Industrial gear lubricant

Abstract

The present technology includes the use of pour point depressants to improve the low temperature viscosity of industrial gear lubricating compositions containing Group IV base oils. The present technology provides an industrial gear lubricating composition comprising a Group IV base oil, a sulfurized olefin, a phosphorus-containing agent, and a poly (meth) acrylate polymer pour point depressant.

Description

Background Technology

[0001] Industrial gearboxes are subjected to extreme operating conditions that can lead to damage, such as wear and tear on internal gearbox components. This damage can shorten the lifespan of industrial gearboxes and result in costly and prolonged maintenance and repair costs, unplanned downtime of equipment containing industrial gearboxes, and similar problems.

[0002] Due to the extreme conditions encountered in some industrial gearboxes, low-temperature viscosity is an important property of lubricant compositions used in industrial gears. However, some additives used to improve other properties of lubricants may negatively affect the low-temperature viscosity of certain base oils. Therefore, there is a need to develop industrial gear lubricant compositions containing additives necessary to protect gearboxes from wear and other harmful conditions while maintaining low-temperature viscosity. Summary of the Invention

[0003] The present invention provides a lubricating composition for industrial gears. The industrial gear lubricating composition comprises an added amount of a poly(meth)acrylate polymer, the poly(meth)acrylate polymer containing at least 10 mol% of one or more alkyl(meth)acrylate monomers having alkyl groups containing 16 or more carbon atoms.

[0004] In one embodiment, the lubricating composition of the present invention comprises (a) a base oil comprising at least 75% by weight of a Group IV base oil; (b) at least one sulfurized olefin present in an amount providing at least 1000 ppm of sulfur to the composition; (c) one or more phosphorus-containing agents in an amount providing at least 100 ppm of phosphorus to the composition; and (d) a poly(meth)acrylate polymer comprising at least 10 mol% of one or more alkyl(meth)acrylate monomers having alkyl groups containing 16 or more carbon atoms.

[0005] The present invention also provides a method for lubricating industrial gears, a method for improving the low-temperature viscosity of an industrial gear lubricant, and the use of poly(meth)acrylate polymer additives as described herein for improving the low-temperature viscosity of lubricating compositions.

[0006] It has been observed that certain additives commonly used in industrial gear lubrication compositions have a detrimental effect on the low-temperature fluidity of the composition. However, the present invention unexpectedly provides improved low-temperature fluidity of lubrication compositions superior to those with similar additives, as indicated by Brinell viscosity measurements (ASTM D2983) at -40°C. Detailed Implementation

[0007] The preferred features and implementation schemes will now be described in a non-restrictive manner.

[0008] This invention relates in part to a lubricating composition comprising: (a) a base oil comprising at least 75% by weight of a Group IV base oil; (b) at least one sulfurized olefin present in an amount providing at least 1000 ppm of sulfur to the composition; (c) one or more phosphorus-containing agents in an amount providing at least 100 ppm of phosphorus to the composition; and (d) a poly(meth)acrylate polymer comprising at least 10 mol% of one or more alkyl(meth)acrylate monomers having alkyl groups containing 16 or more carbon atoms.

[0009] base oil

[0010] In this invention, the base oil is present in a dominant amount for the lubricant composition, or in a concentrate-forming amount for the concentrate and / or additive composition.

[0011] Oils with lubricating viscosity can also be defined as specified in the American Petroleum Institute (API) Base Oil Interchangeability Guidelines. The five groups of base oils are as follows: Group I (sulfur content >0.03 wt% and / or <90 wt% saturated oil, viscosity index 80-120); Group II (sulfur content >0.03 wt% and / or <90 wt% saturated oil, viscosity index 80-120); Group III (sulfur content >0.03 wt% and / or <90 wt% saturated oil, viscosity index 80-120); Group IV (sulfur content >0.03 wt% and / or <90 wt% saturated oil, viscosity index 80-120); Group V (sulfur content >0.03 wt% and / or <90 wt% saturated oil, viscosity index 80-120); Group VI (sulfur content >0.03 wt% and < 0.03% by weight, and > 90% wt% saturated content, viscosity index 80-120; Category III (sulfur content) < 0.03% by weight, and > 90% wt% saturated material, viscosity index > 120); Class IV (all polyalphaolefins (PAOs), such as PAO-2, PAO-4, PAO-5, PAO-6, PAO-7, or PAO-8); and Class V (covering "all others").

[0012] In this invention, suitable oils include synthetic lubricating oils and natural lubricating oils, as well as mixtures thereof. In a fully formulated lubricant, the oil having a lubricating viscosity is typically present in a dominant amount (i.e., greater than 50% by weight). Typically, the oil having a lubricating viscosity is present in an amount of 75% to 98% by weight of the whole composition, and often greater than 80% by weight.

[0013] The base oils with lubricating viscosity used in this invention may include natural and synthetic oils, oils derived from hydrocracking, hydrogenation, and hydrorefining, unrefined oils, refined oils, and re-refined oils, or mixtures thereof. Unrefined oils are oils typically obtained directly from natural or synthetic sources without (or with minimal) further purification. Refined oils are similar to unrefined oils, except that they have undergone further processing in one or more purification steps to improve one or more properties. Purification techniques are known in the art and include solvent extraction, double distillation, acid or alkali extraction, filtration, percolation, and similar processes. Re-refined oils, also known as regenerated oils or reprocessed oils, are obtained through processes similar to those used to obtain refined oils. Re-refined oils are often processed using techniques designed to remove waste additives and oil decomposition products.

[0014] Natural oils that can be used as lubricating oils include animal and vegetable oils (e.g., castor oil, lard), mineral lubricants (such as liquid petroleum), and solvent-treated or acid-treated alkanes, cycloalkanes, or mixed alkanes-cycloalkanes, as well as oils derived from coal or shale or mixtures thereof.

[0015] The industrial gear lubricant of the present invention comprises a synthetic oil having a lubricating viscosity. The synthetic oil may be saturated or unsaturated. Synthetic oils having a lubricating viscosity include hydrocarbon oils such as polymeric olefins and interpolymeric olefins (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); polybenzenes (e.g., biphenyl, terphenyl, alkylated polyphenylene); esters and complex esters of acids derived from plant sources (e.g., diesters, monoesters, saturated polyol esters, trimethylpropane carboxylate esters, neopolyol carboxylate esters, neopentyl glycol esters, pentaerythritol esters, etc.); alkylated diphenyl ethers and alkylated diphenyl sulfides, and their derivatives, analogues, and homologues, or mixtures thereof. In some embodiments, the oil with lubricating viscosity used in this invention is a synthetic oil comprising polymerized polyisobutylene, and in some embodiments, the oil with lubricating viscosity used in this invention is a synthetic oil comprising polymerized polyisobutylene and polyalphaolefin.

[0016] Another type of synthetic oil with lubricating viscosity includes polyol esters, dicarboxylic acid esters, phosphoric acid-containing liquid esters (such as tricresyl phosphate, trioctyl phosphate, and diethyl decane phosphate), or polytetrahydrofuran. Conventional synthetic oils with lubricating viscosity also include those prepared by the Fischer-Tropsch reaction and are typically hydroisomerized Fischer-Tropsch hydrocarbons or waxes. In one embodiment, oils with lubricating viscosity can be prepared via a Fischer-Tropsch gas-liquid synthesis process, as well as other gas-liquid oils.

[0017] This invention comprises a base oil containing at least 75% by weight of Group IV base oil. In another embodiment, the base oil contains at least 85% Group IV base oil. In yet another embodiment, the base oil consists of Group IV base oils. Group IV oils that can be used as base oils in this invention include polyalphaolefin base oils. In another embodiment, the base oil is a mixture of Group IV base oils, wherein the mixture comprises one or more polyalphaolefin base oils with a kinematic viscosity between 4 cSt and 10 cSt at 100°C and one or more polyalphaolefin base oils with a kinematic viscosity greater than 50 cSt at 100°C.

