CN115819304A - Preparation method of molybdenum disulfide catalyzed tetraethylthiuram disulfide - Google Patents
Preparation method of molybdenum disulfide catalyzed tetraethylthiuram disulfide Download PDFInfo
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- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 229910052982 molybdenum disulfide Inorganic materials 0.000 title claims abstract description 29
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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparation method of molybdenum disulfide catalyzed tetraethylthiuram 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, filtering and drying to obtain tetraethylthiuram disulfide crystals. And filling molybdenum disulfide into a micro fixed bed for later use, injecting a reaction solution containing carbon disulfide, secondary amine and alkali and oxygen into the fixed bed simultaneously for heterogeneous catalytic reaction, cooling and crystallizing an effluent solution phase, and filtering and drying to obtain a crystal of tetraethylthiuram disulfide. The purity of the tetraethyl thiuram disulfide obtained by the method reaches more than 98 percent, and the method is green and environment-friendly, has mild conditions, can recycle the catalyst and is easy to separate the product.
Description
Technical Field
The invention belongs to the technical field of rubber accelerator production, and relates to a synthetic method of a tetraethyl disulfide thiuram rubber accelerator, in particular to a green synthetic method of the tetraethyl disulfide thiuram rubber accelerator.
Background
Tetraethylthiuram disulfide, abbreviated as TETD, has the following structural formula:
the thiuram accelerator is a vulcanization accelerator widely applied to rubber products, wherein the tetrahydrocarbyl thiuram disulfide is used as an ultra-fast rubber accelerator, so that the vulcanization temperature can be reduced, the consumption of a vulcanizing agent can be reduced, the physical and mechanical properties of vulcanized rubber can be improved, and simultaneously, active sulfur is easily released at the conventional vulcanization temperature, so that rubber materials can be vulcanized without adding sulfur. The conventional tetraalkylthiuram disulfides mainly include tetramethylthiuram disulfide (TMTD), tetraethylthiuram disulfide (TETD), tetrabenzylthiuram disulfide (TBzTD) and the like. Wherein 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 an excellent second accelerator of thiazole accelerators, and has catalytic action on acid and guanidine accelerators. TETD is also used to treat chronic alcohol addiction. In addition to alcohol, it is also used for the withdrawal treatment of cocaine. In addition, TETD is also being considered by many researchers as an important subject for the treatment of cancer and HIV.
In the traditional process, the preparation method of tetraethyl thiuram disulfide mostly adopts a synthesis path taking secondary amine, carbon disulfide, sodium hydroxide and double oxidation as raw materials. Although the reaction speed of the technology is high, excessive NaOH needs sulfuric acid or hydrochloric acid to neutralize in the reaction process, and an intractable inorganic salt byproduct is generated; secondly, strong acid and strong base added in the reaction process can corrode reaction equipment to a certain degree. CN108147986B discloses Pd-Co-Al mixed with carbon disulfide, diethylamine and hydrogen peroxide 2 O 3 、Pd-Mn-Al 2 O 3 Or Pd-Ni-Al 2 O 3 The method for preparing the tetraethyl thiuram disulfide under the action of any two metal catalysts is simple and convenient to operate on the process, but the used metal catalysts are generally expensive, and meanwhile, the reaction process is easy to form a complex with a reaction intermediate to pollute the product; and the hydrogen peroxide contains a large amount of water, resulting in a medium after the reactionThe method needs water removal and refining, and has high energy consumption, so the method still has great limitation on realizing industrial application.
CN112358428A discloses a method for preparing tetraethylthiuram disulfide through photocatalytic oxidation, in the scheme, secondary amine, carbon disulfide and a catalyst are reacted under the condition of light, cheap dye is used as the catalyst in the reaction, and the green synthesis of the thiuram is realized under the extremely mild condition. The technology has the defects that the dye and the reaction liquid are in a homogeneous phase state, and the purification of the product is inconvenient.
