EP1674557A2 - Schwingungsdämpfende Additivzusammensetzung und Schmierölzusammensetzung diese enthaltend - Google Patents

Schwingungsdämpfende Additivzusammensetzung und Schmierölzusammensetzung diese enthaltend Download PDF

Info

Publication number
EP1674557A2
EP1674557A2 EP05257367A EP05257367A EP1674557A2 EP 1674557 A2 EP1674557 A2 EP 1674557A2 EP 05257367 A EP05257367 A EP 05257367A EP 05257367 A EP05257367 A EP 05257367A EP 1674557 A2 EP1674557 A2 EP 1674557A2
Authority
EP
European Patent Office
Prior art keywords
substituted succinic
lubricating oil
monosuccinimide
hydrocarbyl
shudder
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.)
Granted
Application number
EP05257367A
Other languages
English (en)
French (fr)
Other versions
EP1674557B1 (de
EP1674557A3 (de
Inventor
Juan Alberto Buitrago
Rawis H. Frazier
Tony Cuong Kien Banh
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Chevron Oronite Co LLC
Original Assignee
Chevron Oronite Co LLC
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Chevron Oronite Co LLC filed Critical Chevron Oronite Co LLC
Publication of EP1674557A2 publication Critical patent/EP1674557A2/de
Publication of EP1674557A3 publication Critical patent/EP1674557A3/de
Application granted granted Critical
Publication of EP1674557B1 publication Critical patent/EP1674557B1/de
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M141/00Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
    • C10M141/10Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic phosphorus-containing compound
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28Esters
    • C10M2207/282Esters of (cyclo)aliphatic oolycarboxylic acids
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28Esters
    • C10M2207/283Esters of polyhydroxy compounds
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/28Amides; Imides
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/049Phosphite
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/06Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00Specified use or application for which the lubricating composition is intended
    • C10N2040/04Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
    • C10N2040/042Oil-bath; Gear-boxes; Automatic transmissions; Traction drives for automatic transmissions
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00Specified use or application for which the lubricating composition is intended
    • C10N2040/04Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
    • C10N2040/045Oil-bath; Gear-boxes; Automatic transmissions; Traction drives for continuous variable transmission [CVT]

