Preparation method and industrialized production method of pyrrolidinium with tetrafluoroborate anions

Abstract

The invention provides a preparation method of pyrrolidinium with tetrafluoroborate anions, which comprises the following steps: (1) the one-step synthesis of a coarse product: by taking a non-proton organic solvent as a reaction medium, dropwise adding haloalkanes into a mixture consisting of N-alkyl pyrrolidine and tetrafluoroborate, reacting for obtaining a coarse product liquid, filtering the coarse product liquid by using a centrifuge, and carrying out reduced pressure distillation on filter liquor so as to obtain a coarse product solid; and (2) heating and stirring the coarse product solid so as to dissolve the coarse product solid into an alcohol organic solvent, and sequentially carrying out cooling crystallization, filtration, rinsing and vacuum drying on the obtained product, so that a refined finished product is obtained. The invention also discloses an industrialized production method of pyrrolidinium with tetrafluoroborate anions. The methods disclosed by the invention are implemented through one-step synthesis, cheap and easily-obtained in raw materials, short in synthetic route, mild in reaction conditions, short in reaction time, simple in operation, and relatively low in production cost; prepared products are high in product purity, good in crystal form and high in yield; and environmentally harmful substances are not produced in the production process, thereby facilitating industrialized continuous mass production.

Description

technical field [0001] The invention relates to a preparation method and industrial production method of pyrrolidinium salt with tetrafluoroborate anion. Background technique [0002] At present, many onium salts are widely used in the field of conductive salts of supercapacitors and dielectrics of super batteries due to their good electrical conductivity and wide electrochemical window. Some onium salts, especially those in liquid state at room temperature Salt, due to its advantages of non-volatility and easy separation from the reaction system, is considered to be a green solvent and green catalyst with broad application prospects. According to the designability of onium salts, the introduction of anions and cations with different characteristic functional groups in the synthesis of onium salts can make onium salts have certain characteristic functions or meet specificity requirements. Among them, the onium salt, which is composed of large-volume, low-symmetry organic ca...

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Problems solved by technology

[0003] However, due to the relatively late start of research on dielectrics for supercapacitors and super batteries in my country compared with developed countries in the West, the production of pyrrolidinium tetrafluoroborate has not yet entered the stage of industrial production, resulting in high manufacturing costs. Its market application and promotion bring huge obstacles

There are literature records related to the production method of pyrrolidinium salt with tetrafluoroborate anion, such as: the applicant is East China Normal University, the application number is CN200610116874.9 Chinese patent - "A basic ionic liquid, preparation method and application thereof ", although mentioning the preparation method of basic ionic liquid (two-step synthesis method: first obtain ionic halide by quaternization, then obtain target basic ionic liquid by ion exchange), but it does not mention specific essence It is a synthetic method and purification method, and it is clearly stated in the specification that the alkaline quaternary ammonium salt ionic liquid disclosed in this patent is stable to water and air, and is liquid at room temperature, and it is very easy to absorb water in air with a melting point higher than 200 ° C. The synthesis process and refining process of solid quaternary ammonium salts are not suitable; the applicants are Ocean King Lighting Technology Co., Ltd., Shenzhen Ocean King Lighting Technology Co., Ltd., Shenzhen Ocean King Lighting Engineering Co., Ltd., and the application number is CN201310042656.5 Chinese patent—"Pyrrolidine ionic liquid and its preparation method, electrolyte and capacitor", although it involves the preparation of pyrrolidine ionic liquid, the substituents connected to pyrrolidine required by this patent are only limited to methyl and CH3O(CH2 )n, wherein n is 2, 3 or 4 two substituent ranges, and is also a two-step synthesis method, the reaction process does not involve the selection of organic media and the refining method of the product, for very water-soluble Borate anion onium salt This method is not applicable; the applicant is Merck Patent Co., Ltd., and the application number is CN200580041219.5 Chinese patent - "preparation method of onium salt with tetrafluoroborate anion with reduced halide content" , the borylation process is limited to expensive raw materials such as trialkyloxonium tetrafluoroborate, trialkylsulfonium tetrafluoroborate, triphenyl-n-carbon tetrafluoroborate, etc., and does not mention And the refining method of the product, it is difficult to obtain alkyl oxonium raw materials in the market, so it is difficult to carry out industrial production; the applicants are Wuhan Kaimen Technology Co., Ltd., Guangzhou Kaimen Fine Chemical Co., Ltd., and the application number is CN200910041553.0 in China The patent - "Preparation method of high-purity conductive salt for supercapacitors" announced a three-step synthesis method. The raw material N-ethylpyrrolidine has not yet been industrialized in China, so the production of raw materials is greatly restricted, and the synthesis steps are cumbersome and the temperature is high. , which is not conducive to energy saving and consumption reduction; other synthetic methods such as Japan’s Mitsui Chemicals, Mitsubishi Chemicals, Trioxide, Linggas and other synthetic methods published in Japan use corrosive raw materials such as tetrafluoroboric acid, boron trifluoride, hydrogen fluoride, etc. The raw materials of the equipment have high anti-corrosion requirements, and the raw materials are easy to form by-products that are difficult to remove during the reaction process, which is not convenient for industrialization

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