EP1466023B1 - Quenching oil compositions - Google Patents

Quenching oil compositions Download PDF

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Publication number
EP1466023B1
EP1466023B1 EP02805163A EP02805163A EP1466023B1 EP 1466023 B1 EP1466023 B1 EP 1466023B1 EP 02805163 A EP02805163 A EP 02805163A EP 02805163 A EP02805163 A EP 02805163A EP 1466023 B1 EP1466023 B1 EP 1466023B1
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EP
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Prior art keywords
composition
hydrocarbyl substituted
oil
metal
metal salt
Prior art date
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EP02805163A
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German (de)
English (en)
French (fr)
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EP1466023A1 (en
Inventor
William R. Sweet
Matthew R. Sivik
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Lubrizol Corp
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Lubrizol Corp
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    • 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
    • C10M169/00Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • C10M169/04Mixtures of base-materials and additives
    • C10M169/044Mixtures of base-materials and additives the additives being a mixture of non-macromolecular and macromolecular 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
    • C10M169/00Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • C10M169/04Mixtures of base-materials and additives
    • C10M169/048Mixtures of base-materials and additives the additives being a mixture of compounds of unknown or incompletely defined constitution, non-macromolecular and macromolecular compounds
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21DMODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D1/00General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
    • C21D1/56General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering characterised by the quenching agents
    • C21D1/58Oils
    • 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
    • C10M2203/00Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C10M2203/1006Petroleum or coal fractions, e.g. tars, solvents, bitumen used as base material
    • 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
    • C10M2203/00Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C10M2203/102Aliphatic fractions
    • C10M2203/1025Aliphatic fractions used as base material
    • 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
    • C10M2205/00Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • 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
    • C10M2205/00Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/026Butene
    • 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
    • C10M2205/00Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/06Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing conjugated dienes
    • 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
    • C10M2207/02Hydroxy compounds
    • C10M2207/023Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • 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
    • C10M2207/02Hydroxy compounds
    • C10M2207/023Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/028Overbased salts thereof
    • 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
    • C10M2209/00Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/10Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/101Condensation polymers of aldehydes or ketones and phenols, e.g. Also polyoxyalkylene ether derivatives thereof
    • 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
    • C10M2215/086Imides
    • 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
    • C10M2219/00Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/04Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
    • C10M2219/044Sulfonic acids, Derivatives thereof, e.g. neutral salts
    • 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
    • C10M2219/00Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/04Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
    • C10M2219/046Overbasedsulfonic acid salts
    • 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
    • C10N2020/00Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01Physico-chemical properties
    • C10N2020/02Viscosity; Viscosity index
    • 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
    • C10N2020/00Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01Physico-chemical properties
    • C10N2020/067Unsaturated Compounds
    • 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
    • C10N2030/52Base number [TBN]
    • 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
    • C10N2040/20Metal working
    • 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
    • C10N2040/20Metal working
    • C10N2040/242Hot working

Definitions

  • This invention relates to oil compositions that are useful as quenching oils used in heat treating of metals, particularly ferrous metals such as steel.
  • Desired hardness and strength properties of metals are secured by heat treatment of the metal object.
  • the properties usually depend upon establishment of certain physical structures in the metal.
  • the production of the desired physical structures is obtained by heating the metal to a temperature where the structure is present, then by arresting at the desired point the changes in the internal structure which take place during cooling of the metal from high temperatures. Quick cooling by quenching the heated object in a quenching medium makes it possible to arrest the physical changes at the desired point during cooling.
  • Quenching in the quenching medium is carried out in such a manner that the physical changes in the metal are arrested at the desired point, usually at the point at which maximum hardness is obtained. Subsequently, the heat treated and quenched object may be subjected to treatment at lower temperature (annealing or tempering) to provide the desired degree of toughness and ductility.
  • mineral oil based quenching fluids have been used. Previously, aqueous quenching media were employed. The aqueous fluids provided extremely rapid cooling setting up excessive amounts of internal stress in the object. Mineral oil based fluids avoided this difficulty, but often did not provide a sufficiently high cooling rate to secure desirable properties in pieces formed of materials having high critical cooling rates to develop maximum strength and hardness or to quench pieces of high mass to surface ratios to develop hardness and strength to maximum depth.
  • Durability refers to additive lifetime after being exposed to thermal stressing while consistency relates to constant additive performance over time. Cleanliness is measured using a coker test.
