EP0973853A1 - Polyde und komplexe ester zur verwendung insbesondere in fluorimierten kühlschmierstoffen - Google Patents

Polyde und komplexe ester zur verwendung insbesondere in fluorimierten kühlschmierstoffen

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Publication number
EP0973853A1
EP0973853A1 EP98913796A EP98913796A EP0973853A1 EP 0973853 A1 EP0973853 A1 EP 0973853A1 EP 98913796 A EP98913796 A EP 98913796A EP 98913796 A EP98913796 A EP 98913796A EP 0973853 A1 EP0973853 A1 EP 0973853A1
Authority
EP
European Patent Office
Prior art keywords
acid
hydroxy
ester
refrigerant composition
polyol
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP98913796A
Other languages
English (en)
French (fr)
Inventor
Jari Koistinen
Kari Rissanen
Laura Silvennoinen
Salme Koskimies
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Neste Chemicals Oy
Original Assignee
Neste Chemicals Oy
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from FI971549A external-priority patent/FI111711B/fi
Priority claimed from FI971548A external-priority patent/FI107341B/fi
Application filed by Neste Chemicals Oy filed Critical Neste Chemicals Oy
Publication of EP0973853A1 publication Critical patent/EP0973853A1/de
Withdrawn legal-status Critical Current

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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
    • 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
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    • 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
    • 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
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/2805—Esters 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
    • 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
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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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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    • 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
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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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    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/287—Partial esters
    • C10M2207/289—Partial esters containing free hydroxy groups
    • C—CHEMISTRY; METALLURGY
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    • C10M2207/30—Complex esters, i.e. compounds containing at leasst three esterified carboxyl groups and derived from the combination of at least three different types of the following five types of compounds: monohydroxyl compounds, polyhydroxy xompounds, monocarboxylic acids, polycarboxylic acids or hydroxy carboxylic acids
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    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/30—Complex esters, i.e. compounds containing at leasst three esterified carboxyl groups and derived from the combination of at least three different types of the following five types of compounds: monohydroxyl compounds, polyhydroxy xompounds, monocarboxylic acids, polycarboxylic acids or hydroxy carboxylic acids
    • C10M2207/302—Complex esters, i.e. compounds containing at leasst three esterified carboxyl groups and derived from the combination of at least three different types of the following five types of compounds: monohydroxyl compounds, polyhydroxy xompounds, monocarboxylic acids, polycarboxylic acids or hydroxy carboxylic acids derived from the combination of monocarboxylic acids, dicarboxylic acids and dihydroxy compounds only and having no free hydroxy or carboxyl groups
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/30—Complex esters, i.e. compounds containing at leasst three esterified carboxyl groups and derived from the combination of at least three different types of the following five types of compounds: monohydroxyl compounds, polyhydroxy xompounds, monocarboxylic acids, polycarboxylic acids or hydroxy carboxylic acids
    • C10M2207/302—Complex esters, i.e. compounds containing at leasst three esterified carboxyl groups and derived from the combination of at least three different types of the following five types of compounds: monohydroxyl compounds, polyhydroxy xompounds, monocarboxylic acids, polycarboxylic acids or hydroxy carboxylic acids derived from the combination of monocarboxylic acids, dicarboxylic acids and dihydroxy compounds only and having no free hydroxy or carboxyl groups
    • C10M2207/3025—Complex esters, i.e. compounds containing at leasst three esterified carboxyl groups and derived from the combination of at least three different types of the following five types of compounds: monohydroxyl compounds, polyhydroxy xompounds, monocarboxylic acids, polycarboxylic acids or hydroxy carboxylic acids derived from the combination of monocarboxylic acids, dicarboxylic acids and dihydroxy compounds only and having no free hydroxy or carboxyl 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
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/30—Complex esters, i.e. compounds containing at leasst three esterified carboxyl groups and derived from the combination of at least three different types of the following five types of compounds: monohydroxyl compounds, polyhydroxy xompounds, monocarboxylic acids, polycarboxylic acids or hydroxy carboxylic acids
    • C10M2207/304—Complex esters, i.e. compounds containing at leasst three esterified carboxyl groups and derived from the combination of at least three different types of the following five types of compounds: monohydroxyl compounds, polyhydroxy xompounds, monocarboxylic acids, polycarboxylic acids or hydroxy carboxylic acids derived from the combination of monohydroxy compounds, dihydroxy compounds and dicarboxylic acids only and having no free hydroxy or carboxyl groups
    • 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
    • C10M2207/34—Esters having a hydrocarbon substituent of thirty or more carbon atoms, e.g. substituted succinic acid derivatives
    • C10M2207/345—Esters having a hydrocarbon substituent of thirty or more carbon atoms, e.g. substituted succinic acid derivatives used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2211/00—Organic non-macromolecular compounds containing halogen as ingredients in lubricant compositions
    • C10M2211/02—Organic non-macromolecular compounds containing halogen as ingredients in lubricant compositions containing carbon, hydrogen and halogen only
    • C10M2211/022—Organic non-macromolecular compounds containing halogen as ingredients in lubricant compositions containing carbon, hydrogen and halogen only aliphatic
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • C10M2211/00—Organic non-macromolecular compounds containing halogen as ingredients in lubricant compositions
    • C10M2211/06—Perfluorinated compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • 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
    • C10N2040/02—Bearings
    • 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
    • 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
    • C10N2040/32—Wires, ropes or cables lubricants
    • 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
    • C10N2040/34—Lubricating-sealants
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/36—Release agents or mold release agents
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    • 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
    • C10N2040/38—Conveyors or chain belts
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    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/40—Generators or electric motors in oil or gas winning field
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    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • 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

