CN108147986B - Method for preparing tetraethyl thiuram disulfide - Google Patents
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Abstract
The invention relates to the field of rubber additives, and particularly provides a preparation method of tetraethyl thiuram disulfide. The method can promote the reaction to be carried out efficiently and continuously by utilizing the bimetallic catalyst, improve the conversion rate of the raw materials, and facilitate the condensation reaction and the oxidation reaction to be carried out more easily, thereby improving the yield of the product. The method has simple and convenient process operation, can greatly improve the yield of the product, reduce the production cost, has no three wastes discharge in the preparation process, realizes the reutilization of the mother solution, has no pollution to the environment, simultaneously has stable quality of the prepared product, high purity and uniform components, and can be applied to production practice in a large scale.
Description
Technical Field
The invention relates to the field of rubber auxiliaries, in particular to a preparation method of tetraethylthiuram disulfide.
Background
The rubber industry of China is on the way to move into the market, the synthetic rubber industry forms a relatively complete industrial system, the synthetic rubber industry enters a faster development period, and the consumption of the rubber vulcanization accelerator is increased rapidly.
The vulcanization accelerator, which can be called accelerator for short, is used for accelerating the vulcanization speed, shortening the vulcanization time, reducing the vulcanization temperature, reducing the consumption of vulcanizing agent and simultaneously improving the physical and mechanical properties of vulcanized rubber during rubber vulcanization. Tetraethylthiuram Disulfide (TETD) is used as a superaccelerator and vulcanizing agent for natural rubber, styrene butadiene rubber, nitrile butadiene rubber, butyl rubber, butadiene rubber, and latex.
The effective sulfur content of the tetraethylthiuram disulfide is 11 percent of the mass of the tetraethylthiuram disulfide, is a second accelerator with excellent thiazole accelerators, has catalytic action on acid accelerators and guanidine accelerators, is easy to disperse in rubber materials, has no pollution and no color change, can also be used as a bactericide, an insecticide, a medical intermediate and the like, and is usually used for manufacturing cables, rubberized fabric, rubber shoes, inner tubes, bright-colored products and the like.
The synthesis technology of tetraethyl thiuram disulfide adopts a two-step method for the most part at present: condensation and then oxidation. Firstly, diethylamine, sodium hydroxide and carbon disulfide are condensed at the temperature of 30-40 ℃ to generate sodium diethyldithiocarbamate; then filtering carbon residue, oxidizing the mother liquor by chlorine or nitrous acid and air to generate tetraethyl thiuram disulfide, cooling, filtering, drying and crushing to obtain a finished product with the yield of only 86%. The production process is mature, but has the defects of serious three wastes, higher product consumption quota, high physical labor intensity, poor operation environment and the like; in addition, the oxygen oxidation synthesis process is also a hotspot of current research, and the process comprises the steps of adding a certain amount of diethylamine, a catalyst manganese acetate or EDTA metal complex into a pressure-resistant container, adding a mixed solution consisting of methanol and carbon disulfide, and introducing oxygen under strong stirring to reach a set pressure, wherein the reaction is complete within about 1-3 hours, and the yield is 92-95%. The process is carried out under the pressure state in the production, and reactants in the reaction kettle are gaseous substances and are easy to explode, so that great potential safety hazards exist in the production process, and the energy consumption in the production process is high.
Therefore, it is of great significance to research and develop a method for preparing tetraethyl thiuram disulfide, which has simple process, low toxicity, easy recovery or can completely use solvents and processes, high product yield and high melting point.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The invention aims to provide a method for preparing tetraethyl thiuram disulfide, which solves the technical problems of complicated process, high energy consumption, high three wastes, serious environmental pollution and low yield in the production of tetraethyl thiuram disulfide in the prior art.
In order to achieve the above purpose of the present invention, the following technical solutions are adopted:
the invention provides a preparation method of tetraethyl thiuram disulfide, which comprises the step of reacting reaction raw materials of diethylamine, carbon disulfide and hydrogen peroxide under the action of a bimetallic catalyst to obtain the tetraethyl thiuram disulfide.
