Abstract: | {[2-(dimethylamino)ethyl]cyclopentadienyl}titanium trichloride (CpNTiCl3, 1 ) 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 of n is 2.4 ± 0.2 for CpTiCl3/MAO catalysis of ethylene polymerization; this system does not polymerize propylene. 1 /MAO catalyzes HD polymerization at one-tenth of A H for 1-hexene, probably because of chelation effects in the HD case. The copolymerization of E and P has reactivity ratios of rE = 6.4 and rP = 0.29 at 20°C, and rErP = 1.9, which suggests 1 /MAO may be a multisite catalyst. The copolymerization activity of CpTiCl3/MAO is 50 times smaller than that of CpNTiCl3/MAO. Terpolymerization of E/P/ENB has A of 105 g of polymer/(mol of Ti h), incorporates up to 14 mol % (∼ 40 wt %) of ENB, and high MW's of 1 to 3 × 105. All of these parameters are surprisingly insensitive to the ENB concentration. The E/P/VCH terpolymerization has comparable A value of (1.3 ± 0.3) × 105 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 compared with those obtained previously for three zirconocene precursors: rac-ethylenebis(1-η5-indenyl)dichlorozirconium ( 6 ), rac-(dimethylsilylene)bis(1-η5-indenyl)dichlorozirconium ( 7 ), and ethylenebis(9-η5-fluorenyl)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 terpolymerization, while 6 /MAO is superior in E/P/HD terpolymerization. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 319–328, 1998 |