Pulsed laser polymerisation studies of methyl methacrylate in the presence of AlCl3 and ZnCl2 – evidence of propagation catalysis

文献信息

发布日期 2017-09-06
DOI 10.1039/C7PY01355H
影响因子 5.582
作者

Jing Y. Jiang, Leesa M. Smith, Jason H. Tyrell, Michelle L. Coote


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摘要

A series of pulsed laser polymerisation (PLP) experiments in conjunction with size exclusion chromatography (SEC) was carried out to investigate the effect of Lewis acids AlCl3 and ZnCl2 on the propagation rate constants at a variety of conditions. The Arrhenius parameters were obtained from kinetics data over a temperature range of ∼0–60 °C at 5 mol% Lewis acid loading in bulk methyl methacrylate (MMA). The results showed that the Lewis acids are excellent propagation catalysts with catalysis increasing with the charge on the metal ion. The Lewis acids AlCl3 and ZnCl2 enhanced the propagation rate by around 80% and 40% respectively at 5 mol% loading, reducing the activation energy for the propagation step by 5.8 kJ mol−1 and 2.2 kJ mol−1. Propagation rate coefficient enhancements of up to 100% were obtained when AlCl3 was used at a loading of 10 mol%. The presence of Lewis acid also affects the radical initiation process by complexing with the photoinitiator. This results in both catalysis of initiation and increased triplet lifetimes. These problems could be overcome through optimization of the initiator concentration and laser flashing rate to ensure that IUPAC quality criteria for PLP are met. Despite its strong influence to the kinetics of free radical polymerisation, limited evidence of stereocontrol was observed for both Lewis acids.

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Polymer Chemistry

Polymer Chemistry
CiteScore: 8.6
自引率: 7.3%
年发文量: 457

Polymer Chemistry welcomes submissions in all areas of polymer science that have a strong focus on macromolecular chemistry. Manuscripts may cover a broad range of fields, yet no direct application focus is required.

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