CN107556224B - Preparation method of dialkyl dithiocarbamate and antiwear and antirust complexing agent - Google Patents
Preparation method of dialkyl dithiocarbamate and antiwear and antirust complexing agent Download PDFInfo
- Publication number
- CN107556224B CN107556224B CN201610509476.7A CN201610509476A CN107556224B CN 107556224 B CN107556224 B CN 107556224B CN 201610509476 A CN201610509476 A CN 201610509476A CN 107556224 B CN107556224 B CN 107556224B
- Authority
- CN
- China
- Prior art keywords
- acid
- alkali metal
- carbon disulfide
- reaction
- water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a preparation method of dialkyl dithiocarbamate and an anti-wear and anti-rust complexing agent. The preparation method of dialkyl dithiocarbamate of the invention comprises the following steps: the first step is as follows: reacting hydroxide of alkali metal, secondary amine, dichloromethane and carbon disulfide, and extracting and separating an organic phase from a reaction product by using a solvent; the second step is as follows: mixing the organic phase obtained in the first step with a water-soluble acid solution; the third step: and washing the mixed solution obtained in the second step with water until the mixed solution is neutral, and collecting the product. The dialkyl dithiocarbamate prepared by the method has excellent storage stability and compatibility.
Description
Technical Field
The invention relates to dialkyl dithiocarbamate, in particular to a preparation method of dialkyl dithiocarbamate.
Background
The lubricating oil inevitably contacts with oxygen in the air and metal surfaces in the using process, and is subjected to oxidation reaction and deterioration, so that the viscosity of the oil is increased, the acid value is increased, oil sludge and sediment are generated, and metal parts are corroded and abraded. In order to prolong the service life of the oil product, delay the oxidation process of the oil product and slow down the friction and wear of equipment, an antioxidant and an antiwear agent can be added into the oil product, thereby effectively improving the service performance of the oil product.
Dialkyl dithiocarbamate is used as an ashless multi-effect additive with good oil solubility, has outstanding oxidation resistance, good abrasion resistance and extreme pressure performance, and is widely applied to various oil products such as turbine oil, hydraulic oil, gear oil, internal combustion engine oil and the like and lubricating grease.
The dialkyl dithiocarbamate is generally synthesized by reacting secondary amine with alkali, carbon disulfide and dichloromethane. Different amines give dithiocarbamates with different alkyl groups, of the formula:
wherein R is C2～C10。
4, 4-methylene-bis (dibutyl dithiocarbamate) is a widely used ashless antioxidant and extreme pressure antiwear agent, and is widely used in various petroleum products due to its excellent properties, and more typical commercial products include VANLUBE7723, NA-LUBE ADTC, T323, and the like. The product is generally prepared in a two-step process, in the first step NaOH and di-N-butylamine are reacted in a solvent to form the sodium salt of N, N-dibutyldithiocarbamic acid, which is coupled with dichloromethane to give the final product. The reaction formula is shown as follows:
the patents and literature published at present carry out the preparation of the relevant products according to the method.
US 5,015,368 discloses a process for preparing dialkyldithiocarbamates in a two-step process, which comprises: firstly, slowly dropping carbon disulfide, maintaining a certain temperature, reacting with amine and sodium hydroxide for a period of time, then slowly dropping dichloromethane, maintaining a certain temperature, reacting for a period of time, and carrying out esterification reaction. After the reaction is finished, separating out a liquid phase, and then carrying out reduced pressure distillation to obtain a product, wherein the nitrogen content of the product is 6.5%, and the sulfur content of the product is 30%.
US 5,744,629 discloses a two-step process for preparing lower color dialkyldithiocarbamates by: adding sodium hydroxide, di-n-butylamine and water into an autoclave, cooling the mixture to 5 ℃ under stirring, then slowly dripping carbon disulfide under stirring, controlling the temperature to be not higher than 15 ℃, reacting for a period of time, then slowly dripping excessive dichloromethane, gradually raising the temperature, maintaining a certain reaction temperature, and reacting for a period of time. After the reaction is finished, evaporating dichloromethane, water, unreacted raw materials and byproducts through decompression, cooling, separating an organic phase, washing with water, and then distilling under reduced pressure to obtain a product with the ASTM chroma less than 2.
