EP0571091A1 - Carbonsaüreester enthaltende flüssige Zusammensetzungen - Google Patents

Carbonsaüreester enthaltende flüssige Zusammensetzungen Download PDF

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Publication number
EP0571091A1
EP0571091A1 EP93303329A EP93303329A EP0571091A1 EP 0571091 A1 EP0571091 A1 EP 0571091A1 EP 93303329 A EP93303329 A EP 93303329A EP 93303329 A EP93303329 A EP 93303329A EP 0571091 A1 EP0571091 A1 EP 0571091A1
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EP
European Patent Office
Prior art keywords
carbon atoms
liquid composition
ester
acylating agent
alkyl
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Withdrawn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
EP93303329A
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English (en)
French (fr)
Inventor
Scott Ted Jolley
Kirk Emerson Davis
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.)
Lubrizol Corp
Original Assignee
Lubrizol Corp
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Filing date
Publication date
Application filed by Lubrizol Corp filed Critical Lubrizol Corp
Publication of EP0571091A1 publication Critical patent/EP0571091A1/de
Withdrawn legal-status Critical Current

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    • 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
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    • 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
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    • C10M133/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms
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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
    • C10N2040/34—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 liquid compositions comprising at least one fluorine-containing hydrocarbon, and at least one lubricant. More particularly, the invention relates to liquid compositions useful as refrigeration liquids.
  • Chlorofluorocarbons generally referred to in the industry as CFCs
  • CFCs Chlorofluorocarbons
  • CFCs also have been used because of their unique combination of properties as refrigerants, foam-blowing agents, and specialty solvents within the electronics and aerospace industries.
  • CFCs which have been utilized for these purposes include CFC-13 which is chlorotrifluoromethane, CFC-12 which is dichlorodifluoromethane, and CFC-113 which is 1,2,2-trifluoro-1,1,2-trichloroethane.
  • halogenated hydrocarbons containing at least some hydrogen atoms such as HCFC-22 which is difluorochloromethane, HCFC-123 which is 1,1-dichloro-2,2,2-trifluoroethane, HFC-134a which is 1,1,1,2-tetrafluoroethane and HCFC-141b which is 1,1-dichloro-1-fluoroethane.
  • the ozone depletion potential of these proposed substitutes is significantly less than the ozone depletion potential of the previously used CFCs.
  • the ozone depletion potential is a relative measure of the capability of the material to destroy the ozone layer in the atmosphere. It is a combination of the percentage by weight of chlorine (the atom that attacks the ozone molecule) and the lifetime in the atmosphere.
  • HCFC-22 and HFC-134a generally are recommended as being candidates in refrigerant applications, and HFC-134a is particularly attractive because its ozone depletion potential has been reported as being zero.
  • any of the replacement materials In order for any of the replacement materials to be useful as refrigerants, the materials must be compatible with the lubricant utilized in the compressor.
  • the presently used refrigerants such as CFC-12 are readily compatible with mineral lubricating oils which are utilized as the lubricant in air-conditioner compressors.
  • the above-described refrigerant candidates have different solubility characteristics than the refrigerants presently in use.
  • mineral lubricating oil is incompatible (i.e., insoluble) with HFC-134a.
  • Such incompatibility results in unacceptable compressor life in compression-type refrigeration equipment including refrigerators and air-conditioners including auto, home, commercial, and industrial air-conditioners.
  • the mixture of refrigerant and lubricant In order to perform as a satisfactory refrigeration liquid, the mixture of refrigerant and lubricant must be compatible and stable over a wide temperature range such as from about 0°C and above 80°C or above.
  • the refrigeration liquids In addition to thermal stability, the refrigeration liquids must have acceptable viscosity characteristics which are retained even at high temperatures, and the refrigeration liquid should not have a detrimental effect on materials used as seals in the compressors.
  • compositions comprising a tetrafluoroethane and polyoxyalkylene glycols are discussed in U.S. Patent 4,755,316.
  • the compositions are useful in refrigeration systems.
  • Refrigeration oils are described in U.S. Patents 4,248,726 and 4,267,064 which comprise mixtures of a polyglycol and 0.1 to 10% of glycidyl ether type epoxy compounds, or epoxidized fatty acid monoesters, and optionally, epoxidized vegetable oil.
  • the lubricating oils are reported to be useful in refrigerators using a halogen-containing refrigerant such as Freons 11, 12, 13, 22, 113, 114, 500 and 502 (available from DuPont), and in particular with Freon 12 or 22.
  • U.S. Patent 4,431,557 describes fluid compositions comprised of a fluoro- and chloro-containing refrigerant, a hydrocarbon oil, and an alkylene oxide additive compound which improves the thermal resistance of the oil in the presence of the refrigerant.
  • hydrocarbon oils include mineral oil, alkyl benzene oil, dibasic acid ester oil, polyglycols, etc.
  • the composition may contain other additives including load-carrying additives such as phosphorus acid esters, phosphoric acid esters, etc.
  • fluorocarbon refrigerants include R-11, R-12, R-113, R-114, R-500, etc.
  • U.S. Patent 4,428,854 describes absorption refrigerant compositions for use in refrigeration systems comprising 1,1,1,2-tetrafluoroethane and an organic solvent capable of dissolving the ethane.
  • the solvents disclosed are organic amides, acetonitrile, N-methyl pyrroles, N-methyl pyrrolidine, N-methyl-2-pyrrolidone, nitromethane, various dioxane derivatives, glycol ethers, butyl formate, butyl acetate, diethyl oxalate, diethyl malonate, acetone, methyl ethyl ketone, other ketones and aldehydes, triethyl phosphoric triamide, triethylene phosphate, triethyl phosphate, etc.
  • Stabilized absorption compositions comprising (a) a halogenated hydrocarbon refrigerant, (b) a liquid absorbent of a polyethylene glycol methyl ether, and (c) at least one stabilizer are described in U.S. Patent 4,454,052.
  • stabilizers include phosphate esters, epoxy compounds, and organotin compounds.
  • the polyethylene glycol methyl ether-type compounds are of the general formula CH3-O-(CH2H4O) n R wherein n is an integer of 1 to 6, and R is H, CH3- or CH3CO-.
  • a variety of halogenated hydrocarbons are described including 1,1-difluoromethane, 1,1,1,2-tetra-fluoroethane, etc.
  • U.S. Patent 4,559,154 relates to absorption heat pumps utilizing as working fluid, a saturated fluorohydrocarbon or fluorohydrocarbon ether having from 3 to 5 carbon atoms.
  • Solvents reported to be useful with such fluorohydrocarbons include ethers such as tetraglyme, amides which can be lactams such as the N-alkyl pyrrolidones, sulfonamides and ureas including cyclic ureas.
