US3900409A

US3900409A - Lubricating oil compositions containing sulfurchlorinated styrene derivatives

Info

Publication number: US3900409A
Application number: US432395A
Authority: US
Inventors: Raymond S Dalter; Sidney S White
Original assignee: Cincinnati Milacron Chemicals Inc
Current assignee: Cincinnati Milacron Chemicals Inc
Priority date: 1974-01-10
Filing date: 1974-01-10
Publication date: 1975-08-19
Anticipated expiration: 1992-08-19
Also published as: BR7500009A; FR2257674B3; AU7500574A; JPS50101404A; DE2450019A1; BE824247A; IT1025172B; ZA746587B; NL7500063A; FR2257674A1

Abstract

There is provided a lubricating oil composition which comprises a major amount of lubricating oil and a minor amount of an extreme pressure property improving additive which is a compound having the formula

WHERE R is hydrogen, alkyl of 1 to 4 carbon atoms or chlorine, R'''' is hydrogen or chlorine, R'' is hydrogen or methyl and x is a number from 1 to 10, usually not over 6 and normally 1 to 3. The additive is made by reacting styrene or the appropriate substituted styrene with a sulfurizing agent such as sulfur monochloride or a dichlorosulfane, e.g., sulfur dichloride.

Description

United States Patent 1 1 Dalter et al.

[ 51 Aug. 19, 1975 I LUBRICATING OIL COMPOSITIONS CONTAINING SULFURCl-ILORINATED STYRENE DERIVATIVES [75] Inventors: Raymond S. Dalter, Montgomery;

Sidney S. White, Westchester, both of Ohio [73] Assignee: Cincinnati Milacron Chemicals Inc.,

. Reading, Ohio [22] Filed: Jan. 10, 1974 [21] App]. No.: 432,395

Primary E.\-aminerDelbert E. Gantz Assistant Examiner-I. Vaughn Attorney, Agent, 0:- Firm-Cushman, Darby & Cushman [-5 7] ABSTRACT There is provided a lubricating oil composition which comprises a major amount of lubricating oil and a minor amount of an extreme pressure property improving additive which is a compound having the formula where R is hydrogen, alkyl of 1 to 4 carbon atoms or chlorine, R" is hydrogen or chlorine, R is hydrogen or methyl and x is a number from 1 to 10, usually not over 6 and normally 1 to 3. The additive is made by reacting styrene or the appropriate substituted styrene with a sulfurizing agent such as sulfur monochloride or a dichlorosulfane, e.g., sulfur dichloride.

16 Claims, N0 Drawings LUBRICATING OIL COMPOSITIONS CONTAINING SULFURCI-ILORINATED STYRENE DERIVATIVES FIELD OF THE INVENTION This invention relates to lubricating oil compositions containing sulfur chlorinated styrene and substituted styrene derivatives. In particular, the invention relates to lubricating oil compositions containing sulfur chlorinated styrene derivatives in minor amount sufficient to improve extreme pressure properties thereof, e.g., to create high load carrying capacity and long timetofailure characteristics.

DESCRIPTION OF PRIOR ART Organic sulfur chlorinated compounds have long been known as additives for lubricating oils. These additives impart to the lubricating oil desirable characteristics such as high speed shock resistance, good load carrying capacity, and anti-wear properties. The or ganic sulfur chlorinated compounds disclosed prior to this invention were aliphatic sulfur chlorinated compounds prepared from an aliphatic olefin and sulfur monochloride or sulfur dichloride.

Veatch U.S. Pat. No. 2,592,264 discloses methods of introducing sulfur into motor oil" by reaction of the motor oil with sulfur monochloride using a paraffin oil diluent in the presence of alkali carbonates to take up hydrogen chloride produced and to eliminate loosely bound chloride. The use of volatile solvents such as heptane is also disclosed.

Rausch U.S. Pat. No. 2,943,990 discloses improved cutting oils obtained by sulfurchlorinating a mineral oil. The products are stated to have low sludge forming tendencies.

In Eby U.S. Pat. No. 2,708,l99 there is disclosed a method of producing polysulfides from olefins having from 6 to 30 carbon atoms and sufficient sulfur to fall in the range of from 2 to 3 sulfur atoms per degree of unsaturation in the starting olefin. The products are prepared from sulfur chlorinated aliphatic olefins'and are claimed to have good lubricating characteristics. When applied to olefins of less than 6 carbon atoms the products are found to be insoluble in lubricating oils.

