US20030040445A1 - Refrigerant lubrificant composition comprising a foam-inducing additive - Google Patents

Refrigerant lubrificant composition comprising a foam-inducing additive Download PDF

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Publication number
US20030040445A1
US20030040445A1 US10/207,178 US20717802A US2003040445A1 US 20030040445 A1 US20030040445 A1 US 20030040445A1 US 20717802 A US20717802 A US 20717802A US 2003040445 A1 US2003040445 A1 US 2003040445A1
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Prior art keywords
lubricant composition
foam
lubricant
composition according
refrigerant
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Abandoned
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US10/207,178
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English (en)
Inventor
Stephen Boyde
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Imperial Chemical Industries Ltd
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Imperial Chemical Industries Ltd
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Assigned to IMPERIAL CHEMICAL INDUSTRIES PLC reassignment IMPERIAL CHEMICAL INDUSTRIES PLC ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: BOYDE, STEPHEN
Publication of US20030040445A1 publication Critical patent/US20030040445A1/en
Abandoned 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
    • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • C10M169/04—Mixtures of base-materials and additives
    • C10M169/041—Mixtures of base-materials and additives the additives being macromolecular compounds only
    • 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
    • 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
    • C10M105/02—Well-defined hydrocarbons
    • C10M105/06—Well-defined hydrocarbons aromatic
    • 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
    • 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
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    • C10M147/00—Lubricating compositions characterised by the additive being a macromolecular compound containing halogen
    • C10M147/04—Monomer containing carbon, hydrogen, halogen and oxygen
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    • 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
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    • C10M2203/06—Well-defined aromatic compounds
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    • C10M2203/06—Well-defined aromatic compounds
    • C10M2203/065—Well-defined aromatic compounds used as base material
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    • C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/04—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an alcohol or ester thereof; bound to an aldehyde, ketonic, ether, ketal or acetal radical
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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
    • C10N2040/30—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
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/36—Release agents or mold release agents
    • 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
    • C10N2040/38—Conveyors or chain belts
    • 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
    • C10N2040/40—Generators or electric motors in oil or gas winning field
    • 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
    • C10N2040/42—Flashing oils or marking oils
    • 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
    • C10N2040/44—Super vacuum or supercritical use
    • 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
    • C10N2040/50—Medical uses