[0018] Viscosity grades suitable for industrial gear lubrication compositions are typically ISO 68 to 1000. The viscosity of each grade is the kinematic viscosity at 40°C + / - 10%, as measured by ASTM D445 or ISO 3104. Therefore, ISO 46, which is 46 cSt at 40°C, can have kinematic viscosities ranging from 41.4 cSt to 50.6 cSt at 40°C. The ISO viscosity classification system is defined in ISO 3448. Exemplary viscosity grades are listed in the table below:

[0019] Therefore, in some embodiments, the ISO viscosity grade (VG) of the lubricating composition of the present invention may be 68 to 1000.

[0020] The various oils with lubricating viscosities described can be used alone or in combination. Base oils can be used in the described industrial gear lubricants in the range of about 80% by weight to about 98% by weight, or 80% by weight, 85% by weight, 90% by weight, 95% by weight, 97% by weight, or even 97.5% by weight or 98% by weight, or up to 90% by weight, 95% by weight, 97% by weight, 97.5% by weight, or even 98% by weight.

[0021] Sulfated olefins

[0022] Sulfurized olefins are well-known commercial materials that can be prepared by reacting a single reactant or a mixture of suitable reactants with a sulfur source. The sulfidation reaction is typically carried out at elevated temperatures (e.g., 50°C to 350°C or 100°C to 200°C), under effective stirring, and often in an inert atmosphere such as nitrogen, optionally in the presence of an inert solvent. The sulfiding agent may include elemental sulfur (preferably), hydrogen sulfide, sulfur halides, sodium sulfide, and mixtures of hydrogen sulfide and sulfur or sulfur dioxide. Typically, the amount of sulfur or sulfiding agent used is calculated based on the total olefinic unsaturated groups of the mixture. Typically, 0.5 to 3 moles of sulfur are used per mole of olefinic bond. One type of sulfidized olefin can be prepared according to the detailed teachings of U.S. Patent No. 4,957,651.

[0023] In the case of sulfided alkenes, the reactants can be alkenes. Sulfidable alkenes are diverse in nature and, broadly speaking, are those containing at least one alkene double bond, defined as a non-aromatic double bond; that is, a double bond connecting two aliphatic carbon atoms. In its broadest sense, alkenes can be formed from formula R... 1 R 2 C=CR 3 R 4 Define, where R 1 R 2 R 3 and R 4 Each of these can be a hydrogen or organic group. Generally speaking, the non-hydrogen R group in the above formula can be represented by a group such as -C(R). 5 3. -COOR 5 -COOM, -X, -YR 5 The -Ar group satisfies the condition that each R 5 Independently hydrogen, alkyl, alkenyl, aryl, substituted alkyl, substituted alkenyl, or substituted aryl, provided that any two Rs are hydrogen, alkyl, alkenyl, or aryl. 5 The group can be alkylene or substituted alkylene, thereby forming a ring of up to 12 carbon atoms; M is an equivalent metal cation (preferably of type I or II, for example, sodium, potassium, barium, calcium); X is a halogen (for example, chlorinated, brominated, or iodinated); Y is oxygen or divalent sulfur; Ar is an aryl or substituted aryl group of up to 12 carbon atoms. R 1 R 2 R 3 and R 4 Any two of them can also be used together to form alkylene or substituted alkylene groups, meaning that olefinic compounds can be alicyclic.

[0024] Alkenes are typically alkenes in which each of the aforementioned R groups, which is not hydrogen, is independently alkyl, alkenyl, or aryl. Mono-alkenes and dienes (especially the former) are preferred, and terminal mono-alkenes are particularly preferred; that is, wherein R... 3 and R 4 It is hydrogen and R 1 and R 2 Compounds that are alkyl or aryl, especially those alkyl groups having 1 to 30, or 1 to 16, or 1 to 8, or 1 to 4 carbon atoms (i.e., olefins that are aliphatic). Alkenes having 3 to 30 or 3 to 16 (usually less than 9) carbon atoms may also be used.

[0025] Isobutylene, diisobutylene, butene, propylene and their dimers, trimers and tetramers, and mixtures thereof can be used as alkene compounds for sulfidation, and can be used as terpenoid compounds (i.e., those having the empirical formula C). 10 H 16 Various isomers of terpenes and their various synthetic and naturally occurring oxygen-containing derivatives.

[0026] Other sulfurized olefins include those derived from natural sources such as sulfurized vegetable oils and sulfurized lard (i.e., sulfurized oils typically of animal origin). Examples of natural oils from which such sulfurized olefins can be derived include, but are not limited to, coconut oil, corn oil, cottonseed oil, castor oil, sunflower oil, olive oil, palm oil, peanut oil, rapeseed oil, safflower oil, sesame oil, soybean oil, tallow, lard, fatty acids, and mixtures thereof. Preferred organic portions of sulfurized vegetable oils are those derived from sunflower oil, olive oil, and rapeseed oil.

[0027] In one embodiment, the sulfur component of the additive package of this technology may comprise biodegradable sulfurized olefins derived from natural sources such as sulfurized vegetable oils or sulfurized lard.

[0028] The total sulfur level in sulfurized olefins can be measured according to ASTM D129Q. Whether biodegradable or non-biodegradable, sulfurized olefins may have “high,” “nominal,” or “minimum” levels of total sulfur. A “high” sulfur level means that the sulfurized olefin contains about 30% by weight or more of sulfur. A “nominal” sulfur level means that the sulfurized olefin contains about 10% by weight to about 30% by weight of sulfur, and a “minimum” sulfur level means that the sulfurized olefin contains less than about 10% by weight of sulfur, or about 0.01% by weight to about 10% by weight of sulfur.

[0029] In this invention, sulfurized olefins may be included in a fully formulated lubricant in an amount providing at least 1000 ppm of sulfur to the composition. In some embodiments, sulfurized olefins are present in an amount providing 1000 ppm to 3000 ppm or even 1500 ppm to 2500 ppm of sulfur to the lubricant composition.

[0030] Phosphorus-containing reagents

[0031] The industrial gear lubricant composition of the present invention further contains a phosphorus-containing component, which may be a phosphorus-containing anti-wear agent and / or extreme pressure agent. Such phosphorus-containing agents commonly used in industrial gear lubricants are mostly partially or fully esterified phosphoric acid. These phosphorus-containing agents include, but are not limited to, acidic phosphonates, hydrogen phosphonites, phosphonates, phosphate esters, phosphonates, hypophosphonates, and phosphoramides. Anti-wear agents may also include mono- and di- and tri-alkyl phosphonites; mono- and di- and tri-alkyl phosphonates; monothiophosphonates, di- and tri-alkyl phosphonates, dithiophosphonates, dithiophosphonates, trithiophosphonates, trithiophosphonates, monothiophosphonates, dithiophosphonates, trithiophosphonates, monothiophosphonates, dithiophosphonates, trithiophosphonates, monothiophosphonates, dithiophosphonates, trithiophosphonates, monothiophosphonates, dithiophosphonates, trithiophosphonates, monothiophosphonates, dithiophosphonates, trithiophosphonates, monothiophosphonates, dithiophosphonates, trithiophosphonates, monothiophosphonates, dithiophosphonates, and trithiophosphonates; monothiophosphonites. Esters, monothiophosphonite dialkyl esters, monothiophosphonite trialkyl esters, dithiophosphonite monoalkyl esters, dithiophosphonite dialkyl esters, dithiophosphonite trialkyl esters, trithiophosphonite monoalkyl esters, trithiophosphonite dialkyl esters, trithiophosphonite trialkyl esters, tetrathiophosphonite monoalkyl esters, tetrathiophosphonite dialkyl esters, tetrathiophosphonite trialkyl esters; various alkylphosphonates and thiophosphonates; dialkyl dithiophosphates and their derivatives, as well as various alkylphosphonates and thiophosphonates, etc.

