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CN-121991454-A - Modified environment-friendly bismaleimide resin material and preparation method thereof

CN121991454ACN 121991454 ACN121991454 ACN 121991454ACN-121991454-A

Abstract

The invention belongs to the technical field of polymer composite materials, and particularly relates to a modified environment-friendly bismaleimide resin material and a preparation method thereof. The resin material comprises bismaleimide resin, allyl compounds, amino modified carbon nano tubes and amino modified tetrapod-like zinc oxide whiskers with the mass ratio of 1 (0.01-0.1). The amino modified tetrapod-like zinc oxide whisker and the amino modified carbon nano tube are compounded, the tetrapod-like whisker structure can be intertwined with the carbon nano tube with a one-dimensional linear structure, the dispersion of the carbon nano tube is promoted, and the problem that the carbon nano tube with the one-dimensional linear structure is easy to agglomerate is solved. In addition, the amino modified four-needle whisker also has better stress transmission and dissipation capability than the common one-dimensional whisker, can improve the rigidity of the composite material, can improve the toughness of the composite material at the same time, has wide application, and can be used as a base material for nonmetal material increase.

Inventors

  • Li Yongdu
  • XING YUNLIANG
  • GU WEIKE

Assignees

  • 山东科宜知芯电子材料有限公司
  • 成都科宜高分子科技有限公司

Dates

Publication Date
20260508
Application Date
20260313

Claims (10)

  1. 1. The modified environment-friendly bismaleimide resin material is characterized by comprising the following components in parts by weight: 50-60 parts of bismaleimide resin, 40-50 parts of allyl compound, 0-3 parts of reinforcing filler, wherein the weight of the reinforcing filler is not 0, and the reinforcing filler consists of (0.01-0.1) amino modified carbon nano tubes and amino modified tetrapod-like zinc oxide whiskers in a mass ratio of 1.
  2. 2. The modified environment-friendly bismaleimide resin material according to claim 1 wherein the bismaleimide resin is one or more of 4, 4-bismaleimide diphenylmethane, 4-bismaleimide diphenyl ether and 4, 4-bismaleimide diphenyl sulfone.
  3. 3. The modified environment-friendly bismaleimide resin material according to claim 1 wherein the allylic compound is one or more of diallyl bisphenol A, diallyl bisphenol S and allyl novolac.
  4. 4. The modified environment-friendly bismaleimide resin material according to claim 1 wherein the amino-modified carbon nanotube is a carbon nanotube modified by an aminosilane coupling agent, and the length of the carbon nanotube is 10 μm or less.
  5. 5. The modified environment-friendly bismaleimide resin material according to claim 1 wherein the amino-modified tetrapod-like zinc oxide whiskers are tetrapod-like zinc oxide whiskers modified with an aminosilane coupling agent.
  6. 6. The modified environment-friendly bismaleimide resin material according to claim 5 wherein the aminosilane coupling agent is one or more of gamma-aminopropyl triethoxysilane, gamma-aminopropyl trimethoxysilane, gamma-aminopropyl methyldiethoxysilane, gamma-aminopropyl methyldimethoxysilane, gamma-aminopropyl ethyldimethoxysilane and gamma-aminopropyl ethyldiethoxysilane.
  7. 7. The method for preparing a modified environment-friendly bismaleimide resin material according to any one of claims 1 to 6, comprising the following steps: (1) Uniformly mixing bismaleimide resin and an allyl compound, and heating and prepolymerizing until the solution is transparent to obtain a prepolymer; (2) Adding reinforcing filler into the prepolymer, and uniformly mixing to obtain a mixture; (3) Pouring the mixture into a mold, vacuum defoaming, and heating for curing to obtain the modified environment-friendly bismaleimide resin material.
  8. 8. The method for preparing a modified environment-friendly bismaleimide resin material according to claim 7 wherein the heating temperature is 120-140 ℃.
  9. 9. The method for preparing a modified environment-friendly bismaleimide resin material according to claim 7 wherein the defoaming time is 10 to 30 minutes.
  10. 10. The method for preparing a modified environment-friendly bismaleimide resin material according to claim 7 wherein the heating and curing process is 145-155 ℃ per 1-1.5h+155-165 ℃ per 1-1.5h+175-185 ℃ per 1-1.5h+195-205 ℃ per 1-1.5h.

