EP4294897A1 - Base oil and lubricating fluid composition containing said base oil - Google Patents

Base oil and lubricating fluid composition containing said base oil

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Publication number
EP4294897A1
EP4294897A1 EP23714627.9A EP23714627A EP4294897A1 EP 4294897 A1 EP4294897 A1 EP 4294897A1 EP 23714627 A EP23714627 A EP 23714627A EP 4294897 A1 EP4294897 A1 EP 4294897A1
Authority
EP
European Patent Office
Prior art keywords
base oil
weight
oligomers
oil according
lubricating fluid
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
EP23714627.9A
Other languages
German (de)
French (fr)
Other versions
EP4294897B1 (en
Inventor
Patrick Fries
Olaf Binkle
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.)
Fuchs SE
Original Assignee
Fuchs SE
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 Fuchs SE filed Critical Fuchs SE
Priority to EP24173603.2A priority Critical patent/EP4386069A1/en
Publication of EP4294897A1 publication Critical patent/EP4294897A1/en
Application granted granted Critical
Publication of EP4294897B1 publication Critical patent/EP4294897B1/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

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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
    • 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
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    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M111/00Lubrication compositions characterised by the base-material being a mixture of two or more compounds covered by more than one of the main groups C10M101/00 - C10M109/00, each of these compounds being essential
    • C10M111/04Lubrication compositions characterised by the base-material being a mixture of two or more compounds covered by more than one of the main groups C10M101/00 - C10M109/00, each of these compounds being essential at least one of them being a macromolecular organic compound
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    • 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
    • C10M169/041Mixtures of base-materials and additives the additives being macromolecular compounds only
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    • 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
    • C10M2205/028Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms
    • C10M2205/0285Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms used as base material
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    • 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
    • C10M2207/026Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings with tertiary alkyl groups
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    • 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
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    • C10M2207/00Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28Esters
    • C10M2207/287Partial esters
    • C10M2207/289Partial esters containing free hydroxy groups
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    • C10M2209/00Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/02Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/08Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
    • C10M2209/086Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type polycarboxylic, e.g. maleic acid
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    • C10M2209/00Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/02Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/08Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
    • C10M2209/086Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type polycarboxylic, e.g. maleic acid
    • C10M2209/0863Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type polycarboxylic, e.g. maleic acid used as base material
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    • 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
    • C10M2209/103Polyethers, i.e. containing di- or higher polyoxyalkylene groups
    • C10M2209/105Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing three carbon atoms only
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    • 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
    • C10M2209/103Polyethers, i.e. containing di- or higher polyoxyalkylene groups
    • C10M2209/105Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing three carbon atoms only
    • C10M2209/1055Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing three carbon atoms only used as base material
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    • 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
    • C10M2209/103Polyethers, i.e. containing di- or higher polyoxyalkylene groups
    • C10M2209/106Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing four carbon atoms only
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    • 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
    • C10M2209/103Polyethers, i.e. containing di- or higher polyoxyalkylene groups
    • C10M2209/106Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing four carbon atoms only
    • C10M2209/1065Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing four carbon atoms only used as base material
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    • 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
    • C10M2209/103Polyethers, i.e. containing di- or higher polyoxyalkylene groups
    • C10M2209/107Polyethers, i.e. containing di- or higher polyoxyalkylene groups of two or more specified different alkylene oxides covered by groups C10M2209/104 - C10M2209/106
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    • 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
    • C10M2209/103Polyethers, i.e. containing di- or higher polyoxyalkylene groups
    • C10M2209/107Polyethers, i.e. containing di- or higher polyoxyalkylene groups of two or more specified different alkylene oxides covered by groups C10M2209/104 - C10M2209/106
    • C10M2209/1075Polyethers, i.e. containing di- or higher polyoxyalkylene groups of two or more specified different alkylene oxides covered by groups C10M2209/104 - C10M2209/106 used as base material
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    • C10M2215/00Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/02Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/06Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
    • C10M2215/064Di- and triaryl amines
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    • C10M2215/00Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/08Amides
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    • C10M2215/00Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/22Heterocyclic nitrogen compounds
    • C10M2215/223Five-membered rings containing nitrogen and carbon only
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    • 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
    • C10M2223/04Phosphate esters
    • C10M2223/043Ammonium or amine salts thereof
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    • 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
    • C10M2223/04Phosphate esters
    • C10M2223/047Thioderivatives not containing metallic elements
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    • C10M2229/04Siloxanes with specific structure
    • C10M2229/041Siloxanes with specific structure containing aliphatic substituents
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    • C10N2020/00Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01Physico-chemical properties
    • C10N2020/02Viscosity; Viscosity index
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    • C10N2020/00Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01Physico-chemical properties
    • C10N2020/04Molecular weight; Molecular weight distribution
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    • C10N2030/00Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/02Pour-point; Viscosity index
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    • 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
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    • C10N2030/00Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/12Inhibition of corrosion, e.g. anti-rust agents or anti-corrosives
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    • C10N2030/00Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/18Anti-foaming property
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    • C10N2030/00Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/36Seal compatibility, e.g. with rubber
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    • C10N2030/62Food grade properties
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    • C10N2040/04Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
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    • C10N2040/08Hydraulic fluids, e.g. brake-fluids
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Definitions

  • the present invention relates to a base oil comprising polyalphaolefins, polymer esters and polyalkylene glycols and a lubricating fluid composition containing the base oil and additives.
  • the lubricating fluid composition can be used for the lubrication of gears and for use in hydraulic systems, particularly for lubrication in the food processing industry.
  • a particular area of application of the base oils and lubricating fluid compositions according to the invention are lubricating points that come or can come into contact with food and/or animal feed.
  • Hydraulic and transmission oils consist of a base oil and additives that are added to increase the service life and performance of the lubricating fluid.
  • the base oil can consist of a mixture of different oils.
  • the load on the tooth flanks is gradually applied using a weighted lever that braces one of the shafts against the other. From force level 4, the pinion tooth flanks are inspected for any damage after each force level has been completed. If the force level 12 is reached without the damage occurring, the measurement is complete.
  • the requirement standard for hydraulic oil (DIN 51524-2 HLP) requires at least force level 10
  • the requirement standard for circulating oils (DIN 51517-3 CLP) requires at least force level 12.
  • the result is either “Pass” or “Fail” - works or doesn't work.
  • Another technically relevant requirement that goes beyond DIN 51517-3 is a high micropitting capacity.
  • the ability of a lubricating fluid to avoid the damage caused by micropitting also referred to as “micropitting” is referred to as micropitting capacity.
  • Micropitting occurs on tooth flanks under high loads in the area of mixed friction.
  • the primary influence on the development of micropitting is the thickness of the lubricant film at operating temperature.
  • chemically active additives can significantly promote the development of micropitting.
  • additives that improve the coefficient of friction can help prevent micropitting.
  • US 9347016 B2 describes the use of a dialkyldithiophosphate as an effective component against micropitting.
  • phosphonates and phoshites e.g. dioleyl phosphite
  • succinimides, pyrrolidinones, molybdenum carboxylates and oleylamide are mentioned as friction modifiers to avoid micropitting.
  • US 6184186 B1 claims the use of molybdenum carboxylates and sulfurized isobutylenes to avoid micropitting.
  • the FVA 54 micropitting test is used, which is carried out on an FZG standard clamping testing machine.
  • This test consists of two consecutive parts: a step test to determine the damage force level and a endurance test to assess the tribological long-term behavior.
  • the step test the load is gradually increased from force level 5 to force level 10, with the test duration of each force level being 16 hours.
  • the endurance test initially runs for 80 hours at force level 8 and then 5 x 80 hours at force level 10. After each force level, the pinion is removed and the profile shape deviation and the proportion of gray spots on the tooth flank are determined on three teeth. In addition, the weight loss of the pinion caused by wear is determined.
  • the profile shape deviation is used to determine the damage force level in the step test. If a value of 7.5 pm is exceeded, the damage level is reached. If the limit value is not exceeded after the first five power levels, damage power level 10 is reached. If all six force levels are passed through without exceeding the limit value, the result is given as SKS greater than 10.
  • elastomer compatibility is also important because when the oil is used for a long time, elastomers, such as radial shaft seals, shrink and can lead to leaks. Likewise, oil can cause excessive swelling, which can also lead to leaks.
  • Various types of NBR and FKM elastomers are usually used in industrial transmissions, with the NBR types in particular responding strongly to the composition of the base oil mixture.
  • Hydraulic oils offer protection against wear and corrosion, whereby the wear protection for HLP-classified oils (DIN 51524-2) is improved compared to HL oils (DIN 51524-1) and HVLP-classified oils (DIN 51524-3) are additional In addition to the improved wear protection, they have a more stable temperature-viscosity behavior (viscosity index) and can therefore be used in a wider temperature range.
  • the terpolymer is a polymerized diester selected from a di(C4-C22 alkyl) ester of maleic acid, fumaric acid, 2-methylmaleic acid, 2,3-dimethylmaleic acid, 2-methylfumaric acid, 2,3-dimethylfumaric acid or mixtures as Polymerization product with a C6-C40 alpha-olefin and a C4-C40 alkyl (meth)acrylate.
  • Polyalphaolefins or alkylene oxides are suggested as optional base oils for the lubricant.
  • JP 2007-268697 A discloses oil compositions based on Fischer-Tropsch hydrocarbons and n-paraffins, as well as possibly aromatic and naphthalene hydrocarbon oils.
  • the oil compositions may optionally further contain synthetic oils such as poly-alpha-olefins or polyalkylene glycols or polymers such as polymerization products of unsaturated carboxylic acid esters such as maleic acid ester or fumaric acid ester polymers polymerized with an olefinic monomer.
  • the object of the invention is to provide a base oil and a lubricating fluid containing the base oil, the lubricating fluid being able to be used, among other things, as a transmission oil and/or as a hydraulic oil.
  • the base oil should be such that it can absorb the additives necessary for the lubricating fluid and the additives in the base oil have the desired effect.
  • the raw materials should be selected so that the lubricating fluids can also be used in the food processing industry. The selection of raw materials in the USA is regulated, for example, by the requirements of the US Food and Drug Administration (FDA).
  • the lubricant fluid should, according to one embodiment, meet the CLP standard DIN 51517-3 and, in particular, from viscosity class 220 (ISO VG 220) in the micropitting test according to FVA 54, have a micropitting resistance of the “high” rating level.
  • low viscosity classes of the lubricating fluid In order to be used as hydraulic oil, low viscosity classes of the lubricating fluid must also meet DIN 51524-3 (HVLP). Good compatibility with common NBR elastomers (NBR is the abbreviation for “Nitrile Butadiene Rubber”) and fluorine rubber elastomers (FKM elastomers) is desired in all viscosity classes. Summary of the invention
  • the base oil according to the invention includes:
  • polyalphaolefins as oligomers of C6 to C14 alpha-olefins, in particular C8 to C12 alpha-olefins;
  • polymer esters obtainable as a polymerization product of one or more alpha/beta-unsaturated dicarboxylic acid diesters, the alcohol groups having 3 to 10 carbon atoms, in particular 4 to 8 carbon atoms one or more C4 to C18 alpha-olefins, in particular C10 to C16 alpha-olefins or C12 to C16 alpha-olefins;
  • polyalkylene glycols obtainable from alkylene oxides, the alkylene oxides
  • Propylene oxide and at least one C4 to C8 alkylene oxides are preferred.
  • the base oil includes
  • the above polyalphaolefins, polymer esters and polyalkylene glycols together make up more than 90% by weight, in particular more than 95% by weight, of the base oil.
  • the above polyalphaolefins, polymer esters and polyalkylene glycols preferably add up to 100% by weight in the base oil.
  • the base oil therefore consists of the above components.
  • the polyalphaolefin is an oligomer of a 1-octene, 1-decene and/or 1-dodecene, and in particular an oligomer of 1-octene or 1-decene or 1-octene and 1-decene.
  • the degree of polymerization of the polyalphaolefins can be 3 to 25. Even independently of this, the viscosity of the polyalphaolefins is preferably from 4 to 300 mm 2 /s at 100 ° C (kinematic viscosity determined according to DIN EN ISO 3104).
  • the polyalphaolefins can also be used as hydrogenated products.
  • the polymer esters are preferably copolymers of maleic acid and/or fumaric acid (full) esters and one or more C4 to C18 alpha-olefins.
  • the alcohol groups of the dicarboxylic diesters are in particular linear and/or branched monoalcohols with 3 to 10 carbon atoms, in particular 4 to 8 carbon atoms.
  • the dicarboxylic acids of the dicarboxylic diester preferably have 4 to 12 carbon atoms, in particular 4 to 6 carbon atoms.
  • chain lengths of 10 to 16 carbon atoms, in particular 14 to 16 carbon atoms are preferred. These can be linear and/or branched, preferably linear.
  • the molar ratio of the alpha-olefins to the dicarboxylic acid diesters can be 1.5 to 1 to 1 to 1.5, in particular 1 to 0.9 to 0.9 to 1.
