Sequence Determination and Regulation in the Living Anionic Copolymerization of Styrene and 1,1-Diphenylethylene (DPE) Derivatives

Abstract

The living anionic copolymerization of styrene (St) and 1,1-diphenylethylene (DPE) derivatives were carried out to investigate how the DPE units are distributed along the polymer chain. Based on the combination of timing sample method and exact characterizations, the sequence determination method was established to reveal the sequential distribution of DPE units along the functionalized chains. In the copolymerization of St and DPE-SiH, when DPE-SiH was excessively fed, a strictly alternating structure can be prepared. As the feed ratios of S/D increased, a gradient structure was obtained. Additionally, when the substituent structure of the DPE derivatives changed, the sequence structure could be regulated. It has been confirmed in the copolymerization of St and DPE-SiH/OMe or DPE-SiH/NMe2, that the electron-donating group (-OMe or -NMe2) was introduced into DPE-SiH. Then, the preliminary sequence regulation method was found. Meanwhile the sequence-determined grafting was investigated, and bottlebrush polymers with sequence-determined branches were successfully synthesized. (Figure presented.).