EP1461404B1 - 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 Download PDF

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EP1461404B1
EP1461404B1 EP02795046A EP02795046A EP1461404B1 EP 1461404 B1 EP1461404 B1 EP 1461404B1 EP 02795046 A EP02795046 A EP 02795046A EP 02795046 A EP02795046 A EP 02795046A EP 1461404 B1 EP1461404 B1 EP 1461404B1
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Prior art keywords
operating agent
agent composition
composition according
polyalkylene glycols
groups
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EP1461404A1 (fr
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Jörg Fahl
Jürgen BRAUN
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Fuchs SE
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Fuchs Petrolub SE
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M137/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
    • C10M137/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having no phosphorus-to-carbon bond
    • C10M137/04—Phosphate esters
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M171/00—Lubricating 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
    • C10M171/008—Lubricant compositions compatible with refrigerants
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
    • C10M105/32—Esters
    • C10M105/38—Esters of polyhydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
    • C10M105/32—Esters
    • C10M105/42—Complex 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
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • C10M169/04—Mixtures of base-materials and additives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/283—Esters of polyhydroxy compounds
    • C10M2207/2835—Esters of polyhydroxy compounds used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
    • C10M2209/1033—Polyethers, i.e. containing di- or higher polyoxyalkylene groups used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
    • C10M2209/105—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing three carbon atoms only
    • C10M2209/1055—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing three carbon atoms only used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
    • C10M2209/107—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of two or more specified different alkylene oxides covered by groups C10M2209/104 - C10M2209/106
    • C10M2209/1075—Polyethers, 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
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
    • C10M2209/108—Polyethers, i.e. containing di- or higher polyoxyalkylene groups etherified
    • C10M2209/1085—Polyethers, i.e. containing di- or higher polyoxyalkylene groups etherified used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
    • C10M2209/109—Polyethers, i.e. containing di- or higher polyoxyalkylene groups esterified
    • C10M2209/1095—Polyethers, i.e. containing di- or higher polyoxyalkylene groups esterified used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • C10M2223/041—Triaryl phosphates
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/30—Refrigerators lubricants or compressors lubricants

