Reversible addition–fragmentation chain transfer based copolymers of acrylonitrile and alkyl acrylates as possible precursors for carbon fibers: synthesis and thermal behavior during stabilization

Toms, R.V.; Balashov, M.S.; Gervald, A.Y.; Prokopov, N.I.; Plutalova, A.V.; Chernikova, E.V.

Авторы: Toms Roman V., Balashov Mikhail S., Gervald Alexander Y., Prokopov Nickolay I., Plutalova Anna V., Chernikova Elena V.
Журнал: Polymer International
Год издания: 2021
Издательство: John Wiley & Sons Inc.
Местоположение издательства: United States
Номер статьи: pi.6286
DOI: 10.1002/pi.6286
Аннотация: Copolymers of acrylonitrile and alkyl acrylates with various alkyl substituents (methyl, ethyl, butyl, 2-ethylhexyl and lauryl)were synthesized via reversible addition–fragmentation chain transfer polymerization in dimethylsulfoxide. It is demonstratedthat reactivity of alkyl acrylate in copolymerization decreases with increase of the length of the alkyl substituent. The molarfractions of homodiads and homotriads of acrylonitrile and the number-average sequence length of acrylonitrile unitsdecreases with a decrease in the acrylate content in the copolymer or with an increase in the length of the alkyl substituentin the acrylate. The copolymer composition was held constant throughout copolymerization in all the studied systems resultingin the formation of copolymers with high compositional homogeneity. Additionally the reversible addition–fragmentationchain transfer mechanism provides low dispersity of the copolymers. Both factors enable the effect of the alkyl substituentin alkyl acrylate on the thermal behavior of acrylonitrile copolymers to be carefully revealed. Being inert in the cyclization reaction,alkyl acrylates have no effect on the activation energy of the reaction. However, increase of the length of the alkyl substituentis followed by a slower evolution of the ladder structure. In contrast, in conditions of oxidative stabilization, thestabilization index increases in the order of increase of the number-average sequence length of the acrylonitrile units inthe copolymers. Thus, the use of alkyl acrylates with longer alkyl substituents provides an increase of chain flexibility andthe formation of an enhanced ladder structure during oxidative stabilization which is profitable for carbon fiber production.
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Reversible addition–fragmentation chain transfer based copolymers of acrylonitrile and alkyl acrylates as possible precursors for carbon fibers: synthesis and thermal behavior during stabilizationстатья

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