Kinetic studies on the radical ring-opening polymerization of 2-methylene-1,3,6-trioxocane,Journal of Polymer Science

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Kinetic studies on the radical ring-opening polymerization of 2-methylene-1,3,6-trioxocane
Journal of Polymer Science ( IF 3.9 ) Pub Date : 2023-05-11 , DOI: 10.1002/pol.20230143
Fabian Mehner _{1,

2} , Till Meissner _{1,

2} , Alissa Seifert ₁ , Albena Lederer _{1,

3} , Jens Gaitzsch ₁

Affiliation

Radical ring-opening polymerization (RROP) of cyclic ketene acetals allows for the synthesis of functional and biodegradable polyesters. To gain a better understanding of RROP, kinetic studies of this reaction method are thus essential but still rare. In here we conducted kinetic experiments on RROP of 2-methylene-1,3,6-trioxocan (MTC) for the first time. In line with earlier findings, the kinetic behavior could be distributed into a chain growth, stationary and step growth behavior probably caused by dominating branching and recombination reactions impacting the polymerization with increasing conversion. The impact of reaction conditions, such as monomer concentration, reaction temperature and source of energy input (Oil bath, microwave, UV light) were varied systematically. All of these factors were studied towards their influence on polymerization rate constant, density of branches (DB), polymer dispersity and molar mass. While each of these factors were impacted by the reaction conditions, the DB was only depending on monomer conversion. Elution fractionation of PMTC samples with high conversion proved decreasing DB with increasing molar mass. Altogether, this study gives a holistic insight into the kinetics of MTC under various means of free RROP, paving the way for developing a more hydrophilic polyester with adjustable DB and molecular weight.

中文翻译：

2-亚甲基-1,3,6-三氧杂环己烷自由基开环聚合反应动力学研究

环状乙烯酮缩醛的自由基开环聚合（RROP）可以合成功能性和可生物降解的聚酯。为了更好地了解 RROP，对该反应方法的动力学研究至关重要，但仍然很少。在这里，我们首次对2-亚甲基-1,3,6-三氧肯（MTC）的RROP进行了动力学实验。与早期的发现一致，动力学行为可以分为链增长、静态和阶梯增长行为，这可能是由影响聚合反应并增加转化率的主导支化和重组反应引起的。反应条件的影响，如单体浓度、反应温度和能量输入源（油浴、微波、紫外光）都有系统地变化。研究了所有这些因素对聚合速率常数、支链密度（DB）、聚合物分散性和摩尔质量的影响。虽然这些因素均受到反应条件的影响，但 DB 仅取决于单体转化率。高转化率 PMTC 样品的洗脱分级证明 DB 随着摩尔质量的增加而降低。总而言之，这项研究对 MTC 在各种游离 RROP 方式下的动力学有了全面的了解，为开发具有可调节 DB 和分子量的更亲水性聚酯铺平了道路。高转化率 PMTC 样品的洗脱分级证明 DB 随着摩尔质量的增加而降低。总而言之，这项研究对 MTC 在各种游离 RROP 方式下的动力学有了全面的了解，为开发具有可调节 DB 和分子量的更亲水性聚酯铺平了道路。高转化率 PMTC 样品的洗脱分级证明 DB 随着摩尔质量的增加而降低。总而言之，这项研究对 MTC 在各种游离 RROP 方式下的动力学有了全面的了解，为开发具有可调节 DB 和分子量的更亲水性聚酯铺平了道路。

更新日期：2023-05-11

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