ISSN:
0887-624X
Keywords:
metallocene
;
stereoselective catalyst
;
propylene polymerization
;
Chemistry
;
Polymer and Materials Science
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
A new silolene-bridged compound, racemic (1,4-butanediyl) silylene-bis (1-η5-in-denyl) dichlorozirconium (1) was synthesized by reacting ZrCl4 with C4H8Si (IndLi)2 in THF. 1 was reacted with trialkylaluminum and then with triphenylcarbenium tetrakis (penta-fluorophenyl) borate (2) to produce in situ the zirconocenium ion (1+). This “constraint geometry” catalyst is exceedingly stereoselective for propylene polymerization at low temperature (Tp = -55°C), producing refluxing n-heptane insoluble isotactic poly(propylene) (i-PP) with a yield of 99.4%, Tm = 164.3°C, δHf = 20.22 cal/g and M̄w = 350 000. It has catalytic activities of 107-108 g PP/(mol Zr · [C3H6] · h) in propylene polymerization at the Tp ranging from -55°C to 70°C, and 108 polymer/(mol Zr · [monomer] · h) in ethylene polymerization. The stereospecificity of 1+ decreases gradually as Tp approaches 20°C. At higher temperatures the catalytic species rapidly loses stereochemical control. Under all experimental conditions 1+ is more stereospecific than the analogous cation derived from rac-dimethylsilylenebis (1-η5-indenyl)dichlorozirconium (4). The variations of polymerization activities in ethylene and in propylene for Tp from -55°C to +70°C indicates a Michaelis Mention kinetics. The zirconocenium-propylene π-complex has a larger insertion rate constant but lower thermal stability than the corresponding ethylene π-complex. This catalyst copolymerizes ethylene and propylene with reactivity ratios of comparable magnitude rE ˜ 4rp. Furthermore, rE.rp ˜ 0.5 indicating random copolymer formation. Both 1 and 4 activated with methylaluminoxane (MAO) exhibit much slower polymerization rates, and, under certain conditions, a lower stereo-selectivity than the corresponding 1+ or 4+ system. © 1994 John Wiley & Sons, Inc.
Additional Material:
6 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/pola.1994.080320117
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