CN114907310A - Process for preparing cyclic sulfate - Google Patents
Process for preparing cyclic sulfate Download PDFInfo
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- CN114907310A CN114907310A CN202210545811.4A CN202210545811A CN114907310A CN 114907310 A CN114907310 A CN 114907310A CN 202210545811 A CN202210545811 A CN 202210545811A CN 114907310 A CN114907310 A CN 114907310A
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- 125000004122 cyclic group Chemical group 0.000 title claims abstract description 59
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 title claims abstract description 34
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 47
- 230000003197 catalytic effect Effects 0.000 claims abstract description 43
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 41
- 239000003054 catalyst Substances 0.000 claims abstract description 34
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000001301 oxygen Substances 0.000 claims abstract description 33
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 33
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000007789 gas Substances 0.000 claims abstract description 24
- 239000007800 oxidant agent Substances 0.000 claims abstract description 22
- 230000001590 oxidative effect Effects 0.000 claims abstract description 19
- 238000002360 preparation method Methods 0.000 claims abstract description 18
- 238000005286 illumination Methods 0.000 claims abstract description 14
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical group Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 claims abstract description 11
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 24
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 19
- 239000002904 solvent Substances 0.000 claims description 16
- -1 allyl sulfate Chemical compound 0.000 claims description 14
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 10
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 10
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical group [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 8
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 7
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- VEWLDLAARDMXSB-UHFFFAOYSA-N ethenyl sulfate;hydron Chemical compound OS(=O)(=O)OC=C VEWLDLAARDMXSB-UHFFFAOYSA-N 0.000 claims description 6
- 238000005273 aeration Methods 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 4
- 235000011181 potassium carbonates Nutrition 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 3
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- 125000002947 alkylene group Chemical group 0.000 claims description 3
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 3
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 3
- 239000011736 potassium bicarbonate Substances 0.000 claims description 3
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical group [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 5
- 239000002699 waste material Substances 0.000 abstract description 5
- 238000012545 processing Methods 0.000 abstract description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 24
- 239000000047 product Substances 0.000 description 17
- 239000002585 base Substances 0.000 description 8
- KPZSTOVTJYRDIO-UHFFFAOYSA-K trichlorocerium;heptahydrate Chemical compound O.O.O.O.O.O.O.Cl[Ce](Cl)Cl KPZSTOVTJYRDIO-UHFFFAOYSA-K 0.000 description 7
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 6
- 229910001882 dioxygen Inorganic materials 0.000 description 5
- 239000003513 alkali Substances 0.000 description 4
- 239000012043 crude product Substances 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- JQWHASGSAFIOCM-UHFFFAOYSA-M sodium periodate Chemical compound [Na+].[O-]I(=O)(=O)=O JQWHASGSAFIOCM-UHFFFAOYSA-M 0.000 description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- WDXYVJKNSMILOQ-UHFFFAOYSA-N 1,3,2-dioxathiolane 2-oxide Chemical class O=S1OCCO1 WDXYVJKNSMILOQ-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 239000005708 Sodium hypochlorite Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000011083 cement mortar Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 208000012839 conversion disease Diseases 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 238000002390 rotary evaporation Methods 0.000 description 2
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- ZPFAVCIQZKRBGF-UHFFFAOYSA-N 1,3,2-dioxathiolane 2,2-dioxide Chemical class O=S1(=O)OCCO1 ZPFAVCIQZKRBGF-UHFFFAOYSA-N 0.000 description 1
- OQXNUCOGMMHHNA-UHFFFAOYSA-N 4-methyl-1,3,2-dioxathiolane 2,2-dioxide Chemical compound CC1COS(=O)(=O)O1 OQXNUCOGMMHHNA-UHFFFAOYSA-N 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000002220 antihypertensive agent Substances 0.000 description 1
- 229940127088 antihypertensive drug Drugs 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D327/00—Heterocyclic compounds containing rings having oxygen and sulfur atoms as the only ring hetero atoms
- C07D327/10—Heterocyclic compounds containing rings having oxygen and sulfur atoms as the only ring hetero atoms two oxygen atoms and one sulfur atom, e.g. cyclic sulfates
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention provides a preparation method of cyclic sulfate. The preparation method comprises the following steps: carrying out catalytic oxidation reaction on a reaction system containing cyclic sulfite, a catalyst and an oxidant under the illumination condition to obtain cyclic sulfate; wherein, the oxidant is oxygen-containing gas, and the catalyst is cerium chloride. The cyclic sulfite is used as a reaction raw material, oxygen-containing gas is used as an oxidant, cerium chloride is used as a catalyst, and the cyclic sulfite can be subjected to catalytic oxidation reaction under the condition of illumination to obtain cyclic sulfate. The oxidant and the catalyst are cheaper and easily obtained, so that the production cost can be effectively reduced. Meanwhile, the catalytic oxidation reaction based on the oxidant and the catalyst does not produce additional pollution waste, and the environment-friendly performance is better. Moreover, the preparation method of the invention requires milder reaction conditions and shorter preparation time, and the product with higher purity and yield can be obtained by simply processing the reacted materials.
