MXPA00006543A - Halogenated hydrocarbon refrigerant compositions containing polymeric oil-return agents - Google Patents

Abstract

Refrigerant compositions containing polymeric oil-return agents which solubilize or disperse mineral and synthetic oil lubricants with hydroflurocarbon and hydroflurocarbon/hydrochlorofluorocarbon-based refrigerants are disclosed. These polymeric oil-return agents, such as copolymers of fluorinated and non-fluorinated methacrylates, as a small proportion of an overall refrigerant composition, permit efficient return of mineral and synthetic oil lubricants from non-compressor zones back to a compressor zone in a refrigeration system operating with hydrofluorocarbon and hydrofluorocarbon/hydrochlorofluorocarbon-based refrigerants.

Description

REFRIGERANT COMPOSITIONS OF HALOGENATED HYDROCARBON / CONTAINING POLYMER OIL RETURN AGENTS.

Field of Invention The present invention relates to compositions containing polymeric oil return agents that solubilize or disperse synthetic and mineral oil lubricants with halogenated hydrocarbon refrigerants, allowing an efficient return of lubricants from non-compressor zones to compressor zones in a system of refrigeration.

Background of the Invention Mineral oils and alkylbenzenes are conventionally used as lubricants. in refrigeration systems based on chlorofluorocarbon (CFC). However, the lack of solubility of these lubricants in the replacement, not ozone depletion, of hydrofluorocarbon (HFC) refrigerants has impeded their use and has made necessary the development Ref: 120689 and use of alternative lubricants for HFC refrigeration systems based on polyalkylene glycols (PAGs) and polyol esters (POEs). Although PAGs and POEs are suitable lubricants for HFC-based refrigeration systems, they are extremely hygroscopic and can absorb several thousand ppm (parts per million) of water on exposure to humid air. With this absorption of moisture begin the problems in the cooling system, such as the formation of acids that result in corrosion of the cooling system and the formation of intractable sediments. In contrast, mineral oils and alkylbenzenes are much less hygroscopic and have lower solubility, less than 100 ppm, per water. Additionally, PAG and POE lubricants are considerably more expensive than hydrocarbon lubricants, typically in the order of three to six times more expensive. As a consequence, it is a necessity and an opportunity to solve this solubility problem so that the refrigeration industry can use mineral oil lubricants and alkylbenzene with HFC-based refrigerants.

Hydrochlorofluorocarbon (HCFC) refrigerants are also replaced with CFCs, and currently as mixtures with HFCs. These mixtures of HCFC-based refrigerants are less soluble than CFCs in conventional refrigeration lubricants such as mineral oil. A change from mineral oil lubricant to alkylbenzene is often required when mixtures of HCFCs or HCFC / HFCs are used to replace pure CFC base refrigerants, resulting in more expenses for the refrigeration industry. Therefore, it is a necessity and an opportunity to solve this solubility problem so that the refrigeration industry can use base refrigerants in HCFC and HCFC / HFC with mineral oil lubricants.

Reyes-Gavilán et al., In WO 96/07721 discloses surfactants capable of reducing the interfacial tension between the hydrocarbon lubricant and a coolant immiscible with said hydrocarbon lubricant.

Herré et al., In DD 293364 discloses a heat-pumped oil comprising: hydrorefined mineral oil, paraffin-based, in which the ratio of parafinically bonded carbon to aromatically bonded carbon is from 5: 1 to 15: 1; polymethacrylate; tricresyl phosphate ester; and di-tert-butyl-p-cresol.

Katafuchi et al., In EP 557796 Al discloses a lubricant for use with tetrafluoroethane refrigerant comprising (A) a poly-alpha-olefin or poly-alpha-olefin / synthetic acetyl of alkylbenzene, and (B) a poly oxyalkylene glycol.

Raynolds in US 5017300 describes cooling lubricants comprising acrylic polymers.

Kaneko in US 4946611 describes cooling lubricants comprising polyfluoroalkylsiloxanes.

Thomas et al., In US 5154846 discloses cooling lubricants comprising polybutylene glycol having a fluorinated alkyl group cover on at least one end.

The present invention addresses the aforementioned needs of the refrigeration industry by providing polymeric oil return agents that create a solution or stabilize the oil dispersion lubricants (dispersed phase) in an HFC and / or HCFC base coolant (continuous phase) , allowing to transport improved lubricating oil through the cooling system and return the lubricating oil back to the compressor of the cooling system of the other zones of the cooling system.

Brief Description of the Invention The present invention relates to refrigerant compositions comprising (a) a halogenating hydrocarbon containing at least one carbon atom and one fluoride atom; (b) an oil selected from the group consisting of mineral oils and synthetic oils; and (c) an effective amount of a polymeric oil return agent, wherein said oil return agent forms a stabilized solution or dispersion of said halogenated hydrocarbon and said oil, and wherein said oil return agent comprises less than about 10 weight percent of the refrigerant composition. The polymeric oil return agents of the present invention solubilize or disperse mineral and synthetic oil lubricants with halogenated hydrocarbon refrigerants. Polymeric oil return agents, such as a small portion of the refrigerant composition in general, allow the efficient return of mineral and synthetic oil lubricants from the non-compressor zones back to the compressor zone in a refrigeration system .

Detailed description of the invention.

The present invention relates to refrigerant compositions comprising: (a) a halogenated hydrocarbon containing at least one carbon atom and one fluorine atom; (b) an oil selected from the group consisting of mineral oils and synthetic oils; and (c) an effective amount of a polymeric oil return agent, wherein said polymeric return agent forms a stabilized solution or dispersion of said halogenated hydrocarbon and said oil, and wherein said oil return agent comprises less than about of 10 weight percent of said refrigerant composition.

The present invention also relates to compositions, comprising: (a) a halogenated hydrocarbon containing at least one carbon atom and one fluorine atom; and (b) an effective amount of a polymeric oil return agent, wherein said oil return agent forms a stabilized solution or dispersion of said halogenated hydrocarbon with an oil comprising mineral oils and synthetic oils.

The present invention further relates to lubricating compositions for use with halogenated hydrocarbon refrigerant, comprising: (a) an oil selected from the group consisting of mineral oil and synthetic oils; Y (b) an effective amount of a polymeric oil return agent, wherein said oil return agent forms a stabilized solution or dispersion of said oil with a halogenated hydrocarbon refrigerant.

