CN115819304B - Preparation method of molybdenum disulfide catalyzed tetraethyl thiuram disulfide - Google Patents
Preparation method of molybdenum disulfide catalyzed tetraethyl thiuram disulfide Download PDFInfo
- Publication number
- CN115819304B CN115819304B CN202211125886.3A CN202211125886A CN115819304B CN 115819304 B CN115819304 B CN 115819304B CN 202211125886 A CN202211125886 A CN 202211125886A CN 115819304 B CN115819304 B CN 115819304B
- Authority
- CN
- China
- Prior art keywords
- disulfide
- reaction
- fixed bed
- preparing
- tetraethylthiuram
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- AUZONCFQVSMFAP-UHFFFAOYSA-N disulfiram Chemical compound CCN(CC)C(=S)SSC(=S)N(CC)CC AUZONCFQVSMFAP-UHFFFAOYSA-N 0.000 title claims abstract description 98
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 229910052982 molybdenum disulfide Inorganic materials 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 59
- 238000000034 method Methods 0.000 claims abstract description 50
- 238000001035 drying Methods 0.000 claims abstract description 35
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 18
- 239000001301 oxygen Substances 0.000 claims abstract description 18
- 238000001914 filtration Methods 0.000 claims abstract description 12
- 238000001816 cooling Methods 0.000 claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 9
- 239000003513 alkali Substances 0.000 claims abstract description 6
- 239000002904 solvent Substances 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 4
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 claims description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 29
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 27
- 239000000243 solution Substances 0.000 claims description 19
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 16
- 238000005580 one pot reaction Methods 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 9
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 claims description 8
- 239000003153 chemical reaction reagent Substances 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 6
- 239000012295 chemical reaction liquid Substances 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 3
- 239000013078 crystal Substances 0.000 abstract description 19
- 239000000047 product Substances 0.000 abstract description 15
- -1 carbon disulfide, secondary amine Chemical class 0.000 abstract description 4
- 230000001590 oxidative effect Effects 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 239000000706 filtrate Substances 0.000 abstract description 2
- 238000006555 catalytic reaction Methods 0.000 abstract 1
- 238000011049 filling Methods 0.000 abstract 1
- 238000005406 washing Methods 0.000 description 24
- 238000000967 suction filtration Methods 0.000 description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- 238000004519 manufacturing process Methods 0.000 description 9
- 238000002844 melting Methods 0.000 description 8
- 230000008018 melting Effects 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 238000010309 melting process Methods 0.000 description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 229920001971 elastomer Polymers 0.000 description 5
- 239000005060 rubber Substances 0.000 description 5
- 239000006227 byproduct Substances 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 4
- 229960002447 thiram Drugs 0.000 description 4
- 229920000459 Nitrile rubber Polymers 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910017053 inorganic salt Inorganic materials 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- TXLINXBIWJYFNR-UHFFFAOYSA-N 4-phenylpyridine-2-carbonitrile Chemical compound C1=NC(C#N)=CC(C=2C=CC=CC=2)=C1 TXLINXBIWJYFNR-UHFFFAOYSA-N 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- ZPUCINDJVBIVPJ-LJISPDSOSA-N cocaine Chemical compound O([C@H]1C[C@@H]2CC[C@@H](N2C)[C@H]1C(=O)OC)C(=O)C1=CC=CC=C1 ZPUCINDJVBIVPJ-LJISPDSOSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- WITDFSFZHZYQHB-UHFFFAOYSA-N dibenzylcarbamothioylsulfanyl n,n-dibenzylcarbamodithioate Chemical compound C=1C=CC=CC=1CN(CC=1C=CC=CC=1)C(=S)SSC(=S)N(CC=1C=CC=CC=1)CC1=CC=CC=C1 WITDFSFZHZYQHB-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 238000005502 peroxidation Methods 0.000 description 2
- 230000036632 reaction speed Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 150000003335 secondary amines Chemical class 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- 208000007848 Alcoholism Diseases 0.000 description 1