Description
Technical Field
The invention relates to the field of organic synthesis, in particular to a preparation method of cyclic sulfate.
Background
The cyclic sulfate derivative can be used as an additive of the electrolyte of a power lithium battery, can improve the dynamic property of electrode/electrolyte interface reaction, can inhibit the reduction of the initial capacity of the battery, can increase the initial discharge capacity, can reduce the expansion of the battery after being placed at high temperature, and can greatly improve the charge-discharge performance and cycle number of the battery. The cyclic sulfate derivatives mainly include various compounds such as vinyl sulfate, 4-methyl vinyl sulfate, 4-ethyl vinyl sulfate, 4-propyl vinyl sulfate, and allyl sulfate. In addition, part of cyclic sulfate ester has also been widely used in the pharmaceutical industry, for example, vinyl sulfate ester can be used as an intermediate for synthesizing drugs from hydroxyethylation reagents in organic synthesis, and can also be used as a raw material for synthesizing certain heterocyclic compounds for hardening gelatin, antihypertensive drugs, novel dual surfactants, and the like. Therefore, the preparation method of the cyclic sulfate which is efficient, cheap and green is significant.
In the prior industry, the ethylene sulfite derivative is generally prepared as an intermediate by reacting a diol compound with thionyl chloride, and the ethylene sulfate derivative is synthesized by catalytic oxidation of noble metal ruthenium trichloride, and sodium hypochlorite (CN201610015843.8, EP332521A1 or CN201110116277.7) or sodium periodate (J.Am.chem.Soc.1988, 110, 7538) is generally used as an oxidizing agent.
However, the catalyst in the above-mentioned prior art is expensive and the recovery of the catalyst is complicated. Moreover, the use of sodium periodate, an oxidant, is expensive, while the use of sodium hypochlorite, an oxidant, is also costly and results in a large amount of waste water (CN 200710009981.6). Therefore, further searching for cheap catalyst and using practical green and cheap oxidant is urgent, which will promote the rapid development of lithium battery industry or medicine industry.
Disclosure of Invention
The invention mainly aims to provide a preparation method of cyclic sulfate, which solves the problems of high cost, poor environmental protection and the like in the preparation of the cyclic sulfate in the prior art.
In order to achieve the above object, according to one aspect of the present invention, there is provided a method for preparing a cyclic sulfate ester, the method comprising: carrying out catalytic oxidation reaction on a reaction system containing cyclic sulfite, a catalyst and an oxidant under the illumination condition to obtain cyclic sulfate; the oxidant is oxygen-containing gas, and the catalyst is cerium chloride; wherein, the cyclic sulfite has a structure shown in a formula I, and the cyclic sulfate has a structure shown in a formula II; r 1 、R 2 、R 3 And R 4 Each independently is H or C1-C4 alkyl; r 5 Is a direct bond or alkylene of C1 to C4.
