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One‐Pot Synthesis of Dual Supramolecular Associative PMMA‐Based Copolymers and the Precise Thermal Property Tuning
Author(s) -
Hayashi Mikihiro,
Kimura Takahiro,
Oba Yuta,
Takasu Akinori
Publication year - 2021
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.202000302
Subject(s) - copolymer , supramolecular chemistry , polymer chemistry , chain transfer , pyridine , methacrylate , materials science , thermal stability , monomer , chemistry , polymer , organic chemistry , radical polymerization , molecule
Dual supramolecular associative polymers have attracted attention for efficient physical property modification. Herein, a one‐pot synthesis of dual supramolecular associative poly(methyl methacrylate)‐based copolymers via reversible addition fragmentation chain transfer (RAFT) copolymerization using a novel methacrylate‐type monomer (coded as UP‐MA) bearing a urea bond and a pendant pyridine group is demonstrated. UP‐MA is synthesized by reacting 4‐picolylamine and 2‐isocyanatoethyl methacrylate. The subsequent RAFT copolymerization of UP‐MA and methyl methacrylate (MMA) can be performed by directly adding MMA, a chain transfer agent, and a radical initiator into the reaction solution of UP‐MA. The estimated values of radical reactivity ratio ( r ) for UP‐MA and MMA are close to unity, attaining a nearly ideal random sequence of the dual supramolecular associative units in the copolymer chain. By blending a metal salt into the random copolymer, coordination bonds between the salt and the pyridine groups are formed, and the urea groups simultaneously form hydrogen bonds, generating a dual supramolecular associative network. Precise tuning of the thermal property is realized by changing the fraction of the metal salt and associative groups in the copolymers.