Definitions

  • This invention relates to a lubricant composition and its use in refrigeration systems.
  • the foaming agent assists in generating and sustaining a froth or foam of fine bubbles which acts to absorb and thus attenuate the noise produced by the compressor unit during operation
  • CFCs disclosed in U.S. Pat. No. 3,792,755 include trichloroethylene, dichlorodifluoromethane (R-12) and monochlorodifluoromethane (R-22).
  • HFC hydrofluorocarbon gases
  • suitable base fluids for such synthetic lubricant compositions are polyalkylene glycols, polyol esters, polyvinyl ethers and alkylbenzenes.
  • Known foaming additives are silicon based, for example organosiloxanes or silicones.
  • WO95/12649 discloses a lubricant composition comprising a synthetic polyol ester lubricant and a foam density-increasing additive for use in a refrigerator system with at least one compressor and a halocarbon refrigerant gas, preferably an HFC.
  • the foam density-increasing additive is preferably a siloxane but may also be a halogenated aliphatic polymeric ester (for example Fluorad FC430 available from 3M) and is found to both increase the foam density and control vapour evolution from the compressor.
  • EP 0590238 A1 discloses a compressor for compressing an HFC refrigerant which is characterised by the presence of a lubricant composition consisting of a pentaerythritol ester and a siloxane foaming additive wherein an oil foam layer is created during compressor operation to reduce compressor noise.
  • JP10088173 A2 discloses lubricant compositions for refrigeration compressors for noise reduction comprising HFC refrigerants, ester oil lubricants with at least 2 ester bonds, a hydrolytic stabiliser, an antioxidant and 0.001-0.01 wt. % of silicone oils.
  • silicon-containing foaming additives may not be suitable for all refrigerant systems as they are only partially miscible with the base oil of the lubricant composition. This may lead to separation of the silicon-containing additives in cold parts of the refrigeration system. The loss of the silicone-containing additives may also cause loss of foaming due to additive depletion, fouling of heat exchange surfaces and valve blockage. Furthermore silicones present on metal surfaces prevent painting of such surfaces.
  • the present invention provides a lubricant composition
  • a lubricant composition comprising;
  • a foam-inducing additive which comprises a polyether having the formula
  • R is a partially or fully halogenated alkyl group having 1 to 10 carbon atoms and wherein adjacent R groups may be the same or different
  • n is in the range 1 to 1000 and
  • X and Y are end groups.
  • halogenated we mean that at least one hydrogen atom of the alkyl group has been replaced by a halogen atom.
  • at least one hydrogen atom in each of the carbon atoms of the alkyl group has been replaced by a halogen atom, more preferably all of the hydrogen atoms of the alkyl group have been replaced by halogen atoms so that R is a fully halogenated alkyl group.
  • the halogen atom is a fluorine atom. Especially preferred is when fluorine atoms have replaced all of the hydrogen atoms of the alkyl group.
  • the alkyl group, R may be branched or straight chained and it may be saturated or unsaturated.
  • R preferably has 1 to 7 carbon atoms, more preferably 1 to 4 carbon atoms.
  • Examples of preferred R include —CF 2 — —CF 2 CF 2 —, —CF(CF 3 )—, —CF(CF 3 )CF 2 —, —CF 2 CF 2 CF 2 — and —CF 2 CF 2 CF 2 CF 2 —.
  • R can be chosen such that the polyether is a block, random or graft copolymer or a homopolymer.
  • n is preferably in the range from 1 to 100, more preferably from 1 to 50. n may be the same or different for the R groups.
  • R 1 and R 2 are as defined for R but R 1 is different to R 2 .
  • n1 and n2 may be the same or different.
  • the polyether backbone has two end groups, X and Y.
  • at least one of the end groups X and Y comprises at least one functionalised group.
  • Types of functionalised groups include hydroxyl, ester, ethoxylated hydroxyl, ethoxylated ester, both organic and inorganic, amine, cyano, and amide
  • the or each functionalised group may be positioned on the end group so as to be directly linked to the polyether backbone; or it may be positioned at the extremity of the end group away from the polyether backbone; or it may be positioned within the backbone of the end group.
  • the functionalised group is positioned at the extremity of the end group away from the polyether backbone
  • Other groups that may be present within the or each end group include alkyl and haloalkyl, in particular fluoralkyl.
  • the end group is such that it confers solubility of the foam-inducing additive in the synthetic lubricant base oil.
  • Examples of end groups, which comprise a functionalised group are —CF 2 COOCH 3 , —CF 2 CH 2 OH, —CF 2 CH 2 O(CH 2 CH 2 O) n H and —CF 2 CH 2 OCH 2 CH(OH)CH 2 OH.
