碳硼烷二元酸的合成与耐热性能研究

Study on synthesis and heat resistance of carborane diacid

以A(1,2-碳硼烷)为原料,分别采用琼斯试剂氧化法、CO2法和ClCOOCH3(氯甲酸甲酯)法合成了D(1,2-二羧基碳硼烷);然后D和B(1,2-二羟甲基碳硼烷)进一步酯化缩聚后,成功合成了P6(聚1,2-二羧基碳硼烷-1,2-二羟甲基碳硼烷酯)。研究结果表明:3种合成方法均能成功合成D,其中CO2法是最理想的合成方法;碳硼烷基团的引入,有效提高了P6的耐热性能(N2气氛中P6失重5%时的热解温度为190℃,700℃时的残炭率为59%);P6在耐高温领域中具有良好的应用前景,也是制备耐高温型PU(聚氨酯)胶粘剂的宝贵原材料。

With A （ 1,2- carborane） as raw material, a D （ 1,2-dicarboxyl carborane） was respectively synthesized by Jones reagent oxidation, CO2 or C1COOCH3（methyl chloroformate） methods. Then, the P6[poly（1,2-dicarboxyl carborane-l,2- dihydroxymethyl carborane ester）] was successfully synthesized by further esterification and polycondensation between D and B （ 1,2-dihydroxymethyl carborane）. The research results showed that the CO2 method was an optimal synthesis method in three kinds of synthesis methods,which could successfully synthesize D. The introduced carborane group could effectively enhance the heat resistance of P6 because pyrolysis temperature was 190℃ at 5% weight loss ,and the mass fraction of residual carbon was 59% at 700 ℃ for P6 in N2. The P6 had good application prospect in the field of high-temperature resistance, and it was also a valuable raw material for preparing PU （polyurethane） adhesives with high-temperature resistance.