CN107638877B - Synthesis method of tetramethyl thiuram disulfide - Google Patents
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Abstract
The invention discloses a synthetic method of tetramethylthiuram disulfide (TMTD), which comprises the following steps: firstly, preparing a catalyst, wherein the catalyst is a composite material taking silicon dioxide as a carrier and platinum-rhodium alloy as a catalytic medium; adding raw materials into a reaction kettle, wherein a dimethylamine solution with the mass concentration of 20-50%, carbon disulfide, methanol and a catalyst are added into the reaction kettle to obtain a first mixture, then stirring the first mixture, and then adding a hydrogen peroxide solution with the mass concentration of 2-10% into the first mixture; and finally synthesizing TMTD, wherein oxygen is introduced into the reaction kettle, and the synthesis of the TMTD is carried out, wherein the synthesis temperature is 60-80 ℃, and the synthesis time is 2-10 min. The synthesis method of the invention has the advantages of high TMTD synthesis speed, complete synthesis reaction and prolonged service life of the catalyst.
Description
Technical Field
The invention relates to a synthetic method of a rubber vulcanization accelerator, in particular to a synthetic method of tetramethyl thiuram disulfide.
Background
The rubber vulcanization accelerator TMTD, the chemical name of which is tetramethyl thiuram disulfide, is a fine chemical widely applied at home and abroad. It is mainly used as overspeed accelerator in natural rubber, synthetic rubber and various latex. Meanwhile, the bactericide can also be used as an agricultural bactericide, called thiram for short.
At present, the methods for producing TMTD at home and abroad mainly comprise the following steps: sodium nitrite-air oxidation method, chlorine-air oxidation method, electrolytic oxidation method, etc. The chlorine-air oxidation method has the problems of high production cost, complex process flow, high technical requirement, waste gas and waste water generation, equipment corrosivity and the like.
Prior art document 1 (CN 104744328A) discloses a method for producing TMTD using isopropanol as a solvent, in which a one-step oxidation method is used to produce TMTD, but this method has the following problems: 1. the oxidation reaction is carried out slowly, the reaction time is generally longer than 3 hours, and the production efficiency is greatly influenced; 2. the reaction is not complete, so that a large amount of dimethylamine, carbon disulfide and other substances are remained in the wastewater after the reaction, and the substances have high toxicity, so that a factory needs to purchase special equipment to perform sewage treatment on the substances, and the production cost of the factory is increased.
Prior art document 2 (CN 1299814A) discloses a production method of TMTD, but the method has the following problems: 1. the problems of slow and incomplete oxidation reaction are also existed; 2. during the reaction, strong base NaOH is added to adjust the pH value of reactants, which leads to the sewage discharge not reaching the standard.
The information disclosed in this background section is only for enhancement of understanding of the general background of the invention and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.
Disclosure of Invention
The invention aims to provide a synthetic method of tetramethylthiuram disulfide (TMTD), thereby solving the problems of slow reaction speed, incomplete reaction and excessive pollutants in reaction products in the prior art.
In order to achieve the purpose, the invention provides a synthetic method of tetramethylthiuram disulfide (TMTD), which comprises the following steps: preparing a catalyst, wherein the catalyst is a manganese-containing composite material taking silicon dioxide as a carrier and platinum-rhodium alloy as a catalytic medium, and the preparation method of the catalyst comprises the following steps: putting platinum-rhodium alloy and metal manganese into a ball milling tank for ball milling until the particle diameters of the platinum-rhodium alloy and the metal manganese are 20-100nm to obtain catalyst metal particles, then dissolving the catalyst metal particles in silica gel to obtain catalyst slurry, then performing spray drying on the catalyst slurry to obtain a catalyst precursor, and finally firing the catalyst precursor in a nitrogen atmosphere to obtain the catalyst, wherein the firing temperature is 800-1000 ℃; adding raw materials into a reaction kettle: adding a dimethylamine solution with the mass concentration of 20-50%, carbon disulfide, methanol and a catalyst into a reaction kettle to obtain a first mixture, then stirring the first mixture, and then adding a hydrogen peroxide solution with the mass concentration of 2-10% into the first mixture; synthesizing TMTD: introducing oxygen into the reaction kettle, and synthesizing TMTD, wherein the synthesis reaction equation is as follows:
the synthesis temperature is 60-80 ℃, and the synthesis time is 2-10min, so as to obtain TMTD.
