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Copolymerization of propylene and 1,5-hexadiene with stereospecific metallocene/Al(i-Bu)3/[Ph3C][B(C6F5)4]

✍ Scribed by Il Kim; Yong Shu Shin; Jin Kook Lee

Publisher
John Wiley and Sons
Year
2000
Tongue
English
Weight
179 KB
Volume
38
Category
Article
ISSN
0887-624X

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✦ Synopsis

Copolymerizations of propylene (P) with 1,5-hexadiene (1,5-HD) were carried out with isospecific rac-1,2-ethylenebis(1-indenyl)Zr(NMe 2 ) 2 [rac-(EBI)Zr(NMe 2 ) 2 , 1] and syndiospecific isopropylidene(cyclopentadienyl)(9-fluorenyl)ZrMe 2 [i-Pr(Cp)-(Flu)ZrMe 2 , 2] compounds combined with Al(i-Bu) 3 /[Ph 3 C][B(C 6 F 5 ) 4 ] as a cocatalyst system. Microstructures of poly(propylene-co-1,5-HD) were determined by 1 H NMR, 13 C NMR, Raman spectroscopies and X-ray powder diffraction. The isospecific 1/Al(i-Bu) 3 /[Ph 3 C][B(C 6 F 6 ) 4 ] catalyst showed much higher polymerization rate than 2/Al(i-Bu) 3 /[Ph 3 C][B(C 6 F 6 ) 4 ] system, however, the latter system showed higher incorporation of 1,5-HD (r P ϭ 8.85, r 1,5-HD ϭ 0.274) than the former system (r P ϭ 16.25, r 1,5-HD ϭ 0.34). The high value of r P ϫ r 1,5-HD far above 1 demonstrated that the copolymers obtained by both catalysts are somewhat blocky. The insertion of 1,5-HD proceeded by enantiomorphic site control; however, the diastereoselectivity of the intramolecular cyclization reaction of 1,2-inserted 1,5-HD was independent of the stereospecificity of metallocene compounds, but dependent on the concentration of 1,5-HD in the feed. The insertion of the monomers by enantiomorphic site control could also be realized by Raman spectroscopy and X-ray powder diffraction of the polymers.

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