[0032] Examples of phosphonites include monoalkyl-substituted, dialkyl-substituted, or trialkyl-substituted phosphonites, as well as those having at least one hydrocarbon group comprising four or more carbon atoms, as shown in the following formula: or

[0033] Where R 8 R 6 and R 7 At least one of them may be a hydrocarbon group containing at least four carbon atoms, and the remainder may be hydrogen atoms or hydrocarbon groups. In one embodiment, R 8 R 6 and R 7 All are hydrocarbon groups. These hydrocarbon groups can be alkyl, cycloalkyl, aryl, acyclic, or mixtures thereof. In a configuration containing all three groups R... 8 R 6 and R 7 In the formula, the compound can be a trialkyl-substituted phosphonite, i.e., R 8 R 6 and R 7 All are hydrocarbon groups. The alkyl group can be straight-chain or branched, but is usually straight-chain, and can be saturated or unsaturated, but is usually saturated. R 8 R 6 and R 7Examples of alkyl groups include octyl, 2-ethylhexyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecanyl, octadecyl, octadecenyl, nonadecanyl, eicosyl, or mixtures thereof.

[0034] This includes all amine salts that can form with the aforementioned phosphorus-containing reagents. Amines can be primary, secondary, tertiary, acyclic, or cyclic amines, monoamines or polyamines. They can also be heterocyclic. Amines with aliphatic properties are generally preferred. Specific examples of amines used to produce 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, heptadecanylamine, octadecylamine, decenylamine, dodecenylamine, palmitamide, oleylamine, linoleylamine, di-isoamylamine, di-octylamine, di-(2-ethylhexyl)amine, dilaurylamine, cyclohexylamine, 1,2-propenylamine, 1,3-propanediamine, diethylenetriamine, triethylenetetramine, ethanolamine, triethanolamine, trioctylamine, pyridine, morpholine, 2-methylpiperazine, 1,2-bis(N-piperazinyl-ethane), 1,2-diamine, tetraiminooctadecene, triaminooctadecene, N-hexylaniline, etc. These amines may also be triazoles or triazole derivatives.

[0035] In the implementation scheme, the amine salts of the phosphorus-containing reagent are those shown in the following formula:

[0036] Where R 9 and R 10 Independently, R is an aliphatic group containing approximately 4 to a maximum of approximately 24 carbon atoms. 22 and R 23 Independently, it is a hydrogen atom or an aliphatic group containing about 1 to at most about 18 aliphatic carbon atoms, where the sum of m and n is 3 and X is an oxygen atom or a sulfur atom. In a preferred embodiment, R 9 Containing approximately 8 to a maximum of 18 carbon atoms, R 10 for:

[0037] Where R 11 R is an aliphatic group containing approximately 6 to a maximum of approximately 12 carbon atoms. 22 and R 23 X is a hydrogen atom, m is 2, n is 1, and X is an oxygen atom.

[0038] Specific examples of phosphorus-containing reagents may include tricresyl phosphate, tributyl phosphite, triphenyl phosphite, 2-ethylhexyl phosphate, diisobutylhydrogen phosphite, diisopropyl dithiophosphate, diphenyl phosphate, aliphatic phosphites, etc. Some embodiments of phosphorus-containing reagents may include dialkyl phosphates and diaryl phosphates, as well as their amine salts. Arylphosphonates are also considered, such as commercially available Irgalube from Ciba. ™ 349 and alkyl acid phosphonates, including di-2-ethylhexylphosphonic acid and / or mono-2-ethylhexylphosphonic acid.

[0039] The phosphorus-containing reagent (anti-wear agent or extreme pressure agent) in this invention can be used in an amount sufficient to deliver 100 ppm to 1000 ppm, or 200 ppm to 500 ppm, or even 300 ppm to 450 ppm of phosphorus to the lubricant composition.

[0040] Gather ( methyl ) Acrylic polymer additives

[0041] The lubricating composition of the present invention also contains a poly(meth)acrylate polymer additive, which may also be referred to as a pour point depressant. Pour point depressants can be added to some lubricating oils to prevent the formation of wax crystals in the lubricant at low temperatures. However, Group IV base oils are not considered to contain waxes that will crystallize. Therefore, the use of pour point depressant additives in lubricating oil compositions primarily made from Group IV base oils is unknown.

[0042] Pour point depressants are known in the art and include, but are not limited to, esters of maleic anhydride-styrene copolymers, polymethacrylates; polyacrylates; polyacrylates; condensation products of haloparaffins and aromatic compounds; vinyl carboxylate polymers; and terpolymers of dialkyl fumarate, vinyl esters of fatty acids, ethylene-vinyl acetate copolymers, alkylphenol-formaldehyde condensation resins, alkyl vinyl ethers, and mixtures thereof. In one embodiment, a pour point depressant polymer is used, which comprises a poly(meth)acrylate polymer, wherein the poly(meth)acrylate polymer comprises at least 10 mol% of one or more alkyl(meth)acrylate monomers having alkyl groups containing 16 or more carbon atoms. In one embodiment, the alkyl(meth)acrylate monomer having alkyl groups containing 16 or more carbon atoms comprises stearyl methacrylate. As used herein, the term "(meth)acrylate" means methacrylate or acrylate, as will be readily understood.

[0043] In one embodiment, the poly(meth)acrylate polymer is prepared from a monomer mixture comprising (meth)acrylate monomers containing alkyl groups of different lengths. The (meth)acrylate monomers may contain alkyl groups that are straight-chain, branched, or aromatic groups.

[0044] In one embodiment of the invention, a pour point depressant additive is used, the additive comprising a poly(meth)acrylate polymer, wherein the poly(meth)acrylate polymer comprises at least 10 mol% of one or more alkyl(meth)acrylate monomers having alkyl groups containing 16 or more carbon atoms. In one embodiment, the poly(meth)acrylate polymer additive comprises 10 mol% to 50 mol%, or 15 mol% to 35 mol%, or even 20 mol% to 30 mol% of one or more alkyl(meth)acrylate monomers having alkyl groups containing 16 or more carbon atoms, or 16 to 20 carbon atoms, or even 16 to 18 carbon atoms. In one embodiment, the poly(meth)acrylate polymer additive comprises 10 mol% to 50 mol%, or 15 mol% to 35 mol%, or even 20 mol% to 30 mol% of stearyl methacrylate.

[0045] The poly(meth)acrylate polymer additive may also contain at least 50 mol%, or 50 mol% to 90 mol%, or 65 mol% to 85 mol%, or even 70 mol% to 80 mol% of alkyl (meth)acrylate monomers having alkyl groups containing 12 to 15 carbon atoms. In some embodiments, the poly(meth)acrylate polymer used in this invention may also contain up to 10 mol% of any other monomers capable of copolymerizing with alkyl (meth)acrylate monomers having alkyl groups containing 16 or more carbon atoms. For example, the poly(meth)acrylate polymer additive may optionally contain 0 mol% to 10 mol% or even 0.5 mol% to 5 mol%, or even 1 mol% to 3 mol% of (meth)acrylate monomers having alkyl groups containing 1 to 10 carbon atoms, such as 4 to 8 carbon atoms. In another embodiment, the poly(meth)acrylate polymer additive may optionally contain 0 mol% to 10 mol% or even 0.5 mol% to 5 mol% or even 1 mol% to 3 mol% of a dispersant monomer containing heteroatoms selected from nitrogen or sulfur. In another embodiment, the poly(meth)acrylate polymer additive may optionally contain 0 mol% to 10 mol% or even 0.5 mol% to 5 mol% or even 1 mol% to 3 mol% of an aromatic monomer, such as benzyl methacrylate, phenyl methacrylate, styrene, or terephthalic acid methacrylate.

