Statistical multiblock copolymerization of ethene and higher alpha-olefins via tandem catalysis under reversible trans-alkylation conditions, commonly known as polyolefin chain shuttling, was discovered by means of a High Throughput Experimentation (HTE) approach.(1) The rapid screening of catalyst pairs in the presence of a proper chain shuttling agent (CSA) was key to identify well-working catalyst formulations (something that had been pursued in vain for decades with conventional methods).(2) In recent years, we spent a considerable effort to extend the scope of HTE from discovery to mechanistic investigations.(3) A high-performance polymerization platform (Freeslate PPR48) was integrated with state-of-art polymer characterization tools (including GPC, 13C NMR and A-CEF), and the workflow was optimized for the fast acquisition of large structure-properties databases usable in QSAR studies. The approach was successfully applied to Ziegler-Natta and molecular olefin polymerization catalysts.(3,4) Chain shuttling chemistry represented an extreme challenge, because operating reliably in solution at high temperature under controlled kinetic conditions in HTE scale is highly demanding; on the other hand, exploring exhaustively the complex variables hyperspace of this chemistry with conventional methods is even more problematic, and requires a very long time. In the present talk, we will present for the first time the results of a HTE study of the chain shuttling formulation originally disclosed by Dow Chemical(1), as applied to ethene homopolymerization and ethene/1-hexene copolymerization. Molecular kinetic insight into the process, with special focus on the relationship between trans-alkylation statistics and polymer microstructure, will be provided. References (1) Arriola, D. J.; Carnahan, E. M.; Hustad, P. D. Science 2006, 312, 714-719. (2) Wenzel, T. T.; Arriola, D. J.; Carnahan, E. M.; Hustad, P. D.; Kuhlman, R. L. Top. Organomet. Chem. 2009, 26, 65-104. (3) Busico, V.; Cipullo, R.; Mingione, A.; Rongo, L. Ind. Eng. Chem. Res. 2016, 55, 2686-2695. (4) Busico, V.; Pellecchia, R.; Cutillo, F.; Cipullo, R. Macromol. Rapid Commun. 2009, 30, 1697-1708.

A Mechanistic HTE Approach to ‘Polyolefin Chain Shuttling’

Antonio Vittoria
;
Roberta Cipullo;Felicia Daniela Cannavacciuolo;Vincenzo Busico
2017

Abstract

Statistical multiblock copolymerization of ethene and higher alpha-olefins via tandem catalysis under reversible trans-alkylation conditions, commonly known as polyolefin chain shuttling, was discovered by means of a High Throughput Experimentation (HTE) approach.(1) The rapid screening of catalyst pairs in the presence of a proper chain shuttling agent (CSA) was key to identify well-working catalyst formulations (something that had been pursued in vain for decades with conventional methods).(2) In recent years, we spent a considerable effort to extend the scope of HTE from discovery to mechanistic investigations.(3) A high-performance polymerization platform (Freeslate PPR48) was integrated with state-of-art polymer characterization tools (including GPC, 13C NMR and A-CEF), and the workflow was optimized for the fast acquisition of large structure-properties databases usable in QSAR studies. The approach was successfully applied to Ziegler-Natta and molecular olefin polymerization catalysts.(3,4) Chain shuttling chemistry represented an extreme challenge, because operating reliably in solution at high temperature under controlled kinetic conditions in HTE scale is highly demanding; on the other hand, exploring exhaustively the complex variables hyperspace of this chemistry with conventional methods is even more problematic, and requires a very long time. In the present talk, we will present for the first time the results of a HTE study of the chain shuttling formulation originally disclosed by Dow Chemical(1), as applied to ethene homopolymerization and ethene/1-hexene copolymerization. Molecular kinetic insight into the process, with special focus on the relationship between trans-alkylation statistics and polymer microstructure, will be provided. References (1) Arriola, D. J.; Carnahan, E. M.; Hustad, P. D. Science 2006, 312, 714-719. (2) Wenzel, T. T.; Arriola, D. J.; Carnahan, E. M.; Hustad, P. D.; Kuhlman, R. L. Top. Organomet. Chem. 2009, 26, 65-104. (3) Busico, V.; Cipullo, R.; Mingione, A.; Rongo, L. Ind. Eng. Chem. Res. 2016, 55, 2686-2695. (4) Busico, V.; Pellecchia, R.; Cutillo, F.; Cipullo, R. Macromol. Rapid Commun. 2009, 30, 1697-1708.
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11588/893116
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