CN115745948A - Preparation method of 1, 3-propane sultone - Google Patents
Preparation method of 1, 3-propane sultone Download PDFInfo
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- CN115745948A CN115745948A CN202211526307.6A CN202211526307A CN115745948A CN 115745948 A CN115745948 A CN 115745948A CN 202211526307 A CN202211526307 A CN 202211526307A CN 115745948 A CN115745948 A CN 115745948A
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- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 66
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims abstract description 54
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 47
- WQPMYSHJKXVTME-UHFFFAOYSA-N 3-hydroxypropane-1-sulfonic acid Chemical compound OCCCS(O)(=O)=O WQPMYSHJKXVTME-UHFFFAOYSA-N 0.000 claims abstract description 46
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims abstract description 39
- LAMUXTNQCICZQX-UHFFFAOYSA-N 3-chloropropan-1-ol Chemical compound OCCCCl LAMUXTNQCICZQX-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000007788 liquid Substances 0.000 claims abstract description 32
- 239000007787 solid Substances 0.000 claims abstract description 29
- 239000000047 product Substances 0.000 claims abstract description 21
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 20
- 239000002994 raw material Substances 0.000 claims abstract description 19
- 239000012043 crude product Substances 0.000 claims abstract description 12
- 239000007789 gas Substances 0.000 claims abstract description 10
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 9
- 230000020477 pH reduction Effects 0.000 claims abstract description 8
- 238000006277 sulfonation reaction Methods 0.000 claims abstract description 6
- 238000007363 ring formation reaction Methods 0.000 claims abstract description 5
- 230000009471 action Effects 0.000 claims abstract description 4
- 230000006837 decompression Effects 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 46
- 238000001914 filtration Methods 0.000 claims description 19
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- KJIFKLIQANRMOU-UHFFFAOYSA-N oxidanium;4-methylbenzenesulfonate Chemical compound O.CC1=CC=C(S(O)(=O)=O)C=C1 KJIFKLIQANRMOU-UHFFFAOYSA-N 0.000 claims description 18
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 14
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- 235000010265 sodium sulphite Nutrition 0.000 claims description 8
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 claims description 6
- 229940035437 1,3-propanediol Drugs 0.000 claims description 6
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 claims description 6
- 229940092714 benzenesulfonic acid Drugs 0.000 claims description 6
- 229920000166 polytrimethylene carbonate Polymers 0.000 claims description 6
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 3
- 239000008096 xylene Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- 239000002904 solvent Substances 0.000 abstract description 10
- 231100000053 low toxicity Toxicity 0.000 abstract description 2
- 238000000605 extraction Methods 0.000 abstract 1
- 238000000746 purification Methods 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 description 17
- 238000003756 stirring Methods 0.000 description 16
- 238000003786 synthesis reaction Methods 0.000 description 16
- 230000015572 biosynthetic process Effects 0.000 description 15
- 239000012295 chemical reaction liquid Substances 0.000 description 11
- 238000002156 mixing Methods 0.000 description 11
- 238000002390 rotary evaporation Methods 0.000 description 11
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 8
- 238000001816 cooling Methods 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 238000009833 condensation Methods 0.000 description 5
- 230000005494 condensation Effects 0.000 description 5
- 238000001704 evaporation Methods 0.000 description 5
- 238000003760 magnetic stirring Methods 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 230000002194 synthesizing effect Effects 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 230000018044 dehydration Effects 0.000 description 4
- 238000006297 dehydration reaction Methods 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- YHRUOJUYPBUZOS-UHFFFAOYSA-N 1,3-dichloropropane Chemical compound ClCCCCl YHRUOJUYPBUZOS-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical compound ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 238000010533 azeotropic distillation Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- KCXFHTAICRTXLI-UHFFFAOYSA-N propane-1-sulfonic acid Chemical compound CCCS(O)(=O)=O KCXFHTAICRTXLI-UHFFFAOYSA-N 0.000 description 2
- 238000006798 ring closing metathesis reaction Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N 1-propanol Substances CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000012320 chlorinating reagent Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 150000003983 crown ethers Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000002481 ethanol extraction Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 231100000171 higher toxicity Toxicity 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
