【作者】 王文志；

【导师】 刘民英；

【作者基本信息】 郑州大学 ， 材料学， 2006， 硕士

【摘要】 半芳香尼龙由于具备优异的刚性、耐热性、尺寸稳定性等优点，特别适合生产一些耐热部件、薄壁产品，所以在汽车发动机周边部件开发和电路板表面实装技术领域有大量研究。目前，国外已工业化生产的半芳香尼龙有PA6T、PA9T及其共聚物，其中以PA9T的综合性能较好但成本很高。国内郑州大学自2000年以来，以石油发酵法合成的1，12-十二碳二元胺与对苯二甲酸合成了聚对苯二甲酰十二碳二胺(PA12T)，但得到的PA12T分子量较低，尚不能进行应用研究。本课题为解决目前半芳香尼龙存在的可加工性差或分子量低等问题，以石油发酵法合成的1，12-十二碳二元胺、1，13-十三碳二元胺分别与对苯二甲酸经成盐、预聚合、固相聚合三个步骤，在国内外首次合成出了高分子量、物理机械性能优异和可加工性好的PA12T和聚对苯二甲酰十三碳二胺(PA13T)。论文讨论了聚合条件对聚合物分子量的影响，研究了PA12T和PA13T的物理机械性能、动态力学性能、非等温结晶动力学和热降解过程及其热裂解机理。从研究结果看，PA12T、PA13T从原料来源、合成工艺条件、可加工性等方面优于目前综合性能最好的PA9T，具有广阔的应用前景。本研究工作得到了如下主要结果与结论： 1．以石油发酵法合成的1，12-十二碳二元胺、1，13-十三碳二元胺分别与对苯二甲酸，合成了高分子量的、不经共聚改性即可熔融加工的PA12T和PA13T。 2．探索出了一种绿色环保、新颖有效的半芳香尼龙盐的制备方法。通过盐溶液的PH值来判定成盐反应终点。 3．研究了预聚合和固相聚合工艺条件对聚合物分子量的影响，得到了PA12T和PA13T合适的聚合工艺条件：预聚合温度230℃，反应时间3h，固相聚合温度235℃，反应时间15h，真空度10Pa。并通过FTIR和~1H-NMR图谱分析，对其结构进行了确认。 4．将PA12T和PA13T粒料用通用的注射机注射成各种标准试样，分别进行了物性参数、力学性能、电性能、热性能的测定。结果表明，PA12T和PA13T具有良好的物理机械性能，其拉伸强度、弯曲强度等性能、热变形温度和体积更多还原

【Abstract】 Semiaromatic nylon has been widly used in thermoduric parts and thin-wall products due to its excellent rigidity, thermostability and dimensional stability. The utilization of semiaromatic nylon on automobile industry and surface mount technology is still a hotspot. Up to now, only the PA6T, PA9T and their copolymers were commercially applied. In all these semiaromatic nylons, the PA9T has good integrating properties. The PA12T ( poly(dodecamethyleneterephthalamide)) were synthesized using terephthalic acid and dodecamethylene diamine in Zhengzhou University, but its molecular weight is very low and these is no any application. The objective of our research is to gain the high molecular weight of semiaromatic nylon and excellent process ability. In this paper, two new semiaromatic nylons with high molecular weight, good properties, excellent process ability were synthesized using terephthalic acid and dodecamethylene diamine, tridecamethylene diamine (PA13T ) respectively firstly in the world. The effects of polymerization conditions on reaction were investigated. Meanwhile, the physical, mechanical properties and the dynamic mechanical properties of PA12T and PA13T were characterized. In the meantime, the non-isothermal melt crystallization kinetics, the thermal degradation process and mechanism were also studied. There are many advantages in PA12T and PA13T compared to PA9T, for example, convenient raw materials, advanced synthetic technology, low cost and better process ability, etc. Therefore PA12T and PA13T will be potentially applied in wide fields. The main results of our work are summarized as following:1. The PA12T and PA13T with high molecular weight were synthesized using terephthalic acid with dodecamethylene diamine and tridecamethylene diamine, which could be directly used in melt processing without being modified by更多还原