Definitions

  • the present invention is directed to an improved anti-shudder additive composition that is used in automatic transmission fluids and continuously variable transmissions; and it is also directed to the process of making the same.
  • Srinivasan et al., U.S. Publication No. 2002/0151441 is directed to an automatic transmission fluid with improved anti-shudder properties.
  • the automatic transmission fluids described contain at least 0.2 wt% of a metal-containing detergent, a dispersant, and a mixture of friction modifiers. This automatic transmission fluid is used in electronically controlled converter clutch applications.
  • Ohtani et al., U.S. Patent Number 5,441,656 is directed to an automatic transmission fluid (ATF) that is used to overcome shudder.
  • ATF consists essentially of (i) an N-aliphatic hydrocarbyl-substituted diethanolamine in which the N-aliphatic hydrocarbyl substituent is at least one straight chain aliphatic hydrocarbyl group free of acetylenic unsaturation and having in the range of 14 to 20 carbon atoms, and (ii) an N-aliphatic hydrocarbyl-substituted trimethylenediamine in which the N-aliphatic hydrocarbyl-substituent is at least one straight chain aliphatic hydrocarbyl group free of acetylenic unsaturation and having in the range of about 14 to about 20 carbon atoms.
  • U.S. Patent No. 6,660,695 discloses a power transmission fluid comprising a mixture of a major amount of a lubricating oil and an effective amount of a performance enhancing additive combination comprising: (a) at least one organic phosphite; (b) a calcium detergent and (c) a friction modifier.
  • U.S. Patent No. 5,942,472 discloses a power transmission fluid that is formed which comprise a major amount of lubricating oil and an additive combination comprising (a) a viscosity modifier having a molecular weight no greater than about 175, 000 atomic mass units, and (b) a selected friction modifier.
  • W.S. Patent No. 6,337,309 discloses a lubricating composition for a continuously variable transmission.
  • This composition is zinc free and comprises an (a) ashless polyisobutenyl succinimide dispersant; (b) at least one organic thioether phosphite; (c) a calcium phenate overbased detergent at a concentration such that the total amount of calcium in the fluid is less than about 500 ppm; (d) friction modifiers comprising one or more succinimides and one or more ethoxylated amines; and (e) a primary amide of a long chain carboxylic acid.
  • U.S. Patent No. 6,127,323 discloses a composition and method of improving the anti-shudder durability of power transmitting fluids, particularly those in automatic transmission fluids.
  • This composition comprises a mixture of (1) a major amount of a lubricating oil and (2) an anti-shudder improving effective amount of an additive composition comprising (a) an oil-soluble alkyl phosphonate, (b) an ashless dispersant, and (c) a metallic detergent.
  • U.S. Patent No. 6,225,266 discloses a continuously variable transmission fluid that is zinc-free and comprises (a) an additive dispersant; (b) at least one organic phosphite; (c) a calcium detergent; (d) one or more friction modifiers selected from the group consisting of: succinimides and ethoxylated amines; and (e) a primary amide of a long chain carboxylic acid.
  • an anti-shudder additive composition comprising:
  • the present invention is further directed to a lubricating oil composition
  • a lubricating oil composition comprising:
  • the present invention is further directed to a method of making an anti-shudder additive composition
  • an anti-shudder additive composition comprising:
  • the present invention is further directed to a method of making a transmission fluid comprising:
  • a method of reducing shudder in a transmission comprising:
  • Vehicular transmissions supply the power created by the engine to the wheels of the vehicle. Not only is the transmission's function important to the working of the vehicle, but also it is very complex.
  • the transmission is comprised of numerous components, such as clutches with plates or bands, a torque converter, gears, and optionally, a wet clutch among others. Transmissions are usually either manual, automatic, or continuosly variable. Because of the variety of functions performed by the ATF, it is essential to carefully select ATF additives. Transmission fluid may comprise numerous additives such as dispersants, friction modifiers, anti-wear agents, oxidation inhibitors, detergents, and others to name a few. Friction modifiers are often used to control shudder. Without a suitable fluid, the transmission would not operate at its peak, and the cost of operating the car would may be increased.
  • Friction modifiers are components that reduce friction between surfaces when mild sliding occurs. In general, these components consists of a long linear hydrocarbon chain and a small polar functional group. Examples of friction modifiers include: fatty acids, fatty amines, fatty amides, and esters of fatty acids. Often, friction modifiers are corrosive towards Pb and Cu, common materials in bushings. Also, friction modifiers can cause an undesirable decrease in clutch capacity.
  • TF transmission fluids
  • the anti-shudder additive composition of the present invention comprises an oil-soluble additive composition.
  • This anti-shudder additive composition may be used in lubricating oils, such as but not limited to, automatic transmission fluids and continuously variable transmission fluids, and are particularly effective when used in transmission fluids for electronically controlled converter clutches.
  • the anti-shudder additive composition of the present invention comprises (a) at least one neutral phosphite compound and least one phosphorous-free dispersant selected from (b) at least one hydrocarbyl substituted succinic dispersant selected from the group consisting of a hydrocarbyl bissuccinimide and a hydrocarbyl substituted succinic ester of a polyol and mixtures thereof, wherein the hydrocarbyl substituent has at least 50 carbon atoms, in a proportion that drastically reduces shudder, or friction induced vibration, that is caused by stick-slip phenomena. Because the present invention reduces frictionally induced vibration, a friction modifier is optionally added to the additive composition and/ or the lubricating oil composition.
  • All types of friction modifiers may be added to the anti-shudder additive composition and/or the lubrication oil composition except for ethoxylated amines.
  • the anti-shudder additive composition or the lubricating oil composition does not comprise a primary amide of a long chain carboxylic acid.
  • the lubricating oil composition also contains monosuccinimide, then the ratio of the hydrocarbyl substituted succinic dispersant to monosuccinimide is at least 7:3. More preferred, the ratio of the hydrocarbyl substituted succinic dispersant to monosuccinimide is at least 7.5:2.5. Even more preferred, the ratio of the hydrocarbyl substituted succinic dispersant to monosuccinimide is at least 8:2. Most preferred, the ratio of the hydrocarbyl substituted succinic dispersant to monosuccinimide is at least 9:1.
  • a hydrocarbyl substituted succinic dispersant is mixed with a neutral phosphite compound thereby producing an anti-shudder additive composition.
  • the hydrocarbyl substituted succinic dispersant is a hydrocarbyl bissucinimide. More preferred the bissuccinimide is a borated bissuccinimide.
  • the bissucciminide is the completed reaction product from reaction between one or more polyamine reactants and a hydrocarbon substituted succinic acid or anhydride (or like succinic acylating agent), and is intended to encompass compounds wherein the product may have amide, amidine, and/or salt linkages in addition to the imide linkage of the type that results from the reaction of a primary amino group and anhydride moiety.
  • the bissuccinimide is prepared according to methods that are well known in the art, including but not limited to, the following:
  • alkenyl or alkyl mono-, bis-succinimides and other higher analogs are included within this term.
  • the preparation of the alkenyl-substituted succinic anhydride by reaction with a polyolefin and maleic anhydride has been described, e.g., U.S. Pat. Nos. 3,018,250 and 3,024,195.
  • Such methods include the thermal reaction of the polyolefin with maleic anhydride and the reaction of a halogenated polyolefin, such as a chlorinated polyolefin, with maleic anhydride.
  • Reduction of the alkenyl-substituted succinic anhydride yields the corresponding alkyl derivative.
  • the alkenyl substituted succinic anhydride may be prepared as described in U.S. Pat. Nos. 4,388,471 and 4,450,281 which are totally incorporated herein by reference.
  • Polyolefin polymers for reaction with the maleic anhydride are polymers comprising a major amount of C 2 to C 5 mono-olefin, e.g., ethylene, propylene, butylene, isobutylene and pentene.
  • the polymers can be homopolymers such as polyisobutylene as well as copolymers of 2 or more such olefins such as copolymers of: ethylene and propylene, butylene, and isobutylene, etc.
  • copolymers include those in which a minor amount of the copolymer monomers, e.g., 1 to 20 mole percent is a C 4 to C 8 nonconjugated diolefin, e.g., a copolymer of isobutylene and butadiene or a copolymer of ethylene, propylene and 1,4-hexadiene, etc.
  • a minor amount of the copolymer monomers e.g., 1 to 20 mole percent is a C 4 to C 8 nonconjugated diolefin, e.g., a copolymer of isobutylene and butadiene or a copolymer of ethylene, propylene and 1,4-hexadiene, etc.
  • the polyolefin polymer usually contains from about 10 to 300 carbon atoms, although preferably 10 to 200 carbon atoms; more preferably 12 to 100 carbon atoms and most preferably 20-100 carbon atoms.
  • a particularly preferred class of olefin polymers comprises the polybutenes, which are prepared by polymerization of one or more of 1-butene, 2-butene and isobutene. Especially desirable are polybutenes containing a substantial proportion of units derived from isobutene.
  • the polybutene may contain minor amounts of butadiene which may or may not be incorporated in the polymer. Most often the isobutene units constitute 80%, preferably at least 90%, of the units in the polymer.
  • These polybutenes are readily available commercial materials well known to those skilled in the art. Disclosures thereof will be found, for example, in U.S. Pat. Nos. 3,215,707; 3,231,587; 3,515,669; and 3,579,450, as well as 3,912,764. The above are incorporated by reference for their disclosures of suitable polybutenes.
  • alkylating hydrocarbons may likewise be used with maleic anhydride to produce alkenyl succinic anhydride.
  • suitable alkylating hydrocarbons include cyclic, linear, branched and internal or alpha olefins with molecular weights in the range 100-4,500 or more with molecular weights in the range of 200-2,000 being more preferred.
  • alpha olefins obtained from the thermal cracking of paraffin wax. Generally, these olefins range from 5-20 carbon atoms in length.
  • Another source of alpha olefins is the ethylene growth process which gives even number carbon olefins.
  • Another source of olefins is by the dimerization of alpha olefins over an appropriate catalyst such as the well known Ziegler catalyst. Internal olefins are easily obtained by the isomerization of alpha olefins over a suitable catalyst such as silica.
  • the polyamine employed to prepare the alkenyl or alkyl succinimides is preferably a polyamine having from 2 to about 12 amine nitrogen atoms and from 2 to about 40 carbon atoms.