  • the foam-inducing additive preferably has a molecular weight between 100 and 10000 atomic units, more preferably between 200 and 5000 atomic units. It is present at a level of between 0.0001 to 1.0% by weight in the lubricant composition, preferably at a level of between 0.0001 to 0.05%
  • the synthetic lubricant base oil is selected such that the lubricant composition is compatible with HFC refrigerant gases.
  • it is selected from alkylbenzenes, polyvinyl ethers, polyalkylene glycols and esters.
  • the synthetic lubricant base oil is an ester; more preferably an ester which is a derivative of a polyol, preferably an aliphatic hydrocarbon-based polyol, having from 2 to 6 hydroxyl groups and, preferably, from 3 to 12 carbon atoms.
  • Suitable polyois include neopentyl glycol, pentaerythritol, trimethylolpropane, ditrimethylolpropane and dipentaerythritol.
  • the ester is derived from the reaction of such a polyol with one or more linear or branched, saturated or unsaturated monocarboxylic acids having from 3 to 12 carbon atoms and optionally one or more linear or branched, saturated or unsaturated polycarboxylic acids having from 4 to 54 carbon atoms.
  • the polycarboxylic acids if present, have 2 or 3 carboxyl groups. All of the above acids may be replaced by their esterifiable derivatives, for example anhydrides.
  • Suitable lubricant compositions include the EMKARATE RL range of refrigeration lubricants available from Uniqema, a business of Imperial Chemical Industries plc.
  • the synthetic lubricant base oils for these lubricant compositions are derived from pentaerythritol or oligomers thereof and/or neopentyl glycol reacted with linear and/or branched acids (or their esterifiable derivatives) having from 5 to 10 carbon atoms.
  • the synthetic lubricant base oil has a viscosity at 40° C. from 2 to 500 cSt.
  • the lubricant composition has a viscosity at 40° C. from 2 to 500 cSt.
  • the lubricant composition may further comprise other foaming additives, for example organosiloxanes or silicones. If present, such other foaming additives are at a level of between 0.0001 to 1.0% by weight in the lubricant composition, preferably at a level of between 0.0001 to 0.1%, more preferably at a level between 0.0001 to 0.05%.
  • the lubricant composition may also comprise other functional lubricant additives.
  • Suitable additives include antioxidants, antiwear additives, extreme pressure agents, acid scavengers, stabilisers, surfactants, viscosity index improvers, corrosion inhibitors, metal deactivators or passivators, lubricity improvers or oiliness agents and friction modifiers
  • the present invention provides for use of a lubricant composition in a refrigeration system wherein the lubricant composition comprises
  • a foam-inducing additive which comprises a polyether having the formula
  • R is a partially or fully halogenated alkyl group having 1 to 10 carbon atoms and wherein adjacent R groups may be the same or different
  • n is in the range 1 to 1000 and
  • X and Y are end groups.
  • the refrigerant in the refrigerant system suitably comprises a hydrochlorofluorocarbon (HCFC), an HFC or a blend of refrigerants containing at least one HFC, HCFC or both.
  • HCFC hydrochlorofluorocarbon
  • the refrigerant does not contain any chlorine atoms.
  • Suitable HFC gases include R134a (1,1,1,2-tetrafluoroethane), R-32 (difluoromethane).
  • R-152a (1,1-difluoroethane
  • R-143a (1,1,1-trifluoroethane
  • There may be other components in the refrigerant blend for example hydrocarbons, preferably with 1 to 6 carbon atoms, fluorinated hydrocarbons and other refrigerants, for example carbon dioxide or ammonia.
  • the foaming tendency and foam stability of 200 mls of a lubricant composition comprising EMKARATE RL 22H ex ICI and various levels of foam-inducing additive, Fomblin HC-OH ex Ausimont (HOCH 2 CF 2 O—(CF 2 CF 2 O) p —(CF 2 O) q —CF 2 CH 2 OH), were measured at room temperature (24.5° C.)
  • the foaming tendency of the lubricant composition was determined using the standard test method ASTM D-892-97, Standard Test Method for Foaming Characteristics of Lubricating Oils. The test determines the foam tendency in terms of the volume of foam produced by bubbling air through 200 mls of the lubricant composition.
  • the foam stability is the time taken in seconds for the foam to disappear.
  • Example 1 was repeated except that R134a was bubbled through the lubricant composition instead of air. The results are shown in Table 2.
  • Example 1 was repeated except the Fomblin HC-OH was replaced by Fluorolink E10 (H(OCH 2 CH 2 ) n OCH 2 CF 2 O—(CF 2 CF 2 O) p —(CF 2 O) q —CF 2 CH 2 O(CH 2 CH 2 O) n H) ex Ausimont.
  • the results are shown in Table 3.
  • Fomblin HC—OH ppm) (ml) (seconds) 0 0 0 20 20 0 50 380 135 100 380 219 250 400 206 500 370 220
  • Example 1 was repeated using 250 ppm Fomblin HC-OH and the addition of 120 ppm of 50 cSt Silicone Fluid SWS-101 50 ex Akrochem. The results are shown in Table 6. TABLE 6 Foam Tendency in Foam Stability in Foam Inducing Additive (ppm) Air (ml) Air (seconds) Fomblin HC—OH (250 ppm) and 350 178 Silicone (120 ppm) Silicone (120 ppm) only-Comparative 150 78

