Elementarprozesse löslicher ziegler-katalysatoren. Polymerisationskinetische analyse und mathematische modellierung im system Cp2TiPropylCl/AlEtCl2/ethylen
✍ Scribed by Fink, Gerhard ;Zoller, Welf
- Book ID
- 102938105
- Publisher
- Wiley (John Wiley & Sons)
- Year
- 1981
- Weight
- 603 KB
- Volume
- 182
- Category
- Article
- ISSN
- 0025-116X
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✦ Synopsis
Abstract
This paper deals with the kinetics of the polymerization of ethylene catalysed by the soluble Ziegler‐catalyst Cp~2~TiPropylCl/AlEtCl~2~. By means of a special method it was possible to study the kinetics of the initial instationary homogeneous part of the polymerization. The dependences of the initial rates on the catalyst components prove that the polymerization active species is formed in two successive very dynamic equilibria. The primary complex equilibrium is entirely located on the right hand side, whereas the second equilibrium depends considerably on the ratio of the catalyst components and is shifted on the active species side only at very high Al/Ti ratios. Because of this location of the two successive equilibria the dependence of the polymerization velocity v~p~ on the charged Al concentration (that is, the Al isotherm) has to show a sigmoidal curve course in the inital part, which experimentally is confirmed exactly. Finally, this extensive kinetical analysis leads to the complete reaction scheme of the polyreaction and by mathematical modelling to the quantitative calculation and description of the experimental curves and dependences (e.g., Al‐isotherm).