Further, the bimetallic catalyst comprises Pd-Co-Al2O3、Pd-Mn-Al2O3Or Pd-Ni-Al2O3Any one or a combination of at least two of the above.
Further, the mass of the bimetallic catalyst is 0.2-0.5% of that of diethylamine.
Further, the mass ratio of the diethylamine to the carbon disulfide to the hydrogen peroxide is 1 (1.04-1.25) to 0.84-1.20;
the mass fraction of the hydrogen peroxide is 25-29%.
Further, the preparation method comprises the following steps:
step a): adding carbon disulfide into a solution containing a bimetallic catalyst and diethylamine by adopting a dropwise adding method to react the carbon disulfide and the diethylamine to obtain a first solution;
step b): and dropwise adding hydrogen peroxide into the obtained first solution for reaction to obtain the tetraethylthiuram disulfide after the reaction is finished.
Further, in the step a), the reaction temperature is 15-25 ℃, the dropping time of the carbon disulfide is 1.0-1.5h, and the reaction is continued for 0.5-1.0h after the dropping is finished;
preferably, in the solution containing the bimetallic catalyst and diethylamine, the mass ratio between the solvent and diethylamine is (5.0-7.0): 1.
further, in the step b), firstly, mixing hydrogen peroxide and an organic solvent to obtain a second solution, and then dropwise adding the second solution into the first solution for reaction;
preferably, the organic solvent is a lower alcohol, including methanol, ethanol, isopropanol or n-butanol;
preferably, the reaction temperature is 25-30 ℃, the dropping time is 2.0-3.0h, and the reaction is continued for 0.5-1.0h after the dropping is finished.
Further, the mass ratio of the organic solvent to the hydrogen peroxide is (2.0-3.0): 1.
Further, in the step b), after the dropwise addition of hydrogen peroxide for reaction, sequentially filtering, washing and drying to obtain the tetraethylthiuram disulfide.
Further, the mother liquor obtained after filtration is recycled or recycled;
preferably, 50-70% of the mother liquor obtained after filtration is recycled;
preferably, 30-50% of mother liquor obtained after filtration is recovered and treated to obtain the organic solvent;
preferably, the recovery treatment is carried out by adopting a method of atmospheric distillation recovery;
preferably, the recovered organic solvent is used for preparing a second solution by compounding with hydrogen peroxide.
Compared with the prior art, the invention has the beneficial effects that:
the invention provides a preparation method of tetraethyl thiuram disulfide, which comprises the step of reacting reaction raw materials of diethylamine, carbon disulfide and hydrogen peroxide under the action of a bimetallic catalyst to obtain the tetraethyl thiuram disulfide. The method can promote the reaction to be efficiently and continuously carried out by utilizing the bimetallic catalyst, improve the conversion rate of the raw materials, and facilitate the condensation reaction and the oxidation reaction, thereby improving the yield of the product. The method has simple and convenient process operation, can greatly improve the yield of the product, reduce the production cost, has no three wastes discharge in the preparation process, realizes the reutilization of the mother solution, has no pollution to the environment, simultaneously has stable quality of the prepared product, high purity and uniform components, and can be applied to production practice in a large scale.
Drawings
FIG. 1 is a high performance liquid chromatogram of tetraethylthiuram disulfide for example 6;
FIG. 2 is a high performance liquid chromatogram of tetraethylthiuram disulfide for example 7;
FIG. 3 is a high performance liquid chromatogram of tetraethylthiuram disulfide for example 8;
FIG. 4 is a high performance liquid chromatogram of tetraethylthiuram disulfide for example 9;
FIG. 5 is a high performance liquid chromatogram of tetraethylthiuram disulfide for example 10;
FIG. 6 is a chart of NMR results for tetraethylthiuram disulfide in example 6.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer.
The invention provides a preparation method of tetraethyl thiuram disulfide, which comprises the step of reacting reaction raw materials of diethylamine, carbon disulfide and hydrogen peroxide under the action of a bimetallic catalyst to obtain the tetraethyl thiuram disulfide.
