EP1461404A1 - Agents d'exploitation pour installations frigorifiques et de climatisation au dioxyde de carbone - Google Patents

Agents d'exploitation pour installations frigorifiques et de climatisation au dioxyde de carbone

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Publication number
EP1461404A1
EP1461404A1 EP02795046A EP02795046A EP1461404A1 EP 1461404 A1 EP1461404 A1 EP 1461404A1 EP 02795046 A EP02795046 A EP 02795046A EP 02795046 A EP02795046 A EP 02795046A EP 1461404 A1 EP1461404 A1 EP 1461404A1
Authority
EP
European Patent Office
Prior art keywords
composition according
polyalkylene glycols
groups
operating
operating agent
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
EP02795046A
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German (de)
English (en)
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EP1461404B1 (fr
Inventor
Jörg Fahl
Jürgen BRAUN
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Fuchs SE
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Fuchs Petrolub SE
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Publication of EP1461404A1 publication Critical patent/EP1461404A1/fr
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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
    • C10M171/00Lubricating compositions characterised by purely physical criteria, e.g. containing as base-material, thickener or additive, ingredients which are characterised exclusively by their numerically specified physical properties, i.e. containing ingredients which are physically well-defined but for which the chemical nature is either unspecified or only very vaguely indicated
    • C10M171/008Lubricant compositions compatible with refrigerants
    • 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
    • C10M137/00Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
    • C10M137/02Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having no phosphorus-to-carbon bond
    • C10M137/04Phosphate esters
    • 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
    • C10M105/00Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • C10M105/08Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
    • C10M105/32Esters
    • C10M105/38Esters of polyhydroxy compounds
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M105/00Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • C10M105/08Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
    • C10M105/32Esters
    • C10M105/42Complex esters, i.e. compounds containing at least three esterified carboxyl groups and derived from the combination of at least three different types of the following five types of compound: monohydroxy compounds, polyhydroxy compounds, monocarboxylic acids, polycarboxylic acids and hydroxy carboxylic acids
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • 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
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28Esters
    • C10M2207/283Esters of polyhydroxy compounds
    • C10M2207/2835Esters of polyhydroxy compounds used as base material
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • 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
    • C10M2209/1033Polyethers, i.e. containing di- or higher polyoxyalkylene groups used as base material
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • 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
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/10Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/103Polyethers, 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
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/10Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/103Polyethers, i.e. containing di- or higher polyoxyalkylene groups
    • C10M2209/108Polyethers, i.e. containing di- or higher polyoxyalkylene groups etherified
    • C10M2209/1085Polyethers, i.e. containing di- or higher polyoxyalkylene groups etherified used as base material
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • 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
    • C10M2209/109Polyethers, i.e. containing di- or higher polyoxyalkylene groups esterified
    • C10M2209/1095Polyethers, i.e. containing di- or higher polyoxyalkylene groups esterified used as base material
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • 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
    • C10M2223/041Triaryl phosphates
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/06Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00Specified use or application for which the lubricating composition is intended
    • C10N2040/30Refrigerators lubricants or compressors lubricants

