摘要
以1,4-双(3-氨基丙基)哌嗪为原料通过界面反应制备二氟酰胺单体N,N'-(1,4-哌嗪二基-3,1-丙二基)双(4-氟苯甲酰胺)(FDC-200),并与联苯二砜、4,4’-二氯二苯砜通过高温溶液缩聚反应制备了一系列新型半芳族聚酰胺(SPAS树脂)。通过傅里叶变换红外光谱(FTIR)和核磁氢谱(1H-NMR)表征了新型单体及聚合物的化学结构,结果表明,单体及聚合物已成功制备。半芳族聚酰胺具有优异的热性能,其玻璃化转变温度为149.0~171.2℃,热失重5%所对应的温度为385.8~395.6℃,随着半芳族聚酰胺中二苯砜结构逐渐增加,聚合物的玻璃化转变温度逐渐增高。聚合物具有优异的力学性能,其拉伸强度大于60 MPa且随着二苯砜共聚比例的增加而逐渐增高。二苯砜结构提升了半芳族聚酰胺的疏水性,降低聚合物吸水率至3.7%。此外,二苯砜结构的引入使聚合物变为无定形,提升了半芳族聚酰胺的溶解性,溶解性的增加有效的拓宽了含哌嗪环半芳族聚酰胺的可加工性能。同时分子结构的变化赋予半芳族更好的阻燃性,提高了半芳族聚酰胺的应用领域。
Semi-aromatic polyamides combine the desirable properties of both aromatic and aliphatic polyamides.In this study,a novel difluorobenzamide monomer,N,N’-(1,4-Piperazinediyldi-3,1-propanediyl)bis(4-fluorobenzamide)(FDC-200),was synthesized via a facile interfacial reaction between 1,4-bis(3-aminopropyl)piperazine and 4-fluorobenzoyl chloride.A series of polyamides incorporating piperazine rings were subsequently prepared from this monomer through nucleophilic substitution polymerization.The chemical structures of the monomer and polymers were confirmed by FTIR and¹H-NMR spectroscopy.These novel polyamides exhibited outstanding thermal properties,with glass transition temperatures ranging from 149.0 to 171.4℃and a 5%weight loss temperature exceeding 385℃.The incorporation of a diphenyl sulfone moiety was found to significantly enhance multiple material properties.Specifically,it improved tensile strength(exceeding 60 MPa),increased hydrophobicity(water absorption as low as 3.7%for sample SPAS-50),and enhanced solubility,thereby broadening processability.Furthermore,the diphenyl sulfone structure imparted excellent flame retardancy,with sample SPAS-50 achieving a UL 94 V-1 rating.This work demonstrates a promising strategy for developing high-performance semi-aromatic polyamides with a versatile property profile.
作者
郑鑫源
黄骁
严光明
张刚
杨杰
ZHENG Xinyuan;HUANG Xiao;YAN Guangming;ZHANG Gang;YANG Jie(Analytical&Testing Center,Sichuan University,Chengdu 610064,China;College of Polymer Science and Engineering,Sichuan University,Chengdu 610064,China;State Key Laboratory of Polymer Materials Engineering(Sichuan University),Chengdu 610064,China)
出处
《中国塑料》
北大核心
2025年第10期12-17,共6页
China Plastics
基金
国家重点研发计划(2023YFB3712500)。
关键词
半芳族聚酰胺
哌嗪
亲核反应
溶液加工
semi-aromatic polyamide
piperazine
nucleophilic substitution
processability
