CN104610221B - A kind of preparation method of 1 acrylic 1,3 sultones - Google Patents
A kind of preparation method of 1 acrylic 1,3 sultones Download PDFInfo
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- CN104610221B CN104610221B CN201510026243.7A CN201510026243A CN104610221B CN 104610221 B CN104610221 B CN 104610221B CN 201510026243 A CN201510026243 A CN 201510026243A CN 104610221 B CN104610221 B CN 104610221B
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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
- C07D327/02—Heterocyclic compounds containing rings having oxygen and sulfur atoms as the only ring hetero atoms one oxygen atom and one sulfur atom
- C07D327/04—Five-membered rings
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Abstract
The present invention relates to the preparation method of 1 acrylic 1,3 sultones, comprise the following steps: in the aqueous solution of bisulfites, add propilolic alcohol, through the anion exchange resin of pretreatment, be passed through air, heated and stirred, insulation reaction, obtain mixed liquor；The mixed liquor cooling obtained is filtered, obtains filtrate and filter cake；Described filter cake is loaded in chromatographic column, uses Bronsted acid drip washing, collect leacheate, distill, obtain brown viscous liquid；The brown viscous liquid obtained is down to room temperature, decompression dehydration, obtains 1 acrylic 1,3 sultones.The method that present invention employs ion exchange simplifies operating process, improves reaction yield simultaneously, reduces cost of material, produces for large-scale industrial and provides possibility.
Description
Technical field
The present invention relates to the preparation method of a kind of 1-propenyl-1,3-sulfonic acid lactone, belong to organic compound technology of preparing
Field.
Background technology
1-propenyl-1,3-sulfonic acid lactone is lithium-ion battery electrolytes additive, and it is degradability additive, mainly makees
With being to form SEI (solid elec-trolyte interface) layer at graphite electrode surface, cause to avoid lithium to embed
Battery performance rapid attenuation, improves battery performance.
Having benefited from the fast development of field of lithium ion battery and the huge market space thereof, 1-acrylic-1, in 3-sulfonic acid
Ester is as a kind of additive of good performance, and its synthetic method has obtained studying widely.But owing to yield is low, complex process,
The reason such as relatively costly, fails to realize large-scale industrial production all the time.The conjunction of existing 1-propenyl-1,3-sulfonic acid lactone
Become technique be: with propilolic alcohol as raw material, use addition, acidifying, the synthetic route of dehydration condensation, domestic have two synthesis patents:
CN101456856A and CN101659653A, is to use said synthesis route, is all to use propilolic alcohol and Asia in addition step
Sulfate or bisulfites carry out additive reaction, cause final products yield and pure owing to this step is susceptible to polyreaction
Spend relatively low.
Summary of the invention
In view of problems such as in prior art, yield are low, purity is low, the present invention provides a kind of 1-propenyl-1,3-sulfonic acid lactone
Preparation method, addition step add anion exchange resin, carry out ion exchange with product, thus effectively solve
The problems referred to above, have the advantages such as product yield is high, purity is high, preparation method is simple, be widely used, carry for industrialized production
Having supplied may.
The technical scheme is that
The preparation method of a kind of 1-propenyl-1,3-sulfonic acid lactone, comprises the following steps:
1) in the aqueous solution of bisulfites, add propilolic alcohol, through the anion exchange resin of pretreatment, be passed through sky
Gas, heated and stirred, keep temperature to react, obtain mixed liquor；
2) by step 1) mixed liquor that obtains, cooling is filtered, is obtained filtrate and filter cake；Described filter cake is filled in chromatographic column
In, use Bronsted acid drip washing, collect leacheate, distill, obtain brown viscous liquid；
3) by step 2) in the brown viscous liquid that obtains be down to room temperature, decompression dehydration, obtain 1-acrylic-1,3-sulfonic acid
Lactone.
There is following reaction scheme:
Further, step 1) in, described bisulfites is sodium sulfite or Potassium acid sulfite；Described sodium sulfite
The mass fraction of solution sulfite hydrogen sodium is 20%, and the mass fraction of described bisulfite potassium solution sulfite hydrogen potassium is
22%；Described propilolic alcohol is 2: 1 to 4: 1 with the mol ratio of bisulfites, described bisulfites and the moon through pretreatment
The mass ratio of ion exchange resin is 1: 4 to 1: 6；Described anion exchange resin model is 201 × 7, D201, arbitrary in 717
Kind.
