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Highly efficient ring-opening polymerization of tetrahydrofuran by anhydrous ferric chloride

机译：通过无水氯化物的高效开环聚合四氢呋喃

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摘要

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 (FeCl3), which can be considered as a strong Lewisacid. The polymerization reactions were performed in the presence of acetic anhydride at 20 degrees C with FeCl3, which readily produced poly(tetramethylene ether glycol diester) (PTMG_DE). A maximum yield of 79.2% was obtained within 30 min using a FeCl3 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 FeCl3-acetic anhydride system, other iron-based catalysts such as FeCl2 and FeCl3 center dot 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 FeCl3, propagation by nucleophilic addition of THF, and termination by the acetate anion, accounting for the high activity of the FeCl3 catalyst for THF polymerization. (c) 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019, 136, 47999.
机译：广泛用作商品聚合物制造中广泛用作前体的聚（四亚甲基醚二醇）（PTMG）通常生产四氢呋喃（THF）的催化聚合。在此，我们报告了通过氯化铁（FECL3）催化的THF的阳离子开环聚合的详细研究，其可被认为是强烈的Lewisacid。聚合反应在乙酸酐的情况下在20℃下进行，用FECL3易于产生聚（四亚甲基醚二醇二酯）（PTMG_DE）。在30分钟内使用FECL3至乙酸酐摩尔比为5：4的最大收率为79.2％。所得聚合物通常表现出低分子量和窄的多分散性指数，并且可以使用NaOH水溶液容易地转化为PTMG。与FECL3-乙酸酐系统相比，其他铁基催化剂如FECL2和FECL3中心点6H（2）O在THF的聚合中没有显示出任何显着的活性。所提出的机制涉及由FECL3产生的乙酰阳离子引发，通过乙酸酯阴离子的亲核添加，终止于乙酸根，核对THF聚合的FECL3催化剂的高活性。 （c）2019 Wiley期刊，Inc.J.Phill。聚合物。 SCI。 2019,136,47999。

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