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    公开号:BR112012003705B1
    申请号:R112012003705-6
    申请日:2010-08-16
    公开日:2018-08-07
    发明作者:R.S. Barton William；L. Crawley Seth；E. Mosier Patrick；D. Gieselman Matthew；J. Saccomando Daniel
    申请人:The Lubrizol Corporation；
    IPC主号:
    专利说明:

    (54) Title: LUBRICATING COMPOSITION CONTAINING AN ANTI-WEAR AGENT (51) Int.CI .: C10M 129/66; C10M 129/76 (30) Unionist Priority: 18/08/2009 US 61 / 234,717 (73) Holder (s): THE LUBRIZOL CORPORATION (72) Inventor (s): WILLIAM R.S. BARTON; SETH L. CRAWLEY; PATRICK E. MOSIER; MATTHEWD. GIESELMAN; DANIEL J. SACCOMANDO (85) National Phase Start Date: 17/02/2012
    1/39
    LUBRICANT COMPOSITION CONTAINING AN ANTI-WEAR AGENT
    Field of the Invention
    The invention provides a lubricating composition containing an anti-wear agent and a lubricating viscosity oil. The invention also relates to the use of the lubricating composition in an internal combustion engine.
    History of the Invention
    Lubricating oils are well known to contain a number of active surface additives (including anti-wear agents, dispersants or detergents) used to protect internal combustion engines against corrosion, wear, soot deposits and acid formation. Generally, said surface active additives can have harmful effects on the wear of engine components (both on iron and aluminum based components), bearing corrosion or fuel economy. A common anti-wear additive for engine lubricating oils is zinc dialkyldithiophosphate (ZDDP). ZDDP anti-wear additives are believed to protect the engine by forming a protective film on metal surfaces. The ZDDP can also have a detrimental impact on the economy and fuel efficiency and corrosion of copper. Consequently, engine lubricants may also contain a friction modifier to prevent the harmful impact of ZDDP on fuel economy and corrosion inhibitors to prevent the harmful impact of ZDDP on copper corrosion. Other additives can also increase lead corrosion.
    In addition, engine lubricants containing phosphorus and sulfur compounds have been shown to contribute in part to particulate emissions and emissions of other pollutants. In addition, sulfur and phosphorus tend to poison the catalysts used in catalytic converters,
    2/39 resulting in a reduction in the performance of said catalysts.
    With the increasing control both of the formation of sulfated ash and the release of emissions (typically to reduce the formation of NOx, formation of SOx), there is a desire to reduce the amounts of sulfur, phosphorus and sulfated ash in oils from engines. Consequently, the amounts of phosphorus-containing anti-wear agents, such as ZDDP, detergents with bases, such as calcium or magnesium sulfonates and phenates have been reduced. Consequently, ash-free additives, such as esters of polyhydric alcohols or hydroxyl-containing acids including glycerol monooleate and alkoxylated amines, have been contemplated to provide frictional performance. However, there have been observations that friction modifiers without ash can, in some situations, increase the corrosion of the metal, namely copper or lead. Corrosion of copper and lead can occur from bearings and other metal components of alloy-derived engines using copper or lead. Consequently, there is a need to reduce the amount of corrosion caused by ash-free additives. However, reducing the levels of anti-wear additives and other additives containing ash can result in increased amounts of wear and / or corrosion of copper.
    Canadian Patent CA 1,183,125 (by Barrer, filed September 10, 1981), discloses lubricants for gasoline engines containing alkyl ester tartrates, where the sum of the carbon atoms in the alkyl groups is at least 8. Tartrates are revealed as anti-wear agents. Other references that reveal tartrates and / or tartrimids include the Publication
    3/39
    International WO 2006/044411, and US Patent Applications for internal combustion engines that require reduced amounts of sulfur, sulfated ash and phosphorus. The lubricating composition has anti-wear or anti-fatigue properties. Lubricating compositions are suitable for land vehicles.
    US Patent No. 4,237,022 (by Barrer, filed on December 2, 1980) discloses tartrimides useful as additives in lubricants and fuels for effective reduction in winch and friction, as well as improvement in fuel economy.
    United States Patent No. 5,338,470 (by Hiebert, filed on December 10, 1992) and International Publication WO 2005/087904 (by Migdal, filed on March 11, 2004) disclose lubricants containing at least one ester of hydroxy carboxylic acid or hydroxy polycarboxylic acid (in particular, citrates or ethyl glycolate). The lubricating composition has anti-wear or anti-fatigue properties.
    International Order WO 2008/070307 (by Brown, filed October 22, 2007) discloses engine lubricants containing anti-wear agents based on malonate esters.
    US Patent No. 4,436,640 (by Yamaguchi and filed on May 27, 1982) discloses a lubricating anti-wear agent prepared by a two-step reaction involving (i) reaction glycolic acid with an alcohol containing from 1 to 6 carbon atoms, and (i) reacting the product of (i) with phosphorous penta sulfide. The anti-wear agent is reported to be useful for a set of meat followers.
    Lubricating additives derived from thio-glycolic acid derivatives were considered as
    4/39 additives. Additives from thioglycolic acid derivatives are summarized in a variety of US patents, Japanese patent application and German patent. US Patents include
    4,157,970 (per Yaf f e and deposited in 12 of June in 1979), 4,863,622 (per Chiu, deposited in 05 in September in 1989), 5,132,034 (per Hsu, deposited in 21 in July of 1992 and in
    June), 5,215,549 (by Hsu, deposited on June 1, 1993), and 6,127,327 (by Camenzind and deposited on June 24, 1999). Japanese Patent Applications include 2005139238 A (by Yanagi and filed on June 2, 2005), Japanese Patent Applications 10183161 A (by Imai and filed on July 14, 1998) and 10130679A (by Endo and filed on May 19 1998), 05117680A (by Sato and filed on May 15, 1993). The East German Patent is DD 299533 A5 (by Buechner, published on April 23, 1992).
    Summary of the Invention
    The inventors of this invention have discovered a lubricant composition which is capable of providing at least one of these: anti-wear performance, friction modification (particularly to improve fuel economy) or inhibition of lead or copper corrosion (typically lead).
    As used as a reference here, the amounts of additives present in the disclosed lubricant composition are here quoted on an oil-free basis, that is, amounts of assets.
    In one embodiment, the present invention provides a lubricating composition comprising a lubricating viscosity oil and a compound obtained / capable of being obtained by a process comprising reacting with a glycolic acid, a 2-halo-acetic acid, or an acid
    5/39 lactic acid, or an alkali or alkali metal salts thereof, (typically glycolic acid or 2-halo-acetic acid) with at least one component selected from the group consisting of an amine, an alcohol, and an amino alcohol.
    alcohol can be selected from the group consisting of an alkoxy alcohol, a phenoxy alcohol, a mono alcohol, a diol (can be a 1,2-diol, or a 1,3-diol, or a 1,4-diol, typically 1,2-diol), a triol and a higher polyol (such as a tetraol or pentaol, typically tetraol). The amine can be selected from the group consisting of a mono-amine, a polyamine (such as a diamine, a triamine, or a higher polyamine).
    In one embodiment, the compound obtained / capable of being obtained by the process described here can be prepared by reacting on a 0.9 mole to 6 mole molar ratio basis of any glycolic acid or lactic acid with one mole of alcohol or amine. In one embodiment, the compound obtained / capable of being obtained by the process described here can be prepared by reacting a molar ratio base of 1.2 moles to 6 moles of both glycolic acid and lactic acid with one mole of alcohol or the mine. In one embodiment, the compound obtained / capable of being obtained by the process described here can be prepared by reacting on a molar ratio basis of 1.5 moles to 4 moles of both glycolic acid and lactic acid with one mole of alcohol or the mine. Typically when the alcohol is a mono-alcohol of the general formula R 1 -OH (where R 1 can independently be a hydrocarbon group, typically containing 4 to 30, or 6 to 20, or 8 to 18 carbon atoms) , the molar ratio of both glycolic acid and lactic acid to mono alcohol may be in the range of 1.2 to 6 for one mole of alcohol, or even 1.5 to 4 for one mole of alcohol.