Further, the preprocess method of described anion exchange resin is: wash described anion exchange resin to aqueous phase
Achromaticity and clarification, be soaked in water 24h, then soaks 2h with the hydrochloric acid solution of mass fraction 2%, is washed to pH=4, uses mass fraction
The sodium hydroxide solution of 5% soaks 2h, and being washed to pH is 8-9.
Further, step 1) reaction condition be: be passed through air bubbling with 300-500mL/min, utilize oil bath to heat, rise
Temperature is to interior temperature 85-90 DEG C, and insulation reaction 4h, the mixed liquor obtained can not make fuchsin solution fade.
Further, step 2) in, described Bronsted acid is sulphuric acid, and the mass fraction of described sulphuric acid is 30%-35%, described sulfur
Acid is 1: 1 with the mol ratio of bisulfites；Step 2) in, by step 1) cooling of the mixed liquor that obtains makes at a temperature below 50
DEG C, distillation condition be temperature be 75-80 DEG C, pressure be 0.09MPa.
Further, step 3) in, described decompression dehydration condition is: pressure is 300Pa, and temperature is 90-130 DEG C.
Utilizing total recovery 60%-65% of 1-propenyl-1,3-sulfonic acid lactone that said method prepares, purity is more than
99.9%, fusing point is 82-83 DEG C.
The invention has the beneficial effects as follows:
The present invention have employed the method for ion exchange uniquely and simplifies operating process, improves reaction yield simultaneously, fall
Low cost of material, produces for large-scale industrial and provides possibility.The present invention with propilolic alcohol as raw material, sulfonated reaction, ion
Exchange, acidification reaction, dehydration prepare compound 1-propenyl-1,3-sulfonic acid lactone, total recovery 60%-65%, purity
More than 99.9%, fusing point 82-83 DEG C.
At present, the preparation of 1-propenyl-1,3-sulfonic acid lactone typically uses the synthetic route of addition, acidifying, dehydration condensation,
It is all to use propilolic alcohol and sulphite or bisulfites to carry out additive reaction in addition step, owing to producing when additive reaction
Thing is easily polymerized and causes product yield and purity more all ratios relatively low.
Generally, ion exchange resin is mainly used in separation and the purification of product, in the system of 1-propenyl-1,3-sulfonic acid lactone
Preparation Method does not have relevant report.The present invention uses ion exchange to prepare 1-propenyl-1,3-sulfonic acid lactone present invention choosing
The anion exchange resin selected has special selectivity to the sulfonate in reaction system of the present invention, if using it
Its ion exchange resin will can not reach same effect, even can not successfully prepare target product, and the present invention uses ion
Exchange process prepares the reaction mechanism of 1-propenyl-1,3-sulfonic acid lactone:
It addition, the present invention also selects that optimal experiment condition determines the absorption parameter of suitable ion exchange resin,
The 1-propenyl-1,3-sulfonic acid lactone total recovery making the present invention prepare reaches 60%-65%, purity more than 99.9%, the highest
Product yield in currently available technology and purity.
Detailed description of the invention
Principle and feature to the present invention are described below, and example is served only for explaining the present invention, is not intended to limit
Determine the scope of the present invention.
The preparation method of a kind of 1-propenyl-1,3-sulfonic acid lactone, comprises the following steps:
1) anion exchange resin is carried out pretreatment: wash described anion exchange resin to aqueous phase achromaticity and clarification, use
Water soaking 24h, then soak 2h with the hydrochloric acid solution of mass fraction 2%, it is washed to pH=4, with the sodium hydroxide of mass fraction 5%
Solution soaking 2h, being washed to pH is 8-9.
