催化热分解法制备含P-C键多元异氰酸酯的研究

Preparation of Polyisocyanate Containing P-C Bonds by Catalytic Thermal Decomposition

以二(N-甲氧羰基氨甲基)苄基氧化膦(BCBPO)和三(N-甲氧羰基氨甲基)氧化膦(TCPO)为原料,采用热重法筛选了热分解催化剂,通过催化热分解法制备了含P-C键多元异氰酸酯,并分别采用TG-GC-MS联用法和变温红外光谱法分析了催化热分解BCBPO和TCPO的气态产物和凝聚态产物。结果表明,相对于直接热分解,氧化锌为催化剂热分解BCBPO和TCPO的热分解温度分别降低了29℃和25℃;BCBPO、TCPO在氧化锌催化作用下第一阶段热分解的气态产物为甲醇、凝聚态产物为异氰酸酯;红外光谱分析结果显示,在氧化锌催化作用下,TCPO热分解的凝聚态产物与苯胺反应的固体产物为相应异氰酸酯TPI与苯胺反应的产物脲。

Using di(N-methoxycarbonyl aminomethyl)benzyl phosphine oxide(BCBPO)and tri(N-methoxycarbonyl aminomethyl)phosphine oxide(TCPO)as raw materials,we screened pyrolysis catalyst by a thermogravimetric method,and prepared polyisocyanate containing P-C bonds by a catalytic thermal decomposition method.Moreover,we analyzed the gaseous and condensed products of BCBPO and TCPO by TG-GC-MS and variable temperature FTIR spectroscopy,respectively.The results show that,compared with the direct thermal decomposition,the thermal decomposition temperatures of BCBPO and TCPO under the catalysis of ZnO decrease by 29℃and 25℃,respectively.In the first stage of thermal decomposition of BCBPO and TCPO under the catalysis of ZnO,the gaseous product is methanol,and the condensed product is isocyanate.The results of FTIR analysis show that the solid product of the reaction between the condensed product of TCPO thermal decomposition and aniline under the catalysis of ZnO is urea,which is consistent with the product of the reaction of the corresponding isocyanate TPI with aniline.