On the Absence of Gel Effect in Radical Ring-Opening Polymerization of Ketene Acetals

IF 1 4区化学 Q4 POLYMER SCIENCE

Polymer Science, Series B Pub Date : 2023-12-01 DOI:10.1134/s1560090423600225

引用次数: 0

Abstract

A new kinetic type of gel effect suppression in radical polymerization is described. Ring-opening polymerization of ketene acetals is characterized by auto-deceleration in the course of the reaction rather than the auto-acceleration, as well as increased reaction rate order with respect to the monomer. These features are caused by low reactivity of ketene acetals, as a result of which the addition of primary radicals to the monomer is the rate-limiting step in the initiation reaction. This should lead, firstly, to termination of the growth radicals at the primary radicals, and secondly, to the increased rate order with respect to the monomer concentration and, accordingly, to a decrease in the polymerization rate with its consumption.

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烯酮缩醛的自由基开环聚合中不存在凝胶效应

摘要描述了自由基聚合中一种新的凝胶效应抑制动力学类型。烯酮缩醛的开环聚合反应的特点是反应过程中的自动减速而非自动加速，以及相对于单体的反应速率顺序增加。这些特点是由于烯酮缩醛的反应活性较低，因此在起始反应中，初级自由基与单体的加成是限速步骤。这首先会导致生长自由基在初级自由基上终止，其次会导致相对于单体浓度的速率阶次增加，并相应地导致聚合速率随着单体的消耗而降低。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

Polymer Science, Series B 化学-高分子科学

CiteScore

1.80

自引率

8.30%

发文量

审稿时长

>0 weeks

期刊介绍： Polymer Science, Series B is a journal published in collaboration with the Russian Academy of Sciences. Series B experimental and theoretical papers and reviews dealing with the synthesis, kinetics, catalysis, and chemical transformations of macromolecules, supramolecular structures, and polymer matrix-based composites (6 issues a year). All journal series present original papers and reviews covering all fundamental aspects of macromolecular science. Contributions should be of marked novelty and interest for a broad readership. Articles may be written in English or Russian regardless of country and nationality of authors. All manuscripts are peer reviewed