CN117965009A - Carbon fiber composite material and wire drawing process and application thereof - Google Patents
Carbon fiber composite material and wire drawing process and application thereof Download PDFInfo
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- CN117965009A CN117965009A CN202410084159.XA CN202410084159A CN117965009A CN 117965009 A CN117965009 A CN 117965009A CN 202410084159 A CN202410084159 A CN 202410084159A CN 117965009 A CN117965009 A CN 117965009A
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- carbon fiber
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- epoxy resin
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- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 77
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 77
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 238000005491 wire drawing Methods 0.000 title claims abstract description 64
- 239000002131 composite material Substances 0.000 title claims abstract description 54
- 238000000034 method Methods 0.000 title claims abstract description 33
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 52
- 239000003822 epoxy resin Substances 0.000 claims abstract description 51
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 51
- 229920005668 polycarbonate resin Polymers 0.000 claims abstract description 41
- 239000004431 polycarbonate resin Substances 0.000 claims abstract description 41
- 239000000463 material Substances 0.000 claims abstract description 39
- 238000002360 preparation method Methods 0.000 claims abstract description 35
- 238000002156 mixing Methods 0.000 claims abstract description 33
- 238000001125 extrusion Methods 0.000 claims abstract description 27
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 21
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 16
- 239000012286 potassium permanganate Substances 0.000 claims abstract description 11
- 229920002379 silicone rubber Polymers 0.000 claims abstract description 10
- 230000001590 oxidative effect Effects 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 36
- -1 diethyl diamine Chemical class 0.000 claims description 23
- 238000010438 heat treatment Methods 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 22
- 239000000243 solution Substances 0.000 claims description 17
- 239000011259 mixed solution Substances 0.000 claims description 16
- 239000007787 solid Substances 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- GODZNYBQGNSJJN-UHFFFAOYSA-N 1-aminoethane-1,2-diol Chemical compound NC(O)CO GODZNYBQGNSJJN-UHFFFAOYSA-N 0.000 claims description 10
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 10
- 239000002202 Polyethylene glycol Substances 0.000 claims description 10
- 239000012153 distilled water Substances 0.000 claims description 10
- 229920001223 polyethylene glycol Polymers 0.000 claims description 10
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 10
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 9
- 239000012295 chemical reaction liquid Substances 0.000 claims description 8
- 150000002148 esters Chemical class 0.000 claims description 8
- 238000001746 injection moulding Methods 0.000 claims description 8
- 229920001296 polysiloxane Polymers 0.000 claims description 8
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 8
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 8
- 238000007781 pre-processing Methods 0.000 claims description 8
- 239000004952 Polyamide Substances 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 7
- 229920002647 polyamide Polymers 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 7
- 239000004945 silicone rubber Substances 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 238000004108 freeze drying Methods 0.000 claims description 5
- 235000010344 sodium nitrate Nutrition 0.000 claims description 5
- 239000004317 sodium nitrate Substances 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 5
- 229920001228 polyisocyanate Polymers 0.000 claims description 4
- 239000005056 polyisocyanate Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 230000003647 oxidation Effects 0.000 description 10
- 238000007254 oxidation reaction Methods 0.000 description 10
- 238000012360 testing method Methods 0.000 description 9
- 238000005299 abrasion Methods 0.000 description 7
- LRNRWPYXVVMMLQ-UHFFFAOYSA-N carbonic acid;terephthalic acid Chemical compound OC(O)=O.OC(=O)C1=CC=C(C(O)=O)C=C1 LRNRWPYXVVMMLQ-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 230000006750 UV protection Effects 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 230000032683 aging Effects 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 229920001778 nylon Polymers 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- MTZUIIAIAKMWLI-UHFFFAOYSA-N 1,2-diisocyanatobenzene Chemical compound O=C=NC1=CC=CC=C1N=C=O MTZUIIAIAKMWLI-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 241001391944 Commicarpus scandens Species 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- 230000032798 delamination Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 244000025254 Cannabis sativa Species 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000002457 bidirectional effect Effects 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000001934 delay Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920005575 poly(amic acid) Polymers 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000004154 testing of material Methods 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
-
- A—HUMAN NECESSITIES
- A63—SPORTS; GAMES; AMUSEMENTS
- A63B—APPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT
- A63B69/00—Training appliances or apparatus for special sports
- A63B69/36—Training appliances or apparatus for special sports for golf
- A63B69/3661—Mats for golf practice, e.g. mats having a simulated turf, a practice tee or a green area
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/16—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one other macromolecular compound obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds as constituent
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- Physical Education & Sports Medicine (AREA)
- Manufacturing & Machinery (AREA)
- General Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Reinforced Plastic Materials (AREA)
Abstract
The application relates to the field of carbon fiber composite materials, and particularly discloses a carbon fiber composite material, a wire drawing process and application thereof. The carbon fiber composite material comprises carbon fibers, epoxy resin, polycarbonate resin, oxidized modified graphene, silicon rubber and an auxiliary agent, wherein the oxidized modified graphene is prepared by oxidizing and modifying graphene by potassium permanganate; the preparation method comprises the following steps: mixing, pretreatment, extrusion molding and wiredrawing. The carbon fiber composite material can be used for manufacturing golf mats, and has the advantage of solving the problem that the existing golf mat material is easy to damage.
