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CN-121992661-A - Bio-based polyimide carbon fiber sizing agent and preparation method thereof

CN121992661ACN 121992661 ACN121992661 ACN 121992661ACN-121992661-A

Abstract

The invention relates to the technical field of carbon fiber sizing agents, in particular to a bio-based polyimide carbon fiber sizing agent and a preparation method thereof. The sizing agent comprises the following components of bio-based polyimide, an organic solvent and deionized water, wherein the bio-based polyimide accounts for 0.4-0.6wt% of the sizing agent, the organic solvent accounts for 1.0-3.0wt% of the sizing agent, and the deionized water accounts for 96.4-98.6wt% of the sizing agent. The carbon fiber sized by the sizing agent suspension liquid prepared by the invention can be used for preparing PEI, PEEK and other composite materials, and has good high temperature resistance and excellent interface bonding performance.

Inventors

  • LIANG LIZHU
  • HE ZHICHAO
  • WANG CHANGYU
  • LI JIUCHENG
  • ZHAO JIANHUA

Assignees

  • 中国石油天然气股份有限公司

Dates

Publication Date
20260508
Application Date
20241101

Claims (10)

  1. 1. A bio-based polyimide carbon fiber sizing agent is characterized by comprising the following components of bio-based polyimide, an organic solvent and deionized water, wherein the bio-based polyimide accounts for 0.4-0.6wt% of the sizing agent, the organic solvent accounts for 1.0-3.0wt% of the sizing agent, and the deionized water accounts for 96.4-98.6wt% of the sizing agent.
  2. 2. The sizing agent for bio-based polyimide carbon fibers according to claim 1, wherein the bio-based polyimide is maleopimaric acid dianhydride and diamine.
  3. 3. The sizing agent for biobased polyimide carbon fiber according to claim 2, wherein the diamine monomer is one or more of p-phenylenediamine, m-phenylenediamine, 4' -diaminodiphenyl ether, 3' -dimethyl-4, 4' -diaminodicyclohexylmethane.
  4. 4. The bio-based polyimide carbon fiber sizing agent according to claim 2, wherein the mass ratio of the maleopimaric dianhydride to the diamine is 6.9-7:1.
  5. 5. The bio-based polyimide carbon fiber sizing agent according to claim 1, wherein the organic solvent is one or more of dimethylformamide, dimethylacetamide and dimethyl sulfoxide.
  6. 6. A method for preparing the bio-based polyimide carbon fiber sizing agent according to any one of claims 1 to 5, comprising the following steps: Dissolving bio-based polyimide in an organic solvent, reacting for a period of time under stirring, and standing to obtain a polyamic acid solution; step two, adding a precipitator into the polyamic acid solution to precipitate polyamic acid, filtering, drying the obtained filter cake, and performing thermal imidization reaction at 300-350 ℃ to obtain polyimide powder; And thirdly, 0.4 to 0.6 weight part of polyimide powder is taken and dissolved in 1 to 3 weight parts of organic solvent, deionized water is added to 100 weight parts under high-speed stirring, and sizing agent suspension is obtained.
  7. 7. The method for preparing a bio-based polyimide carbon fiber sizing agent according to claim 6, wherein in the first step, 8-9 parts by weight of bio-based polyimide is dissolved in 60-70 parts by weight of organic solvent, and the solution is stirred and reacted for 2 hours and then is left to stand for 24 hours to obtain a polyamic acid solution.
  8. 8. The method for preparing the bio-based polyimide carbon fiber sizing agent according to claim 6, wherein the precipitant is deionized water or ethanol.
  9. 9. The method for preparing a bio-based polyimide carbon fiber sizing agent according to claim 6, wherein the precipitant is added in an amount of 100ml/60-70g of the organic solvent in the first step.
  10. 10. The method for preparing the bio-based polyimide carbon fiber sizing agent according to claim 6, wherein in the third step, deionized water is added at a rate of 20-40 parts by weight per minute.

