CN115677651B - Preparation method of alkyl sultone - Google Patents
Preparation method of alkyl sultone Download PDFInfo
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- CN115677651B CN115677651B CN202211568302.XA CN202211568302A CN115677651B CN 115677651 B CN115677651 B CN 115677651B CN 202211568302 A CN202211568302 A CN 202211568302A CN 115677651 B CN115677651 B CN 115677651B
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- -1 alkyl sultone Chemical class 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 claims abstract description 42
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000005886 esterification reaction Methods 0.000 claims abstract description 15
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000004519 manufacturing process Methods 0.000 claims abstract description 14
- 239000007787 solid Substances 0.000 claims abstract description 12
- 239000003930 superacid Substances 0.000 claims abstract description 12
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims description 54
- 239000000243 solution Substances 0.000 claims description 48
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 38
- 239000007864 aqueous solution Substances 0.000 claims description 30
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 25
- 239000003054 catalyst Substances 0.000 claims description 20
- DPYHFDVRNNQVON-UHFFFAOYSA-N 1,1-dichloroethane;sulfur trioxide Chemical compound CC(Cl)Cl.O=S(=O)=O DPYHFDVRNNQVON-UHFFFAOYSA-N 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 19
- 238000010438 heat treatment Methods 0.000 claims description 18
- 239000000706 filtrate Substances 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 10
- 238000002479 acid--base titration Methods 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims description 10
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical group [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 125000005233 alkylalcohol group Chemical group 0.000 claims description 9
- 238000010992 reflux Methods 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 7
- 235000010288 sodium nitrite Nutrition 0.000 claims description 5
- 235000010265 sodium sulphite Nutrition 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 238000004821 distillation Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 150000002596 lactones Chemical class 0.000 claims 7
- WQPMYSHJKXVTME-UHFFFAOYSA-N 3-hydroxypropane-1-sulfonic acid Chemical compound OCCCS(O)(=O)=O WQPMYSHJKXVTME-UHFFFAOYSA-N 0.000 abstract description 15
- 239000002994 raw material Substances 0.000 abstract description 12
- GGZCIOXAKUOXRP-UHFFFAOYSA-N 3-hydroxypropyl hydrogen sulfate Chemical compound OCCCOS(O)(=O)=O GGZCIOXAKUOXRP-UHFFFAOYSA-N 0.000 abstract description 10
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 abstract description 8
- 229940035437 1,3-propanediol Drugs 0.000 abstract description 8
- 238000006297 dehydration reaction Methods 0.000 abstract description 8
- 229920000166 polytrimethylene carbonate Polymers 0.000 abstract description 8
- 230000018044 dehydration Effects 0.000 abstract description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 4
- 238000006798 ring closing metathesis reaction Methods 0.000 abstract description 4
- 239000012024 dehydrating agents Substances 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 239000012847 fine chemical Substances 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 150000002148 esters Chemical class 0.000 abstract description 2
- 231100000956 nontoxicity Toxicity 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 16
- YEGPVWSPNYPPIK-UHFFFAOYSA-N 4-hydroxybutane-1-sulfonic acid Chemical compound OCCCCS(O)(=O)=O YEGPVWSPNYPPIK-UHFFFAOYSA-N 0.000 description 9
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 8
- 230000032050 esterification Effects 0.000 description 8
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 description 7
- 239000011259 mixed solution Substances 0.000 description 6
- MXUZSNPHTRQMGP-UHFFFAOYSA-N 4-hydroxybutyl hydrogen sulfate Chemical compound OCCCCOS(O)(=O)=O MXUZSNPHTRQMGP-UHFFFAOYSA-N 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- MHYFEEDKONKGEB-UHFFFAOYSA-N oxathiane 2,2-dioxide Chemical compound O=S1(=O)CCCCO1 MHYFEEDKONKGEB-UHFFFAOYSA-N 0.000 description 3
- 230000020477 pH reduction Effects 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- JHUFGBSGINLPOW-UHFFFAOYSA-N 3-chloro-4-(trifluoromethoxy)benzoyl cyanide Chemical compound FC(F)(F)OC1=CC=C(C(=O)C#N)C=C1Cl JHUFGBSGINLPOW-UHFFFAOYSA-N 0.000 description 2
