Sequence regulation in living anionic terpolymerization of styrene and two categories of 1,1-diphenylethylene (DPE) derivatives

Synthesis of functionalized sequence-controlled polymers by utilizing 1,1-diphenylethylene (DPE) derivatives in living anionic polymerization is an effective method. Considering the capacity of sequence information and the diversity of functionalization, further progress of this method may provide a deep understanding of the copolymerization behavior of various DPE derivatives with commercial monomers. In this paper, we introduced two categories of DPE derivatives in anionic polymerization to enrich a variety of sequence-controlled polymers. The kinetics and monomer sequences of the terpolymerizations of St with two DPE derivatives through a one-step and multi-step feeding process were carefully studied. The results show that the terpolymer sequence displayed intriguing transformations by precisely controlling the reactivity difference between DPE derivatives, and facilely regulating the feed strategies of monomer pairs. The gradient, block and random distributions of two categories of DPE derivative units in the chain can be easily generated. The diversity of Tg values of these terpolymers with similar chemical compositions could prove that the various sequences have distinct effects on polymer properties.