CN114478570B - Preparation method of pentaerythritol sulfate - Google Patents
Preparation method of pentaerythritol sulfate Download PDFInfo
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- CN114478570B CN114478570B CN202111617293.4A CN202111617293A CN114478570B CN 114478570 B CN114478570 B CN 114478570B CN 202111617293 A CN202111617293 A CN 202111617293A CN 114478570 B CN114478570 B CN 114478570B
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- HVTSNLIAMONEHW-UHFFFAOYSA-N [3-hydroxy-2,2-bis(hydroxymethyl)propyl] hydrogen sulfate Chemical compound OCC(CO)(CO)COS(O)(=O)=O HVTSNLIAMONEHW-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims abstract description 22
- -1 sulfur trioxide Lewis base Chemical class 0.000 claims abstract description 20
- 238000007363 ring formation reaction Methods 0.000 claims abstract description 19
- 239000002904 solvent Substances 0.000 claims abstract description 18
- 238000006277 sulfonation reaction Methods 0.000 claims abstract description 17
- 239000002879 Lewis base Substances 0.000 claims abstract description 15
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Inorganic materials O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000012024 dehydrating agents Substances 0.000 claims abstract description 14
- 239000011261 inert gas Substances 0.000 claims abstract description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 239000000741 silica gel Substances 0.000 claims description 12
- 229910002027 silica gel Inorganic materials 0.000 claims description 12
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 12
- 239000012295 chemical reaction liquid Substances 0.000 claims description 10
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 9
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 8
- 239000003208 petroleum Substances 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- DXASQZJWWGZNSF-UHFFFAOYSA-N n,n-dimethylmethanamine;sulfur trioxide Chemical compound CN(C)C.O=S(=O)=O DXASQZJWWGZNSF-UHFFFAOYSA-N 0.000 claims description 7
- UDYFLDICVHJSOY-UHFFFAOYSA-N sulfur trioxide-pyridine complex Substances O=S(=O)=O.C1=CC=NC=C1 UDYFLDICVHJSOY-UHFFFAOYSA-N 0.000 claims description 7
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims description 6
- 239000011592 zinc chloride Substances 0.000 claims description 6
- 235000005074 zinc chloride Nutrition 0.000 claims description 6
- 238000004821 distillation Methods 0.000 claims description 5
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 4
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 239000002808 molecular sieve Substances 0.000 claims description 4
- YYHPEVZFVMVUNJ-UHFFFAOYSA-N n,n-diethylethanamine;sulfur trioxide Chemical compound O=S(=O)=O.CCN(CC)CC YYHPEVZFVMVUNJ-UHFFFAOYSA-N 0.000 claims description 4
- AFDQGRURHDVABZ-UHFFFAOYSA-N n,n-dimethylformamide;sulfur trioxide Chemical compound O=S(=O)=O.CN(C)C=O AFDQGRURHDVABZ-UHFFFAOYSA-N 0.000 claims description 4
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 4
- 238000004073 vulcanization Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 2
- 239000002274 desiccant Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 4
- 239000002994 raw material Substances 0.000 abstract description 8
- 238000009776 industrial production Methods 0.000 abstract description 5
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 238000005580 one pot reaction Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000002000 Electrolyte additive Substances 0.000 description 5
- 238000005481 NMR spectroscopy Methods 0.000 description 5
- 238000001819 mass spectrum Methods 0.000 description 5
- 230000001590 oxidative effect Effects 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 239000003480 eluent Substances 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 238000004811 liquid chromatography Methods 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- 239000007800 oxidant agent Substances 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate group Chemical group S(=O)(=O)([O-])[O-] QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical group OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 241000872931 Myoporum sandwicense Species 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- ZBCOWEFXYZQPAE-UHFFFAOYSA-N [3-hydroxy-2,2-bis(hydroxymethyl)propyl] hydrogen sulfite Chemical compound OCC(CO)(CO)COS(O)=O ZBCOWEFXYZQPAE-UHFFFAOYSA-N 0.000 description 2
- 239000008139 complexing agent Substances 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 230000036571 hydration Effects 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000002619 bicyclic group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- JQWHASGSAFIOCM-UHFFFAOYSA-M sodium periodate Chemical compound [Na+].[O-]I(=O)(=O)=O JQWHASGSAFIOCM-UHFFFAOYSA-M 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D497/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having oxygen and sulfur atoms as the only ring hetero atoms
- C07D497/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having oxygen and sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
- C07D497/10—Spiro-condensed systems
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparation method of pentaerythritol sulfate, and belongs to the technical field of organic synthesis. The method comprises the following steps: in a solvent, a complex of pentaerythritol and sulfur trioxide Lewis base is subjected to sulfonation reaction under the protection of inert gas, a dehydrating agent is added to carry out ring closure reaction after the sulfonation reaction is finished, and pentaerythritol sulfate is obtained through aftertreatment after the ring closure reaction is finished; the molar ratio of the pentaerythritol, the sulfur trioxide Lewis base complex and the dehydrating agent is 1:0.4-0.6:2-5, the temperature of sulfonation reaction is 0-35 ℃, and the temperature of ring closure reaction is 65-80 ℃. In the method, the product can be prepared and obtained by a one-pot method, the process steps are simple, the reaction conditions are milder, the cost of raw materials is greatly reduced, the purity of the pentaerythritol sulfate is ensured, and the method is a preparation method which is more suitable for industrial production.
