spinning mixed solution.

In the preparation of the spinning mixed solution, the UHMWPE powder: the third white oil may have a mass ratio of 6: 94.

The dosage of the glass fiber premix meets the following requirements: the glass fiber is 0.2-10 wt% of the graphene composite ultra-high molecular weight polyethylene fiber, for example: 0.2 wt%, 0.3 wt%, 0.5 wt%, 0.7 wt%, 0.9 wt%, 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, 10 wt%, etc.; preferably 5 to 6.5 wt%, for example: 5 wt%, 5.2 wt%, 5.4 wt%, 5.6 wt%, 5.8 wt%, 6 wt%, 6.2 wt%, 6.4 wt%, 6.5 wt%, etc.

The graphene slurry has the following dosage: the graphene is 0.02-1 wt% of the graphene composite ultra-high molecular weight polyethylene fiber, such as: 0.02 wt%, 0.05 wt%, 0.07 wt%, 0.09 wt%, 0.1 wt%, 0.11 wt%, 0.13 wt%, 0.15 wt%, 0.18 wt%, 0.19 wt%, 0.2 wt%, 0.25 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 0.55 wt%, 0.6 wt%, 0.65 wt%, 0.7 wt%, 0.8 wt%, 0.88 wt%, 0.9 wt%, 1 wt%, etc.; preferably 0.05 wt%.

The dosage of the antioxidant meets the following requirements: the antioxidant is 0.01-1 wt% of the graphene composite ultra-high molecular weight polyethylene fiber, for example: 0.01 wt%, 0.02 wt%, 0.05 wt%, 0.07 wt%, 0.09 wt%, 0.1 wt%, 0.11 wt%, 0.13 wt%, 0.15 wt%, 0.18 wt%, 0.19 wt%, 0.2 wt%, 0.25 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 0.55 wt%, 0.6 wt%, 0.65 wt%, 0.7 wt%, 0.8 wt%, 0.88 wt%, 0.9 wt%, 1 wt%, etc.; preferably 0.1 to 0.5 wt%, for example: 0.1 wt%, 0.12 wt%, 0.13 wt%, 0.15 wt%, 0.17 wt%, 0.2 wt%, 0.23 wt%, 0.25 wt%, 0.26 wt%, 0.28 wt%, 0.3 wt%, 0.33 wt%, 0.35 wt%, 0.4 wt%, 0.42 wt%, 0.45 wt%, 0.48 wt%, 0.5 wt%, etc.

The viscosity average molecular weight of the UHMWPE can be (2-6) multiplied by 10⁶g/mol, for example: 2X 10⁶g/mol、3×10⁶g/mol、4×10⁶g/mol、5×10⁶g/mol、6×10⁶g/mol, etc.; preferably (4-5). times.10⁶g/mol. The antioxidant can be one or more of antioxidant 1010, antioxidant 1076, antioxidant CA, antioxidant 164, antioxidant DNP, antioxidant DLTP or antioxidant TNP.

At 104:

and swelling and mixing the spinning mixed solution to form a molten state, extruding the spinning mixed solution in the molten state, and cooling to form the gel yarn. Wherein the swelling is carried out by heating to 100-140 ℃ in a swelling kettle, such as: 100 deg.C, 105 deg.C, 110 deg.C, 115 deg.C, 120 deg.C, 125 deg.C, 130 deg.C, 135 deg.C, 140 deg.C, etc. The temperature is kept at this temperature for 1-3 h. As a preferred example, the swelling is carried out by raising the temperature to 110 ℃ in a swelling vessel and then maintaining the temperature for 2 hours. The purpose of swelling is to maximize the penetration and diffusion of the solvent into the polymer, which weakens the strong interactions between the macromolecular chains, the more complete this solvation is, the easier it is to go into the dissolution phase. And because the crystalline polymer is in a thermodynamically stable phase state, the molecular chain arrangement is compact and regular, the interaction force among the molecular chains is large, and solvent molecules can hardly enter a crystal region, enough energy must be absorbed firstly to dissolve the crystalline polymer, so that the molecular chain movement is enough to destroy the crystal lattice, and the regular arrangement of the molecular chains is broken. Therefore, UHMWPE needs to swell at a high temperature of more than 100 ℃, and is dissolved when the temperature is higher, white oil can more easily enter the UHMWPE at 100 ℃ and 140 ℃, and the effect is optimal at 110 ℃.

The extrusion adopts a double-screw extruder, the extrusion temperature is increased to 243 ℃ in a stepped manner at 110 ℃, preferably, the length-diameter ratio of the double-screw extruder is 68, and the double-screw extruder consists of a feeding section, a temperature increasing section, a dissolving section and a uniformly mixing section. A certain number of instant entanglement points are still kept on the molecular chain of the swelled UHMWPE, and the UHMWPE is extruded at a stepped temperature, so that macromolecules are dispersed into a solution in an integral coil form, the entanglement points are removed, and the solvation effect of the solvent on the UHMWPE is enhanced.

The cooling is hydraulic cooling.

In 105:

the execution method for preparing the graphene composite ultra-high molecular weight polyethylene fiber from the gel wires comprises the following steps: and (3) carrying out primary drawing, extraction, drying and super-hot drawing on the gel silk to obtain the composite fiber. Wherein the super-power hot drawing adopts 3-level super-power hot drawing, the drawing temperature is 140-146 ℃, for example: 140 deg.C, 141 deg.C, 142 deg.C, 143 deg.C, 145 deg.C, 146 deg.C, etc.

