CN104447457B - A kind of preparation method of 4,4 '-di-2-ethylhexylphosphine oxide (dialkyl dithio Methanamide) - Google Patents
A kind of preparation method of 4,4 '-di-2-ethylhexylphosphine oxide (dialkyl dithio Methanamide) Download PDFInfo
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Abstract
The present invention relates to a kind of 4, the preparation method of 4 ' di-2-ethylhexylphosphine oxides (dibutyl dithio Methanamide), the method comprises the following steps: 1. to the mixed solution and dripping di-n-butylamine of Carbon bisulfide and sodium hydroxide, maintain the temperature between 0～30 DEG C, temperature is risen to 40～60 DEG C after dripping off by di-n-butylamine, continues reaction 1～6 hour；Dripping dichloromethane the most again in solution, be warming up to 50～90 DEG C, react 0.5～8 hour after completing, separating-purifying obtains product.The inventive method changes the feeding manner of material, it is not necessary to the Carbon bisulfide that dropping harmful grade is high, is not required to separately add other solvents, saves response time and operating procedure, and yield is significantly increased, and properties of product are excellent.
Description
Technical field
The invention belongs to organic chemistry filed, relate to a kind of 4, the preparation of 4 '-di-2-ethylhexylphosphine oxide (dialkyl dithio Methanamide)
Method.Specifically, the present invention relates to by secondary for raw material alkylamine, sodium hydrate aqueous solution, Carbon bisulfide, dichloromethane in two steps
React, the method preparing lube oil additive dialkyl dithio amino formate.
Background technology
Day by day flourishing along with the raising of Mechanization Level, particularly auto industry so that lubricating oil industry development also with
Rise.But, oil product in use, due to the reason such as friction, high temperature, moisture and illumination of metal surface, can not
Occurring oxidation reaction to go bad with avoiding, thus cause acid value of lubricating oil to increase, viscosity increases, and generates greasy filth or precipitation, lubrication
Performance is substantially reduced；Along with developing rapidly of modern engine machine technology, lubricating oil uses the raising of temperature, accelerates lubricating oil
Oxidation reaction；Meanwhile, the strict implement of relevant environmental regulation makes lubricating oil face higher antioxygenic property requirement.To oil product
Middle addition antioxygen antiwear additive, can effectively suppress the metamorphic process of oil product, extends the service life of oil product, improves the usability of oil product
Energy.Therefore, develop and there is the lube oil additive of antioxidant and antiwear property become an important topic.
Dialkyl dithio Methanamide and metallic salt thereof are a class preferable antioxygen antiwear lubricating oil additives, at oil product
Middle use, has prominent antioxygenic property and good abrasion resistance and extreme pressure property, the most also have good oil-soluble and
The feature such as ashless, without phosphorus, is widely used in oil products and the greases such as steam turbine oil, I. C. engine oil, hydraulic oil, gear oil
In.
There are some both at home and abroad about the patent of this product and report, are typically all with secondary alkylamine and dichloromethane, alkali molten
Liquid and Carbon bisulfide carry out reacting prepared dialkyl dithio Methanamide, and operating process is comparatively laborious, and Carbon bisulfide volatilization is serious,
Environmental protection and health there is large effect.
United States Patent (USP) US 5744629 discloses the method preparing dialkyl dithio Methanamide.First, sodium hydroxide is made
React in autoclave with Carbon bisulfide with the aqueous solution of di-n-butylamine, control temperature and be not higher than 15 DEG C, react 0.5 hour, then
Slowly instill the dichloromethane of excess, and gradually rise temperature, react 2 hours at 75～80 DEG C.After reaction terminates, enter in two steps
Row decompression distillation, the first step, carry out at a temperature of 45～100 DEG C and under the pressure of 5～50kPa, then carry out at 35～50 DEG C
It is separated, second step, isolated organic facies is carried out again decompression distillation, the final available ASlM color product less than 2.
The method main purpose is to improve product colour, uses low temperature dropping CS2Reaction, the mode of follow-up twice decompression distillation organic facies
Reduce colourity, but operate relatively complicated.Additionally, we are tested by the method, find in the situation that material quantity is less
Lower product yield does not has the highest of patent description.US 3876550 uses two-step method to prepare dialkyl dithio Methanamide.
Uneven in view of the big mixing of material viscosity during low-temp reaction, influencing whether reaction, adding toluene and isopropanol work so using
Play diluting effect for solvent, reduce the viscosity of reaction system, but product yield is the highest, only about 40%, add solvent simultaneously
The operating process reclaimed, additionally also has partial solvent remaining influence product quality in product.Chinese patent CN 1364759A is situated between
Continue a kind of with ethanol as solvent, temperature be 10～60 DEG C to dichloromethane, secondary alkylamine and three kinds of raw materials of NaOH aqueous solution
Mixed solution and dripping Carbon bisulfide, reacts 0.5～5 hour, is warming up to 50～100 DEG C and continues reaction 1～12 hour, separates
Obtain product.The method main purpose is to shorten raw material time for adding, but needs to add solvent, has yield and process costs
Limiting factor.
