CN114262496B - Preparation method of carbon fiber resin matrix composite material for umbrella ribs - Google Patents
Preparation method of carbon fiber resin matrix composite material for umbrella ribs Download PDFInfo
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- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 75
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 75
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 229920005989 resin Polymers 0.000 title claims abstract description 46
- 239000011347 resin Substances 0.000 title claims abstract description 46
- 239000002131 composite material Substances 0.000 title claims abstract description 32
- 239000011159 matrix material Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229920002239 polyacrylonitrile Polymers 0.000 claims abstract description 34
- 239000002243 precursor Substances 0.000 claims abstract description 25
- 230000003647 oxidation Effects 0.000 claims abstract description 17
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 17
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229920001577 copolymer Polymers 0.000 claims abstract description 11
- 238000010000 carbonizing Methods 0.000 claims abstract description 6
- 238000000748 compression moulding Methods 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 43
- 238000003763 carbonization Methods 0.000 claims description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 238000003756 stirring Methods 0.000 claims description 26
- 238000001035 drying Methods 0.000 claims description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 21
- 229940105325 3-dimethylaminopropylamine Drugs 0.000 claims description 20
- IUNMPGNGSSIWFP-UHFFFAOYSA-N dimethylaminopropylamine Chemical compound CN(C)CCCN IUNMPGNGSSIWFP-UHFFFAOYSA-N 0.000 claims description 20
- 150000001875 compounds Chemical class 0.000 claims description 17
- 239000007788 liquid Substances 0.000 claims description 16
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- 239000013067 intermediate product Substances 0.000 claims description 15
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 14
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 14
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 14
- 239000000835 fiber Substances 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 13
- 239000000178 monomer Substances 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 12
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- 238000006116 polymerization reaction Methods 0.000 claims description 11
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 238000004821 distillation Methods 0.000 claims description 10
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 10
- 238000009987 spinning Methods 0.000 claims description 9
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 8
- 238000000280 densification Methods 0.000 claims description 7
- 239000003638 chemical reducing agent Substances 0.000 claims description 6
- 239000003822 epoxy resin Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000007800 oxidant agent Substances 0.000 claims description 6
- 229920000647 polyepoxide Polymers 0.000 claims description 6
- 239000000047 product Substances 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 239000012298 atmosphere Substances 0.000 claims description 5
- 238000009835 boiling Methods 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 238000009998 heat setting Methods 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 238000002166 wet spinning Methods 0.000 claims description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 4
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 4
- 229920005830 Polyurethane Foam Polymers 0.000 claims description 4
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 4
- 239000011496 polyurethane foam Substances 0.000 claims description 4
- 235000010378 sodium ascorbate Nutrition 0.000 claims description 4
- 229960005055 sodium ascorbate Drugs 0.000 claims description 4
- PPASLZSBLFJQEF-RKJRWTFHSA-M sodium ascorbate Substances [Na+].OC[C@@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RKJRWTFHSA-M 0.000 claims description 4
- PPASLZSBLFJQEF-RXSVEWSESA-M sodium-L-ascorbate Chemical group [Na+].OC[C@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RXSVEWSESA-M 0.000 claims description 4
- 238000000967 suction filtration Methods 0.000 claims description 4
- 238000000465 moulding Methods 0.000 claims description 3
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 claims description 2
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 2
- 238000007711 solidification Methods 0.000 claims description 2
- 230000008023 solidification Effects 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 9
- 239000000805 composite resin Substances 0.000 abstract description 5
- 230000001112 coagulating effect Effects 0.000 description 30
- 239000000243 solution Substances 0.000 description 20
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 18
- 230000015271 coagulation Effects 0.000 description 15
- 238000005345 coagulation Methods 0.000 description 15
- 238000005452 bending Methods 0.000 description 12
- 239000007864 aqueous solution Substances 0.000 description 9
- 230000006872 improvement Effects 0.000 description 9
- 235000005074 zinc chloride Nutrition 0.000 description 9
- 239000011592 zinc chloride Substances 0.000 description 9
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 8
- 229920006240 drawn fiber Polymers 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 4
- 239000003365 glass fiber Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 210000000988 bone and bone Anatomy 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229920002545 silicone oil Polymers 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 229910000838 Al alloy Inorganic materials 0.000 description 2
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
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- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- UIERETOOQGIECD-UHFFFAOYSA-N Angelic acid Natural products CC=C(C)C(O)=O UIERETOOQGIECD-UHFFFAOYSA-N 0.000 description 1
- 241001391944 Commicarpus scandens Species 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
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- 238000000576 coating method Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
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- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 229920006253 high performance fiber Polymers 0.000 description 1
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- 239000012535 impurity Substances 0.000 description 1
- 239000012784 inorganic fiber Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
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- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
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- 229910052718 tin Inorganic materials 0.000 description 1
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- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Inorganic Fibers (AREA)
Abstract
The application relates to the technical field of composite materials, and provides a preparation method of a carbon fiber resin-based composite material for umbrella ribs, which comprises the following steps: s1, preparing a polyacrylonitrile-based copolymer; s2, preparing polyacrylonitrile-based precursor; s3, immersing the polyacrylonitrile-based precursor in an ethanol solution of phthalic acid for 30-60 min; s4, pre-oxidation treatment; s5, carbonizing treatment; s6, acidizing for 3-5 hours; s7, modifying the surface of the carbon fiber; s8, compression molding. The application realizes the application of the carbon fiber resin matrix composite material on the umbrella ribs, and solves the problems that the existing carbon fiber and resin interface has weak adhesion and the preparation of products with excellent mechanical properties is difficult.