  • a liquid composition comprising (A) at least one fluorine-containing hydrocarbon containing one to three carbon atoms, and a lubricant comprising (B) at least one ester lubricant selected from the group consisting of (i) an ester of a polyhydroxy compound and a monocarboxylic acylating agent having from about 4 to about 15 carbon atoms, and (ii) an ester of polyhydroxy compound and a combination of a dicarboxylic acylating agent and a monocarboxylic acylating agent having about 7 to about 15 carbon atoms, and (C) at least one additive selected from the group consisting of an alkyl phosphite, an alkyl phosphonic acid ester, a nitrogen-containing heterocycle, and a mixture thereof.
  • the invention in another aspect, relates to a liquid composition
  • a liquid composition comprising (A) a major amount of at least one fluorine-containing hydrocarbon containing 1 or 2 carbon atoms; (B) a minor amount of at least one soluble organic lubricant comprising at least one carboxylic ester of a polyhydroxy compound containing at least 2 hydroxy groups and characterized by the general formula R[OC(O)R1] n (I) wherein R is a hydrocarbyl group, each R1 is independently hydrogen, a straight chain lower hydrocarbyl group, a branched chain hydrocarbyl group, or a straight chain hydrocarbyl group containing from 8 to about 22 carbon atoms provided that at least one R1 group is hydrogen, a lower straight chain hydrocarbyl or a branched chain hydrocarbyl group, or a carboxylic acid- or carboxylic acid ester-containing hydrocarbyl group, and n is at least 2; and (C) a phosphite.
  • the invention in another aspect, relates to a liquid composition
  • a liquid composition comprising (A) at least one fluorine-containing hydrocarbon containing 1 to 2 carbon atoms, and a lubricant (B) at least one ester lubricant selected from the group consisting of (i) an ester of a polyhydroxy compound and a monocarboxylic acylating agent selected from the group consisting of branched monocarboxylic acylating agents having from about 4 to about 20 carbon atoms, straight chain monocarboxylic acylating agents having from 8 to about 22 carbon atoms, and mixtures thereof, and (ii) an ester of polyhydroxy compound and a combination of a dicarboxylic acylating agent and a monocarboxylic acylating agent selected from the group consisting of branched monocarboxylic acylating agents having from about 4 to about 20 carbon atoms, straight chain monocarboxylic acylating agents having from 8 to about 22 carbon atoms, and mixture
  • Liquid compositions also are described wherein the fluorine-containing hydrocarbons also contain other halogens such as chlorine. Methods of lubricating refrigeration systems are also described.
  • the liquid compositions are useful particularly as refrigeration liquids in refrigerators and air-conditioners including automotive, home, commercial and industrial air-conditioners.
  • hydrocarbyl and “hydrocarbylene” denote a group having a carbon atom directly attached to the polar group and having a hydrocarbon or predominantly hydrocarbon character within the context of this invention.
  • hydrocarbylene denote a group having a carbon atom directly attached to the polar group and having a hydrocarbon or predominantly hydrocarbon character within the context of this invention.
  • groups include the following:
  • hydrocarbon-based also has the same meaning and can be used interchangeably with the term hydrocarbyl when referring to molecular groups having a carbon atom attached directly to the polar group.
  • lower as used herein in conjunction with terms such as hydrocarbyl, hydrocarbylene, alkylene, alkyl, alkenyl, alkoxy, and the like, is intended to describe such groups which contain a total of up to 7 carbon atoms, per se, and includes methyl, ethyl, propyl, butyl, pentyl, hexyl, and heptyl groups.
  • Viscosity is kinematic viscosity and is measured by ASTM D-2270.
  • equivalent weight of polyol is determined by dividing the formula weight of the polyol by the number of hydroxyl groups. Equivalents of polyol is determined by dividing the amount of polyol by its equivalent weight.
  • the equivalent weight is determined by dividing the formula weight of the acylating agent or anhydride by the number of carboxylic groups which form esters.
  • an anhydride contributes two carboxyl groups which can form ester. Therefore, the equivalent weight of anhydride, such as succinic anhydride, would be the formula weight of the anhydride divided by the number of carboxyl group.
  • succinic anhydride the number is two.
  • a compound or component When a compound or component is indicated herein as being “soluble”, the compound or component is soluble in the liquid compositions of the invention comprising the fluorine-containing hydrocarbon and the lubricant.
  • a compound or component is considered “soluble” so long as it is soluble in the liquid compositions, even though it may be insoluble in the fluorine-containing hydrocarbon per se.
  • compositions that include the ingredients listed in the claim as well as other ingredients that do not materially affect the basic and novel characteristics of the liquid compositions.
  • fluorine-containing hydrocarbon is a major amount for automotive and commercial and industrial refrigeration systems.
  • lower amounts, e.g. less than 50%, of the fluorine-containing hydrocarbon are useful, such as in household refrigerators.
  • the liquid compositions include at least one fluorine-containing hydrocarbon. That is, the fluorine-containing hydrocarbons contain at least one C-H bond, as well as C-F bonds. In addition to these two essential types of bonds, the hydrocarbon also may contain other carbon-halogen bonds such as C-Cl bonds. Because the liquid compositions of the present invention are primarily intended for use as refrigerants, the fluorine-containing hydrocarbon preferably contains one to three, or to two carbon atoms, and more preferably two carbon atoms.
  • the fluorine-containing hydrocarbons useful in the liquid compositions of the present invention may contain other halogens such as chlorine.
  • the hydrocarbon contains only carbon, hydrogen and fluorine. These compounds containing only carbon, hydrogen and fluorine are referred to herein as fluorohydrocarbons or hydrofluorocarbons.
  • fluorohydrocarbons or hydrofluorocarbons are referred to herein as fluorohydrocarbons or hydrofluorocarbons.
  • the hydrocarbons containing chlorine as well as fluorine and hydrogen are referred to as chlorofluorohydrocarbons or hydrochlorofluorocarbons.
  • the fluorine-containing hydrocarbons useful in the composition of the present invention are to be distinguished from the fully halogenated hydrocarbons which have been and are being used as propellants, refrigerants and blowing agents such as CFC-11, CFC-12 and CFC-113 which have been described above.
  • fluorine-containing hydrocarbons which may be useful in the liquid compositions of the present invention include trifluoromethane (HFC-23), 1,1,1-trifluoroethane (HFC-143a), 1,1-difluoroethane (HFC-152a), 2-chloro-1,1,1,2-tetrafluoroethane (HCFC-124), 1-chloro-1,1,2,2-tetrafluoroethane (HCFC-124a), 1-chloro-1,1-difluoroethane (HCFC-142b), and 1,1,2,2-tetrafluoroethane (HFC-134).
  • refrigerants such as perfluoropropane (HFC-218), perfluorocyclopropane (HFC-216), perfluoropropylene oxide, 1,3-perfluoro propylene oxide and pentafluorodimethyl ether may be used with the lubricant.
