WO2000020539A1 - Additif pour lubrifiants - Google Patents

Additif pour lubrifiants Download PDF

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Publication number
WO2000020539A1
WO2000020539A1 PCT/US1999/022827 US9922827W WO0020539A1 WO 2000020539 A1 WO2000020539 A1 WO 2000020539A1 US 9922827 W US9922827 W US 9922827W WO 0020539 A1 WO0020539 A1 WO 0020539A1
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WIPO (PCT)
Prior art keywords
recited
vessel
tfe
functional group
lubricant
Prior art date
Application number
PCT/US1999/022827
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English (en)
Other versions
WO2000020539A9 (fr
Inventor
Richard Paul Beatty
Peter Arnold Morken
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E.I. Du Pont De Nemours And Company
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 E.I. Du Pont De Nemours And Company filed Critical E.I. Du Pont De Nemours And Company
Priority to JP2000574639A priority Critical patent/JP2002526638A/ja
Priority to AU62810/99A priority patent/AU6281099A/en
Priority to EP99950077A priority patent/EP1117753A1/fr
Priority to BR9914471-9A priority patent/BR9914471A/pt
Priority to KR1020017004199A priority patent/KR20010099666A/ko
Publication of WO2000020539A1 publication Critical patent/WO2000020539A1/fr
Publication of WO2000020539A9 publication Critical patent/WO2000020539A9/fr

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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M127/00—Lubricating compositions characterised by the additive being a non- macromolecular hydrocarbon
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M131/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing halogen
    • C10M131/08—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing halogen containing carbon, hydrogen, halogen and oxygen
    • C10M131/10—Alcohols; Ethers; Aldehydes; Ketones
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M101/00—Lubricating compositions characterised by the base-material being a mineral or fatty oil
    • C10M101/02—Petroleum fractions
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M131/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing halogen
    • C10M131/08—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing halogen containing carbon, hydrogen, halogen and oxygen
    • C10M131/12—Acids; Salts or esters thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M169/00—Lubricating 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
    • C10M169/04—Mixtures of base-materials and additives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C10M2203/1006—Petroleum or coal fractions, e.g. tars, solvents, bitumen used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C10M2203/102—Aliphatic fractions
    • C10M2203/1025—Aliphatic fractions used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C10M2203/104—Aromatic fractions
    • C10M2203/1045—Aromatic fractions used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C10M2203/106—Naphthenic fractions
    • C10M2203/1065—Naphthenic fractions used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C10M2203/108—Residual fractions, e.g. bright stocks
    • C10M2203/1085—Residual fractions, e.g. bright stocks used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2211/00—Organic non-macromolecular compounds containing halogen as ingredients in lubricant compositions
    • C10M2211/04—Organic non-macromolecular compounds containing halogen as ingredients in lubricant compositions containing carbon, hydrogen, halogen, and oxygen
    • C10M2211/042—Alcohols; Ethers; Aldehydes; Ketones
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2211/00—Organic non-macromolecular compounds containing halogen as ingredients in lubricant compositions
    • C10M2211/04—Organic non-macromolecular compounds containing halogen as ingredients in lubricant compositions containing carbon, hydrogen, halogen, and oxygen
    • C10M2211/044—Acids; Salts or esters thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2211/00—Organic non-macromolecular compounds containing halogen as ingredients in lubricant compositions
    • C10M2211/06—Perfluorinated compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/04—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/08—Amides
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/08—Amides
    • C10M2215/082—Amides containing hydroxyl groups; Alkoxylated derivatives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/26—Amines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/28—Amides; Imides
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
    • C10M2219/044—Sulfonic acids, Derivatives thereof, e.g. neutral salts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • C10M2223/047—Thioderivatives not containing metallic elements
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/20—Metal working