Disclosure of Invention
The invention provides a novel method for preparing tetraethyl thiuram disulfide, aiming at the technical limitation existing in the traditional production method of tetraethyl thiuram disulfide.
Aiming at the defects of the prior art, in particular to the problems that the prior art uses corrosive raw materials such as strong acid, strong base, strong oxidizer and the like, so that equipment corrosion, product peroxidation, inorganic salt byproduct generation and the like are easily caused. 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 purpose of the invention is realized by the following technical scheme:
a one-pot method for preparing tetraethyl thiuram disulfide is provided, which takes oxygen as reaction atmosphere, takes carbon disulfide and diethylamine as raw materials, takes molybdenum disulfide as catalyst, and carries out reaction under alkaline condition, thus obtaining the tetraethyl thiuram disulfide.
In the one-pot method, the mol ratio of diethylamine to carbon disulfide to alkaline reagent to 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 above 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 an alkali reagent under a stirring state to obtain a mixed solution, mixing the mixed solution and oxygen at a mixer to form gas-liquid discontinuous flow, then feeding the gas-liquid discontinuous flow into a micro-fixed bed filled with molybdenum disulfide, and cooling, crystallizing, filtering and drying the solution after the solution flows out to obtain the tetraethyl thiuram disulfide.
In the fixed bed method: the residence time of the reaction liquid in the fixed bed is 10-30 minutes, and the reaction temperature is room temperature.
In the fixed bed method: in the continuous flow micro fixed bed method, the flow rate of the mixed solution pumped into the liquid is 0.8-0.12 mL/min, and the flow rate of oxygen is accurately controlled at 2.0-2.5 sccm by a mass flow controller.
In the 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 back pressure valve of 20-75 psi.
In the fixed bed method: the solvent used in the reaction process is ethanol or methanol.
In the fixed bed method: the mol ratio of diethylamine to carbon disulfide to alkaline agent to 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 the tetraethylthiuram disulfide needle crystal.
Compared with the traditional metal salt catalysts such as copper acetate, manganese acetate and the like, the molybdenum disulfide with low price is used as the catalyst, and byproducts formed by intermediate products and metal salts are not generated.
The method uses oxygen as an oxidant, is more environment-friendly than common hydrogen peroxide, and does not need dehydration and refining after reaction.
The possible mechanism of the molybdenum disulfide catalytic oxidation is as follows: oxygen forms superoxide ion free radical on the surface of molybdenum disulfide in the reaction process, and the superoxide ion free radical participates in the subsequent oxidation reaction
The invention utilizes gas-liquid-solid three-phase mixing technology under the microreactor, has high reaction speed, mild conditions, difficult peroxidation, no inorganic salt by-product, high product yield and good quality.
The present invention employs a continuous flow technique. 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 type reaction kettle, the continuous flow technology has stable product quality, excellent quality and stronger market competitiveness.
The tetraethyl thiuram disulfide product obtained by the reaction of the invention is needle-shaped crystal, the melting point is above 70 ℃ (standard product: 70.3-70.9 ℃), and the purity is above 99%.
Drawings
FIG. 1 is a schematic diagram of the synthesis scheme of the present invention.
Detailed Description
For a more clear understanding of the objects, features and significance of the present invention, the present invention will be further described with reference to specific embodiments.
Example 1
This example provides a detailed process for the preparation of tetraethylthiuram disulfide in ethanol solution in a one-pot process, comprising the following steps: adding 50 ml of ethanol into a reaction kettle, then adding 2.3 g of carbon disulfide (30 mmol), 1.8 g of diethylamine (25 mmol) and 2.5 g of triethylamine (25 mmol) in sequence under the condition of stirring, adding 0.5 g of molybdenum disulfide (3.125 mmol) into the reaction system after the dropwise addition is finished, finally introducing oxygen into the upper end of the reaction kettle, and reacting for 12 hours at room temperature. After the reaction, the solution phase obtained by filtering the heterogeneous solution is cooled and crystallized to obtain needle-shaped crystals, and then the needle-shaped crystals are subjected to suction filtration, water washing, drying, recrystallization, water washing, suction filtration and drying to obtain 3.99 g of solid. The steps of suction filtration, water washing and drying are the same as the steps of the conventional tetraethylthiuram disulfide preparation, in the embodiment, the water washing is carried out twice, and the drying temperature is 40 ℃ for 5 hours.