  • the polyamine is reacted with an alkenyl or alkyl succinic anhydride to produce the polyamino alkenyl or alkyl succinimide, employed in this invention.
  • the polyamine is so selected so as to provide at least one basic amine per succinimide.
  • a hydroxy hydrocarbyl oxycarbonyl or a hydroxy polyoxyalkylene oxycarbonyl is believed to efficiently proceed through a secondary or primary amine
  • at least one of the basic amine atoms of the polyamino alkenyl or alkyl succinimide must either be a primary amine or a secondary amine. Accordingly, in those instances in which the succinimide contains only one basic amine, that amine must either be a primary amine or a secondary amine.
  • the polyamine preferably has a carbon-to-nitrogen ratio of from about 1:1 to about 10:1.
  • the polyamine portion of the polyamino alkenyl or alkyl succinimide may be substituted with substituents selected from (A) hydrogen, (B) hydrocarbyl groups of from 1 to about 10 carbon atoms, (C) acyl groups of from 2 to about 10 carbon atoms, and (D) monoketo, monohydroxy, mononitro, monocyano, lower alkyl and lower alkoxy derivatives of (B) and (C).
  • At least one of the substituents on one of the amines of the polyamine is hydrogen, e.g., at least one of the basic nitrogen atoms of the polyamine is a primary or secondary amino nitrogen atom.
  • Hydrocarbyl denotes an organic radical composed of carbon and hydrogen which may be aliphatic, alicyclic, aromatic or combinations thereof, e.g., aralkyl.
  • the hydrocarbyl group will be relatively free of aliphatic unsaturation, i.e., ethylenic and acetylenic, particularly acetylenic unsaturation.
  • the substituted polyamines of the present invention are generally, but not necessarily, N-substituted polyamines.
  • hydrocarbyl groups and substituted hydrocarbyl groups include alkyls such as methyl, ethyl, propyl, butyl, isobutyl, pentyl, hexyl, octyl, etc., alkenyls such as propenyl, isobutenyl, hexenyl, octenyl, etc., hydroxyalkyls, such as 2-hydroxyethyl, 3-hydroxypropyl, hydroxyisopropyl, 4-hydroxybutyl, etc., ketoalkyls, such as 2-ketopropyl, 6-ketooctyl, etc., alkoxy and lower alkenoxy alkyls, such as ethoxyethyl, ethoxypropyl, propoxyethyl, propoxypropyl, 2-(2-ethoxyethoxy)ethyl, 2-(2-(2-ethoxy-ethoxy)ethoxy)ethyl, 3,6,9,12
  • the acyl groups of the aforementioned (C) substituents are such as propionyl, acetyl, etc.
  • the more preferred substituents are hydrogen, C 1 -C 6 alkyls and C 1 -C 6 hydroxyalkyls.
  • substituted polyamine the substituents are found at any atom capable of receiving them.
  • the substituted atoms e.g., substituted nitrogen atoms, are generally geometrically inequivalent, and consequently the substituted amines finding use in the present invention can be mixtures of mono- and polysubstituted polyamines with substituent groups situated at equivalent and/or inequivalent atoms.
  • the more preferred polyamine finding use within the scope of the present invention is a polyalkylene polyamine, including alkylene diamine, and including substituted polyamines, e.g., alkyl substituted polyalkylene polyamine.
  • the alkylene group contains from 2 to 6 carbon atoms, there being preferably from 2 to 3 carbon atoms between the nitrogen atoms.
  • Such groups are exemplified by ethylene, 1,2-propylene, 2,2-dimethylpropylene, trimethylene, etc.
  • polyamines examples include ethylene diamine, diethylene triamine, di(trimethylene)triamine, dipropylene triamine, triethylene tetramine, tripropylene tetramine, tetraethylene pentamine, and pentaethylene hexamine.
  • amines encompass isomers such as branched-chain polyamines and the previously mentioned substituted polyamines, including hydrocarbyl-substituted polyamines.
  • polyalkylene polyamines those containing 2-12 amine nitrogen atoms and 2-24 carbon atoms are especially preferred, and the C 2 -C 5 alkylene polyamines are most preferred, in particular, the lower polyalkylene polyamines, e.g., ethylene diamine, dipropylene triamine, etc.
  • the polyamine component also may contain heterocyclic polyamines, heterocyclic substituted amines and substituted heterocyclic compounds, wherein the heterocycle comprises one or more 5-6 membered rings containing oxygen and/or nitrogen.
  • heterocycles may be saturated or unsaturated and substituted with groups selected from the aforementioned (A), (B), (C) and (D).
  • the heterocycles are exemplified by piperazines, such as 2-methylpiperazine, N-(2-hydroxyethyl)piperazine, 1,2-bis-(N-piperazinyl)ethane, and N,N'-bis(N-piperazinyl)piperazine, 2-methylimidazoline, 3-aminopiperidine, 2-aminopyridine, 2-(3-aminoethyl)-3-pyrroline, 3-aminopyrrolidine, N-(3-aminopropyl)-morpholine, etc.
  • the piperazines are preferred.
  • Typical polyamines that can be used to form the compounds of this invention include the following: ethylene diamine, 1,2-propylene diamine, 1,3-propylene diamine, diethylene triamine, triethylene tetramine, hexamethylene diamine, tetraethylene pentamine, methylaminopropylene diamine, N-(betaaminoethyl)piperazine, N,N'-di(betaaminoethyl)piperazine, N,N'-di(beta-aminoethyl)-imidazolidone-2, N-(beta-cyanoethyl)ethane-1,2-diamine, 1,3,6,9-tetraaminooctadecane, 1,3,6-triamino-9-oxadecane, N-(beta-aminoethyl)diethanolamine, N-methyl-1,2-propanediamine, 2-(2-aminoethylamin
  • propyleneamines bisaminopropylethylenediamines
  • Propyleneamines are prepared by the reaction of acrylonitrile with an ethyleneamine, for example, an ethyleneamine having the formula H 2 N(CH 2 CH NH) z H wherein Z is an integer from 1 to 5, followed by hydrogenation of the resultant intermediate.
  • the product prepared from ethylene diamine and acrylonitrile would be H 2 N(CH 2 ) 3 NH(CH 2 ) 2 NH(CH 2 ) 3 NH 2 .
  • the polyamine used as a reactant in the production of succinimides of the present invention is not a single compound but a mixture in which one or several compounds predominate with the average composition indicated.
  • tetraethylene pentamine prepared by the polymerization of aziridine or the reaction of dichloroethylene and ammonia will have both lower and higher amine members, e.g., triethylene tetramine, substituted piperazines and pentaethylene hexamine, but the composition will be largely tetraethylene pentamine and the empirical formula of the total amine composition will closely approximate that of tetraethylene pentamine.
  • suitable polyamines include tetraethylene pentamine, pentaethylene hexamine, and Dow HPA-X heavy polyamine (number average molecular weight of 275, available from Dow Chemical Company, Midland, Michigan). Such amines encompass isomers, such as branched-chain polyamines, and the previously mentioned substituted polyamines, including hydrocarbyl-substituted polyamines.
  • HPA-X heavy polyamine (“HPA-X”) contains an average of approximately 6.5 amine nitrogen atoms per molecule. Such heavy polyamines generally afford excellent results.
  • polyamino alkenyl or alkyl succinimide refers to both polyamino alkenyl or alkyl mono- and bis-succinimides and to the higher analogs of alkenyl or alkyl poly succinimides.
  • Preparation of the bis- and higher analogs may be accomplished by controlling the molar ratio of the reagents.
  • a product comprising predominantly mono- or bissuccinimide can be prepared by controlling the molar ratios of the polyamine and succinic anhydride.
  • a particularly preferred class of polyamino alkenyl or alkyl succinimides employed in the process of the instant invention may be represented by Formula II: wherein R is alkenyl or alkyl of from 10 to 300 carbon atoms; R 2 is alkylene of 2 to 10 carbon atoms; R 3 is hydrogen, lower alkyl or lower hydroxy alkyl; a is an integer from 0 to 10; and W is --NH 2 or represents a group of Formula III: wherein R is alkenyl or alkyl of from 10 to 300 carbon atoms; with the proviso that when W is the group of Formula III above, then a is not zero and at least one of R 3 is hydrogen.
  • the polyamine employed in preparing the succinimide is often a mixture of different compounds wherein the resulting succinimide has an average composition indicated as the Formula II. Accordingly, in Formula II each value of R 2 and R 3 may be the same as or different from other R 2 and R 3 .
  • R is alkenyl or alkyl, more preferably 10 to 200 carbon atoms, and most preferably 20 to 100 carbon atoms.
  • R 2 is alkylene of 2 to 6 carbon atom and most preferably is either ethylene or propylene.
  • R 3 is hydrogen
  • a is an integer from 1 to 6.
  • polyamino alkenyl or alkyl succinimides may be conveniently viewed as being composed of three moieties that is the alkenyl or alkyl moiety R, the succinimide moiety represented by the formula: and the poiyamino moiety represented by the group
  • the preferred alkylene polyamines employed in this reaction are generally represented by the formula: H 2 N-(R'-NH) a -R'-NH 2 wherein R' is an alkylene moiety of 2 to 10 carbon atoms and a is an integer from about 0 to 10.
  • R' is an alkylene moiety of 2 to 10 carbon atoms and a is an integer from about 0 to 10.
  • the preparation of these alkylene polyamines do not produce a single compound and cyclic heterocycles, such as piperazine, may be included to some extent in the alkylene diamines.
  • the succinimide may be prepared by other methods including, but not limited to, those described in the following: Harrison et al., U.S. Patent No. 5,616,668; Harrison et al., U.S. Patent No. 5,565,528; Harrison et al., U.S. Patent No. 5,753,597; Harrison et al., U.S. Patent No. 6,617,396; Harrison et al., U.S. Patent No. 6,451,920; and Wollenberg et al., U.S. Patent No. 4,746,446.
  • the contents of these references are herein incorporated by reference in their entireties.
  • the post-treated succinimide is made in accordance with methods that are well known in the art including, but not limited to the following: Harrison et al., U.S. Patent No. 5,716,912; Harrison et al., U.S. Patent No. 5,821,205; Harrison et al., U.S. Patent No. 5,849,676; Harrison et al., U.S. Patent No. 5,872,083; Harrison et al., U.S. Patent No. 6,015,776; Harrison et al., U.S. Patent No. 6,107,450; Harrison et al., U.S. Patent No. 6,146,431; Harrison et al., U.S. Patent No. 6,358,892.
  • the phosphorous-free nitrogen containing dispersant may also be post treated, such as by reacting them with boric acid or a similar boron compound to form borated dispersants.
  • boric acid boron acid
  • suitable boron compounds include boron oxides, boron halides and esters of boric acid. Generally from about 0.1 equivalents to 10 equivalents of boron compound to the phosphorous-free nitrogen containing dispersant may be employed.
  • a hydrocarbyl substituted succinic ester of a polyol may be mixed with the neutral phosphite compound.
  • Such succinic esters are usually the reaction product of hydrocarbyl substituted succinic acids or anhydrides (e.g. polyisobutenylsuccinic anhydride) with polyols (e.g. pentaerythritol).
  • the hydrocarbyl substituted ester of a polyol may be prepared as described in U.S. Patent No. 3,381,022, which is herein incorporated by reference, and U.S. Patent No. 4,173,540, which is herein incorporated by reference.
  • Suitable polyols include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, dibutylene glycol, tributylene glycol, and other alkylene glycols in which the alkylene group contains from two to eight carbon atoms.
  • polyhydric alcohols include glycerol, pentaerythritol, 1,2-butanediol, 2,3-hexanediol, 2,4-hexanediol, pinacol, erythritol, arabitol, sorbitol, mannitol, 1,2 - cyclohexanediol, and xylene glycol.
