CN111170985A - Preparation method of allyl sulfate - Google Patents
Preparation method of allyl sulfate Download PDFInfo
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- CN111170985A CN111170985A CN201911376603.0A CN201911376603A CN111170985A CN 111170985 A CN111170985 A CN 111170985A CN 201911376603 A CN201911376603 A CN 201911376603A CN 111170985 A CN111170985 A CN 111170985A
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D327/00—Heterocyclic compounds containing rings having oxygen and sulfur atoms as the only ring hetero atoms
- C07D327/10—Heterocyclic compounds containing rings having oxygen and sulfur atoms as the only ring hetero atoms two oxygen atoms and one sulfur atom, e.g. cyclic sulfates
Abstract
The invention discloses a preparation method of allyl sulfate, belonging to the field of preparation of lithium ion battery additives. The preparation method of the allyl sulfate takes chlorosulfonic acid and 1, 3-propylene glycol as raw materials, and firstly prepares an intermediate (3-hydroxyl propoxy) sulfonic acid; then the intermediate (3-hydroxyl propoxy) sulfonic acid is subjected to intramolecular dehydration and ring closure reaction to obtain the allyl sulfate. The raw materials for synthesizing the propylene sulfate are easy to obtain, the operation process is simple and safe, the product yield is high, and the production period is short; the process of synthesizing the propylene sulfate does not generate wastewater and waste salt, the catalyst and the water-carrying solvent can be recycled, and special equipment is not needed; is suitable for industrial application.
Description
Technical Field
The invention relates to the field of preparation of lithium ion battery additives, and particularly relates to a preparation method of propylene sulfate.
Background
The allyl sulfate is an organic synthetic raw material and is also a novel additive with a sulfate structure for a solid electrolyte phase interface film of a lithium battery and an electrolyte of the lithium battery. The allyl sulfate can reduce the expansion of the battery after high-temperature placement by inhibiting the reduction of the initial capacity of the battery and increasing the initial discharge capacity, improves the charge and discharge performance and the cycle number of the battery, has important influence on the performance of the lithium ion battery, and has great market demand and development prospect.
The existing synthesis process of the allyl sulfate mainly comprises the following steps:
route one:
1, 3-propylene glycol and thionyl chloride are used as initial raw materials to prepare and form an intermediate propylene sulfite ester, and then sodium hypochlorite is used for oxidation reaction to prepare the product propylene sulfate. Oxidation process of propylene sulfite is mainly carried out on ruthenium catalyst (RuO)4、RuCl3) Is catalyzed by sodium hypochlorite or sodium periodate.
And a second route:
1, 3-propylene glycol and sulfur oxyfluoride are used as raw materials, sodium alkoxide is prepared firstly under the alkaline condition, and then the reaction is carried out to prepare the product.
And a third route:
3-iodopropanol sulfate is used as a raw material to prepare the product under the catalysis of silver perchlorate.
The analysis of the synthetic routes reported in the above documents leads to the conclusion that:
route 1: the raw materials and routes used in patent WO2002100813 are relatively simple. The oxidation step, however, produces large amounts of salt-containing wastewater.
Route 2: in patent CN108409708, the reaction is shortened to one-step completion, but more waste salts are generated, and sulfur oxyfluoride is a strong corrosive hazardous gas raw material, and needs to be carried out in a high-pressure reaction kettle, which is high in risk.
The raw materials used in the route 3 are not subjected to industrial production, and the product yield is low.
The existing allyl sulfate synthesis process is not suitable for industrial production, and the development of the allyl sulfate synthesis method suitable for industrial production has important economic and social benefits.
Disclosure of Invention
In order to make up the defects of the prior art, the invention provides a preparation method of the propylene sulfate.
The technical scheme of the invention is as follows:
a preparation method of allyl sulfate takes chlorosulfonic acid and 1, 3-propylene glycol as raw materials, and firstly prepares an intermediate (3-hydroxyl propoxy) sulfonic acid; then the intermediate (3-hydroxyl propoxy) sulfonic acid is subjected to intramolecular dehydration and ring closure reaction to obtain the allyl sulfate.