    6/39
    The compound obtained / capable of being obtained by the process described here can be present in 0.01% to 5% by weight, or 0.1% to 3% by weight, or 0.2% to 1.5% by weight or 0.25% to 1% by weight of the lubricating composition. In one embodiment, the compound can be present at 0.1% to 1% by weight of the lubricating composition.
    When the compound obtained / capable of being obtained by the process described here is a hydrocarbyl substituted glycolate (typically an alkyl glycolate or alkoxy glycolate), it can be present at 0.5% to 1.5% by weight or 0.5% to 1% by weight of the lubricating composition.
    In one embodiment, the invention provides a method for lubricating an internal combustion engine comprising providing the internal combustion engine with a lubricating composition as disclosed herein.
    In one embodiment, the invention provides a method for lubricating an internal combustion engine as described here, wherein the internal combustion engine has surfaces of an aluminum alloy, or aluminum compound. Typically, the lubricant composition for lubricating an aluminum alloy or aluminum compound surface can be a lubricating composition comprising a lubricating viscosity oil and a compound obtained / capable of being obtained by a process comprising reacting with a glycolic acid, a 2halo-acetic acid, or a lactic acid, or an alkali or alkali metal salts thereof (typically glycolic acid or a 2-halo-acetic acid), with at least one component selected from the group consisting of an amine, a alcohol and an amino alcohol. The alcohol can have the formula R 1 OH, where R 1 can be independently of a hydrocarbon group, typically containing 4 to 30, or 6 to 20, or 8 to 18 carbon atoms).
    7/39
    In one embodiment, the invention provides a method for lubricating an internal combustion engine as described here, wherein the aluminum alloy can be a eutectic or a hyper-eutectic aluminum alloy (such as those derived from aluminum silicates) , aluminum oxides, or other ceramic materials).
    In one embodiment, the invention provides a method for lubricating an internal combustion engine as described here, wherein the internal combustion engine has a steel surface. Typically, the lubricating composition for lubricating a steel surface can be a lubricating composition comprising a lubricating viscosity oil and a compound obtained / capable of being obtained by a process comprising reacting with a glycolic acid, a 2-halo-acetic acid, or a lactic acid, or an alkali or alkali metal salts thereof, (typically glycolic acid or a 2-halo-acetic acid) with at least one component selected from the group consisting of an amine, an alcohol, and an amino alcohol .
    In one embodiment, the invention provides a method for lubricating an internal combustion engine as described here, in which the internal combustion engine has a cylinder bore, cylinder block or piston ring that has an aluminum alloy, a composed of aluminum or steel surface (ie containing iron).
    In one embodiment, the invention provides for the use of the above compounds as an anti-wear agent, a friction modifier, or a corrosion inhibitor of lead or copper (typically lead).
    In one embodiment, the invention provides for the use of the above compounds as an anti-wear agent, a friction modifier (particularly to improve fuel economy), or a lead corrosion inhibitor
    8/39 or copper (typically lead) in an internal combustion engine lubricant.
    Anti-wear performance or frictional performance can, for example, be provided by a compound obtained / capable of being obtained by a process comprising reacting with a glycolic acid, a 2-halo-acetic acid, or a lactic acid, or an alkali or alkali metal salts thereof, (typically glycolic acid or a 2-haloacetic acid) with at least one component selected from the group consisting of an amine, an alcohol and an amino alcohol.
    Corrosion of lead or copper can, for example, be provided by a compound obtained / capable of being obtained by a process comprising reacting with glycolic acid, a 2-halo-acetic acid or alkali or alkali metal salts thereof, or acid lactic acid (typically glycolic acid or 2-halo-acetic acid) with at least one alcohol, where the alcohol can be an alkoxy alcohol or a phenoxy alcohol.
    Detailed Description of the Invention
    The present invention provides a lubricating composition and a method for lubricating an engine as disclosed above.
    The compound as described herein can be obtained / capable of being obtained also by a process comprising reacting with lactic acid or glycolic acid with a mono-alcohol or a mono-amine. The compound of this type can typically be similar to a compound represented by formula (1) (see below).
    monoalcohol may include a variety of alcohols having 4 to 30, or 6 to 20,, or 8 to 18 carbon atoms. Alcohols include butanol, 2-methylpentanol, 2-propylheptanol, 2-butyloctanol, 2-ethylhexanol, octanol,
    9/39 nonanol, isooctanol, isononanol, 2-tert-butylheptanol, 3isopropylheptanol, decanol, undecanol, 5-methylundecanol, docecanol, 2-methylldecanol, tridecanol, 5-methyltridecanol, tetradecanol, pentadecanol, hexadecanol, hexadecanol, 2-methyladecanol, 2-tertanol , 4tert-butyloctadecanol, 5-ethyloctadecanol, 3isopropyloctadecanol, octadecanol, nonadecanol, eicosanol, cetileicosanol, stearylicosanol, docosanol and / or eicosiltetratriacontanol. Other useful monoalcohols include oleyl alcohol, stearyl alcohol, coconut alcohol, tallow alcohol, or mixtures thereof.
    Commercially available alcohols include Oxo Alcohol® 7911, Oxo Alcohol® 7900 and Oco Alcohol® 1100 from Monsanto; Alphanol® 79 from ICI; Nafol® 1620, Alfol® 610 and Alfol® 810 from Condea (now Sasol); Epal® 610 and Epal® 810 from Ethyl Corporation; Linevol® 911 and Dobanol® 25 L from Shell AG; Liai® 125 from Condea Augusta, Milan; Dehydad® and Lorol® from Henkel KGaA (now Cognis) as well as Linopol® 7-11 and Acropol® 91 from Ugine Kuhlmann.
    The mono-amine can include a variety of amines having 4 to 30, or 6 to 20, or 8 to 18 carbon atoms. Mono-amine may include butamine, 2-methylpentamine, 2-propylheptamine, 2-butyloctamine, 2-ethylhexamine, octamine, nonamine, isooctamine, isononamine, 2-tert-butylheptamine, 3-isopropylheptamine, decamine, undecamine, 5methylundecamine, trodecamine, dodamine 5-methyltridecamine, pentadecamine, hexadecamine,
    5-isopropylheptadecamine, 5-ethyloctadecamine,
    2-methyldodecamine, · tetradecamine, 2-methylhexadecamine,
    4-tert3heptadecamine, butyloctadecamine, isopropyloctadecamine, octadecamine, nonadecamine, eicosamine, cetileicosamine, stearileiçosamine, docosamine and / or eicosiltetratriacontamina. Other useful mono-amines
    10/39 include oleyl amine, stearyl amine, coconut amine, tallow amine or mixtures thereof.
    The compound as described herein can also be obtained / capable of being obtained by a process comprising reacting a glycolic acid, a 2-haloacetic acid, or a lactic acid or an alkali or alkali metal salts thereof (typically glycolic acid or a 2halo acid acetic) with at least one amine or alcohol, where the alcohol can be a diol, a triol or a higher polyol, and where the amine can be a diamine, a triamine, or a higher polyamine. The alcohol or amine component can also include one or more mono-alcohols or mono-amines. Typically, a compound of this type can be similar to a compound represented by formula (2) (see below).