Myers U.S. Pat. No. 3,471,404 discloses a method of overcoming the low oil solubility of chlorosulfurized lower olefins by first reacting a low molecular weight olefin with sulfur monochloride then reacting the chloro-alkyl sulfide or polysulfide with an alkali sulfide converting the chloro groups to mercaptans and polysulfides.

The claimed advantage of the high sulfur concentration is that the material is light in color and can be diluted with any of the common cutting oils to a predetermined sulfur concentration.

Applicants have discovered that bis(B-chloro-B- phenyl ethyl) sulfide and bis(,B-chloro-B-phenyl ethyl)- polysulfide and derivatives, when combined with lubricating oils, give compositions having exceptionally good extreme pressure lubricating characteristics.

The compounds employed in theinvention have the formula:

-C-CH2 where R is hydrogen, alkyl of l to 4 carbon atoms or chlorine, R" is hydrogen or chlorine, R is hydrogen or methyl and is a number from 1 to 10, usually not over 6, normally 1 to 3 and most preferably 1 to 2. Typical compounds which can be employed in the invention include:

bis( ,B-chloro-B-phenylethyl )sulfide,

bis( B-chloro-B-phenylethyl )disulfide,

bis( fichloro-B-phenyl ethyl )trisulfide,

bis( B-chloro-B-phenylethyl )tetrasulfide,

bis( ,B-chloro-B-phenylethyl )hexasulfide,

bis( B-chloroBmethyl-B-phenylethyl )sulfide,

bis( B-chloro-B-methyl-B-phenylethyl )disulfide, bis( B-chloro-,8-methylB-phenylethyl )trisulfide, bis( B-chloro-B-methyl-B-phenylethyl )tetrasulfide,

bis( B-chloro-B-p-tolylethyl )sulfide,

bis( B-chloro-B-p-tolylethyl )disulfide,

bis( Bchloro-B-o-tolylethyl )sulfide,

bis( B-chloro-B-m-tolylethyl )disulfide,

bis[ B-chloro-B-( p-S-butylphenyl )ethyl]sulfide, bis B-chloro-B-( p-t-butylphenyl )ethyl disulfide bis[B-chloro-B-( p-ethylphenyl )ethyl]sulfide, bis[ B-chloro-B-( p-ethylphenyl )ethyl disulfide,

bis( B-chlorofi-p-chlorophenylethyl )sulfide bis( ,B-chloro-B-p-chlorophenylethyl )disulfide,

bis( B-chloro-B-o-chlorophenylethyl )sulfide, bis( ,8-chloro-B-o-chlorophenylethyl )disulfide,

bis( B-chloro-B-Z,4-dichlorophenylethyl )sulfide, bis( B-chloro-B-Z,4-dichlorophenylethyl )disulfide.

DESCRIPTION OF SPECIFIC EMBODIMENTS The bis(BehloroB-phenylethyl)sulfides or polysulfides of this invention may be derived from styrene itself or from a substituted styrene. The sulfides and polysulfides from styrene, a-methylstyrene and vinyltoluene are the preferred embodiments of the invention because the starting materials are readily available and they give products having exceptionally good extreme pressure lubricating properties. To obtain the oil additives of this invention styrene or a substituted styrene is reacted with sulfur monochloride or a dichlorosulfane, e.g., sulfur dichloride at to C with or without a solvent inert to both reactants. The reaction is allowed to proceed to completion over a period of 3 to 5 hours. The product can then be washed with a small amount of alkali to neutrality or alternately blown with air to remove any retained hydrogen chloride. Without further treatment the product obtained can be used in combination with a lubricating oil as a high temperature lubricant and as an extreme pressure lubricant.

As substituted styrenes there can be used for example styrene, a-methyl styrene, p-vinyl toluene, o-vinyl toluene, m-vinyl toluene, p-ethyl styrene, p-t-butyl styrene, o-t-butyl styrene, m-t-butyl styrene, m-n-butyl styrene, p-n-butyl styrene, p-chlorostyrene, o-chlorostyrene, mchlorostyrene, 2,4-dichloro styrene, etc.

The bis(B-chloro-B-phenyl ethyl)sulfides and polysulfides employed in the present invention can be prepared for example in the manner described in Hageman German Offenlegungsschrift 2,040,817, the entire disclosure of which is incorporated by reference.

