POLYMERIZATIONS OF OLEFINS AND DIOLEFINS CATALYZED BY MONOCYCLOPENTADIENYLTITANIUM COMPLEXES CONTAINING A (DIMETHYLAMINO)ETHYL SUBSTITUENT AND COMPARISON WITH ANSA-ZIRCONOCENE SYSTEMS

{[2-(dimethylamino) ethyl]cyclopentadienyl} titanium trichloride ((CpT iCl3)-Ti-N, i) was activated with methylaluminoxane (MAO) to catalyze polymerizations of ethylene (E), propylene (P), ethylidene norbornene (ENB), vinylcyclohexene (VCH), and 1,4-hexadiene (HD). The dependence of homopolymerization activity (A) of 1/MAO on olefin concentration ([ M](n)) is n = 2.0 +/- 0.5 for E and n = 1.8 +/- 0.2 for P. The value o f n is 2.4 +/- 0.2 for CpTiCl3/MAO catalysis of ethylene polymerizatio n; this system does not polymerize propylene. 1/MAO catalyzes HD polym erization at one-tenth of A(H) for l-hexene, probably because of chela tion effects in the HD case. The copolymerization of E and P has react ivity ratios of r(E) = 6.4 and r(P) = 0.29 at 20 degrees C, and r(E)r( P) = 1.9, which suggests 1/MAO may be a multisite catalyst. The copoly merization activity of CpTiCl3/MAO is 50 times smaller than that of (C pTiCl3)-Ti-N/MAO. Terpolymerization of E/P/ENB has A of 10(5) g of pol ymer/(mel of Ti h), incorporates up to 14 mol % ( similar to 40 wt %) of ENB, and high MW's of 1 to 3 x 10(5). AU of these parameters are su rprisingly insensitive to the ENB concentration. The E/P/VCH terpolyme rization has comparable A value of (1.3 +/- 0.3) X 10(5) g/(mol of Ti h). The incorporation of VCH in terpolymer increases with increasing [ VCH]. Terpolymerization with HD occurs at about one-third of the A of either ENB or VCH; the product HD-EPDM is low in molecular weight and contains less than 4% of HD. These terpolymerization results are compa red with those obtained previously for three zirconocene precursors: r ac-ethylenebis(1-eta(5)-indenyl)dichlorozirconium (6), hylsilylene)bis (1-eta(5)-indenyl)dichlorozirconium (7), and ethylenebis(9-eta(5)-fluo renyl) dichlorozirconium (8). The last compound is a particularly poor terpolymerization catalyst; it incorporates very Little VCH or HD and no ENB at all. 7/MAO is a better catalyst for E/P/VCH terpolymerizati on, while 6/MAO is superior in E/P/HD terpolymerization. (C) 1998 John Wiley & Sons, Inc.