CN111892569A - Synthesis method of 4,4 '-bi-1, 3-dioxolane-2, 2' -diketone - Google Patents
Synthesis method of 4,4 '-bi-1, 3-dioxolane-2, 2' -diketone Download PDFInfo
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Abstract
A synthesis method of 4,4 '-bi-1, 3-dioxolane-2, 2' -dione belongs to the technical field of battery electrolyte additives, imidazole and tetrahydrofuran are added into a reactor under the atmosphere of argon, the temperature is reduced to-5 ℃, phosgene is added dropwise, 0.5-1h of dripping is completed, then the mixture is added into a tetrahydrofuran solution of erythritol dropwise at the temperature of-8-15 ℃, 1-1.5h of dripping is completed, stirring is carried out for 0.5-2h under heat preservation, and the solvent is removed in vacuum to obtain a residue; dissolving the residue in dichloromethane, washing with cold water, drying, concentrating to obtain crude 4,4 '-bi-1, 3-dioxolane-2, 2' -dione, and purifying to obtain refined 4,4 '-bi-1, 3-dioxolane-2, 2' -dione. The raw materials used in the invention are cheap and easily available, the synthesis method is simple and easy to operate, the energy consumption is low, the reaction time is short, the reaction conditions are mild and stable, and the product yield is high and can reach more than 94%.
Description
Technical Field
The invention belongs to the technical field of battery electrolyte additives, and relates to a method for synthesizing 4,4 '-bi-1, 3-dioxolane-2, 2' -dione as a battery electrolyte additive, in particular to a method for synthesizing 4,4 '-bi-1, 3-dioxolane-2, 2' -dione.
Background
The continuous improvement of the performance of the lithium ion battery leads the application range of the lithium ion battery to be wider and wider, but the safety problem and the cycle performance of the lithium ion battery restrict the development of the lithium ion battery to a certain extent. Particularly, safety performance, quick charging performance and cruising ability of the conventional power lithium ion battery for the electric automobile which is hot are all hot problems researched by various research institutions, and the key point for solving the problems is to start from the battery. The factors affecting the safety and the cycle stability of the lithium ion battery are many, and the factors can be mainly divided into two aspects of internal factors and external factors. The internal factors mainly relate to the stability of positive and negative active materials, the characteristics of electrolyte and the compatibility with electrode materials, the stability of diaphragm materials and the like, and the external factors mainly relate to the incorrect use of the battery, the abuse phenomenon in the use process and the like. It has been found through research that the introduction of electrolyte additives is a very effective method, which can improve the characteristics of the electrolyte and the compatibility of the electrolyte and electrode materials, and the addition of small amount has obvious effect. The modification of the electrode material can further improve the cycle stability of the lithium ion battery.
In recent years, many novel multifunctional lithium ion battery electrolyte additives have appeared. The research shows that the 4,4 '-bi-1, 3-dioxolane-2, 2' -diketone with CAS number of 24690-44-6 can effectively improve the structural stability and the thermal stability of the anode and cathode materials of the lithium ion battery as the electrolyte additive. In addition, the 4,4 '-bi-1, 3-dioxolane-2, 2' -diketone has excellent cycle and safety performance under the conditions of high voltage and extremely high temperature, and has great promotion effect on improving the performance of the lithium ion battery. However, the existing synthesis process of 4,4 '-bi-1, 3-dioxolane-2, 2' -dione is still not mature, the problems of expensive raw materials, complex process, low product yield and purity and the like exist in the synthesis process, and the existing synthesis process of 4,4 '-bi-1, 3-dioxolane-2, 2' -dione generally considers that the reaction should be carried out at high temperature, such as 60-130 ℃, and the like, the reaction time is as long as more than 12 hours, and the yield can reach about 88-90%, but the reaction temperature is high, the reaction is unstable, and the reaction time is too long, so that the production efficiency is influenced. Therefore, the research on the synthesis method of the 4,4 '-bi-1, 3-dioxolane-2, 2' -diketone has great practical significance.
Disclosure of Invention
The invention provides a method for synthesizing 4,4 '-bi-1, 3-dioxolane-2, 2' -diketone for solving the technical problems, and the method is simple, low in energy consumption, mild and stable in reaction conditions and high in yield, and raw materials are cheap and easy to obtain.