[0046] In one embodiment, the poly(meth)acrylate polymer may comprise a dispersant monomer; the dispersant monomer includes those monomers that can be copolymerized with (meth)acrylate monomers and contain one or more heteroatoms in addition to the carbonyl group of the (meth)acrylate. The dispersant monomer may contain a nitrogen-containing group, an oxygen-containing group, or a mixture thereof. For example, the dispersant monomer may comprise (meth)acrylamide or a nitrogen-containing (meth)acrylate monomer. Examples of suitable nitrogen-containing compounds include N,N-dimethylacrylamide, N-vinylcarbamates such as N-vinylformamide, vinylpyridine, N-vinylacetamide, N-vinylpropionamide, N-vinylhydroxyacetamide, N-vinylimidazolium, N-vinylpyrrolidone, N-vinylcaprolactam, dimethylaminoethyl acrylate (DMAEA), dimethylaminoethyl methacrylate (DMAEMA), dimethylaminobutylacrylamide, dimethylaminopropyl methacrylate (DMAPMA), dimethylaminopropylacrylamide, dimethylaminopropylmethacrylamide, dimethylaminoethylacrylamide, or mixtures thereof.

[0047] In one embodiment, the poly(meth)acrylate comprises a block copolymer or a graded block copolymer. The block copolymer is formed from a monomer mixture comprising one or more (meth)acrylate monomers, wherein, for example, a first (meth)acrylate monomer forms discrete blocks of a polymer linked to second discrete blocks of a polymer formed from a second (meth)acrylate monomer. While the block copolymer has substantially discrete blocks formed from monomers in the monomer mixture, the graded block copolymer may consist of a relatively pure first monomer at one end and a relatively pure second monomer at the other end. The middle of the graded block copolymer is more of a gradient composition of the two monomers.

[0048] In one embodiment, the poly(meth)acrylate polymer used in this invention can have an architecture selected from linear, branched, hyperbranched, crosslinked, star-shaped (also referred to as “radial”), or combinations thereof. Star-shaped or radial refers to a multi-arm polymer. Such polymers include (meth)acrylate-containing polymers comprising three or more arms or branches, and in some embodiments, containing at least about 20, or at least 50, 100, 200, 350, 500, or 1000 carbon atoms. The arms are typically linked to a multivalent organic moiety that acts as a “core” or “coupling agent.” Multi-arm polymers can be referred to as radial or star-shaped polymers or even “comb” polymers, or polymers having multiple arms or branches in other ways as described herein.

[0049] Star polymers can be prepared by many known polymerization methods, including atom transfer radical polymerization (ATRP), reversible addition-fragmentation chain transfer (RAFT) polymerization, nitride-controlled polymerization (NMP), or anionic polymerization. A detailed discussion of ATRP can be found in the *Handbook of Radical Polymerization*, edited by Krzysztof Matyjaszewski and Thomas P. Davis. Handbook of Radical Polymerization The reaction scheme is given in Chapter 11, pages 523-628, of John Willie & Sons, 2002 (hereinafter referred to as Matyjaszewski). See specifically reaction scheme 11.1 on page 524, reaction scheme 11.4 on page 556, reaction scheme 11.7 on page 571, reaction scheme 11.8 on page 572, and reaction scheme 11.9 on page 575.

[0050] When the core of the polymer contains the functional group of formula (I) above, RAFT polymerization can be used, where Y is composed of -SC(=S)-R 5 It means that R 5 It may be an alkyl group containing 1 to 20 carbon atoms. The Y functional group may be derived from or be part of a chain transfer agent. In some embodiments, the core portion comprises a functional group derived from a compound containing a thiocarbonyl thio group and a free radical leaving group (typically from a chain transfer agent), such as those disclosed in paragraph 0146 of U.S. Application 2007 / 0244018.

[0051] Examples of RAFT chain transfer agents include benzyl 1-(2-pyrrolidone)dithiocarbamate, benzyl (1,2-benzoimide)dithiocarbamate, 2-cyanopropyl-2-yl 1-pyrrolidinyl dithiocarbamate, 2-cyanobutyl-2-yl 1-pyrrolidinyl dithiocarbamate, benzyl 1-imidazolium-dithiocarbamate, N,N-dimethyl-S-(2-cyanopropyl-2-yl)dithiocarbamate, N,N-diethyl-S-benzyl dithiocarbamate, cyanomethyl 1-(2-pyrrolidone)dithiocarbamate, cumyl dithiobenzoate, N,N-diethyl-S-(2-ethoxycarbonylpropyl-2-yl)dithiocarbamate, O-ethyl-S-(1-phenylethyl)xanthate, O-ethyl-S-(2- (ethoxycarbonyl)prop-2-yl)xanthate, O-ethyl-S-(2-cyanoprop-2-yl)xanthate, O-ethyl-S-(2-cyanoprop-2-yl)xanthate, O-ethyl-S-cyanomethylxanthate, O-phenyl-S-benzylxanthate, O-pentafluorophenyl-S-benzylxanthate, 3-benzylthio-5,5-dimethylcyclohex-2-en-1-thione or 3,3-di(benzylthio)-prop-2-en-dithiobenzyl ester, S,S'-bis-(α,α'-disubstituted-α''-acetic acid)-trithiocarbonate, S,S'-bis-(α,α'-disubstituted-α''-acetic acid)-trithiocarbonate or S-alkyl-S'-(-(α,α'-disubstituted-α''-acetic acid)- Trithiocarbonate, dithiobenzoic acid, 4-chlorodithiobenzoic acid, benzyl dithiobenzoate, 1-phenylethyl dithiobenzoate, 2-phenylpropyl-2-yl dithiobenzoate, 1-acetoxyethyl dithiobenzoate, hexa(thiobenzoylthiomethyl)benzene, 1,4-bis(thiobenzoylthiomethyl)benzene, 1,2,4,5-tetra(thiobenzoylthiomethyl)benzene, 1,4-bis-(2-(thiobenzoylthio)propyl-2-yl)benzene, 1-(4-methoxyphenyl)ethyl dithiobenzoate, benzyl dithioacetate, ethoxycarbonyl methyl dithioacetate, 2-(ethoxycarbonyl)propyl-2-yl dithiobenzoate, 2,4,4-trimethylpentyl dithiobenzoate Esters, 2-(4-chlorophenyl)prop-2-yl dithiobenzoate, 3-vinylbenzyl dithiobenzoate, 4-vinylbenzyl dithiobenzoate, S-benzyl diethoxyphosphine dithiocarboxylate, tert-butyl trithioperbenzoate, 2-phenylprop-2-yl 4-chlorodithiobenzoate, 2-phenylprop-2-yl 1-dithionaphthoic acid, dithiobenzoate 4-cyanopentanoate, dibenzyl tetrathioterephthalate, dibenzyl trithiocarbonate, carboxymethyl dithiobenzoate, or poly(ethylene oxide) having dithiobenzoate end groups, or mixtures thereof. RAFT polymerization is also described in more detail in Chapter 12 of Matyjaszewski's work, pages 629-690, and especially pages 664-665.

[0052] For example, a star polymer may comprise: (i) a core moiety comprising a polyvalent (meth)acrylic acid monomer, an oligomer or polymer thereof, or a polyvalent divinyl nonacrylic acid monomer, an oligomer or polymer thereof; and (ii) at least three arms of polymerized alkyl (meth)acrylic acid esters. In one embodiment, the arms of the star polymer may be random copolymers, or more preferably, block or graded block copolymers for the purposes of this invention. The core moiety may comprise functional groups of formula (Ia):

[0053] Where E is independently another part of the core, a polymer arm or monomeric material, or another structural unit as defined in formula (Ia); R 1 A is hydrogen or a straight-chain or branched alkyl group containing 1 to 5 carbon atoms; A is nitrogen or oxygen; and Y is a free radical leaving group selected from the group consisting of one or more atoms or atomic groups that can be transferred via a free radical mechanism under polymerization conditions, a halogen, a nitrooxy group, or a dithioester group. Similar to structure (Iz), the bond shown on the left side of structure (Ia) can typically be attached to the Z group, where Z is a polymeric group, such as a crosslinked polymeric group.

