JPH0430959B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a method for producing a molybdenum compound containing phosphorus and sulfur or a composition containing the same. [Prior art] Molybdenum compounds containing phosphorus and sulfur and methods for producing the same are disclosed in Japanese Patent Publication Nos. 40-8426 and 44-27366.
No. 57-24798, No. 57-24799, JP-A-56-79698, and JP-A-56-110796. It is stated that all of the compounds described in these publications can be used as components of lubricants, but all of them are complex compositions containing considerable amounts of multiple compounds in addition to the target molybdenum compound. However, there are problems such as difficulty in blending it into an appropriate composition as a lubricant, and problems with lubricating performance, especially corrosion of metals such as copper. [Problems to be Solved by the Invention] An object of the present invention is to provide a method by which the target molybdenum compound can be selectively produced and which does not produce by-products. A further object of the present invention is to produce a molybdenum compound containing phosphorus and sulfur that is less corrosive to metals and has excellent lubricating properties such as wear resistance, friction resistance, and oxidation stability. [Means for Solving the Problems] The present invention comprises (a) at least one _hexavalent molybdenum compound; at least one compound selected from alkali sulfides represented by (indicating a group) and (c) general formula (In the formula, X ₁ , X ₂ , Y ₁ , Y ₂ are oxygen or sulfur atoms and may be the same or different. n is a number of 0 or 1, and R ₁ and R ₂ are organic residues and may be the same or different. (which may be different) or a salt thereof, and (d) a reducing agent capable of reducing a hexavalent molybdenum compound to a pentavalent or tetravalent one (excluding the above b and c components). The present invention provides a method for producing a molybdenum compound containing phosphorus and sulfur. The compounds produced by the method of the present invention have the general formula (In the formula, X ₁ , X ₂ , X ₃ , X ₄ , Y ₁ , Y ₂ , Y ₃ , Y ₄
may be the same or different for oxygen or sulfur atoms. n represents the number 0 or 1, R ₁ , R ₂ , R ₃ ,
R ₄ is an organic residue and may be the same or different.
x and y are numbers from 0 to 4, and x+y=4). The hexavalent molybdenum compounds used in the present invention include molybdenum trioxide, molybdenum trioxide hydrate, molybdic acid, ammonium molybdate,
Included are alkali metal salts of molybdate (eg, sodium or potassium), and heteropolyacid salts of molybdate (eg, phosphomolybdate).
Preferred hexavalent molybdenum compounds include those obtained by acidifying phosphomolybdic acid, ammonium molybdate, or alkali metal salts of molybdate with hydrochloric acid, acetic acid, sulfuric acid, etc., and those obtained by acidifying molybdenum trioxide or its hydrate. It is increased by adding an acid or a base. Other useful compounds include MoOCl ₄ , MoO ₂ Cl ₂ , MoO ₂ Br ₂ ,
Hexavalent molybdenum oxyhalides such as Mo ₂ O ₃ Cl ₆ and MoOF ₄ and mixtures thereof can also be used. The hydrogen sulfide used in the present invention may be introduced from outside the system or may be generated within the reaction system. Alkali hydrosulfides or alkali sulfides represented by the general formula M ₂ S (in the formula M represents an alkali metal or ammonium group) include aqueous alkali hydrosulfides, flaky alkali hydrosulfides, sodium sulfide, potassium sulfide, and sulfide. Ammonium etc. are commonly used. Preferred compounds of general formula (1) used in the present invention are those of general formula (In the formula, R ₁ and R ₂ are hydrocarbon residues that may have an ether bond or an ester bond and may be substituted with halogen, etc.) O,O'-diorganophosphorodithioate It is. _R1 , _R2
Preferred examples include methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, amyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl,
hexyl, 1,3-dimethylbutyl, heptyl,
Aliphatic hydrocarbon groups such as octyl, 2-ethylhexyl, nonyl, decyl, dodecyl, tetradecyl, octadecyl, methoxymethyl, methoxyethyl, ethoxyethyl, butoxyethyl, methoxypropyl, ethoxypropyl, butoxypropyl groups, or general formula R ₃ (OR ₄ ) _o (In the formula, R ₃ is a hydrocarbon residue having 1 to 20 carbon atoms, and R ₄ is a hydrocarbon residue having 2 carbon atoms.
~3 hydrocarbon residues, n is a number from 1 to 100), aromatic residues such as phenyl, substituted phenyl, alicyclic residues such as cyclohexyl, substituted cyclohexyl, etc. . Another preferred group of compounds of general formula (1) used in the present invention is the general formula (In the formula, R ₁ and R ₂ are hydrocarbon residues that may have an ether bond or an ester bond, and may be substituted with halogen, etc.; examples of R ₁ and R ₂ include the general formula (3 The compounds shown in ) are similarly mentioned. Another preferred group of compounds of general formula (1) used in the present invention is the general formula (In the formula, R ₁ and R ₂ are hydrocarbon residues that may have an ether bond or an ester bond, and may be substituted with halogen, etc.; examples of R ₁ and R ₂ include the general formula (3 The compounds shown in ) are similarly mentioned. Another preferred group of compounds of general formula (1) used in the present invention is the general formula (In the formula, R ₁ and R ₂ are hydrocarbon residues that may have an ether bond or an ester bond, and may be substituted with halogen, etc.; examples of R ₁ and R ₂ include the general formula (3 The compounds shown in ) are similarly mentioned. Compounds in which S in the >PS' ₂ H moiety is replaced with 0 by treating the compounds of the above general formulas with water or steam can also be used in the present invention. It is also possible to use these phosphorus-containing compounds in combination. Further, the reaction raw materials may be supplied so that these acids or their salts are produced within the reaction system. for example,
In the case of O,O'-dihydrocarbyl hydrogen phosphorodithioate, alcohol and phosphorus pentasulfide are reacted in an inert solvent, or phosphorus pentasulfide is reacted with water without an inert solvent. The reaction may be carried out in the absence of a substance reactive with phosphorus pentasulfide. The reducing agent used in the present invention includes sodium polythionates such as sodium sulfoxylate, sodium dithionite, sodium sulfite, sodium bisulfite, sodium pyrosulfite, sodium thiosulfate, sodium dithionate, and other alkali metals thereof. salts or alkaline earth metal salts, reducing sulfur compounds such as oxygen disulfide, reducing sugars such as glucose, maltose, lactose, maltotriose, manninotriose, formaldehyde, acetaldehyde, propionaldehyde sugar aldehydes, formic acid Reducing acids such as , oxalic acid, ascorbic acid, and salts thereof are commonly used. Reducing agent per molybdenum atom of component (a)
It is used in a proportion of 0.01 mol or more and up to 5 mol. These reducing agents may be used from the beginning of the reaction, may be used from the middle of the reaction, or may be used before all reactions are completed. The molar ratio of component (a) and component (b) is not particularly limited, but the amount of component (b) per 1 equivalent of molybdenum of (a) is 0.05 to
The amount is preferably about 4 equivalents, preferably about 0.08 to 3.8 equivalents. The pH of the reaction system affects the values of x and y in general formula (2) and the reaction yield, so it changes depending on the values of x and y of the target compound, but is usually about 2 to 12. The molar ratio of component (a) to component (c) is not particularly limited, but it is generally preferred that the amount of component (c) be 0.5 to 5 moles, preferably 0.8 to 3 moles, per mole of component (a). In particular, when selective production of a pure compound of general formula (2) is desired, the molar ratio is preferably 0.9 to 1.2, preferably approximately 1. Generally, a reaction temperature around room temperature is sufficient, but 40
The temperature is 140°C to 140°C, preferably 60 to 110°C, and the reaction time is about 2 to 10 hours. A suitable organic solvent, mineral oil, synthetic oil, etc. may be used as a medium for the reaction.
In order to increase the reaction yield, it is desirable to neutralize and ripen after the reaction. The reaction product is generally a colored oily or viscous substance, and the target product can be obtained by distilling off the volatile components under normal pressure or reduced pressure, or by separating it from the reaction solution and washing with water or an organic solvent. I can do it. Fields of use of the compounds obtained by the process of the invention include pyrotechnic and compression ignition internal combustion engines, including automobile and truck engines, two-stroke engines, aircraft piston engines, marine and locomotive diesel engines, etc. Contains crankcase lubricant. They are also used in gas engines, stationary power engines, turbines, etc. Also used in automatic transmission fluids, transaxle lubricants, gear lubricants, metalworking lubricants, hydraulic fluids and other lubricating oil and grease compositions for extreme pressure performance, anti-wear performance, friction mitigation performance, and anti-oxidation performance. Performance etc. can be given. [Example] Example 1 400ml of water and 144g of molybdenum trioxide are placed in a reactor and suspended. Add 120g of flaked sodium bisulfide (70% product) to this under a nitrogen atmosphere, and age at 40-50°C for 1 hour to dissolve molybdenum trioxide. Next, 63g of sodium sulfite was added and the mixture was aged at 40-50°C for 1 hour, and then 370g of di-2ethylhexylphosphorodithionate was added dropwise and the mixture was aged at 60-70°C for 2 hours. 30% sulfuric acid 170gr
After neutralizing with water, reflux is carried out for 5 hours. After cooling, the reaction product was washed with water, degassed, and filtered to obtain a brown liquid.
I got gr. Based on infrared absorption spectrum (IR), magnetic resonance spectrum (NMR), high performance liquid chromatography (HPLC), and elemental analysis values,
It is a mixture of compounds represented by the general formula (2), and R ₁
=R ₂ =R ₃ =R ₄ =2ethylhexyl, X ₁ =X ₂ =
_X3 = _X4 =O, _Y1 = _Y2 = _Y3 = _Y4 =S, and x=1.95. IR chart in Figure 1 and NMR chart in Figure 2
( ¹ H) and FIG. 3 ( ¹³ C), and the HPLC chart is shown in FIG. 4. Elemental analysis values Mo: 19.1% S: 19.6% P: 6.0% Comparative Example 1 The reaction was carried out without using an alkali sulfide or a reducing agent. That is, 500ml of water and 144g of molybdenum trioxide are placed in a reactor and suspended. Add 40g of flaked sodium hydroxide (100% product) to this and mature for 1 hour to dissolve molybdenum trioxide. Next, 370 gr of di-2-ethylhexylphosphorodithionate was added dropwise under a nitrogen atmosphere to give a solution of 60-70 g.
Aging for 2 hours at °C. After neutralization with 170g of 30% sulfuric acid, reflux is performed for 5 hours. After cooling, the reaction product was washed with water, degassed, and filtered to obtain 380 gr of brown liquid. According to HPLC and elemental analysis values, this product has
It was a mixture of compounds represented by general formula (2) containing many impurities. The HPLC chart is shown in Figure 5. Elemental analysis values Mo: 10.6% S: 15.0% P: 7.1% Example 2 500ml of water and 144g of molybdenum trioxide are placed in a reactor and suspended. Add 360g of sodium sulfide (nonahydrate) to this under a nitrogen atmosphere, and heat at 40-50℃.
Aged for 1 hour to dissolve molybdenum trioxide.
Then 26g of L-ascorbic acid was added to give 40-
After aging at 50℃ for 1 hour, add 100g of methanol.
220g of di-isopropylphosphorodithionic acid was added dropwise thereto, and the mixture was aged at 60°C for 2 hours.
After neutralizing with 550g of 20% hydrochloric acid, the mixture was further aged at 60°C for 5 hours, cooled and filtered. The filter cake is washed with water, methanol, and dried to a melting point of 140-143℃.
320g of yellow solid was obtained. When this product was fixed in the same manner as in Example 1, it was found to be a mixture of compounds represented by general formula (2) (x=1.9). Elemental analysis values Mo: 27.1% S: 27.5% P: 8.5% Example 3 300ml of water and ammonium molybdate in a reactor
Add 196gr and dissolve. Add this to 490g of 20% sulfuric acid.
Neutralize with r, add 140g of 40% sodium hydrogen sulfide under a nitrogen atmosphere, and age at 40-50°C for 1 hour. Next, 29g of sodium dithionite was added and the mixture was aged at 40-50°C for 1 hour, and then 200g of methanol was added thereto, followed by dropwise addition of 270g of di-butylphosphorodithionate, and the mixture was aged at 60°C for 3 hours. After neutralizing again with 170g of 20% sulfuric acid, the mixture was further aged at 60°C for 5 hours. After cooling, the reaction product was washed with water, degassed and filtered to obtain 360 gr of brown oil. When this product was fixed in the same manner as in Example 1, it was found to be a mixture of compounds represented by general formula (2) (x=1.9). Elemental analysis values Mo: 24.6% S: 25.0% P: 8.1% Example 4 600ml of water and ammonium molybdate in a reactor
Add 206gr and dissolve. After replacing the inside of the system with nitrogen, hydrogen sulfide gas is sucked in to adjust the pH of the liquid to 3-4. Then, after adding 52g of sodium bisulfite and aging at 40-50℃ for 1 hour,
-Di-methylbutylphosphorodithionic acid 360gr
was added dropwise and aged at 60-70℃ for 2 hours. 30% sulfuric acid
After neutralization with 150 gr, reflux is carried out for 5 hours. After cooling, the reaction product was washed with water and methanol,
After degassing and filtering, 350 gr of brown liquid was obtained. This product was also identified by the same method as in Example 1, and was found to be a mixture of compounds represented by general formula (2) (x=1.95). Elemental analysis values Mo: 21.7% S: 22.1% P: 7.0% Example 5 500ml of water and 144g of molybdenum trioxide are placed in a reactor and suspended. Add 210g of 40% sodium hydrogen sulfide to this under a nitrogen atmosphere and heat at 40-50℃.
Time to mature. Next, 45g of glucose was added and aged at 40-50°C for 1 hour, and then 300g of di-hexylphosphorodithionic acid was added dropwise and the temperature was aged at 40-50°C.
Let it mature for 2 hours. After neutralizing with 220g of 20% hydrochloric acid, reflux is carried out for 3 hours. After cooling, the reaction product was washed with water, degassed and filtered to obtain 420g of brown liquid. This product was also identified by the same method as in Example 1, and was found to be a mixture of compounds represented by general formula (2) (x=1.9). Elemental analysis values Mo: 21.9% S: 22.4% P: 6.7% Example 6 600ml of water and ammonium molybdate in a reactor
Add 206gr and dissolve. After replacing the inside of the system with nitrogen, hydrogen sulfide gas is sucked in to adjust the pH of the liquid to 3-4. Then sodium dithionite 58 gr
After adding and aging at 40-50℃ for 1 hour,
Add 320g of cyclohexylphosphorodithionic acid dropwise and age for 1 hour. After neutralization with 150g of 30% sulfuric acid, reflux is performed for 5 hours. After cooling, a viscous reaction product is obtained. After dissolving in 400g of chloroform, it is washed with water, degassed, and a viscous brown paste of 370g is obtained. This product was also identified by the same method as in Example 1, and was found to be a mixture of compounds represented by general formula (2) (x=1.95). Elemental analysis values Mo: 21.8% S: 22.5% P: 7.2% Example 7 Put 600 ml of water and 144 gr of molybdenum trioxide into a reactor and suspend. Add 280g of 40% sodium hydrogen sulfide to this under a nitrogen atmosphere and heat at 40-50℃.
Time to mature. Then acetaldehyde (80%
Product) After adding 30gr and aging at 40-50℃ for 1 hour, add 700gr di-dodecylphosphorodithionic acid.
was added dropwise and aged at 60-70℃ for 3 hours. 20% sulfuric acid
After neutralization with 490 gr, reflux is carried out for 10 hours. After cooling, the reaction product was washed with water and ethanol,
After degassing and filtering, 365 gr of brown liquid was obtained. This product was also identified by the same method as in Example 1, and was found to be a mixture of compounds represented by general formula (2) (x=1.95). Elemental analysis values Mo: 15.8% S: 15.9% P: 5.1% Example 8 Put 500 ml of water and 72 gr of molybdenum trioxide into a reactor and dissolve them. Add 240g of sodium sulfide (nonahydrate) to this under a nitrogen atmosphere, and heat at 40-50℃.
Aged for 1 hour to dissolve molybdenum trioxide.
Then add 15g of sodium dithionite
After aging at 40-50℃ for 1 hour, naphthenic mineral oil
350g of di-nonylphenylphosphorodithionic acid was added dropwise thereto, and the mixture was aged at 60°C for 3 hours. After neutralization with 330gr of 30% sulfuric acid, 10
Reflux for an hour. After cooling, it was washed with water, degassed and filtered to obtain 650g of brown liquid. The general formula for this product was determined by HPLC, elemental analysis, etc.
It was a mixture of the compound shown in (2) and naphthenic mineral oil (x=1.95). Elemental analysis values Mo: 6.6% S: 6.8% P: 2.1% Usage example 1 The compounds obtained in each example were dissolved in 150 neutral oil with a molybdenum content of 0.06% by weight, and the anti-wear properties were tested using a Shell 4-ball tester. It was measured. (Oil temperature
(Displayed as the diameter of the wear scar after 1 minute at 80℃, load 40Kg, and 1500 rotations)

[Table] Usage Example 2 The compounds obtained in each example were dissolved in 500 neutral oil to a molybdenum content of 0.05% by weight, and the anti-wear properties were measured using a Farex tester.

[Table] Usage Example 3 The compounds obtained in each example were dissolved in 150 neutral oil with a molybdenum content of 0.04% by weight, and the anti-wear performance and friction mitigation performance were measured using a Shell 4-ball tester as an effect of suppressing the increase in oil temperature. did. (At the start of the test, the oil temperature was 80℃, the load was 32Kg, and the rotation was 30℃ at 1800 rpm.
(Displayed in diameter of wear scar and oil temperature after 1 minute)

[Table] Usage Example 4 The antioxidant properties of the compounds obtained in each example were determined by ISO
A comparison was made using an oil deterioration test using the method. Test method: Dissolve 0.06% by weight of molybdenum in 200ml of 150 neutral oil and heat at 165.5℃ for 48 hours.
Air is passed through at a rate of 10 liters/hour in the presence of copper and iron, and the viscosity ratio (rate of increase in viscosity) and increase in oxidation of the oil are measured.

[Table] Usage Example 5 The compounds obtained in each example were dissolved in 150 neutral oil to have a molybdenum content of 0.06% by weight, a copper plate was placed therein, and the solution was heated at 100°C for 3 hours to test the corrosivity to the copper plate. (Based on ASTM D-130)

【table】

〔Effect of the invention〕

The effect of the present invention is to provide a new method for producing oxymolybdenum dialkylphosphorodithiooxysulfide without by-products, and by using this method, it is possible to oxidize more than conventionally used ZDTP or molybdenum-containing lubricant additives. The object of the present invention is to provide a lubricant additive with excellent anti-wear properties, wear-reducing properties, and heat resistance.

[Brief explanation of drawings]

Figures 1, 2, 3, and 4 are of Example 1, respectively.
They are an IR chart, ^{a 1} H-NMR chart, ^{a 13} C-NMR chart, and an HPLC chart. Figure 5 is Comparative Example 1
This is the HPLC chart.

Claims (1)

[Scope of Claims] 1 (a) at least one hexavalent molybdenum compound; (b) hydrogen sulfide, alkali hydrosulfide or general formula M ₂
at least one compound selected from alkali sulfides represented by S (where M represents an alkali metal or ammonium group); and (c) general formula (In the formula, X ₁ , X ₂ , Y ₁ , Y ₂ are oxygen or sulfur atoms and may be the same or different. n represents a number of 0 or 1, and R ₁ and R ₂ are organic residues and are the same) but may be different) or a salt thereof;
(d) A method for producing a molybdenum compound containing phosphorus and sulfur, which comprises reacting a hexavalent molybdenum compound with a reducing agent capable of reducing a hexavalent molybdenum compound to a pentavalent or tetravalent molybdenum compound (excluding components b and c described above).