  • fluorohydrocarbons are often identified merely with the prefix "R” in place of the above letters.
  • HFC-23 is R-23
  • HCFC-124 is R-124, etc.
  • fluorine-containing hydrocarbons which are useful as refrigerants are fluoromethanes and fluoroethanes boiling at a relatively low temperature at atmospheric pressure, e.g., below 30°C. Mixtures of fluorine-containing hydrocarbons may be used, and the amount of each fluorohydrocarbon in the mixture may be varied as desired.
  • fluorohydrocarbon mixtures useful as (A) include: 142(b)/22; 134(a)/23; 22/124/152(a), etc.
  • the useful fluorocarbon refrigerants serve to transfer heat in a refrigeration system by evaporating and absorbing heat at a low temperature and pressure, e.g., near ambient temperature and atmospheric pressure, and by releasing heat on condensing at a higher temperature and pressure.
  • the amount of fluorine-containing hydrocarbon is the level typically used for the refrigeration system.
  • the liquid compositions of the present invention generally contain from about 10%, or about 20% up to about 90%, or to about 85% of the fluorine-containing hydrocarbon.
  • the fluorine-containing hydrocarbon is present in an amount from about 45%, or about 50%, or about 55% up to about 90%, or to about 80%, or to about 75% by weight of the liquid composition.
  • the liquid compositions will comprise from about 50% to about 99% by weight of the fluorine-containing hydrocarbon.
  • the liquid compositions contain from about 70% to about 99% by weight of the fluorine-containing hydrocarbon.
  • the fluorine-containing hydrocarbon is present in an amount from about 10%, or about 25%, or about 30% up to about 55%, or to about 50%, or to about 45% by weight of the lubricant.
  • the fluorine-containing hydrocarbon is present in an amount less than about 45%, then the liquid compositions are generally suited for household refrigeration systems.
  • the liquid compositions also contain a lubricant.
  • the lubricant contains at least one carboxylic ester of a polycarboxylic acylating agent, preferably a dicarboxylic acylating agent and a polyhydroxy compound, or a mixture of monocarboxylic and polycarboxylic acylating agent, preferably dicarboxylic acylating agents and a polyhydroxy compound containing at least two hydroxyl groups and characterized by the general formula R[OC(O)R1] n (I) wherein R is a hydrocarbyl group, each R1 is independently hydrogen, a straight chain lower hydrocarbyl group, a branched chain hydrocarbyl group, or a straight chain hydrocarbyl group containing from about 8 to about 22 carbon atoms provided that at least one R1 group is hydrogen, a lower straight chain hydrocarbyl or a branched chain hydrocarbyl group, or a carboxylic acid- or carboxy
  • the carboxylic ester lubricants utilized as component (B) in the liquid compositions are reaction products of one or more carboxylic acylating agents, e.g. acids or anhydrides (or the lower esters thereof such as methyl, ethyl, etc.), with polyhydroxy compounds containing at least two hydroxyl groups.
  • the polyhydroxy compounds may be represented by the general formula R(OH) n (II) wherein R is a hydrocarbyl group and n is at least 2.
  • the hydrocarbyl group may contain from 4 to about 20 or more carbon atoms, and the hydrocarbyl group may also contain one or more nitrogen and/or oxygen atoms.
  • the polyhydroxy compounds generally will contain from about 2 to about 10 hydroxyl groups and more preferably from about 3 to about 10 hydroxyl groups.
  • the polyhydroxy compound may contain one or more oxyalkylene groups, and, thus, the polyhydroxy compounds include compounds such as polyetherpolyols.
  • the number of carbon atoms and number of hydroxyl groups contained in the polyhydroxy compound used to form the carboxylic esters may vary over a wide range, and it is only necessary that the carboxylic ester produced with the polyhydroxy compounds be soluble in the liquid compositions .
  • the polyhydroxy compounds used in the preparation of the carboxylic esters (I) also may contain one or more nitrogen atoms.
  • the polyhydroxy compound may be an alkanolamine containing from 3 to 6 hydroxyl groups.
  • the polyhydroxy compound is an alkanolamine containing at least two hydroxyl groups and more preferably at least three hydroxyl groups.
  • polyhydroxy compounds useful in the present invention include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, glycerol, neopentyl glycol, 1,2-, 1,3- and 1,4-butanediols, pentaerythritol, dipentaerythritol, tripentaerythritol, triglycerol, trimethylolpropane, di-trimethylolpropane, sorbitol, hexaglycerol, 2,2,4-trimethyl-1,3-pentanediol, etc.
  • the mixtures of any of the above polyhydroxy compounds can be utilized.
  • the carboxylic acylating agents utilized in the preparation of the carboxylic esters useful in the liquid compositions may be characterized by the following general formula R1COOH (III) wherein R1 is (a) H, (b) a straight or branch chain lower hydrocarbyl group (preferably about three to four carbon atoms), (c) a branched chain hydrocarbyl group, or (d) a mixture of one or both of (b) and (c) with a straight chain hydrocarbyl group containing from about 8 to about 22 carbon atoms or (e) a carboxylic acid- or carboxylic acid ester-containing hydrocarbyl group.
  • R1 is (a) H, (b) a straight or branch chain lower hydrocarbyl group (preferably about three to four carbon atoms), (c) a branched chain hydrocarbyl group, or (d) a mixture of one or both of (b) and (c) with a straight chain hydrocarbyl group containing from about 8 to about 22 carbon atoms or (
  • At least one R1 group in the ester product of Formula I must contain a lower straight chain hydrocarbyl group or a branched chain hydrocarbyl group.
  • the straight chain lower hydrocarbyl group (R1) contains from 1 to about 7 carbon atoms, and in a preferred embodiment, contains from 1 to about 5 carbon atoms.
  • the branched chain hydrocarbyl group may contain any number of carbon atoms and will generally contain from 4 to about 20 carbon atoms. In one preferred embodiment, the branched chain hydrocarbon group contains from 5 to 20 carbon atoms and in a more preferred embodiment, contains from about 5 to about 14 carbon atoms.
  • the higher molecular weight straight chain hydrocarbyl group containing from 8 to about 22 carbon atoms will contain in some embodiments, from 8 to about 18 carbon atoms, and in more preferred embodiments from 8 to about 14 carbon atoms.
  • the branched chain hydrocarbyl groups are characterized by the structure -C(R2)(R3)(R4) wherein R2, R3 and R4 are each independently alkyl groups, and at least one of the alkyl groups contains two or more carbon atoms.
  • R2, R3 and R4 are each independently alkyl groups, and at least one of the alkyl groups contains two or more carbon atoms.
