EP0980416B2 - Polyalkylene glycols as lubricants for co 2-based refrigerating machines - Google Patents

Polyalkylene glycols as lubricants for co 2-based refrigerating machines Download PDF

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Publication number
EP0980416B2
EP0980416B2 EP98932037A EP98932037A EP0980416B2 EP 0980416 B2 EP0980416 B2 EP 0980416B2 EP 98932037 A EP98932037 A EP 98932037A EP 98932037 A EP98932037 A EP 98932037A EP 0980416 B2 EP0980416 B2 EP 0980416B2
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Prior art keywords
working composition
polyalkylene glycols
mixtures
composition according
carbon atoms
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EP98932037A
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German (de)
French (fr)
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EP0980416A2 (en
EP0980416B1 (en
Inventor
Jörg Fahl
David F. Pipe
Reiner Knickmeyer
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Shell Internationale Research Maatschappij BV
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Shell Internationale Research Maatschappij BV
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Priority claimed from DE19719132A external-priority patent/DE19719132A1/en
Priority claimed from DE19719430A external-priority patent/DE19719430C1/en
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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
    • C10M107/00—Lubricating compositions characterised by the base-material being a macromolecular compound
    • C10M107/20—Lubricating compositions characterised by the base-material being a macromolecular compound containing oxygen
    • C10M107/30—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M107/32—Condensation polymers of aldehydes or ketones; Polyesters; Polyethers
    • C10M107/34—Polyoxyalkylenes
    • 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
    • C10M111/00—Lubrication 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
    • C10M111/04—Lubrication 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
    • 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
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    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/281—Esters of (cyclo)aliphatic monocarboxylic acids
    • C—CHEMISTRY; METALLURGY
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    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/282—Esters of (cyclo)aliphatic oolycarboxylic acids
    • C—CHEMISTRY; METALLURGY
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    • 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
    • C—CHEMISTRY; METALLURGY
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    • 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
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    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/286—Esters of polymerised unsaturated acids
    • C—CHEMISTRY; METALLURGY
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    • 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
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    • 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
    • C10M2209/104—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing two carbon atoms only
    • C10M2209/1045—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing two carbon atoms only used as base material
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    • 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
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    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • 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
    • C10M2209/106—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing four carbon atoms only
    • C10M2209/1065—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing four 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
    • 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
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    • 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
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    • 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
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • 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
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    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
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    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/30—Refrigerators lubricants or compressors lubricants
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    • C10N2040/34—Lubricating-sealants
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    • C10N2040/36—Release agents or mold release agents
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    • C10N2040/40—Generators or electric motors in oil or gas winning field
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    • C10N2040/42—Flashing oils or marking oils
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    • C10N2040/44—Super vacuum or supercritical use
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    • C10N2040/50—Medical uses

Definitions

  • the invention relates to operating compositions containing polyalkylene glycol-based lubricants which are suitable for lubricating refrigerators, heat pumps and related equipment, such as air conditioners, which are operated solely 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.
  • the lubricant used was glycerin.
  • CFC refrigerants carbon dioxide has barely been used.
  • CFCs fluoro-chloro-hydrocarbons
  • Polypropylene glycols and polyalkylene glycol copolymers containing propylene oxide monomer units have long been known as lubricants.
  • EP 0 844 299 A1 and EP 0 959 121-A1 have earlier priority, but are published after the priority date of the present application, and thus as Article 54 (3) documents, they are to be evaluated only in terms of novelty.
  • carbon dioxide is called. However, it does not disclose the combination of a refrigerant consisting solely of carbon dioxide with polyalkylene glycols containing at least 40% of propylene oxide monomer units.
  • Polyalkylene glycols have already been proposed as lubricants for both processes (see, e.g., Lubricants for Carbon Dioxide, U. Hesse, H.O.Spauschus in Refrigeration Science and Technology, Proceedings, Aarhus Denmark 3-6 Sept. 1996, ISSN 0 151 163).
  • CO 2 behaves very differently with regard to the solubility properties.
  • Subcritical CO 2 is polar, while CO 2 is non-polar in the supercritical region.
  • the polyalkylene glycols according to the invention are soluble in CO 2 over the entire temperature range from the critical temperature T k to below -55 ° C. for higher mass fractions. At lower levels of lubricant, the polyalkylene glycols are no longer or only partially soluble in carbon dioxide.
  • transcritical chillers are made smaller and often have small diameters in the piping systems. This requires sufficient mobility of the lubricant in the corresponding temperature range.
  • the polyalkylene glycols have hydrogen, alkyl, aryl, alkylaryl, aryloxy, alkoxy, alkylaryloxy and / or hydroxyl end groups (c).
  • the alkyl or aryl type end groups preferably have 1 to 8, more preferably 1 to 4, carbon atoms. In the latter case, these are alkyl and / or alkoxy end groups.
  • polyalkylene glycols according to the invention particularly good results in terms of high density and good lubricating properties on the one hand and the properties listed above are achieved if the polyalkylene glycol as the main component, namely at least 60%, propylene oxide units (monomer units of type (a)).
  • the polyalkylene glycols according to the invention are thus either homopolymers, namely polypropylene glycol (or polypropylene oxide), or copolymers, terpolymers, etc., furthermore containing monomer units of type (b).
  • the monomer units may have a statistical distribution or a block structure.
  • the monomer units of type (b) are at least 5% in the polymer chain.
  • the monomer units of type (b) are preferably ethylene oxide and / or butylene oxide units.
  • the polyalkylene glycols of the invention can be prepared by reacting alcohols, including the polyhydric alcohols, as initiator compounds with alkylene oxides 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.
  • hygroscopicity and compatibility are polyalkylene glycols, e.g. after a further etherification step no more free hydroxy groups.
  • polyalkylene glycols which have average molecular weights of from 400 to 3000 g / mol, more preferably from 1000 to 2000 g / mol.
  • the polyalkylene glycols according to the invention are characterized by densities of more than 940 kg / m 3 , and preferably even more than 1000 kg / m 3 , and moreover surprisingly also possess the abovementioned properties which are required for use as refrigerating machine oil in combination with carbon dioxide as the refrigerant are.
  • Polyalkylene glycols with a density of more than 940 kg / m 3 are particularly suitable under these conditions. However, practical tests have shown that those with higher densities, above about 1000 kg / m 3 worked even better. This can be explained by a faster settling of the polyalkylene glycols according to the invention, when complete solubility in the carbon dioxide refrigerant is no longer present.
  • additives such as wear improvers, anti-foaming agents, antioxidants, such as alkylated phenolic antioxidants, e.g. in particular Irganox® L101, viscosity index improvers, corrosion inhibitors or high-pressure additives, in particular phosphate esters.
  • esters or ester mixtures which, according to (1) (a), based on the total carboxylic acid group concentration, consist of at least 60 mol% of n-pentanoic acid, are also preferred; the acid component of (1) (b) consists predominantly of branched monocarboxylic acids, more preferably of 5 to 40 mol% of branched monocarboxylic acids, based on the total carboxylic acid group concentration.
  • the acid components remaining for the complete esterification of all hydroxy groups consist of linear C5 to C10 monocarboxylic acids.
  • all hydroxy groups of the alcohol component are completely esterified.
  • the neopentyl glycol esters according to the invention preferably have densities above 940 kg / m 3 , in general even more than 1000 kg / m 3 .
  • the polyalkylene glycols according to the invention can be used together with neopentyl polyol esters as lubricants, which predominantly, i. to greater than 90%, preferably to about 100%, branched C5 to C10 acid groups, particularly preferably branched C8 to C10 acid groups.
  • neopentyl polyol esters for the definition of the preferred alcohol groups of these neopentyl polyol esters, reference is made to the paragraph above.
  • the proportion of the polyalkylene glycols of the invention is preferably at least 20% by weight, more preferably at least 40% by weight, based on the amount of lubricant (i.e., the lubricants without refrigerants and additives) in 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.
  • Tests have proven the effectiveness of the polyalkylene glycols according to the invention as lubricants in CO 2 refrigeration machines.
  • the viscosity / vapor pressure temperature behavior of a mixture of carbon dioxide and the polyalkylene glycol Triton GL-220® from DEA Mineraloel AG can be taken.

