Partial or total silylation of dextran with hexamethyldisilazane
Identifieur interne : 001778 ( Main/Exploration ); précédent : 001777; suivant : 001779Partial or total silylation of dextran with hexamethyldisilazane
Auteurs : Cécile Nouvel [France] ; Isabelle Ydens [Belgique] ; Philippe Degee [Belgique] ; Philippe Dubois [Belgique] ; Édith Dellacherie [France] ; Jean-Luc Six [France]Source :
- Polymer : (Guildford) [ 0032-3861 ] ; 2002.
Descripteurs français
- Pascal (Inist)
English descriptors
- KwdEn :
Abstract
The silylation reaction of dextran with 1,1,1,3,3,3-hexamethyldisilazane (HMDS) in DMSO was studied as the first step of the synthesis of new amphiphilic polyester-grafted dextrans. According to the experimental conditions, i.e. dextran molar weight, medium temperature and reaction time, HMDS/OH ratio, addition of a catalyst and co-solvent, partially or totally silylated dextrans were recovered. The highest silylation yields were obtained with the lowest molecular weight dextrans. The increase in temperature medium and/or reaction time, the presence of catalyst or co-solvent favored the protection yield. Whatever the dextran used, complete silylation of the polysaccharide chain could be achieved by adequate selection of the experimental conditions. The thermal properties of resulting silylated polysaccharides were investigated by temperature modulated DSC. It was observed that Tg values of partially silylated dextran were maintained between 120 and 140 °C, independently of the dextran molecular weight. Interestingly, DMSO proved to behave as an efficient plasticizer of (partially) silylated dextrans. The partially silylated dextrans were efficiently used as multifunctional macroinitiators for the controlled ring-opening polymerization (ROP) of lactone. The ROP was then promoted from the remaining hydroxyl groups in the presence of tin or aluminium activator. After polymerization and ultimate deprotection of the silylated dextran backbone, amphiphilic polyester-grafted dextrans were readily recovered.
Affiliations:
- Belgique, France
- Grand Est, Lorraine (région)
- Nancy
- Centre national de la recherche scientifique, Laboratoire réactions et génie des procédés, Université de Lorraine
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B.P. 451</s1><s2>54001 Nancy</s2><s3>FRA</s3><sZ>1 aut.</sZ><sZ>5 aut.</sZ><sZ>6 aut.</sZ></inist:fA14><country>France</country><placeName><region type="region" nuts="2">Grand Est</region><region type="old region" nuts="2">Lorraine (région)</region><settlement type="city">Nancy</settlement></placeName><placeName><settlement type="city">Nancy</settlement><region type="region" nuts="2">Grand Est</region><region type="region" nuts="2">Lorraine (région)</region></placeName><orgName type="laboratoire" n="5">Laboratoire réactions et génie des procédés</orgName><orgName type="university">Université de Lorraine</orgName><orgName type="institution">Centre national de la recherche scientifique</orgName></affiliation></author><author><name sortKey="Six, Jean Luc" sort="Six, Jean Luc" uniqKey="Six J" first="Jean-Luc" last="Six">Jean-Luc Six</name><affiliation wicri:level="3"><inist:fA14 i1="01"><s1>Laboratoire de Chimie-Physique Macromoléculaire, UMR CNRS-INPL 7568, Groupe ENSIC, 1 Rue Grandville, B.P. 451</s1><s2>54001 Nancy</s2><s3>FRA</s3><sZ>1 aut.</sZ><sZ>5 aut.</sZ><sZ>6 aut.</sZ></inist:fA14><country>France</country><placeName><region type="region" nuts="2">Grand Est</region><region type="old region" nuts="2">Lorraine (région)</region><settlement type="city">Nancy</settlement></placeName></affiliation></author></analytic><series><title level="j" type="main">Polymer : (Guildford)</title><title level="j" type="abbreviated">Polymer : (Guildf.)</title><idno type="ISSN">0032-3861</idno><imprint><date when="2002">2002</date></imprint></series></biblStruct></sourceDesc><seriesStmt><title level="j" type="main">Polymer : (Guildford)</title><title level="j" type="abbreviated">Polymer : (Guildf.)