The halogenated hydrocarbons of the present invention contain at least one carbon atom and one fluoride atom. Of particular utility are halogenated hydrocarbons having 1-6 carbon atoms containing at least one fluoride atom, optionally containing chloride and oxygen atoms, and having a normal boiling point from -90 ° C to 80 ° C. By normal boiling point it means the temperature at which a vapor pressure of the liquid composition is equal to one atmosphere. These halogenated hydrocarbons can be represented by the general formula CwF2w + 2-.x-yHxClyOz, where w is 1-6, x is 1-9, and is 0-3, and z is 0-2. The preferred halogenated hydrocarbons are those in which it is 1-6, x is 1-5, and is 0-1 and z is 0-1. Such halogenated hydrocarbons are commercially available products from a number of sources such as E.l. du Pont de Nemours &; Co., Fluoroproducts, Wilmington, DE, 19898, USA, or are available from local synthesis companies such as PCR Inc., P.O. Box 1466, Gainesville, Florida, 32602, USA, and also by the synthetic processes described in the art such as The Journal of Fluorine Chemistry, or Chemistry of Organic Fluorine Compounds, edited by Milos Hudlick, published by The MacMillan Company, New York, NY, 1962. Examples are: CC12F2 (CFC-12), CHC12F (HCFC-21), CHC1F2 (HCFC-22), CHF3 (HFC-23), CH2C1 F (HCFC-31), CH2F2 (HFC- 32), CH3F (HFC-41), CHC12CF3 (HCFC-123), CHC1 FCClF2 (HCFC-123a), CHCIFCF3 (HCFC-124), CHF2CC1F2 (HCFC-124a), CHF2CF3 (HFC-125), CH2C1CF3 (HCFC- 133a), CHF2CH2 (HFC-134), CH2FCF3 (HFC-134a), CC1F2CH3 (HCFC-1 2b), CHF2CH2F (HFC-143), CF3CH3 (HFC-143a), CHC1 FCH3 (HCFC-151a), CHF2CH3 (HFC -152a), CHF2CC12CF3 (HCFC-225aa) CHCIFCCIFCF3 (HCFC-225ba), CHF2CC1FCC1F2 (HCFC 225bb), CHC12CF2CF3 (HCFC-225ca) CHCIFCF2CCIF2 (HCFC-225cb), CHF2CF2CC12F (HCFC 225cc), CC1F2CHC1CF3 (HCFC-225da) CC1F2CHFCC1F2 (HCFC-225ea), CF3CHFCCl2F (HCFC-225eb) CHF2CC1FCF3 (HCFC-226ba), CHC1FCF2CF3 (HCFC-226ca) CHF2CF2CC1F2 (HCFC-226cb), CF3CHCICF3 (HCFC-226da) CC1F2CHFCF3 (HCFC-226ea), CHF2CF2CF3 (HFC- 227ca) CF3CFHCF3 (HFC-227ea), CHF2CC1FCHF2 (HCFC-235ba) CH2FCC1FCF3 (HCFC-235bb), CHC1FCF2CHF2 (HCFC-235ca) CH2C1CF2CF3 (HCFC-235cb), CH2FCF2CC1F2 (HCFC-235cc) CHF2CHC1CF3 (HCFC-235da), CHCIFCHFCF3 (HCFC-235ea) CHF2CHFCC1F2 (HCFC-235eb), CC1F2CH2CF3 (HCFC- 235fa) CHF2CF2CHF2 (HFC-236ca), CH2FCF2CF3 (HFC-236cb) CHF2CHFCF3 (HFC-236ea), CF3CH2CF3 (HFC-236fa) CH2FCF2CHF2 (HFC-245ca), CH3CF2CF3 (HFC-245cb) CHF2CHFCHF2 (HFC-245ea), CH2FCHCF3 ( HFC-245eb) CHF2CH2CF3 (HFC-245fa), CH2FCF2CH2F (HFC-254ca) CH2CF2CHF2 (HFC-254cb), CH2FCHCHF2 (HFC-254ea) CH3CHFCF3 (HFC-254eb), CHF2CH2CHF2 (HFC-254fa) CH2FCH2CF3 (HFC-254fb), CH3CF2CH3 (HFC-272ca) CH3CHFCH2F (HFC-272ea), CH2FCH2CH2F (HFC-272fa) CH3CH2CF2H (HFC-272fb), CH3CHFCH3 (HFC-281ea) CH3CH2CH2F (HFC-281fa), CF3CF2CF2CF2H (HFC-329p) CF3CF2CFCHCF3 (HFC-329me ), CF3CF2CF2CFH2 (HFC-388q), CF3CF2CH2CF3 (HFC-338mf), CF3CF2CFHCF2H (HFC-338pe), CF3CFHCF2CF2H (HFC-338pce), CHF2CF2CF2CF2H (HFC-338pcc), CF3CFHCFHCF3 (HFC-338mee), CF3CF2CF2CF2CF2H (HFC-42-llp), CF3CF2CFHCF3 (HFC-42-llmce), CF3CF2CF2CFHCF3 (HFC-42-1 lme), CF3CF2CH2CF2CF3 (HFC-43-1 Omcf), CF3CF2CF2CH2CF3 (HFC- 43-10mf), CF3CF2CF2CF2CFH2 (HFC-43-10q), CF3CF2CF2CFHCF2H (HFC-43 - 1 Ope), CF3CF2CFHCF2CF2H (HFC-43-10pce), CF3CHFCHFCF2CF3 (HFC-43-lOmee), CF2HCF2CF2CF2CF2H (HFC-43-10pccc), CF3CFHCF2CF2CF2H (HFC-43-10pcce), CF3CFHCF2CFHCF3 (HFC-43 - 1 Omece), CF3CF2CF2CF2CF2CF2H (HFC-52-13p), C F9OCH3, and C4FgOC2H5. The preferred halogenated hydrocarbons are: CHC1F2 (HCFC-22), CHF3 (HFC-23), CH2F2 (HFC-32), CHCIFCF3 (HCFC-124), CHF2CF3 (HFC-125), CHF2CHF2 (HFC-134), CH2FCF3 ( HFC-134a), CF3CH3 (HFC-143a), CHF2CH3 (HFC-152a), CHF2CF2CF3 (HFC-227ca), CF3CFHCF3 (HFC-227ea), CF3CH2CF3 (HFC-236f a), CHF2CH2CF3 (HFC-245fa), CHF2CF2CF2H (HFC-338pcc), CF3CHFCHFCF2CF3 (HFC-43 -1 Ornee), and halogenated hydrocarbon compositions similar to azeotropes and azeotropes such as: HCFC-22 / HFC-152a / HCFC-124 (R-401A, R-401B, R-401C), HFC - 125 / HFC-143a / HFC-134a (R-404A), HFC-32 / HFC-125 / HFC-134a (R-407A, R-407B, R-407C), HCFC-22 / HFC-143a / HFC -125 (R-408A), HCFC-22 / HCFC-124 / HCFC-142b (R-409A), HFC-32 / HFC-125 (R-41 OA), and HFC-125 / HFC-143a (R- 507).

The halogenated hydrocarbons of the present invention may further comprise up to 10 percent by weight of at least one hydrocarbon from C3 to C5f for example, propane, propylene, cyclopropane, n-butane, i-butane, and n-pentane. Examples of halogenated hydrocarbons containing such hydrocarbons from C3 to C5 are compositions similar to the azeotropes of HCFC-22 / HFC-125 / propane (R-402A, R-402B) and HCFC-22 / octafluoropropane / propane (R-403A , R-403B).

