Block copolymers of isobutylene with styrene and methyl methacrylate by visible light induced polymerization
Bohdan Mikalai,a Miraslau Makarevich,a Maksim Hulnik,a Dmitriy I. Shiman,a Irina V. Vasilenko,a Sergey V. Kostjukb.
a Research Institute for Physical Chemical Problems of the Belarusian State University, The Republic of Belarus, bogdan.nikolaj59583@gmail.com
b Sorbonne Universite, CNRS, Institut Parisien de Chimie Moleculaire, Equipe Chimie des Polymeres, 4 place Jussieu, 75252 Paris Cedex 05, France
Polyisobutylene (PIB) is a rubbery polymer, which is synthesized exclusively via cationic polymerization. Due to unique properties of the aforementioned polymer, including low gas permeability, chemical resistance and biocompatibility, PIB and its block copolymers are prospective materials for the usage in the electronic industry and medicine1,2. In that regard, the development of new facile and environmentally friendly synthesis of the isobutylene block copolymers is desired. Mechanistic transformation is a promising approach in polymer synthesis that combines different polymerization modes to create novel copolymer structures, unavailable through single polymerization mechanism. Such approach seems even more interesting in a combination with visible light induced polymerization. The latter is a powerful synthetic tool, which allows the one to conduct fast reactions with spatiotemporal control and with low energy and solvent requirements.
Herein, the simple strategy for the preparation of block copolymers of isobutylene with styrene and methyl methacrylate via mechanistic transformation from cationic to photo induced radical polymerization is reported. This strategy involves the synthesis of 2-bromo-2-methylpropanoyl-terminated difunctional polyisobutylene via consecutive cationic polymerization, in situ preparation of hydroxyl terminated polyisobutylene and its acylation by 2-bromo-2-methylpropanoyl bromide. The following Mn2(CO)10-triggered photo induced radical polymerization utilizing this macroinitiator produces multiblock copolymer with styrene and triblock copolymer with methyl methacrylate in bulk conditions3. Thus, the novel straightforward procedure for the synthesis of PIB-based block copolymers was designed, which employed the visible light induced reaction. This approach may open the new simple and cost-efficient way for the preparation of PIB-based block copolymers.
Acknowledgements
This work was supported by State Program for Scientific Research of Belarus “Chemical processes, reagents and technologies, bioregulators and bioorganic chemistry” (project 2.1.01.03).
References
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