  • An especially preferred class of polyhydric alcohols are those having at least three hydroxyl groups, such as pentaerythritol, dipentaerythritol, tripentaerythritol, sorbitol and mannitol. Most preferred is pentaerythritol.
  • ester of pentaerythritol used in this invention may be purchased from Chevron Oronite Company, LLC San Ramon, California and may also be purchased from The Lubrizol Corporation, Wycliffe, Ohio.
  • preferred neutral phosphite compounds include trihydrocarbyl phosphites. More preferred trihydrocarbyl phosphites include trialkyl phosphites. Most preferred trialkyl phosphites include trilauryl phosphite.
  • trilauryl phosphite is manufactured and sold by Rhodia, Inc., Cranbury, New Jersey and is marketed under the trade name Duraphos TLP. According to the MSDS for Duraphos TLP, this compound contains about 90 wt% trilauryl phosphite, 7.5 wt% of dilauryl hydrogen phosphite and less than 0.5 wt% of phenol.
  • a neutral phosphite compound such as trialkyl phosphite, is represented by the following formula: wherein R, R', and R" are independently hydrocarbyl groups having from about 1 to 24 carbon atoms, preferably from about 4 to about 18 carbon atoms, and more preferably from about 6 to 16 carbon atoms.
  • the R, R', and R" groups may be saturated or unsaturated, and straight or branched chain aliphatic hydrocarbyl radical.
  • R, R', and R" groups include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, n-propenyl, n-butenyl, n-hexyl, nonylphenyl, n-dodecyl, n-dodecenyl, hexadecyl, octadecenyl, stearyl, i-stearyl, hydroxystearyl, and the like.
  • R, R' and R" are each alkyl or aryl.
  • Preferred neutral phosphite compounds include trihydrocarbyl phosphites. More preferred trihydrocarbyl phosphites include trialkyl phosphites. Most preferred trialkyl phosphites include trilauryl phosphite, which is manufactured and sold by Rhodia, Inc. and is marketed under the trade name Duraphos TLP.
  • trialkyl phosphite may be synthesized from well known processes such as that described in U.S. Patent No. 2,848,474 which is herein incorporated by reference.
  • the lubricating oil composition of the present invention contains a major amount of oil of lubricating viscosity and a minor amount of the anti-shudder additive composition, which comprises (a) at least one neutral phosphite compound and at least one dispersant selected from and (b) at least one hydrocarbyl substituted succinic dispersant selected from the group consisting of a hydrocarbyl bissuccinimide and a hydrocarbyl substituted succinic ester of a polyol and mixtures thereof, wherein the hydrocarbyl substituent has at least 50 carbon atoms, wherein the additive composition does not comprise an ethoxylated amine; and wherein the additive composition does not comprise a primary amide of a long chain carboxylic acid, provided that if the lubricating oil composition also contains monosuccinimide, then the ratio of the hydrocarbyl substituted succinic dispersant to monosuccinimide is at least 7:3.
  • the ratio of the hydrocarbyl substituted succinic dispersant to monosuccinimide is at least 7.5:2.5. Even more preferred, the ratio of the hydrocarbyl substituted succinic dispersant to monosuccinimide is at least 8:2. Most preferred, the ratio of the hydrocarbyl substituted succinic dispersant to monosuccinimide is 9:1.
  • an effective amount of the anti-shudder additive composition is added to a base oil that is sufficient to lubricate gears and other components which are present in automatic and continuously variable transmissions, as well as reduce the shudder that is caused by friction induced vibration.
  • the lubricating oil composition of the present invention comprises a major amount of oil of lubricating viscosity and a minor amount of the anti-shudder additive package.
  • the lubricating oil composition comprises (a) at least one neutral phosphite compound comprising preferably from about 0.01 wt% to about 1.00 wt% trihydrocarbyl phosphite, such as trialkyl phosphite, such as trilauryl phosphite. More preferably, from about 0.10 wt% to about 0.85 wt% trihydrocarbyl phosphite, such as trialkyl phosphite, such as trilauryl phosphite, is present in the lubricating oil composition.
  • a neutral phosphite compound comprising preferably from about 0.01 wt% to about 1.00 wt% trihydrocarbyl phosphite, such as trialkyl phosphite, such as trilauryl phosphite. More preferably, from about 0.10 wt% to about 0.85 wt% trihydrocarbyl phosphite, such as
  • trihydrocarbyl phosphite such as trialkyl phosphite, such as trilauryl phosphite
  • trihydrocarbyl phosphite such as trialkyl phosphite, such as trilauryl phosphite
  • from about 0.30 wt% to about 0.65 wt% trihydrocarbyl phosphite, such as trialkyl phosphite, such as trilauryl phosphite is present in the lubricating oil composition.
  • component (b) of the lubricating oil composition is a hydrocarbyl bissuccinimide, wherein the hydrocarbyl substituent has at least 50 carbon atoms, comprising preferably from about 0.10 wt% to about 10.0 wt% of bissuccinimide, such as post-treated bissuccinimide, such as borated bissucinimide. More preferably, from about 0.20 wt% to about 8.0 wt% of bissuccinimide, such as post-treated bisuccinimde, such as borated bissuccinimide is in the lubricating oil composition.
  • bissuccinimde such as post-treated bissuccinimide, such as borated bissuccinimide is in the lubricating oil composition.
  • bissuccinimde such as post-treated bissuccinimide, such as borated bissuccinimide is in the lubricating oil composition.
  • from about 0.4 wt% to about 5.0 wt% of bissucnimide, such as post-treated bissuccinimide, such as borated bissuccinimide is in the lubricating oil composition.
  • component (b) of the lubricating oil composition is a hydrocarbyl substituted succinic ester of a polyol and mixtures thereof, wherein the hydrocarbyl substituent has at least 50 carbon atoms, comprising from about 0.10 wt% to about 10.0 wt% of an ester of polyalcohol, such as an ester of pentaerythritol. More preferably, from about 0.20 wt% to about 8.0 wt% of an ester of polyalcohol, such as an ester of pentaerythritol is in the lubricating oil composition.
  • an ester of polyalcohol such as an ester of pentaerythritol is in the lubricating oil composition.
  • from about 0.4 wt% to about 5.0 wt% of an ester of polyalcohol, such as an ester of pentaerythritol is in the lubricating oil composition.
  • component (b) of the lubricating oil composition may be a mixture of the hydrocarbyl bissuccinimide and the hydrocarbyl substituted succinic ester of a polyol.
  • the base oil employed may be any of a wide variety of oils of lubricating viscosity.
  • the base oil of lubricating viscosity used in such compositions may be mineral oils or synthetic oils.
  • the base oils may be derived from synthetic or natural sources.
  • Mineral oils for use as the base oil in this invention include, for example, paraffinic, naphthenic and other oils that are ordinarily used in lubricating oil compositions.
  • Synthetic oils include, for example, both hydrocarbon synthetic oils and synthetic esters and mixtures thereof having the desired viscosity.
  • Hydrocarbon synthetic oils may include, for example, oils prepared from the polymerization of ethylene, polyalphaolefin or PAO oils, or oils prepared from hydrocarbon synthesis procedures using carbon monoxide and hydrogen gases such as in a Fisher-Tropsch process.
  • Useful synthetic hydrocarbon oils include liquid polymers of alpha olefins having the proper viscosity. Especially useful are the hydrogenated liquid oligomers of C 6 to C 12 olefins such as 1-decene trimer.
  • alkyl benzenes of proper viscosity such as didodecyl benzene, can be used.
  • Useful synthetic esters include the esters of monocarboxylic acids and polycarboxylic acids, as well as mono-hydroxy alkanols and polyols. Typical examples are didodecyl adipate, pentaerythritol tetracaproate, di-2-ethylhexyl adipate, dilaurylsebacate, and the like. Complex esters prepared from mixtures of mono and dicarboxylic acids and mono and dihydroxy alkanols can also be used. Blends of mineral oils with synthetic oils are also useful.
  • the base oil can be a refined paraffin type base oil, a refined naphthenic base oil, or a synthetic hydrocarbon or non-hydrocarbon oil of lubricating viscosity.
  • the base oil can also be a mixture of mineral and synthetic oils, Groups I-IV and mixtures thereof. Most preferred base oils are Group II, III and mixtures thereof.
  • Preferred base oils include a blend of Chevron Phillips PAO 4 cSt, which may be purchased from Chevron Phillips, Woodlands, Texas, and RLOP 100 N, which may be purchased from ChevronTexaco Corporation, San Ramon, California.
  • Another preferred base oil is PetroCanad 4 which may be purchased from Petro-Canada, Calgary-Alberta, Canada.
  • additives well known in lubricating oil compositions may be added to the additive composition of the present invention to complete a finished oil.
  • additive components are examples of some of the components that can be favorably employed in the present invention. These examples of additives are provided to illustrate the present invention, but they are not intended to limit it:
  • Anti-oxidants reduce the tendency of mineral oils to deteriorate in service which deterioration is evidenced by the products of oxidation such as sludge and varnish-like deposits on the metal surfaces and by an increase in viscosity.
  • examples of anti-oxidants useful in the present invention include, but are not limited to, phenol type (phenolic) oxidation inhibitors, such as 4,4'-methylene-bis(2,6-di-tert-butylphenol), 4,4'-bis(2,6-di-tert-butylphenol), 4,4'-bis(2-methyl-6-tert-butylphenol), 2,2'-methylene-bis(4-methyl-6-tert-butylphenol), 4,4'-butylidene-bis(3-methyl-6-tert-butylphenol), 4,4'-isopropylidene-bis(2,6-di-tert-butylphenol), 2,2'-methylene-bis(4-methyl-6-nonylphenol), 2,2'-iso
  • Diphenylamine-type oxidation inhibitors include, but are not limited to, alkylated diphenylamine, phenyl-alpha-naphthylamine, and alkylated-alpha-naphthylamine.
  • Other types of oxidation inhibitors include metal dithiocarbamate (e.g., zinc dithiocarbamate), and 15-methylenebis(dibutyldithiocarbamate).
  • these agents reduce wear of moving metallic parts.
  • these agents include, but are not limited to, phosphates which comprise no more than 0.08 wt% of the lubricating oil composition , carbarmates, esters, and molybdenum complexes.
  • Zinc dialky-1-dithiophosphate (primary alkyl, secondary alkyl, and aryl type), diphenyl sulfide, methyl trichlorostearate, chlorinated naphthalene, fluoroalkylpolysiloxane, lead naphthenate, neutralized phosphates, dithiophosphates, and sulfur-free phosphates.
  • Polymethacrylate type polymers ethylene-propylene copolymers, styrene-isoprene copolymers, hydrated styrene-isoprene copolymers, polyisobutylene, and dispersant type viscosity index improvers.
  • Alkyl methacrylate polymers and dimethyl silicone polymers are Alkyl methacrylate polymers and dimethyl silicone polymers.
  • Disalicylidene propylenediamine triazole derivatives, thiadiazole derivatives, and mercaptobenzimidazoles.
  • Alkenyl succinimides alkenyl succinimides modified with other organic compounds, alkenyl succinimides modified by post-treatment with ethylene carbonate or boric acid, pentaerythritols, phenate-salicylates and their post-treated analogs, alkali metal or mixed alkali metal, alkaline earth metal borates, dispersions of hydrated alkali metal borates, dispersions of alkaline-earth metal borates, polyamide ashless dispersants and the like or mixtures of such dispersants.