  • compositions of this kind generally contain a non-chlorinated hydrofluorocarbon based refrigerant composition together with a polyol ester based lubricant mixed therewith.
  • the invention also concerns complex esters according to claim 16 and the use thereof in lubricants.
  • the present invention is based on the finding that polyol or complex esters of 3-hydroxy- 2,2-methyl-3-hydroxy-2,2-dimethylpropionate, i.e. hydroxypivalyl hydroxypivalate, which have good lubricant properties, also exhibit a good or excellent solubility in fluorinated refrigerants and they are therefore suitable for use in refrigerant compositions containing this kind of refrigerants.
  • the polyol esters used comprise the polyol HPHP (hydroxypivalyl hydroxypivalate) as such or together with another polyol, such as NPG,
  • the carboxylic acid is a linear or branched C 5 - C, 8 monocarboxylic acid or a hydroxy acid, such as hydroxypivalic acid or a mixture of mono- and dicarboxylic acids, such as adipic acid, sebasic acid, azelaic acid, dimethvlmalonic acid or cyclic anhydrides.
  • the refrigerant composition according to the present invention is mainly characterized by what is stated in the characterizing parts of claims 1, 3, 5 and 7.
  • the esters of HPHP have good lubricant properties and good solubility in HFC compounds used as refrigerants.
  • the raw materials of said oils can be produced by the economically advantageous oxo-process (hydroformulation).
  • the properties of the oils can easily be modified depending on the application by varying the ratio of the polyols of the ester (the amount of HPHP can be 100 to 5 mol-% of the total amount of polyol), the esterifying carboxylic acid and/or the ratio between the esterifying carboxylic acids.
  • the solubility can be improved and by using dibasic acids the viscosity can be raised.
  • the present esters comprise polyol or complex esters of 3-hydroxy-2,2-methyl-3-hydroxy- 2,2-dimethylpropionate.
  • Polyol ester means i.a. esters having a carboxylic group comprising a monobasic acid or an anhydride thereof.
  • the term “polyol ester” comprises generally also "complex esters” which are esters in which at least a part of the esterifying acids are dibasic. Usually both carboxylic groups of these acids react with an alcohol and yield oligomeric ester compounds, which contain at least two alkohol residues and one carboxylic acid residue.
  • Complex esters also include esters having the carboxylic acid residue formed by a hydroxy acid containing both a hydroxyl group and a carboxylic group.
  • the carboxylic group reacts with the polyol, whereas the hydroxyl group reacts with the carboxylic group of another carboxylic acid.
  • Polyol stands for a compound with at least two hydroxy groups. According to the present invention HPHP can be esterified alone or together with another polyol.
  • These polyols are, e.g., NPG (neopentylglycol), BEPD (2-butyl-2-ethyl- 1,3 -propanediol), ETHD (2-ethyl-l,3- hexanediol), TMP (trimethylol propane), TME (trimethylol ethane), PE (pentaerythritol), TMPD (2,2,4-trimethyl-pentanediol) and CHDM (1,4-dimetylol-cyclohexane).
  • NPG neopentylglycol
  • BEPD (2-butyl-2-ethyl- 1,3 -propanediol
  • ETHD (2-ethyl-l,3- hexanedi
  • polyol ester mixtures are formed by mixing the polyols together and by esterifying the thus formed mixture in situ.
  • a refrigerant composition comprising a polyol ester which completely or almost completely (95 mol-%, or even 100 %) consists of an ester of HPHP.
  • a refrigerant composition comprising in addition to a polyol ester of HPHP an ester of TMP, TME, PE or TMPD at any ratio.
  • HPHP forms the main part of the polyol residue of the ester mixture, i.e. its molar amount is 50 % - 100 %.
  • a refrigerant composition comprising in addition to a polyol ester of HPHP a polyol ester of BEPD, the molar ratio between BEPD and HPHP being 5:95 to 99:1.