- 238000003402 intramolecular cyclocondensation reaction Methods 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000035943 smell Effects 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
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- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention discloses a preparation method of 1, 3-propane sultone. The preparation method of the 1, 3-propane sultone comprises the following steps: (1) 1, 3-propylene glycol and concentrated hydrochloric acid are used as raw materials to react under the action of a catalyst, and the fraction with the temperature of 50-60 ℃ is distilled to be 3-chloro-1-propanol; (2) Sequentially adding a sulfonating agent and water into 3-chloro-1-propanol for sulfonation reaction, dropwise adding concentrated hydrochloric acid into the solid obtained by water removal to adjust the pH value, introducing hydrogen chloride gas into the filtered liquid for acidification to obtain a crude product of 3-hydroxypropanesulfonic acid, adding the crude product of 3-hydroxypropanesulfonic acid into a water-carrying agent for azeotropic purification, extracting a residual base solution after azeotropic extraction by using ethyl acetate, and concentrating to obtain a pure product of 3-hydroxypropanesulfonic acid; (3) And carrying out high-temperature vacuum decompression ring closing reaction on the pure product of the 3-hydroxypropanesulfonic acid to obtain the 1, 3-propane sultone. The invention uses 1, 3-propylene glycol as raw material, has low cost and low toxicity, can be continuously used, can recycle the solvent used in the post-treatment, and can prepare high-yield and high-purity products.
Description
The technical field is as follows:
the invention relates to the technical field of chemical synthesis, in particular to a preparation method of 1, 3-propane sultone.
The background art comprises the following steps:
the 1, 3-propane sultone is colorless or light yellow transparent liquid (above 31 ℃) or colorless transparent crystals (below 31 ℃), is widely applied to the fields of dyes, medicines, surfactants and the like, and is applied to lithium batteries along with the development of green energy lithium ion batteries to enhance the cycle times and the service life of the batteries. In recent years, the application of the compound has become wider and the market demand has increased year by year.
At present, the raw materials for synthesizing the 1, 3-propane sultone mainly comprise the following materials:
(1) The preparation method of the 1, 3-propane sultone is disclosed in patent CN106146453A, wherein allyl alcohol and sodium bisulfite are used as raw materials, water is used as a solvent, sodium persulfate, hydrogen peroxide and ferrous sulfate are used as initiators, sulfuric acid acidification, ethanol extraction and high-temperature rectification are carried out, the raw material allyl alcohol has unsaturated double bonds, reaction site selectivity exists in the reaction, and meanwhile, the raw material allyl alcohol has high toxicity and belongs to a tube product, the cost is high, and sulfuric acid is difficult to remove when acidification is carried out.
Patent CN101456855A discloses a preparation method of 1, 3-propane sultone, which uses allyl alcohol, bisulfite and sulfite as raw materials, water as solvent, crown ether as catalyst, uses hydrochloric acid to acidify hydroxyl-containing propane sulfonate, extracts ethanol, and rectifies at high temperature to obtain 1, 3-propane sultone.
(2) 3-chloropropanol is taken as a raw material, and a patent CN110105326A discloses a preparation method of 1, 3-propane sultone, wherein 3-chloropropanol and sodium sulfite are taken as raw materials, water is taken as a solvent, and hydroxyl-containing propane sulfonate is acidified by hydrochloric acid, so that the cost of the raw material 3-chloropropanol used in the process is relatively high, and the problem of high chloride ion content also exists.
(3) Allyl chloride is used as a raw material, and patent CN104803967A discloses a preparation method of 1, 3-propane sultone, which uses cheap allyl chloride as a raw material to prepare a target product through four steps of substitution, addition, hydrolysis and cyclization, but the allyl chloride belongs to flammable liquid and has corrosive and pungent smells, and the preparation process is dangerous.
(4) 1, 3-dichloropropane is taken as a raw material, and a patent CN108164502A discloses a preparation method of 1, 3-propane sultone, 1, 3-dichloropropane and sulfur dioxide are reacted in acetonitrile in the presence of tetraethylammonium bromide under the action of constant current to obtain the 1, 3-propane sultone, and the 1, 3-dichloropropane which is taken as the raw material belongs to flammable liquid and has higher toxicity.
The method for synthesizing the 1, 3-propane sultone has the defects of higher physical property toxicity of raw materials, higher cost, lower product purity, difficult industrialization and incapability of meeting the market demand of the 1, 3-propane sultone.