The technical scheme adopted by the invention for realizing the purpose is as follows:
the synthesis method of the 4,4 ' -bi-1, 3-dioxolane-2, 2 ' -diketone comprises the steps of adding imidazole and tetrahydrofuran into a reactor under the argon atmosphere, cooling to-5 ℃, starting to dropwise add phosgene, stirring for 0.5-1h after dropwise adding is finished for 0.5-1h, and filtering to obtain filtrate containing 1,1' -carbonyldiimidazole; then, at the temperature of-8 to-15 ℃, dropwise adding the filtrate into a tetrahydrofuran solution of the tetrol, keeping the temperature and stirring for 0.5 to 2 hours after dropwise adding is finished for 1 to 1.5 hours, and removing the solvent in vacuum to obtain a residue; dissolving the residue in dichloromethane, washing with cold water, drying, concentrating to obtain crude 4,4 '-bi-1, 3-dioxolane-2, 2' -dione, and purifying to obtain refined 4,4 '-bi-1, 3-dioxolane-2, 2' -dione.
The mol ratio of phosgene, imidazole and tetrol is 1: (3-6): (0.45-0.8).
Tetrabutanol in tetrahydrofuran (1g/4-4.5 ml). I.e. 4-4.5ml of tetrahydrofuran solution contains 1g of erythritol.
Washing with cold water for 2-3 times.
Drying with anhydrous sodium sulfate and/or calcium oxide.
Concentrating at 50-60 deg.C for 1.5-2h under the vacuum degree of 0.08-0.10 MPa.
The purification is carried out by acetone recrystallization.
The vacuum degree for removing solvent is controlled at 0.08-0.09Mpa, and the vacuum treatment time is 30-40 min.
The invention has the beneficial effects that:
the raw materials used in the invention are cheap and easily available, the synthesis method is simple and easy to operate, the energy consumption is low, the reaction time is short, the reaction conditions are mild and stable, and the product yield is high and can reach more than 94%.
The method adopts low-temperature reaction, breaks through the situation that high-temperature reaction is generally considered to be needed in the prior art, and develops a novel method for synthesizing 4,4 '-bi-1, 3-dioxolane-2, 2' -dione. The technical personnel in the field generally think that when preparing 4,4 '-bi-1, 3-dioxolane-2, 2' -diketone, the reaction is promoted to proceed under high temperature and long time, which is beneficial to the synthesis of 4,4 '-bi-1, 3-dioxolane-2, 2' -diketone; if the temperature is low, the reaction proceeds adversely, the reaction rate is slowed, the yield is low, and the synthesis of 4,4 '-bi-1, 3-dioxolan-2, 2' -dione cannot be attained. Through long-term research, the inventor prepares the 4,4 '-bi-1, 3-dioxolane-2, 2' -diketone by adopting phosgene, imidazole and butyl tetrol as raw materials, can realize reaction synthesis at low temperature in short time, and has the yield of more than 94 percent.
Drawings
Fig. 1 is a graph of the cycle performance of a LP063450AR type square lithium ion battery with a rated capacity of 950 mAh.
FIG. 2 is a graph showing the cycle performance of a rectangular lithium ion battery model LP063450AR with a rated capacity of 950mAh, to which 4,4 '-bi-1, 3-dioxolane-2, 2' -dione according to the present invention is added.
Detailed Description
The present invention will be further described with reference to the following examples.
Detailed description of the preferred embodiments
Example 1
Adding 4.0mol of imidazole and 125ml of tetrahydrofuran into a four-neck flask under the argon atmosphere, cooling to 0 ℃, beginning to dropwise add 1.0mol of phosgene, stirring for 0.5h after dropwise adding is finished, and filtering to obtain filtrate containing 1,1' -carbonyldiimidazole. The filtrate was then added dropwise to a solution of 0.5mol of erythritol in tetrahydrofuran (250ml) at-10 ℃ for 1.5h, stirred for 1h with incubation, and the solvent removed in vacuo to give a residue. The residue was dissolved in dichloromethane and washed twice with cold water. 20g of anhydrous sodium sulfate is added for drying and concentration to obtain a crude product of 4,4 '-bi-1, 3-dioxolane-2, 2' -dione. The crude product was recrystallized to obtain 82.20g of 4,4 '-bi-1, 3-dioxolane-2, 2' -dione as a pure product (yield 94.4%).
The resulting 4,4 '-bi-1, 3-dioxolane-2, 2' -dione was collected and found to have a density of 1.6075g/cm3Boiling point 535.33 deg.C (760mmHg) and purity 99.87% by HPLC.
