CN105001137A - Method for preparing dialkyl dithio carbamic acid ester - Google Patents
Method for preparing dialkyl dithio carbamic acid ester Download PDFInfo
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- CN105001137A CN105001137A CN201510495626.9A CN201510495626A CN105001137A CN 105001137 A CN105001137 A CN 105001137A CN 201510495626 A CN201510495626 A CN 201510495626A CN 105001137 A CN105001137 A CN 105001137A
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Abstract
The invention provides a method for preparing dialkyl dithio carbamic acid ester. The method comprises the following steps: carrying out a reaction between secondary alkyl amine, a sodium hydroxide water solution, methylene chloride and carbon disulfide in ethyl alcohol, then vacuumizing to reduce pressure to distill ethyl alcohol out, adding solvent oil to conduct oil extraction, washing and then conducting reduced pressure distillation so as to obtain dialkyl dithio carbamic acid ester. According to the application, in the process of preparing dialkyl dithio carbamic acid ester, dialkyl dithio carbamic acid ester is synthesized through a one-step method, ethyl alcohol is distilled out at first in the purification process so as to be recycled, and the yield and purity of dialkyl dithio carbamic acid ester cannot be influenced. Experiment results show that the yield of the prepared dialkyl dithio carbamic acid ester can reach 96.5% or higher, and the purity can reach 97% or higher.
Description
Technical field
The present invention relates to compou nd synthesis technical field, particularly relate to a kind of preparation method of dialkyl dithio amino formate.
Background technology
Oil product in use inevitably contacts with the oxygen in air and metallic surface and oxidizing reaction occurs and goes bad, and adds antioxidant in oil product, effectively can react by inhibited oxidation, extend the work-ing life of oil product, improve the use properties of oil product.Dialkyl dithio amino formate uses in oil product has outstanding antioxidant property, abrasion resistance and extreme pressure property, also there is good oil soluble and the feature such as ashless simultaneously, be widely used in turbine oil, hydraulic efficiency oil, gear oil, oil engine wet goods oil products and lubricating grease.
In prior art, dialkyl dithio amino formate is generally reacted by dithiocarbonic anhydride, sodium hydroxide, secondary amine and methylene dichloride to form, and reaction has two-step approach and single stage method.The embodiment 1 of US5015368 discloses the method adopting two-step approach to prepare dialkyl dithio amino formate, is first added by dithiocarbonic anhydride in the mixture containing Di-n-Butyl Amine, sodium hydroxide and water at about 63 DEG C; Then be warming up to 88 DEG C, methylene dichloride is added in above-mentioned reaction mixture, last 4 hours, react 3 hours in 85 ~ 88 DEG C again after adding methylene dichloride, after reaction terminates, isolate liquid phase, underpressure distillation obtains product again, and its nitrogen content is 6.5%, and sulphur content is 30.0%.
US5744629 discloses the method for preparation compared with the dialkyl dithio amino formate of light colour, first, the aqueous solution of sodium hydroxide and Di-n-Butyl Amine and dithiocarbonic anhydride are reacted in autoclave, temperature controls not higher than 15 DEG C, reaction 0.5h, slowly instill excessive methylene dichloride again, and raised temperature gradually, at 75 ~ 80 DEG C of reaction 2h, after reaction terminates, carry out underpressure distillation in two steps, the first step, carry out at 45 ~ 100 DEG C of temperature and under the pressure of 5 ~ 50kPa, then be separated at 35 ~ 50 DEG C, second step, isolated organic phase is carried out a underpressure distillation according to the condition of the first step again, finally can obtain the product that ASlM color is less than 2.
Publication number is a kind of method that the Chinese patent of CN104230775 discloses single stage method and prepares dialkyl dithio amino formate.Secondary alkylamine, dithiocarbonic anhydride, methylene dichloride and aqueous sodium hydroxide solution four kinds of raw materials are inputted in the Continuous Flow tubular reactor of duct characteristic dimension between 0.1 μm ~ 3mm fully or partially through constant flow pump simultaneously, react under 10 ~ 100 DEG C and 0.1 ~ 1.8MPa, control the residence time 10 ~ 100s, material out reacts 1 ~ 12 hour at 10 ~ 100 DEG C with sodium hydroxide solution again, be separated after reaction terminates, vacuum distilling filtration from sodium chloride, obtain transparent liquid dialkyl dithio amino formate compound.