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Description

Die Erfindung betrifft Betriebsmittelzusammensetzungen enthaltend Schmiermittel auf Basis von Polyalkylenglykolen, die sich zur Schmierung von Kältemaschinen, Wärmepumpen und verwandter Anlagen, wie Klimaanlagen, die ausschließlich mit Kohlendioxid als Kältemittel betrieben werden, eignen.The invention relates to operating compositions containing polyalkylene glycol-based lubricants which are suitable for lubricating refrigerators, heat pumps and related equipment, such as air conditioners, which are operated solely with carbon dioxide as a refrigerant.

Kohlendioxid ist bereits zu Beginn der modernen Kältetechnik als Kältemaschinen-Betriebsmittel verwendet worden. So baute die Firma Linde bereits im Jahre 1881 die erste Kompressions-Kältemaschine unter Verwendung von Kohlendioxid als Kältemittel. Noch bis zur Mitte dieses Jahrhunderts wurde Kohlendioxid vorwiegend in Schiffskälteanlagen unterhalb seiner kritischen Temperatur (kritischer Punkt Tk=31,4°C / pk=72,9 bar) eingesetzt. Als Schmiermittel kam Glyzerin zum Einsatz. Später, mit der Einführung der FCKW-Kältemittel, ist Kohlendioxid kaum noch eingesetzt worden.Carbon dioxide has been used as refrigeration equipment at the beginning of modern refrigeration. In 1881, for example, Linde built the first compression chiller using carbon dioxide as a refrigerant. Until the middle of this century, carbon dioxide was mainly used in ship chillers below its critical temperature (critical point T k = 31.4 ° C / p k = 72.9 bar). The lubricant used was glycerin. Later, with the introduction of CFC refrigerants, carbon dioxide has barely been used.

Der Ausstieg aus umweltschädigenden Fluor-Chlor-Kohlenwasserstoffen (FCKW) als Kältemaschinen-Betriebsmittel hat dazu geführt, Kohlendioxid als mögliches Betriebsmittel für Kältemaschinen erneut in Betracht zu ziehen. Kohlendioxid ist leicht und günstig verfügbar und übt keinen schädigenden Einfluß auf die Ozonschicht aus. Kohlendioxid zeichnet sich als Kältemaschinen-Betriebsmittel weiterhin durch eine gegenüber FCKW-Betriebsmitteln höhere isentropische und volumetrische Kühl-Effizienz aus.The phasing out of polluting fluoro-chloro-hydrocarbons (CFCs) as refrigeration equipment has led to reconsideration of carbon dioxide as a possible refrigerant resource. Carbon dioxide is readily and cheaply available and has no harmful effect on the ozone layer. Carbon dioxide continues to be a refrigeration equipment by a comparison with CFC resources higher isentropic and volumetric cooling efficiency.

Erst in den 80er Jahren wurde die-Entwicklungsarbeit mit dem natürlichen Kältemittel CO2 wieder aufgenommen. Erste Versuche zeigten die technischen Möglichkeiten eines transkritischen, auch superkritisch genannten, Kohlendioxid-Kreisprozesses mit Drücken von über 100 bar auf.It was only in the 1980s that the development work with the natural refrigerant CO 2 was resumed. Initial experiments showed the technical possibilities of a transcritical, also supercritical, carbon dioxide cycle with pressures of over 100 bar.

Inzwischen haben verschiedene Forschungsstellen dieses Konzept aufgegriffen und arbeiten an der Realisierung geeigneter Kälteanlagen. Gleichzeitig wird jedoch auch an der Weiterentwicklung des herkömmlichen Verfahrens im subkritischen Bereich gearbeitet.In the meantime, various research institutes have taken up this concept and are working on the realization of suitable refrigeration systems. At the same time, however, the development of the conventional method in the subcritical range is also being worked on.