Definitions

  • the invention relates to operating compositions containing additized lubricants based on polyalkylene glycols and / or Neopentylpolyolestern, which are suitable for the lubrication of refrigerators, air conditioners, heat pumps and related equipment, which are operated with carbon dioxide as a refrigerant.
  • Carbon dioxide has been used as refrigeration equipment at the beginning of modern refrigeration.
  • Linde built the first compression chiller using carbon dioxide as a refrigerant.
  • carbon dioxide was mainly used in ship chillers with subcritical process control.
  • the lubricant used was glycerin.
  • fluoro-chlorohydrocarbon refrigerants carbon dioxide has barely been used.
  • 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 .
  • Investigations have shown that the physical properties and the interactions of different base oils with subcritical and supercritical CO 2 are highly dependent on their chemical structure. Mineral oils are almost immiscible with CO 2 and, in view of the rather moderate high temperature stability compared to synthetic oils, are hardly suitable. In particular, because of their unfavorable phase behavior and comparatively low density, hydrocrack oils, alkylaromatics and polyalphaolefins (PAO) are considered unsuitable for use in systems with suction pressure side accumulators.
  • PAO polyalphaolefins
  • polyalkylene glycols have excellent frictional 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.
  • the 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
  • conventional low-ash active substances 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.
  • Phosphorus-containing high pressure additives are for resource compositions containing carbon dioxide in the EP-A-1008643 .
  • EP-A-1063279 and the WO-A-0148127 (equal EP-A-1243639 ) proposed.
  • tricresyl is a mixture of ortho, para or meta monomethyl substituted phosphates on the phenyl ring.
  • the phosphate ester used in accordance with the invention is used at from 0.1 to 3% by weight, preferably from 0.3 to 1.5% by weight, based on the lubricant.
  • T-butylated triphenyl phosphates are generally prepared by alkylating phenols and reacting with phosphoric trichloride.
  • the phosphate esters used according to the invention have at least one phenyl radical alkylated in the ortho position.
  • the claimed triaryl phosphates are less reactive and have the advantage that they do not cause corrosion or discoloration in most metals. Furthermore, these well-soluble in the claimed base oils active ingredients are characterized by their extremely high thermal and oxidative stability.
  • the claimed phosphates are significantly more stable under the influence of CO 2 and allow high operating temperatures.
  • t-butylated Triphylphosphate are characterized by a high hydrolytic stability.
  • the polyalkylene glycols (PAG) used according to the invention preferably have alkylene oxide units having 1 to 6 carbon atoms (-R-O-) as monomer units.
  • polyalkylene glycols have hydrogen, alkyl, aryl, alkylaryl, aryloxy, alkoxy, alkylaryloxy and / or hydroxy end groups.
  • Alkylaryloxy groups also include arylalkyl (en) oxy groups and alkylaryl groups also arylalkyl (en) groups (eg aryl-CH 2 CH 2 -).
  • the alkyl-type endblocks including the alkoxy type, or aryl Type, including the alkylaryl-type, aryloxy-type and alkylaryloxy-type, preferably have from 6 to 24 carbon atoms, more preferably from 6 to 18 carbon atoms, based on the aryl types, and preferably from 1 to 12 carbon atoms relative to 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 may have a random distribution or a block structure.
  • the polyalkylene glycols are not homopolymers, preferably at least 20%, preferably at least 40%, of all monomer units of polypropylene oxide (PO) can be prepared, and furthermore preferably at least 20% of all monomer units of these polyalkylene glycols can be prepared using ethylene oxide (EO) (PO / EO). copolymers).
  • preferably at least 20%, preferably at least 40%, of all monomer units are preparable from butylene oxide (BO), and furthermore preferably at least 20% of all monomer units of these polyalkylene glycols can be prepared using ethylene oxide (BO / EO copolymers).
  • BO butylene oxide
  • the starting compound is incorporated when using (poly) alcohols in the polymer and referred to in the context of the invention as the end group of the polymer chain.
  • Suitable starting groups are compounds containing active hydrogen, e.g. n-butanol, propylene glycol, ethylene glycol, neopentyl glycols such as pentaerythritol, ethylenediamine, phenol, cresol or other (C 1 - to C 16 - (mono-, di- or tri) -alkyl) -aromatics, (hydroxyalkyl) -aromatics, hydroquinone, aminoethanolamines, triethylenetetramine, Polyamines, sorbitol or other sugars.
  • C-H-acidic compounds such as carboxylic acids or carboxylic anhydrides
  • 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 may optionally be substituted by linear or branched alkyl or alkylene groups, the alkyl or alkylene groups in the Preferably have 1 to 24 and in particular 1 to 18 carbon atoms.