CN 1364759A discloses a one-step method for preparing dialkyl dithiocarbamate, which comprises premixing amine, sodium hydroxide, chloromethane, solvent and the like, then slowly dripping carbon disulfide, reacting for a period of time after maintaining a certain temperature, heating to a higher temperature to continue reacting for a period of time, extracting by gasoline, separating out a liquid phase, and then distilling under reduced pressure to obtain the product.
In related journal, there are also similar synthetic methods, including "the synthesis and performance study of dialkyl dithiocarbamate antioxidant antiwear multifunctional additive" (lubrication and sealing, Vol. 34, No. 9, 2009.09), "the synthesis and performance evaluation of dibutyl dithiocarbamate" (petrochemical corrosion and protection, Vol. 23, No. 6, 2006.10).
The dialkyldithiocarbamate products prepared by the above patents and documents are still somewhat deficient in storage stability and compatibility.
Disclosure of Invention
The invention provides a preparation method of dialkyl dithiocarbamate and an anti-wear and anti-rust complexing agent.
The preparation method of dialkyl dithiocarbamate of the invention comprises the following steps:
the first step is as follows: reacting hydroxide of alkali metal, secondary amine, dichloromethane and carbon disulfide, and extracting and separating an organic phase from a reaction product by using a solvent;
the second step is as follows: mixing the organic phase obtained in the first step with a water-soluble acid solution;
the third step: and washing the mixed solution obtained in the second step with water until the mixed solution is neutral, and collecting the product.
Wherein the hydroxide of an alkali metal is preferably sodium hydroxide.
The secondary amine is preferably dialkylamine, the alkyl group is preferably C1-C8 alkyl, most preferably C2-C6 alkyl, and for example, one or more selected from di-n-propylamine, di-n-butylamine, di-n-pentylamine, and di-n-hexylamine can be used.
The mole ratio of the secondary amine, the carbon disulfide, the hydroxide of the alkali metal and the dichloromethane is 1: 1-1.2: 1-1.5: 0.5 to 0.8, preferably 1: 1-1.1: 1.05-1.2: 0.53 to 0.65.
The reaction conditions of the first step of the method of the invention are as follows: reacting the hydroxide of the alkali metal, secondary amine, dichloromethane and carbon disulfide at 10-40 ℃ for 0.5-2 h, preferably at 15-35 ℃ for 0.5-1 h, and then at 60-90 ℃ for 3-10 h, preferably at 65-85 ℃ for 4-6 h; preferably, the carbon disulfide is added in a dropwise manner, and the dropwise addition time is 0.5-2 hours, preferably 0.5-1 hour; preferably, the dichloromethane is added in a dropwise manner, and the dropwise addition time is 0.5-2 hours, preferably 0.5-1 hour; the carbon disulfide and the dichloromethane can be dripped simultaneously or sequentially, and the dripping order is not particularly limited.
In the first step, preferably, the alkali metal hydroxide, the secondary amine, the dichloromethane and the carbon disulfide are reacted by: firstly, alkali metal hydroxide, secondary amine and carbon disulfide react to generate alkali metal salt of N, N-dialkyl dithiocarbamic acid, and then the generated alkali metal salt of N, N-dialkyl dithiocarbamic acid and dichloromethane generate coupling reaction. The reaction temperature of the alkali metal hydroxide, the secondary amine and the carbon disulfide is 10-40 ℃, preferably 15-35 ℃, and the reaction time is 0.5-2 hours, preferably 0.5-1 hour; the reaction temperature of the generated N, N-dialkyl dithiocarbamic acid alkali metal salt and dichloromethane in the coupling reaction is 60-90 ℃, preferably 65-85 ℃, and the reaction time is 3-10 hours, preferably 4-6 hours.
The solvent for the solvent extraction operation is a hydrocarbon substance with a boiling point of 60-150 ℃, and preferably one or more of 120# solvent gasoline, petroleum ether (60-90 ℃), petroleum ether (90-120 ℃), toluene and benzene.
