Cyclic phosphonates for lubricant applications

Abstract

A lubricant composition comprises (a) an oil of lubricating viscosity and (b) a phosphonate ester free of zinc salts. The phosphonate ester can be a reaction product of (i) a phosphonic acid or a monomeric ester thereof and (ii) a propylene glycol having hydroxyl groups at both the 1 - and 3-positions and one or more of the carbon atoms of the propyl units being substituted by one or more alkyl groups such that the total number of carbon atoms in the propylene glycol ranges from 4 to 12. The molar ratio of (i) to (ii) can range from 0.9:1.1 to 1.1 :0.9.

Description

BACKGROUND

[0001] The technology of the present disclosure relates to cyclic phosphonates and their use in industrial, transmission system, and machine lubricating oil applications.

[0002] The use of various types of phosphonates as lubricant additives is well known. For example, U.S. Publication 2017 / 0335224 to Abraham et al. published November 23, 2017 discloses a phosphonate mixture comprising a condensation product of a phosphonic acid or ester thereof with two glycol mixtures, wherein the two glycols comprise a first alkyl glycol having two hydroxyl groups in a 1,4 or 1,5 or 1,6 relationship, and a second alkylene glycol which is an alkyl substituted 1,3- propylene glycol. The molar ratio of the first glycol and the second glycol in the mixture ranges from 30:70 to 65:35. The publication further suggests that if the ratio is less than about 30:70, the resulting product can lose efficacy, and if the ratio is greater than about 65:35, the compatibility of the mixture with other components in a lubricant formulation can be reduced. While these known phosphonates have excellent wear performance in transmission system applications, it was subsequently discovered that they can be hydrolytically unstable, incompatible with other components that can be present in lubricants, or cause demulsification problems in industrial gear oil (“IGO”) applications. SUMMARY

[0003] Applicants have developed new phosphonate chemistries that provide fluids without compatibility issues, will properly demulsify when used in IGO applications, and provide good extreme pressure properties. In addition, these new phosphonates exhibit excellent performance in transmission system applications. Accordingly, disclosed herein are lubricant compositions comprising a phosphonate. The lubricant composition can comprise (a) an oil of lubricating viscosity and (b) a phosphonate free of zinc salts. The phosphonate can be a reaction product of (i) a phosphonic acid or ester thereof and (ii) a propylene glycol having hydroxyl groups at the 1 and 3 positions and wherein at least one carbon atom of the propane unit is substituted with an alkyl group, such that the total number of carbon atoms in the propylene glycol ranges from 4 to 12. The molar ratio of (i) to (ii) can range from 0.9: 1.1 to 1.1:0.9.

[0004] In some embodiments, the propylene glycol can comprise an alkyl-substituted 1,3- propanediol having one or more alkyl substituents in one or more of the carbon atoms of the propyl unit, such that the total number of carbon atoms in the alkyl-substituted 1,3- propanediol ranges from 5 to 12. In further embodiments, the phosphonate can be the reaction product of three components: (i) a phosphonic acid or monoester thereof and an alcohol mixture comprising (ii) a propylene glycol (as described above) and (iii) a chain alkane diol having hydroxyl groups in a 1,4 or 1,5 or 1,6 relationship. The ratio of the relative molar amounts of the propylene glycol (ii) and the chain alkane diol (iii) in the alcohol mixture can be at least 95:5, such as 95:5, or 95.5:4.5 to 99.5:0.5, or 96:4 to 99:1, or 98:2 to 99:1, or 97:3 to 99:1.

[0005] In other embodiments, the alcohol mixture further comprises (iv) a monohydric alcohol having 2 to 20, 2 to 12, 2 to 8, or 2 to 4 carbon atoms. The monohydric alcohol can be present at 0.1 wt% to 1 wt% based on the total weight of the total alcohol mixture.

[0006] The amount of the disclosed phosphonate useful in the lubricant composition can range from 0.05 wt% to 0.5 wt%, or 0.05 wt% to 0.75 wt%, or 0.05 wt% to 1.0 wt%, or 0.1 wt% to 1.0 wt%, based on the total weight of the lubricant composition.

[0007] The monomeric phosphonate used to make the cyclic phosphonate can comprise dimethyl phosphite. The propylene glycol used to make the cyclic phosphonate can include 2-ethyl-2- butyl-1,3-propanediol, 2-ethyl-1,3-hexanediol, 2,2-dibutyl-1,3-propanediol, 2-methyl-2- propyl-1,3-propanediol, or combinations thereof. The chain alkane diol used to make the phosphonate can include 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, or mixtures thereof.

[0008] In some embodiments, the phosphonate can comprise at least one oligomeric species comprising 2 to 20 or 3 to 20 phosphorus atoms and at least one cyclic monomeric species comprising a single phosphorus atom. In some embodiments, the phosphonate can comprise a cyclic monomeric species comprising a single phosphorus atom and a 3-carbon chain derived from propylene glycol. In these embodiments, the amount of the cyclic monomeric species relative to the amount of the oligomeric species is at least 70 wt% cyclic monomeric species. In another embodiment, the amount of the cyclic monomeric species relative to the amount of the oligomeric species is at least 75 wt%

[0009] In some embodiments, the lubricant can have a Timken rating greater than 45 pounds (lbs) measured using ASTM D2782. In the same or alternative embodiments, the lubricant composition can have a four-ball sintering point of at least 200 kilogram force and a load wear index of at least 50 kilogram force measured using ASTM D2783. These lubricant compositions comprising the disclosed phosphonates can have improved demulsibility (as measured using ASTM D2711 or D1401) and / or storage stability compared to oligomer- dominant phosphonates. DETAILED DESCRIPTION

[0010] Various preferred features and embodiments will be described below by way of non-limiting illustration.

[0011] The lubricant compositions disclosed herein include an oil of lubricating viscosity, as one component, which can be present in a major amount for a lubricant composition or in an amount that the concentrate is formed for a concentrate. Suitable oils include natural lubricating oils and synthetic lubricating oils and mixtures thereof. In a fully formulated lubricant, the oil of lubricating viscosity is typically present in a major amount (i.e., in an amount greater than 50 percent by weight). Typically, the oil of lubricating viscosity is present in an amount of 75 to 95 percent by weight of the composition, and often greater than 80 percent by weight.

[0012] Suitable lubricating technical oils are not overly limited and include any base oil specified in the American Petroleum Institute (API) Base Oil Interchangeability Guidelines. The five categories of base oils are as follows: Group I (sulfur content > 0.03 wt % and / or < 90 wt % saturates, viscosity index 80-120); Group II (sulfur content < 0.03 wt %, and > 90 wt % saturates, viscosity index 80-120); Group III (sulfur content < 0.03 wt %, and > 90 wt % saturates, viscosity index > 120); Group IV (all polyalphaolefins (PAOs), such as PAO-2, PAO-4, PAO-5, PAO-6, PAO-7, or PAO-8); Group V (all other oils not included in Groups I, II, III, or IV). The oil of lubricating viscosity can comprise API Group I, II, III, IV, V oils, or mixtures thereof.

[0013] In some embodiments, the synthetic base oil comprises one or more API Group IV base oils. In some embodiments, the synthetic base oil comprises one or more polyalphaolefins (PAOs). Suitable PAOs include PAO-2, PAO-4, PAO-5, PAO-6, PAO-7, PAO-8, PAO-40, PAO-100, or any combination thereof. In some embodiments, the synthetic base oil comprises PAO-6, PAO-40, PAO-100, or any combination thereof.

[0014] Natural oils that can be used to prepare the lubricants and functional fluids disclosed herein include animal and vegetable oils as well as mineral lubricants, such as liquid petroleum and solvent-treated or acid-treated alkanes, cycloalkanes, or mixed alkane / cycloalkanes, which may be further refined by hydrocracking and hydrorefining processes.

[0015] Synthetic lubricants include hydrocarbon oils and halogen-substituted hydrocarbon oils, such as polymeric olefins and interpolymers (e.g., polybutene, polypropylene, propylene-isobutylene copolymers); poly(1-hexene), poly(1-octene), poly(1-decene), and mixtures thereof; alkylbenzenes (e.g., dodecylbenzene, tetradecylbenzene, dinonylbenzene, di-(2-ethylhexyl)benzene); polyphenylene (e.g., biphenyl, terphenyl, alkylated polyphenylene); alkylated diphenyl ethers and alkylated diphenyl sulfides, and their derivatives, analogs, and homologues, or mixtures thereof. Also included are alkylene oxide polymers and their interpolymers and derivatives, wherein the terminal hydroxyl groups may be modified by esterification or etherification. Also included are esters of dicarboxylic acids with various alcohols, or esters from C5 to C6. 12 Esters prepared from monocarboxylic acids and polyols or polyol ethers. Other synthetic oils include silicone-based oils, liquid esters containing phosphonic acids, and polymeric tetrahydrofurans. In some embodiments, the oil with lubricating viscosity used in this invention is a synthetic oil comprising polymeric polyisobutylene, and in some embodiments, the oil with lubricating viscosity used in this invention is a synthetic oil comprising polymeric polyisobutylene and polyalphaolefins.

[0016] Unrefined, refined, and re-refined natural or synthetic oils may be used in the lubricants disclosed herein. Unrefined oils are oils obtained directly from natural or synthetic sources without further purification. Refined oils have undergone further processing in one or more purification steps to improve one or more properties. For example, refined oils may be hydrogenated to produce oils with improved antioxidant stability. The oil may also be a hydroisomerized oil derived from waxes such as porous paraffin waxes or Fischer-Tropsch synthetic waxes.

[0017] Other oils are often known as traction fluids. These include polymers of: at least one olefin containing 3 to 5 carbon atoms; hydrocarbon molecules containing a non-aromatic cyclic moiety; fluids comprising cycloalkanes having 19 carbon atoms, such as those containing two substituted cyclohexane rings linked by a methylene group; hydrogenated dimers of α-alkylstyrene; hydrogenated polyolefins; and adamantane ethers.

[0018] In some embodiments, a compatibilizer may be used. Suitable compatibilizers include straight-chain saturated alcohols and branched-chain saturated alcohols; however, in some embodiments, the compatibilizer comprises one or more branched-chain saturated alcohols. In some embodiments, the compatibilizer is substantially free of or even completely free of straight-chain saturated alcohols.

[0019] In some embodiments, the compatibilizer includes a branched, saturated primary alcohol. In some embodiments, the compatibilizer is substantially free or even completely free of unsaturated alcohols. In some embodiments, the compatibilizer is substantially free or even completely free of secondary alcohols.

[0020] In some embodiments, the compatibilizer includes one or more Guerbet alcohols. Guerbet alcohols are named after Marcel Guerbet and can be prepared by the Guerbet reaction. In the Guerbet reaction, a primary fatty alcohol is converted to its β-alkylated dimeric alcohol (i.e., a branched, primary saturated alcohol).

[0021] In certain embodiments, such as in a transmission fluid, the oil of lubricating viscosity can include a polyalphaolefin (PAO). Generally, polyalphaolefins are hydrogenated species derived from monomers having 4 to 30, or 4 to 20, or 6 to 16 carbon atoms. An example of a useful PAO includes a PAO derived from 1-decene. These PAOs can have a viscosity of 1.5 mm 2 / s (cSt) to 160 mm 2 / s (cSt) at 100 °C, or a viscosity of 1.5 mm 2 / s (cSt) to 8.5 mm 2 / s (cSt) at 100 °C, or a viscosity of 2.5 mm 2 / s (cSt) to 6.5 mm 2 / s (cSt) at 100 °C, or even a viscosity of 3.5 mm 2 / s (cSt) to 6.5 mm 2 / s (cSt) at 100 °C. In some embodiments, the oil of lubricating viscosity can be a blend of PAOs, which can be selected to provide desired properties, particularly viscosity properties, to the finished lubricant. The oil of lubricating viscosity can also be mixed with a viscosity modifier such that the finished lubricant has a desired viscosity or viscosity profile.

[0022] In some embodiments, such as in an industrial gear oil, the oil of lubricating viscosity can be a Group I base oil having a kinematic viscosity at 40 °C of 8 cSt (mm 2 / s) to 500 cSt (mm 2 / s) or 18 cSt (mm 2 / s) to 500 cSt (mm 2 / s) or 18 cSt (mm 2 / s) to 115 cSt (mm 2 / s). As used herein, the kinematic viscosity at 40°C is measured using the method of ASTM D445. Similar to PAO base oils, in some embodiments, the oil having lubricating viscosity may be a blend of one or more Group I base oils and / or viscosity modifiers to provide the desired properties, particularly viscosity properties, of the finished lubricant. In one embodiment, the oil having lubricating viscosity is a blend of at least two Group I base oils selected and blended such that the viscosity of the finished lubricant is 18 cSt (SUS) to 115 cSt (SUS) or even 100 cSt (SUS) at 40°C.

[0023] In some implementations, such as in industrial gear oils, the kinematic viscosity of the lubricant composition at 40°C is specified in ISO 3448 as being in the range of 41.4 cSt (mm). 2 / s) to 1100cSt(mm) 2 / s) or 61.2cSt(mm) 2 / s) to 748cSt(mm) 2 / s) or 61.2cSt(mm) 2 / s) to 506cSt(mm) 2 Between / s).

[0024] In some embodiments, such as in automatic or manual transmission fluids, the kinematic viscosity of the lubricant composition may be 2.8 cSt (mm²) at 100°C. 2 / s) to 8.0cSt(mm) 2 / s) or 3.0cSt (mm) 2 / s) to 7.0 (mm) 2 / s) or 3cSt (mm) 2 / s) to 6.5cSt(mm) 2 / s).

[0025] phosphorus-containing compound

[0026] The formulations described in this disclosure comprise novel phosphonate compositions. These phosphonate compositions may comprise a single phosphonate species or may comprise two or more phosphonate species. The phosphonate compositions may be zinc-free, i.e., substantially zinc-free. As used herein, "substantially zinc-free" means that the amount of the substance under consideration is less than the amount that would affect the relevant properties of the lubricant in a measurable manner.

[0027] The phosphonate will comprise the reaction product, e.g., condensation product, of phosphonic acid (H3PO3) or a monomer ester thereof (i) with at least one propylene glycol (ii). By "monomer" phosphonate is generally intended to mean a phosphonate, typically comprising one phosphorus atom and having two independent alkyl groups, each alkyl having one to six carbon atoms, which can react with a polyol to form an oligomeric species, polymeric species, or other condensed species. The alkyl groups of the monomer phosphonate can be relatively low molecular weight groups having one to six or one to four carbon atoms, such as methyl, ethyl, propyl, or butyl, such that the alcohol produced upon reaction with an alkylene glycol can be readily removed. An exemplary monomer phosphonate is dimethyl phosphite; other phosphonates include diethyl phosphite, dipropyl phosphite, and dibutyl phosphite. Thus, in some embodiments, the monomer phosphonate used to make the cyclic phosphonate can comprise dimethyl phosphite.

