CN112341369A - Preparation method of dialkyl dithiocarbamate - Google Patents
Preparation method of dialkyl dithiocarbamate Download PDFInfo
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- CN112341369A CN112341369A CN201910724097.3A CN201910724097A CN112341369A CN 112341369 A CN112341369 A CN 112341369A CN 201910724097 A CN201910724097 A CN 201910724097A CN 112341369 A CN112341369 A CN 112341369A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C333/00—Derivatives of thiocarbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C333/14—Dithiocarbamic acids; Derivatives thereof
- C07C333/18—Esters of dithiocarbamic acids
- C07C333/20—Esters of dithiocarbamic acids having nitrogen atoms of dithiocarbamate groups bound to hydrogen atoms or to acyclic carbon atoms
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- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0093—Microreactors, e.g. miniaturised or microfabricated reactors
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
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Abstract
The invention relates to a preparation method of dialkyl dithiocarbamate, which comprises the steps of adding secondary alkylamine, carbon disulfide, dichloromethane and alkali liquor into a microflow tube reactor for reaction, and preparing the dialkyl dithiocarbamate by a one-step method, wherein the reaction temperature is controlled to be 20-100 ℃, and the reaction time is 11-128 s. The method not only optimizes the operation steps, but also obviously shortens the reaction time, can realize continuous production and greatly improves the economic benefit of the product.
Description
Technical Field
The invention belongs to the technical field of compound preparation, and particularly relates to a preparation method of dialkyl dithiocarbamate.
Background
Dialkyl dithiocarbamate and metal salts thereof are good antioxidant and antiwear lubricating oil additives, have outstanding antioxidant performance, good antiwear performance and extreme pressure performance, have the characteristics of good oil solubility, no ash, no phosphorus and the like, and are widely applied to various oil products such as turbine oil, internal combustion engine oil, hydraulic oil, gear oil and the like and lubricating grease.
At home and abroad, patents and reports about dialkyl dithiocarbamate are generally that secondary alkylamine, alkali solution and carbon disulfide are subjected to condensation reaction at low temperature, and dichloromethane is added for reaction to prepare dialkyl dithiocarbamate; the two-step reaction has strict requirements on temperature, the operation process is more complicated, the material volatilization is serious, and the environmental protection and health are greatly influenced.
US patent US5744629 discloses a process for preparing dialkyldithiocarbamates. Firstly, reacting an aqueous solution of sodium hydroxide and di-n-butylamine with carbon disulfide in a high-pressure kettle at the temperature of not higher than 15 ℃ for 0.5 hour, slowly dropping excessive dichloromethane, gradually raising the temperature, and reacting at 75-80 ℃ for 2 hours; after the reaction is finished, reduced pressure distillation is carried out in two steps: the first step is carried out at the temperature of 45-100 ℃ and the pressure of 5-50 kPa, then phase separation is carried out at the temperature of 35-50 ℃, and the second step is carried out, and the separated organic phase is subjected to reduced pressure distillation again, so that the product with the ASTM chromaticity less than 2 can be obtained finally. The method adopts an intermittent two-step method to synthesize dialkyl dithiocarbamate, mainly aims at improving the color of a product, and adopts low-temperature dropwise adding CS2The chroma is reduced by the way of carrying out reaction and then distilling the organic phase twice under reduced pressure, but the operation is complicated, the reaction time is long, and the material consumption and the energy consumption are high.
In the method for preparing dialkyl dithiocarbamate by adopting the batch two-step method in the United states patent US 3876550, the problem that the viscosity of materials is high during low-temperature reaction and the reaction is influenced by uneven mixing is considered, so toluene and isopropanol are added as solvents to play a role in diluting and reduce the viscosity of a reaction system, but the product yield is not high and is only about 40%, meanwhile, the operation process of solvent recovery is increased, and in addition, partial solvent residues also exist in the product to influence the product quality.
