CN-122011444-A - Straw tar phenol-lignin epoxy carbon fiber reinforced composite material and preparation method and application thereof

CN122011444ACN 122011444 ACN122011444 ACN 122011444ACN-122011444-A

Abstract

The invention discloses a straw tar phenol-lignin epoxy carbon fiber reinforced composite material, a preparation method and application thereof, belonging to the technical field of polymer synthesis; mixing the methylolated alkali lignin with acrylic anhydride to perform esterification reaction to obtain acrylated lignin, performing epoxidation reaction on the acrylated lignin, introducing epoxy groups to form epoxy group grafted lignin (lignin epoxy resin), mixing straw tar phenol with the epoxy group grafted lignin to prepare alkali lignin based epoxy resin, preparing prepreg from surface modified carbon fiber, acetone, a curing agent and the alkali lignin based epoxy resin, and performing hot press molding to prepare the straw tar phenol-lignin epoxy carbon fiber reinforced composite material, thereby solving the problems of environmental pollution and high price of bisphenol A type epoxy resin, and leading the composite material prepared by the method to have wide application prospect in various fields.

Inventors

PANG JIUYIN
ZU SHUTONG
JIANG GUIQUAN
LI CHUANPENG
NIU XIAOYI

Assignees

北华大学

Dates

Publication Date: 20260512
Application Date: 20260306

Claims (10)

1. A preparation method of a straw tar phenol-lignin epoxy carbon fiber reinforced composite material is characterized by comprising the steps of carrying out methylolation treatment on alkali lignin to obtain methylolated alkali lignin, mixing the methylolated alkali lignin with acrylic anhydride to carry out esterification reaction to obtain acrylated lignin, carrying out epoxidation reaction on the acrylated lignin, introducing epoxy groups to form epoxy group grafted lignin, mixing straw tar phenol with the epoxy group grafted lignin to prepare alkali lignin based epoxy resin, preparing prepreg from carbon fiber subjected to surface modification treatment, acetone, a curing agent and the alkali lignin based epoxy resin, and carrying out hot press molding to prepare the straw tar phenol-lignin epoxy carbon fiber reinforced composite material.
2. The preparation method of the straw tar phenol-lignin epoxy carbon fiber reinforced composite material is characterized by comprising the steps of dispersing alkali lignin in water to obtain alkali lignin dispersion liquid, adding NaOH solution and ammonia water into the alkali lignin dispersion liquid, stirring uniformly, adding formaldehyde, reacting under heating, adding acid to adjust the pH value of the solution to be acidic, precipitating, centrifuging, washing, and freeze-drying to obtain the methylolated alkali lignin.
3. The preparation method of the straw tar phenol-lignin epoxy carbon fiber reinforced composite material is characterized by comprising the steps of dispersing methylolated alkali lignin in an organic solvent to form uniform suspension, adding acrylic anhydride and pyridine, reacting under the heating condition under the protective atmosphere, pouring the obtained reaction mixture into ice water to separate out precipitate, filtering, washing and vacuum drying to obtain the acrylated lignin.
4. The method for preparing a straw tar phenol-lignin epoxy-based carbon fiber reinforced composite material according to claim 3, wherein the mass ratio of the methylolated alkali lignin, the acrylic anhydride and the pyridine is 1:2:2.
5. The preparation method of the straw tar phenol-lignin epoxy carbon fiber reinforced composite material is characterized by comprising the steps of dispersing acrylated lignin in methylene dichloride, cooling in an ice bath, adding hydrogen peroxide, reacting in the ice bath, adjusting the pH to 6.0-6.5 after the reaction is finished, adding sodium chloride solution to precipitate solid, neutralizing residual acid with saturated sodium bicarbonate solution, washing with water, filtering, and drying in vacuum to obtain the epoxy grafted lignin.
6. The method for preparing the straw tar phenol-lignin epoxy carbon fiber reinforced composite material according to claim 1, wherein the method for preparing the straw tar phenol is characterized by adding a sodium hydroxide solution into straw tar, reacting under heating, filtering, collecting supernatant, adjusting the pH of the supernatant to 3, standing until precipitation is generated, centrifuging and collecting the precipitation, and obtaining the straw tar phenol.
7. The preparation method of the straw tar phenol-lignin epoxy carbon fiber reinforced composite material according to claim 1, which is characterized by comprising the steps of mixing straw tar phenol and lignin grafted by epoxy groups into N, N-dimethylformamide, stirring and dissolving at 60 ℃, heating to 85 ℃, adding sodium hydroxide solution to maintain pH=9, reacting for 3h, neutralizing to neutrality by hydrochloric acid, removing the N, N-dimethylformamide by rotary evaporation, dissolving residues by toluene, washing to remove salt, drying by anhydrous sodium sulfate, and concentrating to obtain brown viscous resin, namely the brown viscous resin.
8. The method for preparing a straw tar phenol-lignin epoxy-based carbon fiber reinforced composite material according to claim 1, wherein the mass ratio of the alkali lignin-based epoxy resin to the total mass of the alkali lignin-based epoxy resin and the surface-modified carbon fiber is 40%; the usage amount of the curing agent is 30% of the mass of the alkali lignin-based epoxy resin.
9. The straw tar phenol-lignin epoxy-based carbon fiber reinforced composite material is characterized by being prepared by the preparation method according to any one of claims 1-8.
10. Use of the straw tar phenol-lignin epoxy-based carbon fiber reinforced composite material according to claim 9 in the aerospace field, the transportation field, the energy environmental protection field and the construction engineering field.

