WO2020224268A1 - Synthesis method for 4,4'-bi-1,3-dioxolane-2,2'-dione - Google Patents

Synthesis method for 4,4'-bi-1,3-dioxolane-2,2'-dione Download PDF

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WO2020224268A1
WO2020224268A1 PCT/CN2019/127304 CN2019127304W WO2020224268A1 WO 2020224268 A1 WO2020224268 A1 WO 2020224268A1 CN 2019127304 W CN2019127304 W CN 2019127304W WO 2020224268 A1 WO2020224268 A1 WO 2020224268A1
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dioxolane
dione
linked
tetrahydrofuran
synthesizing
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PCT/CN2019/127304
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French (fr)
Chinese (zh)
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闫彩桥
葛建民
王军
郝俊
张民
武利斌
侯荣雪
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石家庄圣泰化工有限公司
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Priority to KR1020217007529A priority Critical patent/KR102509669B1/en
Priority to JP2021513778A priority patent/JP7315810B2/en
Publication of WO2020224268A1 publication Critical patent/WO2020224268A1/en

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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D407/00Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00
    • C07D407/02Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing two hetero rings
    • C07D407/04Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D317/00Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
    • C07D317/08Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
    • C07D317/10Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
    • C07D317/32Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D317/34Oxygen atoms
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D317/00Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
    • C07D317/08Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
    • C07D317/10Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
    • C07D317/32Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D317/34Oxygen atoms
    • C07D317/36Alkylene carbonates; Substituted alkylene carbonates
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • H01M10/0525Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/42Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/42Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/056Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566Liquid materials
    • H01M10/0567Liquid materials characterised by the additives
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Definitions

  • the present invention belongs to the technical field of battery electrolyte additives, and relates to the use of 4,4'-dioxolane-2,2'-dione as a battery electrolyte additive, and specifically relates to 4,4'- Synthetic method of bi-1,3-dioxolane-2,2'-dione.
  • the continuous improvement of lithium-ion battery performance has made it more and more widely used, but its safety issues and cycle performance have restricted the development of lithium-ion batteries to a certain extent.
  • the current relatively hot power lithium-ion batteries for electric vehicles, safety performance, fast charging performance, and endurance are hot issues studied by various research institutions.
  • the key to solving these problems should start from the battery itself.
  • the internal cause mainly involves the stability of the positive and negative active materials, the characteristics of the electrolyte itself and its compatibility with electrode materials, and the stability of the separator material.
  • the external cause is mainly the incorrect use of the battery and the abuse during use.
  • electrolyte additives is a very effective method, which can not only improve the characteristics of the electrolyte itself, but also improve the compatibility of the electrolyte and the electrode material, and adding a small amount will have a significant effect .
  • the modification of the electrode material can further improve the cycle stability of the lithium ion battery.
  • the present invention provides a method for synthesizing 4,4'-bi-1,3-dioxolane-2,2'-dione.
  • the synthesis method of the present invention is simple, and the raw materials are cheap and easily available. The energy consumption is low, the reaction conditions are mild and stable, and the yield is high.
  • the molar ratio of phosgene, imidazole and butanetetraol is 1: (3-6): (0.45-0.8).
  • Tetrahydrofuran solution of butanetetraol (1g/4-4.5ml). That is, 4-4.5ml tetrahydrofuran solution contains 1g tetrahydrofuran.
  • the concentration control vacuum is 0.08-0.10MPa, and the concentration is 1.5-2h at a temperature of 50-60°C.
  • the vacuum degree of the solvent is controlled to 0.08-0.09Mpa, and the vacuum treatment time is 30-40min.
  • the raw materials used in the invention are cheap and easily available, the synthesis method is simple and easy to operate, low energy consumption, short reaction time, mild and stable reaction conditions, and high product yield, which can reach more than 94%.
  • This application uses low-temperature reaction, breaking the current situation that is generally believed to require high-temperature reaction, and opens up a new method for synthesizing 4,4'-bi-1,3-dioxolane-2,2'-dione .
  • Those skilled in the art generally believe that in the preparation of 4,4'-bi-1,3-dioxolane-2,2'-dione, high temperature and long time reaction will promote the progress of the reaction, which is beneficial to 4,4' -Synthesis of 1,3-dioxolane-2,2'-dione; if the temperature is low, it will affect the progress of the reaction, slow down the reaction speed, and the yield will be low, even resulting in failure to synthesize 4,4'-dione -1,3-dioxolane-2,2'-dione.
  • Figure 1 is the cycle performance diagram of the LP063450AR square lithium-ion battery with a rated capacity of 950mAh.
  • Fig. 2 is a graph showing the cycle performance of a LP063450AR prismatic lithium ion battery with a rated capacity of 950 mAh added with 4,4'-linked-1,3-dioxolane-2,2'-dione of the present invention.
  • Figure 3 is a mass spectrum of 4,4'-bi-1,3-dioxolane-2,2'-dione prepared by the present invention.
  • Fig. 4 is a partial cut-out view of Fig. 3.
  • the obtained 4,4'-bi-1,3-dioxolane-2,2'-dione was collected, the density was determined to be 1.6075g/cm 3 , the boiling point was 535.33°C (760mmHg), and the purity was 99.87 by HPLC %.
  • the obtained 4,4'-bi-1,3-dioxolane-2,2'-dione was collected, and the measured density was 1.6083g/cm 3 , the boiling point was 535.38°C (760mmHg), and the purity was 99.89 by HPLC. %.
  • the obtained 4,4'-linked-1,3-dioxolane-2,2'-dione was collected and the density was determined to be 1.6078g/cm 3 , the boiling point was 535.47°C (760mmHg), and the purity was 99.91 by HPLC %.
  • the obtained 4,4'-linked-1,3-dioxolane-2,2'-dione was collected, and the measured density was 1.609g/cm 3 , the boiling point was 535.71°C (760mmHg), and the purity was 99.85 by HPLC. %.
  • the obtained 4,4'-bi-1,3-dioxolane-2,2'-dione was collected, and the density was determined to be 1.6087g/cm 3 , the boiling point was 535.64°C (760mmHg), and the purity was 99.86 by HPLC. %.
  • the obtained 4,4'-bi-1,3-dioxolane-2,2'-dione was collected, and the measured density was 1.6073g/cm 3 , the boiling point was 535.38°C (760mmHg), and the purity was 99.86 by HPLC. %.
  • the obtained 4,4'-linked-1,3-dioxolane-2,2'-dione was collected and subjected to mass spectrometric detection.
  • the mass spectra of the detection are shown in Figure 3 and Figure 4, and the measured density is 1.6088g/cm 3 .
  • the boiling point is 535.68°C (760mmHg), and the purity is 99.84% by HPLC.
  • the lithium-ion battery used in the experimental study is the LP063450AR square lithium-ion battery with a rated capacity of 950mAh produced by BYD Co., Ltd.
  • the battery is subjected to 1c rate (950mA) charge-discharge cycle test at 25°C and 5°C respectively, using constant current and constant voltage charging system (CC-CV) and constant current discharge system, the charging and discharging voltage range is 3.0-4.5V, first Charge with 1C constant current to 4.5V, then charge with 4.5V constant voltage until the current is less than 20mA, and then discharge with 1C constant current until the final voltage is 3.0V, so the cycle of charge and discharge is 500 times.
  • the cycle data is collected in LAND-2001T Performed on the battery test system.
  • the battery with the addition of 4,4'-link-1,3-dioxolane-2,2'-dione of the present invention has a battery capacity of 87.6% at 65°C, 500 cycles
  • the battery capacity at 65°C after cycling is 75.2%, but the battery without adding the 4,4'-link-1,3-dioxolane-2,2'-dione of the present invention is the battery at 65°C after 500 cycles
  • the capacity is 59%, end of life. It can be seen that the 4,4'-linked-1,3-dioxolane-2,2'-dione prepared by the present invention can improve the cycle performance of the battery under high voltage and high temperature.
  • LiFePO 4 lithium-ion battery As the research object, the size is 12.cm*7cm*0.8cm, the rated capacity of a single battery is 10Ah, the working voltage is 3.3-4.2V, and the outer shell is aluminum-plastic film, and the low temperature test is carried out. Take 25°C as the low temperature test reference point, starting from 25°C to -20°C, every 5°C is a temperature inspection point, the temperature change rate is 30min/5°C, and the temperature can be carried out after being left for 24h at each temperature point. The performance test, the test results are shown in Table 1.

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Abstract

A synthesis method for 4,4'-bi-1,3-dioxolane-2,2'-dione, relating to the technical field of battery electrolyte additives, and comprising: adding an imidazole and tetrahydrofuran to a reactor in an argon atmosphere, cooling same to -5 to 5ºC, starting dropping phosgene, completing the dropping after 0.5 to 1 h, then dropping the mixture to a tetrahydrofuran solution of erythritol at -8 to -15ºC, completing the dropping after 1 to 1.5 h, maintaining the temperature and stirring same for 0.5 to 2 h, and removing the solvent in vacuum to obtain a residue; dissolving the residue in dichloromethane, washing same by using cold water, drying and then concentrating same to obtain a 4,4'-bi-1,3-dioxolane-2,2'-dione crude product, and purifying the crude product to obtain refined 4,4'-bi-1,3-dioxolane-2,2'-dione. According to the present invention, the raw materials used are easy to obtain, and the synthesis method is simple to operate, low in energy consumption, short in reaction time, mild and stable in reaction conditions, and high in product yield, which is up to 94%.

Description

4,4’-联-1,3-二氧戊环-2,2’-二酮的合成方法Synthesis method of 4,4'-linked-1,3-dioxolane-2,2'-dione 技术领域Technical field
本发明属于电池电解液添加剂的技术领域,涉及将4,4’-联-1,3-二氧戊环-2,2’-二酮用作电池电解液添加剂,具体涉及4,4’-联-1,3-二氧戊环-2,2’-二酮的合成方法。The present invention belongs to the technical field of battery electrolyte additives, and relates to the use of 4,4'-dioxolane-2,2'-dione as a battery electrolyte additive, and specifically relates to 4,4'- Synthetic method of bi-1,3-dioxolane-2,2'-dione.
背景技术Background technique
锂离子电池性能的不断完善已经使其应用范围越来越广泛,但是其安全性问题及循环性能在一定程度上制约了锂离子电池的发展。特别是目前较为火热的电动汽车用动力锂离子电池,安全性能、快速充电性能、续航能力都是各研究机构研究的热点问题,解决这些问题的关键点要从电池本身出发。影响锂离子电池安全性和循环稳定性因素很多,主要可分为内因和外因两个方面。内因主要涉及正负极活性材料的稳定性、电解液本身的特性及其与电极材料的兼容性、隔膜材料的稳定性等,外因主要是电池的不正确使用及使用过程中出现滥用现象等。通过研究发现,电解液添加剂的引入是一个非常有效的方法,它既可改善电解液本身的特性,又可以提高电解液与电极材料的兼容性,并且添加很少的量就会有明显的作用。对电极材料的改性则可更进一步提高锂离子电池的循环稳定性。The continuous improvement of lithium-ion battery performance has made it more and more widely used, but its safety issues and cycle performance have restricted the development of lithium-ion batteries to a certain extent. In particular, the current relatively hot power lithium-ion batteries for electric vehicles, safety performance, fast charging performance, and endurance are hot issues studied by various research institutions. The key to solving these problems should start from the battery itself. There are many factors that affect the safety and cycle stability of lithium-ion batteries, which can be divided into internal and external factors. The internal cause mainly involves the stability of the positive and negative active materials, the characteristics of the electrolyte itself and its compatibility with electrode materials, and the stability of the separator material. The external cause is mainly the incorrect use of the battery and the abuse during use. Through research, it is found that the introduction of electrolyte additives is a very effective method, which can not only improve the characteristics of the electrolyte itself, but also improve the compatibility of the electrolyte and the electrode material, and adding a small amount will have a significant effect . The modification of the electrode material can further improve the cycle stability of the lithium ion battery.