  • the anti-shudder additive composition is prepared by mixing the following two components at elevated temperatures of about 70°F to 195°F, for example, at about 140°F: (a) at least one neutral phosphite compound, such as trihydrocarbyl phosphite, such as trialkyl phosphite, such as trilauryl phosphite; and (b) at least one phosphorous-free hydrocarbyl substituted succinic dispersant selected from the group consisting of a hydrocarbyl bissuccinimide and a hydrocarbyl substituted succinic ester of a polyol and mixtures thereof, wherein the hydrocarbyl substituent has at least 50 carbon atoms.
  • a neutral phosphite compound such as trihydrocarbyl phosphite, such as trialkyl phosphite, such as trilauryl phosphite
  • at least one phosphorous-free hydrocarbyl substituted succinic dispersant selected
  • the additive composition Preferably, from about 0.10 wt% to about 90.9 wt% of at least one neutral phosphite compound is used in the additive composition. More preferably, from about 1.2 wt% to about 81.0 wt% of at least one neutral phosphite compound is used in the additive composition. Even more preferably, from about 3.9 wt% to about 70.0 wt%, and most preferably from about 5.7 wt% to about 61.9 wt%, of at least one neutral phosphite compound is used in the additive composition.
  • At least one hydrocarbyl substituted succinic dispersant selected from the group consisting of a hydrocarbyl bissuccinimde and a hydrocarbyl substituted succinic ester of a polyol and mixtures thereof, wherein the hydrocarbyl substituent has at least 50 atoms is used in the additive composition. More preferably, from about 19.0 wt% to about 98.8 wt% of at least one hydrocarbyl substituted succinic dispersant is used in the additive composition.
  • a first process for making the finished lubricating oil composition comprises the addition of the anti-shudder additive composition described above to a major amount of an oil of lubricating viscosity, with or without other additives present, wherein the major amount is greater than 50 wt%, provided that if the lubricating oil composition also contains monosuccinimide, then the ratio of the hydrocarbyl substituted succinic dispersant to monosuccinimide is at least 7:3. More preferred, the ratio of the hydrocarbyl substituted succinic dispersant to monosuccinimide is at least 7.5:2.5. Even more preferred, the ratio of the hydrocarbyl substituted succinic dispersant to monosuccinimide is at least 8:2.
  • the ratio of the hydrocarbyl substituted succinic dispersant to monosuccinimide is at least 9:1.
  • the anti-shudder additive composition is present in the lubricating oil composition in the range of about 0.11 wt% to about 11.00 wt%, more preferably from about 0.30 wt% to about 8.85 wt%, even more preferably from about 0.50 wt% to about 6.70 wt%, and most preferably from about 0.70 wt% to about 5.65 wt%, based on the total weight of the lubricating oil composition.
  • a second process for making the finished lubricating oil composition comprises the separate addition of either component (a) and component (b) of the anti-shudder additive composition to the oil of lubricating viscosity.
  • a third process for making the finished oil comprises mixing the anti-shudder additive composition, or the individual components of the anti-shudder additive composition, with a second additive package thereby producing a combined additive package.
  • the combined additive package is then added to a majority amount of an oil of lubricating viscosity, wherein the majority amount is greater than 50 wt%.
  • the present invention is used to decrease shudder in transmissions, including but not limited to automatic and continuously variable transmissions.
  • the lubricating oil of the present invention contacts metal components in transmissions to reduce shudder.
  • the anti-shudder additive composition is present in the lubricating oil composition in the range of about 0.11 wt% to about 11.00 wt%, more preferably from about 0.30 wt% to about 8.85 wt%, even more preferably from about 0.50 wt% to about 6.70 wt%, and most preferably from about 0.70 wt% to about 5.65 wt%, based on the total weight of the lubricating oil composition.
  • the anti-shudder additive composition will optionally comprise sufficient inorganic liquid diluent to make it easy to handle during shipping and storage.
  • the anti-shudder additive composition will comprise from about 0.5 wt% to 45 wt% of the organic liquid diluent and preferably about 2 wt% to 20 wt%.
  • Suitable organic diluents which can be used include, for example, solvent refined 100N (i.e., Cit-con 100N), and hydrotreated 100N (i.e., Chevron 100N), and the like.
  • the organic diluent preferably has a viscosity of about 10 to 20 cSt at 100°C.
  • the anti-shudder lubricating oil composition of the present invention typically meets the General Motors Corporation (GM) added anti-shudder test requirements to the DEXRON®-III specification (DEXRON®-III, H Revision, Automatic Transmission Fluid Specification, GMN10055), using the Electronically Controlled Converter Clutch (ECCC or EC 3 ) Test, which may be purchased from IHS Engineering, Inc. at http://www.global.ihs.com.
  • the ECCC Vehicle Performance Test evaluates torque converter shudder and slip speed hunting characteristics by running the vehicle to be tested on a dynamometer through a series of pre-determined speed and load conditions. Actual road tests may also be used to detect whether there is shudder in the transmission.
  • An anti-shudder additive package was prepared by adding 5.25 wt% borated bissuccinimide (from polyisobutenyl [1300 MW] succinic anhydride and a heavy polyamine, HPA-X, available from Dow Chemical Company) dispersant (which comprises about 99 wt% bissuccinimide), 0.033 wt% high overbased (HOB) calcium sulfonate, 0.04 wt% Durad 310 M (which comprises a mixture of organophosphate esters), 0.565 wt% Duraphos TLP (which comprises about 90 wt% trilauryl phosphite and 7.5 w% dilauryl hydrogen phosphite), 0.50 wt% phenolic oxidation inhibitor, 0.40 wt% aminic oxidation inhibitor, 0.1 wt% thiadiazole derivative, 0.75 wt% benzoate ester, 0.002 wt% silicon based foam inhibitor, 0.020 wt
  • An anti-shudder additive package was prepared by adding 4.5 wt% succinate ester of pentaerythritol and polyisobutenyl (1000 MW) succinic anhydride (PIBSA) dispersant, 0.0022 wt% calcium sulfonate, 0.1 wt% polyamide of tetraethylenepentamine (TEPA) and isostearic acid, 0.565 wt% Duraphos TLP (which comprises about 90 wt% trilauryl phosphite and 7.5 wt% dilauryl hydrogen phosphite), 0.02 wt% Duraphos AP 230 (dilauryl hydrogen phosphite), 0.9 wt% phenolic oxidation inhibitor, 0.05 wt% thiadiazole derivative, 0.05 wt% primary aliphatic amine with highly branched alkyl chains (C12-C14), 0.5 wt% benzoate ester, 0.002
  • An anti-shudder additive package was prepared by adding 1.25 wt% borated bissuccinimide dispersant from polyisobutenyl (1300 MW) succinic anhydride and heavy polyamine, HPA-X (which dispersant comprises about 99 wt% bissuccinimide), 3.0 wt% succininate ester of pentaerythritol and polyisobutenyl (1000 MW) succinic anhydride (PIBSA) dispersant dispersant, 0.0022 wt% HOB calcium sulfonate, 0.1 wt% polyamide of TEPA and isostearic acid, 0.565 wt% Duraphos TLP (90 wt% trilauryl phosphite and 7.5 wt% dilauryl hydrogen phosphite), 0.02 wt% Duraphos AP 230 (dilauryl hydrogen phosphite), 0.5 wt% phenolic oxidation inhibitor,
  • An anti-shudder additive package was prepared by adding 1.5 wt% horated bissuccinimide dispersant from polyisobutenyl (1300 MW) succinic anhydride and heavy polyamine, HPA-X (which dispersant comprises about 99 wt% bissuccinimide), 1.5 wt% succininate ester of pentaerythritol and polyisobutenyl (1000 MW) succinic anhydride (PIBSA) dispersant, 0.0022 wt% HOB calcium sulfonate, 0.1 wt% polyamide of TEPA and isostearic acid, 0.565 wt% Duraphos TLP (90 wt% trilauryl phosphite and 7.5 wt% dilauryl hydrogen phosphite), 0.02 wt% Duraphos AP 230 (dilauryl hydrogen phosphite), 0.5 wt% phenolic oxidation inhibitor, 0.4 wt
  • An anti-shudder additive package was prepared by adding 5.25 wt% monosuccinimide dispersant from polyisobutenyl (1000 MW) succinic anhydride and a mixture of diethylene triamine and HPA-X (which dispersant comprises about 50 wt% monosuccinimide and about 50 wt% bissuccinimide), 0.033 wt% HOB calcium sulfonate, 0.04 wt% Durad 310M (mixture of organophosphate esters), 0.565 wt% Duraphos TLP (which comprises about 90 wt% trilauryl phosphite and about 7.5 wt% dilauryl hydrogen phosphite), 0.50 wt% phenolic oxidation inhibitor, 0.40 wt% aminic oxidation inhibitor, 0.1 wt% thiadiazole derivative, 0.75 wt% benzoate ester, 0.002 wt% silicon based foam inhibitor, 0.020
  • An anti-shudder additive package was prepared by adding 5.25 wt% borated bissuccinimide (from polyisobutenyl [1300 MW] succinic anhydride and a heavy polyamine, HPA-X, available from Dow Chemical Company) dispersant (which comprises about 99 wt% bissuccinimide), 0.033 wt% HOB calcium sulfonate, 0.45 wt% Durad 310M (which comprises a mixture of organophosphate esters), 0.50 wt% phenolic oxidation inhibitor, 0.40 wt% aminic oxidation inhibitor, 0.1 wt% thiadiazole derivative, 0.75 wt% benzoate ester, 0.002 wt% silicon based foam inhibitor, 0.020 wt% Unisol Red BHF, and 2.6 wt% PMA-VII (350,000 MW average) to a base oil composition comprised of a base oil blend comprised of about 88.77 wt% RLOP 100 N
  • An anti-shudder additive package was prepared by adding 4.23 wt% monosuccinimide dispersant from polyisobutenyl (1000 MW) succinic anhydride and a mixture of diethylene triamine and HPA-X (which dispersant comprises about 50 wt% monosuccinimide and about 50 wt% bissuccinimide), 1.00 wt% borated bissuccinimide (from polyisobutenyl [1300 MW] succinic anhydride and a heavy polyamine, HPA-X, available from Dow Chemical Company) dispersant (which comprises about 99 wt% bissuccinimide), 0.033 wt% HOB calcium sulfonate, 0.565 wt% Duraphos TLP (which comprises about 90 wt% trilauryl phosphite and about 7.5 wt% dilauryl hydrogen phosphite), 0.02 Duraphos AP-230 (which comprises dilauryl hydrogen
  • the components were blended for approximately two hrs at a temperature of from about 120° F to about 140° F.
  • the ratio of bissuccinimide to monosuccinimide is 6:4.
  • the lubricating oil comprising this anti-shudder additive package failed the GM DEXRON®-III ECCC Test.
  • An anti-shudder additive package was prepared by adding 4.23 wt% monosuccinimide dispersant from polyisobutenyl (1000 MW) succinic anhydride and a mixture of diethylene triamine and HPA-X (which dispersant comprises about 50 wt% monosuccinimide and about 50 wt% bissuccinimide), 1.00 wt% borated bissuccinimide (from polyisobutenyl [1300 MW] succinic anhydride and a heavy polyamine, HPA-X, available from Dow Chemical Company) dispersant (which comprises about 99 wt% bissuccinimide), 0.0022 wt% HOB calcium sulfonate, 0.41 wt% Durad 310 M (which comprises a mixture of organophosphate esters), 0.2 wt% polyamide of TEPA and isostearic acid, 0.30 wt% phenolic oxidation inhibitor, 0.5 wt% aminic oxidation inhibitor,
  • the components were blended for approximately two hrs at a temperature of from about 120° F to about 140° F.
  • the ratio of bissuccinimide to monosuccinimide is 6:4.
  • the lubricating oil comprising this anti-shudder additive package failed the GM DEXRON®-III ECCC Test.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)
EP05257367.2A 2004-12-21 2005-11-30 Schwingungsdämpfende Additivzusammensetzung und Schmierölzusammensetzung diese enthaltend Active EP1674557B1 (de)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US11/021,166 US20060135375A1 (en) 2004-12-21 2004-12-21 Anti-shudder additive composition and lubricating oil composition containing the same