Carbon bisulfide is added drop-wise in secondary amine and sodium hydroxide solution, under low temperature it can be seen that prior art is typically all
Reaction prepares sodium salt, then adds dichloromethane and is alkylated reaction, and the response time is longer, and yield is the highest.Some is also
Other organic solvents be need to separately add, production cost and operating procedure added.Particularly during dropping Carbon bisulfide, due to two sulfur
Changing the hazardous chemical that carbon belongs to inflammable and explosive, boiling point is low, foul smelling, is difficult to avoid that it volatilizees during dropping, thus right
Environment and health have the biggest hidden danger.Additionally, properties of product prepared by a lot of methods have much room for improvement, as on the low side in purity, color and luster is not
The problem such as good.
Summary of the invention
It is an object of the invention to change charging process thus optimize preparation method, it is provided that a kind of 4,4 '-di-2-ethylhexylphosphine oxide
The novel preparation method of (dialkyl dithio Methanamide).
The present invention relates to one 4, the preparation method of 4 '-di-2-ethylhexylphosphine oxide (dialkyl dithio Methanamide), use two steps to close
Cheng Fa, in the first step, instills in Carbon bisulfide and NaOH aqueous solution by alkylamine, low temperature stirring reaction, generates dialkyl group two
The sodium salt of thiocarbamic acid, reaction equation is as follows:
In second step, the sodium salt of above-mentioned preparation and dichloromethane are alkylated coupling and obtain target product, reaction
Equation is as follows:
The main technical schemes of the present invention: 4, the preparation method of 4 '-di-2-ethylhexylphosphine oxide (dialkyl dithio Methanamide), it is special
Levying is the secondary alkylamine of mixed solution and dripping to Carbon bisulfide and sodium hydroxide, maintains the temperature between 0～30 DEG C, secondary alkyl
Temperature is risen to 40～60 DEG C after dripping off by amine, continues reaction 1～6 hour；In solution, drip dichloromethane again, heat up after completing
To 50～90 DEG C, reacting 0.5～8 hour, wash after standing separatory, product is distilled to obtain in decompression.
A kind of preferably preparation method: to the secondary alkyl of mixed solution and dripping of Carbon bisulfide and sodium hydroxide under ice bath
Amine, maintains the temperature between 0～25 DEG C, and temperature is risen to 40～60 DEG C after dripping off by secondary alkylamine, continues reaction 1～5 hour；Again
In solution, drip dichloromethane, then heat to 60～90 DEG C, react 1～6 hour, wash after standing separatory, decompression distillation
Obtain product.
Usually, the speed controlling of material dropping dripped off at 0.5～4 hour；Reaction stands separatory after terminating, and obtain has
Machine is washed with deionized 2～3 times mutually, and vacuum distilling filtration from sodium chloride obtain satisfactory product.Described steaming
Evaporating pressure is 0 ~ 10KPa, and vapo(u)rizing temperature is 40 ~ 100 DEG C.
Described secondary alkylamine is the dialkylamine of carbon number 1～20, preferably di-n-butylamine.Due to secondary alkylamine boiling point relatively
Height, residual is difficult in the product remove, can affect product quality, so the ratio of other raw material should suitably be increased, so that secondary alkane
Completely, secondary alkylamine can be 1:1～1.7, preferably 1:1～1.4 with the mol ratio of Carbon bisulfide to the reaction of base amine.Secondary alkylamine with
The mol ratio of sodium hydroxide can be 1:1～1.6, preferably 1:1～1.3.Secondary alkylamine with the mol ratio of dichloromethane can be
1:0.5～1.0, preferably 1:0.5～0.8.The mass concentration of sodium hydrate aqueous solution can be 10%～75%, preferably 13%～
50%。
The inventive method changes the feeding manner of material, it is not necessary to the Carbon bisulfide that dropping harmful grade is high, is not required to separately add it
His solvent, saves response time and operating procedure, and yield is significantly increased, and properties of product are excellent.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is described in detail.It should be noted that these embodiments are not used
In limiting the scope of the invention, protection scope of the present invention is as the criterion with appending claims.