Description
Technical Field
The application belongs to the technical field of composite materials, and particularly relates to a preparation method of a carbon fiber resin-based composite material for umbrella ribs.
Background
With the development of technology, the umbrella is also continuously updated, and the umbrella is changed from old-time oil paper umbrellas to current umbrellas with various types and kinds. The umbrella rib is an important component structure of the umbrella and can be divided into resin ribs, aluminum alloy ribs, iron ribs, glass fiber ribs and the like according to materials. The iron bones are hard and not easy to break, have good windproof performance, but have long time and are easy to rust; the aluminum alloy bone and the resin bone are relatively light and portable, but are easy to bend and break under strong wind or other external forces. The glass fiber rib has the advantages of good insulation, strong heat resistance, good corrosion resistance, high tensile strength and light weight, but the structural strength is poor, so that the glass fiber rib cannot bear larger stress, and particularly in the structural configuration of the umbrella, the ribs at different positions must bear different forces, for example, the ribs must bear the tension of umbrella cloth, and the supporting ribs must provide proper axial pushing force. In addition, the preparation of the glass fiber has the problems of glass crystallization, high density of raw silk threads, high cost and the like.
The carbon fiber is an inorganic fiber material with carbon content of more than 90%, and has excellent performances such as high specific strength, high specific modulus, low density, high temperature resistance, corrosion resistance and the like. As a high-performance fiber material, the carbon fiber has the inherent properties of the carbon material and the softness and the processability of the fiber material, is known as a novel material with the most vitality in the 21 st century, and is widely applied to various fields such as sports equipment, medical equipment, transportation, aerospace and the like. Although carbon fibers have the various advantages, the carbon fibers are often difficult to use singly, and the defects of each component part are overcome by preparing a composite material, so that the performance of each part is improved. The carbon fiber composite material takes carbon fibers as a reinforcement, and the matrix comprises: resin, metal, ceramic, carbon, or the like. Chinese patent application No.: 201910626968.8A preparation method of carbon fiber composite umbrella ribs comprises the following raw materials: the application uses carbon fiber to match with aluminum and adds other metals to match, wherein, aluminum and other metal simple substances mainly play a role of strengthening, the oxidation resistance and ductility of umbrella ribs are enhanced by adding yttrium, the tensile strength of the umbrella ribs is increased, and the strength of the umbrella ribs is enhanced by adding germanium, tin and cobalt, so that the umbrella ribs made of carbon fiber composite materials have higher tensile strength, specific elastic modulus and fatigue strength.
Carbon fiber resin based composites have many excellent properties, but there are few reports of their application to the manufacture of umbrella ribs. In addition, the carbon fiber has low surface energy and lacks chemical active groups, so that the interfacial adhesion between the carbon fiber and the resin matrix is weak, and the load is difficult to effectively transfer. Therefore, the excellent characteristics of the carbon fiber cannot be exerted, the overall performance of the composite material is improved, and the mechanical property of the composite material is greatly weakened.
Disclosure of Invention
Therefore, in view of the above, the application provides a preparation method of a carbon fiber resin matrix composite material for umbrella ribs, which solves the problems that the existing carbon fiber and resin interface has weak adhesion and is difficult to prepare the umbrella ribs with excellent mechanical properties.
In order to achieve the above purpose, the application is realized by the following technical scheme:
the preparation method of the carbon fiber resin matrix composite material for the umbrella ribs comprises the following steps:
s1, adding deionized water, acrylonitrile, a monomer A and a monomer B into a reaction device, stirring and mixing uniformly, adding a reducing agent and an oxidizing agent, performing polymerization reaction under a nitrogen atmosphere, pouring the obtained product into the deionized water after the reaction is finished to terminate the polymerization reaction, performing vacuum filtration, washing for a plurality of times, and drying after filtration to obtain a polyacrylonitrile-based copolymer;
s2, adding the polyacrylonitrile-based copolymer into a dimethyl sulfoxide solvent, stirring and dissolving for 1-3 hours at the temperature of 60-80 ℃, then feeding into a vacuum drying oven, standing and defoaming for 6-8 hours to obtain a spinning solution with the solid content of 12-18%, and obtaining the polyacrylonitrile-based precursor through a wet spinning process;
s3, immersing the polyacrylonitrile-based precursor into an ethanol solution of which the concentration is 10-20% of phthalic acid, immersing for 30-60 min, and taking out and drying;
s4, heating the dried polyacrylonitrile-based precursor in nitrogen atmosphere for 10-30 min at 160-180 ℃, then sequentially passing through No. 1-4 temperature areas under the air condition, and performing pre-oxidation treatment to obtain pre-oxidized filaments, wherein the temperature of each temperature area is 205-215 ℃, 235-245 ℃, 255-265 ℃ and 270-280 ℃, and the pre-oxidation time of each temperature area is 18-25 min, 12-18 min and 8-16 min;
s5, carbonizing the pre-oxidized fiber under the protection of inert atmosphere to obtain carbon fiber;
s6, mixing the carbon fiber with concentrated nitric acid, acidizing for 3-5 hours at 65-75 ℃, and then drying in an oven;
s7, putting the dried carbon fibers into the finishing liquid, stirring for 2-4 hours at 70-80 ℃ to enable the finishing agent to be attached to the surfaces of the carbon fibers, and taking out and drying;
s8, carrying out compression molding on the surface modified carbon fiber, resin and curing agent to obtain the carbon fiber resin matrix composite.
