INTERACTION OF FULLERENE C60 WITH BENZOYL PEROXIDE AT INITIATION OF RADICAL POLYMERIZATION
INTERACTION OF FULLERENE C60 WITH BENZOYL PEROXIDE AT INITIATION OF RADICAL POLYMERIZATION
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富勒烯 C60 与过氧化苯甲酰在自由基聚合引发时的相互作用
DOI：
10.33184/bulletin-bsu-2020.1.9
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发表时间：
2020
期刊：
影响因子：
--
通讯作者：
Р. Х. Юмагулова
中科院分区：
文献类型：
--
作者：
Р. Диниахметова;Р. Х. Юмагулова
富勒烯C 60与引发剂自由基的相互作用对自由基聚合的初始阶段有很大影响。尽管富勒烯C 60与过氧化苯甲酰（BPO）的相互作用的实验研究以前进行的事实，有没有在文献中的相互作用的产物的共识。本文用实验和量子化学方法研究了富勒烯C60与过氧化苯甲酰（BPO）的相互作用。通过C60-AIBN和C60- BPO体系中C60的消耗速率以及引发剂自由基与C60加成反应的能量特征，比较了自由基对C60的反应活性.结果表明，苯甲酰氧自由基（Ph（COO）·）对富勒烯C60的反应活性比氰异丙基自由基大.对富勒烯C60加成反应进行了量子化学模拟.它示出的前三个苯甲酰氧基自由基的加成去在顶部的富勒烯核的加合物的radylene。Ph（COO）·与富勒烯C60和（PhC（O）O）2C 60的加成反应具有较小的能垒. C60与BPO相互作用产物的EPR谱中没有富勒烯基的特征信号，说明富勒烯C60上连接了偶数个Ph（COO）·。在模拟实验中，富勒烯C60与PB的反应产物是富勒烯C60上苯甲酰氧基的多次加成产物，反应7 h后分离出棕色沉淀物。
The interaction of fullerene C 60 with initiator radicals has great influence on the initial stage of radical polymerization. Despite the fact that an experimental study of the interaction of fullerene C 60 with benzoyl peroxide (BPO) was previously conducted, there is no consensus in the literature about the products of their interaction. In this paper, the interaction of fullerene C 60 with BPO was studied by experimental and quantum chemical meth-ods. The reactivity of the radicals towards fullerene C 60 was compared by the fullerene C 60 consumption rates in the C 60 -AIBN and C 60 - BPO systems and by the energy characteristics of the reaction of addition of the initiator radicals to fullerene C 60 . It is shown that benzoyloxy radicals (Ph(COO) • ) have greater reactivity towards fullerene C 60 than cyanisopropyl radicals. Quantum chemical modeling of the addition of up to 4 Ph(COO) • to fullerene C 60 was carried out. It is shown that the addition of the first three benzoyloxy radicals goes at the tops of the radylene of the fullerene core of the adducts. The addition of Ph(COO) • to fullerene C 60 and bisadduct (PhC(O)O) 2 C 60 has a small energy barrier. There is no signal characteristic of fullerenyl radicals in the EPR spectra of products of interaction C 60 with BPO, therefore, an even number of Ph(COO) • is attached to fullerene C 60 . In the model experiment, the product of interaction of fullerene C 60 with PB is the adduct of multiple addition of benzoyloxy radicals to fullerene C 60 and it is isolated as a brown precipi-tate after 7 h of the reaction.