  • Suitable polyalkylene glycols can be prepared by using appropriate starting alcohol compounds, for example of the following type: in which x and y are 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 bears one or more hydroxy groups.
  • y is greater than 0 and R 1 simultaneously carries one or more hydroxy groups.
  • y is an integer from 1 to 3.
  • R 1 is a linear or branched C 1 to C 18 hydrocarbon group which optionally carries one or more hydroxyl groups.
  • the starting alcohol compound may also be constructed in the same manner from benzene instead of a condensed aromatic such as naphthalene.
  • Cyclic ether alcohols such as hydroxyfurfuryl or hydroxy-tetrahydrofuran, nitrogen or sulfur heterocycles can also be used as starting groups.
  • Such polyalkylene glycols are in WO 01/57164 discloses, which is hereby also made the subject of this application.
  • the polyalkylene glycols according to the invention preferably have a number average molecular weight of from 200 to 3000 g / mol, more preferably from 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 according to DIN 51562.
  • the polyalkylene glycols used according to the invention can be prepared by reacting alcohols, including polyhydric alcohols, as starter compounds with oxiranes, such as ethylene oxide, propylene oxide and / or butylene oxide. After the reaction, these have only one free hydroxy group as end group. Polyalkylene glycols having only one hydroxy group are preferred over those having two free hydroxy groups. With regard to stability, hygroscopicity and compatibility, particular preference is given to polyalkylene glycols which, for example after a further etherification step, no longer have free hydroxyl groups. The alkylation of terminal hydroxyl groups leads to an increase in the thermal stability and an improvement in CO 2 miscibility.
  • the miscibility can furthermore be set so that there are areas of complete miscibility and those with no or only low miscibility in the phase diagram T versus proportion of lubricant in the CO 2 .
  • neopentyl polyol esters may optionally also be used together with the above-described polyalkylene glycols in the equipment according to the invention.
  • Suitable neopentyl polyol esters are esters of neopentyl polyols, such as neopentyl glycol, pentaerythritol and trimethylolpropane, with linear or branched C 4 to C 12 monocarboxylic acids, if appropriate with the addition of corresponding dicarboxylic acids.
  • Pentaerythritol is most commonly available as a technical grade pentaerythritol, which is a mixture of mono-, di- and tripentaerythritol.
  • As alcohol components but also their condensation products such as dipentaerythritol and / or tripentaerythritol are suitable.
  • Complex esters can be prepared by proportionate esterification of polyhydric alcohols with monohydric and polybasic acids, such as C 4 to C 12 dicarboxylic acids. In this way, dimers and oligomers are formed. When using neopentyl glycol and / or trimethylolpropane as the alcohol group complex esters are preferred.
  • the phosphoric acid esters used according to the invention also have, when these neopentyl polyol esters are used alone, i. without the use of polyalkylene glycols, surprisingly proved to be excellent additives for improving the lubricity of neopentyl polyol esters when used together with carbon dioxide as refrigeration equipment.
  • Neopentyl polyol esters because of their less good lubricating properties compared to polyalkylene glycols, have hitherto been considered less suitable for use with carbon dioxide as refrigerating equipment.
  • Neopentyl polyol esters are compounds which are obtainable from neopentyl polyols and carboxylic acids.
  • Neopentylpolyole be polyols denotes that have no ⁇ -hydrogen atoms to the hydroxy group. These are polyols having preferably 2 to 8 hydroxyl groups, one, two or three quaternary carbon atoms and 5 to 21, preferably 5 to 15, carbon atoms, wherein the hydroxyl groups of the polyol as the alcohol component are bonded only to those carbon atoms which in turn are only quaternary carbon atoms have in neighboring position.
  • neopentylpolyol NPG
  • TMP trimethylolpropane
  • PE pentaerythritol
  • the neopentylpolyols as the alcohol component may further contain 1 to 4 ether bridges. Particularly preferred is the alcohol component: 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 neopentylpolyol esters by reacting the corresponding alcohols with mixtures of the corresponding acids. Complete esterification of all hydroxy groups of the neopentylpolyols and acid groups of the optionally used dicarboxylic acids 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.
  • di-phenylamine and di (C1 to C16 alkyl) phenylamines are particularly suitable as antioxidants di-phenylamine and di (C1 to C16 alkyl) phenylamines, for example octylated / butylated di-phenylamine.
  • substituted phenyls it is also possible to use unsubstituted or C 1 - to C 16 -alkyl-substituted naphthyl radicals.
  • the working composition generally contains between 1 and 25% by weight of lubricant - however, depending on the type of refrigerating machine, this size may also be outside the stated range - preferably at least 10% by weight, in particular at least 40% by weight and particularly preferably at least 80 %