    The reaction diol, triol or tetrol can include 1,2,7,8-octanetetraol, 2-butyl-1,3-octanediol, 2-butyl-1,3-nonanediol, 1,2,3-heptanetriol, 1,2- butanediol, neopentyl glycol, pentaerythritol, trimethylolpropane, 1,2-hexanediol, 1,2-octanediol, 1,2, decanediol, 1,2-dodecanediol, 1,2decanediol, 1,2-tetradecanediol, 1,2-hexadecanediol, 1 , 2octadecanediol, 1,2-eicosanediol, 2-ethyl-1,3-hexanediol, 2-butyl-2-ethyl-1,3, propanediol, glycerin or ethylene glycol, or mixtures thereof.
    amino alcohol can include ethanolamine, isopropanolamine, diethanolamine, triethanolamine, diethylethanolamine, dimethylethanolamine, dibultylethanolamine, 3-amino-1,2-propanediol; serinol; 2-amino-2-methyl-1,3propanediol; tris (hydroxymethyl) -aminomethane; Nmethylglucamine, 1-amino-1-deoxy-D-sorbitol; amine diethanol; diisopropanolamine; diethanol amine N-methyl-N, N; triethanolamine; Ν, Ν, Ν ', N'-tetrakis (2-hydroxypropyl) ethylene diamine, 2-amino-2-methyl-1-propanol, 2-dimethylamino-methyl1-propanediol, 2-amino-2-ethyl-l, 3 -propanediol, 2-amino-211/39 methyl-1,3, 3-propanediol, 2-amino-1-butanol and mixtures thereof.
    alkoxy alcohol or phenoxy alcohol can include oleyl ethoxylate, lauryl ethoxylate, stearyl ethoxylate, coconut ethoxylate, tallow ethoxylate, oleyl propoxylate, lauryl propylate, stearyl propoxylate, coconut propoxylate, tallow propoxylate, phenyl ethoxylate, phenyl ethoxylate, phenyl ethoxylate butyl, tert-butyl phenyl propoxylate or mixtures thereof.
    Compound of Formula (1) to Formula (3)
    In one embodiment, the compound as obtained by the process described here can be represented by a compound of the formula (1), or mixtures thereof. In one embodiment, the compound obtained by the process described here can be represented by formula (2), or mixtures thereof.
    In one embodiment, the compound obtained by the process described here can be represented by formula (3), or mixtures thereof.
    compound obtained / capable of being obtained by that described here can be represented by formula (1) or formula (2) or formula (3):
    12/39
    Ο Ζ
    ζ ο formula (1)

    formula (3) where
    Y can be independently oxygen or> NH or> NR X ;
    R 1 can independently be a hydrocarbon group, typically containing 4 to 30, or 6 to 20, or 8 to 18 carbon atoms;
    Z can be hydrogen or methyl (when Z =
    13/39 hydrogen, the compound can be derived from glycolic acid, when Z = methyl the compound can be derived from lactic acid, typically Z can be hydrogen);
    Q can be the residue of a higher diol, triol or polyol, a diamine, a triamine, or higher polyamine, or an amino alcohol (typically Q can be diol, diamine or amino alcohol);
    g can be 2 to 6, or 2 to 3, or 2;
    q can be 1 to 4, or 1 to 3 or 1 to 2;
    n can be 0 to 10, 0 to 6, 0 to 5, 1 to 4, or 1 to 3 (when n is above 0, the compound can be described as a dimer (when n = 1), trimer (when n = 2), or a higher oligomer (when n = 3 to 10.) In one embodiment, n can be 1 to 4, or 1 to 3. In one embodiment, η = 1 and the compound can be a dimer; and
    Ak 1 can be an alkylene group containing from 1 to 5, or from 2 to 4, or from 2 to 3 (typically ethylene) carbon atoms; and b can be 1 to 10, or 2 to 8, or 4 to 6, or 4.
    The compound prepared by the process disclosed here can be considered to be the same as those derivatives of formula (1) or formula (2). In one embodiment, the alcohol can be a mono-alcohol, or diol, where the amine can be a mono-amine or a polyamine (typically a diamine), or an amino alcohol. Typically the diol, diamine or amino alcohol have hydroxy or groups of amino attached to the carbon atoms in such a way as to allow substitution of 1,2or 1,3-, 1,4- (typically 1,2- or 1,3- ).
    In different embodiments, the compound of formula (1) or formula (2) can have Z equal to hydrogen, or n can be 0a5, 1 to 4, oula3, orR 1 can be an alkyl (en) yl group or a group of cycloalkyl.
    In one embodiment, the compound of formula (1) can
    14/39 have Z equal to hydrogen and n can be 1 to 4, or 1 to 3.
    In one embodiment, the compound of formula (1) to formula (3) can be substantially composed of carbon, oxygen, nitrogen and hydrogen.
    In one embodiment, the compound of formula (1) to formula (3) may not contain sulfur or phosphorus.
    In one embodiment, the compound of formula (1) can be represented by formula (la):
    R 1 ,
    The Z
    Z O
    Formula (la) in gue
    R 1 can be a hydrocarbon group, typically containing 4 to 30, or 6 to 20, or 8 to 18 carbon atoms;
    Z can be hydrogen or methyl (when Z = hydrogen, the compound can be derived from glycolic acid, when Z = methyl the compound can be derived from lactic acid); and n can be 0 to 10, 0 to 6, 0 to 5, 1 to 4, or 1 to 3.
    In one embodiment, the compound of formula (1) can be represented by formula (1b):
    The Z
    Formula (lb)
    15/39 when
    R 1 can independently be a hydrocarbyl group, typically containing 4 to 30, or 6 to 20, or 8 to 18 carbon atoms;
    Z can be hydrogen or methyl (when Z = hydrogen, the compound can be derived from glycolic acid, when Z = methyl the compound can be derived from lactic acid);
    U can be hydrogen or R 1 ; and n can be 0 to 10, 0 to 6, 0 to 5, 1 to 4, or 1 to 3.
    In formula (1b) when Z = hydrogen, n = 1, U = hydrogen, the resulting compound can be represented by the formula (lb) (i):
    formula (lb) (i) where R 1 can independently be a hydrocarbon group, typically containing 4 to 30, or 6 to 20, or 8 to 18 carbon atoms.
    Examples of such a compound include oleyl glycolamide-glycolate, stearyl glycolamide-glycolate, coconut glycolamide-glycolate, tallow oleyl glycolamidaglycolate, or mixtures thereof.
    In one embodiment, the compound of formula (2) can be represented by formula (2a):
    16/39
    wherein each R can be independently hydrogen, or a hydrocarbyl group, typically containing 4 to 30, or 6 to 20, or 8 to 18, or 8 to 16 carbon atoms;
    k can be 1 to 4, oula3, 1 to 2, or 1; and
    Y can be independently oxygen or> NH or> NR 1 .
    In a Y modality it can be oxygen, a compound of the formula (2a) (typically obtained by the reaction of a diol with glycolic acid) and the compound can be represented by the formula (2b):

    formula (2b) k can be 1 to 4, or 1 to 2, or 1; and it can be independently hydrogen, or a hydrocarbyl group, typically containing 4 to 30, or 6 to 20, or 8 to 18, or 8 to 16 carbon atoms.
    For the compounds of the formula (2a), they can be prepared from a diol, such as a diglycolic acid ester including 1,2-dodecanediol diglycolate, 2-decanediol diglycolate, 217/39 tetradecanediol diglycolate, or mixtures of these .