The oils of the present invention are oil conventionally used as lubricants in refrigerating apparatus with CFC base refrigerants. Such oils and their properties are described in the 1990 ASHRAE Handbook, Refrigeration Systems and Applications, chapter 8, entitled "Lubricants in Refrigeration Systems" pages 8.1-8.21. The oils of the present invention comprise the family of compounds commonly known in the art as mineral oils. Mineral oils include paraffins (saturated hydrocarbons, straight chain or branched carbon chain), naphthanes (cycloparaffins), aromatics (cyclic hydrocarbons, unsaturated, containing one or more rings characterized by their alternative double bonds), and not hydrocarbons (molecules that contain atoms such as sulfur, nitrogen, or oxygen in addition to carbon and hydrogen). The oils of the present invention further comprise the family of compounds commonly known in the art as synthetic oils. Synthetic oils comprise alkylaryls (such as straight or branched alkyl chain alkylbenzenes), synthetic paraffins, and polyalphaolefins. Examples of commercially available lubricating oils of the present invention are Suniso® 3GS, Sontex® 372LT, and Calume t®R0-30 (all of these last three being naphthenic), Zerol® 150 (an alkylbenzene), and "BVM 100 N" ( a paraffin).

The polymeric oil return agent of the present invention has an average molecular weight number (Mn) of at least about 3,000. In a preferred embodiment, the polymeric oil return agent has an average molecular weight number of at least about 6,000. In a more preferred embodiment, the polymeric oil return agent has an average molecular weight number from about 10,000 to more than 40,000, and in some cases, up to more than 100,000. The polydispersity ("/ Mn, where Mw is the weight-average molecular weight) of the polymeric oil return agent of the present invention is not critical, and is typically between 1 and 5 for good utility polymeric oil return agents. .

The polymeric oil return agent of the present invention may be free of fluorine, .. In a preferred embodiment of the present invention, the polymeric oil return agent contains fluorine. In a preferred embodiment of the present invention wherein the polymeric oil return agent is a random copolymer of fluorinated or non-fluorinated acrylates, the amount of fluoride that contains the polymeric oil return agent is greater than zero and less than 50% by weight, preferably less than about 10% by weight of fluoride and more preferably about 25 percent by weight of fluoride.

The polymeric oil return agent of the present invention includes polymers comprising repeating units of at least one monomer represented by the formulas CH2 = C (R1) C02R2, CH2 = C (R3) C6H4R4, and CH2 = C (R5) C6H4XR6 , wherein X is oxygen or sulfur, R1, R3 and R5 are independently selected from the group consisting of H radicals and C? -C alkyl, and R2, R4, and R6 are independently selected from the group consisting of chain-based radicals carbon containing C, and F, and may further contain H, Cl, oxygen ether, or sulfur in the form of thioether, sulfoxide sulphono groups. Representatives of such radicals are alkyl, alkoxyalkyl, fluoroalkyl, fluoroalkoxyalkyl, alkylphenyl, alkoxyalkylphenyl, fluoroalkylphenyl, fluoroalkoxyalkylphenyl, and fluoroalkoxyfluoroalkyl phenyl radicals. R2 may not be perfluorinated, as such structures are known to be unstable.

Representative alkyl radicals are those identified by the formula -CaH (2a + i) / wherein a is 1-20.

Representative alkoxyalkyl radicals are those identified by the formulas - (CH20) bR7 and - (CHR8CHR90) CR10, wherein b and c are independently selected from 1-20 and R7-R10 are independently selected from H and alkyl radicals represented by the formula CdH (2d + i), where d is 1-20.

Representative fluoroalkyl radicals are those identified by the formula -CeF (2e +? - f) Hf, wherein e is 1-20 and f is from 0 to 2e.

Representative fluoroalkoxyalkyl radicals are those identified by the formulas - (CH20) gR1: L and - (CHR12CHR130) hR14, wherein g and h are independently selected from 1-20, R12 and R13 are independently selected from alkyl radicals represented by the formula - CiH (2i + i), where i is 1-5, and R11 and R14 are independently selected from fluoroalkyl radicals represented by the formula CkF (2k +? + M) Hm, wherein k is 1-20 and m is 0 up to 2k Representative fluoroalkoxyfluoroalkyl radicals are those identified by the formulas - (CR15R160) nR17 and - (CR18R19CR20R21O) PR22, wherein n and p are independently selected from 1-20, R15, R15, R18, R19, R20, and R21 are independently selected from radicals of H, F and fluoroalkyl represented by the formula -CqF (2q +? - r) Ht, wherein q is 1-20 and r is from 0 to 2q, and R17 and R22 are independently selected from fluoroalkyl radicals represented by the formula -C3F (2s +? _ T) Ht where s is 1-20 and t is from 0 to 2s.

Representative alkylphenyl radicals are those identified by the formulas -C6H4CUH (2u + i) and ~ C6H OCuH. { 2u + i), where u is 1-20.

Alkoxyalkylphenyl radicals are those identified by the formulas -C6H4R23 and -C6H PR23, wherein OR23 is selected from the formulas (CH20) vR24 and - (CHR25CHR260) WR27, where v and are independently selected from 1-20 and R24-R27 are independently selected from H radicals and alkyl selected from the group represented by the formula -CxH (2x + i), wherein x is 1-20.

Representative fluoroalkyl phenyl radicals are those identified by the formulas -C6H4CyF (2y +? - z) Hz and -C6H4OCyF (2y +? _ Z) Hz, where y is 1-20 and z is from 0 to 2y.

The fluoroalkoxyalkyl phenyl radicals are those identified by the formulas -CeH4R28 and -C6H4OR28, wherein R28 is selected from the formulas - (CH20) a'R29 and - (CHR30CHR31O) b- R32, wherein a 'and b' are independently selected from 1-20, R30 and R31 are independently selected from alkyl radicals represented by the formula -CC? (2C- + I) / wherein c 'is 1-5, and R29 and R32 are independently selected from fluoroalkyl radicals represented by the formula Cd 'F (2' +? - e ') He', where d 'is 1-20 and e' is from 0 to 2d ', 32e'.

The f luoroalkoxif luoroalkylf enyl radicals are those identified by the formulas -C6H4R33 and -C6H4OR33, wherein R33 is selected from the formulas - (CR34R350) f, R36 and - (CR37R38CR39R40O) g. R41, wherein and independently are selected from 1-20, R34, R, 3J53, R, 3J7 ', RJB, RJS and R, are independently selected from radicals H, F, and fluoroalkyl represented by the formula -Ch' F (2h '+? - i'> H-, where h 'is 1-5 and i' is from 0 to 2h ', and R36 and R41 are independently selected from fluoroalkyl radicals represented by - the formula -Cj »F (2j »+? - k ') H', where j 'is 1-20 and k' is from 0 to 2j '.

R may comprise fluoroalkenyl groups comprising C and F and not containing saturation, available from oligomers or fluoroolefins such as tetrafluoroethylene and hexafluoropropylene. For example, the polymeric oil return agent of the present invention includes polymers comprising repeating units of monomer represented by the formulas CH2 = C / R5) C6H4XR6, wherein X is oxygen, R5 is as previously defined, and R6 is the group -C (CF3) = C (CF (CF3) 2) 2, such a group as a result of the readily available hexafluoropropylene trimer (CF (CF3) = C / CF (CF3) 2) 2).