  • U.S. Patent 2,340,724 relates to quenching oils comprising a light mineral quenching oil and an oil-soluble, heat stable, high molecular weight iso-olefin polymerization product in a controlled amount adequate to produce a quenching oil composition having an initial 5-second quenching speed of at least 22.0 percent without substantially modifying the stress-reducing characteristics of the oil.
  • Polymers of molecular weigh 1,000 to 10,000, and particularly, isobutylene polymerization product, are said to be particularly advantageous.
  • U.S. Patent 3,489,619 relates to oil compositions described as having good high temperature stability and useful as a heat transfer oil for the quenching of metals.
  • the oil comprises a major proportion of a hydrocarbon lubricating oil into which has been dispersed a minor proportion of an alkali metal phosphate, silicate or borate with the aid of a minor proportion of a high molecular weight monocarboxylic acid, dicarboxylic acid or dicarboxylic acid anhydride.
  • U.S. Patent 3,567,640 describes a quenching oil composition comprised of a major portion of a petroleum oil having a viscosity within the range of about 40 to about 300 SUS at 100°F and a flash point in excess of 250°F and about 2% to about 15% by weight of a quench oil additive, which is an oil soluble petroleum resin produced from distillates of cracked petroleum stock having a melting point of at least 40°C and an aniline point value of less than 50°C.
  • U.S. Patent 3,855,014 describes an improved quenching oil composition
  • a quench oil of lubricating viscosity comprising a major amount of a quench oil of lubricating viscosity; a minor amount of at least one carbon-linked poly-phenate metal compound sufficient to improve the anti-staining properties of the composition and at least one naphthyl amine sufficient to improve the resistance to oxidation of the composition.
  • the composition may also include a minor amount of at least one of certain diamine components said to provide further improved oxidation resistance.
  • U.S. Patent 5,015,404 describes an oil composition containing 100 parts by weight of a base oil selected from the group consisting of mineral base oil, synthetic base oil and mixtures thereof, and 0.1 to 20 parts by weight of a hydrogenated oil obtained by hydrogenating an oil selected from the group consisting of coal type tar, oil produced by fractionating coal type tar, a hydrocarbon obtained by thermally cracking petroleum and having a boiling point of not lower than 200°C, a hydrocarbon obtained by catalytically cracking petroleum and having a boiling point of not lower than 200°C, a hydrocarbon obtained by catalytically reforming petroleum and having a boiling point of not lower than 200°C, and mixtures thereof, whereby the hydrogenated oil has the hydrogen-donating properties of not lower than three times the hydrogen-donating properties of the base oil at temperatures of not lower than 350°C.
  • U.S. Patent 5,250,122 discloses a heat treating oil composition which comprises (A) at least one base oil selected from a mineral oil and a synthetic oil each having a sulfur content of not more than 300 ppm and (B) at least one member selected from alkaline earth metal salts of salicylic acid. There is also disclosed a heat treating oil composition which comprises (I) a base oil having a sulfur content of 3 to 1000 ppm consisting of said (A) component and (C) at lease one member selected from a sulfur and a sulfur compound, along with (II) various additives for quenching.
  • This heat treating oil composition is said to be suitable for quenching under the condition of a high oil temperature and capable of obtaining a treated metal excellent in brightness and having a minimized distortion.
  • U.S. Patent 5,376,186 describes a heat treating oil composition which comprises a base oil adjusted to have a total sulfur content of 3 to 1000 ppm comprising (A) at least one base oil selected from a mineral oil and a synthetic oil each having a sulfur content of not more than 300 ppm and (C) at least one member selected from a sulfur and a sulfur compound, and (B) at least one additive selected from an alkaline earth metal salt of sulfonic acid, that of a phenol, alkenyl succinic acid derivatives, fatty acid or its derivatives and phenol-based and amine-based antioxidants.
  • the above-mentioned heat treating oil composition is said to be suitable for quenching under a condition of a high oil temperature to realize a treated metal product having a excellent brightness and little distortion.
  • U.S. Patent 5,487,796 relates to a method of quenching metals, in particular steel alloys includes treatment of the article being quenched in a boiling aqueous solution of sodium tetraborate, with gas being additionally introduced into the quench bath.
