Subhalides of Transition Metals

Among one-component polymerization catalysts subhalides of the transition metals are most similar in composition to the traditional Ziegler-Natta catalysts. In this connection, the study of the simplest one-component catalyst of this type (especially TiCl2) is of great importance for the clarification of still disputable problems of the mechanism of polymerization by two-component catalysts. 

The formation of high polymers of olefins in the presence of titanium halogenides with no specially added organometallic co-catalysts was discovered long ago [see (147), and the references therein], A complete description of various alkyl-free polymerization catalysts based on the use of transition metal chlorides may be found in the review by Boor (17), where a comparison of these catalysts with traditional two-component systems is given. 

High molecular weight linear polyethylene was obtained from ethylene polymerization by TiCl2 (146) this polymer contained only vinyl-type double bonds (less than 0.1 per 1000 carbon atoms). 

Polypropylene formed on TiCl2 contained 25-30% of the isotactic fraction insoluble in hot heptane (146). 

In most cases one-component catalysts based on halogenides of transition metals were obtained with the help of various specific activation pro- 

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Before the 1970s, Ziegler-Natta catalysts for a-olefin production were normally prepared from certain compounds of transition metals of Groups IV-VI of the periodic table (Ti, V, Cr, etc.) in combination with an organoraetallic alkyl or aryl (Table I). Practically all subhalides of transition metals have been claimed as catalysts in stereoregular polymerization. Only those elements with a first work function <4 eV and a first ionization potential <7 V yield sufficiently active halides, that is, titanium, vanadium, chromium, and zirconium (7, Only titanium chlorides have gained widespread acceptance in crystalline polyolefin production. 

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