- 229910020639 Co-Al Inorganic materials 0.000 description 1
- 229910020675 Co—Al Inorganic materials 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 229910018657 Mn—Al Inorganic materials 0.000 description 1
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- 229910003310 Ni-Al Inorganic materials 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- CSNJTIWCTNEOSW-UHFFFAOYSA-N carbamothioylsulfanyl carbamodithioate Chemical compound NC(=S)SSC(N)=S CSNJTIWCTNEOSW-UHFFFAOYSA-N 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- 230000001684 chronic effect Effects 0.000 description 1
- 229960003920 cocaine Drugs 0.000 description 1
- 238000005112 continuous flow technique Methods 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparation method of molybdenum disulfide catalyzed tetraethyl thiuram disulfide, belonging to a chemical synthesis method. Mixing carbon disulfide, secondary amine, alkali and molybdenum disulfide in a solvent, oxidizing in an oxygen atmosphere, filtering after reaction, cooling and crystallizing filtrate, and filtering and drying to obtain tetraethylthiuram disulfide crystals. And filling molybdenum disulfide into the micro fixed bed for standby, simultaneously injecting a reaction solution containing carbon disulfide, secondary amine and alkali and oxygen into the fixed bed for heterogeneous catalytic reaction, cooling and crystallizing the effluent solution phase, and filtering and drying to obtain crystals of tetraethylthiuram disulfide. The purity of the tetraethyl thiuram disulfide obtained by the method reaches more than 98%, the method is environment-friendly, the condition is mild, the catalyst can be recycled, and the product is easy to separate.
Description
Technical Field
The invention belongs to the technical field of rubber accelerator production, and relates to a synthetic method of tetraethylthiuram disulfide rubber accelerators, in particular to a green synthetic method thereof.
Background
Tetraethylthiuram disulfide, TETD for short, has the following structural formula:
the thiuram accelerator is widely applied in rubber products, wherein the thiuram disulfide is used as an overspeed-class rubber accelerator, so that the vulcanization temperature can be reduced, the consumption of the vulcanizing agent can be reduced, the physical and mechanical properties of vulcanized rubber can be improved, active sulfur is easily released at the conventional vulcanization temperature, and the rubber can be vulcanized without adding sulfur. Conventional thiurams include mainly tetramethylthiuram disulfide (TMTD), tetraethylthiuram disulfide (TETD), tetrabenzylthiuram disulfide (TBzTD), and the like. Among them, tetraethylthiuram disulfide (TETD) is used as an overspeed accelerator and a vulcanizing agent for natural rubber, styrene-butadiene rubber, nitrile rubber, butyl rubber, butadiene rubber and latex. Tetraethylthiuram disulfide is a second excellent accelerator for thiazole accelerators, and also has a catalytic effect on acid and guanidine accelerators. TETD is also useful in the treatment of chronic alcohol addiction. Besides alcohol, it is also used for the abstinence treatment of cocaine. In addition, TETD has also been the subject of major study for the treatment of cancer and HIV by many researchers.
In the traditional process, the preparation method of tetraethylthiuram disulfide mostly adopts a synthetic path taking secondary amine, carbon disulfide, sodium hydroxide and double oxidation as raw materials. Although the reaction speed is high, excessive NaOH in the reaction process needs sulfuric acid or hydrochloric acid to neutralize, and inorganic salt byproducts which are difficult to treat are produced; secondly, strong acid and strong alkali added in the reaction process can corrode reaction equipment to a certain extent. CN108147986B discloses a method for preparing carbon disulfide, diethylamine and hydrogen peroxide in Pd-Co-Al 2 O 3 、Pd-Mn-Al 2 O 3 Or Pd-Ni-Al 2 O 3 The method is simple in process operation, but the price of the used metal catalyst is generally high, and meanwhile, a complex is easily formed between the reaction process and a reaction intermediate to pollute a product; and the hydrogen peroxide contains a large amount of water, so that the reacted medium needs to be dehydrated and refined, and the energy consumption is high, so that the method has great limitation in industrial application.
