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A kind of method of chain extension modification benzoxazine resin in maleimide

A technology of maleimide and bismaleimide, which is applied in the field of thermosetting resin preparation, can solve the problems that the toughness of the polymer has not been significantly improved, the curing temperature of the benzoxazine resin is high, and the toughness of the cured product is poor. Achieve the effects of increasing molecular designability, promoting ring-opening reaction, and reducing polymerization reaction temperature

Active Publication Date: 2020-05-19
成都科宜高分子科技有限公司
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0005] However, benzoxazine resins still have disadvantages such as high curing temperature and poor toughness of corresponding cured products.
Based on the flexibility of molecular design of benzoxazine, the Chinese invention patents "A Preparation Method for Bisphenol A-Type Benzoxazine Containing Maleimide" (application number 201310296947.7), "A Kind of Ortho-Maleimide Imine monofunctional benzoxazine monomer and its preparation method" (application number 201610762806.3) and "a maleimide group-terminated benzoxazine oligomer and its preparation method" ( 201611180419.5), etc., the maleimide functional group is introduced into the molecular structure of benzoxazine as the substituent corresponding to the amine source or phenol source, and the crosslinking density of the corresponding polymer is further increased through the reaction of the maleimide functional group. Improve its heat resistance, but the toughness of the polymer has not been significantly improved, or even decreased

Method used

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  • A kind of method of chain extension modification benzoxazine resin in maleimide
  • A kind of method of chain extension modification benzoxazine resin in maleimide
  • A kind of method of chain extension modification benzoxazine resin in maleimide

Examples

Experimental program
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Effect test

Embodiment 1

[0043] Add 500ml of DMF into a three-necked flask equipped with a stirrer, a condenser, and a thermometer, slowly raise the temperature to 65°C, add 1mol (198g) of 4,4'-diaminodiphenylmethane, and pass in nitrogen protection. In this case, the diamine is completely dissolved. Then, slowly raise the temperature to 90°C, add 0.5mol (179g) of diphenylmethane type bismaleimide in batches within 30min, keep the temperature for 1.5h, and then slowly cool to 30-40°C to obtain a compound whose terminal group is an amino group. Bismaleimide and diamine chain extension product solution, kept warm for use.

[0044]Add 1mol (134g) of 2-allylphenol, 2.3mol (69g) of paraformaldehyde and 400ml of toluene into a four-neck flask equipped with a stirrer, condenser, thermometer, and constant pressure funnel, and slowly raise the temperature to 55-60 ℃. Gradually add the above-mentioned amino-terminated bismaleimide and diamine chain extension product solution to the system dropwise, and the dr...

Embodiment 2

[0047] Add 300ml of DMAc into a three-necked flask equipped with a stirrer, a condenser, and a thermometer, slowly heat up to 60°C, add 1.4mol (151.2g) of p-phenylenediamine, and pass in nitrogen protection. Under the condition of stirring, the two The amine is completely dissolved. Then, slowly raise the temperature to 90°C, add 0.5mol (179g) of diphenylmethane type bismaleimide in batches within 40min, keep the temperature for 1.0h, and then slowly cool to 30-40°C to obtain a compound whose terminal group is an amino group. Bismaleimide and diamine chain extension product solution, kept warm for use.

[0048] Add 1.8mol (169.2g) of phenol, 4.1mol (123g) of paraformaldehyde and 600ml of xylene into a four-neck flask equipped with a stirrer, condenser, thermometer, and constant pressure funnel, and slowly raise the temperature to 55-60°C. Gradually add the above-mentioned amino-terminated bismaleimide and diamine chain extension product solution to the system dropwise, and th...

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Abstract

The invention discloses a method for modifying benzoxazine resin through chain extension in maleimide. The method is characterized by synthesizing a prepolymer which takes an amino group as a terminalgroup by adopting diamine for carrying out the chain extension on bismaleimide, using the prepolymer as an amine source, and carrying out Mannich condensation polymerization on the prepolymer with aphenolic compound and formaldehyde (or polyoxymethylene), thus preparing corresponding benzoxazine oligomers. The synthesized prepolymer prepared from the maleimide and the diamine contains a primaryamine terminal group, and meanwhile, a molecular structure also contains a reactive secondary amine group; on one hand, ring-opening reaction of benzoxazine can be promoted, and the curing reaction temperature can be reduced; on the other hand, the prepolymer can be used as a reactive active point and can react with epoxy resin or isocyanate, so that high performance of a polymer can be further realized.

Description

technical field [0001] The invention belongs to the field of thermosetting resin preparation, and in particular relates to a method for modifying benzoxazine resin by internal chain extension of maleimide. Background technique [0002] Bismaleimide (BMI) is a thermosetting resin with excellent heat resistance. It has good heat resistance, radiation resistance, moisture resistance, aging resistance and electrical insulation. Its application range is more and more extensive. However, the bismaleimide resin itself has a high melting point, poor solubility, and poor toughness of the cured product, and the unmodified bismaleimide resin has no practical application value. Aiming at the shortcomings of maleimide resins, research at home and abroad mainly uses diamine compounds, allyl bisphenol A and its derivatives to modify them, and obtains prepolymers with maleimide functional groups as terminal groups. Polymer can not only reduce the melting point of BMI monomer, improve the s...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C08G14/06C08G14/09
CPCC08G14/06
Inventor 夏益青盛玉萍高晨李新跃唐利平侯真良
Owner 成都科宜高分子科技有限公司
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