JPH0446319B2 - - Google Patents

Abstract

New lubricating compositions comprising a major amount of (A) a hydrorefined lubricating oil, and a minor amount, by weight, of the combination of: (B) at least one aliphatic olefinic compound and (C) the sulfurization product of at least one aliphatic aryl aliphatic or alicyclic olefinic hydrocarbon containing from about 3 to 30 carbon atoms. Preferably (B) is a fatty acid or fatty acid ester containing olefinic unsaturation in the acid moiety, and the weight ratio of component B to component C is no greater than 1 : 1.

Description

[Detailed description of the invention]

This invention relates to lubricating compositions based on hydrorefined lubricating oils, and in particular to multi-purpose industrial oils used in gears, hydraulic systems, and the like. This invention generally relates to lubricating compositions containing a large amount of hydrotreated lubricating mineral oil and a small amount of a combination of an aliphatic olefinic compound and a sulfurized olefinic hydrocarbon. A variety of lubricating base oil stocks for preparing lubricating compositions are known. These include:
Includes natural and synthetic oils. Natural oils include paraffinic, naphthenic and mixed paraffinic-naphthenic liquid petroleum as well as solvent-treated or acid-treated mineral oils. Oils of lubricating viscosity derived from coal or shale are also useful base oils. In recent years, it has been suggested that base stocks refined by hydrorefining processes have advantages over solvent extracted oils. This is because hydrorefining produces oils with modified structural properties and improved viscosity properties. It is well known that high pressure generated in certain gears and bearings destroys the lubricating film, thereby damaging machinery and equipment. Due to the harsh conditions of their use, industrial and gear lubricants usually contain additives to maximize their performance under extreme pressure conditions. Certain compounds of metal-reactive elements such as chlorine, sulfur, phosphorus and lead are known to impart extreme pressure properties to various lubricants. Among the various compositions known to accomplish this purpose are various phosphorus- and sulfur-containing compositions (principally salts and esters of dialkylphosphorodithioic acids), and various aliphatic olefinic compounds. There are sulfidation products. These two compounds are used in combination in lubricants,
Improves lubricant performance under extreme pressure conditions. Many of the known sulfidation products of olefinic compounds contain substantial amounts of active sulfur. The presence of active sulfur in lubricants can corrode copper parts, increase wear on metal components, and reduce extreme pressure properties over time. Various compositions obtained by sulfidation of olefins are known to be useful in lubricants. For example, US Pat. No. 4,191,659 describes the preparation of sulfurized olefin-based compositions by catalytically reacting sulfur and hydrogen sulfide with 3 to 30 carbon atoms. This compound is reported to be useful in lubricating compositions, particularly industrial gear lubricants. The purpose of this invention is to provide a novel lubricating composition. According to the invention, (A) a large amount of a hydrorefined lubricating oil; and (B) at least one aliphatic olefinic compound; A lubricating composition is provided that contains a small amount of a species of aliphatic, arylaliphatic or cycloaliphatic olefinic hydrocarbon in combination with a sulfurized product. In a preferred embodiment, the aliphatic olefin compound is at least one unsaturated fatty acid or a fatty acid ester having an olefinic unsaturated bond in the acid site, and the weight ratio of component (B) and component (C) is 1:1. It is as follows. The above compositions based on hydrorefined oils have improved clarity, stability, extreme pressure properties and wear resistance, and reduce corrosion of copper parts. This invention will be explained in more detail below. The composition of this invention contains at least three components: Component (A), which is a major component of this invention, is a hydrorefined lubricating mineral oil. Component (B) is at least one aliphatic olefinic compound, and component (C) is at least one aliphatic, arylaliphatic or cycloaliphatic olefinic compound having from about 3 to about 30 carbon atoms. It is a sulfidation product of hydrocarbons. As mentioned above, component (A) is a hydrorefined lubricating oil. Hydrorefining is a process for treating various feedstocks in which the feedstock is passed with hydrogen over a catalyst at elevated temperature and pressure. The extent of this treatment depends on the type of feedstock, type of catalyst and processing conditions. In this process, hydrogen reacts with sulfur-containing compounds in the feedstock to produce hydrogen sulfide and saturated hydrocarbons. Hydrogen also reacts with nitrogen-containing compounds in the feedstock to produce ammonia. Thus, hydrorefining is particularly useful in treating crude oils containing undesirable amounts of sulfur and nitrogen. Hydrogenating the feedstock improves the color and
neutralized and also reduces carbon residue to some extent. Hydrorefining can be classified into two types depending on the desired result and intended use. The hydrorefined feedstock is used as a feedstock for further processing or as a base oil or blending source for the final lubricant. Hydrogenated oils of various types and viscosities are commercially available. This is because most large-scale oil refiners carry out hydrorefining. Hydrogenated oils have reduced undesirable sulfur and nitrogen content, improved color, improved stability, and relatively high viscosities and neutral viscosity index compared to solvent refined oils. Therefore, it is desirable. However, one of the reasons why it is difficult to use hydrorefined oils is that many additives normally used in lubricating oils are not compatible with hydrorefined oils and therefore cannot be used. That's what it means. A family of hydrotreated oils is available from Gulf Canada under the designation Paraflex. Individual oils are identified by their ISO viscosity number, which corresponds to the viscosity in centistokes at 40°C. Examples of this type of oil are Paraflex 10, Paraflex 100, Paraflex 460 (Bright Stock) and Paraflex