  • Such branched chain alkyl groups, when attached to a carboxyl group are referred to in the industry as neo groups and the acids are referred to a neo acid.
  • the neo acids are characterized as having alpha-alpha-, disubstituted hydrocarbyl groups.
  • R2 and R3 are methyl groups and R4 is an alkyl group containing two or more carbon atoms.
  • any of the above hydrocarbyl groups (R1) may contain one or more carboxy groups or carboxy ester groups such as -COOR5 wherein R5 is a lower alkyl, hydroxyalkyl or a hydroxyalkyloxy group.
  • Such substituted hydrocarbyl groups are present, for example, when the carboxylic acylating agent, R1COOH (III), is a dicarboxylic acylating agent or a monoester of a dicarboxylic acylating agent.
  • the acid, R1COOH (III) is a monocarboxylic acid since polycarboxylic acids tend to form polymeric products if the reaction conditions and amounts of reactants are not carefully regulated. Mixtures of monocarboxylic acids and minor amounts of dicarboxylic acids or anhydrides are useful in preparing the esters (I).
  • carboxylic acylating agents containing a straight chain lower hydrocarbyl group include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid and heptanoic acid and anhydrides of any one thereof.
  • carboxylic acylating agents wherein the hydrocarbyl group is a branched chain hydrocarbyl group include isobutyric acid, 2-ethyl-n-butyric acid, 2-methylbutyric acid, 2,2,4-trimethylpentanoic acid, 2-hexyldecanoic acid, isostearic acid, 2-methylhexanoic acid, 3,5,5-trimethylhexanoic acid, 2-ethylhexanoic acid, isooctanoic acid, isononanoic acid, isoheptanoic acid, isodecanoic acid, neoheptanoic acid, neodecanoic acid, and ISO Acids and NEO Acids available from Exxon Chemical Company, Houston, Texas USA.
  • ISO Acids are isomer mixtures of branched acids and include commercial mixtures such as ISO Heptanoic Acid, ISO Octanoic Acid, and ISO Nonanoic Acid, as well as developmental products such as ISO Decanoic Acids and ISO 810 Acid. Of the ISO Acids, ISO Octanoic acid and ISO Nonanoic acid are preferred.
  • Neo acids include commercially available mixtures such as NEO Pentanoic Acid, NEO Heptanoic Acid, and NEO Decanoic Acid, as well as developmental products such as ECR-909 (NEO C9) Acid, and ECR-903 (NEO C1214) Acid and commercial mixtures of branched chain carboxylic acids such as the mixture identified as NEO 1214 acid from Exxon.
  • the ester is prepared from one of the polyhydroxy compound described above and a monocarboxylic acylating agent having from about 4, or about 5, up to about 15, or to about 12, or to about 10 carbon atoms.
  • the monocarboxylic acylating agent may be linear or branched, preferably branched.
  • Particularly useful monocarboxylic acylating agents include branched monocarboxylic acylating agents having 8 or 9 carbon atoms.
  • the third type of carboxylic acylating agent which can be utilized in the preparation of the carboxylic esters are the acids containing a straight chain hydrocarbyl group containing from 8 to about 22 carbon atoms.
  • these higher molecular weight straight chain acids can be utilized only in combination with one of the other acids described above since the higher molecular weight straight chain acids are not soluble in the fluorohydrocarbons.
  • Examples of such higher molecular weight straight chain acids include decanoic acid, dodecanoic acid, stearic acid, lauric acid, behenic acid, etc.
  • the carboxylic acylating agents utilized to prepare the carboxylic esters may comprise a mixture of a major amount of monocarboxylic acylating agents and a minor amount of dicarboxylic acylating agents.
  • useful dicarboxylic acylating agents include maleic acid or anhydride, succinic acid or anhydride, adipic acid or anhydride, oxalic acid or anhydride, pimelic acid or anhydride, glutaric acid or anhydride, suberic acid or anhydride, azelaic acid or anhydride, sebacic acid or anhydride, etc.
  • the presence of the dicarboxylic acylating agents results in the formation of esters of higher viscosity.
  • the complex esters are formed by having a substantial portion of the dicarboxylic acylating agents react with more than one polyol.
  • the reaction is generally coupling of polyols through the dicarboxylic acylating agent or anhydride.
  • examples of mixtures of mono- and dicarboxylic acylating agents include succinic anhydride and 3,5,5-trimethylhexanoic acid; azelaic acid and 2,2,4-trimethylpentanoic acid; adipic acid and 3,5,5-trimethylhexanoic acid; sebacic acid and isobutyric acid; adipic and a mixture of 50 parts 3,5,5-trimethylhexanoic acid and 50 parts neoheptanoic acid; and neoheptanoic acid and a mixture of 50 parts adipic acid and 50 parts sebacic acid.
  • mixtures containing larger amounts of dicarboxylic acylating agents should be avoided since the product ester will contain larger amounts of polymeric esters, and such mixtures may be insoluble in the fluorohydrocarbons.
  • An example of such a mixture is 80 parts of neoheptanoic acid and 20 parts of succinic acid. Viscosity and average molecular weight of the ester can be increased by increasing the amount of dicarboxylic acid and decreasing the amount of monocarboxylic acylating agent.
  • the carboxylic esters of Formula I and the liquid compositions are prepared, as mentioned above, by reacting at least one carboxylic acylating agent with at least one polyhydroxy compound containing at least two hydroxyl groups.
  • the formation of esters by the interaction of carboxylic acylating agents and alcohols is acid catalyzed and is a reversible process which can be made to proceed to completion by use of a large amount of alcohol or carboxylic acylating agent, or by removal of the water as it is formed in the reaction. If the ester is formed by transesterification of a lower molecular weight carboxylic ester, the reaction can be forced to completion by removal of the low molecular weight alcohol formed as a result of a transesterification reaction.
  • the esterification reaction can be catalyzed by either organic acids or inorganic acids.
  • inorganic acids include sulfuric acids and acidified clays.
  • organic acids can be utilized including paratoluenesulfonic acid and acidic resins, such as Amberlyst 15, etc.
  • Organometallic catalysts include, for example, tetraisopropoxy orthotitanate.
  • the amounts of carboxylic acylating agents and polyhydroxy compounds included in the reaction mixture may be varied depending on the results desired. If it is desired to esterify all of the hydroxyl groups containing in the polyhydroxy compounds, sufficient carboxylic acylating agent should be included in the mixture to react with all of the hydroxyl groups.
  • the carboxylic acylating agents can be reacted sequentially with the polyhydroxy compounds or a mixture of carboxylic acylating agents can be prepared and the mixture reacted with the polyhydroxy compounds.
  • the polyhydroxy compound is first reacted with one carboxylic acylating agent, generally, the higher molecular weight branched chain or straight chain carboxylic acylating agent followed by reaction with the straight chain lower hydrocarbyl carboxylic acylating agent.
