EP0434464B1

EP0434464B1 - Transition-metal free Lubricant

Info

Publication number: EP0434464B1
Application number: EP90314188A
Authority: EP
Inventors: David Kenvyn Walters; Arthur Samuel Thomas
Original assignee: Afton Chemical Ltd
Current assignee: Afton Chemical Ltd
Priority date: 1989-12-22
Filing date: 1990-12-21
Publication date: 1995-02-15
Anticipated expiration: 2010-12-21
Also published as: CA2032940C; CA2032940A1; DE69016976D1; JP2965710B2; GB2239257B; GB8929096D0; GB9027874D0; GB2239257A; JPH04114097A; ES2067701T3; EP0434464A1; DE69016976T2

Description

This invention relates to lubricant composition, and more especially to lubricant compositions which can be used as hydraulic fluids.
Lubricant compositions normally contain a variety of additives incorporated to improve the performance of the lubricant in the environment in which it is to be used. Such additives often contain transition metals. As is well known, there is now a general need, for environmental reasons, to reduce the use of transition metals which are frequently toxic. For example, lubricants used as hydraulic fluids often contain, as an anti-wear additive, a zinc dialkyl dithiophosphate (a so-called "ZDDP"). It is desirable to be able to provide hydraulic fluids which are zinc free. This is especially true where the hydraulic fluid is to be used in agriculture or arboriculture where spillage of the fluid onto cultivated land may occur and cause pollution of the land and of any drainage or river system connected with it.
It is also desirable on practical grounds to be able to provide an additive system which is suitable for use in all types of hydraulic fluid irrespective of the particular equipment in which it will be used. A universal anti-wear (UAW) additive system for use in such hydraulic fluids must be capable of providing fluids capable of meeting the specifications of the leading hydraulic pump manufacturers, e.g. the Haglunds-Denison HFO specification and the Vickers Vane pump specification. It is a further requirement for such fluids that they must meet higher than load stage 10 performance in the FZG test described in more detail below.
European Specification 0086513A describes lubricating oil compositions which may be used as hydraulic fluids, stated to have better anti-wear performance, containing a Group II metal dithiophosphate anti-wear additive and an amino succinic acid or derivative thereof.
Hydraulic fluids incorporating ZDDPs do not always give the required performance in the FZG test.
There is therefore a need for a metal-free universal anti-wear additive system suitable for use in lubricant compositions to be used in, for example, piston and screw compressors, industrial gear systems, and, more particularly, in hydraulic fluids.
Numerous metal-free anti-wear or load carrying additives containing sulphur and optionally phosphorus are known, e.g. from British specification 1542113 or International publication WO87/07637.
According to the present invention, a transition metal-free lubricant composition comprises (a) a metal-free anti-wear or load carrying compatible mixture of additives containing sulphur and phosphorus, comprising as a first ingredient an additive chosen from mono- and/or di-hydrocarbyl phosphates wherein the hydrocarbyl radical is alkyl of up to 12 carbon atoms, and amine salts of di-hydrocarbyl thiophosphates wherein the hydrocarbyl radical may be aryl, alkylaryl, arylalkyl, or aliphatic, and as a second ingredient an additive which is a sulphurized fatty acid ester, and optionally a dialkylpolysulphide, and (b) a corrosion inhibitor in the form of an amino succinate ester of formula