Preferred polymeric oil return agents of the present invention are those selected from the group represented by polymers comprising repeating units of at least one monomer represented by the formula CH2 = C (R1) C02R2, wherein R1 is selected from radicals H, Ci and C2 alkyl, and R2 is selected from alkyl radicals of Cx to C20 and -CH2CH2Ck 'F (2k' + i), wherein k 'is -from 2 to 12. Such polymeric oil return agent of the present invention It is known as Zonyl®PHS sold by EI du Pont de Nemours & Co., Wilmington, DE, 19898, USA and is a random copolymer made by polymerizing 40% by weight of CH2 = C (CH3) C02CH2CH2 (CF2CF2) m- F (also referred to herein as Zonyl® fluoromethacrylate or ZFM) wherein m is from 1 to 12, primarily from 2 to 8, and 60% by weight of lauryl methacrylate (CH2 = C (CH3) C02 (CH2) 11CH3, also referred to herein as AML).

The polymeric oil return agents at 5 of the present invention are employed in an effective amount in the present inventive compositions such as a solution or a stabilized halogenated hydrocarbon dispersion and the lubricating oil is formed. By "dispersion" "Stabilized" means that a dispersion of halogenated hydrocarbon and oil is formed in such a way that the oil returns with the halogenated hydrocarbon from the non-compressor zones to the compressor zone in a refrigeration system in a quantity that maintains acceptable lubrication of the compressor and thus the operation of the refrigeration system in general. In the present inventive compositions, they comprise halogenated hydrocarbon containing at least one carbon atom and one fluoride atom, the oil is selected from the group consisting of mineral oils and synthetic oils, and the polymeric oil return agent, less than about 10 weight percent of the composition, is the polymeric oil return agent. That is an effective amount of polymeric oil return agent in the present composition resulting in a stabilized solution or dispersion of said halogenated hydrocarbon and said oil and the return of the oil in a compressor cooling system from the non-compressor to the compressor zones.

The carrier of the hydrocarbon oil return agent is an optional component of the present inventive compositions and comprises aliphatic hydrocarbon having at least 6 carbon atoms. For example, hexanes, heptanes, octanes, kerosene, and mixtures thereof, and in particular refined kerosene with a sulfur content of less than 0.2% by weight. Isopar®H is a commercially available preferred compound (a high purity iso-paraffinic with low aromatics sold by Exxon Chemical). The carrier of the hydrocarbon oil return agent used in conjunction with the present polymeric oil return agents results in an excellent return of the oil in a compression cooling system from the non-compression zones to the compressor zones. The carrier of the hydrocarbon oil return agent assists in the handling of acrylate-based polymeric oil return agents (viscous and sticky materials under standard conditions) in which the acrylate-based polymeric oil return agent solutions can be formed in the carrier of the hydrocarbon oil return agent. The carrier of the hydrocarbon oil return agent can be used as the polymerization solvent in the preparation of acrylate-based polymeric oil return agents, and thus can be introduced beneficially at this point.

The antifoam agent is an optional component of the present inventive compositions. The antifoaming agent can be used to control the foam in an air conditioning or refrigerant system. Antifoam agents useful in the present invention include, but are not limited to, polydimethylsiloxane (Dow 200), vinyl terminated polydimethylsiloxane (Gelest DMS-V31, DMS-V52), trimethyl-terminated trifluoropropyl methylsiloxane (Dow FS-1265 ), methyl phenyl siloxane (Gelest PMP-5053), and vinyl terminated trifluoropropyl methylsiloxanedimethylsiloxane copolymer (Gelest FMV-4031).

The present compositions comprise an oil, oil, halogenated hydrocarbon return agent, and optionally, an oil return agent carrier, generally comprising 40-99% by weight of halogenated hydrocarbon, 1-60% by weight oil , 0.001-10% by weight of oil return agent, and 0-20% by weight of the oil return agent carrier, based on the total weight of the composition. More preferably, such compositions comprise 50-90% by weight of halogenated hydrocarbon, 10-50% by weight of oil, 0.005-5% by weight of the oil return agent, and 0-10% by weight of the oil. carrier of the oil return agent.

The present compositions further comprise: halogenated hydrocarbon, oil return agent, and optionally, a carrier of the oil return agent; and the oil, oil return agent, and optionally, a carrier of the oil return agent, comprise weight ratios of the identical components with those found in the present compositions comprising halogenated hydrocarbon, oil return agent, and optionally , a carrier of the oil return agent. As it is said, in the present compositions, the weight ratio of the halogenated hydrocarbon to the oil is from about 0.6 (40/60) to about 99 (99/1), the weight ratio of the oil to the oil return agent is from about 0.1 (1/10) to about 60,000 (60 / 0.001), and the weight ratio of the oil return agent carrier to the oil return agent is from about 20,000 (20 / 0.001) to a composition that does not contain carrier oil return agent.

The present invention further comprises processes for producing refrigeration comprising evaporating the present refrigeration compositions in the vicinity of a body to be cooled and processes for producing heat comprising condensing the present refrigeration compositions in the vicinity of a body to be heated.

The present invention further relates to a process for the dispersion of halogenated hydrocarbon in an oil comprising contacting the halogenated hydrocarbon with the oil in the presence of an effective amount of polymeric oil return agent which forms a stabilized solution or dispersion. of the halogenated hydrocarbon and oil, where the halogenated hydrocarbon contains at least one carbon atom and one fluoride atom, and the oil is • select from the group consisting of mineral oils and synthetic oils.

The present invention also relates to processes for returning the oils from a non-compression zone to a compressor zone in a refrigeration system comprising: • 20 (a) contacting the oil in the non-compression zone with at least one halogenated hydrocarbon in the presence of an effective amount of a polymeric oil return agent to form a stabilized solution or dispersion comprising halogenated hydrocarbon and oil; and (b) transferring the oil as the stabilized solution or dispersion from the non-compression zone to the compression zone of the refrigeration system, wherein the halogenated hydrocarbon contains at least one carbon atom and one fluoride atom, and the oil is selected from the group consisting of mineral oils and synthetic oils.

The present invention further relates to processes for transferring an oil from a low pressure zone to a compression zone in a refrigeration system, comprising: (a) contacting the oil in the low pressure zone of the cooling system with at least one halogenated hydrocarbon in the presence of an effective amount of a polymeric oil return agent to form a solution or a stabilized dispersion comprising halogenated hydrocarbon and oil; and (b) transferring the oil as the stabilized solution or dispersion from the low pressure zone to the compression zone of the refrigeration system, wherein the halogenated hydrocarbon contains at least one carbon atom and one fluoride atom, and the oil is selected from the group consisting of mineral oils and synthetic oils.

The present compositions comprising halogenated hydrocarbon and polymeric oil return agent also find utility as cleaning agents for removing hydrocarbon oils and welding fluxes from solid surfaces. Halogenated hydrocarbons, particularly hydrofluorocarbons such as CF3CHFCHFCF2CF3 (HFC-43-1 Ornee), have a limited oil solubility. In addition, the polymeric oil return agent for such halogenated hydrocarbons increases the ability of the halogenated hydrocarbon, particularly hydrofluorocarbon, to at least partially dissolve it and thereby remove the oil and weld flows from the surfaces.