[0028] Sulfur-containing analogs (e.g., phosphonothioates) can also be employed. Other esters include trialkyl phosphites. Mixtures of dialkyl phosphites and trialkyl phosphites can also be used. As noted above, in these species, the alkyl groups can be the same or different, typically each alkyl group independently having one to six or one to four carbon atoms.

[0029] The monomer phosphonate (i) will react or condense with at least one propylene glycol (ii) to form the species of the present technology, which include monomeric cyclic phosphonate species. The propylene glycol can have at least one hydroxyl group in both the 1 - and 3-positions, and one or more of the carbon atoms of the propyl unit is substituted with one or two alkyl groups, such that the total number of carbon atoms in the propylene glycol ranges from 4 to 12. The molar ratio of phosphonic acid or ester (i) to propylene glycol (ii) can range from 0.9: 1.1 to 1.1 :0.9. In some embodiments, the propylene glycol can comprise an alkyl-substituted 1,3-propanediol, one or more of the alkyl substituents of which is on one or more of the carbon atoms of the propyl unit, such that the total number of carbon atoms in the diol ranges from 5 to 12 or 6 to 12 or 7 to 12 or 8 to 12 or, in certain embodiments, 9 to 12 or even 9. That is, the alkyl-substituted propylene glycol can be represented by the general formula

[0030]

[0031] wherein the various R groups can be the same or different and can be hydrogen atoms or alkyl groups, with the proviso that at least one R is an alkyl group and the total number of carbon atoms in the R groups is from 2 to 9 or from 3 to 9, such that the total carbon atoms in the diol will be from 5 to 12 or from 6 to 12, respectively, and the same for other ranges of total carbon amounts. Propylene glycol as referred to herein means that the two hydroxyl groups are in a 1,3 relationship with each other, i.e. separated by a 3 carbon atom chain. Thus, depending on the position of the two hydroxyl groups on the longest alkyl chain of the molecule, propylene glycol can also be named as 2,4-diol or 3,5-diol or 4,6-diol. If the 1,3-propanediol has one or more secondary hydroxyl groups, the molecule will be considered an internal diol. In one embodiment, the number of alkyl substituents is two and the total number of carbon atoms in the molecule is 9. Suitable substituents can include, for example, methyl, ethyl, propyl, and butyl (of the various possible isomers).

[0032] Examples of 1,3-propanediols can include 2,2-dimethyl-1,3-propanediol, 2-ethyl-2-butyl-1,3-propanediol, 2-ethyl-1,3-hexanediol, 2,2-dibutyl-1,3-propanediol, 2,2-diisobutyl-1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol, 2-propyl-1,3-propanediol, 2-butyl-1,3-propanediol, 2-pentyl-1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-methyl-2,4-pentanediol, 2,4-dimethyl-2,4-pentanediol, and 2,4-hexanediol. It should be noted that some of the foregoing nomenclature emphasizes the -1,3-propanediol structure of the molecule for clarity. For example, 2-pentyl-1,3-propanediol can also be named as 2-hydroxymethyl-1-heptanol, but the latter nomenclature does not make the 1,3 nature of the diol very clear. In other embodiments, the 1,3-propanediol can include 2-butyl-2-ethyl-1,3-propanediol (BEPD).

[0033] In further embodiments, the phosphonate ester comprises the reaction product of three components: (i) a phosphonic acid or ester thereof and an alcohol mixture comprising (ii) propylene glycol and (iii) an alkanediol having hydroxyl groups in a 1,4 or 1,5 or 1,6 relationship. In the alcohol mixture, propylene glycol (ii) is always present in greater amounts than the alkanediol (iii). In the alcohol mixture, for every 5 moles of alkanediol, there should be at least 95 moles of propylene glycol (ii). Thus, in some embodiments, the molar ratio of propylene glycol (ii) to alkanediol (iii) in the alcohol mixture is any ratio greater than 95:5. In other embodiments, the ratio of the relative molar amounts of propylene glycol (ii) to alkanediol (iii) in the alcohol mixture can be 95.5:4.5 to 99.5:0.5, or 96:4 to 99:1, or 98:2 to 99:1, or 97:3 to 99:1.

[0034] As noted above, the alkanediol (iii) is a 1,4 or 1,5 or 1,6 alkanediol having hydroxyl groups in a 1,4 or 1,5 or 1,6 relationship to each other, separated by a 4 carbon atom chain, a 5 carbon atom chain, or a 6 carbon atom chain, respectively. The first hydroxyl group can be on carbon number 1, i.e., on the alpha carbon of the diol, or the first hydroxyl can be on a higher numbered carbon. For example, the diol can also be a 2,5- or 2,6- or 2,7- diol or a 3,6- or 3,7- or 3,8- diol, as will be apparent to one skilled in the art. The alkanediol can be branched (e.g., alkyl substituted) or unbranched, and in one embodiment the alkanediol is unbranched. Unbranched diols, i.e., linear diols (a,co-diols) include 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol. Branched or substituted diols include 1,4-pentanediol, 2-methyl-1,5-pentanediol, 3-methyl-1,5-pentanediol, 3,3-dimethyl-1,5-pentanediol, 1,5-hexanediol, 2,5-hexanediol, and 2,5-dimethyl-2,5-hexanediol. For purposes of the technology of the present disclosure, diols having one or more secondary hydroxyl groups, such as 2,5-hexanediol, can be referred to as internal diols. In certain embodiments, the alkanediol (iii) can be 1,6-hexanediol. In other embodiments, the propylene glycol (ii) can comprise 2-butyl-2-ethyl-1,3-propanediol (BEPD), and the alkanediol (iii) can comprise 1,6-hexanediol. The ratio of BEPD to 1,6-hexanediol can be 95.5:4.5 to 99.5:0.5, or 96:4 to 99:1, or 98:2 to 99:1, or 97:3 to 99:1.

[0035] If desired, the alkanediols (iii) can add hydroxyl groups, i.e., more than two hydroxyl groups per molecule, or there can be exactly two hydroxyl groups per molecule. In one embodiment, there are exactly two hydroxyl groups per molecule. Also, care should be taken to avoid over-branching or cross-linking of the product, which can lead to the formation of undesirable gels. Such problems can be avoided by careful control of reaction conditions, such as control of reagent ratios and addition sequences, performing the reaction under conditions of appropriate dilution, and reacting under low acidic conditions. These conditions can be determined by one of skill in the art through routine experimentation alone.

[0036] In other embodiments, the alcohol mixture further comprises (iv) a monohydric alcohol having 2 to 20, 2 to 12, 2 to 8, or 2 to 4 carbon atoms. The monohydric alcohol can be present at 0.1 to 1 mole percent, based on the total weight of the total alcohol mixture.

[0037] The ratio of the relative molar amount of phosphonic acid or its monomeric ester (a) to the total molar amount of diol (b) can be 0.9:1.1 to 1.1:0.9, or 0.95:1.05 to 1.05:0.95, or 0.98:1.02 to 1.02:0.98, or about 1:1.

[0038] In some embodiments, the phosphonate ester can comprise at least one oligomeric species comprising 2 to 20 or 3 to 20 phosphorus atoms and at least one cyclic monomeric species comprising a single phosphorus atom. In some embodiments, the phosphonate ester can comprise a cyclic monomeric species comprising a single phosphorus atom and a 3-carbon chain derived from propylene glycol. In such embodiments, the relative amount of the cyclic monomeric species to the amount of the oligomeric species can be 8:1 to 3:1 or 7.5:1 to 3.5:1 by weight.

[0039] The cyclic phosphonate ester species can comprise one phosphorus atom, one hydrogen atom, and one oxygen atom from the monomeric phosphonate ester reactant, and carbons and oxygens derived from 1,3-propanediol (ii) as 1,3-propanediol is able to participate in oligomerization reactions or cyclic ester formation. The oligomeric species or polymeric species can generally comprise 2 or 3 to 20 phosphorus atoms, or alternatively 5 to 10 phosphorus atoms, linked together by carbons derived from 1,3-propanediol and / or alkanediols having two hydroxyl groups in a 1,4, 1,5, or 1,6 relationship, which alkyl groups are less prone to cyclization with phosphorus to form cyclic monomeric species.

[0040] The product of the disclosed technology can be a mixture of species represented by the structures shown:

[0041]

[0042] (oligomeric species or polymeric species)

[0043] Add (cyclic monomer species)

[0044] where x and y represent the relative amounts of the two diols incorporated into the oligomer. The structure shown is not intended to indicate that the polymer must necessarily be a block polymer, as the structure represented by the x bracket and the y bracket can be more or less randomly distributed, influenced by or dependent upon the availability of the various diol reactants. Each X is independently a terminal group, which can be, for example, an alkyl group such as methyl or a hydrogen atom or a diol-derived structure that is terminated with an OH group. In the scheme above, the alkylene diol is chosen for illustrative purposes only to be 1,6-hexanediol and the 1,3-propanediol is chosen to be 2-butyl-2-ethyl-1,3-propanediol. Using different alkane diols and 1,3-propanediol will form corresponding structures and mixtures.

[0045] The relative amounts of oligomer species and cyclic monomer species in the reaction mixture will depend somewhat on the specific diols chosen and the reaction conditions. In certain embodiments, 75 to 90 percent by weight of the phosphonate will be in cyclic form and 25 to 10 percent by weight of the product will be in oligomeric form.

[0046] When only 1,3-propanediol is used and no alkane diol having two hydroxyl groups in a 1,4 or 1,5 or 1,6 relationship is used, the cyclic phosphonate formed will be about 80 percent of the total weight of ester formed and the oligomeric phosphonate will be about 20 percent of the total weight of ester formed (80:20 weight ratio of cyclic to oligomer).

[0047] For reaction products made from 1,6-hexanediol and 2-butyl-2-ethyl-1,3-propanediol, in the structures above, it is common to use less than 40 mole percent of 1,6-hexanediol and at least 40 mole percent of 1,3-propanediol, as using these alcohols in a 40 mole percent: 60 mole percent ratio produces a phosphonate with a 50:50 weight ratio of cyclic to oligomer. The amount of cyclic product obtained by reaction at 135°C can be approximately as shown in the following table:

[0048] mole % 1,6-hexanediol 4.5 1 mole % 2-butyl-2-ethyl-1,3-propanediol 95.5 99 wt % cyclics 78 88

[0049] The amount of oligomer species can be 100 percent minus the percentage of cyclic phosphonate. It is also possible that regardless of the specific diols employed, mixtures of oligomer and cyclic monomer having the above weight percentages can be made. Thus, in some embodiments, the relative amount of cyclic monomer species to the amount of oligomer species is 8:1 to 3:1 or 7.5:1 to 3.5:1 by weight.

[0050] The condensation reaction between the phosphonic acid or ester and the diol mixture can be accomplished by mixing the reagents and heating until the reaction is substantially complete. Alternatively, the phosphonic acid or ester can be added slowly to a preheated diol mixture. Generally, if a diol mixture is used, both diols will be mixed with the phosphonic acid or ester compound at or nearly the same time, i.e., generally before the reaction with one diol is complete. A small amount of a basic material, such as sodium methoxide, can also be present. If methyl phosphonate is used as the reagent, substantial completion of the reaction can correspond to stopping the release and distillation of methanol from the reaction mixture. Reduced pressure can be advantageously employed in later stages of the reaction to help remove residual methanol. Suitable temperatures include temperatures ranging from 100 °C to 140 °C, such as temperatures from 110 °C to 130 °C or 115 °C to 120 °C. If the reaction temperature employed exceeds about 140 °C, there can be a risk that the desired product cannot be formed in useful yield or in useful purity because of competing reactions that can occur. Generally, the reaction time can be up to 12 hours, depending on the temperature, pressure applied if any, stirring, and other variables. In some cases, a reaction time of 2 hours to 8 hours or 4 hours to 6 hours can be suitable.

[0051] The amount of the above phosphonate ester product used in a lubricant can be sufficient to provide 0.01 wt % to 0.3 wt % or to 0.1 wt % phosphorus to the lubricating oil composition, or in other embodiments, 0.02 wt % to 0.07 wt % or 0.025 wt % to 0.05 wt % phosphorus. The actual amount of the phosphonate ester product corresponding to these amounts of phosphorus will of course depend on its phosphorus content. Suitable amounts of the phosphonate ester product in the lubricant composition can be 0.05 wt % or 0.06 wt % to 2.0 wt %, or 0.1 wt % to 1 wt %, or 0.05 wt % to 0.5 wt %, or 0.1 wt % to 0.3 wt %, or 0.15 wt % to 0.23 wt %, or 0.15 wt % to 0.5 wt %, or 0.2 wt % to 0.3 wt %. In some embodiments, the amount of the disclosed phosphonate ester that can be used in a lubricant composition ranges from 0.05 wt % to 0.5 wt %, or 0.05 wt % to 0.75 wt %, or 0.05 wt %, or 0.1 wt % to 1.0 wt %, based on the total weight of the lubricant composition. When used in an industrial gear oil, the phosphonate ester can be present at 0.1 wt % to 0.5 wt %, based on the total weight of the industrial gear oil. When used in a transmission lubricant, the phosphonate ester can be present at 0.1 wt % to 0.5 wt %, or 0.1 wt % to 0.75 wt %, or 0.1 wt % to 1.0 wt %, based on the total weight of the transmission lubricant. In some embodiments, the phosphonate ester is present in the lubricant composition in an amount that provides 0.005 wt % to 0.3 wt % phosphorus to the lubricant composition, based on the total weight of the lubricant composition.

[0052] These phosphonates provide a fluid without compatibility issues that will demulsify and provide good extreme pressure when used in industrial gear oil applications. Additionally, these phosphonates exhibit superior performance in transmission system applications. It is also surprising that the phosphonates disclosed herein improve Daphnia EC50 performance at 48 hours as measured using OEDC 202 compared to the phosphonates disclosed in Abraham et al. U.S. Pub. 2017 / 0335224.

[0053] other substances

[0054] The lubricants described in the present disclosure can include other materials to provide a lubricant of a given lubricant type or application with desired properties. Suitable additional materials are not overly limited, some of which are described below.

