Copolymerization with Ziegler-Natta catalysts—III. Rates of copolymerization for several olefin pairs

✍ Scribed by I.H. Anderson; G.M. Burnett; W.C. Geddes

• Publisher: Elsevier Science
• Year: 1967
• Tongue: English
• Weight: 488 KB
• Volume: 3
• Category: Article
• ISSN: 0014-3057
• DOI: 10.1016/0014-3057(67)90062-6

✦ Synopsis

Abs/raet--Dilatometry was used to measure the rates of copolymerizations of styrene with hex-l-ene, hept-1 -ene, 4-methylpent-1 -erie and 4-methylbex-1 -erie, in the catalyst system, AIEtr-uTiC13 in toluene.

The copolymerizatinns were found to be first order with respect to TiCI3 and independent of Al/Ti ratio. Increased temperature produced a rapid increase in rate; variation of monomer feed, over the whole range, resulted in a gradual change from one homopolymerization rate to the other. The nature of the a-TiCl3 sample was found to have considerable effect on the rate of copolymerization.

The order of reactivity, both from rate measurements and reactivity ratios, implies that, for the polymerization of a-olefins by heterogeneous Ziegler-Natta catalysts, steric effects outweigh electronic consideration.