Definitions

  • Lubricants of various sorts are widely used in systems containing moving parts which rub against one another, and are primarily used to reduce wear between the parts and/or reduce friction between the parts, usually both.
  • a base material is usually used for the majority of a lubricant composition
  • various additives are usually also used in the composition, such as additives to reduce wear, reduce friction, prolong the life of the lubricant, make the lubricant useful over a wider temperature range, and for many other purposes. Therefore, improved (in price and/or lubricant properties) additives are constantly being sought.
  • This invention concerns a composition
  • a composition comprising: (a) a major portion of a lubricant base; and (b) a minor portion of a first additive which is an organic compound which is grafted with one or more fluorinated olefins; and provided that: said additive contains at least 5 percent by weight of fluorine; and said organic compound contains at least one functional group which can be adsorbed on a metal surface.
  • the invention also concerns an apparatus, comprising: (a) a first part which is metal; (b) a second part which is in apparent contact with said first metal part, and said first part and second part move with respect to one another: and (c) a lubricant which comprises:
  • a major portion of a lubricant base (i) a major portion of a lubricant base; and (ii) a minor portion of a first additive which is an organic compound which is grafted with one or more fluorinated olefins; and provided that: said additive contains at least 5 percent by weight of fluorine; and said organic compound contains at least one functional group which can be adsorbed on a metal surface.
  • Lubricant technology is well known in general, see for instance E. R. Booser, Ed., CRC Handbook of Lubrication, Vol. II, CRC Press, Inc., Boca Raton, FL, U.S.A., (1983), p. 229-315; D. Klamann in B. Elvers, et al., Ed., Ullmann 's Encyclopedia of Industrial Chemistry, Vol. A 15, VCH Verlagsgesellschaft mbH, Weinheim, Germany (1990), p. 424-511; R. M. Mortimer, et al., Ed., Chemistry and Technology of Lubricants, VCH Publishers, New York, 1992; all of which are hereby included by reference.
  • the following terms are defined as:
  • a lubricant base is a material that is the majority of the component of the lubricant system, and which reduces friction and/or wear between the moving components being lubricated, and may also have other useful functions.
  • Useful lubricant bases include petroleum derived (sometimes also called mineral) lubricants, synthetic hydrocarbons, polyether oils, carboxylic esters, phosphoric acid esters, silicone containing oils, and halogenated hydrocarbons and halocarbons. Petroleum derived and synthetic hydrocarbon lubricant bases are preferred and petroleum derived lubricant bases are especially preferred.
  • an organic compound By an organic compound is meant a compound which contains at least one hydrogen atom bound directly to a carbon atom.
  • a functional group any group or moiety containing an element other than carbon, hydrogen and fluorine. These are sometimes called
  • This adsorption may be measured by adsorbing the compound containing the functional group on the metal surface from a solution in n-alkane, as described in A. J. Groszek, Interdisciplinary Approach to Lubricant Technology, NASA SP-318 1973, p. 477-525.
  • forces can include covalent or coordinative bonding, electrostatic or coulombic interactions, and hydrogen bonding.
  • This metal surface herein includes not only the metals themselves, but any other layer normally present on the surface of a particular metal, such as an oxidation layer.
  • aluminum typically has a layer of aluminum oxide (which may be partially hydrated) on its surface.
  • a fluorinated olef ⁇ n any olefin containing at least one fluorine atom. Such an olefin may contain one or more ether groups, and includes vinyl ethers. • By grafting herein is meant that one or more molecules of the fluorinated olefin is covalently bonded to the organic compound by a free radical, anionic or other process, and preferably a free radical process.
  • the organic compounds which are grafted have at least one functional group which can "preferentially" adsorb onto a metal surface, preferably a metal which is actually being used in an apparatus being lubricated.
  • useful functional groups include carboxylic esters, carboxylic acids, carboxylate salts, carboxylic amide, imide, amine, phosphoric or phosphonic acid derivatives such as esters, dithiophosphate ester, ether, hydroxyl, carbonate, hetereocyclic groups (such as N, S and/or O compounds), sulfonic acids that their salts, and analogous sulfur compounds such as thioamides and thioesters.