Publications (3)

Publication Number Publication Date
EP1674557A2 true EP1674557A2 (de) 2006-06-28
EP1674557A3 EP1674557A3 (de) 2010-10-27
EP1674557B1 EP1674557B1 (de) 2016-12-21

Family

ID=36202531

Family Applications (1)

Application Number Title Priority Date Filing Date
EP05257367.2A Active EP1674557B1 (de) 2004-12-21 2005-11-30 Schwingungsdämpfende Additivzusammensetzung und Schmierölzusammensetzung diese enthaltend

Country Status (5)

Country Link
US (1) US20060135375A1 (de)
EP (1) EP1674557B1 (de)
JP (2) JP5656336B2 (de)
CA (1) CA2530846C (de)
SG (2) SG144917A1 (de)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1803796A2 (de) * 2005-12-26 2007-07-04 Chevron Oronite Company LLC Eine Schmierölzusammensetzung für Automatikgetriebe

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4601315B2 (ja) 2004-03-31 2010-12-22 出光興産株式会社 ディーゼルエンジン用潤滑油組成物
US20080128322A1 (en) * 2006-11-30 2008-06-05 Chevron Oronite Company Llc Traction coefficient reducing lubricating oil composition
JP5184214B2 (ja) * 2008-05-27 2013-04-17 Jx日鉱日石エネルギー株式会社 金属ベルト式無段変速機用潤滑油組成物
CN104250579B (zh) * 2013-06-28 2016-09-28 中国石油化工股份有限公司 一种atf-iii自动传动液组合物
CN114450381A (zh) * 2019-10-07 2022-05-06 禾大公司 腐蚀抑制