The invention content is as follows:
the invention solves the problems in the prior art and provides a preparation method of 1, 3-propane sultone, which uses 1, 3-propylene glycol as a raw material, has low cost and low toxicity, can be continuously used, can recycle a solvent used in post-treatment, and can prepare a high-yield and high-purity product.
The invention aims to provide a preparation method of 1, 3-propane sultone, which comprises the following steps:
(1) 1, 3-propylene glycol and concentrated hydrochloric acid are used as raw materials and react under the action of a catalyst, the low fraction of 50-60 ℃ is distilled to be 3-chloro-1-propanol, and the high fraction is circulated to react and distill;
(2) Sequentially adding a sulfonating agent and water into the 3-chloro-1-propanol obtained in the step (1) to perform sulfonation reaction, dropwise adding concentrated hydrochloric acid into the solid obtained after water removal to adjust the pH value to 4-6, filtering, introducing hydrogen chloride gas into the filtered liquid to acidify and saturate the solution, wherein the obtained liquid is a crude 3-hydroxypropanesulfonic acid product, adding the crude 3-hydroxypropanesulfonic acid product into a water-carrying agent to perform azeotropic distillation to remove water and chloride ions, extracting residual base liquid after azeotropic distillation by using ethyl acetate, and concentrating to obtain a pure 3-hydroxypropanesulfonic acid product;
(3) And (3) carrying out high-temperature vacuum decompression ring-closing reaction on the pure 3-hydroxypropanesulfonic acid, and collecting 120-150 ℃ fractions to obtain the 1, 3-propanesultone.
The steps (1) to (3) can be followed by GC to determine the progress of the reaction (i.e., the reaction time).
Preferably, the catalyst in step (1) is selected from more than one of p-toluenesulfonic acid monohydrate, benzenesulfonic acid and zinc chloride. The distillation temperature of the low fraction 3-chloro-1-propanol distilled in the step (1) is 40-60 ℃, and the vacuum degree is 10-100Pa.
In the step (1), hydrochloric acid is taken as a chlorinating agent, and p-toluenesulfonic acid monohydrate is taken as a catalyst, and the reaction equation for synthesizing 3-chloro-1-propanol is shown as the formula I:
formula I
Preferably, the molar ratio of the 1, 3-propanediol to the concentrated hydrochloric acid in the step (1) is 1: (1-5), the molar ratio of the catalyst to the 1, 3-propanediol is (0.01-0.9): 1.
preferably, the reaction temperature in the step (1) is 30-110 ℃, and the reaction time is 3-10 hours.
Preferably, the molar ratio of the 3-chloro-1-propanol to the sulfonating agent in the step (2) is 1 (1-2), and the mass ratio of the water to the sulfonating agent is 2-10: 1.
preferably, the sulfonating agent in the step (2) is sodium sulfite or sodium bisulfite, the sulfonation reaction temperature is 30-110 ℃, and the reaction time is 1-8 hours.
In the step (2), the reaction equation for synthesizing the 3-hydroxypropanesulfonic acid is shown as a formula II by taking sodium sulfite as a sulfonating agent and toluene as a water-carrying agent as an example:
formula II
Preferably, the acidification time in step (2) is 0.5 to 3 hours. The acidification is carried out at normal temperature.
Preferably, the water-carrying agent in step (2) is selected from more than one of toluene, benzene and xylene. The mass ratio of the crude 3-hydroxypropanesulfonic acid to the water-carrying agent is 1.
Preferably, the temperature of the azeotropic mixture in the step (2) is 80-130 ℃ and the time is 1-3 hours.
Preferably, the reaction temperature in the step (3) is 90-180 ℃, and the vacuum degree is 10-100pa.
