偏苯三酸酐聚酯多元醇的合成及其在PU硬泡中的应用研究  

Research on the synthesis of trimellitic anhydride polyester polyols and its application in the PU rigid foams

作　　者：蒋文俊[1,2,3] 姚其胜 范仲勇[2] 侯一斌 陆企亭 

机构地区：[1]上海康达化工新材料股份有限公司,上海201201 [2]复旦大学材料科学系,上海200433 [3]上海胶粘剂工程技术研究中心,上海201201

出　　处：《功能材料》2013年第17期2578-2582,共5页Journal of Functional Materials

基　　金：上海市科学技术委员会资助项目(11DZ2283500);浦东新区科技发展基金资助项目(298.10X-11)

摘　　要：以偏苯三酸酐、乙二醇或1,3-丁二醇为原料,单丁基氧化锡为催化剂,成功合成出多官能高羟值的偏苯三酸酐-乙二醇聚酯多元醇(TEPES)、偏苯三酸酐-1,3-丁二醇聚酯多元醇(TBPES)。结果显示,TE-PES的羟值、数均官能度(fn)及重均官能度(fw)分别为400.0mg KOH/g、6.55、7.31,TBPES的羟值、fn及fw分别为357.2mg KOH/g、5.87、6.49,且TB-PES的分子量分布较TEPES窄。1 H NMR谱与TGA分析表明,在反应过程中二元醇与偏苯三酸酐之间不仅存在单羟基的酯化反应,也存在双羟基的酯化反应;TBPES低温热稳定性比TEPES好,而其高温热稳定性不如后者。以聚醚多元醇GR-835G、TEPES、TB-PES、多亚甲基多苯基多异氰酸酯PM-200为主要原料,制备出多种不同复配多元醇体系的60kg/m3表观密度的PU硬泡。相比单一的GR-835G体系,TEPES与GR-835G的复配体系对PU硬泡压缩模量的改善有利,且其改善效果要好于TBPES与GR-835G的复配体系。同时,TEPES的掺入会损耗一定的压缩强度,而TBPES的掺入能使压缩性能整体都有提高。The trimellitic anhydride-ethanediol polyester （TEPES） and the trimellitic anhydride-l,3-butanediol polyester （TBPES） have been synthesized with trimellitic anhydride （TMA）, ethanediol （EG） or 1,3-butane- diol （1,3-BG） as raw materials, and monobutyl tin oxide as the catalyst. The results show that, the hydroxyl value, number average functionality （fn） and weight average functionality （fw） of TEPES are 400.0rag KOH/ g, 6.55 and 7.3l, respectively. The hydroxyl value, fn and fw of TEPES are 357.2rag KOH/g, 5.87 and 6.49, respectively. It can be seen that TEPES has a wider molecular weight distribution than TBPES. 1H NMR spectra and TGA curves reveal that, during the reaction there are not only a single hydroxyl reaction, but also a dihydroxy esterification reaction between dihydroxy alcohol and TMA, which further verify the GPC re- sults. In addition, the synthesized polyester polyols both have a few raw dihydroxy alcohol, which was also i- dentified by TGA. It was indicated that TBPES has a better low temperature thermal stability than TEPES, while its high temperature thermal stability was worse than TEPES. With the same apparent density 60kg/m3 , the PU rigid foams of different polyo[ synergistic systems, have been prepared with GR-835G, TEPES, TBPES and PM-200, as main raw materials. Comparing to the single system with GR-835G, the compressive modulus of the polyol synergistic system between TEPES and GR-835G, has a greater improvement than that of the polyol synergistic system between TBPES and GR-835G. The compressive strength of PU rigid foams will de- crease with TEPES used, however, the compressive properties can be improved using TBPES.

关 键 词：偏苯三酸酐 二元醇 合成 PU硬泡 压缩性能 

分 类 号：O631.5[理学—高分子化学]