Polymerization of Methyl Acrylate by a 2,6‐Bis(2‐benzimidazyl)pyridine Zirconium Dichloride/MAO Catalyst System

Abstract

Summary: A novel non‐metallocene Zr(IV) complex bearing a bianionic form of the ligand 2,6‐bis(2‐benzimidazolyl)pyridine is synthesized. This Zr complex is an active catalyst for the polymerization of MA via coordination polymerization in the presence of methylaluminoxane MAO. The activity and MWD are increased as the polymerization temperature increases. The maximum activity is observed at Al/Zr molar ratio of 100 and the deactivation is shown above 100, resulting from an inactive bimetallic complex between catalyst and free TMA presented in MAO. Decrease in MWD is observed with higher MAO concentration due to its role in chain transfer during the chain propagation.

Bis(benzimidazolyl, benzothiazolyl, and benzoxazolyl)benzene complexes as catalysts for ethylene polymerization

“…The vanadium complexes of bis(benzimidazole)amine tridentate ligands [N, N, N], were reported as active ethylene polymerization catalyst precursors [28]. After activation with alkylaluminum compounds [28], 2,6-bis(2-benzimidazolyl)pyridine zirconium dichloride / MAO polymerizes methylacrylate [29].…”

Mononuclear complexes with heterocyclic ligands as ethylene polymerization catalysts for single-reactor bimodal polyethylene technology

“…So far, for ethylene polymerization, 1,2-bis(benzimidazolyl) benzene copper [25], titanium, zirconium and vanadium complexes were reported [26][27][28] that can be activated with methyalumoxane (MAO) and then be applied successfully for catalytic ethylene polymerization. The vanadium complexes of bis(benzimidazole) amine tridentate ligands [N,N,N], are active ethylene polymerization catalysts after activation with alkylaluminum compounds [29] and 2,6-bis(2-benzimidazolyl) pyridine zirconium dichloride / MAO polymerizes methylacrylate [30]. Herein we report the first zirconium, titanium and vanadium complexes of 1,2-bis(benzimidazolyl, benzothiazolyl, and benzoxazolyl benzene, and 2,6-bis(benzothiazolyl, benzoxazolyl)pyridine and their applications in catalytic ethylene polymerization after activation with MAO.…”

Ti (IV) Complexes of Some Heterocyclic Ligands Synthesis, Characterization and Ethylene Polymerization Activity

“…The vanadium complexes of bis(benzimidazole)amine tridentate ligands [N, N, N], were reported as active ethylene polymerization catalysts after activation with simple alkylaluminum compounds 31 2,6-Bis(2-benzimidazolyl)pyridine zirconium dichloride / MAO polymerizes methylacrylate 32 Recently, [33][34][35][36][37][38][39] we reported the ethylene polymerization activity of benzimidazole, benzothiazole, benzoxazole and 2-(benzimidazolyl) pyridine titanium zirconium and vanadium complexes. Herein we report on the effect of hetero atom on the activity of zirconium, complexes of bis (benzimidazole), benzothiazole, and benzoxazole), and their behaviour towards ethylene polymerization after activation with methylaluminoxane (MAO).…”