  • Such functional groups are known in the art, see for instance R. M.
  • Preferred functional groups are carboxylic ester, carboxylic acid, hydroxyl, and carboxylic amide, and carboxylic ester, and carboxylic acid are more preferred, and carboxylic ester, is especially preferred.
  • the organic compound (before grafting) has a boiling point at atmospheric pressure of greater than about 150°C, more preferably greater than about 200°C. and especially preferably greater than 250°C.
  • the additive (organic compound after grafting) has a boiling point at atmospheric pressure of greater than about 150°C, more preferably greater than about 200°C, and especially preferably greater than 250°C.
  • the organic compound has a molecular weight of about 100 to about 3,000, more preferably about 250 to 1,500. Grafted polymers, especially those of lower molecular weight, may also be used.
  • any fluorinated olefin that may be free radically grafted onto the chosen organic compound may be used.
  • fluorinated olefins are known in the art, see for instance U.S. Patents 2,562,547 and 5,032,306 both of which are hereby included by reference.
  • the grafting may also be initiated by thermally, photochemically and by irradiation, see B. Ameduri, et al., in Topics in Current Chemistry, Vol. 192. Organofluorine Chemistry, Fluorinated Alkenes and Reactive Intermediates, Springer- Verlag, Berlin, 1997, p. 165-233, which is hereby included by reference.
  • the fluorinated olefin is perfluorinated.
  • R 1 R 2 C CR 3 R 4 wherein R 1 is chlorine, fluorine or hydrogen, R 2 and R 4 are each independently fluorine or hydrogen, R 3 is fluorine, hydrogen, alkyl or fluorinated alkyl, provided that at least one of R 1 , R 2 and R 4 are fluorine or R 3 is fluorinated alkyl. It is more preferred that R 1 , R 2 and R 3 are fluorine, and R 4 is fluorine or perfluoro-n-alkyl containing 1 to 10 carbon atoms.
  • Useful fluorinated olefins include vinyl fluoride, vinylidene fluoride, trifluoroethylene, tetrafluoroethylene, chlorotrifluoroethylene, hexafluoropropylene (HFP), 3,3,4.4,5,5, 6,6,6-nonofluoro- 1-hexene (PFBE), perfluoro(methyl vinyl ether) (PMVE), perfluoro(n-propyl vinyl ether) (PPVE).
  • fluorinated olefins are TFE, chlorotrifluoroethylene, HFP, PFBE, PMVE, vinylidene fluoride, trifluoroethylene, and PPVE, and more preferred fluorinated olefins are TFE. HFP and PMVE. and TFE is especially preferred.
  • the grafting reaction is initiated by typical free radical generators such as organic peroxides.
  • typical free radical generators such as organic peroxides.
  • organic peroxides Such processes are known in the art, see for instance U.S. Patents 2,562,547 and 5.032.306.
  • the procedures described in these references and in the appropriate examples herein illustrate how to carry out these grafting reactions.
  • These grafting reactions usually graft the fluorinated olefin in a random manner, although some positions in the organic compound being grafted may be more favored than others.
  • Some of the organic molecules may be ungrafted, especially if no separation is done on the crude mixture obtained after grafting. Such a separation may be difficult and expensive due to the high boiling point of many of the useful organic compounds.
  • the total amount of fluorine in the grafted compound is based on the weight of the total grafted compound including ungrafted organic molecules when they are present.
  • the fluorinated groups grafted onto the organic compound may contain one or more molecules of fluorinated olefin, depending on the fluorinated olefin used, the organic compound used, the free radical source used, and the grafting conditions.
  • the total amount of fluorine in the grafted organic compound will also be affected by these variables.
  • the grafted organic compound should contain at least about 5 weight percent fluorine, preferably at least about 8 weight percent fluorine, and more preferably at least about 15 weight percent fluorine (elemental analysis).
  • the grafted organic compound should be a liquid.
  • the grafted olefin compound is combined with a lubricant base to form a lubricant.
  • the amount of grafted olefin compound is such that the amount of fluorine in the lubricant (base lubricant plus grafted olefin compound) from the grafted olefin compound is about 200 ppm to about 10 percent by weight, more preferably about 500 ppm to about 3 percent by weight, and especially preferably about 0J0 to about 1.0 percent by weight.
  • the base lubricant and grafted olefin polymer form a single liquid phase at the lubricant use temperature, and/or the entire lubricant composition forms a single liquid phase at the lubricant use temperature.
