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.

中文翻译：

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一种双引发有机受挫 Lewis 对催化剂，用于（生物）丙烯酸酯的活性聚合，以促进无金属多嵌段共聚物的合成


开发强大的催化或方法来合成具有基本和技术意义的多嵌段共聚物是一项永恒的任务。用于甲基丙烯酸酯活性/受控聚合的双引发 Lewis 对 （LP） 催化剂已被证明是全丙烯酸多嵌段共聚物的有效方法。然而，利用通常需要费力合成的金属基路易斯酸 （LA） 和复杂的路易斯碱 （LB） 是必不可少的。本文报道了第一个由三（2,4-二氟苯基）硼烷 [B（2,4-F2C6H3）3] LA 和市售 1,2-双[（二叔丁基膦基）甲基]苯 （DPtBu2） LB 组成的有机双引发 Frustrated Lewis 对 （FLP） 催化剂，它可以介导各种（生物）丙烯酸酯的高效和活性聚合。因此，通过连续添加单体可以很容易地制备具有明确结构的全丙烯酸多嵌段共聚物（直至庚基），从而成功地将 DPtBu2/B（2,4-F2C6H3）3 FLP 建立为一种绿色/可持续和用户友好的聚合催化剂，以方便合成无金属的全丙烯酸多嵌段共聚物。