Description
Technical Field
The application relates to the field of carbon fiber composite materials, in particular to a carbon fiber composite material, a wire drawing process and application thereof.
Background
Golf mats, also known as golf mats or grass mats, are an indispensable aid in golf courses. It is mainly used for protecting turf, preventing golf ball from sinking into ground, providing a stable ball striking surface for player and reducing damage to turf. The material of the golf mat has a critical impact on its performance and life.
Conventional golf mat materials mainly include plastics, rubber, felt, and the like. However, these conventional materials have some drawbacks. These materials are susceptible to damage from external forces due to their low tensile strength and abrasion resistance. Particularly, when the golf club hits the ball, the ground mat material is subjected to strong force, and the impact force easily causes damage to the ground mat material, such as breakage, falling off of brush filaments, and the like. In addition, the conventional floor mat material has poor ultraviolet resistance and is easily aged after long-term exposure to sunlight, which not only affects the service life of the floor mat material, but also may degrade the performance of the floor mat material.
Therefore, the search for a new mat material with higher durability and strength is an urgent need, so that the golf mat can better bear the impact force of a golf club, and the service life of the mat is prolonged.
Disclosure of Invention
In order to provide a novel ground mat material with higher strength and solve the problem that the existing golf ground mat material is easy to damage, the application provides a carbon fiber composite material, and a wire drawing process and application thereof.
In a first aspect, the present application provides a carbon fiber composite material, which adopts the following technical scheme:
The carbon fiber composite material comprises, by weight, 30-50 parts of carbon fibers, 10-20 parts of epoxy resin, 20-30 parts of polycarbonate resin, 5-15 parts of oxidation modified graphene, 5-15 parts of silicone rubber and 1-10 parts of an auxiliary agent, wherein the oxidation modified graphene is prepared by oxidizing and modifying graphene by potassium permanganate.
By adopting the technical scheme, the tensile strength and the wear resistance of the ground mat material can be obviously improved by adopting the carbon fiber as the reinforcing material, so that the ground mat material is more durable and is not easy to be damaged by external force. The carbon fiber has good energy absorption performance, can effectively absorb and disperse impact force generated when a golf club hits a ball, and reduces impact on a ground mat material, thereby reducing the damage risk of the ground mat material. The addition of the oxidized modified graphene can improve the ultraviolet resistance of the floor mat material, reduce the aging problem caused by long-time exposure to sunlight, prolong the service life of the floor mat and maintain better performance. By controlling the proportion of different components and combining the characteristics of materials such as epoxy resin, polycarbonate resin, silicone rubber and the like, the carbon fiber composite material can have the excellent characteristics of strength, wear resistance, ultraviolet resistance, energy absorption and the like, so that the carbon fiber composite material becomes an ideal golf mat material, and the problems that the mat brush wires are easily damaged and broken due to impact and pressure generated when a club is contacted with a mat are solved.
Optionally, the preparation method of the oxidation modified graphene comprises the following steps:
a1, uniformly mixing and stirring graphene powder, sodium nitrate and concentrated sulfuric acid according to a ratio of (5-7) to 3:1 at the temperature of 0 ℃ to obtain a mixed solution;
A2, slowly adding potassium permanganate into the mixed solution, wherein the mass ratio of the potassium permanganate to the graphene powder is (1-3): 5, stirring uniformly to obtain a reaction solution, heating the reaction solution to 30-40 ℃ and preserving heat, reacting for 6-8h, after the reaction is finished, obtaining a dark brown and sticky reaction solution, adding distilled water with the same mass as the mixed solution, heating to 90-95 ℃ and stirring for 20-40min;
a3, cooling to 60-80 ℃, adding distilled water with the mass equal to that of the mixed solution and hydrogen peroxide accounting for 10-20% of that of the mixed solution into the reaction solution, and standing for 1-3h;
And A4, centrifugally separating the reaction liquid after standing, collecting solid matters, cleaning the solid matters by deionized water, and freeze-drying the solid matters to obtain the graphene oxide.