2) in the aqueous solution of mass fraction 20% sodium sulfite or the aqueous solution of mass fraction 22% Potassium acid sulfite,
Add propilolic alcohol, through the anion exchange resin (model is 201 × 7, D201 or 717) of pretreatment, described propilolic alcohol is with sub-
The mol ratio of disulfate is 2: 1 to 4: 1, described bisulfites and the mass ratio of the anion exchange resin through pretreatment
It is 1: 4 to 1: 6, is passed through air bubbling with 300-500mL/min, utilize oil bath to heat, stir simultaneously, be warming up to interior temperature 85-90
DEG C start timing insulation, insulation reaction 4h, obtain mixed liquor, take 1mL mixed liquor, drip the magenta that 1 mass fraction is 1% molten
Liquid, fuchsin solution is colour-fast；
3) by step 1) mixed liquor that obtains, it is cooled to less than 50 DEG C, filters, obtain filtrate and filter cake；By described filter cake
It is filled in chromatographic column, with the dilute sulfuric acid drip washing of mass fraction 30%-35%, described dilute sulfuric acid and sodium sulfite or sulfurous
The mol ratio of potassium hydrogen phthalate is 1: 1, collects leacheate, and temperature 75-80 DEG C, pressure are decompression distillation under the conditions of 0.09MPa, obtain
Brown viscous liquid；
4) by step 2) in the brown viscous liquid that obtains be down to room temperature, assemble oil pump dehydration device, at pressure be
300Pa, temperature be 90-130 DEG C under the conditions of decompression dehydration, decompression distillation obtain white solid, be 1-acrylic-1,3-sulfonic acid
Lactone, total recovery 60%-65% of described 1-propenyl-1,3-sulfonic acid lactone, purity is more than 99.9%, fusing point 82-83 DEG C.
Embodiment 1
Anion exchange resin is carried out pretreatment: washing anion exchange resin (model is 201 × 7) is colourless to aqueous phase
Clarification, be soaked in water 24h, then with the HCl solution of mass fraction 2% immersion 2h, is washed to pH=4, then with mass fraction 5%
Sodium hydroxide solution soaks 2h, and being washed to pH is 8；
41.6g sodium sulfite (0.4mol), tap water 166.5g (9.24mol) is put into successively in 500mL there-necked flask,
Stir the most molten, be further continued for adding 44.8g propilolic alcohol (0.8mol), the above-mentioned anion exchange resin processed of 166.4g, with
300mL/min is passed through air bubbling, oil bath heated and stirred, and reaction system is colourless transparent liquid, is warming up to 85 DEG C of systems of interior temperature
Starting timing insulation, system does not has obvious heat release and punching temperature phenomenon, and insulation 4h reaction is complete, obtains mixed liquor, takes 1mL mixing
Liquid, dripping 1 mass fraction is the fuchsin solution of 1%, and fuchsin solution is colour-fast.
System is cooled to temperature to 49 DEG C, above-mentioned mixed liquor is filtered, obtains filtrate and filter cake；Filter cake is filled in layer
In analysis post, with the above-mentioned chromatographic column of dilute sulfuric acid drip washing of 261.3g mass fraction 30%, collect leacheate；It is transferred to leacheate hold
Amassing as in the single port bottle of 1L, temperature is 75 DEG C, pressure is desolventizing under 0.09MPa reduced pressure, after desolventizing, obtains
50g brown viscous liquid.
Brown viscous liquid is cooled to room temperature, assembles oil pump dehydration device (being made up of still head, air set pipe), pressure
Power is 300Pa, temperature utilizes oil pump to be dehydrated under the conditions of being 90 DEG C, distills to obtain white solid 31.2g, is 1-acrylic-1,3-
Sultones, yield is 65% (the calculating employing following methods of yield: completely, product theoretical yield is in sodium sulfite reaction
0.4mol, i.e. 48.0g, therefore yield is 31.2g/48g=65%, embodiment 2 and embodiment 3 are also adopted by same method and calculate receipts
Rate), the purity of GC detection is 99.96%, and fusing point is 82 DEG C.
Embodiment 2
Anion exchange resin is carried out pretreatment: washing anion exchange resin (model is D201) is colourless clear to aqueous phase
Clearly, be soaked in water 24h, then soaks 2h with the HCl solution of mass fraction 2%, is washed to pH=4, at the hydrogen with mass fraction 5%
Sodium hydroxide solution soaks 2h, and being washed to pH is 9.
