In this contribution, we describe the kinetics associated with the rac-Me2Si[2-Me-4-Ph-Ind]2ZrCl2 (Cat-1)/borate/TIBA catalyzed copolymerization of E/dienes (isoprene (IP), butadiene (BD), 5-ethylidene-2-norbornene (ENB), 4-vinylcyclohexene (VCH) and vinyl norbornene (VNB)), and E/diene/1-hexene (1H) terpolymerization by using thiophenecarbonyl chloride (TPCC) that was used in Ziegler-Natta (Z-N) and metallocene-catalyzed polyethylene (PE) and polypropylene (PP) and E/P polymerizations. In both types of polymerizations, a higher amount of dienes was incorporated when VNB (2.70 mole %) and VCH (1.56 mole %) were added as comonomer, but IP and BD were incorporated with the moderated rate (0.6-1.1 mole %) with higher activities (3.45x106gm/mmolMt·h). The active center [Zr]/[C*] fraction is higher (61%) than previously reported PE polymerizations, especially in the case of E/IP, E/BD and E/IP/1H but lower than E/P (87%) copolymerization. Significantly, IP and BD activated the inactive catalytic sites that were dormant in the PE. The propagation rate constant (kpE) with IP was higher (kp564 Lmol-1s-1), while kpE with VNB (kp379 Lmol-1s-1) and VCH (kp304 Lmol-1s-1), which were lower than PE. This difference is built because of the diffusion barrier in the system. Compared to E/diene copolymers, kpE values in E/diene/1H terpolymerizations for IP, VCH, and VNB are higher and stable except ENB and determine that 1H prevents the insertion of dienes and reduces the crystalline properties resultant moderate kpE. Even though the E/BD copolymers decreased butadiene content of over 2 mol% resulted in better crystalline characteristics, lower diffusion barriers, and a higher kpE value. In concept, IP and BD are linear and readily available for coordination. While VCH, ENB and VNB are cyclic and bulky, metallocene in contact ion pairs cannot accept ENB, VNB, and VCH for coordination and subsequently act as dormant in the polymerization.
