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Protected versus unprotected dextran macroinitiators for ATRP synthesis of Dex‐g‐PMMA

Identifieur interne : 000B50 ( Main/Exploration ); précédent : 000B49; suivant : 000B51

Protected versus unprotected dextran macroinitiators for ATRP synthesis of Dex‐g‐PMMA

Auteurs : Ludovic Dupayage [France] ; Cécile Nouvel [France] ; Jean-Luc Six [France]

Source :

RBID : ISTEX:615ACE3283CD9233524E458E912281B7696A5584

Descripteurs français

English descriptors

Abstract

The synthesis of amphiphilic dextran‐g‐poly(methyl methacrylate) glycopolymers (Dex‐g‐PMMA) is studied using “grafting from” concept and atom transfer radical polymerization. Two strategies have been examined to control the macromolecular parameters of such glycopolymers. One is involving four steps including a protection/deprotection approach and the second one only two steps. The introduction of initiators group onto a protected acetylated dextran (and directly onto dextran) was achieved resulting in protected DexAcBr (and in unprotected DexBr). These two types of polysaccharidic macroinitiators differ in term of solubility (hydrophilic DexBr vs. hydrophobic DexAcBr) and of position of the initiators groups on the glucosidic units (which are the sites of the future grafts). When evaluated as macroinitiators for ATRP of MMA, control was achieved in both cases but DexBr gave much faster polymerization and lower average grafting efficiency compared with DexAcBr or model initiator. Advantages and drawbacks of both pathways have finally been discussed. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010

Url:
DOI: 10.1002/pola.24409


Affiliations:


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Le document en format XML

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<term>Acetylated dextran</term>
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<term>Anhydride</term>
<term>Atom transfer polymerization</term>
<term>Atrp</term>
<term>Average efficiency</term>
<term>Biomacromolecules</term>
<term>Bromine containing polymer</term>
<term>Catalyst residues</term>
<term>Chem</term>
<term>Chemical modification</term>
<term>Chemical reaction kinetics</term>
<term>Copolymer</term>
<term>Dellacherie</term>
<term>Dexac</term>
<term>Dexacbr</term>
<term>Dexacbr macroinitiator</term>
<term>Dexacbr macroinitiators</term>
<term>Dexbr</term>
<term>Dextran</term>
<term>Dextran backbone</term>
<term>Dextran derivatives</term>
<term>Dmso</term>
<term>Dupayage</term>
<term>Ebibr</term>
<term>Esterification</term>
<term>Experimental study</term>
<term>First step</term>
<term>Future grafts</term>
<term>Glucosidic</term>
<term>Glucosidic unit</term>
<term>Glycopolymers</term>
<term>Graft</term>
<term>Graft copolymer</term>
<term>Grafting</term>
<term>Hydrophilic dexbr</term>
<term>Initial dextran</term>
<term>Initiator</term>
<term>Initiator group</term>
<term>Initiator groups</term>
<term>Initiator polymer</term>
<term>Initiators groups</term>
<term>Kinetics</term>
<term>Living copolymer</term>
<term>Macroinitiator</term>
<term>Macroinitiators</term>
<term>Macromolecule</term>
<term>Methyl methacrylate copolymer</term>
<term>Model initiator</term>
<term>Molar</term>
<term>Molar masses</term>
<term>Molar ratio</term>
<term>Monomer</term>
<term>Nouvel</term>
<term>Pathway</term>
<term>Petroleum ether</term>
<term>Pmma</term>
<term>Pmma arms</term>
<term>Pmma chains</term>
<term>Pmma grafts</term>
<term>Polym</term>
<term>Polym chem</term>
<term>Polymer</term>
<term>Polymer chemistry</term>
<term>Polymer science</term>
<term>Polymerization</term>
<term>Polymerization rate</term>
<term>Polysaccharide</term>
<term>Preparation</term>
<term>Radical catalyst</term>
<term>Rate constant</term>
<term>Reaction propagation</term>
<term>Reactivity order</term>
<term>Room temperature</term>
<term>Second generation</term>
<term>Second step</term>
<term>Solubility</term>
<term>Solution polymerization</term>
<term>Unprotected</term>
<term>Unprotected dexbr</term>
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<term>Amorceur radicalaire</term>
<term>Bromure acyle</term>
<term>Cinétique chimique</term>
<term>Constante vitesse</term>
<term>Copolymère greffé</term>
<term>Copolymère vivant</term>
<term>Dextran</term>
<term>Dextrane copolymère greffé</term>
<term>Dérivé du dextrane</term>
<term>Estérification</term>
<term>Etude expérimentale</term>
<term>Greffage</term>
<term>Modification chimique</term>
<term>Méthacrylate de méthyle copolymère</term>
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<term>Polymère amphiphile</term>
<term>Polymère brome</term>
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<term>Polymérisation transfert atome</term>
<term>Propagation réaction</term>
<term>Préparation</term>
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<term>Acetylated dextran</term>
<term>Anhydride</term>
<term>Atrp</term>
<term>Average efficiency</term>
<term>Biomacromolecules</term>
<term>Catalyst residues</term>
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<term>Copolymer</term>
<term>Dellacherie</term>
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<term>Dexacbr</term>
<term>Dexacbr macroinitiator</term>
<term>Dexacbr macroinitiators</term>
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<term>Dextran</term>
<term>Dextran backbone</term>
<term>Dmso</term>
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<term>Ebibr</term>
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<term>Future grafts</term>
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<term>Graft</term>
<term>Hydrophilic dexbr</term>
<term>Initial dextran</term>
<term>Initiator</term>
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<term>Molar</term>
<term>Molar masses</term>
<term>Molar ratio</term>
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<term>Pathway</term>
<term>Petroleum ether</term>
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<term>Pmma arms</term>
<term>Pmma chains</term>
<term>Pmma grafts</term>
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<term>Polym chem</term>
<term>Polymer</term>
<term>Polymer chemistry</term>
<term>Polymer science</term>
<term>Polymerization</term>
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<front>
<div type="abstract" xml:lang="en">The synthesis of amphiphilic dextran‐g‐poly(methyl methacrylate) glycopolymers (Dex‐g‐PMMA) is studied using “grafting from” concept and atom transfer radical polymerization. Two strategies have been examined to control the macromolecular parameters of such glycopolymers. One is involving four steps including a protection/deprotection approach and the second one only two steps. The introduction of initiators group onto a protected acetylated dextran (and directly onto dextran) was achieved resulting in protected DexAcBr (and in unprotected DexBr). These two types of polysaccharidic macroinitiators differ in term of solubility (hydrophilic DexBr vs. hydrophobic DexAcBr) and of position of the initiators groups on the glucosidic units (which are the sites of the future grafts). When evaluated as macroinitiators for ATRP of MMA, control was achieved in both cases but DexBr gave much faster polymerization and lower average grafting efficiency compared with DexAcBr or model initiator. Advantages and drawbacks of both pathways have finally been discussed. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010</div>
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