Definitions

  • the invention relates to equipment compositions containing additive
  • Lubricants based on polyalkylene glycols and / or neopentyl polyol esters which are suitable for the lubrication of refrigeration machines, air conditioning systems, heat pumps and related systems that are operated with carbon dioxide as a refrigerant.
  • Carbon dioxide has been used as a refrigeration machine resource since the beginning of modern refrigeration technology.
  • the Linde company built the first compression refrigeration machine using carbon dioxide as early as 1881
  • halogenated fluorocarbon R134a is mainly used in automotive air conditioning systems and refrigerant mixtures such as e.g. R404A used.
  • refrigerant mixtures such as e.g. R404A used.
  • R744 refrigerant carbon dioxide
  • PAG Polyalkylene glycols
  • oils of certain chemical compounds show the required properties, such as a correspondingly good cold flow behavior as well as a favorable solubility behavior with CO 2 .
  • PAO polyalphaelefms
  • polyalkylene glycols have excellent friction properties.
  • the good absorption on metal surfaces can be attributed to the polar character. Due to this high surface activity and the low viscosity pressure dependence, low friction coefficients are achieved.
  • There are special conditions in the tribological contact areas that are influenced by CO 2 . Particularly when starting up and switching off, there are strong solubility-related effects which hinder the formation of a sufficient lubricating film, so that the lubricating gap can be washed out as a result of dissolved refrigerant, which can be caused, among other things, by the pressure equalization that occurs and changes in the surface tension.
  • the invention is therefore based on the problem of appropriately adding lubricants for carbon dioxide refrigerants so that the mixture of carbon dioxide and lubricants also meet the following requirements in addition to the above:
  • wear protection additives commonly used in the lubricant sector are based on organometallic compounds such as zinc / phosphorus or zinc / sulfur compounds such as zinc dithiophosphate (ZDTP).
  • ZDTP zinc dithiophosphate
  • Common low-ash active ingredients contain no metallic elements and are, for example, organic mono- and polysulfides, saturated and unsaturated Fatty acids, natural and synthetic fatty acid esters, as well as primary and secondary alcohols.
  • Containing equipment compositions for refrigeration machines, heat pumps and related systems, such as air conditioning systems Containing equipment compositions for refrigeration machines, heat pumps and related systems, such as air conditioning systems
  • R optionally represents the same or different for each of the three phenyl radicals and for each n represents H or one or more Cl to C6 hydrocarbon radicals and n possibly identically or differently for each of the three phenyl radicals, represents an integer from 1 to 5, preferably 1, 2 or 3, with the proviso that at least one, preferably at least two, of the three phenyl radicals, particularly preferably all three phenyl radicals,
  • Trikre- sylphosphate is a mixture of ortho-, para- or meta- monomethyl-substituted phosphates on the phenyl ring.
  • the phosphate ester used according to the invention is preferably used in an amount of 0.1 to 3% by weight, particularly preferably in an amount of 0.3 to 1.5% by weight, based on the lubricant.
  • T-Butylated triphenylphosphates are usually produced by alkylation of phenols and reaction with phosphoric acid trichloride.
  • the phosphate esters used according to the invention have at least one phenyl radical alkylated in the ortho position.
  • the triaryl phosphates claimed are less reactive and offer the advantage that they do not cause corrosion or discoloration in most metals. Furthermore, these active ingredients which are readily soluble in the base oils claimed are distinguished by their extraordinarily high thermal and oxidative stability.
  • the phosphates used are significantly more stable under the influence of CO 2 and allow high operating temperatures.
  • t-butylated triphyl phosphates are characterized by high hydrolytic stability.
  • the polyalkylene glycols (PAG) used according to the invention have alkylene oxide units with 1 to 6 carbon atoms (-R-O-) as monomer units.
  • the polyalkylene glycols have hydrogen, alkyl, aryl, alkylaryl, aryloxy, alkoxy, alkylaryloxy and / or hydroxyl end groups. Taking alkylaryloxy