The further improvement is that: the monomer A is any one of methyl acrylate, ethyl acrylate, methyl methacrylate or ethyl methacrylate; the monomer B is any one of methacrylic acid, acrylic acid or itaconic acid.
The further improvement is that: the oxidant is persulfate, and the reducing agent is sodium ascorbate or 1, 3-propylene diamine.
The further improvement is that: the acrylonitrile-based polyurethane foam is characterized in that the acrylonitrile-based polyurethane foam comprises, by mass, 100 parts of acrylonitrile, 2.5-4.5 parts of monomer A, 0.8-1.2 parts of monomer B, 300-400 parts of deionized water, 0.2-0.4 part of reducing agent and 0.2-0.6 part of oxidant.
The further improvement is that: the polymerization reaction temperature in S1 is 56-60 ℃ and the reaction time is 4-6 h.
The further improvement is that: the wet spinning process comprises the following steps: multistage solidification molding, boiling water drafting, water washing, oiling, drying densification, vapor drafting and heat setting.
The further improvement is that: the diameter of the polyacrylonitrile-based precursor is 9-15 mu m.
The further improvement is that: the carbonization treatment in S5 comprises low-temperature carbonization and high-temperature carbonization, wherein the total time of the low-temperature carbonization is 120-150S, 4 temperature areas are arranged in the low-temperature carbonization stage, the temperature of each temperature area is 450 ℃, 600 ℃, 700 ℃ and 780 ℃, the total time of the high-temperature carbonization is 100-120S, 4 temperature areas are arranged in the high-temperature carbonization stage, and the temperature of each temperature area is 850 ℃, 1090 ℃, 1300 ℃ and 1500 ℃.
The further improvement is that: the finishing liquid in S7 is prepared by the following method:
adding 3-dimethylaminopropylamine into a reaction kettle, introducing nitrogen to remove air in the kettle, slowly dropwise adding an ethanol solution of ethyl acrylate, stirring at the temperature of 30-40 ℃ for reaction for 20-30 h, and performing reduced pressure distillation after the reaction is finished to obtain an intermediate product A, wherein the mass ratio of the 3-dimethylaminopropylamine to the ethyl acrylate is 1:6-8;
adding a certain amount of 3-dimethylaminopropylamine into a reaction kettle, introducing nitrogen to remove air in the kettle, slowly dripping an ethanol solution of an intermediate product A, stirring at 38-42 ℃ for reaction for 20-30 hours, performing reduced pressure distillation after the reaction is finished, and purifying to obtain a high molecular compound B with a branched structure, wherein the mass ratio of the 3-dimethylaminopropylamine to the intermediate product A is 4-6:1;
and dissolving the high molecular compound B in an organic solvent, adding gamma- (methacryloyloxy) propyl trimethoxy silane accounting for 3-6% of the mass of the high molecular compound B, and stirring and uniformly mixing to obtain the finishing liquid.
The further improvement is that: the resin is epoxy resin.
By adopting the technical scheme, the application has the beneficial effects that:
the carbon fiber resin-based composite material is applied to preparing the rib material, fully utilizes the characteristics of high performance of carbon fibers and low cost of the resin material, and realizes the portability, corrosion resistance, wind resistance and durability of the umbrella.
The quality of the precursor is one of key factors influencing the quality of the carbon fiber, and the copolymerization composition, compactness, fineness, crystallization, orientation degree, structural uniformity and other structural characteristics and various defects of the precursor determine the performance of the final carbon fiber to a great extent. The raw material components and the process parameters of the polyacrylonitrile-based precursor are optimized, so that the precursor with high orientation, high strength, good thermal stability, uniform fineness, less impurities and less defects is prepared.
The excellent mechanical properties of the polyacrylonitrile-based carbon fiber are determined by the structure of the polyacrylonitrile-based carbon fiber, and the existence of the sheath-core structure seriously affects the mechanical properties of the carbon fiber. The sheath-core structure is formed gradually in the pre-oxidation process, and the precursor with the diameter of 9-15 mu m is prepared by optimizing the process parameters of wet spinning, so that the sheath-core structure in the pre-oxidation process can be eliminated to a certain extent, the carbonization is promoted, and the fiber structure is converted into a disordered graphite structure. The thermal movement of the molecular chain in the preoxidation process is severe, and the chain segment or chain link is seriously de-oriented, so that more conformations appear and the molecular chain is in a thermodynamically stable state. The molecular chain decomposition orientation can directly influence the skin-core structure, for the application, the ethanol solution of phthalic acid is soaked before the polyacrylonitrile-based precursor is pre-oxidized, phthalic anhydride can be formed in the pre-oxidation process of the phthalic acid, the dipole effect among cyano groups is reduced, the orientation degree is improved, and the skin-core structure is eliminated. Meanwhile, the existence of phthalic anhydride can also enhance the mechanical properties of the carbon fiber. The skin-core structure of the fiber in the pre-oxidation process can be improved by carrying out nitrogen pre-treatment before pre-oxidation.
