Nickel Catalyzed Copolymerization of Ethylene and Alkyl Acrylates

Abstract

Ni(II) complexes bearing an o-bis(aryl)phosphinophenolate ligand were synthesized as catalysts for copolymerization of ethylene and alkyl acrylates. When the P-bound aryl group was 2,6-dimethoxyphenyl group, one of the oxygen atoms in the methoxy groups coordinated to the nickel center on its apical position. This complex was a highly active catalyst without any activators to give highly linear and high molecular weight copolymers. The structures of the copolymers were determined by H andC NMR to clarify that the alkyl acrylate comonomers were incorporated in the main chain and that the structures of the copolymers were significantly influenced by the structure of the aryl group in the ligand.

Emerging Palladium and Nickel Catalysts for Copolymerization of Olefins with Polar Monomers

“…[83] These nickel complexes can mediate efficient ethylene copolymerization with fundamental polar monomers,including various acrylates.Surprisingly,very high catalytic activities (up to 3230 kg mol À1 h À1 ), extremely high copolymer molecular weights (M n up to 143,000), and moderate comonomer incorporation (0.3-4.5 mol %) were achieved. [83] These nickel complexes can mediate efficient ethylene copolymerization with fundamental polar monomers,including various acrylates.Surprisingly,very high catalytic activities (up to 3230 kg mol À1 h À1 ), extremely high copolymer molecular weights (M n up to 143,000), and moderate comonomer incorporation (0.3-4.5 mol %) were achieved.…”

Facile synthesis of sterically demanding SHOP‐type nickel catalysts for ethylene polymerization

“…have evaluated the capability of the ethylene polymerization using some bulky phosphino‐phenolate based nickel complexes (Scheme , B ), which exhibited very high activities of up to 10 7 g PE (mol Ni h) − 1 even at 90 °C. More surprisingly, these nickel catalysts are compatible with some polar vinyl monomers . In addition, Gibson et al showed that some modified SHOP catalyst through the introduction of the bulky group adjacent to the oxygen atom (Scheme , A ) could dramatic increased the catalytic activities .…”

“…[21][22][23][24][25] These catalysts were usually ligated by α-diimine, [14,[26][27][28][29][30][31][32] iminopyridyl, [33,34] iminopyrrolyl, [35] salicylaldimine, [36][37][38] and many others. [39] Compared to these branched macrostructures, linear crystalline polyethylenes with high melting temperatures were generally produced by phosphine-containing nickel and palladium catalysts (Scheme 1, A-G) that include SHOP ligands (A), [40][41][42] phosphino-phenolate (B), [43,44] phosphine-sulfonates (C), [45][46][47][48][49] phosphine phosphonic amides (D), [50][51][52] bisphosphine monoxide (E), [53] and other P,N-based ligands (F and G). [54,55] Particularly, some of these catalysts possess comparable even better properties than α-diimine palladium catalysts in copolymerization reactions.…”

Bulky iminophosphine‐based nickel and palladium catalysts bearing 2,6‐dibenzhydryl groups for ethylene oligo‐/polymerization

“…[15][16][17][18][19][20][21][22][23][24] These catalysts were generally ligated by α-diimine, [14,[25][26][27][28][29][30][31] iminopyridyl, [32][33][34] iminepyridazine, [35] iminopyrrolyl, [36] salicylaldimine, [37,38] and many others. However, linear crystalline PEs with high melting temperatures were usually produced by phosphine-containing Ni and Pd catalysts with variable ligands that include that include SHOP (Shell higher olefin process) type ligands, [39][40][41] phosphine-sulfonates, [42][43][44][45] phosphino-phenolate, [46,47] phosphine phosphonic amides, [48,49] bisphosphine Qitong Wu and Wenbing Wang contribute equally to the article.…”

“…monoxide, [50] and many others. Recently, a series of phosphine based Pd catalysts [46,[51][52][53] have emerged as alternatives for copolymerizations of ethylene with polar monomers. Some of these phosphine based catalysts possessed comparable even better properties than α-diimine Pd catalysts in copolymerization reactions.…”