  • carboxylic acylating agent generally, the higher molecular weight branched chain or straight chain carboxylic acylating agent followed by reaction with the straight chain lower hydrocarbyl carboxylic acylating agent.
  • esters also may be formed by reaction of the polyhydroxy compound with the anhydrides of any of the above-described carboxylic acids.
  • esters are easily prepared by reacting the polyhydroxy compounds either with acetic acid or acetic anhydride.
  • the esters are made by reacting a polyol with a mixture of a dicarboxylic acylating agent and a monocarboxylic acylating agent.
  • the amount of dicarboxylic acylating agent and monocarboxylic acylating agent may be varied to obtain a product for the desired result.
  • one equivalent of polyol is reacted with from about 0.07, preferably from about 0.17 to about 0.33, preferably to about 0.23 moles of dicarboxylic acylating agent and from about 0.67, preferably from about 0.77 to about 0.93, preferably to about 0.83 moles of monocarboxylic acylating agent.
  • more than one equivalent of acylating agent, and particularly of monocarboxylic acid may be used.
  • esters by the reaction of carboxylic acylating agents with the polyhydroxy compounds described above can be effected by heating the acylating agents, the polyhydroxy compounds, with or without a catalyst to an elevated temperature while removing water, or low molecular weight alcohols or acids formed in the reaction. Generally, temperatures of from about 75°C to about 200°C or higher are sufficient for the reaction.
  • the reaction is completed when water, or low molecular weight alcohol or acid is no longer formed, and such completion is indicated when water, or low molecular weight alcohols or acids can no longer be removed by distillation.
  • carboxylic esters wherein not all of the hydroxyl groups have been esterified.
  • Such partial esters can be prepared by the techniques described above and by utilizing amounts of the acid or acids which are insufficient to esterify all of the hydroxyl groups.
  • a mixture of 92.1 parts (1 mole) of glycerol and 316.2 parts of acetic anhydride is prepared and heated to reflux.
  • the reaction is exothermic and continues to reflux at 130°C for about 4.5 hours. Thereafter the reaction mixture is maintained at the reflux temperature by heating for an additional 6 hours.
  • the reaction mixture is stripped by heating while blowing with nitrogen, and filtered with a filter aid. The filtrate is the desired ester.
  • a mixture of 872 parts (6.05 moles) of 2-ethylhexanoic acid, 184 parts (2 moles) of glycerol and 200 parts of toluene is prepared and blown with nitrogen while heating the mixture to about 60°C.
  • Para-toluene sulfonic acid (5 parts) is added to the mixture which is then heated to the reflux temperature.
  • a water/toluene azeotrope distills at about 120°C.
  • a temperature of 125-130°C is maintained for about 8 hours followed by a temperature of 140°C for 2 hours while removing water.
  • the residue is the desired ester.
  • a reaction vessel is charged with 23 parts (0.05 mole) of hexaglycerol and 43.3 parts (0.425 mole) of acetic anhydride. The mixture is heated to the reflux temperature (about 139°C) and maintained at this temperature for a total of about 8 hours. The reaction mixture is stripped with nitrogen and then vacuum stripped to 150°C at 15 mm.Hg. The residue is filtered through a filter aid, and the filtrate is the desired ester.
  • the mixture is a two-phase system.
  • Para-toluene sulfonic acid (1 part) is added, and the mixture is heated to 150°C whereupon the reaction commences and water and methanol evolve.
  • 250 parts (2.5 moles) of acetic anhydride are added with stirring.
  • the reaction mixture then is stripped at 150°C and filtered.
  • the filtrate is the desired ester of sorbitol.
  • a mixture of 536 parts (4 moles) of trimethylolpropane and 680 parts (4 moles) of a commercial C810 straight chain methyl ester is prepared, and 5 parts of tetraisopropoxy orthotitanate are added.
  • the mixture is heated to 200°C with nitrogen blowing.
  • Methanol is distilled from the reaction mixture.
  • the reaction temperature is lowered to 150°C, and 408 parts (4 moles) of acetic anhydride are added in a slow stream.
  • a water azeotrope begins to evolve when 50 parts of toluene are added.
  • the distillation ceases.
  • Acetic acid (50 parts) is added and additional water/acetic acid mixture is collected.
  • the acetic acid addition is repeated with heating until no water can be removed by distillation.
  • the residue is filtered and the filtrate is the desired ester.
  • a mixture of 402 parts (3 moles) of trimethylolpropane, 660 parts (3 moles) of a commercial straight chain methyl ester comprising a mixture of about 75% C12 methyl ester and about 25% C14 methyl ester, (CE1270 from Procter & Gamble), and tetraisopropoxy orthotitanate is prepared and heated to 200°C with mild nitrogen blowing. The reaction is allowed to proceed overnight at this temperature, and in 16 hours, 110 parts of methanol is collected. The reaction mixture is cooled to 150°C, and 100 parts of acetic acid and 50 parts of toluene are added followed by the addition of an additional 260 parts of acetic acid. The mixture is heated at about 150°C for several hours yielding the desired ester.
  • a mixture of 408 parts (3 moles) of pentaerythritol and 660 parts (3 moles) of the CE1270 methyl ester used in Example 7 is prepared with 5 parts of tetraisopropyl orthotitanate, and the mixture is heated to 220°C under a nitrogen purge. No reaction occurs. The mixture then is cooled to 130°C, and 250 parts of acetic acid are added. A small amount of para-toluenesulfonic acid is added and the mixture is stirred at about 200°C for 2 days, and 60 parts of methanol are removed. At this time, 450 parts of acetic anhydride are added and the mixture is stirred at 150°C until the acetic acid/water azeotrope no longer evolves. The residue is filtered through a filter aid, and the filtrate is the desired ester of pentaerythritol.
  • a mixture of 850 parts (6.25 moles) of pentaerythritol, 3250 parts (25 moles) of neoheptanoic acid, and 10 parts of tetraisopropoxy orthotitanate is prepared and heated to 170°C. Water is evolved and removed by distillation. When the evolution of water ceases, 50 parts of acidified clay are added and some additional water is evolved. A total of about 250 parts of water is removed during the reaction. The reaction mixture is cooled to room temperature and 310 parts of acetic anhydride are added to esterify the remaining hydroxyl groups. The desired ester is obtained.
  • a mixture of 544 parts (4 moles) of pentaerythritol, 820 parts (4 moles) of Neo 1214 acid, a commercial acid mixture available from Exxon, 408 parts (4 moles) of acetic anhydride and 50 parts of Amberlyst 15 is prepared and heated to about 120°C whereupon water and acetic acid begin to distill. After about 150 parts of water/acetic acid are collected, the reaction temperature increases to about 200°C. The mixture is maintained at this temperature of several days and stripped. Acetic anhydride is added to esterify any remaining hydroxyl groups. The product is filtered and the filtrate is the desired ester.