By adopting the technical scheme, the purity of the oxidized modified graphene can be effectively improved by mixing and reacting in a low-temperature environment and using potassium permanganate as an oxidant. The oxidation modified graphene can increase the stability of the composite material and improve the deformation resistance and ageing resistance of the composite material. Thus, the brush filaments can still maintain good performance and shape in long-time use, and are not easy to break or deform.
Optionally, the carbon fiber has a diameter of 5-10 μm and a length of 0.5-1.5mm.
By adopting the technical scheme, the carbon fiber with smaller diameter can provide higher strength and rigidity.
Optionally, the epoxy resin is modified epoxy resin, and the preparation method of the modified epoxy resin comprises the following steps:
B1, placing epoxy resin and propylene glycol monomethyl ether into a container, wherein the addition mass of the propylene glycol monomethyl ether is 50-70% of that of the epoxy resin, and stirring for 30-50min at 100-120 ℃;
B2, adding polyethylene glycol amine and diethyl diamine into the container, wherein the addition amount of the polyethylene glycol amine is 20-30% of the mass of the epoxy resin, the addition amount of the diethyl diamine is 1-5% of the mass of the epoxy resin, and reacting for 4-6h at 110-130 ℃ to obtain the modified epoxy resin after the reaction is completed.
By adopting the technical scheme, chemical substances such as propylene glycol monomethyl ether, polyethylene glycol amine and the like in the modified epoxy resin can form chemical bonds or physical adsorption with the surfaces of the carbon fibers, so that the interaction force between the carbon fibers and the matrix is enhanced. This effectively prevents delamination and breakage of the fibers and increases the strength of the overall material. Thus, the problems of fiber delamination, breakage and the like can be effectively prevented, and the overall strength and durability of the composite material are improved. The flexibility of the modified epoxy resin can improve the toughness and the impact resistance of the material. The polyethylene glycol amine and the additive such as the diethylenediamine have the elasticity and the ductility of molecular chains, so that the material can better absorb and disperse external impact force.
Optionally, the polycarbonate resin is a modified polycarbonate resin, and the preparation method of the modified polycarbonate resin comprises the following steps:
Placing the polycarbonate resin and polyisocyanate into a container, wherein the addition amount of the polyisocyanate is 0.5-2.5% of the mass of the polycarbonate resin, and reacting for 3-6h at 220-240 ℃ to obtain the modified polycarbonate resin.
By adopting the technical scheme, the modified polycarbonate resin can provide higher strength and hardness, so that the durability and the stability of the composite fiber are enhanced. The brush filaments made of the modified polycarbonate resin can resist corrosion of chemicals and keep the performance and the shape stable. The modified polycarbonate resin generally has better high-temperature resistance and can be kept stable at higher temperature.
Optionally, the silicone rubber is gamma-trifluoropropyl methyl polysiloxane.
Optionally, the auxiliary agent comprises 40-60% of polyamic acid ester and 40-60% of polytetrafluoroethylene.
In a second aspect, the application provides a wire drawing process of a carbon fiber composite material, which adopts the following technical scheme: a wire drawing process of a carbon fiber composite material comprises the following steps:
S1, mixing: mixing the epoxy resin, the polycarbonate resin and the carbon fiber in a mixer to ensure that the components are uniformly mixed;
s2, preprocessing: adding silicon rubber, oxidized modified graphene and an auxiliary agent, continuously mixing in a mixer, and heating at 230-280 ℃;
S3, extrusion molding: during extrusion molding, an injection molding machine with an extruder head is used, and the extrusion temperature is 280-320 ℃;
S4, wire drawing: in the wire drawing process, a wire drawing machine with a constant temperature device is used for carrying out, the wire drawing speed is 0.1-0.5m/s, and the wire drawing temperature is 250-300 ℃; after the wire drawing is completed, the filament-shaped material is cut to a fixed length to prepare the brush hair.
By adopting the technical scheme, the components of the composite material are uniformly dispersed by uniformly mixing, the plasticity, the adhesiveness and the impact resistance are improved by pretreatment heating, the combination of the resin and the carbon fiber is enhanced by extrusion molding, and the carbon fiber is orderly arranged and formed into filaments by a wire drawing process. The effects are combined, so that the brush wire material has higher strength, wear resistance and stability, can effectively impact and pressure when the ball rod is contacted with the brush wire of the floor mat, reduces the problems of damage and breakage of the brush wire, and prolongs the service life and performance of the floor mat.
In a third aspect, the present application provides the use of a carbon fiber composite for the preparation of a golf mat.