Description

Bio-based polyimide carbon fiber sizing agent and preparation method thereof Technical field: the invention relates to the technical field of carbon fiber sizing agents, in particular to a bio-based polyimide carbon fiber sizing agent and a preparation method thereof. The background technology is as follows: Carbon Fiber (CF) is a national important strategic material with many excellent properties including high temperature resistance, high thermal conductivity, high strength modulus, low density, etc. Therefore, the carbon fiber reinforced composite material is widely applied to the fields of aerospace, military, construction, transportation, medical treatment and the like. However, carbon fibers have the disadvantages that the carbon fiber precursor has smooth and brittle surfaces, is extremely easy to generate phenomena of broken filaments and broken filaments, and has weak interaction force with matrix resin during the production, storage, transportation and processing processes, so that the interface performance of the composite material is poor. Therefore, the application of sizing agents has been widely studied and developed in recent years as a method capable of simply and effectively improving the performance of carbon fibers. At present, epoxy resin-based carbon fiber sizing agents are most commonly used, and because epoxy resins are simple to prepare, low in cost and excellent in various performances, but the heat resistance of the epoxy resins is poor and the molding temperature (> 350 ℃) of thermoplastic resins such as Polyetherimide (PEI), polyether ether ketone (PEEK) and the like cannot be reached, therefore, development of carbon fiber sizing agents with good heat resistance and similar structure to matrix thermoplastic resins is needed. Polyimide is one of the most excellent high polymer materials with the comprehensive performance, resists the high temperature of more than 400 ℃, has a structure similar to engineering plastics such as PEI and the like, is an ideal high-temperature resistant sizing agent material, but has few reports at present. The bio-based raw material has the advantages of wide sources, no pollution, low price and the like, and the cost can be greatly reduced by synthesizing the sizing agent by using the bio-based material, and the bio-based raw material better accords with the concept of green sustainable development. The invention comprises the following steps: The invention provides a bio-based polyimide carbon fiber sizing agent and a preparation method thereof, and aims to solve the problems that an epoxy resin-based carbon fiber sizing agent is poor in heat resistance and cannot be matched with matrix resins such as PEI (PEI), PEEK (polyether-ether-ketone) and the like. The technical scheme adopted by the invention is that the bio-based polyimide carbon fiber sizing agent comprises the following components of bio-based polyimide, an organic solvent and deionized water, wherein the bio-based polyimide accounts for 0.4-0.6wt% of the sizing agent, the organic solvent accounts for 1.0-3.0wt% of the sizing agent, and the deionized water accounts for 96.4-98.6wt% of the sizing agent. Further, the bio-based polyimide is maleic pimaric acid dianhydride and diamine. Further, the diamine monomer is one or more of p-phenylenediamine, m-phenylenediamine, 4' -diaminodiphenyl ether and 3,3' -dimethyl-4, 4' -diaminodicyclohexylmethane. Further, the mass ratio of the maleopimaric dianhydride to the diamine is 6.9-7:1. Further, the organic solvent is one or more of dimethylformamide, dimethylacetamide and dimethyl sulfoxide. A preparation method of a bio-based polyimide carbon fiber sizing agent comprises the following steps: Dissolving bio-based polyimide in an organic solvent, reacting for a period of time under stirring, and standing to obtain a polyamic acid solution; step two, adding a precipitator into the polyamic acid solution to precipitate polyamic acid, filtering, drying the obtained filter cake, and performing thermal imidization reaction at 300-350 ℃ to obtain polyimide powder; And thirdly, 0.4 to 0.6 weight part of polyimide powder is taken and dissolved in 1 to 3 weight parts of organic solvent, deionized water is added to 100 weight parts under high-speed stirring, and sizing agent suspension is obtained. In the first step, 8-9 parts by weight of bio-based polyimide is dissolved in 60-70 parts by weight of organic solvent, and the mixture is stirred and reacted for 2 hours and then is kept stand for 24 hours to obtain a polyamic acid solution. Further, the precipitant is deionized water or ethanol. Further, the precipitant is added in an amount of 100ml/60-70g of the organic solvent in the first step. Further, in the third step, the deionized water is added at a rate of 20-40 parts by weight per minute. The beneficial effects of the invention are as follows: (1) The invention synthesizes polyimide by taking the bio-based material as a monomer, has simple preparat