Thus, the present invention further relates to processes for degreasing and solvent cleaning of the vapor phase using the present compositions comprising halogenated hydrocarbon and a polymeric oil return agent. Such steam degreasing processes comprise contacting a substrate to be cleaned, for example, a contaminated waste, tables of electronic circuits composed of metal-silicon, parts made of (for example, stainless steel) metal and the like, with the present compositions of halogenated oil / hydrocarbon return in a liquid phase, and in addition, the halogenated hydrocarbon vapors resulting from the boiling of such compositions. Halogenated hydrocarbon vapors Condensates in the substrate provide a clean distilled halogenated hydrocarbon that also rinses the oil return agent and the excess flow or other residue. The evaporation of the halogenated hydrocarbon from the substrate leaves no residue. The present solvent cleaning processes comprise contacting a substrate to be cleaned with the liquid phase of the present composition comprising a polymeric oil return agent and then removing the substrate from the composition. For floors and oils difficult to remove where a high temperature is necessary to improve the cleaning action of the solvent, or for lines of operation of a large volume of assembly where the cleaning of the substrate must occur efficiently and quickly, the conventional operation of a degreasing steam consists of immersing the part to be cleaned in a pool of boiling solvent that removes the volume of the Soil, then submerging the part in a pool containing a fresh distilled solvent almost at room temperature, and finally exposing the part to solvent vapors on a boiling pool that condenses in the cleaned part. In addition, the part can also be atomized with the distilled solvent before final rinsing. The appropriate degreasing steam in the processes described above are well known in the art. For example, Sherliker et al., In U.S. Patent No. 3,085,918, discloses such degreasing steam comprising a boiling pool, a cleaning sink, a water separator, and other auxiliary equipment.

The present compositions comprising halogenated hydrocarbon and an oil return agent are effective for removing hydrocarbon oil and weld flow residues from a wide range of substrates including metals, such as tungsten, copper, gold, beryllium, stainless steel, aluminum alloys, brass and the like; of glass and ceramic surfaces, such as glass, sapphire, borosilicate glass, aluminum oxide, silicon such as silicon discs used in electronic circuits, flammable aluminum oxide and the like; and plastics such as polyolefin ("Alathon", Rynite®, "Tenite"), polyvinylchloride, polystyrene ("Styron"), polytetrafluoroethylene (Teflon®), tetrafluoroethylene-ethylene copolymers (Tefzel®), polyvinylidene fluoride ("Kynar"), ionomers (Suriyn®), polymers of acrylonitrile-butadiene-styrene (Kralac®), copolymers of phenol-formaldehyde, cellulosic ("Ethocel"), epoxy resins, polyacetal (Delrin® ), poly (p-phenylene oxide) (Noryl®), polyetherketone ("Ultrapek"), polyetheretherketone ("Victrex"), poly (butylene terephthalate) ("Va lox"), polyarylate (Arylon®), glass polymer liquid, polyimide (Vespel®), polyetherimides ("Ultem"), polyamideimides ("Torlon"), poly (p-phenylene sulfide) ("Rython"), polysulfone ("Udel"), and polyaryl sulfone ("Rydel") ").

And emplos In the following examples, the percentages (%) are shown without a reference label to the weight percentage of a given material in the total composition being discussed. Unless otherwise specified, Zonyl®PHS in the Examples refers to a random copolymer made up of 40% by weight of ZFM (Zonyl® fluorocarbonate: CH2 = C (CH3) C02CH2CH2 (CF2CF2) m- F, where m 'is from 1 to 12, primarily from 2 to 8) and 60% by weight of AML (lauryl methacrylate: CH2 = C (CH3) C02 (CH2) nCH3). The error in the oil return measurement is reported to be ± 0.5% by weight.

Example 1 Appropriate containers were filled with mixtures containing 80% by weight of HFC-134a, 20% by weight of benzene alkyl acid Zerol® 150, with and without 0.08% by weight of Zonyl®PHS oil return agent and 0.32% by weight of kerosene carrier. The mixtures were stirred for 10 minutes and then placed in a sonic bath for 30 minutes at room temperature. After removing the bath, time was recorded by visually observing the refrigerant layer and the oil layer when they began to completely separate, visually, the clean phases with the naked eye. The results were recorded in Table 1.

TABLE 1 The results show in addition to Zonyl®PHS a significantly improved dipersability between HFC-134a and alkyl benzene.

Example 2 Appropriate containers were filled with mixtures containing 95% by weight of 1,1,1,2,3,4,4,5,5,5-cafluoropentane (HFC-43-lOmee) and 4.9% by weight of mineral oil Suniso®3GS, with and without 0.02% by weight of Zonyl®PHS oil return agent and 0.08% by weight of kerosene oil return agent carrier. The mixtures were stirred for 10 minutes and then placed in a sonic bath for 30 minutes at room temperature. After removing the bath, time was recorded by visually observing the refrigerant layer and the oil layer when they began to completely separate, visually, the clean phases with the naked eye. The results were recorded in Table 2.

TABLE 2 The results show in addition to Zonyl®PHS a significantly improved dispersibility between HFC-43-10mee and mineral oil.

Example 3 A miscibility test was conducted to determine if a mixed phase can be made for a normally immiscible / double oil refrigerant by the addition of Zonyl® additives. An appropriate container was filled with 1.2 grams of HFC-134a, 0.8g of Suniso®3GS mineral oil, and 0.02 grams of Zonyl®PHS (comprising 80% by weight of kerosene and 20% by weight of Zonyl®PHS), Zonyl ®FSA (23.25% by weight of F (CF2CF2) 3-8CH2CH2SCH2CH2C02Li, 35-40% by weight of water, 35-40% by weight of isopropanol), or Zonyl®FSN (40% by weight of F (CF2CF2) 3.8 (CH2CH20) 3.10H, 40% by weight of water, 40% in weight of isopropanol). The mixtures were visually observed with the naked eye initially for its miscibility observing the number of phases and the clarity (clear or nebulous). The mixtures were then exposed for 5 minutes to ultrasound at room temperature, they were observed, and then they were allowed to rest for 5 minutes and were observed again. The results are shown in Table 3.

TABLE 3 The samples were then heated at 100 ° C for one hour, ultrasonified for 30 minutes at 100 ° C, and then observed at room temperature after 5 minutes, one hour and 24 hours. Only the sample with the oil return agent Zonyl® showed a stable dispersion to form and maintain by the 2 phases.

The data shows that Zonyl®PHS has an improved dispersibility against Zonyl®FSA and Zonyl®FSN of low molecular weight. The Zonyl®PHS mixture is able to perform a stable dispersion of the 2 phases over a long period of time, indicating that the miscibility between the refrigerant and the lubricant is improved.

Example 4 A miscibility test was conducted to determine if a simple phase can be performed for a normally immiscible / double oil refrigerant by the addition of Zonyl®PHS oil return agent. A test tube was filled with 7.5 grams of HFC-43-lOmee refrigerant and 2.5 grams of HAB 22 oil (HAB 22 is a branched alkylbenzene oil sold by Nippon Oil). A mixture of 48% by weight of Zonyl®PHS / 52% by weight carrier of the oil-repelling agent Isopar H (Isopar®H is a high-purity iso-paraffin with low aromatics sold by Exxon Chemical) at 0.5 was added. grams increasing a mixture of HFC-43-10mee / HAB22. After each addition, the tube was shaken for 1 minute, and then allowed to stand for 2 minutes at room temperature. Subsequently, the oil and coolant phases were visually observed by naked eye for nebulosity and change in the level of the coolant / oil interface. Due to density differences between the refrigerant and oil, the oil comprises the top layer., A similar test was also conducted by Surfynol®SE (2,4,7,9-tetramethyl-5-decina-4,7-diol). sold by Air Products). The results are shown in the Table TABLE 4 The results show a mixed phase of normally non-miscible oil / oil that can be made by the addition of Zonyl®PHS / Isopar H. A phase was not carried out with Surfynol®SE.

