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 methyacrylates have demonstrated to be an effective approach to 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 contribution 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 (DPtBu2) 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 DPtBu2/B(2,4-F2C6H3)3 FLP as a green/sustainable and user-friendly polymerization catalysis for convenient synthesis of metal-free all-acrylic multiblock copolymers.