降冰片烯基封端异酰亚胺低聚物的合成及固化  

Synthesis and Curing of Norbornalic Anhydride-Terminated Isoimide Oligomers

作　　者：董建宇 邱瑜 范玉 任佳鑫 熊梓涵 王治江 吴易达 郑楚 翟燕 Dong Jianyu;Qiu Yu;Fan Yu;Ren Jiaxin;Xiong Zihan;Wang Zhijiang;Wu Yida;Zheng Chu;Zhai Yan(Taiyuan Institute of Technology,Department of Material Engineering,Taiyuan 030008,China)

机构地区：[1]太原工业学院材料工程系,太原030008

出　　处：《工程塑料应用》2023年第7期33-37,共5页Engineering Plastics Application

基　　金：山西省基础研究计划项目(202203021211211);国家级大学生创新创业训练项目(202214101007)。

摘　　要：通过探讨不同聚合度异酰亚胺低聚物的热行为及熔体黏度分布,研究无孔隙、高强度热固性聚酰亚胺(PI)的制备。以3,3',4,4'-二苯酮四酸二酐(BTDA)、4,4'-二氨基二苯基甲烷(MDA)为单体,降冰片烯二酸酐(NA)为封端剂,三氟乙酸酐(TFAA)为脱水剂,异丙醇为沉淀剂,通过缩合反应合成出4种不同聚合度的NA封端异酰亚胺低聚物,并以这些低聚物作为前驱体制备热固性PI。采用傅里叶变换红外光谱仪、差示扫描量热仪、流变仪、旋转数字黏度计、万能材料试验机和动态机械热分析仪等表征方法对异酰亚胺低聚物及其热固性PI进行表征。结果表明,不同聚合度的异酰亚胺低聚物在极性溶剂N,N-二甲基乙酰胺(DMAc)中溶解性能优异,其固含量质量分数为20%的DMAc溶液黏度低于70mPa·s。不同聚合度的异酰亚胺低聚物都具有可加工性,其中聚合度为4的异酰亚胺低聚物在低熔体黏度范围下易于加工,加工温度范围为290~330℃,其制备的热固性PI玻璃化转变温度为345℃,拉伸强度为69.4 MPa,弯曲强度为64.2MPa,压缩强度为140.7MPa,耐热性能优异,力学性能高。The preparation of high strength thermosetting polyimide(PI)with no porosity was studied by the thermal behavior and the melt viscosity distribution of isoimide oligomers with different polymerization degrees.Four kinds of norbornalic anhydride(NA)terminated isomimide oligomers with different polymerization degrees were synthesized by condensation reaction using benzo‐phenone-3,3′,4,4′-tetracarboxylic(BTDA),4,4′-diaminodiphenylmethane(MDA)as monomers,NA as sealing agent,trifluoroace‐tic anhydride(TFAA)as dehydrating agent,and isopropyl alcohol as precipitating agent.The thermosetting PI was prepared by the oligomers as precursor system.The performance of the isoimide oligomers and its thermosetting PI were characterized by fourier transform infrared spectroscopy,differential scanning calorimetry,rheometer,viscometer,universal material testing machine and dynamic mechanical analyzer.The results show that the isoimide oligomers with different polymerization degrees have excellent solubility in polar solvent N,N-dimethylacetamide(DMAc),and the viscosity of DMAc solution with solid content of 20 wt%is lower than 70 mPa·s.The isoimide oligomers with different polymerization degrees are all processable.The isoimide oligomers with polymerization degree 4 are easy to process in the range of low melt viscosity,and the processing temperature range is 290-330℃.The thermosetting PI prepared by isoimide oligomers with polymerization degree 4 has excellent heat resistance and high mechanical strength.The glass transition temperature is 345℃,the tensile strength is 69.4 MPa,the bending strength is 64.2 MPa and the compression strength is 140.7 MPa.

关 键 词：降冰片烯二酸酐 异酰亚胺 热固性聚酰亚胺 酰亚胺低聚物 交联固化 

分 类 号：TQ324.8[化学工程—合成树脂塑料工业]