Separating Electronic from Steric Effects in Ethene/α-Olefin Copolymerization: A Case Study on Octahedral [ONNO] Zr-Catalysts

Francesco Zaccaria; Roberta Cipullo; Andrea Correa; Peter H. M. Budzelaar; Vincenzo Busico; Christian Ehm

LAPSE

Living Archive for Process Systems Engineering

LAPSE:2019.0962

Published Article

LAPSE:2019.0962

Separating Electronic from Steric Effects in Ethene/α-Olefin Copolymerization: A Case Study on Octahedral [ONNO] Zr-Catalysts

Francesco Zaccaria, Roberta Cipullo, Andrea Correa, Peter H. M. Budzelaar, Vincenzo Busico, Christian Ehm

August 15, 2019

Four Cl/Me substituted [ONNO] Zr-catalysts have been tested in ethene/α-olefin polymerization. Replacing electron-donating methyl with isosteric but electron-withdrawing chlorine substituents results in a significant increase of comonomer incorporation. Exploration of steric and electronic properties of the ancillary ligand by DFT confirm that relative reactivity ratios are mainly determined by the electrophilicity of the metal center. Furthermore, quantitative DFT modeling of propagation barriers that determine polymerization kinetics reveals that electronic effects observed in these catalysts affect relative barriers for insertion and a capture-like transition state (TS).

Record ID

LAPSE:2019.0962

Keywords

DFT, electronic effects, insertion kinetics, olefin capture, olefin copolymerization, post-metallocene, reactivity ratios, salan catalysts

Subject

Reaction Engineering

Suggested Citation

Zaccaria F, Cipullo R, Correa A, Budzelaar PHM, Busico V, Ehm C. Separating Electronic from Steric Effects in Ethene/α-Olefin Copolymerization: A Case Study on Octahedral [ONNO] Zr-Catalysts. (2019). LAPSE:2019.0962

Author Affiliations

Zaccaria F: Dipartimento di Scienze Chimiche, Università di Napoli Federico II, Via Cintia, 80126 Napoli, Italy; Dipartimento di Chimica, Biologia e Biotecnologie and CIRCC, Università di Perugia, Via Elce di Sotto 8, 06123 Perugia, Italy [ORCID]
Cipullo R: Dipartimento di Scienze Chimiche, Università di Napoli Federico II, Via Cintia, 80126 Napoli, Italy [ORCID]
Correa A: Dipartimento di Scienze Chimiche, Università di Napoli Federico II, Via Cintia, 80126 Napoli, Italy
Budzelaar PHM: Dipartimento di Scienze Chimiche, Università di Napoli Federico II, Via Cintia, 80126 Napoli, Italy [ORCID]
Busico V: Dipartimento di Scienze Chimiche, Università di Napoli Federico II, Via Cintia, 80126 Napoli, Italy
Ehm C: Dipartimento di Scienze Chimiche, Università di Napoli Federico II, Via Cintia, 80126 Napoli, Italy [ORCID]
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Journal Name

Processes

Volume

7

Issue

6

Article Number

E384

Year

2019

Publication Date

2019-06-20