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Sequential synthesis of well-defined poly(vinyl acetate)-block-polystyrene and poly(vinyl alcohol)-block-polystyrene copolymers using difunctional chloroamide-xanthate iniferter

Title
Sequential synthesis of well-defined poly(vinyl acetate)-block-polystyrene and poly(vinyl alcohol)-block-polystyrene copolymers using difunctional chloroamide-xanthate iniferter
Authors
MISHRA, AVNISH KUMARCHOI, CHUNG RYONGMAITI, SANDIPSEO, YE SEONGLEE, KYU SEONGKIM, EUNSEOLKIM, JIN KON
POSTECH Authors
KIM, JIN KON
Date Issued
Mar-2018
Publisher
ELSEVIER SCI LTD
Abstract
The sequential synthesis of well-defined poly(vinyl acetate)-block-polystyrene copolymer (PVAc-b-PS) and poly(vinyl alcohol)-block-polystyrene copolymer (PVA-b-PS) is challenging due to inactive vinyl acetate monomer and active styrene monomer. In this study, sequential polymerizations of vinyl acetate and styrene monomer were carried out by reversible addition-fragmentation chain transfer (RAFT) and atom transfer radical polymerization (ATRP) using an innovative amide based difunctional chloroamide-xanthate iniferter [S-(1-((3-(2-chloropropanamido)propyl) amino)-1-oxopropan-2-yl) O-ethyl xanthate]. Synthesized difunctional iniferter was very stable under basic condition and allowed the sequential reactions without chain-end modification and purification steps. Synthesized iniferter was first used for xanthate-mediated RAFT polymerization of VAc, followed by ATRP of styrene to achieve controlled molecular weight of PVAc-b-PS with lower polydispersity (≤1.3). Then, PVAc-b-PS was successfully converted to the corresponding PVA-b-PS by hydrolysis. Synthesized block copolymers were characterized by size exclusion chromatography, nuclear magnetic resonance spectroscopy, transmission electron microscopy, and dynamic light scattering.
The sequential synthesis of well-defined poly(vinyl acetate)-block-polystyrene copolymer (PVAc-b-PS) and poly(vinyl alcohol)-block-polystyrene copolymer (PVA-b-PS) is challenging due to inactive vinyl acetate monomer and active styrene monomer. In this study, sequential polymerizations of vinyl acetate and styrene monomer were carried out by reversible addition-fragmentation chain transfer (RAFT) and atom transfer radical polymerization (ATRP) using an innovative amide based difunctional chloroamide-xanthate iniferter [S-(1-((3-(2-chloropropanamido)propyl) amino)-1-oxopropan-2-yl) O-ethyl xanthate]. Synthesized difunctional iniferter was very stable under basic condition and allowed the sequential reactions without chain-end modification and purification steps. Synthesized iniferter was first used for xanthate-mediated RAFT polymerization of VAc, followed by ATRP of styrene to achieve controlled molecular weight of PVAc-b-PS with lower polydispersity (≤1.3). Then, PVAc-b-PS was successfully converted to the corresponding PVA-b-PS by hydrolysis. Synthesized block copolymers were characterized by size exclusion chromatography, nuclear magnetic resonance spectroscopy, transmission electron microscopy, and dynamic light scattering.
Keywords
MEDIATED RADICAL POLYMERIZATION; (S)-2-(ETHYL PROPIONATE)-(O-ETHYL XANTHATE); FLUORIDE) BLOCK-COPOLYMERS; ACTIVATION RATE CONSTANTS; RAFT POLYMERIZATION; METHYL-METHACRYLATE; VINYLIDENE FLUORIDE; FACILE SYNTHESIS; AGENT STRUCTURE; ATRP
URI
http://oasis.postech.ac.kr/handle/2014.oak/41163
DOI
10.1016/j.polymer.2018.02.009
ISSN
0032-3861
Article Type
Article
Citation
POLYMER, vol. 139, page. 68 - 75, 2018-03
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 KIM, JIN KON
Dept. of Chemical Enginrg
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