Polypropylenglykole und Polyalkylenglykol- Copolymere enthaltend Propylenoxid-Monomereinheiten sind als Schmiermittel seit langem bekannt.Polypropylene glycols and polyalkylene glycol copolymers containing propylene oxide monomer units have long been known as lubricants.

In der EP 0 421 765-A1 wird deren Kompatibilität mit R134a (1,1,1,2-Tetrafluorethan) als Kältemaschinenbetriebsmittel beschrieben. R134a und Kohlendioxid sind jedoch grundverschiedene Betriebsmittel. Die EP 0 421 765-A1 gibt keinen Hinweis zur Löslichkeit / Mischbarkeit, Kompatibilität, thermischen und hydrolytischen Stabilität von Betriebsmittelzusammensetzungen enthaltend Polyalkylenglykole und Kohlendioxid.In the EP 0 421 765-A1 their compatibility with R134a (1,1,1,2-tetrafluoroethane) is described as refrigeration equipment resources. However, R134a and carbon dioxide are fundamentally different resources. The EP 0 421 765-A1 gives no indication of the solubility / miscibility, compatibility, thermal and hydrolytic stability of working compositions containing polyalkylene glycols and carbon dioxide.

In der EP 0 017 172-A1 werden Polyalkylenglykol - Neopentylpolyolester - Gemische als Schmiermittel für Kompressoren offenbart. Die EP 0 017 172-A1 gibt keinen Hinweis auf Kältemaschinen oder die Verwendung der Schmiermittel in Kältemaschinenbetriebsmitteln.In the EP 0 017 172 A1 Polyalkylene glycol neopentyl polyol ester mixtures are disclosed as lubricants for compressors. The EP 0 017 172 A1 gives no indication of chillers or the use of lubricants in chiller equipment.

Die EP 0 861 883-A2 , WO 98/08912 , EP 0 908 509-A1 , EP 0 844 299-A1 und EP 0 959 121-A1 haben einen früheren Zeitrang, sind jedoch erst nach dem Prioritätstag der vorliegenden Anmeldung veröffentlicht und somit als Artikel 54(3)-Dokumente nur hinsichtlich der Neuheit zu bewerten. In diesen werden sehr unterschiedliche Schmiermittel, u.a. auch Polyalkylenglykole, neben sehr unterschiedlichen Kältemitteln bzw. Kältemittelmischungen offenbart, wobei u.a. auch Kohlendioxid genannt ist. Nicht offenbart ist jedoch die Kombination eines Kältemittels, das ausschließlich aus Kohlendioxid besteht, mit Polyalkylkenglykolen, welche zumindest 40% Propylenoxidmonomereinheiten enthalten.The EP 0 861 883-A2 . WO 98/08912 . EP 0 908 509 A1 . EP 0 844 299 A1 and EP 0 959 121-A1 have earlier priority, but are published after the priority date of the present application, and thus as Article 54 (3) documents, they are to be evaluated only in terms of novelty. In these very different lubricants, including polyalkylene glycols, in addition to very different refrigerants or refrigerant blends are disclosed, among others, carbon dioxide is called. However, it does not disclose the combination of a refrigerant consisting solely of carbon dioxide with polyalkylene glycols containing at least 40% of propylene oxide monomer units.

Für Kohlendioxid als Kältemaschinenbetriebsmittel sind gegenüber konventionellen Kältemitteln wie Fluor/Chlor- oder Fluor-Kohlenwasserstoffen erhöhte Betriebsdrücke und Betriebstemperaturen (bzw. Δp 's und ΔT 's) erforderlich, die hohe Anforderungen an Dichtmaterialien, bewegliche Teile und Schmiermittel stellen. Dies gilt insbesondere für Kältemaschinenanlagen, die in einem transkritischen Kreisprozeß betrieben werden.For carbon dioxide refrigeration equipment, increased operating pressures and operating temperatures (or Δp 's and ΔT' s) are required over conventional refrigerants such as fluorine / chlorine or fluorine hydrocarbons, which places high demands on sealants, moving parts, and lubricants. This applies in particular to refrigeration systems that are operated in a transcritical cycle.

Als Schmiermittel für beide Verfahrensweisen wurden bereits Polyalkylen-Glykole vorgeschlagen (siehe z.B. Lubricants for Carbon Dioxide; U. Hesse, H.O.Spauschus in Refrigeration Science and Technology, Proceedings, Aarhus Denmark 3-6 Sept. 1996, ISSN 0 151 163).Polyalkylene glycols have already been proposed as lubricants for both processes (see, e.g., Lubricants for Carbon Dioxide, U. Hesse, H.O.Spauschus in Refrigeration Science and Technology, Proceedings, Aarhus Denmark 3-6 Sept. 1996, ISSN 0 151 163).

In einem transkritischen Kreisprozeß werden im Laufe des Kompressionszyklusses Zustände durchlaufen, in denen sich das Kohlendioxid als Kältemittel sowohl im subkritischen (unterkritischen) Bereich als auch im superkritischen (überkritischen) Bereich befindet.In a transcritical cycling process, states are passed through the compression cycle in which the carbon dioxide refrigerant is both subcritical and supercritical.

CO2 verhält sich hinsichtlich der Löslichkeiteigenschaften sehr unterschiedlich. Subkritisches CO2 ist polar, während CO2 im superkritischen Bereich unpolarer ist. Die erfindungsgemäßen Polyalkylenglykole sind für höhere Massenanteile Schmiermittel in CO2 über den gesamten Temperaturbereich von der kritischen Temperatur Tk bis unter -55°C löslich. Bei geringeren Anteilen Schmiermittel sind die Polyalkylenglykole nicht mehr oder nur teilweise in Kohlendioxid löslich.CO 2 behaves very differently with regard to the solubility properties. Subcritical CO 2 is polar, while CO 2 is non-polar in the supercritical region. The polyalkylene glycols according to the invention are soluble in CO 2 over the entire temperature range from the critical temperature T k to below -55 ° C. for higher mass fractions. At lower levels of lubricant, the polyalkylene glycols are no longer or only partially soluble in carbon dioxide.

