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

Authors

  • Rachid Jellali,

    1. 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
  • Irène Campistron,

    1. 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
  • Albert Laguerre,

    1. 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
  • Laurence Lecamp,

    1. Laboratoire Polymères, Biopolymères, Surfaces, Équipe MM, UMR 6270, INSA de ROUEN, Avenue de l'Université 76801 Saint-Étienne-du-Rouvray Cedex , France
    Search for more papers by this author
  • Pamela Pasetto,

    Corresponding author
    1. 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,

    1. Laboratoire Polymères, Biopolymères, Surfaces, Équipe MM, UMR 6270, INSA de ROUEN, Avenue de l'Université 76801 Saint-Étienne-du-Rouvray Cedex , France
    Search for more papers by this author
  • Jean-Luc Mouget,

    1. Laboratoire de Physiologie et de Biochimie Végétales, EA 2160, Mer, Molécules, Santé, Université du Maine Avenue O. Messiaen, 72085 Le Mans cedex, 9 France
    Search for more papers by this author
  • Jean-François Pilard

    1. 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

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

Ancillary