- UTBUFLARLRSVFF-UHFFFAOYSA-N 3-chlorobutan-1-ol Chemical compound CC(Cl)CCO UTBUFLARLRSVFF-UHFFFAOYSA-N 0.000 description 2
- VWEYDBUEGDKEHC-UHFFFAOYSA-N 3-methyloxathiolane 2,2-dioxide Chemical compound CC1CCOS1(=O)=O VWEYDBUEGDKEHC-UHFFFAOYSA-N 0.000 description 2
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical compound ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000006277 sulfonation reaction Methods 0.000 description 2
- 240000007695 Nandina domestica Species 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- RZBSVYZMOJXQJU-UHFFFAOYSA-N [Na].CCCO Chemical compound [Na].CCCO RZBSVYZMOJXQJU-UHFFFAOYSA-N 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005282 brightening Methods 0.000 description 1
- 235000019437 butane-1,3-diol Nutrition 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000012320 chlorinating reagent Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 239000000599 controlled substance Substances 0.000 description 1
- 238000006210 cyclodehydration reaction Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 239000004289 sodium hydrogen sulphite Substances 0.000 description 1
- 229940001584 sodium metabisulfite Drugs 0.000 description 1
- 235000010262 sodium metabisulphite Nutrition 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 150000008053 sultones Chemical class 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- OIWCYIUQAVBPGV-DAQGAKHBSA-N {1-O-hexadecanoyl-2-O-[(Z)-octadec-9-enoyl]-sn-glycero-3-phospho}serine Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@H](COP(O)(=O)OC[C@H](N)C(O)=O)OC(=O)CCCCCCC\C=C/CCCCCCCC OIWCYIUQAVBPGV-DAQGAKHBSA-N 0.000 description 1
Classifications
-
- 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
Abstract
The invention discloses a preparation method of alkyl sultone, which belongs to the technical field of fine chemical organic synthesis, and the raw materials selected by the invention are 1, 3-propanediol or 1, 4-butanediol which are bulk chemicals, so that the production cost is relatively low; when the raw material is 1, 3-propylene glycol, the 1, 3-propylene glycol and sulfur trioxide are subjected to esterification reaction to generate 3-hydroxy propoxy sulfonic acid, the sulfur trioxide preferentially reacts with one hydroxyl group of the 1, 3-propylene glycol to generate ester, and the esterification reaction of the other hydroxyl group is effectively avoided when the molar ratio of the sulfur trioxide is controlled; then introducing a reducing agent to reduce the 3-hydroxy propoxy sulfonic acid to generate 3-hydroxy propane sulfonic acid; the solid superacid is adopted to catalyze the dehydration and ring closure of the 3-hydroxy propane sulfonic acid, so that the introduction of a dehydrating agent is avoided, and the environment is friendly; the invention has the advantages of low price, easy acquisition, no toxicity and harm, simple preparation method, high yield and high purity of the alkyl sultone and environmental protection.
Description
Technical Field
The invention belongs to the technical field of fine chemical organic synthesis, and particularly relates to a preparation method of alkyl sultone.
Background
Alkyl sultone, such as 1, 3-propane sultone, is an organic compound, belongs to a novel functional fine chemical material, is an excellent universal sulfonating agent, and is also a key raw material for synthesizing important electroplating additive intermediates PPS, UPS, DPS, MPS, ZPS, POPS, SP and other products. Is an important raw material for producing lithium batteries, and is also applied to brightening agents, dyes, double-ion surfactants and sulfonating agents. The lithium ion battery can also be used in a lithium secondary battery, so that the cycle times and the service life of the battery are enhanced, and the lithium ion battery has a broad market prospect.
The existing sultone synthesis routes mainly comprise the following steps:
patent CN 104803967A uses allyl chloride as raw material, and adds allyl chloride into a certain amount of sodium metabisulfite aqueous solution to prepare sodium allyl sulfonate, then makes addition reaction with sulfuric acid in the presence of catalyst, then makes hydrolysis under alkaline condition, and makes acidification to obtain 3-hydroxy propane sulfonic acid, and makes cyclodehydration in the presence of inert dehydrating agent to obtain 1, 3-propane sultone, in which the reaction of sodium allyl sulfonate and sulfuric acid requires peroxide as catalyst.