Der Erfindung liegt das Problem zugrunde, eine Auswahl möglicher Polyalkylen-Glykole zu finden, die den folgenden Anforderungen an Schmiermittel für CO2-Kältemaschinen genügen:

  • ausgezeichnete thermische und chemische Stabilität
  • sehr gute hydrolytische Stabilität
  • sehr gute Schmierungseigenschaften
  • komplett mischbar in den für die Betriebsmaschinen notwendigen Mischungsverhältnissen
  • eine geringe Hygroskopizität
  • hohe Verträglichkeit mit Dichtmaterialien und
  • gutes Viskositäts-Temperatur-Verhalten.
The invention is based on the problem of finding a selection of possible polyalkylene glycols which meet the following requirements for lubricants for CO 2 refrigerating machines:
  • excellent thermal and chemical stability
  • very good hydrolytic stability
  • very good lubrication properties
  • completely miscible in the mixing ratios necessary for the operating machines
  • a low hygroscopicity
  • high compatibility with sealing materials and
  • good viscosity-temperature behavior.

Dies gilt im besonderen Maße auch für die erschwerten Bedingungen des transkritischen Kältekreisprozesses. Wegen der höheren Drücke und der erhöhten Effizienz werden Kältemaschinen für den transkritischen Bereich kleiner ausgelegt und weisen oft geringe Durchmesser in den Leitungssystemen auf. Dies erfordert eine ausreichende Mobilität des Schmiermittels im entsprechenden Temperaturbereich.This is especially true for the difficult conditions of the transcritical refrigeration cycle process. Because of the higher pressures and increased efficiency, transcritical chillers are made smaller and often have small diameters in the piping systems. This requires sufficient mobility of the lubricant in the corresponding temperature range.

Überraschend haben sich zur Lösung dieser Aufgaben als geeignet erwiesen: Betriebsmittelzusammensetzungen für Kältemaschinen, Wärmepumpen und verwandte Anlagen, wie Klimaanlagen, enthaltend Kohlendioxid als Kältemittel, wobei das Kältemittel ausschließlich aus Kohlendioxid besteht, und Polyalkylenglykole bzw. deren Gemische als Schmiermittel bestehend aus, jeweils bezogen auf die Polymerkette:

  1. (a) zu mindestens 40%, vorzugsweise 60 %, der Monomereinheiten aus Monomereinheiten des Typs -(-CH(CH3)-CH2-O-)- und/oder -(-CH2-CH(CH3)-O-)- und
  2. (b) zum verbleibenden Rest im wesentlichen aus Monomereinheiten des Typs -(-R-O-)- , wobei R eine lineare oder verzweigte, gesättigte Alkylengruppe mit 2 bis 6 Kohlenstoffatomen ist, ggf. 1 bis 2 weitere Oxy-Gruppen (-O-) tragen kann und für jede Monomereinheit verschieden sein kann.
Surprisingly, have proved to solve these tasks as suitable: equipment compositions for refrigerators, heat pumps and related equipment, such as air conditioning systems containing carbon dioxide as a refrigerant, the refrigerant consists exclusively of carbon dioxide, and polyalkylene glycols or mixtures thereof as a lubricant consisting of, in each case based on the polymer chain:
  1. (a) at least 40%, preferably 60%, of monomer units of the type - (- CH (CH 3 ) -CH 2 -O-) - and / or - (- CH 2 -CH (CH 3 ) -O -)- and
  2. (b) to the remainder substantially consisting of monomer units of the type - (- RO -) -, where R is a linear or branched, saturated alkylene group having 2 to 6 carbon atoms, optionally 1 to 2 further oxy groups (-O-) and may be different for each monomer unit.

Die Polyalkylenglykole weisen Wasserstoff-, Alkyl-, Aryl- ,Alkylaryl-, Aryloxy-, Alkoxy- Alkylaryloxy- und/oder Hydroxy-Endgruppen (c) auf. Die Endgruppen vom Alkyl- oder Aryl-Typ haben bevorzugt 1 bis 8, besonders bevorzugt 1 bis 4, Kohlenstoffatome. Für letzteren Fall sind dieses Alkyl- und/oder Alkoxy-Endgruppen.The polyalkylene glycols have hydrogen, alkyl, aryl, alkylaryl, aryloxy, alkoxy, alkylaryloxy and / or hydroxyl end groups (c). The alkyl or aryl type end groups preferably have 1 to 8, more preferably 1 to 4, carbon atoms. In the latter case, these are alkyl and / or alkoxy end groups.

Für die erfindungsgemäßen Polyalkylenglykole werden besonders gute Ergebnisse hinsichtlich hoher Dichte und guten Schmiereigenschaften einerseits und den oben aufgeführten Eigenschaften andererseits erzielt, wenn das Polyalkylenglykol als Hauptkomponente, nämlich zu mindestens 60%, Propylenoxid-Einheiten (Monomereinheiten des Typs (a) ) enthält.For the polyalkylene glycols according to the invention particularly good results in terms of high density and good lubricating properties on the one hand and the properties listed above are achieved if the polyalkylene glycol as the main component, namely at least 60%, propylene oxide units (monomer units of type (a)).

Die erfindungsgemäßen Polyalkylenglykole sind somit entweder Homopolymere, nämlich Polypropylenglykol (bzw. Polypropylenoxid), oder Copolymere, Terpolymere usw. enthaltend weiterhin Monomereinheiten des Typs (b). Für diesem Fall können die Monomereinheiten eine statistische Verteilung oder eine Blockstruktur aufweisen. In einer weiteren Ausführungsform der Erfindung sind die Monomereinheiten des Typs (b) zu mindestens 5 % in der Polymerkette enthalten. Die Monomereinheiten des Typs (b) sind bevorzugt Ethylenoxid- und/oder Butylenoxid-Einheiten.The polyalkylene glycols according to the invention are thus either homopolymers, namely polypropylene glycol (or polypropylene oxide), or copolymers, terpolymers, etc., furthermore containing monomer units of type (b). In this case, the monomer units may have a statistical distribution or a block structure. In a further embodiment of the invention, the monomer units of type (b) are at least 5% in the polymer chain. The monomer units of type (b) are preferably ethylene oxide and / or butylene oxide units.

