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Anionic Polymerizations of Bis(terphenyl) Substituted Butadienes for Precursors of Head‐to‐Head Substituted Polyacetylenes
Author(s) -
Yu Yunhai,
He Junpo
Publication year - 2017
Publication title -
macromolecular chemistry and physics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.57
H-Index - 112
eISSN - 1521-3935
pISSN - 1022-1352
DOI - 10.1002/macp.201700080
Subject(s) - chemistry , terphenyl , polymerization , polymer chemistry , anionic addition polymerization , alkyl , tetrahydrofuran , monomer , photochemistry , polybutadiene , polymer , solvent , copolymer , organic chemistry
A series of butadiene derivatives with m ‐(alkyl)terphenyl substituents at 2,3‐position is synthesized and used for anionic living polymerizations. The controllabilities of the polymerizations of these monomers depend on solvent, temperature, and the alkyl groups on the terphenyl rings. In tetrahydrofuran (THF), the polymerization does not occur or proceeds very slowly at −78 °C. In toluene or cyclohexane, the polymerization proceeds smoothly in the presence of a small amount of THF at 40 °C. Monomer with n ‐butyl substituents on the phenyl ring undergoes polymerization in a well‐controlled manner in hydrocarbon solvent with or without THF additive. The resulting narrow disperse polybutadiene derivatives are characterized by using size exclusion chromatography, nuclear magnetic resonance spectroscopy, and ultraviolet spectroscopy. It is found that the polymer chains are formed almost exclusively by 1,4‐addition. The precursor polymers are converted into polyacetylenes with head‐to‐head regiospecificity by oxidative dehydrogenation using 2,3‐dichloro‐5,6‐dicyano‐1,4‐benzoquinone.