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CN-120923778-B - Modified benzoxazine resin and preparation method and application thereof

CN120923778BCN 120923778 BCN120923778 BCN 120923778BCN-120923778-B

Abstract

The invention relates to the field of benzoxazines, in particular to a modified benzoxazine resin and a preparation method and application thereof, wherein the preparation method of the modified benzoxazine resin comprises the following steps of S1, carrying out a first-stage reaction, namely uniformly stirring an alkyl amine type compound, formaldehyde and an organic solvent, carrying out a heating reaction, wherein the alkyl amine type compound is one or more of short aliphatic chain amine, alicyclic polyamine and monoamine type compound, S2, carrying out a second-stage reaction, namely adding a phenol type compound containing unsaturated hydrocarbon groups, carrying out a heating reaction, and S3, heating and removing small molecular impurities and byproducts under negative pressure to obtain the modified benzoxazine resin.

Inventors

  • XIE JIANQING
  • ZHANG XING
  • Liao Yetong
  • CHEN XINGWEI
  • WEI JIAJUN

Assignees

  • 同宇新材料(广东)股份有限公司

Dates

Publication Date
20260505
Application Date
20250827

Claims (8)

  1. 1. The preparation method of the modified benzoxazine resin is characterized by comprising the following steps of: s1, a first-stage reaction, namely uniformly stirring an alkyl amine compound, formaldehyde and an organic solvent, heating to 60-90 ℃ and carrying out heat preservation reaction for 0.5-2h; The alkyl amine type compound is one or more of short aliphatic chain amine, alicyclic polyamine and monoamine type compound; S2, a second stage reaction, namely adding a phenolic compound containing unsaturated hydrocarbon groups, heating to 70-100 ℃ and preserving heat for 2-5h; s3, heating, and removing small molecular impurities and byproducts under negative pressure to obtain modified benzoxazine resin; wherein the unsaturated hydrocarbon group-containing phenolic compound is a bisphenol compound and/or the alkyl amine compound is a diamine compound.
  2. 2. The method for preparing a modified benzoxazine resin according to claim 1, wherein the carbon chain length of the short aliphatic chain amine is C1-C4.
  3. 3. The method for producing a modified benzoxazine resin according to claim 1, wherein the alicyclic polyamine is cyclohexanediamine, cyclopentanediamine, 4-diaminodicyclohexylmethane, cyclopropylamine, cyclopentylamine, cyclohexylamine, cyclohexanedimethylamine or cyclopentanediamine.
  4. 4. The method for preparing a modified benzoxazine resin according to claim 1, wherein the unsaturated hydrocarbon-based phenolic compound is an allyl-substituted polyphenol compound or an unsaturated hydrocarbon-substituted monophenol compound.
  5. 5. The method for preparing a modified benzoxazine resin according to claim 1, wherein in the step S1, the organic solvent is a polar or nonpolar solvent with a boiling point not higher than 170 ℃; in the step S3, micromolecular impurities and byproducts are removed under the negative pressure for 1-6 hours at the temperature of 100-170 ℃.
  6. 6. A modified benzoxazine resin prepared by the method for preparing a modified benzoxazine resin according to any one of claims 1 to 5, wherein the modified benzoxazine resin has a benzoxazine structure of not less than one unsaturated hydrocarbon group.
  7. 7. A modified benzoxazine resin according to claim 6, wherein the modified benzoxazine resin has a weight average molecular weight greater than 2000.
  8. 8. Use of a modified benzoxazine resin according to any one of claims 6-7 as a circuit dielectric material in a high frequency high speed electronic copper clad laminate.

