High-temperature copolymerization of ethyl esters of vinyl-or isopropenylcyclopropanecarboxylic acids with SO 2 was studied as a route to functionally substituted unsaturated polysulfones. The composition, structure, and some properties of the polysulfones obtained were studied. The copolymerization mechanism was considered.Copolymers of olefins with SO 2 , polysulfones (PSs), show much promise for practice [133]. In particular, they can be used as plastics, materials for concentrating sulfuric acid solutions [1], and coatings for fabrics, paper, and wood [2]. Polysulfone materials are used for insulation and soundproofing. Polysulfones prepared from SO 2 and higher olefins improve the viscosity index of hydrocarbon lubricants [3].
A number of unsaturated 4-methylene-1,3-dioxolanes were synthesized and described and their polymerization carried out in the presence of radical initiators both in mass and in solution. It has been established by data of IR and PMR spectra of the obtained polymers that the homopolymerization of the synthesized monomers proceeds both with the simultaneous participation of a methylene double bond and a dioxolane cycle with the formation of linear structural links with ketoester fragments, and only with the participation of a methylene group with the formation of links with dioxolane cycles as side groups. It has been revealed that the ratio of forming linear and cyclic structural links depends on monomer concentration and polymerization temperature. It has been established that with increase ofthe monomer concentration during polymerization in solution, the fraction of cyclic elementary links is increased, but in all cases of polymerization, the fraction of linear links prevails over the cyclic one. It has been found that with increase of the polymerization temperature, the fraction of links with the opening of the dioxolane cycle in the macrocycleis increased. The kinetics of the polymerization process was studied, and the reaction orders on monomer and initiator revealed, and the activation energy of the process was calculated. The lower value of the reaction order on monomers in comparison with polymerization of vinyl monomers was explained by availability of two various types of growing radicals in the system and their participation in the chain break reactions.
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