In summary, the application has the following beneficial effects:
1. the application realizes excellent tensile strength, wear resistance, ultraviolet resistance and energy absorption performance by controlling the proportion of the carbon fiber, the epoxy resin, the polycarbonate resin, the oxidized modified graphene, the silicon rubber and the auxiliary agent. The carbon fiber provides a strong enhancement effect and energy absorption performance, and the oxidized modified graphene enhances ultraviolet resistance and delays aging.
2. In the application, the oxidation modified graphene and the carbon fiber are preferably compounded, and the oxidation modified graphene and the carbon fiber have excellent mechanical properties, in particular strength and toughness. By combining the two, a synergistic effect can be produced, further enhancing the mechanical properties of the composite. This makes the composite less likely to deform or break when subjected to high loads, and maintains stable performance under high temperature environments, with excellent durability.
3. The method ensures the uniform dispersion of each component, improves the plasticity and the adhesiveness of the material and enhances the binding force of the resin and the carbon fiber through the steps of mixing, pretreatment, extrusion molding, wire drawing and the like. This series of technical measures gives the brush wire material excellent in strength, abrasion resistance and stability.
Detailed Description
The present application will be described in further detail with reference to examples.
Preparation example of oxidized modified graphene
Preparation example 1
A1, mixing 60kg of graphene powder, 30kg of sodium nitrate and 10kg of concentrated sulfuric acid in a reaction container at the temperature of 0 ℃, and uniformly stirring by a mechanical stirrer to obtain a mixed solution;
a2, slowly adding 24kg of potassium permanganate into the mixed solution at an adding speed of 5kg/min, uniformly stirring to obtain a reaction solution, heating a reaction container to enable the reaction solution to be heated to 35+/-2 ℃ and keep the temperature, standing for 7h for reaction, adding 100kg of distilled water after the reaction is completed, starting heating to enable the reaction solution to be heated to 93+/-2 ℃ and stirring for 30min, stopping heating, and naturally cooling;
A3, when the temperature is reduced to 70+/-2 ℃, adding 100kg of distilled water and 15kg of hydrogen peroxide into the reaction liquid, uniformly stirring, and standing for 2 hours;
And A4, centrifugally separating the reaction liquid after standing, collecting solid matters, cleaning the solid matters by deionized water, and freeze-drying the solid matters at the temperature of minus 5 ℃ to obtain the graphene oxide.
Preparation example 2
A1, mixing 50kg of graphene powder, 30kg of sodium nitrate and 10kg of concentrated sulfuric acid in a reaction container at the temperature of 0 ℃, and uniformly stirring by a mechanical stirrer to obtain a mixed solution;
a2, slowly adding 20kg of potassium permanganate into the mixed solution at an adding speed of 5kg/min, uniformly stirring to obtain a reaction solution, heating a reaction container to enable the reaction solution to be heated to 35+/-2 ℃ and keep the temperature, standing for 7h for reaction, adding 90kg of distilled water after the reaction is completed, starting heating to enable the reaction solution to be heated to 93+/-2 ℃ and stirring for 30min, stopping heating, and naturally cooling;
a3, when the temperature is reduced to 70+/-2 ℃, adding 90kg of distilled water and 13.5kg of hydrogen peroxide into the reaction liquid, uniformly stirring, and standing for 2 hours;
And A4, centrifugally separating the reaction liquid after standing, collecting solid matters, cleaning the solid matters by deionized water, and freeze-drying the solid matters at the temperature of minus 5 ℃ to obtain the graphene oxide.
Preparation example 3
A1, mixing 70kg of graphene powder, 30kg of sodium nitrate and 10kg of concentrated sulfuric acid in a reaction container at the temperature of 0 ℃, and uniformly stirring by a mechanical stirrer to obtain a mixed solution;
A2, slowly adding 28kg of potassium permanganate into the mixed solution at an adding speed of 5kg/min, uniformly stirring to obtain a reaction solution, heating a reaction container to enable the reaction solution to be heated to 35+/-2 ℃ and keep the temperature, standing for 7h for reaction, adding 110kg of distilled water after the reaction is completed, starting heating to enable the reaction solution to be heated to 93+/-2 ℃ and stirring for 30min, stopping heating, and naturally cooling;
a3, when the temperature is reduced to 70+/-2 ℃, 110kg of distilled water and 16.5kg of hydrogen peroxide are added into the reaction liquid, and the mixture is stirred uniformly and then kept stand for 2 hours;
And A4, centrifugally separating the reaction liquid after standing, collecting solid matters, cleaning the solid matters by deionized water, and freeze-drying the solid matters at the temperature of minus 5 ℃ to obtain the graphene oxide.