    In one embodiment, Y can be> NH or> NR X , a compound of the formula (2a) (typically obtained by reacting a diamine with glycolic acid) can be represented by the formula (2c):
    on what
    U can be hydrogen or R 1 , R 1 can be a group in hydrocarbon, typically containing of 4 a 30, or 6 to 20, or from 8 to 18 atoms of
    carbon;
    Each R can be independently hydrogen or a hydrocarbyl group, typically containing 4 to 30, or 6 to 20, or 8 to 18, or 8 to 16 carbon atoms; and k can be 1 to 4, or 1 to 3.
    For compounds of formula (2a), they can be prepared from a diamine such as a Duomeen ™ series araine (available from Akzo Nobel) or mixtures thereof. Duomeen can be Duomeen T or Duomeen O. Diamine can be prepared by adding a mono-amine to acrylonitrile, followed by catalytic reduction of the resulting nitrile compound, using, for example, H 2 over Pd / C catalyst, to give the diamine.
    A compound of formula (3) can be obtained from an alkoxy alcohol or phenoxy alcohol reacted with a halo-acetic acid (or alkali or alkali metal salts thereof). The halo-acetic acid 2 can be an acetic acid
    18/39 chlorine, or bromine or chlorine acetic acid or in the form of sodium salts, one embodiment, the iodine compound, or mixtures thereof. Bromine or iodine may be lithium or potassium. In formula (3) it can be derived from 2-chloroacetate acid or 2-chloroacetic acid reacted with an alkoxy alcohol or phenoxy alcohol. The compounds of the type described by formula (3) and their preparations are disclosed in WO 2009/040370, EP 1 354 905 and EP 1 061 064 (all transferred to Clariant GmbH). The compound derived from alkoxy alcohol can include a compound represented by formula (3a):
    The formula (3 a) in which the group of the alkyls can be C 8 alkyl or alkylene ie 1 C 1 to 1 isols (alkyl, for example, includes lauryl, oleyl, stearyl, tallow, coconut or mixtures thereof).
    The compound derived from the alkoxy alcohol can include a compound represented by the formula (3b):

    wherein J can be a straight or branched alkyl group (typically having 4 to 20, or 4 to 12, or 4 to 8 carbon atoms, such as tert-butyl, or 2-ethylhexyl); and 1 can be 0 to 5, or 0 to 2, or 0 to 1.
    The reaction to prepare the compound of the present invention can be performed in a variety of ways
    19/39 different reaction conditions. The reaction can be carried out at a reaction temperature in the range of 70 ° C to 200 ° C, or 90 ° C to 180 ° C, or 100 ° C to 160 ° C. The reaction can be carried out in an inert atmosphere, ie, under nitrogen or argon, typically nitrogen. The reaction can be carried out in the presence or absence of a solvent (typically including a solvent). The solvent includes an aromatic hydrocarbon solvent. The reaction can be carried out in the absence or in the presence of a catalyst (typically in the presence of a catalyst). The catalyst may include methane sulfonic acid, toluene sulfonic acid, benzene sulfonic acid, or C12H25 alkylbenzenesulfonic acid. The catalyst may also include titanium, zirconium or aluminum metal salts that have chloride, bromide, iodide or alkoxide counterions (where the alkyl group in the alkoxide can have 1 to 20, or 1 to 4 atoms of carbon), or mixtures thereof. The catalyst can also include a phosphate of the formula HO (P (0) (OH) O) and -H, where e can be 1 to 5 or 2 to 5. In one embodiment, the catalyst can be a sulfonic acid , typically methane sulfonic acid.
    Examples of an aromatic hydrocarbon solvent include aromatic hydrocarbon solvent include Shellsolv AB® (commercially available from Shell Chemical Company); and toluene extract, Aromatic 200 xylene, Aromatic 150, Aromatic 100, Solvesso 200, Solvesso 150, Solvesso 100, HAN 857® (all commercially available from Exxon Chemical Company), or mixtures thereof. Other aromatic hydrocarbon solvents include xylene, toluene, or mixtures thereof.
    Lubrication Viscosity Oils
    The lubrication composition comprises a lubricating viscosity oil. Such oils include oils
    20/39
    Publication to [0056].
    natural and synthetic, oils derived from hydrocracking, hydrogenation, and hydro-finishing, unrefined, refined, re-refined or mixtures of these. A more detailed description of unrefined, refined and re-refined oils is provided in the
    International WO 2008/147704, paragraphs [0054]
    A more detailed description of natural and synthetic lubricating oils is described in paragraphs [0058] to [0059], respectively of WO 2008/147704. Synthetic oils can also be produced by Fischer-Tropsch reactions and can typically be hydrocarbons or hydro-isomerized greases from Fischer-Tropsch. In one embodiment, oils can be prepared by a synthetic gas-to-liquid procedure from Fischer-Tropsch, as well as other gas-to-liquid oils.
    Lubricating viscosity oils can be defined as specified in the April 2008 version of Appendix E - API Base Oil Interchangeability Guidelines for Passenger Car Engine Oils and Diesel Engine Oils, sections 1.3, Subheading 1.3. Base Stock Categories. In one embodiment, the lubricating viscosity oil may be an oil from Group API I, or Group II, or Group III, or Group IV. In one embodiment, the lubricating viscosity oil may be an oil from API II Group or Group III.
    The amount of the lubricating oil present is typically left after subtracting from the 100% by weight the sum of the amount of the compound of the invention and the other performance additives.
    The lubrication composition can be in the form of a concentrate and / or a fully formulated lubricant. If the lubricant composition of the invention (comprising the viscosity of the equilibrium
    21/39 additives disclosed here) is in the form of a concentrate that can be combined with the additional oil to form, in whole or in part, a finished lubricant, the ratio of these additives to the lubricating viscosity oil and / or to oil diluent includes the ranges from 1:99 to 99: 1 by weight, or 80:20 to 10:90 by weight.
    Other Performance additives
    The composition optionally comprises other performance additives. The other performance additives include at least one of the metal deactivators, viscosity modifiers, detergents, friction modifiers, anti-wear agents, corrosion inhibitors, dispersants, dispersing viscosity modifiers, extreme pressure agents, antioxidants, foam inhibitors, demulsifiers , pour point tranquilizers, sealing swelling agents, and mixtures thereof. Typically, the fully formulated lubricating oil will contain one or more of these performance additives.
    In one embodiment, the lubricating composition also includes other additives. In one embodiment, the invention provides a lubricating composition further comprising at least one of a dispersant, an anti-wear agent, a dispersing viscosity modifier, a friction modifier, a viscosity modifier, an antioxidant, a detergent with a base, or mixtures of these.
    The dispersant of the present invention can be a succinimide dispersant, or mixtures thereof. In one embodiment, the dispersant may be present as a single dispersant. In one embodiment, the dispersant can be present as a mixture of two or three different dispersants, at least one of which can be a succinimide dispersant.
    The succinimide dispersant can be derived from
    22/39 from an aliphatic polyamine, or mixtures thereof. The aliphatic polyamine can be aliphatic polyamine such as an ethylene polyamine, a propylene polyamine, a butylene polyamine, or mixtures thereof. In one embodiment, the aliphatic polyamine can be ethylene polyamine. In one embodiment, the aliphatic polyamine can be selected from the group consisting of ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, fixed polyamine bottoms, and mixtures thereof.
    The dispersant can be an N substituted long chain alkenyl succinimide. Examples of N substituted long chain alkenyl succinimide include polyisobutylene succinimide. Typically, the polyisobutylene from which the polyisobutylene succinic anhydride is derived has a numerical average molecular weight of 350 to 5000, or 550 to 3000 or 750 to 2500. Succinimide dispersants and their preparations are disclosed, for example, in the Patents US No. 3,172,892,
    3,219,666,
    3,433,744,
    3,136,177, 3,340,281, 3,351,552,
    3,381,022,
    3,542,680,
    6,165,235,
    3,444,170,
    3,467,668, 3,501,405,
    3,576,743, 3,632,511, 4,234,435, Re 26,433 and 7,238,650 and EP Patent Application 0.355,895 A.