The carbon fiber is subjected to surface modification, grafted with a long-chain high polymer compound, and a large number of active groups are introduced into the surface to generate chemical bonding action with the resin matrix, so that the interfacial adhesion between the carbon fiber and the resin is improved, and the mechanical property of the composite material is improved. The polymer compound B prepared by the application has a branched structure, can be diffused into a resin molecular chain, forms a physical and chemical entanglement effect of entanglement, and enhances the interface strength between carbon fibers and resin. The gamma- (methacryloyloxy) propyl trimethoxy silane which can react with the resin is added in a proper amount in the finishing liquid, so that the crosslinking between the carbon fiber and the resin is promoted, and the interfacial bonding strength of the carbon fiber and the resin is further enhanced.
Detailed Description
The following describes embodiments of the present application in detail with reference to specific examples, so as to solve the technical problem by applying the technical means to the present application, and the implementation process for achieving the technical effect can be fully understood and implemented accordingly.
Unless otherwise indicated, the technical means employed in the examples are conventional means well known to those skilled in the art, and the reagents and products employed are also commercially available. The sources of the reagents used, the trade names and the members of the list of constituents which are necessary are all indicated at the first occurrence.
Example 1
The preparation method of the carbon fiber resin matrix composite material for the umbrella ribs comprises the following steps:
s1, adding deionized water, acrylonitrile, methyl acrylate and methacrylic acid into a reaction device, stirring and mixing uniformly, adding sodium ascorbate and ammonium persulfate, performing polymerization reaction under a nitrogen atmosphere at the reaction temperature of 56 ℃ for 6 hours, pouring the obtained product into the deionized water after the reaction is finished to terminate the polymerization reaction, performing vacuum suction filtration, washing for a plurality of times, and drying after filtration to obtain the polyacrylonitrile-based copolymer;
based on 100 parts by mass of acrylonitrile, the dosage of methyl acrylate is 2.5 parts, the dosage of methacrylic acid is 1 part, the dosage of deionized water is 300 parts, the dosage of sodium ascorbate is 0.2 part, and the dosage of ammonium persulfate is 0.2 part;
s2, adding a polyacrylonitrile-based copolymer into a dimethyl sulfoxide solvent, stirring and dissolving for 1h at 60 ℃, then feeding into a vacuum drying oven, standing and defoaming for 6h to obtain a spinning solution with the solid content of 12%, spraying the spinning solution through a spinneret orifice, and entering a first coagulation bath, wherein the temperature of the first coagulation bath is 40 ℃, the first coagulation bath adopts a zinc chloride aqueous solution with the concentration of 60%, the coagulation time is 2min, and the coagulation drafting rate is 2.0; then the mixture enters a second coagulating bath, the temperature of the second coagulating bath is 30 ℃, the second coagulating bath adopts a zinc chloride aqueous solution with the concentration of 40 percent, the coagulating time is 1.5min, the coagulating draft ratio is 1.0, then the mixture enters a third coagulating bath, the temperature of the third coagulating bath is 25 ℃, the second coagulating bath adopts a zinc chloride aqueous solution with the concentration of 20 percent, the coagulating time is 1min, and the coagulating draft ratio is 1.0; drawing the solidified fiber in boiling water at 100 ℃, wherein the drawing multiplying power is 6.0, washing the drawn fiber by hot water, washing the drawn fiber by water, wherein the drawing multiplying power is 0.99, adding silicone oil, drying and densification by a hot roller, wherein the densification temperature is 120 ℃, the densification drawing multiplying power is 0.98, carrying out secondary drawing on the dried and densified fiber in an overheated steam environment at 145 ℃, the drawing multiplying power is 2.5, and finally carrying out heat setting at 155 ℃ to obtain a polyacrylonitrile-based precursor with the diameter of 9 mu m;
s3, immersing the polyacrylonitrile-based precursor into an ethanol solution of which the concentration is 10% of phthalic acid, immersing for 60min, and taking out and drying;
s4, heating the dried polyacrylonitrile-based precursor in nitrogen atmosphere for 10min at 180 ℃, then sequentially passing through No. 1-4 temperature areas under the air condition, and performing pre-oxidation treatment to obtain pre-oxidized filaments, wherein the temperature of each temperature area is 205 ℃, 235 ℃, 255 ℃ and 270 ℃, and the pre-oxidation time of each temperature area is 18min, 12min and 8min;