The synthetic route of the allyl sulfate is as follows:
as a preferable scheme, the preparation method of the propylene sulfate comprises the following steps:
1) preparing an intermediate: under the protection of inert gas, adding chlorosulfonic acid dropwise into 1, 3-propylene glycol, and after dropwise adding, keeping the temperature until the reaction is completed to obtain an intermediate (3-hydroxypropoxy) sulfonic acid;
2) dewatering and ring closing: adding a ring closing catalyst and a water-carrying solvent into the reaction system in the step 1), and carrying out reflux water diversion reaction for 2-8 h; and after the dehydration ring-closing reaction is finished, filtering out the catalyst, and purifying to obtain the propylene sulfate product.
The synthetic route of the invention is divided into two steps, wherein chlorosulfonic acid reacts with 1, 3-propanediol to remove micromolecular HCl in the first step; and the second step of intramolecular dehydration ring closing. The first step is completed at low temperature to ensure that monohydroxy of 1, 3-propylene glycol is reacted as much as possible; and in the second step, under a proper catalyst, dehydration and ring closure reaction are carried out at high selectivity to prepare the allyl sulfate.
Further, in the step 1), the temperature is 0-30 ℃ in the process of dropwise adding chlorosulfonic acid to 1, 3-propylene glycol; in the heat preservation process, the temperature of the reaction system is 25-30 ℃. The temperature is kept not higher than 30 ℃ in the dropping process of the chlorosulfonic acid, and the higher yield of the intermediate (3-hydroxyl propoxy) sulfonic acid is ensured.
Preferably, in the step 1), the molar ratio of the chlorosulfonic acid to the 1, 3-propanediol is 1:1 to 1.5: 1.
Preferably, in step 1), the completion of the reaction is judged by monitoring the reaction system by TLC that no 1, 3-propanediol as a starting material remains.
Preferably, in the step 2), the closed-loop catalyst is a modified ZSM-5 molecular sieve. The modified ZSM-5 molecular sieve is used as a catalyst, and the target reaction selectivity is high.
Preferably, in the step 2), the dosage of the ring closing catalyst is 0.5-2% of the mass of the 1, 3-propylene glycol. The dosage of the ring-closing catalyst is 0.5 to 2 percent of the mass of the 1, 3-propylene glycol, thus having higher catalytic efficiency.
As a preferred scheme, the preparation method of the modified ZSM-5 molecular sieve comprises the following steps: soaking the ZSM-5 molecular sieve in dilute acid for 5-10 h, filtering, introducing water vapor for treating for 5-10 h, washing the treated ZSM-5 molecular sieve until the water is neutral, drying, and finally roasting for 1-5 h at 200-500 ℃.
Further, the dilute acid is any one or more of sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid, oxalic acid, stannic chloride and phosphotungstic acid aqueous solution. The dilute acid can be inorganic acid, organic acid or Lewis acid.
Preferably, the concentration of the dilute acid is 5-20%; the dosage of the diluted acid meets the following requirements: 10-50 mL of dilute acid is used per gram of ZSM-5 molecular sieve.
Preferably, the water-containing solvent in the step 2) is any one or more of dichloroethane, dimethyl carbonate, toluene, n-hexane and ethyl acetate.
Preferably, the purification treatment in step 2) is: and (3) filtering the filtrate by using a neutral alumina column, then decompressing and desolventizing to obtain a crude product of the propylene sulfate, hot-melting the crude product of the propylene sulfate by using dichloroethane, filtering while the crude product is hot, cooling the filtrate to separate out a solid, and filtering to obtain a white powdery crystal, namely the purified propylene sulfate.
As another preferable mode, the purification treatment in step 2) is: and (3) filtering the filtrate by using a neutral alumina column, then removing the solvent by pressure reduction until the theoretical yield of the product is 3-5 times that of the product, cooling and filtering to obtain white powdery crystals, namely the purified propylene sulfate.
The invention has the beneficial effects that:
1. the raw materials for synthesizing the propylene sulfate are easy to obtain, the operation process is simple and safe, the product yield is high, and the production period is short;
2. the method for synthesizing the propylene sulfate does not generate wastewater and waste salt, the catalyst and the water-carrying solvent can be recycled, and special equipment is not needed; less waste, low cost and high yield, and is suitable for industrial application.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 is a GC-MS spectrum of the propylene sulfate prepared by the invention;
FIG. 2 is a GC spectrum of a pure product of propylene sulfate obtained in example 4 of the present invention (due to the large sample size, impurity peak due to this detection)Compared withObviously, but according to a peak area method, the purity of the obtained product is more than 99.9 percent);
FIG. 3 is a GC spectrum of a propylene sulfate product obtained in example 5 of the present invention.
