CN101659653A - Preparation method of propenyl-1, 3-sulfonic acid lactone - Google Patents
Preparation method of propenyl-1, 3-sulfonic acid lactone Download PDFInfo
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- CN101659653A CN101659653A CN200910144761A CN200910144761A CN101659653A CN 101659653 A CN101659653 A CN 101659653A CN 200910144761 A CN200910144761 A CN 200910144761A CN 200910144761 A CN200910144761 A CN 200910144761A CN 101659653 A CN101659653 A CN 101659653A
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- propenyl
- sultones
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Abstract
The invention discloses a preparation method of propenyl-1, 3-sulfonic acid lactone, which needs simple devices, has simple technology and comprises the following steps: (1) bisulfite and sulphite aredissolved in water, prepared into aqueous solution, stirred in the temperature of 0-80 DEG C and dropwise added with propargyl alcohol for addition reaction; (2) synthetic fluid is added after beingacidized and reacted by strong acid; (3) the synthetic fluid is directly concentrated in low temperature, thus obtaining viscous mixture; (4) viscous mixture is added with a water-carrying agent and contains water under stirring; and (5) the water-carrying agent is separated and collected, and the collected water-carrying agent is concentrated and crystallized to obtain product propenyl-1, 3-sulfonic acid lactone. The propenyl-1, 3-sulfonic acid lactone prepared by the invention can be used as a lithium cell electrolyte additive.
Description
Technical field
The present invention relates to propenyl-1, the preparation method of 3-sultones as the lithium battery electrolytes additive.
Background technology
Propenyl-1, the 3-sultones, English name: Prop-1-ene-1,3-sultone is for CAS number: 21806-61-1, molecular formula: C
3H
4O
3S, molecular weight: 120.13, density: 1.508, fusing point: 82-83 ℃, boiling point (under the 100Kpa): 257 ℃.
Propenyl-1; a cyclic olefinic bond is arranged in the 3-sultones molecule; this compound is under the condition of gentleness; series of chemical can take place; contain sulfonic acid group in the molecule simultaneously,, radical reactions such as alcoholysis and amine take place under certain condition with alcohol, phenol, mercaptan, amine etc.; introduce sulfonyl group, to improve its chemistry and physical properties.
At present, propenyl-1,3-sultones synthetic mainly contains following several method:
Method one: with the 1-propylene halide is starting raw material, according to following route synthesizing propylene base-1, and the 3-sultones,
In this route, go on foot the 5th from the 4th and go on foot, need under vacuum, remove a large amount of gaseous state etchant gases, be easy to take place polymerization and carbonization, form a large amount of solid viscous mixtures, be gathered in the reactor, be difficult to obtain purpose product propenyl-1, the 3-sultones is difficult to suitability for industrialized production.
The synthetic route of method two is as follows, but this route uses raw material to be difficult to preparation, cost height.
Method three: also having with propargyl alcohol (CH ≡ CCH2OH) is raw material, in the presence of catalyzer, with hydrosulphite and sulphite reaction, separate and obtain 1-hydroxyl-2-propylene-3-sulfonate, under acidic conditions, be converted into 1-hydroxyl-2-propylene-3-sulfonic acid then, under high vacuum, carry out distillation dehydration (vacuum distilling) synchronously again, obtain target product propenyl-1, the 3-sultones.Because propenyl-1, the fusing point of 3-sultones are 82-83 ℃, boiling point (under the 100Kpa) is 257 ℃, and at a certain temperature, its easy open loop or generation polymerization form thick polymkeric substance, are difficult to operation.This method is used catalyzer, and step is many, uses the vacuum distilling operation easier big, is unfavorable for suitability for industrialized production.
Summary of the invention
Technical problem to be solved by this invention is: a kind of do not need additionally to use all better simply propenyl-1 of catalyzer, equipment and technology, the preparation method of 3-sultones will be provided.
