Synthesis of highly reactive polyisobutylene with FeCl3/ether complexes in hexane; kinetic and mechanistic studies

被引：31
作者：
Kumar, Rajeev [1 ]
De, Priyadarsi [2 ]
Zheng, Bin [3 ]
Huang, Kuo-Wei [3 ]
Emert, Jack [4 ]
Faust, Rudolf [1 ]
机构：
[1] Indian Inst Sci Educ & Res Kolkata, Ctr Polymer Res, Dept Chem Sci, Nadia 741246, W Bengal, India
[2] King Abdullah Univ Sci & Technol, KAUST Catalysis Ctr, Thuwal 23556900, Saudi Arabia
[3] King Abdullah Univ Sci & Technol, Div Phys Sci & Engn, Thuwal 23556900, Saudi Arabia
[4] Infineum USA, Linden, NJ 07036 USA
来源：
POLYMER CHEMISTRY | 2015年 / 6卷 / 02期
关键词：
OLEFIN-TERMINATED POLYISOBUTYLENE; MOLECULAR-ORBITAL METHODS; GAUSSIAN-TYPE BASIS; CATIONIC-POLYMERIZATION; CARBOCATIONIC POLYMERIZATION; ISOBUTYLENE; ANHYDRIDE; ENERGY;
D O I：
10.1039/c4py01039f
中图分类号：
O63 [高分子化学（高聚物）];
学科分类号：
070305 ; 080501 ; 081704 ;
摘要：
The kinetics and mechanism of the polymerization of isobutylene catalyzed by FeCl3 center dot ether complexes in hexane at 0 degrees C were investigated. The polymerization rates increased in the diisopropyl ether< 2-chloroethyl ethyl ether < bis(2-chloroethyl) ether order, attributed to electronic effects. The polymerization rates increased with increasing initiator and catalyst concentrations. The first order plots, however, deviated from the linear suggesting that the cation concentration decreases with time. The previously proposed mechanism is inadequate to explain this finding. The decrease in the polymerization rate with time is explained by the low solubility of the H+ROR'FeCl4- complexes that precipitate during polymerization. Based on mechanistic studies the revised mechanism now also includes the equilibrium H+ROR'FeCl4- reversible arrow HCl + FeCl3 center dot ROR'.
引用
收藏
页码：322 / 329
页数：8
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