Publication number is a kind of method that the Chinese patent of CN1159294 discloses single stage method and prepares dialkyl dithio amino formate, in the mixture containing Di-n-Butyl Amine, aqueous sodium hydroxide solution, methylene dichloride and etoh solvent, in 10 ~ 60 DEG C of instillation dithiocarbonic anhydride, dropwise rear reaction 0.5 ~ 5 hour, be warming up to 50 ~ 100 DEG C again and continue reaction 1 ~ 12 hour, gasoline extracting is added for a moment after reaction terminates, isolate organic phase, be washed with water to neutrality, atmospheric and vacuum distillation goes out gasoline and a small amount of water, can obtain yellow transparent product.
When adopting two-step approach to prepare dialkyl dithio amino formate in aforesaid method, methylene dichloride time for adding is long, and reaction process is more loaded down with trivial details; Single stage method Continuous Flow tubular type preparation method installation cost is high, is not suitable for large-scale commercial production; Conventional single stage method prepares the recycle that dialkyl dithio amino formate method cannot realize etoh solvent, adds waste water output, is unfavorable for environmental protection, too increase production cost simultaneously.
Summary of the invention
The technical problem that the present invention solves is the preparation method providing a kind of dialkyl dithio amino formate, and the preparation method of the application can realize the recycle of ethanol, reduces production cost.
In view of this, this application provides a kind of preparation method of dialkyl dithio amino formate, comprising:
Secondary alkylamine, aqueous sodium hydroxide solution, methylene dichloride and dithiocarbonic anhydride are reacted in ethanol, then vacuumize underpressure distillation and go out ethanol, then add solvent oil and carry out oil and carry, after washing, underpressure distillation again, obtains dialkyl dithio amino formate.
Preferably, the detailed process of described reaction is:
Sodium hydroxide, water, secondary alkylamine, ethanol are mixed with methylene dichloride, mixed by the mixture obtained with dithiocarbonic anhydride, be warming up to 40 ~ 50 DEG C, reaction 1 ~ 2h, is then warming up to 60 ~ 80 DEG C, reaction 4 ~ 7h.
Preferably, the vacuum tightness vacuumized described in is-0.01MPa ~-0.09MPa.
Preferably, the vacuum tightness vacuumized described in is-0.05MPa.
Preferably, described secondary alkylamine is the dialkylamine of C2 ~ C10.
Preferably, described secondary alkylamine is Di-n-Butyl Amine.
Preferably, the concentration of aqueous sodium hydroxide solution is 40wt% ~ 50wt%.
Preferably, described solvent oil is 120# solvent oil.
This application provides a kind of preparation method of dialkyl dithio amino formate, comprise: secondary alkylamine, aqueous sodium hydroxide solution, methylene dichloride and dithiocarbonic anhydride are reacted in ethanol, vacuumize underpressure distillation again and go out ethanol, then add solvent oil and carry out extracting, after washing, underpressure distillation again, obtains dialkyl dithio amino formate.The application is in the process preparing dialkyl dithio amino formate, adopt one-step synthesis method dialkyl dithio amino formate, and go out ethanol by vacuumizing underpressure distillation, ethanol recirculation is utilized, reduce waste water output, and make the yield of product and purity higher.Experimental result shows, the yield of dialkyl dithio amino formate prepared by the present invention can reach more than 96.5%, and purity can reach more than 97%.
Embodiment
In order to understand the present invention further, below in conjunction with embodiment, the preferred embodiment of the invention is described, but should be appreciated that these describe just for further illustrating the features and advantages of the present invention, instead of limiting to the claimed invention.
The embodiment of the invention discloses a kind of preparation method of dialkyl dithio amino formate, comprising:
Secondary alkylamine, aqueous sodium hydroxide solution, methylene dichloride and dithiocarbonic anhydride are reacted in ethanol, then vacuumize underpressure distillation and go out ethanol, then add solvent oil and carry out oil and carry, after washing, underpressure distillation again, obtains dialkyl dithio amino formate.
In the preparation process of the dialkyl dithio amino formate that the application provides, first secondary alkylamine, dithiocarbonic anhydride, sodium hydroxide and methylene dichloride are reacted in ethanol, and then vacuumize and distill out ethanol, finally extract, obtain dialkyl dithio amino formate.The application passes through one-step synthesis method dialkyl dithio amino formate, and is steamed by ethanol by vacuumizing distillation, thus realizes the recycling of ethanol, and does not affect yield and the purity of product.
