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Radical polymerization of methyl methacrylate in the presence of methylene blue and organobromides under visible light irradiation
Iranian Polymer Journal ( IF 2.4 ) Pub Date : 2021-06-18 , DOI: 10.1007/s13726-021-00951-8
Dimitry F. Grishin , Oksana S. Lizyakina , Luydmila B. Vaganova , Alexander A. Kaltenberg , Ivan D. Grishin

The visible light-induced polymerization of methyl methacrylate in the presence of methylene blue as a photocatalyst and various bromine-containing organic compounds was first investigated. It was shown that polymerization may be successfully initiated even at low concentrations of methylene blue using conventional LED strips. The polymerization rate and the dependency of molecular weight parameters of the samples on monomer conversion are governed by the nature of light source as well as the structure of the initiator and introducing additional reagents. The use of warm white light seems to be more favorable for conducting the process to high conversions. Electron-donating additives such as aliphatic amines or formic acid accelerate the polymerization and determine the linear increase of molecular weight of the samples with the conversion growth typical for reversible deactivated radical polymerization. The performed quantum-chemical calculations and experimental studies show that the simultaneous realization of the metal-free atom transfer radical polymerization and light-induced stable free radical polymerization mechanisms is possible under the light irradiation. The simultaneous realization of two different processes determines the linear growth of the polymer chain upon conversion but results in average control over molecular weight distribution of the obtained samples.



中文翻译:

亚甲基蓝和有机溴化物存在下可见光照射下甲基丙烯酸甲酯的自由基聚合

首先研究了在作为光催化剂的亚甲蓝和各种含溴有机化合物存在下甲基丙烯酸甲酯的可见光诱导聚合。结果表明,即使使用传统 LED 灯条在低浓度的亚甲蓝下也可以成功引发聚合。聚合速率和样品的分子量参数对单体转化率的依赖性受光源的性质以及引发剂的结构和引入的额外试剂的控制。使用暖白光似乎更有利于将过程进行到高转化率。给电子添加剂如脂肪胺或甲酸加速聚合并确定样品分子量的线性增加,转化率增长是可逆失活自由基聚合典型的转化率增长。进行的量子化学计算和实验研究表明,在光照射下可以同时实现无金属原子转移自由基聚合和光诱导稳定自由基聚合机制。两种不同过程的同时实现决定了聚合物链在转化时的线性增长,但导致对所得样品的分子量分布的平均控制。进行的量子化学计算和实验研究表明,在光照射下可以同时实现无金属原子转移自由基聚合和光诱导稳定自由基聚合机制。两种不同过程的同时实现决定了聚合物链在转化时的线性增长,但导致对所得样品的分子量分布的平均控制。进行的量子化学计算和实验研究表明,在光照射下可以同时实现无金属原子转移自由基聚合和光诱导稳定自由基聚合机制。两种不同过程的同时实现决定了聚合物链在转化时的线性增长,但导致对所得样品的分子量分布的平均控制。

更新日期:2021-06-18
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