Preferably, in the above technical scheme, the particle size of the platinum-rhodium alloy and the metal manganese is 30-80 nm.
Preferably, in the above technical scheme, the mass ratio of the dimethylamine solution, the carbon disulfide, the methanol, the catalyst and the hydrogen peroxide solution is (1-5): 10-20): 0.1-0.3): 1-5.
Preferably, in the above technical solution, the firing temperature is 900-950 ℃.
Preferably, in the above technical scheme, in the step of synthesizing TMTD, the synthesis temperature is 70-75 ℃.
Preferably, in the above technical scheme, in the step of synthesizing TMTD, the synthesis time is 2-3 min.
Preferably, in the above technical scheme, the mass ratio of the dimethylamine solution, the carbon disulfide, the methanol, the catalyst and the hydrogen peroxide solution is 2:2:15:0.2: 2.
Preferably, in the above technical solution, the firing temperature is 920-.
Preferably, in the above technical scheme, in the step of synthesizing TMTD, the synthesis time is 2 min.
Preferably, in the above technical scheme, in the step of synthesizing TMTD, the synthesis temperature is 72-73 ℃.
Compared with the prior art, the invention has the following beneficial effects: 1. the inventor surprisingly finds that the synthesis speed of TMTD synthesized by one-step oxidation method can be greatly increased by adding platinum-rhodium alloy catalyst taking silicon dioxide as carrier in the reaction process, and the synthesis reaction is carried out more thoroughly, thereby overcoming the defects of slow reaction speed and excessive pollutants in the reaction product in the prior art; 2. the particle size of the platinum-rhodium alloy is adjusted by increasing the ball milling time, and the material ratio is adjusted, so that the speed of the synthesis reaction can be further improved, and the synthesis reaction can be further carried out more thoroughly; 3. by controlling the firing temperature of the catalyst and adding the metal manganese, the catalyst poisoning can be prevented, and the service life of the catalyst is prolonged; 4. by introducing oxygen in the synthesis process and increasing the reaction temperature (in the prior art, the reaction temperature is lower than 50 ℃, the reaction temperature is increased to 60-80 ℃ in the invention, and the inventor finds that the increase of the reaction temperature has no adverse effect on the synthesis reaction), the synthesis reaction can be promoted and the synthesis reaction speed can be increased.
Detailed Description
The following detailed description of the present invention is provided in conjunction with the accompanying drawings, but it should be understood that the scope of the present invention is not limited to the specific embodiments.
Throughout the specification and claims, unless explicitly stated otherwise, the word "comprise", or variations such as "comprises" or "comprising", will be understood to imply the inclusion of a stated element or component but not the exclusion of any other element or component.
The chemical reagents used in the present invention are commercially available from chemical stores, the oxygen used is common industrial pure oxygen, the sintering reaction of the catalyst is carried out in a sintering furnace, and the spray method for preparing the catalyst is known in the art (see, for example, prior art document 3: CN 106423189A).
Example 1
Preparing a catalyst, wherein the catalyst is a manganese-containing composite material taking silicon dioxide as a carrier and platinum-rhodium alloy as a catalytic medium, and the preparation method of the catalyst comprises the following steps: putting a platinum-rhodium alloy and metal manganese into a ball milling tank for ball milling until the particle sizes of the platinum-rhodium alloy and the metal manganese are 20-100nm to obtain catalyst metal particles, then dissolving the catalyst metal particles in silica gel to obtain catalyst slurry, then performing spray drying on the catalyst slurry to obtain a catalyst precursor, and finally firing the catalyst precursor in a nitrogen atmosphere to obtain the catalyst, wherein the firing temperature is 1000 ℃; adding raw materials into a reaction kettle: adding a dimethylamine solution with the mass concentration of 20, carbon disulfide, methanol and a catalyst into a reaction kettle to obtain a first mixture, then stirring the first mixture, and then adding a hydrogen peroxide solution with the mass concentration of 2% into the first mixture; synthesizing TMTD: introducing oxygen into the reaction kettle, and synthesizing TMTD at 60 ℃ for 10min to obtain TMTD, wherein the mass ratio of the dimethylamine solution, the carbon disulfide, the methanol, the catalyst and the hydrogen peroxide solution is 1:1:10:0.1: 1. And then measuring the content of the materials in the wastewater to calculate the reaction progress, wherein more than 95 percent of the materials are reacted after measurement and calculation.
