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CN-122011677-A - Method for rapidly preparing epoxy composite material by laser-triggered front line polymerization

CN122011677ACN 122011677 ACN122011677 ACN 122011677ACN-122011677-A

Abstract

The invention discloses a method for rapidly preparing an epoxy composite material by laser-triggered front-line polymerization, which comprises the following steps of (1) ball-milling and dispersing epoxy resin, a monomer, a free radical thermal initiator, a cationic photoinitiator and a carbon nano tube to obtain a component A, (2) ball-milling and dispersing epoxy resin, a monomer, a free radical thermal initiator, a cationic photoinitiator and carbon black to obtain a component B, (3) ball-milling and dispersing epoxy resin, a monomer, a free radical thermal initiator, a cationic photoinitiator and a carbon fiber to obtain a component C, (4) respectively and uniformly mixing A, B, C components, then injecting the mixture into a mold, and irradiating a mold port with laser until polymerization begins. The invention can realize the preparation of the epoxy composite material with high content of dark filler, the polymerization process can be completed in a short period of time, and a new thought is provided for preparing the high-performance composite material by front-line polymerization.

Inventors

  • SANG XINXIN
  • ZHU ZILONG
  • ZHANG CHAO

Assignees

  • 江南大学
  • 郑州大学

Dates

Publication Date
20260512
Application Date
20260205

Claims (10)

  1. 1. A method for rapidly preparing an epoxy composite material by laser-triggered front-line polymerization, which is characterized by comprising the following steps: The method comprises the following steps of (1) performing ball milling and dispersing on 10-90 parts by weight of epoxy resin, 10-100 parts by weight of monomer, 0.25-5 parts by weight of free radical thermal initiator, 0.25-5 parts by weight of cationic photoinitiator and 0.1-10 parts by weight of carbon nano tube to obtain a component A; Step (2), ball-milling and dispersing 10-90 parts of epoxy resin, 10-100 parts of monomer, 0.25-5 parts of free radical thermal initiator, 0.25-5 parts of cationic photoinitiator and 0.1-10 parts of carbon black by weight to prepare a component B; Step (3), ball-milling and dispersing 10-90 parts of epoxy resin, 10-100 parts of monomer, 0.25-5 parts of free radical thermal initiator, 0.25-5 parts of cationic photoinitiator and 0.1-10 parts of carbon fiber by weight to prepare a component C; step (4) respectively mixing the component A, the component B and the component C, and injecting the mixture into a die; Step (5) is excited at the mold port with 980 near infrared laser irradiation of nm until the light source is removed after polymerization has begun.
  2. 2. The method for rapidly preparing an epoxy composite material by laser-triggered front-line polymerization according to claim 1, wherein the epoxy resin is one or more selected from the group consisting of glycidyl ether epoxy resin, glycidyl ester epoxy resin, glycidyl amine epoxy resin, bisphenol a type epoxy vinyl resin.
  3. 3. The method for rapidly preparing an epoxy composite material by laser-triggered front-line polymerization according to claim 1, wherein the monomer is one or more selected from vinyl ethers, aliphatic epoxy monomers and oxacycloalkanes.
  4. 4. A method for rapid preparation of epoxy composite material by laser triggered front-line polymerization according to claim 1, wherein the free radical thermal initiator comprises benzopinacol TPED, azobisisobutyronitrile AIBN, azobisisoheptonitrile ABVN, dibenzoyl peroxide BPO, etc.; The cationic photoinitiator comprises one or more of 4-octoxydiphenyl iodohexafluoroantimonate IOD-8SbF 6 , tetraalkyl (perfluoro-tert-butyloxy) aluminate anions.
  5. 5. The method for rapidly preparing an epoxy composite material by laser-triggered front-line polymerization according to claim 1, wherein the mass ratio of the cationic photoinitiator to the free radical thermal initiator is 1:1.
  6. 6. The method for rapidly preparing the epoxy composite material by laser-triggered front-line polymerization according to claim 1, wherein the length of the carbon fiber is 0.05-1 mm.
  7. 7. The method for rapidly preparing an epoxy composite material by laser-triggered front-line polymerization according to claim 1, wherein the diameter of the carbon nanotube is 0.4-50 nm.
  8. 8. The method for rapid preparation of epoxy composite material by laser triggered front line polymerization according to claim 1, wherein the time of irradiation of the mold port with 980-nm near infrared laser in step (5) is 3-10 s.
  9. 9. An epoxy composite prepared according to the method of any one of claims 1-8.
  10. 10. An epoxy composite according to claim 9, wherein the epoxy composite has a tensile strength of 76-89 MPa, a tensile modulus of elasticity of 3.1-3.9 GPa, a flexural strength of 108-125. 125 MPa, a flexural modulus of 3.9-4.6 GPa, a glass transition temperature of 121-136 ℃ and a cure time of 1-3 min.