1000 (cylinder stock). Component (B) in the compositions of this invention is at least one aliphatic olefinic compound, which generally contains at least 8 and preferably from about 8 to 30 carbon atoms. Olefinic compounds useful as component (B) include 1-octene, 1-octene,
-decene, 1-tetradecene, 1-octadecene, 1-eicosene, and the like may be olefinic hydrocarbons. Aliphatic olefinic compounds having internal double bonds are also useful as component (B), examples of which include 2-decene, 5-decene, 9-octadecene, and the like. α-olefin is preferred;
Particularly preferred are those having 12 to 20 carbon atoms. Mixtures of these olefins are commercially available, and mixtures thereof may also be used. Component (B) is preferably a fatty acid, a fatty acid ester or a mixture thereof. The term "fatty acid" refers to acids that can be obtained by hydrolyzing naturally occurring vegetable or animal fats and oils. These fatty acids usually contain 16 to 20 carbon atoms and are a mixture of saturated and unsaturated fatty acids. Unsaturated fatty acids commonly found in natural vegetable or animal fats may contain one or more double bonds; examples of such acids include palmitoleic acid, oleic acid, and linoleic acid. The acids are linolenic acid, petroselenic acid, erucic acid, gadoleic acid, vaccenic acid, ricinoleic acid and small amounts of compounds with more than 20 carbon atoms, such as behenic acid. Unsaturated fatty acids useful as component (B) include those obtained from tall oil, peanut oil, soybean oil, cottonseed oil,
It may also be a mixture, such as that obtained by hydrolysis of sunflower seed oil or wheat germ oil. Tall oil is a mixture of rosin acids (mainly abietic acid) and unsaturated fatty acids (mainly oleic acid and linoleic acid). This tall oil is a by-product of the sulfate process in the production of wood pulp. The most preferred aliphatic olefin compound as component (B) is a fatty acid ester having an olefinic unsaturated bond in the fatty acid moiety. Particularly preferred among these are naturally occurring esters of fatty oils, namely glycerol, and the above fatty acids, and synthetic esters of similar structure. Examples of natural fats and oils having unsaturated bonds are animal fats and oils such as cattle foot oil, lard oil, depot oil, and beef tallow. Examples of natural vegetable oils useful as component (B) are cottonseed oil, corn oil, poppyseed oil, safflower oil, sesame oil, soybean oil, sunflower seed oil and wheat germ oil. Fatty acid esters useful as component (B) can also be prepared by reacting aliphatic olefinic acids of the type described above, such as oleic acid, linoleic acid, linolenic acid and behenic acid, with alcohols and polyols. Examples of aliphatic alcohols to be reacted with the above acids include methanol, ethanol,
These are monohydric alcohols such as n-propanol, isopropanol, and butanols, and polyhydric alcohols such as ethylene glycol, propylene glycol, trimethylene glycol, neopentyl glycol, and glycerol. Component (C) in the composition of this invention is about 3 to 30
at least one aliphatic having 5 carbon atoms;
It is a sulfurized product of an arylaliphatic or alicyclic olefinic hydrocarbon compound. Sulfurized component (C)
The olefinic hydrocarbon compounds that produce olefinic hydrocarbon compounds vary in nature and contain at least one olefinic double bond, defined as a non-aromatic double bond, linking two aliphatic carbon atoms. . In the broadest sense, this olefin has the formula R ¹ R ² C
=CR ³ R ⁴ (where each R ¹ , R ² , R ³ and R ⁴ are hydrogen or an organic group). Generally, each R in this formula, when other than hydrogen, -R ⁵ , -
C( ^R5 ) ₃ , ^-COOR5 , -CON( ^R5 ) ₂ , -COON
(R ⁵ ) ₂ , −COOM, −CN, −C(R ⁵ )=NR ⁵ , −X or −YR ⁵ (in these, each R ⁵ is independently,
hydrogen, alkyl, alkenyl, aryl, alkylaryl, substituted alkyl, or substituted alkenyl, where the two R ^5s can be alkylene or substituted alkylene forming a ring having up to about 12 carbon atoms; M is 1 an equivalent of a metal cation (preferably a group or group metal such as sodium, potassium, barium, calcium);
is halogen (eg, chloro, bromo, iodo); Y is oxygen or divalent sulfur). Any two of R ¹ , R ² , R ³ and R ⁴ may constitute one alkylene or substituted alkylene group. That is, this olefin is alicyclic. There are no particular limitations on the nature of the substituent, provided that it is compatible or can be compatible with the lubricating environment and does not interfere under the intended reaction conditions. Therefore, it is not used that is unstable enough to decompose harmfully under the reaction conditions used. However, certain substituents such as keto and aldehyde will desirably effect sulfurization. Selection of suitable substituents is within the skill of those skilled in the art and can be performed using routine experimentation. Typical examples of such substituents are the groups mentioned above as well as hydroxy, carboxy, carbalkoxy, amidine, amino, sulfonyl, sulfinyl, sulfonate, nitro, phosphate, phosphite, alkali metal mercapto, and the like. Olefinic hydrocarbon compounds are usually those in which each R that is not hydrogen is independently an alkyl group, alkenyl or (more rarely) a corresponding substituent. Monoolefin and diolefin compounds, particularly the former are preferred, especially those with terminal monoolefin hydrocarbons, ie R ³ and R ⁴ are hydrogen and R ¹ and R ² are alkyl groups (the olefin being aliphatic) . Approximately 3-30