The extraction adopts a continuous multistage closed ultrasonic extractor and a hydrocarbon extraction high-power stretching device, and the extraction temperature is 40 ℃; as a preferred embodiment, the extraction adopts a multi-stage multi-groove quantitative liquid supplementing and draining process to control the oil content after gel silk extraction, an ultrasonic generator is additionally arranged for full extraction, a water circulation mold temperature controller is arranged to accurately control the temperature of the extraction liquid, the temperature difference is less than or equal to +/-1 ℃, and the extraction rate is more than or equal to 99%.

In another embodiment of the present invention, a method 200 for preparing a graphene composite ultra-high molecular weight polyethylene fiber is provided, including:

201: pretreating glass fibers;

202: dispersing glass fibers in first white oil to obtain glass fiber premix;

203: dispersing graphene in second white oil to obtain graphene slurry;

204: mixing the glass fiber premixed solution, the graphene slurry, UHMWPE powder and the antioxidant in third white oil to obtain a spinning mixed solution;

205: swelling and mixing the spinning mixed solution to form a molten state, extruding the spinning mixed solution in the molten state, and cooling to form gel yarns; and

206: and preparing the gel silk into the graphene composite ultra-high molecular weight polyethylene fiber.

The method 200 disclosed in this embodiment is substantially the same as the method 100 for preparing the graphene composite ultra-high molecular weight polyethylene fiber, except that a glass fiber pretreatment step is added, in which the glass fiber is pretreated with a coupling agent before the preparation of the glass fiber premix. The extension step 201 will be explained below.

In 201, the specific processing method is as follows: dissolving the coupling agent in absolute ethyl alcohol, adding glass fiber, mixing uniformly, soaking, drying, grinding, and filtering with 100 meshes. The adding amount of the coupling agent accounts for 0.01-10% of the total mass of the glass fiber, such as: 0.01%, 0.02%, 0.05%, 0.07%, 0.1%, 0.2%, 0.3%, 0.5%, 0.6%, 0.9%, 1%, 2%, 3%, 4%, 5%, 7%, 8%, 10%, etc.; as a preferable scheme of this embodiment, the adding amount of the coupling agent is 0.2% -5% of the total mass of the glass fiber, for example: 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.5%, 2%, 3%, 4%, 5%, etc. The dipping time of the glass fiber in the coupling agent ethanol solution is 10min-5h, for example: 10min, 20min, 30min, 40min, 50min, 1h, 1.5h, 2h, 2.5h, 3h, 3.5h, 4h, 4.5h, 5h, etc. As a preferable scheme of this embodiment, the dipping time of the glass fiber in the coupling agent ethanol solution is 30min to 2h, for example: 30min, 40min, 45min, 50min, 60min, 70min, 80min, 90min, 100min, 120min, etc. The drying temperature is 50-180 ℃, for example: 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃, 150 ℃, 160 ℃, 170 ℃, 180 ℃ and the like; as a preferable scheme of this embodiment, the drying temperature is 80 ℃ to 130 ℃, for example: 80 ℃, 85 ℃, 90 ℃, 95 ℃, 100 ℃, 105 ℃, 110 ℃, 115 ℃, 120 ℃, 125 ℃, 130 ℃, etc. The drying time is 1h-6h, for example: 1h, 2h, 2.5h, 3h, 3.5h, 4h, 5h, 6h, and the like. As a preferable scheme of this embodiment, the drying time is 2h to 3 h.