Description

Modified benzoxazine resin and preparation method and application thereof Technical Field The invention relates to the field of benzoxazines, in particular to a modified benzoxazine resin and a preparation method and application thereof. Background With the rapid development of artificial intelligent chips, 5G communication and intelligent driving of new energy automobiles, electronic components rapidly develop towards higher speed and higher integration level. Under the condition that the wiring density of the ultra-large scale integrated circuit is increased, the resistance of the metal interconnection wire in the electronic component and the capacitance of the interlayer dielectric medium easily form RC delay-CAPACITANCE DELAY effect, so that adverse effects such as signal transmission delay, noise interference and power loss are caused. In order to reduce interconnect delay, power consumption, and cross-talk, it is desirable to develop low Dk, low Df dielectric materials that provide faster signal transmission when the material has a lower dielectric constant, lower signal delay, lower signal propagation loss rate, and higher signal fidelity. The benzoxazine is a benzo six-membered heterocyclic compound synthesized by taking phenolic compounds, amine compounds and formaldehyde as raw materials, can be subjected to ring-opening polymerization under the action of heating or a catalyst to generate a nitrogen-containing reticular structure polymer, and is a novel low-surface energy material with the characteristics of flexible molecular design, small curing volume shrinkage, low surface energy and the like. The conventional bisphenol (bisphenol F and bisphenol A), diamine (ODA and DMA) and other benzoxazine resins in the market can be applied to printed circuit boards, and can meet the application requirements of the medium-low end field, but the high-frequency dielectric property and the heat resistance of the benzoxazine resins cannot meet the application requirements of the high-end field high-integrated circuit dielectric materials, so that the polarity of the materials is required to be weakened, and the dielectric property is further improved, but the monophenol monoamine Shan oxazine ring resin with low olefin groups is easy to cause the abnormal conditions of incomplete polymerization reaction, split phase and the like due to the fact that the polarity of the materials is weakened, and the heat resistance of the materials is insufficient, and the storage stability and the processing property of the materials are poor, so that the benzoxazine resin cannot be industrially applied to high-frequency high-speed electronic copper clad plates. Disclosure of Invention The invention aims to provide a modified benzoxazine resin, a preparation method and application thereof, and solves the problems of insufficient storage stability and processing performance of the existing benzoxazine resin while improving dielectric properties. In order to achieve the purpose, the invention adopts the following technical scheme: A preparation method of modified benzoxazine resin comprises the following steps: s1, a first-stage reaction, namely uniformly stirring an alkyl amine compound, formaldehyde and an organic solvent, and heating for reaction; The alkyl amine type compound is one or more of short aliphatic chain amine, alicyclic polyamine and monoamine type compound; s2, a second-stage reaction, namely adding a phenol compound containing unsaturated hydrocarbon groups, and heating for reaction; S3, heating, and removing small molecular impurities and byproducts under negative pressure to obtain the modified benzoxazine resin. Preferably, the alkyl amine type compound is a diamine type compound and/or the phenol type compound containing an unsaturated hydrocarbon group is a bisphenol type compound. Preferably, in the step S1, heating to 60-90 ℃ and preserving heat for reaction for 0.5-2h; in the step S2, the mixture is heated to 70-100 ℃ and is reacted for 2-5 hours with heat preservation. Preferably, the short fatty chain amine has a carbon chain length of C1-C4. Preferably, the alicyclic polyamine is cyclohexanediamine, cyclopentanediamine, 4-diaminodicyclohexylmethane, cyclopropylamine, cyclopentylamine, cyclohexylamine, cyclohexanedimethylamine, or cyclopentanediamine. Preferably, the unsaturated hydrocarbylphenol compound is an allyl-substituted polyphenol compound or an unsaturated hydrocarbyl-substituted monophenol compound. Preferably, in step S1, the organic solvent is a polar or nonpolar solvent having a boiling point of not higher than 170 ℃; in the step S3, micromolecular impurities and byproducts are removed under the negative pressure for 1-6 hours at the temperature of 100-170 ℃. A modified benzoxazine resin prepared by the method for preparing a modified benzoxazine resin according to any one of the above, wherein the benzoxazine structure of the modified benzoxazine resin is not less than one unsaturated