Example 2
Preparing a catalyst, wherein the catalyst is a manganese-containing composite material taking silicon dioxide as a carrier and platinum-rhodium alloy as a catalytic medium, and the preparation method of the catalyst comprises the following steps: putting a platinum-rhodium alloy and metal manganese into a ball milling tank for ball milling until the particle sizes of the platinum-rhodium alloy and the metal manganese are 20-100nm to obtain catalyst metal particles, then dissolving the catalyst metal particles in silica gel to obtain catalyst slurry, then performing spray drying on the catalyst slurry to obtain a catalyst precursor, and finally firing the catalyst precursor in a nitrogen atmosphere to obtain the catalyst, wherein the firing temperature is 800 ℃; adding raw materials into a reaction kettle: adding a dimethylamine solution with the mass concentration of 30%, carbon disulfide, methanol and a catalyst into a reaction kettle to obtain a first mixture, then stirring the first mixture, and then adding a hydrogen peroxide solution with the mass concentration of 3% into the first mixture; synthesizing TMTD: and introducing oxygen into the reaction kettle, and synthesizing TMTD at 80 ℃ for 2min to obtain TMTD, wherein the mass ratio of the dimethylamine solution, the carbon disulfide, the methanol, the catalyst and the hydrogen peroxide solution is 5:5:20:0.3: 5. And then measuring the content of the materials in the wastewater to calculate the reaction progress, wherein more than 95 percent of the materials are reacted after measurement and calculation.
Example 3
Preparing a catalyst, wherein the catalyst is a manganese-containing composite material taking silicon dioxide as a carrier and platinum-rhodium alloy as a catalytic medium, and the preparation method of the catalyst comprises the following steps: putting a platinum-rhodium alloy and metal manganese into a ball milling tank for ball milling, carrying out long-time ball milling until the particle sizes of the platinum-rhodium alloy and the metal manganese are 30-80nm to obtain catalyst metal particles, then dissolving the catalyst metal particles in silica gel to obtain catalyst slurry, then carrying out spray drying on the catalyst slurry to obtain a catalyst precursor, and finally firing the catalyst precursor in a nitrogen atmosphere to obtain the catalyst, wherein the firing temperature is 900 ℃; adding raw materials into a reaction kettle: adding a dimethylamine solution with the mass concentration of 40%, carbon disulfide, methanol and a catalyst into a reaction kettle to obtain a first mixture, then stirring the first mixture, and then adding a hydrogen peroxide solution with the mass concentration of 5% into the first mixture; synthesizing TMTD: introducing oxygen into the reaction kettle, and synthesizing TMTD at 70 ℃ for 3min to obtain TMTD, wherein the mass ratio of the dimethylamine solution, the carbon disulfide, the methanol, the catalyst and the hydrogen peroxide solution is 2:2:15:0.2: 2. And then measuring the content of the materials in the wastewater to calculate the reaction progress, wherein more than 95 percent of the materials are reacted after measurement and calculation.