Description

Modified environment-friendly bismaleimide resin material and preparation method thereof Technical Field The invention belongs to the technical field of polymer composite materials, and particularly relates to a modified environment-friendly bismaleimide resin material and a preparation method thereof. Background Bismaleimides are a small resin system derived in the development process of polyimide resins, and are thermosetting resins with active functional groups. The imide active end group in the bismaleimide has two carbonyl groups with strong electron withdrawing, so that the electron deficiency of the carbon-carbon double bond reaches the peak, and simultaneously has high reactivity for chemical reaction with other groups. The bismaleimide molecular structure has benzene rings and imide rings with larger steric hindrance and higher rigidity, so that the bismaleimide molecular structure shows excellent comprehensive properties, such as higher heat resistance, flame retardance, higher bending strength, dimensional stability, chemical corrosion resistance and excellent mechanical properties. Is widely applied to the industries of aerospace, military industry, machinery and the like. Bismaleimide resins are important in the field of thermosetting resins and are widely used because of their high temperature resistance, moisture resistance, and oxidation resistance. The internal structure of the bismaleimide monomer contains an amide group, and can generate the reactions such as hydrogen-allyl addition reaction, diels-Alder reaction, michael addition reaction, free radical polymerization and the like. The structure of the bismaleimide determines the property of the bismaleimide to a certain extent, and as the bismaleimide molecular structure contains benzene rings and imide rings, the steric hindrance of the benzene rings is large, and the carbon-carbon bonds cannot rotate randomly, so that the flexibility of the whole molecular chain is not high, and the bismaleimide molecular structure is a rigid chain. Therefore, the bismaleimide resin has high temperature resistance and high mechanical properties. Meanwhile, bismaleimide resins are also widely used as matrix materials for preparing composite materials with excellent properties. However, the rigid backbone makes the bismaleimide resin brittle and poorly soluble, and difficult to mold during processing, so modification of the bismaleimide resin is particularly important. The bismaleimide structure contains an imide ring and a plurality of benzene ring structures with larger volumes, carbon-carbon double bonds in the structure can be conjugated with carbonyl groups at adjacent positions, the carbonyl groups serve as strong electron withdrawing groups, the electron cloud density around the carbon-carbon double bonds can be seriously reduced in a short time, and the carbon-carbon double bonds serve as electron-deficient groups, so that the bismaleimide resin serves as an electron acceptor, and various addition reactions are carried out. The stabilization of the benzene ring structure also imparts excellent properties to aromatic bismaleimides, the most prominent of which is heat resistance, with thermal decomposition temperatures typically above 350 ℃. However, the cross-linking density of the bismaleimide resin is too high, so that the cured product has larger brittleness in the post-treatment process, and the processing range is narrower, thereby greatly limiting the application of the bismaleimide resin in the field of high-strength and high-performance material engineering. Meanwhile, the rigid structure in the bismaleimide molecular structure is a double-edged sword, and excellent mechanical properties can be endowed to the resin. However, in industrial applications, poor toughness of bismaleimide resins is also a key factor limiting development. Therefore, the modification of bismaleimide resins is particularly important. Disclosure of Invention In order to overcome the problems in the prior art, the invention aims to provide a bismaleimide resin composite material which is simple and easy to implement, controllable in process, environment-friendly and suitable for mass production, and a preparation method thereof. The invention solves the technical problems with the following technical proposal: a modified environment-friendly bismaleimide resin material consists of the following components in parts by weight: 50-60 parts of bismaleimide resin, 40-50 parts of allyl compound, 0-3 parts of reinforcing filler, wherein the weight of the reinforcing filler is not 0, and the reinforcing filler consists of (0.01-0.1) amino modified carbon nano tubes and amino modified tetrapod-like zinc oxide whiskers in a mass ratio of 1. Although the bismaleimide resin itself has higher high temperature resistance, excellent mechanical properties and moisture resistance, the characteristics of high melting point, poor solubility in common reagents, higher curing temperature