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Регулирование комплексно-радикальной полимеризации метилметакрилата добавлением гафноцендихлорида

Регулирование комплексно-радикальной полимеризации метилметакрилата добавлением гафноцендихлорида

Abstract

Представлены результаты исследования влияния гафноцендихлорида (ГФЦ) как на процесс полимеризации метилметакрилата (ММА) в интервале температур от 30 до 60 С, так и на молекулярно-массовые характеристики полимера. Методом дилатометрии определены кинетические зависимости протекания процесса,рассчитаны основные кинетические характеристики полимеризации, оценено влияние на них температуры. Показано, что использование гафноцендихлорида позволяет проводить радикальную полимеризацию с высокими скоростями при комнатных и даже при пониженных температурах независимо от типа использованного инициатора (пероксид бензоила или азодиизобутиронитрил). Результаты исследования показали, что процесс полимеризации в области от 30 до 60 С характеризуется небольшой энергией активации, что позволяет использовать этот металлоцен для инициирования низкотемпературной полимеризации. Методами гель-хроматографии и вискозиметрии получены данные по молекулярным массам и полидисперсности синтезированных полимеров. Обнаружено, что полидисперсность ПММА, полученного в присутствии ГФЦ, имеет чёткую тенденцию к снижению. Предположено, что именно взаимодействие гафноцендихлорида с радикалом роста и происходящий при этом переход от классического радикального механизма процесса к комплексно-радикальному приводит к «сужению» молекулярно-массового распределения и снижению полидисперсности.

The research of the hafnocene dichloride’ effect on the methyl methacrylate’s polymerization at the temperature from 30 to 60°С as well as on the molecular mass of PMMA was carried out. The polymerization kinetics were obtained by dilatometry; the basic kinetic parameters were calculated; the influence of temperature on these parameters was shown. It is established that the polymerization can be carried out with high velocity at the room and lower temperature in the presence of hafnocene dichloride, it is not depend on the initiator’s structure (benzoyl peroxide or azo-diiso-butyronitrile). It is established that the polymerization process in the field of 30 to 60°С is characterized by low activation energy, it enables to initiate a low-temperature polymerization by the metallocene. The data on the molecular masses and polydispersity of synthesized polymers were obtained by using of gel chromatography and viscosity methods. It is found that polydispersity of PMMA obtained in the presence of hafnocene dichloride, has a clear downward trend. It is expected that the interaction of hafnocene dichloride with the radical growth results in the narrowing of the molecular mass distribution and reduce polydispersity and moving from the classical radical mechanism of polumerization to complexradical that.

Keywords

КОМПЛЕКСНО-РАДИКАЛЬНАЯ ПОЛИМЕРИЗАЦИЯ,COMPLEX RADICAL POLYMERIZATION,МЕТИЛМЕТАКРИЛАТ,METHYL METHACRYLATE,ГАФНОЦЕНДИХЛОРИД,МИКРОСТРУКТУРА ПОЛИМЕРА,POLYMER'S MICROSTRUCTURE,HAFNOCENE DICHLORIDE

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selected citations
These citations are derived from selected sources.
This is an alternative to the "Influence" indicator, which also reflects the overall/total impact of an article in the research community at large, based on the underlying citation network (diachronically).
BIP!Citations provided by BIP!
popularity
This indicator reflects the "current" impact/attention (the "hype") of an article in the research community at large, based on the underlying citation network.
BIP!Popularity provided by BIP!
influence
This indicator reflects the overall/total impact of an article in the research community at large, based on the underlying citation network (diachronically).
BIP!Influence provided by BIP!
impulse
This indicator reflects the initial momentum of an article directly after its publication, based on the underlying citation network.
BIP!Impulse provided by BIP!
0
Average
Average
Average