Volume 128, Issue 4 pp. 2489-2497
Article

Synthesis and crosslinking kinetic study of epoxidized and acrylated/epoxidized oligoisoprenes: Comparison between cationic and radical photopolymerization

Rachid Jellali

Rachid Jellali

UMR CNRS N° 6283, Méthodologie et Synthèse des Polymères, Département Méthodologie et Synthèse, Institut des Molécules et des Matériaux du Mans, Université du Maine, Avenue Olivier Messiaen, 72085 Le Mans Cedex 9, France

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Irène Campistron

Irène Campistron

UMR CNRS N° 6283, Méthodologie et Synthèse des Polymères, Département Méthodologie et Synthèse, Institut des Molécules et des Matériaux du Mans, Université du Maine, Avenue Olivier Messiaen, 72085 Le Mans Cedex 9, France

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Albert Laguerre

Albert Laguerre

UMR CNRS N° 6283, Méthodologie et Synthèse des Polymères, Département Méthodologie et Synthèse, Institut des Molécules et des Matériaux du Mans, Université du Maine, Avenue Olivier Messiaen, 72085 Le Mans Cedex 9, France

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Laurence Lecamp

Laurence Lecamp

Laboratoire Polymères, Biopolymères, Surfaces, Équipe MM, UMR 6270, INSA de ROUEN, Avenue de l'Université 76801 Saint-Étienne-du-Rouvray Cedex , France

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Pamela Pasetto

Corresponding Author

Pamela Pasetto

UMR CNRS N° 6283, Méthodologie et Synthèse des Polymères, Département Méthodologie et Synthèse, Institut des Molécules et des Matériaux du Mans, Université du Maine, Avenue Olivier Messiaen, 72085 Le Mans Cedex 9, France

UMR CNRS N° 6283, Méthodologie et Synthèse des Polymères, Département Méthodologie et Synthèse, Institut des Molécules et des Matériaux du Mans, Université du Maine, Avenue Olivier Messiaen, 72085 Le Mans Cedex 9, France===Search for more papers by this author
Claude Bunel

Claude Bunel

Laboratoire Polymères, Biopolymères, Surfaces, Équipe MM, UMR 6270, INSA de ROUEN, Avenue de l'Université 76801 Saint-Étienne-du-Rouvray Cedex , France

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Jean-Luc Mouget

Jean-Luc Mouget

Laboratoire de Physiologie et de Biochimie Végétales, EA 2160, Mer, Molécules, Santé, Université du Maine Avenue O. Messiaen, 72085 Le Mans cedex, 9 France

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Jean-François Pilard

Jean-François Pilard

UMR CNRS N° 6283, Méthodologie et Synthèse des Polymères, Département Méthodologie et Synthèse, Institut des Molécules et des Matériaux du Mans, Université du Maine, Avenue Olivier Messiaen, 72085 Le Mans Cedex 9, France

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First published: 05 September 2012
Citations: 8

Abstract

The photoinitiated polymerization of epoxidized hydroxytelechelic cis-1,4-polyisoprene and of a dual system (epoxidized/acrylated) telechelic cis-1,4-polyisoprene in the presence of 2,2-dimethyl-1,2-hydroxyacetophenone or/and hexafluoro-phosphate triarylsulfonium salt has been studied by real-time infrared spectroscopy. The synthesis of photosensitives oligoisoprenes was achieved by chemical modifications of hydroxytelechelic cis-1,4-polyisoprene obtained by controlled degradation of high molecular weight cis-1,4-polyisoprene. Then, the effect of light intensity, photoinitiator concentration, addition of reactive diluent and concentration of functional groups on the photopolymerization process was evaluated. Concerning the cationic process, the results showed that the kinetic profile improves when photoinitiator concentration and light intensity increase. The optimum concentration of triarylsulfonium salt used as photoinitiator was determined as 5% (w/w) and the optimum light intensity was 50 mW cm−2. Reactive diluent (3-ethyl-3-hydroxymethyl oxetane) addition greatly improves the ultimate conversion and the polymerization rate. Subsequently, the photopolymerization kinetic of a dual epoxidized/acrylated system was studied. The results obtained using different photoinitiator mixtures and different intensity of irradiation showed that the crosslinking of acrylate functions at the chain-end prevents the progression of the cationic process at the oxirane groups along the chain. Thus, the mobility of the cationic reactive centers was restricted by the crosslinking at the high conversion of the acrylate double bonds. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013

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