</title><idno type="ISSN">0032-3861</idno></seriesStmt></fileDesc><profileDesc><textClass><keywords scheme="KwdEn" xml:lang="en"><term>Amphiphilic polymer</term><term>Caprolactone copolymer</term><term>Chemical modification</term><term>Dextran</term><term>Dextran derivatives</term><term>Experimental study</term><term>Graft copolymer</term><term>Grafting</term><term>Growth from solution</term><term>Homogeneous reaction</term><term>Lactone</term><term>Operating conditions</term><term>Optimization</term><term>Organic silazane</term><term>Preparation</term><term>Silicon polymer</term><term>Silylation</term></keywords><keywords scheme="Pascal" xml:lang="fr"><term>Dextran</term><term>Modification chimique</term><term>Silylation</term><term>Silazane organique</term><term>Réaction homogène</term><term>Méthode en solution</term><term>Optimisation</term><term>Condition opératoire</term><term>Dextrane dérivé</term><term>Polymère silicium</term><term>Préparation</term><term>Greffage</term><term>Lactone</term><term>Copolymère greffé</term><term>Caprolactone copolymère</term><term>Polymère amphiphile</term><term>Etude expérimentale</term></keywords></textClass></profileDesc></teiHeader><front><div type="abstract" xml:lang="en">The silylation reaction of dextran with 1,1,1,3,3,3-hexamethyldisilazane (HMDS) in DMSO was studied as the first step of the synthesis of new amphiphilic polyester-grafted dextrans. According to the experimental conditions, i.e. dextran molar weight, medium temperature and reaction time, HMDS/OH ratio, addition of a catalyst and co-solvent, partially or totally silylated dextrans were recovered. The highest silylation yields were obtained with the lowest molecular weight dextrans. The increase in temperature medium and/or reaction time, the presence of catalyst or co-solvent favored the protection yield. Whatever the dextran used, complete silylation of the polysaccharide chain could be achieved by adequate selection of the experimental conditions. The thermal properties of resulting silylated polysaccharides were investigated by temperature modulated DSC. It was observed that T<sub>g</sub> values of partially silylated dextran were maintained between 120 and 140 °C, independently of the dextran molecular weight. Interestingly, DMSO proved to behave as an efficient plasticizer of (partially) silylated dextrans. The partially silylated dextrans were efficiently used as multifunctional macroinitiators for the controlled ring-opening polymerization (ROP) of lactone. The ROP was then promoted from the remaining hydroxyl groups in the presence of tin or aluminium activator. After polymerization and ultimate deprotection of the silylated dextran backbone, amphiphilic polyester-grafted dextrans were readily recovered.</div></front></TEI><affiliations><list><country><li>Belgique</li><li>France</li></country><region><li>Grand Est</li><li>Lorraine (région)</li></region><settlement><li>Nancy</li></settlement><orgName><li>Centre national de la recherche scientifique</li><li>Laboratoire réactions et génie des procédés</li><li>Université de Lorraine</li></orgName></list><tree><country name="France"><region name="Grand Est"><name sortKey="Nouvel, Cecile" sort="Nouvel, Cecile" uniqKey="Nouvel C" first="Cécile" last="Nouvel">Cécile Nouvel</name></region><name sortKey="Dellacherie, Edith" sort="Dellacherie, Edith" uniqKey="Dellacherie E" first="Edith" last="Dellacherie">Édith Dellacherie</name><name sortKey="Six, Jean Luc" sort="Six, Jean Luc" uniqKey="Six J" first="Jean-Luc" last="Six">Jean-Luc Six</name></country><country name="Belgique"><noRegion><name sortKey="Ydens, Isabelle" sort="Ydens, Isabelle" uniqKey="Ydens I" first="Isabelle" last="Ydens">Isabelle Ydens</name></noRegion><name sortKey="Degee, Philippe" sort="Degee, Philippe" uniqKey="Degee P" first="Philippe" last="Degee">Philippe Degee</name><name sortKey="Dubois, Philippe" sort="Dubois, Philippe" uniqKey="Dubois P" first="Philippe" last="Dubois">Philippe Dubois</name></country></tree></affiliations></record>Pour manipuler ce document sous Unix (Dilib)
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