Detailed Description
The present invention will be described in detail with reference to examples.
Preparation of modified ZSM-5 molecular sieve
Example 1
The preparation method of the modified ZSM-5 molecular sieve comprises the following steps:
soaking 10g of ZSM-5 molecular sieve in 300mL of 15% dilute hydrochloric acid for 7h, filtering, introducing water vapor for treatment for 6h, washing the treated ZSM-5 molecular sieve until the water is neutral, drying, and finally roasting at 400 ℃ for 3h to obtain the modified ZSM-5 molecular sieve.
Example 2
The preparation method of the modified ZSM-5 molecular sieve comprises the following steps:
dissolving 12g of stannic chloride in 200mL of water, adding 10g of ZSM-5 molecular sieve, soaking for 8h, filtering, introducing water vapor for treating for 5h, washing the treated ZSM-5 molecular sieve until the water is neutral, drying, and finally roasting for 5h at 350 ℃ to obtain the modified ZSM-5 molecular sieve.
Example 3
The preparation method of the modified ZSM-5 molecular sieve comprises the following steps:
soaking 10g of ZSM-5 molecular sieve in 400mL of 10% oxalic acid for 7h, filtering, introducing water vapor for treating for 6h, washing the treated ZSM-5 molecular sieve until the water is neutral, drying, and finally roasting at 400 ℃ for 3h to obtain the modified ZSM-5 molecular sieve.
Example 4:
91.3g (1.2mol) of 1, 3-propanediol is weighed into a 2L three-necked flask, a dry stable nitrogen flow is introduced, the system is sealed and the tail gas is introduced into a tap water absorption bottle. Dropwise adding 146.8g of chlorosulfonic acid (1.26mol), and consuming 1-2 h. The dropping speed is controlled so that the temperature of the system does not exceed 30 ℃. And after the dripping is finished, controlling the temperature of the system to be less than 30 ℃, keeping the temperature and stirring, monitoring the reaction progress by TLC, and stopping keeping the temperature when no raw material 1, 3-propylene glycol remains.
Adding 1g of the modified ZSM-5 catalyst prepared in the example 1 into a reaction system, adding 1000g of dichloroethane, heating to 80-85 ℃, carrying out water reaction until no acid remains, cooling to 20-35 ℃, filtering out the catalyst, passing the filtrate through a neutral alumina column, and removing the solvent under reduced pressure to obtain 157.5g of white blocky solid. The crude product yield was 95%. The crude product is hot-dissolved in 150g of dichloroethane, filtered while hot, the filtrate is cooled to precipitate a solid, and the solid is filtered to obtain 149.1g of white powdery crystals. 99.9% by GC detection (GC pattern shown in fig. 2), 90% overall yield, melting point: 58-62 ℃; the GC-MS spectrum of the purified product is shown in figure 1, and the molecular ion peak of the allyl sulfate is not shown in the GC-MS test process because the allyl sulfate is not stable enough.
Example 5:
182.6g of 1, 3-propanediol is weighed and added into a 5L three-necked bottle. Introducing dry stable nitrogen flow, sealing the system and introducing tail gas into an absorption bottle; 293.6g of chlorosulfonic acid is dripped for 1-2 h. Bubbles emerge in the dropping process; after the dripping is finished, the temperature is raised to 25-30 ℃, the temperature is kept for about 3 hours, the progress is monitored by TLC, and no raw material 1, 3-propylene glycol is left.
Adding 3g of the modified ZSM-5 molecular sieve catalyst prepared in the example 1 and 3000g of toluene into a reaction system, heating to 105-115 ℃, carrying out water reaction until no acid remains, cooling to 30-45 ℃, filtering out the catalyst, passing the filtrate through a neutral alumina column, removing a solvent under reduced pressure until the amount of the filtrate is 3 times of the theoretical amount of the product, cooling, and filtering to obtain 304.7g of white crystalline powder. The GC detection rate is 99.95% (GC is shown in figure 3), and the yield is 92%.
