Premium
Synthesis of Functionalized Polymers by Means of Living Anionic Polymerization, 2. Synthesis of Well‐Defined Chain‐End and in‐Chain Functionalized Polymers with 1,3‐Butadienyl Groups
Author(s) -
Haraguchi Naoki,
Sakaguchi Yoshihiko,
Sugiyama Kenji,
Hirao Akira
Publication year - 2001
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 - 10.1002/1521-3935(20010701)202:11<2221::aid-macp2221>3.0.co;2-l
Subject(s) - polymer chemistry , anionic addition polymerization , living anionic polymerization , chemistry , methyl methacrylate , electrophile , end group , cationic polymerization , polymer , polymerization , macromonomer , methacrylate , living polymerization , radical polymerization , organic chemistry , catalysis
The synthesis of well‐defined functionalized polystyrenes and poly(methyl methacrylate)s with 1,3‐butadienyl groups has been described by the methodology based on the functionalization reactions of living anionic polymers of a new substituted 1,1‐diphenylethylene with a 1,3‐butadienyl group, 1‐[4‐(4‐methylene‐5‐hexenyl)phenyl]‐1‐phenylethylene ( 1 ). Both chain‐end and in‐chain functionalized polystyrenes with one or two 1,3‐butadienyl groups were synthesized by utilizing the addition reactions of living polystyrenes to 1 followed by methanol termination or treatment with appropriate electrophiles. On the other hand, chain‐end and in‐chain functionalized poly(methyl methacrylate)s with one or two 1,3‐butadienyl groups were obtained by the living anionic polymerization of methyl methacrylate with the adduct prepared from 1 and either s ‐BuLi or lithium naphthalenide. The 1,3‐buadienyl groups thus introduced were quantitatively transformed into anhydride or epoxy functions without any side reactions by the (C 2 H 5 ) 2 AlCl‐catalyzed Diels‐Alder reaction or by treatment with 3‐chloroperoxybenzoic acid.