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Synthesis of Silicone‐Methacrylate Copolymers by ATRP Using a Nickel‐Based Supported Catalyst
Author(s) -
Duquesne Emmanuel,
Habimana Jean,
Degée Philippe,
Dubois Philippe
Publication year - 2006
Publication title -
macromolecular chemistry and physics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.57
H-Index - 112
eISSN - 1521-3935
pISSN - 1022-1352
DOI - 10.1002/macp.200600133
Subject(s) - polymer chemistry , copolymer , monomer , polymerization , bromide , dispersity , atom transfer radical polymerization , triphenylphosphine , catalysis , chemistry , nickel , methyl methacrylate , materials science , organic chemistry , polymer
Summary: A nickel (II) bromide catalyst immobilized onto crosslinked diphenylphosphinopolystyrene (PS‐PPh 3 /NiBr 2 ) was used for the synthesis of silicone‐methacrylate copolymers by atom transfer radical polymerization (ATRP) of various methacrylate monomers using ω ‐bromide silicone chains as macroinitiator. The polymerization proved to be very well‐controlled when a sufficient amount of soluble ligand, i.e., triphenylphosphine (PPh 3 ), was added to the polymerization medium. Under these conditions, this technique efficiently led to the production of different copolymers with controlled compositions and molecular weights as well as narrow polydispersity indices ( $\overline M _{\rm w} /\overline M _{\rm n}$ < 1.5). The recovered copolymers proved to be almost free of catalyst residues. Indeed, inductively coupled plasma (ICP) analysis revealed a metal content lower than 100 ppm, representing only a few percent of the initial metal content in the polymerization medium.Synthesis of PDMS block copolymer in toluene catalyzed by PS‐PPh 3 /NiBr 2 in the presence of soluble PPh 3 at 90 °C.