高等学校化学学报2026，Vol.47Issue(7)：176-184,9.DOI:10.7503/cjcu20260074
Ziegler-Natta催化剂催化丙烯聚合的动力学
Polymerization Kinetics of Propylene Catalyzed by Ziegler-Natta Catalysts
摘要
Abstract
This study investigated the propylene polymerization behaviors using particulate Ziegler-Natta(Z-N)catalyst(Cat-P)and slurry Z-N catalysts(Cat-M1 and Cat-M2)derived from Cat-P with different dispersion media.The results demonstrated that Cat-P exhibited the fastest activation,the highest catalytic activity and yielded polypropylene(PP)with the highest isotacticity and the lowest fine powder content(0.6%,mass fraction).In contrast,the slurry catalyst Cat-M1 showed the lowest catalytic activity and produced PP with the highest fine powder content(10.7%)and the lowest isotacticity.The slurry catalyst Cat-M2,prepared by modifying the viscosity and surface tension of dispersion medium M1,exhibited higher catalytic activity,improved isotacticity,and reduced fine powder content compared to Cat-M1.The study elucidated that the dispersion medium with high viscosity and surface tension impeded the diffusion of co-catalyst,external donor,and propylene monomer into the catalyst particles.Diffusion control slowed the formation of highly stereospecific active sites,while also leading to insufficient monomer supply locally,which in turn facilitated the deactivation of some active sites via further reduction by alkylaluminum.Consequently,Cat-M1 exhibited lower initial activity,decreased isotacticity,and increased fine powder generation during the early polymerization stage.The particulate Cat-P and modified Cat-M2 catalysts allowed for rapid initiation and polymerization at the Ti active sites.The rapidly growing polymer chains effectively exerted a"guard effect"to protect the active sites from deactivation.This work clarified the diffusion-controlled effects during the activation and chain propagation of heterogeneous Z-N catalysts,providing a theoretical basis for the stable control of industrial olefin polymerization.关键词
浆液催化剂/Ziegler-Natta催化剂/丙烯/扩散控制/卫兵效应Key words
Slurry catalyst/Ziegler-Natta catalyst/Propylene/Diffusion control/Guard effect分类
化学化工引用本文复制引用
高文霄,赵远进,王爔卉,王人弘,贺爱华..Ziegler-Natta催化剂催化丙烯聚合的动力学[J].高等学校化学学报,2026,47(7):176-184,9.基金项目
泰山学者工程、国家重点研发计划项目[批准号:2022YFB3704700(2022YFB3704702)]和山东省重大科技创新工程项目(批准号:2021CXGC010901)资助. Supported by the Taishan Scholar Program,China,the National Key Research and Development Program of China[No.2022YFB3704700(2022YFB3704702)]and the Major Scientific and Technological Innovation Project of Shandong Province,China(No.2021CXGC010901). （2022YFB3704702）