    The dispersant can also be post-treated by conventional methods by reacting with any of a variety of agents. Among them are compounds of boron, urea, thiourea, dimercaptothiadiazoles, carbon disulfide, aldehydes, ketones, carboxylic acids, hydrocarbon-substituted succinic anhydrides, maleic anhydride, nitriles, epoxides, and phosphorus compounds.
    dispersant can be present in 0.01% to 20% by weight, or 0.1% to 15% by weight, or 0.1% to 10% by weight, or 1% to 6% by weight of the lubricating composition.
    23/39
    In one embodiment, the lubricant composition of the invention further comprises a dispersing viscosity modifier. The dispersing viscosity modifier can be present in 0% to 5% by weight, or 0% to 4% by weight, or 0.05% to 2% by weight of the lubricating composition.
    dispersant viscosity modifier can include functionalized polyolefins, for example, ethylene-propylene copolymers that have been functionalized with an acylating agent, such as maleic anhydride and an amine; polymethacrylates functionalized with an amine, or copolymers of maleic-styrene anhydride which react with an amine. A more detailed description of dispersant viscosity modifiers is disclosed in International Publication WO 2006/015130 or US Patent No. 4,863,623; 6,107,257; 6,107,258; and 6,117,825. In. In one embodiment, the dispersing viscosity modifier can include those described in US Patent No. 4,863,623 (see column 2, row 15 to column 3, row 52) or in International Publication WO 2006/015130 (see page 2, paragraph [0008 ] and examples of preparations are described in paragraphs [0065] to [0073]).
    In one embodiment, the friction modifier can be selected from the group consisting of long chain fatty acid derivatives of amines, long chain fatty esters or long chain fatty epoxides; fatty imidazolines; amine salts of alkylphosphoric acids; fatty alkyl tartrates; alkyl fatty tartrimides; and. alkyl fatty tartramides. The friction modifier can be present in 0% to 6% by weight, or 0.05% to 4% by weight, or 0.1% to 2% by weight of the lubricating composition.
    In one embodiment, the invention provides a lubricating composition that further includes an agent
    24/39 anti-wear containing phosphorus. Typically, the phosphorus-containing anti-wear agent may be a zinc dialkyldithiophosphate, or mixtures thereof. Zinc dialkyldithiophosphates are known in the art. The anti-wear agent can be present in 0% to 15% by weight or 0.1% to 10% by weight, or 0.5% to 5% by weight of the lubricating composition and can be used in an amount consistent with providing the level desired low phosphorus described elsewhere here.
    In one embodiment, the invention provides a lubricating composition further comprising a molybdenum compound. The molybdenum compound can be selected from the group consisting of molybdenum dialkyldithiophosphates, molybdenum dithiocarbamates, amine salts of molybdenum compounds, and mixtures thereof. The molybdenum compound can provide the lubricating composition with 0 to 1000 ppm, or 5 to 1000 ppm, or 10 to 750 ppm, 5 ppm to 300 ppm, or 20 ppm to 250 ppm molybdenum.
    In one embodiment, the invention provides a lubricating composition further comprising an over-base detergent. The base detergent can be selected from the group consisting of non-sulfur containing phenates, sulfur-containing phenates, sulfonates, salixarates, salicylates and mixtures thereof. Typically, a detergent with base may be a sodium, calcium or magnesium salt of the phenates, sulfur-containing phenates, sulfonates, salixarates and salicylates. Phenates and salicylates with base typically have a total base number of 180 to 450 TBN. Base based sulfonates typically have a total base number of 250 to 600, or 300 to 500. Base based detergents are known in the art. In one embodiment, the sulfonated detergent may be an alkyl benzene sulfonated detergent
    25/39 predominantly linear having a metal ratio of at least 8 as described in paragraphs [0026] to [0037] of US Patent Application No. 2005065045 (and granted as US No. 7,407,919). The predominantly linear sulfonated alkyl benzene detergent can be particularly useful to assist in improving fuel economy. Base based detergents are known in the art. The detergent with base may be present in 0% to 15% by weight, or 0.1% to 10% by weight, or 0.2% to 8% by weight of the lubricating composition.
    In one embodiment, the lubricating composition includes an antioxidant, or mixtures thereof. The antioxidant can be present in 0% to 15% by weight, or 0.1% to 10% by weight, or 0.5% to 5% by weight of the lubricating composition.
    Antioxidants include sulfurized olefins, alkylated diphenylamines (typically dinonyl diphenylamine, dioctyl diphenylamine), molybdenum phenols (such as octyl diphenylamine, hindered, molybdenum dithiocarbamate compounds), The antioxidant of or mixtures of these, hindered phenol generally contains a group of secondary butyl and / or tertiary butyl group as a sterically hindered group. The phenol group can also be substituted with a hydrocarbyl group (typically linear or branched alkyl) and / or a connecting group linking to a second aromatic group. Examples of suitable hindered phenol antioxidants include 2,6-di-tert-butylphenol, 4-methyl-2,6-di-tertbutylphenol, 4-ethyl-2,6-di-tert-butylphenol, 4-propyl-2 , 6-ditert-butylphenol or 4-butyl-2,6-di-tert-butylphenol or 4dodecyl-2,6-di-tert-butylphenol. In one embodiment, the hindered phenol antioxidant may be an ester and may include, i.e., Irganox ™ L-135 from Ciba. A more detailed description of the chemistry of the hindered phenol antioxidant
    26/39 containing ester is found in US Patent No. 6,559,105.
    Examples of suitable friction modifiers include long-chain fatty acid derivatives of amines, esters or epoxides; fatty imidazolines, such as condensation products of carboxylic acids and polyalkylene polyamines; amine salts of alkylphosphoric acids; fatty alkyl tartrates; alkyl fatty tartrimides; or fatty alkyl tartramides;
    Friction modifiers can also cover materials such as sulfurized fatty compounds and olefins, molybdenum dialkyldithiophosphates, molybdenum dithiocarbamates, sunflower oil or monoesters of a polyol and an aliphatic carboxylic acid.
    In one embodiment, the friction modifier can be selected from the group consisting of derivatives of long chain fatty acids from amines, esters or epoxides; fatty alkyl tartrates; fatty alkyl tartrimides; and fatty alkyl tartramides. Fatty alkyl tartrates; fatty alkyl tartrimides; and fatty alkyl tartramides.
    In one embodiment, the friction modifier may be a long-chain fatty acid ester. In another embodiment, the long-chain fatty acid ester may be a monoester and in another embodiment, the long-chain fatty acid ester may be a (tri) glyceride.
    Other performance additives, such as corrosion inhibitors include those described in paragraphs 5 to 8 of Application No. US 05/038319, published as W02006 / 047486, octylamine octanoate, condensation products of dodecenyl succinic acid or anhydride and a fatty acid, such as oleic acid with a polyamine. In one embodiment, corrosion inhibitors include the Synalox® corrosion inhibitor. The corrosion inhibitor
    27/39
    Synalox® can be a homopolymer or copolymer of propylene oxide. The Synalox® corrosion inhibitor is described in more detail in a product brochure with Form No. 11801453-0702 AMS, published by The Dow Chemical Company. The product brochure is entitled SYNALOX Lubricants, High Performance Polyglycols for Demanding Applications.