[0054] Examples of polyvalent unsaturated (meth)acrylate monomers that can be used to form polymer cores include ethylene glycol diacrylate, ethylene glycol di(meth)acrylate, diethylene glycol diacrylate, diethylene glycol di(meth)acrylate, glycerol diacrylate, glycerol triacrylate, mannitol hexaacrylate, cyclohexanediol diacrylate, 1,4-phenylene glycol di(meth)acrylate, neopentyl glycol diacrylate, 1,3-propanediol diacrylate, 1,5-pentanediol di(meth)acrylate, bis-acrylates and bis-acrylates of polyethylene glycol with a molecular weight of 200-4000. (Meth)acrylates, polycaprolactone diacrylate, 1,1,1-trimethylolpropane diacrylate, 1,1,1-trimethylolpropane triacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, triethylene glycol diacrylate, triethylene glycol diacrylate, 1,1,1-trimethylolpropane tri(meth)acrylate, hexamethylene glycol diacrylate, hexamethylene glycol diacrylate, vinyl methacrylate, allyl methacrylate, or alkylene bis-(meth)acrylamide.

[0055] Examples of polyvalent or divalent unsaturated non-acrylic monomers that can be used to form polymer cores include divinylbenzene, ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, poly(ethylene glycol) divinyl ether, butanediol divinyl ether, and bicyclo[2.2.1]hept-2,5-diene.

[0056] The amount of the core or coupling agent can be suitable for providing the previously prepared polymeric arm to the core in monomeric, oligomeric, or polymeric form to provide a star polymer. As mentioned above, even though several variables may be involved, those skilled in the art can easily determine the appropriate amount with minimal experimentation. For example, if an excess of coupling agent is used, or if excess unreacted monomers from the formation of the polymeric arm remain in the system, crosslinking may occur instead of star formation. Typically, the molar ratio of polymeric arm to coupling agent can be from 50:1 to 1.5:1 (or 1:1), or 30:1 to 2:1, or 10:1 to 3:1, or 7:1 to 4:1, or 4:1 to 1:1. In other embodiments, the molar ratio of polymeric arm to coupling agent can be from 50:1 to 0.5:1, or 30:1 to 1:1, or 7:1 to 2:1. The desired ratio can also be adjusted to take into account the length of the arm; longer arms sometimes allow or require more coupling agent than shorter arms.

[0057] The arms of the star polymer may themselves be (meth)acrylate polymers or oligomers containing (meth)acrylate moieties condensed with alcohol moieties to provide alkyl groups. The arms of the star polymers described herein may be block or graded block copolymers as described above. In one embodiment, the star polymer comprises at least 3 arms, in another embodiment at least 5 arms, in another embodiment at least 7 arms, in another embodiment at least 10 arms, such as 12 to 100, 14 to 50, or 16 to 40 arms. In one embodiment, the star polymer may have 120 arms or less, in another embodiment 80 arms or less, in another embodiment 60 arms or less. In some embodiments, each star may have 3 to 20, 5 to 20, or 6 to 15, or 7 to 8 arms. Such multi-armed polymers and their preparation are described in more detail in WO2015 / 142482, September 24, 2015, specifically in paragraphs 0017 to 0064.

[0058] The molecular weight of poly(meth)acrylate polymers can be determined using known methods, such as gel permeation chromatography (“GPC”) using polystyrene standards. Methods for determining the molecular weight of polymers are well-known. These methods are described, for example, in: (i) PJ Flory, "Principles of Polymer Chemistry", Cornell University Press 91953), Chapter VII, pp. 266–315; or (ii) "Macromolecules, an Introduction to Polymer Science", edited by FA Bovey and FH Winslow, Academic Press (1979), pp. 296–312.

[0059] The weight-average molecular weight (M) of linear poly(meth)acrylates of the present invention as described herein, in random, block, or other forms, is... w The range can be from 1,000 Daltons to 400,000 Daltons, or from 5,000 Daltons to 50,000 Daltons, or even from 5,000 Daltons to 200,000 Daltons, or even from 5,000 Daltons to 150,000 Daltons, or even from 8,000 Daltons to 100,000 Daltons, or from 10,000 Daltons to 80,000 Daltons.

[0060] The radial, crosslinked, or star-shaped copolymers of the present invention can be derived from linear random or diblock copolymers having the molecular weights described above. The weight-average molecular weight of the star polymers of the present invention can be from 10,000 Daltons to 1,500,000 Daltons, or from 40,000 Daltons to 1,000,000 Daltons, or from 300,000 Daltons to 850,000 Daltons.

[0061] In one embodiment, the poly(meth)acrylate polymer used in the present invention comprises or is composed of a linear poly(meth)acrylate polymer.

[0062] Other additives

[0063] Industrial gear lubricants may contain other additive components suitable for industrial gear lubricants. Any combination of conventional additive components suitable for industrial gear applications may be used.

[0064] In addition to the aforementioned sulfurized olefins, phosphorus-containing reagents, and poly(meth)acrylate polymers, other additive components that may be present in the industrial gear additive package include, but are not limited to, foam inhibitors, demulsifiers, antioxidants, dispersants, metal passivators (such as copper passivators), phosphorus-containing anti-wear agents, viscosity modifiers, detergents, or some mixture thereof. Other additive components may each be present in the range of 50 ppm, 75 ppm, 100 ppm, or even 150 ppm up to 10 wt%, 9 wt%, 8 wt%, 7 wt%, 6 wt%, 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%, where the wt% values ​​are relative to the individual components of a fully formulated industrial gear lubricant. However, it should be noted that when considered separately from oils with lubricating viscosity, some additives (including viscosity-modifying polymers, which may alternatively be considered part of oils with lubricating viscosity) may be present in higher amounts, including up to 30%, 40%, or even 50% by weight. Additives may be used alone or as a mixture thereof.

[0065] In one embodiment, the lubricating composition contains a branched hydrocarbon alcohol. The branched hydrocarbon group of the alcohol can be... - Branched and may contain 8 to 60, 8 to 30, or 8 to 16 carbon atoms. Examples of branched alcohols include, but are not limited to, 2-ethylhexanol, 2-butyloctanol, 2-hexyldecanol, 2-octyldodecanol, 2-decyltetradecanol, or mixtures thereof. Commercially available branched alcohols that can be used in this invention include Isofol, which is available from Sasol. ® Branched Guerbet alcohol.

[0066] Defoamers (also known as foam inhibitors) are known in the art and include, but are not limited to, silicone and non-silicone foam inhibitors. Examples of silicones include dimethyl silicone and polysiloxanes. Examples of non-silicone 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 may be present in the composition at 0.001% to 0.012% by weight, 0.004% by weight, or even 0.001% to 0.003% by weight.

[0067] Demulsifiers are those known in the art and include, but are not limited to, derivatives of propylene oxide, ethylene oxide, polyoxyenols, alkylamines, amino alcohols, diamines, or polyamines that react continuously with ethylene oxide or substituted ethylene oxide or mixtures thereof. Examples of demulsifiers include polyethylene glycol, polyethylene oxide, polypropylene oxide, (ethylene oxide-propylene oxide) polymers, and mixtures thereof. In some embodiments, the demulsifier is a polyether. The demulsifier may be present in the composition from 0.002% by weight to 0.2% by weight.

[0068] The compositions of this technology may also include rust inhibitors. Suitable rust inhibitors include alkylamine salts of dialkyl dithiophosphate, alkylamine salts of alkyl aromatic sulfonic acids and fatty carboxylic acids or their esters, nitrogen-containing carboxylic acid esters, ammonium sulfonates, imidazolines, monothiophosphates or esters or any combination thereof, or mixtures thereof.

[0069] Examples of alkylamine salts of dialkyl dithiophosphates in this technology include, but are not limited to, diheptyl, dioctyl, or dinonyl dithiophosphates with ethylenediamine, morpholine, or Primene. ™ 81R or the reaction products of mixtures thereof.