  • the polymer esters in particular have an average molecular weight of 1000 to 5000 g/mol and in particular! 500 to 2500 g/mol (each as a number average).
  • the molar ratio of the alpha-olefins to the dicarboxylic acid diesters can be 1.5 to 1 to 1 to 1.5, in particular 1 to 0.9 to 0.9 to 1.
  • the polyalkylene glycols comprise 30-70 mol% of propylene oxide and 70-30 mol% of C4 to C8 alkylene oxides, in particular butylene oxide, or in particular consist of these.
  • the polyalkylene glycols are preferably soluble at room temperature in the polyalphaolefins or polyalphaolefin mixtures with which they are used together.
  • the lubricating fluid composition comprises the base oil according to at least one of the preceding claims, and at least one of the following additives
  • the lubricating fluid composition preferably comprises or consists of at least:
  • the lubricating fluid composition comprises or consists of:
  • the lubricating fluid composition includes the base oil and at least one of the following additives:
  • an amine-reacted alkyl phosphate in particular mono- or di-C1- to C12-alkyl phosphate, as a wear protection additive, in particular 0.01 to 2% by weight, preferably 0.1 to 0.6% by weight and/or
  • polyol monoester in particular a C12 to C24 fatty acid ester of optionally ethoxylated polyols, in particular optionally ethoxylated sorbitan mono-oleate, as a friction modifier, in particular 0.01 to 2% by weight, preferably 0.05 to 0, 3% by weight.
  • the amine-reacted alkyl phosphate is preferably a mono- or di-C1 to C12 alkyl phosphate reacted with at least C10 to C18 alkyl amines.
  • the reaction is preferably carried out in such a way that the alkyl phosphate is neutralized or partially neutralized. Suitable examples are mono- and diisooctyl esters of phosphoric acid reacted with tert-alkylamines and C12 to C14 primary amines (CAS Reg. No. 68187-67-7) or mono- and di-hexyl phosphoric acid reacted with tetra-methylnonylamine and C11 - to C14 alkylamines.
  • Commercial products include Irgalube® 349 from BASF SE or Additin® RC 3760 from LANXESS (CAS Reg. No. 80939-62-4).
  • the amine-reacted alkyl phosphate is a wear protection additive.
  • the polyol monoester is preferably a C12 to C24 fatty acid ester of polyols such as glycerin, polyglycerin or sorbitan.
  • the polylol can also be completely or partially ethoxylated. Suitable examples are polysorbate 20, polysorbate 40, polysorbate 60, polysorbate 120, glyceryl monostearate, glyceryl monooleate, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate or polyglyceryl-4-isostearate.
  • the C12 to C24 mono fatty acid esters of possibly partially ethoxylated polyols act as friction modifiers.
  • the base oil in a lubricating fluid composition or the lubricating fluid composition can be used as a hydraulic and gear oil, particularly in the food processing industry and/or the feed processing industry.
  • polyalphaolefins, polymer esters and polyalkylene glycols are not chemically pure products and if they are mentioned in the singular, this also means a mixture of different molecules, each of which individually corresponds to the specified specification.
  • Hydraulic and transmission oils consist of a base oil and additives that are added to increase the service life and performance of the lubricating fluid.
  • a mixture of the above polyalphaolefins, polymer esters and polyalkylene glycols is used as the base oil in the present invention.
  • the polyalphaolefins are oligomers of in particular linear 1-alkenes, in particular 1-octene, 1-decene and/or 1-dodecene, which are produced, for example, using Lewis acid catalysts (e.g.
  • the polyalphaolefin can, for example, be an oligomer of 50 to 80 wt. % 1 - decene and 50 to 20% by weight 1 -dodecene.
  • the polyalphaolefins are a mixture of a1) oligomers of 1-decene and b1) oligomers of 1-octene or a mixture of a2) oligomers of 1-dodecene and b2) oligomers of 1-octene and/or 1- Decen.
  • oligomers a1) or a2) can be characterized in more detail as follows: 5 to 95% by weight of oligomers a1) or a2) and 5 to 95% by weight of oligomers b1) or b2).
  • the polyalphaolefins can be produced by metallocene catalysis.
  • polyalphaolefins of different viscosities for example oligomers with a viscosity of 4 to 100 mm 2 /s at 100°C and oligomers with a viscosity of 50 to 300 mm 2 /s at 100°C.
  • Polymer esters are polymers resulting from C,C linkages that contain side chains with ester groups. In the present case, this includes in particular the copolymers of alpha, beta-unsaturated dicarboxylic acid esters, such as maleic or fumaric acid esters with, in particular, unbranched alpha-olefins. Polymer esters and their production are described, for example, in DE 3223694 C2 and US 5435928 A.
  • the polyalkylene glycols are the polymeric reaction products of water and/or a mono- or dihydric starting alcohol with 1,2-epoxides such as ethylene oxide, propylene oxide and/or butylene oxide, which include at least propylene oxide and at least one C4 to C8 alkylene oxide.
  • 1,2-epoxides such as ethylene oxide, propylene oxide and/or butylene oxide, which include at least propylene oxide and at least one C4 to C8 alkylene oxide.
  • the polyalkylene glycols are present, for example, as homopolymers of butylene oxide or as copolymers of propylene oxide and butylene oxide. Copolymers which consist of 30-70% propylene oxide and 70-30% butylene oxide are preferably used here.
  • the polyalkylene glycols in particular have one or two terminal hydroxy groups.
  • a swelling agent in the lubricating fluid composition typically an ester
  • too high a swelling agent content leads to excessive swelling, which can also lead to leaks.
  • Various types of NBR and FKM elastomers are used in industrial transmissions, with the NBR types in particular responding strongly to the composition, ie the polarity, of the base oil mixture.
  • esters examples include monoesters, diesters, polyol esters, and complex esters, for example of C1 to C18 alcohols with a C2 to C18 carboxylic acid.
  • the mono- and diesters in question here include the esters of linear or branched monohydric alcohols such as methanol, ethanol, isopropanol, isobutanol, 2-ethylhexanol, 3,5,5-trimethylhexanol or 7-methyloctanol with typical fatty acids or dicarboxylic acids, such as such as caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, oleic acid, linoleic acid, linolenic acid, adipic acid, suberic acid, sebacic acid or phthalic acid.
  • the polyol esters include the formal reaction products of linear or branched carboxylic acids with polyhydric alcohols such as glycerol, neopentyl glycol, trimethylolpropane, pentaerythritol or dipentaerythritol.
  • the proportion of swelling agent is chosen so that the volume expansion of the elastomer does not exceed 10%. As a rule, this means that the swelling agent is contained in the lubricating fluid composition in a proportion of 0.5 to 6% by weight, in particular 1 to 4% by weight.
  • An example is di(2-ethylhexyl) sebacate.
  • the polyalkylene glycol used also acts as a swelling agent.
  • antioxidants include: sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfit
  • primary antioxidants such as amine compounds (e.g. alkylamines or 1-phenylamino-naphthalene), aromatic amines such as phenylnaphtylamines or diphenylamines or polymeric hydroxyquinolines (e.g. TMQ), phenolic compounds (e.g. 2.6-di-tert-butyl-4- methylphenol), organic dithiocarbamates or dithiophosphates;
  • amine compounds e.g. alkylamines or 1-phenylamino-naphthalene
  • aromatic amines such as phenylnaphtylamines or diphenylamines or polymeric hydroxyquinolines (e.g. TMQ)
  • phenolic compounds e.g. 2.6-di-tert-butyl-4- methylphenol
  • organic dithiocarbamates or dithiophosphates e.g. 2.6-di-tert-butyl-4- methylphenol
  • secondary antioxidants such as phosphites, e.g. tris(2,4-ditert-butylphenyl phosphite) or bis(2,4-ditert-butylphenyl) pentaerythritol diphosphite or thioethers (e.g. cresol thioether);
  • phosphites e.g. tris(2,4-ditert-butylphenyl phosphite) or bis(2,4-ditert-butylphenyl) pentaerythritol diphosphite or thioethers (e.g. cresol thioether);
  • High pressure additives and/or wear protection additives such as organic sulfur compounds such as polysulfides or sulfurized olefins, thiophosphates (e.g. triphenylthiophosphate) and dithiophosphates, phosphites and phosphonates (e.g. di-n-octyl phosphonate), phosphates (e.g. substituted triphenyl phosphates). or amine-neutralized alkyl phosphates), inorganic or organic boron compounds, thiocarbamates and dithiocarbamates (e.g. methylene bis(dibutyldithiocarbamate));
  • Corrosion inhibitors such as sulfonates, such as petroleum sulfonate, dinonyl naphthalene sulfonate; neutral or overbased calcium sulfonates, magnesium sulfonates, sodium sulfonates, calcium and sodium naphthalene sulfonates, sulfonic acid esters, amine phosphates; N-methyl-N-(1-oxo-9-octadecenyl)glycine;
  • Metal deactivators such as benzotriazoles, such as methylbenzotriazole dialkylamine, sterically hindered phenols, sodium nitrite;
  • Viscosity improvers such as polymethacrylate, polyisobutylene, polystyrenes
  • Friction reducers some with anti-wear properties such as organic acids (e.g. isostearic acid), fatty acid esters of possibly partially ethoxylated polyols such as glycerol or sorbitan, partial glycerides, animal or vegetable oils, dialkyl hydrogen phosphonates, carboxamides such as oleylamides, organic compounds based on polyethers and amides, e.g. alkyl polyethylene glycol. col tetradecylene glycol ether, alkyl succinates, PIBSI (polyisobutylene succinic acid imide) or PIBSA (polyisobutylene succinic anhydride).
  • organic acids e.g. isostearic acid
  • fatty acid esters of possibly partially ethoxylated polyols such as glycerol or sorbitan
  • partial glycerides animal or vegetable oils
  • dialkyl hydrogen phosphonates carboxamides such as o
  • Solids The use of particles (boron nitride, silicon dioxide, layered silicates such as bentonite, carbon nanotubes) is possible in gear oils to achieve certain properties. In order not to produce negative effects with regard to tribological performance, very small particles (so-called nanoparticles with particle sizes of less than 500 nm, preferably less than 100 nm, particularly preferably less than 50 nm) are used.
  • a portion of the amount of base oil e.g. 5 to 25% by weight
  • the additives which are particularly oil-soluble but are generally present as a solid under normal conditions
  • the temperature is reduced to less than 60°C.
  • Liquid and optionally oil-insoluble additives and solids as well as the remaining amount of base oil are then added and mixed by further stirring until the mixture is completely homogeneous.
  • the lubricating fluid composition according to the invention is particularly suitable for use in industrial gears (spur gears, helical gears, bevel gears, hypoid and planetary gears) and hydraulic systems, especially those used in the food or feed industry.
  • a gearbox is a machine element with which movement variables (e.g. change in force, torque) can be changed. Depending on the design of the gearbox, it is surrounded by a housing and lubricated with a lubricating fluid. Seals are used to prevent leakage of the lubricating fluid. In addition to special design properties, the sealing materials must also be chemically stable against the lubricating fluids used.
  • Elastomer compatibility therefore plays an important role in lubricant development. The same also applies to the durability of hydraulic seals that are used to seal hydraulic systems filled with hydraulic oils.
  • a lubricating fluid was developed for use as a transmission and hydraulic oil which meets the requirements of DIN 51517-3 (more precisely: the tests for relative volume change, change in Shore A hardness, tensile strength and elongation at break described in DIN ISO 1817). ) as well as the dynamic elastomer compatibility test (Freudenberg test specification FS PLM 111 0008).
  • Part of the base oil quantity (5-25%), here the polar oil components namely ester and polyalkylene glycol, are introduced together with the additives that are solid at room temperature and heated to 90 to 110 ° C with continuous stirring until a clear solution is obtained.
  • the temperature is reduced to less than 60°C.
  • the liquid additives are then added and mixed by further stirring for approx. 15 minutes until the mixture is completely homogeneous. When it cools down further to temperatures below 40°C, the oil can be bottled.
  • formulations each contain an additive package.
  • PAO 6 polyalphaolefin Spectrasyn 6, ExxonMobil Chemical
  • Syn-fluid PAO 6 cSt Chevron Phillips Chemical
  • Durasyn 166 Ineos Oligomers
  • mPAO 150 Polyalphaolefin, metallocene catalyzed: Spectrasyn Elite 150, ExxonMobil Chemical; Synfluid mPAO 150 cSt, Chevron Phillips Chemical
  • Additive package triphenylphosphorothionate, phenolic antioxidant, aminic antioxidant, sorbitan monooleate, N-methyl-N-(1-oxo-9-octadecenyl)glycine, polydimethylsiloxane and benzotriazole derivative, where the sorbitan monooleate is the friction modifier used.
  • Table 1 The following methods were used in Tables 1 and 2: kV 40 [mm 2 /s] Kinematic viscosity at 40 ° C determined according to DIN
  • the polymer esters and the polyalkylene glycol used are very suitable additives to the PAO oil because they are able to maintain the high viscosity index.