Example 6:
example 6 in comparison to example 4, the modified ZSM-5 molecular sieve prepared in example 2 was used as the ring-closing catalyst, specifically:
91.3g (1.2mol) of 1, 3-propanediol is weighed into a 2L three-necked flask, a dry stable nitrogen flow is introduced, the system is sealed and the tail gas is introduced into a tap water absorption bottle. Dropwise adding 146.8g of chlorosulfonic acid (1.26mol), and consuming 1-2 h. The dropping speed is controlled so that the temperature of the system does not exceed 30 ℃. And after the dripping is finished, controlling the temperature of the system to be less than 30 ℃, keeping the temperature and stirring, monitoring the reaction progress by TLC, and stopping keeping the temperature when no raw material 1, 3-propylene glycol remains.
Adding 1g of the modified ZSM-5 catalyst prepared in the example 2 into a reaction system, adding 1000g of dichloroethane, heating to 80-85 ℃, carrying out water reaction until no acid remains, cooling to 20-35 ℃, filtering out the catalyst, passing the filtrate through a neutral alumina column, and removing the solvent under reduced pressure to obtain 152.0g of white blocky solid. The crude yield was 91.8%. The crude product was hot-dissolved in 150g of dichloroethane, filtered while hot, the filtrate was cooled to precipitate a solid, which was filtered to obtain 141.7g of white powdery crystals. 99.76% by GC detection, 85.6% total yield, melting point: 58 to 62 ℃.
Example 7:
example 7 compared to example 5, the ring-closing catalyst used the modified ZSM-5 molecular sieve prepared in example 2, specifically:
182.6g of 1, 3-propanediol is weighed and added into a 5L three-necked bottle. Introducing dry stable nitrogen flow, sealing the system and introducing tail gas into an absorption bottle; 293.6g of chlorosulfonic acid is dripped for 1-2 h. Bubbles emerge in the dropping process; after the dripping is finished, the temperature is raised to 25-30 ℃, the temperature is kept for about 3 hours, the progress is monitored by TLC, and no raw material 1, 3-propylene glycol is left.
Adding 3g of the modified ZSM-5 molecular sieve catalyst prepared in the example 2 and 3000g of toluene into a reaction system, heating to 105-115 ℃, carrying out water reaction until no acid remains, cooling to 30-45 ℃, filtering out the catalyst, passing the filtrate through a neutral alumina column, removing a solvent under reduced pressure until the amount of the filtrate is 3 times of the theoretical amount of the product, cooling, and filtering to obtain 284.8g of white crystalline powder. 99.88% by GC detection and 86% yield.
Example 8:
example 8 in comparison to example 4, the ring-closing catalyst used the modified ZSM-5 molecular sieve prepared in example 3, specifically:
91.3g (1.2mol) of 1, 3-propanediol is weighed into a 2L three-necked flask, a dry stable nitrogen flow is introduced, the system is sealed and the tail gas is introduced into a tap water absorption bottle. Dropwise adding 146.8g of chlorosulfonic acid (1.26mol), and consuming 1-2 h. The dropping speed is controlled so that the temperature of the system does not exceed 30 ℃. And after the dripping is finished, controlling the temperature of the system to be less than 30 ℃, keeping the temperature and stirring, monitoring the reaction progress by TLC, and stopping keeping the temperature when no raw material 1, 3-propylene glycol remains.
Adding 1g of the modified ZSM-5 catalyst prepared in the example 3 into a reaction system, adding 1000g of dichloroethane, heating to 80-85 ℃, carrying out water reaction until no acid remains, cooling to 20-35 ℃, filtering out the catalyst, passing the filtrate through a neutral alumina column, and removing the solvent under reduced pressure to obtain 158g of white blocky solid. The crude yield was 95.4%. The crude product is hot-dissolved in 150g of dichloroethane, filtered while hot, the filtrate is cooled to precipitate a solid, and the solid is filtered to obtain 149.1g of white powdery crystals. 99.9% by GC detection, 90% total yield, melting point: 58 to 62 ℃.
Example 9:
example 9 in comparison to example 5, the ring-closing catalyst used the modified ZSM-5 molecular sieve prepared in example 3, specifically:
182.6g of 1, 3-propanediol is weighed and added into a 5L three-necked bottle. Introducing dry stable nitrogen flow, sealing the system and introducing tail gas into an absorption bottle; 293.6g of chlorosulfonic acid is dripped for 1-2 h. Bubbles emerge in the dropping process; after the dripping is finished, the temperature is raised to 25-30 ℃, the temperature is kept for about 3 hours, the progress is monitored by TLC, and no raw material 1, 3-propylene glycol is left.
