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Insights into the Nature of Self‐Extinguishing External Donors for Ziegler‐Natta Catalysis: A Combined Experimental and DFT Study
Author(s) -
Vipin Raj K.,
Kumawat Jugal,
Dhamaniya Sunil,
Subaramanian Murugan,
Balaraman Ekambaram,
Kumar Gupta Virendra,
Vanka Kumar,
Grubbs Robert H.
Publication year - 2021
Publication title -
chemcatchem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.497
H-Index - 106
eISSN - 1867-3899
pISSN - 1867-3880
DOI - 10.1002/cctc.202001493
Subject(s) - catalysis , natta , alkyl , chemistry , polymerization , polymer , covalent bond , chain termination , titanium , combinatorial chemistry , polymer chemistry , organic chemistry , radical polymerization
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, D 1 (2,2,2‐trifluoroethyl myristate) and D 2 (2,2,2‐trifluoroethyl palmitate) that show self‐extinguishing properties, followed by a systematic DFT study to understand this peculiar property of these donors. D 1 and D 2 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.