In the second step, the water-soluble acid solution can be selected from inorganic acid and/or organic acid, the inorganic acid is preferably one or more of hydrochloric acid, nitric acid, sulfuric acid and phosphoric acid, and most preferably hydrochloric acid; the organic acid is preferably one or more of formic acid, acetic acid and oxalic acid, most preferably acetic acid.
The mass concentration of the water-soluble acid solution is 5-40%, preferably 10-30%.
The mass ratio of the organic phase to the water-soluble acid solution is 5-50: 1, preferably 5 to 20: 1.
the pH value of the mixed organic phase and water-soluble acid solution is 1.0-7.0, preferably 4.0-6.5.
In the third step, the solvent and a small amount of water are preferably distilled off from the water-washed neutral mixture under normal pressure or reduced pressure to obtain the dialkyldithiocarbamate product.
The solvent may or may not be added in each reaction step. The solvent is preferably a C1-C4 alcohol, most preferably ethanol. The addition amount of the solvent is 20-50%, preferably 25-40% of the amount of the secondary amine.
The dialkyl dithiocarbamate prepared by the method has excellent storage stability and compatibility.
The invention also provides an anti-wear and anti-rust compound agent, which comprises the dialkyl dithiocarbamate and the anti-rust agent prepared by the method, wherein the mass ratio of the dialkyl dithiocarbamate to the anti-rust agent is 10: 1-1: 10, preferably 5: 1-1: 5. the rust inhibitor is alkenyl succinic acid derivative, preferably alkenyl succinic acid and/or alkenyl succinic acid ester, and for example, one or more of dodecenyl succinic acid, octadecenyl succinic acid, dodecenyl succinic acid ester, octadecenyl succinic acid ester, dodecenyl succinic acid half ester and octadecenyl succinic acid half ester can be selected.
The antiwear and antirust complexing agent has excellent compatibility and storage stability.
The invention also provides a lubricating oil composition, which comprises the anti-wear and anti-rust compound agent and lubricating base oil, wherein the anti-wear and anti-rust compound agent accounts for 0.1-10%, preferably 0.3-5% of the total mass of the lubricating oil composition.
The lubricating oil composition of the present invention has very excellent storage stability.
Detailed Description
The invention is further illustrated by the following examples.
The raw material sources are as follows:
di-n-butylamine, Zhejiang Jiande industry organic chemical Co., Ltd
Carbon disulfide, Hebei Yongqing Dilunke chemical Co Ltd
Methylene chloride, Shandong Haihua group
T203, zinc dialkyldithiophosphate, tin-free south additive plant
T746, dodecenylsuccinic acid, tin-free south additive plant
T747 Dodecenyl succinic acid half ester, Luzhou Luborun refining additive Co Ltd
T323, di-n-butyl dithiocarbamate, Tanshowa additive plant
Example 1
16.8g of sodium hydroxide and 33.6g of water are added into a 250ml three-necked bottle with a cooling tube to prepare a sodium hydroxide aqueous solution (the mass concentration is 33 percent), then 51.6g of di-n-butylamine, 18g of ethanol and 17.7g of dichloromethane are added into the sodium hydroxide aqueous solution, the mixture is stirred uniformly, 31.6g of carbon disulfide is slowly dripped into the mixture, the volatilized carbon disulfide and dichloromethane are condensed by the cooling tube, and the reaction temperature is controlled within 30 ℃. After the addition of carbon disulfide is completed, the reaction is carried out for 1 hour in the temperature range. Then, the temperature was raised to 70 ℃ and the reaction was continued for 5 hours. After the reaction is finished, 70g of solvent gasoline is added, extraction is carried out for 20 minutes, an alcohol water phase and sodium chloride solid are separated, 10g of dilute hydrochloric acid solution with the concentration of 15% is added into an organic phase, stirring is carried out for 20 minutes, the PH value of a mixed phase is measured to be about 5.0, the remaining organic phase is washed to be neutral after the water phase is separated, reduced pressure distillation (the vacuum degree is 650mmHg) is carried out again, the organic phase is steamed to the temperature of 150 ℃ in a reactor, gasoline does not flow out any more, and finally a yellow liquid product is obtained, wherein the yield is 92.1%.