[0070] Suitable hydrocarbon amine salts of hydrocarbon aromatic sulfonic acids used in the rust inhibitor packages of this technology are represented by the following formula:

[0071] Cy can be a benzene ring or a naphthalene ring. R 12 It is a hydrocarbon group having about 4 to about 30 carbon atoms, preferably about 6 to about 25 carbon atoms, and more preferably about 8 to about 20 carbon atoms. z independently has 1, 2, 3, or 4, and most preferably z has 1 or 2. R 13 R 14 and R 15 Independently, it is hydrogen, a branched alkyl chain, or a straight-chain alkyl chain, and in some embodiments, R 13 R 14 and R 15 At least one or even both of them are hydrogen, and further, where R 13 R 14 and R 15 At least one of them is a hydrocarbon group containing at least 8 carbon atoms. Suitable for R 13 R 14 and R 15Examples of alkyl groups include, but are not limited to, butyl, sec-butyl, isobutyl, tert-butyl, pentyl, n-hexyl, sec-hexyl, n-octyl, 2-ethyl, hexyl, ethyl-hexyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecanyl, octadecyl, octadecenyl, nonadecanyl, eicosyl, or mixtures thereof. Examples of alkylamine salts of hydrocarbon aromatic sulfonic acids of this technology include, but are not limited to, ethylenediamine salts of dinonylnaphthalenesulfonic acid. Examples of suitable fatty carboxylic acids or their esters include glycerol monooleate and oleic acid.

[0072] Examples of suitable nitrogen-containing carboxylic acid esters include oleoylsarcosine. Rust inhibitors can be present in the range of 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 industrial gear lubricants. Rust inhibitors of this technology can be used alone or as mixtures thereof.

[0073] The compositions of this technology may also include metal passivators. Metal passivators are used to neutralize the catalytic effect of metals in industrial gear lubricants that promote oxidation. Suitable metal passivators include, but are not limited to, triazoles, tolyltriazoles, thiadiazoles, or combinations thereof, and their derivatives. Examples include benzotriazoles, benzimidazoles, 2-alkyldithiobenzimidazoles, 2-alkyldithiobenzothiazoles, 2-(N,N'-dialkyldithiocarbamoyl)benzothiazoles, 2,5-bis(alkyldithio)-1,3,4-thiadiazoles, 2,5-bis(N,N'-dialkyldithiocarbamoyl)-1,3,4-thiadiazoles, derivatives of 2-alkyldithio-5-mercaptothiadiazoles, or mixtures thereof. The amount of these additives in the total composition may be from 0.01% to 0.25% by weight. In some embodiments, the metal passivator is a hydrocarbon-substituted benzotriazole compound. The hydrocarbon-substituted benzotriazole compound comprises at least one of the following ring positions: 1-, 2-, 4-, 5-, 6-, or 7-benzotriazole. The hydrocarbon group contains about 1 to about 30 carbon atoms, preferably about 1 to about 15 carbon atoms, more preferably about 1 to about 7 carbon atoms, and most preferably, the metal passivator is 5-methylbenzotriazole alone or a mixture thereof. The metal passivator may be present in the range of 0.001% to 0.5% by weight, 0.01% to 0.04% by weight, or 0.015% to 0.03% by weight of the industrial gear lubricant. The metal passivator may also be present in the composition at 0.002% by weight or 0.004% by weight to 0.02% by weight. The metal deactivator may be used alone or as a mixture thereof.

[0074] Antioxidants may also be present, including (i) alkylated diphenylamines and (ii) substituted hydrocarbon monosulfides. In some embodiments, the alkylated diphenylamines of this technology are dinonylated diphenylamine and dioctylated diphenylamine. In some embodiments, the substituted hydrocarbon monosulfide includes n-dodecyl-2-hydroxyethyl sulfide, 1-(tert-dodecylthio)-2-propanol, or combinations thereof. In some embodiments, the substituted hydrocarbon monosulfide is 1-(tert-dodecylthio)-2-propanol. The antioxidant package may also contain hindered phenols. Examples of suitable hydrocarbon groups for the hindered phenol include, but are not limited to, 2-ethylhexyl or n-butyl esters, dodecyl, or mixtures thereof. Examples of methylene-bridged sterically 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 may be present in the composition at 0.01% to 6.0% by weight or 0.02% to 1% by weight. Additives may be present in the composition at 1% by weight, 0.5% by weight, or less.

[0075] In some embodiments, the industrial gear lubricant additives of this technology comprise nitrogen-containing dispersants, such as hydrocarbon-substituted nitrogen-containing additives. Suitable hydrocarbon-substituted nitrogen-containing additives include ashless dispersants and polymeric dispersants. Ashless dispersants are named as such because, when used, they do not contain metals and therefore generally do not contribute sulfated ash when added to lubricants. However, once they are added to lubricants that include metal-containing species, they can, of course, interact with the surrounding metals. Similarly, some derivatives of ashless dispersants can be derivatized and contain molecules that form ash, such as borate derivatives. Ashless dispersants are characterized by polar groups attached to relatively high molecular weight hydrocarbon chains. Examples of such substances include succinimidyl dispersants, Mannich dispersants, and their borate derivatives.

[0076] In one embodiment, the lubricating composition of the present invention may contain a detergent. In some embodiments, the detergent may be a metal-containing detergent. In some embodiments, the metal-containing detergent may be a calcium or magnesium detergent. In one embodiment, the metal-containing detergent may also be a highly alkaline detergent with a total base number in the range of 30 to 500 mg KOH / g equivalent. In another embodiment, the metal-containing detergent may be a neutral detergent with a total base number of 0 to 30, or even 0 to 10, or even 30 or lower, or even 10 or lower mg KOH / g equivalent. The detergent may be selected from sulfur-free phenolates, sulfur-containing phenolates, sulfonates, salicylates, salicylates, and mixtures thereof, or their borate equivalents. The detergent may be borated with a borater (such as boric acid), such as borated highly alkaline calcium sulfonate or magnesium sulfonate detergents, or mixtures thereof. The detergent may be present in the hydraulic composition at 0% to 5% by weight, or 0.001% to 1.5% by weight, or 0.005% to 1% by weight, or 0.01% to 0.5% by weight. In some embodiments, the lubricating composition of the present invention is substantially free of or contains no metal-containing detergent.

[0077] In some embodiments, the industrial gear additive package or the resulting industrial gear lubricant composition comprises a demulsifier, a corrosion inhibitor, a friction modifier, or a combination of two or more thereof. In some embodiments, the corrosion inhibitor comprises toluenetriazole. In other embodiments, the industrial gear additive package or the resulting industrial gear lubricant composition comprises one or more polysulfides; one or more phosphamide salts; one or more thiophosphates, one or more thiadiazoles, toluenetriazoles, polyethers and / or alkenylamines; one or more ester copolymers; one or more carboxylic acid esters; one or more succinimide dispersants, or any combination thereof.

[0078] In the industrial gear lubrication composition of the present invention, the oil having a lubricating viscosity may be present in amounts ranging from 80 wt%, 85 wt%, 90 wt%, 95 wt%, 97 wt%, or even 97.5 wt% or 98 wt%; the amount of sulfurized olefins is from about 0.1 wt% to about 0.9 wt%, or from about 0.2 wt% to about 0.8 wt%, or from about 0.4 wt% to about 0.6 wt%, and the amount of zinc dialkyl dithiophosphate is from about 0.05 wt% to about 0.8 wt%, or from about 0.1 wt% to about 0.6 wt%, or from about 0.15 wt% to about 0.5 wt%, or even from about 0.2 wt% to about 0.4 wt%. Preferably, the industrial gear lubrication composition contains up to about 6000 ppm of sulfur, of which no more than about 3000 ppm is delivered by sulfurized olefins.

[0079] The industrial gear lubricant of this technology meets the performance requirements of industrial gear lubricants and meets the standards set for environmental friendliness.

