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Living Anionic Polymerization of 4‐Trimethylstannylstyrene
Author(s) -
Takagi Naoto,
Higashihara Tomoya
Publication year - 2019
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.201900176
Subject(s) - anionic addition polymerization , polymer chemistry , chemistry , living anionic polymerization , living polymerization , polymerization , dispersity , copolymer , monomer , tetrahydrofuran , molar mass distribution , nucleophile , carbanion , chain transfer , molar mass , butyllithium , styrene , living free radical polymerization , reversible addition−fragmentation chain transfer polymerization , radical polymerization , polymer , organic chemistry , catalysis , solvent
The living anionic polymerization of 4‐trimethylstannylstyrene in tetrahydrofuran at −78 °C, initiated with sec ‐butyllithium, is achieved for the first time. Unwanted side reactions, such as the nucleophilic attack of a carbanion to the stannyl group, may be suppressed through the equimolar addition of dibutylmagnesium (Bu 2 Mg) to the initiator. The suppression of side reactions allows the control of the molecular weight of poly(4‐trimethylstannylstyrene) and maintains low molar‐mass dispersity ( Đ M ) values of less than 1.1. By increasing the feed ratio of the monomer to the initiator, the molecular weight increases proportionally, indicating a highly controllable polymerization reaction. Controlled syntheses of block and statistical copolymers derived from styrene and 4‐trimethylstannylstyrene are successfully developed due to the similar nucleophilicity of their living chain termini.