Example 2
A250 ml three-necked flask equipped with a cooling tube was charged with 17.1g of sodium hydroxide and 68.4g of water to prepare an aqueous sodium hydroxide solution (20% by mass). Then 51.6g of di-n-butylamine and 20.4g of dichloromethane are added, the mixture is stirred uniformly, 32.2g of carbon disulfide is slowly dropped, the volatilized carbon disulfide and dichloromethane are condensed by a cooling tube, and the reaction temperature is controlled within the range of 25 ℃. After the carbon disulfide is added, the temperature is maintained within the range, and the reaction is carried out for 1 hour. Then, the temperature was raised to 70 ℃ and the reaction was continued for 5 hours. After the reaction is finished, 70g of solvent gasoline is added, stirring is carried out for 20 minutes, an alcohol water phase and sodium chloride solid are separated out, 20g of dilute hydrochloric acid solution with the concentration of 10% is added into an organic phase, stirring is carried out for 40 minutes, the PH value of a mixed phase is measured to be about 4.5, the water phase is separated out, washing is carried out until the water phase is neutral, and then normal reduced pressure distillation (the vacuum degree is 650mmHg) is carried out until the temperature in a reactor is about 150 ℃ and no gasoline flows out. A yellow liquid can be obtained, i.e. the product, with a yield of 93.0%.
Example 3
A250 ml three-necked flask equipped with a cooling tube was charged with 16.6g of sodium hydroxide and 36.2g of water to prepare an aqueous sodium hydroxide solution (33% by mass). Then 51.6g of di-n-butylamine and 18g of ethanol are added, the mixture is stirred evenly, 31.6g of carbon disulfide is slowly dripped, the volatilized carbon disulfide is condensed by a cooling tube, and the reaction temperature is controlled within 35 ℃. After the carbon disulfide is added, the reaction is carried out for 1 hour, 17.7g of dichloromethane is added dropwise, the temperature is raised to 80 ℃, and the reaction is carried out for 4 hours. After the reaction is finished, adding 70g of solvent gasoline, stirring for 20 minutes, separating out an alcohol water phase and sodium chloride solids, adding 10g of an acetic acid solution with the concentration of 15% into the organic phase, stirring for 60 minutes, measuring the pH value of the mixed phase to be about 5.5, washing the separated water phase to be neutral, distilling under normal and reduced pressure (the vacuum degree is 650mmHg), and steaming until no gasoline flows out at the temperature of about 150 ℃ in the reactor. A yellow liquid can be obtained, namely the product, and the yield is 91.0%.
Example 4
A250 ml three-necked flask equipped with a cooling tube was charged with 17.6g of sodium hydroxide and 85g of water to prepare an aqueous sodium hydroxide solution (mass concentration: 17%). Then 51.6g of di-n-butylamine is added, the mixture is stirred evenly, 31.6g of carbon disulfide is slowly dripped, the volatilized carbon disulfide is condensed by a cooling tube, and the reaction temperature is controlled within 30 ℃. After the carbon disulfide is added, the reaction is carried out for 1 hour, 19.7g of dichloromethane is added dropwise, the temperature is raised to 75 ℃, and the reaction is carried out for 4 hours. After the reaction is finished, adding 70g of solvent gasoline, stirring for 20 minutes, separating out an alcohol water phase and sodium chloride solids, adding 20g of 20% acetic acid solution into the organic phase, stirring for 30 minutes, measuring the pH value of the mixed phase to be about 4.0, washing the separated water phase to be neutral, distilling under normal and reduced pressure (the vacuum degree is 650mmHg), and steaming until no gasoline flows out at the temperature of about 150 ℃ in the reactor. A yellow liquid can be obtained, namely the product, and the yield is 90.5%.
Comparative example 1
The preparation was carried out according to patent CN 1364759A.