  • lubricant preferably at least 10% by weight, in particular at least 40% by weight and particularly preferably at least 80 %
  • Polyalkylene glycols and / or Neopentylpolyol esters are based on all ingredients of the equipment.
  • the fraction of the particularly preferred polyalkylene glycols having at least one aromatic group is preferably at least 20% by weight, more preferably at least 40% by weight, in particular at least 80% by weight, based on the lubricant proportion (ie the lubricants without refrigerants and additives) the resource composition.
  • the proportion of neopentylpolyol ester lubricant is preferably from 20 to 60% by weight, particularly preferably from 40 to 60% by weight, based in each case on the lubricant proportion in the equipment composition.
  • the polyalkylene glycols used in the compositions according to the invention are preferably miscible (soluble) in the CO 2 over the entire temperature range from the critical temperature T k to below -40 ° C. for higher mass fractions. At lower levels of lubricant, these polyalkylene glycols are no longer or only partially miscible with liquid carbon dioxide (soluble). Investigations of CO 2 -effected Iüimanikcontractn show that due to the good miscibility of polyol ester lubricants, in particular pentaerythritol, a correspondingly high solubility is achieved.
  • a so-called partial miscibility i. a miscibility gap present in a certain temperature range for certain mixing ratios is of great interest here. Due to the advantageous temperature / Lösbergs can also be used for this case refrigerators that work without oil sump or oil return.
  • the lubricant according to the invention in the range between greater than 0 and 20 wt.%, Preferably greater than 0 and 5 wt.%, Concentration of the lubricant in the refrigerant at temperatures of 15 ° C and lower (to -40 ° C, preferably -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 complete miscibility with the equipment on. Outside these areas, i. e.g. between greater than 5 and less than 30 wt.% greater than 20 and less than 30 wt.% Lubricant in the refrigerant, there is preferably a miscibility gap.
  • the above criterion is prepared, for example, from C1 to C4 alkyl terminated polyalkylene glycols using starting alcohols having aryl groups. Examples include cresols, p-hexylphenol or (hydroxymethyl) benzene. Such polyalkylene glycols are further defined in the subclaims.
  • the general calculation bases generally used for bearing dimensioning do not take into account the influence of different base fluids nor the effect of additives, but rely primarily on the viscosity of the mixture. Important influencing factors such as the presence of gases, as in this special case CO 2 are not included in these calculations, although these play a very significant role. In order to gain insights into this, lifetime tests under practical conditions are necessary.
  • test parameters are chosen so that an optimum test time is achieved for the test.
  • the experimental parameters are summarized in Table 1.
  • the axial load of the axial cylindrical roller bearings (geometry AXK 18 x 35 x 4.5) to be examined takes place via disk spring packages and can be adjusted with the aid of spacers of different thicknesses. It is checked until at least one bearing fails due to damage.
  • the test parameters are as follows: ⁇ i> Table 1: Test Parameters ⁇ / i> parameter Abbreviation [unit] value Axial load Pa [N] 8000 Hertzian pressure (roll): Pmax [N / mm 2 ] 1622 rotation speed n [min -1 ] 800 CO 2 pressure P [bar] 50 oil temperature T oil [° C] 90
  • ND 8 is a commercial product of the Japanese compressor manufacturer NIPPONDENSO (manufactured by the company Idemitsu Kosan) with, inter alia, about 1-2% by weight of tricresyl phosphate and 0.5% by weight of BHT (2,6-di- tert- butyl-4-). methylphenol).
  • SP10 and SP20 are commercial products of Japanese compressor manufacturer SANDEN (also manufactured by Idemitzu Kosan) with similar additives.
  • polyalkylene glycol lubricating oils used with preference show (P4) even without the addition of phosphoric acid esters a lubricating behavior which corresponds to the additized terminally methylated polyalkylene glycol (compare PAG oil ND 8).
  • P4 polyalkylene glycol lubricating oils used with preference show (P4) even without the addition of phosphoric acid esters a lubricating behavior which corresponds to the additized terminally methylated polyalkylene glycol (compare PAG oil ND 8).
  • P4 polyalkylene glycol lubricating oils used with preference show (P4) even without the addition of phosphoric acid esters a lubricating behavior which corresponds to the additized terminally methylated polyalkylene glycol (compare PAG oil ND 8).
  • Table 2 clearly show that the claimed additive combination in combination with the claimed base fluids under the influence of compressed CO 2 significantly prolongs the service life. This effect is also particularly evident in connection with highly soluble neopenty