The chemical reaction formula for preparing the tetraethyl thiuram disulfide (TETD) is as follows:
the diethylamine is colorless liquid, and has the characteristics of strong basicity, corrosivity, easy volatilization, flammability and the like; boiling point 55 deg.C, relative density (water 1)0.71, and optionally mixing with water or ethanol; appearance and properties: colorless liquid with ammonia odor.
The carbon disulfide is colorless or light yellow transparent liquid, and the pure product has an ethereal smell and is easy to volatilize; melting point: -111.9 ℃ and density 1.26g/cm3Relative vapor density (air ═ 1)2.64, boiling point 46.2 ℃; insoluble in water, soluble in ethanol, ether and other organic solvents, and can dissolve sulfur simple substance. Carbon disulfide is used in the manufacture of rayon, pesticides, accelerators, and the like, and also as a solvent.
Hydrogen peroxide (chemical formula: H)2O2) Pure hydrogen peroxide is a pale blue, viscous liquid,can be mixed and dissolved with water in any proportion, is a strong oxidant, and the water solution is commonly called hydrogen peroxide and is colorless transparent liquid.
The method can promote the reaction to be carried out efficiently and continuously by utilizing the bimetallic catalyst, improve the conversion rate of the raw materials, and facilitate the condensation reaction and the oxidation reaction to be carried out more easily, thereby improving the yield of the product. The method has simple and convenient process operation, can greatly improve the yield of the product, reduce the production cost, has no three wastes discharge in the preparation process, realizes the reutilization of the mother solution, has no pollution to the environment, simultaneously has stable quality of the prepared product, high purity and uniform components, and can be applied to production practice in a large scale.
In one embodiment of the invention, the bimetallic catalyst comprises Pd-Co-Al2O3、Pd-Mn-Al2O3Or Pd-Ni-Al2O3Any one or a combination of at least two of the above. The viscosity of the reaction liquid is very high, the mixing and contact of the raw materials can be insufficient, and the addition of the bimetallic catalyst can greatly improve the reaction efficiency, accelerate the reaction rate and enable the reaction to be more sufficient. The reaction rate and the yield of product can be further increased by preference to bimetallic catalysts.
In one embodiment of the invention, the bimetallic catalyst mass is between 0.2% and 0.5% of the mass of diethylamine. The proper amount of catalyst can ensure the smooth and efficient reaction, the reaction efficiency is reduced by too little catalyst, and the purity of the tetraethylthiuram disulfide is influenced by too much catalyst. The bimetallic catalyst is typically, but not limited to, 0.2%, 0.3%, 0.4%, or 0.5% by mass of diethylamine.
In one embodiment of the invention, the mass ratio of the diethylamine to the carbon disulfide to the hydrogen peroxide is 1 (1.04-1.25) to 0.84-1.20; the mass fraction of the hydrogen peroxide is 25-29%. The hydrogen peroxide mass fraction in hydrogen peroxide is typically, but not limited to, 25%, 26%, 27.5%, or 29%; the mass ratio of diethylamine, carbon disulfide and hydrogen peroxide is typically, but not limited to, 1: 1.04: 0.84, 1: 1.04: 0.94, 1: 1.04: 1.04, 1: 1.04: 1.20, 1: 1.10: 0.84, 1: 1.10: 0.94, 1: 1.10: 1.04, 1: 1.10: 1.20, 1: 1.18: 0.84, 1: 1.18: 0.94, 1: 1.18: 1.04, 1: 1.18: 1.20, 1: 1.25: 0.84, 1: 1.25: 0.94, 1: 1.25: 1.04 or 1: 1.25: 1.20; .
In one embodiment of the present invention, the preparation method comprises the steps of:
step a): adding carbon disulfide into a solution containing a bimetallic catalyst and diethylamine by adopting a dropwise adding method to react the carbon disulfide and the diethylamine to obtain a first solution;
step b): and dropwise adding hydrogen peroxide into the obtained first solution for reaction to obtain the tetraethylthiuram disulfide after the reaction is finished.
The dropwise addition of the carbon disulfide and the hydrogen peroxide is separated, so that the reaction can be carried out more fully, the temperature can be controlled better in the operation process, the reaction efficiency is further improved, and the product conversion rate is improved.
