EP4623053A1 - Powertrain lubricant containing polyether - Google Patents
Powertrain lubricant containing polyetherInfo
- Publication number
- EP4623053A1 EP4623053A1 EP23825665.5A EP23825665A EP4623053A1 EP 4623053 A1 EP4623053 A1 EP 4623053A1 EP 23825665 A EP23825665 A EP 23825665A EP 4623053 A1 EP4623053 A1 EP 4623053A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- lubricant composition
- group
- carbon atoms
- dispersant
- amine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M161/00—Lubricating compositions characterised by the additive being a mixture of a macromolecular compound and a non-macromolecular compound, each of these compounds being essential
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- C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
- C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
- C10M2203/102—Aliphatic fractions
- C10M2203/1025—Aliphatic fractions used as base material
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- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
- C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
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- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
- C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
- C10M2205/022—Ethene
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- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
- C10M2205/04—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing aromatic monomers, e.g. styrene
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- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/02—Hydroxy compounds
- C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
- C10M2207/026—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings with tertiary alkyl groups
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- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/28—Esters
- C10M2207/282—Esters of (cyclo)aliphatic oolycarboxylic acids
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- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
- C10M2209/084—Acrylate; Methacrylate
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- C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
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- C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
- C10M2209/105—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing three carbon atoms only
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- C10M2209/109—Polyethers, i.e. containing di- or higher polyoxyalkylene groups esterified
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- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
- C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
- C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
- C10M2215/064—Di- and triaryl amines
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- C10M2215/24—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions having hydrocarbon substituents containing thirty or more carbon atoms, e.g. nitrogen derivatives of substituted succinic acid
- C10M2215/28—Amides; Imides
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- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/10—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring
- C10M2219/104—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring containing sulfur and carbon with nitrogen or oxygen in the ring
- C10M2219/106—Thiadiazoles
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- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
- C10M2223/04—Phosphate esters
- C10M2223/043—Ammonium or amine salts thereof
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- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
- C10M2223/04—Phosphate esters
- C10M2223/047—Thioderivatives not containing metallic elements
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- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
- C10M2223/049—Phosphite
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- C10M2229/00—Organic macromolecular compounds containing atoms of elements not provided for in groups C10M2205/00, C10M2209/00, C10M2213/00, C10M2217/00, C10M2221/00 or C10M2225/00 as ingredients in lubricant compositions
- C10M2229/04—Siloxanes with specific structure
- C10M2229/041—Siloxanes with specific structure containing aliphatic substituents
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- C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
- C10N2020/01—Physico-chemical properties
- C10N2020/04—Molecular weight; Molecular weight distribution
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- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/04—Detergent property or dispersant property
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- C10N2030/12—Inhibition of corrosion, e.g. anti-rust agents or anti-corrosives
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- C10N2040/14—Electric or magnetic purposes
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- C10N2060/00—Chemical after-treatment of the constituents of the lubricating composition
- C10N2060/01—Chemical after-treatment of the constituents of the lubricating composition by organic hydroxy group containing compounds
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- C10N2060/00—Chemical after-treatment of the constituents of the lubricating composition
- C10N2060/12—Chemical after-treatment of the constituents of the lubricating composition by phosphorus or a compound containing phosphorus, e.g. PxSy
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Definitions
- the lubricating composition of the invention (com- prising the additives disclosed herein) is in the form of a concentrate which may be combined with additional oil to form, in whole or in part, a finished lubri- cant
- the ratio of the of these additives to the oil of lubricating viscosity and/or to diluent oil include the ranges of 1:99 to 99:1 by weight, or 80:20 to 10:90 by weight.
- the base oil has a kinematic viscosity at 100° C. from 2 mm2/s (centi Stokes-cSt) to 16 mm2/s, from 3 mm2/s to 10 mm2/s, or even from 4 mm2/s to 8 mm2/s.
- the ability of a base oil to act as a solvent may be a con- tributing factor in increasing the frequency of LSPI events during operation of a direct fuel-injected engine.
- Base oil solvency may be measured as the ability of unadditized base oil to act as a solvent for polar constituents.
- base oil solvency decreases as the base oil group moves from Group I to Group IV (PAO). That is, solvency of base oil may be ranked as follows for oil of a given kinematic viscosity: Group I>Group II>Group II>Group IV.
- Synthetic esters may comprise esters of dicarboxylic acids (e.g., phthalic acid, succinic acid, alkyl succinic acids and alkenyl succinic acids, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic acid, alkyl malonic acids, and alkenyl malonic acids) with any of variety of monohydric alcohols (e.g., butyl alcohol, hexyl alcohol, dodecyl alco- hol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoether, and propylene glycol).
- dicarboxylic acids e.g., phthalic acid, succinic acid, alkyl succinic acids and alkenyl succinic acids, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, l
- esters include dibutyl adipate, di(2-ethylhexyl) sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl azelate, dioctyl phthalate, didecyl phthalate, dieicosyl seba- cate, the 2-ethylhexyl diester of linoleic acid dimer, and the complex ester formed by reacting one mole of sebacic acid with two moles of tetraethylene glycol and two moles of 2-ethylhexanoic acid.
- Natural esters include fatty acid triglyc- erides, hydrolyzed or partially hydrolyzed triglycerides, or transesterified tri- glyceride esters, such as fatty acid methyl ester (or FAME).
- Suitable triglycer- ides include, but are not limited to, palm oil, soybean oil, sunflower oil, rape- seed oil, olive oil, linseed oil, and related materials.
- Other sources of triglycer- ides include, but are not limited to, algae, animal tallow, and zooplankton. Methods for producing bio-lubricants from natural triglycerides are described in, e.g., United States Patent Publication 2011/0009300A1.
- the alcohol includes one or more Guerbet alco- hols. Guerbet alcohols may be described as alcohols made via the Guerbet reac- tion, which was named after Marcel Guerbet.
- R2 and R3 may contain from 4 to 14, or even from 6 to 12 carbon atoms. In still further embodiments, R2 and R3 contain 6 and 8, or 10 and 12 carbon atoms.
- Suitable examples of the alcohol useful in the invention include 2-ethylhexanol, 2-butyloctanol, 2-hex- yldecanol, 2-octyldodecanol, 2-decyltetradecanol, 2-dodecylhexadecanol, or any combination thereof. These types of alcohols are commercially available from Sasol and marketed as ISOFOL® alcohols.
- the polyethers of formulae I is present in an amount from 0.05 to 1 weight % of the lubricating composition.
- the polyether is prepared from an alkylphenol.
- the alkyl group of the alkylphenols can be 1 to 30 carbon atoms, in another embodi- ment 10 to 20 carbon atoms.
- R5 group of each of the formulae II above may be located in the para position relative to the oxyalkylated group, and the resultant formula is repre- sented by the structure: wherein variables R2 to R5, and n, are defined previously.