Example 4
Preparing a catalyst, wherein the catalyst is a manganese-containing composite material taking silicon dioxide as a carrier and platinum-rhodium alloy as a catalytic medium, and the preparation method of the catalyst comprises the following steps: putting a platinum-rhodium alloy and metal manganese into a ball milling tank for ball milling until the particle sizes of the platinum-rhodium alloy and the metal manganese are 20-100nm to obtain catalyst metal particles, then dissolving the catalyst metal particles in silica gel to obtain catalyst slurry, then performing spray drying on the catalyst slurry to obtain a catalyst precursor, and finally firing the catalyst precursor in a nitrogen atmosphere to obtain the catalyst, wherein the firing temperature is 950 ℃; adding raw materials into a reaction kettle: adding a dimethylamine solution with the mass concentration of 50%, carbon disulfide, methanol and a catalyst into a reaction kettle to obtain a first mixture, then stirring the first mixture, and then adding a hydrogen peroxide solution with the mass concentration of 10% into the first mixture; synthesizing TMTD: introducing oxygen into the reaction kettle, and synthesizing TMTD at 75 ℃ for 3min to obtain TMTD, wherein the mass ratio of the dimethylamine solution, the carbon disulfide, the methanol, the catalyst and the hydrogen peroxide solution is 2:2:15:0.2: 2. And then measuring the content of the materials in the wastewater to calculate the reaction progress, wherein more than 95 percent of the materials are reacted after measurement and calculation.
Comparative example 1
Adding raw materials into a reaction kettle: adding a dimethylamine solution with the mass concentration of 50%, carbon disulfide, methanol and a catalyst into a reaction kettle to obtain a first mixture, then stirring the first mixture, and then adding a hydrogen peroxide solution with the mass concentration of 10% into the first mixture; synthesizing TMTD: introducing oxygen into the reaction kettle, and synthesizing TMTD at 75 ℃ for 3h to obtain TMTD, wherein the mass ratio of the dimethylamine solution, the carbon disulfide, the methanol, the catalyst and the hydrogen peroxide solution is 2:2:15:0.2: 2. No catalyst was used in this comparative example. And then, measuring the content of the materials in the wastewater to calculate the reaction progress, wherein only about 70 percent of the materials are reacted through measurement and calculation. The toxic substances in the wastewater are more. And the reaction product TMTD was found to have been oxidized and the product quality was poor. It can be seen that the reaction temperature cannot be higher than 50 ℃ without the addition of the catalyst, otherwise a high-quality product cannot be obtained.
Comparative example 2
Preparing a catalyst, wherein the catalyst is a manganese-containing composite material taking silicon dioxide as a carrier and platinum-rhodium alloy as a catalytic medium, and the preparation method of the catalyst comprises the following steps: putting a platinum-rhodium alloy and metal manganese into a ball milling tank for ball milling, so as to shorten the ball milling time, wherein the particle size of the platinum-rhodium alloy and the metal manganese is more than 200nm, so as to obtain catalyst metal particles, then dissolving the catalyst metal particles in silica gel, so as to obtain catalyst slurry, then performing spray drying on the catalyst slurry, so as to obtain a catalyst precursor, and finally, firing the catalyst precursor in a nitrogen atmosphere, so as to obtain a catalyst, wherein the firing temperature is 950 ℃; adding raw materials into a reaction kettle: adding a dimethylamine solution with the mass concentration of 50%, carbon disulfide, methanol and a catalyst into a reaction kettle to obtain a first mixture, then stirring the first mixture, and then adding a hydrogen peroxide solution with the mass concentration of 10% into the first mixture; synthesizing TMTD: introducing oxygen into the reaction kettle, and synthesizing TMTD at 75 ℃ for 3min to obtain TMTD, wherein the mass ratio of the dimethylamine solution, the carbon disulfide, the methanol, the catalyst and the hydrogen peroxide solution is 2:2:15:0.2: 2. And then measuring the content of the materials in the wastewater to calculate the reaction progress, wherein about 60 percent of the materials are reacted after measurement and calculation. The inventors have found that the reaction proceeds to a lesser extent due to catalyst poisoning, resulting in a lower extent of reaction under preferred conditions.