According to one embodiment of the present invention, the coupling agent may be one or a mixture of two or more of silane coupling agents. The silane coupling agent is adoptedA-150, A-151, A-171, KH-550, KH-560, KH-570, KH-580, KH-590, KH-902 or KH-792. A-150, A-151, A-171, KH-550, KH-560, KH-570, KH-580, KH-590, KH-902, or KH-792 are grades of silane coupling agents, and the properties of different grades of coupling agents are different, these grades being internationally recognized grades. The silane coupling agent is a low molecular organosilicon compound with a special structure, the general formula of which is RSiX3, wherein R represents an active functional group with affinity or reaction capability with polymer molecules, such as oxy, vinyl, epoxy, amido, aminopropyl and the like; x represents an alkoxy group capable of hydrolysis, such as a halogen, an alkoxy group, an acyloxy group, or the like. In the coupling process, firstly, the X group forms silanol, and then reacts with hydroxyl on the surface of the inorganic powder particles to form hydrogen bonds and condense into-SiO-M covalent bonds (M represents the surface of the inorganic powder particles). Meanwhile, silanol of each molecule of silane is mutually associated and oligomerized to form a film with a net structure to cover the surfaces of the powder particles, so that the surfaces of the inorganic powder are organized. The coupling agent A-150 is vinyl trichlorosilane, colorless liquid is dissolved in an organic solvent, and hydrolysis and alcoholysis are easy. Molecular formula is CH₂＝CHSiCl₃Molecular weight 161.5, boiling point 90.6 deg.C, density 1.265g/cm³It is suitable for use as a surface treating agent for glass fiber and a treating agent for reinforced plastic laminates. The coupling agent A-151 is vinyl triethoxysilane with a molecular formula of CH₂＝CHSi(OCH₂CH₃)₃. Soluble in organic solvents and insoluble in water at pH 7, and is suitable for polymer-based polyethylene, polypropylene, unsaturated polyester, etc., as well as glass fiber, plastic, glass, cable, ceramic, etc. The coupling agent A-171 is vinyl trimethoxy silane with a molecular formula of CH₂＝CHSi(OCH₃)₃. Colorless transparent liquid with density of 0.95-0.99g/cm³The refractive index is 1.38-1.40, the boiling point is 123 ℃, the polymer has the functions of a coupling agent and a crosslinking agent, and suitable polymer types comprise polyethylene, polypropylene, unsaturated polyester and the like, and are commonly used for glass fibers, plastics, glass, cables, ceramics, rubber and the like. The coupling agent KH-550 is gamma-aminopropyl triethoxysilane, the density is 0.942g/ml, the melting point is-70 deg.C, and the boiling point isPoint 217 deg.C, refractive index 1.42-1.422, flash point 96 deg.C. The composite material is applied to mineral filled thermoplastic and thermosetting resins such as phenolic aldehyde, polyester, epoxy, PBT, polyamide, carbonate and the like, can greatly improve the physical and mechanical properties such as dry-wet bending strength, compressive strength, shear strength and the like and wet-state electrical properties of reinforced plastics, and improves the wettability and the dispersibility of the filler in polymers. The coupling agent KH-560 is gamma-glycidoxypropyltrimethoxysilane, is mainly used for caulks and sealants of polysulfide and polyurethane, and is used for adhesives of epoxy resin, filled or reinforced thermosetting resin, glass fiber or glass reinforced thermoplastic resin and the like. The coupling agent KH-570 is methacryloxy silane, is colorless or yellowish transparent liquid, is dissolved in acetone, benzene, ether and carbon tetrachloride, and reacts with water. Boiling point 255 deg.C, density 1.04g/ml, refractive index 1.429, flash point 88 deg.C. The product is mainly used for unsaturated polyester resin, and can also be used for polybutylene, polyethylene and ethylene propylene diene monomer. The coupling agent KH-580 is gamma-mercaptopropyltriethoxysilane, corresponds to the mark A-1891 (USA), is colorless transparent liquid with slightly special odor, and is easily soluble in various solvents such as ethanol, acetone, benzene, toluene and the like. Is insoluble in water, but is susceptible to hydrolysis upon contact with water or moisture. Boiling point 82.5 deg.C, specific gravity 1.000(20 deg.C), flash point 87 deg.C, and molecular weight 238. The coupling agent KH-590 is gamma-mercaptopropyltrimethoxysilane, also known as 3-mercaptopropyltrimethoxysilane, has the molecular weight of 196.3399, the density of 1.057g/ml, the boiling point of 213-215 ℃, the refractive index of 1.441-1.443 and the flash point of 88 ℃, and is commonly used as a glass fiber treating agent and a crosslinking agent. The coupling agent KH-792 is N-beta- (aminoethyl) -gamma-aminopropyl trimethoxy silane, and the molecular formula is NH₂(CH₂)₂NH(CH₂)₃Si(OCH₃)₃The molecular weight is 222, the density is 1.010-1.030g/ml, the boiling point is 259 ℃, the refractive index is 1.4425-1.4460, the flash point is 138 ℃, and the organic solvent is soluble. The coupling agent KH-902 is gamma-aminopropyl methyl diethoxy silane, and the molecular formula is NH₂(CH₂)₃SiCH₃(OC₂H₅)₂Molecular weight of 191.34, density of 0.9160 +/-0.0050 g/ml, boiling point of 85-88 ℃/1.07KPa, and refractive index of 1.4270 +/-0.0050, is suitable for most organic and inorganic materials.

In another embodiment of the present invention, there is provided a graphene composite ultra-high molecular weight polyethylene fiber, in which glass fiber and graphene are mixed, and the content of the glass fiber is 0.2 to 10 wt%, for example: 0.2 wt%, 0.3 wt%, 0.5 wt%, 0.7 wt%, 0.9 wt%, 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, 10 wt%, etc.; preferably 5 wt% to 6.5 wt%, for example: 5 wt%, 5.2 wt%, 5.4 wt%, 5.6 wt%, 5.8 wt%, 6 wt%, 6.2 wt%, 6.4 wt%, 6.5 wt%, etc. The content of graphene is 0.02 to 1 wt%, for example: 0.02 wt%, 0.05 wt%, 0.07 wt%, 0.09 wt%, 0.1 wt%, 0.11 wt%, 0.13 wt%, 0.15 wt%, 0.18 wt%, 0.19 wt%, 0.2 wt%, 0.25 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 0.55 wt%, 0.6 wt%, 0.65 wt%, 0.7 wt%, 0.8 wt%, 0.88 wt%, 0.9 wt%, 1 wt%, etc.; preferably 0.05 wt%. The term "glass fiber" as used herein is to be interpreted broadly and includes glass fibers in the narrow sense as well as glass fibers treated by some modification method.

According to a preferred embodiment of the invention, the diameter of the glass fiber is 3-10um, for example: 3um, 4um, 5um, 6um, 7um, 8um, 9um, 10um, etc.; preferably 5-7um, for example: 5um, 5.5um, 5.7um, 6um, 6.2um, 6.5um, 6.8um, 7um, etc. The glass fibers have an average length of 30um to 100um, for example: 30um, 32um, 35um, 40um, 45um, 48um, 50um, 55um, 59um, 60um, 65um, 70um, 75um, 80um, 82um, 85um, 88um, 90um, 95um, 100um, etc.; preferably 50-70um, for example: 50um, 52um, 53um, 55um, 57um, 59um, 60um, 61um, 63um, 65um, 66um, 68um, 70um, etc. The glass fibers have a length in the range of 10-600um, for example: 10-500um, 20-550um, 50-200um, 30-60um, 35-150um, 40-400um, 60-300um, 55-350um, 80-150um, etc.; preferably 50-400um, for example: 50-300um, 60-200um, 60-400um, 50-100um, 70-150um, etc.