- the oxyalkylated hydrocarbyl phenol of the present invention is represented by Formula II(b) wherein R5 can be a linear or branched aliphatic group having from 1 to 30 car- bon atoms, in another embodiment 10 to 20 carbon atoms, R2 can be hydrogen or an alkyl group having 1 to 5 carbon atoms, and R3 can be hydrogen, an C1- C4 alkyl group, -C(O)R4 wherein R4 can be a C1-C4 alkyl group and n can be an integer from 10-40 (15-35 or 20-30 or 22-26) m can be an integer from 1 to 3.
- R5 can be a linear or branched aliphatic group having from 1 to 30 car- bon atoms, in another embodiment 10 to 20 carbon atoms
- R2 can be hydrogen or an alkyl group having 1 to 5 carbon atoms
- R3 can be hydrogen, an C1- C4 alkyl group, -C(O)R4 wherein R4 can be
- the oxyalkylated group of the oxyalkylated hydrocarbyl phenol has the formula —(R1O) neighborhood—, wherein R1 is an ethylene, propylene, butylene group, or mixtures thereof; and n may independently be from 1 to 50, or 1 to 20, or 1 to 10, or 2 to 5.
- the oxyalkylated group of the oxyalkylated hydrocarbyl phenol may be either a homopolymer or copolymer or oligomers thereof. If the oxyalkylated group is in the form of a copolymer, or oligomer thereof, the oxyalkylated group may have either random or block architecture.
- the oxyalkylated hydrocarbyl phenol can be prepared by reacting a hy- drocarbyl substituted phenol with an alkylene oxide (typically ethylene oxide, propylene oxide or butylene oxide), optionally in the presence of a base catalyst. Typically the reaction occurs in the presence of a base catalyst.
- the base catalyst may include, but is not limited to, sodium chloroace- tate, sodium hydride or potassium hydroxide
- the aliphatic hydrocarbyl group (also represented by R4) is linear or branched, typically with at least one branching point.
- the aliphatic hydrocarbyl group typically has one, although it may in some embodiments be desirable to have to R4 groups, with the second group being methyl. If a second R4 group is present and is methyl, then the oxyalkylated hydrocarbyl phenol is a cresol. [0058] In different embodiments, the oxyalkylated hydrocarbyl phenol of the present invention is present in an amount ranging from 0.01 weight % to 5 weight %, or 0.05 to 3.5 weight %, or 0.1 to 2.5 weight % of the lubricating composition. Typically, the polyethers of formulae I is present in an amount from 0.25 to 2 weight % of the lubricating composition.
- the polyether is prepared from a hydrocarbyl carbox- ylic acid with from 8 to 24 carbon atoms, in another embodiment from 12 to 24 carbon atoms in yet another embodiment from 14-18 carbon atoms.
- the polyether may comprise an oxyalkylated hy- drocarbyl phenol represented by Formula III: Formula III wherein the hydrocarbyl group R1 is a linear or branched aliphatic group having from 7 to 23 carbon atoms, in another embodiment 11 to 23 or 13 to17 carbon atoms R2 is hydrogen or an alkyl group having 1 to 5 carbon atoms, and R3 is hydrogen, an C1-C4 alkyl group, or -C(O)R4, R4 is a C1-C4 alkyl group and n is an integer from 10-40 (15-35 or 20-30 or 22-26) m is an integer from 1 to 3.
- Examples of the oxyalkylated hydrocarbyl carboxylic acids include but are not limited to tall oil fatty acid initiated polypropyleneoxide (22-24) ester- ol, butanol initiated polypropyleneoxide (23-25) ether-tallow fatty acid ester, tallow fatty acid initiated polypropyleneoxide (22-24) ester-ol.
- alkox- ylates can be made from the reaction of a fatty acid such as tall oil fatty acids (TOFA) that is, the mixture of fatty acids predominately oleic and linoleic and contains residual rosin acids or tallow acid that is, the mixture of fatty acids pre- dominately stearic, palmitic and oleic with an alcohol terminated polyether such as polypropylene glycol in the presence of an acidic catalyst, usually methane sulphonic acid.
- TOFA tall oil fatty acids
- alkoxylates can also be made from the reaction of glyc- erol dioleate and propylene oxide in the presence of catalyst [0062]
- the lubricant in the method contains oil-soluble amine salt or amine ad- ducts of a phosphoric acid ester, such as those taught in U.S. Pat. Nos. 5,354,484, 5,763,372, and 5,942,470.
- the amine salts or adducts of a phosphoric acid ester may be prepared by reacting a phosphoric acid ester with ammonia or a basic nitrogen compound, such as an amine.
- the salts may be formed sepa- rately, and then the salt of the phosphoric acid ester may be added to the lubri- cating composition.
- the phosphoric acid esters useful in preparing the amine salts of the present invention may be characterized by the formula; wherein R1 is hydrogen or a hydrocarbyl group, R2 is a hydrocarbyl group, and both X groups are either O or S.
- a preferred method of preparing compositions containing (I) comprises reacting at least one hydroxy compound of the formula ROH with a phosphorus compound of the formula P2X5 wherein R is a hydrocarbyl group and X is O or S.
- the phosphorus-containing compositions obtained in this manner are mix- tures of phosphorus compounds, and are generally mixtures of mono- and dihy- drocarbyl-substituted phosphoric and/or dithiophosphoric acids depending on a choice of phosphorus reactant (i.e., P205 or P2S5).
- the hydroxy compound used in the preparation of the phosphoric acid esters of this invention are char- acterized by the formula ROH wherein R is a hydrocarbyl group.
- the hydroxy compound reacted with the phosphorus compound may comprise a mixture of hydroxy compounds of the formula ROH wherein the hydrocarbyl group R con- tains from about 1 to 40 carbon atoms.
- the amine salt of the substituted phosphoric acid ester ultimately prepared is soluble in the lubricating compositions of the present invention.
- the R group will contain at least 2 carbon atoms, typically 4 to 40, or 6 to 39, or 6 to 18, or 8 to 18 carbon atoms.
- the R group may be aliphatic or aromatic such as alkyl, aryl, alkaryl, aralkyl and alicyclic hydrocarbon groups.
- ROH hydroxy compounds of the formula ROH
- ROH includes, for example, ethyl alcohol, iso-pro- pyl, n-butyl alcohol, amyl alcohol, hexyl alcohol, 2-ethyl-hexyl alcohol, nonyl alcohol, dodecyl alcohol, stearyl alcohol, amyl phenol, octyl phenol, nonyl phe- nol, methyl cyclohexanol, alkylated naphtha, etc.
- the preferred alcohols, ROH are aliphatic alcohols and more particu- larly, primary aliphatic alcohols containing at least about 4 carbon atoms.