A250 ml three-necked flask equipped with a cooling tube was charged with 17.6g of sodium hydroxide and 36.2g of water to prepare an aqueous sodium hydroxide solution (33% by mass). Then 51.6g of di-n-butylamine, 18g of ethanol and 17.7g of dichloromethane are added, the mixture is stirred uniformly, 31.6g of carbon disulfide is slowly dropped, the volatilized carbon disulfide and dichloromethane are condensed by a cooling tube, and the reaction temperature is controlled within the range of 30 ℃. After the carbon disulfide is added, the temperature is maintained within the range, and the reaction is carried out for 0.5 h. Then, the temperature was raised to 75 ℃ and the reaction was continued for 5 hours. After the reaction, 70g of solvent gasoline is added, after extraction, an alcohol-water phase and sodium chloride solid are separated by a separating funnel, and then the gasoline and a small amount of water are evaporated under reduced pressure. The product was obtained as a yellow liquid in 88.2% yield.
Comparative example 2
The preparation is carried out according to patent US 5,015,368.
A250 ml three-necked flask equipped with a cooling tube was charged with 17.6g of sodium hydroxide and 36.2g of water to prepare an aqueous sodium hydroxide solution (33% by mass). Then 51.6g of di-n-butylamine and 18g of ethanol are added, the mixture is stirred evenly, 31.6g of carbon disulfide is slowly dripped, the volatilized carbon disulfide is condensed by a cooling tube, and the reaction temperature is controlled within 30 ℃. After the carbon disulfide is added, the temperature is maintained within the range, and the reaction is carried out for 1 hour. Then, 17.7g of dichloromethane was added dropwise, and the temperature was raised to 75 ℃ for further reaction for 4 hours. After the reaction, 70g of solvent gasoline is added, after extraction, an alcohol-water phase and sodium chloride solid are separated by a separating funnel, and then the gasoline and a small amount of water are evaporated under reduced pressure. The product was obtained as a yellow liquid in 89.1% yield.
Comparative example 3
The preparation is carried out according to patent US 5,744,629.
16.1g of sodium hydroxide and 104g of water are added into a 250ml three-necked flask with a cooling tube to prepare a sodium hydroxide aqueous solution (with the mass concentration of 14 percent), 51.6g of di-n-butylamine is added into the sodium hydroxide aqueous solution to be stirred uniformly, 31.6g of carbon disulfide is slowly dripped into the sodium hydroxide aqueous solution, and the volatilized carbon disulfide is condensed by the cooling tube, wherein the reaction temperature is controlled to be about 5 ℃. After the carbon disulfide is added, the temperature is maintained within the range, and the reaction is carried out for 0.5 h. Then, 20.5g of dichloromethane was added dropwise, and the temperature was raised to 70 ℃ for further reaction for 4 hours. After the reaction is finished, the product is obtained as light yellow liquid by normal and reduced pressure treatment, and the yield is 94.3%.
Storage stability test of Dialkyldithiocarbamates
The examples, comparative examples and commercial dialkyldithiocarbamate products were tested for storage stability under the following conditions: condition 1, room temperature, transparent glass bottle, storage time is 360 days; 2, storing at-10 ℃ for 90 days; and 3, sun drying, sealing by using a transparent glass bottle, and storing for 30 days. The test results are shown in Table 1.
TABLE 1
As can be seen from Table 1, the dialkyldithiocarbamates of the present invention have better storage stability properties.
Compatibility of dialkyl dithio carbamate
The compatibility of dialkyl dithiocarbamate is evaluated by selecting I type, II type and PAO synthetic base oil under the condition of room temperature. The examples, comparative examples and commercial dialkyldithiocarbamate products were dosed at 0.5% in each lubricating base oil, T203 was dosed at 1% and the test time was 180 days. The test results are shown in Table 2.
TABLE 2
Storage stability test of antiwear and antirust complexing agent
The dialkyl dithio carbamate of the examples, the comparative examples and the market is respectively mixed with the dodecenyl succinic acid derivative according to different proportions, and the stability of the complexing agent is observed after the dialkyl dithio carbamate is stored for 180 days at normal temperature. The composition of the antiwear and antirust compound agent and the storage stability test results are shown in Table 3.
TABLE 3
From the above results, it can be seen that the dialkyl dithiocarbamate and the antiwear and antirust compound agent of the present invention have better compatibility, and can be applied to different types of lubricating base oils.
Claims (13)
1. A process for preparing a dialkyl dithiocarbamate, comprising:
the first step is as follows: reacting hydroxide of alkali metal, secondary amine, dichloromethane and carbon disulfide, and extracting and separating an organic phase from a reaction product by using a solvent;
the second step is as follows: mixing the organic phase obtained in the first step with a water-soluble acid solution;
the third step: and washing the mixed solution obtained in the second step with water until the mixed solution is neutral, and collecting the product.