According to a preferred embodiment of the present invention, the graphene may adopt a graphene powder having a single-layer or multi-layer structure; preferablyThe sheet diameter of the graphene with the single-layer or multi-layer structure can be 0.5-5 um, for example: 0.5um, 1um, 1.5um, 2um, 2.5um, 3um, 3.5um, 4um, 4.5um, 5um, etc.; the thickness can be 0.5 to 30nm, for example: 0.5um, 5um, 10um, 15um, 20um, 25um, 30um, etc.; more preferably, the graphene with the single-layer or multi-layer structure has a specific surface area of 200-1000 m²G, for example: 200m²/g、300m²/g、400m²/g、500m²/g、600m²/g、700m²/g、800m²/g、900m²/g、1000m²,/g, etc.

According to a preferred embodiment of the invention, the viscosity average molecular weight of the UHMWPE may be (2-6) x 10⁶g/mol, for example: 2X 10⁶g/mol、3×10⁶g/mol、4×10⁶g/mol、5×10⁶g/mol、6×10⁶g/mol, etc.; preferably (4-5). times.10⁶g/mol。

In another embodiment of the present invention, a graphene composite ultra-high molecular weight polyethylene fiber is provided, which is prepared according to the methods provided by the above two method embodiments.

In the preparation method disclosed by the invention, the glass fiber and the graphene are dispersed in white oil and then swell together with UHMWPE powder in the white oil, and then are prepared into the gel silk, the spinning technology adopts the simplest technology in the prior art, and the equipment requirement is not high. Furthermore, after the glass fiber is subjected to coupling agent grafting treatment, UHMWPE is subjected to filling modification, and graphene is added for reinforcement, so that the problem of poor glass fiber dispersibility under the condition of high viscoelasticity of ultrahigh molecular weight polyethylene can be solved, and the cutting resistance of the UHMWPE fiber is effectively improved on the basis of ensuring the flexibility of the yarn. The coupling agent is adopted to carry out surface treatment on the glass fiber, so that the wettability between the fiber and the matrix is improved, a mechanical micro buffer area is formed, the bonding force between interfaces is improved, and the dispersion performance of the glass fiber dispersion liquid can be obviously improved.

In the method disclosed by the invention, the glass fiber obtained by the surface treatment method of the coupling agent has excellent wear resistance, can be well compatible with UHMWPE and an oily solvent, and solves the problem that the glass fiber is uniformly dispersed in the UHMWPE fiber. Compared with untreated glass fiber, the oleophylic and hydrophobic performances of the glass fiber modified by the coupling agent are obviously enhanced (see attached figures 1-4).

The gel silk prepared by the method of the invention is observed under an optical microscope, and the graphene and the glass fiber can be uniformly dispersed in the gel silk without large-scale agglomeration, and the dispersion condition of the graphene and the glass fiber in the composite fiber of the final product can be reflected laterally (see attached figures 5-6). In addition, the glass fiber and the polyethylene matrix are well coated and embedded together (see attached figures 7-8), and the fiber section is prepared by using an ultralow temperature ion grinding method (see attached figures 9-10), the glass fiber is tightly wrapped in the ultrahigh molecular weight polyethylene substrate seen from the section, the glass fiber and the polyethylene substrate form effective and firm interface combination, the compatibility is good, and the problems of gaps or breakage or falling of the glass fiber are avoided. The modified glass fiber surface has the function of forming chemical bonds with resin, plays a role in bridging in resin matrix composite materials, can improve the wettability between the fiber and polyethylene, and improves the interface bonding strength between interfaces.

The new process adopted by the invention does not change the traditional jelly spinning process, the preparation process is simple, only the oleophylic modification process of the glass fiber is added in the aspect of production cost, and the cost performance is higher.

The preferred embodiments of the present invention will be described in conjunction with the accompanying drawings, and it will be understood that they are described herein for the purpose of illustration and explanation and not limitation.

Example 1:

referring to fig. 13, a method for preparing a graphene composite ultra-high molecular weight polyethylene fiber.

1) Pretreatment of glass fibers

Dissolving 0.05kg of silane coupling agent KH-550 in absolute ethanol, adding 5kg of glass fiber (diameter is 5-7um, length is 50-400um, average length is 70um), mixing uniformly (KH-550 accounts for 1% of glass fiber), soaking for 30min, oven drying at 120 deg.C for 2h, grinding, and filtering with 100 mesh sieve for use.

2) Preparation of glass fiber premix

The treated glass fiber is poured into 15kg of white oil for premixing (the concentration of the glass fiber premix is 25 percent), and then the mixture is stirred for 15min at a high speed by an emulsifying machine, wherein the rotating speed is 3500 rpm.

3) Preparation of graphene slurry

0.05kg of graphene and 2g of dispersing agent AFCONA 4010 are added into 0.95kg of white oil (the concentration of graphene slurry is 5%, and the dispersing agent accounts for 0.2% of the slurry), stirred for 10min by a high-speed shearing machine, and then fed into a sand mill for grinding for about 6h until the particle size D99 of the graphene is less than 7um, and then discharged.

4) Preparation of spinning mixture

Mixing the solutions of steps 2) and 3) at high speed for 15min, adding into a mixture containing 94.8kg UHMWPE powder (viscosity average molecular weight of 5 × 10)⁶g/mol) and 1485.2kg of white oil (glass fiber accounts for 5% of the weight of the ultra-high molecular weight polyethylene fiber, and graphene accounts for 0.05% of the weight of the ultra-high molecular weight polyethylene fiber), and finally 0.2kg of antioxidant 1010 is added to prepare a spinning mixed solution with a certain concentration.