Further, the reaction system also comprises alkali; preferably, the base is a carbonate and/or bicarbonate; more preferably, the carbonate is selected from sodium carbonate and/or potassium carbonate; more preferably, the bicarbonate is selected from potassium bicarbonate and/or sodium bicarbonate.
Further, in the catalytic oxidation reaction process, the pressure of oxygen in the oxygen-containing gas is controlled to be 1.5-5 atm.
Furthermore, the volume concentration of oxygen in the oxygen-containing gas is 20-100%.
Furthermore, in the catalytic oxidation reaction process, the aeration flow of oxygen-containing gas is 100-150 mL/min per liter of reaction system.
Further, the molar ratio of the catalyst to the cyclic sulfite is 1: 10-50, preferably 1: 10-20; the molar ratio of the catalyst to the base is 1:0.5 to 2.
Further, in the catalytic oxidation reaction process, the reaction time is 12-36 h, and the reaction temperature is 40-70 ℃; preferably, in the catalytic oxidation reaction process, the reaction time is 24-36 h, and the reaction temperature is 45-70 ℃.
Further, in the catalytic oxidation reaction process, the illumination intensity is 10-100 mW/cm -2 (ii) a And/or the light source is blue light with the wavelength of 400-500 nm.
Further, the reaction system also comprises a solvent; preferably, the solvent is selected from one or more of dichloroethane, acetonitrile, chloroform, dimethylformamide or dimethylacetamide; the preferred solvent is acetonitrile; preferably, the mass-volume ratio of the cyclic sulfite to the solvent is 0.01-0.1 g/mL.
Further, the cyclic sulfate is one or more of vinyl sulfate, 4-methyl vinyl sulfate, 4-ethyl vinyl sulfate, 4-propyl vinyl sulfate, and allyl sulfate.
The cyclic sulfite is used as a reaction raw material, oxygen-containing gas is used as an oxidant, cerium chloride is used as a catalyst, and the cyclic sulfite can be subjected to catalytic oxidation reaction under the condition of illumination to obtain cyclic sulfate. First, the above-mentioned oxidizing agents and catalysts are cheaper and more readily available, thereby allowing production costs to be reduced more effectively. And secondly, the catalytic oxidation reaction based on the oxidant and the catalyst does not produce additional pollution waste, so that the environment-friendly performance is better. Moreover, the preparation method of the invention requires milder reaction conditions and shorter preparation time, and the product with higher purity and yield can be obtained by simply processing the reacted materials (such as extraction, filtration and the like). In a word, based on the preparation method, the cyclic sulfite is prepared more economically, greener, more environmentally friendly and more efficiently.
Detailed Description
It should be noted that, in the present application, the embodiments and features of the embodiments may be combined with each other without conflict. The present invention will be described in detail with reference to examples.
As described in the background of the invention section, the prior art has problems of high cost and poor environmental protection when preparing cyclic sulfate. In order to solve the problem, the invention provides a preparation method of cyclic sulfate, which comprises the following steps: the reaction system containing the cyclic sulfite, the catalyst and the oxidant is subjected to catalytic oxidation reaction under the illumination condition to obtain the cyclic sulfate. The oxidant is oxygen-containing gas; the catalyst is cerium chloride. Wherein, the cyclic sulfite has a structure shown in a formula I, and the cyclic sulfate has a structure shown in a formula II; r is 1 、R 2 、R 3 And R 4 Each independently is H or C1-C4 alkyl; r 5 Is a direct bond or alkylene of C1 to C4.
The cyclic sulfite is used as a reaction raw material, oxygen-containing gas is used as an oxidant, cerium chloride is used as a catalyst, and the cyclic sulfite can be subjected to catalytic oxidation reaction under the condition of illumination to obtain cyclic sulfate. First, the above-mentioned oxidizing agents and catalysts are cheaper and more readily available, thereby allowing production costs to be reduced more effectively. And secondly, the catalytic oxidation reaction based on the oxidant and the catalyst does not produce additional pollution waste, so that the environment-friendly performance is better. Moreover, the preparation method of the invention requires milder reaction conditions and shorter preparation time, and the product with higher purity and yield can be obtained by simply processing the reacted materials (such as extraction, filtration and the like). In a word, based on the preparation method, the cyclic sulfite is prepared more economically, greener, more environmentally and more efficiently.