in which R₁ and R₂ are each alkyl of 1 to 30, preferably 1 to 12, carbon atoms, R₃, R₄ and R₅ are each hydrogen or alkyl of 1 to 4 carbon atoms, and R₆ and R₇ are each hydrogen, alkyl of 1 to 30 carbon atoms, or an acyl group derived from a saturated or unsaturated carboxylic acid of up to 30 carbon atoms, at least one of R₆ and R₇ being a said acyl group. Preferably R₁ and R₂ are each alkyl of 3 to 6 carbon atoms, e.g. isobutyl, R₃, R₄ and R₅ are each hydrogen, and R₆ and R₇ are each alkyl of 15 to 20 carbon atoms or an acyl radical derived from a saturated or unsaturated dicarboxylic acid containing 4 to 10 carbon atoms, e.g. octadecyl, octadecenyl, of 3-carboxyl-1-oxo-2-propenyl. An especially preferred component (b) is aspartic acid, N-(3-carboxy-1-oxo-2-propenyl)-N-octadecyl-bis(2-methylpropyl)ester. These amino-succinate esters are described in the above-mentioned European specification 0086513A.
Suitable metal-free, and preferably ashless, anti-wear or load carrying additives are, for example, mono- and/or di-hydrocarbyl phosphates wherein the hydrocarbyl radical is alkyl of up to 12 carbon atoms, e.g. n-butyl, iso-butyl, n-amyl, n-octyl, 2-ethylhexyl or n-dodecyl, or a mixture thereof.
Other metal-free anti-wear or load carrying additives which can be used in the compositions of the present invention are amine salts of di-hydrocarbyl thiophosphates wherein the hydrocarbyl radical may be aryl, e.g. phenyl, alkylaryl, e.g. alkylphenyl in which the alkyl contains up to 12 carbon atoms, arylalkyl, or aliphatic, e.g. alkyl of up to 12 carbon atoms. Examples of such thiophosphates include diphenylthiophosphate, dinonylphenyl thiophosphate, di-n-butyl thiophosphate, di-isobutyl thiophosphate and di-2-ethylhexyl thiophosphate.
The mixture of metal-free anti-wear or load carrying additives which are used in the invention also includes a sulphurized fatty acid ester, e.g. a sulphurized vegetable oil or animal fat such as rape seed oil or lard oil.
Suitable commercially available sulphurised fatty ester materials of this type include Sulperm 10S (trade mark of Keil Chemical) and EP oil GE10 (Hornett). These typically contain about 9.5% and about 8.5-9.5% sulphur, respectively.
Dialkylpolysulphides such as t-nonyl trisulphide or t-dodecyl pentasulphide can also be used in the anti-wear or load-carrying additive.
The sulphur-containing anti-wear or load carrying additive is advantageously prepared in the way described in our British Patent Application No. 8829597.7 (continued under Application No. 8928565.4 and published as GB-A-2226028). These anti-wear or load-carrying additives are amine salts of dihydrocarbyl thiophosphates of formula:

(RO)₂PSO⁻.HN⁺R₈R₉R₁₀

in which the radicals R are the same or different and each is a substituted or unsubstituted hydrocarbyl radical of up to 20 carbon atoms and R₈, R₉ and R₁₀ are each hydrogen or substituted or unsubstituted hydrocarbyl radicals of up to 22 carbon atoms, not more than 2 of R₈, R₉ and R₁₀ being hydrogen. When produced by the process of the aforesaid application, such salts have a purity of at least 95% and have little reactivity towards copper, and less than 3% of a phosphite of formula (RO)₂POH in which R is as hereinbefore defined or amine salt thereof. Preferred such amine salts are those in which R is alkyl of 3 to 8 carbon atoms or phenyl and each of R₈, R₉ and R₁₀ is hydrogen or an alkyl cycloalkyl or alkenyl radical of 4 to 22 carbon atoms, not more than 2 of R₈, R₉ and R₁₀ being hydrogen. Preferably R is phenyl, R₈ and R₉ are hydrogen, and R₁₀ is mixed C₁₂ -C₁₄ tertiary alkyl.
Such amine salts are made by forming a mixture of sulphur and the amine in the liquid state, adding to the mixture a phosphite ester of formula (RO)₂POH in an amount at least equivalent to the amount of sulphur under conditions such that the sulphur reacts with the ester but the reaction temperature does not rise above 130°C, and then continuing the reaction until the solid sulphur has substantially disappeared from the reaction mixture. The quantity of amine is adjusted if necessary so that the total quantity of amine is at least equivalent to the quantity of the phosphite ester.
The proportions of components (a) and (b) in the lubricant compositions of the invention are preferably from 0.05 to 3%, preferably 0.1% to 1.5%, of the antiwear or load carrying additive and from 0.002% to 0.5%, preferably 0.05 to 0.25%, by weight of the corrosion inhibitor, such percentages being by weight based on the total weight of the lubricant composition.
The lubricant composition may include as the base fluid any mineral or non-mineral oil suitable for use as a lubricant, or more especially as a hydraulic fluid. Such base stocks include paraffinic lubricating oil base stocks of mineral origin, synthetic oils such as polyalphaolefins, e.g. hydrogenated polydecene, synthetic lubricant esters, such as dialkyl adipates and azelates (in which the alkyl groups typically have 1 to 20 carbon atoms each, e.g. dioctyl azelate, dinonyl adipate, or di-2-ethyl-hexylazelate) and oils of biological origin including more particularly lubricant vegetable oils such as rape seed oil, jojoba oil, cotton seed oil, peanut oil or palm oil.
It is a particular advantage of the invention that the combination of components (a) and (b) as set out above is compatible with a variety of oils of natural, especially vegetable, origin suitable for use as hydraulic fluids. Such natural oils are biodegradable, and in consequence the present invention makes it possible to provide an effective hydraulic fluid based on a biodegradable base stock such as rape seed oil or jojoba oil and incorporating additives which are free from heavy metals.
When it is to be used in an acidic environment, it can be desirable to incorporate in a lubricant composition of the present invention a third component, viz. (c) an alkaline earth metal alkylbenzene sulphonate, alkylnaphthalene sulphonate, petroleum sulphonate, alkylphenate, alkyl sulphurized phenate, or alkylsalicylate. This material is usually overbased and may also be sulphurized. A sulphurized overbased calcium alkylphenate in which the alkyl group is paranonyl, or a calcium dinonylnaphthalene-sulphonate is preferably used. The proportion of such additional additive is usually in the range 0.005 to 0.50% based on the total weight of the composition. Such compositions are not ashless, but they do not contain heavy metals and thus achieve one of the major objectives of the present invention.
The lubricant compositions of the present invention may incorporate other additives conventionally used in lubricants, for example:

(i) Additional corrosion inhibitors, e.g. amine salts of carboxylic acids such as octylamine octanoate, condensation products of dodecenyl succinic acid or anhydride and a fatty acid such as oleic acid with a polyamine, e.g. a polyalkylene polyamine such as triethylenetetramine, and half esters of alkenyl succinic acids in which the alkenyl radical contains 8 to 24 carbon atoms with alcohols such as polyglycols.
(ii) Ashless dispersants, especially those made by reaction of a polyolefin maleic anhydride reaction product with a polyalkylene polyamine such as triethylene tetramine or tetraethylene pentamine. In such dispersants, the polyolefin is typically polyisobutene having a number average molecular weight of 900 to 1200.
In some circumstances, it may be advantageous to boronate such ashless dispersants. While boron is non-metal, it is ash-forming and its use in the compositions of the invention is not preferred.
(iii) Antioxidants including, for example, phenolic antioxidants such as 2,6-di-tert-butylphenol, 2,6-di-tert-butyl-4-methylphenol, and 4,4′(-methylenebis(2,6-di-tert-butyl-phenol), sulphurized phenolic antioxidants such as 4,4′-thiobis(6-tert-butyl-o-cresol) and aromatic amines such as di(nonylphenyl)amine and octylated phenyl-alpha-naphthylamine. Mixtures of phenolic antioxidants and aromatic amine antioxidants (e.g. ETHYL ^R Antioxidant 728 and/or 733 with Naugalube 438L trademark of Uniroyal Chemical Company) are preferred.
(iv) Copper deactivators, e.g. benzotriazole and its derivatives, thiadiazoles and their derivatives, or tricresyl phosphite.
(v) Demulsifying agents, more particularly, surfactants which are preferably ashless, e.g. non-ionic surfactants such as polyglycols.
(vi) Viscosity index improvers, e.g. poly(alkylmethacrylates) and olefin copolymers such as ethylene/propylene and styrene/isoprene copolymers, and dispersant viscosity index improvers such as copolymers of an alkylmethacrylate with N-vinylpyrrolidone and olefin copolymers grafted with nitrogen-containing monomers such as diallylformamide.
(vii) Pour point depressants such as poly(alkylmethacrylates).
(viii) Anti-foam agents, e.g. products based on silicones and poly(alkylacrylates).