5) Preparation of composite fibers

And (3) keeping the temperature of the spinning mixed solution in a swelling kettle at 110 ℃ for 2h, mixing the spinning mixed solution into a molten state through a storage kettle, a feeding kettle and a double-screw extruder, controlling the flow rate through a metering pump (28rpm), extruding the molten state from a spinning assembly, and carrying out water bath shock cooling at 10 ℃ to obtain the gel silk. And standing and balancing the gel silk for 24 hours at room temperature, and performing primary stretching, extraction, drying and 3-level super-power hot drawing at the temperature of 140-146 ℃ to obtain the composite fiber.

Example 2:

1) Pretreatment of glass fibers

Dissolving 6.5g of silane coupling agent KH-560 in absolute ethanol, adding 6.5kg of glass fiber (diameter is 3-7um, length is 10-400um, average length is 50um), mixing uniformly (KH-560 accounts for 0.1% of glass fiber), soaking for 10min, oven drying at 180 deg.C for 1h, grinding, and filtering with 100 mesh sieve for use.

2) Preparation of glass fiber premix

The treated glass fiber is poured into 123.5kg of white oil for premixing (the concentration of the glass fiber premix is 5 percent), and then the mixture is stirred at high speed for 30min by an emulsifying machine at the rotating speed of 5000 rpm.

3) Preparation of graphene slurry

0.02kg of graphene and 1g of dispersing agent PE are added into 0.98kg of white oil (the concentration of graphene slurry is 2%, the dispersing agent accounts for 0.1%), stirred for 20min by a high-speed shearing machine, and then put into a sand mill to be ground for about 6h, and then the material is discharged when the particle size D99 of the graphene is less than 7 um.

4) Preparation of spinning mixture

Mixing the solutions obtained in steps 2) and 3) at high speed for 15min, adding into a mixture containing 92.98kg of UHMWPE powder (viscosity average molecular weight of 2 × 10)⁶g/mol) and 1456.69kg of white oil (glass fiber accounts for 6.5% of the weight of the ultra-high molecular weight polyethylene fiber, and graphene accounts for 0.02% of the weight of the ultra-high molecular weight polyethylene fiber), and finally 0.5kg of antioxidant DNP is added to prepare a spinning mixed solution with a certain concentration.

5) Preparation of composite fibers

And (3) keeping the temperature of the spinning mixed solution in a swelling kettle at 100 ℃ for 3h, mixing the spinning mixed solution into a molten state through a storage kettle, a feeding kettle and a double-screw extruder, controlling the flow rate through a metering pump (28rpm), extruding the molten state from a spinning assembly, and carrying out water bath shock cooling at 10 ℃ to obtain the gel silk. And standing and balancing the gel silk for 24 hours at room temperature, and performing primary stretching, extraction, drying and 3-level super-power hot drawing at the temperature of 140-146 ℃ to obtain the composite fiber.

Example 3:

1) Pretreatment of glass fibers

Dissolving 0.02kg of silane coupling agent KH-570 in absolute ethyl alcohol, adding 0.2kg of glass fiber (the diameter is 3-10um, the length is 10-600um, and the average length is 30um), uniformly mixing (the content of KH-570 in the glass fiber is 10%), soaking for 2h, drying at 50 ℃ for 6h, grinding, and filtering with 100 meshes for later use.

2) Preparation of glass fiber premix

The treated glass fiber is poured into 1.8kg of white oil for premixing (the concentration of the glass fiber premix is 10 percent), and then the mixture is stirred for 1 hour at a high speed by an emulsifying machine, wherein the rotating speed is 3000 rpm.

3) Preparation of graphene slurry

1kg of graphene and 1kg of dispersant AFCONA 4701 are added into 98kg of white oil (the concentration of graphene slurry is 1 percent, the dispersant accounts for 1 percent), stirred for 30min by a high-speed shearing machine, and then put into a sand mill to be ground for about 6h, and then discharged when the particle size D99 of the graphene is less than 7 um.

4) Preparation of spinning mixture

Mixing the solutions obtained in steps 2) and 3) at high speed for 30min, and adding into a mixture containing 98.7kg UHMWPE powder (viscosity average molecular weight of 6 × 10)⁶g/mol) and 1546.3kg of white oil (glass fiber accounts for 0.2% of the weight of the ultra-high molecular weight polyethylene fiber, and graphene accounts for 1% of the weight of the ultra-high molecular weight polyethylene fiber), and finally 0.1kg of antioxidant CA is added to prepare a spinning mixed solution with a certain concentration.

5) Preparation of composite fibers

And (3) keeping the temperature of the spinning mixed solution in a swelling kettle at 140 ℃ for 1h, mixing the spinning mixed solution into a molten state through a storage kettle, a feeding kettle and a double-screw extruder, controlling the flow rate through a metering pump (28rpm), extruding the molten state from a spinning assembly, and carrying out water bath shock cooling at 10 ℃ to obtain the gel silk. And standing and balancing the gel silk for 24 hours at room temperature, and performing primary stretching, extraction, drying and 3-level super-power hot drawing at the temperature of 140-146 ℃ to obtain the composite fiber.

Example 4:

1) Pretreatment of glass fibers

Dissolving 0.02kg of silane coupling agent KH-570 in absolute ethyl alcohol, adding 10kg of glass fiber (the diameter is 3-10um, the length is 50-600um, and the average length is 100um), uniformly mixing (the KH-570 accounts for 0.2% of the glass fiber), soaking for 5h, drying at 80 ℃ for 3h, grinding, and filtering with 100 meshes for later use.