CN112358428A discloses a method for preparing tetraethylthiuram disulfide by photocatalytic oxidation, the scheme makes secondary amine, carbon disulfide and catalyst react under the condition of illumination, and the reaction uses cheap dye as catalyst, so that green synthesis of thiuram is realized under extremely mild condition. The disadvantage of this technique is that the dye and the reaction solution are in a homogeneous phase state, which brings inconvenience to the purification of the product.
Disclosure of Invention
Aiming at the technical limitations existing in the traditional production method of tetraethylthiuram disulfide, the invention provides a novel method for preparing the tetraethylthiuram disulfide.
Aiming at the defects of the prior art, in particular to the problems that the prior art uses strong acid, strong alkali, strong oxidant and other corrosive raw materials, which are easy to cause equipment corrosion, product peroxidation, inorganic salt byproduct generation and the like. The invention provides a method for preparing tetraethylthiuram disulfide, which has the advantages of rapid conversion, environmental protection, catalyst recycling, safe process and low cost.
The aim of the invention is achieved by the following technical scheme:
a one-pot method for preparing tetraethyl thiuram disulfide is characterized in that oxygen is used as a reaction atmosphere, carbon disulfide and diethylamine are used as raw materials, molybdenum disulfide is used as a catalyst, and the reaction is carried out under alkaline conditions, so that the tetraethyl thiuram disulfide can be obtained.
In the one-pot method, the mol ratio of diethylamine, carbon disulfide, alkaline reagent and molybdenum disulfide is 1: (1.0-1.5): 1: (0.1-0.3).
In the one-pot method, the reaction time is 8-12 hours, and the reaction temperature is room temperature.
In the one-pot method, the alkaline reagent is triethylamine.
In the one-pot method, the solvent used in the reaction process is ethanol or methanol.
A method for preparing tetraethyl thiuram disulfide by a fixed bed method comprises the steps of sequentially adding carbon disulfide, diethylamine and alkali reagent under a stirring state to obtain a mixed solution, mixing the mixed solution and oxygen at a mixer to form a gas-liquid intermittent flow, then entering a micro fixed bed filled with molybdenum disulfide, cooling, crystallizing, filtering and drying after the solution flows out, so as to obtain the tetraethyl thiuram disulfide.
In the above fixed bed method: the retention time of the reaction liquid in the fixed bed of the continuous flow micro fixed bed method is 10-30 minutes, and the reaction temperature is room temperature.
In the above fixed bed method: the flow rate of the mixed solution pumped into the liquid in the continuous flow micro-fixed bed method is 0.8-0.12 mL/min, and the flow rate of oxygen is precisely controlled to be 2.0-2.5 sccm by a mass flow controller.
In the above fixed bed method: the pressure of the whole continuous flow system in the continuous flow micro-fixed bed method is 0.5-0.8 MPa, and the pressure is controlled by a 20-75 psi back pressure valve.
In the above fixed bed method: the solvent used in the reaction process is ethanol or methanol.
In the above fixed bed method: the mol ratio of diethylamine, carbon disulfide, alkaline reagent and molybdenum disulfide is 1: (1.0-1.5): 1: (0.1-1).
The post-treatment of the two synthesis methods adopts cooling crystallization and recrystallization to obtain tetraethylthiuram disulfide needle-shaped crystals.
The invention uses cheap molybdenum disulfide as catalyst, compared with traditional metal salt catalyst such as copper acetate, manganese acetate, etc., the invention does not generate by-products formed by intermediate products and metal salts.
The invention uses oxygen as oxidant, which is more environment-friendly than the common hydrogen peroxide, and the reaction does not need to remove water and refine.