Example 5 The return oil was tested in an oil return apparatus as follows. Liquid refrigerant was fed from a pressurized cylinder through a copper tube to a heater where it was vaporized. The refrigerant vapor was then passed through a pressure regulator and a metering valve to control the flow at a constant rate of 1,000-1,100 cc per minute and a pressure of 1 atmosphere. The refrigerant vapor is fed to another copper tube 180 cm long and 0.635 cm outer diameter formed in a U-shape placed in a constant temperature bath. The U-shaped tube (tube U) started with a straight vertical section of 37 cm long and then curved to a horizontal section of 27 cm in length at the bottom of the bath. The tube was raised vertically in a zig-zag pattern with four lengths of 23 cm, followed by another vertical straight section of 23 cm in length. The tube U was filled with 10 grams of oil, optionally containing oil return agent and oil return agent carrier, which was added to the tube U through the 37 cm vertical tube. The refrigerant vapor was slowly passed through the oil in the U-tube. The refrigerant and the oil were removed from the tube U and collected in a receiver and the refrigerant was allowed to evaporate. The oil was then weighed to determine how much was carried out from the tube U by the refrigerant.

Refrigerant R401A (53% by weight of HCFC-22, 13% by weight and HFC-152a and 34% by weight of HCFC-124) was placed in the refrigerant cylinder. Mineral oil or Suniso®3GS and Zonyl®PHS oil, optionally with the carrier of the kerosene oil return agent, was placed in the copper U-tube, where the total oil and the oil return agent, and the carrier of the oil return agent is equal to 10 grams. The bath at constant temperature was maintained at a temperature of -20 ° C. Refrigerant vapor was fed through the U-tube at a flow rate of 1,100 cubic centimeters per minute and the weight of the oil in the receiver was measured at time intervals of 6, 10, 20 and 30 minutes. The data is shown in Table 5 below.

TABLE 5 The data shows that the addition of Zonyl®PHS to mineral oil improves the return of oil and in particular, when kerosene is used as a carrier.

Example 6 The apparatus and procedure of Example 5, with exceptions discussed below, was used for refrigerant test R401A (53% by weight of HCFC-22, 13% by weight of HFC-152a and 34% by weight of HCFC-124) . Suniso®3GS mineral oil, with and without additives, was compared with Zerol® 150. The constant-temperature bath was maintained at 0 ° C, the results are shown in Table 6.

TABLE 6 The results show that the oil return is significantly improved against the Zerol®150 with the addition of Zonyl®PHS alone or with ZonylOOHS / kerosene mixtures for mineral oil.

Example 7 The apparatus and method of Example 5 was used for the refrigerant test R401A (53% by weight of HCFC-22, 13% by weight of HFC-152a and 34% by weight of HCFC-124). The Suniso®3GS, with and are additives, was compared with the Zerol®150. The results are shown in Table 7.

TABLE 7 The results show that the mineral oil oil return is significantly improved with the addition of Zonyl®PHS, optionally with Isopar®H, or with mixtures of 100% AML / Isopar®H. In this refrigerant / oil system, the Zonyl®OHS copolymer fluorinated with Isopar®H is preferred over the non-fluorinated LMA homopolymer since the return of the Zonyl®PHS / Isopar®H oil exceeds the Zerol® 150. In this way, a Retrofitting from a CFC / mineral oil refrigerant system for an HCFC refrigerant should be done in the usual practice of changing the oil to alkyl benzene.

Example 8 The apparatus and method of Example 5 was used to evaluate the different carriers of the oil return agent for the Zonyl®PHS oil return agent. The refrigerant was R401A (53% by weight of HCFC-22, 13% by weight of HFC-152a and 34% by weight of HCFC-124). The oil tested was Suniso®3GS mineral oil. The results are shown in Table 8.

TABLE 8 The results show that kerosene, pentene and octane are all carriers of the effective oil return agent for Zonyl®PHS.

Example 9 The apparatus and procedure of Example 5, with exceptions discussed below, was used for refrigerant test R 410a (50% by weight of HFC-22 and 50% by weight of HFC-125). Polyol ester oil (Mobil EAL Arctic-22CC) was used as a baseline to compare performance against Zerol® 150 with the addition of oil return agent. The constant temperature bath was maintained at 0 ° C, the results are shown in Table 9.

TABLE 9 The results show that the oil return performance of R410a using Zerol® 150 containing 0.4% Zonyl®HS + 3% Isopar H is better than just the POE. The performance against Isopar® alone in Zerol®150 was also improved.

Example 10 The apparatus and method of Example 5, with the exceptions discussed below, were used to test the R404A refrigerant (44% by weight of HFC-125, 52% by weight of HFC-143a and 4% by weight of HFC-134a ). the oil was HBA 22 (HAB 22 is a branched alkylbenzene oil sold by Nippon Oil). Various copolymers of fluorinated acrylate ZFM (fluoromet acrylate Zonyl®: CH2 = C (CH3) C02CH2CH2 (CF2CF2) m ?, where m 'is from 1 to 12, primarily from 2 to 8) and lauryl methacrylate (LMA) were compared. These copolymers are shown in Table 10 in the form of, for example, "40/60 ZFM / LMA", which indicates a random copolymer synthesized from 40% by weight of ZFM and 60% by weight of AML. The constant temperature bath was maintained at -20 ° C and refrigerant vapor was passed through the U-tube for 20 minutes. The weight% of F (fluoride) in the polymers was measured by combustion analysis. The results are shown in Table 10.

TABLE 10 The results show that the oil return is. significantly improved with the addition of the Zonyl®PHS / Isopar mixture to hard alkylbenzene oil (HB 22). The concentrations of Zonyl®PHS from 0.4 to 1.0% by weight of the general composition are effective as it is in a 50/50 copolymer of ZFM / LMA. The 100% LMA homopolymer and 100% ZFM also show some improvements in oil return, although 0.4% of Zonyl®PHS (40/60 of ZFM / LMA copolymer) + 3% of Isopar®H is more effective.

Example 11 The apparatus and method of Example 5 was used for refrigerant test R401A. The oil was Suniso®3GS mineral oil compared to a Zerol®150 alkyl benzene baseline. Various copolymers of fluorinated acrylate ZFM (Zonyl® fluoromethacrylate: CH2 = C (CH3) C02CH2CH2 (CF2CF2) m, F, where m 'is from 1 to 12, primarily from 2 to 8), lauryl methacrylate (LMA), or methacrylate of stearyl (SM) were compared. These copolymers are shown in Table 11 in the form of, for example, "40/60 ZFM / LMA", which indicates a random copolymer synthesized from 40% by weight of ZFM and 60% by weight of AML. The weight% of F (fluoride) in the polymers was measured by combustion analysis. The results are shown in Table 11.