  • Groups are also understood to mean arylalkyl (en) oxy groups and alkylaryl and arylalkyl (en) groups (eg aryl-CH 2 CH 2 -).
  • the end groups of the alkyl type, including the alkoxy type, or aryl Types, including the alkylaryl type, aryloxy type and alkylaryloxy type preferably have 6 to 24 carbon atoms based on the aryl types, particularly preferably 6 to 18 carbon atoms and preferably 1 to 12 carbon atoms based on the alkyl types.
  • the polyalkylene glycols according to the invention are thus either homopolymers, namely polypropylene glycol (or polypropylene oxide), or copolymers, terpolymers, etc.
  • the monomer units can have a statistical distribution or a block structure. If the polyalkylene glycols are not homopolymers, preferably at least 20%, preferably at least 40%, of all monomer units can be produced from polypropylene oxide (PO), and furthermore preferably at least 20% of all monomer units of these polyalkylene glycols can be produced using ethylene oxide (EO) (PO / EO- copolymers).
  • PO polypropylene oxide
  • EO ethylene oxide
  • preferably at least 20%, preferably at least 40%, of all monomer units can be produced from butylene oxide (BO), and furthermore at least 20% of all monomer units of these polyalkylene glycols can preferably be produced using ethylene oxide (BO / EO copolymers).
  • BO butylene oxide
  • ethylene oxide BO / EO copolymers
  • the starting compound is incorporated into the polymer when using (poly) alcohols and is also referred to in the sense of the invention as the end group of the polymer chain.
  • Suitable starting groups are compounds which contain active hydrogen, such as e.g. n-butanol, propylene glycol, ethylene glycol, neopentyl glycols such as pentaerythritol, ethylenediamine, phenol, cresol or other (Cl- to C16- (mono-, di- or tri-) alkyl) aromatics, (hydroxyalkyl) aromatics, hydroquinone, aminoethanolamines, Triethylene tetramines, polyamines, sorbitol or other sugars.
  • active hydrogen such as e.g. n-butanol, propylene glycol, ethylene glycol, neopentyl glycols such as pentaerythritol, ethylenediamine, phenol, cresol or other (Cl- to C16
  • the polyalkylene glycols preferably have aryl groups or corresponding heteroaromatic groups, for example incorporated into the polymer chain, as side groups or end groups; the groups can optionally be substituted by linear or branched alkyl or alkylene groups, the alkyl or alkylene groups in the Preferably have a total of 1 to 18 carbon atoms.
  • Suitable polyalkylene glycols can be produced, for example, using appropriate starting alcohol compounds, for example of the following type:
  • x and y represent an integer from 0 to 6, x + y is less than 7, x + y is greater than 1 and either y is greater than 0 (preferably 1 to 3) or R 1 carries one or more hydroxyl groups. It is also possible that y is greater than 0 and R 1 carries one or more hydroxyl groups at the same time.
  • Y is preferably an integer from 1 to 3.
  • R 1 stands for a linear or branched Cl to C18 hydrocarbon group which optionally carries one or more hydroxyl groups.
  • the starting alcohol compound can also be constructed in the same way from a condensed aromatic, such as naphthalene, instead of from benzene.
  • Cyclic ether alcohols such as hydroxyfurfuryl or hydroxy-tetrahydrofuran, nitrogen or sulfur heterocycles can also be used as starting groups.
  • Such polyalkylene glycols are disclosed in WO 01/57164, which is hereby also made the subject of this application.
  • the polyalkylene glycols according to the invention preferably have an average molecular weight (number average) of 200 to 3000 g / mol, particularly preferably of 400 to 2000 g / mol.
  • the kinematic viscosity of the polyalkylene glycols is preferably 10 to 400 mm 2 / s (cSt) at 40 ° C. measured in accordance with DIN 51562.
  • the polyalkylene glycols used according to the invention can be prepared by reacting alcohols, including polyalcohols, as starter compounds with oxiranes such as ethylene oxide, propylene oxide and / or butylene oxide. After the reaction, these only have a free hydroxyl group as the end group. Polyalkylene glycols with only one hydroxyl group are compared to those with two free ones
  • Hydroxy groups preferred. Particularly preferred in terms of stability, hygroscopicity and compatibility are polyalkylene glycols which, for example after a further etherification step, no longer have any free hydroxyl groups.
  • the alkylation of terminal hydroxyl groups leads to an increase in thermal stability and an improvement in CO 2 miscibility.