2. A process according to claim 1, wherein the secondary amine is a dialkylamine.
3. The process of claim 1, wherein the molar ratio of secondary amine, carbon disulfide, alkali metal hydroxide to methylene chloride is from 1: 1-1.2: 1-1.5: 0.5 to 0.8.
4. The method according to claim 1, wherein the reaction conditions of the first step are: reacting the hydroxide of the alkali metal, secondary amine, dichloromethane and carbon disulfide at 10-40 ℃ for 0.5-2 h, and then reacting at 60-90 ℃ for 3-10 h.
5. The process according to claim 1, wherein in the first step, the hydroxide of an alkali metal, the secondary amine, the methylene chloride and the carbon disulfide are reacted by: firstly, alkali metal hydroxide, secondary amine and carbon disulfide react to generate alkali metal salt of N, N-dialkyl dithiocarbamic acid, and then the generated alkali metal salt of N, N-dialkyl dithiocarbamic acid and dichloromethane generate coupling reaction.
6. The method according to claim 5, wherein the reaction temperature of the alkali metal hydroxide, the secondary amine and the carbon disulfide is 10-40 ℃, and the reaction time is 0.5-2 h; the reaction temperature of the generated N, N-dialkyl dithiocarbamic acid alkali metal salt and dichloromethane in the coupling reaction is 60-90 ℃, and the reaction time is 3-10 h.
7. The process according to claim 1, characterized in that the solvent of said solvent extraction operation is a hydrocarbon having a boiling point between 60 and 150 ℃.
8. The method according to claim 1, wherein the solvent of the solvent extraction operation is one or more of 120# solvent gasoline, 60-90 ℃ petroleum ether, 90-120 ℃ petroleum ether, toluene and benzene.
9. The method according to claim 1, wherein in the second step, the water-soluble acid solution is selected from inorganic acids and/or organic acids.
10. The method of claim 9, wherein the inorganic acid is one or more of hydrochloric acid, nitric acid, sulfuric acid, and phosphoric acid; the organic acid is one or more of formic acid, acetic acid and oxalic acid.
11. The method according to claim 1, wherein the water-soluble acid solution has a mass concentration of 5 to 40%.
12. The method according to claim 1, wherein the mass ratio of the organic phase to the water-soluble acid solution is 5 to 50: 1.
13. the method according to claim 1, wherein the organic phase has a pH of 1.0 to 7.0 after being mixed with the water-soluble acid solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610509476.7A CN107556224B (en) | 2016-06-30 | 2016-06-30 | Preparation method of dialkyl dithiocarbamate and antiwear and antirust complexing agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610509476.7A CN107556224B (en) | 2016-06-30 | 2016-06-30 | Preparation method of dialkyl dithiocarbamate and antiwear and antirust complexing agent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107556224A CN107556224A (en) | 2018-01-09 |
| CN107556224B true CN107556224B (en) | 2020-02-28 |
Family
ID=60968822
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610509476.7A Active CN107556224B (en) | 2016-06-30 | 2016-06-30 | Preparation method of dialkyl dithiocarbamate and antiwear and antirust complexing agent |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107556224B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110551047A (en) * | 2019-07-30 | 2019-12-10 | 上海裕诚化工有限公司 | Preparation method of dialkyl dithiocarbamate |
| CN112341369A (en) * | 2019-08-07 | 2021-02-09 | 中石化南京化工研究院有限公司 | Preparation method of dialkyl dithiocarbamate |
| CN111560281B (en) * | 2020-05-22 | 2022-08-19 | 北京白云新材科技有限公司 | Engine oil enhancer as well as preparation method and application thereof |
| CN111690133B (en) * | 2020-06-23 | 2021-08-10 | 华南理工大学 | Polyalkenyl dithiocarbamate compound and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1137518A (en) * | 1995-02-03 | 1996-12-11 | 匈牙利莫尔奥拉加齐帕里有限公司 | Improved process for manufacturing methylene-bis (dibutyl-dithiocarbamate) with ASTM colour less than colour |