Preparation example of modified epoxy resin
Preparation example 4
B1, placing 100kg of SST-2331 epoxy resin and 60kg of propylene glycol monomethyl ether into a container, and stirring for 40min at 110+/-5 ℃ by adopting a mechanical stirrer;
B2, adding 25kg of polyethylene glycol amine and 3kg of diethyl diamine into a container, and reacting for 5 hours at 120+/-5 ℃ to obtain the modified epoxy resin after the reaction is completed.
Preparation example 5
B1, placing 100kgSST-2331 epoxy resin and 60kg propylene glycol monomethyl ether into a container, and stirring for 40min at 110+/-5 ℃ by adopting a mechanical stirrer;
And B2, adding 20kg of polyethylene glycol amine and 3kg of diethyl diamine into the container, and reacting for 5 hours at 120+/-5 ℃ to obtain the modified epoxy resin after the reaction is completed.
Preparation example 6
B1, placing 100kgSST-2331 epoxy resin and 60kg propylene glycol monomethyl ether into a container, and stirring for 40min at 110+/-5 ℃ by adopting a mechanical stirrer;
B2, adding 30kg of polyethylene glycol amine and 3kg of diethyl diamine into a container, and reacting for 5 hours at 120+/-5 ℃ to obtain the modified epoxy resin after the reaction is completed.
Preparation example of modified polycarbonate resin
Preparation example 7
100Kg of a poly (terephthalic acid) carbonate and 1.5kg of a poly (phenylene diisocyanate) were placed in a container and reacted at 230.+ -. 5 ℃ for 4 hours to obtain a modified polycarbonate resin.
Preparation example 8
100Kg of a poly (terephthalic acid) carbonate and 0.5kg of a poly (phenylene diisocyanate) were placed in a container and reacted at 230.+ -. 5 ℃ for 4 hours to obtain a modified polycarbonate resin.
Preparation example 9
100Kg of a poly (terephthalic acid) carbonate and 2.5kg of a poly (phenylene diisocyanate) were placed in a container and reacted at 230.+ -. 5 ℃ for 4 hours to obtain a modified polycarbonate resin.
Examples
Example 1
A wire drawing process of a carbon fiber composite material comprises the following steps:
S1, mixing: 10kgSST-2331 epoxy resin, 20kg of poly (terephthalic acid) carbonate and 30kg of carbon fiber are mixed in a mixer to ensure uniform mixing of the components;
S2, preprocessing: adding 5kg of gamma-trifluoropropyl methyl polysiloxane, 5kg of oxidized modified graphene and 1kg of auxiliary agent, continuously mixing in a mixer, and heating at 260 ℃;
s3, extrusion molding: during extrusion molding, an injection molding machine with an extruder head is used, and the extrusion temperature is 300 ℃;
S4, wire drawing: in the wire drawing process, a wire drawing machine with a constant temperature device is used for carrying out, the wire drawing speed is 0.3m/s, and the wire drawing temperature is 280 ℃; after the wire drawing is completed, the filament-shaped material is cut to a fixed length to prepare the brush hair.
Wherein, the oxidized modified graphene is prepared by a preparation example 1; the auxiliary agent is polyamide acid ester 50% and polytetrafluoroethylene 50%; the diameter of the carbon fiber is 5-10 mu m, and the length is 0.5-1.5mm.
Example 2
A wire drawing process of a carbon fiber composite material comprises the following steps:
s1, mixing: mixing 20kgSST-2331 epoxy resin, 30kg of poly (terephthalic acid) carbonate and 50kg of carbon fiber in a mixer to ensure uniform mixing of the components;
S2, preprocessing: 15kg of gamma-trifluoropropyl methyl polysiloxane, 15kg of oxidized modified graphene and 10kg of auxiliary agent are added, and the mixture is continuously mixed in a mixer, and the mixture is heated at 260 ℃;
s3, extrusion molding: during extrusion molding, an injection molding machine with an extruder head is used, and the extrusion temperature is 300 ℃;
S4, wire drawing: in the wire drawing process, a wire drawing machine with a constant temperature device is used for carrying out, the wire drawing speed is 0.3m/s, and the wire drawing temperature is 280 ℃; after the wire drawing is completed, the filament-shaped material is cut to a fixed length to prepare the brush hair.
Wherein, the oxidized modified graphene is prepared by a preparation example 1; the auxiliary agent is polyamide acid ester 50% and polytetrafluoroethylene 50%; the diameter of the carbon fiber is 5-10 mu m, and the length is 0.5-1.5mm.
Example 3
A wire drawing process of a carbon fiber composite material comprises the following steps:
S1, mixing: 15kgSST-2331 epoxy resin, 25kg of poly (terephthalic acid) carbonate and 40kg of carbon fiber are mixed in a mixer to ensure uniform mixing of the components;
s2, preprocessing: adding 10kg of gamma-trifluoropropyl methyl polysiloxane, 10kg of oxidized modified graphene and 5kg of auxiliary agent, continuously mixing in a mixer, and heating at 260 ℃;
s3, extrusion molding: during extrusion molding, an injection molding machine with an extruder head is used, and the extrusion temperature is 300 ℃;
S4, wire drawing: in the wire drawing process, a wire drawing machine with a constant temperature device is used for carrying out, the wire drawing speed is 0.3m/s, and the wire drawing temperature is 280 ℃; after the wire drawing is completed, the filament-shaped material is cut to a fixed length to prepare the brush hair.
Wherein, the oxidized modified graphene is prepared by a preparation example 1; the auxiliary agent is polyamide acid ester 50% and polytetrafluoroethylene 50%; the diameter of the carbon fiber is 5-10 mu m, and the length is 0.5-1.5mm.
Example 4
A drawing process of a carbon fiber composite material, which is different from example 3 in that: wherein, the oxidation modified graphene is prepared from preparation example 2.
Example 5
A drawing process of a carbon fiber composite material, which is different from example 3 in that: wherein, the oxidation modified graphene is prepared from preparation example 3.
Example 6
A drawing process of a carbon fiber composite material, which is different from example 3 in that: wherein the epoxy resin is a modified epoxy resin, and the modified epoxy resin is prepared from preparation example 4.
Example 7
A drawing process of a carbon fiber composite material, which is different from example 3 in that: wherein the epoxy resin is a modified epoxy resin, and the modified epoxy resin is prepared from preparation example 5.
Example 8
A drawing process of a carbon fiber composite material, which is different from example 3 in that: wherein the epoxy resin is a modified epoxy resin, and the modified epoxy resin is prepared from preparation example 6.
Example 9
A drawing process of a carbon fiber composite material, which is different from example 6 in that: wherein the polycarbonate resin was a modified polycarbonate resin, and the modified polycarbonate resin was prepared in preparation example 7.
Example 10
A drawing process of a carbon fiber composite material, which is different from example 6 in that: wherein the polycarbonate resin was a modified polycarbonate resin, and the modified polycarbonate resin was prepared in preparation example 8.
Example 11
A drawing process of a carbon fiber composite material, which is different from example 6 in that: wherein the polycarbonate resin was a modified polycarbonate resin, and the modified polycarbonate resin was prepared in preparation example 9.
Comparative example
Comparative example 1
A wire drawing process of a carbon fiber composite material comprises the following steps:
S1, mixing: 15kg of epoxy resin, 25kg of polycarbonate resin and 40kg of carbon fiber are mixed in a mixer to ensure uniform mixing of the components;
S2, preprocessing: adding 10kg of gamma-trifluoropropyl methyl polysiloxane, 10kg of graphene and 5kg of auxiliary agent, continuously mixing in a mixer, and heating at 260 ℃;
s3, extrusion molding: during extrusion molding, an injection molding machine with an extruder head is used, and the extrusion temperature is 300 ℃;
S4, wire drawing: in the wire drawing process, a wire drawing machine with a constant temperature device is used for carrying out, the wire drawing speed is 0.3m/s, and the wire drawing temperature is 280 ℃; after the wire drawing is completed, the filament-shaped material is cut to a fixed length to prepare the brush hair.
Wherein, the oxidized modified graphene is prepared by a preparation example 1; the auxiliary agent is polyamide acid ester 50% and polytetrafluoroethylene 50%; the diameter of the carbon fiber is 5-10 mu m, and the length is 0.5-1.5mm.
Comparative example 2
A wire drawing process of a carbon fiber composite material comprises the following steps:
S1, mixing: 15kg of epoxy resin, 25kg of polycarbonate resin and 40kg of carbon fiber are mixed in a mixer to ensure uniform mixing of the components;
s2, preprocessing: adding 10kg of gamma-trifluoro propyl methyl polysiloxane and 5kg of auxiliary agent, continuously mixing in a mixer, and heating at 260 ℃;
s3, extrusion molding: during extrusion molding, an injection molding machine with an extruder head is used, and the extrusion temperature is 300 ℃;
S4, wire drawing: in the wire drawing process, a wire drawing machine with a constant temperature device is used for carrying out, the wire drawing speed is 0.3m/s, and the wire drawing temperature is 280 ℃; after the wire drawing is completed, the filament-shaped material is cut to a fixed length to prepare the brush hair.