48.1g Potassium acid sulfite (0.4mol), tap water 166.5g (9.24mol) is put into successively in 500mL there-necked flask,
Stirring, until all dissolving, adds 89.6g propilolic alcohol (1.6mol), 288.6g anion exchange resin in solution, with
500mL/min is passed through air bubbling, oil bath heated and stirred, and reaction system is colourless transparent liquid, is warming up to 90 DEG C of systems of interior temperature
Starting timing insulation, system does not has obvious heat release and punching temperature phenomenon, and insulation 4h reaction is complete, obtains mixed liquor, takes 1mL mixing
Liquid, dripping 1 mass fraction is the fuchsin solution of 1%, and fuchsin solution is colour-fast.
System is cooled to temperature 30 DEG C, above-mentioned mixed liquor is filtered, obtain filtrate and filter cake；Filter cake is filled in chromatography
In post, with the above-mentioned chromatographic column of dilute sulfuric acid drip washing of 224.0g mass fraction 35%, collect leacheate；Leacheate is transferred to volume
For in the single port bottle of 1L, temperature is 80 DEG C, pressure is desolventizing under 0.09MPa reduced pressure, after desolventizing, obtains 55g
Brown viscous liquid.
Brown viscous liquid is cooled to room temperature, assembles oil pump dehydration device (being made up of still head, air set pipe), pressure
Power is 300Pa, and temperature utilizes oil pump to be dehydrated under the conditions of being 130 DEG C, distills to obtain white solid 28.8g, is 1-acrylic-1,3-
Sultones, yield is 60%, and GC detection purity is 99.97%, and fusing point is 83 DEG C.
Embodiment 3
Anion exchange resin is carried out pretreatment: washing anion exchange resin (model is 717) is colourless clear to aqueous phase
Clearly, be soaked in water 24h, then soaks 2h with the HCl solution of mass fraction 2%, is washed to pH=4, then the hydrogen with mass fraction 5%
Sodium hydroxide solution soaks 2h, and being washed to pH is 8.5；
41.6g sodium sulfite (0.4mol), tap water 166.5g (9.24mol) is put into successively in 500mL there-necked flask,
Stir the most molten, in above-mentioned solution, add 67.2g propilolic alcohol (1.2mol), the above-mentioned anion exchange resin processed of 208g,
Being passed through air bubbling, oil bath heated and stirred with 400mL/min, reaction system is colourless transparent liquid, is warming up to 87 DEG C of bodies of interior temperature
System starts timing insulation, and system does not has obvious heat release and punching temperature phenomenon, and insulation 4h reaction is complete, obtains mixed liquor, takes 1mL mixing
Liquid, dripping 1 mass fraction is the fuchsin solution of 1%, and fuchsin solution is colour-fast.
System is cooled to temperature to 20 DEG C, above-mentioned mixed liquor is filtered, obtains filtrate and filter cake；Filter cake is filled in layer
In analysis post, with the above-mentioned chromatographic column of dilute sulfuric acid drip washing of 245.0g mass fraction 32%, collect leacheate；It is transferred to leacheate hold
Amassing as in the single port bottle of 1L, temperature is 78 DEG C, pressure is desolventizing under 0.09MPa reduced pressure, after desolventizing, obtains
58g brown viscous liquid.
Brown viscous liquid is cooled to room temperature, assembles oil pump dehydration device (being made up of still head, air set pipe), pressure
Power is 300Pa, temperature utilizes oil pump to be dehydrated under the conditions of being 110 DEG C, distills to obtain white solid 30.7g, is 1-acrylic-1,3-
Sultones, yield is 64%, and GC detection purity is 99.99%, and fusing point is 82.5 DEG C.
The foregoing is only presently preferred embodiments of the present invention, not in order to limit the present invention, all spirit in the present invention and
Within principle, any modification, equivalent substitution and improvement etc. made, should be included within the scope of the present invention.