  • a mixture of 1088 parts (8 moles) of pentaerythritol, 1360 parts (8 moles) of a commercial methyl ester of an acid mixture comprising about 55% of C8, 40% of C10 and 4% of C6 acids ("CE810 Methyl Ester", Procter & Gamble), 816 parts of acetic anhydride and 10 parts of paratoluene sulfonic acid is prepared and heated to reflux. About 500 parts of a volatile material are removed. A water azeotrope mixture then distills resulting in the removal of about 90 parts of water. Acetic anhydride (700 parts) is added and the mixture is stirred as a water/acetic acid mixture is removed. The reaction is continued until no more water is evolved and no free hydroxyl groups remain (by IR). The reaction product is stripped and filtered.
  • a mixture of 508 parts (2 moles) of dipentaerythritol, 812 parts (8 moles) of acetic anhydride, 10 parts of acidified clay as catalyst and 100 parts of xylene is prepared and heated to 100°C. This temperature is maintained until the solid dipentaerythritol is dissolved.
  • a water/acetic acid azeotrope is collected, and when the rate of evolution diminishes, the reaction mixture is blown with nitrogen. About 100-200 parts of acetic acid are added and the reaction is continued as additional water/acetic acid/xylene azeotrope is collected.
  • the reaction mixture is stripped and filtered. The filtrate is the desired product which solidifies.
  • a mixture of 320 parts (1.26 moles) of dipentaerythritol, 975 parts (1.25 moles) of neoheptanoic acid and 25 parts of Amberlyst 15 catalyst is prepared and heated to 130°C. At this temperature water evolution is slow, but when the temperature is raised to 150°C, about 65% of the theory water is collected. The last amounts of water are removed by heating to 200°C. The product is a dark viscous liquid.
  • a mixture of 372 parts (1 mole) of tripentaerythritol, 910 parts (7 moles) of neoheptanoic acid and 30 parts of Amberlyst 15 catalyst is prepared and heated to 110°C as water is removed. The mixture is heated for a total of 48 hours, and unreacted acid is removed by stripping the mixture. The residue is the desired ester.
  • a mixture of 1032 parts (6 moles) of neodecanoic acid, 450 parts (3 moles) of triethylene glycol and 60 parts of Amberlyst 15 is prepared and heated to 130°C. A water azeotrope is evolved and collected. The residue is the desired product.
  • a mixture of 1032 parts (6 moles) of neodecanoic acid and 318 parts (3 moles) of diethylene glycol is prepared and heated to 130°C in the presence of 20 parts of Amberlyst 15. After heating for 24 hours and removing about 90 parts of water, 20 parts of Amberlyst 15 are added and the reaction is conducted for another 24 hours. The reaction is stopped when the theory amount of water is obtained, and the residue is the desired ester.
  • a reaction vessel is charged with 2010 parts (15 moles) of trimethylolpropane, 6534 parts (45 moles) of 2,2,4-trimethylpentanoic acid (available commercially from Exxon Corporation under the trade name ISO Octanoic acid), and 8 parts of methanesulfonic acid.
  • the mixture is heated to 150°C and water is removed. The temperature is increased to 200°C and the temperature is maintained for eight hours. After water evolution, the reaction mixture is vacuum stripped to 200°C and 20 mm Hg. The residue is filtered and the filtrate is the desired product.
  • the product has a neutralization acid number of 0.06 and a kinematic viscosity of 32 cSt at 40°C.
  • a reaction vessel is charged with 2814 parts (21 moles) of trimethylolpropane, 6854 parts (67 moles) of isopentanoic acid (available commercially from Union Carbide), which is a mixture of 66% by weight valeric acid and 34% by weight 2-methylbutyric acid), 5 parts methanesulfonic acid, 50 parts of an aromatic solvent.
  • the reaction mixture is heated to 145°C over three hours.
  • the reaction mixture is heated to 165°C over three hours.
  • the temperature of the mixture is maintained for 13 hours.
  • a total of 1100 milliters of water is collected.
  • the reaction mixture is vacuum stripped to 180-200°C and 10-15 mm Hg.
  • the residue is filtered and the filtrate is the desired product.
  • the product has a 0.009 acid number, and a kinematic viscosity of 10.2 cSt at 40°C and 2.65 cSt at 100°C.
  • a reaction vessel is charged with 2345 parts (17.5 moles) of trimethylolpropane, and 8295 parts (52.5 moles) of 3,5,5 trimethylhexanoic acid (available commercially from Exxon Corporation under the trade name ISO Nonanoic acid). The mixture is heated to 150°C and the temperature is maintained for 12 hours. The reaction mixture is then heated to 200°C and the temperature is maintained for 38 hours. The reaction is then heated to 220°C and the temperature is maintained for 14 hours. The reaction mixture is vacuum stripped to 200°C and 10-15 mm Hg. Alumina (275 parts) is added to the residue and the residue is filtered. The filtrate is the desired product. The product has a zero acid number, and a kinematic viscosity of 52.8 cSt at 40°C and 7.1 cSt at 100°C.
  • a mixture of 200 parts (2 moles) of succinic anhydride and 62 parts (1 mole) of ethylene glycol is heated to 120°C, and the mixture becomes a liquid.
  • Five parts of acidic clay are added as catalyst, and an exotherm to about 180°C occurs.
  • Isooctanol 260 parts, 2 moles
  • the reaction mixture is maintained at 130°C as water is removed.
  • a small amount of propanol is added and the mixture is stirred at 100°C overnight.
  • the reaction mixture then is filtered to remove traces of oligomers, and the filtrate is the desired ester.
  • a mixture of 200 parts (2 moles) of succinic anhydride, 62 parts (1 mole) of ethylene glycol and 1 part of paratoluene sulfonic acid is prepared and heated to 80-90°C. At this temperature, the reaction begins and an exotherm to 140°C results. The mixture is stirred at 130-140°C for 15 minutes after 160 parts (2 moles) of 2,2,4-trimethylpentanol are added. Water evolves quickly, and when all of the water is removed, the residue is recovered as the desired product.
  • a mixture of 294 parts (3 moles) of maleic anhydride and 91 parts (1.5 moles) of ethylene glycol is prepared and heated at about 180°C whereupon a strong exotherm occurs and the temperature of the mixture is raised to about 120°C.
  • 222 parts (3 moles) of n-butyl alcohol and 10 parts of Amberlyst 15 are added. Water begins to evolve and is collected. The reaction mixture is maintained at 120°C until 50 parts of water is collected. The residue is filtered, and the filtrate is the desired product.
