两步法制备热塑性聚酰亚胺  

Thermoplastic polyimide prepared by two-stepped method

作　　者：叶淑娴 杨硕 曹民 陈小铃 文联磊 龙健宇 王丰 姜苏俊 杨汇鑫 YE Shuxian;YANG Shuo;CAO Min;CHEN Xiaoling;WEN Lianlei;LONG Jianyu;WANG Feng;JIANG Sujun;YANG Huixin(Kingfa Science&Technology Co.,Ltd.,Guangzhou 510663,China;Guangdong Province Special Engineering Plastics Enterprise Key Laboratory,Guangzhou 510663,China;Zhuhai Vanteque Specialty Engineering Plastics Co.,Ltd.,Zhuhai 519050,China)

机构地区：[1]金发科技股份有限公司,广州510663 [2]广东省特种工程塑料企业重点实验室,广州510663 [3]珠海万通特种工程塑料有限公司,广东珠海519050

出　　处：《工程塑料应用》2025年第1期57-64,共8页Engineering Plastics Application

基　　金：广东省科技计划专项(2023B1212070027)。

摘　　要：为了更好地研究热塑性聚酰亚胺(TPI)的反应过程及过程中发生的副反应,采用传统的两步法制备Ultem■结构TPI树脂。第一步反应为合成聚酰胺酸(PAA),研究了不同反应温度、反应时间、反应浓度、封端剂含量对PAA合成的影响,发现反应温度越低,制备的PAA相对黏度(η_(r))越大,其中20℃是比较适宜的制备温度和储存温度;比较了PAA储存24h后η_(r)的变化,发现η_(r)越小的PAA溶液储存后的η_(r)变化越小。第二步为热亚胺化合成TPI,比较了直接高温、两步升温和程序升温热亚胺化制备TPI的方法,发现只有程序升温热亚胺化法才能制备出颜色较浅且无交联结构的TPI树脂。通过合成不同ηr的PAA溶液并进行程序升温热亚胺化,发现PAA与亚胺化后的TPI树脂的η_(r)基本一致。对TPI树脂结构和性能进行表征,发现其核磁结构和红外结构完全与Ultem■结构树脂一致;TPI的玻璃化转变温度为220℃,与Ultem■相差1℃;热稳定性基本与Ultem■结构一致,失重5%时的温度(T_(d5%))为523℃,比存在交联结构的TPI树脂(T_(d5%)=473℃)的热稳定性高。In order to study the reaction process of thermoplastic polyimide(TPI)and the side reactions,the same TPI structure as Ultem■resin was prepared by traditional two-step method.In the synthesis of polyamide acid(PAA)in the first step,the different conditions of temperature,time,concentration and end agent content were studied,as well as the relative viscosity(η_(r))change of PAA after being stored for 24 h.The results show that the lower the reaction temperature,the greater the η_(r) of the prepared PAA,and 20℃ is the appropriate preparation temperature and storage temperature.In the second step of TPI synthesis by thermal imidization,three methods of thermal imidization were compared,such as direct high temperature method,two-stepped heating,and programmed temperature.The TPI resin prepared by thermal imidization via programmed temperature was lightcolored and not cross-linked.The PAA with different η_(r) were synthesized and theirηr changed little before and after imidization.The structures and properties of TPI resin were characterized,and it is found that the nuclear magnetic resonance structure and infrared structure of TPI resin are completely consistent with Ultem■structure.The glass transition temperature of TPI is 220℃,which is 1℃ different from that of Ultem■.The thermal stability is basically the same as that of Ultem■structure,with the temperature at 5% weight loss(T_(d5%))of 523℃,which is higher than that of TPI resin with cross-linked structure(T_(d5%)=473℃).

关 键 词：聚酰胺酸 热塑性聚酰亚胺 热亚胺化 相对黏度 储存 

分 类 号：O633.4[理学—高分子化学]