In one embodiment of the invention, in the step a), the reaction temperature is 15-25 ℃, the dropping time of the carbon disulfide is 1.0-1.5h, and the reaction is continued for 0.5-1.0h after the dropping is finished;
the reaction temperature is typically, but not limited to, 15 ℃, 18 ℃, 20 ℃, 22 ℃ or 25 ℃; the dropping time is typically but not limited to 1.0h, 1.1h, 1.2h, 1.3h, 1.4h or 1.5 h; the reaction time continued after the end of the dropwise addition is typically, but not limited to, 0.5h, 0.6h, 0.7h, 0.8h, 0.9h or 1.0 h.
Preferably, in the solution containing the bimetallic catalyst and diethylamine, the mass ratio between the solvent and diethylamine is (5.0-7.0): 1.
the solvent in the solution containing the bimetallic catalyst and diethylamine includes, but is not limited to, lower alcohols including methanol, ethanol, isopropanol or n-butanol. The mass ratio of solvent to diethylamine is typically, but not limited to, 5.0:1, 5.5:1, 6.0:1, 6.5:1, or 7.0: 1.
In one embodiment of the invention, in the step b), firstly, hydrogen peroxide and an organic solvent are mixed to obtain a second solution, and then the second solution is dropwise added into the first solution for reaction;
preferably, the organic solvent is a lower alcohol, including methanol, ethanol, isopropanol or n-butanol;
the hydrogen peroxide is easy to decompose when meeting heat and light, the stability of the hydrogen peroxide can be improved by premixing the hydrogen peroxide and the organic solvent, and the hydrogen peroxide can be better mixed with the first solution when being dripped into the first solution, so that the reaction is accelerated, and the loss of the hydrogen peroxide is reduced. Organic solvents include, but are not limited to, lower alcohols, including methanol, ethanol, isopropanol, or n-butanol.
Preferably, the reaction temperature is 25-30 ℃, the dropping time is 2.0-3.0h, and the reaction is continued for 0.5-1.0h after the dropping is finished.
The reaction temperature is typically, but not limited to, 25 ℃, 26 ℃, 27 ℃, 28 ℃, 29 ℃ or 30 ℃; the dropping time is typically but not limited to 2.0h, 2.1h, 2.2h, 2.3h, 2.4h, 2.5h, 2.6h, 2.7h, 2.8h, 2.9h or 3.0 h; the reaction time continued after the end of the dropwise addition is typically, but not limited to, 0.5h, 0.6h, 0.7h, 0.8h, 0.9h or 1.0 h.
In one embodiment of the present invention, the mass ratio of the organic solvent to the hydrogen peroxide is (2.0-3.0): 1. The mass ratio of the organic solvent to the hydrogen peroxide is typically, but not limited to, 2.0:1, 2.3:1, 2.6:1, 2.8:1, or 3.0: 1.
In one embodiment of the invention, after the dropwise addition of hydrogen peroxide in the step b) is finished, the tetraethylthiuram disulfide is obtained by filtering, washing and drying in sequence.
And after the reaction is finished, filtering to remove reaction liquid, washing the obtained tetraethyl thiuram disulfide to remove the reaction liquid, drying the washed tetraethyl thiuram disulfide, and drying or airing to obtain the finished tetraethyl thiuram disulfide.
In one embodiment of the invention, the mother liquor obtained after filtration is recycled or recycled; the filtered mother liquor can be directly used for the next solvent to prepare a solution containing a bimetallic catalyst and diethylamine for producing tetraethylthiuram disulfide; the mother liquor after filtration can also be used for removing water and mixing hydrogen peroxide, and the mother liquor can be recycled.
Preferably, 50-70% of the mother liquor obtained after filtration is recycled;
preferably, 30-50% of mother liquor obtained after filtration is recovered and treated to obtain the organic solvent;
preferably, the recovery treatment is carried out by adopting a method of atmospheric distillation recovery;
preferably, the recovered organic solvent is used for preparing a second solution by compounding with hydrogen peroxide.
In order to facilitate a further understanding of the present invention, the technical solutions of the present invention will now be described in detail with reference to the preferred embodiments.