  • a mixture of 1072 parts (8 moles) of trimethylolpropane, 2080 parts (16 moles) of neoheptanoic acid and 50 parts of Amberlyst 15 is prepared and heated to about 130°C.
  • a water/acid azeotrope evolves and is removed.
  • 584 parts (4 moles) of adipic acid are added and the reaction continues to produce an additional 450 parts of distillate.
  • 65 parts of trimethylolpropane are added to the mixture and additional water is removed. The residue is filtered and the filtrate is the desired ester.
  • Esters are prepared by reacting mixtures of isononanoic acid (1) and adipic acid (2) with trimethylolpropane (3), in the presence of a tetraisopropoxy orthotitanate catalyst.
  • the reactants are charged to a flask and heated until reaction ceases, as indicated by termination of water collection in a distillation trap, at which point the reaction mixture has reached about 220°C.
  • a vacuum is applied to remove volatile components, and the flask contents are cooled and filtered to produce the liquid ester product.
  • Example 25 The procedure of Example 25 is used to prepare esters from isononanoic acid (1), adipic acid (2) and neopentylglycol (3), giving the following product properties: Moles Catalyst, Viscosity, cSt Molecular Product (1) (2) (3) grams 40°C 100°C Weight A 2 1 2 2 80 10.5 588 B 10.7 6.7 12 5 106 13.2 665 C 8.3 8.3 12.5 8 220 22.1 758
  • Example 25 The procedure of Example 25 is used to prepare esters from isononanoic acid (1), isooctanoic acid (2), isobutyric acid (3), adipic acid (4) and pentaerythritol (5), giving the following product properties: Moles Catalyst Product (1) (2) (3) (4) (5) grams A 7 7 7 1.5 6 5 B 7.2 7.2 6 1.8 6 5 Product Viscosity, cSt Molecular 40°C 100°C Weight A 149.5 14.0 733 B 194 16.9 802
  • Example 25 The procedure of Example 25 is used to prepare the ester in Table 3.
  • TABLE 3 Moles Adipic iso Nonanoic Example TMP(1) Acid Acid (2) Comparative Example 1 0 3 28A 1 0.1 2.8 28B 1 0.125 2.75 28C 1 0.25 2.45 28D 1 0.30 2.4 28E 1 0.35 2.3 Viscosity @ 40°C @ 100°C Example 52.25 7.25 28A 69.4 8.65 28B 76.6 9.14 28C 119 12.3 28D 140 14 28E 185 16.8
  • the carboxylic ester lubricants preferably contain branched alkyl groups and generally are free of acetylenic and aromatic unsaturation. Some ester which contain such unsaturation may be insoluble in the fluorine-containing hydrocarbons. In one embodiment, the soluble ester lubricants of this invention also are preferably free of olefinic unsaturation except that some olefinic unsaturation may be present so long as the lubricant is soluble.
  • the carboxylic esters are soluble in the fluorine-containing hydrocarbons and, in particular, in the fluorohydrocarbons such as 1,1,1,2-tetrafluoroethane.
  • the carboxylic esters are soluble over a wide temperature range and, in particular, at low temperatures.
  • the solubility of the lubricants in fluorohydrocarbons such as 1,1,1,2-tetrafluoroethane at low temperatures is determined in the following manner.
  • the lubricant (0.5 gram) is placed in a thick-walled glass vessel equipped with a removable pressure gauge.
  • the liquid compositions comprise a major amount of a fluorine-containing hydrocarbon and a minor amount of at least one soluble organic lubricant comprising at least one carboxylic ester.
  • major amount is meant an amount greater than 50% by weight such as 50.5%, 70%, 99%, etc.
  • minor amount includes amounts less than 50% by weight such as 1%, 5%, 20%, 30% and up to 49.9%.
  • the liquid compositions will comprise from about 70% to about 99% of the fluorine-containing hydrocarbon and from about 1 to about 30% by weight of the lubricant. In other embodiment, the liquid compositions may contain from about 5% to about 20% by weight of the lubricant.
  • the liquid compositions may additionally contain (C) at least one additive selected from the group consisting of an alkyl phosphite, an alkyl phosphonic acid ester, a nitrogen-containing heterocycle, and a mixture thereof.
  • the phosphite and/or the alkyl phosphonic acid ester are present in an amount sufficient to provide antiwear and/or extreme pressure properties to the lubricant and liquid composition.
  • the phosphite and/or the alkyl phosphonic acid ester are present in an amount to provide 0.001%, or to 0.015%, or about 0.025%, to about 1%, or to about 0.5%, or to about 0.2% by weight phosphorus to the lubricant.
  • the nitrogen-containing heterocycle is present in an amount from about 0.001%, or about 0.02%, or about 0.03% up to about 5%, or to about 2%, or to about 1%, or to about 0.5% by weight of the lubricant.
  • the phosphite and/or the alkyl phosphonic acid ester provide beneficial antiwear and extreme pressure properties to the liquid compositions.
  • the phosphite may be a dialkyl or trialkyl phosphite, preferably a dialkyl phosphite.
  • the alkyl phosphonic acid ester may be an alkyl phosphonic acid diester, preferably a dialkylester.
  • the alkyl groups of the phosphite and the phosphonic acid ester independently contain from 1, or about 3 to about 20, or to about 18, or to about 8 carbon atoms. In one embodiment, the phosphite and the phosphonic acid ester have alkyl groups independently containing from about 3 to about 6, or to about 5 carbon atoms.
  • dialkyl phosphites are commercially available, such as lower dialkyl phosphites, which are preferred.
  • Lower dialkyl phosphites include dimethyl, diethyl, dipropyl, dibutyl, dipentyl and dihexyl phosphites.
  • Phosphites and their preparation are known and many phosphites are available commercially.
  • mixed alkyl phosphites, made from a mixture of alcohols are useful in the present invention. Examples of mixtures of alcohols include ethyl and butyl alcohol; propyl and pentyl alcohol; and methyl and pentyl alcohol.
  • a particularly useful phosphite is dibutyl phosphite.
  • Alkyl phosphonic acid esters are prepared by means known to those in the art.
  • alkyl phosphonic acid esters may be prepared by reacting an alkyl halide with a trialkyl phosphite.
  • alkyl phosphonic acid esters include diethyl, butylphosphonate; dibutyl,butylphosphonate; 2-ethylhexyl,2-ethylhexylphosphonate, etc.
  • the lubricant may additionally contain a nitrogen-containing heterocycle, such as dimercaptothiadiazoles, triazoles, amino-mercaptothiadiazoles, imidazoles, thiazoles, tetrazoles, hydroxyquinolines, oxazolines, imidazolines, thiophenes, indoles, indazoles, quinolines, benzoxazines, dithiols, oxazoles, oxatriazoles, pyridines, piperazines, triazines, and derivatives of any one or more thereof.