Example 2
Adding 3.0mol of imidazole and 62ml of tetrahydrofuran into a four-neck flask under the argon atmosphere, cooling to-2 ℃, beginning to dropwise add 1.0mol of phosgene, stirring for 0.6h after dropwise adding is finished, and filtering to obtain filtrate containing 1,1' -carbonyldiimidazole. The filtrate was then added dropwise to a solution of 0.45mol of erythritol in tetrahydrofuran (220ml) at-8 ℃ for 1h, stirred at RT for 1.5h and the solvent removed in vacuo to give a residue. The residue was dissolved in dichloromethane and washed twice with cold water. 20g of anhydrous sodium sulfate is added for drying and concentration to obtain a crude product of 4,4 '-bi-1, 3-dioxolane-2, 2' -dione. The crude product was recrystallized to obtain 74.4g of 4,4 '-bi-1, 3-dioxolane-2, 2' -dione (yield 94.96%).
The resulting 4,4 '-bi-1, 3-dioxolane-2, 2' -dione was collected and found to have a density of 1.6083g/cm3Boiling point 535.38 deg.C (760mmHg) and purity 99.89% by HPLC.
Example 3
Adding 5.0mol of imidazole and 204ml of tetrahydrofuran into a four-neck flask under the argon atmosphere, cooling to-5 ℃, beginning to dropwise add 1.0mol of phosgene, stirring for 0.8h after dropwise adding is finished, and filtering to obtain filtrate containing 1,1' -carbonyldiimidazole. The filtrate was then added dropwise to a solution of 0.7mol of erythritol in tetrahydrofuran (384ml) at-12 ℃ for 1.2h, stirred at the same temperature for 0.8h and the solvent removed in vacuo to give a residue. The residue was dissolved in dichloromethane and washed twice with cold water. 20g of anhydrous sodium sulfate is added for drying and concentration to obtain a crude product of 4,4 '-bi-1, 3-dioxolane-2, 2' -dione. The crude product was recrystallized to obtain 82.95g of 4,4 '-bi-1, 3-dioxolane-2, 2' -dione as a pure product (yield 95.29%).
The resulting 4,4 '-bi-1, 3-dioxolane-2, 2' -dione was collected and found to have a density of 1.6078g/cm3Boiling point 535.47 deg.C (760mmHg) and 99.91% purity by HPLC.
Example 4
Adding 6.0mol of imidazole and 164ml of tetrahydrofuran into a four-neck flask under the argon atmosphere, cooling to 5 ℃, starting to dropwise add 1.0mol of phosgene, stirring for 1h after 1h of dropwise adding, and filtering to obtain filtrate containing 1,1' -carbonyldiimidazole. The filtrate was then added dropwise to a solution of 0.6mol of erythritol in tetrahydrofuran (307ml) at-15 deg.C, after 1.5h addition, stirring at room temperature for 2h, and the solvent was removed in vacuo to give a residue. The residue was dissolved in dichloromethane and washed twice with cold water. 20g of anhydrous sodium sulfate is added for drying and concentration to obtain a crude product of 4,4 '-bi-1, 3-dioxolane-2, 2' -dione. The crude product was recrystallized to give 83.4g of 4,4 '-bi-1, 3-dioxolane-2, 2' -dione as a pure product (yield 95.8%).
The resulting 4,4 '-bi-1, 3-dioxolane-2, 2' -dione was collected and found to have a density of 1.609g/cm3Boiling point 535.71 deg.C (760mmHg) and 99.85% purity by HPLC.
Example 5
Adding 4.0mol of imidazole and 136ml of tetrahydrofuran into a four-neck flask under the argon atmosphere, cooling to 3 ℃, beginning to dropwise add 1.0mol of phosgene, stirring for 0.7h after dropwise adding is finished, and filtering to obtain filtrate containing 1,1' -carbonyldiimidazole. The filtrate was then added dropwise to a solution of 0.8mol of erythritol in tetrahydrofuran (420ml) at-13 ℃ for 1.3h, stirred at RT for 0.5h and the solvent removed in vacuo to give a residue. The residue was dissolved in dichloromethane and washed twice with cold water. 20g of anhydrous sodium sulfate is added for drying and concentration to obtain a crude product of 4,4 '-bi-1, 3-dioxolane-2, 2' -dione. The crude product was recrystallized to obtain 83.74g of 4,4 '-bi-1, 3-dioxolane-2, 2' -dione as a pure product (yield 96.2%).
The resulting 4,4 '-bi-1, 3-dioxolane-2, 2' -dione was collected and found to have a density of 1.6087g/cm3Boiling point 535.64 deg.C (760mmHg) and 99.86% purity by HPLC.
Example 6
Adding 4.0mol of imidazole and 125ml of tetrahydrofuran into a four-neck flask under the argon atmosphere, cooling to-3 ℃, beginning to dropwise add 1.0mol of phosgene, stirring for 0.9h after dropwise adding is finished, and filtering to obtain filtrate containing 1,1' -carbonyldiimidazole. The filtrate was then added dropwise to a solution of 0.5mol of erythritol in tetrahydrofuran (268ml) at-9 deg.C for 1.4h, stirred at RT for 1.8h, and the solvent removed in vacuo to give a residue. The residue was dissolved in dichloromethane and washed twice with cold water. 20g of anhydrous sodium sulfate is added for drying and concentration to obtain a crude product of 4,4 '-bi-1, 3-dioxolane-2, 2' -dione. The crude product was recrystallized to give 84g of 4,4 '-bi-1, 3-dioxolane-2, 2' -dione as a pure product (yield 96.5%).
The resulting 4,4 '-bi-1, 3-dioxolane-2, 2' -dione was collected and found to have a density of 1.6073g/cm3Boiling point 535.38 deg.C (760mmHg) and 99.86% purity by HPLC.
Example 7
Adding 4.0mol of imidazole and 125ml of tetrahydrofuran into a four-neck flask under the argon atmosphere, cooling to-1 ℃, starting to dropwise add 1.0mol of phosgene, stirring for 0.6h after dropwise adding is finished, and filtering to obtain filtrate containing 1,1' -carbonyldiimidazole. The filtrate was then added dropwise to a solution of 0.45mol of erythritol in tetrahydrofuran (240ml) at-11 ℃ for 1.2h, stirred at RT for 1.2h and the solvent removed in vacuo to give a residue. The residue was dissolved in dichloromethane and washed twice with cold water. 20g of anhydrous sodium sulfate is added for drying and concentration to obtain a crude product of 4,4 '-bi-1, 3-dioxolane-2, 2' -dione. The crude product was recrystallized to obtain 76.23g of 4,4 '-bi-1, 3-dioxolane-2, 2' -dione as a pure product (yield 97.3%).
The resulting 4,4 '-bi-1, 3-dioxolane-2, 2' -dione was collected and found to have a density of 1.6088g/cm3Boiling point 535.68 deg.C (760mmHg) and 99.84% purity by HPLC.
Second, test Performance
First, high temperature Performance study
The lithium ion battery adopted in the experimental study is a LP063450AR type square lithium ion battery with the rated capacity of 950mAh, which is produced by BYD GmbH. The battery is subjected to 1C multiplying power (950mA) charge-discharge cycle test at 25 ℃ and 5 ℃ respectively, a constant current and constant voltage charge system (CC-CV) and a constant current discharge system are adopted, the charge-discharge voltage range is 3.0-4.5V, the battery is firstly charged to 4.5V with a constant current of 1C, then charged with a constant voltage of 4.5V until the current is less than 20mA, and then discharged to the end voltage of 3.0V with a constant current of 1C, so that the battery is charged and discharged for 500 times in a cycle, and the collection of cycle data is carried out on a LAND-2001T type battery test system.
Referring to fig. 1, after 300 cycles, the capacity retention of the battery cycled at 25 ℃ is 88.8%, while the capacity of the battery cycled at 65 ℃ is only 73.1%, and the capacity decays rapidly, so that the cycling stability of the LP063450AR type square lithium ion battery with the rated capacity of 950mAh, produced by the byddy gmbh, is worse than the cycling stability at 25 ℃. It is also found from fig. 1 that the discharge capacity of the battery at 65 c is higher than the rated capacity of the battery, and the analysis is caused by the fact that the viscosity of the electrolyte is decreased at high temperature, thereby accelerating the migration rate of lithium ions, making the utilization rate of active lithium high, and the lithium battery exhibits higher charge and discharge capacity.
In order to verify that the 4,4 '-bi-1, 3-dioxolane-2, 2' -dione prepared by the invention has the function of improving the high-temperature performance of the battery, a LP063450AR type square lithium ion battery with the rated capacity of 950mAh, which is produced by BYD corporation, is taken as a test object, 4 '-bi-1, 3-dioxolane-2, 2' -dione with the mass of 2% of the electrolyte is added into the electrolyte of the battery, and the same operation is repeated to detect the high-temperature cycle performance of the battery.