TABLE 11 The results show that the addition of 20/80, 40/60 and 50/50% by weight of Zonyl®PHS / Isopar®H to mineral oil provides better oil return than alkylbenzene. The 67/33 weight ratio of ZFM / SM with Isopar®H also improves the return of mineral oil.

Example 12 The apparatus and method of Example 5 was used for refrigerant test R401A. The oil was Suniso®3GS mineral oil compared to a Zerol®150 alkyl benzene baseline. Various copolymers of fluorinated acrylate ZFM and LMA polymerized at different molecular weights were compared. These copolymers are shown in Table 11 in the form of, for example, "40/60 of ZFM / LMA", which indicates a random copolymer synthesized from 40% by weight of ZFM and 60% by weight of AML with the different molecular weights also shown. The weight% of F (fluoride) in the polymers was measured by combustion analysis. The results are shown in Table 12.

TABLE 12 The results show that 40/60 Zonyl®PHS polymerizes with an average number of molecular weights ranging from 6,660 to 40,000 having a significantly improved oil return against 3GS, Zerol®150, and Isopar®H only in 3GS.

Example 13 The apparatus and method of Example 5 was used for the refrigerant test R401A, with various oil return additives, Zonyl®PHS, Surfynol®SE, and fluorinated polystyrene CF3 (CF2) 7 (CH2CHC6H5) nCl, where Mn is 2.688 and the average of n is about 21. The synthesis of this polymer is described in U.S. Patent No. 5,773,538. The oil was Suniso®3GS mineral oil compared to the base line of the alkyl benzene oil Zerol®150.

The results are shown in Table 13.

TABLE 13 The results show that the oil return is better than with Zerol®150 with the addition of Zonyl®PHS / Isopar mixtures for 3GS. Surfynol®SE and fluorinated polystyrene CF3 (CF2) 7 (CH2CHC6H5) nCl are not effective oil return additives, performing worse than Isopar®H alone.

Example 1 .

The bottom of a vacuum flask was filled with either HAB, Zerol®150 or 3GS lubricant to add 0.4% Zonyl®PHS and Isopar®H. The vacuum was removed and foaming was observed. Different antifoam agents were slowly added until foam was significantly reduced. The anti-foam agent Dow 200 is polydimethylsiloxane, 350 centistokes. Dow FS-1265 is trimethyl terminated with trifluoropropyl methylsiloxane. Gelest FMV-4031 is vinyl terminated with tri fluoropropyl methylsiloxane. Gelest DMS-V52 is vinyl terminated with polydimethyl siloxane. The results are shown in Table 14.

TABLE 14 The results show that, all tested antifoam agents are effective in the 3GS mineral oil lubricant. The Dow FS-1265, FMV-4031 and DMS-V52 are effective with alkylbenzene lubricants.

Example 15 The apparatus and procedure of Example 5, with exceptions discussed below, was used for refrigerant test R402A (38% by weight of HCFC-22, 60% by weight of HFC-125 and 2% by weight of propane) with Zonyl ®PHS and different antifoam agents. Dow FS-1265 is trimethyl terminated with trifluoropropyl ethylsiloxane. Gelest FMV-4031 is vinyl terminated with trifluoropropyl methylsiloxane. The constant temperature bath was maintained at 0 ° C. The results are shown in Table 15.

TABLE 15 The results also show that the antifoam agent does not have a significant effect on the return performance of Zonyl®PHS oil.

Example 16 The Zonyl®PHS was tested for thermal stability. Samples of stainless steel, aluminum, and copper were placed in sealed glass tubes containing R401A refrigerant, 3GS oil, and 0.4% by weight of Zonyl®PHS, optionally with 3% by weight of Isopar®H. The tubes were maintained for 14 days at 175 ° C. The results are shown in Table 16.

TABLE 16 The results show that the Zonyl®PHS is thermally stable, has a minimal effect on the metals tested and does not cause acid formation.

Example 17 The viscosity of the lubricating oil samples 3GS and HAB22 were measured by the method ASTM D446 to determine the effect of the addition of oil return agent. The results are shown in Table 17.

TABLE 17 The results show a 'desirable tendency in the viscosity system. The viscosity of the oil / Zonyl®PHS is slightly higher at high temperature than the pure oil that protects the compressor. The viscosity of the oil / Zonyl®PHS is lower at low temperature than the aid oil flowing through the evaporator.

Example 18 Tests were conducted to determine whether R404A (44% by weight of HFC-125, 52% by weight of HFC-143a, and 4% by weight of HFC-134a) can be used in the case of a frozen food display of Hussmann supermarket (Model HICA-0146-PLK), using conventional Suniso 3GS lubricating oil. The exhibitor case was disassembled with a Copeland semi-hermetic reciprocating compressor (model KAL-016L) equipped with a light glass in the oil pan. The case of frozen food was installed in the interior room of an environmental chamber and the condensing unit was installed in the exterior room. The two units were connected by a copper pipe with an outside diameter of 5/8 inches (1.5875 cm) in the suction line and by a copper pipe of 1/2 inch (1.27 cm) in outside diameter in the line of liquid. A cylinder of 300 ce was installed between the two valves in the liquid line. To determine the oil circulation, the valves were closed to trap an oil / coolant sample during the operation of the system. The cylinder sample was removed and weighed, the refrigerant was slowly evaporated, and then the cylinder was reweighed to determine the amount of refrigerant. The weight of the excess oil was used to calculate the% of oil in the coolant or the% of oil in circulation. The R502 refrigerant (48.8% by weight (48.8% by weight of HCFC-22, 51.2% by weight of CFC-115 (chloropentaf luoroethane)) with 3GS oil was used as a baseline to make a comparison. show in Table 18.

TABLE 18 * The oil level in the light glass was dripped under observation.

No foam was observed during the test using anti-foam agents, and the results show in addition to the Zonyl®PHS / Isopar®H / Ant iespuma that provides a comparable oil return with the R502 / 3GS and R404A / POE refrigerant / oil combinations and also comparable in capacity and efficiency. The capacity and efficiency of Zonyl®PHS / I sopar®H / Ant iespuma are also improved against IsopardH alone. In the R404A / 3GS test, the oil level in the compressor pool was dripped under observation into the light glass indicating if the oil could be trapped anywhere else in the system.

Example 19 A Sears Coldspot refrigerator manufactured by Whirlpool with an Embraco reciprocating compressor was used to evaluate the oil circulation. The refrigerator originally operates with CFC-12 (dichlorodifluoromethane) and mineral oil. The refrigerator was refilled with mixtures of R401A and Zerol®150 alkylbenzene oil or Suniso 3GS mineral acid with Zonyl®PHS / Isopar®H. the freezer compartment was maintained at -18 ° C and the refrigerant compartment at 3 ° C. The samples were taken from the circulating oil and the results are shown in Table 19.

TABLE 19 Permanent Regimen% by weight of Wats Oil in Consumed Circulation CFC-12 / 3GS 1.60 164.4 R401A / Zerol®150 1.85 166.4 R401A / 3GS 1.44 164.5 R401A / (3GS + 0.4% 1.85 164.1 of Zonyl®PHS + 3% of Isopar®H) The temperature profiles in all the tests were consistent. The R401A data shows the addition of Zonyl®PHS / Isopar® H for mineral oil provides oil circulation comparable to a conversion to Zerol®150. Oil circulation is also significantly improved against CFC-12 / mineral oil and R4 OlA / mineral without adding mineral oil return agent. The energy efficiency was not calculated directly, but the wats consumed in the permanent regime gave an indication that the power consumed was similar in all tests. The results indicate that a conversion of CFC-12 to R401A can be carried out without an oil change.