[0055] phosphorus-containing anti-wear and / or extreme pressure agent

[0056] In some embodiments, in addition to the novel phosphonates disclosed herein, these lubricant compositions can include known phosphorus-containing antiwear and / or extreme pressure agents. These known phosphorus-containing antiwear and / or extreme pressure agents that are commonly used in industrial gear lubricants are mostly partially or fully esterified phosphates. All of these are suitable for use in the lubricant compositions disclosed herein, including industrial gear lubricant compositions. Such antiwear agents include, but are not limited to, acid phosphonates, hydrogen phosphonites, phosphonites, phosphonates, phosphonates, phosphinates, and phosphonamides. Antiwear agents can further include monohydrocarbyl phosphonites, dihydrocarbyl phosphonites, and trihydrocarbyl phosphonites; monohydrocarbyl phosphonates, dihydrocarbyl phosphonates, and trihydrocarbyl phosphonates; monothiophosphonate monohydrocarbyls, monothiophosphonate dihydrocarbyls, monothiophosphonate trihydrocarbyls, dithiophosphonate monohydrocarbyls, dithiophosphonate dihydrocarbyls, dithiophosphonate trihydrocarbyls, trithiophosphonate monohydrocarbyls, trithiophosphonate dihydrocarbyls, trithiophosphonate trihydrocarbyls, tetrathiophosphonate monohydrocarbyls, tetrathiophosphonate dihydrocarbyls, and tetrathiophosphonate trihydrocarbyls; monothiophosphonite monohydrocarbyls, monothiophosphonite dihydrocarbyls, monothiophosphonite trihydrocarbyls, dithiophosphonite monohydrocarbyls, dithiophosphonite dihydrocarbyls, dithiophosphonite trihydrocarbyls, trithiophosphonite monohydrocarbyls, trithiophosphonite dihydrocarbyls, trithiophosphonite trihydrocarbyls, tetrathiophosphonite monohydrocarbyls, tetrathiophosphonite dihydrocarbyls, tetrathiophosphonite trihydrocarbyls; various hydrocarbyl phosphonates and thiophosphonates; various hydrocarbyl phosphonites and thiophosphonites; and the like.

[0057] Examples of phosphonites include monohydrocarbyl-substituted phosphonites, dihydrocarbyl-substituted phosphonites, or trihydrocarbyl-substituted phosphonites, and those having at least one hydrocarbyl group comprising 4 or more carbon atoms, as shown by the following formula:

[0058]

[0059] wherein at least one of R 8 , R 6 and R 7 may be a hydrocarbyl group containing at least 4 carbon atoms and the others can be hydrogen atoms or hydrocarbyl groups. In one embodiment, R 8 , R 6 and R 7 are all hydrocarbyl groups. The hydrocarbyl groups can be alkyl, cycloalkyl, aryl, acyclic hydrocarbyl or mixtures thereof. In the formula having all three groups R 8 , R 6 and R 7 , the compound can be a trihydrocarbyl-substituted phosphite, i.e., R 8 , R 6 and R 7 are all hydrocarbyl groups. The alkyl groups can be straight chain alkyl or branched chain, typically straight chain, and saturated alkyl or unsaturated, typically saturated. Examples of alkyl groups for R 8 , R 6 and R 7 include octyl, 2-ethylhexyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, octadecenyl, nonadecyl, eicosyl or mixtures thereof.

[0060] include amine salts that can be formed with the above-described phosphorus-containing anti-wear agents. The amines can be primary, secondary, tertiary, acyclic or cyclic, mono- or polyamines. They can also be heterocyclic. Amines having aliphatic character are generally preferred. Some specific examples of amines for use in producing amine salts in phosphorus-containing anti-wear agents include octylamine, decylamine, C10, C12, C14 and C16 tertiary alkyl primary amines (or combinations thereof), laurylamine, hexadecylamine, heptadecylamine, octadecylamine, decenylamine, dodecenylamine, palmitamide, oleylamine, linoleylamine, di-isoamylamine, di-octylamine, di-(2-ethylhexyl)amine, dilaurylamine, cyclohexylamine, 1,2-propylene amine, 1,3-propanediamine, diethylene triamine, triethylene tetramine, ethanolamine, triethanolamine, trioctylamine, pyridine, morpholine, 2-methylpiperazine, 1,2-bis(N-piperazinyl-ethane), 1,2-diamine, tetraiminooctadecene, triaminooctadecene, N-hexyl aniline, and the like. These amines can also be triazoles or triazole derivatives.

[0061] In embodiments, the amine salt of the phosphorus-containing anti-wear agent is of the formula:

[0062]

[0063] wherein R 9 and R 10 are independently aliphatic groups containing from about 4 to up to about 24 carbon atoms, R 22 and R23 independently a hydrogen atom or an aliphatic group containing from about 1 to a maximum of about 18 aliphatic carbon atoms, the sum of m and n is 3 and X is an oxygen atom or a sulfur atom. In preferred embodiments, R 9 containing from about 8 to a maximum of 18 carbon atoms, R 10 is:

[0064]

[0065] wherein R 11 is an aliphatic group containing from about 6 to a maximum of about 12 carbon atoms, R 22 and R 23 is a hydrogen atom, m is 2, n is 1 and X is an oxygen atom.

[0066] Specific examples of phosphorus-containing anti-wear agents can include tricresyl phosphonate, tributyl phosphinite, triphenyl phosphinite, 2-ethylhexyl phosphonate, diisobutyl phosphonite, diisopropyl dithiophosphonate, diphenyl phosphonate, fatty phosphonites, and the like. Some embodiments of phosphorus-containing anti-wear agents can include dialkyl phosphonates and diaryl phosphonates and their amine salts. Aryl phosphonates are also contemplated, such as the commercially available Irgalube TM 349and alkyl acidic phosphonates, including di- and / or mono-2-ethylhexyl phosphonic acid.

[0067] In embodiments, the phosphorus-containing anti-wear agent is an alkyl phosphonate amine salt that is substantially free of sulfur having at least 30 mole percent phosphorus atoms in an alkyl pyrophosphonate ester (sometimes referred to as a POP structure), as opposed to a phosphonate (or monomeric phosphonate) structure as described in (WO 2017 / 079016).

[0068] In some embodiments, the added phosphorus-containing compound can be a zinc- containing phosphonate. An example of a zinc-containing composition is zinc dialkyldithiophosphonate.

[0069] dispersant

[0070] The compositions of the present application can also include nitrogen-containing dispersants, such as hydrocarbyl-substituted nitrogen-containing additives. Suitable hydrocarbyl- substituted nitrogen-containing additives include ashless dispersants and polymeric dispersants. Ashless dispersants are so named because, when employed, they do not contain metals, and thus do not typically contribute to sulfated ash when added to lubricants. However, once they are added to a lubricant that includes metal-containing species, they can certainly interact with the surrounding metals. Ashless dispersants are characterized by polar groups attached to a relatively high molecular weight hydrocarbon chain. Examples of such materials include succinimide dispersants, Mannich dispersants, and their borated derivatives.

[0071] Succinimide dispersants are carboxyl dispersants prepared by reacting a hydrocarbon-substituted succinic anhydride or its reactive equivalent with an amine such as poly(ethyleneamine). The hydrocarbon substituents typically contain an average of at least 8, 20, 30, or 35 carbon atoms, and up to 350, 200, or 100 carbon atoms. In one embodiment, the hydrocarbon group is derived from a polyolefin such as polyisobutylene, and the hydrocarbon group may have an M of at least 500, for example, 500, 700, 800, or 900, and up to 5000, 2500, 2000, or 1500. n (Number-average molecular weight). In one embodiment, polydispersity (Mn) w / M n The concentration is at least 1.5. Substituted succinic acid acylators can react with amines (including those mentioned above) and heavy amine products called amine still bottoms. The amount of amine reacting with the acylator is typically in an amount providing a CO:N molar ratio of 1:2 to 1:0.75. If the reaction is carried out with an alcohol, the resulting dispersant will be an ester dispersant. If both amine and alcohol functional groups are present, a mixture of amide, ester, and possibly imide functional groups can be present, whether in separate molecules or in the same molecule (as in the condensed amines mentioned above). These are called ester-amide dispersants.

[0072] "Amine dispersants" are reaction products of relatively high molecular weight aliphatic or alicyclic halides and amines (such as polyalkylene polyamines). "Mannich dispersants" are reaction products of alkylphenols, in which the alkyl group contains at least 30 carbon atoms, with aldehydes (especially formaldehyde) and amines (especially polyalkylene polyamines). "Ester dispersants" are similar to the succinimide dispersants described above, except that they can be considered as preparations via the reaction of a hydrocarbon acylating agent with an aliphatic polyol (such as glycerol, pentaerythritol, or sorbitol), as described in U.S. Patent 3,381,022. Aromatic succinates can also be prepared; see US2010 / 0286414.

[0073] Post-treated dispersants can also be used. They are typically obtained by reacting a carboxyl (e.g., succinimide), amine, or Mannich dispersant with certain reagents such as urea, thiourea, carbon disulfide, aldehyde, ketone, carboxylic acid, hydrocarbon-substituted succinic anhydride, nitrile, epoxide, boron compound such as boric acid (to obtain a "boronated dispersant"), phosphorus compound such as phosphoric acid or anhydride, 2,5-dimercaptothiadiazole (DMTD), or aromatic diacid having an acid group in the 1,3 or 1,4 position on the benzene ring (such as terephthalic acid). Mixtures of dispersants can also be used. In one embodiment, a dispersant is present that is a boronated dispersant that is further functionalized with a sulfur or phosphorus moiety. In one embodiment, the boronated dispersant can be a boronated polyisobutylene succinimide dispersant, where the polyisobutylene portion thereof can have a number average molecular weight of 750 to 2200 or 750 to 1350 or 750 to 1150.

[0074] In one embodiment, both a boronated dispersant and a non-boronated dispersant can be present. The non-boronated dispersant can be a hydrocarbyl-substituted succinimide, such as a polyisobutylene succinimide, where the polyisobutylene portion thereof has a number average molecular weight of about 750 to about 2200 or about 750 to about 1350 or about 750 to about 1150.

[0075] The boronated dispersant and the non-boronated dispersant can be obtained or obtainable from succinic anhydride by an "ene" or "thermal" reaction, by a process known as the "direct alkylation process." The "ene" reaction mechanism and general reaction conditions are outlined in Maleic Anhydride, pp. 147-149, B. C. Trivedi and B. C. Culbertson, Plenum Press, 1982. The non-boronated dispersant prepared by a process including an "ene" reaction can be a polyisobutylene succinimide having carbon ring present on less than 50 mole percent, 0 mole percent to less than 30 mole percent, 0 mole percent to less than 20 mole percent, or 0 mole percent of the dispersant molecules. The "ene" reaction can have a reaction temperature of 180 °C to less than 300 °C or 200 °C to 250 °C or 200 °C to 220 °C.

[0076] The boronated and non-boronated dispersants can also be obtained or obtainable from a chlorine-assisted process, which typically involves a Diels-Alder reaction resulting in the formation of carbon ring linkages. This process is known to those skilled in the art. The chlorine-assisted process can produce a non-boronated dispersant that is a polyisobutylene succinimide having carbon ring present on 50 mole percent or greater or 60 mole percent to 100 mole percent (typically 100 mole percent) of the dispersant molecules. The thermal and chlorine-assisted processes are described in more detail in U.S. Patent 7,615,521, columns 4-5 and Preparation Examples A and B.

[0077] The dispersant can be prepared from a polyolefin as the hydrocarbyl group, and in certain embodiments, the polyolefin can be a highly vinylidene polyisobutylene, i.e., having greater than 50%, 70%, or 75% terminal vinylidene groups (alpha and beta isomers). In certain embodiments, the succinimide dispersant can be prepared by a direct alkylation route. In other embodiments, it can comprise a mixture of direct alkylation and chloro-route dispersants. In certain embodiments, the dispersant component can be a mixture of multiple dispersants, which can be of different types; optionally, at least one can be a succinimide dispersant.

[0078] The non-boronated dispersant can have a nitrogen to carbonyl ratio (N:CO ratio) of 1 :5 to 10:1, 1 :2 to 10:1, 1 :1 to 10:1, 1 :1 to 5:1, or 1 :1 to 2:1. In one embodiment, the non-boronated dispersant can have a N:CO ratio of 1 :1 to 10:1, or 1 :1 to 5:1, or 1 :1 to 2:1. The boronated dispersants of the present invention can be prepared in a manner such that the N:CO ratio is 0.9:1 to 1.6:1, 0.95:1 to 1.5:1, or 1 :1 to 1.4:1.

[0079] For example, the amount of one or more dispersants in the composition can be 0.3 wt% to 10 wt%. In other embodiments, the amount is 0.5% to 7% or 1% to 5% of the final blended fluid formulation. In a concentrate, the amount will be proportionally higher.

[0080] detergent

[0081] The composition can also include a detergent, i.e., a metal salt of an organic acid containing a lipophilic moiety. The organic acid moiety of the detergent is typically a sulfonate, carboxylate, phenate, or salicylate. The metal moiety of the detergent is typically an alkali or alkaline earth metal. Suitable metals include sodium, calcium, potassium, and magnesium. The detergent can be a neutral detergent or an overbased detergent. In a neutral detergent, the organic acid moiety is stoichiometrically equivalent to the metal base moiety. Alternatively, the detergent can be overbased, meaning that there is an excess of metal present beyond that stoichiometrically required to form a neutral metal salt. Suitable overbased organic salts include organic sulfonates having substantial lipophilic character. Organic sulfonates are well known in the lubricant and detergent arts. The sulfonate compounds can contain on average 10 to 40 carbon atoms or 12 to 36 carbon atoms or 14 to 32 carbon atoms. Similarly, phenates, salicylates, and carboxylates have substantial lipophilic character. Typically, the excess metal present will be in excess of the ratio required to neutralize the acid, up to 30:1 in equivalent, preferably 5:1 to 18:1.

[0082] The amount of detergent used in the composition can generally be from 0.01 wt% to 10 wt% or from 0.025 wt% to 3 wt%, for example from 0.1 wt% to 6 wt% or from 0.2 wt% to 5 wt% or from 0.5 wt% to 4 wt% or from 1 wt% to 3 wt% or from 0.1 wt% to 1.0 wt% on an oil-free basis. If the detergent is overbased, it is typically composed of about 50% oil, the oil having a TBN range of 10 to 1000 or 10 to 600 or 200 or greater or 200 to 600 or 250 to 1000 on an oil-free basis. Overbased detergents, both borated and non-borated, are described in U.S. Patents 5,403,501 and 4,792,410. More detailed descriptions of the expressions "metal ratio", TBN, and "soap content" are known to those skilled in the art and explained in the standard textbook entitled Chemistry and Technology of Lubricants (3rdEdition, R.M. Mortier and S.T. Orszulik, Editors, 2010, pages 219 to 220, subheading 7.2.5 Classification of Detergents). TBN can be measured according to ASTM D4739.

[0083] In certain embodiments, the detergent can include a calcium-containing detergent. In certain embodiments, the calcium-containing detergent can be a calcium sulfonate or calcium phenate detergent, and in some embodiments a calcium sulfonate detergent.

[0084] In one embodiment, the sulfonate detergent can be a predominantly linear alkylbenzene sulfonate detergent having a metal ratio of at least 8, as described in paragraphs

[0026] to

[0037] of US 7,407,919. The linear alkylbenzene can have a benzene ring attached at any position on the linear chain, typically at the 2-, 3- or 4-position, or mixtures thereof. The predominantly linear alkylbenzene sulfonate detergent can provide benefits in fuel economy. In one embodiment, the sulfonate detergent can be a metal salt of one or more oil-soluble alkylbenzene sulfonate compounds as disclosed in paragraphs

[0046] to

[0053] of US 2008 / 0119378.