  • a higher viscosity index means a higher lubricant film thickness at operating temperature, which contributes to better wear protection.
  • a purely PAO-based formulation (Experiment 1) does not offer sufficient elastomer compatibility. NBR elastomers shrink and can lead to leaks. Formulations that contain either polyalkylene glycol (Experiment 2) or esters (Experiment 3) show only slight volume losses. The best result is achieved with a formulation that, in addition to POA, contains both esters and polyalkylene glycol (PAG) (Experiment 4). Furthermore, the purely PAO-based formulation cannot guarantee corrosion protection against salt water despite the same additives.
  • test 4 Compared to the ester-containing but polyalkylene glycol-free version (test 3), the air separation capacity in test 4 is not improved. Table 2
  • Test series 2 shows that the content of amine-neutralized alkyl phosphates among the additives plays a decisive role in the passing or failing of the important mechanical-dynamic tests.
  • a low content (Experiment 5)
  • a high gray stain resistance can be achieved even without the addition of polyalkylene glycol.
  • damage power level 11 can only be achieved in the FZG test.
  • test 6 With a higher content of amine phosphates and in the presence of polyalkylene glycol (test 6), damage force level greater than 12 is achieved in the FZG test, but the micropitting capacity is inadequate.
  • the amine phosphate content reduced in experiment 4 can be compensated for by the oil-soluble polyalkylene glycol without having negative effects in the micropitting test.
  • the base oil mixture described here supports the anti-corrosion properties and elastomer compatibility of the lubricant and allows for a balanced additive formulation that is suitable for “food grade” lubricants and meets the sometimes conflicting requirements.

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Abstract

The invention relates to a base oil comprising polyalphaolefins, polymer esters and polyalkylene glycols, and a lubricating fluid composition containing said base oil. The lubricating fluid composition can be used for lubricating transmissions and for use in hydraulic systems, particularly for lubrication in the food preparation industry.

Description

Basisöl und Schmierfluidzusammensetzung enthaltend das Basisöl Base oil and lubricating fluid composition containing the base oil
Die vorliegende Erfindung betrifft ein Basisöl, umfassend Polyalphaolefine, Polymerester und Polyalkylenglykole und eine Schmierfluidzusammensetzung enthaltend das Basisöl und Additive. Die Schmierfluidzusammensetzung kann zur Schmierung von Getrieben und zum Einsatz in Hydrauliksystemen eingesetzt werden, insbesondere zur Schmierung im Bereich der lebensmittelverarbeitenden Industrie. Ein besonderes Anwendungsgebiet der erfindungsgemäßen Basisöle und Schmierfluidzusammensetzungen sind Schmierstellen, die mit Lebens- und/oder Futtermitteln in Kontakt kommen bzw. kommen können. The present invention relates to a base oil comprising polyalphaolefins, polymer esters and polyalkylene glycols and a lubricating fluid composition containing the base oil and additives. The lubricating fluid composition can be used for the lubrication of gears and for use in hydraulic systems, particularly for lubrication in the food processing industry. A particular area of application of the base oils and lubricating fluid compositions according to the invention are lubricating points that come or can come into contact with food and/or animal feed.
Einführung und Stand der Technik Introduction and state of the art
Hydraulik- und Getriebeöle bestehen aus einem Basisöl sowie Additiven, die zur Steigerung der Lebensdauer und Leistungsfähigkeit des Schmierfluids zugesetzt werden. Das Basisöl kann aus einer Mischung unterschiedlicher Öle bestehen. Hydraulic and transmission oils consist of a base oil and additives that are added to increase the service life and performance of the lubricating fluid. The base oil can consist of a mixture of different oils.
Zur Bestimmung der Leistungsfähigkeit eines Schmierfluids werden verschiedene mechanisch-dynamische Prüfungen durchgeführt. Die Forschungsstelle für Zahnräder und Getriebebau der Technischen Universität München (FZG) hat einen Prüfstand entwickelt, mit dem sich Schmierstoffe für Getriebe auf ihre Eignung testen lassen, ein Fressen der Oberflächen und Flanken von Zahnrädern zu verhindern. Eine wichtige Kenngröße für Industriegetriebeöle ist die Schadenskraftstufe im FZG-Test A/8,3/90 nach DIN ISO 14635-1. In diesem Test wird die Fresstragfähigkeit von Schmierstoffen auf einer FZG-Zahnrad-Verspannungs-Prüfmaschine ermittelt. Dazu läuft ein Prüfzahnradpaar mit einer speziellen Zahngeometrie in dem zu prüfenden Schmierfluid. Temperatur und Drehzahl sind vorgegeben. Die Belastung der Zahnflanken wird über einen mit Gewichten belasteten Hebel, der eine der Wellen gegen die andere verspannt, stufenweise belastet. Ab Kraftstufe 4 werden die Ritzelzahnflanken nach Beendigung jeder Kraftstufe auf etwaige Beschädigungen untersucht. Wenn die Kraftstufe 12 ohne Auftreten des Schadensbildes erreicht wird, ist die Messung beendet. Die Anforderungsnorm für Hydrauliköl (DIN 51524-2 HLP) fordert mindestens die Kraftstufe 10, in der Anforderungsnorm für Umlauföle (DIN 51517-3 CLP) wird mindestens die 12. Kraftstufe gefordert. Das Ergebnis ist entweder “Pass” oder “Fail” - funktioniert oder funktioniert nicht. Eine weitere technisch relevante, über die DIN 51517-3 hinaus gehende Anforderung ist eine hohe Graufleckentragfähigkeit. Als Graufleckentragfähigkeit wird die Eigenschaft eines Schmierfluids bezeichnet, das Schadensbild der Graufleckigkeit (auch als „Micropitting“ bezeichnet) zu vermeiden. To determine the performance of a lubricating fluid, various mechanical-dynamic tests are carried out. The Research Center for Gears and Transmission Engineering at the Technical University of Munich (FZG) has developed a test bench with which lubricants for transmissions can be tested for their ability to prevent seizure of the surfaces and flanks of gears. An important parameter for industrial gear oils is the damage force level in the FZG test A/8.3/90 according to DIN ISO 14635-1. In this test, the seizing resistance of lubricants is determined on an FZG gear tension testing machine. For this purpose, a pair of test gears with a special tooth geometry runs in the lubricating fluid to be tested. Temperature and speed are specified. The load on the tooth flanks is gradually applied using a weighted lever that braces one of the shafts against the other. From force level 4, the pinion tooth flanks are inspected for any damage after each force level has been completed. If the force level 12 is reached without the damage occurring, the measurement is complete. The requirement standard for hydraulic oil (DIN 51524-2 HLP) requires at least force level 10, while the requirement standard for circulating oils (DIN 51517-3 CLP) requires at least force level 12. The result is either “Pass” or “Fail” - works or doesn't work. Another technically relevant requirement that goes beyond DIN 51517-3 is a high micropitting capacity. The ability of a lubricating fluid to avoid the damage caused by micropitting (also referred to as “micropitting”) is referred to as micropitting capacity.
Graufleckigkeit entsteht auf Zahnflanken unter hoher Belastung im Bereich der Mischreibung. Primären Einfluss auf das Entstehen von Graufleckigkeit hat die bei Betriebstemperatur herrschende Schmierfilmdicke. Darüber hinaus kann der Einsatz chemisch aktiver Additive maßgeblich das Entstehen von Graufleckigkeit begünstigen. Der Zusatz von Reibwert-verbessernden Additiven (Friction Modifier) kann zur Vermeidung von Graufleckigkeit beitragen. In US 9347016 B2 wird die Verwendung eines Dialkyldithiophosphats als wirksame Komponente gegen Micropitting beschrieben. In EP 0949320 A2 werden Phosphonate und Phoshite (z.B. Dioleylphosphit), Succinimide, Pyrrolidinone, Molybdäncarboxylate und Oley- lamid als Friction Modifier zur Vermeidung von Micropitting genannt. US 6184186 B1 beansprucht die Verwendung von Molybdän-Carboxylaten und geschwefelten Isobutylenen zur Vermeidung von Micropitting. Micropitting occurs on tooth flanks under high loads in the area of mixed friction. The primary influence on the development of micropitting is the thickness of the lubricant film at operating temperature. In addition, the use of chemically active additives can significantly promote the development of micropitting. The addition of additives that improve the coefficient of friction (friction modifier) can help prevent micropitting. US 9347016 B2 describes the use of a dialkyldithiophosphate as an effective component against micropitting. In EP 0949320 A2, phosphonates and phoshites (e.g. dioleyl phosphite), succinimides, pyrrolidinones, molybdenum carboxylates and oleylamide are mentioned as friction modifiers to avoid micropitting. US 6184186 B1 claims the use of molybdenum carboxylates and sulfurized isobutylenes to avoid micropitting.
Um die Graufleckentragfähigkeit eines Schmierfluids zu bestimmen, wird der FVA 54 Micropitting-Test verwendet, der an einer FZG-Standard-Verspann-Prüfma- schine durchgeführt wird. Dieser Test besteht aus zwei aufeinanderfolgenden Teilen: Ein Stufentest zur Ermittlung der Schadenskraftstufe und ein Dauertest zur Beurteilung des tribologischen Langzeitverhaltens. Im Stufentest wird die Last schrittweise von Kraftstufe 5 bis Kraftstufe 10 erhöht, wobei die Prüfdauer jeder Kraftstufe 16 Stunden beträgt. Der Dauertest läuft zunächst 80 h bei Kraftstufe 8 und dann 5 x 80 h bei Kraftstufe 10. Nach jeder Kraftstufe wird das Ritzel ausgebaut und an drei Zähnen die Profilformabweichung und der Graufleckenanteil der Zahnflanke ermittelt. Zudem wird der durch Verschleiß hervorgerufene Gewichtsverlust des Ritzels bestimmt. Zur Bestimmung der Schadenskraftstufe im Stufentest wird die Profilformabweichung herangezogen. Wird ein Wert von 7,5 pm überschritten, ist die Schadenskraftstufe erreicht. Wird nach den ersten fünf Kraftstufen der Grenzwert nicht überschritten, so ist Schadenskraftstufe 10 erreicht. Werden alle sechs Kraftstufen ohne Überschreiten des Grenzwerts durchlaufen, wird das Ergebnis als SKS größer 10 angegeben. Für die Praxis ist außerdem die Elastomerverträglichkeit von Bedeutung, da bei langer Nutzung des Öls Elastomere, z.B. Radialwellendichtringe, schrumpfen und zu Undichtigkeit führen können. Gleichermaßen kann ein Öl eine zu starke Quellung verursachen, was ebenfalls zu Undichtigkeit führen kann. In Industriegetrieben kommen i.d.R. verschiedene NBR- und FKM-Elastomertypen zum Einsatz, wobei besonders die NBR-Typen stark auf die Zusammensetzung der Basisölmischung ansprechen. To determine the micropitting capacity of a lubricating fluid, the FVA 54 micropitting test is used, which is carried out on an FZG standard clamping testing machine. This test consists of two consecutive parts: a step test to determine the damage force level and a endurance test to assess the tribological long-term behavior. In the step test, the load is gradually increased from force level 5 to force level 10, with the test duration of each force level being 16 hours. The endurance test initially runs for 80 hours at force level 8 and then 5 x 80 hours at force level 10. After each force level, the pinion is removed and the profile shape deviation and the proportion of gray spots on the tooth flank are determined on three teeth. In addition, the weight loss of the pinion caused by wear is determined. The profile shape deviation is used to determine the damage force level in the step test. If a value of 7.5 pm is exceeded, the damage level is reached. If the limit value is not exceeded after the first five power levels, damage power level 10 is reached. If all six force levels are passed through without exceeding the limit value, the result is given as SKS greater than 10. In practice, elastomer compatibility is also important because when the oil is used for a long time, elastomers, such as radial shaft seals, shrink and can lead to leaks. Likewise, oil can cause excessive swelling, which can also lead to leaks. Various types of NBR and FKM elastomers are usually used in industrial transmissions, with the NBR types in particular responding strongly to the composition of the base oil mixture.
Zur Schmierung von Industriegetrieben im Bereich der lebensmittelverarbeitenden Industrie sind, da ein möglicher Kontakt des Schmierfluids mit dem Lebensmittel nicht gänzlich auszuschließen ist, Schmierfluide zu verwenden, die physiologisch unbedenklich sind. Die Auswahl an Rohstoffen, die zur Herstellung von lebensmittelgeeigneten („food grade“, (H1 )) Schmierfluiden verwendet werden können, ist gegenüber technischen Schmierfluiden stark eingeschränkt. Sämtliche oben genannten „Friction Modifier“ sind für die Formulierung von „food grade“ Schmierfluid nicht gestattet. For the lubrication of industrial gears in the food processing industry, since possible contact of the lubricating fluid with the food cannot be completely ruled out, lubricating fluids that are physiologically harmless must be used. The selection of raw materials that can be used to produce food grade (H1) lubricating fluids is very limited compared to technical lubricating fluids. All of the above-mentioned “friction modifiers” are not permitted for the formulation of “food grade” lubricating fluid.