In the scheme 2, allyl alcohol is used as a raw material, is added with sodium bisulphite to generate 3-hydroxy propane sodium sulfonate, and then is subjected to acidification, dehydration and ring closure to obtain 1, 3-propane sultone,
in the route, the cost of using the allyl alcohol as a raw material is relatively high, the allyl alcohol is used as a controlled drug, and in addition, peroxide is used as an initiator in the addition process.
Patent CN 114181190A provides a process for preparing 2, 4-butane sultone, which comprises reacting 1, 3-butanediol, chlorinating agent and catalyst to obtain 3-chloro-1-butanol; then, the obtained 3-chloro-1-butanol is subjected to sulfonation, acidification and cyclization in sequence, so that 2, 4-butane sultone can be obtained;
the method uses the chloridizing reagent, and needs the catalyst to catalyze the reaction, the waste salt amount is larger, and the concentrated sulfuric acid sulfonation reaction is also needed, so that the product yield is lower and the production cost is higher.
The existing synthetic route of the 1, 3-propane sultone takes the allyl alcohol as the raw material, so that the toxicity is high and the production cost is high; when alkyl alcohol is used as a raw material, a chloro reagent and a catalyst are introduced, and the amount of waste salt is large; the high vacuum dehydration adopted during the dehydration and closing of the 3-hydroxy propane sulfonic acid has higher requirements on equipment, and if the water-carrying agent is introduced for dehydration, the energy consumption is higher, so that certain pollution to the environment exists.
Disclosure of Invention
In view of the above, the present invention provides a method for producing an alkyl sultone. The method takes alkyl alcohol as a raw material, and prepares the alkyl sultone through sulfur trioxide esterification, reduction, dehydration and ring closure.
The invention aims to achieve the aim, and the aim is achieved by the following technical scheme:
a process for the preparation of an alkyl sultone comprising the steps of:
adding an alkyl alcohol-dichloroethane solution into a reactor, dropwise adding a sulfur trioxide-dichloroethane solution into the reactor, controlling the temperature of the reactor to be 0-30 ℃ in the dropwise adding process, and continuously carrying out esterification reaction for 1h after the completion of dropwise adding of the sulfur trioxide-dichloroethane solution, and removing solvent dichloroethane by reduced pressure distillation to obtain hydroxyalkoxy sulfonic acid;
the alkyl alcohol-dichloroethane solution consists of the following components in percentage by mass: 2 and dichloroethane;
the sulfur trioxide-dichloroethane solution consists of the following components in mass ratio of 1:1, mixing sulfur trioxide and dichloroethane;
the alkyl alcohol is 1, 3-propylene glycol or 1, 4-butanediol;
the molar ratio of the sulfur trioxide to the alkyl alcohol is 0.98-1: 1, a step of;
the dropping speed of the sulfur trioxide-dichloroethane solution is 0.04 kg-0.08 kg/min;
step->Adding the obtained hydroxyalkoxyl sulfonic acid into deionized water, adding a reducing agent, heating to 80-100 ℃, and carrying out reflux reaction for 3-6 hours to obtain a reaction solution after the reaction is finished;
the reducing agent is sodium sulfite or sodium nitrite;
the molar ratio of the hydroxyalkoxyl sulfonic acid to the reducing agent is 1:1-1.05;
the mass ratio of the hydroxyalkoxyl sulfonic acid to the deionized water is 1:2-3;
go to step->Adding sulfuric acid aqueous solution with the mass concentration of 20-25% into the obtained reaction solution, acidifying the pH value of the reaction solution to 1-2, filtering, wherein the filtrate is hydroxysulfonic acid aqueous solution, determining the mass of hydroxysulfonic acid in the hydroxysulfonic acid aqueous solution by an acid-base titration method, heating the hydroxysulfonic acid aqueous solution to 120-180 ℃, adding a solid superacid catalyst for reaction for 3-8 hours, filtering after the reaction is finished, and carrying out reduced pressure distillation on the filtrate to obtain alkyl sultone;
the dosage of the solid super acid catalyst is 1% -5% of the mass of the hydroxysulfonic acid;
the solid super acid catalyst is SO 4 2- /Fe 2 O 3 Or SO 4 2- /TiO 2 。
Preferably, the molar ratio of sulfur trioxide to alkyl alcohol is 1:1.
Preferably, the steps areThe reaction temperature is 0-10 ℃.