[0085] In one embodiment, the sulfonate detergent can be a branched alkylbenzene sulfonate detergent. The branched alkylbenzene sulfonate can be prepared by isomerization of alpha olefins, oligomers of lower molecular weight olefins, or combinations thereof. Suitable oligomers include tetramers, pentamers and hexamers of propylene and / or butene. In other embodiments, the alkylbenzene sulfonate detergent can be derived from toluene alkylate, i.e. the alkylbenzene sulfonate can have at least two alkyl groups, at least one of which is a methyl group and the other of which is a linear or branched alkyl group as described above.

[0086] The phenate detergent is typically derived from a p-hydrocarbyl phenol or, in general, an alkyl phenol. This type of alkyl phenol can be combined with sulfur and be overbased, combined with aldehyde and be overbased, or carboxylated and form a salicylate detergent. Suitable alkyl phenols or alkyl salicylates include those alkylated with oligomers of propylene, i.e., tetrapropylene phenol (i.e., p-dodecylphenol or PDDP) and pentapropylene phenol. Suitable alkyl phenols or alkyl salicylates also include those alkylated with oligomers of butylene, particularly tetramer and pentamer of n-butylene. Other suitable alkyl phenols or alkyl salicylates include those alkylated with a-olefins, isomerized a-olefins, and polyolefins such as polyisobutylene. In one embodiment, the lubricant composition includes less than 0.2 wt% or less than 0.1 wt% or even less than 0.05 wt% of a phenate detergent or salicylate detergent derived from PDDP. In one embodiment, the lubricant composition includes no phenate detergent or salicylate detergent derived from PDDP. In one embodiment, the lubricant composition includes a phenate detergent or salicylate detergent prepared from PDDP, such detergent containing less than 1.0 wt% unreacted PDDP or less than 0.5 wt% unreacted PDDP or substantially no PDDP.

[0087] The metal-containing detergent can deliver an amount of 130 ppm to 600 ppm or 160 ppm to 400 ppm or in other embodiments, 300 to 10,000 ppm of metal to the lubricant formulation, and in some embodiments, this amount of calcium. The total amount of detergent can be as described above. The term "ppm" means parts per million by weight.

[0088] antifoam

[0089] The compositions of the present application can also include a defoamer, also known as a foam inhibitor, which are known in the art and include, but are not limited to, organosilicones and non-silicon foam inhibitors. Examples of organosilicones include dimethylsiloxanes and polysiloxanes. Examples of non-silicon foam inhibitors include, but are not limited to, polyethers, polyacrylates and mixtures thereof and copolymers of ethyl acrylate, 2-ethylhexyl acrylate and optionally vinyl acetate. In some embodiments, the defoamer is a polyacrylate. The defoamer can be present in the composition from 0.001 wt% to 0.012 wt% or 0.004 wt% or even 0.001 wt% to 0.003 wt%.

[0090] demulsifier

[0091] The compositions of the present technology can also include a demulsifier, which are known in the art and include, but are not limited to, derivatives of propylene oxide, ethylene oxide, polyoxyalkylene alcohols, alkyl amines, amino alcohols, di- or polyamines, or mixtures thereof, which are reacted sequentially with ethylene oxide or substituted ethylene oxide. Examples of demulsifiers include polyethylene glycols, polyethylene oxides, polypropylene oxides, (ethylene oxide-propylene oxide) polymers, and mixtures thereof. In some embodiments, the demulsifier is a polyether. The demulsifier can be present in the composition from 0.002 wt% to 0.2 wt%.

[0092] pour point depressant

[0093] Pour point depressants are known in the art and include, but are not limited to, esters of maleic anhydride-styrene copolymers, polymethacrylates; polyacrylates; polyacrylamides; condensation products of halogenated paraffins and aromatic compounds; carboxylic acid vinyl ester polymers; and terpolymers of a dialkyl fumarate, a vinyl ester of a fatty acid, ethylene-vinyl acetate copolymer, an alkylphenol formaldehyde condensation resin, an alkyl vinyl ether, and mixtures thereof.

[0094] rust inhibitor

[0095] The compositions of the present technology can also include a rust inhibitor. Suitable rust inhibitors include a hydrocarbyl amine salt of a dialkyldithiophosphoric acid, a hydrocarbyl amine salt of a hydrocarbylaromatic sulfonic acid, and a fatty carboxylic acid or ester thereof, an ester of a nitrogen-containing carboxylic acid, an ammonium sulfonate, an imidazoline, a monothiophosphate salt or ester, or any combination thereof; or mixtures thereof.

[0096] Examples of the hydrocarbyl amine salt of a dialkyldithiophosphoric acid of the present technology include, but are not limited to, a reaction product of diheptyl, dioctyl, or dinonyl dithiophosphoric acid with ethylenediamine, morpholine, Primene TM 81R or mixtures thereof.

[0097] Suitable hydrocarbyl amine salts of a hydrocarbylaromatic sulfonic acid for use in the rust inhibitor package of the present technology are represented by the formula:

[0098]

[0099] wherein Cy is a benzene ring or a naphthalene ring; R 12 is a hydrocarbyl group having from about 4 to about 30 carbon atoms, preferably, from about 6 to about 25 carbon atoms, more preferably, from about 8 to about 20 carbon atoms; z is independently 1, 2, 3, or 4, and most preferably, z is 1 or 2; and R 13 , R 14 and R 15independently hydrogen, a branched alkyl chain, or a straight alkyl chain, where the branched alkyl chain or straight alkyl chain has from about 1 to about 30 carbon atoms, in other embodiments from about 4 to about 24 carbon atoms or even from about 6 to about 20 carbon atoms, and in some embodiments from about 8 or 10 to about 16 carbon atoms. In some embodiments, at least one or even two of R 13 , R 14 , and R 15 are independently hydrogen, a branched alkyl chain, or a straight alkyl chain, and in some embodiments, at least one or even two of R 13 , R 14 , and R 15 are hydrogen, and further where at least one of R 13 , R 14 , and R 15 is a hydrocarbyl group comprising at least 8 carbon atoms. Examples of hydrocarbyl amine salts of hydrocarbyl arenesulfonic acids of the present technology include, but are not limited to, ethylenediamine salts of dinonylnaphthalene sulfonic acid. Examples of suitable fatty carboxylic acids or esters thereof include glycerol monooleate and oleic acid.

[0100] Examples of suitable esters of nitrogen-containing carboxylic acids include oleoyl sarcosine. The rust inhibitor can be present in the range of 0.001 wt.% to 1.0 wt.%, 0.02 wt.% to 0.2 wt.%, 0.03 wt.% to 0.15 wt.%, 0.04 wt.% to 0.12 wt.%, or 0.05 wt.% to 0.1 wt.% of the industrial gear lubricant. The rust inhibitor of the present technology can be used alone or as a mixture thereof.

[0101] metal deactivator

[0102] The compositions of the present technology can also include a metal deactivator. Metal deactivators are used to neutralize the catalytic effect of metals in promoting oxidation in industrial gear lubricants. Suitable metal deactivators include, but are not limited to, triazoles, tolyltriazoles, thiadiazoles, or combinations thereof, and derivatives thereof. Examples include derivatives of benzotriazole, benzimidazole, 2-alkyldithiobenzimidazole, 2-alkyldithiobenzothiazole, 2-(N,N'-dialkyldithiocarbamoyl)benzothiazole, 2,5-bis(alkyldithio)-l,3,4-thiadiazole, 2,5-bis(N,N'-dialkyldithiocarbamoyl)-l,3,4-thiadiazole, 2-alkyldithio-5-mercaptotiadiazole, or mixtures thereof. These additives can be used in amounts of 0.01 wt% to 0.25 wt% in the total composition. In some embodiments, the metal deactivator is a hydrocarbyl-substituted benzotriazole compound. The hydrocarbyl-substituted benzotriazole compound includes at least one of the following ring positions: 1-, 2-, 4-, 5-, 6-, or 7-benzotriazole. The hydrocarbyl group contains from about 1 to about 30 carbon atoms, preferably, from about 1 to about 15 carbon atoms, more preferably, from about 1 to about 7 carbon atoms, and most preferably, the metal deactivator is 5-methylbenzotriazole alone or mixtures thereof. The metal deactivator can be present in the industrial gear lubricant in the range of 0.001 wt% to 0.5 wt%, 0.01 wt% to 0.04 wt%, or 0.015 wt% to 0.03 wt%. The metal deactivator can also be present in the composition from 0.002 wt% or 0.004 wt% to 0.02 wt%. The metal deactivator can be used alone or as a mixture thereof.

[0103] antioxidant

[0104] An antioxidant can also be present, including (i) an alkylated diphenylamine, and (ii) a substituted hydrocarbyl monosulfide. In some embodiments, the alkylated diphenylamine of the present technology is bisnonylized diphenylamine and bisoctylated diphenylamine. In some embodiments, the substituted hydrocarbyl monosulfide includes n-dodecyl-2-hydroxyethyl sulfide, l-(tert-dodecylthio)-2-propanol, or combinations thereof. In some embodiments, the substituted hydrocarbyl monosulfide is l-(tert-dodecylthio)-2-propanol. The antioxidant can also include a hindered phenol. Examples of suitable hydrocarbyl groups for the hindered phenol include, but are not limited to, 2-ethylhexyl or n-butyl ester, dodecyl, or mixtures thereof. Examples of methylene-bridged hindered phenols include, but are not limited to, 4,4 ’ methylene- bis(6-tert-butyl-o-cresol), 4,4 ’ methylene- bis(2-tert-amyl-o-cresol), 2,2 ’ methylene- bis(4-methyl-6-tert-butylphenol), 4,4 ’- methylene-bis(2,6-di-tert-butylphenol) or mixtures thereof. The antioxidant can be present in the composition from 0.01 wt% to 6.0 wt% or from 0.02 wt% to 1 wt%. The additive can be present in the composition at 1 wt%, 0.5 wt% or less.

[0105] extreme pressure agent

[0106] The composition of the present application can also include a sulfur-containing compound. Suitable sulfur-containing compounds include sulfurized olefins and polysulfides. The sulfurized olefin or polysulfide can be derived from isobutylene, butene, propylene, ethylene, or some combination thereof. In some examples, the sulfur-containing compound is a sulfurized olefin derived from any of the above natural oils or synthetic oils or even some combination thereof. For example, the sulfurized olefin can be derived from a vegetable oil. The extreme pressure agent can be present in the lubricant composition in the range of 0 wt% to 5 wt%, 0.01 wt% to 4 wt%, or 0.1 wt% to 3 wt%, based on the total weight of the lubricant composition.

[0107] viscosity modifier

[0108] One component that is often used is a viscosity modifier. Viscosity modifiers (VMs) and dispersant viscosity modifiers (DVMs) are well known. Examples of VMs and DVMs are polymethacrylates, polyacrylates, polyolefins, styrene-maleic ester copolymers, and similar polymeric species, including homopolymers, copolymers, and graft copolymers. As used herein, the expressions “(meth)acrylic acid,” “(meth)acrylate,” and related terms are intended to encompass both acrylic acid functionality as well as methacrylic acid functionality. Typically, “(meth)acrylic acid,” “(meth)acrylate,” and related terms are intended to include either methacrylic acid or methacrylate.

[0109] In one embodiment, the lubricant composition as described herein can include from 0.1 wt% to 5 wt% (or from 0.5 wt% to 4 wt%) of a linear polymer having dispersant functionality. The linear polymer can have a weight average molecular weight of 5,000 to 25,000 or 8000 to 20,000. (All weight average molecular weights are measured by GPC (gel permeation chromatography) using polystyrene standards having a weight average molecular weight in the range of 350 to 2,000,000.) In one embodiment, the linear polymer can include a poly(meth)acrylate or mixtures thereof. The linear polymer can be present in the composition from 0.1 wt% to 5 wt%, 0.1 wt% to 4 wt%, 0.2 wt% to 3 wt%, 0.5 wt% to 3 wt%, or 0.5 wt% to 4 wt% of the lubricant composition.

[0110] In some embodiments, the linear polymer may have a composition comprising a poly(meth)acrylate polymer derived from a monomer composition comprising: (a) 50% to 95% or 60% to 80% by weight of an alkyl methacrylate, wherein the alkyl group of the (meth)acrylate has 10 to 15 carbon atoms; (b) 1% to 40% or 4% to 35% by weight of an alkyl methacrylate, wherein the alkyl group of the (meth)acrylate has 1 to 9 carbon atoms; (c) 1% to 10% or 1% to 8% by weight of a dispersant monomer; (d) 0% to 4%, 0% to 2% or 0% by weight of a vinyl aromatic monomer (typically styrene); and (e) 0% to 9% or 0% to 6% by weight of an alkyl methacrylate, wherein the alkyl group of the (meth)acrylate has 16 to 18 carbon atoms. In one embodiment, the linear polymer may comprise 0% to 20% by weight of 16 to 18 (meth)acrylate alkyl esters.

[0111] The dispersant monomers that may be present are typically nitrogen-containing monomers. These nitrogen-containing monomers may include vinyl-substituted nitrogen heterocyclic monomers, dialkylaminoalkyl ester monomers of (meth)acrylate, dialkylaminoalkyl (meth)acrylamide monomers, tert-(meth)acrylamide monomers, and ureo(meth)acrylates. Some examples include N,N-dimethylacrylamide, N-vinylamides (such as N-vinylformamide), vinylpyridine, N-vinylacetamide, N-vinyl-n-propionamide, N-vinylhydroxyacetamide, N-vinylimidazolium, N-vinylpyrrolidone, N-vinylcaprolactam, dimethylaminoethyl acrylate (DMAEA), dimethylaminoethyl acrylate (DMAEMA), dimethylaminobutylacrylamide, dimethylaminopropyl (meth)acrylamide (DMAPMA), dimethylaminopropylacrylamide, dimethylaminopropylmethacrylamide, dimethylaminoethylacrylamide, or mixtures thereof. The dispersant monomer may also be an oxygen-containing compound. The oxygen-containing compound may include hydroxyalkyl (meth)acrylates, such as 3-hydroxypropyl (meth)acrylate, 3,4-dihydroxybutyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2,5-dimethyl-1,6-hexanediol (meth)acrylate, 1,10-decanediol (meth)acrylate, and carbonyl-containing (meth)acrylates such as 2-carboxyethyl (meth)acrylate, carboxymethyl (meth)acrylate, and (meth)acrylate. Zolpidemyl ethyl ester, N-(methacryloyloxy)formamide, (meth)acetone acrylate, N-methacrylomorpholine, N-methacryloyl-2-pyrrolidone, N-(2-methacryloyloxyethyl)-2-pyrrolidone, N-(3-methacryloyloxypropyl)-2-pyrrolidone, N-(2-methacryloyloxypentadecanyl)-2-pyrrolidone, N-(3-methacryloyloxyheptadecyl)-2-pyrrolidone; diol di(meth)acrylates such as ethylene glycol (meth)acrylate, 1,4-butanediol (meth)acrylate, 2-butoxyethyl (meth)acrylate, 2-ethoxyethoxymethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate or mixtures thereof. This type of linear polymer is described in more detail in paragraphs

[0019] and

[0031] through

[0067] of US 6,124,249 or EP 0 937 769 A1.