  • a refrigerant composition comprising in addition to a polyol ester of HPHP a polyol ester of
  • NPG NPG, ETHD or CHDM.
  • HPHP or a mixture of HPHP and some other polyol is esterified with a linear or branched C 4 to C, 8 carboxylic acid or an anhydride thereof.
  • aliphatic, linear or branched, saturated or unsaturated C 4 -C, 8 -carboxylic acids which can be used for preparing the ester, the following can be mentioned:
  • I saturated, linear C 4 -C 18 -carboxylic acids butanoic acid (butyric acid), pentanoic acid (valeric acid), hexanoic acid (caproic acid), heptanoic acid, octanoic acid (caprylic acid), decanoic acid (capric acid), dodecanoic acid (lauric acid) and hexadecanoic acid (palmitic acid) and mixtures thereof;
  • II saturated, branched C 4 -C, 6 -carboxylic acids isobutanoic acid, 2-ethylhexanoic acid, isononanoic acid and 3,5,5-trimethylhexanoic acid;
  • the ratios between the various linear and branched carboxylic acids can vary within large boundaries.
  • the linear carboxylic acid(s) is (are) present in amounts of 1 to 100 mol-%, preferably about 10 to 90 mol-% of the amount of carboxylic acids.
  • the amount of branched carboxylic acids is 99 to 1 mol-%, preferably about 90 to 10 mol-%.
  • polyolesters which contain 10 to 50 mol-% of at least one linear carboxylic acid and 90 to 50 mol-% of a branched carboxylic acid.
  • Esterifying hydroxy acids are, e.g., hydroxypivalic acid (HPAA), lactic acid, citric acid and dimethylolpropionic acid (DMPA).
  • HPAA hydroxypivalic acid
  • lactic acid lactic acid
  • citric acid dimethylolpropionic acid
  • the esterifying carboxylic acid used can comprise dibasic carboxylic acids, such as oxalic acid, malonic acid, dimethylmalonic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, pimelic acid, suberic acid and azelaic acid. It is also possible to use cyclic anhydrides, such as succinic anhydride or alkyl derivaties thereof, or trimellitic anhydride. Small amounts of aromatic anhydrides, such as phthalic anhydride are also possible.
  • dibasic carboxylic acids such as oxalic acid, malonic acid, dimethylmalonic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, pimelic acid, suberic acid and azelaic acid.
  • cyclic anhydrides such as succinic anhydride or alkyl derivaties thereof, or trimellitic anhydride. Small amounts of aromatic anhydrides, such as phthalic anhydride are also possible.
  • the degree of esterification of the polyols is 50 to 100 %, preferably as high as possible, at least about 90 %.
  • the ratio between the mono- and dibasic carboxylic acids is 50 : 50 to 99 : 1.
  • the polyol esters/mixed esters/complex esters of HPHP or HPHP and at least another polyol can be used for preparing refrigerant compositions. These contain as a refrigerant one or several chlorine-free hydrofluorocarbon(s) (a refrigerant) in which the ester is dissolved.
  • hydrofluorocarbon 134 (1,1,2,2-tetrafluoroethane), hydrofluorocarbon 134a, hydrofluorocarbon 143 (1,1,2-trifluoroethane), hydrofluorocarbon 143a (1,1,1-trifluoroethane), hydrofluorocarbon 152 (1,2-difluoroethane) and hydrofluorocarbon 152a (lJ-difluoroethane).
  • hydrofluorocarbon 134a is generally preferred.
  • Mixtures of hydrofluorocarbons can also be employed. Examples include hydrofluorocarbon mixture 407 (mixture of hydrocarbons 32, 125 and
  • hydrofluorocarbon mixture 410 mixture of hydrocarbon 32 and 125.
  • the viscosity requirement for the ester is, according to ISO- standard, between 5 and 200 cSt (40 °C). Low (5 - 10) and intermediate (22 - 32) viscosities are needed for, e.g., refrigerators and other small refrigeration devices. High viscosity (46 - 68) compositions are used for, e.g., cooling equipment of air conditioners.
