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Synthesis of highly reactive polyisobutylene by catalytic chain transfer in hexanes at elevated temperatures; determination of the kinetic parameters

Content Provider	Royal Society of Chemistry (RSC)
Author	Rajasekhar, Tota Faust, Rudolf Emert, Jack
Copyright Year	2017
Abstract	The kinetics and mechanism of the polymerization of isobutylene (IB) using an ethylaluminum dichloride (EADC)·bis(2-chloroethyl) ether (CEE) complex as a catalyst in conjunction with tert-butyl chloride (t-BuCl) as an initiator in hexanes at 0 °C have been previously reported. In an effort to further study the catalyst performance, we have investigated the polymerization at elevated temperatures. Polymerization rates increased while molecular weights and exo-olefin contents (90–78%) decreased with increasing temperature. At elevated temperatures the first-order plots are curved upward, suggesting that the formation of the tert-butyloxonium ion is slower at higher temperatures. 1H NMR studies confirmed that the t-butyloxonium ion is stable up to 15 °C but slowly decomposes at 20 °C. Linear first order plots were obtained when the polymerization was carried out with the tert-butyloxonium ion preformed at 10 °C. The slope of the first order plots that is proportional to the steady state concentration of carbenium ions increased 2, 3 and 4 fold at 10, 15 and 20 °C relative to that at 0 °C. Kinetic parameters of activation–deactivation were determined using model reactions. The rate constant of activation at 0 °C (ka = 3 × 10−4 s−1) increased 2, 3.4 and 4 fold at 10, 15 and 20 °C, respectively, in line with the rate increases. The deactivation rate constant, kd = 1010 L mol−1 s−1 was at the diffusion-limit.
Starting Page	2852
Ending Page	2859
Page Count	8
File Format	HTM / HTML PDF
ISSN	17599954
Volume Number	8
Issue Number	18
Journal	Polymer Chemistry
DOI	10.1039/c7py00415j
Language	English
Publisher	Royal Society of Chemistry
Access Restriction	Open
Subject Keyword	Central and Eastern Europe Ether Isobutylene Polymerization Tert-Butyl chloride Ion Nuclear magnetic resonance
Content Type	Text
Resource Type	Article
Subject	Organic Chemistry Biochemistry Bioengineering Biomedical Engineering Polymers and Plastics

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