Olefin polymerization ethylene-based polymers

Several combinatorial approaches to the discovery of transition metal based catalysts for olefin polymerization have been described. In one study Brookhart-type polymer-bound Ni- and Pd-(l,2-diimine) complexes were prepared and used in ethylene polymerization (Scheme 3).60,61 A resin-bound diketone was condensed with 48 commercially available aminoarenes having different steric properties. The library was then split into 48 nickel and 48 palladium complexes by reaction with [NiBr2(dme)] and [PdClMe(COD)], respectively, all 96 pre-catalysts being spatially addressable. 

Brookhart and co-workers [79-81] introduced catalysts based largely on chelating, nitrogen-based ligands that are active for the homopolymerization of ethylene and the copolymerization of ethylene with 1-olefins and polar comonomers (31). Ni, Co, Fe or Pd are used as late transition metals. The diimine ligands have big substituents to prevent 6-hydride elimination. Ni(II) or Pd(II) complexes form cations by combination with MAO and polymerize ethylene to highly branched polymers with molecular weights up to one million. The activities reach TON... 

Suzuki and Suga reported the use of clays as solid acids to support and activate metallocene catalysts for olefin polymerization. They were able to use much less alkylaluminmn cocatalyst relative to solution polymerization conditions. The clays were slurried with AlMeg in toluene, then treated with a solution containing zirconocene dichloride, II, and AIMeg. The metallocenium cation was presumed formed via abstraction of chloride and/or methyl ligands by acidic sites on the surface of the clay, and the low basicity of the clay smface was proposed to stabilize the coordinatively unsaturated cation. Propylene was copolymerized with 250 psi ethylene at 70°C. For acid-treated KIO montmorillonite, an activity of 3300 X 10 kg polymer/(g Zr h) was obtained. Catalysts based on vermiculite, kaolin, and synthetic hectorite all showed lower but still appreciable activities. In this brief report, the Al/Zr ratio was not specified, and the clay dispersion was not reported. 

A different approach of modeling ethylene-based copolymers is presented using acyclic diene metathesis (ADMEl) polymerization. Monomer s)mtiiesis dictates final polymer structure due to step-growth chemistry yielding only to olefin metathesis. While copolymerization of ethylene with a-olefins produces random distribution of alkyl branches along the PE backbone, polymerization of one kind of symmetric macromonomer produces PE with a perfectly known primary structure, as seen in Figure 1. 

PB base polymers are semicrystalUne isotactic thermoplastic polyolefins. They are derived from the polymerization of butene-1 monomer with or without other alpha-olefin monomers utilizing a Ziegler-Natta type of catalyst. Their unique crystallization behavior means longer open times of adhesive and sealant formulations compared to other commonly used polymers such as polyethylene and ethylene-vinyl acetate copolymer (EVA). Polybutylene (PB), also called polybutene-1 or poly-1-butene, is different from polybutene or polyisobutylene (PIB). PIB is amorphous and rubbery, and comes in the form of a viscous liquid or big, hard block (6 in. in length and width or could be larger). PB base polymers are sup-pUed in the form of small pellets (about 0.25 in. in diameter) or nibs. 

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