In a preferred embodiment, the present inventors have also unexpectedly found that oxygen inevitably is activated as a peroxy anionic radical O2 in the above reaction system when using an oxygen-containing gas as a catalyst ·- ，O2 ·- Can participate in the reaction and be converted into peroxy anions, and a large amount of peroxy anions can hinder the forward marching property of the catalytic oxidation reaction, thereby promoting lower raw material conversion rate and lower product yield. Therefore, the inventor of the invention further adds alkali into the reaction system, thereby effectively realizing the beneficial effects of promoting reaction conversion and improving reaction yield. This is because the base can react with the peroxy anion to consume the peroxy anion. Preferably, the base is a carbonate and/or bicarbonate. More preferably, the carbonate is selected from sodium carbonate and/or potassium carbonate. The bicarbonate is selected from potassium bicarbonate and/or sodium bicarbonate. Based on the method, the reagent is cheaper and easily obtained, so that the production cost can be effectively reduced. Meanwhile, the environment-friendly plastic cement mortar does not additionally generate pollution waste, and is better in environmental protection.
In a preferred embodiment, the pressure of oxygen in the oxygen-containing gas is controlled to be 1.5 to 5 atm. Based on this, the catalytic oxidation reaction efficiency is better. In the catalytic oxidation reaction process, the aeration flow of the oxygen-containing gas is 100-150 mL/min. Based on this, the catalyst is continuously and smoothly introduced into the catalytic oxidation reaction system, the forward progress of the reaction is better, the stability of the reaction system is better, and the reaction efficiency is better.
In a preferred embodiment, the oxygen-containing gas has an oxygen concentration of 20 to 100% by volume. The oxygen-containing gas may be pure oxygen, air, or a mixture of oxygen and an inert gas (for example, the volume concentration of oxygen in the oxygen-containing gas is 20%, 40%, 60%, 80%, or 100%), and the inert gas may be one or both of nitrogen and argon. The cerium chloride may be anhydrous cerium chloride or heptahydrate cerium chloride. Based on this, the oxidant and the catalyst are cheaper and easily obtained, so that the production cost can be more effectively reduced. Meanwhile, the environment-friendly plastic cement mortar does not additionally generate pollution waste, and is better in environmental protection.
In order to further improve the efficiency of the catalytic oxidation reaction, it is preferable that the molar ratio of the catalyst to the cyclic sulfite is 1: 10-50, preferably 1:10 to 20, for example, 1:10, 1:12, 1:14, 1:16 or 1: 20. The molar ratio of catalyst to base is 1:0.5 to 2, for example, 1:1, 1:0.5, 1:1.5, 1:1.8 or 1: 2.
In order to further balance the stability and high efficiency of the catalytic oxidation reaction, the reaction time is preferably 12-36 h, preferably 24-36 h, for example, 24h, 36h, 30h, 28h or 33h, in the catalytic oxidation reaction process; the reaction temperature is 40 to 70 ℃, preferably 45 to 70 ℃, for example, 50 ℃, 70 ℃, 45 ℃, 55 ℃, 60 ℃ or 65 ℃.
In a preferred embodiment, the illumination intensity is 10-100 mW/cm during the catalytic oxidation reaction -2 For example, it may be 10mW/cm -2 、30mW/cm -2 、100mW/cm -2 、50mW/cm -2 、80mW/cm -2 Or 40mW/cm -2 (ii) a The light source is blue light with the wavelength of 400-500 nm. Based on this, cerium chloride has stronger catalytic activity, so that the catalytic oxidation reaction efficiency of the cyclic sulfite can be greatly improved, the conversion rate of raw materials is higher, and the product yield is higher.