The reaction equation for synthesizing 1, 3-propane sultone is shown as formula III:
compared with the prior art, the invention has the following advantages:
1. the conventional reduced pressure distillation method for obtaining 1, 3-propane sultone requires a high temperature of more than 100 ℃ to dehydrate 3-hydroxypropanesulfonic acid into rings, and the method has the following consequences that under a reduced pressure environment, at the same time under the condition of more than 100 ℃, the 1, 3-propane sultone which is a product of intramolecular dehydration and ring closure and the dehydrated water are distilled out simultaneously, so that the water generated by the reaction cannot be effectively removed, the water generated by the reaction still exists in the distilled product, and the product can be decomposed to a certain extent under the environment with water, which indicates that the direct reduced pressure distillation and dehydration cannot solve the problem. The invention uses water-carrying agent under normal pressure, firstly takes out water and chloride ions in a 3-hydroxy propane sulfonic acid system, the 3-hydroxy propane sulfonic acid generates intramolecular dehydration and cyclization with the rise of temperature, the product 1, 3-propane sultone can not be simultaneously taken out under normal pressure, after taking out the water generated by intramolecular cyclization, only the product 1, 3-propane sultone and water-carrying agent remain in the system, at this time, reduced pressure distillation is carried out, and the water-carrying agent and the high-purity water-free 1, 3-propane sultone are respectively obtained.
2. The raw material 1, 3-propylene glycol used in the invention is nontoxic, has low cost, high reaction rate in the chlorination process, can be recycled and has high utilization rate;
3. the sulfonation process is simple, after acidification by hydrochloric acid, hydrogen chloride gas is used for treatment, the acidification degree is improved, simultaneously, the solid is easy to be completely saturated and separated out, and the solid impurities of the 3-hydroxypropanesulfonic acid are reduced.
Description of the drawings:
FIG. 1 is a hydrogen spectrum of 3-hydroxypropanesulfonic acid obtained in example 1;
FIG. 2 is a hydrogen spectrum of 1, 3-propane sultone obtained in example 1.
The specific implementation mode is as follows:
the following examples are further illustrative of the present invention and are not intended to be limiting thereof.
Unless otherwise defined, all terms of art used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention. Unless otherwise specified, the experimental materials and reagents used herein are all conventional commercial products in the art. The following examples were all commercially available as biological enzymes.
Example 1
The preparation method of the 1, 3-propane sultone comprises the following steps:
synthesis of 1-1, 3-chloro-1-propanol
Adding 1, 3-propylene glycol (10g, 0.132mol) and p-toluenesulfonic acid monohydrate (5 percent, namely the mass percentage of the p-toluenesulfonic acid monohydrate to the 1, 3-propylene glycol) into a two-mouth bottle with magnetic stirring at room temperature, heating to 90 ℃, slowly dropwise adding concentrated hydrochloric acid (26.04 g) in the heating process to adjust the pH value to 5, maintaining the reaction temperature at 90 ℃, and performing closed condensation under reflux to prevent the hydrochloric acid from being excessively volatilized; and (3) tracing the reaction liquid by using GC, stopping the reaction when detecting that the content of the 1, 3-propylene glycol is lower than 10 percent of that of the 1, 3-propylene glycol in the initial reaction, reacting for 6 hours totally, cooling to 50-60 ℃, and decompressing to obtain a fraction, namely 3-chloro-1-propanol (yield is 84 percent), wherein the rest high fraction substance is continuously reacted and recycled.
Synthesis of 1-2, 3-hydroxypropanesulfonic acid
Adding 3-chloro-1-propanol (10.48g, 0.111mol), sodium sulfite (14.49 g) and deionized water (100 mL) into a two-neck bottle, mixing, stirring, and heating to 60 ℃ for reaction; tracking the reaction liquid by using GC, stopping the reaction when no 3-chloro-1-propanol is detected, removing water by rotary evaporation, slowly dripping hydrochloric acid into the obtained solid while stirring in an ice bath to fully and uniformly stir the solid, and then maintaining the room temperature for reaction; filtering, introducing hydrogen chloride gas into the liquid to saturate the liquid until no solid is separated out, maintaining for 30 minutes, filtering again to obtain the liquid which is a crude product of the 3-hydroxypropanesulfonic acid (yield is 95%), mixing the crude product of the 3-hydroxypropanesulfonic acid (14.77g, 0.105mol) with 46g of toluene, carrying water at normal pressure at 108 ℃ until no water is carried out, completely evaporating the solvent, washing the solid at the bottom of a bottle with ethyl acetate (10mL x 5) after the solid is cooled, filtering, and carrying out rotary evaporation on the liquid (50 ℃) to remove the ethyl acetate to obtain a pure product of the 3-hydroxypropanesulfonic acid (purity is 99%).