    Metal deactivators including benzotriazole derivatives (typically tolyltriazole), dimercaptothiadiazole derivatives, 1,2,4-triazoles, benzimidazoles, 2-alkyldithiobenzimidazoles, or 2-alkyldithiobenzothiazoles; foam inhibitors including ethyl acrylate and 2-ethylhexylacrylate copolymers and optionally vinyl acetate; demulsifiers including polymers of trialkyl phosphates, polyethylene glycols, polyethylene oxides, polypropylene oxides and (ethylene oxide-propylene oxide); pour point calming agents including maleic-styrene anhydride esters, polymethacrylates, polyacrylates or polyacrylamides may be useful. Foam inhibitors that may be useful in the compositions of the invention include copolymers of ethyl acrylate and 2-ethylhexyl acrylate and optionally vinyl acetate; demulsifiers including phosphate polymers
    from trialquil r polyethylene glycols, in oxides in polyethylene, in polypropylene oxides and in (oxide in ethylene-oxide in propylene). The pour point soothing what can to be
    useful in the compositions of the invention include polyalphaolefins, maleic anhydride-styrene esters, poly (meth) acrylates, polyacrylates or polyacrylamides.
    In different embodiments, the lubricating composition can have a composition as described in the following table:
    28/39
    Additive Modalities (% by weight) THE B Ç Compound revealedon here 0.01 to 5 0.1 to 3 0.2 to 1.5 Dispersant 0.05 to 12 0.75 to 8 0.5 to 6 Modifierviscositydispersant 0 to 5 0 to 4 0.05 to 2 Detergent with overbase 0 to 15 0.1 to 10 0.2 to 8 Antioxidant 0 to 15 0.1 to 10 0.5 to 5 Anti-wear agent 0 to 15 0.1 to 10 0.3 to 5 Modifierfriction 0 to 6 0.05 to 4 0.1 to 2 Modifierviscosity 0 to 10 0.5 to 8 1 to 6 Any otheradditiveperformance 0 to 10 0 to 8 0 to 6 Viscosity oillubricant Balance a100% Balance a100% Balance a100%
    Industrial Application
    The lubricating composition can be used in an internal combustion engine. The internal combustion engine may or may not have an Exhaust Gas Recirculation system. The internal combustion engine can be adjusted with an emission control system or a turbocharger. Examples of the emission control system include diesel particulate filters (DPF), or systems that employ selective catalytic reduction (SCR).
    In one embodiment, the internal combustion engine can be an engine fueled with diesel (typically a heavy-duty diesel engine), an engine fueled with
    29/39
    one motor In an one motor one motor
    gasoline, an engine fueled with natural gas or an engine fueled with a gasoline / alcohol mixture. modality, the internal combustion engine can be fueled with diesel and in another mode, fueled with gasoline.
    The internal combustion engine can be a 2-stroke or a 4-stroke engine. Suitable internal combustion engines include marine diesel engines, aviation piston engines, low-load diesel engines and car or truck engines.
    The lubricating composition for an internal combustion engine can be suitable for any engine lubricant regardless of the content of sulfated, phosphorous or sulfur ash (ASTM D-874). The sulfur content of the engine oil lubricant may be 1% by weight or less, or 0.8% by weight or less, or 0.5% by weight or less, or 0.3% by weight or smaller. In one embodiment, the sulfur content can be in the range of 0.001% to 0.5% by weight or from 0.01% to 0.3% by weight. The phosphorous content may be 0.2% by weight or less, or 0.12% by weight or less, or 0.1% by weight or less, or 0.085% by weight or less, or 0, 08% by weight or less, or even 0.06% by weight or less, 0.055% by weight or less, or 0.05% by weight or less. In one embodiment, the phosphorous content can be from 100 ppm to 1000 ppm, or from 200 ppm to 600 ppm. The total sulfated ash content can be 2% by weight or less, or 1.5% by weight or
    smaller, or in 1.1% in Weight or smaller, or in 1% by weight smaller, or in 0.8% in Weight or smaller, or of 0 , 5% by weight smaller, or in 0.4% in Weight or smaller. In an modality,
    sulfated ash content can be from 0.05% to 0.9% by weight, or from 0.1% to 0.2% by weight or from 0.45% by weight.
    In one embodiment, the lubricating composition can
    30/39 is a motor oil, wherein the lubricating composition can be characterized as having at least one of (i) a sulfur content of 0.5% by weight or less, (ii) a phosphorus content of 0, 1% by weight or less, and (iii) a content with sulfated ash of 1.5% by weight or less.
    The following examples provide illustrations of the invention. These examples are not exhaustive and are not intended to limit the scope of the invention.
    Examples
    Preparative Example 1 (EX1) is 1,2docecanediol diglycolate. A 1-liter flange flask is fitted with a PTFE gasket, a flange cap, a nitrogen inlet providing a 200 cm 3 / min nitrogen flow, coupled thermo, an overhead stirrer with a PTFE gasket and a Dean separator -Stark adjusted with double-walled water-cooled condenser. The flask is loaded with glycolic acid (105.77 g), toluene (250 g), 1.2dodecanediol (190.9 g) and methane sulfonic acid (6.45 g). The reaction is heated to 105 ° C, the mixture is started at 50 ° C at 200 rpm and increased to 350 rpm as the reaction becomes homogeneous. As the temperature approaches 105 ° C, a milky solution begins to collect and separate in the Dean-Stark separator. The first 100 ml fluid is collected and dispensed. The temperature is raised to 135 ° C and reflux is maintained for 18 hours. The flask is equipped for vacuum disassembly and the vacuum is gradually increased to 50 mm Hg (equivalent to 6 kPa) and maintained for 1 hour. The contents of the flask are cooled to 70 ° C and the vacuum is released. The viscous colored oil is transferred while hot to produce 248.97 g of the product.
    Preparative Example 2 (EX2) is oleyl glycolate. A 2 liter round-bottom flange flask equipped with mechanical stirrer, coupled thermometer, coupled thermometer line
    31/39 subsurface nitrogen spray and Dean-Stark separator with condenser is mounted. 69.98 g of glycolic acid, 246.58 g of oleyl alcohol and 750 cm 3 of xylene are loaded into the flask. Then, 6.28 g of methane sulfonic acid are added and the reaction is heated to 145 ° C in a blanket, with stirring. Xylene is allowed to flow back for 3 hours. The heat is then removed and allowed to cool overnight with a nitrogen purge. The solvent is then stripped off on a rotary evaporator. The product is then heated in an oven at 100 ° C, causing the solid to melt. The reaction produces 300 g of product.
    Preparative Example 3 (EX3) is oleyl glycolate glycolamide. A 250 cm 3 round-bottom flask is loaded with 20 g of toluene, 50 g of oleyl amine, and 28.43 g of glycolic acid. The flask is then heated to 100 ° C under a nitrogen atmosphere (flow rate 200 cm 3 / min). The flask is then kept at 100 ° C and shaken for 18 hours with a stirring speed of 250
    rpm. 0 bottle is so heated at 110 ° C and agitated per 2 hours. The bottle is so heated at 130 ° C and agitated per 4 hours. The bottle is so heated at 150 ° C and agitated per 4 hours before he cool to room temperature. THE reaction produces 69.4 g · Example Preparatory 4 (EX4) is ester of acid
    glycolic acid alcohol (molar ratio of 1: 2.5). A 1-liter bottle with 4 necks equipped with an overhead stirrer, thermometric capsule, sub-surface entrance with nitrogen line, and Dean-Stark separator with condenser is loaded with 250 g of alcohol, 176.8 g of glycolic acid, 150 g of toluene. The flask is then heated to 120 ° C under a nitrogen atmosphere (flow rate 200 cm 3 / min) and shaken at 250 rpm. 6.4 g of methane sulfonic acid are then added and the flask is
    32/39 heated to 135 ° C and stirred for 26 hours. The flask is then heated to 150 ° C and maintained for 2 hours. The flask is then vacuum distilled at a pressure of 6 kPa (equivalent to 50 mm Hg) for 2 hours. The flask is then cooled to room temperature and 258.3 g of dark colored fatty product is obtained.