s5, carbonizing the pre-oxidized fiber under the protection of inert atmosphere to obtain carbon fiber;
the carbonization treatment comprises low-temperature carbonization and high-temperature carbonization, wherein the total time of the low-temperature carbonization is 120s, the low-temperature carbonization stage is provided with 4 temperature areas, the temperature of each temperature area is 450 ℃, 600 ℃, 700 ℃, 780 ℃, the total time of the high-temperature carbonization is 100s, the high-temperature carbonization stage is provided with 4 temperature areas, and the temperature of each temperature area is 850 ℃, 1090 ℃, 1300 ℃ and 1500 ℃;
s6, mixing the carbon fiber with concentrated nitric acid, acidizing for 3 hours at 65 ℃, and then drying in an oven;
s7, putting the dried carbon fibers into the finishing liquid, stirring for 4 hours at 70 ℃ to enable the surfaces of the carbon fibers to be attached with the finishing agent, and taking out and drying;
the finishing liquid is prepared by the following steps:
adding 3-dimethylaminopropylamine into a reaction kettle, introducing nitrogen to remove air in the kettle, slowly dropwise adding an ethanol solution of ethyl acrylate, stirring at 30 ℃ for reaction for 20 hours, and performing reduced pressure distillation after the reaction is finished to obtain an intermediate product A, wherein the mass ratio of the 3-dimethylaminopropylamine to the ethyl acrylate is 1:6;
adding a certain amount of 3-dimethylaminopropylamine into a reaction kettle, introducing nitrogen to remove air in the kettle, slowly dropwise adding an ethanol solution of an intermediate product A, stirring at 38 ℃ for reaction for 20 hours, performing reduced pressure distillation after the reaction is finished, and purifying to obtain a high molecular compound B with a branched structure, wherein the mass ratio of the 3-dimethylaminopropylamine to the intermediate product A is 4:1;
the high molecular compound B is dissolved in an organic solvent, and gamma- (methacryloyloxy) propyl trimethoxy silane accounting for 3% of the mass of the high molecular compound B is added, and the mixture is stirred and mixed uniformly to obtain finishing liquid;
s8, preparing epoxy resin and a curing agent into prepreg resin according to a mass ratio of 2:1, uniformly coating the prepreg resin on release paper on a pre-dipping machine to prepare a resin film, stretching the surface-modified carbon fiber by a stretching device of the pre-dipping machine, and superposing the surface-modified carbon fiber and the prepreg resin under the pressure of a hot press roll to prepare the prepreg; cutting the obtained prepreg into a proper size, paving the prepreg in a forming die, forming and curing the prepreg under a molding press, setting the heating temperature of the die to 180 ℃, setting the pressure to 5MPa, and demolding and cutting the molded prepreg into the carbon fiber resin-based composite material for the umbrella rib.
The carbon fiber resin matrix composite material prepared in this example was tested for flexural strength, flexural modulus and interfacial shear strength. The bending strength and the bending modulus are tested according to GB/T1449-2005, and the result shows that the bending strength of the carbon fiber resin matrix composite material prepared by the embodiment is 1.75GPa, and the bending modulus is 162GPa. The interfacial shear strength was measured at a loading rate of 0.5 μm/s using a universal tester (Instron 5667, instron Co., USA), and the result showed that the interfacial shear strength of the carbon fiber resin matrix composite material prepared in this example was 58.1MPa.
Example 2
The preparation method of the carbon fiber resin matrix composite material for the umbrella ribs comprises the following steps:
s1, adding deionized water, acrylonitrile, ethyl acrylate and acrylic acid into a reaction device, stirring and mixing uniformly, then adding 1, 3-propylene diamine and ammonium persulfate, carrying out polymerization reaction under a nitrogen atmosphere at the reaction temperature of 58 ℃ for 5 hours, pouring the obtained product into the deionized water after the reaction is finished to terminate the polymerization reaction, carrying out reduced pressure suction filtration, washing for a plurality of times, and drying after filtration to obtain the polyacrylonitrile-based copolymer;
the method comprises the following steps of (1) taking 100 parts by mass of acrylonitrile, 3.5 parts of ethyl acrylate, 0.8 part of acrylic acid, 350 parts of deionized water, 0.3 part of 1, 3-propylene diamine and 0.4 part of ammonium persulfate;