Embodiment 1: by 242g(3.15mol) Carbon bisulfide and 636g sodium hydrate aqueous solution (mass fraction is 20%) add
Enter in four-hole bottle, start after stirring to drip 394g(3mol) di-n-butylamine, control temperature is at about 10 DEG C, after 2 hours
Di-n-butylamine drips off, and temperature rises to 50 DEG C, continues reaction 2 hours；140g(1.65mol is dripped again in solution) dichloromethane
Alkane, is warming up to 70 DEG C after within 2 hours, dripping off, react 2.5 hours, and reaction terminates.Wash after separatory, in 5KPa condition and 70 DEG C of conditions
Lower decompression distillation obtains light yellow clear oily liquids, yield 94.3%.Its kinematic viscosity 15.16cSt, nitrogen content 6.81, colourity
0.5。
Embodiment 2: by 251g(3.3mol) Carbon bisulfide and 636g sodium hydrate aqueous solution (mass fraction is 20%) add
In four-hole bottle, start after stirring to drip 394g(3mol) di-n-butylamine, reacts under ice bath, and maintains the temperature at 10 DEG C of left sides
The right side, after 2 hours, di-n-butylamine drips off, and temperature rises to 50 DEG C, continues reaction 2 hours；140g is dripped again in solution
(1.65mol) dichloromethane, is warming up to 75 DEG C after within 2 hours, dripping off, react 2.5 hours, and reaction terminates.Wash after separatory,
Distillation of reducing pressure under the conditions of 5KPa condition and 70 DEG C obtains light yellow clear oily liquids, yield 95.1%.Its kinematic viscosity
15.29cSt, nitrogen content 6.78, colourity 1.0.
Embodiment 3: by 242g(3.15mol) Carbon bisulfide and 848g sodium hydrate aqueous solution (mass fraction is 15%) add
Enter in four-hole bottle, start after stirring to drip 394g(3mol) di-n-butylamine, maintain the temperature at about 15 DEG C under ice bath,
After 1.8 hours, di-n-butylamine drips off, and temperature rises to 50 DEG C, continues reaction 2 hours；187g(1.8mol is dripped again) in solution
Dichloromethane, is warming up to 75 DEG C after within 2 hours, dripping off, react 2.5 hours, and reaction terminates.Wash after separatory, in 3KPa condition and 75
Distillation of reducing pressure under the conditions of DEG C obtains light yellow clear oily liquids, yield 95.8%.Its kinematic viscosity 15.56cSt, nitrogen content
6.78, colourity 0.5.
Embodiment 4: by 323g(4.2mol) Carbon bisulfide and 875g sodium hydrate aqueous solution (mass fraction is 20%) add
In four-hole bottle, start after stirring to drip 526g(4mol) di-n-butylamine, maintain the temperature at about 15 DEG C, after 2 hours two
N-butylamine drips off, and temperature rises to 55 DEG C, continues reaction 2 hours；187g(2.2mol is dripped again in solution) dichloromethane, 2
Being warming up to 80 DEG C after hour dripping off, react 2 hours, reaction terminates.Wash after separatory, reduce pressure under the conditions of 3KPa condition and 75 DEG C
Distillation obtains light yellow clear oily liquids, yield 95.3%.Its kinematic viscosity 15.46cSt, nitrogen content 6.78, colourity 0.5.
Embodiment 5: by 323g(4.2mol) Carbon bisulfide and 875g sodium hydrate aqueous solution (mass fraction is 20%) add
In four-hole boiling flask, start after stirring to drip 526g(4mol) di-n-butylamine, maintain the temperature at about 10 DEG C, after 2 hours
Di-n-butylamine drips off, and temperature rises to 55 DEG C, continues reaction 2.5 hours；187g(2.2mol is dripped again in solution) dichloromethane
Alkane, is warming up to 75 DEG C after within 2 hours, dripping off, react 2.5 hours, and reaction terminates.Wash after separatory, in 5KPa condition and 75 DEG C of conditions
Lower decompression distillation obtains light yellow clear oily liquids, yield 94.9%.Its kinematic viscosity 15.36cSt, nitrogen content 6.72, colourity
1.0。
Comparative example 1: by 394g(3mol) di-n-butylamine and 636g sodium hydrate aqueous solution (mass fraction is 20%) join
In four-hole boiling flask, start after stirring to drip 242g(3.15mol) Carbon bisulfide, maintain the temperature at about 15 DEG C under ice bath, 2
After hour, Carbon bisulfide drips off, and temperature rises to 50 DEG C, continues reaction 2 hours；187g(1.8mol is dripped again in solution) two
Chloromethanes, is warming up to 75 DEG C after within 2 hours, dripping off, react 2.5 hours, and reaction terminates.Wash after separatory, 3KPa condition and 75 DEG C
Under the conditions of reduce pressure distillation obtain brownish red transparent oily liquid, yield 89.2%.Its kinematic viscosity 15.13cSt, nitrogen content 6.65,
Colourity 2.0.