And detecting the obtained finished product: the appearance is white crystal, the melting point is 71.6 ℃ (melting range: 70.9-71.6 ℃), the purity is 99.0 percent, and the yield is 90 percent.
Example 2
This example provides a detailed process for the preparation of tetraethylthiuram disulfide in methanol solution in a one-pot process, comprising the following steps: adding 50 ml of methanol into a reaction kettle, then adding 2.3 g of carbon disulfide (30 mmol), 1.8 g of diethylamine (25 mmol) and 2.5 g of triethylamine (25 mmol) dropwise in sequence under the condition of stirring, adding 0.5 g of molybdenum disulfide (3.125 mmol) into the reaction system after the dropwise addition is finished, and finally introducing oxygen into the upper end of the reaction kettle to react for 12 hours at room temperature. After the reaction, the solution phase obtained by filtering the heterogeneous solution is cooled and crystallized to obtain needle-shaped crystals, and then the needle-shaped crystals are subjected to suction filtration, water washing, drying, recrystallization, water washing, suction filtration and drying to obtain 3.92 g of solid. The steps of suction filtration, water washing and drying are the same as the steps of the conventional tetraethylthiuram disulfide preparation, in the embodiment, the water washing is carried out twice, and the drying temperature is 40 ℃ for 5 hours.
And detecting the obtained finished product: the appearance is white crystal, the melting point is 71.3 ℃ (melting range: 70.6-71.3 ℃), the purity is 98.7%, and the yield is 88%.
Example 3
This example provides a detailed process for the preparation of tetraethylthiuram disulfide in ethanol solution in a one-pot process, comprising the following steps: 50 ml of ethanol was added to the reaction kettle, 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) in this order with stirring. After 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 to react at room temperature for 8 hours. After the reaction, the filtrate is filtered, cooled and crystallized to obtain needle-shaped crystals, and then the needle-shaped crystals are filtered, washed, dried, recrystallized, washed, filtered and dried to obtain 3.21 g of solid. The steps of suction filtration, water washing and drying are the same as the steps of the conventional tetraethylthiuram disulfide preparation, in the embodiment, the water washing is carried out twice, and the drying temperature is 40 ℃ for 5 hours.
And detecting the obtained finished product: the appearance is white crystal, the melting point is 72.0 ℃ (melting range: 71.4-72.0 ℃), the purity is 97.9%, and the yield is 72%.
Example 4
This example provides a detailed process for the preparation of tetraethylthiuram disulfide in ethanol solution in a one-pot process, comprising the following steps: adding 50 ml of ethanol into a reaction kettle, then adding 1.9 g of carbon disulfide (25 mmol), 1.8 g of diethylamine (25 mmol) and 2.5 g of triethylamine (25 mmol) dropwise in sequence under the condition of stirring, adding 0.5 g of molybdenum disulfide (3.125 mmol) into the reaction system after dropwise addition, and finally introducing oxygen at the upper end of the reaction kettle to react for 12 hours at room temperature. After the reaction, the solution phase obtained by filtering the heterogeneous solution is cooled and crystallized to obtain needle-shaped crystals, and then the needle-shaped crystals are filtered, washed, dried, recrystallized, washed, filtered and dried to obtain 3.74 g of solid. The steps of suction filtration, water washing and drying are the same as the steps of the conventional preparation of tetraethylthiuram disulfide, in the embodiment, the water washing is carried out twice, and the drying temperature is 40 ℃ for 5 hours.
And detecting the obtained finished product: the appearance is white crystal, the melting point is 71.5 ℃ (melting range: 70.7-71.5 ℃), the purity is 98.9%, and the yield is 84%.