- examples of the preferred monohydric alcohols ROH which are use- ful in the present invention include, amyl alcohol, 1-octanol, 1-decanol, 1-do- decanol, 1-tetradecanol, 1-hexadecanol, 1-octadecanol, oleyl alcohol, linoleyl alcohol, linolenyl alcohol, phytol, myricyl alcohol, lauryl alcohol, myristyl alco- hol, cetyl alcohol, stearyl alcohol and behenyl alcohol.
- the amine salts of the present invention can be prepared by reaction of the above-described phosphoric acid esters such as represented by Formula I with at least one amino compound which may be a primary amine, a secondary amine, a tertiary amine, or mixtures thereof.
- the amine may be aliphatic, or cy-root, aromatic or non-aromatic, Typically, aliphatic.
- the amine includes an aliphatic amine such as a tertiary-aliphatic primary amine.
- Suitable primary amines include ethylamine, propyl amine, butylamine, 2-ethylhexylamine, bis-(2-ethylhexyl)amine, octylamine, and do- decylamine, as well as such fatty amines as n-octylamine, n-decylamine, n-do- decyl amine, n-tetradecylamine, n-hexadecylamine, n-octadecylamine and oleyamine.
- fatty amines include commercially available fatty amines such as "Armeen®” amines (products available from Akzo Chemicals, Chicago, Ill.), such as Armeen C, Armeen 0, Armeen OL, Armeen T, Armeen H T, Armeen S and Armeen S D, wherein the letter designation relates to the fatty group, such as coco, oleyl, tallow, or stearyl groups.
- Armeen® products available from Akzo Chemicals, Chicago, Ill.
- Armeen C Armeen 0, Armeen OL
- Armeen T Armeen T
- Armeen H T Armeen H T
- Armeen S and Armeen S D wherein the letter designation relates to the fatty group, such as coco, oleyl, tallow, or stearyl groups.
- Examples R include isopropyl, isobutyl, n-butyl, sec-butyl, the various amyl, n-hexyl, methylisobutyl, carbinyl, heptyl, 2-ethylhexyl, isooctyl, nonyl, behenyl, decyl, dodecyl, and tridecyl groups.
- Illustrative lower alkylphenyl R groups include butylphenyl, amylphenyl, heptylphenyl, etc.
- Examples of mix- tures of R groups include: 1-butyl and 1-octyl; 1-pentyl and 2-ethyl-l-hexyl; iso- butyl and n-hexyl; isobutyl and isoamyl; 2-propyl and 2-methyl-4-pentyl; iso- propyl and sec-butyl; and isopropyl and isooctyl.
- the dithiophosphoric acid may be reacted with an epoxide or a glycol. This reaction product may be used alone, or further reacted with a phosphorus acid, anhydride, or lower ester.
- EXAMPLE B-2 A mixture of 667 grams of phosphorus pentoxide and the reaction prod- uct of 3514 grams of diisopropyl phosphorodithioic acid with 986 grams of pro- pylene oxide at 50° C. is heated at 85° C. for 3 hours and filtered. The filtrate contains 15.3% by weight phosphorus, 19.6% by weight sulfur, and an acid number of 126 (bromophenol blue).
- Acidic phosphoric acid esters may be reacted with ammonia, an amine compound or a metallic base to form an ammonium or metal salt. The salts may be formed separately and then the salt of the phosphorus acid ester may be added to the lubricating composition.
- the amine may be a fatty (C4_30) amine which in- clude n-hexylamine, n-octylamine, n-decylamine, n-dodecylamine, n-tetradecyl- amine, n-hexadecylamine, n-octadecylamine, oleylamine, etc.
- fatty amines include commercially available fatty amines such as “Armeen” amines (products available from Armak Chemicals, Chicago, Ill.), such as Armak’s ArmeenC, Armeen-O, Armeen-OL, Armeen-T, Armeen-HT, Armeen S and Armeen SD, wherein the letter designation relates to the fatty group, such as co- coa, oleyl, tallow, or soya groups.
- the phosphorus antiwear agent may be the amine salt comprise a species represented by formula (I) or (II):
- the phosphorous amine salt is prepared or preparable by the reaction of phosphorus pentoxide with a secondary alcohol having about 3 to about 12 car- bon atoms and reacting the product thereof with a hydrocarbyl amine.
- the hy- drocarbyl amine may comprise at least one Ci-C20, C4-C18, or C6-C14 hydro- carbyl group.
- the phos- phorus pentoxide may be reacted with about 2.2 to about 3.1 moles, or about 2.3 to about 2.8 moles, or 2.4 to 2.4 per mole of P2O5, of the secondary alcohol at a temperature of about 30° C. to about 60° C.
- the alkyl phosphate amine salt may comprise up to about 60 mole per- cent of the phosphorus atoms in mono- or di-alkyl-orthophosphate salt struc- tures.
- the alkyl phosphate amine salt may comprise at least about 50 to about 80, or 55 to 65 mole percent of the phosphorus atoms in an alkyl pyrophosphate salt structure.
- the hydrocarbyl amine can be a hindered amine represented by formula (III) R3—NR5—R4 wherein R3, R4, and R5 are inde- pendently a Cl-C30 hydrocarbyl group.
- R3, R4, and R5 can independently be a Q-C ⁇ , C4-C18, or C6-C14 hydrocarbyl group.
- the hindered hydrocarbyl amine may have at least one aromatic group.
- the hydrocarbyl amine can be an aromatic amine having an alkyl group attached directly to a nitrogen atom that salts with the phosphate and wherein the nitrogen atom may optionally be further alkylated.
- the hydrocarbyl amine can be a tertiary alkyl amine with at least two branched alkyl groups.
- the at least two branched alkyl groups can independently be branched at the a or the ⁇ position.
- the at least two branched alkyl groups can both be branched at the ⁇ position.
- the alkyl group or groups of the alkylphosphate structure may comprise 4-methylpent-2-yl groups.
- the corrosion inhibitor includes (i) a 2,5-bis(alkyl- dithio)-1,3,4-thiadiazole, (ii) a benzotriazole containing a hydrocarbyl substitu- tion on at least one of the following ring positions 4- or 5- or 6- or 7-, or (iii) a benzotriazole containing a hydrocarbyl substitution (typically a benzotriazole further reacted with an aldehyde and an amine) at least one of the following ring positions 1- or 2-.
- the corrosion inhibitor includes 2,5-bis(alkyl-dithio)- 1,3,4-thiadiazoles.
- the alkyl groups of 2,5-bis(alkyl- dithio)-1,3,4-thiadiazoles contain 1 to about 30, or about 2 to about 25, or 4 to about 20, or about 6 to about 16 carbon atoms.
