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

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-835 G、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-835 G 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-1 ,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 400.0mg KOH/g,6.55 and 7.31,respectively.The hydroxyl value,fn and fw of TEPES are 357.2mg KOH/g,5.87 and 6.49,respectively.It can be seen that TEPES has a wider molecular weight distribution than TBPES.1 H 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 polyol 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.