  • the miscibility can also be set such that there is in the phase diagram T versus lubricant content in the CO 2 areas of complete miscibility and those with little or no miscibility.
  • Neopentyl polyol esters and lubricant mixtures are suitable end groups.
  • neopentyl polyol esters can optionally also be used together with the polyalkylene glycols described above in the equipment according to the invention.
  • Suitable neopentyl polyol esters are esters of neopentyl polyols, such as neopentyl glycol, pentaerythritol and trimethylol propane, with linear or branched C4 to C12 monocarboxylic acids, if appropriate with the addition of appropriate dicarboxylic acids.
  • Pentaerythritol is usually available as technical pentaerythritol, which is a mixture of mono-, di- and tripentaerythritol.
  • their condensation products such as dipentaerythritol and / or tripentaerythritol, are also suitable as alcohol components.
  • Tripentaerythritol preferably mixtures which predominantly contain dipentaerythritol.
  • Complex esters can be prepared by partial esterification of polyhydric alcohols with monohydric and polyhydric acids, such as C 4 to C 12 dicarboxylic acids. This creates dimers and oligomers. Complex esters are preferred when using neopentyl glycol and / or and trimethylol propane as the alcohol group.
  • the phosphoric acid esters used according to the invention were found to be effective even when these neopentyl polyol esters were used, i.e. Without the use of polyalkylene glycols, surprisingly proven to be excellent additives for improving the lubricating effect of the neopentyl polyol esters when used together with carbon dioxide as refrigeration equipment. Because of their less good lubricating properties - compared to polyalkylene glycols - neopentyl polyol esters have hitherto been regarded as less suitable for use together with carbon dioxide as operating media in refrigeration machines.
  • neopentyl polyol esters Compounds which are obtainable from neopentyl polyols and carboxylic acids are referred to as neopentyl polyol esters.
  • Polyols are used as neopentyl polyols denotes those which do not have any hydrogen atoms which are in the ⁇ -position to the hydroxy group. These are polyols with preferably 2 to 8 hydroxyl groups, one, two or three quaternary carbon atoms and 5 to 21, preferably 5 to 15, carbon atoms, the hydroxyl groups of the polyol as the alcohol component being connected only to those carbon atoms, which in turn are only have quaternary carbon atoms in the adjacent position.
  • neopentylpoylol NPG
  • TMP trimethylolpropane
  • PE pentaerythritol
  • the neopentyl polyols as alcohol component can further contain 1 to 4 ether bridges.
  • the alcohol component is particularly preferred: pentaerythritol and / or dipentaerythritol (DPE) and / or tripentaerythritol (TPE).
  • Preferred acid components are n-pentanoic acid, n-heptanoic acid, octanoic acid, decanoic acid, 2-ethylhexanoic acid, 3, 5, 5-trimethylhexanoic acid and 2-hexyldecanoic acid and other Guerbet acids, or mixtures thereof.
  • Adipic and dodecanedioic acids are particularly suitable for the preparation of complex esters. It has proven to be advantageous to prepare the neopentyl polyol esters by reacting the corresponding alcohols with mixtures of the corresponding acids. Complete esterification of all the hydroxyl groups of the neopentyl polyols and acid groups of the dicarboxylic acids which may be used is preferred.
  • the polyalkylene glycols used according to the invention can be used together with neopentyl polyol esters as lubricants.
  • neopentyl polyol esters As lubricants, reference is made to the above paragraphs.
  • Particularly suitable as a further additive are di-phenylamine and
  • Di- (C1 to C16 alkyl) phenylamines for example octylated / butylated di-phenylamine.
  • substituted phenyls unsubstituted or C1- to C16-alkyl-substituted naphthyl radicals can also be used.
  • the operating agent composition generally contains between 1 and 25% by weight of lubricant - this size can, however, also be outside the specified range, depending on the type of refrigeration machine - preferably at least 40% by weight, preferably at least 80% by weight, of the additives for the operating medium are polyalkylene glycols and / or neopentyl polyols, based on all the constituents of the operating medium.