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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)

Claims (19)

  1. Composition d'agents d'exploitation comprenant
    (A) du dioxyde de carbone à titre d'agent réfrigérant,
    (B) des polyalkylène glycols et/ou des esters de néopentyl polyol comme agents lubrifiants et
    (C) 0,1 à 3 % en poids, par rapport à l'agent lubrifiant, d'un ester de
    phosphate de la structure suivante :
    Figure imgb0006
     dans laquelle
    R identique ou différent pour chacun des trois radicaux phényles et le cas échéant identique ou différent pour chaque n, représente H ou un ou plusieurs radicaux hydrocarbures en C1 à C6, et
    n identique ou différent pour chacun des trois radicaux phényles, représente un nombre entier de 1 à 5,
    à la condition qu'au moins pour un des trois radicaux phényles,
    R est le tert-butyle et/ou l'isopropyle.
  2. Composition d'agents d'exploitation selon la revendication 1, comprenant de 0,3 à 1,5 % en poids d'ester de phosphate, par rapport à l'agent lubrifiant.
  3. Composition d'agents d'exploitation selon l'une des revendications précédentes, caractérisée en ce que les polyalkylène glycols ne présentent pas de groupes hydroxy libres.
  4. Composition d'agents d'exploitation selon l'une des revendications précédentes, caractérisée en ce que la composition d'agents d'exploitation comprend des polyalkylène glycols qui se composent, par rapport à la chaîne polymérique et aux motifs monomères d'oxyde d'alkylène mis en oeuvre, de :
    - motifs monomères de type -(-CH(CH3)-CH2-O-)- ou -(-CH2-CH(CH3)-O-)-,
    - 20 à 80 % de motifs monomères de type -(-CH(CH3)-CH2-O-)- ou -(-CH2-CH(CH3)-O-)- et pour le reste de motifs monomères de type -(CH2-CH2-O-)- ou
    - 20 à 80 % de motifs monomères de type -(-CH(CH2CH3)-CH2-O-)- ou -(-CH2-CH(CH2CH3)-O-)- et pour le reste de motifs monomères de type -(CH2-CH2-O-)-.
  5. Composition d'agents d'exploitation selon l'une des revendications précédentes, caractérisée en ce que la composition d'agents d'exploitation comprend des polyalkylène glycols qui présentent un poids moléculaire moyen (moyen en nombre) de 200 à 3000 g/mol.
  6. Composition d'agents d'exploitation selon l'une des revendications précédentes, caractérisée en ce que les polyalkylène glycols comprennent des groupes aryles ou hétéroaromatiques.
  7. Composition d'agents d'exploitation selon la revendication 6, caractérisée en ce que les polyalkylène glycols sont des groupes aryles ou des groupes hétéroaromatiques substitués avec des groupes alkyles ou alkylènes linéaires ou ramifiés, où les groupes alkyles ou alkylènes présentent au total 1 à 24 atomes de carbone.
  8. Composition d'agents d'exploitation selon l'une des revendications précédentes, caractérisée en ce que les polyalkylène glycols présentent les groupes terminaux suivants :
    - des groupes terminaux alkyle, aryle, alkylaryle, aryloxy, alcoxy et/ou alkylaryloxy ayant de 1 à 24 atomes de carbone.
  9. Composition d'agents d'exploitation selon l'une des revendications précédentes, caractérisée en ce que la composition d'agents d'exploitation comprend des esters ou un mélange d'esters, où les esters peuvent être fabriqués par conversion des néopentyl polyols, particulièrement préférentiellement du pentaérythrite, du dipentaérythrite et/ou du tripentaérythrite, avec des acides carboxyliques linéaires et/ou ramifiés en C4 à C12, le cas échéant en ajoutant des diacides carboxyliques en C4 à C12.
  10. Composition d'agents d'exploitation selon la revendication 9, caractérisée en ce que les néopentyl polyols sont le pentaérythrite, le dipentaérythrite et/ou le tripentaérythrite.
  11. Composition d'agents d'exploitation selon l'une des revendications précédentes, caractérisée en ce que l'agent d'exploitation comprend des esters de néopentyl polyol et des polyalkylène glycols.
  12. Composition d'agents d'exploitation selon l'une des revendications précédentes, caractérisée en ce que la composition d'agents d'exploitation comprend au moins 10 % en poids de polyalkylène glycols et/ou de polyesters de néopentyle selon l'une des revendications précédentes, par rapport à tous les ingrédients de l'agent d'exploitation.
  13. Composition d'agents d'exploitation selon l'une des revendications précédentes, caractérisée en ce que l'agent d'exploitation se compose, en plus des esters de phosphate et de l'agent réfrigérant, de manière prépondérante de polyalkylène glycols et/ou de polyesters de néopentyle selon l'une des revendications précédentes, par rapport au pourcentage en poids.
  14. Composition d'agents d'exploitation selon l'une des revendications 1 à 12, caractérisée en ce que l'agent d'exploitation se compose, en plus des esters de phosphate et de l'agent réfrigérant, exclusivement de polyalkylène glycols et/ou de polyesters de néopentyle selon l'une des revendications précédentes.
  15. Composition d'agents d'exploitation selon l'une des revendications précédentes, caractérisée en ce que l'agent d'exploitation comprend également de la diphénylamine, des di-(alkyl en C1 à C16)phénylamines comme antioxydants, et/ou des composés dans lesquels un ou les deux groupes phényles sont remplacés par des groupes naphtyles.
  16. Utilisation de la composition d'agents d'exploitation selon l'une des revendications précédentes dans des installations frigorifiques.
  17. Utilisation de la composition d'agents d'exploitation selon la revendication 16 dans des installations frigorifiques de véhicules.
  18. Utilisation de la composition d'agents d'exploitation selon la revendication 16 dans des installations de congélation (températures d'évaporation de moins de -30°C), où des lubrifiants, qui comprennent à plus de 90 % en poids des esters de néopentyl polyol, sont mis en oeuvre.
  19. Utilisation de la composition d'agents d'exploitation selon la revendication 17 dans des installations de climatisations de véhicules de tourisme, où des lubrifiants, qui comprennent à plus de 90 % en poids des polyalkylène glycols, sont mis en oeuvre.
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
DE10164056 2001-12-29
DE10164056A DE10164056B4 (de) 2001-12-29 2001-12-29 Betriebsmittel für Kohlendioxid-Kälte- und Klimaanlagen
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 EP1461404A1 (fr) 2004-09-29
EP1461404B1 true EP1461404B1 (fr) 2010-11-10

