A Novel Consecutive Chain Transfer Reaction to p-Methylstyrene and Hydrogen during Metallocene-Mediated Olefin Polymerization
- 1 May 2001
- journal article
- research article
- Published by American Chemical Society (ACS) in Journal of the American Chemical Society
- Vol. 123 (21), 4871-4876
- https://doi.org/10.1021/ja0039280
Abstract
This paper describes the first example of consecutive chain transfer reaction, first to p-methylstyrene (or styrene) and then to hydrogen, during metallocene-catalyzed propylene polymerization by rac-Me2Si[2-Me-4-Ph(Ind)]2ZrCl2/MAO complex. The PP molecular weight is inversely proportional to the molar ratio of [p-methylstyrene]/[propylene] and [styrene]/[propylene] with the chain transfer constants of ktr/kp = 1/6.36 and 1/7.5, respectively. Although hydrogen does not influence the polymer molecular weight, it greatly affects the catalyst activity. Each PP chain formed contains a terminal p-methylstyrene (or styrene) unit. The terminal p-MS unit can be metalated to form a stable polymeric anion for living anionic polymerization to prepare new PP diblock copolymers, such as PP-b-PS, which are very difficult to prepare by other methods. The overall process resembles a transformation reaction from metallocene to living anionic polymerization.Keywords
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