- suitable 2,5-bis(al- kyl-dithio)-1,3,4-thiadiazoles include 2,5-bis(tert-octyldithio)-1,3,4-thiadiazole, 2,5-bis(tert-nonyldithio)-1,3,4-thiadiazole, 2,5-bis(tert-decyldithio)-1,3,4-thiadi- azole, 2,5-bis(tert-undecyldithio)-1,3,4-thiadiazole, 2,5-bis(tert-dodecyldithio)- 1,3,4-thiadiazole, or mixtures thereof.
- the corrosion inhibitor may be used alone or in combination with two, three or more corrosion inhibitors.
- the corrosion inhibitor includes a mixture of (i) a 2,5-bis(alkyl-dithio)-1,3,4-thiadiazole, (ii) a benzotri- azole containing a hydrocarbyl substitution on at least one of the following ring positions 4- or 5- or 6- or 7-, and (iii) a benzotriazole containing a hydrocarbyl substitution (typically a benzotriazole further reacted with an aldehyde and an amine) on at least one of the following ring positions, 1- or 2-.
- the corrosion inhibitor is a thiadiazole.
- Thiadi- azole corrosion inhibitors may be present alone or in mixtures with other thiadi- azole corrosion inhibitors or other azole corrosion inhibitors in ranges including about 0.01 wt % to about 1 wt %, or about 0.05 wt % to about 0.9 wt %, or about 0.1 wt % to about 0.8 wt %, or about 0.2 wt % to about 0.7 wt % of the lubricant additive composition or 0.2 wt % to about 0.5 wt % or 0.25 wt % to about 0.35 wt % of the lubricant additive composition.
- the lubricant can also include other additives, such as, for example, dis- persants, antioxidants, viscosity modifiers, detergents, and other antiwear agents (besides the amine(thio)phosphates above), to name a few.
- additives such as, for example, dis- persants, antioxidants, viscosity modifiers, detergents, and other antiwear agents (besides the amine(thio)phosphates above), to name a few.
- Dispersants can include, for example, “succinimide dispersants,” a spe- cies of carboxylic dispersants prepared by the reaction of a hydrocarbyl-substi- tuted succinic anhydride or reactive equivalent thereof with an amine such as a poly(ethyleneamine); “amine dispersants,” which are reaction products of rela- tively high molecular weight aliphatic or alicyclic halides and amines, such as polyalkylene polyamines; “Mannich dispersants,” i.e., the reaction products of alkyl phenols in which the alkyl group contains at least 30 carbon atoms with al- dehydes (especially formaldehyde) and amines (especially polyalkylene polyam- ines); and “ester dispersants,” similar to the above-described succinimide dis- persants except that they may be seen as having been prepared by reaction of a hydrocarbyl acylating agent and a polyhydric aliphatic
- Another class of ashless dispersant is high molecular weight esters. These materials are similar to the above described succinimides except that they may be seen as having been prepared by reaction of a hydrocarbyl acylating agent and a polyhydric aliphatic alcohol such as glycerol, pentaerythritol, or sor- bitol. Such materials are described in more detail in U.S. Pat. No.3,381,022.
- Aromatic succinate esters may also be prepared as described in United States Patent Publication 2010/0286414. In some instances, these ester type dispersants can be post-treated with an amine such as a poly(ethyleneamine). [0095] Post-treated dispersants may also be used.
- Post-treated dispersants are generally obtained by reacting a carboxylic (e.g., succinimide), amine or Man- nich dispersant with reagents such as urea, thiourea, carbon disulfide, aldehydes, ketones, carboxylic acids, hydrocarbon-substituted succinic anhydrides, nitriles, epoxides, boron compounds such as boric acid (to give “borated dispersants” as noted above), phosphorus compounds such as phosphorus acids or anhydrides, 2,5-dimercaptothiadiazole (DMTD), or an aromatic diacid having acid groups in 1,3 or 1,4 positions on a benzene ring (such as terepthahlic acid).
- a carboxylic e.g., succinimide
- amine or Man- nich dispersant with reagents such as urea, thiourea, carbon disulfide, aldehydes, keto
- Borated dispersants are generally obtained by reacting a carboxylic (e.g., succinimide), amine or Mannich dispersant with a boron compound reagent, such as boric acid (to give “borated dispersants”). Dispersants and their method of production are well-known in the art.
- the borated dispersant may be further functionalized with a sulfur or phosphorus moiety.
- the dispersant component in the borated dispersant may be a mixture of multiple dispersants which may be of different types; optionally at least one may be a succinimide dispersant.
- the borated dispersant may be a borated polyisobutylene succin- imide dispersant, in which the polyisobutylene portion thereof may have a num- ber average molecular weight of 750 to 2200, or 750 to 1350, or 750 to 1150.
- the borated dispersant(s) may be prepared in such a way to have a N:CO ratio of 0.9:1 to 1.6:1, or 0.95:1 to 1.5:1, or 1:1 to 1.4:1.
- the amount of borated dis- persant in the compositions may be, for instance, 0.05 to 2.0 percent by weight. In other embodiments, the amount is 0.1 to 1.0 percent or 0.15 to 0.75 percent of the final blended fluid formulation.
- the amounts will be pro- portionately higher.
- Mixtures of dispersants can also be used.
- the dispersant can have a ni- trogen content of greater than or equal to about 11,000 ppm by weight of the dispersant, or greater than or equal to about 11,500ppm or greater than or equal to about 12,000 ppm.
- the total amount of dispersant or dispersants, whether post-treated or not (e.g., borated or non-borated, but preferably borated) or combinations thereof, in the compositions may be, for instance, 0.01 to 3 percent by weight, or, for ex- ample, 0.025 to 2.75 percent or 0.05 to 2.5 weight percent of the final blended fluid formulation, although in a concentrate, the amounts will be proportionately higher.
- the dispersant may provide less than 250 ppm boron, or less than 200 ppm boron, or even less than 150 ppm bo- ron, or less than 100 ppm boron, or less than 90 ppm boron, or even less than 80 ppm boron to the composition, and in some instances less than 70 ppm boron to the composition.
- the dispersant can be prepared by a process that involves the presence of small amounts of chlorine or other halogen, as de- scribed in U.S. Pat. No. 7,615, 521 (see, e.g., col.4, lines 18-60 and preparative example A).
- Such dispersants typically have some carbocyclic structures in the attachment of the hydrocarbyl substituent to the acidic or amidic "head” group.
- the dispersant can be prepared by a thermal process in- volving an "ene” reaction, without the use of any chlorine or other halogen, as described in U.S. Pat. No.7,615,521; dispersants made in this manner are often derived from high vinylidene (i.e. greater than 50% terminal vinylidene) poly- isobutylene(See col.4, line 61 to col.5, line 30 and preparative example B).
- Such dispersants typically do not contain the above-described carbocyclic struc- tures at the point of attachment.
- the polymer substrate will be an olefin polymer such as that described above.
- the olefin polymer substrate employed in the derivatized graft copoly- mer will contain grafted carboxylic acid functionality or a reactive equivalent of carboxylic acid functionality (e.g., anhydride or ester).
