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 1/catalyst 2/CSA 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 also challenging, 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 illustrated.
A Mechanistic HTE Approach to ‘Polyolefin Chain Shuttling’ / Vittoria, Antonio; Cipullo, Roberta; Cannavacciuolo, Felicia Daniela; Busico, Vincenzo. - (2017), pp. 29-29. (Intervento presentato al convegno Advances in Polyolefins XI tenutosi a Santa Rosa (CA), USA nel 24-27 Settembre 2017).
A Mechanistic HTE Approach to ‘Polyolefin Chain Shuttling’
Vittoria, Antonio;CIPULLO, ROBERTA;
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 1/catalyst 2/CSA 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 also challenging, 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 illustrated.I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.