Preferably, the molar ratio of the hydroxyalkoxysulfonic acid to the reducing agent is 1:1.01 to 1.03.
Preferably, the acidifying pH is 1.
Preferably, the dosage of the solid super acid catalyst is 2% -3% of the mass of the hydroxysulfonic acid.
Preferably, the steps ofThe heating temperature is 150-170 ℃.
Preferably, the steps ofThe reaction time is 5-8 h.
The preparation method of the alkyl sultone comprises the following synthetic routes (taking 1, 3-propylene glycol as an example):
。
the raw materials selected by the invention are 1, 3-propanediol or 1, 4-butanediol, which are bulk chemicals, the production cost is relatively low, 1, 3-propanediol is taken as an example, 1, 3-propanediol and sulfur trioxide are subjected to esterification reaction to generate 3-hydroxypropoxy sulfonic acid, the sulfur trioxide preferentially reacts with one hydroxyl of the 1, 3-propanediol to generate ester, the esterification reaction of the other hydroxyl is effectively avoided when the molar ratio of sulfur trioxide is controlled, and the esterification yield is more than 99%; then introducing a reducing agent to reduce the 3-hydroxy propoxy sulfonic acid to generate 3-hydroxy propane sulfonic acid; the solid superacid is adopted to catalyze the dehydration and ring closure of the 3-hydroxy propane sulfonic acid, so that the introduction of a dehydrating agent is avoided, and the environment is friendly.
Compared with the prior art, the invention has the following beneficial effects:
according to the preparation method of the alkyl sultone, the yield of hydroxyalkoxyl sulfonic acid prepared by alkyl alcohol and sulfur trioxide is more than 99%, the yield of hydroxyalkoxyl sulfonic acid prepared by reduction reaction is more than 95%, the yield of solid superacid catalytic esterification dehydration reaction is more than 95%, and the yield of the whole process product is more than 90%. Compared with the prior art, the method has the advantages of low production cost, obvious reduction of three wastes, no use of toxic reagents and organic solvents, high product yield, economy, environmental protection and easy realization of industrialization.
The preparation method of the alkyl sultone has the advantages of low raw material cost, easy acquisition, no toxicity and harm, simple preparation method, high yield, high purity and environmental friendliness.
Detailed Description
The foregoing is further elaborated by the following description of embodiments of the present invention, which are given by way of example only, and should not be construed as limiting the scope of the present invention. All techniques implemented based on the above description of the invention are within the scope of the invention.
Solid superacid catalyst SO used in the present invention 4 2- /Fe 2 O 3 And SO 4 2- /TiO 2 Purchased from Nandina chemical Co., ltd., specification 200 mesh.
When the mass of the hydroxysulfonic acid in the aqueous solution of the hydroxysulfonic acid is measured by an acid-base titration method, a part of the aqueous solution of the hydroxysulfonic acid is taken for acid-base titration, and then the mass of the hydroxysulfonic acid in the total aqueous solution of the hydroxysulfonic acid is converted.
Example 1
Adding 0.7kg of 1, 3-propanediol and 1.4kg of dichloroethane into a reactor, dropwise adding a mixed solution of 0.7kg of sulfur trioxide and 0.7kg of dichloroethane into the reactor for esterification, controlling the dropwise adding speed of a sulfur trioxide-dichloroethane solution to be 0.04kg/min, controlling the temperature of the reactor to be 0 ℃ in the dropwise adding process, continuing to react for 1h after the dropwise adding of the sulfur trioxide-dichloroethane solution is finished, and distilling under reduced pressure to remove the solvent dichloroethane to obtain 1.42kg of 3-hydroxypropoxy sulfonic acid with the product yield of 99.2%; adding the obtained 3-hydroxy propoxy sulfonic acid into 2.84kg of deionized water, adding 1.15kg of sodium sulfite, heating to 80 ℃ for reflux reaction for 3 hours, and obtaining a reaction solution after the reaction is finished; adding 20% sulfuric acid aqueous solution into the obtained reaction solution, acidifying the reaction solution to pH 1, filtering to obtain filtrate of 3-hydroxy propanesulfonic acid aqueous solution, detecting 1.21kg of 3-hydroxy propanesulfonic acid by acid-base titration to obtain 95.2% yield, heating the 3-hydroxy propanesulfonic acid aqueous solution to 120deg.C, adding 0.012kg of SO 4 2- /Fe 2 O 3 The catalyst reacts for 3 hours, after the reaction is finished, the filtrate is filtered, and the 1.01kg of 1, 3-propane sultone is obtained through vacuum rectification, the yield is 95.9%, the total yield of the product is 90.2%, and the purity is 99.9%.