Referring to fig. 2, after 300 cycles, the capacity of the battery at 65 ℃ was 87.6% with the addition of the 4,4 '-bi-1, 3-dioxolane-2, 2' -dione of the present invention, and 75.2% with the addition of the battery at 65 ℃ after 500 cycles, whereas the capacity of the battery at 65 ℃ after 500 cycles with no addition of the 4,4 '-bi-1, 3-dioxolane-2, 2' -dione of the present invention was 59%, and the life was over. Therefore, the 4,4 '-bi-1, 3-dioxolane-2, 2' -diketone prepared by the invention can improve the cycle performance of the battery under high voltage and high temperature.
Second, study of Low temperature Properties
With LiFePO4The lithium ion battery is a research object, the size of the lithium ion battery is 12.cm x 7cm x 0.8cm, the rated capacity of the single battery is 10Ah, the working voltage is 3.3-4.2V, and the shell is an aluminum plastic film, and low-temperature tests are carried out. And (3) taking 25 ℃ as a low-temperature test reference point, starting from 25 ℃ to-20 ℃, taking a temperature investigation point every 5 ℃, and carrying out a performance test at the temperature point after standing for 24 hours at the temperature point, wherein the test result is shown in table 1.
TABLE 1 Effect of temperature on discharge Capacity (0.5C)
As can be seen from Table 1 above, the lower the temperature, the more the capacity fade is, indicating that the subject of the experiment has a problem of poor low temperature cycle performance.
In order to verify that the 4,4 '-bi-1, 3-dioxolane-2, 2' -diketone prepared by the invention has the function of improving the low-temperature performance of the battery, the same LiFePO is adopted4The lithium ion battery is taken as a research object, 4 '-bi-1, 3-dioxolane-2, 2' -diketone with the electrolyte accounting for 2 percent of the mass of the electrolyte is added into the electrolyte of the battery, the same operation is repeated, and the low-temperature cycle performance of the battery is detected, and the result is shown in table 2.
TABLE 2 Effect of temperature on discharge Capacity (0.5C)
As can be seen from table 2, the addition of the 4,4 '-bi-1, 3-dioxolane-2, 2' -dione according to the present invention improves the low-temperature cycle performance of the battery.
Claims (8)
- The synthesis method of the 1.4,4 ' -bi-1, 3-dioxolane-2, 2 ' -dione is characterized by comprising the steps of adding imidazole and tetrahydrofuran into a reactor under the argon atmosphere, cooling to-5 ℃, starting to dropwise add phosgene, stirring for 0.5-1h after dropwise addition is finished, and filtering to obtain filtrate containing 1,1' -carbonyldiimidazole; then, at the temperature of-8 to-15 ℃, dropwise adding the filtrate into a tetrahydrofuran solution of the tetrol, keeping the temperature and stirring for 0.5 to 2 hours after dropwise adding is finished for 1 to 1.5 hours, and removing the solvent in vacuum to obtain a residue; dissolving the residue in dichloromethane, washing with cold water, drying, concentrating to obtain crude 4,4 '-bi-1, 3-dioxolane-2, 2' -dione, and purifying to obtain refined 4,4 '-bi-1, 3-dioxolane-2, 2' -dione.
- 2. The method of synthesizing 4,4 '-bi-1, 3-dioxolane-2, 2' -dione as claimed in claim 1, wherein the molar ratio of phosgene, imidazole, and erythritol is 1: (3-6): (0.45-0.8).
- 3. The method of synthesizing 4,4 '-bi-1, 3-dioxolane-2, 2' -dione as claimed in claim 1, wherein the solution of butanetetraol in tetrahydrofuran is (1g/4-4.5 ml).
- 4. The method of synthesizing 4,4 '-bi-1, 3-dioxolane-2, 2' -dione as claimed in claim 1, wherein washing with cold water is carried out 2 to 3 times.
- 5. The method for synthesizing 4,4 '-bi-1, 3-dioxolane-2, 2' -dione as claimed in claim 1, wherein the drying is carried out using anhydrous sodium sulfate and/or calcium oxide.
- 6. The method for synthesizing 4,4 '-bi-1, 3-dioxolane-2, 2' -dione as claimed in claim 1, wherein the concentration is carried out under a vacuum degree of 0.08-0.10MPa and at a temperature of 50-60 ℃ for 1.5-2 hours.
- 7. The method of claim 1, wherein the purification is performed by recrystallization from acetone.