Wherein, the oxidized modified graphene is prepared by a preparation example 1; the auxiliary agent is polyamide acid ester 50% and polytetrafluoroethylene 50%; the diameter of the carbon fiber is 5-10 mu m, and the length is 0.5-1.5mm.
Comparative example 3
A wire drawing process of a carbon fiber composite material comprises the following steps:
S1, mixing: 15kg of epoxy resin, 25kg of polycarbonate resin and 40kg of nylon fiber are mixed in a mixer to ensure uniform mixing of the components;
s2, preprocessing: adding 10kg of gamma-trifluoropropyl methyl polysiloxane, 10kg of oxidized modified graphene and 5kg of auxiliary agent, continuously mixing in a mixer, and heating at 260 ℃;
s3, extrusion molding: during extrusion molding, an injection molding machine with an extruder head is used, and the extrusion temperature is 300 ℃;
S4, wire drawing: in the wire drawing process, a wire drawing machine with a constant temperature device is used for carrying out, the wire drawing speed is 0.3m/s, and the wire drawing temperature is 280 ℃; after the wire drawing is completed, the filament-shaped material is cut to a fixed length to prepare the brush hair.
Wherein, the oxidized modified graphene is prepared by a preparation example 1; the auxiliary agent is polyamide acid ester 50% and polytetrafluoroethylene 50%; the nylon fiber has a diameter of 5-10 μm and a length of 0.5-1.5mm.
Performance test
Test method
Abrasion resistance test: using a simulated friction tester, loading 500g, testing for 1000 times, and adopting a bidirectional scraping mode; recording the weight of the sample at the end of the test, and calculating the wear loss and the friction coefficient;
Thermal stability test: using a thermogravimetric analyzer to perform thermogravimetric analysis in air at a heating rate of 10 ℃/min, and recording the melting point of the material;
rigidity and mechanical strength test: and respectively carrying out tensile test and bending test by using a universal material testing machine at a test temperature and a test humidity required by a mechanical property test standard, and calculating the elastic modulus and the elongation of the material.
Table 1 statistics of test data
It can be seen from the combination of example 3 and comparative examples 1-2 and the combination of table 1 that the oxidatively modified graphene has higher strength and rigidity, and can enhance the strength and rigidity of the composite material. Therefore, the carbon fiber composite material is used in the brush, so that the strength and durability of the brush wires can be improved, and the brush wires can bear the impact and pressure of the club movement. The oxidation modified graphene can improve the wear resistance of the composite material. In golf games, players often need to wipe golf balls, and the hairbrushes made of the oxidized modified graphene can effectively clean the spherical surfaces and improve the flying performance of the balls, and meanwhile, the hairbrushes can resist abrasion and prolong the service lives of the hairbrushes. The oxidation modified graphene can increase the stability of the composite material and improve the deformation resistance and ageing resistance of the composite material. Thus, the brush filaments can still maintain good performance and shape in long-time use, and are not easy to break or deform.
It can be seen from the combination of example 3 and comparative example 3 and the combination of table 1 that the carbon fiber has extremely high strength and rigidity, and is a very strong and hard fiber. In comparison, nylon fibers have lower strength and stiffness. Therefore, the strength and rigidity of the brush wire material can be obviously improved by using the carbon fiber in the carbon fiber composite material, so that the brush wire material is more durable and has better compression resistance and impact resistance. The carbon fiber has excellent abrasion resistance and can effectively resist friction and abrasion. Nylon fibers, by contrast, have poor abrasion resistance. Therefore, the use of carbon fibers in the brush wire material can increase the service life and durability of the brush wire, and reduce the damage and breakage of the brush wire caused by frequent use and friction.
It can be seen from the combination of examples 1 to 3 and table 1 that by controlling the ratio of carbon fiber, epoxy resin, polycarbonate resin, oxidized modified graphene, silicone rubber and auxiliary agent, a carbon fiber composite material with higher performance can be obtained, wherein the ratio of example 3 is optimal.
It can be seen from the combination of examples 3 to 5 and table 1 that the strength and durability of the brush filaments can be further improved by adjusting the preparation method of the oxidation-modified graphene.
It can be seen from the combination of examples 6-11 and Table 1 that the modified epoxy resin has better wear resistance and can increase the service life of the brush. The modified epoxy resin can provide better flexibility by adding propylene glycol monomethyl ether, polyethylene glycol amine and other substances. The modified epoxy resin has better temperature resistance and can keep stability at higher temperature. The modified polycarbonate resin can provide higher strength and hardness, thereby enhancing durability and stability of the brush. The modified polycarbonate resin generally has better high-temperature resistance and can be kept stable at higher temperature.