[0112] Another viscosity-modifying polymer that may be present is a star polymer. In one embodiment, the lubricant composition of the present invention includes a viscosity modifier comprising the star polymer and linear polymer described herein. The star polymer may be derived from a monomer composition comprising (meth)acrylate C. 12 -15 alkyl ester (about 80% by weight) and about 20% by weight of a monomer mixture consisting of methyl methacrylate, 2-ethylhexyl methacrylate and ethylene glycol dimethacrylate. Specific embodiments of the star polymers disclosed herein can also be found in paragraphs

[0021] to

[0061] of WO2007 / 127660 (published by Baker et al. on 8 November 2007 and assigned to The Lubrizol Corporation). Baker discloses various star polymer compositions and methods of preparation.

[0113] The (meth)acrylic polymer having a star architecture can have three or more arms comprising a poly(meth)acrylate polymer that can be derived from a monomer composition comprising: (a) 50 to 100 percent by weight of an alkyl (meth)acrylate, wherein the alkyl group of the (meth)acrylate has 12 to 15 carbon atoms; (b) 0 to 40 percent by weight of an alkyl (meth)acrylate, wherein the alkyl group of the (meth)acrylate has 1 to 9 carbon atoms; (c) 0 to 10 percent by weight of a dispersant monomer (as described above), (d) 0 to 5 percent by weight, 0 to 2 percent by weight, or 0 percent by weight of a vinyl aromatic monomer (typically styrene); and (e) 0 to 20 percent by weight, 0 to 10 percent by weight, or 0 percent by weight of an alkyl (meth)acrylate, wherein the alkyl group of the (meth)acrylate has 16 to 18 carbon atoms.

[0114] The star polymer can have a weight average molecular weight of 100,000 to 1,300,000, 125,000 to 1,000,000, 150,000 to 950,000, or 200,000 to 800,000.

[0115] As used herein, the shear stability index (SSI) of the star polymer can be determined by the 20 hour KRL test (Koeln-Rheinidt cone roller bearing test). Test procedures are set forth in CEC-L-45-99 or equivalent test method DIN 51350-6-KRL / C. The SSI of the star polymer can be in the range of 0 to 100, 0 to 80, 0 to 60, 0 to 50, 0 to 20, 0 to 15, 0 to 10, or 0 to 5. Examples of suitable ranges for SSI include 1 to 5, 10 to 25, or 25 to 65.

[0116] The star polymer can be a homopolymer or a copolymer, i.e., its arms can be homopolymers or copolymers (i.e., comprising two or more monomer types). In one embodiment, the star polymer can be a copolymer. The star polymer can be a star polymer having a random, tapered, diblock, triblock, or multiblock structure. Typically, the star polymer has a random or tapered structure.

[0117] The star-shaped polymer can be obtained / is available by controlled radical polymerization. Examples of controlled radical polymerization techniques include RAFT, ATRP, or oxynitride-mediated processes. The star-shaped polymer can also be obtained / is available by anionic polymerization. In one embodiment, the star-shaped polymer can be obtained / is available by RAFT, ATRP, or anionic polymerization. In one embodiment, the star-shaped polymer can be obtained / is available by RAFT or ATRP polymerization. In one embodiment, the star-shaped polymer can be obtained / is available by RAFT polymerization. Methods for preparing polymers using ATRP, RAFT, or oxynitride-mediated techniques are disclosed in the Examples section of International Publication WO 2006 / 047398, see Examples 1 to 47.

[0118] This star-shaped polymer can be prepared using techniques known in the art, employing either a core-first, arm-later or arm-first, core-later method. Typically, the star-shaped polymer is prepared using RAFT or ATRP (usually RAFT) polymerization techniques via the "arm-first, core-later" method.

[0119] Some commercially available VMs and DVMs include polyisobutylene (such as Indopol from BP Amoco). TM Or obtained from ExxonMobil's Parapol TM ); olefin copolymers (such as those derived from Lubrizol) 7060, 7065, and 7067 and HC-2000, HC-1100, and HC-600); hydrogenated styrene-diene copolymers (such as Shellvis from Shell). TM 40 and 50, and those from Lubrizol 7308 and 7318); styrene / maleic acid ester copolymers, which are dispersant copolymers (such as those obtained from Lubrizol). 3702 and 3715); polymethacrylates, some of which have dispersant properties (such as Viscoplex from RohMax). TM Series, Hitec from Afton TM A series of viscosity index improvers and those derived from Lubrizol 7702 7727、 7725 and 7720C); olefin-grafted-polymethacrylate polymers (such as Viscoplex from RohMax) TM 2-500 and 2-600); and hydrogenated polyisoprene star polymers (such as Shellvis from Shell). TM200 and 260). Viscosity modifiers that can be used are described in U.S. Patents 5,157,088, 5,256,752 and 5,395,539. Depending on the application, the VM and / or DVM can be used in functional fluids at concentrations of up to 50 wt% or up to 20 wt%. Concentrations of 1 wt% to 20 wt%, 1 wt% to 12 wt%, 3 wt% to 10 wt%, or alternatively, 20 wt% to 40 wt% or 20 wt% to 30 wt% can be used. The viscosity and / or dispersant modifier can be added to an oil of lubricating viscosity to form a finished lubricant having a kinematic viscosity in the range of 60 cSt (mm 2 / s) to 1000 cSt (mm 2 / s) at 40°C.

[0120] friction modifier

[0121] Another component that can be used in the compositions of the present application is a friction modifier. Friction modifiers are well known to those skilled in the art and include such materials as: fatty phosphites, fatty acid amides, fatty epoxides, borated fatty epoxides, fatty amines, glycerol esters, borated glycerol esters, alkoxylated fatty amines, borated alkoxylated fatty amines, metal salts of fatty acids, sulfurized olefins, fatty imidazolines, condensation products of carboxylic acids and polyalkylene polyamines, metal salts of alkylsalicylic acids, amine salts of alkylphosphoric acids, and mixtures thereof. Representatives of each of these types of friction modifiers are known and commercially available and are described in more detail in US-2006-0172899.

[0122] The amine friction modifier described in the above U.S. applications is a tertiary amine of the general structure R 1 R 2 NR 3 where R 3 can be an alkyl group containing a polyol (i.e., a group containing 2 or more hydroxyl groups) or a group containing one or more hydroxyl groups and one or more amine groups. For example, R 3 can be -CH2-CHOH-CH2OH or homologs thereof containing, for example, 3 to 8 carbon atoms or 3 to 6 carbon atoms or 3 to 4 carbon atoms and 2, 3, 4 or more hydroxyl groups (typically no more than one hydroxyl group per carbon atom). A typical resulting product can be represented by the formula

[0123] R 1 R 2 N-CH2-CHOH-CH2OH

[0124] or homologs thereof, where R 1 and R 2alkyl group independently of the other alkyl group. Such products can be obtained by reaction of a dialkyl amine with an epoxide or chlorohydroxy compound. For example, reaction of a secondary amine with glycidol (2,3-epoxy-1-propanol) or "chloroglycol" (i.e., 3-chloropropane-1,2-diol) can be effective. Such materials based on the reaction of dicocoamine with one or more moles of glycidol or chloroglycol can be used to provide friction-modifying properties. If reacted with multiple moles of glycidol or chloroglycol or other epoxy alkanols or chlorodiols, dimeric or oligomeric ether-containing groups, i.e., hydroxyl-substituted alkoxyalkyl groups, can be produced.

[0125] Another friction modifier can be an amide represented by the structure R 3 -C(=O)-NR 1 R 2 where R 1 and R 2 each independently is a hydrocarbyl group having at least 6 carbon atoms, such as 6 to 24 carbon atoms, and R 3 is a hydroxyalkyl group having 1 to 6 carbon atoms. Such materials can be prepared from the reaction of a carboxylic acid or its reactive equivalent with an amino alcohol. Examples include the reaction product of isostearic acid or alkyl succinic anhydride with trishydroxymethyl aminomethane. Such friction modifiers are described in more detail in U.S. Patent 7,381,691 to Adams et al., June 3, 2008.

[0126] In certain embodiments, the lubricant composition can contain a friction modifier component comprising (a) an N-substituted oxalic acid bisamide or amide-ester containing at least two hydrocarbyl groups having from about 12 to about 22 carbon atoms; or (β) a condensation product of (i) an aromatic polycarboxylic acid or mixtures thereof or its reactive equivalents having at least two carboxyl groups in positions that allow the formation of a cyclic imide having 5 or 6 atoms in the ring; with (ii) an aliphatic primary amine or alcohol containing from about 6 to about 80 carbon atoms; or both (a) and (β). The presence of one or more of such friction modifiers (a) or (β) can impart good friction performance to a driveline device such as an automatic transmission.

[0127] The component described as (a) can be represented by the formula

[0128]

[0129] In this structure, at least two of R are independently radicals comprising a hydrocarbyl group of 1 to 22 carbon atoms, and at most two of the R radicals are hydrogen or a hydrocarbyl group of 10 or fewer carbon atoms. In other embodiments, one or more of the R radicals can independently contain 12 to 20 or 12 to 18 or 12 to 16 or 12 to 14 or 14 to 20 or 14 to 18 or 14 to 16 carbon atoms. If two hydrocarbyl groups of 12 to 22 carbon atoms are present, they can both be on the same nitrogen atom or they can be on different nitrogen atoms; i.e., R 3 and R 4 may alternatively be R 1 and R 4 may be hydrogen. The hydrocarbyl groups can be the same or different within a given molecule or within a mixture of molecules in the total composition.

[0130] Since at least two of the radicals R 1 , R 2 , R 3 and R 4 in the above structure comprise a hydrocarbyl group of 12 to 22 carbon atoms, such radicals can be such hydrocarbyl groups, e.g., alkyl groups having 12 to 22 carbon atoms. Alternatively, such radicals can comprise such hydrocarbyl groups as part of a larger structure. That is, such radicals can have a general structure such as R 5 R 6 N-R 9 , where one or both of R 5 and R 6 is a hydrocarbyl group of 12 to 22 carbons, and optionally one of R 5 and R 6 may be hydrogen or a shorter hydrocarbyl group. R 9 may be a hydrocarbylene linking group, such as methylene, ethene, propene or butene, and in some cases a 1-3-propene group.

[0131] Thus, in some embodiments, the substituted oxalate bisamide can comprise a species of about the following structure, where two of the radicals R 1 , R 2 , R 3 and R 4 are independently alkyl groups having about 12 to about 22 carbon atoms. Such species can have a structure such as:

[0132]

[0133] where each R 1 and R 2independently an alkyl group having from about 12 to about 18 carbon atoms. Such materials can be obtained or obtainable by known methods such as the reaction of a dialkyl amine with an alkyl oxalate such as ethyl oxalate.

[0134] In another embodiment, the N-substituted oxalyl bisamide or amide-ester of (a) includes an amide-ester represented by the formula:

[0135]

[0136] In this embodiment, R 1 and R 2 may independently be a hydrocarbyl group having from 12 to 22 carbon atoms, as defined elsewhere herein, and R 10 may be a hydrocarbyl group having from 1 to 22 carbon atoms. In certain embodiments, R 10 is a methyl, ethyl, n-propyl, i-propyl, n-butyl, sec-butyl, i-butyl, or t-butyl group.

[0137] In certain embodiments, the friction modifier (a) can be represented by the formula:

[0138]

[0139] where R 5 and R 7 are independently a hydrocarbyl group having from about 12 to about 22 carbon atoms, and R 6 and R 8 are independently hydrogen or a hydrocarbyl group having 10 or fewer carbon atoms or a hydrocarbyl group having from about 12 to about 22 carbon atoms. Suitable diamines for making such products include those available from Akzo in the "Duomeen" series, which have the general structure such as

[0140]

[0141] These and other friction modifiers represented herein as (a) are described in more detail in U.S. Patent 8,691,740 to Vickerman et al., April 8, 2014.

[0142] With respect to the friction modifier labeled (b), the aromatic polycarboxylic acid or its reactive equivalent can be a diacid, triacid, tetraacid, or higher acid (or reactive equivalent). If the reaction product is a monoimide, the polycarboxylic acid will contain at least two acid (or equivalent) groups. If the reaction product is a diimide, the polycarboxylic acid will contain at least four acid (or equivalent) groups. The positioning of the acid groups is such as to allow (but not require) the formation of 5- or 6-membered cyclic imides, which means that they can be, for example, in ortho positions to each other on the aromatic ring.

[0143] The reactive equivalents of carboxylic acids include acids, esters, acyl halides such as acyl chlorides, and anhydrides. Anhydrides, particularly cyclic anhydrides, are often used because of their ready availability and ease of reactivity. The condensation products of the (b) component can have, but need not have, a cyclic imide structure: they can contain, for example, ester or amide groups or imidazoline groups.

[0144] The carboxylic acid groups can be attached directly to the aromatic group, or they can be attached indirectly through an intervening carbon atom. An example of the latter class of materials is an aromatic ring substituted with at least one succinic acid (or anhydride) group, with other ring substituents optionally present as well, such as phenyl succinic acid or anhydride.

[0145] The amount of friction modifier, whether as a single component or as a mixture of separate friction modifiers, can be 0.1 to 5 wt% or 0.2 to 2 wt% or 0.4 to 1.5 wt%.

[0146] extender

[0147] The compositions of the present application can include a compatibilizer or solubilizer to improve the solubility of the polar additives and sludge. In some embodiments, the compatibilizer can include an ester or an alkylated naphthalene. The ester can include a dibasic acid ester with a monohydric alkyl alcohol and a polyhydric alcohol ester of a monobasic carboxylic acid. The former type of ester includes, for example, esters of dicarboxylic acids such as phthalic acid, succinic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic acid, alkyl malonic acid, alkenyl malonic acid, and the like, with a wide variety of alcohols such as butanol, hexanol, dodecanol, 2-ethylhexanol, and the like. Specific examples of these types of esters include dibutyl adipate, di(2-ethylhexyl) sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl azelate, dioctyl phthalate, didecyl phthalate, bis- eicosyl sebacate, and the like.

[0148] Particularly useful synthetic esters are those obtained by reacting one or more polyols, preferably a hindered polyol such as neopentyl polyol; for example, neopentyl glycol, trimethylol ethane, 2-methyl-2-propyl-l,3-propanediol, trimethylol propane, pentaerythritol, and dipentaerythritol, with an alkane acid containing at least 4 carbon atoms, preferably C5 to C 30 Acids, such as saturated straight-chain aliphatic acids, including octanoic acid, decanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, and behenic acid, or corresponding branched-chain aliphatic acids or unsaturated aliphatic acids, such as oleic acid, or mixtures of any of these.