  • the viscosity of the prepared esters can be adjusted as desired by suitably selecting esterifying carboxylic acid components and/or by adding a further polyol to the BEPD.
  • esterifying carboxylic acid components and/or by adding a further polyol to the BEPD.
  • conventional linear or branched carboxylic acids C 4 - C 12
  • adipic acid e.g., adipic acid
  • Their viscosity indeces are about 100 and pour points below -40 °C. They are suitable for use in smallish cooling equipment.
  • By increasing the amount of a branched carboxylic acid it is possible to increase the solubility of the esters.
  • the viscosity of the product can be increased.
  • the cold properties and good solubility remain.
  • Mixing HPHP with another polyol before esterification makes it possible to increase even further without impairing the solubility .
  • the viscosity increase to the range of high viscosity.
  • the complex esters of HPHP as well as complex esters of HPHP and some other polyol are already as such novel products which can be used in lubricant compositions for different aims.
  • the esters work as base oil of these compositions and additives are usually employed in amounts of 0 to 20 wt.-% in the compositions for the purpose of modifying the compositions such that they are better suited for various applications.
  • the esters are suitable not only for use in refrigerant compositions but also for all applications mentioned in the introduction of the specification.
  • additives which can be used in the refrigerant liquid compositions include, e.g., the following: antioxidants, antiwear agents, detergents, defoaming agents and corrosion inhibitors.
  • Suitable antioxidants include phenols, such as 2,6-di-t-butyl-4-methylphenol and 4,4'- methylene-bis(2,6-di-t-butylphenol); aromatic amines, such as p,p-dioctylphenylamine, monooctyldiphenylamine, phenothiazine, 3,7-dioctylphenothiazine, phenyl- 1- naphthylamine, phenyl-2-naphthylamine, alkylphenyl- 1 -naphthatalamines and alkyl- phenyl-2-naphthal-amines, as well as sulphur-containing compounds, e.g. dithiophosphates, phosphitest, sulphides and dithio metal salts, such as benzothiazole, tin- dialkyldithiophosphates and zinc diaryldithiophosphates.
  • Suitable antiwear agents include, for example, phosphates, phosphate esters, phosphites, thiophosphites, e.g. zinc dialkyl dithiophosphates, zinc diaryldithiophosphates, tricresyl phosphates, chlorinated waxes, sulphurised fats and olefins, such as thiodipropionic esters, dialkyl sulphides, dialkyl polysulphides, alkyl-mercaptanes, dibenzothiophenes and 2,2'- dithiobis(benzothiazole); organic lead compounds, fatty acids, molybdenum complexes, such as molybdenum disulphide, halogen substituted organosilicon compounds, organic silicon compounds, borates and halogen-substituted phosphorus compounds.
  • phosphates phosphate esters, phosphites, thiophosphites, e.g. zinc dialkyl
  • sulphonates aromatic sulphonic acids, which are substituted with alkyl having a long chain
  • phosphonates thiophosphonates
  • phonolates metal salts of alkylphenols, and alkyl sulphides.
  • Typical defoaming agents include silicon oils, e.g. dimethylpolysilozane and organic silicon compounds such as diethyl silicates.
  • Organic acids, amines, phosphates, alcohols, sulphonates and phosphites are examples of corrosion inhibitors.
  • the esters according to the invention are prepared by a conventional esterification reaction wherein a polyol or a mixture of polyols is (are) reacted with an acid mixture in the presence of a catalyst or without a catalyst.
  • Various acids such as sulphuric acid, hydrochloric acid, p-toluene sulphonic acid, butyl titanate, tinoxide etc., are suitable catalysts for carrying out the invention.
  • a particularly advantageous catalyst is tinoxide.
