A. Borriello et al., ISOTACTIC 1-BUTENE POLYMERIZATION PROMOTED BY C2- SYMMETRICAL METALLOCENE CATALYSTS, Macromolecular chemistry and physics, 198(4), 1997, pp. 1257-1270
1-Butene polyinsertion promoted by two typical C-2-symmetric zirconoce
ne catalysts (i.e. rac-ethylenebis(1-indenyl)ZrCl2 (1) and rac-dimethy
lsilylbis(1-indenyl)ZrCl2) (2) was investigated under both hydrooligom
erization and polymerization conditions and compared with that of prop
ene. It was found that, in spite of a similar regiospecificity for the
two monomers, the fraction of ''dormant'' sites is higher in 1-butene
polymerization, as a result of a (much) lower reactivity of a 2,1 las
t-inserted unit. Accordingly, in the investigated cases, 2,1 units of
1-butene were not incorporated in the growing chains but either isomer
ized to 4,1 units or remained at the chain end until they underwent ch
ain transfer via beta-hydrogen elimination. Experimental evidence is a
lso presented of an epimerization reaction of the growing poly(1-buten
e) chain with a 1,2 last-inserted unit, leading to a decrease of polym
er stereoregularity with decreasing monomer concentration.