A kinetic study of polymerization of ethylene with Al-TiCl4 catalyst

✍ Scribed by Fukui, Kenichi ;Shimidzu, Takeo ;Yagi, Tetsuya ;Fukumoto, Satoshi ;Kagiya, Tsutomu ;Yuasa, Sachio

• Publisher: John Wiley and Sons
• Year: 1961
• Weight: 547 KB
• Volume: 55
• Category: Article
• ISSN: 0022-3832
• DOI: 10.1002/pol.1961.1205516131

✦ Synopsis

Abstract

This study of Al–TiCl~4~ catalysts for olefin polymerization continues work reported in preceding papers but with the use of aluminum wire under constant pressures. The use of aluminum having a very small surface area was convenient for the kinetic study of the reaction mechanism. The reaction time is divided into four periods. The first and second are connected with active‐center formation and are considered to be a kind of induction period. The third is a stationary period in which the rate is proportional to the square of pressure and the activation energy is ca. 16 kcal./mole. In the fourth period the rate is proportional to pressure and decreases gradually owing to a rate‐controlling diffusion step through the polymer layer produced. A kinetic consideration is proposed and a reaction scheme formulated for initiation, propagation, transfer, and termination. An ethylene‐propylene copolymerization study was also carried out, and lead to the supposition of a cationic mechanism in respect to the present type of polymerization.