Description
Technical Field
The invention relates to the technical field of organic synthesis, in particular to a preparation method of pentaerythritol sulfate.
Background
Electrolyte additives refer to small amounts of additives added to the electrolyte to improve the electrochemical performance of the electrolyte and to improve the quality of the cathode deposition. The electrolyte additive is some natural or artificial organic or inorganic compound, and does not participate in electrode reaction in the electrolysis process, but can improve the electrochemical performance of an electrolyte system, influence the discharge condition of ions and lead the electrolysis process to be in a better state. The electrolyte additives are generally used in small amounts but are an integral part of the electrolyte system.
The pentaerythritol sulfate compound contains sulfate groups and has the following structural formula:
。
pentaerythritol sulfate can be more easily reduced and/or decomposed into radicals and/or ions during charging of a lithium battery, and thus, the radicals and/or ions can be combined with lithium ions to form a suitable solid electrolyte interface film on an anode, improving reversibility of intercalation/deintercalation of lithium ions, resulting in an increase in discharge capacity and an improvement in life characteristics of manufactured batteries, and is a lithium battery electrolyte additive having higher commercial value.
Most of the preparation methods of pentaerythritol sulfate reported at present are that glycol compounds react with thionyl chloride to obtain corresponding cyclic sulfite, and then the cyclic sulfite is further oxidized to obtain the cyclic sulfate. The patent with the application number of CN 201811501930.X discloses a preparation method of pentaerythritol sulfate, which comprises the following steps: mixing pentaerythritol sulfite, a second organic solvent, a catalyst and an oxidant, putting the mixture into a reactor, wherein the second organic solvent is incompatible with the target product pentaerythritol sulfate, the catalyst adopts a titanium-silicon molecular sieve, the oxidant is hydrogen peroxide, stirring and reacting for 2-6 hours at normal temperature, filtering the reaction solution after the reaction is finished, adding a third solvent into filter residues, heating and stirring for 4-6 hours, filtering to obtain a crude product solution, and washing and crystallizing the crude product solution to obtain a finished product pentaerythritol sulfate. The preparation method of pentaerythritol sulfite comprises the following steps: and (3) dropwise adding pentaerythritol into the first organic solvent, simultaneously introducing nitrogen, controlling the temperature to be 60-90 ℃ after the dropwise adding of the thionyl chloride is completed, reacting for 12-16 hours, and carrying out post-treatment after the reaction is completed to obtain the product.
The common problems of the method are that the quality of the product is affected because thionyl chloride is used in the reaction process, the introduced chloride ions are difficult to remove, the damage of the thionyl chloride to the human body is relatively large, the safety is poor, the produced hydrochloric acid has corrosiveness to equipment, and in addition, the oxidation system uses more NaIO 4 -RuCl 3 .3H 2 O system, catalyst containing rare metals such as rubidium and titanium and oxidant NaIO 4 The cost is too high, and the large-scale industrial production is not realized.
The patent with the application number of CN201910607304.7 discloses a preparation method for synthesizing pentaerythritol bicyclic sulfate by using dimethyl sulfate and pentaerythritol through a one-step method under the action of a catalyst. The method needs to react for 10 hours at 60-150 ℃ and then react for 3-6 hours at 120-150 ℃ with heat preservation, and has the problems of high reaction temperature and long reaction time.
It is therefore of great commercial importance to develop a process for the preparation of pentaerythritol sulphate which is cost-effective and suitable for industrial production.