Synthesis of 1-3, 1, 3-propane sultone
The obtained 3-hydroxy propane sulfonic acid is distilled under reduced pressure at 130 ℃ and 10pa, and the fraction at 120 ℃ to 150 ℃ is collected, namely the light yellow or colorless 1, 3-propane sultone (yield is 92%).
Comparative example 1
The same as example 1, except that: adding 3-chloro-1-propanol (18.77g, 0.198mol), sodium sulfite (30.03 g) and deionized water (150 mL) into a two-neck bottle, mixing, stirring, and heating to 60 ℃ for reaction; tracking the reaction liquid by using GC, stopping the reaction when no 3-chloro-1-propanol is detected, removing water by rotary evaporation, slowly dripping hydrochloric acid into the obtained solid while stirring in an ice bath to fully and uniformly stir the solid, and then maintaining the room temperature for reaction; filtering, introducing hydrogen chloride gas into the liquid to saturate the liquid until no solid is separated out, maintaining for 30 minutes, and filtering again to obtain the liquid, namely the crude product of the 3-hydroxypropanesulfonic acid (yield is 95%). Directly distilling the crude product of 3-hydroxypropanesulfonic acid at the temperature of 130 ℃ and the vacuum degree of 10pa, wherein the yield of 1, 3-propanesultone obtained by molecular dehydration and ring closure at high temperature and high pressure is 50 percent, and meanwhile, the undistilled fraction is carbonized into black solid impurities.
Example 2
The preparation method of the 1, 3-propane sultone comprises the following steps:
synthesis of 2-1, 3-chloro-1-propanol
Adding 1, 3-propylene glycol (10g, 0.132mol) and benzenesulfonic acid (5 percent, namely the mass percent of benzenesulfonic acid/1, 3-propylene glycol) into a two-mouth bottle with magnetic stirring at room temperature, heating to 80 ℃, slowly dropwise adding concentrated hydrochloric acid (39.06 g) in the heating process to adjust the pH value to 4, maintaining the reaction temperature at 80 ℃, and performing closed condensation reflux to prevent the hydrochloric acid from being excessively volatilized; and (3) tracing the reaction liquid by using GC, stopping the reaction when the content of the 1, 3-propylene glycol is detected to be lower than 10 percent of that of the 1, 3-propylene glycol in the initial reaction, reducing the temperature to 50-60 ℃, and obtaining a fraction, namely 3-chloro-1-propanol (the yield is 80 percent) by reducing the pressure, wherein the rest high fraction substances are continuously reacted and recycled.
Synthesis of 2-2, 3-hydroxypropanesulfonic acid
Adding 3-chloro-1-propanol (9.98g, 0.105mol), sodium bisulfite (27.98 g) and deionized water (150 mL) into a two-mouth bottle, mixing, stirring, and heating to 60 ℃ for reaction; the reaction liquid is tracked by GC, the reaction is stopped when no 3-chlorine-1-propanol is detected, water is removed by rotary evaporation, the obtained solid is stirred and slowly dripped with hydrochloric acid under ice bath to be fully and uniformly stirred, and then the reaction is carried out at room temperature; filtering, introducing hydrogen chloride gas into the liquid to saturate the liquid until no solid is separated out, maintaining for 60 minutes, and filtering again to obtain the liquid, namely the crude product of the 3-hydroxypropanesulfonic acid (yield is 93%). Mixing crude 3-hydroxypropanesulfonic acid (13.687 mol, 0.097mol) with 40g of benzene, carrying water at 110 ℃ under normal pressure until no more water is carried out, completely evaporating the solvent, cooling the bottom solid, washing with ethyl acetate (10mL x 5), filtering, and carrying out rotary evaporation of the liquid (50 ℃) to remove ethyl acetate to obtain a pure 3-hydroxypropanesulfonic acid product.
Synthesis of 2-3, 1, 3-propane sultone
Distilling 3-hydroxypropanesulfonic acid at 120 ℃ and 20pa under reduced pressure, and collecting the fraction at 120 ℃ to 150 ℃, namely pale yellow or colorless 1, 3-propanesultone (yield is 94%).
