IndiumV3, Main, Repository, bibRecord, 000594

Ring-Opening Polymerization of rac- and meso-Lactide Initiated by Indium Bis(phenolate) Isopropoxy Complexes

Identifieur interne : 000594 ( Main/Repository ); précédent : 000593; suivant : 000595

Ring-Opening Polymerization of rac- and meso-Lactide Initiated by Indium Bis(phenolate) Isopropoxy Complexes

Auteurs : RBID : Pascal:13-0368994

Descripteurs français

Pascal (Inist)
- Lactique acide polymère, Polymère syndiotactique, Polymérisation catalyseur complexe, Polymérisation ouverture cycle, Polymérisation solution, Polymérisation stéréospécifique, Complexe d'indium, Complexe aryloxy, Complexe alcoxy, Complexe dinucléaire, Cinétique chimique, Constante vitesse, Energie activation, Etude expérimentale.

English descriptors

KwdEn :
- Activation energy, Alkoxy complex, Aryloxy complex, Chemical reaction kinetics, Complex catalyst polymerization, Dinuclear complex, Experimental study, Indium complex, Lactic acid polymer, Rate constant, Ring opening polymerization, Solution polymerization, Stereospecific polymerization, Syndiotactic polymer.

Abstract

Ring-opening polymerization of rac- and meso-lactide initiated by indium bis(phenolate) isopropoxides {1,4-dithiabutanediylbis(4,6-di-tert-butylphenolate)}(isopropoxy)indium (1) and {1,4-dithiabutanediylbis(4,6-di(2-phenyl-2-propyl)phenolate)}(isopropoxy)indium (2) is found to follow first-order kinetics for monomer conversion. Activation parameters ΔH? and ΔS? suggest an ordered transition state. Initiators 1 and 2 polymerize meso-lactide faster than rac-lactide. In general, compound 2 with the more bulky cumyl ortho-substituents in the phenolate moiety shows higher polymerization activity than 1 with tert-butyl substituents. meso-Lactide is polymerized to syndiotactic poly(meso-lactides) in THF, while polymerization of rac-lactide in THF gives atactic poly(rac-lactides) with solvent-dependent preferences for heterotactic (THF) or isotactic (CH₂Cl₂) sequences. Indium bis(phenolate) compound rac-(1,2-cyclohexanedithio-2,2'-bis(4,6-di(2-phenyl-2-propyl)phenolato}(isopropoxy)indium (3) polymerizes meso-lactide to give syndiotactic poly(meso-lactide) with narrow molecular weight distributions and rac-lactide in THF to give heterotactically enriched poly(rac-lactides).

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Pascal:13-0368994

Le document en format XML

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<author><name sortKey="Kapelski, Andreas" uniqKey="Kapelski A">Andreas Kapelski</name>
<affiliation wicri:level="3"><inist:fA14 i1="01"><s1>Institute of Inorganic Chemistry, RWTH Aachen University, Landoltweg 1</s1>
<s2>52074 Aachen</s2>
<s3>DEU</s3>
<sZ>1 aut.</sZ>
<sZ>2 aut.</sZ>
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<country>Allemagne</country>
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<region type="district" nuts="2">District de Cologne</region>
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<author><name sortKey="Okuda, Jun" uniqKey="Okuda J">Jun Okuda</name>
<affiliation wicri:level="3"><inist:fA14 i1="01"><s1>Institute of Inorganic Chemistry, RWTH Aachen University, Landoltweg 1</s1>
<s2>52074 Aachen</s2>
<s3>DEU</s3>
<sZ>1 aut.</sZ>
<sZ>2 aut.</sZ>
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<region type="district" nuts="2">District de Cologne</region>
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<title level="j" type="abbreviated">J. polym. sci., Part A, Polym. chem.</title>
<title level="j" type="main">Journal of polymer science. Part A. Polymer chemistry</title>
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<term>Aryloxy complex</term>
<term>Chemical reaction kinetics</term>
<term>Complex catalyst polymerization</term>
<term>Dinuclear complex</term>
<term>Experimental study</term>
<term>Indium complex</term>
<term>Lactic acid polymer</term>
<term>Rate constant</term>
<term>Ring opening polymerization</term>
<term>Solution polymerization</term>
<term>Stereospecific polymerization</term>
<term>Syndiotactic polymer</term>
</keywords>
<keywords scheme="Pascal" xml:lang="fr"><term>Lactique acide polymère</term>
<term>Polymère syndiotactique</term>
<term>Polymérisation catalyseur complexe</term>
<term>Polymérisation ouverture cycle</term>
<term>Polymérisation solution</term>
<term>Polymérisation stéréospécifique</term>
<term>Complexe d'indium</term>
<term>Complexe aryloxy</term>
<term>Complexe alcoxy</term>
<term>Complexe dinucléaire</term>
<term>Cinétique chimique</term>
<term>Constante vitesse</term>
<term>Energie activation</term>
<term>Etude expérimentale</term>
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<front><div type="abstract" xml:lang="en">Ring-opening polymerization of rac- and meso-lactide initiated by indium bis(phenolate) isopropoxides {1,4-dithiabutanediylbis(4,6-di-tert-butylphenolate)}(isopropoxy)indium (1) and {1,4-dithiabutanediylbis(4,6-di(2-phenyl-2-propyl)phenolate)}(isopropoxy)indium (2) is found to follow first-order kinetics for monomer conversion. Activation parameters ΔH? and ΔS? suggest an ordered transition state. Initiators 1 and 2 polymerize meso-lactide faster than rac-lactide. In general, compound 2 with the more bulky cumyl ortho-substituents in the phenolate moiety shows higher polymerization activity than 1 with tert-butyl substituents. meso-Lactide is polymerized to syndiotactic poly(meso-lactides) in THF, while polymerization of rac-lactide in THF gives atactic poly(rac-lactides) with solvent-dependent preferences for heterotactic (THF) or isotactic (CH<sub>2</sub>
Cl<sub>2</sub>
) sequences. Indium bis(phenolate) compound rac-(1,2-cyclohexanedithio-2,2'-bis(4,6-di(2-phenyl-2-propyl)phenolato}(isopropoxy)indium (3) polymerizes meso-lactide to give syndiotactic poly(meso-lactide) with narrow molecular weight distributions and rac-lactide in THF to give heterotactically enriched poly(rac-lactides).</div>
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Cl<sub>2</sub>
) sequences. Indium bis(phenolate) compound rac-(1,2-cyclohexanedithio-2,2'-bis(4,6-di(2-phenyl-2-propyl)phenolato}(isopropoxy)indium (3) polymerizes meso-lactide to give syndiotactic poly(meso-lactide) with narrow molecular weight distributions and rac-lactide in THF to give heterotactically enriched poly(rac-lactides).</s0>
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<s1>ACT</s1>
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<s2>NK</s2>
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Ring-Opening Polymerization of rac- and meso-Lactide Initiated by Indium Bis(phenolate) Isopropoxy Complexes

Ring-Opening Polymerization of rac- and meso-Lactide Initiated by Indium Bis(phenolate) Isopropoxy Complexes

Descripteurs français

English descriptors

Abstract

Links toward previous steps (curation, corpus...)

Links to Exploration step

Le document en format XML

Pour manipuler ce document sous Unix (Dilib)

Pour mettre un lien sur cette page dans le réseau Wicri