Polydiene-based liquid rubber can be used to prepare high-frequency copper-clad plates, and it is also the most critical raw material for photosensitive elastomers used in flexible resin plates. The molecular structure control requirements of high-performance liquid rubber are very high, and special living anionic initiation systems and polymerization processes need to be developed to achieve stable control of the product structure. In this study, a series of novel polar modifiers were synthesized by introducing alkyl substituents and N/O-containing heteroatoms into the cycloamine ring (1,2-dipiperidinoethane (DPE) derivatives). High vinyl polybutadiene (90% < 1,2-units < 99%) with quantitative tertiary-amine functionalization (0%–25% molar ratio) was synthesized by in situ copolymerization using 4-dimethylaminomethylstyrene (VBA) as a comonomer. The polymerization process has obvious characteristics of being controllable and living under mild conditions. The fine structure of the product was analyzed by ¹H NMR, FTIR, GPC, and DSC. In situ anionic copolymerization provides a new way for developing high-performance liquid rubber.

The combination of a living anionic technology and a unique alternating strategy provided an exciting opportunity to prepare novel and well-defined poly(1,3-pentadiene-co-syrene-co-1,1-diphenylethylene) resins consisting of three alternating sequences of modules (A/B/C zwitterions). “A” being Styrene (St)/1,3-pentadiene (PD), “B” being diphenylethylene (DPE)/PD, “A” being DPE/St, respectively, A wide composition range of new polyolefin resins, i.e., poly (A-co-B), poly (A-co-C), and poly (B-co-C), with controlled molecular weight and very narrow molecular weight and composition distributions have been prepared by a one-pot living characteristic method. In the section of kinetic analysis, the terpolymer yields and kinetic parameters were strongly dependent on the feed/comonomer ratio as well as the content of the alternating structure. The competition copolymerization behaviors of A/B, B/C, and A/C were studied in detail in this work. By contrast, the microstructure and the thermal property of the resulting terpolymer were investigated via Nuclear magnetic resonance (NMR) and Differential scanning calorimetry (DSC) analysis. The results of 1H NMR tracking the change of [Aromatic ring]/[C=C] value indicated the distinctive copolymer-ization behavior of the selective “alternating-modules”. The glass transition temperature (T_g) was very sensitive to the terpolymer composition. By contrast to poly(A-ran-B) with only one obvious T_g, there were two T_gs in the A/C and B/C copolymerization cases. Moreover, the desirable high T_g ~ 140 °C resin was limited to the terpolymers with up to 50 mol % DPE. Finally, the “ABC-X” mechanism was proposed to interpret the unique terpolymerization behavior, which belongs to the classical “bond-forming initiation” theory.