A dual-initiating organic frustrated Lewis pair catalyst for living polymerizations of (bio)acrylates to facilitate the synthesis of metal-free multiblock copolymers†

The development of powerful catalysis or methodologies for the synthesis of fundamentally and technologically important multiblock copolymers is a perpetual task. Dual-initiating Lewis pair (LP) catalysts for living/controlled polymerizations of methacrylates have been demonstrated to be an effective approach towards all-acrylic multiblock copolymers. However, the utilization of metal-based Lewis acids (LAs) and complicated Lewis bases (LBs) that typically require laborious syntheses are essential. This article reports the first organic dual-initiating frustrated Lewis pair (FLP) catalysts consisting of tris(2,4-difluorophenyl)borane [B(2,4-F₂C₆H₃)₃] LA and commercially available 1,2-bis[(di-tert-butylphosphino)methyl]benzene (DP^tBu₂) LB, which can mediate efficient and living polymerizations of various (bio)acrylates. Accordingly, all-acrylic multiblock copolymers (up to hepta blocks) with well-defined structures can be readily prepared via sequential monomer addition, thus successfully establishing DP^tBu₂/B(2,4-F₂C₆H₃)₃ FLP as a green/sustainable and user-friendly polymerization catalyst for the convenient synthesis of metal-free all-acrylic multiblock copolymers.