Nitroxide-Mediated Radical Ring-Opening Copolymerization: Chain-End Investigation and Block Copolymer Synthesis

Well‐defined, degradable copolymers are successfully prepared by nitroxide‐mediated radical ring opening polymerization (NMrROP) of oligo(ethylene glycol) methyl ether methacrylate (OEGMA) or methyl methacrylate (MMA), a small amount of acrylonitrile (AN) and cyclic ketene acetals (CKAs) of differen...

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Bibliographic Details
Published in:Macromolecular rapid communications. Vol. 35; no. 4; pp. 484 - 491
Main Authors: Delplace, Vianney, Harrisson, Simon, Tardy, Antoine, Gigmes, Didier, Guillaneuf, Yohann, Nicolas, Julien
Format: Journal Article
Language:English
Published: Germany Blackwell Publishing Ltd 01.02.2014
Wiley-VCH Verlag
Subjects:
Acrylonitrile - chemistry
biodegradable
block copolymer
Block copolymers
Chains (polymeric)
Chemical Sciences
Degradation
Ethylenes - chemistry
Ketones - chemistry
kinetics (polym.)
living polymerization
Magnetic Resonance Spectroscopy
Methacrylates - chemistry
Methylmethacrylate - chemistry
Nitrogen Oxides - chemistry
nitroxide-mediated polymerization (NMP)
Nuclear magnetic resonance
Phosphorus - chemistry
Polymerization
Polymers - chemical synthesis
Polymers - chemistry
Polymethyl methacrylates
Radicals
Synthesis
Terminals
block copolymer
nitroxide-mediated polymerization (NMP)
biodegradable
kinetics (polym.)
living polymerization
ISSN:1022-1336, 1521-3927, 1521-3927
Online Access:Get full text
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Summary:Well‐defined, degradable copolymers are successfully prepared by nitroxide‐mediated radical ring opening polymerization (NMrROP) of oligo(ethylene glycol) methyl ether methacrylate (OEGMA) or methyl methacrylate (MMA), a small amount of acrylonitrile (AN) and cyclic ketene acetals (CKAs) of different structures. Phosphorous nuclear magnetic resonance allows in‐depth chain‐end characterization and gives crucial insights into the nature of the copoly­mer terminal sequences and the living chain fractions. By using a small library of P(OEGMA‐co‐AN‐co‐CKA) and P(MMA‐co‐AN‐co‐CKA) as macroinitiators, chain extensions with styrene are performed to furnish (amphiphilic) block copolymers comprising a degradable segment. Degradable block copolymers are successfully prepared by nitroxide‐mediated radical ring‐opening polymerization and characterized by phosphorous nuclear magnetic resonance, allowing the nature of the copolymer terminal sequences to be elucidated and the living chain fractions to be calculated. The synthesis of block copolymers comprising a degradable block is also reported.
Bibliography:ArticleID:MARC201300809
istex:968228453120249A6B3CF7F3D3A8F4B4A504D2E9
ark:/67375/WNG-PZSB502L-2
French National Research Agency - No. ANR-11-JS08-0005
CNRS and French
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ISSN:1022-1336
1521-3927
1521-3927
DOI:10.1002/marc.201300809