Example 5
This example provides a detailed process for the preparation of tetraethylthiuram disulfide in ethanol solution in a one-pot process, comprising the following steps: adding 50 ml of ethanol into a reaction kettle, then adding 2.3 g of carbon disulfide (30 mmol), 1.8 g of diethylamine (25 mmol) and 2.5 g of triethylamine (25 mmol) dropwise in sequence under the condition of stirring, adding 1.0 g of molybdenum disulfide (6.25 mmol) into the reaction system after dropwise addition, and finally introducing oxygen into the upper end of the reaction kettle to react for 12 hours at room temperature. After the reaction, the solution phase obtained by filtering the heterogeneous solution is cooled and crystallized to obtain needle-shaped crystals, and the needle-shaped crystals are subjected to suction filtration, water washing, drying, recrystallization, water washing, suction filtration and drying to obtain 4.05 g of solid. The steps of suction filtration, water washing and drying are the same as the steps of the conventional tetraethylthiuram disulfide preparation, in the embodiment, the water washing is carried out twice, and the drying temperature is 40 ℃ for 5 hours.
And detecting the obtained finished product: the appearance is white crystal, the melting point is 72.1 ℃ (melting range: 71.3-72.1 ℃), the purity is 99.0%, and the yield is 91%.
Example 6
This example provides a detailed process for the preparation of tetraethylthiuram disulfide in a continuous flow microfed-fixed bed, the steps of which are as follows: and (3) preparing a micro fixed bed filled with molybdenum disulfide, namely filling 2.17 g of molybdenum disulfide into a fixed bed with the inner diameter of 4.6mm and the length of 15.0cm, and sealing and filtering two ends of the fixed bed by using absorbent cotton and a sieve plate. 50 ml of ethanol is taken and added with 2.3 g of carbon disulfide (30 mmol), 1.8 g of diethylamine (25 mmol) and 2.5 g of triethylamine (25 mmol) in turn under the condition of stirring to prepare a solution before reaction. The reaction liquid (flow rate: 0.1 mL/min) is pumped by a constant flow pump, the molar flow (2.25 sccm) of the introduced oxygen is accurately controlled by a mass flow controller, the liquid in the reactor and the oxygen are mixed at a mixer to form discontinuous flow with the liquid/gas length ratio of 1/2, the discontinuous flow enters a micro fixed bed filled with molybdenum disulfide, the residence time in the micro fixed bed is 18 minutes, the liquid flows out of the micro fixed bed and then flows through a 40psi back pressure valve, the system pressure is 0.6MPa, the liquid finally flows into a collection tank, after the completion, needle-shaped crystals are cooled and crystallized, and then the solid with the weight of 3.92 g is obtained by suction filtration, water washing, drying, recrystallization, water washing, suction filtration and drying. In this example, the mixture was washed twice with water and dried at 40 ℃ for 5 hours. And detecting the obtained finished product: the appearance is white crystal, the melting point is 71.6 ℃ (melting range: 70.9-71.6 ℃), the purity is 98.8%, and the yield is 88%.
Example 7
This example provides a detailed process for the preparation of tetraethylthiuram disulfide in a continuous flow microfed-fixed bed, the steps of which are as follows: and (3) preparing a micro fixed bed filled with molybdenum disulfide, namely filling 2.17 g of molybdenum disulfide into a fixed bed with the inner diameter of 4.6mm and the length of 15.0cm, and sealing and filtering two ends of the fixed bed by using absorbent cotton and a sieve plate. 50 ml of ethanol is taken and added with 2.3 g of carbon disulfide (30 mmol), 1.8 g of diethylamine (25 mmol) and 2.5 g of triethylamine (25 mmol) in turn under the condition of stirring to prepare a solution before reaction. Pumping reaction liquid (flow rate: 0.1 mL/min) by using a constant flow pump, accurately controlling the molar flow (2.25 sccm) of introduced oxygen by using a mass flow controller, mixing the liquid in the reactor and the oxygen at a mixer to form gas-liquid discontinuous flow with liquid/gas of 1/2, allowing the gas-liquid discontinuous flow to enter a micro fixed bed filled with molybdenum disulfide, allowing the gas-liquid discontinuous flow to stay in the micro fixed bed for 18 minutes, allowing the liquid to flow out of the micro fixed bed and then flow through a back pressure valve of 20psi, allowing the system pressure to be 0.45MPa, allowing the liquid to finally flow into a collection tank, cooling and crystallizing after the system pressure is finished, and then performing suction filtration, water washing, drying, recrystallization, water washing, suction filtration and drying to obtain 3.47 g of solid. In this example, the mixture was washed twice with water and dried at 40 ℃ for 5 hours. And detecting the obtained finished product: the appearance is white crystal, the melting point is 71.4 ℃ (melting range: 70.6-71.4 ℃), the purity is 99.0 percent, and the yield is 78 percent.