The possible mechanism of the molybdenum disulfide catalytic oxidation of the invention is: in the reaction process, oxygen forms superoxide ion free radicals on the surface of molybdenum disulfide, and the superoxide ion free radicals participate in subsequent oxidation reaction
The invention utilizes the gas-liquid-solid three-phase mixing technology under the microreactor, has the advantages of high reaction speed, mild condition, difficult peroxidation, no inorganic salt byproduct generation, high product yield and good quality.
The present invention employs continuous flow techniques. Compared with the traditional reaction device, the continuous flow technology can greatly shorten the reaction time, has small amplification effect and greatly improves the productivity. The occupied area of the device can be greatly reduced, and the land resources are saved. In addition, compared with the batch production of the traditional batch reaction kettle, the continuous flow technology has stable product quality, excellent quality and stronger market competitiveness.
The tetraethylthiuram disulfide product obtained by the reaction is needle-shaped crystals, the melting point is above 70 ℃ (standard substance: 70-70.9 ℃), and the purity is above 99%.
Drawings
FIG. 1 is a schematic diagram of the synthetic scheme of the present invention.
Detailed Description
The invention will be further described with reference to specific examples for a clearer understanding of the objects, features and meaning of the invention.
Example 1
The present example provides a detailed process for preparing tetraethylthiuram disulfide in an ethanol solution in one pot, comprising the steps of: 50 ml of ethanol is added into a reaction kettle, then 2.3 g of carbon disulfide (30 mmol), 1.8 g of diethylamine (25 mmol) and 2.5 g of triethylamine (25 mmol) are added into the reaction kettle in sequence under the condition of stirring, after the addition, 0.5 g of molybdenum disulfide (3.125 mmol) is added into the reaction system, finally oxygen is introduced into the upper end of the reaction kettle, and the reaction is carried out for 12 hours at room temperature. Filtering the heterogeneous solution after the reaction, cooling the solution phase to crystallize needle-shaped crystals, carrying out suction filtration, washing, drying, recrystallizing, washing, carrying out suction filtration and drying to obtain 3.99 g of solid. The steps of suction filtration, water washing and drying are the same as those of the conventional preparation of tetraethylthiuram disulfide, and in the embodiment, the steps of water washing are carried out twice, and the drying temperature is 40 ℃ and the drying time is 5 hours.
The obtained finished product is detected: the appearance is white crystal, the melting point is 71.6 ℃ (melting process is 70.9-71.6 ℃), the purity is 99.0%, and the yield is 90%.
Example 2
The present example provides a detailed process for preparing tetraethylthiuram disulfide in methanol solution in one pot, comprising the steps of: 50 ml of methanol is added into a reaction kettle, then 2.3 g of carbon disulfide (30 mmol), 1.8 g of diethylamine (25 mmol) and 2.5 g of triethylamine (25 mmol) are added into the reaction kettle in sequence under the condition of stirring, after the addition, 0.5 g of molybdenum disulfide (3.125 mmol) is added into the reaction system, finally oxygen is introduced into the upper end of the reaction kettle, and the reaction is carried out for 12 hours at room temperature. Filtering the heterogeneous solution after the reaction, cooling the solution phase to crystallize needle-shaped crystals, carrying out suction filtration, washing, drying, recrystallizing, washing, carrying out suction filtration and drying to obtain 3.92 g of solid. The steps of suction filtration, water washing and drying are the same as those of the conventional preparation of tetraethylthiuram disulfide, and in the embodiment, the steps of water washing are carried out twice, and the drying temperature is 40 ℃ and the drying time is 5 hours.
The obtained finished product is detected: the appearance is white crystal, the melting point is 71.3 ℃ (melting process is 70.6-71.3 ℃), the purity is 98.7%, and the yield is 88%.