  • the supply of gas enables a continuous operation in a wide range of application and avoids the use of conventional less environmentally friendly quenching media (oils).
  • U.S. Patent 5,879,743 describes a wear-resistant hardfacing and a method for applying such a hardfacing.
  • a finely powdered, wear-resistant alloy and a polyvinyl alcohol (PVA) solution slurry is coated onto the metal surface of a tool, implement, or similar item to be hardfaced.
  • PVA polyvinyl alcohol
  • a binding coating of PVA solution may be applied to the metal surface followed by application of a layer of a powdered alloy.
  • the metal surface is heated to the fusion temperature of the alloy in vacuum, in an inert gas atmosphere, or in hydrogen atmosphere.
  • the metal item with the fused coating is heat treated to impart desired mechanical properties to the part substrate material.
  • the method of the present invention gives a smooth, dense coating of the wear-resistant hardfacing without nonmetallic inclusions.
  • U.S. Patent 6,239,082 describes petroleum quench oils described as effective for high speed cooling of heated metals and metal hardening.
  • the petroleum quench oils contain natural or synthetic base oils having a minimum flash point of about 120°C and a combination of poly(iso)alkylene and poly(iso)alkylene succinic anhydride or succinic acid.
  • a method for cooling heated metal to harden it, improve the metallurgical consistency, improve machinability and reduce residue on quenched metal parts is also disclosed comprising quenching the heated metal part in a quench oil containing natural or synthetic base oils having a minimum flash point of about 120°C and a combination of poly(iso)alkylene and poly(iso)alkylene succinic anhydride or succinic acid.
  • the quench oils of the instant invention afford durability, consistency and suitable quenching characteristics.
  • Suitable quenching characteristics include a high maximum cooling rate and a high maximum cooling rate temperature signifying collapse of the vapor barrier between the workpiece and the quenching oil, and a lower cooling rate (6-8°C) after the workpiece has reached 300°C to prevent thermal distortion/cracking.
  • the instant invention is directed to a quenching oil composition
  • a quenching oil composition comprising
  • hydrocarbyl or “hydrocarbon based” mean that the group being described has predominantly hydrocarbon character within the context of this invention. These include groups that are purely hydrocarbon in nature, that is, they contain only carbon and hydrogen. They may also include groups containing substituents or atoms which do not alter the predominantly hydrocarbon character of the group. Such substituents may include halo-, alkoxy-, nitro-, hydroxyl, etc. These groups also may contain heteroatoms. Suitable heteroatoms will be apparent to those skilled in the art and include, for example, sulfur, nitrogen and oxygen. Therefore, while remaining predominantly hydrocarbon in character within the context of this invention, these groups may contain atoms other than carbon present in a chain or ring otherwise composed of carbon atoms.
  • no more than about three non-hydrocarbon substituents or heteroatoms, and preferably no more than one, will be present for every 10 carbon atoms in the hydrocarbon or hydrocarbon based groups.
  • the groups are purely hydrocarbon in nature, that is, they are essentially free of atoms other than carbon and hydrogen.
  • the quenching oil compositions of this invention comprise at least one oil having kinematic viscosity (ASTM Test Method D-445) at 40°C ranging from about 4 to about 45 mm 2 sec -1 (40 to about 210 SUS) and having a saturated content from about 80% to about 100%. Both mineral oils and synthetic oils are useful. Mixtures of these oils are useful.
  • the oil is a paraffinic mineral oil, particularly a solvent refined paraffinic oil.
  • the oil is a hydrotreated mineral oil having kinematic viscosity of about 60 to about 90 SUS.
  • the oil is a poly-alphaolefin oligomer, preferably a polyoctene or polydecene oligomer.
  • useful oils examples include Excel/Paralube 70N, Excel/Paralube 75HC, (both from Pennzoil/Conoco) and Ergon® Hygold P70N.
  • the quenching oil compositions of this invention contain (2) a polyolefin having M n ranging from about 300 to about 10,000, preferably from about 500 to about 5,000 and more often from about 1,000 to about 3,000 and often ranging from about 1,500 to about 3,000.
  • the polyolefin is an aliphatic polyolefin derived from at least one alpha olefin containing from 3 to about 8 carbon atoms.
  • Polyisobutylene is particularly preferred.