In the process preparing dialkyl dithio amino formate, first raw material mixes, to react by the application.The process of the application's raw material mixing is specially:
Sodium hydrate solid is mixed with water, obtains aqueous sodium hydroxide solution;
In described aqueous sodium hydroxide solution, add secondary alkylamine, ethanol, methylene dichloride successively, obtain mixture;
Dithiocarbonic anhydride is added in described mixture.
According to the present invention, after raw material mixing, then carry out the reaction of secondary alkylamine, sodium hydroxide, methylene dichloride and dithiocarbonic anhydride, described reaction principle is as follows:
Described in the application, secondary alkylamine is preferably the dialkylamine of C1 ~ C10, is more preferably Di-n-Butyl Amine.That carries out to make reaction is more abundant, and first said mixture is reacted 1 ~ 2h by the application at 40 ~ 50 DEG C, and then reacts 4 ~ 7h at 60 ~ 80 DEG C.
After above-mentioned reaction is carried out, then carry out the process of purifying.The application carries out vacuumizing underpressure distillation and goes out ethanol, by ethanol distillation out, carries out recycle to make ethanol.The described vacuum tightness vacuumized is preferably-0.01MPa ~-0.09MPa, is more preferably-0.05MPa.After ethanol distillation is gone out, then add solvent oil and carry out extracting, make separation of oil wherein out.Described solvent oil is preferably 120# solvent oil.
According to the present invention, finally isolated oil phase is washed to neutrality, then atmospheric and vacuum distillation, solvent oil wherein and a small amount of water are distillated, namely obtains dialkyl dithio amino formate.
This application provides a kind of preparation method of dialkyl dithio amino formate, first sodium hydroxide, secondary alkylamine, methylene dichloride and dithiocarbonic anhydride react by it, again the product obtained is vacuumized, underpressure distillation goes out ethanol, and then add solvent oil and carry out extracting, isolate oil phase, finally oil phase is washed, underpressure distillation goes out gasoline and water, namely obtains dialkyl dithio amino formate.The application, can recycle by distilling out ethanol in the process preparing dialkyl dithio amino formate, reduces waste water output, is beneficial to environmental protection, reduces production cost, and make the yield of product and purity higher.Experimental result shows, the purity of dialkyl dithio amino formate can reach more than 97%, and yield can reach more than 96.5%.
In order to understand the present invention further, below in conjunction with embodiment, the preparation method to dialkyl dithio amino formate provided by the invention is described in detail, and protection scope of the present invention is not limited by the following examples.
Embodiment 1
23.21g sodium hydrate solid is added in the four-hole boiling flask being furnished with prolong, add 30g water dissolution again, after being cooled to room temperature, add Di-n-Butyl Amine 64.62g successively, ethanol 24.62g, methylene dichloride 24.48g, then at 30 DEG C, dithiocarbonic anhydride 39.78g is dripped, after dropwising, be warming up to 40 DEG C of reaction 1h, and then be warming up to 65 DEG C of reaction 5h, then underpressure distillation goes out ethanol, vacuum tightness-0.05MPa, 120# solvent oil 80g extracting 0.5h is added after ethanol steams, separating funnel is adopted to isolate upper oil phase, upper oil phase is washed to neutrality, atmospheric and vacuum distillation goes out gasoline and a small amount of water again, obtain light yellow transparent liquid product, productive rate is 97.1%, purity is 97.2%.
Embodiment 2
18.57g sodium hydrate solid is added in the four-hole boiling flask being furnished with prolong, add 24g water dissolution again, after being cooled to room temperature, add Di-n-Butyl Amine 51.69g successively, the ethanol 19.69g that embodiment 1 steams, methylene dichloride 19.58g, then at 35 DEG C, dithiocarbonic anhydride 31.37g is dripped, after dropwising, be warming up to 45 DEG C of reactions 1 hour, and then be warming up to 70 DEG C of reactions 5 hours, then underpressure distillation goes out ethanol, vacuum tightness-0.05MPa, 120# solvent oil 64g extracting is added after ethanol steams., 05h, separating funnel is adopted to isolate upper oil phase, upper oil phase is washed to neutrality, atmospheric and vacuum distillation goes out gasoline and a small amount of water again, obtain light yellow transparent liquid product, productive rate is 96.9%, purity is 97.8%.