Description

Method for rapidly preparing epoxy composite material by laser-triggered front line polymerization Technical Field The invention relates to the technical field of preparation of polymer composite materials, in particular to a rapid curing method of an epoxy resin/dark filler composite system based on laser thermal effect triggering front line polymerization (Frontal Polymerization, FP), which is suitable for efficient molding of composite materials with high content of dark fillers such as carbon fibers, carbon nanotubes, carbon black and the like. Background In recent years, epoxy-based composite materials, especially systems composited with high-performance carbonaceous materials (carbon fibers, carbon nanotubes, carbon black, etc.), are excellent representatives of modern material science and engineering. The epoxy resin has excellent cohesiveness, chemical resistance and designability, and excellent mechanical, electrical and thermal properties of the reinforcement/filler, so that the epoxy resin realizes light weight, high performance, multifunction and long service life, and becomes a key enabling material for promoting technical innovation and industrial upgrading in various fields such as aerospace, new energy, traffic, electronics and sports. The importance of the material is not only in the remarkable improvement of the performance of the existing products, but also in that the material provides a wide material foundation for a more efficient, intelligent and sustainable technical solution in the future. At present, epoxy-based composite materials are often prepared in a heat curing mode, curing agents (such as amines, anhydrides and the like) are added into a resin formula, and a three-dimensional polymer network is generated through a crosslinking curing reaction. Thermal curing generally requires a long reaction time, and generally requires a reaction under a high-temperature environment, which is time-consuming and energy-consuming and is liable to cause environmental pollution. Ultraviolet light-initiated free radical-induced cationic front-line polymerization (UV-RICFP) is a novel front-line polymerization mode, in which onium salt photoinitiators are first photolyzed to produce superacids, which protonate monomer molecules and initiate polymerization. The heat released by this process warms the sample, causing the radical thermal initiator to decompose into radicals. The iodonium salt has high enough oxidizing property, and the generated free radical and the iodonium salt generate oxidation-reduction reaction, so that the iodonium salt releases another molecule of super acid, and polymerization is continuously initiated to form a front line, and the photo-curing of the epoxy resin can be rapidly realized. However, due to the weak penetration of UV light and the shielding of the filler from UV light, UV-RICFP is difficult to produce in front of high content dark filler composites. Therefore, the development of a novel front-line polymerization preparation method which has the characteristics of simplicity, convenience, rapidness, energy conservation, environmental protection and the like and can realize the preparation of the high-content deep-color filler epoxy composite material has very important significance and value. Disclosure of Invention The invention aims to solve the problems, and provides a rapid curing method of an epoxy resin/dark filler composite system based on laser thermal effect triggering front line polymerization. The invention adopts a laser mode to trigger front line polymerization so as to overcome the shielding effect of filler on ultraviolet light in the UV-RICFP process, the system is heated to the decomposition temperature of a thermal initiator through the thermal effect of the filler to decompose the thermal initiator into free radicals, then the free radicals and iodonium salt in the system are subjected to redox action to decompose a molecule of super acid, thereby initiating epoxy ring opening in the system and starting polymerization heat release, at the moment, a light source is removed, and the system continuously decomposes the free radical thermal initiator by the heat generated by the polymerization heat release, so that circulation is realized, a front line is formed, and the curing of the system is completed. The whole polymerization process is completed within a few minutes, and laser-triggered front-line polymerization provides a new idea for preparing the epoxy composite material by front-line polymerization. The technical scheme adopted by the invention is as follows: the first object of the invention is to provide a method for rapidly preparing an epoxy composite material by laser-triggered front-line polymerization, which comprises the following steps: The method comprises the following steps of (1) performing ball milling and dispersing on 10-90 parts by weight of epoxy resin, 10-100 parts by weight of monomer, 0.25-5 parts by weight of free ra