Description

Straw tar phenol-lignin epoxy carbon fiber reinforced composite material and preparation method and application thereof Technical Field The invention belongs to the technical field of polymer synthesis, and particularly relates to a straw tar phenol-lignin epoxy carbon fiber reinforced composite material, and a preparation method and application thereof. Background Fossil energy depletion and pollution exacerbation have prompted the search for sustainable alternatives to petrochemicals. Lignin is the second largest natural polymeric material next to cellulose and can be obtained from agricultural or pulp industry waste. The carbon fiber precursor contains a large amount of aromatic ring structures, can be used as a precursor for preparing the carbon fiber, can reduce the cost by more than 50% compared with polyacrylonitrile-based carbon fiber, and has the advantages of obvious low cost and sustainability. The carbon content of lignin is about 60% -66%, which is far higher than that of cellulose (about 40%), and the lignin is provided with an aromatic skeleton, and can be self-crosslinked in the carbonization process at 800-2800 ℃, so that the preoxidation time is reduced by more than 30%, and the energy consumption is reduced by 20%. In addition, the straw tar is a product of the treatment process such as straw pyrolysis, and the effective utilization degree is low. The extraction of straw tar phenol from straw tar is one of methods for improving the comprehensive utilization rate of straw. However, the straw tar is widely considered as a byproduct in the pyrolysis process in the industry, and has the advantages of complex components, more impurities, high treatment cost, direct combustion as fuel and great difficulty in high-value utilization. More than 90% of carbon fibers in the world depend on petroleum derived Polyacrylonitrile (PAN) as a precursor, and the production thereof needs to undergo complex spinning, pre-oxidation and carbonization processes, and the energy consumption accounts for more than 30% of the total cost. The carbon fiber is used as a novel composite material reinforcement body with multiple excellent performances such as high strength, low density, corrosion resistance, high temperature resistance and the like, and has the function core of solving the technical bottleneck of traditional material metal, plastic and glass fiber in a specific scene through performance energization, and is widely permeated in the fields of aerospace, transportation, energy environmental protection, constructional engineering and the like. After the carbon fiber (reinforcement) is combined with the epoxy resin (matrix), the formed carbon fiber reinforced epoxy resin composite material (Carbon Fiber Reinforced Epoxy Polymer, abbreviated as CFRP) is one of the most widely used advanced composite materials at present. The combination of the carbon fiber and the epoxy resin is essentially the precise complementation of the reinforcement (high strength) and the matrix (strong bonding and easy forming), wherein the epoxy resin enables the carbon fiber to be 'usable, good and durable', the carbon fiber enables the epoxy resin to be 'strengthened, rigid and light', and the finally formed CFRP becomes one of core materials for solving the contradiction between the light weight and high performance of the modern industry. In the current epoxy resin production, bisphenol A type epoxy resin is most commonly used, and is prepared by condensation reaction of bisphenol A and epichlorohydrin under alkaline condition, and the consumption of the bisphenol A type epoxy resin accounts for about 70 to 80 percent of the total consumption of the epoxy resin. However, the bisphenol A type epoxy resin product cannot actively lead to the market due to the lag in production process and higher production cost, and has the problems of great harm to the environment and human bodies and the like. Therefore, by fusing material innovation, process innovation and intelligent technology, a biomass substitute of bisphenol A with low cost and no pollution is searched, and the development of industry to high performance, greenization and intelligent is promoted to be a hot spot of current research. Disclosure of Invention In order to solve the technical problems, the invention provides a straw tar phenol-lignin epoxy carbon fiber reinforced composite material, and a preparation method and application thereof. The carbon fiber reinforced composite material adopting the straw tar phenol-lignin-based epoxy resin as the matrix has excellent performances, and the raw material modified lignin particles (methylolated alkali lignin and epoxidized lignin) used by the resin matrix have the advantages of high activity, good performance, wide sources, low cost, reproducibility, degradability and recycling and the like, so that the problems of environmental pollution and high price of bisphenol A epoxy resin are solved, and the composite material prepare