[0149] In some embodiments, the compatibilizer can include one or more saturated alcohols. Suitable compatibilizers include linear saturated alcohols and branched saturated alcohols, however in some embodiments, the compatibilizer includes one or more branched saturated alcohols. In some embodiments, the compatibilizer is substantially free or even completely free of linear saturated alcohols.

[0150] In some embodiments, the compatibilizer includes branched primary saturated alcohols. In some embodiments, the compatibilizer is substantially free or even completely free of unsaturated alcohols. In some embodiments, the compatibilizer is substantially free or even completely free of secondary alcohols.

[0151] In some embodiments, the compatibilizer includes one or more Guerbet alcohols. Guerbet alcohols are named after Marcel Guerbet and can be prepared by the Guerbet reaction. In the Guerbet reaction, a primary fatty alcohol is converted to its beta-alkylated dimeric alcohol (i.e., a branched primary saturated alcohol).

[0152] In some embodiments, the compatibilizer includes at least one compound having the structure: HO— CH2— (R 1 )n— CR 2 R 3 R 4 where R 1 is an alkylene group containing 1 to 20 carbon atoms, n is 0 or 1, and R 2 , R 3 , and R 4 each independently are hydrogen or an alkyl group containing 1 to 20 carbon atoms. In some embodiments, n is zero and R 2 and R 3 are alkyl groups and R 4 is hydrogen. In such embodiments, R 2 and R 3 may contain 4 to 14 or even 6 to 12 carbon atoms. In further embodiments, R 2 and R 3 contain 6 and 8 or 10 and 12 carbon atoms.

[0153] Examples of compatibilizers suitable for use in the present application include 2-ethylhexanol, 2-butyloctanol, 2-hexyldecanol, 2-octyldodecanol, 2-decyltetradecanol, 2-dodecylhexadecanol, or any combination thereof. These types of alcohols are commercially available from Sasol and are sold as ISOFOL alcohols.

[0154] In some embodiments, the compatibilizer includes 2-hexyldecanol, 2-decyltetradecanol, or any combination thereof. In some embodiments, the compatibilizer includes 2-hexyldecanol. In some embodiments, the compatibilizer includes 2-decyltetradecanol.

[0155] The compatibilizer can be present at 2 weight percent or more in the industrial lubricant composition. In some embodiments, the compatibilizer is present at 2 to 20 weight percent or even 2 to 10 weight percent in the industrial lubricant composition.

[0156] polyfunctional substance

[0157] Other optional materials include various compounds that can exhibit a variety of performance benefits, including friction modification (especially friction reduction), antiwear performance, or other benefits. Such materials are compounds that are typically obtained or obtainable by processes that include reacting a hydroxy acid with at least one member selected from amines, alcohols, and amino alcohols. The product can include esters, amides, or imides. Examples include oleyl tartrimide (an imide formed from oleyl amine and tartaric acid) and oleyl diesters (from, for example, mixed C 12 -C 16 Other related materials that can be used typically include esters, amides, and imides of other hydroxy carboxylic acids, including hydroxy polycarboxylic acids, for example, acids such as tartaric acid, citric acid, lactic acid, malic acid, glycolic acid, hydroxy propionic acid, hydroxy glutaric acid, and mixtures thereof. These materials are described in more detail in U.S. Publication 2006-0079413 and PCT Publication WO 2010 / 077630. Such derivatives of hydroxy carboxylic acids (or compounds derived from hydroxy carboxylic acids), if present, can typically be present in the lubricating composition in an amount of 0.1 to 5 weight percent or 0.2 to 3 weight percent or greater than 0.2 to 3 weight percent.

[0158] Another optional material can be an ester of a polyacid, for example, an ester of a diacid, such as a dialkyl adipate, for example, ditridecyl adipate. Such esters can provide performance as a solubilizing agent or a seal swell agent. If present, the amount can be 0.01 to 2 weight percent or 0.05 to 1.5 weight percent or 0.1 to 1.0 weight percent or 0.3 to 0.8 weight percent.

[0159] Other optional materials include antioxidants, i.e., oxidation inhibitors, including hindered phenolic antioxidants, secondary aromatic amine antioxidants such as di-nonyl diphenylamine, and such well-known variants as mono-nonyl diphenylamine and diphenylamines having other alkyl substituents such as mono- or di-octyl, sulfurized phenolic antioxidants, oil-soluble copper compounds, phosphorus-containing antioxidants, and organic sulfides, disulfides, and polysulfides such as 2-hydroxyalkyl, alkyl sulfides, or 1-tert-dodecylthio-2-propanol or sulfurized 4-carbon butoxy cyclohexene or other sulfurized olefins. In one embodiment, the antioxidant can be an amine antioxidant which can be phenyl-alpha-naphthylamine (PANA) or a hydrocarbyl-substituted diphenylamine or mixtures thereof. The hydrocarbyl-substituted diphenylamine can include mono- or di-C4to C 16 - or C6to C 12 - or C9-alkyl diphenylamine. For example, the hydrocarbyl-substituted diphenylamine can be octyl diphenylamine or di-octyl diphenylamine, di-nonyl diphenylamine, typically di-nonyl diphenylamine. In one embodiment, the antioxidant can be a hindered phenolic antioxidant. Such materials typically contain a secondary butyl and / or tertiary butyl group as the steric hindering group. The phenolic group is typically further substituted with a hydrocarbyl group and / or a bridging group to a second aromatic group. Examples of suitable hindered phenolic antioxidants include 2,6-di-tert-butylphenol, 4-methyl-2,6-di-tert-butylphenol, 4-ethyl-2,6-di-tert-butylphenol, 4-propyl-2,6-di-tert-butylphenol, or 4-butyl-2,6-di-tert-butylphenol, or 4-dodecyl-2,6-di-tert-butylphenol. In one embodiment, the hindered phenolic antioxidant can be an ester and can include, for example, Irganox L-135 or 3-(3,5-di-tert-butyl-4-hydroxyphenyl)butyric acid butyl ester from Ciba. TM L-135 or 3-(3,5-di-tert-butyl-4-hydroxyphenyl)butyric acid butyl ester.

[0160] When present, the antioxidant can be present at 0.1 wt % to 1.2 wt % or 0.2 wt % to 1 wt % or 0.3 wt % to 1.0 wt % or 0.4 wt % to 0.9 wt % or 0.5 wt % to 0.8 wt % of the lubricating composition.

[0161] Other optional components include seal swell compositions such as isodecyl cyclobutane sulfone or phthalate esters designed to keep the seal pliable. Also permissible are pour point depressants such as alkyl naphthalenes, polymethacrylates, vinyl acetate / fumarate or / maleate copolymers, and styrene / maleate copolymers. Another material is an anti-wear agent such as zinc dialkyldithiophosphates. Another optional material can be C8to C 20Alkyl amine salts, which are present in an amount to provide 100 ppm to 2000 ppm by weight of phosphorus to the lubricant composition. These optional materials are known to those skilled in the art, are generally commercially available, and are described in more detail in published European Patent Application 761,805. Another material that can be present is a borate ester such as a trialkyl borate, which can be used as an extreme pressure / anti-wear agent. The alkyl groups thereof can contain 4 to 12 carbon atoms or 6 to 10 carbon atoms or 8 carbon atoms. In one embodiment, the trialkyl borate includes tri-(2-ethylhexyl) borate. The amount of alkyl borate, if present, can be 0.1 wt% to 1 wt% or 0.2 wt% to 0.7 wt% or 0.3 wt% to 0.4 wt%. Known materials such as corrosion inhibitors (e.g., tolyltriazole, dimercaptothiadiazoles), dyes, fluidity agents, odor masks, and antifoams can also be included. Organic borate esters and organic borate salts can also be included.

[0162] Other components that can be present include various sulfur-containing materials such as dimercaptothiadiazoles and derivatives thereof, which can be used as corrosion inhibitors, metal deactivators, or rust inhibitors. One particular material is 2,5-dimercapto-l,3,4-thiadiazole (DMTD); derivatives thereof are often used. Derivatives of DMTD include: (a) 2-hydrocarbyldithio-5-mercapto-l,3,4-thiadiazoles or 2,5-bis-(hydrocarbyldithio)-l,3,4-thiadiazoles and mixtures thereof, such as 1,3,4-thiadiazole, 2,5-bis(tert-nonyldithio); (b) carboxylic acid esters of DMTD; (c) condensation products of alpha-halogenated aliphatic monocarboxylic acids with DMTD; (d) reaction products of unsaturated cyclic hydrocarbons and unsaturated ketones with DMTD; (e) reaction products of aldehydes and diaryl amines with DMTD; (f) amine salts of DMTD; (g) dithiocarbamate derivatives of DMTD; (h) reaction products of aldehydes and alcohol or aromatic hydroxyl compounds and DMTD; (i) reaction products of aldehydes, mercaptans, and DMTD; (j) 2-hydrocarbylthio-5-mercapto-l,3,4-thiadiazoles; (k) products obtained by mixing oil-soluble dispersants with DMTD; and mixtures thereof. Compositions a) through k) are described in U.S. Patent No. 4,612,129. Suitable amounts of DMTD can include 0.01 wt% to 15 wt%, 0.02 wt% to 10 wt%, 0.05 wt% to 5 wt%, and 0.1 wt% to 3 wt%.

[0163] The above components can be in the form of a fully formulated lubricant or in the form of a concentrate in a lesser amount of lubricating oil. If they are present in a concentrate, their concentration is generally proportional to their concentration in the more dilute form in the final blend.

[0164] The above-described lubricant compositions can be used to lubricate a mechanical device by supplying the lubricant thereto. Mechanical devices that can benefit from the present lubricants are not particularly limited, but can include internal combustion engines (including gasoline or diesel fuel or hybrid fuel or hybrid engines), gears, hydraulic systems, and transmissions, including automatic transmissions, manual transmissions, and variations thereof, such as dual clutch transmissions and continuously variable transmissions, including push belt transmissions and traction drives.

[0165] industrial gear

[0166] The disclosed lubricant compositions can contain other additive components suitable for industrial gear lubricants. Any combination of conventional additive components suitable for industrial gear applications can be used, including the other materials described above.

[0167] In addition to the novel phosphonate esters described above, other additive components that can be present in the industrial gear additive package include, but are not limited to, foam inhibitors, demulsifiers, pour point depressants, antioxidants, dispersants, metal deactivators (such as copper deactivators), other phosphorus-containing antiwear agents, viscosity modifiers, extreme pressure agents, or some mixture thereof. These additives can each be present from 50 ppm, 75 ppm, 100 ppm, or even 150 ppm to at most 5 wt%, 4 wt%, 3 wt%, 2 wt%, or even 1.5 wt% or 75 ppm to 0.5 wt%, 100 ppm to 0.4 wt%, or 150 ppm to 0.3 wt%, with the wt% values being with respect to the individual component of the fully formulated industrial gear lubricant. It is noted, however, that some additives, including viscosity-modifying polymers, which can alternatively be considered part of the base fluid having a lubricating viscosity, can be present in higher amounts when considered separately from the oil having a lubricating viscosity, including at most 30 wt%, 40 wt%, or even 50 wt%. The additives can be used individually or as mixtures thereof.

[0168] The disclosed compositions can also include one or more antiwear additives and / or extreme pressure agents, one or more rust inhibitors and / or corrosion inhibitors, one or more foam inhibitors, one or more demulsifiers, or any combination thereof.

[0169] In some embodiments, the industrial lubricant additive package or the resulting industrial lubricant composition is substantially free or even completely free of phosphorus amine salts, dispersants, or both.

[0170] In some embodiments, the industrial gear additive package or the resulting industrial gear lubricant composition includes a demulsifier, an anticorrosive, a friction modifier, or a combination of two or more thereof. In some embodiments, the anticorrosive includes a tolyltriazole. In other embodiments, the industrial gear additive package or the resulting industrial gear lubricant composition includes one or more polyepisulfides; one or more phosphorus amine salts; one or more thiophosphates, one or more thiadiazoles, tolyltriazoles, polyethers, and / or alkenyl amines; one or more ester copolymers; one or more carboxylic acid esters; one or more succinimide dispersants, or any combination thereof.

[0171] In some embodiments, the industrial gear additive package includes one or more phosphorus amine salts, but in an amount such that the additive package or, in other embodiments, the resulting industrial gear lubricant composition contains no more than 1.0 wt.%, or even no more than 0.75 wt.% or 0.6 wt.% of such materials. In other embodiments, the industrial gear additive package or the resulting industrial gear lubricant composition is substantially free or even completely free of phosphorus amine salts.

[0172] In one embodiment, the technology can include a three-part mixture of phosphorus amine salts, phosphates, and phosphites.

[0173] In some embodiments, the industrial gear additive package or the resulting industrial gear lubricant composition includes a demulsifier, an anticorrosive, a friction modifier, or a combination of two or more thereof. In some embodiments, the anticorrosive includes a tolyltriazole. In other embodiments, the industrial gear additive package or the resulting industrial gear lubricant composition includes one or more polyepisulfides; one or more phosphorus amine salts; one or more thiophosphates, one or more thiadiazoles, tolyltriazoles, polyethers, and / or alkenyl amines; one or more ester copolymers; one or more carboxylic acid esters; one or more succinimide dispersants, or any combination thereof.

[0174] The industrial gear lubricant additive package can be mixed with an oil of lubricating viscosity to make an industrial gear lubricant that meets or exceeds environmentally friendly standards while providing equivalent or improved industrial gear lubricant performance. For a lubricant composition, the oil of lubricating viscosity can be present in a major amount, or for a concentrate and / or additive composition, in an amount that the concentrate is formed. The oil of lubricating viscosity can be biodegradable or non-biodegradable.

[0175] In industrial gear lubricants: the oil of lubricating viscosity can be present from 80 wt%, 85 wt%, 90 wt%, 95 wt%, 97 wt%, or even 97.5 wt% or 98 wt% oil to at most 90 wt%, 95 wt%, 97 wt%, 97.5 wt%, or even 98 wt%; and the industrial gear lubricant additive package can be present from 1 wt%, 1.5 wt%, or even 2 wt% to at most 2 wt%, 3 wt%, 4 wt%, 5 wt%, 7 wt%, or even 10 wt%.

[0176] In a concentrate of industrial gear additives: the oil of lubricating viscosity can be present from 1 wt%, 5 wt%, even 10 wt% oil to at most 10 wt%, 20 wt%, 30 wt%, 40 wt%, or even 45 wt% or 49 wt%; and the industrial gear lubricant additive package can be present from 20 wt%, 25 wt%, 25.5 wt%, 27.5 wt%, 30 wt%, 35 wt%, 45 wt%, or even 45 wt% to at most 45 wt%, 47.5 wt%, or even 49.5 wt%.