  • a nitrogen-containing heterocycle such as dimercaptothiadiazoles, triazoles, amino-mercaptothiadiazoles, imidazoles, thiazoles, tetrazoles, hydroxyquinolines, oxazolines, imidazolines, thiophenes, indoles, indazoles, quinolines, benzoxazines, dithiols,
  • the nitrogen containing heterocycle is a triazole or derivative thereof, a thiazole or derivative thereof, a mercaptothiazole or derivative thereof and a thiadiazole or derivative thereof, preferably a triazole or derivative thereof.
  • These additives provide metal deactivating, metal passivating and corrosion controlling character to the liquid compositions.
  • useful metal deactivators include dimercaptothiadiazoles and derivatives thereof, substituted and unsubstituted triazoles (e.g., benzotriazole, tolyltriazole, octylbenzotriazole, and the like), mercaptobenzothiazoles, etc.
  • the triazole is a benzotriazole or an alkylbenzotriazole in which the alkyl group contains 1 to about 20 carbon atoms, preferably 1 to about 8 carbon atoms.
  • the nitrogen containing heterocycle (C) may also be the reaction product of at least one of the above triazoles, at least one amine and an aldehyde or aldehyde precursor.
  • the triazole is preferably a benzotriazole.
  • the amine can be one or more mono- or polyamines. These monoamines and polyamines can be primary amines, secondary amines or tertiary amines. Examples of polyamines include polyalkylenepolyamines, and heterocyclic polyamines.
  • the polyalkyleneamines include polyethylenepolyamines, such as diethylenetriamine, triethylenetrimine, tetraethylenepentaamine, etc.
  • the aldehyde is typically a hydrocarbon-based aldehyde, preferably a lower aliphatic aldehyde.
  • Suitable aldehydes include formaldehyde, benzaldehyde, acetaldehyde, the butyraldehydes, hydroxybutyraldehydes and heptanals, as well as aldehyde precursors which react as aldehydes under the conditions of the reaction such as paraformaldehyde, paraldehyde, formalin and methanal.
  • Formaldehyde and its precursors e.g., paraformaldehyde, trioxane
  • Mixtures of aldehydes may be used.
  • Reomet® 39 An example of a useful triazole derivative is Reomet® 39. This material is a triazole derivative available commercially from Ciba-Geigy Corporation.
  • the liquid compositions are characterized as having improved thermal and chemical stability over a wide temperature range.
  • the liquid compositions have improved antiwear and corrosion stability properties.
  • the liquid compositions have beneficial viscosity properties.
  • Preferably the liquid compositions have a viscosity of 5-400 centistokes (cSt) measured at 40°C.
  • Liquid compositions containing carboxylic esters derived from neo polyols such as neopentylglycol, trimethylolpropane and pentaerythritol, have beneficial thermal and hydrolytic stability.
  • Liquid compositions containing carboxylic esters derived from branched acids, such as iso or neo acids, preferably neo acids have improved thermal and hydrolytic stability.
  • the carboxylic esters are derived from the above polyols, a polycarboxylic acid and an iso or neo acid.
  • the liquid composition may contain one carboxylic ester reaction product or in another embodiment, the liquid compositions may contain a blend of two or more carboxylic ester reaction products.
  • a liquid composition of a desired viscosity may be prepared by blending a higher viscosity carboxylic ester with a lower viscosity carboxylic ester.
  • Other additives if soluble in the liquid, known to be useful for improving the properties of halogen-containing hydrocarbon refrigerants can be included in the liquid compositions to improve the characteristics of the liquid as a refrigerant.
  • hydrocarbon oils such as mineral oil generally are not included in and are most often excluded from the liquid compositions of the invention, particularly when the fluorine-containing hydrocarbon contains no other halogens.
  • Hydrocarbon lubricants may be present if the liquid compositions are used to retrofit a compressor system which had previously used a hydrocarbon lubricant.
  • additives may be included in the liquid compositions of the present invention to enhance the performance of the liquids include extreme-pressure and anti-wear agents, oxidation and thermal-stability improvers, corrosion-inhibitors, viscosity-index improvers, pour point and/or floc point depressants, detergents, dispersants, anti-foaming agents, viscosity adjusters, metal deactivators, etc. As noted above, these supplementary additives must be soluble in the liquid compositions of the invention.
  • phosphates include phosphates, phosphate esters, thiophosphates such as zinc diorganodithiophosphates, chlorinated waxes, sulfurized fats and olefins, organic lead compounds, fatty acids, molybdenum complexes, borates, halogen-substituted phosphorous compounds, sulfurized Diels Alder adducts, organic sulfides, metal salts of organic acids, etc.
  • Sterically hindered phenols, aromatic amines, dithiophosphates, sulfides and metal salts of dithioacids are useful examples of oxidation and thermal stability improvers.
  • VI improvers include polyolefins such as polyester, polybutene, polymethacrylate, polyalkyl styrenes, etc.
  • Pour point and floc point depressants include polymethacrylates, ethylene- vinyl acetate copolymers, succinamic acid-olefin copolymers, ethylene-alpha olefin copolymers, etc.
  • Detergents include sulfonates, long-chain alkyl-substituted aromatic sulfonic acids, phenylates, metal salts of alkyl phenols, alkyl phenol-aldehyde condensation products, metal salts of substituted salicylates, etc.
  • Silicone polymers are a well known type of anti-foam agent. Viscosity adjusters are exemplified by polyisobutylene, polymethacrylates, polyalkyl styrenes, naphthenic oils, alkyl benzene oils, polyesters, polyvinyl chloride, polyphosphates, etc.
  • liquid compositions of the present invention are particularly useful as refrigerants in various refrigeration systems which are compression-type systems such as refrigerators, freezers, and air-conditioners including automotive, home and industrial air-conditioners.
  • compression-type systems such as refrigerators, freezers, and air-conditioners including automotive, home and industrial air-conditioners.
  • air-conditioners including automotive, home and industrial air-conditioners.
  • the following examples are illustrative of the liquid compositions of the present invention. Parts by Wt.
  • Example B 1,1,1,2-tetrafluoroethane 85 Lubricant of Example 19 15 DBBP 0.2
  • Example C HFC-134a 55 Lubricant of Example 6 45 Dibutyl phosphite 0.05 benzotriazole 0.01
  • Table 2 contains further examples of the liquid compositions of the present invention.
  • Table 2 F E H I J HFC-134 80 85 55 90 45 Lubricant of Example: I 20 V 15 10 VII 45 55

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JPH06108081A (ja) 1994-04-19
CN1077984A (zh) 1993-11-03
KR940005782A (ko) 1994-03-22
AU3711893A (en) 1993-11-04
CA2094857A1 (en) 1993-10-29
MX9302437A (es) 1994-06-30
BR9301005A (pt) 1993-11-03

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