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Engineering & Computer Science (AREA)
  • Lubricants (AREA)
US10/207,178 2000-01-31 2002-07-30 Refrigerant lubrificant composition comprising a foam-inducing additive Abandoned US20030040445A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
GBGB0001981.0A GB0001981D0 (en) 2000-01-31 2000-01-31 Refrigerant lubricant compositions
GB0001981.0 2000-01-31
PCT/GB2001/000255 WO2001057165A1 (en) 2000-01-31 2001-01-24 Refrigerant lubricant composition comprising a foam-inducing additive

Related Parent Applications (1)

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US20070187639A1 (en) * 2006-01-13 2007-08-16 Leck Thomas J Refrigerant additive compositions containing perfluoropolethers
US20070284555A1 (en) * 2006-01-13 2007-12-13 Leck Thomas J Refrigerant additive compositionis containing perfluoropolyethers
US20070284078A1 (en) * 2006-01-13 2007-12-13 Leck Thomas J Refrigerant compositions containing perfluoropolyethers
US8663494B2 (en) 2006-09-01 2014-03-04 E I Du Pont De Nemours And Company Terpene, terpenoid, and fullerene stabilizers for fluoroolefins

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US7098173B2 (en) * 2002-11-19 2006-08-29 General Motors Corporation Thermally stable antifoam agent for use in automatic transmission fluids
JP2008266656A (ja) * 2008-07-04 2008-11-06 Tonengeneral Sekiyu Kk 潤滑油組成物

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US20070187639A1 (en) * 2006-01-13 2007-08-16 Leck Thomas J Refrigerant additive compositions containing perfluoropolethers
US20070284555A1 (en) * 2006-01-13 2007-12-13 Leck Thomas J Refrigerant additive compositionis containing perfluoropolyethers
US20070284078A1 (en) * 2006-01-13 2007-12-13 Leck Thomas J Refrigerant compositions containing perfluoropolyethers
US7759532B2 (en) 2006-01-13 2010-07-20 E.I. Du Pont De Nemours And Company Refrigerant additive compositions containing perfluoropolyethers
US20100243948A1 (en) * 2006-01-13 2010-09-30 E. I. Du Pont De Nemours And Company Refrigerant Additive Compositions Containing Perfluoropolyethers
US8049046B2 (en) 2006-01-13 2011-11-01 E.I. Du Pont De Nemours And Company Refrigerant additive compositions containing perfluoropolyethers
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US8426657B2 (en) 2006-01-13 2013-04-23 E I Du Pont De Nemours And Company Refrigerant additive compositions containing perfluoropolyethers
US8758641B2 (en) 2006-01-13 2014-06-24 E I Du Pont De Nemours And Company Refrigerant additive compositions containing perfluoropolyethers
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US8663494B2 (en) 2006-09-01 2014-03-04 E I Du Pont De Nemours And Company Terpene, terpenoid, and fullerene stabilizers for fluoroolefins

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CN1396949A (zh) 2003-02-12
TWI225515B (en) 2004-12-21
MY136416A (en) 2008-09-30
GB0001981D0 (en) 2000-03-22
ATE340840T1 (de) 2006-10-15
ES2270978T3 (es) 2007-04-16
CN1210387C (zh) 2005-07-13
EP1252278B1 (en) 2006-09-27
JP5767130B2 (ja) 2015-08-19
JP2012132014A (ja) 2012-07-12
KR100675248B1 (ko) 2007-01-29
JP2003522254A (ja) 2003-07-22
AU2001230330A1 (en) 2001-08-14
KR20020068545A (ko) 2002-08-27
WO2001057165A1 (en) 2001-08-09
DE60123386D1 (de) 2006-11-09

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