[0177] The industrial gear lubricants of the present technology can meet the performance requirements demanded of industrial gear lubricants as well as standards set for being environmentally friendly.

[0178] Industrial gear oils (IGO) must maintain specific performance levels in typical bench tests that are part of well-known industry gear certifications such as USS 224, AGMA 9005-D94, recently replaced by AGMA 9005-E02, DIN 51517-3:2009-06, Falex Cincinnati, etc. Regarding anti-wear / extreme pressure performance, bench tests include, for example, ASTM D2783 Standard Test Method for Measuring Lubricant Extreme Pressure Characteristics (Four-Ball Method), Standard Test Method for Measuring Lubricant Extreme Pressure Characteristics (Timken Method) (ASTM D2782). Other tests include ASTM D4172 Standard Test Method for Antiwear Characteristics of Lubricating Fluids, FZG Wear (DIN ISO 14635-1), or ASTM D5182 Standard Test Method for Evaluating the Load Carrying Capacity of Oils (FZG Visual Method), Copper Corrosion Protection (ASTM D130, ISO 2160), Oxidation Control (ASTM D2893, DIN EN ISO 4263-4, S-200), Rust Protection (ASTM D665, ISO 7120), Static Seal Compatibility (DIN EN ISO 1817), Demulsibility (ASTM D2711, ASTM D1401, ISO 6614), Foam Control (ASTM D892, ISO 6247), etc. Stability of the lubricant can be measured using D1401 Standard Test Method for Water Separability of Petroleum and Synthetic Fluids.

[0179] In some embodiments, the lubricant can have a Timken rating greater than 45 pounds measured using D2782. In the same or alternative embodiments, the lubricant composition can have a four-ball weld point of at least 200 kilogram force and a load wear index of at least 45 kilogram force measured using D2783.

[0180] The disclosed technology includes methods of making the above-described industrial gear lubricants and / or industrial gear additive concentrates. Such methods include mixing the components together. No particular order or manner of addition is believed to significantly affect the results.

[0181] The present invention also includes methods of adding one of the industrial gear lubricants described herein to an industrial gear box and then operating the industrial gear box.

[0182] The industrial lubricant additive package can be present in the total industrial lubricant from 1 to 5 weight percent, or in other embodiments from 1, 1.5 or even 2 weight percent up to 2, 3, 4, 5, 7 or even 10 weight percent. The amount of industrial gear additive package that can be present in the industrial gear concentrate composition of the present invention is an amount corresponding to the weight percent values described above, where these values are considered in the absence of oil (i.e., they can be considered as pbw values along with the actual amount of oil present).

[0183] In some embodiments, the lubricant composition can be an industrial gear lubricant. The industrial gear lubricant can comprise:

[0184] 0.1 to 0.5 weight percent of the disclosed phosphonate ester,

[0185] 0.0001 to 0.15 weight percent of an anti-corrosive selected from 2,5-bis(tert- dodecyl dithio)-1,3,4-thiazolium, tolyltriazole, or mixtures thereof,

[0186] an oil of lubricating viscosity,

[0187] 0.02 to 3 weight percent of an antioxidant selected from an amino acid antioxidant or a phenolic antioxidant, or mixtures thereof,

[0188] 0.005 to 1.5 weight percent of a borated succinimide or a non-borated succinimide,

[0189] 0.001 to 1.5 weight percent of a neutral or slightly overbased calcium naphthenate (typically neutral or slightly overbased calcium dinonylnaphthalene sulfonate), and

[0190] 0.001 to 2 weight percent or 0.01 to 1 weight percent of an anti-wear agent selected from zinc dialkyldithiophosphates, zinc dialkylphosphates, amine salts of phosphoric acid or esters, or mixtures thereof (different from the phosphonate ester of the present invention).

[0191] The industrial gear lubricant can further comprise a formulation defined in the following table:

[0192]

[0193] Specific examples of industrial gear lubricants include those summarized in the following table:

[0194]

[0195] transmission system application

[0196] In some embodiments, the lubricant composition can be a manual transmission lubricant. Manual transmissions can include (on an oil-free basis) the formulations in the following table:

[0197] component treatment rate range corrosion inhibitor 0.1 to 1 antioxidant 0.2 to 0.5 detergent 0.1 to 1.5 succinimide dispersant 0.5 to 2 viscosity modifier 0 to 10 phosphonate sufficient to deliver 350 ppm to 1000 ppm phosphorus base oil balance to 100

[0198] As used herein, the term "condensation product" is intended to encompass esters, amides, imides, and other such species that can be prepared by the condensation reaction of an acid or a reactive equivalent of an acid (e.g., an acid halide, an anhydride, or an ester) with an alcohol or an amine, regardless of whether the condensation reaction is actually carried out to directly produce the product. Thus, for example, a particular ester can be prepared by a transesterification reaction rather than directly by a condensation reaction. The resulting product is still considered a condensation product.

[0199] Unless otherwise specified, the amount of each chemical component described is exclusive of any solvent or diluent oil, which can be customarily present in the commercial material, that is, on an active chemical basis, as opposed to a basis of the weight of the commercial product. Unless otherwise specified, each chemical or composition referred to herein should be interpreted as being a commercial grade product, which can contain impurities, derivatives and other such materials normally present in such products.

[0200] As used herein, the term "hydrocarbyl substituent" or "hydrocarbyl group" is used in its ordinary sense by those of ordinary skill in the art. Specifically, it refers to a group having a carbon atom directly linked to the rest of the molecule and predominantly having the properties of a hydrocarbon. Examples of hydrocarbyl groups include:

[0201] hydrocarbon substituents, i.e., aliphatic (e.g., alkyl or alkenyl), alicyclic (e.g., cycloalkyl, cycloalkenyl) substituents and aromatic, aliphatic and alicyclic substituted aromatic substituents, and cyclic substituents where the ring is completed through another portion of the molecule (e.g., two substituents together form a ring);

[0202] substituted hydrocarbon substituents, i.e., substituents which contain non-hydrocarbon groups which do not alter the predominantly hydrocarbon nature of the substituent (e.g., halogen (particularly chlorine and fluorine), hydroxy, alkoxy, mercapto, alkylmercapto, nitro, nitroso, and sulfoxy);

[0203] hetero substituents, i.e., substituents which, in the context of the present application, while having the predominantly hydrocarbon character, contain atoms other than carbon in the ring or chain which complete the ring. Hetero atoms include sulfur, oxygen, nitrogen, and include substituents such as pyridyl, furanyl, thienyl, and imidazolyl. Typically, there will be no more than two or no more than one non-hydrocarbon substituents for every ten carbon atoms in the hydrocarbyl group; typically, there are no non-hydrocarbon substituents in the hydrocarbyl group.

[0204] It is known that some of the above materials can interact in the final formulation, such that the components of the final formulation can be different from those that are initially added. For example, metal ions (e.g., of a detergent) can migrate to other acidic or anionic sites of other molecules. The products formed thereby, including the products formed upon employing the composition of the present application in its intended use, can not be susceptible of easy description. All such modifications and reactions products are included within the scope of the present application. The present application includes a composition prepared by admixing the components described above.

[0205] examples

[0206] The product was prepared by reacting dimethyl phosphite (DMPH) with 2-butyl-2- ethyl-1,3-propanediol (BEPD) or an alcohol mixture comprising 2-butyl-2-ethyl-1,3- propanediol (BEPD) and 1,6-hexanediol.

[0207] The following is an example of a specific synthesis without any 1,6-hexanediol: A 5 L flask was charged with 2-butyl-2-ethyl-1,3-propanediol (12.0 mol) and dimethyl phosphite (12.08 mol) and heated to 150 °C. Methanol was removed by continuous distillation under a stream of nitrogen (1 cfh). After 4 h, the collection of methanol had diminished. The mixture was vacuum stripped to 3 torr / 150 °C to remove any trace amounts of methanol and unreacted DMPH. After 1 h, the product was stirred as a colorless liquid.

[0208] Another sample was prepared using an alcohol mixture comprising 99 mole % 2-butyl-2-ethyl-1,3-propanediol (BEPD) and 1 mole % 1,6-hexanediol, those of ordinary skill in the art will understand how to vary the alcohol mixture to obtain the various embodiments disclosed and / or claimed herein: A 5 L flask was charged with 2-butyl-2-ethyl-1,3-propanediol (2.73 mol), 1,6-hexanediol (0.028 mol), and dimethyl phosphite (2.73 mol) and heated to 135 °C. Methanol was removed by continuous distillation under a stream of nitrogen (1 cfh). After 5 h, the collection of methanol had diminished. The mixture was vacuum stripped to 50 torr / 135 °C to remove any trace amounts of methanol and unreacted DMPH. After 0.5 h, the product was stirred as a colorless liquid.

[0209] Additional samples were prepared in a similar manner as described above, repeating the 99:1 mole ratio as well as 98:2, 97:3, 96:4, and 95.5:4.5, 95:5, and 90:10 mole ratios.

[0210] The prepared phosphonate ester was added to a blend of Group I oils of lubricating viscosity to make an ISO 100 finished lubricant (100 cSt viscosity at 40°C). The treat rate of the phosphonate ester (250 ppm phosphorus) in the finished lubricant was 0.203 wt.%. The samples were tested using ASTM D1401, D2782, D2783, and storage stability testing was performed. The properties of the lubricants were then tested and summarized in Table 1 below.

[0211] For ASTM D1401, 40 mL of the prepared sample and 40 mL of distilled water were stirred in a graduated cylinder at about 54°C for about 5 minutes. The amount of separation was measured after every 5 minute test until there was less than or equal to 3 mL of emulsion remaining or the final time of 60 minutes was reached. The emulsion can be measured as follows: oil mL / water mL / emulsion mL (time min). The first number is the amount of oil layer (mL), the second number is the amount of water layer (mL), and the last number is the amount of emulsion (mL). Time is recorded in minutes. Typically, 3 mL or less of emulsion is required at 30 minutes. In a typical industrial gear oil specification, 3 mL or less of emulsion is required in 30 minutes.

[0212] For ASTM D2782, the fluid sample was preheated to 37.8°C ± 2.8°C (100°F ± 5°F) before starting the test. Two determinations were made: the minimum load (rating value) at which the rotating cup and stationary block break the film of lubricant under test and cause a scratch or seizure; and the maximum load (OK value) at which the rotating cup will not break the film of lubricant and cause a scratch or seizure between the rotating cup and stationary block. In a typical industrial gear oil specification, a 60 lb OK load is required.

[0213] For ASTM D2783, the tester was operated with a steel ball rotating against three steel balls held stationary in a cradle by a load. The rotational speed was 1760 rpm ± 40 rpm. The lubricating fluid was brought to between 18°C and 35°C (65°F to 95°F) and then subjected to a series of tests at increasing loads for a 10 second duration until seizure occurred. In a typical industrial gear oil specification, a load wear index of 45 kg or greater is required.

[0214] For the storage stability test, the samples were stored at -18°C, 0°C, room temperature (RT), and 65°C for 4 weeks. The samples at each temperature were rated weekly. Additionally, the samples held at -18°C, 0°C, or 65°C were rated when the samples were cooled or heated back to room temperature.

[0215] table 1

[0216]

[0217] A - Control treated with oligomer-based phosphonate at 0.168 wt% (250 ppm phosphorus) based on total lubricant weight.

[0218] B - 3 is a repeat of Example 2.

[0219] C - 200 kg sinter point. All others have 250 kg sinter point.

[0220] Examples 1 to 7 show improved demulsibility performance compared to the control. In addition to demulsibility, Examples 1 to 6 show improvement in Timken and four ball wear tests compared to the control.

[0221] The above phosphonate can be formulated into the lubricating properties of a continuously variable transmission (CVT) fluid. The lubricating oil can contain the following components (percent by weight): dispersant (borated and / or treated with dimercaptothiadiazole, 3.1%); overbased calcium detergent (0.41%); borate ester friction modifier (0.12%); borate ester alkyl (0.35%); ethoxylated amine friction modifier (0.03%); friction stabilizer (0.08%); alkyl acetamide (1%); long chain hydroxyalkyl amine (0.08%); ester synthetic fluid (0.4%); antioxidant (0.8%); substituted triazole (0.02%); substituted thiadiazole (0.1%); seal swell agent (0.5%); pour point depressant (0.1%); viscosity index improver (7.92%); commercially available antifoam agent (0.1%); mineral base oil (balance to = 100%). The phosphonate can be added to the CVT formulation at 0.26 wt%. For comparison purposes, a conventional phosphite, dibutyl phosphite (dibutyl phosphite hydroxide, "DBP") can also be used at 0.26 wt%.

[0222] The fully formulated lubricant can be tested using a 3-element variable speed friction tester (VSFT) test. In this test, three belt elements from a CVT belt are positioned against a metal surface, lubricated with the test fluid, to simulate the contact interface of an actual CVT belt and pulley. After a short break-in period, several cycles are run at a temperature of 100°C, at a speed varying between 300 rpm and 0 rpm, at a load of 306.5 kg. The static coefficient of friction is the maximum value obtained during each cycle.

[0223] The phosphonate described above can be formulated into the lubricating properties of an automatic transmission fluid. The transmission fluid contains 3.37 wt% borated succinimide dispersant, 1.42 wt% friction modifier, 0.22 wt% metal-containing detergent, 0.08 wt% anti-wear agent, 0.11 wt% friction stabilizer, 1.68 wt% polymeric viscosity modifier, and 2.99 wt% of a combination of one or more seal swell agents, antioxidant, anti-foam agent, pour point depressant, and corrosion inhibitor. The formulation can be prepared in mineral oil. The phosphonate can be added at 0.2 wt%. For comparison purposes, a conventional phosphonate, dibutyl phosphite (dibutyl hydrogen phosphite, "DBP") can also be used at 0.26 wt%. The fully formulated lubricant can be subjected to Mercon V four-ball testing according to ASTM D4172 and Mercon Falex EP testing according to ASTM D3233.

[0224] A lubricant formulation can be prepared for testing of the lubricating properties of a dual clutch transmission fluid, featuring the following components: nitrogen-containing dispersant (3%), corrosion inhibitor (0.5%); overbased calcium sulfonate detergent (0.12%); friction modifier (0.49%); friction stabilizer (0.1%); antioxidant (0.6%); seal swell agent (0.35%); anti-foam agent (0.02%); viscosity modifier (10.9%); mineral base oil (balance to = 100%). The phosphonate can be added at 0.26 wt% to the dual clutch formulation. For comparison purposes, a conventional phosphite, dibutyl phosphite (dibutyl hydrogen phosphite, "DBP") can also be used at 0.26 wt%.

[0225] A lubricant formulation is prepared for testing of the lubricating properties of a manual transmission fluid, featuring the following components of the base formulation in Table 2 below.