Disclosure of Invention
The embodiment of the invention provides a preparation method of pentaerythritol sulfate, which comprises the following steps: in a solvent, the pentaerythritol and sulfur trioxide Lewis base complex are subjected to sulfonation reaction under the protection of inert gas (specifically, nitrogen), a dehydrating agent is added to carry out ring closure reaction after the sulfonation reaction is finished, and pentaerythritol sulfate is obtained through aftertreatment after the ring closure reaction is finished. Wherein the molar ratio of pentaerythritol, sulfur trioxide Lewis base complex and dehydrating agent is 1:0.4-0.6:2-5, the temperature of sulfonation reaction is 0-35 ℃, and the temperature of ring closure reaction is 65-80 ℃.
The post-processing process in the embodiment of the invention comprises the following steps: cooling the reaction liquid to room temperature, filtering, distilling under reduced pressure to remove solvent, separating solid by petroleum ether through a silica gel column, concentrating and drying to obtain powdery pentaerythritol sulfate.
Wherein, the sulfur trioxide Lewis base complex in the embodiment of the invention is selected from sulfur trioxide pyridine complex, sulfur trioxide N, N-dimethylformamide complex, sulfur trioxide trimethylamine complex or sulfur trioxide triethylamine complex and the like; and can be specifically a sulfur trioxide pyridine complex or a sulfur trioxide trimethylamine complex. This patent adopts sulfur trioxide lewis base complex to have following advantage: 1. the quantitative reaction is more convenient; 2. incomplete sulfonation can not occur; 3. the product with high purity can be obtained; 4. is basically neutral and is favorable for reaction.
Wherein the solvent in the embodiments of the present invention is free of water or used after a non-hydration treatment, the non-hydration treatment method comprises distillation, adding a desiccant, molecular sieve drying, filtering or a combination thereof.
The solvent in the embodiment of the invention is one or more selected from dichloroethane, dioxane, toluene, n-hexane and the like, and can be specifically dichloroethane. The solvent may be used in the following amounts: pentaerythritol with solvent according to 1mol: (1000-2500) mL.
The dehydrating agent in the embodiment of the invention is one or more selected from anhydrous magnesium sulfate, anhydrous calcium chloride, zinc chloride, silica gel, phosphorus pentoxide, dicyclohexylcarbodiimide and the like, and can be specifically anhydrous magnesium sulfate, zinc chloride or dicyclohexylcarbodiimide.
Wherein, the time of the vulcanization reaction in the embodiment of the invention is 2-4 hours.
Wherein, the time of the ring closing reaction in the embodiment of the invention is 4-6 hours.
Specifically, the preparation method of pentaerythritol sulfate in the embodiment of the invention comprises the following steps: in a solvent, a complex of pentaerythritol and sulfur trioxide Lewis base is subjected to sulfonation reaction under the protection of inert gas, a dehydrating agent is added to carry out ring closure reaction after the sulfonation reaction is finished, reaction liquid is cooled to room temperature after the ring closure reaction is finished, then the reaction liquid is filtered, reduced pressure distillation is carried out to remove the solvent, and solid matters are separated by petroleum ether through a silica gel column, concentrated and dried, thus obtaining powdery pentaerythritol sulfate. Wherein the molar ratio of pentaerythritol, sulfur trioxide Lewis base complex and dehydrating agent is 1:0.4-0.6:2-5. Wherein the temperature of the sulfonation reaction is 0-35 ℃, and the time of the vulcanization reaction is 2-4 hours. Wherein the temperature of the ring closing reaction is 65-80 ℃, and the time of the ring closing reaction is 4-6 hours. Wherein the sulfur trioxide Lewis base complex is selected from sulfur trioxide pyridine complex, sulfur trioxide N, N-dimethylformamide complex, sulfur trioxide trimethylamine complex or sulfur trioxide triethylamine complex, the solvent is selected from one or more of dichloroethane, dioxane, toluene and N-hexane, and the dehydrating agent is selected from one or more of anhydrous magnesium sulfate, anhydrous calcium chloride, zinc chloride, silica gel, phosphorus pentoxide, dicyclohexylcarbodiimide and the like.
The preparation method of pentaerythritol sulfate provided by the invention can be prepared by adopting a one-pot method, compared with the preparation method of closing ring and oxidizing in the prior art, the process is simplified, meanwhile, the reaction raw materials are all basic bulk chemicals, compared with the sulfonation reaction process of hydrochloric acid in the prior art, the introduction of chloride ions and the corrosiveness of the hydrochloric acid on equipment are avoided, the reaction conditions are milder (the reaction temperature is room temperature and 65-80 ℃ respectively and the reaction time is short), the preparation method of pentaerythritol sulfate is low in cost and high in efficiency, and is suitable for industrial production, and the purity of the pentaerythritol sulfate product obtained by the preparation method is higher (up to 99.5 percent) and can meet the requirement of the product quality as a lithium battery electrolyte additive.
