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Successive Synthesis of Regular and Asymmetric Star‐Branched Polymers by Iterative Methodology Based on Living Anionic Polymerization Using Functionalized 1,1‐Diphenylethylene Derivatives
Author(s) -
Hirao Akira,
Inoue Kyoichi,
Higashihara Tomoya
Publication year - 2006
Publication title -
macromolecular symposia
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.257
H-Index - 76
eISSN - 1521-3900
pISSN - 1022-1360
DOI - 10.1002/masy.200650805
Subject(s) - polymer , polystyrene , polymer chemistry , anionic addition polymerization , ethylene , materials science , methylene , living anionic polymerization , polymerization , chemistry , catalysis , organic chemistry , composite material
In order to achieve the successive synthesis of star‐branched polymers, we have developed a new iterative methodology which involves only three sets of the reactions in each iterative process: (a) a coupling reaction of a living anionic polymer with 1,1‐bis(3‐chloromethylphenyl)ethylene to prepare a DPE‐chain‐functionalized polymer, (b) an addition reaction of sec ‐BuLi to the DPE‐chain‐functionalized polymer, followed by treatment with 1‐(4‐(4‐bromobutyl)phenyl)‐1‐phenylethylene to prepare a new DPE‐chain‐functionalized polymer whose DPE is separated by four methylene units from the main chain, and (c) a coupling reaction of 1,1‐bis(3‐chloromethylphenyl)ethylene with the polymer anion derived from the newly prepared DPE‐chain‐functionalized polymer and sec ‐BuLi. With this methodology, a series of well‐defined 4‐arm, 8‐arm, and 16‐arm regular star‐branched polystyrenes as well as 4‐arm A 2 B 2 , 8‐arm A 4 B 4 , and 16‐arm A 8 B 8 asymmetric star‐branched polymers comprising polystyrene and poly(α‐methylstyrene) segments have been successively synthesized.