Structure-activity Relationships in Olefin Polymerization by Group (IV) Catalysts
Abstract
The study of olefin polymerization by homogeneous transition metal catalysts continues to be a field of considerable interest. Much of the success of these catalysts derives from the ability to tune their activity through catalyst and experimental design. Comparative analysis among catalyst families, however, remains a largely unrealized goal, primarily due to a lack of proper quantitative kinetic analysis. In this work, we have detailed our examination of several Group IV amine bis(phenolate) catalysts to elucidate fundamental rate constant-structure relationships. In our analysis, we demonstrated that steric changes to a relevant structural position leads to systematic changes to insertion and chain transfer rate constants. Additionally, we established similar relationships between electronic variations and elementary rate constants. In doing this we validated a proposed mechanism for each catalyst, which notably included catalyst isomerization leading to dormancy. We conclude with a direction forward, by assessing the challenges inherent in applying the methods described herein to the more complex task of copolymerization analysis, and a representative example of the analysis required to describe this system.
Degree
Ph.D.
Advisors
Ren, Purdue University.
Subject Area
Inorganic chemistry|Polymer chemistry
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