For solving the problems of the technologies described above, the technical solution used in the present invention is: described propenyl-1, the preparation method of 3-sultones comprises the steps:
(1) be raw material with hydrosulphite and sulphite, raw material is soluble in water, be made into mass concentration and be 10%～70% the aqueous solution, wherein the molar ratio of bisulfite group and inferior sulfate radical group is 1: 0.1～1: 10, and optimum molar ratio scope is 1: 0.5～1: 1.5; 0～80 ℃ and stir under, drip propargyl alcohol, carry out addition reaction, the mol ratio of bisulfite group and propargyl alcohol is 5: 1～1: 5, optimum is 2: 1～1: 2; Optimum temps during above-mentioned reaction is 40～60 ℃
(2) above-mentioned reaction adds strong acid, the synthetic liquid behind the acidification reaction after finishing again;
(3) the synthetic liquid after the above-mentioned acidifying is directly carried out cryoconcentration, obtain viscous mixture; Temperature during cryoconcentration is 30～100 ℃, and optimum is 50～70 ℃;
(4) in above-mentioned viscous mixture, add the band aqua, under agitation be with water;
(5) the above-mentioned band aqua of separated and collected carries out condensing crystal and recrystallization to the band aqua of collecting, and obtains product propenyl-1, the 3-sultones;
(6) to above-mentioned product propenyl-1, the 3-sultones carries out drying at 0～83 ℃, obtains further high-quality propenyl-1, the 3-sultones.The optimum drying temperature is 50～80 ℃, pressure is 0～-0.1MPa;
The strong acid that adds in the above-mentioned steps (two) is the mixture of any in the middle of acid iodide, hydrochloric acid, nitric acid, sulfuric acid, the Hydrogen bromide or at least two kinds.
Above-mentioned band aqua is any in sherwood oil, benzene,toluene,xylene, normal hexane, the ethyl acetate.Best band aqua is benzene or ethyl acetate;
The used solvent of crystallization and recrystallization is any one in sherwood oil, benzene,toluene,xylene, normal hexane, ethyl acetate, methylene dichloride, Skellysolve A, hexane, pentamethylene, heptane, ether, ethanol, methyl alcohol, propyl carbinol, propyl alcohol, the Virahol in the above-mentioned steps.
Beneficial effect of the present invention is: one, building-up reactions, acidifying, be dehydrated into ring, these three steps are all carried out in a reactor, and the centre does not need to separate and purify, and operation steps is simple; Two, do not need additionally to add catalyzer, directly synthesize; Three, use benzene etc. as the dehydration of band water solvent, extract product propenyl-1 simultaneously, the 3-sultones, condensing crystal, operating equipment is simple, and step is succinct, does not have a large amount of generation of waste materials; Four, the product purity quality height that obtains of this technology, purity is greater than 99.9%, and moisture is less than 10ppm, and cl content is less than 1ppm.
Embodiment
Below by specific embodiment invention is described, but these embodiment should not constitute any limitation of the invention.
Embodiment one
1, NaHSO
3105g (1moL), Na
2SO
331.6g (0.25moL), above-mentioned two materials all are dissolved in 300g H
2Among the O, be mixed with solution a;
2, taking by weighing 56g (1moL) propiolic alcohol is solution b;
3, in 2000mL four neck flasks, add entry 300g, Na
2SO
331.6g (0.25moL);
4, under 30～50 ℃, in four neck flasks, drip solution a, b simultaneously, and stir simultaneously, drip time 0.5h;
5,30～50 ℃ of reactions down;
6, add excessive a little concentrated hydrochloric acid (concentrated hydrochloric acid of 230g mass concentration 35%) the acidifying 1h of theoretical amount;
7, concentrated filtrate gets thick thing 250g to brown thick thing;
8, add 1000mL benzene, under reflux state, divide water, to anhydrous telling;
9, collect the about 905g of upper strata benzene liquid, condensing crystal gets propenyl-1,3-sultones crude product;
10, at 60 ℃ of following vacuum-drying 12h, get propenyl-1,3-sultones 36g, yield 30%, purity assay is 99.95%, moisture 5ppm, cl content are 0.5ppm.
