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Methyl methacrylate as solvent for the thermal decomposition of the cyclic molecule pinacolone diperoxide: Toward the polymerization process
Journal of Polymer Science Part A: Polymer Chemistry Pub Date : 2019-03-15 , DOI: 10.1002/pola.29355 Karla Delgado‐Rodríguez 1 , Francisco J. Enríquez‐Medrano 1 , Adriana Berenice Espinoza‐Martínez 1 , Gastón P. Barreto 2 , Gabriel Merino 3 , Graciela Morales 1
Journal of Polymer Science Part A: Polymer Chemistry Pub Date : 2019-03-15 , DOI: 10.1002/pola.29355 Karla Delgado‐Rodríguez 1 , Francisco J. Enríquez‐Medrano 1 , Adriana Berenice Espinoza‐Martínez 1 , Gastón P. Barreto 2 , Gabriel Merino 3 , Graciela Morales 1
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The decomposition rate constant (kd) of pinacolone diperoxide (PDP, 3,6‐diterbutyl‐3,6‐dimethyl‐1,2,4,5‐tetraoxacyclohexane) in methyl methacrylate (MMA) is determined by the kinetic study of its thermal decomposition at temperatures from 110 °C to 140 °C. The calculated kd values for PDP are higher than the corresponding values previously determined and reported for diethyl ketone triperoxide (DEKTP, 3,3,6,6,9,9‐hexaethyl‐1,2,4,5,7,8‐hexaoxacyclononane), for example, at 140 °C the kd for PDP is 75.4 × 10−5 s−1, while for DEKTP, it is 50.6 × 10−5 s−1. The difference in the kd between 130 °C and 140 °C indicates that the decomposition mechanism, sequential and/or concerted, is a function of temperature. The conformations of both initiators justify the higher kd for PDP in MMA than DEKTP, where one single conformer is found for PDP, whereas 212 conformers are found for DEKTP. Bulk polymerization of MMA using PDP as the initiator reveals also the presence of an induction period, such as in DEKTP case. This work provides mechanistic insights into the interactions among the bifunctional cyclic peroxide PDP and the MMA monomer and their influence on the polymerization kinetics. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 997–1007
中文翻译：
甲基丙烯酸甲酯作为溶剂分解环状分子频哪酮二氧化物的热分解：迈向聚合过程
品他克龙二过氧化物（PDP，3,6-二叔丁基-3,6-二甲基-1,2,4,5-四氧杂环己烷）在甲基丙烯酸甲酯（MMA）中的分解动力学常数（k d）是通过对其动力学的研究来确定的在110°C至140°C的温度下发生热分解。计算出的PDP的k d值高于先前确定和报告的二乙基酮三氧化物（DEKTP，3,3,6,6,9,9-六乙基-1,2,4,5,7,8-例如，在140°C下，PDP的k d为75.4×10 -5 s -1，而DEKTP的k d为50.6×10 -5 s -1。在差ķ d如果温度介于130°C和140°C之间，则说明分解机理（依序和/或一致）是温度的函数。两种引发剂的构象都证明MMA中PDP的k d高于DEKTP，后者在PDP中发现一个单一的构象异构体，而在DEKTP中发现212个构象异构体。使用PDP作为引发剂的MMA本体聚合也揭示了诱导期的存在，例如在DEKTP情况下。这项工作提供了对双功能环过氧化物PDP和MMA单体之间的相互作用及其对聚合动力学的影响的机械见解。分级为4 +©2019 Wiley Periodicals，Inc.J.Polym。科学，A部分：Polym。化学 2019，57，997-1007
更新日期：2019-03-15
中文翻译：
甲基丙烯酸甲酯作为溶剂分解环状分子频哪酮二氧化物的热分解：迈向聚合过程
品他克龙二过氧化物（PDP，3,6-二叔丁基-3,6-二甲基-1,2,4,5-四氧杂环己烷）在甲基丙烯酸甲酯（MMA）中的分解动力学常数（k d）是通过对其动力学的研究来确定的在110°C至140°C的温度下发生热分解。计算出的PDP的k d值高于先前确定和报告的二乙基酮三氧化物（DEKTP，3,3,6,6,9,9-六乙基-1,2,4,5,7,8-例如，在140°C下，PDP的k d为75.4×10 -5 s -1，而DEKTP的k d为50.6×10 -5 s -1。在差ķ d如果温度介于130°C和140°C之间，则说明分解机理（依序和/或一致）是温度的函数。两种引发剂的构象都证明MMA中PDP的k d高于DEKTP，后者在PDP中发现一个单一的构象异构体，而在DEKTP中发现212个构象异构体。使用PDP作为引发剂的MMA本体聚合也揭示了诱导期的存在，例如在DEKTP情况下。这项工作提供了对双功能环过氧化物PDP和MMA单体之间的相互作用及其对聚合动力学的影响的机械见解。分级为4 +©2019 Wiley Periodicals，Inc.J.Polym。科学，A部分：Polym。化学 2019，57，997-1007
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