Branching in Metallocene Polymerizations

Long-chain branching (LCB), generally less than 0.1 branch per 1000 carbons, has been observed in some metallocene polymerizations of ethylene and propene [Nele and Soares, 2002 Soares, 2002 Weng et al., 2002]. The presence of even small amounts of LCB improves melt strength and melt processability of narrow PDI polymers. Thus, it is often useful to choose conditions, such as the metallocene, temperature, and other reaction conditions, that deliberately introduce long chain branching. 

Short branches, specifically ethyl branches up to about 2 mol%, are formed in the polymerization of ethylene by meso-ansa zirconocenes containing unsubstituted cyclo-pentadienyl and indenyl ligands [Melillo et al., 2002]. Ethyl branches form by an isomerization process in which the usual P-hydride transfer to monomer is immediately followed by reinsertion of the vinyl-terminated polymer into the formed ethyl-zirconium bond. 

LCB results from the copolymerization of ethylene or propene with vinyl-terminated polymer formed during the polymerization. Since vinyl double bonds are more reactive in copolymerization than other types of double-bond end groups, LCB is increased under conditions that generate higher vinyl contents. This can be accomplished by choice of initiator and reaction conditions. Tandem polymerization is also useful, such as by using two initiators, one of which produces a vinyl-terminated oligomer (referred to as a macromonomer or macromer) [Komon and Bazan, 2001 Quijada et al., 2001 Wang et al., 2000]. 

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