Tris(2,4-difluorophenyl)borane/Triisobutylphosphine Lewis Pair: A Thermostable and Air/Moisture-Tolerant Organic Catalyst for the Living Polymerization of Acrylates

Lewis pair polymerization (LPP) has emerged as a powerful tool for the efficient polymerization of polar vinyl monomers. However, air/moisture, highly sensitive metal-based catalysts, and low reaction temperatures are necessary for achieving highly active LPP with a high degree of control. In this contribution, we report the development of a robust Lewis pair (LP) organic catalyst based on tris(2,4-difluorophenyl)borane and triisobutylphosphine, which not only renders efficient and living LPP of acrylates for the first time at ambient or even industrially relevant temperature (60–80 °C) but also allows the polymerization under an open-air condition. Accordingly, well-defined multiblock acrylic copolymers have been synthesized successfully over a broad reaction temperature range. Good thermal stability, appreciable air/moisture tolerance, high efficiency, and precise controllability of this LP organic catalyst thus establish LPP as a truly green/sustainable and practical polymerization methodology.