Claims (8)
1. the preparation method of a 1-propenyl-1,3-sulfonic acid lactone, it is characterised in that comprise the following steps:
1) in the aqueous solution of bisulfites, propilolic alcohol is added, through the anion exchange resin of pretreatment, described anion
Exchanger resin model is any one in 201 × 7 and D201, is passed through air, heated and stirred, keeps temperature to react, is mixed
Close liquid；Described bisulfites is 1:4 to 1:6 with the mass ratio of the anion exchange resin through pretreatment；Described anion
The preprocess method of exchanger resin is: washing described anion exchange resin to aqueous phase achromaticity and clarification, be soaked in water 24h, then uses
The hydrochloric acid solution of mass fraction 2% soaks 2h, is washed to pH=4, soaks 2h, water with the sodium hydroxide solution of mass fraction 5%
Being washed till pH is 8-9；
2) by step 1) filter after the cooling of the mixed liquor that obtains, obtain filtrate and filter cake；Described filter cake is filled in chromatographic column,
Use Bronsted acid drip washing, collect leacheate, distill, obtain brown viscous liquid；
3) by step 2) in the brown viscous liquid that obtains be down to room temperature, decompression dehydration, obtain 1-acrylic-1, in 3-sulfonic acid
Ester.
The preparation method of a kind of 1-propenyl-1,3-sulfonic acid lactone, it is characterised in that step 1)
In, described bisulfites is sodium sulfite or Potassium acid sulfite.
The preparation method of a kind of 1-propenyl-1,3-sulfonic acid lactone, it is characterised in that step 1)
In, the mass fraction of described sodium sulfite solution sulfite hydrogen sodium is 20%；Described bisulfite potassium solution sulfite
The mass fraction of hydrogen potassium is 22%.
The preparation method of a kind of 1-propenyl-1,3-sulfonic acid lactone, it is characterised in that step 1)
In, described propilolic alcohol is 2:1 to 4:1 with the mol ratio of bisulfites.
The preparation method of a kind of 1-propenyl-1,3-sulfonic acid lactone, it is characterised in that described matter
Son acid is sulphuric acid, and the mass fraction of described sulphuric acid is 30%-35%, and described sulphuric acid is 1:1 with the mol ratio of bisulfites.
6., according to the preparation method of 1-propenyl-1,3-sulfonic acid lactone a kind of described in any one of claim 1 to 5, its feature exists
In, step 1) in, described in be passed through the speed of air be 300-500mL/min, the temperature of described heating is 85-90 DEG C, described instead
The time answered is 4h.
7., according to the preparation method of 1-propenyl-1,3-sulfonic acid lactone a kind of described in any one of claim 1 to 5, its feature exists
In, step 2) in, described distillation condition be temperature be 75-80 DEG C, pressure be 0.09MPa.
8., according to the preparation method of 1-propenyl-1,3-sulfonic acid lactone a kind of described in any one of claim 1 to 5, its feature exists
In, step 3) in, described decompression dehydration condition is: temperature is 90-130 DEG C, and pressure is 300Pa.
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| CN1256267A (en) * | 1998-11-09 | 2000-06-14 | 河北省望都县冀都精细化工有限公司 | Preparation of pyridine propane sultones |
| CN1331051A (en) * | 2000-06-28 | 2002-01-16 | 中国石油化工股份有限公司 | Corrosion-retarding compound scaling inhibitor for treating middle- or high-hardness circulating water |
| CN101456856A (en) * | 2009-01-07 | 2009-06-17 | 石家庄圣泰化工有限公司 | Preparation method of 1-propylene-1, 3-sultone |
| CN101659653A (en) * | 2009-08-28 | 2010-03-03 | 张家港市国泰华荣化工新材料有限公司 | Preparation method of propenyl-1, 3-sulfonic acid lactone |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57171958A (en) * | 1981-04-17 | 1982-10-22 | Konishiroku Photo Ind Co Ltd | Preparation of 1-hydroxypropane derivative |
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2015
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| CN1256267A (en) * | 1998-11-09 | 2000-06-14 | 河北省望都县冀都精细化工有限公司 | Preparation of pyridine propane sultones |
| CN1331051A (en) * | 2000-06-28 | 2002-01-16 | 中国石油化工股份有限公司 | Corrosion-retarding compound scaling inhibitor for treating middle- or high-hardness circulating water |
| CN101456856A (en) * | 2009-01-07 | 2009-06-17 | 石家庄圣泰化工有限公司 | Preparation method of 1-propylene-1, 3-sultone |
| CN101659653A (en) * | 2009-08-28 | 2010-03-03 | 张家港市国泰华荣化工新材料有限公司 | Preparation method of propenyl-1, 3-sulfonic acid lactone |
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