Neodymium-Mediated Coordinative Chain Transfer Polymerization of Isoprene in the Presence of External Donors

Nd-based polydiene elastomers, including NdIR and NdBR, are regarded as indispensable key raw materials in preparing green tires with excellent performance capabilities, but their wide application is still limited by the relative higher cost of Nd precatalysts. Nd-mediated coordinative chain transfer polymerization (CCTP) of diene provides an effective strategy to reduce the precatalyst cost, because this method involves very high atom economy, i.e., each Nd molecule can generate multiple polymer chains. Nevertheless, all possible factors that could influence such CCTP behaviors are still mostly unexplored to date. In this report, the basic chemistry on the influence of external donors on the overall CCTP behaviors of isoprene was established for the first time. It was found that increasing the amount of external donors had a negative influence on the chain transfer efficiencies, resulting in gradually decreasing atom economies. Catalyst addition order studies revealed that the coordination of donors with cationic Nd active species, rather than alkylaluminium CTAs, contributed mostly to such decreased efficiencies. Moreover, it was found that when the ratio of donors and Nd compounds was higher than 1.0, the CCTP behaviors were corrupted, resulting in polymers with broad distributions, as well as resulting in low atom economies; nevertheless, when the ratio was lower than 0.5, the system still displayed CCTP characteristics, implying that the critical ratio for maintaining the CCTP was 0.5. Additionally, when such a ratio was 0.01, the high atom economy was almost the same as donor-free CCTP systems. Detailed kinetic studies at such a ratio demonstrated that the donor-contained system proceeded in a well-controlled manner, as concluded from the good linear relationship between the Mn of the PIps against the polymer yields, as well as the good linearity between the Mn against the (IP)/(Nd) ratios. Such maintained CCTP properties also allowed for seeding two-step polymerizations to prepare diblock copolymers with precisely controlled molecular weights. Expanding the types of donors to more phosphine, oxygen, and nitrogen containing compounds showed that they also affected the CCTP behaviors depending on their steric and electronic properties.