Example 3
The present example provides a detailed process for preparing tetraethylthiuram disulfide in an ethanol solution in one pot, comprising the steps of: 50 ml of ethanol was added to the reaction vessel, followed by dropwise addition of 2.3 g of carbon disulfide (30 mmol), 1.8 g of diethylamine (25 mmol) and 2.5 g of triethylamine (25 mmol) with stirring. After the completion of the dropwise addition, 0.5 g of molybdenum disulfide (3.125 mmol) was added to the reaction system, and finally oxygen was introduced into the upper end of the reaction vessel, and the reaction was carried out at room temperature for 8 hours. Filtering after the reaction, cooling the obtained filtrate to crystallize needle-shaped crystals, carrying out suction filtration, washing, drying, recrystallizing, washing, carrying out suction filtration and drying to obtain 3.21 g of solid. The steps of suction filtration, water washing and drying are the same as those of the conventional preparation of tetraethylthiuram disulfide, and in the embodiment, the steps of water washing are carried out twice, and the drying temperature is 40 ℃ and the drying time is 5 hours.
The obtained finished product is detected: the appearance is white crystal, the melting point is 72.0 ℃ (melting process: 71.4-72.0 ℃), the purity is 97.9%, and the yield is 72%.
Example 4
The present example provides a detailed process for preparing tetraethylthiuram disulfide in an ethanol solution in one pot, comprising the steps of: 50 ml of ethanol is added into a reaction kettle, 1.9 g of carbon disulfide (25 mmol), 1.8 g of diethylamine (25 mmol) and 2.5 g of triethylamine (25 mmol) are added into the reaction kettle in sequence under the condition of stirring, after the dripping is finished, 0.5 g of molybdenum disulfide (3.125 mmol) is added into the reaction system, and finally oxygen is introduced into the upper end of the reaction kettle for reaction for 12 hours at room temperature. Filtering the heterogeneous solution after the reaction, cooling the solution phase to crystallize needle-shaped crystals, carrying out suction filtration, washing, drying, recrystallizing, washing, carrying out suction filtration and drying to obtain 3.74 g of solid. The steps of suction filtration, water washing and drying are the same as those of the conventional preparation of tetraethylthiuram disulfide, and in the embodiment, the steps of water washing are carried out twice, and the drying temperature is 40 ℃ and the drying time is 5 hours.
The obtained finished product is detected: the appearance is white crystal, the melting point is 71.5 ℃ (melting process is 70.7-71.5 ℃), the purity is 98.9%, and the yield is 84%.
Example 5
The present example provides a detailed process for preparing tetraethylthiuram disulfide in an ethanol solution in one pot, comprising the steps of: 50 ml of ethanol is added into a reaction kettle, then 2.3 g of carbon disulfide (30 mmol), 1.8 g of diethylamine (25 mmol) and 2.5 g of triethylamine (25 mmol) are added into the reaction kettle in sequence under the condition of stirring, after the dripping is finished, 1.0 g of molybdenum disulfide (6.25 mmol) is added into the reaction system, finally oxygen is introduced into the upper end of the reaction kettle, and the reaction is carried out for 12 hours at room temperature. Filtering the heterogeneous solution after the reaction, cooling the solution phase to crystallize needle-shaped crystals, carrying out suction filtration, washing, drying, recrystallizing, washing, carrying out suction filtration and drying to obtain 4.05 g of solid. The steps of suction filtration, water washing and drying are the same as those of the conventional preparation of tetraethylthiuram disulfide, and in the embodiment, the steps of water washing are carried out twice, and the drying temperature is 40 ℃ and the drying time is 5 hours.
The obtained finished product is detected: the appearance is white crystal, the melting point is 72.1 ℃ (melting process: 71.3-72.1 ℃), the purity is 99.0%, and the yield is 91%.