Die Anforderungen an ein Hydrauliköl für den industriellen Einsatz sind in DIN 51524-1 , DIN 51524-2 und DIN 51524-3 beschrieben. Hydrauliköle bieten einen Schutz gegen Verschleiß und Korrosion, wobei der Verschleißschutz bei HLP-klas- sifizierten Ölen (DIN 51524-2) gegenüber den HL-Ölen (DIN 51524-1 ) verbessert ist und HVLP-klassifizierte Öle (DIN 51524-3) zusätzlich zu dem verbesserten Verschleißschutz eine stabileres Temperatur-Viskositätsverhalten (Viskositätsindex) aufweisen und daher in einem weiteren Temperaturbereich einsetzbar sind. The requirements for a hydraulic oil for industrial use are described in DIN 51524-1, DIN 51524-2 and DIN 51524-3. Hydraulic oils offer protection against wear and corrosion, whereby the wear protection for HLP-classified oils (DIN 51524-2) is improved compared to HL oils (DIN 51524-1) and HVLP-classified oils (DIN 51524-3) are additional In addition to the improved wear protection, they have a more stable temperature-viscosity behavior (viscosity index) and can therefore be used in a wider temperature range.
Weiterhin ist ein hoher Viskositätsindex gewünscht. Druckverluste in hydraulischen Anlagen senken den Wirkungsgrad. Diese können bei tiefen Temperaturen durch eine Viskositätszunahme des Fluids und bei hohen Temperaturen durch Leckage, bedingt durch Viskositätsabnahme des Fluids, auftreten. Ein hoher Wirkungsgrad über einen weiten Temperaturbereich kann folglich mit Ölen mit hohem Viskositätsindex erreicht werden. Furthermore, a high viscosity index is desired. Pressure losses in hydraulic systems reduce efficiency. These can occur at low temperatures due to an increase in viscosity of the fluid and at high temperatures due to leakage caused by a decrease in viscosity of the fluid. High efficiency over a wide temperature range can therefore be achieved with oils with a high viscosity index.
Als Basisöle für „food-grade“ Hydraulik- und Getriebeöle sind in der Vergangenheit hochraffinierte Weißöle, Gas-to-Liquid (GTL) -Öle, Polyalphaolefine, Polyisobuty- lene, Polyalkylenglykole, alkylierte Naphthaline, native und synthetische Ester sowie Mischungen dieser Komponenten diskutiert worden. US 2021/0348079 A offenbart Schmiermittel auf Basis eines Terpolymers aus Diester, Olefin und Acrylat. Das Terpolymer ist ein polymerisierter Diester, ausgewählt aus einem Di(C4-C22-alkyl)ester der Maleinsäure, Fumarsäure, 2-Methyl- maleinsäure, 2,3-Dimethylmaleinsäure, 2-Methylfumarsäure, 2,3-Dimethylfumar- säure oder Mischungen als Polymerisationsprodukt mit einem C6-C40-alpha-Ole- fin und einem C4-C40-Alkyl(meth)acrylat. Als fakultative Basisöle für das Schmiermittel werden u.a. Polyalphaolefine oder Alkylenoxide vorgeschlagen. In the past, highly refined white oils, gas-to-liquid (GTL) oils, polyalphaolefins, polyisobutylenes, polyalkylene glycols, alkylated naphthalenes, native and synthetic esters and mixtures of these components have been discussed as base oils for “food-grade” hydraulic and gear oils been. US 2021/0348079 A discloses lubricants based on a terpolymer made of diester, olefin and acrylate. The terpolymer is a polymerized diester selected from a di(C4-C22 alkyl) ester of maleic acid, fumaric acid, 2-methylmaleic acid, 2,3-dimethylmaleic acid, 2-methylfumaric acid, 2,3-dimethylfumaric acid or mixtures as Polymerization product with a C6-C40 alpha-olefin and a C4-C40 alkyl (meth)acrylate. Polyalphaolefins or alkylene oxides are suggested as optional base oils for the lubricant.
Die JP 2007-268697 A offenbart Öl-Zusammensetzungen auf der Basis von Fi- scher-Tropsch Kohlenwasserstoffen und n- Paraffinen, sowie ggf. aromatischen und napthalinischen Kohlenwasserstoff-Ölen. Die Öl-Zusammensetzungen können fakultativ weiterhin synthetische Öle wie Poly-alpha-olefine oder Polyalkylenglykole oder Polymere enthalten, wie Polymerisationsprodukte von ungesättigten Carbonsäureesten wie Maleinsäureester- oder Fumarsäureester-Polymere polymerisiert mit einem olefinischen Monomer. JP 2007-268697 A discloses oil compositions based on Fischer-Tropsch hydrocarbons and n-paraffins, as well as possibly aromatic and naphthalene hydrocarbon oils. The oil compositions may optionally further contain synthetic oils such as poly-alpha-olefins or polyalkylene glycols or polymers such as polymerization products of unsaturated carboxylic acid esters such as maleic acid ester or fumaric acid ester polymers polymerized with an olefinic monomer.
Aufgabe der Erfindung Task of the invention
Aufgabe der Erfindung ist die Bereitstellung eines Basisöls und eines Schmierfluids enthaltend das Basisöl, wobei das Schmierfluid unter anderem als Getriebeöl und/oder als Hydrauliköl einsetzbar sein soll. Das Basisöl soll so beschaffen sein, dass es die für das Schmierfluid notwendigen Additive aufnehmen kann und die Additive in dem Basisöl die gewünschte Wirkung entfalten. Nach einer Ausführungsform sollen die Rohstoffe so ausgewählt sein, dass die Schmierfluide auch in der lebensmittelverarbeitenden Industrie eingesetzt werden können. Die Rohstoffauswahl wird in den U.S.A. z.B. durch die Vorgaben der U.S. Food and Drug Administration (FDA) reguliert. Als Getriebeöl soll das Schmierstofffluid nach einer Ausgestaltung die CLP-Norm DIN 51517-3 erfüllen und darüber hinaus insbesondere ab der Viskositätsklasse 220 (ISO VG 220) im Micropitting-Test nach FVA 54 eine Graufleckentragfähigkeit der Bewertungsstufe „high“ aufweisen. Um als Hydrauliköl eingesetzt werden zu können, sollen auch niedrige Viskositätsklassen des Schmierfluids DIN 51524-3 (HVLP) erfüllen. In allen Viskositätsklassen ist eine gute Verträglichkeit gegenüber gängigen NBR-Elastomeren (NBR ist die Abkürzung für „Nitrile Butadien Rubber“) und Fluor-Kautschuk-Elastomeren (FKM-Elastomere) gewünscht. Zusammenfassung der Erfindung The object of the invention is to provide a base oil and a lubricating fluid containing the base oil, the lubricating fluid being able to be used, among other things, as a transmission oil and/or as a hydraulic oil. The base oil should be such that it can absorb the additives necessary for the lubricating fluid and the additives in the base oil have the desired effect. According to one embodiment, the raw materials should be selected so that the lubricating fluids can also be used in the food processing industry. The selection of raw materials in the USA is regulated, for example, by the requirements of the US Food and Drug Administration (FDA). As a gear oil, the lubricant fluid should, according to one embodiment, meet the CLP standard DIN 51517-3 and, in particular, from viscosity class 220 (ISO VG 220) in the micropitting test according to FVA 54, have a micropitting resistance of the “high” rating level. In order to be used as hydraulic oil, low viscosity classes of the lubricating fluid must also meet DIN 51524-3 (HVLP). Good compatibility with common NBR elastomers (NBR is the abbreviation for “Nitrile Butadiene Rubber”) and fluorine rubber elastomers (FKM elastomers) is desired in all viscosity classes. Summary of the invention
Die Aufgabe wird gelöst durch den Gegenstand der unabhängigen Ansprüche. Vorteilhafte Ausgestaltungen sind Gegenstand der Unteransprüche oder nachfolgend beschrieben. The task is solved by the subject matter of the independent claims. Advantageous refinements are the subject of the subclaims or described below.
Das erfindungsgemäße Basisöl umfasst: The base oil according to the invention includes:
50-98 Gew.%, vorzugsweise 81 bis 96 Gew.%, Polyalphaolefine als Oligomere von C6- bis C14- alpha-Olefinen, insbesondere C8- bis C12- al- pha-Olefinen; 50-98% by weight, preferably 81 to 96% by weight, polyalphaolefins as oligomers of C6 to C14 alpha-olefins, in particular C8 to C12 alpha-olefins;
1 -25 Gew.%, vorzugsweise 2 bis 15 Gew.%, Polymerester erhältlich als Polymerisationsprodukt von einem oder mehreren alpha/beta-ungesät- tigten Dicarbonsäurediestern, wobei die Alkohol-Gruppen 3 bis 10 Kohlenstoffatome aufweisen, insbesondere 4 bis 8 Kohlenstoffatome, mit einem oder mehreren C4- bis C18- alpha-Olefinen, insbesondere C10- bis C16- alpha-Olefinen oder C12- bis C16- alpha-Olefinen; 1-25% by weight, preferably 2 to 15% by weight, of polymer esters obtainable as a polymerization product of one or more alpha/beta-unsaturated dicarboxylic acid diesters, the alcohol groups having 3 to 10 carbon atoms, in particular 4 to 8 carbon atoms one or more C4 to C18 alpha-olefins, in particular C10 to C16 alpha-olefins or C12 to C16 alpha-olefins;
1 -25 Gew.%, vorzugsweise 2 bis 4 Gew.%, Polyalkylenglykole erhältlich aus Alkylenoxiden, wobei die Alkylenoxide 1-25% by weight, preferably 2 to 4% by weight, polyalkylene glycols obtainable from alkylene oxides, the alkylene oxides
Buthylenoxid oder Butethylene oxide or
Propylenoxid und zumindest ein C4- bis C8- Alkylenoxide umfassen. Propylene oxide and at least one C4 to C8 alkylene oxides.
Nach einer anderen Ausgestaltung umfasst das Basisöl According to another embodiment, the base oil includes
81 - 96 Gew.% der obigen Polyalphaolefine; 81 - 96% by weight of the above polyalphaolefins;
2 - 15 Gew.% der obigen Polymerester; 2 - 15% by weight of the above polymer esters;
2 - 4 Gew.% der obigen Polyalkylenglykole. 2 - 4% by weight of the above polyalkylene glycols.
Nach einer anderen Ausgestaltung machen obige Polyalphaolefine, Polymerester und Polyalkylenglykole zusammen mehr als 90 Gew.%, insbesondere mehr als 95 Gew.% des Basisöls aus. Vorzugsweise addieren sich obige Polyalphaolefine, Polymerester und Polyalkylenglykole im Basisöl zu 100 Gew.%. Damit besteht das Basisöl aus obigen Komponenten. According to another embodiment, the above polyalphaolefins, polymer esters and polyalkylene glycols together make up more than 90% by weight, in particular more than 95% by weight, of the base oil. The above polyalphaolefins, polymer esters and polyalkylene glycols preferably add up to 100% by weight in the base oil. The base oil therefore consists of the above components.
Das Polyalphaolefin ist nach einer Ausführungsform ein Oligomer von einem 1-Oc- ten, 1 -Decen und/oder 1 -Dodecen, und insbesondere ein Oligomer von 1 -Octen oder 1 -Decen oder 1 -Octen und 1 -Decen. Der Polymerisationsgrad der Polyalphaolefine kann 3 bis 25 betragen. Auch unabhängig hiervon beträgt die Viskosität der Polyalphaolefine vorzugsweise von 4 bis 300 mm2/s bei 100°C (kinematische Viskosität bestimmt nach DIN EN ISO 3104). Die Polyalphaolefine können auch als hydrierte Produkte eingesetzt werden. According to one embodiment, the polyalphaolefin is an oligomer of a 1-octene, 1-decene and/or 1-dodecene, and in particular an oligomer of 1-octene or 1-decene or 1-octene and 1-decene. The degree of polymerization of the polyalphaolefins can be 3 to 25. Even independently of this, the viscosity of the polyalphaolefins is preferably from 4 to 300 mm 2 /s at 100 ° C (kinematic viscosity determined according to DIN EN ISO 3104). The polyalphaolefins can also be used as hydrogenated products.