[0226] table 2

[0227]

[0228] fluid 1 test

[0229] four ball wear test (a test widely used in the industry)

[0230] Conditions: Falex ball, 60 min, 1200 rpm, 40 Kg test duration of 3600 seconds and at the temperatures given below. Average wear scar diameter taken from three readings.

[0231]

[0232] fe8 roller bearing test

[0233] The FE8 wear test can be used to evaluate the effect of lubricants on the frictional behavior and wear of various bearings, including cylindrical roller thrust bearings, under service conditions. Two test cylindrical roller thrust bearings 81212 are installed in the FE8 test rig, subjected to axial bearing load, operated at a specific speed and kept at a test temperature. Full test details are given below. The apparatus and test system comply with DIN 51819 T1-T3. The test is conducted in duplicate to confirm the results.

[0234] conditions

[0235] test parameters

[0236]

[0237]

[0238] In the wear test, the weight loss of the bearing components reflects the ability of the lubricant to protect the bearing. The formulation (Fluid 1) containing the cyclic phosphonate of the invention achieved 80 hours without interruption of the subsequent washer, cage, and roller weight loss (mg).

[0239] fluid 1

[0240] housing washer 8 6 shaft washer 6 4 cage 50 3 roller 5 <2

[0241] Fluid 3

[0242] housing washer 2 2 shaft washer <2 2 cage 58 41 roller <2 <2

[0243] The wear properties of a manual transmission fluid containing the component were evaluated under mixed lubrication and boundary lubrication conditions at two different temperatures according to the DGMK 377-01 procedure (DGMK 377-01: Method for the evaluation of the wear properties of lubricants). The DGMK test is a five-stage test, four stages lasting 24 hours, and the last stage is 48 hours. The C-PT type test gears were run in the FZG test rig under the conditions shown in the table below. The pinion and wheel gears were weighed at the start of the test. At the end of each stage, the gears were inspected for damage (for scuffing, scoring polish, and wear), and the cumulative weight loss of Fluid 1 (both pinion and wheel gears) is reported in Table 3 below.

[0244] table 3

[0245]

[0246] Note: The value for the gear tooth condition is the number of pinion + wheel teeth affected.

[0247] The weight loss values are corrected measurements using a set of reference gears.

[0248] Each individual measurement of pinion or wheel mass is subject to a weighing uncertainty of ±5 mg.

[0249] fluid 2 test

[0250] Similarly, the anti-wear performance of Fluid 2 was evaluated using a different test C / 0.05 / 90:120 / 12, again using C-PT type gears in the FZG rig under the conditions shown in Table 2. This is a three-stage test, each stage lasting 20 hours. The pinion and wheel gears were weighed at the start of the test. At the end of each 20-hour stage, the gears were inspected for damage (for scuffing, scoring and wear) and the cumulative weight loss was reported. A small oil aliquot was taken every 4 hours and the iron content was determined using ICP (by ASTM D5185). The test results for Fluid 2 are shown in Table 4 below.

[0251] table 4

[0252]

[0253] Note: The value for the gear tooth condition is the number of pinion + wheel teeth affected.

[0254] The weight loss values are corrected measurements using a set of reference gears.

[0255] The iron concentration was determined from ASTM D5185 analysis of samples taken during the test rig run.

[0256] Each of the documents referred to above is incorporated herein by reference. The mention of any document is not an admission that it is prior art with respect to any jurisdiction. All numerical quantities in the description specified in units of measurement shall be understood, unless otherwise specified, to be modified in all instances by the term "about." Unless otherwise indicated, each chemical or composition referred to herein should be interpreted as being a commercial grade product available from a commercial vendor, which can contain impurities, derivatives and other such materials normally existing with such products. However, the amount of each chemical component is presented exclusive of any solvent or diluent oil, which can be customarily present in the commercial material. It is to be understood that the upper and lower amount, range, and ratio amounts described herein can be independently combined. Similarly, the ranges and amounts for each element of the application can be used together with ranges or amounts for any of the other elements. As used herein, the expression "consisting essentially of permits the inclusion of substances that do not materially affect the basic and novel characteristics of the composition under consideration.

Claims

1. A lubricant composition comprising: (a) an oil of lubricating viscosity and (b) a phosphonate ester composition free of zinc salts, the phosphonate ester comprising (i) a reaction product of a phosphonic acid or monomeric phosphonate ester with an alcohol mixture comprising (ii) an alkyl-substituted 1,3-propanediol having one or more alkyl substituents on one or more of the carbon atoms of the propyl units, such that the total number of carbon atoms in the alkyl-substituted 1,3-propanediol ranges from 5 to 12; and (iii) an alkanediol having two hydroxyl groups in a 1,4 or 1,5 or 1,6 relationship; and wherein the ratio of the relative molar amounts of the propanediol (ii) and the alkanediol (iii) in the alcohol mixture is greater than 95:5; and wherein the molar ratio of (i) to the total amount of diol is 0.9: 1.1 to 1.1 : 0.9; and wherein the phosphonate ester composition comprises at least one oligomeric species comprising 2 to 20 phosphorus atoms and at least one cyclic monomeric species comprising a single phosphorus atom, wherein the relative amount of the cyclic monomeric species relative to the amount of the oligomeric species is 8: 1 to 3: 1 by weight.

2. The lubricant composition of claim 1, wherein the ratio of the relative molar amounts of the propanediol (ii) and the alkanediol (iii) in the alcohol mixture is 96:4 to 99:

1.

3. The lubricant composition of claim 1, wherein the alcohol mixture further comprises (iv) a monohydric alcohol having 2 to 20 carbon atoms, and wherein the monohydric alcohol is present at 0.1 to 1 weight percent based on the total weight of the total alcohol mixture.

4. The lubricant composition of claim 3, wherein the alcohol mixture further comprises (iv) a monohydric alcohol having 2 to 12 carbon atoms, and wherein the monohydric alcohol is present at 0.1 to 1 weight percent based on the total weight of the total alcohol mixture.

5. The lubricant composition of claim 3, wherein the alcohol mixture further comprises (iv) a monohydric alcohol having 2 to 8 carbon atoms, and wherein the monohydric alcohol is present at 0.1 to 1 weight percent based on the total weight of the total alcohol mixture.

6. The lubricant composition of claim 3, wherein the alcohol mixture further comprises (iv) a monohydric alcohol having 2 to 4 carbon atoms, and wherein the monohydric alcohol is present at 0.1 to 1 weight percent based on the total weight of the total alcohol mixture.

7. The lubricant composition of claim 2, wherein the alcohol mixture further comprises (iv) a monohydric alcohol having 2 to 20 carbon atoms, and wherein the monohydric alcohol is present at 0.1 to 1 weight percent based on the total weight of the total alcohol mixture.

8. The lubricant composition of claim 7, wherein the alcohol mixture further comprises (iv) a monohydric alcohol having 2 to 12 carbon atoms, and wherein the monohydric alcohol is present at 0.1 to 1 weight percent based on the total weight of the total alcohol mixture.

9. The lubricant composition of claim 7, wherein the alcohol mixture further comprises (iv) a monohydric alcohol having 2 to 8 carbon atoms, and wherein the monohydric alcohol is present at 0.1 to 1 weight percent based on the total weight of the total alcohol mixture.

10. The lubricant composition of claim 7, wherein the alcohol mixture further comprises (iv) a monohydric alcohol having 2 to 4 carbon atoms, and wherein the monohydric alcohol is present at 0.1 to 1 weight percent based on the total weight of the total alcohol mixture.

11. The lubricant composition of any one of claims 1 to 10, wherein the amount of the phosphonate composition ranges from 0.05 to 1.0 weight percent based on the total weight of the lubricant composition.

12. The lubricant composition of claim 11, wherein the amount of the phosphonate composition ranges from 0.05 to 0.75 weight percent based on the total weight of the lubricant composition.

13. The lubricant composition of claim 11, wherein the amount of the phosphonate composition ranges from 0.05 to 0.5 weight percent based on the total weight of the lubricant composition.

14. The lubricant composition of claim 11, wherein the amount of the phosphonate composition ranges from 0.1 to 1.0 weight percent based on the total weight of the lubricant composition.

15. The lubricant composition of any one of claims 1 to 10 and 12 to 14, wherein the monomeric phosphonate comprises dimethyl phosphite.

16. The lubricant composition of claim 11, wherein the monomeric phosphonate comprises dimethyl phosphite.

17. The lubricant composition of any one of claims 1 to 10 and 12 to 14, wherein the propylene glycol (ii) comprises 2-ethyl-2-butyl-1,3-propanediol, 2-ethylhexane-1,3-diol, 2,2-dibutyl-1,3- propanediol, 2-methyl-2-propyl-1,3-propanediol, or a combination thereof.

18. The lubricant composition of claim 16, wherein the propylene glycol (ii) comprises 2-ethyl-2-butyl-1,3-propanediol, 2-ethylhexane-1,3-diol, 2,2-dibutyl-1,3- propanediol, 2-methyl-2-propyl-1,3-propanediol, or a combination thereof.

19. The lubricant composition of any one of claims 1 to 10 and 12 to 14, wherein the alkanediol (iii) comprises 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, or a mixture thereof.

20. The lubricant composition of claim 16, wherein the alkanediol (iii) comprises 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, or a mixture thereof.

21. The lubricant composition of any one of claims 1 to 10 and 12 to 14, wherein the phosphonate composition comprises at least one oligomeric species comprising 3 to 20 phosphorus atoms and at least one cyclic monomeric species comprising a single phosphorus atom.

22. The lubricant composition of claim 20, wherein the phosphonate composition comprises at least one oligomeric species comprising 3 to 20 phosphorus atoms and at least one cyclic monomeric species comprising a single phosphorus atom.

23. The lubricant composition of any one of claims 1 to 10 and 12 to 14, wherein the cyclic monomeric species comprises a single phosphorus atom and a 3 carbon atom chain derived from the propylene glycol (ii).

24. The lubricant composition of claim 22, wherein the cyclic monomeric species comprises a single phosphorus atom and a 3 carbon atom chain derived from the propylene glycol (ii).

25. The lubricant composition of claim 21, wherein the relative amount of cyclic monomeric species to the amount of oligomeric species in the phosphonate composition is 7.5: 1 to 3.5: 1 by weight.

26. The lubricant composition of claim 22, wherein the relative amount of cyclic monomeric species to the amount of oligomeric species in the phosphonate composition is 7.5: 1 to 3.5: 1 by weight.

27. The lubricant composition of claim 23, wherein the relative amount of cyclic monomeric species to the amount of oligomeric species in the phosphonate composition is 7.5: 1 to 3.5: 1 by weight.

28. The lubricant composition of claim 24, wherein the relative amount of cyclic monomeric species to the amount of oligomeric species in the phosphonate composition is 7.5: 1 to 3.5: 1 by weight.

29. The lubricant composition of any one of claims 1 to 10, 12 to 14, and 24-28, wherein the oil of lubricating viscosity is a Group I base oil.

30. The lubricant composition of claim 29, wherein the kinematic viscosity of the Group I base oil is 18 cSt to 115 cSt at 40 °C.

31. The lubricant composition of any one of claims 1 to 10, 12 to 14, and 24 to 28, further comprising at least one dispersant, viscosity modifier, antioxidant, or antiwear agent.

32. The lubricant composition of claim 31, comprising a substituted thiadiazole antiwear agent.

33. The lubricant composition of any one of claims 1 to 10, 12 to 14, and 24 to 28, wherein the lubricant composition has a Timken rating of greater than 45 pounds measured using D2782.

34. The lubricant composition of claim 32, wherein the lubricant composition has a Timken rating of greater than 45 pounds measured using D2782.

35. The lubricant composition of any one of claims 1 to 10, 12 to 14, and 24 to 28, wherein the lubricant composition has a four-ball sintering point of at least 200 kilogram force and a load wear index of at least 45 kilogram force measured using D2783.

36. The lubricant composition of claim 34, wherein the lubricant composition has a four-ball sintering point of at least 200 kilogram force and a load wear index of at least 45 kilogram force measured using D2783.

37. A method for lubricating a mechanical device, the method comprising supplying thereto the lubricant composition of any one of claims 1 to 36.

38. The method of claim 37, wherein the mechanical device is a driveline component.

39. The method of claim 38, wherein the driveline component is an automatic transmission, a manual transmission, a dual clutch transmission, or a continuously variable transmission.

40. The method of claim 39, wherein the driveline component is a push belt transmission or a traction drive.

41. The method of claim 38, wherein the mechanical device comprises a gear.

42. Use of a zinc salt-free phosphonate ester composition in a lubricant composition, wherein the phosphonate ester composition comprises (i) a reaction product of a phosphonic acid or a monomeric phosphonate ester with an alcohol mixture, the alcohol mixture comprising (ii) an alkyl-substituted 1,3-propanediol having one or more alkyl substituents on one or more of the carbon atoms of the propyl units, such that the total number of carbon atoms in the alkyl-substituted 1,3-propanediol ranges from 5 to 12; and (iii) a chain alkane diol having two hydroxyl groups in a 1,4 or 1,5 or 1,6 relationship; and wherein the ratio of the relative molar amounts of the propanediol (ii) and the chain alkane diol (iii) in the alcohol mixture is greater than 95:5; and wherein the molar ratio of (i) to the total amount of diols is 0.9: 1.1 to 1.1:0.9; and wherein the phosphonate ester composition comprises at least one oligomeric species comprising 2 to 20 phosphorus atoms and at least one cyclic monomeric species comprising a single phosphorus atom, wherein the relative amount of the cyclic monomeric species relative to the amount of the oligomeric species is 8: 1 to 3: 1 by weight to improve Timken performance measured using D2782 and / or four-ball sintering point measured using D2783 and / or demulsibility measured using D1401 and / or stability of the lubricant composition.

43. The use of claim 42, wherein the phosphonate ester composition comprises (i) a reaction product of a phosphonic acid or a monomeric phosphonate ester with an alcohol mixture, the alcohol mixture comprising (ii) an alkyl-substituted 1,3-propanediol having one or more alkyl substituents on one or more of the carbon atoms of the propyl units, such that the total number of carbon atoms in the alkyl-substituted 1,3-propanediol ranges from 5 to 12; and (iii) a chain alkane diol having two hydroxyl groups in a 1,4 or 1,5 or 1,6 relationship; and wherein the ratio of the relative molar amounts of the propanediol (ii) and the chain alkane diol (iii) in the alcohol mixture is greater than 95:5; and wherein the molar ratio of (i) to the total amount of diols is 0.9: 1.1 to 1.1:0.9; and wherein the phosphonate ester composition comprises at least one oligomeric species comprising 2 to 20 phosphorus atoms and at least one cyclic monomeric species comprising a single phosphorus atom, wherein the relative amount of the cyclic monomeric species relative to the amount of the oligomeric species is 8: 1 to 3: 1 by weight to improve Timken performance measured using D2782 and / or four-ball sintering point measured using D2783 and / or demulsibility measured using D1401 and / or stability of the lubricant composition.

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