Example 6
This example provides a detailed process for preparing tetraethylthiuram disulfide in a continuous flow micro fixed bed, comprising the steps of: 2.17 g of molybdenum disulfide is filled into a fixed bed with the inner diameter of 4.6mm and the length of 15.0cm, and absorbent cotton and a sieve plate are used for sealing and filtering at two ends. 50 mL of ethanol was taken and 2.3 g of carbon disulfide (30 mmol), 1.8 g of diethylamine (25 mmol) and 2.5 g of triethylamine (25 mmol) were sequentially added dropwise under stirring to prepare a pre-reaction solution. The reaction liquid (flow rate: 0.1 mL/min) is pumped by a constant flow pump, the mass flow controller precisely controls the molar flow (2.25 sccm) of the introduced oxygen, the reactor liquid and the oxygen are mixed at a mixer to form an intermittent flow with the liquid/gas length ratio of 1/2, the intermittent flow enters a micro-fixed bed filled with molybdenum disulfide, the residence time in the micro-fixed bed is 18 minutes, the liquid flows through a back pressure valve of 40psi after flowing out of the micro-fixed bed, the system pressure is 0.6MPa, the liquid finally flows into a collecting tank, and needle-shaped crystals are cooled and crystallized after the end, and 3.92 g of solids are obtained through suction filtration, water washing, drying, recrystallization, water washing, suction filtration and drying. In this example, the water was washed twice and the drying temperature was 40℃for 5 hours. The obtained finished product is detected: the appearance is white crystal, the melting point is 71.6 ℃ (melting process is 70.9-71.6 ℃), the purity is 98.8%, and the yield is 88%.
Example 7
This example provides a detailed process for preparing tetraethylthiuram disulfide in a continuous flow micro fixed bed, comprising the steps of: 2.17 g of molybdenum disulfide is filled into a fixed bed with the inner diameter of 4.6mm and the length of 15.0cm, and absorbent cotton and a sieve plate are used for sealing and filtering at two ends. 50 mL of ethanol was taken and 2.3 g of carbon disulfide (30 mmol), 1.8 g of diethylamine (25 mmol) and 2.5 g of triethylamine (25 mmol) were sequentially added dropwise under stirring to prepare a pre-reaction solution. The reaction liquid (flow rate: 0.1 mL/min) is pumped by a constant flow pump, the mass flow controller precisely controls the molar flow (2.25 sccm) of the introduced oxygen, the reactor liquid and the oxygen are mixed at a mixer to form a gas-liquid intermittent flow with the liquid/gas of 1/2, the gas-liquid intermittent flow enters a micro-fixed bed filled with molybdenum disulfide, the residence time in the micro-fixed bed is 18 minutes, the liquid flows through a back pressure valve of 20psi after flowing out of the micro-fixed bed, the system pressure is 0.45MPa, the liquid finally flows into a collecting tank, and needle-shaped crystals are cooled and crystallized after the end, and the needle-shaped crystals are subjected to suction filtration, water washing, drying, recrystallization, water washing, suction filtration and drying to obtain 3.47 g of solid. In this example, the water was washed twice and the drying temperature was 40℃for 5 hours. The obtained finished product is detected: the appearance is white crystal, the melting point is 71.4 ℃ (melting process is 70.6-71.4 ℃), the purity is 99.0%, and the yield is 78%.
Comparative example 1
The comparative example differs from example 1 in that:
molybdenum disulfide is not added in the whole reaction system, and the rest conditions are kept consistent. After the reaction, no signal of tetraethylthiuram disulfide was detected by liquid chromatography. It can be seen that the importance of molybdenum disulfide for tetraethylthiuram disulfide synthesis is indispensable for the reaction.
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 (10)
1. A method for preparing tetraethyl thiuram disulfide by a one-pot method is characterized in that the method takes oxygen as a reaction atmosphere, takes carbon disulfide and diethylamine as raw materials, takes molybdenum disulfide as a catalyst, and reacts under alkaline conditions to obtain the tetraethyl thiuram disulfide.
2. The method for preparing tetraethylthiuram disulfide by the one-pot method according to claim 1, wherein the molar ratio of diethylamine, carbon disulfide, alkaline reagent and molybdenum disulfide is 1: (1.0-1.5): 1: (0.1-0.3).
3. The method for preparing tetraethylthiuram disulfide by the one-pot method according to claim 1, wherein the reaction time is 8 to 12 hours, and the reaction temperature is room temperature.