2) Preparation of glass fiber premix

The treated glass fiber is poured into 23.33kg of white oil for premixing (the concentration of the glass fiber premix is 30 percent), and then the mixture is stirred at high speed for 5min by an emulsifying machine at the rotating speed of 10000 rpm.

3) Preparation of graphene slurry

0.05kg of graphene and 6.25g of dispersing agent AFCONA 4700 are added into 0.475kg of white oil (the concentration of graphene slurry is 8%, and the dispersing agent accounts for 1% of the slurry), stirred for 30min by a high-speed shearing machine, and then fed into a sand mill for grinding for about 6h until the particle size D99 of the graphene is less than 7um, and then discharged.

4) Preparation of spinning mixture

Mixing the solutions obtained in steps 2) and 3) at high speed for 30min, adding into a mixture containing 88.95kg UHMWPE powder (viscosity average molecular weight of 4 × 10)⁶g/mol) and 1393.55kg of white oil (glass fiber accounts for 10% of the weight of the ultra-high molecular weight polyethylene fiber, and graphene accounts for 0.05% of the weight of the ultra-high molecular weight polyethylene fiber), and finally 1kg of antioxidant 1076 is added to prepare a spinning mixed solution with a certain concentration.

5) Preparation of composite fibers

Example 5:

1) Pretreatment of glass fibers

Dissolving 0.5kg of silane coupling agent KH-550 in absolute ethanol, adding 10kg of glass fiber (the diameter is 3-10um, the length is 50-600um, and the average length is 85um), uniformly mixing (the KH-550 accounts for 5% of the glass fiber), soaking for 1h, drying at 130 ℃ for 2h, grinding, and filtering with 100 meshes for later use.

2) Preparation of glass fiber premix

The treated glass fiber (diameter 3-10um, length 50-600um, average length 85um) is poured into 23.33kg white oil for premixing (concentration of glass fiber premix is 30%), and then stirred at high speed for 10min by an emulsifying machine at 8000 rpm.

3) Preparation of graphene slurry

0.05kg of graphene and 0.05kg of dispersing agent AFCONA 4010 are added into 0.95kg of white oil (the concentration of graphene slurry is 5 percent, and the dispersing agent accounts for 5 percent of the slurry), stirred for 20min by a high-speed shearing machine, and then fed into a sand mill for grinding for about 6h until the particle size D99 of the graphene is less than 7um, and then discharged.

4) Preparation of spinning mixture

Mixing the solutions obtained in steps 2) and 3) at high speed for 30min, adding into a mixture containing 88.95kg UHMWPE powder (viscosity average molecular weight of 3 × 10)⁶g/mol) and 1393.55kg of white oil (glass fiber accounts for 10% of the weight of the ultra-high molecular weight polyethylene fiber, and graphene accounts for 0.05% of the weight of the ultra-high molecular weight polyethylene fiber), and finally 1kg of antioxidant 1076 is added to prepare a spinning mixed solution with a certain concentration.

5) Preparation of composite fibers

And (3) keeping the temperature of the spinning mixed solution in a swelling kettle at 130 ℃ for 2h, mixing the spinning mixed solution into a molten state through a storage kettle, a feeding kettle and a double-screw extruder, controlling the flow rate through a metering pump (28rpm), extruding the molten state from a spinning assembly, and carrying out water bath shock cooling at 10 ℃ to obtain the gel silk. And standing and balancing the gel silk for 24 hours at room temperature, and performing primary stretching, extraction, drying and 3-level super-power hot drawing at the temperature of 140-146 ℃ to obtain the composite fiber.

Example 6:

referring to fig. 14, a method for preparing a graphene composite ultra-high molecular weight polyethylene fiber.

1) Preparation of glass fiber premix

5kg of glass fiber (diameter of 5-7um, length of 50-400um, average length of 70um) is poured into 15kg of white oil for premixing (concentration of glass fiber premix liquid is 25%), and then the mixture is stirred at a high speed of 3500rpm for 15min by an emulsifying machine.

2) Preparation of graphene slurry

3) Preparation of spinning mixture

Mixing the solutions of steps 1) and 2) at high speed for 15min, adding into a mixture containing 94.8kg UHMWPE powder (viscosity average molecular weight of 5 × 10)⁶g/mol) and 1485.2kg of white oil (glass fiber accounts for 5% of the weight of the ultra-high molecular weight polyethylene fiber, and graphene accounts for 0.05% of the weight of the ultra-high molecular weight polyethylene fiber), and finally 0.2kg of antioxidant 1010 is added to prepare a spinning mixed solution with a certain concentration.

4) Preparation of composite fibers

The cutting resistance of the graphene composite UHMWPE fiber obtained by the method is obviously improved, and referring to the test data in the following table 1, according to the method disclosed by the invention, the test result of the cutting resistance of the graphene composite ultrahigh molecular weight polyethylene fiber prepared by the embodiments of the invention shows the predicted load capacity and ANSI grade of the composite fiber prepared by the glass fiber and the graphene with different addition amounts, wherein the larger the predicted load is, the higher the strength of the prepared composite fiber is, and the higher the ANSI grade is, the stronger the cutting resistance of the prepared composite fiber is.