Embodiment 3
34.82g sodium hydrate solid is added in the four-hole boiling flask being furnished with prolong, add 45g water dissolution again, after being cooled to room temperature, add Di-n-Butyl Amine 96.93g successively, ethanol 36.93g, methylene dichloride 36.72g, then at 25 DEG C, dithiocarbonic anhydride 59.67g is dripped, after dropwising, be warming up to 40 DEG C of reactions 1 hour, and then be warming up to 70 DEG C of reactions 5 hours, then underpressure distillation goes out ethanol, vacuum tightness-0.05MPa, 120# solvent oil 120g extracting half hour is added after ethanol steams, upper oil phase is isolated with separating funnel, be washed to neutrality, atmospheric and vacuum distillation goes out gasoline and a small amount of water again, obtain light yellow transparent liquid product, productive rate 97.3%, purity 98.2%.
Embodiment 4
27.85g sodium hydrate solid is added in the four-hole boiling flask being furnished with prolong, add 36g water dissolution again, after being cooled to room temperature, add Di-n-Butyl Amine 77.54g successively, the ethanol 29.53g that embodiment 3 steams, methylene dichloride 29.37g, then at 30 DEG C, dithiocarbonic anhydride 47.06g is dripped, after dropwising, be warming up to 45 DEG C of reactions 1 hour, and then be warming up to 70 DEG C of reactions 5 hours, then underpressure distillation goes out ethanol, vacuum tightness-0.05MPa, 120# solvent oil 96g extracting half hour is added after ethanol steams, upper oil phase is isolated with separating funnel, be washed to neutrality, atmospheric and vacuum distillation goes out gasoline and a small amount of water again, obtain light yellow transparent liquid product, productive rate 97.5%, purity 98.5%.
The explanation of above embodiment just understands method of the present invention and core concept thereof for helping.It should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention, can also carry out some improvement and modification to the present invention, these improve and modify and also fall in the protection domain of the claims in the present invention.
To the above-mentioned explanation of the disclosed embodiments, professional and technical personnel in the field are realized or uses the present invention.To be apparent for those skilled in the art to the multiple amendment of these embodiments, General Principle as defined herein can without departing from the spirit or scope of the present invention, realize in other embodiments.Therefore, the present invention can not be restricted to these embodiments shown in this article, but will meet the widest scope consistent with principle disclosed herein and features of novelty.
Claims (8)
1. a preparation method for dialkyl dithio amino formate, comprising:
Secondary alkylamine, aqueous sodium hydroxide solution, methylene dichloride and dithiocarbonic anhydride are reacted in ethanol, then vacuumize underpressure distillation and go out ethanol, then add solvent oil and carry out oil and carry, after washing, underpressure distillation again, obtains dialkyl dithio amino formate.
2. preparation method according to claim 1, is characterized in that, the detailed process of described reaction is:
Sodium hydroxide, water, secondary alkylamine, ethanol are mixed with methylene dichloride, mixed by the mixture obtained with dithiocarbonic anhydride, be warming up to 40 ~ 50 DEG C, reaction 1 ~ 2h, is then warming up to 60 ~ 80 DEG C, reaction 4 ~ 7h.
3. preparation method according to claim 1, is characterized in that, described in the vacuum tightness that vacuumizes be-0.01MPa ~-0.09MPa.
4. preparation method according to claim 1, is characterized in that, described in the vacuum tightness that vacuumizes be-0.05MPa.
5. preparation method according to claim 1, is characterized in that, described secondary alkylamine is the dialkylamine of C2 ~ C10.
6. preparation method according to claim 5, is characterized in that, described secondary alkylamine is Di-n-Butyl Amine.
7. preparation method according to claim 1, is characterized in that, the concentration of aqueous sodium hydroxide solution is 40wt% ~ 50wt%.
8. preparation method according to claim 1, is characterized in that, described solvent oil is 120# solvent oil.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| CN110551047A (en) * | 2019-07-30 | 2019-12-10 | 上海裕诚化工有限公司 | Preparation method of dialkyl dithiocarbamate |
| WO2020103847A1 (en) * | 2018-11-23 | 2020-05-28 | 北京师范大学 | Heavy metal removing preparation, synthesis method for same, and applications thereof |
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Cited By (4)
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| 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 |
| CN107556224B (en) * | 2016-06-30 | 2020-02-28 | 中国石油化工股份有限公司 | Preparation method of dialkyl dithiocarbamate and antiwear and antirust complexing agent |
| WO2020103847A1 (en) * | 2018-11-23 | 2020-05-28 | 北京师范大学 | Heavy metal removing preparation, synthesis method for same, and applications thereof |
| CN110551047A (en) * | 2019-07-30 | 2019-12-10 | 上海裕诚化工有限公司 | Preparation method of dialkyl dithiocarbamate |
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