CN114478570A - Preparation method of pentaerythritol sulfate - Google Patents
Preparation method of pentaerythritol sulfate Download PDFInfo
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- CN114478570A CN114478570A CN202111617293.4A CN202111617293A CN114478570A CN 114478570 A CN114478570 A CN 114478570A CN 202111617293 A CN202111617293 A CN 202111617293A CN 114478570 A CN114478570 A CN 114478570A
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- pentaerythritol
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- sulfate
- sulfur trioxide
- complex
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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 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 27
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical class OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000002904 solvent Substances 0.000 claims abstract description 20
- -1 sulfur trioxide Lewis base Chemical class 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 238000007363 ring formation reaction Methods 0.000 claims abstract description 19
- 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
- 238000001914 filtration Methods 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 10
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 9
- 239000012295 chemical reaction liquid Substances 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
- 238000001816 cooling Methods 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
- 238000004821 distillation 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
- 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
- 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
- 230000018044 dehydration Effects 0.000 claims description 3
- 238000006297 dehydration reaction Methods 0.000 claims description 3
- 239000002274 desiccant Substances 0.000 claims description 2
- 208000005156 Dehydration Diseases 0.000 claims 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 9
- 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 1
- 239000000047 product Substances 0.000 description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000002000 Electrolyte additive Substances 0.000 description 5
- 239000012043 crude product Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 230000001590 oxidative effect Effects 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate group Chemical group S(=O)(=O)([O-])[O-] QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 238000005481 NMR spectroscopy Methods 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
- 238000004949 mass spectrometry Methods 0.000 description 4
- 238000012544 monitoring process Methods 0.000 description 4
- 239000007800 oxidant agent Substances 0.000 description 4
- 238000001228 spectrum 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
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 125000002619 bicyclic group Chemical group 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 239000003960 organic solvent Substances 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
- 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
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 229910052701 rubidium Inorganic materials 0.000 description 2
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 241000872931 Myoporum sandwicense Species 0.000 description 1
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 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
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 230000006872 improvement Effects 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
- 238000001819 mass spectrum Methods 0.000 description 1
- 150000002739 metals Chemical class 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
- 239000000376 reactant Substances 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
Images
Classifications
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- 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
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- 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, belonging to the technical field of organic synthesis. The method comprises the following steps: in a solvent, carrying out sulfonation reaction on pentaerythritol and sulfur trioxide Lewis base complexes under the protection of inert gas, adding a dehydrating agent to carry out ring closing reaction after the sulfonation reaction is finished, and carrying out post-treatment after the ring closing reaction is finished to obtain pentaerythritol sulfate; 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 temperature of the ring closure reaction is 65-80 ℃. In the method, the product can be prepared by a one-pot method, the process steps are simple, the reaction conditions are milder, the raw material cost is greatly reduced, the product purity of the pentaerythritol sulfate is ensured, and the method 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
The electrolyte additive refers to a small amount of additive added to the electrolyte to improve the electrochemical performance of the electrolyte and improve the quality of cathode deposition. The electrolyte additive is some natural or artificial organic or inorganic compounds, generally does not participate in the electrode reaction of the electrolytic process, but can improve the electrochemical performance of an electrolyte system, influence the discharge condition of ions and enable the electrolytic process to be in a better state. The electrolyte additive is generally used in small amounts, but is an indispensable part of the electrolyte system.
The compound of pentaerythritol sulfate contains a sulfate group, and the structural formula is shown as follows:
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 interfacial film on an anode, improving reversibility of intercalation/deintercalation of lithium ions, thereby resulting in an increase in discharge capacity and an improvement in life characteristics of a battery manufactured, and is a lithium battery electrolyte additive having higher commercial value.
Most of the methods for preparing pentaerythritol sulfate which are disclosed and reported at present firstly react diol compounds with thionyl chloride to obtain corresponding cyclic sulfite, and then the cyclic sulfite is further oxidized to obtain cyclic sulfate. For example, patent application No. CN 201811501930.X discloses a preparation method of pentaerythritol sulfate, comprising 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 a target product pentaerythritol sulfate, the catalyst adopts a titanium-silicon molecular sieve, the oxidant is hydrogen peroxide, stirring and reacting at normal temperature for 2-6 hours, carrying out suction filtration on reaction liquid after the reaction is finished, adding a third solvent into filter residues, heating and stirring for 4-6 hours, carrying out suction filtration 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 the pentaerythritol sulfite comprises the following steps: and (2) dripping thionyl chloride into pentaerythritol in a first organic solvent, introducing nitrogen, controlling the temperature to be 60-90 ℃ after the dripping of the thionyl chloride is finished, reacting for 12-16 hours, and performing post-treatment after the reaction is finished to obtain the product.
The method has the common problems that because thionyl chloride is used in the reaction process, introduced chloride ions are difficult to remove to influence the quality of the product, and the thionyl chloride has great harm to human bodies and poor safety, the generated hydrochloric acid has corrosivity to equipment, and in addition, NaIO is used in an oxidation system mostly4-RuCl3.3H2O system, catalyst containing rare metal rubidium and titanium and oxidant NaIO4The cost is too high, which is not beneficial to realizing large-scale industrial production.
The invention discloses a preparation method for synthesizing pentaerythritol bicyclic sulfate by using dimethyl sulfate and pentaerythritol in one step under the action of a catalyst, which comprises the steps of taking pentaerythritol and dimethyl sulfate as raw materials, heating the solvent, the dimethyl sulfate and the catalyst to 60-65 ℃ under the protection of nitrogen, fully dissolving, adding pentaerythritol in batches under reflux at 70 ℃ for starting reaction, continuously heating the reaction to 150 ℃, condensing and refluxing to separate a reactant methanol to obtain a pentaerythritol bicyclic sulfate crude product, filtering and distilling the crude product obtained by the reaction, washing and purifying the crude product by using the solvent, and drying in vacuum to obtain a target product pentaerythritol bicyclic sulfate refined product. The method needs to react for 10 hours at 60-150 ℃, and then the reaction is carried out for 3-6 hours at the temperature of 120-150 ℃, which has the problems of high reaction temperature and long reaction time.
Therefore, the development of a preparation method of pentaerythritol sulfate which has low cost and high efficiency and is suitable for industrial production has important commercial value.
Disclosure of Invention
The embodiment of the invention provides a preparation method of pentaerythritol sulfate, which comprises the following steps: in a solvent, carrying out sulfonation reaction on a pentaerythritol and sulfur trioxide Lewis base complex under the protection of inert gas (specifically nitrogen), adding a dehydrating agent to carry out ring closing reaction after the sulfonation reaction is finished, and carrying out post-treatment after the ring closing reaction is finished to obtain pentaerythritol sulfate. Wherein, the mol 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 temperature of the 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 the solvent, separating the solid with petroleum ether through a silica gel column, concentrating and drying to obtain the powdered pentaerythritol sulfate.
The sulfur trioxide lewis base complex in the embodiment of the present invention is selected from sulfur trioxide pyridine complex, sulfur trioxide N, N-dimethylformamide complex, sulfur trioxide trimethylamine complex, sulfur trioxide triethylamine complex, and the like; specifically, a sulfur trioxide pyridine complex or a sulfur trioxide trimethylamine complex can be mentioned. The sulfur trioxide lewis base complex adopted by the method has the following advantages: 1. quantitative reaction is more convenient; 2. incomplete sulfonation can not occur; 3. high-purity products can be obtained; 4. is basically neutral, and is beneficial to the reaction.
The solvent in the embodiment of the invention contains no water or is used after being subjected to anhydrous treatment, and the anhydrous treatment method comprises distillation, drying agent addition, filtration after being dried by a molecular sieve or a combination thereof.
The solvent in the embodiment of the present invention is one or more selected from dichloroethane, dioxane, toluene, n-hexane, and the like, and may specifically be dichloroethane. Wherein, the dosage of the solvent can be as follows: pentaerythritol and solvent according to 1 mol: (1000-2500) mL.
The dehydrating agent in the embodiment of the present invention is one or more selected from anhydrous magnesium sulfate, anhydrous calcium chloride, zinc chloride, silica gel, phosphorus pentoxide, dicyclohexylcarbodiimide, and the like, and specifically may be anhydrous magnesium sulfate, zinc chloride, or dicyclohexylcarbodiimide.
