Polymerization kinetics of bicyclic olefins and mechanism with symmetrical ansa-metallocene catalysts associated with active center count: relationship between their activities and structure and activation path

Abstract

Copolymerization of ethylene (E) with 5-vinyl-2-norbornene (VNB) catalyzed by ansa-metallocenes allows the precise control of essential polymeric properties such as comonomer incorporation, molecular weight (M_w), and polydispersity (Đ). Significant efforts have been devoted to synthesizing and developing novel catalysts, cocatalysts, and activators, although the fundamental elements of catalytic processes remain unclear. For example, it is questionable how polymeric catalysts are divided across dormant and active sites and how this distribution affects the order of monomers for the propagation rate, which widely vary in the literature. Furthermore, although the empirical correlation between the monomers and average M_w has been established in many systems, the fundamental processes of chain termination remain unknown. Furthermore, the involvement of ion-pairing in metallocene-catalyzed polymerization and the termination mechanisms are also contentious issues. In this study, we describe the use of a quenched-labeling technique based on acyl chloride to selectively quench the zirconium metal–polymeric bond, which can be used to study the kinetics, active site [Zr][C*] counting, copolymer microstructure, and molecular weight distribution (MWD) to determine the rate laws for chain initiation, chain propagation rate (R_p), propagation rate constant (k_p) and chain termination. In addition, we also predict previously unknown chemical characteristics of E/bicyclic copolymerization processes, where either a cis-endocyclic double bond with steric properties or a vinyl exocyclic double bond affects the activity, i.e., [Zr]/[*C], (R_p) and (k_p). All these properties require the implementation of a particular kinetic mechanism that assumes the low activity of the building copolymer chains incorporating a single ethylene/VNB unit, i.e., the Cp₂Zr–C₂H₅ group, in the ethylene addition process in the Cp₂Zr–C bond. Due to β-agostic stabilization, the Cp₂Zr–C₂H₅ group exhibits a distinct feature. These effects were confirmed experimentally, such as the E/VNB co-polymer activity and VNB mol%, propagation rate decrease in the polymerization time (t_p) of 120 s to 1800 s, crystalline properties, and significant increase in molecular weight. The active center [Zr]/[*C] fraction considerably increased in the initial (t_p) 840 s, and subsequently tended to the steady stage of 33%, which is lower than previously reported E homo- and E/P copolymerization. The lower [C*]/[Zr] in both the early and stable stages, decrease in VNB mol%, and R_p with t_p can be associated with the more significant fraction of Cp₂Zr–CH₂CH₃-type dormant site by the β-agostic hydrogen interaction with the Cp₂Zr metal. The t_p versus R_pE, R_pVNB, k_pE, k_pVNB, and [Zr]/[C*] count could be fitted to a model that invokes deactivation of the growing polymer chains. In the case of the thermal behavior of the copolymers (melting temperature (T_m) and crystalline temperature (ΔH_m)), T_m varied from 101 °C to 121 °C, while ΔH_m varied from 9 to 16 (J g⁻¹).