Drawings
To further illustrate the purity and structural characterization of the product, the following figures are given:
FIG. 1 is a mass spectrum of pentaerythritol sulfate prepared according to the present invention;
FIG. 2 is a nuclear magnetic resonance diagram of pentaerythritol sulfate prepared according to the present invention;
FIG. 3 is a liquid chromatogram of pentaerythritol sulfate prepared in example 1;
FIG. 4 is a liquid chromatogram of pentaerythritol sulfate prepared in example 2;
FIG. 5 is a liquid chromatogram of pentaerythritol sulfate prepared in example 3;
FIG. 6 is a liquid chromatogram of pentaerythritol sulfate prepared in example 4.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Example 1:
13.6g of pentaerythritol, 8.0g of sulfur trioxide pyridine complex and 250mL of distilled water-removed dichloroethane are put into a 500mL three-port bottle, nitrogen is introduced after full stirring and mixing, the reaction is carried out at room temperature for 4 hours, the liquid phase is monitored that the pentaerythritol raw material is basically free of residue, 60g of anhydrous magnesium sulfate is added into the three-port bottle, the temperature is raised to 80 ℃ for 4 hours, the reaction liquid is cooled to room temperature and then filtered, the filtrate is distilled under reduced pressure, the solid is separated by a petroleum ether silica gel column, the eluent with target polarity is concentrated and dried, 20.4g of white powdery pentaerythritol sulfate is obtained, the yield is 78%, the purity is 99.57% by liquid chromatography measurement, and the target pentaerythritol sulfate compound is determined by hydrogen spectrum identification of mass spectrum and nuclear magnetic resonance. Liquid chromatogram data of the product are shown in table 1:
TABLE 1
。
Example 2:
13.6g of pentaerythritol, 9.5g of sulfur trioxide pyridine complex and 250mL of dichloroethane after molecular sieve water removal are added into a 500mL three-port bottle, nitrogen is introduced after full stirring and mixing, the reaction is carried out for 2 hours at room temperature, the liquid phase is monitored that the pentaerythritol raw material basically has no residue, 27g of dicyclohexylcarbodiimide is added into the three-port bottle, the temperature is raised to 65 ℃ for reaction for 6 hours, the reaction liquid is cooled to room temperature and then filtered, the filtrate is distilled under reduced pressure, the solid is separated by a petroleum ether through a silica gel column, the eluent with target polarity is concentrated and dried, 18.2g of pentaerythritol sulfate in white powder form is obtained, the yield is 70%, the purity is 99.45% through liquid chromatography determination, and the target pentaerythritol sulfate compound is determined through hydrogen spectrum identification of mass spectrum and nuclear magnetic resonance. Liquid chromatogram data of the product are shown in table 2:
TABLE 2
。
Example 3:
13.6g of pentaerythritol, 7.0g of sulfur trioxide trimethylamine complex and 100mL of anhydrous magnesium sulfate are put into a 500mL three-port bottle, dichloroethane dried is stirred and mixed fully, nitrogen is introduced, the reaction is carried out for 2.5h at room temperature, the fact that the pentaerythritol raw material is basically free of residue is monitored by liquid phase, 36g of anhydrous magnesium sulfate is added into the three-port bottle, the temperature is raised to 80 ℃ for 4h, the reaction liquid is cooled to room temperature and filtered, the filtrate is distilled under reduced pressure, the solid is separated by petroleum ether through a silica gel column, the eluent with target polarity is concentrated and dried, 19.5g of pentaerythritol sulfate which is white powder is obtained, the yield is 75%, the purity is 99.76% by liquid chromatography measurement, and the pentaerythritol sulfate compound which is the target is determined by hydrogen spectrum identification of mass spectrum and nuclear magnetic resonance. Liquid chromatogram data of the product are shown in table 3:
TABLE 3 Table 3
。
Example 4:
13.6g of pentaerythritol and 7.0g of sulfur trioxide trimethylamine complex are put into a 500mL three-necked flask, 200mL of dichloroethane after water removal by distillation is fully stirred and mixed, nitrogen is introduced, the reaction is carried out at room temperature for 2 hours, the liquid phase is monitored that the pentaerythritol raw material basically has no residue, 27g of zinc chloride is added into the three-necked flask, the temperature is raised to 75 ℃ for reaction for 5 hours, the reaction liquid is cooled to room temperature and then filtered, the filtrate is distilled under reduced pressure, the solid is separated by a petroleum ether silica gel column, the eluent with target polarity is concentrated and dried, 20.0g of pentaerythritol sulfate in white powder form is obtained, the yield is 77%, the purity is 99.52% by liquid chromatography measurement, and the product is determined to be the target pentaerythritol sulfate compound by hydrogen spectrum identification of mass spectrum and nuclear magnetic resonance. Liquid chromatogram data of the product are shown in table 4:
TABLE 4 Table 4
。
According to the implementation process, the preparation method of pentaerythritol sulfate is simple in synthesis steps, the adopted raw materials are bulk chemicals, the introduction of chloride ions and the corrosion cost of hydrochloric acid to equipment are avoided in the selection of the raw materials, compared with the prior art that a catalyst containing rare metals including titanium and a catalyst containing rare metals, an oxidant NaIO4 and the like are required to be used, the cost is greatly reduced, the reaction condition is mild, the product purity of pentaerythritol sulfate is ensured, and the preparation method is more suitable for industrial production.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (6)
1. A process for the preparation of pentaerythritol sulphate, the process comprising: in a solvent, a complex of pentaerythritol and sulfur trioxide Lewis base is subjected to sulfonation reaction under the protection of inert gas, a dehydrating agent is added to carry out ring closure reaction after the sulfonation reaction is finished, and pentaerythritol sulfate is obtained through aftertreatment after the ring closure reaction is finished; the molar ratio of the pentaerythritol to the sulfur trioxide Lewis base complex to the dehydrating agent is 1:0.4-0.6:2-5, the temperature of sulfonation reaction is 0-35 ℃, and the temperature of ring closure reaction is 65-80 ℃;
the sulfur trioxide lewis base complex is selected from sulfur trioxide pyridine complex, sulfur trioxide N, N-dimethylformamide complex, sulfur trioxide trimethylamine complex or sulfur trioxide triethylamine complex;
the solvent is free of water or is used after anhydrous treatment, and the anhydrous treatment method comprises distillation, adding a drying agent, drying by a molecular sieve, and filtering or a combination thereof;
the dehydrating agent is selected from one or more of anhydrous magnesium sulfate, anhydrous calcium chloride, zinc chloride, silica gel, phosphorus pentoxide and dicyclohexylcarbodiimide;
the structural formula of pentaerythritol sulfate is shown below:
。
2. the method for producing pentaerythritol sulfate according to claim 1, wherein the post-treatment process comprises: cooling the reaction liquid to room temperature, filtering, distilling under reduced pressure to remove solvent, separating solid by petroleum ether through a silica gel column, concentrating and drying to obtain powdery pentaerythritol sulfate.
3. The method for producing pentaerythritol sulfate according to claim 1, wherein the solvent is one or more selected from the group consisting of dichloroethane, dioxane, toluene and n-hexane.
4. The method for producing pentaerythritol sulfate according to claim 1, wherein the time of the vulcanization reaction is 2 to 4 hours.
5. The process for producing pentaerythritol sulfate according to claim 1, wherein the period of the ring closure reaction is 4 to 6 hours.
6. The method for producing pentaerythritol sulfate according to claim 1, wherein the method comprises: in a solvent, a complex of pentaerythritol and sulfur trioxide Lewis base is subjected to sulfonation reaction under the protection of inert gas, a dehydrating agent is added to carry out ring closure reaction after the sulfonation reaction is finished, a reaction liquid is cooled to room temperature after the ring closure reaction is finished, then the reaction liquid is filtered, reduced pressure distillation is carried out to remove the solvent, and a solid is separated by petroleum ether through a silica gel column, concentrated and dried, so that powdery pentaerythritol sulfate can be obtained; the molar ratio of the pentaerythritol to the sulfur trioxide Lewis base complex to the dehydrating agent is 1:0.4-0.6:2-5; the temperature of the sulfonation reaction is 0-35 ℃, and the time of the vulcanization reaction is 2-4 hours; the temperature of the ring closing reaction is 65-80 ℃, and the time of the ring closing reaction is 4-6 hours; the sulfur trioxide lewis base complex is selected from sulfur trioxide pyridine complex, sulfur trioxide N, N-dimethylformamide complex, sulfur trioxide trimethylamine complex or sulfur trioxide triethylamine complex, the solvent is selected from one or more of dichloroethane, dioxane, toluene and N-hexane, and the dehydrating agent is selected from one or more of anhydrous magnesium sulfate, anhydrous calcium chloride, zinc chloride, silica gel, phosphorus pentoxide and dicyclohexylcarbodiimide.
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