Adding 3g of the modified ZSM-5 molecular sieve catalyst prepared in the example 3 and 3000g of toluene into a reaction system, heating to 105-115 ℃, carrying out water reaction until no acid remains, cooling to 30-45 ℃, filtering out the catalyst, passing the filtrate through a neutral alumina column, removing a solvent under reduced pressure until the amount of the filtrate is 3 times of the theoretical amount of the product, cooling, and filtering to obtain 298.5g of white crystalline powder. The GC detection rate is 99.91 percent, and the yield is 90.16 percent.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; such modifications and substitutions do not depart from the spirit and scope of the present invention, and they should be construed as being included in the following claims and description.
Claims (10)
1. A preparation method of allyl sulfate is characterized by comprising the following steps: chlorosulfonic acid and 1, 3-propylene glycol are taken as raw materials, and an intermediate (3-hydroxyl propoxy) sulfonic acid is prepared; then the intermediate (3-hydroxyl propoxy) sulfonic acid is subjected to intramolecular dehydration and ring closure reaction to obtain the allyl sulfate.
2. The process for the preparation of propylene sulfate as claimed in claim 1, comprising the steps of:
1) preparing an intermediate: under the protection of inert gas, adding chlorosulfonic acid dropwise into 1, 3-propylene glycol, and after dropwise adding, keeping the temperature until the reaction is completed to obtain an intermediate (3-hydroxypropoxy) sulfonic acid;
2) dewatering and ring closing: adding a ring closing catalyst and a water-carrying solvent into the reaction system in the step 1), and carrying out reflux water diversion reaction for 2-8 h; and after the dehydration ring-closing reaction is finished, filtering out the catalyst, and purifying to obtain the propylene sulfate product.
3. The process for the preparation of propylene sulfate as claimed in claim 2, wherein: in the step 1), the chlorosulfonic acid is dripped into the 1, 3-propylene glycol at the temperature of 0-30 ℃; in the heat preservation process, the temperature of the reaction system is 25-30 ℃.
4. The process for the preparation of propylene sulfate as claimed in claim 2, wherein: in the step 1), the molar ratio of chlorosulfonic acid to 1, 3-propanediol is 1: 1-1.5: 1.
5. The process for the production of propylene sulfate as claimed in claim 2, 3 or 4, wherein: in the step 2), the closed-loop catalyst is a modified ZSM-5 molecular sieve.
6. The process for the preparation of propylene sulfate as claimed in claim 2, wherein: in the step 2), the dosage of the ring closing catalyst is 0.5-2% of the mass of the 1, 3-propylene glycol.
7. The method for preparing the propylene sulfate as claimed in claim 5, wherein the modified ZSM-5 molecular sieve is prepared by the following steps: soaking the ZSM-5 molecular sieve in dilute acid for 5-10 h, filtering, introducing water vapor for treating for 5-10 h, washing the treated ZSM-5 molecular sieve until the water is neutral, drying, and finally roasting for 1-5 h at 200-500 ℃.
8. The process for the preparation of propylene sulfate as claimed in claim 7, wherein: the dilute acid is one or more of sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid, oxalic acid, stannic chloride and phosphotungstic acid aqueous solution.
9. The method for preparing propylene sulfate as claimed in claim 7, wherein the dilute acid concentration is 5-20%; the dosage of the diluted acid meets the following requirements: 10-50 mL of dilute acid is used per gram of ZSM-5 molecular sieve.
10. The process for the preparation of propylene sulfate as claimed in claim 2, wherein: the solvent with water in the step 2) is any one or more of dichloroethane, dimethyl carbonate, toluene, n-hexane and ethyl acetate.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114591289A (en) * | 2022-03-29 | 2022-06-07 | 中南大学 | Preparation method of vinyl sulfate |
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| CN107629032A (en) * | 2017-10-25 | 2018-01-26 | 上海康鹏科技有限公司 | A kind of preparation method of cyclic sulfates |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114591289A (en) * | 2022-03-29 | 2022-06-07 | 中南大学 | Preparation method of vinyl sulfate |
| CN114591289B (en) * | 2022-03-29 | 2023-08-25 | 中南大学 | Preparation method of vinyl sulfate |
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