s2, adding a polyacrylonitrile-based copolymer into a dimethyl sulfoxide solvent, stirring and dissolving for 2 hours at 70 ℃, then feeding the mixture into a vacuum drying oven, standing and defoaming for 7 hours to obtain a spinning solution with the solid content of 15%, spraying the spinning solution through a spinneret orifice, and entering a first coagulation bath, wherein the temperature of the first coagulation bath is 40 ℃, the first coagulation bath adopts a zinc chloride aqueous solution with the concentration of 60%, the coagulation time is 2 minutes, and the coagulation drafting rate is 2.0; then the mixture enters a second coagulating bath, the temperature of the second coagulating bath is 30 ℃, the second coagulating bath adopts a zinc chloride aqueous solution with the concentration of 40 percent, the coagulating time is 1.5min, the coagulating draft ratio is 1.0, then the mixture enters a third coagulating bath, the temperature of the third coagulating bath is 25 ℃, the second coagulating bath adopts a zinc chloride aqueous solution with the concentration of 20 percent, the coagulating time is 1min, and the coagulating draft ratio is 1.0; drawing the solidified fiber in boiling water at 100 ℃ with a drawing multiplying power of 5.0, washing the drawn fiber with hot water, washing the drawn fiber with water with a drawing multiplying power of 0.99, adding silicone oil, drying and densifying the drawn fiber by a hot roller at a densification temperature of 120 ℃, and carrying out secondary drawing on the dried and densified fiber in an overheated steam environment at 145 ℃, wherein the drawing multiplying power is 2.0, and finally carrying out heat setting at 155 ℃ to obtain a polyacrylonitrile-based precursor with a diameter of 15 mu m;
s3, immersing the polyacrylonitrile-based precursor into an ethanol solution of which the concentration is 15 percent of phthalic acid, taking out and drying after 45 minutes of immersion,
s4, heating the dried polyacrylonitrile-based precursor in nitrogen atmosphere for 20min at 170 ℃, then sequentially passing through No. 1-4 temperature areas under the air condition, and performing pre-oxidation treatment to obtain pre-oxidized filaments, wherein the temperature of each temperature area is 210 ℃, 240 ℃, 260 ℃ and 275 ℃, and the pre-oxidation time of each temperature area is 22min, 15min, 16min and 12min;
s5, carbonizing the pre-oxidized fiber under the protection of inert atmosphere to obtain carbon fiber;
the carbonization treatment comprises low-temperature carbonization and high-temperature carbonization, wherein the total time of the low-temperature carbonization is 135s, 4 temperature areas are arranged in the low-temperature carbonization stage, the temperature of each temperature area is 450 ℃, 600 ℃, 700 ℃, 780 ℃, the total time of the high-temperature carbonization is 110s, 4 temperature areas are arranged in the high-temperature carbonization stage, and the temperature of each temperature area is 850 ℃, 1090 ℃, 1300 ℃ and 1500 ℃;
s6, mixing the carbon fiber with concentrated nitric acid, acidizing for 4 hours at 70 ℃, and then drying in an oven;
s7, putting the dried carbon fibers into the finishing liquid, stirring for 3 hours at 75 ℃ to enable the surfaces of the carbon fibers to be attached with the finishing agent, and taking out and drying;
the finishing liquid is prepared by the following steps:
adding 3-dimethylaminopropylamine into a reaction kettle, introducing nitrogen to remove air in the kettle, slowly dropwise adding an ethanol solution of ethyl acrylate, stirring at 35 ℃ for reaction for 25 hours, and performing reduced pressure distillation after the reaction is finished to obtain an intermediate product A, wherein the mass ratio of the 3-dimethylaminopropylamine to the ethyl acrylate is 1:7;
adding a certain amount of 3-dimethylaminopropylamine into a reaction kettle, introducing nitrogen to remove air in the kettle, slowly dropwise adding an ethanol solution of an intermediate product A, stirring at 40 ℃ for reaction for 25 hours, performing reduced pressure distillation after the reaction is finished, and purifying to obtain a high molecular compound B with a branched structure, wherein the mass ratio of the 3-dimethylaminopropylamine to the intermediate product A is 5:1;
the high molecular compound B is dissolved in an organic solvent, and gamma- (methacryloyloxy) propyl trimethoxy silane accounting for 5% of the mass of the high molecular compound B is added, and the mixture is stirred and mixed uniformly to obtain finishing liquid;
s8, carrying out compression molding on the surface modified carbon fiber, epoxy resin and curing agent to obtain the carbon fiber resin matrix composite.
The bending strength of the carbon fiber resin matrix composite prepared by the embodiment is 1.79GPa, the bending modulus is 164GPa, and the interfacial shear strength is 61.5MPa.