4. The method for preparing tetraethylthiuram disulfide by a one-pot method according to claim 1 or 2, wherein the basic reagent is triethylamine.
5. The method for preparing tetraethylthiuram disulfide by the one-pot method according to claim 1, wherein the solvent used in the reaction process is ethanol or methanol.
6. A method for preparing tetraethylthiuram disulfide by a fixed bed method is characterized in that: and sequentially adding carbon disulfide, diethylamine and an alkali reagent under a stirring state to obtain a mixed solution, mixing the mixed solution with oxygen at a mixer to form a gas-liquid intermittent flow, then entering a micro fixed bed filled with molybdenum disulfide, cooling, crystallizing, filtering and drying after the solution flows out to obtain tetraethylthiuram disulfide.
7. The method for preparing tetraethylthiuram disulfide by a fixed bed process according to claim 6, wherein the residence time of the reaction liquid in the fixed bed by the continuous flow micro fixed bed process is 10 to 30 minutes, and the reaction temperature is room temperature.
8. The method for preparing tetraethylthiuram disulfide according to claim 6, wherein the flow rate of the mixed solution pumped into the liquid in the continuous flow micro fixed bed method is 0.8-0.12 mL/min, and the flow rate of oxygen is controlled to be 2.0-2.5 sccm by a mass flow controller; the pressure of the whole continuous flow system in the continuous flow micro-fixed bed method is 0.5-0.8 MPa, and the pressure is controlled by a 20-75 psi back pressure valve.
9. The method for preparing tetraethylthiuram disulfide by a fixed bed process according to claim 6, wherein the molar ratio of diethylamine, carbon disulfide, alkaline reagent, molybdenum disulfide is 1: (1.0-1.5): 1: (0.1-1).
10. The method for preparing tetraethylthiuram disulfide by a fixed bed process according to claim 6, wherein the solvent used in the reaction process is ethanol or methanol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211125886.3A CN115819304B (en) | 2022-09-16 | 2022-09-16 | Preparation method of molybdenum disulfide catalyzed tetraethyl thiuram disulfide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211125886.3A CN115819304B (en) | 2022-09-16 | 2022-09-16 | Preparation method of molybdenum disulfide catalyzed tetraethyl thiuram disulfide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115819304A CN115819304A (en) | 2023-03-21 |
| CN115819304B true CN115819304B (en) | 2024-03-08 |
Family
ID=85523645
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211125886.3A Active CN115819304B (en) | 2022-09-16 | 2022-09-16 | Preparation method of molybdenum disulfide catalyzed tetraethyl thiuram disulfide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115819304B (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108147986A (en) * | 2017-12-20 | 2018-06-12 | 蔚林新材料科技股份有限公司 | The preparation method of tetraethylthiuram disulfide |
| CN108395393A (en) * | 2018-05-15 | 2018-08-14 | 清华大学 | A kind of green synthesis method of thiurams thiofide |
| CN110526845A (en) * | 2018-05-25 | 2019-12-03 | 李志安 | A kind of pollution-free high-efficient rate preparation method of tetraethylthiuram disulfide |
| CN110526846A (en) * | 2018-05-25 | 2019-12-03 | 李志安 | The efficient preparation process of the Environmental Safety of pharmaceutical grade tetraethylthiuram disulfide |
| CN112358428A (en) * | 2020-11-20 | 2021-02-12 | 鹤壁元昊化工有限公司 | Method for preparing thiuram disulfide by photocatalytic oxidation |
| CN113666855A (en) * | 2021-09-07 | 2021-11-19 | 山东斯递尔化工科技有限公司 | Method for preparing tetrabenzylthiuram disulfide |
| CN114790156A (en) * | 2022-05-07 | 2022-07-26 | 鹤壁元昊化工有限公司 | Preparation method of tetraalkyl thiuram monosulfide |
