Reaction product of isobutylene, sulfur monohalide and alkali metal mercaptide
United States Patent 3925414
A compound obtained by reacting isobutylene and a sulfur halide to produce an adduct; reacting the adduct thus produced with an alkali metal mercaptide in a nonreactive liquid medium to obtain a product comprising a compound having the structure: ##SPC1## And separating this compound from said product. This compound is particularly useful as an extreme pressure additive in lubricant compositions.
US Patent References:
Reaction products of sulphur chloride with olefins and processes for producing the same
Kimball et al. - July 1947 - 2249312
/3703505.html
Horodysky et al. - November 1972 - 3703505
Reaction products of sulphur chloride with olefins and processes for producing the same
Kimball et al. - July 1947 - 2249312
/3703505.html
Horodysky et al. - November 1972 - 3703505
Inventors:
Landis, Phillip S. (Woodbury, NJ)
Okorodudu, Abraham O. M. (West Deptford, NJ)
Okorodudu, Abraham O. M. (West Deptford, NJ)
Application Number:
05/453610
Publication Date:
12/09/1975
Filing Date:
03/22/1974
View Patent Images:
Export Citation:
Assignee:
Mobil Oil Corporation (New York, NY)
Primary Class:
Other Classes:
508/300
International Classes:
C07D341/00; C07D341/00
Field of Search:
260/327R,608,139
Primary Examiner:
Winters, Sherman D.
Attorney, Agent or Firm:
Huggett I, Charles Barclay Raymond Kaufman Benjamin A. W.
Claims:
We claim
1. A compound having the structure: ##SPC3##
2. A process for preparing a compound having the structure recited in claim 1, consisting essentially of reacting isobutylene and a sulfur monohalide to produce an adduct; reacting the adduct thus produced with an alkali metal mercaptide in a non-reactive liquid medium to obtain a product comprising the compound described in claim 1; and separating said compound from said product.
3. A process as defined in claim 2 wherein said reactions are conducted at a temperature from about 0°C. to about 150°C.
4. A process as defined in claim 2 wherein said reactions are conducted at a temperature from about 20°C to about 60°C.
5. A process as defined in claim 2 wherein isobutylene and the sulfur monohalide are reacted in a mole ratio of from about 0.5:1 to about 2.5:1.
6. A process as defined in claim 2 wherein isobutylene and the sulfur monohalide are reacted in a mole ratio of from about 1:1 to about 2:1.
7. A process as defined in claim 2 wherein the adduct and the alkali metal mercaptide are reacted in a mole ratio of from about 1:1 to about 1:5.
8. A process as defined in claim 2 wherein the adduct and the alkali metal mercaptide are reacted in a mole ratio of from about 1:1 to about 1:2.5.
9. A process as defined in claim 2 wherein the sulfur monohalide is sulfur monochloride.
10. A process as defined in claim 2 wherein the alkali metal mercaptide is sodium mercaptide.
11. A process as defined in claim 2 wherein the liquid medium is a lower alcohol.
12. A process as defined in claim 2 wherein the liquid medium is ethyl alcohol.
1. A compound having the structure: ##SPC3##
2. A process for preparing a compound having the structure recited in claim 1, consisting essentially of reacting isobutylene and a sulfur monohalide to produce an adduct; reacting the adduct thus produced with an alkali metal mercaptide in a non-reactive liquid medium to obtain a product comprising the compound described in claim 1; and separating said compound from said product.
3. A process as defined in claim 2 wherein said reactions are conducted at a temperature from about 0°C. to about 150°C.
4. A process as defined in claim 2 wherein said reactions are conducted at a temperature from about 20°C to about 60°C.
5. A process as defined in claim 2 wherein isobutylene and the sulfur monohalide are reacted in a mole ratio of from about 0.5:1 to about 2.5:1.
6. A process as defined in claim 2 wherein isobutylene and the sulfur monohalide are reacted in a mole ratio of from about 1:1 to about 2:1.
