The poly(vinylpyridine) (PVP) based (co)polymers are of particular interest in materials science, due to their multifunctionality and diverse applications. So far, there is no report on the sequence-regulated copolymerization of vinylpyridines (VPs) and methacrylate monomer in one-step manner yet. Here we designed and synthesized a series of guanidine phosphines as Lewis base (LB), which is combined with bulky organoaluminium to construct Lewis pairs (LPs) for polymerization of VPs. The living/controlled polymerization of 4-vinylpyridine (4-VP) or 2-vinylpyridine (2-VP) can be accomplished with remarkable efficiency by such Lewis pair polymerization (LPP), furnishing polymers with high molecular weight (up to 288 kg/mol) and narrow molecular weight distribution (as low as 1.17). Mechanistic studies reveal the interaction of LPs and formation of zwitterionic intermediates, providing solid evidences to support the proposed polymerization mechanism. More importantly, by simply adjusting the LA dosage, this LPP strategy realizes the unprecedented control over the sequence regulation of 2-VP-based copolymers from gradient to block in one-step manner, regardless of the monomer ratio, which greatly expands the versatility of the LPP.

聚（乙烯基吡啶）（PVP）基（共）聚合物由于其多功能性和多样化的应用而在材料科学中特别受关注。目前，尚未见乙烯基吡啶(VPs)与甲基丙烯酸酯单体一步顺序共聚的报道。在这里，我们设计并合成了一系列作为路易斯碱（LB）的胍膦，其与大体积有机铝结合构建路易斯对（LP）用于VP的聚合。通过这种路易斯对聚合（LPP），可以以显着的效率完成4-乙烯基吡啶（4-VP）或2-乙烯基吡啶（2-VP）的活性/受控聚合，提供高分子量（高达288 kg / mol）和窄分子量分布（低至1.17）。机理研究揭示了LPs的相互作用和两性离子中间体的形成，为支持所提出的聚合机理提供了坚实的证据。更重要的是，通过简单地调整LA用量，这一LPP策略实现了前所未有的对2-VP基共聚物从梯度到嵌段的序列调控的一步控制，无论单体比例如何，这极大地扩展了2-VP基共聚物的通用性。 LPP。