新型可溶性聚氨酯酰亚胺嵌段共聚物的合成

Synthesis of Novel Soluble Polyester-urethane-imide Block Copolymers

经4步反应合成了新型含羧基结构的聚酯型可溶性聚氨酯酰亚胺嵌段共聚物。运用三羟甲基丙烷(TMP)与邻苯二甲酸酐按摩尔比1∶1通过高压溶剂热反应生成新型邻苯二甲酸单三羟甲基丙烷酯,再与1,6-己二酸按摩尔比6∶5反应生成双羟基封端、数均分子量为2192的聚酯二元醇。将此聚酯二元醇分别与2,4-甲苯二异氰酸酯(TDI)和二苯甲烷二异氰酸酯(MDI)按摩尔比1∶2进行异氰酸酯(NCO)封端,制得NCO封端的PU预聚体,该预聚体与均苯四甲酸酐(PMDA)按摩尔比1∶1,在60℃下经48h扩链和亚胺化反应,产物经傅里叶变换红外光谱仪(FT-IR)及1HNMR表征和溶解性测试,表明成功制得2种可溶性聚氨酯酰亚胺嵌段共聚物。

The novel soluble polyester-urethane-imide block copolymers containing carboxyl structure were synthesized successfully by four steps of synthesis reaction. Phthalic carboxyl monoester diols （PCMD） were synthesized by the high-pressure solvent-heat reaction of 1,1,1-trimethylolpropane （TMP） with phthalic anhydride（PA） at a molar ratio of 1：1. Then the hydroxyl-terminated polyester with phthalic carboxyl（Ma ca. 2 192） was prepared by the condensation reaction of monomer PCMD and hexanedioic acid at a molar ratio of 6：5. The NCO-terminated polyurethane prepolymers were formed from the reaction of polyester diols with phthalic carboxyl and tolylene-2, 4-Diisocyanate（TDI） or with methylenedi-p-phenyl diisocyanate（MDI） at a molar ratio of 1 ： 2, respectively. Finally, the soluble polyuethane-imide block copolymers were synthesized by the chain extending reaction and imidization of the PU prepolymer with 1,2,4,5-benzenetetracarboxylic dianhydride （PMDA） at a molar ratio of 1 ： 1 and 60 ℃ for 48 h. The reaction processes were controlled by titration analysis and traced by FT-IR. The in-process products and the polyester-urethane-imide block copolymers were characterized by ^1H NMR and FTIR. The solubility of the products was tested.