Embodiment two
1, NaHSO
3105g (1moL) is dissolved in 300g H
2Among the O, obtain solution a;
2, taking by weighing 56g (1moL) propiolic alcohol is solution b;
3, in 2000mL four neck flasks, add entry 300g, Na
2SO
331.6g (0.25moL);
4, under 30～50 ℃, in four neck flasks, drip solution a, b simultaneously, and stir simultaneously, drip time 1h;
5,30～50 ℃ of reactions down;
6, add excessive a little concentrated hydrochloric acid (concentrated hydrochloric acid of 230g mass concentration 35%) the acidifying 1h of theoretical amount;
7, concentrated filtrate gets thick thing 220g to brown thick thing;
8, add 1000mL benzene, under reflux state, divide water, to anhydrous telling;
9, collect upper strata benzene liquid 870g, condensing crystal gets propenyl-1,3-sultones crude product;
10, at 60 ℃ of following vacuum-drying 12h, get propenyl-1,3-sultones 25g, yield 20%, purity assay is 99.98%, moisture 8ppm, cl content are 0.8ppm.
Embodiment three
1, in 2000mL four neck flasks, adds NaHSO
3105g (1moL), Na
2SO
363g (0.5moL), above-mentioned two materials all are dissolved in 600g H
2Among the O, be mixed with solution a;
2, taking by weighing 56g (1moL) propiolic alcohol is solution b;
3, under 30～50 ℃, in reactor, drip a, b simultaneously, and stir simultaneously, drip time 2h;
4,30～50 ℃ of reactions down;
5, add excessive a little concentrated hydrochloric acid (concentrated hydrochloric acid of 230g mass concentration 35%) the acidifying 5h of theoretical amount;
6, concentrated filtrate gets thick thing 240g to brown thick thing;
7, add 1000mL benzene liquid and under reflux state, divide water, to anhydrous telling;
8, collect the about 900g of upper strata benzene liquid, condensing crystal gets propenyl-1,3-sultones crude product.
9, at 60 ℃ of following vacuum-drying 12h, get propenyl-1,3-sultones 40g, yield 33%, purity assay is 99.96%, moisture 7ppm, cl content are 0.1ppm.
Claims (9)
1, propenyl-1, the preparation method of 3-sultones is characterized in that: comprise the steps:
(1) be raw material with hydrosulphite and sulphite, raw material is soluble in water, be made into mass concentration and be 10%～70% the aqueous solution, wherein the molar ratio of bisulfite group and inferior sulfate radical group is 1: 0.1～1: 10; 0～80 ℃ and stir under, drip propargyl alcohol, carry out addition reaction, the mol ratio of bisulfite group and propargyl alcohol is 5: 1～1: 5;
(2) above-mentioned reaction adds strong acid, the synthetic liquid behind the acidification reaction after finishing again;
(3) the synthetic liquid after the above-mentioned acidifying is directly carried out cryoconcentration, obtain viscous mixture; Temperature during cryoconcentration is 30～100 ℃;
(4) in above-mentioned viscous mixture, add the band aqua, under agitation be with water;
(5) the above-mentioned band aqua of separated and collected carries out condensing crystal to the band aqua of collecting, and obtains product propenyl-1, the 3-sultones;
(6) to above-mentioned product propenyl-1, the 3-sultones carries out drying at 0～83 ℃, obtains further high-quality propenyl-1, the 3-sultones.
2, preparation method according to claim 1 is characterized in that: the optimum molar ratio scope of described bisulfite group and inferior sulfate radical group is 1: 0.5～1: 1.5; The mol ratio optimum of described bisulfite group and propargyl alcohol is 2: 1～1: 2.