7. A process as defined in claim 2 wherein the adduct and the alkali metal mercaptide are reacted in a mole ratio of from about 1:1 to about 1:5.
8. A process as defined in claim 2 wherein the adduct and the alkali metal mercaptide are reacted in a mole ratio of from about 1:1 to about 1:2.5.
9. A process as defined in claim 2 wherein the sulfur monohalide is sulfur monochloride.
10. A process as defined in claim 2 wherein the alkali metal mercaptide is sodium mercaptide.
11. A process as defined in claim 2 wherein the liquid medium is a lower alcohol.
12. A process as defined in claim 2 wherein the liquid medium is ethyl alcohol.
Description:
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to new compositions of matter and, more particularly, to new compositions of matter, especially useful as extreme pressure additives in lubricating compositions, such as lubricating oils and greases.
2. Description of the Prior Art
It is known that extreme pressure properties can be incorporated in lubricant compositions, such as liquid hydrocarbons and greases, by incorporating therein sulfurized olefins as extreme pressure additives. In this respect, such additives have heretofore been found to be deficient in lacking a relatively high non-corrosive sulfur content which is found to be particularly desirable in imparting good extreme pressure and anti-wear properties. In additives of this type it is also highly desirable that they be odorless and colorless, from a commercial standpoint. These latter characteristics have also been found lacking in present commercial sulfurized extreme pressure additives.
SUMMARY OF THE INVENTION
It has now been found that improved extreme pressure properties can be imparted to lubricant compositions by incorporating therein minor amounts of a relatively high sulfurcontent additive which, in addition, does not impart odor to the lubricant and is also colorless. As more fully hereinafter described, this novel extreme pressure additive is obtained by reacting isobutylene and a sulfur halide to produce the corresponding adduct; reacting the adduct thus produced with an alkali metal mercaptide in a non-reactive liquid medium to obtain a product comprising a compound having the structure: ##SPC2##
And separating the compound thus produced from the aforesaid reaction mixture. The compound thus produced is found to have a melting point of approximately 254°C.
In general, the aforementioned reactions are conducted at ambient temperature. In most operations the reactions are conducted at a temperature from about 0°C. to about 150°C. and preferably at a temperature from about 20°C. to about 60°C. Insofar as the production of the adduct is concerned, sufficient sulfur halide is employed to react with all of the isobutylene. In general, for most operations, isobutylene and the sulfur halide are reacted in a mole ratio of from about 0.5:1 to about 2.5:1 and preferably in a mole ratio of from about 1:1 to about 2:1 by weight. Insofar as the reaction between the adduct and the alkali metal mercaptide is concerned, sufficient alkali metal mercaptide is employed to react with all of the adduct. In general, for most operations, the adduct and the alkali metal mercaptide are reacted in a mole ratio of from about 1:1 to about 1:5 and preferably in a mole ratio of from about 1:1 to about 1:2.5 by weight. Any alkali metal mercaptide may be employed for reaction with the adduct, as hereinbefore described, and may include sodium mercaptide, potassium mercaptide, lithium mercaptide, or calcium mercaptide. Any sulfur monohalide may be used for reaction with isobutylene and may include sulfur monochloride, or a combination of a sulfur dihalide and elemental sulfur to produce the corresponding sulfur monohalide which may also be employed as an equivalent reagent. Any non-reactive liquid medium may be employed for carrying out the reaction between the adduct and the alkali metal mercaptide and may include lower alcohols such as methanol, ethanol, propanol, butanol. The resulting extreme pressure compound, suitable for use as an extreme pressure lubricant additive is found to have a sulfur content of about 50%, by weight, and is odorless and colorless. This compound represents about 45%, by weight, of the product resulting from the reaction of the aforementioned adduct and the alkali metal mercaptide. The remaining portion of the aforementioned product comprises about 55%, by weight, a mixture of unsaturated sulfides and polysulfides.