  • the polyol is reacted with the acid component by using an equivalent amount of acid, a deficient amount of acid or a surplus of acid; the excess acid amounts to typically a maximum of 10 mol-%, preferably about 0.1 to 5 mol-%, in particular about 1 mol-%.
  • the reaction temperature is 150 to 230 °C, preferably 170 to 220 °C and in particular about 190 to 210 °C.
  • the esterification can be carried out as a batch or semibatch process for example by adding the remaining acid later on.
  • the most typical embodiment comprises carrying out esterification in the melt phase but it is also possible to use a hydrocarbon-type medium, such as toluene or xylene.
  • the product is neutralized either with conventional bases (NaOH, NaHCO 3 , Na 2 CO 3 etc.) or with organic amines and are then washed.
  • the degree of purification of the ester product is preferably over 85 %, in particular over 90 % and the acid number of the ester is preferably below 0.1 mg KOH/g.
  • Solubility in fluorinated hydrocarbons was determined as follows: 1 ml of the studied ester was put into a test tube which was closed with a stopper. The test tube was placed in a cold bath at a temperature of -30 °C. When the temperature of the test tube and the ester had reached -30 °C (after about 5 minutes), a fluorinated refrigerant, such as R-134a, was added to make a total volume of 10 ml.
  • a fluorinated refrigerant such as R-134a
  • the ester-refrigerant mixture was allowed to stand in the bath at -30 °C with possibly a light occasional stirring. After about 15 minutes the mixture was visually assessed and it was determined whether the mixture contained one or two phases. If the ester and the refrigerant liquid formed one phase, the ester is completely dissolved in the refrigerant liquid. If there are two phases present in the mixture, the ester is either partially or completely insoluble in the refrigerant liquid.
  • esters of HPHP is described in the following using the esters of HPHP and heptanoic acid as an example.
  • the raw materials were weighed into a glass bulb according to the following recipe: HPHP 50 g and heptanoic acid 64.6 g.
  • the catalyst used comprised 0.17 g tinoxide.
  • the esterification was carried out by stirring using a mixer with an electric motor and by nitrigating the reaction mixture at about 210 °C. The reaction was complete wihin 7 hours.
  • Tinoxide was removed by filtration. Excess acid was neutralized from the reaction mixture with 2 - 5 wt-% triethylamine. The neutralization was carried out at 80 °C for 3 hours. Warm water (2 - 5 wt-%) was added to the reaction mixture and it was mixed cautiously. The solvent of the reaction mixture comprised heptane. Any formed aminocarboxylic acid salt or complex was separated. The solvent and the unreacted triethylamine were removed by vacuum distillation. The end product was filtered. The results are summarized in Table 1.
  • esters of HPHP is illustrated by using the preparation of an ester of HPHP and isobutyric anhydride as an example.
  • the raw materials were weighed into a glass reactor according to the following recipe: HPHP 17.5 g and isobutyric anhydride 19.36 g.
  • the catalyst used comprised 0.37 g methanesulphonic acid.
  • the esterification was carried out by adding the anhydride and the catalyst from a dropping funnel to the HPHP during 2 hours, and then the reaction mixture was stirred at about 150 °C for 2 hours.
  • Cmplex esters of HPHP is described using the ester of HPHP, octanoic acid and adipic ester as an example.
  • the raw materials were weighed into a glass reactor according to the following recipe: HPHP 100 g, octanoic acid 94.8 g and adipic acid 24.0 g.
  • the catalyst used comprised 0.328 g tinoxide. acid.
  • the esterification was carried out by stirring and nitrigating the reaction mixture at about 210 °C. The reaction was complete within 7 hours.
  • BEPD 2-butyl-2-ethyl- 1,3 -propanediol
  • NPG neopentylglycol