Wherein, the time of the vulcanization reaction in the embodiment of the invention is 2 to 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 present invention includes: in a solvent, carrying out sulfonation reaction on pentaerythritol and sulfur trioxide Lewis base complexes under the protection of inert gas, adding a dehydrating agent to carry out ring closing reaction after the sulfonation reaction is finished, cooling the reaction liquid to room temperature after the ring closing reaction is finished, filtering, carrying out reduced pressure distillation to remove the solvent, separating the solid with petroleum ether through a silica gel column, concentrating and drying to obtain powdery pentaerythritol sulfate. Wherein 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. 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. 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, etc., the solvent is selected from one or more of dichloroethane, dioxane, toluene, N-hexane, etc., and the dehydrating agent is selected from one or more of anhydrous magnesium sulfate, anhydrous calcium chloride, zinc chloride, silica gel, phosphorus pentoxide, dicyclohexylcarbodiimide, etc.
Compared with the preparation method of firstly closing the ring and then oxidizing in the prior art, the preparation method of pentaerythritol sulfate provided by the invention has the advantages that the process is simplified, meanwhile, the reaction raw materials are all basic bulk chemicals, compared with the sulfonation reaction process generated by hydrochloric acid in the prior art, the introduction of chloride ions and the corrosion of the hydrochloric acid generation to equipment are avoided, the reaction conditions are milder (the reaction temperature is respectively room temperature and 65-80 ℃, and the reaction time is short), the preparation method of pentaerythritol sulfate is low in cost, high in efficiency and suitable for industrial production, the purity of the pentaerythritol sulfate product obtained by the preparation method is higher (reaches 99.5%), and the requirement of the product on the quality as a lithium battery electrolyte additive can be met.
Drawings
To further illustrate the purity and structure 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 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 those skilled in the art will appreciate that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
Example 1:
adding 13.6g of pentaerythritol, 8.0g of sulfur trioxide pyridine complex and 250mL of dichloroethane subjected to water removal by distillation into a 500mL three-necked flask, fully stirring and mixing, introducing nitrogen, reacting for 4 hours at room temperature, monitoring the existence of the pentaerythritol raw material basically by liquid phase, adding 60g of anhydrous magnesium sulfate into the three-necked flask, heating to 80 ℃ for reacting for 4 hours, cooling the reaction liquid to room temperature, filtering, distilling the filtrate under reduced pressure, separating the solid by using petroleum ether to pass through a silica gel column, concentrating the eluent with target polarity, and drying to obtain 20.4g of white powdery pentaerythritol sulfate with yield of 78%, determining the purity by liquid chromatography to be 99.57%, and determining the target pentaerythritol sulfate compound by mass spectrometry and nuclear magnetic resonance hydrogen spectrum identification. The liquid chromatogram data of the product are shown in table 1:
TABLE 1
Example 2:
adding 13.6g of pentaerythritol, 9.5g of sulfur trioxide pyridine complex into a 500mL three-neck flask, adding 250mL of dichloroethane subjected to molecular sieve dehydration, fully stirring and mixing, introducing nitrogen, reacting for 2 hours at room temperature, monitoring the existence of pentaerythritol raw materials by a liquid phase, adding 27g of dicyclohexylcarbodiimide into the three-neck flask, heating to 65 ℃ for reacting for 6 hours, cooling the reaction liquid to room temperature, filtering, distilling the filtrate under reduced pressure, separating solids by a petroleum ether silica gel column, concentrating the target polar eluent, and drying to obtain 18.2g of white powdery pentaerythritol sulfate, wherein the yield is 70%, the purity is 99.45% by liquid chromatography, and the target pentaerythritol sulfate compound is determined by mass spectrometry and hydrogen spectrum identification of nuclear magnetic resonance. The liquid chromatogram data of the product are shown in table 2:
TABLE 2
Example 3:
adding 13.6g of pentaerythritol, 7.0g of sulfur trioxide trimethylamine complex and 100mL of dichloroethane dried by anhydrous magnesium sulfate into a 500mL three-necked bottle, fully stirring and mixing, introducing nitrogen, reacting for 2.5 hours at room temperature, monitoring by a liquid phase that the pentaerythritol raw material is basically not remained, adding 36g of anhydrous magnesium sulfate into the three-necked bottle, heating to 80 ℃ for reacting for 4 hours, cooling the reaction liquid to room temperature, filtering, distilling the filtrate under reduced pressure, separating the solid by using petroleum ether through a silica gel column, concentrating the eluent with target polarity, and drying to obtain 19.5g of white powdery pentaerythritol sulfate with yield of 75%, determining the purity of 99.76% by a liquid chromatography, and determining the target pentaerythritol sulfate compound by mass spectrometry and hydrogen spectrum identification of nuclear magnetic resonance. The liquid chromatogram data of the product are shown in table 3:
TABLE 3
Example 4:
adding 13.6g of pentaerythritol, 7.0g of sulfur trioxide trimethylamine complex into a 500mL three-neck flask, adding 200mL of dichloroethane subjected to water removal by distillation, fully stirring and mixing, introducing nitrogen, reacting for 2 hours at room temperature, monitoring the existence of pentaerythritol raw materials by a liquid phase, adding 27g of zinc chloride into the three-neck flask, heating to 75 ℃ for reacting for 5 hours, cooling the reaction liquid to room temperature, filtering, distilling the filtrate under reduced pressure, separating solids by using petroleum ether through a silica gel column, concentrating the eluent with the target polarity, and drying to obtain 20.0g of white powdery pentaerythritol sulfate with the yield of 77%, determining the purity by the liquid chromatography of 99.52%, and determining the target pentaerythritol sulfate compound by mass spectrometry and nuclear magnetic resonance hydrogen spectrum identification. The liquid chromatogram data of the product are shown in table 4:
TABLE 4
Through the implementation process, the preparation method of the pentaerythritol sulfate provided by the invention is simple in synthesis step, the adopted raw materials are basic bulk chemicals, the corrosion cost of equipment caused by the introduction of chloride ions and the generation of hydrochloric acid is avoided in the selection of the raw materials, compared with the prior art that a catalyst containing rare metals rubidium and titanium, an oxidant NaIO4 and the like are required, the cost is greatly reduced, the reaction condition is mild, the product purity of the pentaerythritol sulfate is ensured, and the preparation method is more suitable for industrial production.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (9)
1. A method for preparing pentaerythritol sulfate, which is characterized by comprising the following steps: in a solvent, carrying out sulfonation reaction on pentaerythritol and sulfur trioxide Lewis base complexes under the protection of inert gas, adding a dehydrating agent to carry out ring closing reaction after the sulfonation reaction is finished, and carrying out post-treatment after the ring closing reaction is finished to obtain pentaerythritol sulfate; 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 temperature of the ring closure reaction is 65-80 ℃.
2. The method of preparing 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 the solvent, separating the solid with petroleum ether through a silica gel column, concentrating and drying to obtain the powdered pentaerythritol sulfate.
3. The process for the preparation of pentaerythritol sulfate according to claim 1, characterized in that 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.
4. The method of claim 1, wherein the solvent is free of water or used after dehydration treatment, and the dehydration treatment method comprises distillation, addition of a drying agent, filtration after drying by molecular sieve, or a combination thereof.
5. The method of claim 1, wherein the solvent is one or more selected from dichloroethane, dioxane, toluene and n-hexane.
6. The method for producing pentaerythritol sulfate according to claim 1, wherein the dehydrating agent is one or more selected from the group consisting of anhydrous magnesium sulfate, anhydrous calcium chloride, zinc chloride, silica gel, phosphorus pentoxide, and dicyclohexylcarbodiimide.
7. The process for producing pentaerythritol sulfate according to claim 1, wherein the time of the vulcanization reaction is 2 to 4 hours.
8. The process for producing pentaerythritol sulfate according to claim 1, wherein the time of the ring-closing reaction is 4 to 6 hours.
9. The method of preparing pentaerythritol sulfate according to claim 1, wherein the method comprises: in a solvent, carrying out sulfonation reaction on pentaerythritol and sulfur trioxide Lewis base complexes under the protection of inert gas, adding a dehydrating agent to carry out ring closing reaction after the sulfonation reaction is finished, cooling the reaction liquid to room temperature after the ring closing reaction is finished, filtering, carrying out reduced pressure distillation to remove the solvent, separating the solid with petroleum ether through a silica gel column, concentrating and drying to obtain powdery pentaerythritol sulfate; 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 a sulfur trioxide pyridine complex, a sulfur trioxide N, N-dimethylformamide complex, a sulfur trioxide trimethylamine complex or a 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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