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Controlled polymerization of functional monomers and synthesis of block copolymers using a β-phosphonylated nitroxide

Identifieur interne : 001709 ( Main/Exploration ); précédent : 001708; suivant : 001710

Controlled polymerization of functional monomers and synthesis of block copolymers using a β-phosphonylated nitroxide

Auteurs : T. Diaz [France] ; A. Fischer [France] ; A. Jonquikres [France] ; A. Brembilla [France] ; P. Lochon [France]

Source :

Macromolecules [ 0024-9297 ] ; 2003.

RBID : Pascal:03-0251666

Descripteurs français

Pascal (Inist)
- Régulateur réaction, Nitroxyle, Phosphonate organique, Polymérisation radicalaire, Polymérisation masse, Acrylamide dérivé polymère, Pyridine(4-vinyl)polymère, Polymère vivant, Préparation, Acrylamide dérivé copolymère, Copolymère biséquencé, Pyridine(4-vinyl)copolymère, Etude expérimentale, Acrylamide(N,N-diméthyl) polymère, Acrylamide(N,N-diméthyl) copolymère.

English descriptors

KwdEn :
- Acrylamide derivative copolymer, Acrylamide derivative polymer, Bulk polymerization, Diblock copolymer, Experimental study, Free radical polymerization, Living polymer, Nitroxyl, Organic phosphonate, Preparation, Pyridine(4-vinyl) copolymer, Pyridine(4-vinyl) polymer, Reaction regulator.

Abstract

4-Vinylpyridine (4VP) and N,N-dimethylacrylamide (DMAA) were polymerized in a controlled manner using a β-phosphonylated nitroxide (N-tert-butyl-N-( 1-diethylphosphono-2,2-dimethyl-propyl) nitroxide, commonly designated as DEPN) as a control agent. Compared to the results that had previously been reported for the nitroxide-mediated radical polymerization (NMRP) with 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO), the polymerization of 4VP was much faster and very well controlled up to higher monomer conversions. Unlike 4VP, the controlled radical polymerization of DMAA using different types of nitroxides had so far remained limited to a very low conversion range (typically inferior to 10%). The use of DEPN gave rise to a very significant improvement of the NMRP of DMAA by providing a good reaction control up to high conversion (approximately 60%). For the first time, the ability of DEPN to control the homopolymerization of DMAA even at high conversion allowed the synthesis of poly(DMAA-b-4VP) block copolymers with a hydrophilic poly(DMAA) block which was longer than the poly(4VP) block. This particular feature should fairly improve the hydrosolubility of the derived amphiphilic cationic polymers, which can be obtained by simple quaternization of the former block copolymers, and extend the scope of their applications.

Affiliations:

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Le document en format XML

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<series><title level="j" type="main">Macromolecules</title>
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<term>Polymérisation masse</term>
<term>Acrylamide dérivé polymère</term>
<term>Pyridine(4-vinyl)polymère</term>
<term>Polymère vivant</term>
<term>Préparation</term>
<term>Acrylamide dérivé copolymère</term>
<term>Copolymère biséquencé</term>
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<front><div type="abstract" xml:lang="en">4-Vinylpyridine (4VP) and N,N-dimethylacrylamide (DMAA) were polymerized in a controlled manner using a β-phosphonylated nitroxide (N-tert-butyl-N-( 1-diethylphosphono-2,2-dimethyl-propyl) nitroxide, commonly designated as DEPN) as a control agent. Compared to the results that had previously been reported for the nitroxide-mediated radical polymerization (NMRP) with 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO), the polymerization of 4VP was much faster and very well controlled up to higher monomer conversions. Unlike 4VP, the controlled radical polymerization of DMAA using different types of nitroxides had so far remained limited to a very low conversion range (typically inferior to 10%). The use of DEPN gave rise to a very significant improvement of the NMRP of DMAA by providing a good reaction control up to high conversion (approximately 60%). For the first time, the ability of DEPN to control the homopolymerization of DMAA even at high conversion allowed the synthesis of poly(DMAA-b-4VP) block copolymers with a hydrophilic poly(DMAA) block which was longer than the poly(4VP) block. This particular feature should fairly improve the hydrosolubility of the derived amphiphilic cationic polymers, which can be obtained by simple quaternization of the former block copolymers, and extend the scope of their applications.</div>
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Controlled polymerization of functional monomers and synthesis of block copolymers using a β-phosphonylated nitroxide

Controlled polymerization of functional monomers and synthesis of block copolymers using a β-phosphonylated nitroxide

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Descripteurs français

English descriptors

Abstract

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