Example 3
The preparation method of the carbon fiber resin matrix composite material for the umbrella ribs comprises the following steps:
s1, adding deionized water, acrylonitrile, methyl methacrylate and itaconic acid into a reaction device, stirring and mixing uniformly, then adding 1, 3-propylene diamine and potassium persulfate, carrying out polymerization reaction under nitrogen atmosphere at the reaction temperature of 60 ℃ for 4 hours, pouring the obtained product into deionized water to terminate the polymerization reaction after the reaction is finished, carrying out vacuum suction filtration, washing for a plurality of times, and drying after filtration to obtain a polyacrylonitrile-based copolymer;
based on 100 parts by mass of acrylonitrile, the dosage of methyl methacrylate is 4.5 parts, the dosage of itaconic acid is 1.2 parts, the dosage of deionized water is 400 parts, the dosage of 1, 3-propylene diamine is 0.4 part, and the dosage of potassium persulfate is 0.6 part;
s2, adding a polyacrylonitrile-based copolymer into a dimethyl sulfoxide solvent, stirring and dissolving for 3 hours at 80 ℃, then feeding the mixture into a vacuum drying oven, standing and defoaming for 8 hours to obtain a spinning solution with 18% of solid content, spraying the spinning solution through a spinneret orifice, and entering a first coagulation bath, wherein the temperature of the first coagulation bath is 40 ℃, the first coagulation bath adopts a zinc chloride aqueous solution with the concentration of 60%, the coagulation time is 2 minutes, and the coagulation drafting rate is 2.0; then the mixture enters a second coagulating bath, the temperature of the second coagulating bath is 30 ℃, the second coagulating bath adopts a zinc chloride aqueous solution with the concentration of 40 percent, the coagulating time is 1.5min, the coagulating draft ratio is 1.0, then the mixture enters a third coagulating bath, the temperature of the third coagulating bath is 25 ℃, the second coagulating bath adopts a zinc chloride aqueous solution with the concentration of 20 percent, the coagulating time is 1min, and the coagulating draft ratio is 1.0; drawing the solidified fiber in boiling water at 100 ℃ with a drawing multiplying power of 4.0, washing the drawn fiber with hot water, washing the drawn fiber with water with a drawing multiplying power of 0.99, adding silicone oil, drying and densifying the drawn fiber by a hot roller at a densification temperature of 120 ℃, and carrying out secondary drawing on the dried and densified fiber in an overheated steam environment at 145 ℃, wherein the drawing multiplying power is 3.0, and finally carrying out heat setting at 155 ℃ to obtain a polyacrylonitrile-based precursor with a diameter of 12 mu m;
s3, immersing the polyacrylonitrile-based precursor into an ethanol solution of which the concentration is 20 percent of phthalic acid, taking out and drying after immersing for 30 minutes,
s4, heating the dried polyacrylonitrile-based precursor in nitrogen atmosphere for 30min at 160 ℃, then sequentially passing through No. 1-4 temperature areas under the air condition, and performing pre-oxidation treatment to obtain pre-oxidized filaments, wherein the temperature of each temperature area is 215 ℃, 245 ℃, 265 ℃, 280 ℃ and the pre-oxidation time of each temperature area is 25min, 18min and 16min respectively;
s5, carbonizing the pre-oxidized fiber under the protection of inert atmosphere to obtain carbon fiber;
the carbonization treatment comprises low-temperature carbonization and high-temperature carbonization, wherein the total time of the low-temperature carbonization is 150s, 4 temperature areas are arranged in the low-temperature carbonization stage, the temperature of each temperature area is 450 ℃, 600 ℃, 700 ℃, 780 ℃, the total time of the high-temperature carbonization is 120s, 4 temperature areas are arranged in the high-temperature carbonization stage, and the temperature of each temperature area is 850 ℃, 1090 ℃, 1300 ℃ and 1500 ℃;
s6, mixing the carbon fiber with concentrated nitric acid, acidizing for 5 hours at 75 ℃, and then drying in an oven;
s7, putting the dried carbon fibers into the finishing liquid, stirring for 2 hours at 80 ℃ to enable the surfaces of the carbon fibers to be attached with the finishing agent, and taking out and drying;
the finishing liquid is prepared by the following steps:
adding 3-dimethylaminopropylamine into a reaction kettle, introducing nitrogen to remove air in the kettle, slowly dropwise adding an ethanol solution of ethyl acrylate, stirring at 40 ℃ for reaction for 30 hours, and performing reduced pressure distillation after the reaction is finished to obtain an intermediate product A, wherein the mass ratio of the 3-dimethylaminopropylamine to the ethyl acrylate is 1:8;
adding a certain amount of 3-dimethylaminopropylamine into a reaction kettle, introducing nitrogen to remove air in the kettle, slowly dropwise adding an ethanol solution of an intermediate product A, stirring at 42 ℃ for reaction for 30 hours, performing reduced pressure distillation after the reaction is finished, and purifying to obtain a high molecular compound B with a branched structure, wherein the mass ratio of the 3-dimethylaminopropylamine to the intermediate product A is 6:1;
the high molecular compound B is dissolved in an organic solvent, and gamma- (methacryloyloxy) propyl trimethoxy silane accounting for 6% of the mass of the high molecular compound B is added, and the mixture is stirred and mixed uniformly to obtain finishing liquid;
s8, carrying out compression molding on the surface modified carbon fiber, epoxy resin and curing agent to obtain the carbon fiber resin matrix composite.
The bending strength of the carbon fiber resin matrix composite prepared by the embodiment is 1.76GPa, the bending modulus is 161GPa, and the interfacial shear strength is 60.6MPa.
In addition to the epoxy resins described above, the resins used in the present application may also be phenolic resins, polyethersulfones, polyphenylene sulfides, polyetheretherketones, polyetherimides, and polyimides.
Comparative example 1
The difference from example 1 is that: step S3 is omitted, and the other steps are the same as in embodiment 1.
The bending strength of the prepared carbon fiber resin matrix composite is 1.56GPa, the bending modulus is 147GPa, and the interfacial shear strength is 55.4MPa.
Comparative example 2
The difference from example 1 is that: steps S6 and S7 are omitted, and the other steps are the same as in example 1.
The bending strength of the prepared carbon fiber resin matrix composite is 1.32GPa, the bending modulus is 125GPa, and the interfacial shear strength is 51.9MPa.
The above description is illustrative of the embodiments using the present teachings, and is not intended to limit the scope of the present teachings to any particular modification or variation of the present teachings by those skilled in the art.