Comparative example 3
Preparing a catalyst, wherein the catalyst is a manganese-containing composite material taking silicon dioxide as a carrier and platinum-rhodium alloy as a catalytic medium, and the preparation method of the catalyst comprises the following steps: putting a platinum-rhodium alloy into a ball milling tank for ball milling, shortening the ball milling time, wherein the particle size of the platinum-rhodium alloy is 20-100nm to obtain catalyst metal particles, dissolving the catalyst metal particles in silica gel to obtain catalyst slurry, performing spray drying on the catalyst slurry to obtain a catalyst precursor, and finally firing the catalyst precursor in a nitrogen atmosphere to obtain the catalyst, wherein the firing temperature is 950 ℃; adding raw materials into a reaction kettle: adding a dimethylamine solution with the mass concentration of 50%, carbon disulfide, methanol and a catalyst into a reaction kettle to obtain a first mixture, then stirring the first mixture, and then adding a hydrogen peroxide solution with the mass concentration of 10% into the first mixture; synthesizing TMTD: introducing oxygen into the reaction kettle, and synthesizing TMTD at 75 ℃ for 3min to obtain TMTD, wherein the mass ratio of the dimethylamine solution, the carbon disulfide, the methanol, the catalyst and the hydrogen peroxide solution is 2:2:15:0.2: 2. No metallic manganese was added in this comparative example. And then measuring the content of the materials in the wastewater to calculate the reaction progress, wherein about 60 percent of the materials are reacted after measurement and calculation. The inventors have found that the reaction proceeds to a lesser extent due to catalyst poisoning, resulting in a lower extent of reaction under preferred conditions.
Comparative example 4
The firing temperature of the catalyst was 700 ℃. Other experimental conditions were the same as in example 4. And then measuring the content of the materials in the wastewater to calculate the reaction progress, wherein about 60 percent of the materials are reacted after measurement and calculation. The inventors have found that the reaction proceeds to a lesser extent due to catalyst poisoning, resulting in a lower extent of reaction under preferred conditions.
Comparative example 5
In the synthesis of TMTD, the synthesis temperature was 40 ℃ and the synthesis time was 3min, and other experimental conditions were the same as in example 4. And then measuring the content of the materials in the wastewater to calculate the reaction progress, wherein about 70 percent of the materials are reacted after measurement and calculation.
Comparative example 6
In the synthesis of TMTD, the synthesis temperature was 90 ℃ and the synthesis time was 1min, and other experimental conditions were the same as in example 4. And then measuring the content of the materials in the wastewater to calculate the reaction progress, wherein about 70 percent of the materials are reacted after measurement and calculation. The product TMTD is oxidized and the product quality is poor.
Comparative example 7
In the synthesis of TMTD, oxygen was not introduced, and the other experimental conditions were the same as in example 4. And then measuring the content of the materials in the wastewater to calculate the reaction progress, wherein about 85 percent of the materials are reacted after measurement and calculation.
The foregoing descriptions of specific exemplary embodiments of the present invention have been presented for purposes of illustration and description. It is not intended to limit the invention to the precise form disclosed, and obviously many modifications and variations are possible in light of the above teaching. The exemplary embodiments were chosen and described in order to explain certain principles of the invention and its practical application to enable one skilled in the art to make and use various exemplary embodiments of the invention and various alternatives and modifications as are suited to the particular use contemplated. It is intended that the scope of the invention be defined by the claims and their equivalents.
Claims (10)
1. A synthetic method of tetramethyl thiuram disulfide (TMTD) is characterized by comprising the following steps: the synthesis method comprises the following steps:
preparing a catalyst: the catalyst is a manganese-containing composite material with silicon dioxide as a carrier and platinum-rhodium alloy as a catalytic medium, and the preparation method of the catalyst comprises the following steps: putting a platinum-rhodium alloy and metal manganese into a ball milling tank for ball milling until the particle sizes of the platinum-rhodium alloy and the metal manganese are 20-100nm to obtain catalyst metal particles, then dispersing the catalyst metal particles in silica gel to obtain catalyst slurry, then performing spray drying on the catalyst slurry to obtain a catalyst precursor, and finally firing the catalyst precursor in a nitrogen atmosphere to obtain the catalyst, wherein the firing temperature is 800-1000 ℃;
adding raw materials into a reaction kettle: adding a dimethylamine solution with the mass concentration of 20-50%, carbon disulfide, methanol and a catalyst into the reaction kettle to obtain a first mixture, then stirring the first mixture, and then adding a hydrogen peroxide solution with the mass concentration of 2-10% into the first mixture;
synthesizing TMTD: introducing oxygen into the reaction kettle, and synthesizing TMTD, wherein the synthesis reaction equation is as follows:
the synthesis temperature is 60-80 ℃, and the synthesis time is 2-10min, so as to obtain TMTD.
