2007•Journal of Polymer Science Part A Polymer ChemistryRequires access

Homo‐ and copolymerization of ethylene and norbornene with bis(β‐diketiminato) titanium complexes activated with methylaluminoxane

Yongfei Li, Haiyang Gao, Qing Feng Wu

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Abstract

Abstract Homo‐ and copolymerization of ethylene and norbornene were investigated with bis(β‐diketiminato) titanium complexes [ArNC(CR3)CHC(CR3)NAr]2TiCl2 (R = F, Ar = 2,6‐diisopropylphenyl 2a; R = F, Ar = 2,6‐dimethylphenyl 2b; R = H, Ar = 2,6‐diisopropylphenyl 2c; R = H, Ar = 2,6‐dimethylphenyl 2d) in the presence of methylaluminoxane (MAO). The influence of steric and electric effects of complexes on catalytic activity was evaluated. With MAO as cocatalyst, complexes 2a–d are moderately active catalysts for ethylene polymerization producing high‐molecular weight polyethylenes bearing linear structures, but low active catalysts for norbornene polymerization. Moreover, 2a–d are also active ethylene–norbornene (E–N) copolymerization catalysts. The incorporation of norbornene in the E–N copolymer could be controlled by varying the charged norbornene. 13C NMR analyses showed the microstructures of the E–N copolymers were predominantly alternated and isolated norbornene units in copolymer, dyad, and triad sequences of norbornene were detected in the E–N copolymers with high incorporated content of norbornene. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 93–101, 2008

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Abstract Homo‐ and copolymerization of ethylene and norbornene were investigated with bis(β‐diketiminato) titanium complexes [ArNC(CR3)CHC(CR3)NAr]2TiCl2 (R = F, Ar = 2,6‐diisopropylphenyl 2a; R = F, Ar = 2,6‐dimethylphenyl 2b; R = H, Ar = 2,6‐diisopropylphenyl 2c; R = H, Ar = 2,6‐dimethylphenyl 2d) in the presence of methylaluminoxane (MAO). The influence of steric and electric effects of complexes on catalytic activity was evaluated. With MAO as cocatalyst, complexes 2a–d are moderately active catalysts for ethylene polymerization producing high‐molecular weight polyethylenes bearing linear structures, but low active catalysts for norbornene polymerization. Moreover, 2a–d are also active ethylene–norbornene (E–N) copolymerization catalysts. The incorporation of norbornene in the E–N copolymer could be controlled by varying the charged norbornene. 13C NMR analyses showed the microstructures of the E–N copolymers were predominantly alternated and isolated norbornene units in copolymer, dyad, and triad sequences of norbornene were detected in the E–N copolymers with high incorporated content of norbornene. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 93–101, 2008

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Available abstract

Abstract Homo‐ and copolymerization of ethylene and norbornene were investigated with bis(β‐diketiminato) titanium complexes [ArNC(CR3)CHC(CR3)NAr]2TiCl2 (R = F, Ar = 2,6‐diisopropylphenyl 2a; R = F, Ar = 2,6‐dimethylphenyl 2b; R = H, Ar = 2,6‐diisopropylphenyl 2c; R = H, Ar = 2,6‐dimethylphenyl 2d) in the presence of methylaluminoxane (MAO). The influence of steric and electric effects of complexes on catalytic activity was evaluated. With MAO as cocatalyst, complexes 2a–d are moderately active catalysts for ethylene polymerization producing high‐molecular weight polyethylenes bearing linear structures, but low active catalysts for norbornene polymerization. Moreover, 2a–d are also active ethylene–norbornene (E–N) copolymerization catalysts. The incorporation of norbornene in the E–N copolymer could be controlled by varying the charged norbornene. 13C NMR analyses showed the microstructures of the E–N copolymers were predominantly alternated and isolated norbornene units in copolymer, dyad, and triad sequences of norbornene were detected in the E–N copolymers with high incorporated content of norbornene. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 93–101, 2008

Key concepts: Methylaluminoxane, Norbornene, Copolymer, Polymer chemistry, Ethylene, Polymerization, Chemistry, Catalysis

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