Example 3
The preparation method of the 1, 3-propane sultone comprises the following steps:
synthesis of 3-1, 3-chloro-1-propanol
Adding 1, 3-propylene glycol (10g, 0.132mol) and benzenesulfonic acid (9 percent, namely the amount percentage of benzenesulfonic acid/1, 3-propylene glycol) into a two-mouth bottle with magnetic stirring at room temperature, heating to 90 ℃, slowly dropwise adding concentrated hydrochloric acid (39.06 g) in the heating process to adjust the pH value to 4, maintaining the reaction temperature at 90 ℃, and performing closed condensation under reflux to prevent the hydrochloric acid from being excessively volatilized; and (3) tracing the reaction liquid by using GC, stopping the reaction when the content of the 1, 3-propylene glycol is detected to be lower than 10 percent of that of the 1, 3-propylene glycol in the initial reaction, reducing the temperature to 50-60 ℃, and obtaining a fraction, namely 3-chloro-1-propanol (the yield is 82 percent) by reducing the pressure, wherein the rest high fraction substances are continuously reacted and recycled.
Synthesis of 3-2, 3-hydroxypropanesulfonic acid
Adding 3-chloro-1-propanol (10.23g, 0.108mol), sodium bisulfite (27.98 g) and deionized water (150 mL) into a two-mouth bottle, mixing, stirring, and heating to 80 ℃ for reaction; tracking the reaction liquid by using GC, stopping the reaction when no 3-chloro-1-propanol is detected, removing water by rotary evaporation, slowly dripping hydrochloric acid into the obtained solid while stirring in an ice bath to fully and uniformly stir the solid, and then maintaining the room temperature for reaction; filtering, introducing hydrogen chloride gas into the liquid to saturate the liquid until no solid is separated out, maintaining for 60 minutes, and filtering again to obtain the liquid, namely the crude product of the 3-hydroxypropanesulfonic acid (yield is 95%). Mixing the obtained crude 3-hydroxypropanesulfonic acid (14.38g, 0.102mol) with 45g of xylene, carrying water at 110 ℃ under normal pressure until no more water is carried out, completely evaporating the solvent, cooling the bottle bottom solid, washing with ethyl acetate (10mL × 5), filtering, and carrying out liquid rotary evaporation (50 ℃) to remove the ethyl acetate to obtain a pure 3-hydroxypropanesulfonic acid.
Synthesis of 3-3, 1, 3-propane sultone
Distilling the pure product of the 3-hydroxypropanesulfonic acid at high temperature (160 ℃,10 pa) under reduced pressure, and collecting the fraction of 120-150 ℃, namely pale yellow or colorless 1, 3-propanesultone (yield 93.5%).
Example 4
The preparation method of the 1, 3-propane sultone comprises the following steps:
synthesis of 4-1, 3-chloro-1-propanol
Adding 1, 3-propylene glycol (10g, 0.132mol) and p-toluenesulfonic acid monohydrate (1 percent, namely the mass percent of the p-toluenesulfonic acid monohydrate to the 1, 3-propylene glycol) into a two-mouth bottle with magnetic stirring at room temperature, heating to 30 ℃, slowly dropwise adding concentrated hydrochloric acid (13 g) in the heating process to adjust the pH value to 5, keeping the reaction temperature at 30 ℃, and performing closed condensation under reflux to prevent the hydrochloric acid from being excessively volatilized; and tracking the reaction liquid by using GC, stopping the reaction when detecting that the content of the 1, 3-propanediol is lower than 10 percent of that of the 1, 3-propanediol in the initial reaction, reacting for 10 hours totally, heating to 50-60 ℃, decompressing to obtain a fraction, namely 3-chloro-1-propanol (yield is 50 percent), and continuously reacting the rest high fraction substances for recycling.