Claims (4)
1. A preparation method of a carbon fiber resin matrix composite material for umbrella ribs is characterized by comprising the following steps: the method comprises the following steps:
s1, adding deionized water, acrylonitrile, a monomer A and a monomer B into a reaction device, stirring and mixing uniformly, adding a reducing agent and an oxidizing agent, carrying out polymerization reaction under a nitrogen atmosphere at the temperature of 56-60 ℃ for 4-6 hours, pouring the obtained product into the deionized water after the reaction is finished to terminate the polymerization reaction, carrying out reduced pressure suction filtration, washing for multiple times, and drying after filtration to obtain the polyacrylonitrile-based copolymer;
s2, adding the polyacrylonitrile-based copolymer into a dimethyl sulfoxide solvent, stirring and dissolving for 1-3 hours at the temperature of 60-80 ℃, then feeding into a vacuum drying oven, standing and defoaming for 6-8 hours to obtain a spinning solution with the solid content of 12-18%, and carrying out a wet spinning process on the spinning solution to obtain the polyacrylonitrile-based precursor, wherein the wet spinning process comprises the following steps: multistage solidification molding, boiling water drawing, water washing, oiling, drying densification, vapor drawing and heat setting, wherein the diameter of the polyacrylonitrile-based precursor is 9-15 mu m;
s3, immersing the polyacrylonitrile-based precursor into an ethanol solution of which the concentration is 10-20% of phthalic acid, immersing for 30-60 min, and taking out and drying;
s4, heating the dried polyacrylonitrile-based precursor in nitrogen atmosphere for 10-30 min at 160-180 ℃, then sequentially passing through No. 1-4 temperature areas under the air condition, and performing pre-oxidation treatment to obtain pre-oxidized filaments, wherein the temperature of each temperature area is 205-215 ℃, 235-245 ℃, 255-265 ℃ and 270-280 ℃, and the pre-oxidation time of each temperature area is 18-25 min, 12-18 min and 8-16 min;
s5, carbonizing the pre-oxidized fiber under the protection of inert atmosphere to obtain carbon fiber;
the carbonization treatment comprises low-temperature carbonization and high-temperature carbonization, wherein the total time of the low-temperature carbonization is 120-150 s, 4 temperature areas are arranged in the low-temperature carbonization stage, the temperature of each temperature area is 450 ℃, 600 ℃, 700 ℃, 780 ℃, the total time of the high-temperature carbonization is 100-120 s, 4 temperature areas are arranged in the high-temperature carbonization stage, and the temperature of each temperature area is 850 ℃, 1090 ℃, 1300 ℃ and 1500 ℃;
s6, mixing the carbon fiber with concentrated nitric acid, acidizing for 3-5 hours at 65-75 ℃, and then drying in an oven;
s7, putting the dried carbon fibers into the finishing liquid, stirring for 2-4 hours at 70-80 ℃ to enable the finishing agent to be attached to the surfaces of the carbon fibers, and taking out and drying;
the finishing liquid is prepared by the following steps:
adding 3-dimethylaminopropylamine into a reaction kettle, introducing nitrogen to remove air in the kettle, slowly dropwise adding an ethanol solution of ethyl acrylate, stirring at the temperature of 30-40 ℃ for reaction for 20-30 h, and performing reduced pressure distillation after the reaction is finished to obtain an intermediate product A, wherein the mass ratio of the 3-dimethylaminopropylamine to the ethyl acrylate is 1:6-8;
adding a certain amount of 3-dimethylaminopropylamine into a reaction kettle, introducing nitrogen to remove air in the kettle, slowly dripping an ethanol solution of an intermediate product A, stirring at 38-42 ℃ for reaction for 20-30 hours, performing reduced pressure distillation after the reaction is finished, and purifying to obtain a compound B with a branched structure, wherein the mass ratio of the 3-dimethylaminopropylamine to the intermediate product A is 4-6:1;
the compound B is dissolved in an organic solvent, gamma- (methacryloyloxy) propyl trimethoxy silane accounting for 3-6% of the mass of the compound B is added, and the mixture is stirred and mixed uniformly to obtain finishing liquid;
s8, carrying out compression molding on the surface modified carbon fiber, resin and curing agent to obtain a carbon fiber resin matrix composite;
the acrylonitrile-based polyurethane foam is characterized in that the acrylonitrile-based polyurethane foam comprises, by mass, 100 parts of acrylonitrile, 2.5-4.5 parts of monomer A, 0.8-1.2 parts of monomer B, 300-400 parts of deionized water, 0.2-0.4 part of reducing agent and 0.2-0.6 part of oxidant.
2. The method for preparing the carbon fiber resin matrix composite for umbrella ribs according to claim 1, wherein the method comprises the following steps: the monomer A is any one of methyl acrylate, ethyl acrylate, methyl methacrylate or ethyl methacrylate; the monomer B is any one of methacrylic acid, acrylic acid or itaconic acid.
3. The method for preparing the carbon fiber resin matrix composite for umbrella ribs according to claim 1, wherein the method comprises the following steps: the oxidant is persulfate, and the reducing agent is sodium ascorbate or 1, 3-propylene diamine.
4. The method for preparing the carbon fiber resin matrix composite for umbrella ribs according to claim 1, wherein the method comprises the following steps: the resin is epoxy resin.
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