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A new macroinitiator for the synthesis of triblock copolymers PA12-b-PDMS-b-PA12

Authors

  • R. Rached,

    1. Laboratoire des Sciences du Génie Chimique, Unité Propre de Recherche 6811 CNRS, Groupe ENSIC, 1 rue Grandville, B.P. 451, 54001 Nancy Cedex, France
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  • S. Hoppe,

    1. Laboratoire des Sciences du Génie Chimique, Unité Propre de Recherche 6811 CNRS, Groupe ENSIC, 1 rue Grandville, B.P. 451, 54001 Nancy Cedex, France
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  • A. Jonquieres,

    1. Laboratoire de Chimie Physique Macromoléculaire, Unité Mixte de Recherche CNRS-INPL 7568, Groupe ENSIC, 1 rue Grandville, B.P. 451, 54001 Nancy Cedex, France
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  • P. Lochon,

    1. Laboratoire de Chimie Physique Macromoléculaire, Unité Mixte de Recherche CNRS-INPL 7568, Groupe ENSIC, 1 rue Grandville, B.P. 451, 54001 Nancy Cedex, France
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  • F. Pla

    Corresponding author
    1. Laboratoire des Sciences du Génie Chimique, Unité Propre de Recherche 6811 CNRS, Groupe ENSIC, 1 rue Grandville, B.P. 451, 54001 Nancy Cedex, France
    • Laboratoire des Sciences du Génie Chimique, Unité Propre de Recherche 6811 CNRS, Groupe ENSIC, 1 rue Grandville, B.P. 451, 54001 Nancy Cedex, France
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Abstract

A new PDMS macroinitiator is proposed for the anionic ring-opening polymerization of lactams. This α,ω-dicarbamoyloxy caprolactam PDMS macroinitiator was readily obtained in quantitative yield, by an original synthesis scheme in two steps, which involved the scarcely reported reaction of isocyanates with silanol groups. It was then shown that this bifunctional macroinitiator enabled to synthesize triblock copolymers PA12-b-PDMS-b-PA12 by polymerization of lauryl lactam (LL) at high temperature (200°C) in inert atmosphere under conditions compatible with reactive extrusion processes. Another related high molar weight α,ω-diacyllactam PDMS macroinitiator was also successfully used in the polymerization of LL under the same conditions, therefore overcoming the limitations formerly reported for this type of macroinitiators during the polymerization ε-caprolactam (ε-CL) at a much lower temperature (80°C). Triblock copolymers with a wide range of PA12 /molar weights (Mn: ∼ 10,800–250,000 Da) were eventually obtained by using both types of macroinitiators. DMTA and DSC analyses showed that their thermal properties were strongly dependent upon their respective contents in soft and hard blocks. Such triblock copolymers already appear very promising for the highly effective in situ compatibilization of PA12/PDMS blends as shown by recent complementary results obtained in our laboratory. © 2006 Wiley Periodicals, Inc. J Appl PolymSci 102: 2818–2831, 2006

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