Die Polymerester sind vorzugsweise Copolymere von Maleinsäure- und/oder Fumarsäure(voll)estern und einem oder mehreren C4- bis C18-alpha-Olefinen. Die Alkohol-Gruppen der Dicarbonsäurediester sind insbesondere lineare und/oder verzweigte Monoalkohole mit 3 bis 10 Kohlenstoffatomen, insbesondere 4 bis 8 Kohlenstoffatomen. Die Dicarbonsäuren des Dicarbonsäurediesters weisen vorzugsweise 4 bis 12 Kohlenstoffatome, insbesondere 4 bis 6 Kohlenstoffatome auf. Für die alpha-Olefine der Polymerester sind Kettenlängen von 10 bis 16 Kohlenstoffatomen, insbesondere 14 bis 16 Kohlenstoffatomen bevorzugt. Diese können linear und/oder verzweigt sein, vorzugsweise linear. Das Molverhältnis der alpha- Olefine zu den Dicarbonsäurediestern kann 1 ,5 zu 1 bis 1 zu 1 ,5, insbesondere 1 zu 0,9 bis 0,9 zu 1 betragen. Die Polymerester haben insbesondere ein mittleres Molekulargewicht von 1000 bis 5000 g/mol und insbesondere! 500 bis 2500 g/mol (jeweils als Zahlenmittel). The polymer esters are preferably copolymers of maleic acid and/or fumaric acid (full) esters and one or more C4 to C18 alpha-olefins. The alcohol groups of the dicarboxylic diesters are in particular linear and/or branched monoalcohols with 3 to 10 carbon atoms, in particular 4 to 8 carbon atoms. The dicarboxylic acids of the dicarboxylic diester preferably have 4 to 12 carbon atoms, in particular 4 to 6 carbon atoms. For the alpha-olefins of the polymer esters, chain lengths of 10 to 16 carbon atoms, in particular 14 to 16 carbon atoms, are preferred. These can be linear and/or branched, preferably linear. The molar ratio of the alpha-olefins to the dicarboxylic acid diesters can be 1.5 to 1 to 1 to 1.5, in particular 1 to 0.9 to 0.9 to 1. The polymer esters in particular have an average molecular weight of 1000 to 5000 g/mol and in particular! 500 to 2500 g/mol (each as a number average).
Das Molverhältnis der alpha-Olefine zu den Dicarbonsäurediestern kann 1 ,5 zu 1 bis 1 zu 1 ,5, insbesondere 1 zu 0,9 bis 0,9 zu 1 , betragen. The molar ratio of the alpha-olefins to the dicarboxylic acid diesters can be 1.5 to 1 to 1 to 1.5, in particular 1 to 0.9 to 0.9 to 1.
Die Polyalkylenglykole umfassen nach einer Ausgestaltung 30-70 mol% Propylenoxid und 70-30 mol% C4- bis C8- Alkylenoxide, insbesondere Butylenoxid, oder bestehen insbesondere aus diesen. Die Polyalkylenglykole sind vorzugsweise in den Polyalphaolefinen bzw. Polyalphaolefin-Gemischen, mit denen sie zusammen eingesetzt werden, bei Raumtemperatur löslich. According to one embodiment, the polyalkylene glycols comprise 30-70 mol% of propylene oxide and 70-30 mol% of C4 to C8 alkylene oxides, in particular butylene oxide, or in particular consist of these. The polyalkylene glycols are preferably soluble at room temperature in the polyalphaolefins or polyalphaolefin mixtures with which they are used together.
Die Schmierfluidzusammensetzung umfasst das Basisöl nach zumindest einem der vorhergehenden Ansprüche, und zumindest eines der folgenden AdditiveThe lubricating fluid composition comprises the base oil according to at least one of the preceding claims, and at least one of the following additives
- amin-umgesetztes Alkylphosphat und/oder - amine-reacted alkyl phosphate and/or
- Polyolmonoester. Die Schmierfluidzusammensetzung umfasst oder besteht vorzugsweise aus zumindest: - Polyol monoester. The lubricating fluid composition preferably comprises or consists of at least:
- 90 bis 98 Gew.% des Basisöls; - 90 to 98% by weight of the base oil;
- 0,01 bis 2 Gew.%, vorzugsweise 0,1 bis 0,3 Gew.%, des nachgenannten Friction-Modifiers, und/oder - 0.01 to 2% by weight, preferably 0.1 to 0.3% by weight, of the friction modifier mentioned below, and/or
0,01 bis 2 Gew.%, vorzugsweise 0,05 bis 0,6 Gew.%, des nachgenannten Verschleißschutzadditivs, bezogen auf das Basisöl; und 0.01 to 2% by weight, preferably 0.05 to 0.6% by weight, of the wear protection additive mentioned below, based on the base oil; and
- sonstige weitere Additive, insbesondere 0,1 bis 2 Gew.% der weiteren Additive. - other additional additives, in particular 0.1 to 2% by weight of the other additives.
Nach einer Ausgestaltung umfasst oder besteht die Schmierfluidzusammensetzung aus: According to one embodiment, the lubricating fluid composition comprises or consists of:
- 94 bis 98 Gew.% des Basisöls; - 94 to 98% by weight of the base oil;
- 0,01 bis 2 Gew.%, vorzugsweise 0,1 bis 0,3 Gew.%, des nachgenannten Friction-Modifiers, und/oder - 0.01 to 2% by weight, preferably 0.1 to 0.3% by weight, of the friction modifier mentioned below, and/or
0,01 bis 2 Gew.%, vorzugsweise 0,05 bis 0,6 Gew.%, des nachgenannten Verschleißschutzadditivs, bezogen auf das Basisöl; 0.01 to 2% by weight, preferably 0.05 to 0.6% by weight, of the wear protection additive mentioned below, based on the base oil;
- sonstige weitere Additive, insbesondere 0,1 bis 2 Gew.% der weiteren Additive. - other additional additives, in particular 0.1 to 2% by weight of the other additives.
Die Schmierfluidzusammensetzung umfasst das Basisöl und zumindest eines der folgenden Additive: The lubricating fluid composition includes the base oil and at least one of the following additives:
- ein amin-umgesetztes Alkylphosphat, insbesondere mono- oder di- C1- bis C12- Alkylphosphat, als Verschleißschutzadditiv, insbesondere 0,01 bis 2 Gew.%, vorzugsweise 0,1 bis 0,6 Gew.% und/oder - an amine-reacted alkyl phosphate, in particular mono- or di-C1- to C12-alkyl phosphate, as a wear protection additive, in particular 0.01 to 2% by weight, preferably 0.1 to 0.6% by weight and/or
- einen Polyolmonoester, insbesondere einen C12- bis C24- Fettsäureester von ggf. ethoxylierten Polyolen, insbesondere ggf. ethoxyliertes Sorbitan- mono-oleat, als Friction-Modifier insbesondere jeweils 0,01 bis 2 Gew.%, vorzugsweise 0,05 bis 0,3 Gew.%. - a polyol monoester, in particular a C12 to C24 fatty acid ester of optionally ethoxylated polyols, in particular optionally ethoxylated sorbitan mono-oleate, as a friction modifier, in particular 0.01 to 2% by weight, preferably 0.05 to 0, 3% by weight.
Das amin-umgesetzte Alkylphosphat ist vorzugsweise ein mono- oder di- C1- bis C12- Alkylphosphat umgesetzt mit zumindest C10- bis C18-Alkylaminen. Vorzugsweise erfolgt die Umsetzung so, dass das Alkylphosphat neutralisiert bzw. teilneutralisiert ist. Geeignete Beispiele sind Mono- und Diisooctylester der Phosphorsäure umgesetzt mit tert-Alkylaminen und C12- bis C14- primären Aminen (CAS Reg. No. 68187-67-7) oder Phosphorsäure-mono- und di-hexylester umgesetzt mit tetra-Methylnonylamin und C11- bis C14- Alkylaminen. Handelsprodukte sind z.B. Irgalube® 349 der BASF SE oder Additin® RC 3760 der LANXESS (CAS Reg. Nr. 80939-62-4). Das amin-umgesetzte Alkylphosphat ist ein Verschleißschutzadditiv. The amine-reacted alkyl phosphate is preferably a mono- or di-C1 to C12 alkyl phosphate reacted with at least C10 to C18 alkyl amines. The reaction is preferably carried out in such a way that the alkyl phosphate is neutralized or partially neutralized. Suitable examples are mono- and diisooctyl esters of phosphoric acid reacted with tert-alkylamines and C12 to C14 primary amines (CAS Reg. No. 68187-67-7) or mono- and di-hexyl phosphoric acid reacted with tetra-methylnonylamine and C11 - to C14 alkylamines. Commercial products include Irgalube® 349 from BASF SE or Additin® RC 3760 from LANXESS (CAS Reg. No. 80939-62-4). The amine-reacted alkyl phosphate is a wear protection additive.
Der Polyolmonoester ist vorzugsweise ein C12- bis C24- Fettsäureester von Polyolen wie Glycerin, Polyglycerin oder Sorbitan. Das Polylol kann auch ganz oder teilweise ethoxyliert vorliegen. Geeignete Beispiele sind Polysorbat 20, Polysorbat 40, Polysorbat 60, Polysorbat 120, Glycerylmonostearat, Glycerylmonooleat, Sorbitanmonolaurat, Sorbitanmonopalmitat, Sorbitanmonostearat, Sorbitanmonooleat oder Polyglyceryl-4-isostearat. The polyol monoester is preferably a C12 to C24 fatty acid ester of polyols such as glycerin, polyglycerin or sorbitan. The polylol can also be completely or partially ethoxylated. Suitable examples are polysorbate 20, polysorbate 40, polysorbate 60, polysorbate 120, glyceryl monostearate, glyceryl monooleate, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate or polyglyceryl-4-isostearate.
Die C12- bis C24- mono-Fettsäureester von ggf. teilweise ethoxylierten Polyolen wirken als Friction-Modifier. The C12 to C24 mono fatty acid esters of possibly partially ethoxylated polyols act as friction modifiers.
Das Basisöl in einer Schmierfluidzusammensetzung oder die Schmierfluidzusammensetzung können als Hydraulik- und Getriebeöl eingesetzt werden, insbesondere in der Lebensmittel verarbeitenden Industrie und/oder der Futtermittel verarbeitenden Industrie. The base oil in a lubricating fluid composition or the lubricating fluid composition can be used as a hydraulic and gear oil, particularly in the food processing industry and/or the feed processing industry.
Die Gew. %-Angaben beziehen sich jeweils auf die Gesamtzusammensetzung (wenn nicht ausdrücklich anders angegeben) und gelten jeweils unabhängig voneinander. The percentages by weight refer to the overall composition (unless expressly stated otherwise) and apply independently of one another.
Obige Polyalphaolefine, Polymerester und Polyalkylenglykole sind keine chemisch reinen Produkte und wenn diese im Singular genannt sind, so meint dies auch ein Stoffgemisch aus unterschiedlichen Molekülen, die jeweils einzeln der angegebenen Spezifikation entsprechen. The above polyalphaolefins, polymer esters and polyalkylene glycols are not chemically pure products and if they are mentioned in the singular, this also means a mixture of different molecules, each of which individually corresponds to the specified specification.
Detaillierte Beschreibung der Erfindung Detailed description of the invention
Hydraulik- und Getriebeöle bestehen aus einem Basisöl sowie Additiven, die zur Steigerung der Lebensdauer und Leistungsfähigkeit des Schmierfluids zugesetzt werden. Als Basisöl wird in der vorliegenden Erfindung eine Mischung aus obigen Polyalphaolefinen, Polymerestern und Polyalkylenglykolen eingesetzt. Bei den Polyalphaolefinen handelt es sich um Oligomere von insbesondere linearen 1 -Alkenen, insbesondere 1 -Octen, 1 -Decen und/oder 1-Dodecen, die z.B. unter Verwendung von Lewis-Säure-Katalysatoren (z.B. US 6824671 B2) oder Metal- locen-Katalysatoren (mPAOs, US 9365663 B2, US 9701595 B2) hergestellt werden und deren kinematische Viskosität bei 100°C (kV 100) zwischen 2 und 300 mm2/s liegen kann Das Polyalphaolefin kann z.B. ein Oligomer aus 50 bis 80 Gew.-% 1 - Decen und 50 bis 20 Gew.-% 1 -Dodecen sein. Hydraulic and transmission oils consist of a base oil and additives that are added to increase the service life and performance of the lubricating fluid. A mixture of the above polyalphaolefins, polymer esters and polyalkylene glycols is used as the base oil in the present invention. The polyalphaolefins are oligomers of in particular linear 1-alkenes, in particular 1-octene, 1-decene and/or 1-dodecene, which are produced, for example, using Lewis acid catalysts (e.g. US 6824671 B2) or metallocene -Catalysts (mPAOs, US 9365663 B2, US 9701595 B2) are produced and whose kinematic viscosity at 100 ° C (kV 100) can be between 2 and 300 mm 2 /s. The polyalphaolefin can, for example, be an oligomer of 50 to 80 wt. % 1 - decene and 50 to 20% by weight 1 -dodecene.
Nach einer Ausgestaltung sind die Polyalphaolefine eine Mischung von a1 ) Oligo- meren von 1 - Decen und b1 ) Oligomeren von 1 -Octen oder eine Mischung von a2) Oligomeren von 1 -Dodecen und b2) Oligomeren von 1 -Octen und/oder 1 -Decen.According to one embodiment, the polyalphaolefins are a mixture of a1) oligomers of 1-decene and b1) oligomers of 1-octene or a mixture of a2) oligomers of 1-dodecene and b2) oligomers of 1-octene and/or 1- Decen.
