CN110483473A - A kind of solvent-free method for preparing 1,3- propane sultone - Google Patents
A kind of solvent-free method for preparing 1,3- propane sultone Download PDFInfo
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- CN110483473A CN110483473A CN201910845331.8A CN201910845331A CN110483473A CN 110483473 A CN110483473 A CN 110483473A CN 201910845331 A CN201910845331 A CN 201910845331A CN 110483473 A CN110483473 A CN 110483473A
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- propane sultone
- solvent
- hydroxy
- added
- deionized water
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- 238000000034 method Methods 0.000 title claims abstract description 24
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 title claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 39
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- 239000008367 deionised water Substances 0.000 claims abstract description 28
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 28
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims abstract description 26
- 239000000920 calcium hydroxide Substances 0.000 claims abstract description 26
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims abstract description 26
- WQPMYSHJKXVTME-UHFFFAOYSA-N 3-hydroxypropane-1-sulfonic acid Chemical compound OCCCS(O)(=O)=O WQPMYSHJKXVTME-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000007864 aqueous solution Substances 0.000 claims abstract description 24
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 24
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000003999 initiator Substances 0.000 claims abstract description 17
- 238000002360 preparation method Methods 0.000 claims abstract description 17
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims abstract description 16
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Diammonium sulfite Chemical compound [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 claims abstract description 14
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 claims abstract description 14
- 239000007787 solid Substances 0.000 claims abstract description 14
- 230000020477 pH reduction Effects 0.000 claims abstract description 12
- 239000011259 mixed solution Substances 0.000 claims abstract description 11
- 238000001914 filtration Methods 0.000 claims abstract description 9
- 235000011132 calcium sulphate Nutrition 0.000 claims abstract description 8
- 230000007062 hydrolysis Effects 0.000 claims abstract description 8
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 8
- HMAYDSZQASQAHN-UHFFFAOYSA-N azane;3-hydroxypropane-1-sulfonic acid Chemical compound [NH4+].OCCCS([O-])(=O)=O HMAYDSZQASQAHN-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000001175 calcium sulphate Substances 0.000 claims abstract description 6
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 5
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims abstract description 3
- 235000011130 ammonium sulphate Nutrition 0.000 claims abstract description 3
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- 230000000977 initiatory effect Effects 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims 1
- 239000005864 Sulphur Substances 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- 150000003863 ammonium salts Chemical class 0.000 claims 1
- 239000012266 salt solution Substances 0.000 claims 1
- 239000002904 solvent Substances 0.000 abstract description 7
- -1 3- hydroxy-propanesulfonic acid calcium Chemical compound 0.000 abstract description 6
- 239000002699 waste material Substances 0.000 abstract description 3
- 238000005956 quaternization reaction Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 16
- 238000003756 stirring Methods 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- CLHYKAZPWIRRRD-UHFFFAOYSA-N 1-hydroxypropane-1-sulfonic acid Chemical class CCC(O)S(O)(=O)=O CLHYKAZPWIRRRD-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- AOSFMYBATFLTAQ-UHFFFAOYSA-N 1-amino-3-(benzimidazol-1-yl)propan-2-ol Chemical compound C1=CC=C2N(CC(O)CN)C=NC2=C1 AOSFMYBATFLTAQ-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000010907 mechanical stirring Methods 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- AKUNSTOMHUXJOZ-UHFFFAOYSA-N 1-hydroperoxybutane Chemical compound CCCCOO AKUNSTOMHUXJOZ-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 229960000935 dehydrated alcohol Drugs 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000000638 solvent extraction Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000003983 crown ethers Chemical class 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N dimethylmethane Natural products CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 150000002085 enols Chemical class 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229960004756 ethanol Drugs 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- MGNVWUDMMXZUDI-UHFFFAOYSA-N propane-1,3-disulfonic acid Chemical compound OS(=O)(=O)CCCS(O)(=O)=O MGNVWUDMMXZUDI-UHFFFAOYSA-N 0.000 description 1