Die erfindungsgemäßen Polyalkylenglykole können durch Umsetzung von Alkoholen, einschließlich der Polyalkohole, als Starterverbindungen mit Alkylenoxiden wie Ethylenoxid, Propylenoxid und/oder Butylenoxid hergestellt werden. Diese weisen nach der Umsetzung nur noch eine freie Hydroxygruppe als Endgruppe auf. Polyalkylenglykole mit nur einer Hydroxygruppe sind gegenüber denen mit zwei freien Hydroxygruppen bevorzugt.The polyalkylene glycols of the invention can be prepared by reacting alcohols, including the polyhydric alcohols, as initiator compounds with alkylene oxides 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.

Besonders bevorzugt hinsichtlich der Stabilität, Hygroskopizität und Kompatibilität sind Polyalkylenglykole, die z.B. nach einem weiteren Veretherungsschritt keine freien Hydroxygruppen mehr aufweisen.Particularly preferred in terms of stability, hygroscopicity and compatibility are polyalkylene glycols, e.g. after a further etherification step no more free hydroxy groups.

Hinsichtlich der Molekulargewichte sind solche Polyalkylenglykole bevorzugt, die mittlere Molekulargewichte von 400 bis 3000 g/mol, besonders bevorzugt von 1000 bis 2000 g/mol aufweisen.With regard to the molecular weights, preference is given to those polyalkylene glycols which have average molecular weights of from 400 to 3000 g / mol, more preferably from 1000 to 2000 g / mol.

Die erfindungsgemäßen Polyalkylenglykole zeichnen sich durch Dichten von über 940 kg/m3, und vorzugsweise sogar über 1000 kg/m3, aus und besitzen darüber hinaus überraschend auch die oben aufgeführten Eigenschaften, die für einen Einsatz als Kältemaschinenöl in Kombination mit Kohlendioxid als Kältemittel erforderlich sind.The polyalkylene glycols according to the invention are characterized by densities of more than 940 kg / m 3 , and preferably even more than 1000 kg / m 3 , and moreover surprisingly also possess the abovementioned properties which are required for use as refrigerating machine oil in combination with carbon dioxide as the refrigerant are.

Überraschend wurde festgestellt, daß der Rücktransport der Polyalkylenglykol - Schmiermittel zum Kompressor bei weniger guter Löslichkeit dann besonders gut gewährleistet ist, wenn ihre Dichte deutlich über der des flüssigen Kohlendioxids in diesem Temperatur-/ Druckbereich liegt. In einem solchen Falle findet sogar unter den besonderen Bedingungen in CO2-Kältemaschinen eine effektive Phasentrennung statt, bei der das erfindungsgemäße Polyalkylenglykol entsprechend seiner höheren Dichte die untere, das Kohlendioxid die obere Phase bildet. Ein Rückfluß des Polyalkylenglykols zum Kompressor ist somit bei entsprechendem Anlagedesign gewährleistet. Dies ist für die Mischungsverhältnisse CO2-Kältemittel/Polyalkylenglykol-Schmiermittels wichtig, für die eine vollständige Löslichkeit des Schmiermittels in CO2 nicht mehr gegeben ist.Surprisingly, it has been found that the return transport of the polyalkylene glycol lubricant to the compressor with less good solubility is ensured particularly well if its density is significantly higher than that of the liquid carbon dioxide in this temperature / pressure range. In such a case, even under the particular conditions in CO 2 refrigeration machines, an effective phase separation takes place in which the polyalkylene glycol according to the invention forms the lower phase, the carbon dioxide the upper phase in accordance with its higher density. A reflux of the polyalkylene glycol to the compressor is thus ensured with the appropriate system design. This is important for the CO 2 refrigerant / polyalkylene glycol lubricant mixture ratios for which complete solubility of the lubricant in CO 2 is no longer present.

Polyalkylenglykole mit einer Dichte von über 940 kg/m3 sind unter diesen Verhältnissen besonders geeignet. Praktische Versuche haben aber ergeben, daß solche mit höheren Dichten, über etwa 1000 kg/m3 noch besser funktionierten. Dies kann mit einem schnelleren Absetzen der erfindungsgemäßen Polyalkylenglykole erklärt werden, wenn eine vollständige Löslichkeit im Kohlendioxid-Kältemittel nicht mehr gegeben ist.Polyalkylene glycols with a density of more than 940 kg / m 3 are particularly suitable under these conditions. However, practical tests have shown that those with higher densities, above about 1000 kg / m 3 worked even better. This can be explained by a faster settling of the polyalkylene glycols according to the invention, when complete solubility in the carbon dioxide refrigerant is no longer present.

Zusätzlich können in der Betriebsmittelzusammensetzungen übliche Additive wie Verschleißverbesserer, Anti-Schaummittel, Antioxidantien, wie alkylierte phenolische Antioxidantien wie z.B. insbesondere Irganox® L101, ViskositätsindexVerbesserer, Korrosionsschutzmittel oder auch Hochdruck-Additive, wie insbesondere Phosphat-Ester, enthalten sein.In addition, conventional additives such as wear improvers, anti-foaming agents, antioxidants, such as alkylated phenolic antioxidants, e.g. in particular Irganox® L101, viscosity index improvers, corrosion inhibitors or high-pressure additives, in particular phosphate esters.