Diese Mischungen können wie folgt näher charakterisiert werden: 5 - 95 Gew.% von Oligomeren a1 ) oder a2) und 5 bis 95 Gew.% von Oligomeren b1 ) oder b2). Die Polyalphaolefine können durch Metallocen-Katalyse hergestellt sein. These mixtures can be characterized in more detail as follows: 5 to 95% by weight of oligomers a1) or a2) and 5 to 95% by weight of oligomers b1) or b2). The polyalphaolefins can be produced by metallocene catalysis.
Oft ist es vorteilhaft, Polyalphaolefine unterschiedlicher Viskosität zu mischen z.B. Oligomeren mit einer Viskosität von 4 bis 100 mm2/s bei 100°C und Oligomeren mit einer Viskosität von 50 bis 300 mm2/s bei 100°C. It is often advantageous to mix polyalphaolefins of different viscosities, for example oligomers with a viscosity of 4 to 100 mm 2 /s at 100°C and oligomers with a viscosity of 50 to 300 mm 2 /s at 100°C.
Als Polymerester werden aus C,C-Verknüpfung hervorgegangene Polymere bezeichnet, die Seitenketten mit Estergruppen beinhalten. Darunter fallen vorliegend insbesondere die Copolymere von alpha, beta ungesättigten Dicarbonsäureestern, wie der Malein- oder Fumarsäureester mit insbesondere unverzweigten alpha-Ole- finen. Polymerester und deren Herstellung werden z.B. in der DE 3223694 C2 und US 5435928 A beschrieben. Polymer esters are polymers resulting from C,C linkages that contain side chains with ester groups. In the present case, this includes in particular the copolymers of alpha, beta-unsaturated dicarboxylic acid esters, such as maleic or fumaric acid esters with, in particular, unbranched alpha-olefins. Polymer esters and their production are described, for example, in DE 3223694 C2 and US 5435928 A.
Die Polyalkylenglykole sind die polymeren Reaktionsprodukte von Wasser und/oder eines ein- oder zweiwertigen Start-Alkohols mit 1 ,2-Epoxiden wie Ethylenoxid, Propylenoxid und/oder Butylenoxid, wobei mindestens umfasst sind Propylenoxid und zumindest ein C4- bis C8- Alkylenoxid. Die Polyalkylenglykole liegen z.B. als Homopolymere von Butylenoxid oder als Copolymere von Propylenoxid und Butylenoxid vor. Copolymere, die aus 30-70% Propylenoxid und 70-30% Butylenoxid bestehen, sind vorliegend bevorzugt eingesetzt. Die Polyalkylenglykole weisen insbesondere eine oder zwei endständige Hydroxy-Gruppen auf. The polyalkylene glycols are the polymeric reaction products of water and/or a mono- or dihydric starting alcohol with 1,2-epoxides such as ethylene oxide, propylene oxide and/or butylene oxide, which include at least propylene oxide and at least one C4 to C8 alkylene oxide. The polyalkylene glycols are present, for example, as homopolymers of butylene oxide or as copolymers of propylene oxide and butylene oxide. Copolymers which consist of 30-70% propylene oxide and 70-30% butylene oxide are preferably used here. The polyalkylene glycols in particular have one or two terminal hydroxy groups.
Für die Elastomerverträglichkeit ist ein Zusatz eines Quellungsmittels in der Schmierfluidzusammensetzung, typischerweise eines Esters, wünschenswert. Gleichermaßen führt ein zu hoher Gehalt an Quellungsmittel zu einer zu starken Quellung, was ebenfalls zu Undichtigkeit führen kann. In Industriegetrieben kommen verschiedene NBR- und FKM-Elastomertypen zum Einsatz, wobei besonders die NBR-Typen stark auf die Zusammensetzung, d.h. die Polarität der Basisölmischung ansprechen. For elastomer compatibility, addition of a swelling agent in the lubricating fluid composition, typically an ester, is desirable. Likewise, too high a swelling agent content leads to excessive swelling, which can also lead to leaks. Various types of NBR and FKM elastomers are used in industrial transmissions, with the NBR types in particular responding strongly to the composition, ie the polarity, of the base oil mixture.
Beispielhaft als Quellmittel genannt seien als Ester Monoester, Diester, Polyolester, und Komplexester, z.B. von C1- bis C18- Alkoholen mit einer C2- bis C18- Carbonsäure. Zu den hier in Frage kommenden Mono- und Diestern zählen die Ester von linearen oder verzweigten einwertigen Alkoholen wie Methanol, Ethanol, Isopropanol, Isobutanol, 2-Ethylhexanol, 3,5,5-Trimethylhexanol oder 7-Methyloctanol mit typischen Fettsäuren oder Dicarbonsäuren, wie etwa Caprylsäure, Caprinsäure, Laurinsäure, Myristinsäure, Palmitinsäure, Stearinsäure, Isostearinsäure, Ölsäure, Linolsäure, Linolensäure, Adipinsäure, Suberinsäure, Sebacinsäure oder Phthalsäure. Zu den Polylolestern zählen die formalen Reaktionsprodukte von linearen oder verzweigten Carbonsäuren mit mehrwertigen Alkoholen wie Glycerin, Neopentylglycol, Trimethylolpropan, Pentaerythritol oder Dipentaerythritol. Der Anteil des Quellmittels wird so gewählt, dass sich eine Volumenausdehnung des Elastomers von nicht mehr als 10% ergibt. In der Regel bedeutet dies, dass das Quellmittel in einem Anteil von 0,5 bis 6 Gew.%, insbesondere 1 bis 4 Gew%, in der Schmierfluidzusammensetzung enthalten ist. Ein Beispiel ist Di(2-Ethylhexyl)-sebacat. Allerdings wurde festgestellt, dass das eingesetzte Polyalkylenglykol auch als Quellmittel wirkt. Examples of swelling agents that may be mentioned as esters include monoesters, diesters, polyol esters, and complex esters, for example of C1 to C18 alcohols with a C2 to C18 carboxylic acid. The mono- and diesters in question here include the esters of linear or branched monohydric alcohols such as methanol, ethanol, isopropanol, isobutanol, 2-ethylhexanol, 3,5,5-trimethylhexanol or 7-methyloctanol with typical fatty acids or dicarboxylic acids, such as such as caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, oleic acid, linoleic acid, linolenic acid, adipic acid, suberic acid, sebacic acid or phthalic acid. The polyol esters include the formal reaction products of linear or branched carboxylic acids with polyhydric alcohols such as glycerol, neopentyl glycol, trimethylolpropane, pentaerythritol or dipentaerythritol. The proportion of swelling agent is chosen so that the volume expansion of the elastomer does not exceed 10%. As a rule, this means that the swelling agent is contained in the lubricating fluid composition in a proportion of 0.5 to 6% by weight, in particular 1 to 4% by weight. An example is di(2-ethylhexyl) sebacate. However, it was found that the polyalkylene glycol used also acts as a swelling agent.
Weitere mögliche Zusatzstoffe für die Schmierfluidzusammensetzung sind Antioxidationsmittel, Verschleißschutzmittel, Korrosionsschutzmittel, Detergentien, Farbstoffe, Reibungsminderer, Viskositätsverbesserer, Hochdruckadditive, Metalldeaktivatoren und nanoskalige Feststoffe. Beispielhaft genannt seien: Other possible additives for the lubricating fluid composition are antioxidants, anti-wear agents, anti-corrosion agents, detergents, dyes, friction reducers, viscosity improvers, high-pressure additives, metal deactivators and nanoscale solids. Examples include:
• primäre Antioxidationsmittel wie Amin-Verbindungen (z.B. Alkylamine oder 1- Phenylaminonaphthalin), aromatische Amine, wie z.B. Phenylnaphtylamine oder Diphenylamine oder polymere Hydroxychinoline (z. B. TMQ), Phenol-Verbindungen (z.B. 2.6-Di-tert-butyl-4-methylphenol), organische Dithiocarbamate oder Dithiophosphate; • primary antioxidants such as amine compounds (e.g. alkylamines or 1-phenylamino-naphthalene), aromatic amines such as phenylnaphtylamines or diphenylamines or polymeric hydroxyquinolines (e.g. TMQ), phenolic compounds (e.g. 2.6-di-tert-butyl-4- methylphenol), organic dithiocarbamates or dithiophosphates;
• sekundäre Antioxidationsmittel wie Phosphite, z.B. Tris(2,4-ditert-butylphenylp- hosphit) oder Bis(2,4-ditert-butylphenyl)-pentaerythritoldiphosphit oder Thioether (z.B. Kresolthioether); • secondary antioxidants such as phosphites, e.g. tris(2,4-ditert-butylphenyl phosphite) or bis(2,4-ditert-butylphenyl) pentaerythritol diphosphite or thioethers (e.g. cresol thioether);
• Hochdruckadditive und/oder Verschleißschutzadditive wie organische Schwefelverbindungen wie z.B. Polysulfide oder geschwefelte Olefine, Thiophosphate (z.B. Triphenylthiophosphat) und Dithiophosphate, Phosphite und Phosphonate (z.B. Di-n-Octylphosphonat), Phosphate (z.B. substituierte Triphenylphosphate oder aminneutralisierte Alkylphosphate), anorganische oder organische Borverbindungen, Thiocarbamate und Dithiocarbamate (z.B. Methylen-bis(dibutyldithi- ocarbamat)); • High pressure additives and/or wear protection additives such as organic sulfur compounds such as polysulfides or sulfurized olefins, thiophosphates (e.g. triphenylthiophosphate) and dithiophosphates, phosphites and phosphonates (e.g. di-n-octyl phosphonate), phosphates (e.g. substituted triphenyl phosphates). or amine-neutralized alkyl phosphates), inorganic or organic boron compounds, thiocarbamates and dithiocarbamates (e.g. methylene bis(dibutyldithiocarbamate));
• Korrosionsschutzmittel wie Sulfonate, wie z.B. Petroleumsulfonat, Dinonylnaph- thalinsulfonat; neutrale oder überbasische Calciumsulfonate, Magnesiumsulfonate, Natriumsulfonate, Calcium- und Natrium-Naphthalinsulfonate, Sulfonsäureester, Aminphosphate; N-Methyl-N-(1-oxo-9- octadecenyl)glycin; • Corrosion inhibitors such as sulfonates, such as petroleum sulfonate, dinonyl naphthalene sulfonate; neutral or overbased calcium sulfonates, magnesium sulfonates, sodium sulfonates, calcium and sodium naphthalene sulfonates, sulfonic acid esters, amine phosphates; N-methyl-N-(1-oxo-9-octadecenyl)glycine;
• Metalldeaktivatoren wie Benzotriazole, wie z.B. Methylbenzotriazoldialkylamin, sterisch gehinderte Phenole, Natriumnitrit; • Metal deactivators such as benzotriazoles, such as methylbenzotriazole dialkylamine, sterically hindered phenols, sodium nitrite;
• Viskositätsverbesserer wie z.B. Polymethacrylat, Polyisobutylen, Polystyrole;• Viscosity improvers such as polymethacrylate, polyisobutylene, polystyrenes;
• Reibungsminderer teilweise mit Verschleißschutzeigenschaften wie organische Säuren (z.B. Isostearinsäure), Fettsäureester von ggf. teilweise ethoxylierten Polyolen wie Glycerin oder Sorbitan, Partialglyceride, tierische oder pflanzliche Öle, Dialkylhydrogenphosphonate, Carbonsäureamide wie z.B. Oleylamide, organische Verbindungen auf Polyether- und Amidbasis, z.B. Alkylpolyethylengly- koltetradecylenglykolether, Alkylsuccinate, PIBSI (Polyisobutylenbernsteinsäu- reimid) oder PIBSA (Polyisobutylenbernsteinsäureanhydrid). • Friction reducers, some with anti-wear properties such as organic acids (e.g. isostearic acid), fatty acid esters of possibly partially ethoxylated polyols such as glycerol or sorbitan, partial glycerides, animal or vegetable oils, dialkyl hydrogen phosphonates, carboxamides such as oleylamides, organic compounds based on polyethers and amides, e.g. alkyl polyethylene glycol. col tetradecylene glycol ether, alkyl succinates, PIBSI (polyisobutylene succinic acid imide) or PIBSA (polyisobutylene succinic anhydride).
• Feststoffe: In Getriebeölen ist die Verwendung von Partikeln (Bornitrid, Siliciumdioxid, Schichtsilikate wie beispielsweise Bentonite, Carbon Nanotubes) möglich, um bestimmte Eigenschaften zu erzielen. Um keine negativen Effekte hinsichtlich der tribologischen Performance zu erzeugen, werden insbesondere sehr kleine Partikel (sogenannte Nanopartikel mit Partikelgrößen kleiner 500 nm, bevorzugt kleiner 100 nm, besonders bevorzugt kleiner 50 nm) verwendet. • Solids: The use of particles (boron nitride, silicon dioxide, layered silicates such as bentonite, carbon nanotubes) is possible in gear oils to achieve certain properties. In order not to produce negative effects with regard to tribological performance, very small particles (so-called nanoparticles with particle sizes of less than 500 nm, preferably less than 100 nm, particularly preferably less than 50 nm) are used.