- KCXFHTAICRTXLI-UHFFFAOYSA-N propane-1-sulfonic acid Chemical compound CCCS(O)(=O)=O KCXFHTAICRTXLI-UHFFFAOYSA-N 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- 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
-
- Y—GENERAL 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of solvent-free preparations 1, the method of 3- propane sultone is using propenyl and ammonium sulfite as reaction raw materials, deionized water is medium, first ammonium sulfate and deionized water are stirred, temperature is at 20-50 DEG C, by methacrylaldehyde, initiator and deionized water, which are made into mixed solution and are added dropwise to beaker, to be carried out catalysis reaction and generates the aqueous solution of 3- hydroxy-propanesulfonic acid ammonium, it adds calcium hydroxide and carries out quaternization, the concentrated sulfuric acid is added after the completion of alkalization to carry out acidification and then obtain 3- hydroxy-propanesulfonic acid and solid calcium sulphate, the aqueous solution of 3- hydroxy-propanesulfonic acid is obtained by filtration, concentrated rectification under vacuum obtains target product, middle a certain amount of calcium hydroxide and water is added kettle is residual, hydrolysis obtains the aqueous solution of 3- hydroxy-propanesulfonic acid calcium, the concentrated sulfuric acid is added and carries out acidification filtering, obtain 3- hydroxy-propanesulfonic acid Aqueous solution, concentrated rectification under vacuum obtain target product；Present invention process is simple, raw material is simple, do not need solvent, generate without waste, yield can reach 95%.
Description
Technical field
The present invention relates to lithium-ion battery electrolytes additive agent fields, and in particular to can add as lithium-ion battery electrolytes
Add the solvent-free method for preparing 1,3- propane sultone of agent.
Background technique
The structural formula of 1,3- propane sultone are as follows:1,3- propane sultone is widely used in dyestuff, medicine,
The fields such as surfactant, lithium battery；It about the preparation method of 1,3- propane sultone, all has been reported that both at home and abroad, application number
To disclose a kind of preparation method for synthesizing 1,3- propane sultone in the Chinese patent specification of 20081023414.X,
For method using bisulfites, sulphite and propenyl as raw material, water is medium, and crown ether is catalyst, in 40~100 DEG C of temperature
The lower reaction of degree is generated as the reaction mixture of hydroxyl propane sulfonic acid salt, then adds in the reaction mixture of hydroxyl propane sulfonic acid salt
Enter hydrochloric acid to be acidified, be added followed by dehydrated alcohol and extracted and filtered, obtain the reaction mixture of hydroxyl propane sulfonic acid,
The reaction mixture of obtained hydroxyl propane sulfonic acid is subjected to high temperature rectifying again and obtains target product 1,3- propane sultone.
It is that reaction needs certain temperature and time using the shortcomings that above-mentioned preparation method, solvent is inflammable and explosive, recycles second
It is perishable to equipment containing acidity in alcohol；It needs using dehydrated alcohol, the ethanol dehydration of recycling was recycled to anhydrous relatively difficult
There is loss in journey, difficulty is handled in production, higher cost distills the easy intermolecular polymerization of 3- hydroxy-propanesulfonic acid at high temperature,
Influence product yield.
Summary of the invention
The object of the present invention is to provide one kind can not have to solvent, reaction temperature is low, the simple inexpensive, simple process of raw material,
Product molar high income, waste are few, be easy to get to high-purity product 1,3 propane sultones preparation method.