- the reactive carboxylic acid functionality will typically be present as a pendant group attached by, for instance, a grafting process.
- An ethylenically unsaturated carboxylic acid material is typically radi- cally grafted onto the polymer backbone.
- These materials which are attached to the polymer typically contain at least one ethylenic bond (prior to reaction) and at least one, such as two, carboxylic acid (or its anhydride) groups or a polar group which is convertible into said carboxyl groups by oxidation or hydrolysis.
- Maleic anhydride or a derivative thereof is suitable. It grafts onto the olefin pol- ymer, (e.g., ethylene copolymer or terpolymer) to give two carboxylic acid func- tionalities.
- additional unsaturated carboxylic materials include ma- leic anhydride, itaconic anhydride, or the corresponding dicarboxylic acids, such as maleic acid, fumaric acid and their esters, as well as cinnamic acid and esters thereof.
- the ethylenically unsaturated carboxylic acid material may be radically grafted onto the polymer (such as the ethylene/propylene copolymer).
- the free- radical induced grafting of ethylenically unsaturated carboxylic acid materials may also be conducted in solvents, such as hexane or mineral oil.
- the free-radical initiators which may be used include peroxides, hydrop- eroxides, and azo compounds, typically those which have a boiling point greater than about 100°C and which decompose thermally within the grafting tempera- ture range to provide free radicals.
- Representative of these free-radical initiators include azobisisobutyronitrile and 2,5-dimethyl-hex-3-yne-2,5-bis-tertiary-butyl peroxide.
- the initiator may be used in an amount of 0.005% to 1% by weight based on the weight of the reaction mixture solution.
- the grafting may be car- ried out in an inert atmosphere, such as under nitrogen blanketing.
- the resulting polymer intermediate is characterized by having carboxylic acid acylating func- tions within its structure.
- the unsaturated carboxylic acid material such as maleic anhydride, can be first condensed with a monoamine or polyam- ine, typically having a single primary amino group (described below) and the condensation product itself then grafted onto the polymer backbone in analo- gous fashion to that described above.
- the amount of the reactive carboxylic acid on the polymer chain, and in particular the amount of grafted carboxylic acid on the chain is typically 0.5 to 8 weight percent, or 1 to 7 weight percent, or 1.5 to 6 weight percent, based on the weight of the polymer backbone, or in some embodiments 2 to 5 weight percent. In some embodiments the amount of the reactive carboxylic acid on the polymer chain, and in particular the amount of grafted carboxylic acid on the chain can be from about 1 to about 2, or in other embodiments from about 2 to 3, or from about 3 to 4 weight percent or 4 to 5 weight percent. These numbers represent the amount of carboxyl-containing species with particular reference to maleic anhydride as the graft material.
- the amounts may be adjusted to account for car- boxyl-containing species having higher or lower molecular weights or greater or lesser amounts of acid functionality per molecule, as will be apparent to the per- son skilled in the art.
- the grafting may be of an extent to provide an acid func- tionalized polymer having a total acid number (TAN per ASTM D664) of 5 to 100, 10 to 80, or 15 to 75, or 20 to 70, or about 20 to about 60 or 65 mgKOH/g.
- the acid-containing polymer is reacted with a monoamine or a polyam- ine typically having a single primary amino group.
- the olefin polymer is an ethylene/propylene copolymer
- said polyamine is not a poly(eth- yleneamine).
- the reaction may consist of condensation to form an imide, amide, or half-amide or amide-ester (assuming a portion of alcohol is also reacted) or an amine salt.
- a primary amino group will typically condense to form an amide or, in the case of maleic anhydride, an imide.
- the amine will have a single primary amino group, that is, it will not have two or more primary amino groups (except perhaps a very small an inconse- quential amount of additional primary amino groups within the entire amine component, e.g., less than 5% or 2% or 1% or 0.5%, or 0.01 to 0.1%, especially 1% or less, such as 0.01 to 1%, of amine groups being primary). This feature will minimize the amount of crosslinking that might otherwise occur.
- Poly(eth- yleneamine)s may generally, and in an oversimplified manner, be depicted as H2N-(C2H4-NH-)n-C2H4-NH2, where n may be, for instance, 2 through 6.
- Suitable primary amines may include aromatic amines, such as amines wherein a carbon atom of the aromatic ring structure is attached directly to the amino nitrogen.
- the amines may be monoamines or polyamines.
- the aromatic ring will typically be a mononuclear aromatic ring (i.e., one derived from ben- zene) but can include fused aromatic rings, such as those derived from naphtha- lene.
- aromatic amines include aniline, N-alkylanilines such as N- methylaniline, and N-butylaniline, di-(para-methylphenyl)amine, naphthyla- mine, 4-aminodiphenylamine, N,N-dimethylphenylenediamine, 4-(4-nitro- phenylazo)aniline (disperse orange 3), sulfamethazine, 4-phenoxyaniline, 3-ni- troaniline, 4-aminoacetanilide, 4-amino-2-hydroxy-benzoic acid phenyl ester (phenyl amino salicylate), N-(4-amino-5-methoxy-2-methyl-phenyl)-benzamide (fast violet B), N-(4-amino-2
- aromatic amines include amino- substituted aromatic compounds and amines in which an amine nitrogen is a part of an aromatic ring, such as 3-aminoquinoline, 5-aminoquinoline, and 8-amino- quinoline. Also included are aromatic amines such as 2-aminobenzimidazole, which contains one secondary amino group attached directly to the aromatic ring and a primary amino group attached to the imidazole ring.
- amines include N-(4-anilinophenyl)-3-aminobutanamide (i.e., ⁇ -NH- ⁇ -NH- COCH2CH(CH3)NH2).
- Additional aromatic amines include aminocarbazoles, aminoindoles, aminopyrroles, aminoindazolinones, aminoperimidines, mercap- totriazoles, aminophenothiazines, aminopyridines, aminopyrazines, aminopy- rimidines, pyridines, pyrazines, pyrimidines, aminothiadiazoles, aminothiothi- adiazoles, and aminobenzotriaozles.
- Suitable amines include 3-amino-N- (4-anilinophenyl)-N-isopropyl butanamide, and N-(4-anilinophenyl)-3- ⁇ (3-ami- nopropyl)-(cocoalkyl)amino ⁇ butanamide.
- Other aromatic amines which can be used include various aromatic amine dye intermediates containing multiple aro- matic rings linked by, for example, amide structures. Examples include materi- als of the general structure ⁇ -CONH- ⁇ -NH2 where the phenyl groups may be substituted.
- Suitable aromatic amines include those in which the amine nitrogen is a substituent on an aromatic carboxylic compound, that is, the nitrogen is not sp2 hybridized within an aromatic ring.