Example 1
The embodiment is a method for preparing tetraethylthiuram disulfide, which comprises the following steps:
under normal pressure, 270g of n-butanol and 0.09g of Pd-Mn-Al were added2O3Adding into a 1000ml four-mouth bottle, stirring and mixing, then adding 60g diethylamine, controlling the temperature to be 12 ℃, beginning to dropwise add 60g carbon disulfide, controlling the temperature to be 12 ℃ in the dropwise adding process, and controlling the dropwise adding time to be 40 min; after the dropwise addition is finished, controlling the temperature to be 12 ℃ and reacting for 20 min; heating to 22 ℃, starting to dropwise add 48g of hydrogen peroxide, controlling the dropwise adding speed to enable the reaction temperature to be 22 ℃, and controlling the dropwise adding time to be 1.5 h; then preserving the heat and reacting for 20 min; and after the heat preservation is finished, filtering, washing, drying and packaging.
Example 2
The embodiment is a method for preparing tetraethylthiuram disulfide, which comprises the following steps:
480g of n-butanol and 0.36g of Pd-Mn-Al were added under normal pressure2O3Adding the mixture into a 1000ml four-mouth bottle, stirring and mixing, then adding 60g of diethylamine, controlling the temperature to be 28 ℃, and beginning to dropwise add 78g of carbon disulfide, wherein the temperature is controlled to be 28 ℃ in the dropwise adding process, and the dropwise adding time is 40 min; after the dropwise addition is finished, controlling the temperature to be 28 ℃ and reacting for 20 min; heating to 35 ℃, starting to dropwise add 75g of hydrogen peroxide, controlling the dropwise adding speed to enable the reaction temperature to be 35 ℃, and controlling the dropwise adding time to be 1.5 h; then preserving the heat and reacting for 20 min; and after the heat preservation is finished, filtering, washing, drying and packaging.
Example 3
The embodiment is a method for preparing tetraethylthiuram disulfide, which comprises the following steps:
300g of n-butanol and 0.12g of Pd-Mn-Al were added under normal pressure2O3Adding the mixture into a 1000ml four-mouth bottle, stirring and mixing, then adding 60g of diethylamine, controlling the temperature to be 15 ℃, beginning to dropwise add 62.4g of carbon disulfide, controlling the temperature to be 15 ℃ in the dropwise adding process, and controlling the dropwise adding time to be 1.0 h; after the dropwise addition is finished, controlling the temperature to be 15 ℃ and reacting for 0.5 h; heating to 25 ℃, beginning to dropwise add 50.4g of hydrogen peroxide, controlling the dropwise adding speed to enable the reaction temperature to be 25 ℃, and controlling the dropwise adding time to be 2.0 h; then preserving the heat and reacting for 0.5 h; and after the heat preservation is finished, filtering, washing, drying and packaging.
Example 4
The embodiment is a method for preparing tetraethylthiuram disulfide, which comprises the following steps:
300g of n-butanol and 0.12g of Pd-Mn-Al were added under normal pressure2O3Adding the mixture into a 1000ml four-mouth bottle, stirring and mixing, then adding 60g of diethylamine, controlling the temperature to be 15 ℃, beginning to dropwise add 62.4g of carbon disulfide, controlling the temperature to be 15 ℃ in the dropwise adding process, and controlling the dropwise adding time to be 1.0 h; after the dropwise addition is finished, controlling the temperature to be 15 ℃ and reacting for 0.5 h; heating to 25 ℃, starting to dropwise add a mixed solution of 50.4g of hydrogen peroxide and 100.8g of n-butanol, controlling the dropwise adding speed to ensure that the reaction temperature is 25 ℃ and the dropwise adding time is 2.0 h; then preserving the heat and reacting for 0.5 h; and after the heat preservation is finished, filtering, washing, drying and packaging.