[0080] Industrial gear oils (IGOs) must maintain specific performance levels in typical bench tests that are part of well-known industrial gear certifications such as USS 224 and AGMA 9005-D94, which have recently been superseded by AGMA 9005-E02, DIN51517-3:2009-06, and Fives Cincinnati. For extreme pressure performance, bench tests include, for example, Fourball EP (ASTM D2783) and Timken (ASTM D2782). Other tests include four-ball abrasion (ASTM D4172), FZG scratch (DIN ISO 14635-1), copper corrosion protection (ASTM D130, ISO 2160), oxidation control (ASTM D2893, DIN EN ISO 4263-4, S-200), rust prevention (ASTM D665, ISO 7120), static seal compatibility (DIN EN ISO1817), demulsibility (ASTM D2711, ASTM D1401, ISO 6614), and foam control (ASTM D892, ISO 6247).

[0081] This invention includes a method for preparing the above-mentioned industrial gear lubricant and / or industrial gear additive concentrate. Such a method involves mixing the components together. No specific order or manner of addition is considered to significantly affect the results.

[0082] The present invention also includes a method of adding one of the industrial gear lubricants described herein to an industrial gearbox and then operating the industrial gearbox.

[0083] As used herein, the term "condensation product" is intended to encompass esters, amides, imides, and other materials of this kind that can be prepared by the condensation reaction of an acid or its reaction equivalent (e.g., an acid halide, anhydride, or ester) with an alcohol or amine, regardless of whether the condensation reaction actually takes place to directly produce the product. Thus, for example, a particular ester may be prepared by transesterification rather than directly by a condensation reaction. The resulting product is still considered a condensation product.

[0084] Unless otherwise stated, the amounts of each chemical component described do not include any solvents or diluents that are commonly found in commercial substances, i.e., based on active chemicals. However, unless otherwise stated, each chemical or composition mentioned herein should be interpreted as a commercial-grade substance that may contain isomers, byproducts, derivatives, and other such substances generally understood to be present in commercial-grade forms.

[0085] As used herein, the term "hydrocarbon substituent" or "hydrocarbon group" is used in its ordinary sense, as is well known to those skilled in the art. Specifically, it refers to a group having a carbon atom directly connected to the rest of the molecule and having predominantly hydrocarbon properties. Examples of hydrocarbon groups include: hydrocarbon substituents, including aliphatic, alicyclic, and aromatic substituents; substituted hydrocarbon substituents, i.e., substituents containing a non-hydrocarbon group that, in the context of this art, does not alter the predominantly hydrocarbon properties of the substituent; and heterosubstituents, i.e., substituents that similarly have predominantly hydrocarbon properties but contain non-carbons in a ring or chain. A more detailed definition of the term "hydrocarbon substituent" or "hydrocarbon group" is found in paragraphs

[0137] through

[0141] of published application US 2010-0197536.

[0086] It is known that some of the substances described above can interact in the final formulation, such that the composition of the final formulation may differ from those initially added. For example, metal ions (e.g., metal ions in detergents) can migrate to other acidic or anionic sites of other molecules. The resulting products, including those formed when the compositions of this technique are used for their intended purpose, may not be easily described. However, all such modifications and reaction products are included within the scope of this invention; this technique covers compositions prepared by mixing the aforementioned components.

[0087] Example

[0088] A series of lubricants were prepared as shown in Table 1.

[0089] Table 1 - Lubricant Formulations 1

[0090] 1. Unless otherwise specified, all processing rates are oil-free.

[0091] 2. Top treated with foam inhibitor (4 ppm)

[0092] 3. Polyalphaolefin base oil with a kinematic viscosity (KV100) of 5.8 cSt at 100°C.

[0093] 4. Polyalphaolefin base oil with a kinematic viscosity (KV100) of 158 cSt at 100°C

[0094] 5. Other additives include foam inhibitors, corrosion inhibitors, and polyether compatibilizers.

[0095] 6.Type II diluent oil contained in the additive

[0096] The advantages of the lubricating composition of the present invention can also be demonstrated by evaluating the lubricating composition according to various tests, including but not limited to 4-ball wear (ASTM D4172), 4-ball EP (ASTM D2783), oxidation (ASTM D2893, at 121°C), oxidation (ASTM D2893, at 95°C), steel corrosion (ASTM D665B), copper corrosion (ASTM D130, 3h, 100°C), demulsibility (ASTM D2711B), foaming (ASTM D892), FZG scratch A / 8.3 / 90 (ASTM D5182), and FE-8 (DIN 51819-3).

[0097] Specific aspects of the invention are set forth more fully in the following provisions.

[0098] Clause 1: An industrial gear lubrication composition comprising: (a) a base oil comprising at least 75% by weight of a Group IV base oil; (b) at least one sulfurized olefin present in an amount providing at least 1000 ppm of sulfur to the composition; (c) one or more phosphorus-containing agents in an amount providing at least 100 ppm of phosphorus to the composition; and (d) a poly(meth)acrylate polymer comprising at least 10 mol% of one or more alkyl(meth)acrylate monomers having alkyl groups containing 16 or more carbon atoms.

[0099] Clause 2: The composition according to Clause 1, wherein the sulfurized olefin is present in an amount of 1,000 ppm to 3,000 ppm sulfur to the composition.

[0100] Clause 3: The composition according to any of the preceding clauses, wherein the sulfurized olefin is present in an amount of 1,500 ppm to 2,500 ppm sulfur to the composition.

[0101] Clause 4: The composition according to any of the preceding clauses, wherein the one or more phosphorus-containing agents are present in an amount of 100 ppm to 1000 ppm phosphorus to the composition.

[0102] Clause 5: The composition according to any of the preceding clauses, wherein the one or more phosphorus-containing agents are present in an amount of 200 ppm to 500 ppm phosphorus to the composition.

[0103] Clause 6: The composition according to any of the preceding clauses, wherein the one or more phosphorus-containing agents are present in an amount of 300 ppm to 450 ppm phosphorus to the composition.

[0104] Clause 7: The composition according to any of the preceding clauses, wherein the polymethacrylate polymer comprises 10 mol% to 50 mol% of one or more alkyl (meth)acrylate monomers having alkyl groups containing 16 or more carbon atoms.

[0105] Clause 8: The composition according to any of the preceding clauses, wherein the polymethacrylate polymer comprises 15 mol% to 35 mol% of one or more alkyl (meth)acrylate monomers having alkyl groups containing 16 or more carbon atoms.

[0106] Clause 9: The composition according to any of the preceding clauses, wherein the polymethacrylate polymer comprises 20 mol% to 30 mol% of one or more alkyl (meth)acrylate monomers having alkyl groups containing 16 or more carbon atoms.

[0107] Clause 10: The composition according to any of the preceding clauses, wherein the (meth)acrylate alkyl ester monomer comprises or is composed of stearyl methacrylate.

[0108] Clause 11: The composition according to any of the preceding clauses, wherein the poly(meth)acrylate polymer comprises 50 mol% to 90 mol% of alkyl(meth)acrylate monomers containing 8 to 15 carbon atoms.

[0109] Clause 12: The composition according to any of the preceding clauses, wherein the poly(meth)acrylate polymer comprises 65 mol% to 85 mol% of alkyl(meth)acrylate monomers containing 8 to 15 carbon atoms.

[0110] Clause 13: The composition according to any of the preceding clauses, wherein the poly(meth)acrylate polymer comprises 70 mol% to 80 mol% of alkyl(meth)acrylate monomers containing 8 to 15 carbon atoms.

[0111] Clause 14: The composition according to any one of Clauses 11 to 13, wherein the alkyl methacrylate monomer containing 8 to 15 carbon atoms comprises lauryl methacrylate or is composed of therefrom.

[0112] Clause 15: The composition according to any of the preceding clauses, wherein the poly(meth)acrylate polymer optionally contains another monomer that can be copolymerized with the alkyl(meth)acrylate monomer.

[0113] Clause 16: The composition according to any of the preceding clauses, wherein the poly(meth)acrylate polymer contains up to 10 mol% or up to 5 mol% of another monomer that can be copolymerized with the alkyl(meth)acrylate monomer.