Citations (31)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2848474A (en) 1953-10-19 1958-08-19 Monsanto Chemicals Method of producing and recovering trimethyl phosphite
US2992708A (en) 1954-01-14 1961-07-18 Lyon George Albert Air circulating wheel structure
US3018250A (en) 1959-08-24 1962-01-23 California Research Corp Lubricating oil compositions containing nu-dialkylaminoalkyl alkenyl succinimides
US3024195A (en) 1959-08-24 1962-03-06 California Research Corp Lubricating oil compositions of alkylpiperazine alkenyl succinimides
US3100673A (en) 1963-08-13 Dyeings and prints possessing fastness
US3172892A (en) 1959-03-30 1965-03-09 Reaction product of high molecular weight succinic acids and succinic anhydrides with an ethylene poly- amine
US3215707A (en) 1960-06-07 1965-11-02 Lubrizol Corp Lubricant
US3231587A (en) 1960-06-07 1966-01-25 Lubrizol Corp Process for the preparation of substituted succinic acid compounds
US3272746A (en) 1965-11-22 1966-09-13 Lubrizol Corp Lubricating composition containing an acylated nitrogen compound
US3381022A (en) 1963-04-23 1968-04-30 Lubrizol Corp Polymerized olefin substituted succinic acid esters
US3515669A (en) 1967-11-06 1970-06-02 Lubrizol Corp High molecular weight carboxylic acid ester stabilized metal dispersions and lubricants and fuels containing the same
US3579450A (en) 1963-04-23 1971-05-18 Lubrizol Corp Lubricants and fuels containing epoxide treated esters
US3912764A (en) 1972-09-29 1975-10-14 Cooper Edwin Inc Preparation of alkenyl succinic anhydrides
US4173540A (en) 1977-10-03 1979-11-06 Exxon Research & Engineering Co. Lubricating oil composition containing a dispersing-varnish inhibiting combination of polyol ester compound and a borated acyl nitrogen compound
US4342709A (en) 1980-12-08 1982-08-03 Stauffer Chemical Company Process for producing diethyl phosphite
US4388471A (en) 1982-04-30 1983-06-14 Chevron Research Company Process for the preparation of alkenyl succinic anhydrides
US4450281A (en) 1982-12-29 1984-05-22 Chevron Research Company Process for the preparation of a polyalkenyl succinic anhydride
US4746446A (en) 1984-07-20 1988-05-24 Chevron Research Company Modified succinimides
US5441656A (en) 1994-02-10 1995-08-15 Ethyl Petroleum Additives, Inc. Automatic transmission fluids and additives therefor
US5565528A (en) 1993-12-13 1996-10-15 Chevron Chemical Company Polymeric dispersants having polyalkylene and succinic groups
US5716912A (en) 1996-04-09 1998-02-10 Chevron Chemical Company Polyalkylene succinimides and post-treated derivatives thereof
US5753597A (en) 1996-08-20 1998-05-19 Chevron Chemical Company Polymeric dispersants
US5821205A (en) 1995-12-01 1998-10-13 Chevron Chemical Company Polyalkylene succinimides and post-treated derivatives thereof
US5942472A (en) 1997-06-12 1999-08-24 Exxon Chemical Patents Inc. Power transmission fluids of improved viscometric and anti-shudder properties
US6015776A (en) 1998-09-08 2000-01-18 Chevron Chemical Company Polyalkylene polysuccinimides and post-treated derivatives thereof
US6107450A (en) 1998-12-15 2000-08-22 Chevron Chemical Company Llc Polyalkylene succinimides and post-treated derivatives thereof
US6127323A (en) 1997-04-21 2000-10-03 Exxon Chemical Patents Inc. Power transmission fluids containing alkyl phosphonates
US6225266B1 (en) 1999-05-28 2001-05-01 Infineum Usa L.P. Zinc-free continuously variable transmission fluid
US6451920B1 (en) 1999-11-09 2002-09-17 Chevron Chemical Company Llc Process for making polyalkylene/maleic anhydride copolymer
US20020151441A1 (en) 2001-02-14 2002-10-17 Sanjay Srinivasan Automatic transmission fluids with improved anti-shudder properties
US6660695B2 (en) 2002-03-15 2003-12-09 Infineum International Ltd. Power transmission fluids of improved anti-shudder properties

Family Cites Families (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5137980A (en) * 1990-05-17 1992-08-11 Ethyl Petroleum Additives, Inc. Ashless dispersants formed from substituted acylating agents and their production and use
US5652201A (en) * 1991-05-29 1997-07-29 Ethyl Petroleum Additives Inc. Lubricating oil compositions and concentrates and the use thereof
US5451920A (en) * 1992-10-06 1995-09-19 Martin Marietta Energy Systems, Inc. Thick film hydrogen sensor
JP3650629B2 (ja) * 1993-10-29 2005-05-25 東燃ゼネラル石油株式会社 潤滑油組成物
US5477736A (en) * 1994-03-14 1995-12-26 General Electric Company Ultrasonic transducer with lens having electrorheological fluid therein for dynamically focusing and steering ultrasound energy
US5750476A (en) * 1995-10-18 1998-05-12 Exxon Chemical Patents Inc. Power transmitting fluids with improved anti-shudder durability
US5840663A (en) * 1996-12-18 1998-11-24 Exxon Chemical Patents Inc. Power transmitting fluids improved anti-shudder durability
US5872063A (en) * 1998-01-12 1999-02-16 Taiwan Semiconductor Manufacturing Company Ltd. Self-aligned contact structures using high selectivity etching
JP3977940B2 (ja) * 1998-10-07 2007-09-19 新日本石油株式会社 金属ベルト式無段変速機用潤滑油組成物
JP3977942B2 (ja) * 1998-10-07 2007-09-19 新日本石油株式会社 金属ベルト式無段変速機用潤滑油組成物
JP4663843B2 (ja) * 2000-03-29 2011-04-06 Jx日鉱日石エネルギー株式会社 潤滑油組成物
EP1138753A3 (de) * 2000-03-31 2002-05-22 Chevron Oronite Company LLC Schmiermittelzusammensetzung für luftgekühlte Zweitakt-Brennkraftmaschinen
JP4294827B2 (ja) * 2000-04-03 2009-07-15 新日本石油株式会社 潤滑油組成物
JP4015355B2 (ja) * 2000-09-29 2007-11-28 新日本石油株式会社 潤滑油組成物
DE10123553A1 (de) * 2001-05-15 2002-11-21 Basf Ag Verfahren zur Herstellung von Polyalkenylsuccinimidprodukten, neue Polyalkenylsuccinimidprodukte mit verbesserten Eigenschaften, Zwischenprodukte und Verwendungen
US20030166474A1 (en) * 2002-01-31 2003-09-04 Winemiller Mark D. Lubricating oil compositions with improved friction properties
US20050101494A1 (en) * 2003-11-10 2005-05-12 Iyer Ramnath N. Lubricant compositions for power transmitting fluids