  • the polyolefin is an olefin-polyene, preferably diene, especially preferred non-conjugated diene, copolymer, derived from at least one olefin, preferably an alpha olefin containing from about 3 to about 8 carbon atoms and the ratio of total number of moles of olefin to moles of polyene ranges from about 100:1 to about 1:1, preferably 25:1 to 1:2 and most preferably, 15:1 to 1:1.
  • the olefin is isobutylene.
  • Useful polymers of this type are commercially available, for example from BASF and BP Chemicals.
  • the polyolefin is an olefin-diene copolymer comprising from about 0.5 to about 5 moles of units derived from diene per mole of copolymer based on M n of copolymer.
  • the polyolefin is an olefin-polyene copolymer, wherein the olefin contains from 3 to about 8 carbon atoms and weight ratio of olefin to polyene ranges from about 250:1 to about 1:4, preferably 25:1 to 1:2 and most preferably 15:1 to 1:1.
  • the olefin comprises isobutylene.
  • olefin-diene copolymers examples include butyl rubbers (isobutylene-isoprene) and commercially available ethylene-propylene-diene terpolymers sold by Uniroyal Chemicals under the tradename TRILENE®.
  • the quenching oil compositions of this invention contain at least one member selected from the group consisting of a metal salt of hydrocarbyl substituted phenols, salicylic acids, carboxylic acids, and sulfonic acids and alkaline earth metal salts of hydrocarbyl substituted saligenin derivatives.
  • the metal salts may be acidic, neutral or basic, often referred to as 'overbased'.
  • MR metal ratio
  • a basic salt containing twice the amount of metal compared to the stoichiometric amount has a metal ratio (MR) of 2.
  • MR metal ratio
  • the metal ratio of metal salts of phenols and salicylic acids ranges from about 0.5 to about 5, preferably from about 0.5 to about 2 and the metal ratio of metal salts of sulfonic acids ranges from about 1 to about 20, preferably from about 1 to about 3.
  • the basicity of the metal salts used in the present invention generally is expressed in terms of a total base number TBN).
  • TBN is the amount of acid (perchloric or hydrochloric) needed to neutralize all of the metal salt's basicity.
  • the amount of acid is expressed as potassium hydroxide equivalents.
  • Total base number is determined by the procedure described in ASTM D-2896.
  • the metal salt has TBN ranging from about 45 to about 900, preferably from about 100 to about 800.
  • Neutral and acidic salts are generally prepared by contacting the acidic reactant with a metal reactant to form the salt.
  • Overbased materials are prepared by reacting an acidic material (typically an inorganic acid or lower carboxylic acid, preferably carbon dioxide) with a mixture comprising an acidic organic compound, a reaction medium comprising at least one inert, organic solvent for said acidic organic material, a stoichiometric excess of a metal base, and a promoter.
  • an acidic material typically an inorganic acid or lower carboxylic acid, preferably carbon dioxide
  • reaction medium comprising at least one inert, organic solvent for said acidic organic material, a stoichiometric excess of a metal base, and a promoter.
  • the acidic organic compounds useful in making the metal salts of the present invention include carboxylic acids, sulfonic acids, phenols and hydrocarbyl substituted saligenin derivatives or mixtures of two or more thereof.
  • Salicylic acids are considered as both phenols and carboxylic acids.
  • Salicylic acids can be aliphatic hydrocarbon-substituted salicylic acids wherein each aliphatic hydrocarbon substituent contains an average of at least about 8 carbon atoms per substituent.
  • Sulfonic acids useful in the invention include the sulfonic and thiosulfonic acids.
  • the sulfonic acids include the mono- or polynuclear aromatic or cycloaliphatic compounds.
  • Illustrative examples of sulfonic acids include hydrocarbyl substituted naphthalene sulfonic acids, hydrocarbyl substituted benzene sulfonic acids, petroleum sulfonic acid and the like.
  • Phenols useful in making the metal salts used in this the invention can be represented by the formula (R 1 ) a -Ar-(OH) b , wherein R 1 is a hydrocarbon group; Ar is an aromatic group; a and b are independently numbers of at least one, the sum of a and b being in the range of two up to the number of displaceable hydrogens on the aromatic nucleus or nuclei of Ar.
  • phenol is used herein, it is to be understood that this term refers to both mononuclear and polynuclear aromatic compounds.