Weiterhin können die erfindungsgemäßen Polyalkylenglykole zusammen mit Neopentylpolyolestern als Schmiermittel eingesetzt werden. Solche Ester sind beispielsweise in der deutschen Patentanmeldung DE 197 19 132 der RWE-DEA Aktiengesellschaft für Mineralöl und Chemie, eingereicht am 07.05.1997, ausgewiesen. Diese Ester bzw. das Estergemisch besteht vorzugsweise aus Neopentyl polyolestern der folgenden Art:

  1. (1) einer Säurekomponente, wobei die Säurekomponente,
    1. (a) bezogen auf die Gesamtcarbonsäuregruppenkonzentration, aus mindestens 40 mol% n-Pentansäure besteht und
    2. (b) zu dem verbleibenden Rest aus linearen oder verzweigten C6- bis C10- Monocarbonsäuren und / oder verzweigten C5- Monocarbonsäuren besteht, und
  2. (2) einer Alkoholkomponente mit 4 bis 8 Hydroxygruppen, einem, zwei oder drei quartären Kohlenstoffatomen und 5 bis 21 , vorzugsweise 5 bis 15, Kohlenstoffatomen, wobei die -OH-Gruppen des Polyhydroxyalkohols als Alkoholkomponente vorzugsweise mit solchen Kohlenstoffatomen verbunden sind, die ihrerseits lediglich quartäre Kohlenstoffatome in Nachbarstellung aufweisen. Der Polyhydroxyalkohol als Alkoholkomponente kann weiterhin 0 bis 4, bevorzugt 0 , 1 oder 2, Etherbrücken enthalten. Besonders bevorzugt ist die Alkoholkomponente: Pentaerythritol und / oder Dipentaerythritol und / oder Tripentaerythritol. In einer weiteren Ausgestaltung enthält die Betriebsmittelzusammensetzung einen Ester oder ein Estergemisch, dessen Alkoholkomponente bezogen auf die Gesamtalkoholgruppenkonzentration (der Ester) zu mindestens 50 mol% aus Dipentaerythritol und / oder Tripentaerythritol besteht. Ester mit diesen Alkoholgruppen haben sich insbesondere für Kältemaschienen, die im transkritischen Bereich betrieben werden, bewährt.
Furthermore, the polyalkylene glycols according to the invention can be used together with Neopentylpolyolestern as a lubricant. Such esters are for example in the German patent application DE 197 19 132 RWE-DEA Aktiengesellschaft für Mineralöl und Chemie, filed on 07.05.1997. These esters or the ester mixture is preferably from neopentyl polyol esters of the following type:
  1. (1) an acid component, wherein the acid component,
    1. (A) based on the total carboxylic acid group concentration, consists of at least 40 mol% of n-pentanoic acid and
    2. (b) to the remainder of linear or branched C6 to C10 monocarboxylic acids and / or branched C5 monocarboxylic acids, and
  2. (2) an alcohol component having 4 to 8 hydroxy groups, one, two or three quaternary carbon atoms and 5 to 21, preferably 5 to 15, carbon atoms, wherein the -OH groups of the polyhydric alcohol as the alcohol component are preferably linked to such carbon atoms which in turn are only have quaternary carbon atoms in neighboring position. The polyhydric alcohol as the alcohol component may further contain 0 to 4, preferably 0, 1 or 2, ether bridges. Particularly preferred is the alcohol component: pentaerythritol and / or dipentaerythritol and / or tripentaerythritol. In another embodiment, the resource composition contains an ester or an ester mixture whose alcohol component based on the total alcohol group concentration (the ester) is at least 50 mol% of dipentaerythritol and / or tripentaerythritol. Esters with these alcohol groups have proven particularly useful for chillers operating in the transcritical range.

Hinsichtlich der Säurekomponente gelten auch unabhängig voneinander solche Ester oder Estergemisch als bevorzugt, deren Säurekomponente nach (1)(a) bezogen auf die Gesamtcarbonsäuregruppenkonzentration aus mindestens 60 mol% n-Pentansäure besteht; deren Säurekomponente nach (1)(b) überwiegend aus verzweigter Monocarbonsäuren, besonders bevorzugt aus, bezogen auf die Gesamtcarbonsäuregruppenkonzentration, aus 5 bis 40 mol% verzweigter Monocarbonsäuren besteht. Für letzteren Fall bestehen die zur vollständigen Veresterung aller Hydroxygruppen verbleibenden Säurekomponenten aus linearen C5- bis C10-Monocarbonsäuren. Vorzugsweise sind in dem Ester oder dem Estergemisch alle Hydroxygruppen der Alkoholkomponente vollständig verestert. Die erfindungsgemäßen Neopentylglykolester weisen bevorzugt Dichten über 940 kg/m3, in der Regel sogar über 1000 kg/m3.With regard to the acid component, those esters or ester mixtures which, according to (1) (a), based on the total carboxylic acid group concentration, consist of at least 60 mol% of n-pentanoic acid, are also preferred; the acid component of (1) (b) consists predominantly of branched monocarboxylic acids, more preferably of 5 to 40 mol% of branched monocarboxylic acids, based on the total carboxylic acid group concentration. For the latter case, the acid components remaining for the complete esterification of all hydroxy groups consist of linear C5 to C10 monocarboxylic acids. Preferably, in the ester or ester mixture all hydroxy groups of the alcohol component are completely esterified. The neopentyl glycol esters according to the invention preferably have densities above 940 kg / m 3 , in general even more than 1000 kg / m 3 .

Nach einer weiteren Ausgestaltung der Erfindung können die erfindungsgemäßen Polyalkylenglykole zusammen mit Neopentylpolyolestern als Schmiermittel eingesetzt werden, welche überwiegend, d.h. zu größer 90 % , vorzugsweise zu etwa 100 %, verzweigte C5- bis C10- Säure-Gruppen, besonders bevorzugt verzweigte C8- bis C10- Säure-Gruppen, aufweisen. Bezüglich der Definition der bevorzugten Alkoholgruppen dieser Neopentylpolyolester wird auf den obigen Absatz Bezug genommen.According to a further embodiment of the invention, the polyalkylene glycols according to the invention can be used together with neopentyl polyol esters as lubricants, which predominantly, i. to greater than 90%, preferably to about 100%, branched C5 to C10 acid groups, particularly preferably branched C8 to C10 acid groups. For the definition of the preferred alcohol groups of these neopentyl polyol esters, reference is made to the paragraph above.