The bis(B-chloro-B-phenyl ethyl)sulf1des disulfides and higher polysulfides are oil soluble extreme pressure additives for cutting fluids, lubricating oils, transmission fluids, or greases. These sulfides, disulfides and higher polysulfides can be used in conventional lubrieating base media, such as naphthenic or paraffmic mineral oils and synthetic lubricants, such as hydrocarbon fluids, glycol ether fluids, polysiloxane fluids, e.g., poly(dimethyl siloxane) fluids, acetals, polyphenyl ethers and the synthetic ester lubricants produced from monohydric alcohols and polycarboxylic acids and polyhydric alcohols, such as trimethylolpropane and pentaerythritol and carboxylic acids having from six to twenty carbon atoms, e.g., adipic acids sebaeic acid and 1.20 eicosanediocic acid.

The extreme pressure additives of the present invention are preferably employed with hydrocarbon oils, most preferably paraffinic mineral oils. The lubricating compositions employed in the invention contain a major amount of a lubricating oil and a minor amount suffieient to improve extreme pressure properties thereof of the mono or polysulfides of the types set forth above. Thus the composition can contain 0.001 to 20 percent, more usually 0.01 to percent, preferably not over 5 percent of the mono or polysulfide additive. Of course, mixtures of bis(B-chloro-phenyl ethyl) sulfides and/or polysulfldes can be used in the invention.

EVALUATIONS OF LUBRICATING COM POSITIONS The lubricating compositions of this invention were evaluated by the Mean Hertz Load Test, the Falex Test, and the Shell Four-Ball Wear Test. The Hertz Test is used to determine the extreme pressure (EP) properties or load-carrying capacity of lubricants. The Shell Test is used to determine the relative wear-preventing properties of lubricants on sliding metal surfaces operating under boundary lubrication conditions. The Falex Test measures antiwear properties of lubricants under extreme pressure.

The results of the Mean Hertz Load Test are listed in Table 1.

Table 11 lists results of the Shell Four-Ball Wear Tests showing average scar diameter.

In comparing the capabilities of various lubricants, the results of both the Extreme Pressure and Wear Test should be considered. Lubricants that have good extreme pressure properties are not always equally effective in reducing wear rates at less severe loads, and conversely.

The Wear-Load Test is conducted at a constant load, constant temperature, set rpm, and specific duration of time. The scar diameter of the balls on the wear load is reported and used in comparison with the scar diameters from tests of other lubricants.

Table 111 lists experimental results of the Falex Extreme Pressure Tests on the base oil (100/100 naphthenic oil), bis-(B-chloro-B-phenyl ethyl)disulfide, bis(B-chloro-B-tolyl ethyl )disulfide,

TABLE I MEAN HERTZ LOAD TEST RESULTS EXTREME PER CENT BY PRESSURE ADDITIVE WEIGHT VALUE bis([3-chloro-B-phenyl cthyl)- 0.25 33.37

disulfide 0.50 52.31 1.00 67.54 2.00 79.54 5.00 92.58 Sulfumhlorinatcd alpha pinene 0.50 37.52 1.00 50.50 2.00 61.43

All experiments were carried out in a mid-continent SAE oil. *Sulfurchlorinated alpha pinene with and without other sulfur chlorinated olefins or fatty esters is the most commonly used commercial oil additive for extreme pressure luhricaliort for heavy duty Cutting operations.

TABLE II SHELL FOUR-BALL WEAR TEST RESULTS AVERAGE PER CENT BY SCAR ADDITIVE WEIGHT DIAMETER bis( B-chloro-B-phenyl ethyl disulfide 0.25 0.593 mm 0.50 0.646 mm 1.00 0.657 mm 2.00 0.883 mm 5.00 0.699 mm Sulfurchlorinated alpha pinene 0.50 0.593 mm 1.00 0.670 mm 2.00 0.732 mm TABLE III FALEX TEST RESULTS CONCEN- POUNDS TRATION PRESSURE ADDlTlVE PER CENT APPLIED Base Oil /100*** naphthenic oil) 100.00 F l.000* bis(B-chloro-fiphenyl ethyl) disulfide 0.05 P 4,500** 0.10 P 4,500 0.25 P 4,500 0.50 P 4.500 1.00 P 4,500 Sulfur chlorinated alpha-pinene 0.50 F 3,500 1.00 F 3,750 I 2.00 F 4,250 bis(/3-chloroB-methyLB-phenyl ethyl )disulfide 0.25 F 4,250 bis( B-chloro-B-tolyl ethyl disulfide 0.25 P 4,500

'F indicates failure at the corresponding pressure. "P indicates test passage at the pressure limit of the test method. *"Saybolt Universal seconds at 100 F,

bis(B-ehloro-B-methyl-B-phenyl ethyl)disulfide, and sulfur chlorinated alpha-pinene. The latter with or without other added sulfur'chloride and olefins is the most widely used commercial lubricating oil additive for heavy duty cutting operations.