Example 5
The embodiment is a method for preparing tetraethylthiuram disulfide, which comprises the following steps:
300g of methanol and 0.21g of Pd-Ni-Al are mixed under normal pressure2O3Adding the mixture into a 1000ml four-mouth bottle, stirring and mixing, then adding 42.86g of diethylamine, controlling the temperature to be 25 ℃, beginning to dropwise add 53.58g of carbon disulfide, controlling the temperature to be 25 ℃ in the dropwise adding process, and controlling the dropwise adding time to be 1.5 h; after the dropwise addition is finished, controlling the temperature to be 25 ℃ and reacting for 1.0 h; heating to 30 ℃, starting to dropwise add a mixed solution of 51.43g of hydrogen peroxide and 154.30g of methanol, controlling the dropwise adding speed to ensure that the reaction temperature is 30 ℃ and the dropwise adding time is 3.0 h; then preserving the heat and reacting for 1.0 h; after the heat preservation is finishedAnd (5) filtering, washing, drying and packaging.
Example 6
The embodiment is a method for preparing tetraethylthiuram disulfide, which comprises the following steps:
under the condition of normal pressure, 300g of ethanol and 0.12g of Pd-Mn-Al are added2O3Adding the mixture into a 1000ml four-mouth bottle, stirring and mixing, then adding 60g of diethylamine, controlling the temperature to be 18 ℃, beginning to dropwise add 62.46g of carbon disulfide, controlling the temperature to be 18 ℃ in the dropwise adding process, and controlling the dropwise adding time to be 1.0 h; after the dropwise addition is finished, the temperature is controlled to be 18 ℃ and the reaction is carried out for 1.0 h; heating to 26 ℃, starting to dropwise add a mixed solution of 50.73g of hydrogen peroxide and 101.46g of ethanol, controlling the dropwise adding speed to enable the reaction temperature to be 26 ℃, and controlling the dropwise adding time to be 2.5 h; then preserving the heat and reacting for 0.5 h; and after the heat preservation is finished, filtering, washing, drying and packaging. The high performance liquid chromatogram of the tetraethylthiuram disulfide product is shown in figure 1, and the nuclear magnetic spectrum result of the tetraethylthiuram disulfide is shown in figure 6.
Example 7
The embodiment is a method for preparing tetraethylthiuram disulfide, which comprises the following steps:
under the condition of normal pressure, 300g of ethanol and 0.12g of Pd-Mn-Al are added2O3Adding the mixture into a 1000ml four-mouth bottle, stirring and mixing, then adding 50g of diethylamine, controlling the temperature to be 18 ℃, beginning to dropwise add 62.46g of carbon disulfide, controlling the temperature to be 18 ℃ in the dropwise adding process, and controlling the dropwise adding time to be 1.0 h; after the dropwise addition is finished, the temperature is controlled to be 18 ℃ and the reaction is carried out for 1.0 h; heating to 26 ℃, starting to dropwise add a mixed solution of 50.73g of hydrogen peroxide and 101.46g of ethanol, controlling the dropwise adding speed to enable the reaction temperature to be 26 ℃, and controlling the dropwise adding time to be 2.5 h; then preserving the heat and reacting for 0.5 h; and after the heat preservation is finished, filtering, washing, drying and packaging. The high performance liquid chromatogram of the tetraethylthiuram disulfide product is shown in figure 2.
Example 8
The embodiment is a method for preparing tetraethylthiuram disulfide, which comprises the following steps:
250g of isopropanol and 0.1g of Pd-Co-Al are added under normal pressure2O3Adding the mixture into a 1000ml four-mouth bottle, stirring and mixing, then adding 35.71g of diethylamine, controlling the temperature to be 20 ℃, beginning to dropwise add 37.17g of carbon disulfide, controlling the temperature to be 20 ℃ in the dropwise adding process, and controlling the dropwise adding time to be 1.3 h; after the dropwise addition is finished, the temperature is controlled to be 20 ℃ and the reaction is carried out for 0.5 h; heating to 28 ℃, starting to dropwise add a mixed solution of 36.23g of hydrogen peroxide and 108.69g of isopropanol, controlling the dropwise adding speed to ensure that the reaction temperature is 28 ℃ and the dropwise adding time is 3.0 h; then preserving the heat and reacting for 0.5 h; and after the heat preservation is finished, filtering, washing, drying and packaging. The high performance liquid chromatogram of the tetraethylthiuram disulfide product is shown in figure 3.