-
2022
- 2022-09-16 CN CN202211125886.3A patent/CN115819304B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108147986A (en) * | 2017-12-20 | 2018-06-12 | 蔚林新材料科技股份有限公司 | The preparation method of tetraethylthiuram disulfide |
| CN108395393A (en) * | 2018-05-15 | 2018-08-14 | 清华大学 | A kind of green synthesis method of thiurams thiofide |
| CN110526845A (en) * | 2018-05-25 | 2019-12-03 | 李志安 | A kind of pollution-free high-efficient rate preparation method of tetraethylthiuram disulfide |
| CN110526846A (en) * | 2018-05-25 | 2019-12-03 | 李志安 | The efficient preparation process of the Environmental Safety of pharmaceutical grade tetraethylthiuram disulfide |
| CN112358428A (en) * | 2020-11-20 | 2021-02-12 | 鹤壁元昊化工有限公司 | Method for preparing thiuram disulfide by photocatalytic oxidation |
| CN113666855A (en) * | 2021-09-07 | 2021-11-19 | 山东斯递尔化工科技有限公司 | Method for preparing tetrabenzylthiuram disulfide |
| CN114790156A (en) * | 2022-05-07 | 2022-07-26 | 鹤壁元昊化工有限公司 | Preparation method of tetraalkyl thiuram monosulfide |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115819304A (en) | 2023-03-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102321028B (en) | Method for synthesizing 2-methyl-5-nitroimidazole-1-ethanol | |
| CN108586295B (en) | Continuous production method of vulcanization accelerator DPG | |
| CN101735171A (en) | Method for synthesizing thiofide NS by oxygen oxidation method | |
| CN101717378B (en) | Method for synthesizing rubber vulcanization accelerator DM by oxygen oxidization | |
| CN115819304B (en) | Preparation method of molybdenum disulfide catalyzed tetraethyl thiuram disulfide | |
| JP2011507830A (en) | Method for producing N-methylpyrrolidone | |
| CN113121368A (en) | Method for preparing gamma-aminopropanol by one-step catalytic hydrogenation and application thereof | |
| CN111808054A (en) | Preparation method of ionic liquid and application of ionic liquid in cyclohexanone synthesis | |
| CN103420777B (en) | Method for continuously synthesizing 1, 5, 9-cyclododecatriene | |
| CN114105905A (en) | Preparation method and synthesis system of N-tertiary butyl-2-benzothiazole sulfonamide | |
| CN113149911B (en) | Preparation method of high-purity 5-aminobenzimidazole ketone | |
| CN111393402B (en) | N & lt/EN & gt acid/quaternary ammonium salt composite catalytic CO 2 Method for preparing cyclic carbonate by cycloaddition with epoxide | |
| CN114478243A (en) | Method for synthesizing dihydroxy dimethyl terephthalate by oxygen catalytic oxidation method | |
| CN110437051B (en) | Preparation method of aluminum acetylacetonate | |
| CN110172029B (en) | Method for continuously synthesizing 2-amino-2-methyl-1-propanol | |
| CN108484505B (en) | Preparation method of 2-methylimidazole | |
| CN108997143B (en) | Self-acid-binding integrated production method of N, N-dimethyl chloroethylamine and tetramethyl ethylenediamine | |
| CN112250600A (en) | Process method for improving yield of N, N' -diisopropylcarbodiimide product | |
| CN115745846B (en) | Preparation method of metformin hydrochloride | |
| CN110105303A (en) | A method of using liquid chlorine as oxidant continuous production aniline fluid bed | |
| CN105017002B (en) | Reaction separation synchronous process for preparing adipic acid by oxidizing cyclohexene with hydrogen peroxide | |
| CN115784861B (en) | Method for producing trichloroacetone by continuous microchannel technology | |
| CN113248355B (en) | Preparation method of p-chlorobenzaldehyde | |
| CN118439979B (en) | Preparation method of chlorosulfonyl isocyanate | |
| CN112409150B (en) | Preparation method of dibenzoyl methane |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |