Open AccessSynthesis of α‐maleimide‐ω‐dienyl heterotelechelic poly(methyl methacrylate) and its cyclization by the intramolecular Diels–Alder reaction
Author(s) -
Mizawa Takahide,
Takenaka Katsuhiko,
Shiomi Tomoo
Publication year - 2000
Publication title -
journal of polymer science part a: polymer chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.768
H-Index - 152
eISSN - 1099-0518
pISSN - 0887-624X
DOI - 10.1002/(sici)1099-0518(20000101)38:1<237::aid-pola29>3.0.co;2-y
Subject(s) - maleimide , polymer chemistry , chemistry , intramolecular force , methyl methacrylate , tetrahydrofuran , polymerization , diels–alder reaction , double bond , alkoxide , polymer , organic chemistry , catalysis , solvent
The synthesis of heterotelechelic poly(methyl methacrylate) (PMMA) containing α‐maleimide‐ω‐dienyl end‐groups and its subsequent intramolecular cyclization are described. The anionic polymerization of methyl methacrylate was carried out with 3‐ tert ‐butyldimethylsilyloxypropyl‐1‐lithium and 5‐bromo‐1,3‐pentadiene as the initiator and terminator, respectively, to synthesize α‐hydroxy‐ω‐dienyl‐PMMA. The introduction of the maleimide group to the α chain end by the reaction of the sodium salt of the polymer with N ‐(3‐chloromethylphenyl)‐maleimide or N ‐(3‐bromomethylphenyl)‐maleimide was not successful because of the nucleophilic addition of alkoxide to the carboncarbon double bond of the maleimide group. When 4,4′‐bismaleimidediphenylether was allowed to react with the alkoxide, the aimed α‐maleimide‐ω‐dienyl‐PMMA was obtained in a good yield. Ring closure by the intramolecular Diels–Alder reaction was carried out by the heating of the dilute polymer solution in tetrahydrofuran. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 237–246, 2000