Example 2
Adding 0.9kg of 1, 4-butanediol and 1.8kg of dichloroethane into a reactor, dropwise adding a mixed solution of 0.8kg of sulfur trioxide and 0.8kg of dichloroethane into the reactor for esterification, controlling the dropwise adding speed of the sulfur trioxide-dichloroethane solution to be 0.08kg/min, controlling the temperature of the reactor to be 30 ℃ in the dropwise adding process, continuing to react for 1h after the dropwise adding of the sulfur trioxide-dichloroethane solution is finished, and distilling under reduced pressure to remove the solvent dichloroethane to obtain 1.68kg of 4-hydroxy-butoxyThe yield of the product of the monosulfonic acid is 99.1 percent; adding the obtained 4-hydroxy butoxy sulfonic acid into 5.04kg of deionized water, adding 0.71kg of sodium nitrite, heating to 100 ℃ for reflux reaction for 6 hours, and carrying out reduction reaction to obtain a reaction solution after the reaction is finished; adding 25% sulfuric acid aqueous solution into the obtained reaction solution, acidifying the reaction solution to pH 2, filtering to obtain 4-hydroxybutanesulfonic acid aqueous solution, detecting the mass of the 4-hydroxybutanesulfonic acid by acid-base titration to be 1.45kg, obtaining 95.5% yield, heating the 4-hydroxybutanesulfonic acid aqueous solution to 180 ℃, adding 0.07kg SO 4 2- /TiO 2 The catalyst reacts for 8 hours, after the reaction is finished, the filtrate is filtered, and the 1.23kg of 1, 4-butane sultone is obtained through vacuum distillation, the yield is 96.2 percent, the total yield of the product is 90.4 percent, and the purity is 99.9 percent.
Example 3
Adding 0.9kg of 1, 4-butanediol and 1.8kg of dichloroethane into a reactor, dropwise adding a mixed solution of 0.8kg of sulfur trioxide and 0.8kg of dichloroethane into the reactor for esterification, controlling the dropwise adding speed of a sulfur trioxide-dichloroethane solution to be 0.05kg/min, controlling the temperature of the reactor to be 0 ℃ in the dropwise adding process, continuing to react for 1h after the dropwise adding of the mixed solution of sulfur trioxide and dichloroethane is finished, and distilling under reduced pressure to remove the solvent dichloroethane to obtain 1.69kg of 4-hydroxybutoxysulfonic acid with the product yield of 99.5%; adding the obtained 4-hydroxy butoxy sulfonic acid into 4.2kg of deionized water, adding 1.26kg of sodium sulfite, heating to 90 ℃ for reflux reaction for 4 hours, and obtaining a reaction solution after the reaction is finished; adding 22% sulfuric acid aqueous solution into the obtained reaction solution, acidifying the reaction solution to pH 1, filtering to obtain 4-hydroxybutanesulfonic acid aqueous solution, detecting 1.47kg of 4-hydroxybutanesulfonic acid by acid-base titration to obtain 96.1% yield, heating the 4-hydroxybutanesulfonic acid aqueous solution to 120deg.C, adding 0.03kg of SO 4 2- /Fe 2 O 3 The catalyst reacts for 4 hours, after the reaction is finished, the filtrate is filtered, and the 1.25kg of 1, 4-butane sultone is obtained through vacuum rectification, the yield is 96.5%, the total yield of the product is 91.9%, and the purity is 99.9%.