The technical proposal for solving the technical problem of the invention is: using in a kind of solvent-free preparation 1,3- propane sulfonic acid
The method of ester, includes the following steps, S1, using propenyl and ammonium sulfite as reaction raw materials, and deionized water is medium, at three mouthfuls
Ammonium sulfate is added in flask to be stirred with deionized water, maintains the temperature between 20-50 DEG C, then by methacrylaldehyde, initiator and
Deionized water, which is made into mixed solution in certain proportion and is added dropwise in three-necked flask, to be carried out catalysis and reaction and generates 3- hydroxyl third
Ichthyodin；S2, a certain amount of calcium hydroxide progress alkali will be added in the aqueous solution obtained above containing 3- hydroxy-propanesulfonic acid ammonium
Change reaction, a certain amount of concentrated sulfuric acid is added after the completion of alkalization and carries out acidification and then obtains 3- hydroxy-propanesulfonic acid and solid sulphuric acid
The aqueous solution of 3- hydroxy-propanesulfonic acid is finally obtained by filtration in calcium；S3, the concentrated rectification under vacuum of the aqueous solution of 3- hydroxy-propanesulfonic acid is obtained
To target product 1,3- propane sultone；S4, by rectifying terminates in step S3 kettle it is residual be added a certain amount of calcium hydroxide and
Water, hydrolysis obtain the aqueous solution of 3- hydroxy-propanesulfonic acid calcium, and the concentrated sulfuric acid is then added and carries out acidification filtering, to obtain 3- hydroxyl
The aqueous solution of base propane sulfonic acid, concentrated rectification under vacuum obtain 1,3- propane sultone.
Reaction equation of the invention are as follows:
1、
2、
3、
3、
4、
As a further improvement of the foregoing solution, the initiator in the step S1 is tert-butyl hydroperoxide, propenyl
Molar ratio with ammonium sulfite is 1:(1~2), the mass percent of ammonium sulfite solution is 50%-70%, methacrylaldehyde, initiation
The molar ratio of methacrylaldehyde, initiator and deionized water is 1:(0.01~0.1 in the mixed solution of agent and deionized water): (2~
3)。
As a further improvement of the foregoing solution, the mole of the calcium hydroxide in the step S2 is rubbing for ammonium sulfite
You measure, and the mole that sulfuric acid is added is the mole of calcium hydroxide.
As a further improvement of the foregoing solution, the calcium hydroxide weight in the step S4 is the 0.1~3 of the residual weight of kettle
Times, the weight ratio of calcium hydroxide and water is 1:1.5, and the mole of the calcium hydroxide of the mole and addition of the concentrated sulfuric acid is identical.
As a further improvement of the foregoing solution, the catalysis reaction time 2-5 hours in the step S1.
As a further improvement of the foregoing solution, the temperature during the acidification in the step S2 and the step S4
Degree is 60~70 DEG C, and the acidification time is 1~2 hour.
As a further improvement of the foregoing solution, the concentration rectification under vacuum in the step S3 and the step S4 is being collected
The temperature of fraction is 110~140 DEG C, and vacuum degree is 20~70Pa.
As a further improvement of the foregoing solution, the hydrolysis temperature in the step S4 is 80~90 DEG C, hydrolysis time 3
~4 hours.
As a further improvement of the foregoing solution, propylene in the mixed solution of the methacrylaldehyde, initiator and deionized water
The molar ratio of aldehyde, initiator and deionized water is 1:(0.01~0.1): (2~3).
As a further improvement of the foregoing solution, the weight of the calcium hydroxide is 0.5~1 times of the residual weight of kettle.
Compared with prior art, the method for solvent-free preparation 1, the 3- propane sultone of one kind provided by the present invention utilizes
Hydrolysis generation ammonium bisulfite occurs in water and reacts production 3- hydroxy-propanesulfonic acid ammonium with propenyl for ammonium sulfite, by strong
3- hydroxy-propanesulfonic acid ammonium is converted 3- hydroxy-propanesulfonic acid calcium by the principle of alkali weak base, soluble easily in water, is then added equimolar
The concentrated sulfuric acid obtains the intermediate product 3- hydroxy-propanesulfonic acid of high-purity so that calcium salt all generates calcium sulfate precipitation, finally decompression essence
It evaporates to obtain target product 1,3- propane sultone；Entire reaction system carries out in water phase；
And using tert-butyl hydroperoxide as reaction initiator, stable mixing can be made into deionized water, propenyl
Solution is added dropwise in ammonium sulfite aqueous solution, only needs a dropwise addition head tank, saves equipment investment；Initiator t-butyl peroxy
The use for changing hydrogen, greatly reduces synthesis reaction temperature, shortens the reaction time, improve the conversion ratio of propenyl.With sulfurous
Sour ammonium is reaction raw materials, is stablized compared with ammonium bisulfite, and convenient transportation is cheap, reduces production cost, passes through calcium hydroxide alkali
The 3- hydroxy-propanesulfonic acid of solid calcium sulphate and high-purity is obtained after change and sulfuric acid acidification, this process does not need solvent, all in water
The step of completing in phase, saving solvent extraction, precipitation concentration and solvent recovery processing, this step is simple to operation, safety
Risk is low, is easily suitble to large-scale industrial production.