    Preparative Example 5 (EX5) is oleyl polyglycolate (1: 4 molar ratio). Ο EX5 is similar to EX4, except that the amount of glycolic acid is 4 moles of glycolic acid per mole of oleyl alcohol instead of 2.5 moles.
    Preparative Example 6 (EX6) is stearyl glycolate prepared in a similar way as ο EX2, except on a molar basis the amount of oleyl alcohol is replaced by stearyl alcohol.
    Preparative Example 7 (EX7) is 2-ethylhexyl glycolate. A 1-liter bottle with 4 necks equipped with an overhead stirrer, thermometric capsule, sub-surface entrance with nitrogen line, and DeanStark separator with condenser is loaded with 200 g of 2-ethylhexanol, 11.2 g of glycolic acid, 300 g of toluene. The flask is then heated to 130 ° C under a nitrogen atmosphere (flow rate 200 cm 3 / min) and mixed at 250 rpm for 3 hours. 10.1 g of methane sulfonic acid are then added and the flask is heated to 135 ° C and stirred for 16 hours. The flask is then cooled to room temperature before adding 200 cm 3 of sodium bicarbonate solution. The product is then extracted with 1.6 liters of methylene chloride at 150 ° C and kept for 2 hours before washing
    with bicarbonate solution in saturated sodium (100 cm 3 ), water (2 x 200 cm 3 ) and dry under sulfonate in magnesium. 0 resulting product is an oil without color (250.6 g) ·
    Preparative Example7 (EX7) is 2-ethylhexylglycolamide. A 1 liter bottle with 4 necks
    33/39 equipped with an overhead stirrer, thermometric capsule, subsurface inlet with nitrogen line, and Dean-Stark separator with condenser is loaded with 200 g of 2-ethylhexylamine, 114.7 g of glycolic acid, 200 g of xylene . The flask is then heated to 150 ° C under a nitrogen atmosphere (flow rate 200 cm 3 / min) and shaken at 250 rpm for 3 hours. The flask is then vacuum distilled at a pressure of 6 kPa (equivalent to 50 mm Hg) for 3 hours. The flask is then cooled to room temperature and 214.3 g of dark colored fatty product is obtained.
    Preparative Example 8 (EX8) is glycolic acid ethoxylate oleyl ether obtained from Aldrich (CAS Number 57635-48-0).
    Preparative Example 9 (EX9) is glycolic acid ethoxylate lauryl ether obtained from Aldrich (CAS Number 220622-96-8).
    Preparative Example 10 (EX10) is glycolic acid tertbutylphenyl ethoxylate obtained from Aldrich (CAS Number 104909-82-2).
    SAE 15W-30 Engine Lubricants
    A series of SAE 15W-30 engine lubricants are prepared containing antioxidants (mixture of hindered phenols and alkylated diphenylamines), 0.5% by weight of zinc dialkyldithiophosphate, a mixture of detergents (including calcium sulfonate and calcium phenate), a succinimide dispersant, and still containing 0.25% by weight or 0.50% by weight, or 1.0% by weight of a product from EX1 to EX10.
    Comparative Example 1 (CE1) is a SAE 5W-30 lubricant the same as those described above, except that it does not contain a product from example EX1 to EX6.
    Comparative Example 2 (CE2) is an SAE lubricant
    34/39
    5W-30 the same as CE1, except that it contains 0.5% by weight of fatty tartrate. CE2 is similar to example 21 of W02005087904, except that dibutyl tartrate has been replaced by fatty tartrate.
    Test 1: Frictional Performance in HFRR SAE 5W-30 lubricants are evaluated by frictional performance of frictional lubrication and wear on a programmed high frequency alternating temperature (HFRR) equipment available from PCS Instruments. The HFRR conditions for the evaluations are 500 g of load, 75 minutes in duration, 1000 micrometer impacts, frequency of 20 Hertz, and a temperature profile of 15 minutes at 40 ° C followed by a temperature rise at 160 ° C in a rate of 2 ° C per minute. The upper test piece is a 6 mm diameter steel ball (ANSI E52100, Rockwell hardness 'C' from 58 to 66 and a surface finish of Ra <0.05 pm), the lower test specimen is both a flat steel disc (ANSI E-52100, Vickers HV30 hardness 190 to 210 and a surface finish of Ra <0.02 pm) or an aluminum specimen of similar size. Both upper and lower specimens are available together by PCS Instruments (Part Number HFRSSP). The coefficient of friction, wear and potential contact are then measured. The friction coefficient is calculated by dividing the measured frictional force parallel to the reciprocity direction by the applied load. The contact potential is measured by applying a small electrical potential between the upper and lower test specimens. If the instrument measures the entire applied electrical potential, this is indicative of an electrically insulating layer between the upper and lower test specimens, this is generally interpreted as the formation of a chemical protective film on the
    35/39 surfaces. If no protective film is formed, metal-to-metal contact exists between the upper and lower test specimens and the measured electrical potential drops to zero. The intermediate values are indicative of partial or incomplete protection films. The contact potential is generally presented as a percentage of the applied electrical potential and the required percentage film thickness. The results of wear, friction coefficient and contact potential obtained are shown in the following table.
    Example in Product Scar Scar CoF Potential lubricant in in in in 5W-30 Example Wear Wear Contact Fe (gm) Al (gm) CE1 0 252 298 0.124 97 LI EX1 205 219 0.117 96 L2 EX2 271 322 0.121 92 L3 EX3 218 232 0.107 96 L4 EX4 221 233 0.128 97 L5 EX5 199 249 0.112 94 L6 EX6 231 275 0.121 96 L7 EX1 196 198 0.121 96 L8 EX2 219 242 0.120 97 L9 EX3 171 195 0.084 97 IOL EX4 209 240 0.118 96 Lll EX5 179 223 0.117 97 L12 EX6 258 277 0.107 96 L13 EX1 213 169 0.123 96 L14 EX2 215 233 0.109 97 L15 EX3 181 160 0.085 97 L16 EX4 220 230 0.109 95 L17 EX5 N / M N / M N / M N / M L18 EX6 212 235 0.117 97
    Comments:
    36/39
    Examples of Lubricants 1 The 6 contain 0.25% by weight of a prepared compound at the EX1 a EX6, respectively. Examples of Lubricants 7 The 12 contain 0.5% by weight of a prepared compound at the EX1 a EX6, respectively. Examples of Lubricants 13 The 18 contain 1.0% by weight of a prepared compound at the EX1 a EX6,
    respectively.
    The results of wear scars shown above for Fe (iron) and Al (aluminum) surfaces are the average of two experiments per sample.
    The coefficient of friction (CoF) and the contact potential are averaged over two experiments per sample.
    N / M indicates unmeasured data points.