Example 9
The embodiment is a method for preparing tetraethylthiuram disulfide, which comprises the following steps:
250g of isopropanol and 0.1g of Pd-Co-Al are added under normal pressure2O3Adding the mixture into a 1000ml four-mouth bottle, stirring and mixing, then adding 35.71g of diethylamine, controlling the temperature to be 20 ℃, beginning to dropwise add 37.17g of carbon disulfide, controlling the temperature to be 20 ℃ in the dropwise adding process, and controlling the dropwise adding time to be 1.3 h; after the dropwise addition is finished, the temperature is controlled to be 20 ℃ and the reaction is carried out for 0.5 h; heating to 28 ℃, starting to dropwise add a mixed solution of 42.27g of hydrogen peroxide and 126.81g of isopropanol, controlling the dropwise adding speed to ensure that the reaction temperature is 30 ℃ and the dropwise adding time is 3.0 h; then preserving the heat and reacting for 0.5 h; and after the heat preservation is finished, filtering, washing, drying and packaging. The high performance liquid chromatogram of the tetraethylthiuram disulfide product is shown in figure 4.
Example 10
The embodiment is a method for preparing tetraethylthiuram disulfide, which comprises the following steps:
under normal pressure, 260g of methanol and 0.17g of Pd-Ni-Al are added2O3Adding the mixture into a 1000ml four-mouth bottle, stirring and mixing, then adding 43.33g of diethylamine, controlling the temperature to be 22 ℃, beginning to dropwise add 45.11g of carbon disulfide, controlling the temperature to be 22 ℃ in the dropwise adding process, and controlling the dropwise adding time to be 1.0 h; after the dropwise addition is finished, the temperature is controlled to be 22 ℃ and the reaction is carried out for 1.0 h; the temperature was raised to 28 ℃ and a mixed solution of 43.96g of hydrogen peroxide and 109.90g of methanol was added dropwise at a rate such that the reaction temperature was 28 ℃ and the addition time was 2.5 h; then preserving the heat and reacting for 0.7 h; and after the heat preservation is finished, filtering, washing, drying and packaging. The high performance liquid chromatogram of the tetraethylthiuram disulfide product is shown in figure 5.
Comparative example 1
A preparation process of tetraethyl thiuram disulfide comprises the following preparation steps: 115g of isopropanol (150ml) were placed in a reactor, 40.5g of diethylamine were placed in the reactor at room temperature, and the stirrer was started to stir for 5 min; pressing 39g of carbon disulfide into an overhead tank by hydraulic pressure, starting stirring, slowly dripping the carbon disulfide into a reactor, heating up quickly at the moment, controlling the dripping speed, and starting cooling water, but the last liquid seal water cannot be put in; pumping 40g of hydrogen peroxide into an overhead tank by using a pump, slowly dripping hydrogen peroxide after carbon disulfide is slightly dripped, and dripping hydrogen peroxide after carbon disulfide is dripped; after the hydrogen peroxide is dripped, stirring for 30min, standing for 10min, filtering the materials in a suction filtration barrel, washing TETD light yellow granular matters with a small amount of water, vacuum-drying, drying in a drying room at 50 ℃, drying for 50h to obtain the tetraethylthiuram disulfide, and measuring moisture, melting point and ash content.
Comparative example 2
This comparative example is a process for the preparation of tetraethylthiuram disulfide and is different from example 8 in that the catalyst used in the comparative example is Co-Al2O3The rest of the raw materials and the preparation process parameters are the same as those of example 8.
Comparative example 3
This comparative example is a process for the preparation of tetraethylthiuram disulfide and is different from example 9 in that the catalyst used in the comparative example is Pd-Al2O3The rest of the raw materials and the preparation process parameters were the same as in example 9.
Comparative example 4
This comparative example is a method for producing tetraethylthiuram disulfide, and is different from example 10 in that the catalyst used in the comparative example is Mn-Al2O3The rest of the raw materials and the preparation process parameters were the same as those of example 10.