Specific embodiment
Embodiment 1
With mechanical stirring, thermometer, Dropping feeder, condenser pipe 3000L three-necked flask in, be added ammonium sulfite 580g
(5mol) is stirred with deionized water 1000g, then at 45 DEG C, while propenyl 290g (5mol), initiator uncle is added dropwise
The mixed solution of butylhydroperoxide 40g and deionized water 200g, time for adding are 3 hours, keep the temperature 1 hour, sampling measures third
Then reaction terminates when enol content is less than 1%；375g (5mol) calcium hydroxide solid is added in reaction solution, in 40-50 DEG C of temperature
Degree lower stirring 2 hours, after reaction is generated without gas, then concentrated sulfuric acid 500g (5mol) is slowly added dropwise, controls temperature in 60-70
Between DEG C；It is stirred after completion of dropwise addition 2 hours, through the aqueous solution and calcium sulfate of 3- hydroxypropanesulfonic acid is obtained by filtration after cooling
130 DEG C~140 DEG C fractions are collected in solid, aqueous solution rectification under vacuum under the pressure of 30-40pa of 3- hydroxypropanesulfonic acid, from
And the 1 of high-purity is obtained, 3- propane sultone 533g, content 99.9%, kettle residual is 112g；In the residual middle addition solid of kettle
Calcium hydroxide 46g and deionized water 100g is heated with stirring to 80 DEG C and reaction 4 hours is hydrolyzed, the concentrated sulfuric acid is added after cooling
60g controls 60-70 DEG C of temperature, stirs 2 hours, cooled and filtered obtains the aqueous solution of 3- hydroxypropanesulfonic acid, in 30-40pa
Pressure under rectification under vacuum, collect 130 DEG C~140 DEG C fractions, obtain 1,3- propane sultone 52g (content 99.9%),
1,3- propane sultone 585g is finally always obtained, calculating molar yield is 95.79%.
Embodiment 2
With mechanical stirring, thermometer, Dropping feeder, condenser pipe 3000L three-necked flask in, be added ammonium sulfite
151g (1.3mol) and deionized water 220g is stirred, and then at 45 DEG C, while propenyl 58g (1mol) is added dropwise, and is caused
The mixed solution of agent tert-butyl hydroperoxide 8g and deionized water 40g, time for adding are 1.5 hours, keep the temperature 2 hours, sampling is surveyed
Then reaction terminates when obtaining propylene alcohol content less than 1%；97g (1.3mol) calcium hydroxide solid is added in reaction solution, in 40-50
It is stirred 2 hours at a temperature of DEG C, after reaction is generated without gas, then concentrated sulfuric acid 130g (1.3mol) is slowly added dropwise, control temperature
Between 60-65 DEG C；It is stirred after completion of dropwise addition 1 hour, through the aqueous solution of 3- hydroxypropanesulfonic acid is obtained by filtration after cooling
And calcium sulphate solid, the wherein aqueous solution of 3- hydroxypropanesulfonic acid rectification under vacuum under the pressure of 30-40pa, 130 DEG C of collection~
140 DEG C of fractions, to obtain 1, the 3- propane sultone 103.5g of high-purity, content 99.9%, kettle residual is 23g；In
The residual middle addition solid calcium hydroxide 15g and deionized water 20g of kettle is heated with stirring to 85 DEG C and reaction 3 hours is hydrolyzed, after cooling
Concentrated sulfuric acid 20g is added, controls 60-65 DEG C of temperature, stirs 1 hour, cooled and filtered obtains the aqueous solution of 3- hydroxypropanesulfonic acid,
In the rectification under vacuum under the pressure of 30-40pa, 130 DEG C~140 DEG C fractions are collected, the rectification under vacuum under the pressure of 30-40pa obtains
To 1,3- propane sultone 12.8g (content 99.9%), 1,3- propane sultone 116.3g is finally always obtained, calculates
Molar yield is 95.21%.