| CN105001137A (en) * | 2015-08-13 | 2015-10-28 | 新乡市瑞丰新材料股份有限公司 | Method for preparing dialkyl dithio carbamic acid ester |
| CN105176638A (en) * | 2015-06-30 | 2015-12-23 | 上海禾泰特种润滑科技股份有限公司 | Chain lubricating oil composite agent and preparation method thereof |
| CN105503676A (en) * | 2014-09-25 | 2016-04-20 | 中国石油化工股份有限公司 | Safe production method for low-chroma methylene bis(dialkyldithioformamide) |
-
2016
- 2016-06-30 CN CN201610509476.7A patent/CN107556224B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1137518A (en) * | 1995-02-03 | 1996-12-11 | 匈牙利莫尔奥拉加齐帕里有限公司 | Improved process for manufacturing methylene-bis (dibutyl-dithiocarbamate) with ASTM colour less than colour |
| CN105503676A (en) * | 2014-09-25 | 2016-04-20 | 中国石油化工股份有限公司 | Safe production method for low-chroma methylene bis(dialkyldithioformamide) |
| CN105176638A (en) * | 2015-06-30 | 2015-12-23 | 上海禾泰特种润滑科技股份有限公司 | Chain lubricating oil composite agent and preparation method thereof |
| CN105001137A (en) * | 2015-08-13 | 2015-10-28 | 新乡市瑞丰新材料股份有限公司 | Method for preparing dialkyl dithio carbamic acid ester |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107556224A (en) | 2018-01-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107556224B (en) | Preparation method of dialkyl dithiocarbamate and antiwear and antirust complexing agent | |
| US4098705A (en) | Sulfur containing molybdenum dihydrocarbyldithiocarbamate compound | |
| EP2662351B1 (en) | Alkylated heterocyclic reaction products useful as antioxidants | |
| AU2007233234A1 (en) | Lubricant oil additive compositions | |
| CA2405936A1 (en) | Dithiocarbamates containing alkylthio and hydroxy substituents | |
| CN107974328B (en) | Lubricating oil composition and method for improving wear resistance and friction reduction performance of lubricating oil | |
| CN110790725A (en) | Preparation method of lubricating oil additive containing thiadiazole group | |
| CN109233936B (en) | High-temperature-resistant polyester lubricating oil base oil and preparation method thereof | |
| CN101219982A (en) | Alkyl xanthogenic acid acetic ester for additive for lubricant oil and method for producing the same | |
| CN107974326B (en) | Antioxidant antiwear agent, preparation method thereof and lubricating oil composition | |
| RU2669925C2 (en) | Lubricating oil additive and lubricating oil composition | |
| CN114763337B (en) | Lubricating oil additive and preparation method and application thereof | |
| CN114736237A (en) | Preparation method of di-isooctyl zinc dithiophosphate | |
| CN107974327B (en) | Lubricating oil composition and method for improving antirust performance of lubricating oil | |
| CN111057041B (en) | Sulfurized phenolic ester derivative and preparation method and application thereof | |
| KR101278872B1 (en) | Norbornene dialkyl ester containing dialkyl dithiocarbamate compounds, antiwear additives and lubricant comprising the same | |
| KR101785337B1 (en) | Free-metal dicarboxylic acid derivatives and antiwear additives and lubricant compositions comprising the same | |
| US2693447A (en) | Lubricants containing metal salts of fatty acid derivatives of dithiocarbamic acid | |
| CN114106905B (en) | Lubricating oil composition containing lubricating oil additive for enhancing molybdenum performance at low temperature | |
| EP0909755A1 (en) | Thio-/mercapto-derivatives and use as antioxidant additives | |
| CN110204501B (en) | Benzotriazole derivative containing dithioamino acid group and preparation method and application thereof | |
| CN110205181B (en) | Ester group-containing benzothiazole derivative lubricating oil additive and preparation and application thereof | |
| CN112760158B (en) | Gasoline engine lubricating oil composition and preparation method thereof | |
| CN111088094B (en) | Automatic transmission fluid and preparation method thereof | |
| CN112694934B (en) | Gear oil composition and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |