JPS5949296A - Additive for lubrication oil and its preparation - Google Patents

Abstract

PURPOSE:To provide an additive for lubrication oil, capable of reducing the friction and improving the extreme-pressure property of an oil, and suitable for gasoline engine, etc., by using an organomolybdenum compound represented by a specific formula and containing phosphorus atom and sulfur atom in the molecule, as a main component. CONSTITUTION:The lubrication oil additive contains the compound of formula I [R is 3-20C alkyl, alkenyl, cycloalkyl, cycloalkenyl, alkaryl, group of formula II(R' is 3-20C alkyl, alkenyl cycloalkyl, cycloalkenyl or alkaryl; R'' is 2-4C alkylene; n is 0-3) or group of formulaIII]. The above compound can be prepared by mixing 1 mole of an acidic ester of dithiophosphoric acid of formula IVthoroughly with equivalent amount of a strongly basic compound and 1/2 equivalent amount of molybdenum trioxide, adding equivalent amount of an acid, based on said strongly basic compound, to the mixture, and heating the composition at >=50 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a lubricant/111 additive based on an inorganic compound containing a molybdenum atom in the molecule, and a method for producing the same.

In recent years, there has been a movement to lower the viscosity of lubricating oil used in gasoline engines and diesel engines with the aim of saving consumption of petroleum resources. However, when the viscosity of the lubricating oil is lowered, the rupture of the liquid film on the LSI surface becomes more likely to occur, and therefore the 4'+:j area increases and the lubrication t'tan surface increases. A phenomenon of increased wear is observed.

In order to solve the second problem, it is effective to use additives that improve the extreme pressure properties. There is a growing trend to use additives that have the following effects: Such additives include Frixion Modifier E+---u? ! It is called l'I? It is something that Examples of this friction modifier include higher fatty acid esters, amides, higher aliphatic amines,
Although primary aliphatic phosphoric acid esters are common, recently molybdenum compounds have been used.In addition to inorganic compounds such as molybdenum disulfide (MnS2), molybdenum compounds include several The molybdenum compound No. 1 has been used for this purpose. In particular, molybdenum salts of 41-thiophosphoric acid containing phosphorus and sulfur in the molecule are known to have excellent effects.

The fact that molybdenum compounds containing sulfur and phosphorus atoms in their molecules have a tendency to extreme pressure is disclosed in Japanese Patent Publication No. 40-8426 and III+' Publication No. 4
8-2204 (a).

For example, in Japanese Patent Publication No. 40-8426 [(RX)
2P X-X '13. MOXI, (X is 0 or S,
ai2b is a lubricating oil composition containing a molybdenum compound consisting of 4 to 8).

Furthermore, in Japanese Patent Publication No. 48-2204, there is also
L grease and ((RO)21' S -S )2M02
3202 is described.

However, as can be seen in these patents, the composition and performance of a compound consisting of dithioline f112 ester and molybdenum and its performance vary greatly depending on the manufacturing conditions (1).

4. Invention 11 and others also discovered that various molybdenum compounds C, 2 and 1 were used as sorption modifiers. [10'] Recognized that a compound containing bar and sulfur element f improves the performance of the saw, and arrived at the present invention. Specify the reaction conditions between the varnish and the inorganic liveden compound.
The extreme pressure propensity of the compound prepared by changing the 14 ability? J+
'/': t÷Coefficient reduction ability is Kl! As soon as I inspected the
- It has been found that the compound represented by the general formula (1) exhibits the most preferable performance. Furthermore, we conducted intensive research on a method for producing the compound represented by the general formula ('1) with as high a purity as possible, and found that under certain limited production conditions (
The present invention was achieved by finding the most efficient way to manufacture this within the range of /1.

The present invention provides a moisturizer containing a high proportion of the J compound which exhibits particularly poor extreme pressure properties and wear resistance among the molybdenum salts of organic thiophosphoric acids. F' relates to an oil additive and a method for producing the same.

More specifically, general formula % formula % (1) [wherein R is an alkyl group having 3 to 20 carbon atoms, an alkenyl group, a cycloalkyl group, an ncucoalkenyl group, an alkaryl group, a general formula R' 0(R”O)nR”
(R' is an alkyl group, alkenyl group, cycloalkyl group, cycloalkenyl group having 3 to 20 carbon atoms,
represents an alkaryl group, R'' represents an alkylene group having 2 to 4 carbon atoms, and n represents a positive number of 0 to 3), general formula R'S
(R'O)nR'(R',R'' and n are the same as above.

) represents the same or different groups selected from the group consisting of

] This is a lubricating oil characterized by containing -ζ as a base component, which is an additive for lubricating oil that reduces friction and improves extreme pressure properties, and further has the general formula % Formula % (2) [In the formula, rs is an alkyl group having 3 to 20 carbon atoms, an alkenyl group, an I:I alkyl group, an alkenyl group, an alkaryl group, and a general formula R'0
1fo) R''(R' represents an alkyl group having 3 to 20 carbon atoms, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, an alkaryl group, and R'' represents an alkylene group having 2 to 4 carbon atoms. , n represents a positive number of θ to 3), the same or different selected from the group consisting of the general formula R'S (R''0) TIRo (R', R'' and n are the same as above) Indicates the group. ] To 1 mole of acidic ester of dithiophosphoric acid, add an equivalent amount of a strong basic compound and about 1/2 equivalent of molybdenum trioxide, mix well, and then add the above strong base to the mixture. In the following general formula % formula % (1) (wherein R is the same as above), which is characterized by adding an acid of about -C to the compound and heating it at 50°C or higher. The present invention relates to a method for producing an additive that reduces friction and improves extreme pressure properties of a lubricating oil containing the compound shown above as a main component.

The alkyl group having 3 to 20 carbon atoms, which is the R portion of the compound represented by the general formula (1) of the present invention, ranges from a propyl group to an eicosyl group, and ranges from a straight chain to a moderately branched one. n-butyl group, isobutyl group; = n-hexyl group, methylpropyl group, n-
Octyl group, 2-ethylhexyl group, isononyl group, n
Those having 4 to 12 carbon atoms, such as -decyl group, isodecyl group, n-dodesol group, and itodecyl group, are preferable.

The alkenyl group has 3 to 20 carbon atoms and 1 to 20 carbon atoms.
Those having two double bonds can be used, but those having 4 to 12 carbon atoms and one double bond are particularly preferred.

As the cycloalkyl group, those having 3 to 20 carbon atoms can be used, but in particular, cyclohexyl group, methylcyclo1.1
Hexyl group, conytyl group 1: I hexyl J is very old.

In addition, the Schiff summer alkenyl group and C have 3 to 20 carbon atoms.
Particularly preferred are the cyclor,lhexenyl group, the methylcycloIII=, the cyclo-,'-l group, and the edylcyclo1:1hexenyl group.

In addition to phenyl di^, examples of the alkaryl group include methylph, 1. Nyl group, ethylhexyl group, bilphenyl 7i Sengen and', 1 to 2 (hard alleki 11
Preferred are substituted sonyl groups.

Furthermore, R and C in general formula (1) are R'O(R″0
), , R'' Manokowa R'S (R''O), , A substituent containing a niethyl group or a 1,000-onythyl group represented by ``R'' can also be used for I. Carbon number 3
Particularly preferred are groups consisting of ethyleneoxy l-' (-1 adduct, br'l + dianordoxy F adduct, etc.) or mercaptan.

In addition, the two groups constituting R include the alkyl group, cycloalkenyl group, alkaryl group, and the general formula R'
0(R''0)T. lR' and the general formula R'S (R2
O)nR'' may be the same group on each side or may be different groups.

