氯硅烷功能化非共轭α,ω-双烯烃对聚丙烯多相共聚物中乙丙橡胶相形态的可控研究  

Controlling Phase Morphology of EPR in Polypropylene Heterophasic Copolymer by Dichlorosilane-Functionalized Nonconjugatedα,ω-Diolefin

作　　者：尹学敏 秦亚伟[1,2] 王莉 义建军[3] 董金勇[1,2] Xue-min Yin;Ya-wei Qin;Li Wang;Jian-jun Yi;Jin-yong Dong(Key Laboratory of Engineering Plastics,Institute of Chemistry,Chinese Acadamy of Sciences,Beijing 100190;University of Chinese Acadamy of Sciences,Beijing 100049;Petrochemical Research Institute of PetroChina Co.,Ltd.,Beijing 102206)

机构地区：[1]中国科学院化学研究所中国科学院工程塑料重点实验室,北京100190 [2]中国科学院大学,北京100049 [3]中国石油天然气股份有限公司石油化工研究院,北京102206

出　　处：《高分子学报》2020年第6期641-648,I0005,共9页Acta Polymerica Sinica

基　　金：国家自然科学基金(基金号21574143,51373178)资助项目。

摘　　要：基于Ziegler-Natta催化剂进行丙烯多相共聚是制备聚丙烯多相共聚物的主要方法之一,由于线性乙丙橡胶(EPR)极易发生流动会影响聚合物的颗粒形态和橡胶相的相形态,因此,本文通过在聚合中引入氯硅烷功能化非共轭α,ω-双烯烃,使其参与乙丙无规共聚并使EPR发生同步交联,以解决上述问题.结果显示,氯硅烷功能化非共轭α,ω-双烯烃引入后EPR分子链之间形成交联结构,有效抑制了EPR液滴的流动和聚集,使聚合物具有良好的颗粒形态,EPR相以较小的相畴尺寸均匀地分散在PP基体中,而且硅氯基团遇水发生缩合反应可进一步提高支化/交联效率,进一步稳定聚合物的相形态,聚合物的力学性能得到较大的提升.Heterophasic copolymerization of propylene based on Ziegler-Natta catalyst is one of the major methods for preparing polypropylene/ethylene propylene rubber(PP/EPR)heterophasic copolymer.Compared with traditional physical blending method,PP/EPR heterophasic copolymer can achieve even dispersion of EPR phase in PP matrix with smaller phase domain size.However,for linear EPR,it is prone to flow and aggregate during polymerization,resulting in adhesion between/among polymer particles.In addition,the PP/EPR heterophasic copolymer will undergo significant phase separation during melt processing,and the EPR droplets will aggregate into larger rubber particles.Moreover,the longer the melting processing time,the more serious the phase separation of PP phase and EPR phase,and the larger the size of rubber particles.Therefore,it is very important to control the particle morphology and EPR phase morphology of propylene heterophasic copolymer.In this study,a dichlorosilane functionalized nonconjugatedα,ω-diolefin,di(5-hexenyl)dichlorosilane,was introduced into the polymerization and participated in the random copolymerization of ethylene/propylene to prompt cross-linking of EPR.The results showed that the dichlorosilane functionalized nonconjugatedα,ω-diolefin rendered the formation of cross-linked EPR,and the flow and aggregation of EPR droplets were effectively controlled.The surface morphology of PP/EPR copolymer particles was observed by SEM,which showed that all samples had good particle morphology.TEM and AFM results showed that EPR was evenly dispersed in the PP matrix with a small phase domain size.Moreover,the condensation reaction of the Si―Cl group in the presence of water further enhanced the branching/cross-linking of the copolymer,which led to a greater extent stabilized the phase morphology of the copolymer.As a result,the mechanical properties of PP/EPR copolymer were greatly improved.

关 键 词：Ziegler-Natta催化剂 氯硅烷功能化非共轭α ω-双烯烃 聚丙烯多相共聚物 相形态 

分 类 号：TQ317[化学工程—高聚物工业]