  • the proportion of the particularly preferred polyalkylene glycols with at least one aromatic group is preferably at least 20% by weight, particularly preferably at least 40% by weight, in particular at least 80% by weight, based on the
  • Lubricant content i.e. the lubricants without refrigerants and additives in the operating fluid composition.
  • the proportion of neopentyl polyol esters as lubricants is preferably 20 to 20 when using lubricant mixtures of different classes of compounds
  • the polyalkylene glycols used in the compositions according to the invention are preferably miscible (soluble) for higher mass fractions of lubricants in CO 2 over the entire temperature range from the critical temperature Tk to below -40 ° C., in some cases also below -55 ° C. With smaller proportions of lubricants, these polyalkylene glycols are no longer miscible or only partially miscible with liquid carbon dioxide (soluble).
  • polyol ester lubricants such as pentaerythritol esters in particular, a correspondingly high solubility is achieved.
  • a so-called partial miscibility i.e. a mixture gap existing in a certain temperature range for certain mixing ratios is of great importance here
  • chillers that work without oil sump or oil return can also be used for this case.
  • the lubricant according to the invention preferably has in the range between greater than 0 and 20% by weight, preferably greater than 0 and 5% by weight, concentration of the lubricant in the refrigerant at temperatures of 15 ° C. and below (to -40 ° C., preferably to -55 ° C) and in the range of 30 and 60% by weight concentration in the relevant temperature range from -40 ° C (or -55 ° C) to + 30 ° C fully miscible with the equipment. Outside of these areas, i.e. e.g. between greater than 5 and less than 30% by weight »greater than 20 and less than 30% by weight of lubricant in the refrigerant, there is preferably a mixture gap.
  • the above criterion is e.g. polyalkylene glycols from C1 to C4 alkyl end groups capped using
  • the calculation bases that are generally used for dimensioning bearings do not take into account the influence of different basic liquids or the effect of additives, but are mainly based on the mixture viscosity.
  • test parameters are selected so that they are optimal for the examination
  • Test time is reached.
  • the test parameters are summarized in Table 1.
  • the axial load on the axial cylindrical roller bearings to be examined (geometry AXK 18 x 35 x 4.5) is carried out by means of disc spring assemblies and can be adjusted using spacers of different thicknesses. Testing continues until at least one bearing fails due to damage.
  • the test parameters are as follows:
  • ND 8 is a commercial product of the Japanese compressor manufacturer NIPPONDENSO (manufactured by Idemitsu Kosan) with, among other things, approx. 1-2% by weight tricresyl phosphate and 0.5% by weight BHT (2,6-di-tert-butyl-4- methylphenol) added.
  • SP10 and SP 20 are
  • the preferred polyalkylene glycol lubricating oils show (P4) a lubrication behavior even without the addition of phosphoric acid esters that corresponds to the added terminally methylated polyalkylene glycol (see PAG oil ND 8).
  • P4 phosphoric acid esters that corresponds to the added terminally methylated polyalkylene glycol
  • Table 2 clearly show that the additive used in combination with the basic liquids used under the influence of compressed CO 2 significantly extends the service life. This effect is particularly clear in connection with highly soluble neopentyl polyol esters.
  • Axial piston machines are favored for CO 2 applications in cars because of their compact design and uniform flow rates. In the course of the first endurance tests with prototype compressors, the lubrication of the extremely stressed roller bearings proved to be particularly problematic.
  • Tricresyl phosphate or triphenyl phosphate Tricresyl phosphate or triphenyl phosphate.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Lubricants (AREA)
  • Sorption Type Refrigeration Machines (AREA)
EP02795046A 2001-12-29 2002-12-24 Agents d'exploitation pour installations frigorifiques et de climatisation au dioxyde de carbone Expired - Lifetime EP1461404B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10164056A DE10164056B4 (de) 2001-12-29 2001-12-29 Betriebsmittel für Kohlendioxid-Kälte- und Klimaanlagen
DE10164056 2001-12-29
PCT/DE2002/004741 WO2003057804A1 (fr) 2001-12-29 2002-12-24 Agents d'exploitation pour installations frigorifiques et de climatisation au dioxyde de carbone