Example 4
0.7kg of 1, 3-propanediol and 1.4kg of dichloroethane were fed into a reactor into which were droppedAdding 0.74kg of sulfur trioxide and 0.74kg of dichloroethane to perform esterification reaction, controlling the dropping speed of the sulfur trioxide-dichloroethane solution to be 0.06kg/min, controlling the temperature of a reactor in the dropping process to be 10 ℃, continuing to react for 1h after the completion of the dropping of the sulfur trioxide-dichloroethane solution, and distilling under reduced pressure to remove the solvent dichloroethane to obtain 1.43kg of 3-hydroxypropoxy sulfonic acid, wherein the product yield is 99.5%; adding the obtained 3-hydroxy propoxy sulfonic acid into 2.86kg of deionized water, adding 0.65kg of sodium nitrite, heating to 90 ℃ for reflux reaction for 5 hours, and obtaining a reaction solution after the reaction is finished; adding 24% sulfuric acid aqueous solution into the obtained reaction solution, acidifying the reaction solution to pH 1, filtering to obtain filtrate of 3-hydroxy propanesulfonic acid aqueous solution, detecting 1.24kg 3-hydroxy propanesulfonic acid by acid-base titration to obtain 96.3% yield, heating the 3-hydroxy propanesulfonic acid aqueous solution to 140 deg.C, adding 0.04kg SO 4 2- /TiO 2 The catalyst reacts for 7 hours, after the reaction is finished, the filtrate is filtered, and the 1.04kg of 1, 3-propane sultone is obtained through vacuum rectification, the yield is 96.6%, the total yield of the product is 92.7%, and the purity is 99.9%.
Example 5
Adding 0.9kg of 1, 4-butanediol and 1.8kg of dichloroethane into a reactor, dropwise adding a mixed solution of 0.8kg of sulfur trioxide and 0.8kg of dichloroethane into the reactor for esterification, controlling the dropwise adding speed of a sulfur trioxide-dichloroethane solution to be 0.06kg/min, controlling the temperature of the reactor to be 5 ℃ in the dropwise adding process, continuing to react for 1h after the dropwise adding of the sulfur trioxide-dichloroethane solution is finished, and distilling under reduced pressure to remove the solvent dichloroethane to obtain 1.69kg of 4-hydroxybutoxysulfonic acid with the product yield of 99.4%; adding the obtained 4-hydroxy butoxy sulfonic acid into 3.38kg of deionized water, adding 0.7kg of sodium nitrite, heating to 90 ℃ for reflux reaction for 5 hours, and obtaining a reaction solution after the reaction is finished; adding 20% sulfuric acid aqueous solution into the obtained reaction solution, acidifying the reaction solution to pH 1, filtering to obtain 4-hydroxybutanesulfonic acid aqueous solution, detecting the mass of the 4-hydroxybutanesulfonic acid by acid-base titration to 1.48kg, obtaining 96.4% yield, heating the 4-hydroxybutanesulfonic acid aqueous solution to 150deg.C, adding 0.037kg SO 4 2- /TiO 2 Reacting the catalyst for 5h, filtering after the reaction is finished, and filteringThe liquid is decompressed and rectified to obtain 1.26kg of 1, 4-butane sultone, the yield is 96.4%, the total yield of the product is 92.6%, and the purity is 99.9%.
Example 6
Adding 0.7kg of 1, 3-propanediol and 1.4kg of dichloroethane into a reactor, dropwise adding a mixed solution of 0.73kg of sulfur trioxide and 0.73kg of dichloroethane into the reactor for esterification, controlling the dropwise adding speed of a sulfur trioxide-dichloroethane solution to be 0.05kg/min, controlling the temperature of the reactor to be 20 ℃ in the dropwise adding process, continuing to react for 1h after the dropwise adding of the sulfur trioxide-dichloroethane solution is finished, and distilling under reduced pressure to remove the solvent dichloroethane to obtain 1.42kg of 3-hydroxypropoxy sulfonic acid with the product yield of 99.3%; adding the obtained 3-hydroxy propoxy sulfonic acid into 3.55kg of deionized water, adding 1.19kg of sodium sulfite, heating to 90 ℃ for reflux reaction for 4 hours, and obtaining a reaction solution after the reaction is finished; adding 20% sulfuric acid aqueous solution into the obtained reaction solution, acidifying the reaction solution to pH 1, filtering to obtain filtrate of 3-hydroxy propanesulfonic acid aqueous solution, detecting 1.22kg of 3-hydroxy propanesulfonic acid by acid-base titration to obtain 95.7% yield, heating the 3-hydroxy propanesulfonic acid aqueous solution to 170deg.C, adding 0.049kg of SO 4 2- /TiO 2 The catalyst reacts for 7 hours, after the reaction is finished, the filtrate is filtered, and the 1.02kg of 1, 3-propane sultone is obtained through vacuum rectification, the yield is 96.2%, the total yield of the product is 90.9%, and the purity is 99.9%.