[0114] Clause 17: A composition according to any of the preceding clauses, wherein the poly(meth)acrylate polymer optionally comprises a monomer having 1 to 10 or 4 to 8 carbon atoms.

[0115] Clause 18: The composition according to Clause 17, wherein the poly(meth)acrylate polymer contains 0 mol% to 10 mol% of a monomer containing 1 to 10 or 4 to 8 carbon atoms.

[0116] Clause 19: The composition according to Clause 18, wherein the poly(meth)acrylate polymer contains up to 1 mol% to 5 mol% of a monomer containing 1 to 10 or 4 to 8 carbon atoms.

[0117] Clause 20: The composition according to any of the preceding clauses, wherein the poly(meth)acrylate polymer is present in an amount of 0.05% by weight to 0.5% by weight of the composition.

[0118] Clause 21: The composition according to any of the preceding clauses, wherein the poly(meth)acrylate polymer is present in an amount of 0.1% to 0.4% by weight of the composition.

[0119] Clause 22: The composition according to any of the preceding clauses further comprises a branched hydrocarbon alcohol having 10 or more carbon atoms.

[0120] Clause 23: The composition according to Clause 22, wherein the branched hydrocarbon alcohol comprises a β-branched alcohol containing 12 or more carbon atoms.

[0121] Clause 24: The composition according to any of the preceding clauses, wherein the base oil comprises at least 85% by weight of Group IV base oil.

[0122] Clause 25: A composition according to any of the preceding clauses, wherein the base oil is a mixture of Group IV base oils, wherein the mixture comprises one or more polyalphaolefin base oils having a kinematic viscosity between 4 cSt and 10 cSt at 100°C and one or more polyalphaolefin base oils having a kinematic viscosity greater than 50 cSt at 100°C.

[0123] Clause 26: The composition according to any of the preceding clauses, wherein the phosphorus-containing reagent comprises a hydrocarbon phosphite, a hydrocarbon phosphonate, a hydrocarbon phosphate, a hydrocarbon amine salt of dihydrophosphoric acid or trihydrophosphoric acid, or any combination thereof.

[0124] Clause 27: The composition according to any of the preceding clauses, wherein the phosphorus-containing agent comprises dioleoyl phosphite.

[0125] Clause 28: The composition according to any of the preceding clauses, wherein the phosphorus-containing agent comprises the (2-ethylhexyl)amine salt of isooctyl phosphate.

[0126] Clause 29: The composition according to any of the preceding clauses, wherein the sulfurized olefin comprises an olefin having 4 to 12 carbon atoms.

[0127] Clause 30: The composition according to any of the preceding clauses, wherein the sulfurized olefin comprises sulfurized isobutylene.

[0128] Clause 31: The composition according to any of the preceding clauses, wherein the kinematic viscosity of the composition at 40°C is at least 150 cSt.

[0129] Clause 32: A method of lubricating an industrial gear, the method comprising supplying the gear with a lubricating composition according to any of the preceding clauses.

[0130] Clause 33: A method for improving the low-temperature viscosity of an industrial gear lubricant, the method comprising supplying the gear with a lubricating composition according to any one of Clauses 1 to 31.

[0131] Clause 34: Use of poly(meth)acrylate polymer additives for improving the low-temperature viscosity of industrial gear lubrication compositions, wherein the industrial gear lubrication compositions have the composition according to any one of Clauses 1 to 31.

[0132] Each of the foregoing references is incorporated herein by reference, including any prior application claiming priority thereto, whether or not specifically listed above. Reference to any reference is not an admission that the reference conforms to the prior art or constitutes general knowledge of a person skilled in the art in any jurisdiction. Unless expressly stated in the examples or otherwise, all numerical quantities of matter, reaction conditions, molecular weight, number of carbon atoms, etc., specified in this specification should be understood to be modified by the word “about.” It should be understood that the upper and lower limits of the quantities, ranges, and proportions described herein can be combined independently. Similarly, the ranges and quantities of each element of this art can be used in conjunction with the ranges or quantities of any other element.

[0133] As used herein, “substantially free” means that the amount of the substance under consideration is below the amount that would affect fluid-related properties in a measurable manner. “Substantially free” can also mean that the substance under consideration was not intentionally added to the composition, but does not exclude the presence of such a material as a contaminant. “Substantially free” can also mean that the substance under consideration may be present in amounts below the detection limits of standard test methods now known to or developed by those skilled in the art. In some embodiments, “substantially free” may mean less than 10 ppm by weight or even less than 5 ppm by weight.

[0134] As used herein, the transitional term “comprising,” synonymous with “comprising,” “containing,” or “characterized in,” is inclusive or open-ended and does not exclude additional, unlisted elements or method steps. However, in every use of “comprising” herein, it is intended that the term also cover the phrases “consistently composed of” and “composed of” as alternative embodiments, wherein “consisting of” excludes any elements or steps not specified, and “consisting of” allows the inclusion of additional, undescribed elements or steps that do not substantially affect the essential or essential and novel characteristics of the composition or method under consideration.

[0135] While certain representative embodiments and details have been shown for the purpose of illustrating the subject matter, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the scope of the subject matter. In this respect, the scope of this technology is defined only by the following claims.

Claims

1. An industrial gear lubricating composition comprising: (a) a base oil, wherein the base oil comprises at least 75 wt% of a Group IV base oil; (b) at least one sulfurized olefin, the at least one sulfurized olefin present in an amount to provide at least 1000 ppm sulfur to the composition; (c) one or more phosphorus-containing agents in an amount to provide at least 100 ppm of phosphorus to the composition; and (d) a poly(meth)acrylate polymer, wherein the poly(meth)acrylate polymer comprises at least 10 mol% of one or more alkyl (meth)acrylate monomers having an alkyl group containing 16 or more carbon atoms.

2. The composition of claim 1, wherein the poly(meth)acrylate polymer comprises 50 mol% to 90 mol% of alkyl (meth)acrylate monomers containing 8 to 15 carbon atoms.

3. The composition of any preceding claim, wherein the poly(meth)acrylate polymer is present in an amount of 0.05 wt% to 0.5 wt% of the composition.

4. The composition of any preceding claim, further comprising a branched hydrocarbyl alcohol containing 10 or more carbon atoms.

5. The composition of claim 4, wherein the branched hydrocarbyl alcohol comprises a beta-branched alcohol containing 12 or more carbon atoms.

6. The composition of any preceding claim, wherein the base oil comprises at least 85 wt% of a Group IV base oil.

7. The composition of any preceding claim, wherein the base oil is a mixture of Group IV base oils, wherein the mixture comprises one or more polyalphaolefin base oils having a kinematic viscosity at 100°C between 4 cSt and 10 cSt and one or more polyalphaolefin base oils having a kinematic viscosity at 100°C greater than 50 cSt.

8. The composition of any preceding claim, wherein the phosphorus-containing agent comprises a hydrocarbyl phosphite, a hydrocarbyl phosphonate, a hydrocarbyl phosphate, a dihydrocarbyl phosphinic acid or a trihydrocarbyl phosphinic acid, or a hydrocarbyl amine salt of any combination thereof.

9. The composition of any preceding claim, wherein the sulfurized olefin comprises an olefin containing 4 to 12 carbon atoms.

10. The composition of any preceding claim, wherein the sulfurized olefin comprises sulfurized isobutylene.

11. The composition of any preceding claim, wherein the composition has a kinematic viscosity at 40°C of at least 150 cSt.

12. A method of lubricating an industrial gear, the method comprising supplying to the gear a lubricating composition according to any preceding claim.

13. A method of improving the low temperature viscosity of an industrial gear lubricant, the method comprising supplying to the gear a lubricating composition according to any one of claims 1 to 11.

14. Use of a poly(meth)acrylate polymer additive to improve the low temperature viscosity of an industrial gear lubricating composition, wherein the industrial gear lubricating composition has a composition according to any one of claims 1 to 11.

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