Der Anteil der erfindungsgemäßen Polyalkylenglykole beträgt vorzugsweise mindestens 20 Gew.%, besonders bevorzugt mindestens 40 Gew.%, bezogen auf den Schmiermittel-Anteil (d.h. die Schmiermittel ohne Kältemittel und Additive) in der Betriebsmittelzusammensetzung. Der Anteil der Neopentylpolyolester als Schmiermittel beträgt bei Einsatz von Schmiermittelgemischen unterschiedlicher Verbindungsklassen vorzugsweise 20 bis 60 Gew.%, besonders bevorzugt 40 bis 60 Gew.%, jeweils bezogen auf den Schmiermittel - Anteil in der Betriebsmittelzusammensetzung.The proportion of the polyalkylene glycols of the invention is preferably at least 20% by weight, more preferably at least 40% by weight, based on the amount of lubricant (i.e., the lubricants without refrigerants and additives) in the resource composition. When using lubricant mixtures of different compound classes, 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.

Versuche haben die Wirksamkeit der erfindungsgemäßen Polyalkylenglykole als Schmiermittel in CO2-Kältemaschinen unter Beweis gestellt. Der Figur 1 kann beispielsweise das Viskositäts-/Dampfdruck- Temperaturverhalten eines Gemisches aus Kohlendioxid und dem Polyalkylenglykol Triton GL-220® der DEA Mineraloel AG (Butanol gestartetes Polypropylenoxid) entnommen werden.Tests have proven the effectiveness of the polyalkylene glycols according to the invention as lubricants in CO 2 refrigeration machines. Of the FIG. 1 For example, the viscosity / vapor pressure temperature behavior of a mixture of carbon dioxide and the polyalkylene glycol Triton GL-220® from DEA Mineraloel AG (butanol-initiated polypropylene oxide) can be taken.

Claims (15)

  1. Working compositions for refrigeration machines containing carbon dioxide as a refrigerant and polyalkylene glycols and/or mixtures thereof, wherein the polyalkylene glycols consist of the following, based on the polymer chain:
    (a) at least 40 %, preferably at least 60 %, of the monomer units of monomer units of the type -(-CH(CH3)-CH2-O-)- and/or -(-CH2-CH(CH3)-O-)- and
    (b) monomer units of the type -(-R-O-)- for the remainder, wherein R is a linear or branched, saturated alkyl group with two to six carbon atoms, optionally has one to two other oxy groups (-O-) and may be different for each monomer unit,
    (c) comprises terminal groups which are
    (i) hydrogen and/or hydroxyl terminal groups and/or
    (ii) alkyl, aryl, alkylaryl, aryloxy, alkoxy and/or alkylaryloxy terminal groups
    whereby the refrigerant consists exclusively of carbon dioxide.
  2. Working composition according to Claim 1, characterized in that the working composition contains polyalkylene glycols and/or mixtures thereof,
    (c) having terminal groups which are
    (i) hydrogen and/or hydroxyl terminal groups and/or
    (ii) alkyl, aryl, alkylaryl, aryloxy, alkoxy and/or alkylaryloxy terminal groups having one to eight carbon atoms, preferably one or four carbon atoms.
  3. Working composition according to one of the preceding claims, characterized in that the working composition contains polyalkylene glycols and/or the mixtures thereof, whose monomers of the type (b) constitute at least 5 % of the monomer units of the molecule.
  4. Working composition according to one of the preceding claims, characterized in that the working composition contains polyalkylene glycols and/or the mixtures thereof, whose monomers of the type (b) are ethylene oxide units and/or butylene oxide units, respectively are synthesized therefrom.
  5. Working composition according to one of the preceding claims, characterized in that the working composition contains polyalkylene glycols and/or mixtures thereof, having only one free hydroxyl group per molecule.
  6. Working composition according to one Claims 1 through 4, characterized in that the working composition contains polyalkylene glycols and/or mixtures thereof, which do not have any free hydroxyl groups per molecule.
  7. Working composition according to one of the preceding claims, characterized in that the working composition contains polyalkylene glycols and/or mixtures thereof, having a mean molecular weight of 400 to 3000 g/mol, especially preferably 1000 to 2000 g/mol.
  8. Working composition according to one of the preceding claims, characterized in that the working composition also contains esters or an ester mixture, whereby the esters are neopentylpolyol esters.
  9. Working composition according to Claim 8, characterized in that the neopentylpolyol esters consist of
    (1) an acid component, whereby the acid component consists of
    (a) at least 40 mol % n-pentanoic acid, based on the total carboxylic acid group concentration,
    (b) linear or linear or branched C6- to C10- monocarboxylic acids and/or branched C5- monocarboxylic acids for the remainder, and
    (2) an alcohol component with 4 to 8 hydroxyl groups, one, two or three quaternary carbon atoms, 5 to 21 carbon atoms and 0 to 4 ether linkages.
  10. Working composition according to Claim 8, characterized in that the neopentylpolyol esters consist of
    (1) a C5- to C10-acid component, whereby the acid component consists of at least 90 mol % branched carboxylic acids, based on the total carboxylic acid group concentration, and
    (2) an alcohol component with 4 to 8 hydroxyl groups, one, two or three quaternary carbon atoms, 5 to 21 carbon atoms and 0 to 4 ether linkages.
  11. Working composition according to one of the preceding claims, characterized in that the working composition contains polyalkylene glycols or polyalkylene glycol / ester mixtures, each according to one of the preceding claims, having a density of more than 940 kg/m3, preferably more than 1000 kg/m3.
  12. Working composition according to one of the preceding claims, characterized in that the working composition contains only polyalkylene glycols according to one of Claims 1 through 7 or polyalkylene glycol / ester mixtures according to one of Claims 8 through 11 as lubricants.
  13. Use of the polyalkylene glycols or polyalkylene glycol-ester mixtures according to one of the preceding claims as a lubricant in refrigeration machines which are operated with carbon dioxide, whereby the refrigerant consists exclusively of carbon dioxide.
  14. Use according to Claim 13, characterized in that the working composition is carried in a transcritical circulating process.
  15. Use according to Claim 13, characterized in that the working composition is carried exclusively in a subcritical circulating process.
EP98932037A 1997-05-07 1998-04-29 Polyalkylene glycols as lubricants for co 2-based refrigerating machines Expired - Lifetime EP0980416B2 (en)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
DE19719132A DE19719132A1 (en) 1997-05-07 1997-05-07 Polyol esters as lubricants for CO¶2¶ chillers
DE19719132 1997-05-07
DE19719430 1997-05-12
DE19719430A DE19719430C1 (en) 1997-05-12 1997-05-12 Working composition used as lubricant for refrigerators
PCT/DE1998/001196 WO1998050499A2 (en) 1997-05-07 1998-04-29 Polyalkylene glycols as lubricants for co2-based refrigerating machines