Embodiment 3
With mechanical stirring, thermometer, Dropping feeder, condenser pipe 3000L three-necked flask in, be added ammonium sulfite 174g
(1.5mol) is stirred with deionized water 250g, then at 45 DEG C, while propenyl 58g (1mol), initiator uncle is added dropwise
The mixed solution of butylhydroperoxide 9g and deionized water 50g, time for adding are 1 hour, keep the temperature 2 hours, sampling measures propylene
Then reaction terminates when alcohol content is less than 1%；The calcium hydroxide solid of 112g (1.5mol) is added in reaction solution, at 40-50 DEG C
At a temperature of stir 2 hours, after reaction is generated without gas, then concentrated sulfuric acid 150g (1.5mol) is slowly added dropwise, control temperature exists
Between 50-60 DEG C；Be stirred after completion of dropwise addition 2 hours, be obtained by filtration after cooling 3- hydroxypropanesulfonic acid aqueous solution and
Calcium sulphate solid, aqueous solution rectification under vacuum under the pressure of 30-40pa of 3- hydroxypropanesulfonic acid are collected 130 DEG C~140 DEG C and are evaporated
Point, to obtain 1, the 3- propane sultone 104.1g of high-purity, content 99.9%, kettle residual is 24.2g；In kettle is residual
Solid calcium hydroxide 15g and deionized water 20g is added, is heated with stirring to 85 DEG C and reaction 3 hours is hydrolyzed, be added after cooling dense
Sulfuric acid 20g controls 60-65 DEG C of temperature, stirs 2 hours, cooled and filtered obtains the aqueous solution of 3- hydroxypropanesulfonic acid, in 30-
130 DEG C~140 DEG C fractions are collected in rectification under vacuum under the pressure of 40pa, and obtaining 1,3- propane sultone 12.6g, (content is
99.9%) 1,3- propane sultone 116.7g, is finally always obtained, calculating molar yield is 95.54%.
The invention has the benefit that the solvent-free method for preparing 1,3- propane sultone of one kind of the present invention with
Tert-butyl hydroperoxide is reaction initiator, can be made into stable mixed solution with deionized water, propenyl, be added dropwise to sulfurous
In sour aqueous ammonium, a dropwise addition head tank is only needed, saves equipment investment；The use of initiator tert-butyl hydroperoxide, significantly
Synthesis reaction temperature is reduced, the reaction time is shortened, improves the conversion ratio of propenyl.Using ammonium sulfite as reaction raw materials,
Stablize compared with ammonium bisulfite, convenient transportation is cheap, production cost is reduced, after calcium hydroxide alkalization and sulfuric acid acidification
The 3- hydroxy-propanesulfonic acid of solid calcium sulphate and high-purity is obtained, this process does not need solvent, all completes in water phase, saves
The step of solvent extraction, precipitation concentration and solvent recovery are handled, this step is simple to operation, and security risk is low, is easily suitble to
Large-scale industrial production, simple process can reach 95% or more without waste generation, yield.
It is obvious to a person skilled in the art that invention is not limited to the details of the above exemplary embodiments, Er Qie
In the case where without departing substantially from spirit or essential attributes of the invention, the present invention can be realized in other specific forms.Therefore, no matter
From the point of view of which point, the present embodiments are to be considered as illustrative and not restrictive, and the scope of the present invention is by appended power
Benefit requires rather than above description limits, it is intended that all by what is fallen within the meaning and scope of the equivalent elements of the claims
Variation is included within the present invention.
In addition, it should be understood that although this specification is described in terms of embodiments, but not each embodiment is only wrapped
Containing an independent technical solution, this description of the specification is merely for the sake of clarity, and those skilled in the art should
It considers the specification as a whole, the technical solutions in the various embodiments may also be suitably combined, forms those skilled in the art
The other embodiments being understood that.