Particularly preferred are olefinic compounds having from about 3 to 20 carbon atoms. The olefinic hydrocarbon compound may be an arylaliphatic compound, especially one in which the aryl group is phenyl or substituted phenyl group. Specific examples include styrene, α-methylstyrene, vinyltoluene, and 4-ethylvinylbenzene. Propylene, isobutene and their dimers, trimers and tetramers, as well as mixtures thereof, are particularly preferred olefinic hydrocarbon compounds. Among these, isobutene and diisobutene are particularly desirable because they are readily available and can be made into compounds with particularly high sulfur content. The sulfurizing agent used in the production of component (C) is, for example,
These include sulfur, sulfur halides (such as sulfur monochloride and sulfur dichloride), and mixtures of hydrogen sulfide and sulfur or sulfur dioxide. Sulfur-hydrogen sulfide mixtures are preferred and are often mentioned below. However, other sulfiding agents may be used instead. The amounts of sulfur and hydrogen sulfide per mole of olefinic compound are usually about 0.3 to 3.0 gram atoms and about 0.1 to 1.5 moles, respectively. Preferred ranges are about 0.5-2.0 gram atoms and about 0.4-1.25 moles, respectively, and the most desirable ranges are about
0.8-1.8 gram atoms and about 0.4-0.8 moles. The sulfurization reaction temperature is generally about 50-350°C. A preferred range is about 100-200°C, and a particularly preferred range is about 125-180°C. It is often preferred to carry out this reaction under superpressure. This overpressure is autogenous pressure (i.e., the pressure that naturally occurs during the reaction process)
It can and usually is, but it can also be an externally applied pressure. The exact pressure developed during the reaction depends on factors such as the design and operation of the reaction system, the reaction temperature, and the vapor pressures of the reactants and products, and can change during the course of the reaction. It is often advantageous to add to the reaction mixture a substance useful as a sulfurization catalyst. This substance is acidic,
Basic or neutral, but preferably basic substances are also nitrogen bases such as ammonia and amines. The amount used is generally about 0.05 to 2.0% of the weight of the olefinic compound. With the preferred ammonia or amine catalysts, about every 0.0005 to 0.5 mole per mole of olefin.
A proportion of 0.001 to 0.1 mole is preferred. After the sulfidation reaction, the reaction vessel is typically evacuated, by atmospheric distillation, vacuum distillation or stripping, or by passing an inert gas such as nitrogen under suitable temperature and pressure. It is therefore preferable to remove substantially all low boiling point substances. An optional treatment in the preparation of component (C) is to treat the sulfurized product obtained as described above to reduce active sulfur. An example is treatment with alkali metal sulfides as described in US Pat. No. 3,498,915. Other optional treatments may be performed to improve the qualities of the sulfided product, such as odor, color and corrosivity, or to remove insoluble by-products. US Pat. No. 4,119,549 describes suitable sulfurized products as component (C), and the examples include specific sulfurized products. The following examples are examples of the preparation of such products. Example 1 A jacketed high pressure reactor equipped with a stirrer and an internal cooling coil was charged with 629 parts (19.6 moles) of sulfur. Circulating cooling salt water through the cooling coil,
The reactor was cooled before charging the gaseous reactants. After sealing the reactor, evacuate to about 6 torr, cool,
1100 parts (19.6 moles) of isobutene, 334 parts (9.8 moles) of hydrogen sulfide, and 7 parts of n-butylamine were charged. Through steam to the external jacket, approx.
The reactor was heated to approximately 170°C over a period of time. A maximum pressure of 720 psig was reached at about 138° C. during this heating. The pressure began to decrease before reaching the upper atmosphere maximum reaction temperature and continued to decrease at a constant rate as the gaseous reactants were consumed. After about 4.75 hours at about 171°C, unreacted hydrogen sulfide and isobutene were exhausted to the recovery system. After the pressure inside the reactor was reduced to normal pressure, the sulfurized mixture was recovered as a liquid. As previously mentioned, the sulfiding agent may be sulfur, in which case the reaction involves combining the olefinic compound and sulfur with stirring in an inert atmosphere (e.g., nitrogen).
This is done by heating at 100-250℃ (usually about 150-210℃). The weight ratio of olefin and sulfur is 15:
It may be as large as 1, but generally it is about 5:1 or more.
The ratio is 10:1. It is often preferred to add sulfur in small amounts to the olefin. Although it is generally preferred that the reaction mixture consist solely of olefin and sulfur, the reaction may be carried out in an inert solvent such as an alcohol, ether, ester, aliphatic hydrocarbon, or halogenated aromatic hydrocarbon that is liquid at the reaction temperature employed. It may be carried out in the presence of After the reaction, insoluble by-products can be removed, usually by filtration at elevated temperatures (about 80-120°C). The filtrate is the desired sulfurized product. The compositions of this invention typically contain component (B) and component (C) in a weight ratio of 1:1 or less. Typically, the weight ratio of component (B) to component (C) will be from about 0.2:1 to about 1:1, more preferably from about 0.2:1 to about 0.5:1. The following examples are examples of combinations of component (B) and component (C) useful in this invention.