Chinese patent CN1364759A discloses a preparation method of dialkyl dithiocarbamate, which comprises the steps of dropwise adding carbon disulfide into a mixed solution of dichloromethane, secondary alkylamine and NaOH aqueous solution at the temperature of 10-60 ℃ by taking ethanol as a solvent, reacting for 0.5-5 hours, heating to 50-100 ℃, continuing to react for 1-12 hours, and separating to obtain a product. The method mainly aims to shorten the dropping time of the raw materials, but needs to add an additional organic solvent, increases the steps of extraction, solvent recovery and the like, and limits the yield and the process cost.
U.S. Pat. Nos. 5015368 and 4967007 disclose a process for preparing dialkyldithiocarbamates in a two-step process. The said patent adopts raising reaction temperature to reduce the viscosity of the reaction system, and the produced product has dark color and low yield.
Therefore, in the prior art, carbon disulfide is generally added into a secondary alkylamine and sodium hydroxide solution dropwise to react at a low temperature to prepare sodium salt, and then dichloromethane is added to carry out alkylation reaction, so that the reaction time is long, and the yield is not high. Some of them need additional organic solvent, which increases production cost and operation steps. Particularly, in the process of dropwise adding the carbon disulfide and the dichloromethane, the volatilization of the carbon disulfide and the dichloromethane is difficult to avoid, and great hidden dangers are brought to the environment and the health. In addition, the product performance of many methods needs to be improved, and problems such as low purity, poor color and luster exist.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to provide a preparation method of dialkyl dithiocarbamate aiming at the defects of the prior art. The method adopts a micro-flow tube reaction technology to replace the traditional intermittent method, and utilizes a constant flow pump to add the raw materials of secondary alkylamine, alkali liquor, carbon disulfide and dichloromethane into a micro-flow tube reactor to synthesize the dialkyl dithiocarbamate in one step, thereby not only optimizing the operation steps, but also obviously shortening the reaction time, realizing continuous production and greatly improving the economic benefit of the product.
The technical scheme is as follows: the purpose of the invention is realized by the following technical scheme:
the micro-reactor technology is newly developed in recent years, has the characteristics of high-efficiency heat transfer and mass transfer, and has obvious advantages compared with the traditional intermittent mode: the method has the advantages of shortening the reaction time, having good material mixing effect, being capable of obviously reducing the energy consumption and material consumption, and the like. The invention provides a preparation method of dialkyl dithiocarbamate, which comprises the steps of adding secondary alkylamine, carbon disulfide, dichloromethane and alkali liquor into a microflow tube reactor for reaction, and preparing the dialkyl dithiocarbamate by a one-step method.
The reaction temperature is controlled to be 20-100 ℃, and preferably 35-75 ℃.
The reaction time is 11-128 s, preferably 30-70 s.
The secondary alkylamine is a dialkylamine having 1 to 20 carbon atoms, preferably a dialkylamine having 4 to 8 carbon atoms. Further preferred is di-n-butylamine.
Since the secondary alkylamine has a high boiling point and remains in the product with difficulty in removal, which affects the quality of the product, it is necessary to increase the ratio of other raw materials appropriately to complete the reaction of the secondary alkylamine.
The molar ratio of the secondary alkylamine to the carbon disulfide to the dichloromethane is 1: 1-1.7: 0.5-1.0.
Preferably, the molar ratio of the secondary alkylamine to the carbon disulfide to the dichloromethane is 1: 1-1.4: 0.5-0.8.
The alkali liquor is an inorganic alkali solution, preferably a sodium hydroxide solution.
The mass concentration of the alkali liquor is 10-75%, and preferably 15-50%.
The molar ratio of the secondary alkylamine to the base is 1:1 to 1.6, preferably 1:1 to 1.3.
The treatment method after the reaction is as follows: and after discharging, standing and separating, washing the obtained organic phase with deionized water for 2-3 times, and performing vacuum distillation to obtain a product meeting the requirements.