From these data it can be observed that bis(B-chloro- B-phenyl ethyl)disulfide and its derivatives give test results superior to the common commercial product sulfurchlorinated alpha-pinene. In addition, the products of this invention show higher flash-fire properties and have a much lighter color than the sulfur chlorinated alpha-pinene.

For example, bis(B-chloro-B-phenyl ethyl )disulfide and its derivative are typically ASTM Dl500-color l-3 C -CH S where R is hydrogen, alkyl of l to 4 carbon atoms or chlorine, R" is hydrogen or chlorine, R is hydrogen or methyl and is a number from 1 to l0.

2. A lubricating oil composition according to claim 1, wherein is l to 6.

3. A lubricating oil composition according to claim 2 wherein is l to 4.

4. A lubricating oil composition according to claim 3 wherein is l to 2.

5. A lubricating oil composition according to claim 4 wherein x is 2.

6. A lubricating oil composition according to claim 4 wherein the lubricating oil is a hydrocarbon oil.

7. A lubricating oil composition according to claim 6 wherein the oil is a mineral oil.

8. A lubricating oil composition according to claim 1 in which said additive is bis(B-chlor0-B-phenyl ethyl) sulfide.

9. A lubricating oil composition according to claim 1 in which said additive is bis(Bchloro-/3-phenyl ethyl )disulfide.

10. A lubricating oil composition according to claim 1 in which said additive is bis(B-chloro-B-methyl-B- phenyl ethyl)-sulfide.

l]. A lubricating oil composition according to claim 1 in which said additive is bis(B-chloro-B methyl-B- phenyl ethyl)-disulfide.

12. A lubricating oil composition according to claim 1 in which said additive is bis(,8-chloro-B-tolyl ethyl)- sulfide.

13. A lubricating oil composition according to claim 1 in which said additive is bis(B-chloro-B-tolyl ethyl )disulfide.

14. A lubricating oil composition according to claim 4 wherein the additive is present in an amount of 0.001 to 20 percent.

15. A lubricating oil composition according to claim 14 wherein the additive is present in an amount of 0.01 to 20 percent.

16. A lubricating oil composition according to claim 15 wherein the additive is present in an amount of 0.05

to 5 percent.

Disclaimer 3,900,409.Raym0nd S. Daltew, Montgomery, and Sidney S. White, Westchester, Ohio. LU BRIOATIN G OIL COMPOSITIONS CON TAIN ING SULFUR-CHLORINATED STYREN E DERIVATIVES. Patent dated Aug. 19, 1975. Disclaimer filed June 28, 1976 by the assignee, Oz'ncinnatz' Milacwon Ohemz'cgls, Ina. Hereby enters this disclaimer to claims 1-9 and 14-16 of said patent.

[Oficz'al Gazette August 10, 1976.]

Claims

1. A LUBRICATING OIL COMPOSITION COMPRISING: A. A MAJOR AMOUNT OF A LUBRICATING OIL, AND B. A MINOR AMOUNT SUFFICIENT TO IMPROVE EXTREME PRESSURE PROPERTIES THEREOF OF AN ADDITIVE HAVING THE FORMULA:

2. A lubricating oil composition according to claim 1, wherein x is 1 to 6.

3. A lubricating oil composition according to claim 2 wherein x is 1 to 4.

4. A lubricating oil composition according to claim 3 wherein x is 1 to 2.

5. A lubricating oil composition according to claim 4 wherein x is 2.

8. A lubricating oil composition according to claim 1 in which said additive is bis( Beta -chloro- Beta -phenyl ethyl) sulfide.

9. A lubricating oil composition according to claim 1 in which said additive is bis( Beta -chloro- Beta -phenyl ethyl)disulfide.

10. A lubricating oil composition according to claim 1 in which said additive is bis( Beta -chloro- Beta -methyl- Beta -phenyl ethyl)-sulfide.

11. A lubricating oil composition according to claim 1 in which said additive is bis( Beta -chloro- Beta -methyl- Beta -phenyl ethyl)-disulfide.

12. A lubricating oil composition according to claim 1 in which said additive is bis( Beta -chloro- Beta -tolyl ethyl)sulfide.

13. A lubricating oil composition according to claim 1 in which said additive is bis( Beta -chloro- Beta -tolyl ethyl)disulfide.

16. A lubricating oil composition according to claim 15 wherein the additive is present in an amount of 0.05 to 5 percent.