【摘要】 在聚丙烯（PP）分子链上引入氮杂环功能单体可以制备热氧稳定性能优异的氮杂环功能化聚丙烯（NHPP），然而目前研究主要聚焦于NHPP的合成和热氧稳定性的提升，不同氮杂环结构对其晶体结构的影响尚不清晰。通过选取具有吡咯、吲哚、咔唑基团的氮杂环单体与丙烯共聚制备了吡咯功能化PP（PPPy-R11和PPPy-R6）、吲哚功能化PP（PPId-R6）和咔唑功能化PP（PPCz-R6），对NHPP的晶体结构、熔融行为及非等温结晶动力学进行研究。结果表明，氮杂环功能单体的掺入未导致PP晶体结构发生变化，但随着共聚单体空间位阻的增加，结晶度按大小顺序表现为PP>PPPy-R11>PPPy-R6>PPId-R6>PPCz-R6，且NHPP的熔点与PP相比下降了31～38℃；Jeriorny法和Mo法拟合的Avrami指数n值和Ozawa指数m值分别为3.6～4.5和2.9～3.4，表明NHPP与PP都采用均相成核方式三维生长；Jeriorny法拟合的修正后结晶速率常数（Z_c）、半结晶时间(t_1/2)以及Mo法拟合反应结晶速率值均表明NHPP结晶速率低于PP,NHPP中PPPy-R11总结晶速率最慢，降温速率为5℃/min时，Z_c值较PP下降了0.18,t_1/2较PP增加了0.51 min;Friedman法拟合结果表明相对结晶度小于50%时，NHPP较PP需要更高的有效活化能；NHPP中热氧化稳定性按高低顺序呈现为PPPy>PPId>PPCz。相关研究为NHPP的熔体加工参数和性能调控提供了理论参考。更多还原

【Abstract】 Nitrogen heterocyclic functionalized polypropylene（NHPP） with excellent thermal and oxygen stability can be prepared by introducing nitrogen heterocyclic functional monomer into the molecular chain of polypropylene（PP）. However,the current research mainly focuses on the synthesis and thermal stability of NHPP,and the influence of its different nitrogen-containing heterocyclic structures on the crystal structure remains unclear. In this work,pyrrole functionalized PP（PPPy-R11 and PPPy-R6）, indole functionalized PP（PPId-R6） and carbazole functionalized PP（PPCz-R6） were prepared by the copolymerization of pyrrole,indole and carbazole groups with propylene. The crystal structure,melting behavior and non-isothermal crystallization kinetics of NHPP were studied. The research results show that the incorporation of nitrogen heterocyclic functional monomer does not change the crystal structure of PP. However,with the increase in the steric hindrance of comonomers,the crystallinity follows the order of PP>PPPy-R11>PPPy-R6>PPId-R6>PPCz-R6,and the melting point of NHPP decreases by 31-38 ℃ compared with that of PP. The results of Jeziorny and Mo show that Avrami index（n） ranges from 3.6-4.5 and Ozawa index（m） ranges from 2.9-3.4,which indicates homogeneous nucleation with three-dimensional growth for NHPP. Modified crystallization rate constant（Z_c）,half crystallization time(t_1/2) fitted by Jeriorny method and values of reaction crystallization rate fitted by Mo method shows that crystallization rate of NHPP is lower than those of PP. PPPy-R11 shows the lowest crystallization rate among NHPP,with 0.18 lower Z_c and 0.51 min longer t_1/2 than those of PP at a cooling rate of 5 ℃/min. The result of Friedman analysis shows that all NHPP require the higher effective activation energy than PP when the relative crystallinity is lower than 50%. The thermal oxidation stability in the NHPP in descending order is as follows:PPPy>PPId>PPCz. This work provides a theoretical reference for the melt processing parameters and performance control of NHPP.更多还原