In some alternative embodiments, the catalytic oxidation reaction of the present invention may be performed by autoclave type, high pressure microchannel reactor, or high pressure microfluidic type. In a more preferred embodiment, the invention selects an autoclave mode to obtain the product, and the catalytic oxidation reaction is carried out in a photochemical autoclave reactor. The photochemical high-pressure reactor has simple and reliable structure, economy, durability, complete accessories and safe high pressure, is generally provided with a miniature direct current motor, a pressure gauge, an explosion-proof device, an air inlet valve and a sampling valve in a standard manner, and can further realize reaction tests more conveniently.
In order to further provide a more suitable reaction environment for the catalytic oxidation reaction, so as to further improve the reaction efficiency, in a preferred embodiment, the reaction system further comprises a solvent. Preferably, the solvent is selected from one or more of dichloroethane, acetonitrile, chloroform, dimethylformamide or dimethylacetamide, more preferably acetonitrile. Further preferably, the mass-to-volume ratio of the cyclic sulfite to the solvent is 0.01 to 0.1g/mL, and may be, for example, 0.01g/mL, 0.03g/mL, 0.05g/mL, 0.08g/mL, or 0.1 g/mL.
In a preferred embodiment, after the catalytic oxidation reaction is finished, the reaction material is subjected to rotary evaporation to remove the recovered solvent, and then the system is transferred to a separating funnel, and 800-1200 mL of water and 200-800 mL of dichloromethane are added for full washing. Drying the organic phase with anhydrous sodium sulfate, then carrying out reduced pressure distillation to recover dichloromethane, carrying out vacuum pumping on the residual materials to obtain a crude product of the cyclic sulfate, and recrystallizing the crude product with dichloromethane to obtain the cyclic sulfate with higher purity.
In some preferred embodiments, the cyclic sulfate is vinyl sulfate, 4-methyl vinyl sulfate, 4-ethyl vinyl sulfate, 4-propyl vinyl sulfate, or propylene sulfate. Based on the preparation method of the invention, the cyclic sulfate product can be obtained with high yield and high purity more effectively.
The present application is described in further detail below with reference to specific examples, which should not be construed as limiting the scope of the invention as claimed.
Example 1
To the photochemical high-pressure reactor, cerium chloride heptahydrate (10 mol%, 30mmol), sodium bicarbonate (10 mol%, 30mmol), 32.4 g of ethylene sulfite (0.3mol), 3 l of acetonitrile solvent were added in this order. And continuously introducing into the reactor at a flow rate of 100mL/minOxygen gas pressure is maintained at 1.5 atm. Under the irradiation of 455nm blue light LED, the illumination intensity is 30mW/cm -2 Stirring the mixture at 50 ℃ for 24 hours to finish the reaction, recovering the acetonitrile solvent by rotary evaporation, transferring the mixture to a separating funnel, adding 1000 ml of water and 500 ml of dichloromethane, fully washing, drying an organic phase by using anhydrous sodium sulfate, then carrying out reduced pressure distillation to recover the dichloromethane, carrying out vacuum pumping on the residue to obtain a crude product of the vinyl sulfate, and recrystallizing the crude product by using the dichloromethane to obtain 24 g of white crystal vinyl sulfate. Nuclear magnetic hydrogen spectroscopy, H NMR (CDCl) 3 )：4.76(4H)ppm。
Example 2
Sequentially adding 10 mol% and 30mmol cerium chloride heptahydrate, 10 mol% and 30mmol sodium carbonate, 0.3mol 4-methyl ethylene sulfite and 3L dimethyl formamide solvent into a photochemical high-pressure reactor, continuously introducing air at a flow rate of 150ml/min, keeping the pressure of oxygen in air at 5atm, and under the irradiation of 425nm blue light LED, illuminating at an illumination intensity of 100mW/cm -2 After the reaction was completed by stirring at 70 ℃ for 36 hours, the reaction was carried out under reduced pressure to recover the solvent, which was then transferred to a separatory funnel, 1000 ml of water and 500 ml of methylene chloride were added, followed by washing thoroughly, drying the organic phase with anhydrous sodium sulfate and then recovering the methylene chloride by distillation under reduced pressure, and the residue was subjected to distillation under reduced pressure (50-51 ℃ C./1 mmHg) to obtain 32.3 g of transparent liquid, vinyl 4-methylsulfate. The molecular weight for gas chromatography is 138.1.