The following data and examples will serve to illustrate the marked degree in extreme pressure improvement imparted by the novel additives of the present invention to lubricant compositions. It will be understood, however, that it is not intended the invention be limited to the particular lubricant compositions disclosed nor the particular additive for imparting extreme pressure properties. Various modifications thereof can be employed and will be readily apparent to those skilled in the art.
EXAMPLE 1
Sulfur monochloride (1013g, 7.5 moles) was charged into a 3-L. 4-necked reaction flask equipped with a mechanical stirrer, condenser (drying tube attached) a thermometer, and a sub-surface gas sparger. While keeping the temperature between 45°-50°C., isobutylene was passed over 60g of methanol into the reaction flask over an 8-hour period, during which 716g(12.8 moles) of isobutylene was consumed. The reaction mixture was then purged at 40°C. with a stream of nitrogen for 30 minutes and then filtered to yield 1579g of a light amber liquid.
Sodium mercaptide, (1200g) and 1250 ml of ethanol were charged into a 5-L. reaction flask fitted with a stirrer, condenser (drying tube attached) thermometer and an addition funnel. After stirring to get a good dispersion of the solids, 620g of the above, isobutylene-sulfur monochloride adduct was added rapidly and carefully at first to attain a temperature of 45°C. and then dropwise from the addition funnel. The addition took about 2 hours. By carefully regulating the addition, the temperature was kept at close to 40°C. and excessive foaming (H 2 S evolution) was avoided.
Following the aforementioned addition, the reaction mixture was heated, while stirring at 45°-50°C. for an additional 3 hours. After cooling to room temperature, it was filtered, the solids washed with hexane, and the filtrate allowed to stay overnight under house vacuum.
The solids were washed with water and ether and a water insoluble white solid product was collected. The solid product which precipitated from the filtrate was collected and washed several times with water and ether and dried. The combined solids were further purified by stirring vigorously in water and a little ether, collected and dried to yield 250g of white solid product, having a sulfur content of 53%. This product was found to have the structure hereinbefore described.
An S.A.E. 90 solvent-refined Mid-Continent oil having a pour point of 25°F. was next subjected to the standard Four-Ball Wear Test for determining improvement in anti-wear properties. This test is described in U.S. pat. No. 3,423,316. In general, in this test, three steel balls of 52-100 steel are held in a ball cup. A fourth ball positioned on a rotatable vertical axis is brought into contact with the three balls and is rotated against them. The force which the fourth ball is held against the three stationary balls may be varied according to a desired load. The test lubricant is added to the ball cup and acts as a lubricant for the rotation. At the end of the test, the steel balls are investigated for wear-scar; the extent of scarring represents the effectiveness of the lubricant as an antiwear agent. In the data of the following Table I, are shown the results obtained in which the aforementioned base stock oil was subjected to the Four-Ball Wear Test.
TABLE I ______________________________________ 4-Ball Wear Test-Scar Diameter (mm) 1/2" Balls, 52-100 Steel, 60 Kg, 1/2 hr. Speed Temp. Ex. °F 500 RPM 1000 RPM 1500 RPM 2000 RPM ______________________________________ 2 Room 0.50 0.60 0.88 2.34 3 200 0.60 1.06 1.86 2.23 ______________________________________
The above-described product of Example I was next incorporated into the base stock lubricating oil of Table I in a concentration of 0.5%, by weight, and then subjected to the aforementioned Four-Ball Wear Test. The results obtained are shown in the following Table II.
TABLE II ______________________________________ 4-Ball Wear Test-Scar Daimeter (mm) 1/2" Balls, 52-100 Steel, 60 Kg, 1/2 hr. Speed Temp. 500 1000 1500 2000 Ex. °F. RPM RPM RPM RPM ______________________________________ 4 Base Oil Room 0.46 0.50 0.60 0.80 +0.5% (Wt) 5 of Product 200 0.50 0.63 0.75 0.90 of Example I ______________________________________
It will be apparent from the comparative data of Table I and II that the novel compounds of the present invention are markedly effective as anti-wear additives. While compositions and components therefore it will be understood, by those skilled in the art, that departure from the preferred embodiments can be effectively made and are within the scope of specification.
1. Field of the Invention
This invention relates to new compositions of matter and, more particularly, to new compositions of matter, especially useful as extreme pressure additives in lubricating compositions, such as lubricating oils and greases.
2. Description of the Prior Art
It is known that extreme pressure properties can be incorporated in lubricant compositions, such as liquid hydrocarbons and greases, by incorporating therein sulfurized olefins as extreme pressure additives. In this respect, such additives have heretofore been found to be deficient in lacking a relatively high non-corrosive sulfur content which is found to be particularly desirable in imparting good extreme pressure and anti-wear properties. In additives of this type it is also highly desirable that they be odorless and colorless, from a commercial standpoint. These latter characteristics have also been found lacking in present commercial sulfurized extreme pressure additives.
SUMMARY OF THE INVENTION
It has now been found that improved extreme pressure properties can be imparted to lubricant compositions by incorporating therein minor amounts of a relatively high sulfurcontent additive which, in addition, does not impart odor to the lubricant and is also colorless. As more fully hereinafter described, this novel extreme pressure additive is obtained by reacting isobutylene and a sulfur halide to produce the corresponding adduct; reacting the adduct thus produced with an alkali metal mercaptide in a non-reactive liquid medium to obtain a product comprising a compound having the structure: ##SPC2##
And separating the compound thus produced from the aforesaid reaction mixture. The compound thus produced is found to have a melting point of approximately 254°C.
In general, the aforementioned reactions are conducted at ambient temperature. In most operations the reactions are conducted at a temperature from about 0°C. to about 150°C. and preferably at a temperature from about 20°C. to about 60°C. Insofar as the production of the adduct is concerned, sufficient sulfur halide is employed to react with all of the isobutylene. In general, for most operations, isobutylene and the sulfur halide are reacted in a mole ratio of from about 0.5:1 to about 2.5:1 and preferably in a mole ratio of from about 1:1 to about 2:1 by weight. Insofar as the reaction between the adduct and the alkali metal mercaptide is concerned, sufficient alkali metal mercaptide is employed to react with all of the adduct. In general, for most operations, the adduct and the alkali metal mercaptide are reacted in a mole ratio of from about 1:1 to about 1:5 and preferably in a mole ratio of from about 1:1 to about 1:2.5 by weight. Any alkali metal mercaptide may be employed for reaction with the adduct, as hereinbefore described, and may include sodium mercaptide, potassium mercaptide, lithium mercaptide, or calcium mercaptide. Any sulfur monohalide may be used for reaction with isobutylene and may include sulfur monochloride, or a combination of a sulfur dihalide and elemental sulfur to produce the corresponding sulfur monohalide which may also be employed as an equivalent reagent. Any non-reactive liquid medium may be employed for carrying out the reaction between the adduct and the alkali metal mercaptide and may include lower alcohols such as methanol, ethanol, propanol, butanol. The resulting extreme pressure compound, suitable for use as an extreme pressure lubricant additive is found to have a sulfur content of about 50%, by weight, and is odorless and colorless. This compound represents about 45%, by weight, of the product resulting from the reaction of the aforementioned adduct and the alkali metal mercaptide. The remaining portion of the aforementioned product comprises about 55%, by weight, a mixture of unsaturated sulfides and polysulfides.
The following data and examples will serve to illustrate the marked degree in extreme pressure improvement imparted by the novel additives of the present invention to lubricant compositions. It will be understood, however, that it is not intended the invention be limited to the particular lubricant compositions disclosed nor the particular additive for imparting extreme pressure properties. Various modifications thereof can be employed and will be readily apparent to those skilled in the art.
EXAMPLE 1
Sulfur monochloride (1013g, 7.5 moles) was charged into a 3-L. 4-necked reaction flask equipped with a mechanical stirrer, condenser (drying tube attached) a thermometer, and a sub-surface gas sparger. While keeping the temperature between 45°-50°C., isobutylene was passed over 60g of methanol into the reaction flask over an 8-hour period, during which 716g(12.8 moles) of isobutylene was consumed. The reaction mixture was then purged at 40°C. with a stream of nitrogen for 30 minutes and then filtered to yield 1579g of a light amber liquid.
Sodium mercaptide, (1200g) and 1250 ml of ethanol were charged into a 5-L. reaction flask fitted with a stirrer, condenser (drying tube attached) thermometer and an addition funnel. After stirring to get a good dispersion of the solids, 620g of the above, isobutylene-sulfur monochloride adduct was added rapidly and carefully at first to attain a temperature of 45°C. and then dropwise from the addition funnel. The addition took about 2 hours. By carefully regulating the addition, the temperature was kept at close to 40°C. and excessive foaming (H 2 S evolution) was avoided.
Following the aforementioned addition, the reaction mixture was heated, while stirring at 45°-50°C. for an additional 3 hours. After cooling to room temperature, it was filtered, the solids washed with hexane, and the filtrate allowed to stay overnight under house vacuum.
The solids were washed with water and ether and a water insoluble white solid product was collected. The solid product which precipitated from the filtrate was collected and washed several times with water and ether and dried. The combined solids were further purified by stirring vigorously in water and a little ether, collected and dried to yield 250g of white solid product, having a sulfur content of 53%. This product was found to have the structure hereinbefore described.
An S.A.E. 90 solvent-refined Mid-Continent oil having a pour point of 25°F. was next subjected to the standard Four-Ball Wear Test for determining improvement in anti-wear properties. This test is described in U.S. pat. No. 3,423,316. In general, in this test, three steel balls of 52-100 steel are held in a ball cup. A fourth ball positioned on a rotatable vertical axis is brought into contact with the three balls and is rotated against them. The force which the fourth ball is held against the three stationary balls may be varied according to a desired load. The test lubricant is added to the ball cup and acts as a lubricant for the rotation. At the end of the test, the steel balls are investigated for wear-scar; the extent of scarring represents the effectiveness of the lubricant as an antiwear agent. In the data of the following Table I, are shown the results obtained in which the aforementioned base stock oil was subjected to the Four-Ball Wear Test.
TABLE I ______________________________________ 4-Ball Wear Test-Scar Diameter (mm) 1/2" Balls, 52-100 Steel, 60 Kg, 1/2 hr. Speed Temp. Ex. °F 500 RPM 1000 RPM 1500 RPM 2000 RPM ______________________________________ 2 Room 0.50 0.60 0.88 2.34 3 200 0.60 1.06 1.86 2.23 ______________________________________
The above-described product of Example I was next incorporated into the base stock lubricating oil of Table I in a concentration of 0.5%, by weight, and then subjected to the aforementioned Four-Ball Wear Test. The results obtained are shown in the following Table II.
TABLE II ______________________________________ 4-Ball Wear Test-Scar Daimeter (mm) 1/2" Balls, 52-100 Steel, 60 Kg, 1/2 hr. Speed Temp. 500 1000 1500 2000 Ex. °F. RPM RPM RPM RPM ______________________________________ 4 Base Oil Room 0.46 0.50 0.60 0.80 +0.5% (Wt) 5 of Product 200 0.50 0.63 0.75 0.90 of Example I ______________________________________
It will be apparent from the comparative data of Table I and II that the novel compounds of the present invention are markedly effective as anti-wear additives. While compositions and components therefore it will be understood, by those skilled in the art, that departure from the preferred embodiments can be effectively made and are within the scope of specification.