The distillation pressure is 0-70 KPa, and the distillation temperature is 40-100 ℃.
Generally, the reaction temperature of the micro-flow tube is controlled to be 20-100 ℃, and the retention time is 11-128 s; and standing and separating after the reaction is finished, wherein the vacuum distillation pressure is 0-70 KPa, and the distillation temperature is 40-100 ℃.
Has the advantages that:
(1) the method adopts the microflow tube reactor to synthesize the dialkyl dithiocarbamate by one step, changes the traditional batch reaction mode, and solves the problems of complex operation, long reaction time and serious pollution of the traditional batch reaction. The preparation method adopts a brand-new micro-flow tube reaction technology, has simple operation, can realize continuous production, greatly shortens the reaction time, and has the product performance similar to that of imported products (7723 products produced by American Vant Birt company).
(2) According to the preparation method disclosed by the invention, in the process of preparing the dialkyl dithiocarbamate, other solvents are not required to be added, the preparation steps are simple, the product basically remains in an organic layer during liquid separation, and operations such as extraction are not required. The prepared dialkyl dithiocarbamate has the product performance meeting the international advanced index, the product color is better, and the yield is obviously improved to more than 92 percent.
Detailed Description
The technical solution of the present invention is described in detail by the following specific examples, but the scope of the present invention is not limited to the examples.
Example 1:
respectively pumping 129g (1mol) of di-n-butylamine, 80.7g (1.05mol) of carbon disulfide, 47g (0.55mol) of dichloromethane and 283g of aqueous solution of sodium hydroxide (1.06mol) with the mass fraction of 15% into a microflow tube reactor, controlling the temperature to be 40 ℃, adjusting the feeding speed to ensure that the retention time of the materials in the reactor is 12s (namely the reaction time), transferring the materials to a liquid separator after the reaction is finished, separating out a water phase after standing, adding water to wash out alkali and sodium chloride, and carrying out reduced pressure distillation under the conditions of 5KPa and 70 ℃ to obtain light yellow transparent oily liquid, wherein the yield is 92.8%. All performance indexes of the product are qualified. The oxidation stability, the anti-extrusion performance and the anti-wear performance of the product are examined, and the results show that the product of the embodiment has good application performance, and the oxidation stability and the anti-extrusion performance are even better than those of the product of the American 7723.
Example 2:
respectively pumping 129g (1mol) of di-n-butylamine, 107g (1.41mol) of carbon disulfide, 68g (0.8mol) of dichloromethane and 520g of aqueous solution of sodium hydroxide (1.3mol) with the mass fraction of 10% into a microflow tube reactor, controlling the temperature to be 25 ℃, adjusting the feeding speed to ensure that the retention time of the materials in the reactor is 35s, transferring the materials to a liquid distributor after the reaction is finished, removing an aqueous phase after standing, adding water to wash alkali and sodium chloride, and carrying out reduced pressure distillation under the conditions of 70KPa and 98 ℃ to obtain light yellow transparent oily liquid, wherein the yield is 95.2%. All performance indexes of the product are qualified.
Example 3:
387g (3mol) of di-n-butylamine, 251g (3.3mol) of carbon disulfide, 140g (1.65mol) of dichloromethane and 205.7g of aqueous solution with the mass fraction of 70 percent of sodium hydroxide (3.6mol) are respectively pumped into a microflow tube reactor, the temperature is controlled to be 75 ℃, the retention time of the materials in the reactor is 50s by adjusting the feeding speed, the materials are transferred to a liquid separator after the reaction is finished, the aqueous phase is separated after the reaction is kept still, water is added to wash out alkali and sodium chloride, and the light yellow transparent oily liquid is obtained by reduced pressure distillation under the conditions of 50KPa and 85 ℃, and the yield is 96.6 percent. All performance indexes of the product are qualified.