All such additional ingredients must of course be compatible with components (a) and (b) but, subject to this, they are used in the usual proportions.
The compositions of the invention are conveniently supplied to the formulator of the finished lubricant composition in the form of an additive concentrate comprising the components (a) and (b) as aforesaid, alone or preferably with a relatively small amount of suitable base oil to facilitate handling, and optionally with one or more of the additional ingredients mentioned above. In such concentrates the amounts of components (a) and (b) are proportioned such that when the concentrate is blended into a base fluid to provide a finished lubricant composition in which the concentration of component (a) is from 0.05 to 3% by weight and preferably from 0.1 to 1.5% by weight based on the total weight of the lubricant composition, the concentration of component (b) is from 0.002 to 0.5% by weight and preferably from 0.05 to 0.25 by weight based on the total weight of the lubricant composition. Thus the ratio of (a) to (b) in such concentrates is preferably 30:1 to 0.4:1. The proportion of component (b) in the concentrate is preferably from 0.1 to 50% by weight, especially 0.1 to 10%, and most commonly 1 to 5% by weight of the concentrate.
The following Examples illustrate the invention.

EXAMPLE 1

Hydraulic fluid blends were prepared using as the base stock an ISO 46 mineral base oil having a kinematic viscosity range at 40°C of from 41.4 to 50.6 cSt (41.4 to 50.6 x 10⁻⁶ m²/s). The additives incorporated were as stated below Tables I and II which follow. Each blend was evaluated for clarity and by the IP 135B corrosion test. The latter test involved stirring a mixture of 300 ml of the hydraulic fluid with 30 ml of artificial sea water at a temperature of 60°C with a steel cylinder immersed in the mixture. The test was run in duplicate for 24 hours with each blend and the immersed steel specimens were then examined for signs of rusting. For a pass, no rust must be visible on the specimen.
The blends were also examined by the FZG test (IP334/79). In this test two steel spur gears were rotated together with oil dip lubrication for a series of 15 minute stages. The relative torque between the gears was increased by a fixed amount after each stage and the gears were run together for a given period after which they were examined for wear or damage. The result of the test is quoted in terms of the final pass stage and the first fail stage. To be satisfactory, the pass stage must be higher than 10.

The following Tables I and II set out the compositions of the hydraulic fluids tested and the results obtained with each. Blend 4, 5, 6, 7 and 10 are in accordance with the present invention. The other blends are for comparison.

TABLE 1

CONCENTRATIONS IN WT PERCENTAGE IN ISO46 HYDRAULIC FLUID BASE OIL
Blend	1	2	3	4	5	6
Component A1	0.07	0.07	0.07	0.07	0.07	0.1
Component A2	0.19	0.19	0.19	0.19	0.19	0.12
Component B	-	-	-	0.02	0.02	0.015
Corrosion Inhib. D	0.065	-	0.04	0.03	0.025	0.025
Corrosion Inhib. E	-	0.02	-	-	-	-
Corrosion Inhib. F.	-	-	0.075	-	-	-
FZG Load Stage Fail	12 Pass	9 Pass/10 Fail	Not Tested	12 Pass	12 Pass	12 Pass
IP 135 B Test Result	Fail Moderate Rust	Fail Severe Rust	Not Tested	Pass No rust	Pass No rust	Pass No rust
Clarity of Blended fluid	Clear	Clear	Cloudy	Clear	Clear	Clear
Component A1 was the Primene 81R salt of diphenylthiophosphate. (Primene 81R is a trademark of a commercially available mixture of tertiary alkyl primary amines in which the tertiary alkyl radicals contain 12 to 14 carbon atoms each, from Rohm and Haas Inc.). Component A2 was a blend of 36% di-t-nonyl polysulphide and 64% sulphurised fatty ester. Component B was aspartic acid, N-(3 carboxy-2-oxo-2-propenyl)-N-octadecyl-bis(2-methylpropyl)ester. Corrosion Inhibitor D was a condensation product of dodecenyl succinic acid and oleic acid with a polyethylene polyamine. Corrosion Inhibitor E was octylamine octanoate. Corrosion Inhibitor F was a modified imidazoline (Monamulse CI - trademark of Mona Industries Inc.)

