脂肪族尼龙交联耐热剂的分子设计及构效关系研究

It is of great significance to investigate the molecular design of the heat resistant agent and the relation between the micro-structure of the interface and properties, which aming at the good processing performance, low cost and high temperature resistance of the aliphatic polyamide (PA)-based composites. The applicant takes into account ofintroducing the spontaneously cross-linking group and the donor-acceptor –intergrated with hydrogen bonds on N-Phenylmaleimide.The influence on the thermalstability of the momnomer, caused by the introduced groups, will be further explored. The results willprovide the reference for the design and synthesis of the new heat-resisting monomer.Specially, the copolymerization methods of the ternary copolymer N-phenyl maleic acid imide, maleic anhydride and styrene will be investegated with the purpose of illustrating the relation between the structure of the molecular and heat-resisting properties, which allow to construct the new strategies of designating and synthing the heat-resisting agents. Taking the aliphatic nylon 6 / ternary copolymer composites as a model, The comprehensive characteristics including the interface size, microstructure, mechanical properties and heat resistance in the composites will be investigated to establish the influential mechanism of the ternary copolymer heat resistant agent on aliphatic nylons. This will provide theoretical basis for the industrial production of heat-resistant aliphatic nylons. The successful implementation of this apllicaton will provide the theoretical fundament for synthesis of maleimide-maleic anhydride copolymer and the technical support for the development of heat-resistant nylon 6. In addition, the results will expand the apllication of the polyamide material field, and which will creat the significant scientific values and social benefits.

探索耐热剂的分子设计、界面分子尺度微观结构与复合材料性质构效关系，对开发加工性能好、成本低、耐高温的脂肪族尼龙复合材料具有重要意义。本项目拟对N-苯基马来酰亚胺引入可自然交联基团和强氢键受-给体，阐明该功能基团引入后对该单体的热稳定性影响，为新型耐热剂单体的设计与合成提供参考；研究N-苯基马来酸亚胺、马来酸酐和苯乙烯三元共聚物的合成方法以及分子结构对其物理化学性质的影响，阐明功能基团引入后对该三元共聚物的热稳定性影响，为耐热剂的设计与合成提供思路；以尼龙6 /三元共聚物耐热剂复合材料作为研究模型，探索复合材料的综合性质，如界面尺寸、微观结构、力学性能及耐热性能，建立三元共聚物耐热剂与脂肪族尼龙构效关系新机制，为耐热脂肪族尼龙的工业生产提供理论依据。本项目的成功实施，为脂肪族尼龙耐热改性剂的合成提供分子结构设计的理论依据，为耐热尼龙开发提供新的技术支撑，研究成果具有重要的科学价值和社会效益。

本项目以脂肪族尼龙用耐热剂的开发及作用机理研究为目标。探索耐热剂单体的合成、共聚耐热剂的合成、耐热剂在尼龙6中的应用及作用机理。取得系列的研究成果：（1）通过优化一步法合成工艺，选择阻聚剂对苯二酚使在温和的条件下，缩短反应时间及流程，节约50%反应溶剂的用量，合成N-苯基马来酰亚胺（NPMI）的产率达到了95%。（2）合成系列共聚耐热剂，研究其合成动力学，为马来酸酐类共聚型耐热剂的合成奠定理论基础。（3）将系列耐热剂在PA6中应用，阐明耐热剂的作用机理；聚（N-苯基马来酰亚胺-alt-苯乙烯）（PNS）加入可以促进PA6的结晶度提高，诱导由γ向α晶型转变；扫描电子显微镜（SEM）表明PNS刚性粒子分散在PA6中既能够诱导PA6结晶，又能限制分子链的自由度，阻碍PA6的分子运动，提高PA6的耐热性能；氟基的引入使聚（N-（4-氟基苯基）马来酰亚胺-alt-苯乙烯（PFS）提高复合材料的刚性和粘度（η），使PFS与PA6发生界面络合形成氢键，也可使诱导PA6由γ晶型向α晶型转变的能力增强，PA6/PFS复合材料的耐热性能优于PA6/PCS复合材料；辐照后引发聚（N-（4-羧基苯基）马来酰亚胺-alt-苯乙烯（PCT）与PA6发生固态界面反应的i-PA6/PCT-10%复合材料与PA6/PFS-10%复合材料相比，刚性和η均有提高，证实在辐照条件下PCT与PA6发生固态界面交联反应形成网络结构，提高PA6/PCT复合材料的耐热性能。添加量为10%时，PA6复合材料耐热性能的变化为：i-PA6/PCT＞PA6/PFS＞PA6/PCS＞PA6/PNS。通过上述研究设计了不同分子结构的马来酸酐类耐热剂，提高了尼龙6的耐热性，为拓展尼龙6的推广应用具有重大的现实意义。.培养硕士研究生3名，博士研究生1名，共发表学术论文11篇，其中SCI论文7篇，EI检索3篇和CSCD中文核心1篇，申请国家发明专利6项，其中已授权2项。