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The copolymerization of ethylene (E) with isoprene (Ip) was performed catalyzed by a symmetrical catalyst exhibiting a silicon bridge [rac-Me 2 Si(2-Me-4-Ph-Ind) 2 ZrCl 2 with the combination of borate/TIBA activator. The effect of cocatalyst, Ip concentration, and polymerization temperature on the activity, molecular weight (Mw), distribution (MWD), comonomer composition, chain structure (regio- and stereoselectivity), and resulting side reactions were logically addressed. Gel-permeation chromatography (GPC) was used to characterize the Mw and polydispersity, while nuclear magnetic resonance (NMR) was employed for the chain structure of the polymers. The catalytic activity was significantly lower by increasing the Ip concentration in the feed, and the isoprene content in resulting polymers was lower under the reaction condition, leading to higher activity. Insertion of isoprene units in polymer structure demonstrates the higher regioselectivity for the 3,4 connections than the 1,4 connections and is expected to be a high-resistance polymer against acids. The MWD presented monomodal even with a higher concentration (1.44 mol/L) and did not appear as low Mw peaks of Ip. The Mw was higher with a broader MWD when purely TIBA was used as a cocatalyst, and it significantly reduced and presented a narrowed MWD with TEA in the cocatalyst. The higher efficiency of the catalyst for the higher insertion of Ip (C=C double bond) effectively modifies the polymer backbone. It is expected to be a promising candidate for easily degradable and favorable solutions for solving environmental problems caused by PE. wastes. [Display omitted] • Environmentally benign methodology reaction conditions (low temperature and pressure) are hallmarks of this approach. • Ethylene α-olefin (linear conjugated diene) copolymerization catalyzed with a symmetrical Single-site homogeneous catalyst. • Ethylene α-olefin (linear conjugated diene) copolymerization catalyzed with a symmetrical Single-site homogeneous catalyst. • The MWD demonstrated monomodal even with a higher concentration of isoprene (1.44 mol/L). • Increased insertion of isoprene may lead to easily degradable and beneficial solutions for PE waste environmental issues. [ABSTRACT FROM AUTHOR]