Publications (3)

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EP0980416A2 EP0980416A2 (en) 2000-02-23
EP0980416B1 EP0980416B1 (en) 2003-07-09
EP0980416B2 true EP0980416B2 (en) 2009-06-10

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Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TW546372B (en) 1998-12-11 2003-08-11 Idemitsu Kosan Co Refrigerator oil composition, and method of using the composition for lubrication
TW552302B (en) * 1999-06-21 2003-09-11 Idemitsu Kosan Co Refrigerator oil for carbon dioxide refrigerant
JP2001073945A (en) * 1999-08-31 2001-03-21 Sanyo Electric Co Ltd Hermetic electric compressor
ATE439416T1 (en) * 1999-12-28 2009-08-15 Idemitsu Kosan Co USE OF OIL COMPOSITION FOR CARBON DIOXIDE REFRIGERATOR
MY125381A (en) 2000-03-10 2006-07-31 Sanyo Electric Co Refrigerating device utilizing carbon dioxide as a refrigerant.
JP2002194368A (en) 2000-10-17 2002-07-10 Nippon Mitsubishi Oil Corp Freezer oil
DE10209987A1 (en) * 2002-03-07 2003-09-25 Clariant Gmbh Thermally stable polyalkylene glycols as lubricants for refrigeration machines
US7861541B2 (en) 2004-07-13 2011-01-04 Tiax Llc System and method of refrigeration
EP2215363B1 (en) 2007-10-24 2017-06-28 Emerson Climate Technologies, Inc. Scroll compressor for carbon dioxide refrigerant
JP5779668B2 (en) * 2014-01-07 2015-09-16 Ｊｘ日鉱日石エネルギー株式会社 Refrigerating machine oil for carbon dioxide refrigerant and fluid composition for refrigerating machine

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0384724A1 (en) † 1989-02-22 1990-08-29 Nippon Oil Co. Ltd. A method for lubricating refrigerating machines
WO1997003153A1 (en) † 1995-07-10 1997-01-30 Idemitsu Kosan Co., Ltd. Refrigerator oil and method for lubricating therewith
WO1997007182A1 (en) † 1995-08-18 1997-02-27 Imperial Chemical Industries Plc Refrigerant compositions
JPH1046169A (en) † 1996-08-06 1998-02-17 Idemitsu Kosan Co Ltd Lubricating oil composition for refrigerator
WO1998008912A1 (en) † 1996-08-30 1998-03-05 Imperial Chemical Industries Plc Refrigerant compositions

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA1139295A (en) * 1979-04-02 1983-01-11 Robert Carswell Rotary screw compressor lubricants
JP2673587B2 (en) * 1989-10-03 1997-11-05 東燃株式会社 1.1.1.2-Refrigerating Lubricating Oil Using Tetrafluoroethane Refrigerant
JP4079469B2 (en) * 1996-06-25 2008-04-23 出光興産株式会社 Refrigerator oil composition
EP2284247A3 (en) * 1996-11-27 2011-03-23 Idemitsu Kosan Co., Ltd. Lubricating oil composition for refrigerators and method for lubrication with the composition
TW385332B (en) * 1997-02-27 2000-03-21 Idemitsu Kosan Co Refrigerating oil composition

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0384724A1 (en) † 1989-02-22 1990-08-29 Nippon Oil Co. Ltd. A method for lubricating refrigerating machines
WO1997003153A1 (en) † 1995-07-10 1997-01-30 Idemitsu Kosan Co., Ltd. Refrigerator oil and method for lubricating therewith
WO1997007182A1 (en) † 1995-08-18 1997-02-27 Imperial Chemical Industries Plc Refrigerant compositions
JPH1046169A (en) † 1996-08-06 1998-02-17 Idemitsu Kosan Co Ltd Lubricating oil composition for refrigerator
WO1998008912A1 (en) † 1996-08-30 1998-03-05 Imperial Chemical Industries Plc Refrigerant compositions

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
"Kälte technik/Öl-Kältemittel-Systeme", 19 November 1997, article JÖRG FAHL: "Schmierstoffe für den Einsatz mit Kohlendioxid als Kältemittel", pages: 375 - 379 †
"Kirk Othmer Encyclopedia of chemical Technology", vol. 10, 1966, article "Glycols" †
"Ucon Fluids & Lubricants", 1955, article "Union Carbide Specialty Chemicals Division", pages: 3 - 6 †
HESSE U.; SPAUSCHUSS H.O.: "Lubricants for Carbon Dioxide", REFRIGERATION SCIENCE AND TECHNOLOGY PROCEEDINGS, no. 14, 3 September 1996 (1996-09-03) - 6 September 1996 (1996-09-06), AARHUS/DK, pages 605 - 608 †

Also Published As

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AU8208998A (en) 1998-11-27
EP0980416A2 (en) 2000-02-23
DK0980416T4 (en) 2009-10-12
DE19880588D2 (en) 2000-04-13
DE59808991D1 (en) 2003-08-14
AR012666A1 (en) 2000-11-08
EP0980416B1 (en) 2003-07-09
WO1998050499A3 (en) 1999-02-04
DK0980416T3 (en) 2003-10-20
WO1998050499A2 (en) 1998-11-12

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