Comparative example 2: according to the method for United States Patent (USP) US 5744629 explanation, by 64g(1.6mol) NaOH, 206.8g
(1.6mol) di-n-butylamine and 416g water join in four-hole bottle, and under agitation mixture are cooled to 5 DEG C.Under agitation will
During 121.6g(1.6mol) Carbon bisulfide is added slowly to mixture, and make temperature be less than 15 DEG C, after adding Carbon bisulfide, continue
Stir 0.5 hour.It is subsequently adding 81.6g(excess 20%) dichloromethane, and temperature is slowly increased to 45 DEG C is alkylated anti-
Should, then react 2 hours at 75 DEG C.Reaction carries out distillation of reducing pressure for the first time after terminating, steam part water and unreacted material.
Carry out decompression distillation after standing separation aqueous phase again, after washing, obtain light yellow product.Due to product directly be washing after isolated,
The transparency is poor, need to distill again and just become clarification.Product yield is 88.1%, its kinematic viscosity 14.11cSt, nitrogen content
6.19, colourity 1.5.
Claims (7)
1. one kind 4, the preparation method of 4 '-di-2-ethylhexylphosphine oxide (dialkyl dithio Methanamide), it is characterized in that to Carbon bisulfide and hydrogen
The secondary alkylamine of mixed solution and dripping of aqueous solution of sodium oxide, maintains the temperature between 0～30 DEG C, secondary alkylamine add after by temperature
Degree rises to 40～60 DEG C, continues reaction 1～6 hour；In solution, drip dichloromethane again, after completing, be warming up to 50～90 DEG C,
Reacting 0.5～8 hour, wash after standing separatory, product is distilled to obtain in decompression；The speed controlling of described material dropping is little in 0.5～4
Time add；Described secondary alkylamine is 1:1～1.7 with the mol ratio of Carbon bisulfide, and secondary alkylamine with the mol ratio of sodium hydroxide is
1:1～1.6, secondary alkylamine is 1:0.5～1.0 with the mol ratio of dichloromethane；The mass fraction of sodium hydrate aqueous solution used
It is 10%～75%.
Preparation method the most according to claim 1, it is characterised in that to Carbon bisulfide and sodium hydrate aqueous solution under ice bath
The secondary alkylamine of mixed solution and dripping, maintain the temperature between 0～25 DEG C, temperature is risen to 40～60 by secondary alkylamine after adding
DEG C, continue reaction 1～5 hour；In solution, drip dichloromethane again, then heat to 60～90 DEG C, react 1～6 hour, quiet
Washing after putting separatory, product is distilled to obtain in decompression.
Preparation method the most according to claim 1 and 2, it is characterised in that wherein said distillation pressure is 0 ~ 10KPa,
Vapo(u)rizing temperature is 40 ~ 100 DEG C.
Preparation method the most according to claim 1, it is characterised in that described secondary alkylamine is the secondary of carbon number 1～20
Alkylamine.
5. according to the preparation method described in claim 1 or 4, it is characterised in that described secondary alkylamine is di-n-butylamine.
6. the preparation method stated according to claim 1, it is characterised in that the mol ratio of secondary alkylamine and Carbon bisulfide be 1:1 ~
1.4, the mol ratio of secondary alkylamine and sodium hydroxide is 1:1 ~ 1.3, the mol ratio of secondary alkylamine and dichloromethane be 1:0.5 ~
0.8。
7. the preparation method stated according to claim 1, it is characterised in that the mass fraction of sodium hydrate aqueous solution used is 13 ~
50%。
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| 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 |
| CN107200703B (en) * | 2016-03-18 | 2019-06-04 | 中国石油化工股份有限公司 | The method for preparing Keywords dibutyl dithiocarbamate using supergravity reactor |
| CN111321028A (en) * | 2018-12-13 | 2020-06-23 | 中国石油天然气股份有限公司 | Ashless antioxidant lubricating oil additive, compound lubricating oil additive and lubricating oil composition containing additives |
| CN110551047A (en) * | 2019-07-30 | 2019-12-10 | 上海裕诚化工有限公司 | Preparation method of dialkyl dithiocarbamate |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5015368A (en) * | 1990-06-15 | 1991-05-14 | The Lubrizol Corporation | Ore flotation process using carbamate compounds |
| 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 |
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| JP2011012043A (en) * | 2009-07-03 | 2011-01-20 | Kawaguchi Kagaku Kogyo Kk | New vulcanization accelerator imparting dynamic durability to vulcanized rubber composition |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5015368A (en) * | 1990-06-15 | 1991-05-14 | The Lubrizol Corporation | Ore flotation process using carbamate compounds |
| 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 |
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Address after: Liuhe District of Nanjing City, Jiangsu province 210048 geguan Road No. 699 Patentee after: China Petroleum & Chemical Corp. Patentee after: SINOPEC NANJING CHEMICAL RESEARCH INSTITUTE Co.,Ltd. Address before: Liuhe District of Nanjing City, Jiangsu province 210048 geguan Road No. 699 Patentee before: China Petroleum & Chemical Corp. Patentee before: Nanhua Group Research Institute |
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