- 8. The method for synthesizing 4,4 '-bi-1, 3-dioxolane-2, 2' -dione as claimed in claim 1, wherein the degree of vacuum for removing the solvent is controlled to be 0.08-0.09Mpa and the vacuum treatment time is 30-40 min.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910367828.3A CN111892569A (en) | 2019-05-05 | 2019-05-05 | Synthesis method of 4,4 '-bi-1, 3-dioxolane-2, 2' -diketone |
| PCT/CN2019/127304 WO2020224268A1 (en) | 2019-05-05 | 2019-12-23 | Synthesis method for 4,4'-bi-1,3-dioxolane-2,2'-dione |
| JP2021513778A JP7315810B2 (en) | 2019-05-05 | 2019-12-23 | Method for synthesizing 4,4'-bi-1,3-dioxolane-2,2'-dione |
| KR1020217007529A KR102509669B1 (en) | 2019-05-05 | 2019-12-23 | Method for synthesizing 4,4'-bi-1,3-dioxolane-2,2'-dione |
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| CN201910367828.3A CN111892569A (en) | 2019-05-05 | 2019-05-05 | Synthesis method of 4,4 '-bi-1, 3-dioxolane-2, 2' -diketone |
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| JP (1) | JP7315810B2 (en) |
| KR (1) | KR102509669B1 (en) |
| CN (1) | CN111892569A (en) |
| WO (1) | WO2020224268A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115583934A (en) * | 2022-09-30 | 2023-01-10 | 河北圣泰材料股份有限公司 | Preparation method of 4,4 '-bi-1, 3-dioxolane-2, 2' -diketone |
Citations (2)
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| EP0692476A2 (en) * | 1994-07-11 | 1996-01-17 | Bayer Ag | Improved process for the preparation of N,N'-carbonyldiazoles, specifically N,N-carbonyl-diimidazole |
| CN1910163A (en) * | 2004-01-20 | 2007-02-07 | 默克公司 | Antidiabetic oxazolidinediones and thiazolidinediones |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1147540A (en) * | 1966-04-19 | 1969-04-02 | Grace W R & Co | Butanetetrol dicarbonates and their production |
| US6977254B2 (en) | 2001-04-12 | 2005-12-20 | Wyeth | Hydroxy cyclohexenyl phenyl carboxamides tocolytic oxytocin receptor antagonists |
| DE10359797A1 (en) | 2003-12-19 | 2005-07-21 | Bayer Chemicals Ag | Process for the preparation of N, N'-carbonyldiazoles |
| US7964626B2 (en) | 2004-03-30 | 2011-06-21 | Hodogaya Chemical Co., Ltd. | Process for producing N,N′-carbonyldiimidazole |
| CN108808066B (en) | 2017-04-28 | 2020-04-21 | 深圳新宙邦科技股份有限公司 | Lithium ion battery non-aqueous electrolyte and lithium ion battery |
| CN112898265A (en) | 2019-11-18 | 2021-06-04 | 石家庄圣泰化工有限公司 | Preparation method of 4,4 '-bi-1, 3-dioxolane-2, 2' -diketone |
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- 2019-05-05 CN CN201910367828.3A patent/CN111892569A/en not_active Withdrawn
- 2019-12-23 JP JP2021513778A patent/JP7315810B2/en active Active
- 2019-12-23 KR KR1020217007529A patent/KR102509669B1/en active IP Right Grant
- 2019-12-23 WO PCT/CN2019/127304 patent/WO2020224268A1/en active Application Filing
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0692476A2 (en) * | 1994-07-11 | 1996-01-17 | Bayer Ag | Improved process for the preparation of N,N'-carbonyldiazoles, specifically N,N-carbonyl-diimidazole |
| CN1910163A (en) * | 2004-01-20 | 2007-02-07 | 默克公司 | Antidiabetic oxazolidinediones and thiazolidinediones |
Non-Patent Citations (1)
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| M. ROTH ET AL.: "Highly Water-Soluble Alpha-Hydroxyalkylphenone Based Photoinitiator for Low-Migration Applications", 《MACROMOL. CHEM. PHYS》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115583934A (en) * | 2022-09-30 | 2023-01-10 | 河北圣泰材料股份有限公司 | Preparation method of 4,4 '-bi-1, 3-dioxolane-2, 2' -diketone |
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| JP2022530931A (en) | 2022-07-05 |
| JP7315810B2 (en) | 2023-07-27 |
| KR20210044829A (en) | 2021-04-23 |
| KR102509669B1 (en) | 2023-03-14 |
| WO2020224268A1 (en) | 2020-11-12 |
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