Zur Herstellung der erfindungsgemäßen Schmierfluidzusammensetzung wird z.B. ein Teil der Basisölmenge (z.B. 5 bis 25 Gew.%) zusammen mit den Additiven, die insbesondere öllöslich sind, aber unter Normalbedingungen in der Regel als Feststoff vorliegen, vorgelegt und unter kontinuierlichem Rühren auf 90 bis 110°C erhitzt, um ein Lösen dieser Additive im Basisöl zu gewährleisten. Durch Zugabe einer weiteren Portion des Basisöls wird die Temperatur auf kleiner 60°C gesenkt. Danach werden flüssige und optional ölunlösliche Additive und Feststoffe sowie die verbleibende Basisölmenge zugegeben und durch weiteres Rühren so lange gemischt, bis eine vollständige Homogenität der Mischung erreicht ist. To produce the lubricating fluid composition according to the invention, for example, a portion of the amount of base oil (e.g. 5 to 25% by weight) is introduced together with the additives, which are particularly oil-soluble but are generally present as a solid under normal conditions, and are heated to 90 to 110° with continuous stirring C heated to ensure that these additives dissolve in the base oil. By adding another portion of the base oil, the temperature is reduced to less than 60°C. Liquid and optionally oil-insoluble additives and solids as well as the remaining amount of base oil are then added and mixed by further stirring until the mixture is completely homogeneous.
Die erfindungsgemäße Schmierfluidzusammensetzung ist besonders geeignet zur Verwendung in Industriegetrieben (Stirnrad-, Schrägstirnrad-, Kegelrad-, Hypoid- und Planetengetriebe) und Hydrauliksystemen, insbesondere solchen, die in der Lebensmittel- oder Futtermittelindustrie eingesetzt werden. Ein Getriebe ist ein Maschinenelement mit dem Bewegungsgrößen (z.B. Änderung einer Kraft, eines Drehmoments) geändert werden können. Abhängig von der Bauart der Getriebe werden diese von einem Gehäuse umgeben und mit einem Schmierfluid geschmiert. Um das Auslaufen des Schmierfluids zu verhindern, werden Dichtungen verwendet. Die Dichtmaterialien müssen neben speziellen konstruktiven Eigenschaften auch chemisch gegen die verwendeten Schmierfluide stabil sein. The lubricating fluid composition according to the invention is particularly suitable for use in industrial gears (spur gears, helical gears, bevel gears, hypoid and planetary gears) and hydraulic systems, especially those used in the food or feed industry. A gearbox is a machine element with which movement variables (e.g. change in force, torque) can be changed. Depending on the design of the gearbox, it is surrounded by a housing and lubricated with a lubricating fluid. Seals are used to prevent leakage of the lubricating fluid. In addition to special design properties, the sealing materials must also be chemically stable against the lubricating fluids used.
Damit spielt bei der Schmierstoffentwicklung die Elastomerverträglichkeit eine wichtige Rolle. Selbiges gilt auch für die Beständigkeit von Hydraulikdichtungen, die zur Abdichtung der mit Hydraulikölen gefüllten hydraulischen Systeme eingesetzt werden. Elastomer compatibility therefore plays an important role in lubricant development. The same also applies to the durability of hydraulic seals that are used to seal hydraulic systems filled with hydraulic oils.
Im Rahmen der vorliegenden Erfindung wurde ein Schmierfluid zur Verwendung als Getriebe- und Hydrauliköl entwickelt, welches die Anforderungen aus DIN 51517-3 (genauer: die in DIN ISO 1817 beschriebenen Prüfungen zur relativen Volumenänderung, Änderung der Shore-A-Härte, Zugfestigkeit und Bruchdehnung) sowie die dynamische Elastomerverträglichkeitsprüfung (Freudenberg Prüfvorschrift FS PLM 111 0008) erfüllt. As part of the present invention, a lubricating fluid was developed for use as a transmission and hydraulic oil which meets the requirements of DIN 51517-3 (more precisely: the tests for relative volume change, change in Shore A hardness, tensile strength and elongation at break described in DIN ISO 1817). ) as well as the dynamic elastomer compatibility test (Freudenberg test specification FS PLM 111 0008).
Versuchsbeispiele: Experimental examples:
Herstellung: Production:
Ein Teil der Basisölmenge (5-25%), hier die polaren Ölkomponenten nämlich Ester und Polyalkylenglykol, werden zusammen mit den bei Raumtemperatur festen Additiven vorgelegt und unter kontinuierlichem Rühren auf 90 bis 110°C erhitzt, bis eine klare Lösung vorliegt. Durch Zugabe der verbleibenden (nicht erwärmten) Basisölmenge wird die Temperatur auf kleiner 60°C gesenkt. Danach werden die flüssigen Additive zugegeben und durch weiteres Rühren ca. 15 min gemischt, bis eine vollständige Homogenität der Mischung erreicht ist. Bei weiterer Abkühlung auf Temperaturen kleiner 40°C kann das Öl abgefüllt werden. Part of the base oil quantity (5-25%), here the polar oil components namely ester and polyalkylene glycol, are introduced together with the additives that are solid at room temperature and heated to 90 to 110 ° C with continuous stirring until a clear solution is obtained. By adding the remaining (not heated) amount of base oil, the temperature is reduced to less than 60°C. The liquid additives are then added and mixed by further stirring for approx. 15 minutes until the mixture is completely homogeneous. When it cools down further to temperatures below 40°C, the oil can be bottled.
Neben den aufgeführten Basisölkomponenten enthalten die Formulierungen jeweils ein Additivpaket. In addition to the base oil components listed, the formulations each contain an additive package.
Folgende Stoffe wurden eingesetzt: PAO 6 Polyalphaolefin: Spectrasyn 6, ExxonMobil Chemical; Syn- fluid PAO 6 cSt, Chevron Phillips Chemical; Durasyn 166, Ineos Oligomers mPAO 150 Polyalphaolefin, metallocen katalysiert: Spectrasyn Elite 150, ExxonMobil Chemical; Synfluid mPAO 150 cSt, Chevron Phillips Chemical The following substances were used: PAO 6 polyalphaolefin: Spectrasyn 6, ExxonMobil Chemical; Syn-fluid PAO 6 cSt, Chevron Phillips Chemical; Durasyn 166, Ineos Oligomers mPAO 150 Polyalphaolefin, metallocene catalyzed: Spectrasyn Elite 150, ExxonMobil Chemical; Synfluid mPAO 150 cSt, Chevron Phillips Chemical
Di(2-Ethylhexyl)-se- Priolube 1856, Croda; Nycobase 20307 FG, Nyco; Lubricit bacat DOS, Zschimmer&Schwarz Di(2-Ethylhexyl)-se-Priolube 1856, Croda; Nycobase 20307 FG, Nyco; Lubricit bacat DOS, Zschimmer&Schwarz
Polymerester Ketjenlube 240, Italmatch Polymer ester Ketjenlube 240, Italmatch
Polyalkylenglycol UCON OSP-32, DOW Polyalkylene glycol UCON OSP-32, DOW
Verschleißschutzadditiv amin-neutralisiertes Alkylphosphat, Irgalube 349, BASF SEWear protection additive amine-neutralized alkyl phosphate, Irgalube 349, BASF SE
-Additiv (AW-Additiv) -Additive (AW additive)
Additivpaket Triphenylphosphorothionat, phenolisches Antioxidans, amini- sches Antioxidans, Sorbitanmonooleat, N-Methyl-N-(1-oxo- 9- octadecenyl)glycin, Polydimethylsiloxan und Benzotriazol- Derivat, wobei das Sorbitanmonooleat der eingesetzte Friction-Modifier ist. Additive package triphenylphosphorothionate, phenolic antioxidant, aminic antioxidant, sorbitan monooleate, N-methyl-N-(1-oxo-9-octadecenyl)glycine, polydimethylsiloxane and benzotriazole derivative, where the sorbitan monooleate is the friction modifier used.
Tabelle 1 Folgende Methoden wurden in den Tabellen 1 und 2 angewandt: kV 40 [mm2/s] Kinematische Viskosität bei 40°C bestimmt nach DINTable 1 The following methods were used in Tables 1 and 2: kV 40 [mm 2 /s] Kinematic viscosity at 40 ° C determined according to DIN
EN ISO 3104 EN ISO 3104
VI Viskositätsindex nach DIN ISO 2909 VI viscosity index according to DIN ISO 2909
LAV Luftabscheidevermögen bei 75°C bestimmt nach DINLAV air separation capacity at 75°C determined according to DIN
ISO 9120 ISO 9120
Elastomerverträglichkeit nach DIN ISO 1817, 168h bei 100°C für 72 NBR 902 Korrosionsschutz gegenüber Stahlfingertest nach DIN ISO 7120-B Stahl, synth. Meerwasser FZG A/8,3/90, SKS erreichte Schadenskraftstufe im FZG-Test A/8,3/90 nach DIN ISO 14635-1 Elastomer compatibility according to DIN ISO 1817, 168h at 100°C for 72 NBR 902 Corrosion protection against steel finger test according to DIN ISO 7120-B Steel, synthetic seawater FZG A/8.3/90, SKS achieved damage force level in the FZG test A/8.3 /90 according to DIN ISO 14635-1
FE8, mw50 / mk50 [mg] berechnete Verschleißwerte der Wälzkörper / des Käfigs (50% Verschleißwahrscheinlichkeit) im FE8-Test (D-7, 5/80-80) nach DIN 51819-3 FE8, mw50 / mk50 [mg] calculated wear values of the rolling elements / cage (50% probability of wear) in the FE8 test (D-7, 5/80-80) according to DIN 51819-3
Micropitting, Profilabw. [pm] FVA 54, Profilabweichung Nach LS 9 Micropitting, erreichte SchaFVA 54, erreichte Schadenskraftstufe (SKS), Bewerdenskraftstufe, Bewertung tung GFT = Graufleckentragfähigkeit high = hoch Micropitting, profile deviation [pm] FVA 54, profile deviation After LS 9 micropitting, achieved SchaFVA 54, achieved damage force level (SKS), damage force level, evaluation GFT = micropitting capacity high = high
Die verwendeten Polymerester und das Polyalkylenglycol sind sehr gut geeignete Zusätze zu dem PAO-ÖI, da sie in der Lage sind, den hohen Viskositätsindex aufrecht zu erhalten. Ein höherer Viskositätsindex bedeutet eine höhere Schmierfilmdicke bei Betriebstemperatur, was zu einem besseren Verschleißschutz beiträgt. The polymer esters and the polyalkylene glycol used are very suitable additives to the PAO oil because they are able to maintain the high viscosity index. A higher viscosity index means a higher lubricant film thickness at operating temperature, which contributes to better wear protection.
Eine rein PAO-basierte Formulierung (Versuch 1 ) bietet keine hinreichende Elastomerverträglichkeit. NBR-Elastomere schrumpfen und können zu Undichtigkeiten führen. Formulierungen, die entweder Polyalkylenglykol (Versuch 2) oder Ester (Versuch 3) enthalten, zeigen nur leichte Volumenverluste. Das beste Ergebnis wird mit einer Formulierung erzielt, die neben POA sowohl Ester als auch Polyalkylenglycol (PAG) enthält (Versuch 4). Weiterhin kann mit der rein PAO-basierten Formulierung trotz gleicher Additivierung der Korrosionsschutz gegenüber Salzwasser nicht gewährleistet werden. A purely PAO-based formulation (Experiment 1) does not offer sufficient elastomer compatibility. NBR elastomers shrink and can lead to leaks. Formulations that contain either polyalkylene glycol (Experiment 2) or esters (Experiment 3) show only slight volume losses. The best result is achieved with a formulation that, in addition to POA, contains both esters and polyalkylene glycol (PAG) (Experiment 4). Furthermore, the purely PAO-based formulation cannot guarantee corrosion protection against salt water despite the same additives.
Gegenüber der esterhaltigen aber Polyalkylenglykol-freien Version (Versuch 3) wird das Luftabscheidevermögen in Versuch 4 nicht verbessert. Tabelle 2 Compared to the ester-containing but polyalkylene glycol-free version (test 3), the air separation capacity in test 4 is not improved. Table 2
Versuchsreihe 2 zeigt, dass unter den Additiven der Gehalt an aminneutralisierten Alkylphosphaten einen entscheidenden Anteil am Bestehen oder Nichtbestehen der wichtigen mechanisch-dynamischen Prüfungen hat. Bei einem niedrigen Gehalt (Versuch 5) kann auch ohne Zusatz von Polyalkylengykol eine hohe Graufleckentragfähigkeit erreicht werden. Dafür kann im FZG-Test nur Schadenskraftstufe 11 erreicht werden. Mit höherem Gehalt an Aminphosphaten und im Beisein von Polyalkylenglykol (Versuch 6) wird im FZG-Test Schadenskraftstufe größer 12 erreicht, aber die Graufleckentragfähigkeit ist unzureichend. Der in Versuch 4 reduzierte Aminphosphat-Gehalt kann durch das öllösliche Polyalkylenglykol ausgeglichen werden, ohne negative Effekte im Micropitting-Test aufzuweisen. Test series 2 shows that the content of amine-neutralized alkyl phosphates among the additives plays a decisive role in the passing or failing of the important mechanical-dynamic tests. At a low content (Experiment 5), a high gray stain resistance can be achieved even without the addition of polyalkylene glycol. However, damage power level 11 can only be achieved in the FZG test. With a higher content of amine phosphates and in the presence of polyalkylene glycol (test 6), damage force level greater than 12 is achieved in the FZG test, but the micropitting capacity is inadequate. The amine phosphate content reduced in experiment 4 can be compensated for by the oil-soluble polyalkylene glycol without having negative effects in the micropitting test.
