Fluorinated and ring-substituted bisbenzimidazole copper complexes for ethylene/acrylate copolymerization

• Published in: Journal of polymer science. Part A, Polymer chemistry Polymer chemistry, 2006-03, Vol.44 (6), p.1817-1840
• Main Authors: Baugh, Lisa Saunders, Sissano, Joseph A., Kacker, Smita, Berluche, Enock, Stibrany, Robert T., Schulz, Donald N., Rucker, Steven P.
• Format: Article
• Language: English
• Subjects: Applied sciences; Copolymerization; copper catalysts; Exact sciences and technology; metal-organic catalysts/organometallic catalysts; Organic polymers; Physicochemistry of polymers; polyacrylates; polyethylene (PE); Preparation, kinetics, thermodynamics, mechanism and catalysts
• ISSN: 0887-624X; 1099-0518
• DOI: 10.1002/pola.21269

Bisbenzimidazole copper dichloride complexes (CuBBIMs), when activated with methylaluminoxane, catalyze the random copolymerization of ethylene with acrylates to produce highly linear functional copolymers. To probe the sensitivity of the copolymerization to the catalyst structure, a series of CuBBIM catalysts with various steric, electronic, and geometric ligand characteristics was prepared, including CuBBIMs having benzimidazole ring substituents and ligand backbones of various lengths. Four different acrylates were also evaluated as comonomers (t‐butyl acrylate, methyl acrylate, t‐butyl methacrylate, and methyl methacrylate). Although no obvious ligand‐based influences on copolymerization were identified, the structure of the acrylate comonomer was found to exert significant effects. Copolymers prepared with t‐butyl methacrylate comonomer exhibited the highest ethylene contents (31–63%), whereas those prepared with methyl acrylate contained only minor amounts of ethylene (