近几年,不乏出现许多新型多功能锂离子电池电解液添加剂。而经我们研究发现,CAS号为24690-44-6的4,4’-联-1,3-二氧戊环-2,2’-二酮,其作为电解液添加剂能够有效改善锂离子电池正、负极材料的结构稳定性及热稳定性。另外,4,4’-联-1,3-二氧戊环-2,2’-二酮在高电压极高低温条件下均表现出优良的循环及安全性能,对提高锂离子电池性能具有很大的促进作 用。但现有的4,4’-联-1,3-二氧戊环-2,2’-二酮合成工艺仍不成熟,合成过程中通常存在原材料价格昂贵、工艺复杂、产品收率及纯度低等问题,并且目前在4,4’-联-1,3-二氧戊环-2,2’-二酮的合成工艺中普遍认为应该采用高温进行反应,例如60-130℃等,反应时间长达12小时以上,虽然收率能达到88-90%左右,但是反应温度高,反应不稳定,反应时间过长影响生产效率。因此,研究4,4’-联-1,3-二氧戊环-2,2’-二酮的合成方法具有极大的现实意义。In recent years, many new multifunctional lithium ion battery electrolyte additives have appeared. However, our research found that 4,4'-linked-1,3-dioxolane-2,2'-dione with CAS number 24690-44-6 can effectively improve lithium ion batteries as an electrolyte additive The structural stability and thermal stability of the positive and negative electrode materials. In addition, 4,4'-linked-1,3-dioxolane-2,2'-dione exhibits excellent cycling and safety performance under high voltage, extremely high and low temperature conditions, which is useful for improving the performance of lithium-ion batteries. Great promotion. However, the existing 4,4'-linked-1,3-dioxolane-2,2'-dione synthesis process is still immature, and the synthesis process usually involves expensive raw materials, complex processes, product yield and purity Low-level problems, and currently in the synthesis process of 4,4'-linked-1,3-dioxolane-2,2'-dione, it is generally believed that high temperature should be used for the reaction, such as 60-130°C, etc. The time is more than 12 hours, although the yield can reach about 88-90%, but the reaction temperature is high, the reaction is unstable, and the reaction time is too long, which affects the production efficiency. Therefore, it is of great practical significance to study the synthesis method of 4,4'-linked-1,3-dioxolane-2,2'-dione.
发明内容Summary of the invention
本发明为解决上述技术问题,提供了一种4,4’-联-1,3-二氧戊环-2,2’-二酮的合成方法,本发明合成方法简单,原材料廉价易得,能耗低,反应条件温和稳定,收率高。In order to solve the above technical problems, the present invention provides a method for synthesizing 4,4'-bi-1,3-dioxolane-2,2'-dione. The synthesis method of the present invention is simple, and the raw materials are cheap and easily available. The energy consumption is low, the reaction conditions are mild and stable, and the yield is high.
本发明为实现其目的采用的技术方案是:The technical scheme adopted by the present invention to achieve its purpose is:
4,4’-联-1,3-二氧戊环-2,2’-二酮的合成方法,在氩气气氛下将咪唑、四氢呋喃加入到反应器中,冷却降温至-5~5℃,开始滴加光气,0.5-1h滴毕,搅拌0.5-1h,过滤,得到含1,1'-羰基二咪唑的滤液;之后在-8~-15℃温度下,将该滤液滴加到丁四醇的四氢呋喃溶液中,1-1.5h滴毕,保温搅拌0.5-2h,并真空除去溶剂,得到残余物;将残余物溶于二氯甲烷中,并用冷水洗涤,干燥后浓缩得到4,4’-联-1,3-二氧戊环-2,2’-二酮粗品,将粗品进行提纯得到精制的4,4’-联-1,3-二氧戊环-2,2’-二酮。The synthesis method of 4,4'-linked-1,3-dioxolane-2,2'-dione, adding imidazole and tetrahydrofuran into the reactor under argon atmosphere, cooling down to -5~5℃ , Start to add phosgene dropwise, 0.5-1h to finish, stir for 0.5-1h, filter to obtain the filtrate containing 1,1'-carbonyldiimidazole; then at -8~-15℃, the filtrate is added dropwise to In the tetrahydrofuran solution of butanetetraol, the dripping is completed for 1-1.5h, the temperature is kept and stirred for 0.5-2h, and the solvent is removed in vacuo to obtain a residue; the residue is dissolved in dichloromethane, washed with cold water, dried and concentrated to obtain 4, 4'-Bi-1,3-dioxolane-2,2'-dione crude product, the crude product is purified to obtain refined 4,4'-dioxolane-2,2' -Diketone.
光气、咪唑、丁四醇的摩尔比为1:(3-6):(0.45-0.8)。The molar ratio of phosgene, imidazole and butanetetraol is 1: (3-6): (0.45-0.8).
丁四醇的四氢呋喃溶液(1g/4-4.5ml)。即4-4.5ml四氢呋喃溶液中含有1g丁四醇。Tetrahydrofuran solution of butanetetraol (1g/4-4.5ml). That is, 4-4.5ml tetrahydrofuran solution contains 1g tetrahydrofuran.
冷水洗涤2-3次。Wash 2-3 times in cold water.
干燥采用无水硫酸钠和/或氧化钙干燥。Dry using anhydrous sodium sulfate and/or calcium oxide.
浓缩控制真空度为0.08-0.10MPa,于温度50-60℃下浓缩1.5-2h。The concentration control vacuum is 0.08-0.10MPa, and the concentration is 1.5-2h at a temperature of 50-60℃.
提纯采用丙酮进行重结晶。Purification uses acetone for recrystallization.
真空除去溶剂的真空度控制为0.08-0.09Mpa,真空处理时间为30-40min。The vacuum degree of the solvent is controlled to 0.08-0.09Mpa, and the vacuum treatment time is 30-40min.
本发明的有益效果是:The beneficial effects of the present invention are:
本发明所用原材料廉价易得,合成方法简便易操作,能耗低,反应时间短,反应条件温和稳定,产品收率高,可达94%以上。The raw materials used in the invention are cheap and easily available, the synthesis method is simple and easy to operate, low energy consumption, short reaction time, mild and stable reaction conditions, and high product yield, which can reach more than 94%.
本申请采用低温反应,打破了现有普遍认为需要高温反应的局面,开拓了一种新的合成4,4’-联-1,3-二氧戊环-2,2’-二酮的方法。本领域技术人员普遍认为在制备4,4’-联-1,3-二氧戊环-2,2’-二酮时,高温、长时间反应会促进反应的进行,有利于4,4’-联-1,3-二氧戊环-2,2’-二酮的合成;如果低温,会影响反应的进行,减缓反应速度,收率低,甚至会导致不能合成4,4’-联-1,3-二氧戊环-2,2’-二酮。发明人经过长期的研究,采用光气、咪唑、丁四醇为原料来制备4,4’-联-1,3-二氧戊环-2,2’-二酮,可以实现低温、短时间的反应合成,并且收率达到94%以上。This application uses low-temperature reaction, breaking the current situation that is generally believed to require high-temperature reaction, and opens up a new method for synthesizing 4,4'-bi-1,3-dioxolane-2,2'-dione . Those skilled in the art generally believe that in the preparation of 4,4'-bi-1,3-dioxolane-2,2'-dione, high temperature and long time reaction will promote the progress of the reaction, which is beneficial to 4,4' -Synthesis of 1,3-dioxolane-2,2'-dione; if the temperature is low, it will affect the progress of the reaction, slow down the reaction speed, and the yield will be low, even resulting in failure to synthesize 4,4'-dione -1,3-dioxolane-2,2'-dione. After long-term research, the inventors used phosgene, imidazole, and butanetetraol as raw materials to prepare 4,4'-bi-1,3-dioxolane-2,2'-dione, which can achieve low temperature and short time The reaction is synthesized, and the yield reaches more than 94%.
附图说明Description of the drawings
图1是额定容量为950mAh的LP063450AR型方形锂离子电池的循环性能图。Figure 1 is the cycle performance diagram of the LP063450AR square lithium-ion battery with a rated capacity of 950mAh.
图2是添加本发明4,4’-联-1,3-二氧戊环-2,2’-二酮的额定容量为950mAh的LP063450AR型方形锂离子电池的循环性能图。Fig. 2 is a graph showing the cycle performance of a LP063450AR prismatic lithium ion battery with a rated capacity of 950 mAh added with 4,4'-linked-1,3-dioxolane-2,2'-dione of the present invention.
图3是本发明制备的4,4’-联-1,3-二氧戊环-2,2’-二酮的质谱图。Figure 3 is a mass spectrum of 4,4'-bi-1,3-dioxolane-2,2'-dione prepared by the present invention.
图4是图3的局部截取图。Fig. 4 is a partial cut-out view of Fig. 3.
具体实施方式Detailed ways
下面结合具体实施例对本发明作进一步的说明。The present invention will be further described below in conjunction with specific embodiments.
一、具体实施例One, specific embodiment
实施例1Example 1
在氩气气氛下将4.0mol咪唑、125ml四氢呋喃加入到四口烧瓶中,冷却降温至0℃,开始滴加1.0mol光气,0.5h滴毕,搅拌0.5h,过滤,得到含1,1'-羰基二咪唑的滤液。之后在-10℃温度下,将该滤液滴加到含0.5mol丁四醇的四氢呋喃(250ml)溶液中,1.5h滴毕,保温搅拌1h,并真空除去溶剂,得到残余物。将残余物溶于二氯甲烷中,并用冷水洗涤两次。加入20g无水硫酸钠干燥,浓缩得到4,4’-联-1,3-二氧戊环-2,2’-二酮粗品。粗品经过重结晶得到82.20g4,4’-联-1,3-二氧戊环-2,2’-二酮纯品(收率94.4%)。Under argon atmosphere, add 4.0mol imidazole and 125ml tetrahydrofuran into a four-necked flask, cool down to 0℃, start dripping 1.0mol phosgene, drip for 0.5h, stir for 0.5h, and filter to obtain 1,1' -The filtrate of carbonyl diimidazole. Afterwards, at a temperature of -10°C, the filtrate was added dropwise to a solution of 0.5 mol tetrahydrofuran (250 ml) of tetrahydrofuran (250 ml), and the dropping was completed in 1.5 hours. After stirring for 1 hour, the solvent was removed in vacuo to obtain a residue. The residue was dissolved in dichloromethane and washed twice with cold water. Add 20g of anhydrous sodium sulfate to dry and concentrate to obtain crude 4,4'-bi-1,3-dioxolane-2,2'-dione. The crude product was recrystallized to obtain 82.20 g of pure 4,4'-dioxolane-2,2'-dione (yield 94.4%).
收集所得的4,4’-联-1,3-二氧戊环-2,2’-二酮,测定密度为1.6075g/cm 3,沸点为535.33℃(760mmHg),通过HPLC检测纯度为99.87%。 The obtained 4,4'-bi-1,3-dioxolane-2,2'-dione was collected, the density was determined to be 1.6075g/cm 3 , the boiling point was 535.33°C (760mmHg), and the purity was 99.87 by HPLC %.
实施例2Example 2
在氩气气氛下将3.0mol咪唑、62ml四氢呋喃加入到四口烧瓶中,冷却降温至-2℃,开始滴加1.0mol光气,0.6h滴毕,搅拌0.6h,过滤,得到含1,1'-羰基二咪唑的滤液。之后在-8℃温度下,将该滤液滴加到含0.45mol丁四醇的四氢呋喃(220ml)溶液中,1h滴毕,保温搅拌1.5h,并真空除去溶剂,得到残余物。将残余物溶于二氯甲烷中,并用冷水洗涤两次。加入20g无水硫酸钠干燥,浓缩得到4,4’-联-1,3-二氧戊环-2,2’-二酮粗品。粗品经过重结晶得74.4g 4,4’-联-1,3-二氧戊环-2,2’-二酮纯品(收率94.96%)。Under argon atmosphere, 3.0mol imidazole and 62ml tetrahydrofuran were added to the four-necked flask, cooled to -2°C, and 1.0mol phosgene was added dropwise. After 0.6h, the mixture was stirred for 0.6h and filtered to obtain the content of 1,1 '-Carbonyl diimidazole filtrate. Then, at -8°C, the filtrate was added dropwise to a tetrahydrofuran (220 ml) solution containing 0.45 mol of tetrahydrofuran (220 ml) for 1 hour, the mixture was kept warm and stirred for 1.5 hours, and the solvent was removed in vacuo to obtain a residue. The residue was dissolved in dichloromethane and washed twice with cold water. Add 20g of anhydrous sodium sulfate to dry and concentrate to obtain crude 4,4'-bi-1,3-dioxolane-2,2'-dione. The crude product was recrystallized to obtain 74.4 g of pure 4,4'-dioxolane-2,2'-dione (yield 94.96%).
收集所得的4,4’-联-1,3-二氧戊环-2,2’-二酮,测定密度为1.6083g/cm 3,沸点为535.38℃(760mmHg),通过HPLC检测纯度为99.89%。 The obtained 4,4'-bi-1,3-dioxolane-2,2'-dione was collected, and the measured density was 1.6083g/cm 3 , the boiling point was 535.38°C (760mmHg), and the purity was 99.89 by HPLC. %.
实施例3Example 3
在氩气气氛下将5.0mol咪唑、204ml四氢呋喃加入到四口烧瓶中,冷却降温至-5℃,开始滴加1.0mol光气,0.8h滴毕,搅拌0.8h,过滤,得到含1,1'-羰基二咪唑的滤液。之后在-12℃温度下,将该滤液滴加到含0.7mol丁四醇的四氢呋喃(384ml)溶液中,1.2h滴毕,保温搅拌0.8h,并真空除去溶剂,得到残余物。将残余物溶于二氯甲烷中,并用冷水洗涤两次。加入20g无水硫酸钠干燥,浓缩得到4,4’-联-1,3-二氧戊环-2,2’-二酮粗品。粗品经过重结晶得到82.95g 4,4’-联-1,3-二氧戊环-2,2’-二酮纯品(收率95.29%)。Add 5.0 mol imidazole and 204 ml tetrahydrofuran to a four-necked flask under argon atmosphere, cool down to -5°C, start to add 1.0 mol phosgene dropwise, drop for 0.8h, stir for 0.8h, and filter to obtain a content of 1,1 '-Carbonyl diimidazole filtrate. Then, at -12°C, the filtrate was added dropwise to a tetrahydrofuran (384 ml) solution containing 0.7 mol of butane erythritol for 1.2 hours, and the mixture was kept and stirred for 0.8 hours, and the solvent was removed in vacuo to obtain a residue. The residue was dissolved in dichloromethane and washed twice with cold water. Add 20g of anhydrous sodium sulfate to dry and concentrate to obtain crude 4,4'-bi-1,3-dioxolane-2,2'-dione. The crude product was recrystallized to obtain 82.95 g 4,4'-dioxolane-2,2'-dione pure product (yield 95.29%).
收集所得的4,4’-联-1,3-二氧戊环-2,2’-二酮,测定密度为1.6078g/cm 3,沸点为535.47℃(760mmHg),通过HPLC检测纯度为99.91%。 The obtained 4,4'-linked-1,3-dioxolane-2,2'-dione was collected and the density was determined to be 1.6078g/cm 3 , the boiling point was 535.47°C (760mmHg), and the purity was 99.91 by HPLC %.
实施例4Example 4
在氩气气氛下将6.0mol咪唑、164ml四氢呋喃加入到四口烧瓶中,冷却降温至5℃,开始滴加1.0mol光气,1h滴毕,搅拌1h,过滤,得到含1,1'-羰基二咪唑的滤液。之后在-15℃温度下,将该滤液滴加到含0.6mol丁四醇的四氢呋喃(307ml)溶液中,1.5h滴毕,保温搅拌2h,并真空除去溶剂,得到残余物。将残余物溶于二氯甲烷中,并用冷水洗涤两次。加入20g无水硫酸钠干燥,浓缩得到4,4’-联-1,3-二氧戊环-2,2’-二酮粗品。粗品经过重结晶得到83.4g 4,4’-联-1,3-二氧戊环-2,2’-二酮纯品(收率95.8%)。Add 6.0mol imidazole and 164ml tetrahydrofuran into a four-neck flask under argon atmosphere, cool down to 5℃, start to add 1.0mol phosgene dropwise, drop for 1h, stir for 1h, filter, and obtain 1,1'-carbonyl group The filtrate of diimidazole. Then, at a temperature of -15°C, the filtrate was added dropwise to a solution of 0.6 mol tetrahydrofuran (307 ml) of tetrahydrofuran (307 ml), and the drop was completed in 1.5 hours. After stirring for 2 hours, the solvent was removed in vacuo to obtain a residue. The residue was dissolved in dichloromethane and washed twice with cold water. Add 20g of anhydrous sodium sulfate to dry and concentrate to obtain crude 4,4'-bi-1,3-dioxolane-2,2'-dione. The crude product was recrystallized to obtain 83.4 g of pure 4,4'-dioxolane-2,2'-dione (yield 95.8%).
收集所得的4,4’-联-1,3-二氧戊环-2,2’-二酮,测定密度为1.609g/cm 3,沸点为535.71℃(760mmHg),通过HPLC检测纯度为99.85%。 The obtained 4,4'-linked-1,3-dioxolane-2,2'-dione was collected, and the measured density was 1.609g/cm 3 , the boiling point was 535.71°C (760mmHg), and the purity was 99.85 by HPLC. %.
实施例5Example 5
在氩气气氛下将4.0mol咪唑、136ml四氢呋喃加入到四口烧瓶中,冷却降温至3℃,开始滴加1.0mol光气,0.7h滴毕,搅拌0.7h,过滤,得到 含1,1'-羰基二咪唑的滤液。之后在-13℃温度下,将该滤液滴加到含0.8mol丁四醇的四氢呋喃(420ml)溶液中,1.3h滴毕,保温搅拌0.5h,并真空除去溶剂,得到残余物。将残余物溶于二氯甲烷中,并用冷水洗涤两次。加入20g无水硫酸钠干燥,浓缩得到4,4’-联-1,3-二氧戊环-2,2’-二酮粗品。粗品经过重结晶得到83.74g 4,4’-联-1,3-二氧戊环-2,2’-二酮纯品(收率96.2%)。Under argon atmosphere, 4.0mol imidazole and 136ml tetrahydrofuran were added to a four-necked flask, cooled to 3°C, and 1.0 mol phosgene was added dropwise. After 0.7h, the mixture was stirred for 0.7h and filtered to obtain 1,1' -The filtrate of carbonyl diimidazole. Then, at -13°C, the filtrate was added dropwise to a solution of 0.8 mol tetrahydrofuran (420 ml) of tetrahydrofuran (420 ml) for 1.3 hours, the mixture was kept and stirred for 0.5 hours, and the solvent was removed in vacuo to obtain a residue. The residue was dissolved in dichloromethane and washed twice with cold water. Add 20g of anhydrous sodium sulfate to dry and concentrate to obtain crude 4,4'-bi-1,3-dioxolane-2,2'-dione. The crude product was recrystallized to obtain 83.74 g of pure 4,4'-dioxolane-2,2'-dione (yield 96.2%).
收集所得的4,4’-联-1,3-二氧戊环-2,2’-二酮,测定密度为1.6087g/cm 3,沸点为535.64℃(760mmHg),通过HPLC检测纯度为99.86%。 The obtained 4,4'-bi-1,3-dioxolane-2,2'-dione was collected, and the density was determined to be 1.6087g/cm 3 , the boiling point was 535.64°C (760mmHg), and the purity was 99.86 by HPLC. %.
实施例6Example 6
在氩气气氛下将4.0mol咪唑、125ml四氢呋喃加入到四口烧瓶中,冷却降温至-3℃,开始滴加1.0mol光气,0.9h滴毕,搅拌0.9h,过滤,得到含1,1'-羰基二咪唑的滤液。之后在-9℃温度下,将该滤液滴加到含0.5mol丁四醇的四氢呋喃(268ml)溶液中,1.4h滴毕,保温搅拌1.8h,并真空除去溶剂,得到残余物。将残余物溶于二氯甲烷中,并用冷水洗涤两次。加入20g无水硫酸钠干燥,浓缩得到4,4’-联-1,3-二氧戊环-2,2’-二酮粗品。粗品经过重结晶得到84g 4,4’-联-1,3-二氧戊环-2,2’-二酮纯品(收率96.5%)。Under argon atmosphere, 4.0mol imidazole and 125ml tetrahydrofuran were added to a four-necked flask, cooled to -3°C, and 1.0 mol phosgene was added dropwise. After 0.9h, the mixture was stirred for 0.9h and filtered to obtain 1,1 '-Carbonyl diimidazole filtrate. Afterwards, at -9°C, the filtrate was added dropwise to a solution of 0.5 mol tetrahydrofuran (268 ml) of tetrahydrofuran (268 ml) for 1.4 hours, kept and stirred for 1.8 hours, and the solvent was removed in vacuo to obtain a residue. The residue was dissolved in dichloromethane and washed twice with cold water. Add 20g of anhydrous sodium sulfate to dry and concentrate to obtain crude 4,4'-bi-1,3-dioxolane-2,2'-dione. The crude product was recrystallized to obtain 84 g of pure 4,4'-dioxolane-2,2'-dione (yield 96.5%).
收集所得的4,4’-联-1,3-二氧戊环-2,2’-二酮,测定密度为1.6073g/cm 3,沸点为535.38℃(760mmHg),通过HPLC检测纯度为99.86%。 The obtained 4,4'-bi-1,3-dioxolane-2,2'-dione was collected, and the measured density was 1.6073g/cm 3 , the boiling point was 535.38°C (760mmHg), and the purity was 99.86 by HPLC. %.
实施例7Example 7
在氩气气氛下将4.0mol咪唑、125ml四氢呋喃加入到四口烧瓶中,冷却降温至-1℃,开始滴加1.0mol光气,0.6h滴毕,搅拌0.6h,过滤,得到含1,1'-羰基二咪唑的滤液。之后在-11℃温度下,将该滤液滴加到含0.45mol丁四醇的四氢呋喃(240ml)溶液中,1.2h滴毕,保温搅拌1.2h,并真空除去溶剂,得到残余物。将残余物溶于二氯甲烷中,并用冷水洗涤两次。加 入20g无水硫酸钠干燥,浓缩得到4,4’-联-1,3-二氧戊环-2,2’-二酮粗品。粗品经过重结晶得到76.23g 4,4’-联-1,3-二氧戊环-2,2’-二酮纯品(收率97.3%)。Under argon atmosphere, 4.0mol imidazole and 125ml tetrahydrofuran were added to the four-necked flask, cooled to -1°C, and 1.0mol phosgene was added dropwise. After 0.6h, the mixture was stirred for 0.6h and filtered to obtain 1,1 '-Carbonyl diimidazole filtrate. Afterwards, at a temperature of -11°C, the filtrate was added dropwise to a tetrahydrofuran (240 ml) solution containing 0.45 mol of tetrahydrofuran (240 ml) for 1.2 hours, kept and stirred for 1.2 hours, and the solvent was removed in vacuo to obtain a residue. The residue was dissolved in dichloromethane and washed twice with cold water. Add 20 g of anhydrous sodium sulfate, dry, and concentrate to obtain crude 4,4'-dioxolane-2,2'-dione. The crude product was recrystallized to obtain 76.23 g 4,4'-dioxolane-2,2'-dione pure product (yield 97.3%).
收集所得的4,4’-联-1,3-二氧戊环-2,2’-二酮进行质谱检测,检测其质谱图参见图3和图4,测定密度为1.6088g/cm 3,沸点为535.68℃(760mmHg),通过HPLC检测纯度为99.84%。 The obtained 4,4'-linked-1,3-dioxolane-2,2'-dione was collected and subjected to mass spectrometric detection. The mass spectra of the detection are shown in Figure 3 and Figure 4, and the measured density is 1.6088g/cm 3 . The boiling point is 535.68°C (760mmHg), and the purity is 99.84% by HPLC.
二、试验性能2. Test performance
一、高温性能研究1. High temperature performance research
实验研究采用的锂离子电池为比亚迪股份有限公司生产的额定容量为950mAh的LP063450AR型方形锂离子电池。将电池分别在25℃和5℃下进行1c倍率(950mA)充放电循环测试,采用恒流恒压充电制度(CC-CV)和恒流放电制度,充放电电压范围为3.0-4.5V,首先以1C恒流充电至4.5V,再以4.5V恒压充电直至电流小于20mA,然后以1C恒流放电至终止电压为3.0V,如此循环充放电500次,循环数据的采集在LAND-2001T型电池测试系统上进行。The lithium-ion battery used in the experimental study is the LP063450AR square lithium-ion battery with a rated capacity of 950mAh produced by BYD Co., Ltd. The battery is subjected to 1c rate (950mA) charge-discharge cycle test at 25℃ and 5℃ respectively, using constant current and constant voltage charging system (CC-CV) and constant current discharge system, the charging and discharging voltage range is 3.0-4.5V, first Charge with 1C constant current to 4.5V, then charge with 4.5V constant voltage until the current is less than 20mA, and then discharge with 1C constant current until the final voltage is 3.0V, so the cycle of charge and discharge is 500 times. The cycle data is collected in LAND-2001T Performed on the battery test system.
参见图1,经过300次循环后,25℃下循环的电池其容量保持率为88.8%,而65℃下电池的容量仅为73.1%,容量衰减迅速,可见该比亚迪股份有限公司生产的额定容量为950mAh的LP063450AR型方形锂离子电池在65℃下的循环稳定性要差于25℃下的循环稳定性。从图1中还发现电池在65℃下放电容量要高于电池的额定容量,分析原因为在高温时电解质的粘度降低,从而加快了锂离子的迁移速率,使活性锂的利用率变高,从而锂电池展现出较高的充放电容量。Referring to Figure 1, after 300 cycles, the capacity retention rate of the battery cycled at 25°C is 88.8%, while the capacity of the battery at 65°C is only 73.1%, and the capacity decays rapidly. This shows the rated capacity produced by BYD Co., Ltd. The cycle stability of the 950mAh LP063450AR prismatic lithium-ion battery at 65°C is worse than that at 25°C. It is also found from Figure 1 that the discharge capacity of the battery at 65°C is higher than the rated capacity of the battery. The reason is that the viscosity of the electrolyte decreases at high temperatures, which accelerates the migration rate of lithium ions and increases the utilization rate of active lithium. As a result, lithium batteries exhibit higher charge and discharge capacity.
为了验证本发明制得的4,4’-联-1,3-二氧戊环-2,2’-二酮具有提高电池高温性能的功能,我们以比亚迪股份有限公司生产的额定容量为950mAh的 LP063450AR型方形锂离子电池为试验对象,向该电池的电解液中加入电解液质量2%的4,4’-联-1,3-二氧戊环-2,2’-二酮,重复上述相同操作,进行电池高温循环性能的检测。In order to verify that the 4,4'-linked-1,3-dioxolane-2,2'-dione prepared by the present invention has the function of improving the high temperature performance of the battery, we used the rated capacity produced by BYD Co., Ltd. to be 950mAh The LP063450AR square lithium-ion battery is the test object. Add 2% of the electrolyte mass of 4,4'-dioxolane-2,2'-dione to the electrolyte of the battery, repeat Perform the same operation as above to test the high temperature cycle performance of the battery.
参见图2,经过300次循环后,添加本发明4,4’-联-1,3-二氧戊环-2,2’-二酮的电池65℃下电池的容量为87.6%,500次循环后65℃下电池的容量为75.2%,而未添加本发明4,4’-联-1,3-二氧戊环-2,2’-二酮的电池500次循环后65℃下电池的容量为59%,寿命结束。可见,本发明制备的4,4’-联-1,3-二氧戊环-2,2’-二酮可以提高高电压、高温下电池的循环性能。Referring to Figure 2, after 300 cycles, the battery with the addition of 4,4'-link-1,3-dioxolane-2,2'-dione of the present invention has a battery capacity of 87.6% at 65°C, 500 cycles The battery capacity at 65°C after cycling is 75.2%, but the battery without adding the 4,4'-link-1,3-dioxolane-2,2'-dione of the present invention is the battery at 65°C after 500 cycles The capacity is 59%, end of life. It can be seen that the 4,4'-linked-1,3-dioxolane-2,2'-dione prepared by the present invention can improve the cycle performance of the battery under high voltage and high temperature.
二、低温性能研究2. Low temperature performance research
以LiFePO 4锂离子电池为研究对象,尺寸12.cm*7cm*0.8cm,单块电池额定容量为10Ah,工作电压为3.3-4.2V,外壳为铝塑薄膜,进行低温试验。以25℃为低温测试基准点,从25℃开始至-20℃,每5℃为一温度考察点,温度变化速率为30min/5℃,每个温度点下搁置24h后方可进行该温度点下的性能测试,测试结果参见表1。 Taking LiFePO 4 lithium-ion battery as the research object, the size is 12.cm*7cm*0.8cm, the rated capacity of a single battery is 10Ah, the working voltage is 3.3-4.2V, and the outer shell is aluminum-plastic film, and the low temperature test is carried out. Take 25℃ as the low temperature test reference point, starting from 25℃ to -20℃, every 5℃ is a temperature inspection point, the temperature change rate is 30min/5℃, and the temperature can be carried out after being left for 24h at each temperature point. The performance test, the test results are shown in Table 1.
表1 温度对放电容量(0.5C)的影响Table 1 The influence of temperature on discharge capacity (0.5C)
Figure PCTCN2019127304-appb-000001
Figure PCTCN2019127304-appb-000001
由上表1可以看出,温度越低,容量衰减越严重,说明本实验研究对 象存在低温循环性能差的问题。From Table 1 above, it can be seen that the lower the temperature, the more serious the capacity attenuation, indicating that the subject of this experiment has the problem of poor low-temperature cycle performance.