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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)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Lubricants (AREA)
EP98913796A 1997-04-11 1998-04-14 Polyde und komplexe ester zur verwendung insbesondere in fluorimierten kühlschmierstoffen Withdrawn EP0973853A1 (de)

Applications Claiming Priority (7)

Application Number Priority Date Filing Date Title
FI971549A FI111711B (fi) 1997-04-11 1997-04-11 Etenkin fluorattujen jäähdytysnesteiden kanssa käytettävät polyoli- ja kompleksiesterit
FI971549 1997-04-11
FI971548 1997-04-11
FI971548A FI107341B (fi) 1997-04-11 1997-04-11 Fluorattujen jäähdytysnesteiden kanssa käytettävät kompleksiesterit
FI980730 1998-03-31
FI980730A FI980730A (fi) 1997-04-11 1998-03-31 Etenkin fluorattujen jäähdytysnesteiden kanssa käytettävät polyoli- ja kompleksiesterit
PCT/FI1998/000329 WO1998046706A1 (en) 1997-04-11 1998-04-14 Polyol and complex esters for use with, in particular, fluorinated refrigerants

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EP0973853A1 true EP0973853A1 (de) 2000-01-26

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EP (1) EP0973853A1 (de)
JP (1) JP2001526712A (de)
AU (1) AU6836198A (de)
FI (1) FI980730A (de)
WO (1) WO1998046706A1 (de)

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JP5275578B2 (ja) * 2007-03-27 2013-08-28 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
US8419968B2 (en) * 2008-11-13 2013-04-16 Chemtura Corporation Lubricants for refrigeration systems
EP3320066B1 (de) * 2015-07-09 2021-04-07 Cargill, Incorporated Verwendung von säureanhydridbeschleunigern zur herstellung von hochreinen polyolestern

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JP2801703B2 (ja) * 1989-09-01 1998-09-21 花王株式会社 冷凍機油
DK0435253T3 (da) * 1989-12-28 1994-06-20 Nippon Oil Co Ltd Køleolier til brug sammen med hydrogenholdige halogencarbonkølemidler
WO1993024587A1 (en) * 1992-06-03 1993-12-09 Henkel Corporation Blended polyol ester lubricants for refrigerant heat transfer fluids
ATE230005T1 (de) * 1993-11-09 2003-01-15 Cognis Corp Verfahren zum schmieren einer fahrzeugklimaanlage

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See references of WO9846706A1 *

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AU6836198A (en) 1998-11-11
FI980730A (fi) 1998-10-12
JP2001526712A (ja) 2001-12-18
FI980730A0 (fi) 1998-03-31
WO1998046706A1 (en) 1998-10-22

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