Table 1: the cutting resistance test comparison result of the graphene composite ultra-high molecular weight polyethylene fiber

Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims

1. A preparation method of graphene composite ultra-high molecular weight polyethylene fibers is characterized by comprising the following steps:

preparing a glass fiber premix: dispersing glass fibers in first white oil to obtain glass fiber premix liquid, wherein the glass fiber premix liquid contains 10-25 wt% of glass fibers;

preparing graphene slurry: dispersing graphene in second white oil to obtain graphene slurry, wherein the concentration of the graphene in the graphene slurry is 2-5 wt%;

cooling to form gel silk; and

preparing the gel wires into graphene composite ultra-high molecular weight polyethylene fibers;

modifying the glass fiber by using a coupling agent in advance, and then preparing glass fiber premix; the specific treatment method comprises the following steps: dissolving a coupling agent in absolute ethyl alcohol, adding glass fiber, uniformly mixing, soaking, drying, grinding and filtering by a 100-mesh sieve;

the graphene slurry is prepared by the following method:

adding graphene and a dispersing agent into second white oil, stirring by a high-speed shearing machine, and grinding by a sand mill until the particle size D99 of the graphene is less than 7 um;

the execution method for preparing the graphene composite ultra-high molecular weight polyethylene fiber from the gel wires comprises the following steps: and (3) carrying out primary drawing, extraction, drying and super-hot drawing on the gel silk to obtain the composite fiber.

2. The method for preparing the graphene composite ultra-high molecular weight polyethylene fiber according to claim 1, wherein the glass fiber premix solution contains 25 wt% of glass fiber.

3. The method for preparing the graphene composite ultra-high molecular weight polyethylene fiber according to claim 1, wherein the glass fiber is dispersed in the first white oil by pouring the glass fiber into the first white oil for premixing, and then stirring at a high speed by using an emulsifying machine until a uniform slurry is formed.

4. The method for preparing graphene composite ultra-high molecular weight polyethylene fiber according to claim 3, wherein the stirring speed of the high-speed stirring is 3000-10000 rpm.

5. The method for preparing the graphene composite ultra-high molecular weight polyethylene fiber according to claim 4, wherein the stirring speed of the high-speed stirring is 3500 rpm.

6. The method for preparing the graphene composite ultra-high molecular weight polyethylene fiber according to claim 3, wherein the stirring time of the high-speed stirring is 5-60 min.

7. The method for preparing the graphene composite ultra-high molecular weight polyethylene fiber according to claim 6, wherein the stirring time of the high-speed stirring is 10-30 min.

8. The method for preparing the graphene composite ultra-high molecular weight polyethylene fiber according to claim 7, wherein the stirring time of the high-speed stirring is 15 min.

9. The method of claim 1, wherein the glass fiber has a diameter of 3-10 um.

10. The method of claim 9, wherein the glass fiber has a diameter of 5-7 um.

11. The method of claim 1, wherein the average length of the glass fiber is 30-100 um.

12. The method of preparing a graphene composite ultra-high molecular weight polyethylene fiber according to claim 1, wherein the average length of the glass fiber is 50-70 um.

13. The method of claim 1, wherein the glass fiber has a length ranging from 10 to 600 um.

14. The method of preparing a graphene composite ultra-high molecular weight polyethylene fiber according to claim 13, wherein the length of the glass fiber is in the range of 50-400 um.

15. The method for preparing the graphene composite ultra-high molecular weight polyethylene fiber according to claim 1, wherein the addition amount of the coupling agent is 0.1-10% of the total mass of the glass fiber.

16. The method for preparing the graphene composite ultra-high molecular weight polyethylene fiber according to claim 15, wherein the addition amount of the coupling agent accounts for 0.2-5% of the total mass of the glass fiber.

17. The method for preparing the graphene composite ultra-high molecular weight polyethylene fiber according to claim 1, wherein the soaking time of the glass fiber in the coupling agent ethanol solution is 10min-5 h.

18. The method for preparing the graphene composite ultra-high molecular weight polyethylene fiber according to claim 1, wherein the soaking time of the glass fiber in the coupling agent ethanol solution is 30min-2 h.

19. The method for preparing the graphene composite ultra-high molecular weight polyethylene fiber according to claim 1, wherein the drying temperature is 50 ℃ to 180 ℃.

20. The method for preparing the graphene composite ultra-high molecular weight polyethylene fiber according to claim 19, wherein the drying temperature is 80 ℃ to 130 ℃.

21. The method for preparing the graphene composite ultra-high molecular weight polyethylene fiber according to claim 1, wherein the drying time is 1-6 h.

22. The method for preparing the graphene composite ultra-high molecular weight polyethylene fiber according to claim 21, wherein the drying time is 2h to 3 h.

23. The method for preparing the graphene composite ultra-high molecular weight polyethylene fiber according to claim 1, wherein the coupling agent is one or a mixture of two or more silane coupling agents.

24. The method for preparing the graphene composite ultra-high molecular weight polyethylene fiber according to claim 23, wherein the silane coupling agent is one or a mixture of more than two of A-150, A-151, A-171, KH-550, KH-560, KH-570, KH-580, KH-590, KH-902 or KH-792.

25. The method for preparing the graphene composite ultra-high molecular weight polyethylene fiber according to claim 1, wherein the high-speed shearing machine stirs for 10 min.

26. The method for preparing the graphene composite ultra-high molecular weight polyethylene fiber according to claim 1, wherein zirconia beads are used as grinding media during grinding by the sand mill.

27. The method of claim 26, wherein the zirconia beads have a particle size of 0.6 to 0.8 mm.

28. The method for preparing the graphene composite ultra-high molecular weight polyethylene fiber according to claim 1, wherein the rotation speed of the sand mill during grinding is 1500-2800 rpm.

29. The method for preparing the graphene composite ultra-high molecular weight polyethylene fiber according to claim 1, wherein the dispersant is one or a combination of two or more of PSS, SDBS, SDS, commercial BYK series and commercial AFCONA series.