The present embodiment is only for explanation of the present application and is not to be construed as limiting the present application, and modifications to the present embodiment, which may not creatively contribute to the present application as required by those skilled in the art after reading the present specification, are all protected by patent laws within the scope of claims of the present application.
Claims (9)
1. The carbon fiber composite material is characterized by comprising, by weight, 30-50 parts of carbon fibers, 10-20 parts of epoxy resin, 20-30 parts of polycarbonate resin, 5-15 parts of oxidized modified graphene, 5-15 parts of silicone rubber and 1-10 parts of an auxiliary agent, wherein the oxidized modified graphene is prepared by oxidizing and modifying graphene by potassium permanganate.
2. The carbon fiber composite material of claim 1, wherein: the preparation method of the oxidized modified graphene comprises the following steps:
a1, uniformly mixing and stirring graphene powder, sodium nitrate and concentrated sulfuric acid according to a ratio of (5-7) to 3:1 at the temperature of 0 ℃ to obtain a mixed solution;
A2, slowly adding potassium permanganate into the mixed solution, wherein the mass ratio of the potassium permanganate to the graphene powder is (1-3): 5, stirring uniformly to obtain a reaction solution, heating the reaction solution to 30-40 ℃ and preserving heat, reacting for 6-8h, after the reaction is finished, obtaining a dark brown and sticky reaction solution, adding distilled water with the same mass as the mixed solution, heating to 90-95 ℃ and stirring for 20-40min;
A3, cooling to 60-80 ℃, adding distilled water with the mass equal to that of the mixed solution and hydrogen peroxide accounting for 10-20% of that of the mixed solution into the reaction solution, and standing for 1-3h;
And A4, centrifugally separating the reaction liquid after standing, collecting solid matters, cleaning the solid matters by deionized water, and freeze-drying the solid matters to obtain the graphene oxide.
3. The carbon fiber composite material of claim 1, wherein: the diameter of the carbon fiber is 5-10 mu m, and the length is 0.5-1.5mm.
4. The carbon fiber composite material of claim 1, wherein: the epoxy resin is modified epoxy resin, and the preparation method of the modified epoxy resin comprises the following steps:
b1, placing epoxy resin and propylene glycol monomethyl ether into a container, wherein the addition mass of the propylene glycol monomethyl ether is 50-70% of that of the epoxy resin, and stirring for 30-50min at 100-120 ℃;
B2, adding polyethylene glycol amine and diethyl diamine into the container, wherein the addition amount of the polyethylene glycol amine is 20-30% of the mass of the epoxy resin, the addition amount of the diethyl diamine is 1-5% of the mass of the epoxy resin, and reacting for 4-6h at 110-130 ℃ to obtain the modified epoxy resin after the reaction is completed.
5. The carbon fiber composite material of claim 1, wherein: the polycarbonate resin is modified polycarbonate resin, and the preparation method of the modified polycarbonate resin comprises the following steps:
Placing the polycarbonate resin and polyisocyanate into a container, wherein the addition amount of the polyisocyanate is 0.5-2.5% of the mass of the polycarbonate resin, and reacting for 3-6h at 220-240 ℃ to obtain the modified polycarbonate resin.
6. The carbon fiber composite material of claim 1, wherein: the silicone rubber is gamma-trifluoropropyl methyl polysiloxane.
7. The carbon fiber composite material of claim 1, wherein: the auxiliary agent comprises 40-60% of polyamide acid ester and 40-60% of polytetrafluoroethylene.
8. A drawing process of a carbon fiber composite material according to any one of claims 1 to 7, characterized in that: the method comprises the following steps:
S1, mixing: mixing the epoxy resin, the polycarbonate resin and the carbon fiber in a mixer to ensure that the components are uniformly mixed;
s2, preprocessing: adding silicon rubber, oxidized modified graphene and an auxiliary agent, continuously mixing in a mixer, and heating at 230-280 ℃;
S3, extrusion molding: during extrusion molding, an injection molding machine with an extruder head is used, and the extrusion temperature is 280-320 ℃;
S4, wire drawing: in the wire drawing process, a wire drawing machine with a constant temperature device is used for carrying out, the wire drawing speed is 0.1-0.5m/s, and the wire drawing temperature is 250-300 ℃; after the wire drawing is completed, the filament-shaped material is cut to a fixed length to prepare the brush hair.
9. Use of the carbon fiber composite material of claim 1, wherein: the carbon fiber composite material is used for preparing a golf mat.
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