  • the grafted olefin compound and base lubricant should not react with one another to form deleterious products (of course at high operating temperatures lubricants may degrade but this is not included in this statement).
  • a particular functional group may react with a particular lubricant base, but usually a suitable combination of either a particular grafted organic compound or particular lubricant base with a counterpart can be found with minimal experimentation. Such a reaction at times may be benign or even beneficial.
  • the overall lubricant composition may include other additives that are conventionally added to lubricants for various purposes. These include oxidation inhibitors (including antioxidants and metal oxidation inhibitors), viscosity index improvers, pour point depressants, detergents and dispersants, extreme pressure additives, demulsifiers. corrosion inhibitors, emulsifiers and emulsifying aids, dyes and deblooming agents, fluorescent additives, antifoam agents, and (other) antiwear and friction modifiers.
  • the entire lubricant may be a solid, semisolid (grease) or liquid at room temperature, but is preferably a liquid at the operating temperature of the thing being lubricated.
  • Lubricants are generally employed where two parts are in contact and move with respect to one another.
  • the lubricants containing the grafted organic compound it is preferred that at least one of the parts, and preferably both of the these parts are metallic. It is also preferred that for the particular metal present the functional group of the additive adsorbs to that metal.
  • the choice of (a) functional group(s) is often not critical in this respect, although a particular functional group may be better with some metals than others.
  • a nonmetallic part may be a ceramic, a thermoplastic, or a thermoset. Any combination ("composite") of metals and any of the nonmetallic materials may also be used. If nonmetals are used, they may bear functional groups which can interact with the functional group of the additive.
  • Metals useful for the moving part(s) include ferrous metals such as steel, stainless steel and cast iron, aluminum, and zinc and zinc alloys such as die cast metals, titanium, vanadium, chromium, molybdenum, nickel, lead, tin, copper, and their alloys, such as bronze and brass. Preferred metals are ferrous metals.
  • the metal of the two parts may be the same or different. Of course more than two moving parts may be present in such an apparatus.
  • the lubricant may be distributed to the places where it is needed by conventional means, such as a lubricant (oil) pump, or just be present where needed.
  • the relative performance of the materials of the present invention as additives in a mineral oil base fluid was evaluated.
  • a grade of oil such as 15 ON might be used as one component for blending of an oil for use in an internal combustion engine.
  • the 150 N contains no additives. This 150N oil was tested according to the modified BOCLE method numerous times, and the average of these results is summarized in Table 2.
  • the crude material was distilled at reduced pressure to remove light side-products as well as unreacted dodecane. Then 1 fraction was collected, "F2" boiling at 88°C/0.01 Pa (44.58 g). The pot material was then distilled by the Kugelrohr method, collecting 102J g of oil “Kl” boiling at 109°C/0.01 Pa, and 52 g of oil “K2" boiling at 140°C/0.01 Pa. Elemental analysis, ⁇ NMR, 19 F NMR, and FTIR indicate that the product has -(CF2CF 2 ) n H chains attached to the dodecane backbone.
  • a stainless steel, 1-L stirred vertical autoclave in a barricade was charged with 250 g (1.44 mol) of dimethyl adipate and 20 g (0J4 mol) of t-butyl peroxide.
  • the vessel was closed and pressurized to 3.45 MPa with nitrogen and vented.
  • the vessel was then charged to 410 kPa with TFE and vented three times.
  • the vessel was stirred at 500 rpm and heated to 140°C and TFE was added at a rate to maintain the pressure between 786-1500 kPa.
  • a total of 414 g (4J4 mol) TFE was added over a 5 h period.
  • TFE total of 78 g (0.78 mol) TFE was added over a 4.5 h period.
  • the vessel was cooled, then charged with an additional 10 g (0.07 mol) of t-butyl peroxide, pressure-vented as described before, then fed an additional 92 g (0.92 mol) of TFE at 140°C over a 3.5 h period, then held at 140°C for 4 h.
  • the vessel was cooled and 385 g of milky white material were collected.
  • the analytical data were consistent with a plurality of -CF 2 CF 2 H and -(CF 2 CF 2 ) n H groups per diester.
  • the vessel was rinsed with acetone, the acetone wash was concentrated by rotary evaporation, and the residue was combined with the bulk crude to afford 402.2 g of milky-white liquid.