Example 4:
respectively pumping 516g (4mol) of di-n-butylamine, 323g (4.2mol) of carbon disulfide, 221g (2.6mol) of dichloromethane and 875g of sodium hydroxide aqueous solution with the mass fraction of 20% into a microflow tube reactor, controlling the temperature to be 98 ℃, adjusting the feeding speed to ensure that the retention time of materials in the reactor is 100s, transferring the materials to a liquid separator after the reaction is finished, removing an aqueous phase after standing, adding water to wash out alkali and sodium chloride, and distilling under reduced pressure at 55KPa and 45 ℃ to obtain light yellow transparent oily liquid with the yield of 93.9%. All performance indexes of the product are qualified.
Example 5:
516g (4mol) of di-n-butylamine, 323g (4.2mol) of carbon disulfide, 187g (2.2mol) of dichloromethane and 875g of sodium hydroxide aqueous solution (the mass fraction is 20%) are respectively pumped into a microflow tube reactor, the temperature is controlled to be 70 ℃, the retention time of materials in the reactor is 120s by adjusting the feeding speed, the materials are transferred to a liquid separator after the reaction is finished, the aqueous phase is separated after the reaction is kept still, water is added to wash out alkali and sodium chloride, and light yellow transparent oily liquid is obtained by reduced pressure distillation under the conditions of 5KPa and 80 ℃, and the yield is 92.6%. All performance indexes of the product are qualified.
Example 6:
186g (1mol) of di-n-hexylamine, 80.7g (1.05mol) of carbon disulfide, 47g (0.55mol) of dichloromethane and 80g of aqueous solution of sodium hydroxide (1.2mol) with the mass fraction of 60% are respectively pumped into a microflow tube reactor, the temperature is controlled to be 40 ℃, the retention time of the materials in the reactor is 90s by adjusting the feeding speed, the materials are transferred to a liquid separator after the reaction is finished, the aqueous phase is separated after the reaction is kept still, the water is added to wash the alkali and the sodium chloride, and the light yellow transparent oily liquid is obtained by reduced pressure distillation under the conditions of 5KPa and 90 ℃, and the yield is 93.5%. The product meets the indexes of qualified samples.
Example 7:
387g (3mol) of di-n-butylamine, 251g (3.3mol) of carbon disulfide, 140g (1.65mol) of dichloromethane and 636g of sodium hydroxide aqueous solution with the mass fraction of 20% are respectively pumped into a microflow tube reactor, the temperature is controlled to be 80 ℃, the retention time of materials in the reactor is 90s by adjusting the feeding speed, the materials are transferred to a liquid separator after the reaction is finished, the aqueous phase is separated after the reaction is kept still, the water is added to wash out alkali and sodium chloride, and the light yellow transparent oily liquid is obtained by reduced pressure distillation under the conditions of 5KPa and 75 ℃, and the yield is 92.1%. All performance indexes of the product are qualified.
Comparative example 1:
394g (3mol) of di-n-butylamine and 636g of sodium hydroxide aqueous solution (the mass fraction is 20%) are added into a four-neck flask, after uniform stirring, 242g (3.15mol) of carbon disulfide are added dropwise, the temperature is kept at about 15 ℃ under ice bath, after 2 hours, the carbon disulfide is added dropwise, the temperature is raised to 50 ℃, and the reaction is continued for 2 hours; 187g (1.8mol) of methylene chloride was added dropwise to the solution, and after dropping over 2 hours, the temperature was raised to 75 ℃ to complete the reaction for 2.5 hours. After separation, the mixture was washed with water and distilled under reduced pressure at 75 ℃ under 3KPa conditions to obtain a reddish brown transparent oily liquid with a yield of 89.2%.