Example 3
The only difference from example 1 is that no sodium bicarbonate was added.
Example 4
Only differs from example 1 in that the molar ratio of cerium chloride heptahydrate to sodium bicarbonate is 1: 0.5.
example 5
Only differs from example 1 in that the molar ratio of cerium chloride heptahydrate to sodium bicarbonate is 1: 2.
example 6
Only differs from example 1 in that the molar ratio of cerium chloride heptahydrate to sodium bicarbonate is 1: 3.
example 7
Only differs from example 1 in that the molar ratio of cerium chloride heptahydrate to sodium bicarbonate is 1: 0.1.
example 8
The only difference from example 1 is that the sodium bicarbonate was replaced equimolar with potassium carbonate.
Example 9
The only difference from example 1 is that the oxygen gas pressure is 1 atm.
Example 10
The only difference from example 1 is that the oxygen gas pressure was 8 atm.
Example 11
The only difference from example 1 is that the oxygen gas pressure is 3.5 atm.
Example 12
The only difference from example 1 is that the light source is light at a wavelength of 325 nm.
Example 13
The only difference from example 1 is that the illumination light source is a light wave having a wavelength of 655 nm.
Example 14
The difference from example 1 is only that the illumination intensity is 10mW/cm -2 。
Example 15
The only difference from example 1 is that the illumination intensity is 200mW/cm -2 。
Example 16
The only difference from example 1 was that the aeration flow rate of the oxygen-containing gas was 80 mL/min.
Example 17
The only difference from example 1 was that the aeration flow rate of the oxygen-containing gas was 200 mL/min.
The product yields of the examples are shown in table 1.
TABLE 1
| Yield of | |
| Example 1 | 65％ |
| Example 2 | 78％ |
| Example 3 | 10％ |
| Example 4 | 68％ |
| Example 5 | 66％ |
| Example 6 | 60％ |
| Example 7 | 40％ |
| Example 8 | 70％ |
| Example 9 | 20％ |
| Example 10 | 60％ |
| Example 11 | 68％ |
| Example 12 | 40％ |
| Example 13 | 33％ |
| Example 14 | 67％ |
| Example 15 | 50％ |
| Example 16 | 50％ |
| Example 17 | 63％ |
As can be seen from the comparison of example 1, example 2 to example 17 and example 3, the present invention, when applied to a cyclic sulfate production process using an oxygen-containing gas as a catalyst, results in low reaction efficiency without adding a base. The addition of alkali can promote the reaction conversion rate to be improved, the reaction yield is greatly improved, and the alkali is selected from carbonate and/or bicarbonate to achieve the beneficial effects.
As can be seen from a comparison of examples 1 and 4 to 7, the molar ratio of the catalyst to the base was 1: when the amount of the catalyst is 0.5 to 2 (for example, examples 1, 4 and 5), the efficiency of the catalytic oxidation reaction is higher and the product yield is higher. And the molar ratio of catalyst to said base is not in the range of 1: the product yield is low when the ratio is 0.5 to 2 (for example, examples 6 and 7).
As can be seen from a comparison between example 1 and examples 9 to 11, the oxygen gas pressure is controlled to be 1.5 to 5atm (for example, examples 1 and 11). Based on the method, the catalytic oxidation reaction efficiency is better, and the product yield is higher. When the pressure of the oxygen gas is not in the range of 1.5 to 5atm (for example, examples 9 and 10), the yield of the product is low.
As can be seen from the comparison among examples 1, 12 and 13, when the light source is blue light with a wavelength of 400 to 500nm (for example, example 1), cerium chloride in the catalytic oxidation reaction of cyclic sulfite has stronger catalytic activity, so that the reaction efficiency can be greatly improved, the conversion rate of raw materials is higher, and the product yield is higher. When the wavelength of the light source is out of the above range (for example, examples 12 and 13), the catalytic oxidation effect on the cyclic sulfite is slightly weak, and the yield of the product is low.