While the foregoing describes the embodiments of the present invention, it is not intended to limit the scope of the present invention, and various modifications or variations may be made by those skilled in the art without the need for inventive effort on the basis of the technical solutions of the present invention.
Claims (8)
1. A preparation method of alkyl sultone is characterized in that: the method comprises the following steps:
(1) adding an alkyl alcohol-dichloroethane solution into a reactor, dropwise adding a sulfur trioxide-dichloroethane solution into the reactor, controlling the temperature of the reactor to be 0-30 ℃ in the dropwise adding process, and continuously carrying out esterification reaction for 1h after the completion of dropwise adding of the sulfur trioxide-dichloroethane solution, and removing solvent dichloroethane by reduced pressure distillation to obtain hydroxyalkoxy sulfonic acid;
the alkyl alcohol-dichloroethane solution consists of the following components in percentage by mass: 2 and dichloroethane;
the sulfur trioxide-dichloroethane solution consists of the following components in mass ratio of 1:1, mixing sulfur trioxide and dichloroethane;
the alkyl alcohol is 1, 3-propylene glycol or 1, 4-butanediol;
the molar ratio of the sulfur trioxide to the alkyl alcohol is 0.98-1: 1, a step of;
the dropping speed of the sulfur trioxide-dichloroethane solution is 0.04 kg-0.08 kg/min;
(2) adding the hydroxyalkoxyl sulfonic acid obtained in the step (1) into deionized water, adding a reducing agent, heating to 80-100 ℃, and carrying out reflux reaction for 3-6 hours to obtain a reaction solution after the reaction is finished;
the reducing agent is sodium sulfite or sodium nitrite;
the molar ratio of the hydroxyalkoxyl sulfonic acid to the reducing agent is 1:1-1.05;
the mass ratio of the hydroxyalkoxyl sulfonic acid to the deionized water is 1:2-3;
(3) adding a sulfuric acid aqueous solution with the mass concentration of 20-25% into the reaction solution obtained in the step (2), acidifying the reaction solution to a pH value of 1-2, filtering, wherein the filtrate is a hydroxysulfonic acid aqueous solution, determining the mass of hydroxysulfonic acid in the hydroxysulfonic acid aqueous solution by an acid-base titration method, heating the hydroxysulfonic acid aqueous solution to 120-180 ℃, adding a solid superacid catalyst for reaction for 3-8 hours, filtering after the reaction is finished, and distilling the filtrate under reduced pressure to obtain alkyl sultone;
the dosage of the solid super acid catalyst is 1% -5% of the mass of the hydroxysulfonic acid;
the solid super acid catalyst is SO 4 2- /Fe 2 O 3 Or SO 4 2- /TiO 2 。
2. The method for producing an alkylsulfonic acid lactone according to claim 1, wherein: the molar ratio of sulfur trioxide to alkyl alcohol is 1:1.
3. The method for producing an alkylsulfonic acid lactone according to claim 1, wherein: the reaction temperature in the step (1) is 0-10 ℃.
4. The method for producing an alkylsulfonic acid lactone according to claim 1, wherein: the molar ratio of the hydroxyalkoxysulfonic acid to the reducing agent is 1:1.01 to 1.03.
5. The method for producing an alkylsulfonic acid lactone according to claim 1, wherein: the acidifying pH value is 1.
6. The method for producing an alkylsulfonic acid lactone according to claim 1, wherein: the dosage of the solid super acid catalyst is 2% -3% of the mass of the hydroxysulfonic acid.
7. The method for producing an alkylsulfonic acid lactone according to claim 1, wherein: the heating temperature in the step (3) is 150-170 ℃.
8. The method for producing an alkylsulfonic acid lactone according to claim 1, wherein: the reaction time in the step (3) is 5-8 h.
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| CN105348254A (en) * | 2015-12-11 | 2016-02-24 | 何琦 | Method for preparing 1,3-propane sultone |
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| CN114805288A (en) * | 2021-01-20 | 2022-07-29 | 武汉松石科技股份有限公司 | Method for preparing 2, 4-butane sultone |
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