Comparative example 2:
according to the method described in U.S. Pat. No. 5,965,629, 64g (1.6mol) of NaOH, 206.8g (1.6mol) of di-n-butylamine and 416g of water are introduced into a four-necked flask and the mixture is cooled to 5 ℃ with stirring. 121.6g (1.6mol) of carbon disulphide are slowly added to the mixture with stirring, the temperature is not allowed to exceed 15 ℃, and after addition of the carbon disulphide, stirring is continued for 0.5 hour. 81.6g (20% excess) of dichloromethane were then added and the alkylation reaction was carried out by slowly raising the temperature to 45 ℃ and then reacting at 75 ℃ for 2 hours. After the reaction is finished, carrying out first reduced pressure distillation to distill off part of water and unreacted materials. And (4) standing to separate a water phase, then carrying out reduced pressure distillation, and washing with water to obtain a light yellow product. Because the product is directly obtained by separation after water washing, the product has poor transparency and needs to be distilled again to become clear. The product yield was 88.1%.
As can be seen from comparative examples 1 and 2, the yield of the comparative example is lower than that of the preparation method of the invention, and the comparative example has dark color and poor color.
As noted above, while the present invention has been shown and described with reference to certain preferred embodiments, it is not to be construed as limited thereto. Various changes in form and detail may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. A preparation method of dialkyl dithiocarbamate is characterized in that secondary alkylamine, carbon disulfide, dichloromethane and alkali liquor are added into a microflow tube reactor for reaction, and dialkyl dithiocarbamate is prepared by a one-step method.
2. The method of claim 1, wherein the reaction temperature is controlled to 20 to 100 ℃, preferably 35 to 75 ℃.
3. The method of claim 1, wherein the reaction time is 11 to 128s, preferably 30 to 70 s.
4. The method according to claim 1, wherein the secondary alkylamine is a dialkylamine having 1 to 20 carbon atoms, preferably 4 to 8 carbon atoms.
5. The method according to claim 1, wherein the molar ratio of the secondary alkylamine to the carbon disulfide to the methylene chloride is 1:1 to 1.7:0.5 to 1.0.
6. The method according to claim 5, wherein the molar ratio of the secondary alkylamine to the carbon disulfide to the methylene chloride is 1:1 to 1.4:0.5 to 0.8.
7. The method of claim 1, wherein the lye is an inorganic base solution, preferably a sodium hydroxide solution.
8. The preparation method according to claim 1 or 7, wherein the mass concentration of the alkali liquor is 10-75%, preferably 15-50%.
9. The method according to claim 1 or 7, wherein the molar ratio of the secondary alkylamine to the base is 1:1 to 1.6, preferably 1:1 to 1.3.
10. The production method according to claim 1, wherein the treatment method after the reaction is: after discharging, standing, separating liquid, washing with water, and distilling under reduced pressure to obtain a product; the distillation pressure is 0-70 KPa, and the distillation temperature is 40-100 ℃.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104557644A (en) * | 2013-10-09 | 2015-04-29 | 中国石油化工股份有限公司 | Method for preparing dialkyl dithiocarbamate by utilization of continuous flow tubular reactor |
| CN107200703A (en) * | 2016-03-18 | 2017-09-26 | 中国石油化工股份有限公司 | The method that Keywords dibutyl dithiocarbamate is prepared using supergravity reactor |
| CN107556224A (en) * | 2016-06-30 | 2018-01-09 | 中国石油化工股份有限公司 | The preparation method of dialkyl dithio amino formate and wear-resistant antirust complexing agent |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104230775A (en) * | 2013-06-18 | 2014-12-24 | 中国石油化工股份有限公司 | Method for preparing dialkyl aminodithioformic acid by using one-step method |
| CN104557644A (en) * | 2013-10-09 | 2015-04-29 | 中国石油化工股份有限公司 | Method for preparing dialkyl dithiocarbamate by utilization of continuous flow tubular reactor |
| CN107200703A (en) * | 2016-03-18 | 2017-09-26 | 中国石油化工股份有限公司 | The method that Keywords dibutyl dithiocarbamate is prepared using supergravity reactor |
| CN107556224A (en) * | 2016-06-30 | 2018-01-09 | 中国石油化工股份有限公司 | The preparation method of dialkyl dithio amino formate and wear-resistant antirust complexing agent |
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