Claims (10)
1. a kind of method of solvent-free preparation 1,3- propane sultone, which comprises the following steps:
S1, using propenyl and ammonium sulfite as reaction raw materials, deionized water is medium, in three-necked flask be added ammonium sulfate with
Deionized water is stirred, and is maintained the temperature between 20-50 DEG C, then by methacrylaldehyde, initiator and deionized water with certain ratio
Example, which is made into mixed solution and is added dropwise in three-necked flask, to be carried out catalysis and reaction and generates 3- hydroxy-propanesulfonic acid ammonium；
S2, will be added in the aqueous solution obtained above containing 3- hydroxy-propanesulfonic acid ammonium a certain amount of calcium hydroxide alkalize it is anti-
It answers, a certain amount of concentrated sulfuric acid is added after the completion of alkalization and carries out acidification and then obtains 3- hydroxy-propanesulfonic acid and solid calcium sulphate,
The aqueous solution of 3- hydroxy-propanesulfonic acid is finally obtained by filtration；
S3, the concentrated rectification under vacuum of the aqueous solution of 3- hydroxy-propanesulfonic acid is obtained into target product 1,3- propane sultone；
S4, a certain amount of calcium hydroxide and water is added by rectifying terminates in step S3 kettle is residual, hydrolysis obtains 3- hydroxy-propanesulfonic acid
Then the aqueous solution of calcium is added the concentrated sulfuric acid and carries out acidification filtering, so that the aqueous solution of 3- hydroxy-propanesulfonic acid is obtained, it is concentrated
Rectification under vacuum obtains 1,3- propane sultone.
2. the method for solvent-free preparation 1, the 3- propane sultone of one kind according to claim 1, which is characterized in that institute
The initiator in step S1 is stated as tert-butyl hydroperoxide, the molar ratio of propenyl and ammonium sulfite is 1:(1~2), sulfurous acid
The mass percent of ammonium salt solution is 50%-70%, methacrylaldehyde, initiation in the mixed solution of methacrylaldehyde, initiator and deionized water
The molar ratio of agent and deionized water is 1:(0.01~0.1): (2~3).
3. the method for solvent-free preparation 1, the 3- propane sultone of one kind according to claim 1, which is characterized in that institute
The mole for stating the calcium hydroxide in step S2 is the mole of ammonium sulfite, and the mole that sulfuric acid is added is rubbing for calcium hydroxide
You measure.
4. the method for solvent-free preparation 1, the 3- propane sultone of one kind according to claim 1, which is characterized in that institute
State 0.1~3 times that calcium hydroxide weight in step S4 is the residual weight of kettle, the weight ratio of calcium hydroxide and water is 1:1.5, dense sulphur
The mole of acid is identical with the mole of the calcium hydroxide of addition.
5. the method for solvent-free preparation 1, the 3- propane sultone of one kind according to claim 1, which is characterized in that institute
State the catalysis reaction time 2-5 hours in step S1.
6. the method for solvent-free preparation 1, the 3- propane sultone of one kind according to claim 1, which is characterized in that institute
The temperature stated during the acidification in step S2 and the step S4 is 60~70 DEG C, and the acidification time is 1~2
Hour.
7. the method for solvent-free preparation 1, the 3- propane sultone of one kind according to claim 1, which is characterized in that institute
It is 110~140 DEG C that the concentration rectification under vacuum in step S3 and the step S4, which is stated, collecting the temperature of fraction, and vacuum degree is
20~70Pa.
8. the method for solvent-free preparation 1, the 3- propane sultone of one kind according to claim 1, which is characterized in that institute
Stating the hydrolysis temperature in step S4 is 80~90 DEG C, and hydrolysis time is 3~4 hours.
9. the method for solvent-free preparation 1, the 3- propane sultone of one kind according to claim 2, which is characterized in that institute
The molar ratio for stating methacrylaldehyde, initiator and deionized water in the mixed solution of methacrylaldehyde, initiator and deionized water is 1:(0.01
~0.1): (2~3).
10. the method for solvent-free preparation 1, the 3- propane sultone of one kind according to claim 4, which is characterized in that
The weight of the calcium hydroxide is 0.5~1 times of the residual weight of kettle.
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