新型烯丙基芳香二胺的合成及其固化特性研究

收稿日期 2006-02-22

基金项目 国家自然科学基金资助项目(50403025)

作者简介 刘金刚(1973 ),男,博士,副研究员,研究方向:高性能聚合物电子材料。E -mail:liujg@iccas ac cn

新型烯丙基芳香二胺的合成及其固化特性研究

刘金刚,赵晓娟,杨海霞,石津旗

(中国科学院化学研究所高技术材料实验室,北京100080)

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!摘!要:以溴丙烯和芳香族二酚为原料,通过缩合、重排2步反应制备了一系列烯丙基二酚化合物。以所合成的烯丙基二酚为原料,进一步与4-溴硝基苯,通过Williamson 反应和还原反应制备了一系列新型烯丙基取代二胺单体。以2,2-双[4∀-(4#-氨基苯氧基)-3∀-烯丙基苯基]丙烷(A PAP)为例,研究了其对环氧树脂以及双马来酰亚胺树脂的固化行为。结果表明,这类二胺固化剂对于上述树脂体系均具有良好的固化效果,固化物具有良好的耐热性能以及耐溶剂稳定性。

关键词:烯丙基;二胺;固化剂;环氧树脂;双马来酰亚胺

中图分类号:T Q246 3;T Q323 5!!文献标识码:A !!文章编号:1002-7432(2006)03-0005-04

Synthesis and properties of novel allyl -containing diamine curing agents

LIU Jin-gang,ZHAO Xiao-juan,YANG Hai-xia,SH I Jin-qi

(Laboratory o f Advanced Polymer Materials,I nstitute o f Chemistry,Chinese Academy of Sciences,Beij ing 100080)Abstract:A series of allyl bisphenol compounds had been synthesized via the condensation reaction of ally l bro m ide and arom atic diphenols,followed by thermally rearrang ement reaction.Novel allyl-containing diamine curing agents w ere developed by the Williamson ∀s reaction of the obtained ally l bisphenol compounds and 4-bro mo-1-nitrobenzene,follow ed by reduction reactions.The curing properties of the new curing agent,2,2-bis [4∀-(4#-aminophenox y )-3∀-allylphenyl]propane (APAP)to epox y and bismaleimides were re searched.It w as shown that the curing agent exhibited good curing effect to the resins,the curing reactions of APAP-BM DM and APAP-DGEBA w ere taken place over a wide range of temperature,their temperature at exothermal peak were 256 2and 190 7degrees respectively,the g lass transition temperature of cured APAP-DGEBA w as 154 4degrees but there w as not occured the g lass state transition for the cured APAP-BM DM in test conditions and the curing resin show ed good thermal stability and solvent-resistance,such that the starting decomposition temperature of APAP-BMDM cured and the carbon residue in 700degrees w ere 426 8degrees and 46 5percent and w ere increased w ith 52 6deg rees and 23 4percent respectivelly more than that of APAP -DGEBA cured and the tw o thermosets were hardly dissoved in common solvents such as NM P DMF DMAc phenol solvent and strong basic (30%NaOH)、strong acid (concentrated sulfuric acid)solutions.Key words:allyl;diamine;curing agent;epox y;bismaleimide 0!引!言

固化剂在高性能聚合物基复合材料的基础与应用研究中占有十分重要的地位[1]

。固化剂的好坏将直接影响固化物的综合性能,因此对于新型固化

剂的研究非常活跃[2]。环氧树脂与双马来酰亚胺(BMI)是2种应用广泛的热固性树脂,对于这2类树脂的固化研究在整个树脂研究体系中占有很大的比重。环氧树脂的固化剂种类很多,其中芳香族二胺单体是一类优良的固化剂,由其固化的环氧树脂具有良好的耐高温与环境稳定性[3]。

BM I 树脂在加热过程中自身可发生交联反应,由于交联密度高,致使固化物的脆性较大[4]。近年来,对于BM I 树脂的增韧研究取得了显著的进

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第21卷第3期Vol 21!No 3!

2006年5月

M ay !2006热固性树脂

Thermosetting Resin