  • Polynuclear groups can be of the fused type wherein an aromatic nucleus is fused at two points to another nucleus or of the linked type wherein at least two nuclei (either mononuclear or polynuclear) are linked through bridging linkages to each other.
  • Saligenin also known as salicyl alcohol and o-hydroxybenzyl alcohol and derivatives thereof are useful for preparing metal salts used in this invention.
  • alkaline earth metal salts of saligenin derivatives of the present invention can be represented by the formula where M is a valence of an alkaline earth metal, and the identity, description, and amounts of other symbols are as set forth hereinbelow.
  • m can be 0 to 10. This means that the number of rings can be 1 to 11, although it is to be understood that the upper limit of "m” is not a critical variable.
  • m is 2 to 9, more preferably 3 to 6.
  • At least one ring, and preferably most of the rings contain at least one R 1 substituent, which is a hydrocarbyl group, preferably an alkyl group, containing 1 to 60 carbon atoms, more preferably 7 to 18 carbon atoms.
  • the R 1 groups will normally comprise a mixture of various chain lengths, so that the foregoing numbers usually represent an average number of carbon atoms in the R 1 groups (number average).
  • Each ring in the structure will be substituted with 0, 1, 2, or 3 such R 1 groups (that is, each p is independently 0, 1, 2, or 3, most typically 1, and different rings in a given molecule may contain different numbers of such substituents.
  • At least one aromatic ring in the molecule must contain at least one R 1 group, and the total number of carbon atoms in all the R 1 groups in the molecule should be at least 7, preferably at least 12.
  • the X and Y groups may be seen as groups derived from formaldehyde or a formaldehyde source, by condensative reaction with the aromatic molecule. While various species of X and Y may be present in the molecules in question, the commonest species comprising X are CHO (aldehyde functionality) and CH 2 OH (hydroxymethyl functionality); similarly the commonest species comprising Y are CH 2 (methylene bridge) and CH 2 OCH 2 (ether bridge). The relative molar amounts of these species in a sample of the above material can be determined by 1 H/ 13 C NMR as each carbon and hydrogen nucleus has a distinctive environment and produces a distinctive signal.
  • Alkaline earth metal salts of hydrocarbyl substituted saligenin derivatives are described in detail in U.S. Patent 6,310,009 which is hereby incorporated herein by reference.
  • the metal compounds useful in making the metal salts are generally any Group 1 or Group 2 metal compounds (CAS version of the Periodic Table of the Elements), including alkali metals (sodium, potassium, lithium, etc.) and Group 1b metals such as copper.
  • Group 2 metals of the metal base include the Group 2a alkaline earth metals (magnesium, calcium, barium, etc.) as well as the Group 2b metals such as zinc or cadmium
  • a promoter is a chemical employed to facilitate the incorporation of metal into the basic metal compositions.
  • suitable promoters is found in U.S. Patents 2,777,874, 2,695,910, and 2,616,904.
  • the metal of the metal salt comprises at least one of Group 1 and Group 2 metal, preferably, an alkali and/or an alkaline earth metal.
  • the metal salt is an alkaline earth metal salt.
  • the metal salt comprises a metal salt of sulfur or methylene coupled hydrocarbyl substituted phenols or salicylic acids.
  • the composition comprises a metal salt of a hydrocarbyl substituted phenol.
  • the composition comprises a metal salt of a Mg or Ca methylene coupled C 7-15 aliphatic group substituted phenate.
  • the composition comprises an alkaline earth metal salt of hydrocarbyl substituted saligenin derivatives.
  • the composition comprises a metal salt of a hydrocarbyl substituted salicylic acid. In another embodiment, the composition comprises a metal salt of a hydrocarbyl substituted sulfonic acid. In yet another embodiment, the composition comprises a metal salt of a hydrocarbyl substituted carboxylic acid.
  • Mixtures of two or more of these metal salts may be used.
  • the quenching oil compositions of this invention may, in an optional embodiment, also contain hydrocarbyl substituted succinic derivatives selected from the group consisting of esters, amides, ester-amides, imides, amine salts, acid-esters, acid-amides ester-amine salts, amide-amine-salts and acid-amine salts.
  • the hydrocarbyl substituent typically has M n ranging from about 500 to about 5000, preferably from about 900 to about 2500.
