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Termination Mechanism in the Anionic Polymerization of Methyl Methacrylate

 

作者: R.P. Chaplin,   Sena Yaddehige,  

 

期刊: Journal of Macromolecular Science: Part A - Chemistry  (Taylor Available online 1980)
卷期: Volume 14, issue 1  

页码: 23-31

 

ISSN:0022-233X

 

年代: 1980

 

DOI:10.1080/00222338008063206

 

出版商: Taylor & Francis Group

 

数据来源: Taylor

 

摘要:

Recent studies have revealed that at temperatures around 200°K in tetrahydrofuran solvent, poly(methy1 methacrylate) ion pairs are long-lived and very reactive. At higher temperatures however termination of the ion pairs occurs, as evidenced by the broadening of the molecular weight distribution of the resultant polymer and by the incomplete polymerization of the monomer. Three mechanisms have been proposed to describe these termination reactions; an inter molecular reaction with the monomer ester function, an intramolecular cyclization of the anion, or reaction with the polymer ester function. In the absence of monomer only the last two mechanisms can be operative. A series of experiments was undertaken in which the molecular weight distribution broadening with temperature increase was measured under typical polymerization conditions or in the absence of monomer. The effect of each of the three counterions Li, Na, and K was also monitored. The results obtained are discussed in terms of these three possible termination mechanisms. Termination rate constants calculated from the molecular weight distribution are also presented.

 

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