Synthesis of 4-2, 3-hydroxypropanesulfonic acid
Adding 3-chloro-1-propanol (6.22g, 0.066 mol), sodium sulfite (2.117 g) and deionized water (3 mL) into a two-mouth bottle, mixing, stirring, and heating to 30 ℃ for reaction; tracing the reaction liquid by using GC, stopping the reaction when no 3-chloro-1-propanol is detected, removing water by rotary evaporation, stirring the obtained solid in an ice bath while slowly dropwise adding hydrochloric acid to fully and uniformly stir the solid, and then maintaining the room temperature for reaction; filtering, introducing hydrogen chloride gas into the liquid to saturate the liquid until no solid is separated out, maintaining for 60 minutes, filtering again to obtain the liquid which is a crude product of the 3-hydroxypropanesulfonic acid (yield is 85%), mixing the crude product of the 3-hydroxypropanesulfonic acid (7.86g, 0.056 mol) with 30g of toluene, carrying water at the normal pressure for 3 hours at the temperature of 80 ℃, carrying no water out, completely evaporating the solvent, washing the solid at the bottom of a bottle with ethyl acetate (5 mL. About.5) after cooling, filtering, and carrying out rotary evaporation on the liquid (50 ℃) to remove the ethyl acetate to obtain a pure product of the 3-hydroxypropanesulfonic acid (purity is 99%).
Synthesis of 4-3, 1, 3-propane sultone
Distilling the obtained 3-hydroxy propane sulfonic acid at 90 deg.C under reduced pressure of 100pa, and collecting 120-150 deg.C fraction, which is pale yellow or colorless 1, 3-propane sultone (yield 60%).
Example 5
The preparation method of the 1, 3-propane sultone comprises the following steps:
synthesis of 5-1, 3-chloro-1-propanol
Adding 1, 3-propylene glycol (10g, 0.132mol) and p-toluenesulfonic acid monohydrate (9 percent, namely the mass percent of the p-toluenesulfonic acid monohydrate to the 1, 3-propylene glycol) into a two-mouth bottle with magnetic stirring at room temperature, heating to 30 ℃, slowly dropwise adding concentrated hydrochloric acid (65 g) in the heating process to adjust the pH value to 5, keeping the reaction temperature at 110 ℃, and performing closed condensation under reflux to prevent the hydrochloric acid from being excessively volatilized; and (3) tracing the reaction liquid by using GC, stopping the reaction when detecting that the content of the 1, 3-propylene glycol is lower than 10 percent of that of the 1, 3-propylene glycol in the initial reaction, reacting for 3 hours totally, cooling to 50-60 ℃, and decompressing to obtain a fraction, namely 3-chloro-1-propanol (yield is 70 percent), wherein the rest high fraction substance is continuously reacted and recycled.
Synthesis of 5-2, 3-hydroxypropanesulfonic acid
Adding 3-chloro-1-propanol (8.73g, 0.092mol), sodium sulfite (28.73 g) and deionized water (287 mL) into a two-neck bottle, mixing, stirring, and heating to 110 ℃ for reaction; tracing the reaction liquid by using GC, stopping the reaction when no 3-chloro-1-propanol is detected, removing water by rotary evaporation, stirring the obtained solid in an ice bath while slowly dropwise adding hydrochloric acid to fully and uniformly stir the solid, and then maintaining the room temperature for reaction; filtering, introducing hydrogen chloride gas into the liquid to saturate the liquid until no solid is separated out, maintaining for 3 hours, filtering again to obtain the liquid which is the crude 3-hydroxypropanesulfonic acid (yield is 94%), mixing the crude 3-hydroxypropanesulfonic acid (12.12g, 0.086 mol) with 45g of toluene, carrying water at the temperature of 130 ℃ for 1 hour under normal pressure, removing no water, completely evaporating the solvent, cooling the solid at the bottom of the bottle, washing with ethyl acetate (2mL 05), filtering, and carrying out rotary evaporation on the liquid (50 ℃) to remove ethyl acetate to obtain the pure 3-hydroxypropanesulfonic acid (purity is 99%).
Synthesis of 5-3, 1, 3-propane sultone
Distilling the obtained 3-hydroxy propane sulfonic acid at 180 ℃ under reduced pressure of 10pa, and collecting the fraction at 120-150 ℃ to obtain pale yellow or colorless 1, 3-propane sultone (yield 88%).
The above embodiments are only for the purpose of helping understanding the technical solution of the present invention and the core idea thereof, and it should be noted that those skilled in the art can make several improvements and modifications to the present invention without departing from the principle of the present invention, and these improvements and modifications also fall within the protection scope of the claims of the present invention.