1. The most effective method for producing the compound represented by the general formula ((RO)2P-S)2, MoOS is as follows:
- General formula (RO)2P-SH C In the formula, R is 3 to 20 (lIII
Alkyl group, alkenyl group, cycloalkyl group, cycloalkenyl group, alkaryl group having carbon atoms of group, alkenyl group, Schiff l
Represents a corekyl group, cycloalkenyl group, alkaryl group, R'' represents an alkylene group having 2 to 4 carbon atoms, and n represents an alkylene group having 2 to 4 carbon atoms;
Indicates a positive number of ~3. ), general formula R'S(R"O)nR
"(R', R" and n are the same as above.) The same or different groups are selected from the group consisting of "(R', R" and n are the same as above). ] To the acidic ethyl ITnyl of dithiophosphoric acid, add the compound and about 1/2 equivalent of molybdenum dioxide, and mix in a 3-diet. After that, the best method is to add about the same amount of acid to the strong basic compound described above and heat the mixture at 5[]'Cu)-J2).
preferable.

l(<R0)21'' -S Compounds represented by with a molar ratio of 4:J to 5
Apply in the quality range of 0° (~100°C)
In this case, it is diluted with an aromatic solvent such as toluene, chlorine, octane, or a paraffinic solvent such as octane. You can also react.

Examples of strong basic compounds added to 1 (RO) and P-3It include caustic soda, caustic potash, aqueous ammonia,
Suitable examples include organic compounds such as l'nu-ethylamine, triditylamine, and the like. Moreover, these strong basic compounds can also be added as an aqueous solution. Each time a strong basic compound is added, heat is generated, and the temperature of the reaction solution reaches 90~90℃.
It can reach 100℃.

Next, stir while cooling for about 10 minutes to 2 hours.
Add acid at 60"C. The acid to be added is preferably a strong acid such as hydrochloric acid, sulfuric acid, or acetic acid. In this case, the temperature of the reaction solution will rise again by adding the acid, but the temperature should not exceed 90 to 110°C while heating. The reaction is continued for 3 to 6 hours. Water is produced in this reaction, so add a suitable solvent that can azeotrope with water (for example, l-luene, octane, etc.) to remove the produced water from the system. You can take a method to remove it.

After the reaction is completed, the reaction solution contains insoluble salts produced by the reaction between the strong basic compound and the acid, and therefore it is desirable to remove these salts by filtration or washing with water. If the product is a solid, the salts produced can be removed by dissolving it in a suitable solvent and filtering or washing with water.

The product thus obtained contains at least 50% of the compound represented by the general formula (1),
This product can be used as it is as a lubricating oil additive without any special treatment such as TI'J, but if necessary, it can be treated with an adsorbent, reprocessed, crystallized, etc. Therefore, even higher purity Nishi-no-Konara may be used as a 1fJI/h ura additive.

The obtained moisture of the present invention? fM71II additives should be moistened with oil or grease.
By adding 1.3 to 2% of this additive, it is possible to improve the quality of lubricating oils and greases by adding them to gasoline. For 1 engine or G)? When used for engine applications, the friction of the lubricating oil is significantly reduced, thereby reducing the number of twists. Similarly, it is also effective to reduce the consumption of 31.4 kg by adding it to various industrial and transportation moistures.

Next, C, Examples, 11. The present invention will be explained as follows. Unless otherwise specified, the nerds are 9 and %t, C4B-C.
Heavy neck and expressed as weight %.

Example 1 Di-2ethylhexyldithiophosphoric acid 665 was added to a 2e 4 tube flask equipped with a stirrer, thermometer and reflux condenser.
g (1,88 mol), molybdenum trioxide 135. g
(0.94g>,) Add 143g of toluene, and while stirring thoroughly, add 301g of 25% caustic soda water 18 liquid (1,
88 mol) was added dropwise. The temperature of the reaction solution rose with the dropwise addition and reached 80 to 70°C, and the mixture was stirred at this temperature for about 30 minutes. Next, the mixture was cooled and when the temperature reached around 60°C, 93 g (0.93 mol) of concentrated sulfuric acid was added dropwise. At this time, the temperature of the reaction solution rises again, but after further heating,
95℃? The reaction was carried out for about 5 hours at a high quality. At the beginning of the reaction, the color of the reaction solution was reddish-purple, but it gradually turned yellow-brown and became a-brown at the end of the reaction. After the reaction was completed, the mixture was allowed to stand and cooled, the lower aqueous layer was removed, and 1-toluene was distilled off to obtain 158 g of a dark brown viscous liquid. Further, residual inorganic salts were removed by filtration to obtain a final product.

- Part of the product was taken, centrifuged, and chromatographed using MI. 1:
Niro said that the components were separated using the +-tonography method.
It was possible to separate into five orders. Table 1 shows the type of developing solution, the content of each component, properties, and elemental analysis results.

Table 1 Fraxion No. 2 in Table 1 contains 7 of the total products.
2.3% of the component /:j: Molecular weight determined by pressure feeding method.

The measurement result was 835, and it was found that the compound represented by 1((C8H□70)2Ps)2MoOS was produced at a considerably high rate as shown below.

A comparison of the elemental analysis results and molecular weight measurement results of the main product with these calculated values is as follows.

Old calculation value: C32H6B O5P 2 S 5 M (l
As, C: 45.2%, H: 8.0%, P near, 3%.

S: 18.8%, M: 11.3% Molecular weight -850 Actual value: C: 45.0%, H near, 8%, P near, 4%.

S: 18.4%, M: 11.0% Molecule 9:835 It can be seen that the measured values and calculated values are in good agreement.

Example 2 In a reactor similar to Example 1, 70% of didodecyldithiophosphoric acid was added.
Add 0g (1.5 mol) and 130g of 1 mol, and add 50% i'I'I potash water/8 liquid 16B while stirring thoroughly.
g (1,5T nyl) was added dropwise. 106 g (0.75 mol) of molybdenum trioxide was added to this, and the mixture was stirred for about 30 minutes to dissolve B%i. Then 35% #hydrochloric acid 7
7g<o, 75 mol) was added dropwise. At this time, the temperature of the liquid will reach the epigastric level, but it will be heated further (approximately 3
Time reacted. After the reaction is complete, leave it to cool and remove the lower layer (
After removing the aqueous layer, 250 g of 1-toluene was added and stirred for 1'I', and the reaction solution was washed with water.
After standing still, the lower layer was removed. After repeating this water washing operation two more times, 1-toluene was distilled off to obtain a brown viscous liquid.

A portion of the obtained product was taken, centrifuged in the same manner as in Example 1, and separated using the Toglasoy method. It was found that 76.3% of the product was developed by carbon tetrachloride. Ta.

The elemental analysis results and molecular M/ItlI determination results for this component were as follows.

Calculated values: C48H]DOO5P2 S5 Mo as C: 53.6%, H: 9.3%, p'): 5.7%
.

S: 14.9%, M: 8.9% Molecular weight: 10'74 Actual value: C: 52.6%, f(: 9.5%, P: 5.6%.

S: 15.2%, M: 8.7% Molecular weight: 1091 From the results below, it can be seen that the actual measured value and the total W value agree well.

Example 3 ~ Into the same reactor as in Example 1, 620 g (2 moles) of di(p-cresyl)dithiophosphoric acid and 141 g (2 moles) of molybdenum trioxide were added.
1 mole) and 180 g of RL-heptane were added, and while stirring thoroughly, 25% aqueous solution was added. l Soda aqueous solution 320g (2
mol) was added dropwise. The temperature of the reaction solution is increased by the dropwise addition of
-The temperature reached around 70°C. After stirring at the same temperature for about 20 minutes and confirming that it was uniformly dissolved, 10 l of concentrated sulfuric acid (approx. Perform the same operation as in 1 to obtain the product in reaction 4 of 732+<.

The elemental content of one component of the reaction product JJi' and the molecular film measurement results are as follows.

i1'l')9411'j'C281';1((L
)5P285 M' as (:, : 44.19
6. II: 3.7%, l): lJ, 1%.

S: 21.0%, M: 12°6% Molecule-Ki: 762 Actual measurement 1if1: C: 43.2%, 11: 3.5%, r': 9.2%.

S: 19. f1%, M:I2.1% quantity near 92 It can be seen that the measured values and calculated values are in good agreement.

Example 4 Lauryl mercaptan was reacted with 11 moles of "C ethylene/oxy" in alcohol at 80 to 85° C. using one Lewis acid as a solvent. C1,2I25 S CH2CI20 )2
761g of dithiophosphoric acid ester represented by P-3I-1
(1,3'T-nyl) was placed in the same reactor as in Example 1, and 500 g of n-'''butane was added to it.
Furthermore, 25% caustic soda aqueous solution 208 bis(1
, 3) was added thereto, and 94 g (0.65 mol) of molybdenum trioxide was added with stirring. After stirring at 70-75°C for about 30 minutes, 136 g of 35% concentrated FA acid (1
, 3 moles) were added. By this dropwise addition, the tM of the reaction solution
The temperature rose by 1 degree, but the mixture was further heated and kept at the reflux temperature of rl-hebutane (approximately 100 degrees Celsius) and reacted for 5 hours.

After the reaction was completed, the mixture was allowed to stand and cooled, and the lower layer (aqueous layer) was removed. Add 300g of water and heat at 50-60°C for about 30 minutes.
After stirring for 0 minutes, the mixture was allowed to stand at the same temperature to remove FIN. After repeating this water washing operation two more times, n-
Hebutane was distilled off to obtain 824 g of final product.

A portion of the obtained product was taken and centrifuged in the same manner as in Example 1, and the components were separated using a 1:17 tograph method. -j was found to be 64.5%.

The results of elemental analysis of this main component and the molecular weight measurement results by osmotic pressure method are as follows.

Old value "56", 1.1.605 P2. ”'
9 M') as C: 51.1%, II: 3°8%, l
':/1.7%.

S: 21.9%, M near, 3% Molecular weight: l314 Actual value: C: 5 (1.8%, IT: 9.1%, P: 4.1%.

S: 21.5%, Mnear, 5% Molecular weight: 125B From the above results, it can be seen that the measured value and the calculated value 6 are in good agreement.

Example 5 The products obtained according to Examples 1 to 4 were hydrated. Iura (1
Test oils were prepared by dissolving 0.5% and 1.0% in 507Pf neutral oil), and the friction coefficient was measured using a pendulum-type oil-based friction tester manufactured by Shinko Zoki Co., Ltd.

Measuring strip/1 has a total load of 300g and a maximum contact surface of 2/1.
The initial amplitude was set to 0.5 radian at 1 kg/'Ill'' and an oil temperature of 100±1''C, and the deflection angle at the fifth vibration was read to calculate the friction coefficient.

The measured coefficient of friction tended to decrease as the number of measurements increased.

The relationship between the number of measurements of the product of Example 1 and the component of fraction No. 2 separated by chromatography and the measured frictional tV coefficient is illustrated in FIG. 1 for each portion.

In the figure, ■ indicates the product obtained in Example 1 with 0.5% added to No. 150 neutral oil, and ■ indicates the component of fraction fish 2, which was obtained by separating the product obtained in Example 1 by chromatography. 0 to No. 150 New I-Ral Oil
．． 5% added, ■ is the actual product (1% of the product obtained in 9.jl was added to No. 150 neutral oil, ■ is a graph of the live figure obtained in Example 1) The component of fraction No. 2 separated by 150
No. 21, 1% added to Toral oil, ■ is a graph that does not show the control (no additive, No. 150 neutral oil).

The friction coefficients of the products of Examples 1 to 4 after the 30th measurement are shown in Table 2 below, and by adding a small amount of the products of the present invention, the friction coefficient of the oil (divided by the coefficient of friction) It can be seen that the value has decreased significantly.

Table 2 Examples (j) No. 100 New 1-Ral Oil and 5 were used for the purpose of determining the extreme pressure performance of the products made according to Examples 1-4.
Add 0.5% of each product listed in - to No. 00 neutral oil.
and 1.0%, and wear marks and load resistance were measured using a Shell A fast 4-ball tester. The results are shown in Table 3, and it was found that by adding a small amount of the product of the present invention to a lubricating oil, the extreme low-temperature properties were significantly improved.

Margin below this page Table 3

[Brief explanation of the drawing]

The 11th M+ was 1q] in Example 1 and the fraction N
o, 0.5% and 1.0% of component 2 added/I
A? This is a graph showing the relationship between the number of measurements (horizontal axis) and the friction coefficient (vertical axis) of Fk oil (neutral oil No. 150). ■... 0.5% of the product obtained in Example 1 was added to No. 150 neutral oil. ■... The product obtained in Example 1 was separated using a 1st column and a fraction tooth 2. 0.5% of the component was added to No. 150 neutral oil■...The product obtained in Example 1 was added to No. 150 neutral oil by 1.
% added ■... Fraction No. 2 was separated by chromatography from the 1q product in Example 1. 150
1% added to No. 150 Neutral Oil...Control (no additives, only No. 150 Neutral Oil) Patent Applicant: Sanyo Chemical Industries, Ltd. Agent
Person Patent Attorney Yasuhiro Funakoshi Figure 1 b 7 (, l 7) DoJ Dob
jU] - rudder〃 1 city - irises - 1 day
No. 16 (l l 69 No. 2, Name of the invention Jun〆Qingpo's punishment and its production i14〕j゛ Law 3,
Supplement 11-Relationship with the currency 1B'l ノlH'l l1lIl? Ii person 4, generation immediate person 8601-13 Yellow 0
75-571-11225, Roku 1 Masa, Date of Order I τj Procedural Amendment January 30, 1982 1, Case Indication ll 1115 Filo Permit Application No. 160169 2 Name of Invention Jun 11'1 Oil additive and The manufacturing method 3.7 Relationship with the city attorney case Patent applicant mountain')
14, agent 601-13 Tomi 075-
571-11226, Subject of amendment 7, Contents of amendment 1 In the Detailed Description of the Invention section of the specification, page 7, lines 8 to 9, the words rR'o (R"O)R" are rR'o
Correct to (R"0)nR"J. 2 In the 5th line of page 12 of the same page, the phrase “i<waeru” is replaced with “
Correct to "add". 3. On page 14, line 1 of the same page, it says "represents the highest percentage".
Corrected to [-does not represent power loss%]. 4 ``1M:'' on page 16, line IO of the same page is replaced by rM
o: Corrected to J. 5 Same as above, page 16, line 14, 1M=” is replaced by rM
o: Corrected to J. 6 Change the "M:" on the 3rd line of page 18 of the same page to rMo.
:” is corrected. 7 "M:" on the 7th line of page 1 of "Ibid."
Mo: Corrected to J. 8 Replace “M:” on page 19, line 8 of the same page with rMo
: Correct to J. 9 Same + - Change the "M:" on the 12th line of tmg to r
Mo: Corrected to J. 10 Change “M:” in line 8 of page 2I of the above to r
Mo: Correction to J. 11 The ``M:'' on page 21, line 12 of the same page,
Correct to rMo:j. that's all

Claims (1)

[Claims] 11th - General formula) % formula % (1) c In the formula, R is an alkyl group, alkenyl group, cycloalkyl group, cycloalkenyl group, alkyl group having 3 to 20111a carbon atoms. Ryl group, general formula R'O(R2O)
nR'(R' is Al4 having 3 to 20 carbon atoms
2 group, alkenyl group, cycloalkyl group, cycloalkenyl group, alkaryl group, and RIT has 2 to 2 carbon atoms.
4, and n represents a positive number of O to 3. ),
Contains a compound represented by the general formula R'S ('R''0), which represents the same or different method selected from the group consisting of R''(R',R'' and n are the same as above). An additive for lubricating oils that reduces friction and improves extreme pressure properties. 2. The following general formula % formula % (2) [wherein R represents 3 to 20 carbon atoms] Alkyl group, alkenyl group, cycloalkyl group, cycloalkenyl group, alkaryl group having the general formula R'0(R'0)nR''(
R' represents an alkyl group, alkenyl group, cycloalkyl group, cycloalkenyl group, or alkaryl group having 3 to 20 carbon atoms, R'' represents an alkylene group having 2 to 4 carbon atoms, and n is O to 3 ), the general formula R'S (
R′0)nR′/(R′, R″ and n are the same as above.) represents the same or different group selected from the group consisting of To this, add an equivalent amount of a strong basic compound and about 1/2 equivalent of molybdenum dioxide and mix thoroughly, then add about an equivalent amount of acid to the above strong basic compound and heat the mixture at 50°C or higher. The main component is a compound represented by the following general formula ((RO)2P-3)2MnOS (wherein R is the same as above), which is characterized by the following: ＝ Reduces and improves extreme pressure properties.
A method for producing an additive.