Organometallic nickel catalysts bound to polymeric matrices in the oligomerization and/or polymerization of olefins with a replica of the support morphology

Late-Metal Catalysts for Ethylene Homo- and Copolymerization

“…Using these synthetic routes, the backbone and aryl substituents are readily varied, enabling the preparation of arrays of ligands with independent control over the steric and electronic effects at the metal center. Simple arrays can be extended to exhaustive libraries using techniques well-developed in the pharmaceutical industry. , A variety of approaches to the synthesis of polymer-bound ligands for polymerization catalysts have been disclosed, − and elegant solid-phase techniques for synthesizing, screening, and encoding nickel and palladium catalysts based upon α-diimines and other ligands have been developed. − The development of sound analytical techniques for characterization of the resulting polymers is more problematic, but advances are being made. For instance, electrospray ionization mass spectrometry provides implicit encoding of the catalyst identities by the mass of the catalyst residue remaining on the polymer chain…”

“…When the nickel catalysts were combined with supported chromium catalysts, branched polyethylene (5.0 methyl-ended branches per 1000 carbon atoms) was produced by the chromium copolymerizing ethylene with the α-olefins that were produced in situ by the nickel catalyst . Like the catalysts above, nickel catalysts with anionic ligands may themselves be supported on inorganic supports , and polymeric supports. − …”

“…Simple arrays can be extended to exhaustive libraries using techniques well-developed in the pharmaceutical industry. 90,91 A variety of approaches to the synthesis of polymerbound ligands for polymerization catalysts have been disclosed, [92][93][94][95][96][97][98][99][100][101] and elegant solid-phase techniques for synthesizing, screening, and encoding nickel and palladium catalysts based upon R-diimines and other ligands have been developed. [102][103][104] The development of sound analytical techniques for characterization of the resulting polymers is more problematic, but advances are being made.…”

“…186 Like the catalysts above, nickel catalysts with anionic ligands may themselves be supported on inorganic supports 378,379 and polymeric supports. [92][93][94][95][96] In addition to P-O-based systems, other neutral nickel complexes capable of polymerizing ethylene included the diphosphallyl complex, 11. Polymerizations based upon these ligands required the sterically bulky substituent shown to produce linear high molecular weight polyethylene.…”

Nickel-based solid catalysts for ethylene oligomerization – a review

“…Consequently, significant research efforts have been directed to the development of heterogeneous processes for ethylene oligomerization. Three main classes of solid catalysts have been reported: (i) solid acids, [24][25][26][27][28][29][30] (ii) nickel complexes immobilized on polymers and oxides, [31][32][33][34][35] and (iii) nickel supported on inorganic porous materials. [36][37][38][39][40][41][42][43] Acid catalysts, such as supported phosphoric acid, zeolites, silica-aluminas and macroporous sulfonic resins demonstrated high potential for the oligomerization of C3+ olefins.…”