  • the volatile components of this mixture were removed by vacuum distillation (190°C/67 Pa/1.5 h) to leave 368.7 g milky-white liquid residue, density 1.12 g mL. Elemental analysis was 58.77% C, 8.27% H, 29.51% F.
  • a 1 L steel shaker tube was charged with 200 g Jayflex-DIDA and 2.5 g ( 17 mmol) t-butyl peroxide.
  • the vessel was closed, cooled, and evacuated, then 150 g (1 mol) of hexafluoropropene (HFP) were added.
  • the vessel was heated with shaking at 135°C for 1 h and 140°C for 6 h.
  • the contents of the vessel were removed and then heated in vacuo for 2 h at 180°C.
  • the clear, homogeneous liquid product had the following composition by elemental analysis (duplicate): 69.26-69.39% C, 10.77-10.98% H, 9.03-8.79% F. 19 F NMR -74.4 (m), -1 10 -125 (m), -206 -215 (m).
  • a 1 L steel shaker tube was charged with 200 g Jayflex-DIDA and 5 g (34 mmol) t-butyl peroxide.
  • the vessel was closed, cooled, and evacuated, then 300 g (2 mol) of hexafluoropropene (HFP) were added.
  • the vessel was heated at 135°C for 1 h and 140°C for 6 h.
  • the contents of the vessel were removed and then heated in vacuo for 2 h at 180°C.
  • the clear, homogeneous liquid product had the following composition by elemental analysis (duplicate): 67.75-67.79% C, 10.2-10.47% H, 12.53-12.72% F.
  • 1 F NMR -74.4 (m), -1 10 -125 (m), -206 to -215 (m).
  • a 0.36 L steel shaker tube was charged with 80 g Jayflex-DIDA and 7 g (0.05 mol) t-butyl peroxide.
  • the vessel was closed, cooled, and evacuated, then 60 g (0.36 mol) of perfluoromethylvinyl ether (PMVE) were added.
  • the vessel was heated at 140°C for 5 h.
  • the contents of the vessel were removed and then heated in vacuo for 1.5 h at 140°C.
  • the cloudy liquid product (106 g) had the following composition by elemental analysis: 55.91% C, 7.91% H, 19.62% F.
  • EXAMPLE 16 Reaction of PFBE with Ditridecyl Dodecanedioate A 0.4 L steel shaker tube was charged with 100 g of ditridecyl dodecanedioate (Hatcol 2907, mixture of Cl 1-C14 alcohols used for ester, product of Hatco Co ⁇ ., Fords, NJ), 30 g of perfluorobutylethylene (0.122 mol, PFBE), 100 ml of lJ-dichlorobenzene (ODCB) and 3 g (0.02 mol) of t-butyl peroxide. The vessel was closed, cooled, and evacuated. The vessel was heated with shaking at 140°C for 16 h.
  • ditridecyl dodecanedioate Heatcol 2907, mixture of Cl 1-C14 alcohols used for ester, product of Hatco Co ⁇ ., Fords, NJ
  • perfluorobutylethylene (0.122 mol, PFBE
  • ODCB lJ-
  • the vessel was then charged to 410 kPa with TFE and vented three times.
  • the vessel was stirred at 500 rpm and heated to 140°C and TFE was added at a rate to maintain the pressure between 662-1560 kPa.
  • a total of 356 g (3.56 mol) TFE was added over a 4.5 h period.
  • the vessel was cooled and 530 g of cloudy liquid were collected.
  • the volatile components of this mixture were removed by vacuum distillation (190°C/13 Pa/2 h) to leave 415 g crude product. Elemental analysis was 46.39% C, 5.41% H, 38.15% F. 19 F NMR overlapping signals from -110 to -138 ppm.
  • the crude material was distilled at 25-180°C/13 Pa to remove low-boiling impurities and unreacted n-decyl succinic anhydride.
  • the residue was distilled by the Kugeirohr method, collecting 13.6 g of material boiling at 25-168°C/0.01 Pa, which was contaminated by n-decyl succinic anhydride.
  • the undistilled pot residue weighed 63.7 g.
  • the grafted organic compound is given in the column headed "Graft of Ex.”, and if more than one fraction of the product was made, the fraction used can be determined by the "Wt. % F in Grafted Compound".
  • the total amount of fluorine in the lubricant from the grafted compound is given by the "Wt. % F in Lubricant" column.
  • a 1-L stirred vertical autoclave was charged with 275 g of Jayflex-DIDA and 20 g (0.14 mol) of t-butyl peroxide.
  • the vessel was closed and pressurized to 3.45 MPa with nitrogen and vented.
  • the vessel was then charged to 410 kPa with TFE and vented 3 times.
  • the vessel was stirred at 500 ⁇ m and heated to 150°C and TFE was added at a rate to maintain pressure between 723-1600 kPa.
  • a total of 138 g (1.38 mol) TFE was added over a 3.5 h period. After a 12 h hold period at 150°C, the vessel was cooled and the contents were collected.
  • the vessel was rinsed with acetone, the acetone wash was concentrated by rotary evaporation, and the residue was combined with the bulk crude to afford 411.3 g of crude product.
  • the volatile components of this mixture were removed by vacuum distillation (195°C/67 Pa/2 h) to leave 370.5 g residue. Elemental analysis was 5936% C, 8,40% H, 23.48% F. 19 F NMR overlapping signals from -106 to -138 ppm.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Lubricants (AREA)