- the amine may also be non-aromatic, or in other words, an amine in which an amino nitrogen is not attached directly to a carbon atom of an aromatic ring, or in which an amine nitrogen is not a part of an aromatic ring, or in which an amine nitrogen is not a substituent on an aromatic carboxylic compound.
- non-aromatic amines may be considered to be aliphatic, or cycloaliphatic.
- Such amines may be straight, or branched or functionalized with some functional group.
- the non-aromatic amines can include monoamines hav- ing, e.g., 1 to 8 carbon atoms, such as methylamine, ethylamine, and propyla- mine, as well as various higher amines. Diamines or polyamines can also be used, and typically will have only a single primary amino group.
- non-aromatic amines can be used alone or in combination with each other or in combination with aromatic amines.
- the amount of aromatic amine may, in some embodiments, be a minor amount com- pared with the amount of the non-aromatic amines, or in some instance, the composition may be substantially free or free of aromatic amine.
- the grafted olefin polymer may have a nitrogen content, calculated using ASTM D5291, of 0.05 to 3 percent by weight, or 0.1 to 2.5, or 0.15 to 2, or 0.2 to 1.75, or 0.25 to 1.6 percent by weight.
- the lubricant additive composition may also include antioxidants, e.g., aromatic amine antioxidants, hindered phenolic antioxidants including ester- containing hindered phenolic antioxidants, and sulfurized olefin antioxidants. These antioxidants may be present in amounts of 0.01 to 5, or 0.15 to 3or 0.2 to 1.5, 0.2 to 1 or 0.25 to 0.7 percent by weight.
- the lubricant additive composition of the invention includes an aryl amine antioxidant.
- the aryl amine antioxidant may be a phe- nyl- ⁇ -naphthylamine (PANA) or a hydrocarbyl substituted diphenylamine, or mixtures thereof.
- the hydrocarbyl substituted diphenylamine may include mono- or di- C4 to C16-, or C6 to C12-, or C9- alkyl diphenylamine.
- the hydrocarbyl substituted diphenylamine may be octyl diphenylamine, or di-octyl diphenylamine, dinonyl diphenylamine, typically dinonyl diphenyla- mine.
- the aryl amine antioxidant may be present at 0.2 wt % to 1.2 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 lubricant additive composition.
- the hindered phenol antioxidant often contains a secondary butyl and/or a tertiary butyl group as a sterically hindering group. The phenol group is often further substituted with a hydrocarbyl group and/or a bridging group linking to a second aromatic group.
- hindered phenol antioxidants examples 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-bu- tylphenol, or 4-dodecyl-2,6-di-tert-butylphenol.
- Antioxidants also include sulfurized olefins such as mono-, or disulfides or mixtures thereof. These materials generally have sulfide linkages having 1 to 10 sulfur atoms, for instance, 1 to 4, or 1 or 2.
- Materials which can be sulfurized to employ as sulfurized antioxidants in the lubricant additive composition can include oils, fatty acids and esters, olefins and polyolefins made thereof, ter- penes, or Diels-Alder adducts. Details of methods of preparing some such sulfu- rized materials can be found in U.S. Pat. Nos.3,471,404 and 4,191,659.
- Sulfurized olefins are well known commercial materials, and those which are substantially nitrogen-free, that is, not containing nitrogen functionality, are readily available.
- the olefinic compounds which may be sulfurized are diverse in nature. They contain at least one olefinic double bond, which is defined as a non-aromatic double bond; that is, one connecting two aliphatic carbon atoms.
- R groups in the above formula which are not hydrogen may be satisfied by such groups as —C(R*5)3, —COOR*5, — COOM, —X, —YR*5 or —Ar, wherein each R 5 is independently hydrogen, al- kyl, alkenyl, aryl, substituted alkyl, substituted alkenyl or substituted aryl, with the proviso that any two R 5 groups can be alkylene or substituted alkylene whereby a ring ofup to 12 carbon atoms is formed; M is one equivalent of a metal cation (preferably Group I or II, e.g., sodium, potassium, barium, cal- cium); X is halogen (e.g., chloro, bromo, or iodo);Y is oxygen or divalent sul- fur; Ar is an aryl or substituted aryl group of up to 12 carbon atoms.
- M is one equivalent of a metal cation (preferably Group I or II, e
- the olefin component comprises at least one olefin.
- This olefin is pref- erably an aliphatic olefin, which usually will contain 4 to 40 carbon atoms, pref- erably from 8 to 36 or 12 to 18 carbon atoms. Terminal olefins, or alpha-olefins, are preferred, especially those having from 12 to 20 carbon atoms. Mixtures of these olefins are commercially available, and such mixtures are contemplated for use in this invention.
- the sulfurized olefin can be prepared by reacting a single reactant or a mixture of appropriate reactants with a source of sulfur.
- the sulfurization reac- tion generally is affected at an elevated temperature, e.g., 50-350° C. or 100- 200° C., with efficient agitation and often in an inert atmosphere such as nitro- gen, optionally in the presence of an inert solvent.
- the sulfurizing agents useful in the process of the present invention include elemental sulfur, which is pre- ferred, hydrogen sulfide, sulfur halide, sodium sulfide and a mixture of hydro- gen sulfide and sulfur or sulfur dioxide. Usually, the amount of sulfur or sulfu- rizing agent employed calculated based on the total olefinic unsaturation of the mixture.
- the olefinic compound is usually one in which each R group, above, which is not hydrogen is independently alkyl, alkenyl or aryl group.
- Monoole- finic and diolefinic compounds, particularly the former, are preferred, and espe- cially terminal monoolefinic hydrocarbons; that is, those compounds in which R 3 and R 4 are hydrogen and R 1 and R 2 are alkyl or aryl, especially alkyl (that is, the olefin is aliphatic) having 1 to 30, or 1 to 16, or 1 to 8, or 1 to 4 carbon atoms.
- the poly(meth)acrylate polymer may be derived from a monomer com- position comprising:(a) 50 wt % to 95 wt %, or 60 wt % to 80 wt % of an alkyl (meth)acrylate, wherein the alkyl group of the (meth)acrylate has 10 to 15 car- bon atoms; (b) 1 wt % to 40 wt %, or 4 wt % to 35 wt % of an alkyl (meth)acry- late, wherein the alkyl group of the (meth)acrylate has 1 to 9 carbon atoms; (c) 1 wt % to 10 wt %, or 1 wt % to 8 wt % of a monomer having dispersant function- ality, (d) 0 wt % to 4 wt %, or 0 wt % to 2 wt %, or 0 wt
- the linear polymer may contain 0 wt % to 20 wt % of 16 to 18 alkyl (meth)acrylate.
- the linear polymer can include a poly(meth)acrylate (typically a polymethacrylate) with units derived from a mixture of alkyl (meth)acrylate ester monomers containing, (a) 8 to 24, or 10 to 18, or 12 to 15 carbon atoms in the alcohol-derived portion of the ester group and (b) 6 to 11, or 8 to 11, or 8 carbon atoms in the alcohol-derived portion of the ester group, and which have 2-(C1-4 alkyl)-substituents, and optionally, at least one monomer selected from the group consisting of (meth)acrylic acid esters containing 1 to 7 carbon atoms in the alcohol-derived portion of the ester group and which are different from (meth)acrylic acid esters (a) and (b), vinyl aromatic compounds (or vinyl aromatic monomers); and nitrogen-containing vinyl monomer
- the linear polymer of this type is described in more detail in US 6,124,249, or EP 0937769 A1 paragraphs [0019] and [0031] to [0067].
- the linear polymer may fur- ther contain a third monomer.
- the third monomer may be styrene, or mixtures thereof.
- the third monomer may be present in an amount 0% to 25% of the pol- ymer composition, or from 1% to 15% of the composition, 2% to 10% of the composition, or even from 1% to 3% of the composition.
- the ester groups may contain 2 to 65%, or 5 to 60% of the ester groups having branched alkyl groups.
- the branched alkyl groups may be ⁇ -branched and may contain 8 to 60, or 8 to 30, or 8 to 16 carbon atoms.
- branched alkyl groups may be derived from 2-ethylhexanol, 2-butyloctanol, 2- hexyldecanol, 2-octyldodecanol, 2-decyltetradecanol, or mixtures thereof, or commercially available alcohols such as Isofol® branched Guerbet alcohols available from Sasol.
- the C1-4 alkyl substituents may be methyl, ethyl, and any isomers of propyl and butyl.
- the weight average molecular weight of the linear poly(meth)acrylate may be 45,000 or less, or 35,000 or less, or 25,000 or less, or 8000 to 25,000, or, 10,000 to 35,000, or 12,000 to 20,000.
- the linear polymer may be called a viscosity modifier, or a dispersant viscosity modifier as it may exhibit dispersant functionality. Reference to a “dispersant viscosity modifier” herein is exclusive of dispersants, which are a separate class of compounds.
- the linear polymer may be used as a sole viscos- ity modifier (or dispersant viscosity modifier) present at 0.5 wt % to 4 wt % of a linear (meth)acrylic polymer viscosity modifier having dispersant functionality, wherein the linear polymer has a weight average molecular weight of 5,000 to 25,000, or 10,000 to 20,000, and wherein oil the of lubricating viscosity has a kinematic viscosity at 100°C of 4 to 6 cSt (mm2/s) and a viscosity index of 120 to 150.
- the lubricant additive composition in one embodiment may contain only two linear polymer viscosity modifiers having dispersant functionality, wherein the linear polymer has a weight average molecular weight of 5,000 to 25,000, or 10,000 to 20,000.
- the lubricant additive composition may comprise 0.1 wt% to 4 wt % (or 0.2 wt % to 3 wt %) of a linear (meth)acrylic polymer viscos- ity modifier having dispersant functionality, wherein the linear polymer has a weight average molecular weight of greater than 25,000 to 400,000 (or to 350,000) or 30,000 to 150,000.
- the lubricant additive composition may comprise a linear polymer vis- cosity modifier having dispersant functionality comprises: 0.1 wt % to 5 wt % (or 1 wt % to 4 wt %) of a linear (meth)acrylic polymer viscosity modifier hav- ing dispersant functionality, wherein the linear polymer has a weight average molecular weight of 10,000 to 20,000; and 0.1 wt % to 4 wt % (or 1 wt % to 3 wt %) of a linear (meth)acrylic polymer viscosity modifier having dispersant functionality, wherein the linear polymer has a weight average molecular weight of greater than 20,000 to 250,000 (or 30,000 to 150,000).
- the molecular weight of the viscosity modifier has been determined using known methods, such as GPC analysis using polysty- rene standards. Methods for determining molecular weights of polymers are well known. The methods are described for instance: (i) P.J. Flory, “Principles of star polymer Chemistry”, Georgia University Press 91953), Chapter VII, pp 266-315; or (ii) “Macromolecules, an Introduction to star polymer Science”, F. A. Bovey and F. H. Winslow, Editors, Academic Press (1979), pp 296-312. [0141] Another type of viscosity modifier that may be employed is an ethylene ⁇ -olefin copolymer.
- the ethylene ⁇ -olefin copolymer includes those with a backbone containing 1 to 3 different ⁇ -olefin monomers (beside the ethylene monomer), in one embodiment 1 to 3 different ⁇ -olefin monomers and in yet an- other embodiment 1 ⁇ -olefin monomer in addition to the ethylene monomer.
- the ⁇ -olefin monomers include 3 to 20, and in other embodiments 3 to 12, or 3 to 10, or 3 to 6, or 3 to 4 carbon atoms, and in another embodiment 3 carbon atoms (i.e., propylene).
- the olefin may be an alpha olefin of the above listed number of carbon atoms.
- the ethylene ⁇ -olefin copolymer will have greater than 5 percent by weight ethylene monomer units, and in some embodiments at least 10 percent and up to 90 percent, or 15 to 85, or 20 to 80, or 30 to 50 percent by weight eth- ylene monomer units. In certain embodiments the amount of ethylene monomer will be 30-50 weight percent; in other embodiments the amount of ethylene monomer will be 75 to 85, or 79 to 81, weight percent. Otherwise expressed, the amount of ethylene monomer may be 15 to 90 or 25 to 85 or 40 to 60 or 45 to 55 mole percent.
- co-monomers examples include propylene, 1-butene, 1-hex- ene, 1-octene, 4-methyl-l-pentene, 1-decene, 1-dodecene, 1-tridecene, 1-tetrade- cene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene or mixtures thereof.
- the co-monomer may be 1-butene, propylene or mixtures thereof.
- ⁇ -olefin copolymers examples include ethylene-propylene copoly- mers and ethylene-1-butene copolymers and mixtures thereof.
- the polymer (c) may have a kinematic viscosity at 100° C. of at least 35 or at least 50 or at least 100 or at least 500 mm2/s at 100° C. In certain embodi- ments the polymer (c) may have a kinematic viscosity at 100° C. of at least about 500 or at least about 1000 mm2/s or 1500 mm2/s or 2000 mm2/s, which feature will distinguish it from similar materials of much lower viscosity that might be used as base oils.
- the lubricant for the method can further contain a metal-containing detergent.
- the metal-containing detergent may be an over- based detergent. Overbased detergents otherwise referred to as overbased or su- perbased salts are characterized by a metal content in excess of that which would be necessary for neutralization according to the stoichiometry of the metal and the particular acidic organic compound reacted with the metal.
- the overbased detergent may be selected from the group consisting of non-sulfur containing phenates, sulfur containing phenates, sulfonates, salixarates, salicy- lates, and mixtures thereof.
- Examples of unsaturated carboxylic esters include methyl acrylate, ethyl acrylate, 2-ethylhexyl acrylate, 2-hydroxy- ethyl acrylate, ethyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypro- pyl methacrylate, 2-hydroxypropyl acrylate, ethyl maleate, butyl maleate, and 2- ethylhexyl maleate.
- the foregoing list includes mono- as well as diesters of ma- leic, fumaric, and citraconic acids.
- the other antiwear can be, for example, a dithiophosphate.
- a dithio- phosphate ester can be formed by reaction of a dithiophosphoric acid repre- sented by (RO)2PSSH with an unsaturated compound.
- the unsaturated compounds is an unsaturated carboxylic acid or ester.
- unsaturated carboxylic acids or anhydrides include acrylic acids or esters, meth- acrylate acid or esters, itaconic acid or ester, fumaric acid or esters, and maleic acid, anhydride, or esters.
- the other antiwear can also be a sulfur containing phosphite.
- Sulfur con- taining phosphites can include, for example, a material represented by the for- mula [R1O(OR2)(S)PSC2H4(C)(O)OR4O]nP(OR5)2-n(O)H, wherein R1 and R2 are each independently hydrocarbyl groups of 3 to 12 carbon atoms, or 6 to 8 carbon atoms, or wherein R1 and R2 together with the adjacent O and P atoms form a ring containing 2 to 6 carbon atoms; R4 is an alkylene group of 2 to 6 carbon atoms or 2 to 4 carbon atoms; R5 is hydrogen or a hydrocarbyl group of 1 to about 12 carbon atoms; and n is 1 or 2.
- R1O(OR2)(S)PSC2H4(C)(O)OR4O]nP(OR5)2-n(O)H wherein R1 and R2 are each independently hydrocarbyl groups of 3 to 12 carbon atoms, or 6 to 8
- the C12-22 hydrocarbyl phosphite may be present in the lubricant composition at about 0.05 wt.% to about 1.5 wt.% of the lubricant composition, or from about 0.1 wt.% to about 1.0 wt.% of the lubricant composition.
- the amount of each chemical component described is presented exclu- sive of any solvent or diluent oil, which may be customarily present in the com-tapal material, that is, on an active chemical basis, unless otherwise indicated.
- hydrocarbyl refers to a group having a carbon atom directly attached to the remainder of the molecule, where the group in- cludes at least carbon and hydrogen atoms. If the hydrocarbyl group comprises more than one carbon atom, then those carbons need not necessarily be linked to each other. For example, at least two of the carbons may be linked via a suitable element or group.
- hydrocarbyl refers to a group having a carbon atom directly attached to the remainder of the molecule, where the group consists of carbon, hydrogen, optionally one or more heteroa- toms provided the heteroatoms do not alter the predominantly hydrocarbon nature of the substituent.
- the heteroatom may link at least two of the carbons in the hydrocarbyl group, and optionally no more than two non-hydrocarbon sub- stituents. Suitable heteroatoms will be apparent to those skilled in the art and in- clude, for instance, sulphur, nitrogen, oxygen, phosphorus and silicon.
- hydrocarbyl contains heteroatoms
- no more than two heteroatoms will be present for every ten carbon atoms in the hydrocarbyl group.
- Suitable non-hydrocarbon substituents will also be apparent to those skilled in the art and include, for instance, halo, hydroxy, alkoxy, mercapto, alkylmercapto, nitro, ni- troso, and sulphoxy.
- Examples of hydrocarbyls within the context of the present technology therefore include: - hydrocarbon groups selected from aliphatic (e.g. alkyl or alkenyl), ali- cyclic (e.g.
- - substituted hydrocarbon groups selected from hydrocarbon groups de- fined in (i) substituted with no more than two non-hydrocarbon sub- stituents and/or one or more hydrocarbon substituents, the non-hydro- carbon substituents being selected from the group consisting of halo, hydroxy, alkoxy, mercapto, alkylmercapto, nitro, nitroso, and sulphoxy;
- - hetero-containing hydrocarbon groups selected from hydrocarbon groups defined in (i) containing one or more heteroatom in the ring or chain, provided that the group has no more than two heteroatoms pre- sent for every ten carbon atoms in the group, the heteroatoms being selected from sulphur, nitrogen, oxygen, phosphorus and silicon.
- hetero-containing hydrocarbon groups may be substituted with no more than two non-hydrocarbon substituents and/or one or more hydrocar- bon substituents.
- hydrocarbyl refers to a group having a carbon atoms directly attached to the remainder of the molecule, where the group consists of carbon and hydrogen atoms.
- the formation of conducting layers results in detection of energy flow outside of the intended path. This is detected via the induced magnetic field caused by the flow of current.
- the fluid tested is contained within a closed, vented vessel. Temperature is measured in both the solution and vapor space via two Platinum Resistance Thermometers (PRTs). Vapor retention is controlled using a condenser.
- PRTs Platinum Resistance Thermometers
- Vapor retention is controlled using a condenser.
- data is acquired by the data acquisition component and processed by the data pro- cessing component. Analysis at the end of the test includes resistance measure- ments, used oil analysis (ICP), microscopy and elemental analysis of the depos- ited material, e.g., via energy dispersive X-ray analysis (EDAX). Further details of this test method are disclosed in PCT Appl.
- WO 2021/247428 Three lubricant compositions INV1, INV 2 and COMP1 were tested in the CLDT to evaluate the effects of the polyether additive in preventing conduc- tive layer deposits.
- the composition of these lubricant compositions is outlined in Table 1.
- Table 1. Lubricant Compositions
- Table 2. Conducting layer deposits are formed in COMP1 in both the vapor phase and in solution over the test period of 499 hours. INV1 and INV2 contain- ing does not form conducting layer deposits. Table 2. CLDT results.
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Abstract
Description
Claims
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US202263427477P | 2022-11-23 | 2022-11-23 | |
| PCT/US2023/080531 WO2024112665A1 (en) | 2022-11-23 | 2023-11-20 | Powertrain lubricant containing polyether |
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| Publication Number | Publication Date |
|---|---|
| EP4623053A1 true EP4623053A1 (en) | 2025-10-01 |
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ID=89224490
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP23825665.5A Pending EP4623053A1 (en) | 2022-11-23 | 2023-11-20 | Powertrain lubricant containing polyether |
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| Country | Link |
|---|---|
| EP (1) | EP4623053A1 (en) |
| CN (1) | CN120202279A (en) |
| WO (1) | WO2024112665A1 (en) |
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| US20180057769A1 (en) * | 2015-07-07 | 2018-03-01 | Exxonmobil Research And Engineering Company | Method and composition for preventing or reducing engine knock and pre-ignition in high compression spark ignition engines |
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| CN120202279A (en) | 2025-06-24 |
| WO2024112665A1 (en) | 2024-05-30 |
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