Claims (10)
1. A preparation method of 1, 3-propane sultone is characterized by comprising the following steps:
(1) 1, 3-propanediol and concentrated hydrochloric acid are taken as raw materials, and react under the action of a catalyst, and low fraction at 50-60 ℃ is distilled to obtain 3-chloro-1-propanol;
(2) Sequentially adding a sulfonating agent and water into the 3-chloro-1-propanol obtained in the step (1) to carry out sulfonation reaction, dropwise adding concentrated hydrochloric acid into a solid obtained by water removal to adjust the pH value to 4-6, filtering, introducing hydrogen chloride gas into the filtered liquid to acidify and saturate the solution, wherein the obtained liquid is a crude product of 3-hydroxypropanesulfonic acid, adding the crude product of 3-hydroxypropanesulfonic acid into a water-carrying agent to carry out azeotropy for purifying water and chloride ions, extracting a residual base solution after azeotropy by using ethyl acetate, and concentrating to obtain a pure product of 3-hydroxypropanesulfonic acid;
(3) And (3) carrying out high-temperature vacuum decompression ring-closing reaction on the pure 3-hydroxypropanesulfonic acid, and collecting 120-150 ℃ fractions to obtain the 1, 3-propanesultone.
2. The method according to claim 1, wherein the catalyst in step (1) is one or more selected from the group consisting of p-toluenesulfonic acid monohydrate, benzenesulfonic acid and zinc chloride.
3. The method according to claim 1 or 2, wherein the molar ratio of 1, 3-propanediol to concentrated hydrochloric acid in step (1) is 1: (1-5), the molar ratio of the catalyst to the 1, 3-propylene glycol is (0.01-0.9): 1.
4. the method according to claim 1, wherein the reaction temperature in the step (1) is 30 to 110 ℃ and the reaction time is 3 to 10 hours.
5. The preparation method according to claim 1, wherein the molar ratio of the 3-chloro-1-propanol to the sulfonating agent in the step (2) is 1 (1-2), and the mass ratio of the water to the sulfonating agent is 2-10: 1.
6. the method according to claim 1 or 5, wherein the sulfonating agent in step (2) is sodium sulfite or sodium bisulfite, the sulfonation reaction temperature is 30 ℃ to 110 ℃, and the reaction time is 1 to 8 hours.
7. The method according to claim 1, wherein the acidification time in the step (2) is 0.5 to 3 hours.
8. The method according to claim 1, wherein the water-carrying agent in step (2) is one or more selected from the group consisting of toluene, benzene, and xylene.
9. The process according to claim 1 or 8, wherein the azeotropic mixture in the step (2) is heated at 80 to 130 ℃ for 1 to 3 hours.
10. The method according to claim 1, wherein the reaction temperature in step (3) is 90 ℃ to 180 ℃ and the degree of vacuum is 10 to 100pa.
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|---|---|---|---|---|
| JP2002179600A (en) * | 2000-12-08 | 2002-06-26 | Tosoh Corp | Method for producing high-purity 3-chloro-1-propanol |
| CN101157681A (en) * | 2007-11-01 | 2008-04-09 | 姜俊 | Method for preparing 1,3 propane sultone |
| CN104803967A (en) * | 2015-04-20 | 2015-07-29 | 荣成青木高新材料股份有限公司 | Method for preparing 1,3-propane sultone |
| CN110105326A (en) * | 2019-02-26 | 2019-08-09 | 武汉松石科技股份有限公司 | A kind of preparation method of 1,3- propane sultone |
| CN110668918A (en) * | 2019-10-22 | 2020-01-10 | 邹平铭兴化工有限公司 | Chemical synthesis method of 3-chloro-1-propanol |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002179600A (en) * | 2000-12-08 | 2002-06-26 | Tosoh Corp | Method for producing high-purity 3-chloro-1-propanol |
| CN101157681A (en) * | 2007-11-01 | 2008-04-09 | 姜俊 | Method for preparing 1,3 propane sultone |
| CN104803967A (en) * | 2015-04-20 | 2015-07-29 | 荣成青木高新材料股份有限公司 | Method for preparing 1,3-propane sultone |
| CN110105326A (en) * | 2019-02-26 | 2019-08-09 | 武汉松石科技股份有限公司 | A kind of preparation method of 1,3- propane sultone |
| CN110668918A (en) * | 2019-10-22 | 2020-01-10 | 邹平铭兴化工有限公司 | Chemical synthesis method of 3-chloro-1-propanol |
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