Blends 1-6 contained the same levels of conventional antioxidant, copper deactivator and demulse aid.
Blends 2 and 5 additionally contained a boronated polyisobutenyl succinimide ashless dispersant in conventional amount. In blend 6, component A1 was prepared in the way described in GB-A-2226028.
Blends 7, 8 and 9 contained the same levels of conventional antioxidant, copper deactivator, VI improver and demulse aid.
Blend 10 similar to blends 7 to 9 but contained a boronated polybutenyl succinimide ashless dispersant in conventional amount and no VI improver.

EXAMPLE 2

A blend 11 was prepared having the same composition as blend 6 described in Example 1 except that the base oil was rape seed oil. The results in the FZG test, the IP135B test, and the clarity of the blend were the same as those obtained with blend 6.

EXAMPLE 3

A blend 12 was prepared having the same composition as blend 6 described in Example 1 except that component A1 was used at a concentration of 0.11 weight percent, and component A2 was composed entirely of the sulphurised fatty ester (Sulperm 10S). Blend 12 produced the same FZG, IP135B, and clarity results as blend 6. In performance testing, blend 12 met the requirements of the Haglunds-Denison HFO specification, the Cincinnati Milacron P68, P69 and P70 specifications, and the Vickers vane pump specification.

EXAMPLE 4

A blend 13 was prepared by blending the additive components of blend 12 described in Example 3 in the same concentrations as blend 12 with rape seed oil. Blend 13 gave the same FZG, IP135B, and clarity results as blend 11 described in Example 2. In further testing blend 13 was found to satisfy the pump test requirements of the Haglunds-Denison HFO specification, as well as the Cincinnati Milacron thermal stability test procedure "A". In this latter test procedure, a copper rod and an iron rod are kept in contact with each other under the surface of 200 milliliters of test oil in a beaker for 7 days at a constant temperature of 135°C. On completion of the test it was found that passing ratings were achieved relative to sludge formation, iron rod performance and weight change of the copper rod.

Claims

A transition metal-free lubricant composition comprising (a) a metal-free anti-wear or load-carrying compatible mixture of additives containing sulphur and phosphorus, comprising as a first ingredient an additive chosen from mono- and/or di-hydrocarbyl phosphates wherein the hydrocarbyl radical is alkyl of up to 12 carbon atoms, and amine salts of di-hydrocarbyl thiophosphates wherein the hydrocarbyl radical may be aryl, alkylaryl, arylalkyl, or aliphatic, and as a second ingredient an additive which is a sulphurized fatty acid ester, and (b) a corrosion inhibitor in the form of an amino succinate ester of formula
in which R₁ and R₂ are each alkyl of 1 to 30 carbon atoms, R₃, R₄ and R₅ are each hydrogen or alkyl of 1 to 4 carbon atoms, and R₆ and R₇ are each hydrogen, alkyl of 1 to 30 carbon atoms, or an acyl group derived from a saturated or unsaturated carboxylic acid of up to 30 carbon atoms, at least one of R₆ and R₇ being a said acyl group.
A lubricant composition according to claim 1 in which, in the said amino succinate ester, R₁ and R₂ are each alkyl of 3 to 6 carbon atoms, R₃, R₄ and R₅ are each hydrogen, and R₆ and R₇ are each alkyl of 15 to 20 carbon atoms or an acyl radical derived from a saturated or unsaturated dicarboxylic acid containing 4 to 10 carbon atoms.
A lubricant composition according to claim 1 wherein the corrosion inhibitor is aspartic acid, N-(3-carboxy-1-oxo-2-propenyl)-N-octadecyl-bis(2-methylpropyl) ester.
A lubricant composition according to any one of claims 1 to 3 wherein the said amine salt of a di-hydrocarbyl thiophosphate is a salt of diphenylthiophosphate, dinonylphenyl thiophosphate, di-n-butyl thiophosphate, di-isobutyl thiophosphate, di-2-ethylhexyl thiophosphate or a mixture thereof.
A lubricant composition according to any one of claims 1 to 3 wherein the said amine salt of a di-hydrocarbyl thiophosphate has the formula:

(RO)₂PSO⁻.HN⁺R₈R₉R₁₀

in which the radicals R are the same or different and each is a substituted or unsubstituted hydrocarbyl radical of up to 20 carbon atoms and R₈, R₉ and R₁₀ are each hydrogen or a substituted or unsubstituted hydrocarbyl radical of up to 22 carbon atoms, not more than 2 of R₈, R₉ and R₁₀ being hydrogen.
A lubricant composition according to claim 5 wherein R is alkyl of 3 to 8 carbon atoms or phenyl and each of R₈, R₉ and R₁₀ is hydrogen or an alkyl, cycloalkyl or alkenyl radical of 4 to 22 carbon atoms each, not more than two of R₈, R₉ and R₁₀ being hydrogen.
A lubricant composition according to any one of claims 1 to 6 wherein the anti-wear or load-carrying additive also comprises a dialkylpolysulphide.
A lubricant composition according to any one of claims 1 to 3 wherein the anti-wear or load-carrying additive comprises a combination of (i) an amine salt of a dihydrocarbyl thiophosphate of formula:

(RO)₂PSO⁻.HN⁺R₈R₉R₁₀

in which the radicals R are phenyl, R₈ and R₉ are hydrogen and R₁₀ is mixed C₁₂-C₁₄ tertiary alkyl; (ii) a sulphurized fatty acid ester and (iii) a dialkylpolysulphide.
A lubricant composition according to any one of the preceding claims containing also a lubricant base stock, wherein the lubricant base stock is a paraffinic lubricating oil base stock of mineral origin, a synthetic polyalphaolefin, a synthetic lubricant ester or an oil of biological origin.
A lubricant composition according to claim 9 in which the base stock is a biodegradable vegetable oil.
A lubricant composition according to claim 10 in which the vegetable oil is a rape seed oil.
A lubricant composition according to any one of the preceding claims which contains also an alkaline earth metal alkylbenzene sulphonate, alkaline earth metal alkylnaphthalene sulphonate, alkaline earth metal petroleum sulphonate, alkaline earth metal alkylphenate, alkaline earth metal alkyl sulphurized phenate or alkaline earth metal alkylsalicylate.
A lubricant composition according to claim 12 in which the proportion of the said alkaline earth metal salt is in the range 0.005 to 0.50% based on the total weight of the lubricant composition.
A lubricant composition according to any one of the preceding claims containing 0.05 to 3% by weight of the said anti-wear or load-carrying additive and from 0.002% to 0.5% by weight of the said corrosion inhibitor.
A lubricant composition according to claim 14 containing 0.1 to 1.5% by weight of the anti-wear or load-carrying additive and from 0.05 to 0.25% by weight of the corrosion inhibitor.
A lubricant composition according to any one of the preceding claims containing in addition one or more additional corrosion inhibitors, ashless dispersants, antioxidants, copper deactivators, demulsifying agents, viscosity index improvers, pour-point depressants, and/or anti-foam agents.
Use of a lubricant composition according to any one of claims 1 to 16 as a hydraulic fluid.
A lubricant composition according to any one of claims 1 to 16 in the form of an additive concentrate.