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首页> 外文期刊>Journal of Applied Polymer Science >A Methanesulfonic Acid/Sulfuric Acid-Based Route for Easily-Controllable Chloromethylation of Poly(ether ether ketone)
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A Methanesulfonic Acid/Sulfuric Acid-Based Route for Easily-Controllable Chloromethylation of Poly(ether ether ketone)

机译：基于甲磺酸/硫酸的途径可轻松控制聚醚醚酮的氯甲基化

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摘要

A mixed methanesulfonic acid/sulfuric acid solvent based chlromethylation of poly(ether ether ketone) (PEEK) is described. Methanesulfonic acid is the solvent, sulfuric acid is the catalyst, and chloromethyl octyl ether (CMOE) is the chloromethylating reagent. H-1-NMR spectra confirmed the successful synthesis of chloromethylated PEEK (CMPEEK). The effects of polymer concentration, catalyst/polymer ratio, and reaction temperature on the rate of PEEK chloromethylation were investigated. In order to minimize crosslinking, the PEEK concentration must be kept very low (< 2%). The reaction rate increases with increased catalyst/polymer ratio and reaction temperature. The activation energy of PEEK chloromethylation is 30.9 kJ mol(-1). The extent of reaction for the new route is more easily controllable as compared with the previous sulfuric acid based route. The reaction rate constant at 25 degrees C for the new route is 1.29 h(-1) which is lower than that for chloromethylation by concentrated sulfuric acid at -10 degrees C (rate constant 1.88 h(-1)). As a result, the degree of chloromethylation of CMPEEK can be easily controlled at room temperature using this mixed solvent. (c) 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 41404.
机译：描述了基于甲磺酸/硫酸溶剂的混合甲基聚醚醚酮的氯甲基化（PEEK）。甲磺酸是溶剂，硫酸是催化剂，氯甲基辛基醚（CMOE）是氯甲基化试剂。 H-1-NMR光谱证实了氯甲基化PEEK（CMPEEK）的成功合成。研究了聚合物浓度，催化剂/聚合物比和反应温度对PEEK氯甲基化速率的影响。为了最大程度地减少交联，必须将PEEK的浓度保持在非常低的水平（<2％）。反应速率随着催化剂/聚合物比和反应温度的增加而增加。 PEEK氯甲基化的活化能为30.9 kJ mol（-1）。与先前的基于硫酸的路线相比，新路线的反应程度更易于控制。新路线在25摄氏度下的反应速率常数为1.29 h（-1），低于在-10摄氏度下通过浓硫酸进行氯甲基化的反应速率常数（速率常数1.88 h（-1））。结果，使用该混合溶剂可以在室温下容易地控制CMPEEK的氯甲基化程度。 （c）2014 Wiley Periodicals，Inc. J. Appl。 Polym。科学2015，132，41404。

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