Die hier beschriebene Basisölmischung unterstützt Korrosionsschutzeigenschaften und Elastomerverträglichkeit des Schmierstoffs und gestattet eine für „food grade“- Schmierstoffe geeignete und ausgewogene Additivierung, die den zum Teil gegensätzlichen Anforderungen gerecht wird. The base oil mixture described here supports the anti-corrosion properties and elastomer compatibility of the lubricant and allows for a balanced additive formulation that is suitable for “food grade” lubricants and meets the sometimes conflicting requirements.

Claims

Patentansprüche Patent claims
1 . Basisöl umfassend 1 . Comprehensive base oil
50 - 98 Gew.% Polyalphaolefine als Oligomere von C6- bis C14- alpha-Olefinen;50 - 98% by weight of polyalphaolefins as oligomers of C6 to C14 alpha-olefins;
1 - 25 Gew.% Polymerester als Polymerisationsprodukt von einem oder mehreren alpha/beta-ungesättigten Dicarbonsäure- diestern, wobei die Alkohol-Gruppen 3 bis 10 Kohlenstoffatome aufweisen; und 1 - 25% by weight of polymer ester as a polymerization product of one or more alpha/beta-unsaturated dicarboxylic acid diesters, the alcohol groups having 3 to 10 carbon atoms; and
C4- bis C18- alpha-Olefinen; C4 to C18 alpha-olefins;
1 - 25 Gew.% Polyalkylenglykole erhältlich aus Alkylenoxiden, wobei die Alkylenoxide Butylenoxid oder 1 - 25% by weight of polyalkylene glycols obtainable from alkylene oxides, the alkylene oxides being butylene oxide or
Propylenoxid und zumindest ein C4- bis C8- Alkylenoxid umfassen. Propylene oxide and at least one C4 to C8 alkylene oxide.
2. Das Basisöl nach Anspruch 1 umfassend 2. The base oil according to claim 1 comprising
81 - 96 Gew.% der Polyalphaolefine; 81 - 96% by weight of the polyalphaolefins;
2 - 15 Gew.% der Polymerester; 2 - 15% by weight of the polymer esters;
2 - 4 Gew.% der Polyalkylenglykole. 2 - 4% by weight of the polyalkylene glycols.
3. Das Basisöl nach Anspruch 1 oder 2, wobei die Polyalphaolefine, Polymerester und Polyalkylenglykole zusammen mehr als 90 Gew.%, insbesondere mehr als 95 Gew.%, des Basisöls ausmachen und vorzugsweise sich die Polyalphaolefine, die Polymerester und die Polyalkylenglykole zu 100 Gew.% im Basisöl addieren. 3. The base oil according to claim 1 or 2, wherein the polyalphaolefins, polymer esters and polyalkylene glycols together make up more than 90% by weight, in particular more than 95% by weight, of the base oil and preferably the polyalphaolefins, the polymer esters and the polyalkylene glycols make up 100% by weight Add .% in the base oil.
4. Das Basisöl nach zumindest einem der vorhergehenden Ansprüche, wobei die Alkohol-Gruppen der Dicarbonsäurediester lineare und/oder verzweigte Monoalkohole mit 3 bis 10 Kohlenstoffatomen, insbesondere 4 bis 8 Kohlenstoffatomen, sind. 4. The base oil according to at least one of the preceding claims, wherein the alcohol groups of the dicarboxylic diesters are linear and / or branched monoalcohols with 3 to 10 carbon atoms, in particular 4 to 8 carbon atoms.
5. Das Basisöl nach zumindest einem der vorhergehenden Ansprüche, wobei die Dicarbonsäure des Dicarbonsäurediesters 4 bis 12 Kohlenstoffatome, insbesondere 4 bis 6 Kohlenstoffatome aufweist. 5. The base oil according to at least one of the preceding claims, wherein the dicarboxylic acid of the dicarboxylic diester has 4 to 12 carbon atoms, in particular 4 to 6 carbon atoms.
6. Das Basisöl nach zumindest einem der vorhergehenden Ansprüche, wobei die alpha-Olefine der Polymerester 10 bis 16 Kohlenstoffatome, insbesondere 14 bis 16 Kohlenstoffatome, aufweisen. 6. The base oil according to at least one of the preceding claims, wherein the alpha-olefins of the polymer esters have 10 to 16 carbon atoms, in particular 14 to 16 carbon atoms.
7. Das Basisöl nach zumindest einem der vorhergehenden Ansprüche, wobei der Dicarbonsäurediester ein Maleinsäurediester und/oder ein Fumarsäurediester ist. 7. The base oil according to at least one of the preceding claims, wherein the dicarboxylic diester is a maleic diester and / or a fumaric diester.
8. Das Basisöl nach zumindest einem der vorhergehenden Ansprüche, wobei das Molverhältnis der alpha-Olefine zu den Dicarbonsäurediestern 1 ,5 zu 1 bis 1 zu 1 ,5, insbesondere 1 zu 0,9 bis 0,9 zu 1 , beträgt. 8. The base oil according to at least one of the preceding claims, wherein the molar ratio of the alpha-olefins to the dicarboxylic diesters is 1.5 to 1 to 1 to 1.5, in particular 1 to 0.9 to 0.9 to 1.
9. Das Basisöl nach zumindest einem der vorhergehenden Ansprüche, wobei der Polymerester ein mittleres Molekulargewicht von 1000 bis 5000 g/mol, insbesondere 1500 bis 2500 g/mol, jeweils als Zahlenmittel aufweist. 9. The base oil according to at least one of the preceding claims, wherein the polymer ester has an average molecular weight of 1000 to 5000 g/mol, in particular 1500 to 2500 g/mol, in each case as a number average.
10. Das Basisöl nach zumindest einem der vorhergehenden Ansprüche, wobei das oder die Polyalphaolefine durch eines oder mehrere der folgenden Eigenschaften gekennzeichnet sind: a) die Polyalphaolefine sind Oligomere von 1-Octen, 1-Decen und/oder 1-Dode- cen; b) der Polymerisationsgrad der Polyalphaolefine beträgt 3 bis 25; c) die Polyalphaolefine weisen eine Viskosität von 4 bis 300 mm2/s bei 100°C auf; d) das Polyalphaolefin ist ein hydriertes Oligomer; e) das Polyalphaolefin ein Oligomer aus 50 bis 80 Gew.-% 1-Decen und 50 bis 20 Gew.-% 1-Dodecen ist; f) das Polyalphaolefin ist eine Mischung von Oligomeren, wobei zumindest ein Oligomer durch Metallocen-Katalyse hergestellt ist; und g) das Polyalphaolefin eine Mischung von 10. The base oil according to at least one of the preceding claims, wherein the polyalphaolefin(s) are characterized by one or more of the following properties: a) the polyalphaolefins are oligomers of 1-octene, 1-decene and/or 1-dodecene; b) the degree of polymerization of the polyalphaolefins is 3 to 25; c) the polyalphaolefins have a viscosity of 4 to 300 mm 2 /s at 100 ° C; d) the polyalphaolefin is a hydrogenated oligomer; e) the polyalphaolefin is an oligomer of 50 to 80% by weight of 1-decene and 50 to 20% by weight of 1-dodecene; f) the polyalphaolefin is a mixture of oligomers, at least one oligomer being produced by metallocene catalysis; and g) the polyalphaolefin is a mixture of
Oligomeren mit einer Viskosität von 4 bis 100 mm2/s bei 100°C und Oligomeren mit einer Viskosität von 50 bis 300 mm2/s bei 100°C. Oligomers with a viscosity of 4 to 100 mm 2 /s at 100°C and oligomers with a viscosity of 50 to 300 mm 2 /s at 100°C.
11 . Das Basisöl nach zumindest einem der vorhergehenden Ansprüche, wobei das Polyalphaolefin eine Mischung von a1 ) Oligomeren von 1- Decen und b1) Oligomeren von 1-Octen enthält; oder wobei das Polyalphaolefin eine Mischung von a2) Oligomeren von 1-Dodecen und b2) Oligomeren von 1-Octen und/oder 1-Decen ist oder enthält. 11. The base oil according to at least one of the preceding claims, wherein the polyalphaolefin contains a mixture of a1) oligomers of 1-decene and b1) oligomers of 1-octene; or wherein the polyalphaolefin is or contains a mixture of a2) oligomers of 1-dodecene and b2) oligomers of 1-octene and/or 1-decene.
12. Das Basisöl nach Anspruch 11 , wobei das Polyalphaolefin eine Mischung von Oligomeren a) und b) ist mit 12. The base oil according to claim 11, wherein the polyalphaolefin is a mixture of oligomers a) and b).
5 - 95 Gew.% von Oligomeren a1 ) oder a2) und 5 - 95% by weight of oligomers a1) or a2) and
5 - 95 Gew.% von Oligomeren b1 ) oder b2). 5 - 95% by weight of oligomers b1) or b2).
13. Das Basisöl nach zumindest einem der vorhergehenden Ansprüche, wobei das Polyalkylenglykol erhältlich ist aus Alkylenoxiden, wobei die Alkylenoxide 30-70 mol% Propylenoxid und 13. The base oil according to at least one of the preceding claims, wherein the polyalkylene glycol is obtainable from alkylene oxides, the alkylene oxides being 30-70 mol% propylene oxide and
70-30 mol% C4- bis C8- Alkylenoxide, insbesondere Butylenoxid, umfassen. 70-30 mol% C4 to C8 alkylene oxides, especially butylene oxide.
14. Schmierfluidzusammensetzung umfassend das Basisöl nach zumindest einem der vorhergehenden Ansprüche, und zumindest eines der folgenden Additive14. Lubricating fluid composition comprising the base oil according to at least one of the preceding claims, and at least one of the following additives
- amin-umgesetztes Alkylphosphat und/oder - amine-reacted alkyl phosphate and/or
- Polyolmonoester. - Polyol monoester.
15. Die Schmierfluidzusammensetzung nach Anspruch 14 umfassend 15. Comprising the lubricating fluid composition of claim 14
- 0,01 bis 2 Gew.%, vorzugsweise 0,1 bis 0,6 Gew.% des oder der amin-um- gesetzten Alkylphosphate, und/oder - 0.01 to 2% by weight, preferably 0.1 to 0.6% by weight of the amine-reacted alkyl phosphate(s), and/or
- 0,01 bis 2 Gew.%, vorzugsweise 0,05 bis 0,3 Gew.% des oder der Polyolmonoester. - 0.01 to 2% by weight, preferably 0.05 to 0.3% by weight of the polyol monoester(s).
16. Die Schmierfluidzusammensetzung nach Anspruch 14 oder 15, wobei 16. The lubricating fluid composition of claim 14 or 15, wherein
- - die Estergruppe des Polyolmonoesters eine C12- bis C24- Fettsäure ist und das Polyol des Polyolmonoesters ggf. ethoxyliert ist, und/oder - - the ester group of the polyol monoester is a C12 to C24 fatty acid and the polyol of the polyol monoester is optionally ethoxylated, and/or
- die amin-umgesetzten Alkylphosphate mit zumindest C10- bis C18- Alkylaminen umgesetzt sind und das Alkylphosphate vorzugsweise ein mono- oder di- C1- bis C12- Alkylphosphat ist. - the amine-reacted alkyl phosphates are reacted with at least C10 to C18 alkyl amines and the alkyl phosphate is preferably a mono- or di-C1 to C12 alkyl phosphate.
17. Verwendung des Basisöls nach zumindest einem der Ansprüche 1 bis 13 in einer Schmierfluidzusammensetzung oder der Schmierfluidzusammensetzung nach zumindest einem der Ansprüche 14 bis 16 als Hydraulik- und Getriebeöl, insbesondere in der Lebensmittel verarbeitenden Industrie und/oder der Futtermittel verarbeitenden Industrie. 17. Use of the base oil according to at least one of claims 1 to 13 in a lubricating fluid composition or the lubricating fluid composition according to at least one of claims 14 to 16 as a hydraulic and transmission oil, in particular in the food processing industry and / or the feed processing industry.
EP23714627.9A 2022-05-11 2023-03-23 Base oil and lubricating fluid composition containing said base oil Active EP4294897B1 (en)

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