Well-defined second-order nonlinear optical polymers by controlled radical polymerization, via multifunctional macromolecular chain transfer agent: Design, synthesis, and characterizations

Anne-Lise Roy 1 Chong Bui 1 Ileana Rau 2 F. Kajzar 2 Bernadette Charleux 3 Maud Save 4 David Kreher 5 André-Jean Attias 1
1 LCP - Chimie des polymères
IPCM - Institut Parisien de Chimie Moléculaire, UPMC - Université Pierre et Marie Curie - Paris 6, CNRS - Centre National de la Recherche Scientifique : UMR7610
2 Department of General Chemistry
3 C2P2 - Laboratoire de Chimie, Catalyse, Polymères et Procédés, R 5265
4 IPREM - Institut Pluridisciplinaire de Recherche sur l'Environnement et les Matériaux
5 DCSO - Laboratoire de synthèse organique
Abstract : To address the issue of the aggregation in second-order nonlinear optical (NLO) polymers we developed an approach based on the synthesis of a multifunctional macromolecular chain transfer agent. The controlled monomer insertion polymerization into the main chain by a 'reversible addition-fragmentation chain transfer' (RAFT) mechanism allows the spatial arrangement of the NLO chromophores along the polymeric chain in order to obtain sequence-ordered polymers. In a first step, a novel trithiocarbonate based macroinitiator containing the disperse red 19 (DR19) units in the main chain was synthesized by polycondensation; in a second step, this polymeric precursor was applied to the synthesis of a sequentially ordered polymer by controlled insertion radical polymerization of styrene. Size exclusion chromatography (SEC), nuclear magnetic resonance (NMR) data revealed that, (i) for the first time, polystyrenes (PS) bearing DR19 dyes covalently bounded were obtained, and (ii) both the insertion reaction and the length of the polystyrene segments were accurately controlled. Whatever the incorporated dye amount, all the copolymers were soluble in common solvents. Second-order optical nonlinearity in corona-poled thin films was evaluated, and second harmonic coefficients up to 80 pm/V were determined for loading ratio lower than 10 wt-% (DR19/PS). This approach opens up opportunities for the incorporation of more efficient chromophores even in apolar matrices.
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Article dans une revue
Polymer, Elsevier, 2014, 55 (3), pp.782-787. 〈10.1016/j.polymer.2013.12.059〉
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Contributeur : Denis Roura <>
Soumis le : vendredi 11 avril 2014 - 09:43:10
Dernière modification le : lundi 17 décembre 2018 - 01:26:56

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Anne-Lise Roy, Chong Bui, Ileana Rau, F. Kajzar, Bernadette Charleux, et al.. Well-defined second-order nonlinear optical polymers by controlled radical polymerization, via multifunctional macromolecular chain transfer agent: Design, synthesis, and characterizations. Polymer, Elsevier, 2014, 55 (3), pp.782-787. 〈10.1016/j.polymer.2013.12.059〉. 〈hal-00977392〉

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