Patent Citations (41)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3100673A (en) 1963-08-13 Dyeings and prints possessing fastness
US2848474A (en) 1953-10-19 1958-08-19 Monsanto Chemicals Method of producing and recovering trimethyl phosphite
US2992708A (en) 1954-01-14 1961-07-18 Lyon George Albert Air circulating wheel structure
US3219666A (en) 1959-03-30 1965-11-23 Derivatives of succinic acids and nitrogen compounds
US3172892A (en) 1959-03-30 1965-03-09 Reaction product of high molecular weight succinic acids and succinic anhydrides with an ethylene poly- amine
US3018250A (en) 1959-08-24 1962-01-23 California Research Corp Lubricating oil compositions containing nu-dialkylaminoalkyl alkenyl succinimides
US3018291A (en) 1959-08-24 1962-01-23 California Research Corp Nu-dialkylaminoalkyl alkenyl succinimides
US3024195A (en) 1959-08-24 1962-03-06 California Research Corp Lubricating oil compositions of alkylpiperazine alkenyl succinimides
US3024237A (en) 1959-08-24 1962-03-06 California Research Corp Alkenyl succinimides of piperazines
US3231587A (en) 1960-06-07 1966-01-25 Lubrizol Corp Process for the preparation of substituted succinic acid compounds
US3215707A (en) 1960-06-07 1965-11-02 Lubrizol Corp Lubricant
US3381022A (en) 1963-04-23 1968-04-30 Lubrizol Corp Polymerized olefin substituted succinic acid esters
US3579450A (en) 1963-04-23 1971-05-18 Lubrizol Corp Lubricants and fuels containing epoxide treated esters
US3272746A (en) 1965-11-22 1966-09-13 Lubrizol Corp Lubricating composition containing an acylated nitrogen compound
US3515669A (en) 1967-11-06 1970-06-02 Lubrizol Corp High molecular weight carboxylic acid ester stabilized metal dispersions and lubricants and fuels containing the same
US3912764A (en) 1972-09-29 1975-10-14 Cooper Edwin Inc Preparation of alkenyl succinic anhydrides
US4173540A (en) 1977-10-03 1979-11-06 Exxon Research & Engineering Co. Lubricating oil composition containing a dispersing-varnish inhibiting combination of polyol ester compound and a borated acyl nitrogen compound
US4342709A (en) 1980-12-08 1982-08-03 Stauffer Chemical Company Process for producing diethyl phosphite
US4388471A (en) 1982-04-30 1983-06-14 Chevron Research Company Process for the preparation of alkenyl succinic anhydrides
US4450281A (en) 1982-12-29 1984-05-22 Chevron Research Company Process for the preparation of a polyalkenyl succinic anhydride
US4746446A (en) 1984-07-20 1988-05-24 Chevron Research Company Modified succinimides
US5565528A (en) 1993-12-13 1996-10-15 Chevron Chemical Company Polymeric dispersants having polyalkylene and succinic groups
US5616668A (en) 1993-12-13 1997-04-01 Chevron Chemical Company Polymeric dispersants having polyalkylene and succinic groups
US5441656A (en) 1994-02-10 1995-08-15 Ethyl Petroleum Additives, Inc. Automatic transmission fluids and additives therefor
US6358892B1 (en) 1995-12-01 2002-03-19 Chevron Chemical Company Polyalkylene succinimides and post-treated derivatives thereof
US5821205A (en) 1995-12-01 1998-10-13 Chevron Chemical Company Polyalkylene succinimides and post-treated derivatives thereof
US5849676A (en) 1995-12-01 1998-12-15 Chevron Chemical Company Post-treated derivatives of polyalkylene succinimides
US5872083A (en) 1995-12-01 1999-02-16 Chevron Chemical Company Post-treated derivatives of polyalkylene succinimides
US5716912A (en) 1996-04-09 1998-02-10 Chevron Chemical Company Polyalkylene succinimides and post-treated derivatives thereof
US5753597A (en) 1996-08-20 1998-05-19 Chevron Chemical Company Polymeric dispersants
US6127323A (en) 1997-04-21 2000-10-03 Exxon Chemical Patents Inc. Power transmission fluids containing alkyl phosphonates
US5942472A (en) 1997-06-12 1999-08-24 Exxon Chemical Patents Inc. Power transmission fluids of improved viscometric and anti-shudder properties
US6146431A (en) 1998-09-08 2000-11-14 Chevron Chemical Company Llc Polyalkylene polysuccinimides and post-treated derivatives thereof
US6015776A (en) 1998-09-08 2000-01-18 Chevron Chemical Company Polyalkylene polysuccinimides and post-treated derivatives thereof
US6107450A (en) 1998-12-15 2000-08-22 Chevron Chemical Company Llc Polyalkylene succinimides and post-treated derivatives thereof
US6225266B1 (en) 1999-05-28 2001-05-01 Infineum Usa L.P. Zinc-free continuously variable transmission fluid
US6337309B1 (en) 1999-05-28 2002-01-08 Infineum International Ltd Zinc-free continuously variable transmission fluid
US6451920B1 (en) 1999-11-09 2002-09-17 Chevron Chemical Company Llc Process for making polyalkylene/maleic anhydride copolymer
US6617396B1 (en) 1999-11-09 2003-09-09 Chevron Oronite Company Llc Process for making polyalkylene/maleic anhydride copolymer
US20020151441A1 (en) 2001-02-14 2002-10-17 Sanjay Srinivasan Automatic transmission fluids with improved anti-shudder properties
US6660695B2 (en) 2002-03-15 2003-12-09 Infineum International Ltd. Power transmission fluids of improved anti-shudder properties

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
KIRK-OTHMER'S: "ENCYCLOPEDIA OF CHEMICAL TECHNOLOGY", vol. 2, pages: 99 - 116
KUGIMIYA, TAKANORI: "Effects of Additives of ATF and Components of Friction Material for AT on µ-v Characteristics", JAPANESE JOURNAL OF TRIBOLOGY, vol. 45, no. 3, 2000
NOLLER'S: "CHEMISTRY OF ORGANIC COMPOUNDS", 1957, SAUNDERS
SIDGEWICK'S: "THE ORGANIC CHEMISTRY OF NITROGEN", 1966, CLARENDON PRESS

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1803796A2 (de) * 2005-12-26 2007-07-04 Chevron Oronite Company LLC Eine Schmierölzusammensetzung für Automatikgetriebe
EP1803796A3 (de) * 2005-12-26 2007-08-22 Chevron Oronite Company LLC Eine Schmierölzusammensetzung für Automatikgetriebe

Also Published As

Publication number Publication date
CA2530846C (en) 2015-07-14
EP1674557B1 (de) 2016-12-21
JP5656336B2 (ja) 2015-01-21
SG123702A1 (en) 2006-07-26
SG144917A1 (en) 2008-08-28
CA2530846A1 (en) 2006-06-21
US20060135375A1 (en) 2006-06-22
EP1674557A3 (de) 2010-10-27
JP2013216916A (ja) 2013-10-24
JP2006176776A (ja) 2006-07-06

Similar Documents

Publication Publication Date Title
JP4677359B2 (ja) 潤滑組成物
JP5113309B2 (ja) 亜鉛を含有しない連続可変トランスミッション流体
KR100696146B1 (ko) 개선된 진동 방지 특성을 가지는 동력 전달 유체
CA2747730C (en) Lubricating oil additives comprising post-treated succinic derivatives
KR101684346B1 (ko) 마찰개선제 및 트랜스미션 오일
US20070082826A1 (en) Power transmission fluids having extended durability
KR101679097B1 (ko) 윤활제에 마찰 조정제로서의 아민 유도체
KR101679096B1 (ko) 윤활제에 마찰 조정제로서의 아민 유도체
KR101703368B1 (ko) 윤활제의 마찰 조정제로서의 이미드 및 비스-아미드
KR20130139334A (ko) 연장된 셔더방지 내구성을 가진 연속가변변속기 유체
JP2016180102A (ja) 建設機械用潤滑油組成物
JP2001513140A (ja) 潤滑剤組成物
EP1674557B1 (de) Schwingungsdämpfende Additivzusammensetzung und Schmierölzusammensetzung diese enthaltend
CN105073963A (zh) 自动变速机用润滑油组合物
US20070066498A1 (en) Power transmitting fluids and additive compositions
JP2005524758A (ja) カルシウム過塩基化界面活性剤およびマグネシウム過塩基化界面活性剤の組合せを含有する連続可変トランスミッション用流体
US20100317554A1 (en) Lubricating oil composition
CN117467491A (zh) 用于施工机械的润滑油组合物
AU687150B2 (en) Oil soluble friction increasing additives for power transmission fluids
CN111492043B (zh) 受阻胺封端的丁二酰亚胺分散剂和含有其的润滑组合物
JP6510963B2 (ja) 潤滑油組成物
US20180142180A1 (en) Automatic transmission fluid
CA3193618A1 (en) Lubricating oil containing alkyl phosphonic acid
CN118715310A (zh) 润滑油组合物

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI SK TR

AX Request for extension of the european patent

Extension state: AL BA HR MK YU

PUAL Search report despatched

Free format text: ORIGINAL CODE: 0009013

AK Designated contracting states

Kind code of ref document: A3

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI SK TR

AX Request for extension of the european patent

Extension state: AL BA HR MK YU

17P Request for examination filed

Effective date: 20110420

AKX Designation fees paid

Designated state(s): DE FR GB NL

17Q First examination report despatched

Effective date: 20111121

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

INTG Intention to grant announced

Effective date: 20160721

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): DE FR GB NL

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602005050942

Country of ref document: DE

REG Reference to a national code

Ref country code: NL

Ref legal event code: FP

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602005050942

Country of ref document: DE

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 13

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20170922

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 14

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 20201113

Year of fee payment: 16

REG Reference to a national code

Ref country code: DE

Ref legal event code: R082

Ref document number: 602005050942

Country of ref document: DE

Representative=s name: HL KEMPNER PATENTANWAELTE, SOLICITORS (ENGLAND, DE

Ref country code: DE

Ref legal event code: R082

Ref document number: 602005050942

Country of ref document: DE

Representative=s name: HL KEMPNER PATENTANWALT, RECHTSANWALT, SOLICIT, DE

REG Reference to a national code

Ref country code: NL

Ref legal event code: MM

Effective date: 20211201

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20211201

P01 Opt-out of the competence of the unified patent court (upc) registered

Effective date: 20230522

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20230929

Year of fee payment: 19

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20231012

Year of fee payment: 19

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20231003

Year of fee payment: 19