Publications (2)

Publication Number Publication Date
EP1461404A1 true EP1461404A1 (fr) 2004-09-29
EP1461404B1 EP1461404B1 (fr) 2010-11-10

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Application Number Title Priority Date Filing Date
EP02795046A Expired - Lifetime EP1461404B1 (fr) 2001-12-29 2002-12-24 Agents d'exploitation pour installations frigorifiques et de climatisation au dioxyde de carbone

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US (1) US7303693B2 (fr)
EP (1) EP1461404B1 (fr)
JP (1) JP2005514492A (fr)
KR (1) KR100695190B1 (fr)
AT (1) ATE487780T1 (fr)
AU (1) AU2002360924A1 (fr)
DE (2) DE10164056B4 (fr)
DK (1) DK1461404T3 (fr)
ES (1) ES2356123T3 (fr)
WO (1) WO2003057804A1 (fr)

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JP4927349B2 (ja) * 2005-05-11 2012-05-09 出光興産株式会社 冷凍機油組成物、これを用いた圧縮機及び冷凍装置
US20070004605A1 (en) * 2005-06-27 2007-01-04 Kaoru Matsumura Lubricants for refrigeration systems
JP4863742B2 (ja) * 2006-03-23 2012-01-25 Jx日鉱日石エネルギー株式会社 二酸化炭素冷媒用冷凍機油組成物
JP5572284B2 (ja) 2007-02-27 2014-08-13 Jx日鉱日石エネルギー株式会社 冷凍機油および冷凍機用作動流体組成物
JP2009074018A (ja) * 2007-02-27 2009-04-09 Nippon Oil Corp 冷凍機油および冷凍機用作動流体組成物
JP5193485B2 (ja) * 2007-03-27 2013-05-08 Jx日鉱日石エネルギー株式会社 冷凍機油及び冷凍機用作動流体組成物
CN201972923U (zh) 2007-10-24 2011-09-14 艾默生环境优化技术有限公司 涡旋机
WO2009057475A1 (fr) * 2007-10-29 2009-05-07 Nippon Oil Corporation Huile de réfrigérateur et composition de fluide actif pour machine réfrigérante
US9989280B2 (en) * 2008-05-02 2018-06-05 Heatcraft Refrigeration Products Llc Cascade cooling system with intercycle cooling or additional vapor condensation cycle
US8476210B2 (en) * 2008-09-09 2013-07-02 Glenn Short Composition for compressor working fluid for applications with soluble gas or gas condensates
RU2011134285A (ru) * 2009-01-16 2013-02-27 Кемтура Корпорейшн Рабочие флюиды на основе диоксида углерода для систем охлаждения и кондиционирования воздуха
CN102292420A (zh) * 2009-01-26 2011-12-21 科聚亚公司 用于冷冻体系的多醇酯润滑剂的制备
WO2011127132A1 (fr) * 2010-04-06 2011-10-13 Chemtura Corporation Huile de réfrigération et compositions contenant un réfrigérant à base de dioxyde de carbone
DE102012000588B4 (de) * 2012-01-16 2017-01-05 Hydro Aluminium Deutschland Gmbh Verfahren zum Abtrennen von Kühlschmierstoff aus Lagerschmiermittel
JP6195429B2 (ja) 2012-03-29 2017-09-13 Jxtgエネルギー株式会社 冷凍機用作動流体組成物及び冷凍機油
EP3094700A4 (fr) 2014-01-16 2017-07-26 Shrieve Chemical Products, Inc. Composition de lubrifiant frigorifique synthétique desséchant
JP6059320B2 (ja) * 2015-10-30 2017-01-11 Jxエネルギー株式会社 冷凍機用作動流体組成物及び冷凍機油

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Also Published As

Publication number Publication date
US20050127320A1 (en) 2005-06-16
US7303693B2 (en) 2007-12-04
DE10164056A1 (de) 2003-07-10
AU2002360924A1 (en) 2003-07-24
KR100695190B1 (ko) 2007-03-19
DE10164056B4 (de) 2006-02-23
ES2356123T3 (es) 2011-04-05
JP2005514492A (ja) 2005-05-19
ATE487780T1 (de) 2010-11-15
KR20040075914A (ko) 2004-08-30
EP1461404B1 (fr) 2010-11-10
DE50214767D1 (de) 2010-12-23
DK1461404T3 (da) 2011-02-21
WO2003057804A1 (fr) 2003-07-17

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