超分子助剂对间规聚苯乙烯构象和结晶行为的调控  

Regulation of supramolecular additives on conformation and crystallization behaviors of syndiotactic polystyrene

作　　者：沈赢洲 刘磊[1] 种锦轩 张凯[1] 尹波[1] SHEN Yingzhou;LIU Lei;CHONG Jinxuan;ZHANG Kai;YIN Bo(College of Polymer Science and Engineering,State Key Laboratory of Polymer Materials Engineering,Sichuan University,Chengdu 610065,China)

机构地区：[1]四川大学高分子科学与工程学院,高分子材料工程国家重点实验室,成都610065

出　　处：《中国塑料》2024年第12期1-7,共7页China Plastics

基　　金：四川省科技厅2022年国际科技创新合作项目(2022YFH0085)。

摘　　要：通过熔融共混法制备了间规聚苯乙烯(sPS)/N,N'-二苯基对苯二甲酰胺(DPHT)复合材料。利用sPS与DPHT之间的π-π相互作用,对sPS分子链的构象和结晶行为进行调控。结果表明,DPHT在sPS基体中存在自由分子和自组装体两种状态,DPHT的加入,提高了sPS的全反式构象(TTTT)含量,并在DPHT形成自组装体时达到最大值,且DPHT自组装结构还能有效提高sPS中β晶型的含量;当降温速率较小时(5℃/min或2℃/min),sPS/DPHT中sPS的β晶占比较α晶多,而当降温速率升高至10℃/min时,sPS中α晶含量更多;当DPHT以自由分子状态分散在sPS基体中时,DPHT与sPS之间的相互作用反而限制了sPS的结晶能力(结晶度由41%降低至35.9%);当DPHT处于自组装状态分散在sPS中时,DPHT的自组装体会在sPS结晶过程中作为晶核促进sPS的结晶(结晶度由36.1%提升至38.2%)。因此,基于DPHT与sPS之间的相互作用,成功实现了在熔融加工过程中对于sPS构象和结晶行为的调控。Syndiotactic polystyrene(sPS)/N,N'-diphenylterephthalamide(DPHT)blends were prepared through melt blending,and the conformation and crystallization behaviors of sPS were regulated by utilizing theπ-πinteractions be-tween sPS and DPHT.The results indicated that there were two dispersion states for DPHT,i.e.,free molecule or as self-assemblies,existing in the sPS matrix.The addition of DPHT increased the content of the all-trans conformation(TTTT)of sPS and reached a maximum when the self-assemblies were formed for DPHT.Moreover,the self-assem-bled structures of DPHT effectively increased the content ofβ-crystals in sPS.The proportion of theβ-crystals was high-er than that of theα-crystals in the sPS/DPHT blends at a slow cooling rate of 5 or 2℃/min.However,theα-crystal content in sPS was higher when the cooling rate was increased to 10℃/min.When DPHT was molecularly dispersed in the sPS matrix,theπ-πinteraction between DPHT and sPS restricted the crystallization ability of sPS,resulting in a de-crease in the degree of crystallinity from 41%to 35.9%.When DPHT was in the self-assembly state,the self-assem-blies of DPHT acted as a nucleating agent to promote the crystallization of sPS,leading to an increase in the degree of crystallinity from 36.1%to 38.2%.Therefore,the conformation and crystallization behaviors of sPS were successfully regulated during melt processing through theπ-πinteractions between DPHT and sPS.

关 键 词：间规聚苯乙烯 构象 结晶行为 Π-Π相互作用 

分 类 号：TQ325.2[化学工程—合成树脂塑料工业]