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Matrix polarity effects on microphase separation in zwitterionomers, 1. Synthesis of the model random zwitterionomers
Author(s) -
Bieglé Alain,
Galin JeanClaude
Publication year - 2000
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(20000801)201:13<1442::aid-macp1442>3.0.co;2-2
Subject(s) - epichlorohydrin , chemistry , polymer chemistry , copolymer , chloride , mesophase , organic chemistry , polymer , phase (matter)
In order to analyze the matrix polarity effects on the potential microphase separation in zwitterionomers, well controlled multi‐step chemical modifications of atactic and amorphous poly(epichlorohydrin) (PEC, T g = –22°C) were designed for the synthesis of four homologous series of zwitterionic A i B copolymers. They segregate into their flexible polyether chain segments consisting of various A i units —CH 2 —CH(CH 2 R i )—O— of finely tuned polarity such as epichlorohydrin (PEC, R i = Cl), glycidol (PGOH, R i = OH), glycidyl acetate (PGAC, R i = O—CO—CH 3 ) or glycidyl‐ p ‐nitrobenzoate (PGNB, R i = O—CO—C 6 H 4 —NO 2 ) and highly dipolar and constant B units —CH 2 —CH[—CH 2 — O—(CH 2 ) 2 —N + (C 2 H 5 ) 2 —(CH 2 ) 2 — O—CO—C – (CN) 2 ]—O— of the ammonio‐ethoxydicyanoethenolate type (μ = 25.9 D, molar fraction F B < 0.3). All the reactions were performed in homogeneous DMAC solution, namely: S N 2 substitution of PEC by sodium 2‐(diethylamino)ethanethiolate; S N 2 substitution of PGOH (activated as sodium alcoholate) by 2‐(diethylamino)ethyl chloride or its zwitterionic derivative; quaternization of tertiary amino copolymers by 2,2‐dicyanoketene ethylene acetal; acylations of PGOH zwitterionomers by acetic anhydride or p ‐nitrobenzoyl chloride. These reactions were sufficiently selective and efficient to lead to the target pure zwitterionomers of high enough chain length (DP w > 200), of well controlled composition and of quasi‐bernouillan microstructure. They may be thus considered as good model systems for structural studies.