Family

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

Country Status (10)

Country Link
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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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
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
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
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
WO2009055009A2 (fr) 2007-10-24 2009-04-30 Emerson Climate Technologies, Inc. Compresseur à spirale pour réfrigérant à dioxyde de carbone
RU2474601C2 (ru) * 2007-10-29 2013-02-10 Ниппон Ойл Корпорейшн Холодильное масло и композиция рабочего вещества для холодильной установки
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
WO2010083100A1 (fr) 2009-01-16 2010-07-22 Chemtura Corporation Fluides de travail à base de dioxyde de carbone pour des systèmes de réfrigération et de conditionnement d'air
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
RU2554858C2 (ru) * 2010-04-06 2015-06-27 Кемтура Корпорейшн Холодильное масло и композиции с хладагентом на основе диоксида углерода
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
WO2015109095A1 (fr) 2014-01-16 2015-07-23 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
AU2002360924A1 (en) 2003-07-24
US20050127320A1 (en) 2005-06-16
ES2356123T3 (es) 2011-04-05
DE10164056A1 (de) 2003-07-10
JP2005514492A (ja) 2005-05-19
DK1461404T3 (da) 2011-02-21
KR100695190B1 (ko) 2007-03-19
DE50214767D1 (de) 2010-12-23
WO2003057804A1 (fr) 2003-07-17
DE10164056B4 (de) 2006-02-23
EP1461404A1 (fr) 2004-09-29
US7303693B2 (en) 2007-12-04
ATE487780T1 (de) 2010-11-15
KR20040075914A (ko) 2004-08-30

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