为了验证本发明制得的4,4’-联-1,3-二氧戊环-2,2’-二酮具有提高电池低温性能的功能,我们以上述相同的LiFePO 4锂离子电池为研究对象,向该电池的电解液中加入电解液质量2%的4,4’-联-1,3-二氧戊环-2,2’-二酮,重复上述相同操作,进行电池低温循环性能的检测,结果参见表2。 In order to verify that the 4,4'-linked-1,3-dioxolane-2,2'-dione prepared by the present invention has the function of improving the low temperature performance of the battery, we used the same LiFePO 4 lithium ion battery as the research Subject: Add 2% of the electrolyte mass of 4,4'-dioxolane-2,2'-dione to the electrolyte of the battery, repeat the same operation as above, and perform the battery low-temperature cycle performance The results are shown in Table 2.
表2 温度对放电容量(0.5C)的影响Table 2 The influence of temperature on discharge capacity (0.5C)
Figure PCTCN2019127304-appb-000002
Figure PCTCN2019127304-appb-000002
由表2可知,加入本发明的4,4’-联-1,3-二氧戊环-2,2’-二酮后,可以改善电池的低温循环性能。It can be seen from Table 2 that the addition of the 4,4'-linked-1,3-dioxolane-2,2'-dione of the present invention can improve the low-temperature cycle performance of the battery.

Claims (8)

  1. 4,4’-联-1,3-二氧戊环-2,2’-二酮的合成方法,其特征在于,在氩气气氛下将咪唑、四氢呋喃加入到反应器中,冷却降温至-5~5℃,开始滴加光气,0.5-1h滴毕,搅拌0.5-1h,过滤,得到含1,1'-羰基二咪唑的滤液;之后在-8~-15℃温度下,将该滤液滴加到丁四醇的四氢呋喃溶液中,1-1.5h滴毕,保温搅拌0.5-2h,并真空除去溶剂,得到残余物;将残余物溶于二氯甲烷中,并用冷水洗涤,干燥后浓缩得到4,4’-联-1,3-二氧戊环-2,2’-二酮粗品,将粗品进行提纯得到精制的4,4’-联-1,3-二氧戊环-2,2’-二酮。The synthesis method of 4,4'-bi-1,3-dioxolane-2,2'-dione is characterized in that imidazole and tetrahydrofuran are added to the reactor under argon atmosphere, and the temperature is cooled down to- 5~5℃, start to add phosgene dropwise, 0.5-1h to finish, stir for 0.5-1h, filter to obtain a filtrate containing 1,1'-carbonyldiimidazole; then at -8~-15℃, the The filtrate was added dropwise to the tetrahydrofuran solution of tetrahydrofuran for 1-1.5h, the temperature was kept and stirred for 0.5-2h, and the solvent was removed in vacuo to obtain a residue; the residue was dissolved in dichloromethane and washed with cold water, after drying Concentrate to obtain crude 4,4'-bi-1,3-dioxolane-2,2'-dione. Purify the crude product to obtain refined 4,4'-bi-1,3-dioxolane- 2,2'-Diketone.
  2. 根据权利要求1所述的4,4’-联-1,3-二氧戊环-2,2’-二酮的合成方法,其特征在于,光气、咪唑、丁四醇的摩尔比为1:(3-6):(0.45-0.8)。The method for synthesizing 4,4'-linked-1,3-dioxolane-2,2'-dione according to claim 1, wherein the molar ratio of phosgene, imidazole and butanetetraol is 1: (3-6): (0.45-0.8).
  3. 根据权利要求1所述的4,4’-联-1,3-二氧戊环-2,2’-二酮的合成方法,其特征在于,丁四醇的四氢呋喃溶液(1g/4-4.5ml)。The method for synthesizing 4,4'-linked-1,3-dioxolane-2,2'-dione according to claim 1, wherein the tetrahydrofuran solution of butanetetraol (1g/4-4.5 ml).
  4. 根据权利要求1所述的4,4’-联-1,3-二氧戊环-2,2’-二酮的合成方法,其特征在于,冷水洗涤2-3次。The method for synthesizing 4,4'-linked-1,3-dioxolane-2,2'-dione according to claim 1, characterized in that it is washed 2-3 times in cold water.
  5. 根据权利要求1所述的4,4’-联-1,3-二氧戊环-2,2’-二酮的合成方法,其特征在于,干燥采用无水硫酸钠和/或氧化钙干燥。The method for synthesizing 4,4'-linked-1,3-dioxolane-2,2'-dione according to claim 1, characterized in that the drying uses anhydrous sodium sulfate and/or calcium oxide drying .
  6. 根据权利要求1所述的4,4’-联-1,3-二氧戊环-2,2’-二酮的合成方法,其特征在于,浓缩控制真空度为0.08-0.10MPa,于温度50-60℃下浓缩1.5-2h。The method for synthesizing 4,4'-linked-1,3-dioxolane-2,2'-dione according to claim 1, wherein the concentration control vacuum degree is 0.08-0.10MPa, and the temperature Concentrate at 50-60°C for 1.5-2h.
  7. 根据权利要求1所述的4,4’-联-1,3-二氧戊环-2,2’-二酮的合成方法,其特征在于,提纯采用丙酮进行重结晶。The method for synthesizing 4,4'-linked-1,3-dioxolane-2,2'-dione according to claim 1, characterized in that acetone is used for recrystallization for purification.
  8. 根据权利要求1所述的4,4’-联-1,3-二氧戊环-2,2’-二酮的合成方法,其特征在于,真空除去溶剂的真空度控制为0.08-0.09Mpa,真空处理时间为30-40min。The method for synthesizing 4,4'-linked-1,3-dioxolane-2,2'-dione according to claim 1, characterized in that the degree of vacuum for removing the solvent in vacuum is controlled to be 0.08-0.09Mpa , The vacuum treatment time is 30-40min.
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