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Pressure‐assisted strategy for the synthesis of vinyl pyrrolidone‐based macro‐star photoiniferters. A route to star block copolymers
Author(s) -
Maksym Paulina,
Tarnacka Magdalena,
Bernat Roksana,
Bielas Rafał,
Mielańczyk Anna,
Hachuła Barbara,
Kaminski Kamil,
Paluch Marian
Publication year - 2020
Publication title -
journal of polymer science
Language(s) - English
Resource type - Journals
eISSN - 2642-4169
pISSN - 2642-4150
DOI - 10.1002/pol.20200037
Subject(s) - copolymer , polymer chemistry , star (game theory) , materials science , methyl methacrylate , polymer , monomer , raft , chain transfer , composite material , radical polymerization , mathematical analysis , mathematics
Abstract Star‐shaped 1‐vinyl‐2‐pyrrolidone (VP)‐based polymers having four pendant arms were produced via high‐pressure RAFT using the trithiocarbonate‐functionalized core. The use of compression ( p = 250 MPa) significantly reduced or eliminated star‐star/star‐chain coupling side reactions and termination process characteristics the for “ core‐first ” R ‐type approach, still allowing for a “ pseudo‐living ” reaction course up to very high monomer conversion (>98%). Consequently, tailored and highly living star‐shaped poly(1‐vinyl‐2‐pyrrolidone)s (PVP) in a wide range of molecular weights M n = 2.0–175.6 kg/mol ( Đ = 1.18–1.80) have been obtained. The chain extension of the produced polymer was carried out with methyl methacrylate (MMA) via photo‐induced RAFT ( λ = 365 nm) in the presence of tertiary amine catalyst, yielding well‐defined amphiphilic star‐shaped block copolymers. DSC measurements showed that synthesized star‐shaped PVP homopolymers revealed much lower glass transition temperature values compared to their commercially supplied linear analogs.