Test examples
Tetraethylthiuram disulfide was produced according to the production methods described in examples 1 to 10 and comparative examples 1 to 4, the product yield was calculated, and the initial melting point and the tetraethylthiuram disulfide purity were tested.
As can be seen from the above examples 1-10, the preparation method provided by the invention has the advantages that the appearance of the target product is white crystal, the yield is above 95.0%, the initial melting point is not lower than 69 ℃, and the product purity is more than 99.0%. The overall performance of the product is greatly improved, and compared with comparative examples 1-4, the use of the bimetallic catalyst greatly improves the reaction rate and promotes the reaction to be more complete. The preparation method provided by the invention greatly improves the yield of the tetraethyl thiuram disulfide, has simple preparation process, can directly recycle the filtrate obtained after the production is finished, greatly simplifies the operation process and reduces the production cost.
While particular embodiments of the present invention have been illustrated and described, it would be obvious that various other changes and modifications can be made without departing from the spirit and scope of the invention. It is therefore intended to cover in the appended claims all such changes and modifications that are within the scope of this invention.
Claims (16)
1. A preparation method of tetraethyl thiuram disulfide is characterized in that reaction raw materials diethylamine, carbon disulfide and hydrogen peroxide are reacted under the action of a bimetallic catalyst to obtain the tetraethyl thiuram disulfide;
the bimetallic catalyst comprises Pd-Co-Al2O3、Pd-Mn-Al2O3Or Pd-Ni-Al2O3Any one or a combination of at least two of the above.
2. The method according to claim 1, wherein the mass of the bimetallic catalyst is 0.2-0.5% of the mass of diethylamine.
3. The preparation method of claim 1, wherein the mass ratio of the diethylamine to the carbon disulfide to the hydrogen peroxide is 1 (1.04-1.25) to (0.84-1.20);
the mass fraction of the hydrogen peroxide is 25-29%.
4. The method for preparing according to any one of claims 1 to 3, comprising the steps of:
step a): adding carbon disulfide into a solution containing a bimetallic catalyst and diethylamine by adopting a dropwise adding method to react the carbon disulfide and the diethylamine to obtain a first solution;
step b): and dropwise adding hydrogen peroxide into the obtained first solution for reaction to obtain the tetraethylthiuram disulfide after the reaction is finished.
5. The preparation method according to claim 4, wherein in the step a), the reaction temperature is 15-25 ℃, the dropping time of the carbon disulfide is 1.0-1.5h, and the reaction is continued for 0.5-1.0h after the dropping is finished.
6. The method according to claim 4, wherein in the solution containing the bimetallic catalyst and diethylamine in step a), the mass ratio between the solvent and diethylamine is (5.0-7.0): 1.
7. the preparation method according to claim 4, wherein in the step b), the reaction temperature is 25-30 ℃, the dropping time is 2.0-3.0h, and the reaction is continued for 0.5-1.0h after the dropping is finished.
8. The preparation method according to claim 4, wherein in the step b), the hydrogen peroxide and the organic solvent are mixed to obtain a second solution, and then the second solution is dropwise added into the first solution for reaction.
9. The method according to claim 8, wherein the organic solvent is a lower alcohol, and the lower alcohol is methanol, ethanol, isopropanol or n-butanol.
10. The preparation method according to claim 8, wherein the mass ratio of the organic solvent to the hydrogen peroxide is (2.0-3.0): 1.
11. The preparation method according to claim 4, wherein in the step b), after the dropwise addition of hydrogen peroxide is completed, the tetraethylthiuram disulfide is obtained by filtering, washing with water and drying in sequence.
12. The method according to claim 11, wherein the mother liquor obtained after filtration is recycled or recovered.
13. The method according to claim 12, wherein 50 to 70% of the mother liquor obtained after filtration is recycled.
14. The method according to claim 12, wherein the organic solvent is obtained by recovering 30 to 50% of the mother liquor obtained after the filtration.
15. The method according to claim 12, wherein the recovery treatment is carried out by an atmospheric distillation recovery method.
16. The method according to claim 12, wherein the recovered organic solvent is used to prepare the second solution by combining with hydrogen peroxide.
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