基于对苯二甲酸/异氰酸酯反应的芳香族聚酰胺的合成  

Synthesis of aromatic polyamides based on reaction of terephthalic acid and isocyanate

作　　者：韩福林 董杰[1,2] 李琇廷 许青松 赵昕[1,2] 张清华[1,2] HAN Fulin;DONG Jie;LI Xiuting;XU Qingsong;ZHAO Xin;ZHANG Qinghua(College of Materials Science and Engineering,Donghua University,Shanghai,China;State Key Laboratory for Modification of Chemical Fibers and Polymer Material,Donghua University,Shanghai,China)

机构地区：[1]东华大学材料科学与工程学院,上海 [2]东华大学纤维材料改性国家重点实验室,上海

出　　处：《东华大学学报（自然科学版）》2024年第5期36-42,共7页Journal of Donghua University(Natural Science)

基　　金：国家重点研发计划(2022YFB3603102);国家自然科学基金(52373318);安徽省重点研究与开发计划(2022a05020065)。

摘　　要：以对苯二甲酸(TPA)、甲苯二异氰酸酯(TDI)和4,4’-二苯基甲烷二异氰酸酯(MDI)为反应单体,基于羧基与异氰酸酯基团的反应合成了芳香族聚酰胺。利用傅里叶变换红外光谱、核磁共振氢谱等测试研究了聚酰胺的化学结构与性能。研究结果表明,所合成聚合物的分子质量为(3.18~7.81)×10^(4) g/mol,且随着TDI含量的提高,聚酰胺溶解度提高,分子质量有明显提升。所制备的聚酰胺薄膜具有优越的力学性能,拉伸强度和模量分别为98~127 MPa和3.33~3.95 GPa,断裂伸长率高于20%,通过调控TDI/MDI的摩尔比可将其断裂伸长率提高至50%,表现出优异的柔韧性。所制备的聚酰胺薄膜的玻璃化转变温度(t g)均高于290℃;在氮气中,薄膜10%热失重温度为431~447℃,这表明该类芳香族聚酰胺具有优异的热稳定性。同时,聚酰胺薄膜颜色较浅,薄膜的截止波长均低于383 nm,在530 nm波长处的透光率均接近80%,表明其具有良好的光学透明性。A series of new aromatic polyamide(PA)was successfully synthesized based on the polymerization between toluene diisocyanate(TDI),4,4’-diphenyl diisocyanate(MDI)and terephthalic acid(TPA),and the structure and properties synthesized PA were systematically characterized.The molecular weight(M n)of the synthesized polyamides increases with the increase of the proportion of TDI,which ranges from 3.18×10^(4) g·mol^(-1) to 7.81×104 g·mol^(-1).The breaking strength and tensile modulus of the PA films are 98-127 MPa and 3.33-3.95 GPa,respectively,and the elongation at break is higher than 20%.The elongation at break of the PA films can be modified by changing the TDI/MDI molar ratio,which can reach over 50%,indicating an excellent toughness behavior of the films.The glass transition temperature(t g)is higher than 290℃,and the temperatures of 10%weight loss of the films in nitrogen are 431-447℃,demonstrating a certain thermal stability of the films.The cutoff wavelength of the PA film is lower than 383 nm,and the transmittance at the wavelength of 530 nm is more than 80%,which exhibits a certain degree of transparency.

关 键 词：芳香族聚酰胺 对苯二甲酸 二异氰酸酯 结构与性能 

分 类 号：TB324[一般工业技术—材料科学与工程]