Abstract

L'invention concerne des composés organiques, contenant des groupes fonctionnels choisis et greffés au moyen d'oléfines fluorées. Ces composés constituent d'excellents additifs de lubrifiants réduisant l'usure et/ou la friction, et il sont notamment utiles dans des lubrifiants de métaux.
PCT/US1999/022827 1998-10-02 1999-09-30 Additif pour lubrifiants WO2000020539A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
JP2000574639A JP2002526638A (ja) 1998-10-02 1999-09-30 潤滑剤用添加物
AU62810/99A AU6281099A (en) 1998-10-02 1999-09-30 Additive for lubricants
EP99950077A EP1117753A1 (fr) 1998-10-02 1999-09-30 Additif pour lubrifiants
BR9914471-9A BR9914471A (pt) 1998-10-02 1999-09-30 Composição e aparelho
KR1020017004199A KR20010099666A (ko) 1998-10-02 1999-09-30 윤활제용 첨가제

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US10284598P 1998-10-02 1998-10-02
US60/102,845 1998-10-02

Publications (2)

Publication Number Publication Date
WO2000020539A1 true WO2000020539A1 (fr) 2000-04-13
WO2000020539A9 WO2000020539A9 (fr) 2000-09-21

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PCT/US1999/022827 WO2000020539A1 (fr) 1998-10-02 1999-09-30 Additif pour lubrifiants

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EP (1) EP1117753A1 (fr)
JP (1) JP2002526638A (fr)
KR (1) KR20010099666A (fr)
AR (1) AR020699A1 (fr)
AU (1) AU6281099A (fr)
BR (1) BR9914471A (fr)
WO (1) WO2000020539A1 (fr)

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2433844A (en) * 1943-04-23 1948-01-06 Du Pont Organic fluoroethers and their preparation
US2562547A (en) * 1944-12-11 1951-07-31 Du Pont Fluorinated compounds
US2715107A (en) * 1953-04-14 1955-08-09 Shell Dev Lubricating compositions
US3124533A (en) * 1964-03-10 Fluorine containing esters of poly-
US3284355A (en) * 1963-09-12 1966-11-08 Mobil Oil Corp Lubricating compositions
GB1076543A (en) * 1964-01-28 1967-07-19 Gen Aniline & Film Corp Alkylating polymeric or copolymeric lactams
US4185031A (en) * 1978-09-27 1980-01-22 The United States Of America As Represented By The Secretary Of The Air Force Fluorinated phosphinic acids
EP0116417A2 (fr) * 1983-01-20 1984-08-22 The Electricity Council Procédé pour la préparation d'éthers fluorés
GB2245587A (en) * 1990-05-10 1992-01-08 Ici Plc Heat transfer device lubricant

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3124533A (en) * 1964-03-10 Fluorine containing esters of poly-
US2433844A (en) * 1943-04-23 1948-01-06 Du Pont Organic fluoroethers and their preparation
US2562547A (en) * 1944-12-11 1951-07-31 Du Pont Fluorinated compounds
US2715107A (en) * 1953-04-14 1955-08-09 Shell Dev Lubricating compositions
US3284355A (en) * 1963-09-12 1966-11-08 Mobil Oil Corp Lubricating compositions
GB1076543A (en) * 1964-01-28 1967-07-19 Gen Aniline & Film Corp Alkylating polymeric or copolymeric lactams
US4185031A (en) * 1978-09-27 1980-01-22 The United States Of America As Represented By The Secretary Of The Air Force Fluorinated phosphinic acids
EP0116417A2 (fr) * 1983-01-20 1984-08-22 The Electricity Council Procédé pour la préparation d'éthers fluorés
GB2245587A (en) * 1990-05-10 1992-01-08 Ici Plc Heat transfer device lubricant

Also Published As

Publication number Publication date
AU6281099A (en) 2000-04-26
WO2000020539A9 (fr) 2000-09-21
BR9914471A (pt) 2001-06-26
AR020699A1 (es) 2002-05-22
KR20010099666A (ko) 2001-11-09
EP1117753A1 (fr) 2001-07-25
JP2002526638A (ja) 2002-08-20

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