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Insights into the Nature of Self‐Extinguishing External Donors for Ziegler-Natta Catalysis: A Combined Experimental and DFT Study

Raj, K. Vipin and Kumawat, Jugal and Dhamaniya, Sunil and Subaramanian, Murugan and Balaraman, Ekambaram and Gupta, Virendra Kumar and Vanka, Kumar and Grubbs, Robert H. (2021) Insights into the Nature of Self‐Extinguishing External Donors for Ziegler-Natta Catalysis: A Combined Experimental and DFT Study. ChemCatChem, 13 (2). pp. 674-681. ISSN 1867-3880.

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Developing donors for Ziegler‐Natta (ZN) catalysis to control the polymerization reaction and produce polymers with desirable properties has always been challenging due to the multi‐component nature of the catalytic systems. Here, we have developed a new synthetic protocol for making two external donors, D₁ (2,2,2‐trifluoroethyl myristate) and D₂ (2,2,2‐trifluoroethyl palmitate) that show self‐extinguishing properties, followed by a systematic DFT study to understand this peculiar property of these donors. D₁ and D₂ can undergo parallel reactions with aluminum and titanium species present in the system to produce ketones and aldehydes, which are poisons for ZN catalytic systems, thus explaining their self‐extinguishing nature. The non‐covalent interaction between the long alkyl chain of the donors with the surface plays a vital role in determining the donors′ self‐extinguishing nature. There is a significant thermodynamic preference for the binding of the donor with the longer alkyl chain at the titanium center. The current work, therefore, provides interesting insights into how self‐extinguishing donors function in ZN catalytic systems.

Item Type:Article
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Grubbs, Robert H.0000-0002-0057-7817
Additional Information:© 2020 Wiley‐VCH GmbH. Issue Online: 26 January 2021; Version of Record online: 19 November 2020; Accepted manuscript online: 22 October 2020; Manuscript revised: 21 October 2020; Manuscript received: 15 September 2020. K. V. R. wishes to acknowledge CSIR for providing senior research fellowship. K. V. R. and K. V. also acknowledge the Multi‐Scale simulation and Modeling project MSM for the computational facilities. K. V. also thanks DST‐SERB (EMR/2014/000013) for providing financial assistance. E. B. acknowledges IISER‐Tirupati and SERB, India (Grant No: CRG/2018/002480/OC). The authors declare no conflict of interest.
Funding AgencyGrant Number
Council of Scientific and Industrial Research (India)UNSPECIFIED
Department of Science and Technology (India)EMR/2014/000013
Science and Engineering Research Board (SERB)CRG/2018/002480/OC
Subject Keywords:Ziegler-Natta catalysis; self-extinguishing; donors; non-covalent interactions; DFT
Issue or Number:2
Record Number:CaltechAUTHORS:20201027-085106547
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Official Citation:K. Vipin Raj, J. Kumawat, S. Dhamaniya, M. Subaramanian, E. Balaraman, V. Kumar Gupta, K. Vanka, R. H. Grubbs, ChemCatChem 2021, 13, 674. DOI: 10.1002/cctc.202001493
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:106293
Deposited By: Tony Diaz
Deposited On:27 Oct 2020 16:59
Last Modified:28 Jan 2021 18:51

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