As can be seen from the comparison among examples 1, 14 and 15, the light intensity during the catalytic oxidation reaction is 10-100 mW/cm -2 In the case (for example, example 1 and example 14), the catalytic oxidation reaction efficiency of the cyclic sulfite can be greatly improved, the conversion rate of the raw material is higher, and the product yield is higher. When the amount is outside the above range (for example, example 15), the product yield is low.
As is clear from a comparison of examples 1, 16 and 17, the flow rate of the oxygen-containing gas introduced is 100 to 150mL/min (for example, example 1). Based on this, the catalyst is continuously and smoothly introduced into the catalytic oxidation reaction system, the forward reaction progress is better, the reaction system stability is better, the reaction efficiency is better, and the product yield is higher. Outside the above range (e.g., examples 16 and 17), the product yield is slightly decreased.
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and various modifications and changes will occur to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A preparation method of cyclic sulfate is characterized by comprising the following steps: carrying out catalytic oxidation reaction on a reaction system containing cyclic sulfite, a catalyst and an oxidant under the illumination condition to obtain the cyclic sulfate; the oxidant is oxygen-containing gas, and the catalyst is cerium chloride; wherein the content of the first and second substances,
the cyclic sulfite has a structure shown in a formula I, and the cyclic sulfate has a structure shown in a formula II;
R 1 、R 2 、R 3 and R 4 Each independently is H or C1-C4 alkyl; r 5 Is a direct bond or alkylene of C1 to C4.
2. The process for producing a cyclic sulfate according to claim 1, wherein the reaction system further comprises a base;
preferably, the base is a carbonate and/or bicarbonate;
more preferably, the carbonate is selected from sodium carbonate and/or potassium carbonate;
more preferably, the bicarbonate is selected from potassium bicarbonate and/or sodium bicarbonate.
3. The method for producing a cyclic sulfate according to claim 1 or 2, wherein the pressure of oxygen in the oxygen-containing gas is controlled to 1.5 to 5atm during the catalytic oxidation reaction.
4. The process for producing a cyclic sulfate according to any one of claims 1 to 3, wherein the volume concentration of oxygen in the oxygen-containing gas is 20 to 100%.
5. The process for producing a cyclic sulfate according to any one of claims 1 to 4, wherein the aeration flow rate of the oxygen-containing gas per liter of the reaction system during the catalytic oxidation reaction is 100 to 150 mL/min.
6. The method according to claim 2, wherein the molar ratio of the catalyst to the cyclic sulfite is 1: 10-50, preferably 1:10 to 20 parts;
the molar ratio of the catalyst to the base is 1:0.5 to 2.
7. The method for preparing cyclic sulfate according to any one of claims 1 to 6, wherein the reaction time is 12 to 36 hours and the reaction temperature is 40 to 70 ℃ during the catalytic oxidation reaction;
preferably, in the catalytic oxidation reaction process, the reaction time is 24-36 h, and the reaction temperature is 45-70 ℃.
8. The method for producing a cyclic sulfate according to any one of claims 1 to 7, wherein the intensity of light irradiation during the catalytic oxidation reaction is 10 to 100mW/cm -2 (ii) a And/or
The light source is blue light with the wavelength of 400-500 nm.
9. The process for the preparation of a cyclic sulfate according to any one of claims 1 to 8, wherein the reaction system further comprises a solvent;
preferably, the solvent is selected from one or more of dichloroethane, acetonitrile, chloroform, dimethylformamide or dimethylacetamide; preferably the solvent is acetonitrile;
preferably, the mass-to-volume ratio of the cyclic sulfite to the solvent is 0.01-0.1 g/mL.
10. The method of any one of claims 1 to 9, wherein the cyclic sulfate is one or more of vinyl sulfate, 4-methyl vinyl sulfate, 4-ethyl vinyl sulfate, 4-propyl vinyl sulfate, and allyl sulfate.
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| CN109988145A (en) * | 2019-05-13 | 2019-07-09 | 福建博鸿新能源科技有限公司 | A kind of preparation method of sulfuric acid vinyl ester |
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