Synthetic Applications of Nonpolymerizable Monomers in Living Cationic Polymerization: Functional Polyisobutylenes by End-Quenching
- 1 June 1995
- journal article
- research article
- Published by Taylor & Francis in Journal of Macromolecular Science, Part A
- Vol. 32 (6) , 1137-1153
- https://doi.org/10.1080/10601329508011031
Abstract
The chemistry and kinetics of 1,1-diphenylethylene (DPE) addition to living polyisobutylene was studied at -80°C in methyl chloride/n-hexanes or methylcyclohexane 40/60 v/v. Only monoaddition occurred even when large (9-fold) excess of 1,1-diphenylethylene was used. The kinetics of addition was established by 1H-NMR spectroscopy and by conductivity measurements. The methanol-quenched polymer of the DPE-capped PIB carried exclusively –OCH3 functionality, suggesting that all diphenyl alkyl chain-ends are ionized, which was confirmed by conductivity studies. It was determined that the diphenyl alkyl chain-ends are completely ionized when [TiCl4]/[chain end] ≥ 2 for chain-end concentrations ≥ 10−3 M. Close to quantitative end-quenching was achieved with 1-methoxy-1-(trimethylsiloxy)-2-methyl-1-propene and 1-cyclohexenyloxy-trimethylsilane.Keywords
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