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Highly efficient ring‐opening polymerization of tetrahydrofuran by anhydrous ferric chloride
Author(s) -
Yang Hee Jung,
Yoon Seok Won,
Park Hee Sun,
Lee Kyu Hyung,
Hur Nam Hwi
Publication year - 2019
Publication title -
journal of applied polymer science
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.575
H-Index - 166
eISSN - 1097-4628
pISSN - 0021-8995
DOI - 10.1002/app.47999
Subject(s) - polymerization , polymer chemistry , cationic polymerization , acetic anhydride , tetrahydrofuran , chemistry , ring opening polymerization , dispersity , ether , chloride , catalysis , polymer , organic chemistry , solvent
Poly(tetramethylene ether glycol) (PTMG), widely used as a precursor in the fabrication of commodity polymers, is typically produced byacid‐catalyzed polymerization of tetrahydrofuran (THF). Herein, we report a detailed investigation of the cationic ring‐opening polymerization of THF catalyzed by ferric chloride (FeCl 3 ), which can be considered as a strong Lewisacid. The polymerization reactions were performed in the presence of acetic anhydride at 20°C with FeCl 3 , which readily produced poly(tetramethylene ether glycol diester) (PTMG_DE). A maximum yield of 79.2% was obtained within 30 min using a FeCl 3 to acetic anhydride molar ratio of 5:4. The resulting polymers generally exhibited low molecular weights and a narrow polydispersity index and could be easily converted into PTMG using aqueous NaOH. In contrast with the FeCl 3 ‐acetic anhydride system, other iron‐based catalysts such as FeCl 2 and FeCl 3 ·6H 2 O did not show any noticeable activity in the polymerization of THF. The proposed mechanism involves initiation of the acetyl cation generated by FeCl 3 , propagation by nucleophilic addition of THF, and termination by the acetate anion, accounting for the high activity of the FeCl 3 catalyst for THF polymerization. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136 , 47999.

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