2. The method of synthesis according to claim 1, characterized in that: the particle size of the platinum-rhodium alloy and the metal manganese is 30-80 nm.
3. The method of synthesis according to claim 1, characterized in that: the mass ratio of the dimethylamine solution to the carbon disulfide to the methanol to the catalyst to the hydrogen peroxide solution is (1-5) to (10-20) to (0.1-0.3):
(1-5)。
4. the method of synthesis according to claim 1, characterized in that: the firing temperature is 900-950 ℃.
5. The method of synthesis according to claim 1, characterized in that: in the step of synthesizing TMTD, the synthesis temperature is 70-75 ℃.
6. The method of synthesis according to claim 1, characterized in that: in the step of synthesizing TMTD, the synthesis time is 2-3 min.
7. The method of synthesis according to claim 3, characterized in that: the mass ratio of the dimethylamine solution to the carbon disulfide to the methanol to the catalyst to the hydrogen peroxide solution is 2:2:15:0.2: 2.
8. The method of synthesis according to claim 4, characterized in that: the firing temperature is 920-930 ℃.
9. The method of synthesis according to claim 1, characterized in that: in the step of synthesizing TMTD, the synthesis time is 2 min.
10. The method of synthesis according to claim 5, characterized in that: in the step of synthesizing TMTD, the synthesis temperature is 72-73 ℃.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5015752A (en) * | 1984-10-27 | 1991-05-14 | Akzo N.V. | Thiuram polysulfide |
| CN1096024A (en) * | 1992-12-30 | 1994-12-07 | 孟山都公司 | catalytic oxidation |
| CN1944505A (en) * | 2006-10-30 | 2007-04-11 | 濮阳市蔚林化工有限公司 | Production method of rubber vulcanization accelerator tetrabenzylthiuram disulfide |
| CN104593808A (en) * | 2013-10-30 | 2015-05-06 | 青岛旺裕橡胶制品有限公司 | Preparation method of rubber promoter tetramethyl thiuram disulfide |
| CN106966935A (en) * | 2017-03-30 | 2017-07-21 | 山东斯递尔化工科技有限公司 | A kind of method that utilization micro-reaction device continuously prepares tetramethylthiuram disulfide |
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- 2017-09-28 CN CN201710896996.2A patent/CN107638877B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5015752A (en) * | 1984-10-27 | 1991-05-14 | Akzo N.V. | Thiuram polysulfide |
| CN1096024A (en) * | 1992-12-30 | 1994-12-07 | 孟山都公司 | catalytic oxidation |
| CN1944505A (en) * | 2006-10-30 | 2007-04-11 | 濮阳市蔚林化工有限公司 | Production method of rubber vulcanization accelerator tetrabenzylthiuram disulfide |
| CN104593808A (en) * | 2013-10-30 | 2015-05-06 | 青岛旺裕橡胶制品有限公司 | Preparation method of rubber promoter tetramethyl thiuram disulfide |
| CN106966935A (en) * | 2017-03-30 | 2017-07-21 | 山东斯递尔化工科技有限公司 | A kind of method that utilization micro-reaction device continuously prepares tetramethylthiuram disulfide |
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Address after: Chongwen Zhen Jia Luo Pu Cun, Lingchuan County, Jincheng City, Shanxi Province 048300 Patentee after: Jincheng Tiancheng Technology Co.,Ltd. Address before: 048399 Chongwen Town, Lingchuan County, Jincheng City, Shanxi Province, Jiaxu Pak Village Patentee before: JINCHENG SKY SUCCESS CHEMICAL Co.,Ltd. |
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Denomination of invention: Synthesis of tetramethylthiuram disulfide Effective date of registration: 20230209 Granted publication date: 20200714 Pledgee: Agricultural Bank of China Limited Lingchuan County Sub-branch Pledgor: Jincheng Tiancheng Technology Co.,Ltd. Registration number: Y2023140000008 |