摘要
报道了功能性全氟膦酸酯乙烯基醚的合成方法。全氟乙烯基醚磺酰氟经硼氢化钠还原和浓硫酸酸化转化为全氟乙烯基醚亚磺酸,脱亚磺酸和碘化后得到全氟乙烯基醚碘代烷,收率约58%。基于金属试剂-卤化物的交换反应,以全氟乙烯基醚碘代烷和卤(氯/溴)代膦酸酯为反应物,在正丁基锂或格式试剂存在下进行低温反应;或基于Michaelis-Becker反应,在二(三甲基硅基)氨基钠或锂等化学计量下与亚磷酸二乙酯进行反应,均可以成功获得目标单体全氟膦酸酯乙烯基醚,2种路线的分离收率分别为34%和25%。该方法避免使用毒性大的氯气或液溴保护不饱和双键,极大简化了合成步骤,为功能性全氟乙烯基醚类单体和全氟膦酸酯乙烯醚的合成提供了新途径。
Herein,a new synthesis method of perfluorophosphonate vinyl ether for phosphonic acid-based proton exchange membrane was reported.Perfluorinated sulfonyl vinyl ether was converted to perfluorinated sulfinic acid vinyl ether by sodium borohydride reduction and sulfuric acid acidification,and followed by iodination to obtain perfluorovinyl ether iodide with 58%yield.Based on the metal-halogen exchange reaction,perfluorovinyl ether iodide and halogenated(chlorine/bromine)phosphate ester were dissolved under nitrogen atmosphere,and then n-butyl lithium or Grignard reagent was dropwise added to the reaction at low temperature;according to the Michaelis-Becker reaction,perfluorovinyl ether iodide was mixed with diethyl phosphite,then sodium or lithium bis(trimethylsilyl)amide was slowly added,both methods could successfully produce perfluorophosphonate vinyl ether with yields of 34%and 25%,respectively.This strategy avoids the protection of unsaturated double bonds with highly toxic chlorine gas or liquid bromine,greatly simplifies the synthesis process compared to the reported ones,and provides a new way to synthesize functional perfluorinated vinyl ether monomers.
作者
宋莹莹
葛玮
史翔
魏刚
李冰
李长坤
董常明
姜学松
SONG Ying-Ying;GE Wei;SHI Xiang;WEI Gang;LI Bing;LI Chang-Kun;DONG Chang-Ming;JIANG Xue-Song(School of Chemistry and Chemical Engineering,Shanghai Jiao Tong University,Shanghai 200240,China;State Key Laboratory of Fluorinated Functional Membrane Materials,Shandong Dongyue Future Hydrogen Energy Co.Ltd.,Zibo 256401,China)
出处
《应用化学》
CAS
CSCD
北大核心
2024年第4期512-520,共9页
Chinese Journal of Applied Chemistry
基金
国家重点研发计划(Nos.2021YFB4001100,2021YFB4001101)资助。