Comparative example 1
The comparative example differs from example 1 in that:
molybdenum disulfide is not added in the whole reaction system, and the other conditions are kept consistent. After the reaction, a liquid chromatography detection shows that no signal of the tetraethylthiuram disulfide is found. Therefore, the importance of the molybdenum disulfide on the synthesis of the tetraethyl thiuram disulfide is indispensable to the reaction.
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 (10)
1. A method for preparing tetraethyl thiuram disulfide by a one-pot method is characterized in that oxygen is used as 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 condition, so that the tetraethyl thiuram disulfide can be obtained.
2. The method for preparing tetraethylthiuram disulfide according to claim 1, wherein the molar ratio of diethylamine to carbon disulfide to the alkaline agent to molybdenum disulfide is 1: (1.0-1.5): 1: (0.1-0.3).
3. The one-pot tetraethylthiuram disulfide production method according to claim 1, wherein the reaction time is 8 to 12 hours and the reaction temperature is room temperature.
4. The one-pot process for the production of tetraethylthiuram disulfide according to claim 1 or 2, wherein the basic agent is triethylamine.
5. The method for preparing tetraethylthiuram disulfide according to claim 1, wherein the solvent used in the reaction is ethanol or methanol.
6. A method for preparing tetraethyl thiuram disulfide by a fixed bed method is characterized by comprising the following steps: and sequentially adding carbon disulfide, diethylamine and an alkali reagent under a stirring state to obtain a mixed solution, mixing the mixed solution and oxygen at a mixer to form gas-liquid discontinuous flow, then entering a micro-fixed bed filled with molybdenum disulfide, and cooling, crystallizing, filtering and drying the solution after the solution flows out to obtain the tetraethylthiuram disulfide.
7. The method for preparing tetraethylthiuram disulfide according to claim 6, wherein the residence time of the reaction solution in the fixed bed 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 by a mass flow controller to be 2.0-2.5 sccm; 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 back pressure valve of 20-75 psi.
9. The method for preparing tetraethylthiuram disulfide according to claim 6, wherein the molar ratio of diethylamine to carbon disulfide to the alkaline agent to molybdenum disulfide is 1: (1.0-1.5): 1: (0.1-1).
10. The method for preparing tetraethylthiuram disulfide according to claim 6, wherein the solvent used in the reaction is ethanol or methanol.
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| 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 |
| CN110526846A (en) * | 2018-05-25 | 2019-12-03 | 李志安 | The efficient preparation process of the Environmental Safety of pharmaceutical grade tetraethylthiuram disulfide |
| CN110526845A (en) * | 2018-05-25 | 2019-12-03 | 李志安 | A kind of pollution-free high-efficient rate preparation method of 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 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| CN110526846A (en) * | 2018-05-25 | 2019-12-03 | 李志安 | The efficient preparation process of the Environmental Safety of pharmaceutical grade tetraethylthiuram disulfide |
| CN110526845A (en) * | 2018-05-25 | 2019-12-03 | 李志安 | A kind of pollution-free high-efficient rate preparation method of 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 |
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