[Table] Products

Claims (1)

[Claims] 1. (A) A large amount of hydrorefined lubricating oil, and (B)
at least one aliphatic olefinic compound and (C)
A lubricating composition comprising a small amount of at least one aliphatic, arylaliphatic or cycloaliphatic olefinic compound containing from about 3 to 30 carbon atoms in combination with a sulfurized product. 2. The composition according to claim 1, wherein component (B) is at least one unsaturated fatty acid or a fatty acid ester having an olefinic unsaturated bond in the acid site. 3. The composition according to claim 2, wherein component (B) is at least one fatty acid ester. 4. The composition according to claim 3, wherein component (B) is at least one fatty oil. 5. The composition according to claim 4, wherein component (B) is soybean oil. 6. The composition according to claim 2, wherein component (B) is at least one fatty acid. 7. The composition according to claim 6, wherein component (B) is tall oil acid. 8. The composition of claim 1, wherein the weight ratio of component (B) to component (C) is about 1:1 or less. 9. The composition of claim 8, wherein the weight ratio of component (B) to component (C) is about 0.2:1 to 0.5:1. 10. The composition according to any one of claims 1 to 9, wherein component (C) is a sulfurized product of at least one aliphatic olefinic compound having about 3 to 20 carbon atoms. . 11. The composition according to claim 10, wherein component (C) is a sulfurized product of at least one of propylene, isobutene and dimers, trimers and tetramers thereof. 12. The composition according to claim 10, wherein component (C) is obtained by reacting an olefinic compound with halogenated sulfur or a mixture of sulfur and hydrogen sulfide. 13. The composition according to claim 11, wherein component (C) is obtained by reacting isobutene with a mixture of sulfur and hydrogen sulfide. 14. The composition according to claim 11, wherein component (C) is obtained by reacting isobutene with sulfur halide. 15. The composition according to claim 14, wherein the sulfur halide is sulfur monochloride. 16 (A) A large amount of hydrorefined lubricating oil, and
(B) Sulfurization of at least one unsaturated fatty acid or fatty acid ester having an olefinic unsaturated bond in the acid moiety and (C) at least one aliphatic olefinic compound containing about 3 to 20 carbon atoms. A lubricating composition comprising about 0.01 to 10% by weight of a combination with a substance in a weight ratio of 1:1 or less.