  • the quenching oil compositions of this invention typically comprise from about 0.2% to about 10%, preferably to about 5% by weight of the aliphatic polyolefin (2), and a total of from 0.2% to about 10% by weight of a metal salt of hydrocarbyl substituted phenols, salicylic acids and sulfonic acids and alkaline earth metal salts of hydrocarbyl substituted saligenin derivatives, and optionally at least one of hydrocarbyl substituted succinic esters, amides, ester-amides, imides, amine salts, acid-esters, acid-amides, ester-amine salts, amide-amine salts and acid-amine salts, provided that the composition comprises at least one of a metal salt and a succinic derivative.
  • the succinic derivatives are present in amounts ranging from about 0.1% to about 5% by weight.
  • the composition comprises from about 0.2% to about 5% by weight of the aliphatic polyolefin (2), and (3)(a) from about 0.2% to about 5% by weight of at least one metal salt wherein the weight ratio of (2):(3)(a) ranges from about 10: 1 to about 1: 10.
  • the composition comprises from about 0.2% to about 5% by weight of the aliphatic polyolefin (2), a total of from about 0.2% to about 4% by weight of (3)(a) at least one metal salt; and a total of from about 0.1 % to about 4% by weight of at least one hydrocarbyl substituted succinic derivative selected from the group consisting of amides, imides, amine salts, acid-amides and acid-amine salts wherein the weight ratio of polyolefin : metal salt : succinic derivative ranges from about (20-40) : (40-70) : (10-20).
  • This invention also relates to a method of heat treating metals comprising heating the metal to a temperature above its critical temperature and thereafter cooling the metal by immersion thereof into a quenching oil bath comprising the quenching oil composition of this invention.
  • the additive components may be incorporated into the base oil as individual components, added thereto in any order.
  • the additive components are added to the base oil as a concentrate which comprises the desired additives in appropriate ratios which, when incorporated into the base oil, provide a finished quenching oil composition containing the desired amount of each additive.
  • a series of quenching oil compositions is prepared, each member of the series containing 2% by weight of one of additive concentrates 1-5 in Pennzoil/Conoco Excel Paralube 75-HC (75N) oil.
  • a second series is prepared, each member of the series containing 4% by weight of one of additive concentrates 1-2 and 4-5 in the same oil.
  • a third series is prepared, each member containing 6% by weight of additive concentrates 1-2, and 4-5 in the same oil.
  • Each sample is subjected to a one-minute quench test and a 3 hour panel coker test.
  • the quench test quantifies the cooling characteristics of the quench oil sample and the panel coker test measures the tendency of the quench oil sample to stain and/or form deposits on hot metal surfaces. Similar results between corresponding heat stressed and unstressed oils samples provide an indication of durability and consistency of the test oils.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Thermal Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Lubricants (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Devices For Conveying Motion By Means Of Endless Flexible Members (AREA)
EP02805163A 2001-12-18 2002-12-16 Quenching oil compositions Revoked EP1466023B1 (en)

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US34161201P 2001-12-18 2001-12-18
US341612P 2001-12-18
PCT/US2002/040160 WO2003052145A1 (en) 2001-12-18 2002-12-16 Quenching oil compositions

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AT (1) ATE307908T1 (ja)
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WO2005087955A1 (ja) * 2004-03-10 2005-09-22 Idemitsu Kosan Co., Ltd. 減圧焼入れ用焼入油及び焼入れ方法
CN111868269A (zh) * 2018-03-28 2020-10-30 出光兴产株式会社 热处理油组合物
CN111886349A (zh) * 2018-03-28 2020-11-03 出光兴产株式会社 热处理油组合物
CN111074045B (zh) * 2019-12-30 2021-11-12 南京科润工业介质股份有限公司 一种快速光亮淬火油及其制备方法

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JP4278809B2 (ja) * 2001-10-23 2009-06-17 出光興産株式会社 歯車用熱処理油組成物及びそれを用いて処理した歯車

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US20050011597A1 (en) 2005-01-20
ATE307908T1 (de) 2005-11-15
AU2002357258A1 (en) 2003-06-30
WO2003052145A1 (en) 2003-06-26
DE60206968D1 (de) 2005-12-01
EP1466023A1 (en) 2004-10-13
DE60206968T2 (de) 2006-07-27
CA2470953A1 (en) 2003-06-26
JP2005513200A (ja) 2005-05-12

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