    Test 2: Lead Corrosion Test
    The lubricants described above (LEI a LEIO and CLl) are evaluated in a lead corrosion test as defined in Method ASTM D6594-06. The amount of lead (Pb) in the oils at the end of the test is measured and compared to the amount at the beginning of the test. The lower lead content in the oil indicates decreased lead corrosion. In general, the results obtained for each lubricant are as follows:
    Lubricant Example Lead (ppm) CE2 86 EX2 72 EX5 40 EX6 66
    SAE 15W-30 Engine Lubricants
    A series of three SAE 15W30 engine lubricants (L19 to L21) are prepared containing antioxidants
    37/39 (mixture of hindered phenols and alkylated diphenylamines), zinc dialyldithiophosphate, a detergent mixture (including calcium sulfonate and calcium phenate), a succinimide dispersant, and still containing 0.1% by weight of EX8 to EX10 , respectively. The compositions are characterized as having about 0.11% by weight of phosphorus, 0.12% by weight of zinc and 0.22% by weight of calcium.
    Comparative Example 3 (CE3) is prepared in a formulation similar to that of L19, except that it does not contain a glycolate as described in EX8 to EX10.
    L19 to L21 and CE3 are evaluated in a lead corrosion test as defined in Method ASTM D659406 (see above for more information). The data obtained are as follows:
    Lubricant Example Lead (ppm) CE3 66 L19 50 L20 58 L21 48
    In general, all the data presented indicates that the lubricant composition of the invention (for example, an internal combustion engine lubricant) containing a compound of the invention provides one or more anti-wear, friction modifier performance (particularly to improve fuel economy ), performance or inhibition of lead corrosion.
    It is known that some of the materials described above can interact in the final formulation, so that the components of the final formulation may be different from those that are initially added. Products formed in this way, including products formed using the lubricating composition of this
    38/39 invention in its intended use, may not be susceptible to easy description. However, all said modifications and reaction products are included within the scope of the present invention; the present invention encompasses lubricant composition prepared by mixing the components described above.
    As used herein, the term alkyl (en) yl includes alkyl and alkenyl.
    Each of the documents referred to above is incorporated by reference. Except in the Examples, or where otherwise explicitly stated, all numerical quantities in this description specifying material quantities, reaction conditions, molecular weights, number of carbon atoms, and the like, are to be understood as modified by the word about. Unless otherwise indicated, each chemical or composition referred to herein must be interpreted as being a commercial-scale material that may contain isomers, by-products, derivatives, and other said materials that are normally understood to be present on the commercial scale. However, the amount of each chemical component is shown as exclusive to any solvent or diluent oil, which may be generally present in commercial material, unless otherwise indicated. It should be understood that the upper and lower quantity, range, and ratio limits defined here can be combined independently. Similarly, the ranges and amounts for each element of the invention can be used together with ranges or amounts for any of the other elements.
    As used here, the term hydrocarb substituent or hydrocarb group is used in its common sense, which is well known to those with
    39/39 skill in technique. Specifically, it refers to a group having a carbon atom attached directly to the remainder of the molecule and having a predominantly hydrocarbon character. Examples of hydrocarbon groups include: hydrocarbon substituents, including aliphatic, alicyclic, and aromatic substituents; substituted hydrocarbon substituents, that is, substituents containing groups of non-hydrocarbons which, in the context of this predominantly invention, do not alter the hydrocarbon nature of the substituent; and hetero substituents, that is, substituents that similarly have a predominantly hydrocarbon character, but contain instead of carbon in a ring or chain. A more detailed definition of the term hydrocarbon substituent or hydrocarb group is described in paragraphs [0118] to [0119] of the International Publication
    W02008147704.
    While the invention has been explained in relation to its preferred embodiments, it should be understood that several modifications of these will become apparent to those of skill in the art by the time they read the specification. Therefore, it should be understood that the invention disclosed herein is intended to cover said modifications as they fall within the scope of the appended claims.
    1/3
    权利要求:
    Claims (6)
    [1]
    1. Lubricant composition characterized by comprising a lubricating viscosity oil and a compound obtained / capable of being obtained by a process that
    5 comprises reacting a glycolic acid, or an alkali or alkali metal salt thereof, with at least one component selected from the group consisting of an alcohol and an amino alcohol, in which the compound is represented by the formula (la):
    Z O formula (la) in which
    R 1 is a hydrocarbyl group, typically containing 4 to 30 carbon atoms;
    Z is hydrogen, and
    15 nédela4, and where the compound is present at 0.01 to 5% by weight of the lubricating composition.
    [2]
    Lubricant composition according to claim 1, characterized in that n is from 1 to 3.
    Lubricating composition according to any one of claims 1 to 2, characterized in that the alcohol is a mono-alcohol having formula R 1 -OH, wherein R 1 is a hydrocarbon group, containing from 4 to 30, or from 6 to 20, or 8 to 18 carbon atoms, and where the compound obtained is
    25 prepared by reacting, on a molar ratio basis, from 1.2 moles to 6 moles of glycolic acid with one mole of mono-alcohol.
    4. Lubricant composition, according to claim 1, characterized by the alcohol being selected
    Petition 870180047363, of 06/04/2018, p. 6/10
    2/3 from the group consisting of an alkoxy alcohol and a diol.
    Lubricating composition according to claim 1, characterized by the compound of formula
    5 (1a) be derived from the above consisting substantially of carbon, oxygen, nitrogen and hydrogen only.
    6. Lubricant composition according to claim 1, characterized by the compound of the formula
    10 (1a) does not contain sulfur or phosphorus.
    Lubricating composition according to claim 1, characterized in that R 1 is an alkyl (en) yl group, or a cycloalkyl group.
    Lubricating composition according to any one of claims 1 to 7, characterized in that the compound obtained / capable of being obtained by the process is present in 0.1% to 3% by weight, or 0.2% to 1.5 % by weight of the lubricating composition.
    Lubricant composition according to any one of claims 1 to 8, characterized in that the compound obtained / capable of being obtained by the process is present in 0.25% to 1% by weight of the lubricant composition.
    Lubricant composition according to any one of claims 1 to 9, characterized by
    25 have (i) a sulfur content of 0.5% by weight or less, (ii) a phosphorus content of 0.1% by weight or less, and (iii) a sulfated ash content of 1.5% in weight or less.
    Lubricating composition according to any one of claims 1 to 10, characterized by
    30 further comprising a phosphorus-containing anti-wear agent, wherein the anti-wear agent is zinc dialkylldithiophosphate.
    12. Lubricant composition, according to
    Petition 870180047363, of 06/04/2018, p. 7/10
    [3]
    Any one of claims 1 to 11, characterized in that it further comprises a detergent with excess of base, wherein the detergent with excess of base is selected from the group consisting of phenates, phenates containing sulfur,
    [4]
    5 sulfonates, salixarates, salicylates, and mixtures thereof.
    13. Method for lubricating an internal combustion engine characterized in that it comprises providing the internal combustion engine with a lubricating composition as defined in any one of claims 1 to 12.
    [5]
    14. Method according to claim 13, characterized in that the internal combustion engine has a cylinder orifice, cylinder block, or piston ring having a steel surface.
    [6]
    15. Method according to claim 13,
    15 characterized by the internal combustion engine having a cylinder orifice, cylinder block or piston ring having an aluminum alloy or aluminum composite surface.
    Petition 870180047363, of 06/04/2018, p. 8/10
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    同族专利:
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    US20130296208A1|2013-11-07|
    CN104479807A|2015-04-01|
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    法律状态:
    2018-03-06| B06A| Notification to applicant to reply to the report for non-patentability or inadequacy of the application according art. 36 industrial patent law|
    2018-07-10| B09A| Decision: intention to grant|
    2018-08-07| B16A| Patent or certificate of addition of invention granted|
    优先权:
    申请号 | 申请日 | 专利标题
    US23471709P| true| 2009-08-18|2009-08-18|
    US61/234,717|2009-08-18|
    PCT/US2010/045576|WO2011022317A1|2009-08-18|2010-08-16|Lubricating composition containing an antiwear agent|
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