30. The method of preparing a graphene composite ultra-high molecular weight polyethylene fiber according to claim 29, wherein the commercial AFCONA series employs AFCONA 4010, AFCONA 4700 or AFCONA 4701; the commercial BYK series employs BYK-P104S.

31. The method for preparing the graphene composite ultra-high molecular weight polyethylene fiber according to claim 1, wherein the graphene is graphene powder having a single-layer or multi-layer structure.

32. The method for preparing the graphene composite ultra-high molecular weight polyethylene fiber according to claim 31, wherein the graphene of the single-layer or multi-layer structure has a sheet diameter of 0.5 to 5um and a thickness of 0.5 to 30 nm.

33. The method for preparing the graphene composite ultra-high molecular weight polyethylene fiber according to claim 32, wherein the graphene with the single-layer or multi-layer structure has a specific surface area of 200-1000 m²/g。

34. The method for preparing graphene composite ultra-high molecular weight polyethylene fiber according to claim 1, wherein the viscosity average molecular weight of the UHMWPE is 2 x 10⁶-6×10⁶ g/mol。

35. The method for preparing graphene composite ultra-high molecular weight polyethylene fibers according to claim 34, wherein the viscosity average molecular weight of the UHMWPE is 4 x 10⁶～5×10⁶ g/mol。

36. The method for preparing the graphene composite ultra-high molecular weight polyethylene fiber according to claim 1, wherein the antioxidant is one or a combination of more than two of antioxidant 1010, antioxidant 1076, antioxidant CA, antioxidant 164, antioxidant DNP, antioxidant DLTP or antioxidant TNP.

37. The method for preparing the graphene composite ultra-high molecular weight polyethylene fiber according to claim 1, wherein the mixing of the glass fiber premix, the graphene slurry, the UHMWPE powder and the antioxidant in the third white oil is performed by:

38. The method for preparing graphene composite ultra-high molecular weight polyethylene fiber according to claim 37, wherein in the preparation of the spinning mixture, the UHMWPE powder: the mass ratio of the third white oil is 6: 94.

39. The method of preparing the graphene composite ultra-high molecular weight polyethylene fiber according to claim 37, wherein the glass fiber is 0.2 to 10 wt% of the graphene composite ultra-high molecular weight polyethylene fiber.

40. The method of preparing the graphene composite ultra-high molecular weight polyethylene fiber according to claim 39, wherein the glass fiber is 5 to 6.5 wt% of the graphene composite ultra-high molecular weight polyethylene fiber.

41. The method of preparing a graphene composite ultra-high molecular weight polyethylene fiber according to claim 37, wherein the graphene is 0.02 to 1 wt% of the graphene composite ultra-high molecular weight polyethylene fiber.

42. The method of claim 41, wherein the graphene is 0.05 wt% of the graphene composite ultra-high molecular weight polyethylene fiber.

43. The method for preparing the graphene composite ultra-high molecular weight polyethylene fiber according to claim 37, wherein the antioxidant is 0.01 to 1 wt% of the graphene composite ultra-high molecular weight polyethylene fiber.

44. The method for preparing the graphene composite ultra-high molecular weight polyethylene fiber according to claim 43, wherein the antioxidant is 0.1-0.5 wt% of the graphene composite ultra-high molecular weight polyethylene fiber.

45. The method for preparing the graphene composite ultra-high molecular weight polyethylene fiber according to claim 1, wherein the swelling is performed by heating to 100-140 ℃ in a swelling kettle and keeping the temperature for 1-3 h.

46. The method for preparing the graphene composite ultra-high molecular weight polyethylene fiber according to claim 45, wherein the swelling is carried out by heating to 110 ℃ in a swelling kettle and keeping the temperature for 2 hours.

47. The method for preparing the graphene composite ultra-high molecular weight polyethylene fiber according to claim 1, wherein a twin-screw extruder is adopted for the extrusion, and the extrusion temperature is increased in a stepwise manner from 110 ℃ to 243 ℃.

48. The method for preparing the graphene composite ultra-high molecular weight polyethylene fiber according to claim 47, wherein the length-diameter ratio of the twin-screw extruder is 68, and the twin-screw extruder comprises a feeding section, a temperature raising section, a dissolving section and a uniformly mixing section.

49. The method of claim 1, wherein the cooling is performed by hydraulic cooling.

50. The method for preparing the graphene composite ultra-high molecular weight polyethylene fiber according to claim 1, wherein the super-power hot drawing adopts 3-level super-power hot drawing, and the drawing temperature is 140-146 ℃.

51. The method for preparing the graphene composite ultra-high molecular weight polyethylene fiber according to claim 1, wherein a continuous multi-stage closed ultrasonic extractor and a hydrocarbon extraction high-power stretching device are adopted for extraction, and the extraction temperature is 40 ℃.

52. The method for preparing the graphene composite ultra-high molecular weight polyethylene fiber according to claim 51, wherein the extraction adopts a multi-stage multi-groove quantitative liquid supplementing and draining process to control the oil content after the gel silk extraction, an ultrasonic generator is additionally arranged for full extraction, a water circulation mold temperature controller is arranged to accurately control the temperature of the extraction solution, the temperature difference is less than or equal to +/-1 ℃, and the extraction rate is more than or equal to 99%.

53. A graphene composite ultra-high molecular weight polyethylene fiber prepared by the method of any one of claims 1 to 38, wherein the fiber contains glass fiber and graphene, the content of the glass fiber is 0.2 to 10 wt%, and the content of the graphene is 0.02 to 1 wt%.

54. The graphene composite ultra-high molecular weight polyethylene fiber according to claim 53, wherein the content of glass fiber in the fiber is 5-6.5 wt%, and the content of graphene is 0.05 wt%.