3, preparation method according to claim 1 is characterized in that: the optimum temps when reacting in the step () is 40～60 ℃;
4, preparation method according to claim 1 and 2 is characterized in that: the strong acid that adds in the step (two) is the mixture of any in the middle of acid iodide, hydrochloric acid, nitric acid, sulfuric acid, the Hydrogen bromide or at least two kinds.
5, preparation method according to claim 1 and 2 is characterized in that: the temperature optimum that in the step (three) the synthetic liquid after the acidifying is carried out cryoconcentration is 50～70 ℃.
6, preparation method according to claim 1 and 2 is characterized in that: the band aqua is any in sherwood oil, benzene,toluene,xylene, normal hexane, the ethyl acetate.
7, preparation method according to claim 6 is characterized in that: the band aqua is benzene or ethyl acetate;
8, preparation method according to claim 1 and 2 is characterized in that: the used solvent of crystallization is any one in sherwood oil, benzene,toluene,xylene, normal hexane, ethyl acetate, methylene dichloride, Skellysolve A, hexane, pentamethylene, heptane, ether, ethanol, methyl alcohol, propyl carbinol, propyl alcohol, the Virahol.
9, preparation method according to claim 1 and 2 is characterized in that: drying temperature is 50～80 ℃, pressure is 0～-0.1MPa.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102231441A (en) * | 2011-05-17 | 2011-11-02 | 华南师范大学 | Sulfur-containing electrolyte with film forming function for lithium ion battery as well as preparation method and application thereof |
| CN102807552A (en) * | 2012-07-31 | 2012-12-05 | 福建创鑫科技开发有限公司 | Method for synthetizing 2, 4-butane sulfonic acid lactone |
| CN104610221A (en) * | 2015-01-19 | 2015-05-13 | 烟台海川化学制品有限公司 | Preparation method of 1-propenyl-1,3-sultone |
| CN106187987A (en) * | 2016-07-12 | 2016-12-07 | 武汉松石科技股份有限公司 | A kind of environmental protection method of purification of acrylic 1,3 sultones |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101456856B (en) * | 2009-01-07 | 2013-03-13 | 石家庄圣泰化工有限公司 | Method for preparing 1-propone-1,3-sultone |
-
2009
- 2009-08-28 CN CN2009101447613A patent/CN101659653B/en active Active
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102231441A (en) * | 2011-05-17 | 2011-11-02 | 华南师范大学 | Sulfur-containing electrolyte with film forming function for lithium ion battery as well as preparation method and application thereof |
| CN102807552A (en) * | 2012-07-31 | 2012-12-05 | 福建创鑫科技开发有限公司 | Method for synthetizing 2, 4-butane sulfonic acid lactone |
| CN104610221A (en) * | 2015-01-19 | 2015-05-13 | 烟台海川化学制品有限公司 | Preparation method of 1-propenyl-1,3-sultone |
| CN104610221B (en) * | 2015-01-19 | 2016-11-30 | 烟台海川化学制品有限公司 | A kind of preparation method of 1 acrylic 1,3 sultones |
| CN106187987A (en) * | 2016-07-12 | 2016-12-07 | 武汉松石科技股份有限公司 | A kind of environmental protection method of purification of acrylic 1,3 sultones |
| CN106187987B (en) * | 2016-07-12 | 2019-01-25 | 武汉松石科技股份有限公司 | A kind of environmentally friendly method of purification of acrylic -1,3- sultones |
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| CN101659653B (en) | 2012-10-31 |
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Address after: 215600 No.35 Nanhai Road, Jiangsu Yangzijiang International Chemical Industrial Park, Zhangjiagang, Suzhou, Jiangsu Province Patentee after: Zhangjiagang Guotai-Huarong New Chemical Materials Co.,Ltd. Address before: 215631 Jiangsu province Zhangjiagang City gold town after Cheng Cheng Road No. 112 Patentee before: Zhangjiagang Guotai-Huarong New Chemical Materials Co.,Ltd. |
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