It is noted that in relation to this date, the best method known to the applicant to carry out the aforementioned invention, is that which is clear from the present description of the invention.

Having described the invention as above, the content of the following is claimed as property.

Claims (16)

Claims

1. A refrigerant composition, characterized in that it comprises: (a) a halogenated hydrocarbon containing at least one carbon atom and a fluorine atom (b) at least one oil selected from the group consisting of paraffins, naphthenes, aromatics and polyalphaolefins; and (c) a polymeric oil return agent, comprising a polymer containing at least one monomer represented by the formulas CH2 = C (R1) C02R2 and CH2 = C (R3) C6H4R; wherein R1 and R3 are independently selected from the group consisting of hydrogen radicals and C1 to C4 alkyl; wherein R2 is a fluorinated hydrocarbon radical which may also contain oxygen or other halogen atoms; wherein R 4 is a hydrocarbon radical which may also contain oxygen and halogen atoms; and wherein the oil return agent comprises less than 10 weight percent of the refrigerant composition.

2. The composition of the rei indication 1, characterized in that it comprises from 40 to 99 percent by weight of halogenated hydrocarbon, from 1 to 60 percent by weight of oil, and from 0.001 to 10 percent by weight of a polymeric oil return agent.

3. The composition of claim 1, characterized in that the halogenated hydrocarbon contains from one to six carbon atoms and at least one fluoride atom, has a boiling point from -90 ° C to 80 ° C, and optionally contains chlorine and hydrogen atoms. oxygen.

4. The composition of claim 1, characterized in that it further comprises a carrier of the hydrocarbon oil return agent having at least 6 carbon atoms.

5. The composition of claim 1, characterized in that it also comprises an anti-foam agent.

6. The composition of claim 1, characterized in that the halogenated hydrocarbon is selected from the group consisting of: CC12F2 (CFC-12), CHC12F (HCFC-21), CHCl F2 (HCFC-22), CHF3 (HFC-23), CH2C1F (HCFC-31), CH2F2 (HFC-32), CH3F (HFC-41), CHC12CF3 (HCFC-123), CHCl FCC1 F2 (HC FC-123a), CHCIFCF3 (HCFC-124), CHF2CC1F2 (HCFC-124a), CHF2CF3 (HFC-125), CH2C1CF3 (HCFC-133a), CHF2CH2 (HFC-134), CH2FCF3 (HFC-134a), CC1 F2CH3 (HCFC-142b), CHF2CH2F (HFC-143), CF3CH3 (HFC- 143a), CHCl FCH3 (HCFC-151a), CHF2CH3 (HFC-152a), CHF2CC12CF3 (HC FC-225aa), CHCIFCCIFCF3 (HCFC-225ba), CHF2CC1FCC1F2 (HCFC-225bb) , CHC12CF2CF3 (HCFC-225ca), CHC1FCF2CC1F2 (HCFC-225cb), CHF2CF2CC12F (HCFC-225cc), CC1F2CHC1CF3 (HCFC-225da), CC1F2CHFCC1F2 (HCFC-225ea), CF3CH'FCC12F (HCFC-225eb), CHF2CC1FCF3 (HCFC-226ba), CHC1FCF2CF3 (HCFC-226ca), CHF2CF2CC1F2 (HCFC-226cb), CF3CHC1CF3 (HCFC-226da), CC 1F2CHFCF3 (HCFC-226ea), CHF2CF2CF3 (HFC-227ca), CF3CFHCF3 (HFC-227ea), CHF2CC1FCHF2 (HCFC-235ba), CH2FCC1FCF3 (HCFC-235bb), CHC1FCF2CHF2 (HCFC-235ca), CH2C1CF2CF3 (HCFC-235cb), CH2FCF2CC1F2 (HCFC-235cc), CHF2CHC1CF3 (HCFC-235da), CHCIFCHFCF3 (HCFC-235ea), CHF2CHFCC1F2 (HCFC-235eb), CC1F2CH2CF3 (HCFC-235fa), CHF2CF2CHF2 (HFC-236ca), CH2FCF2CF3 (HFC-236cb), CHF2CHFCF3 (HFC-236ea), CF3CH2CF3 (HFC-236fa), CH2FCF2CHF2 (HFC-245ca), CH3CF2CF3 (HFC-245cb), CHF2CHFCHF2 (HFC-245ea), CH2FCHCF3 ( HFC-245eb), CHF2CH2CF3 (HFC-245fa), CH2FCF2CH2F (HFC-254ca), CH2CF2CHF2 (HFC-254cb), CH2FCHCHF2 (HFC-254ea), CH3CHFCF3 (HFC-254eb), CHF2CH2CHF2 (HFC-254fa), CH2FCH2CF3 (HFC -254fb), CH3CF2CH3 (HFC-272ca), CH3CHFCH2F (HFC-272ea), CH2FCH2CH2F (HFC-272fa), CH3CH2CF2H (HFC-272fb), CH3CHFCH3 (HFC-281ea), CH3CH2CH2F (HFC-281fa), CF3CF2CF2CF2H (HFC- 329p), CF3CF2CFCHCF3 (HFC-329me), CF3CF2CF2CFH2 (HFC-338-q), CF3CF2CH2CF3 (HFC-338mf), CF3CF2CFHCF2H (HFC-338pe), CF3CFHCF2CF2H (HFC-338pce), CHF2CF2CF2CF2H (HFC-338pcc), CF3CFHCFHCF3 (HFC-338mee), CF3CF2CF2CF2CF2H (HFC-42-llp), CF3CF2CFHCF3 (HFC-42 -llmce ), CF3CF2CF2CFHCF3 (HFC-42-llme), CF3CF2CH2CF2CF3 (HFC-43-1 Omcf), CF3CF2CF2CH2CF3 (HFC-43-10mf), CF3CF2CF2CF2CFH2 (HFC-43-10q), CF3CF2CF2CFHCF2H (HFC-43-10pe), CF3CF2CFHCF2CF2H (HFC-43-10pce), CF3CHFCHFCF2CF3 (HFC-43-10mee), CF2HCF2CF2CF2CF2H (HFC-43-10pccc), CF3CFHCF2CF2CF2H (HFC -43-1 Opcce), CF3CFHCF2CFHCF3 (HFC-43-10mece), CF3CF2CF2CF2CF2CF2H (HFC-52-13p), C4F9OCH3, and C F9OC2H5.

7. The composition of claim 1, characterized in that the halogenated hydrocarbon is selected from the group consisting of: CHC1F2 (HCFC-22), CHF3 (HFC-23), CH2F2 (HFC-32), CHCl FCF3 (HC FC-124), CHF2CF3 (HFC-125), CHF2CHF2 (HFC-134), CH2FCF3 (HFC-134a), CF3CH3 (HFC-143a), CHF2CH3 (HFC-152a), CHF2CF2CF3 (HFC-227ca), CF3CFHCF3 (HFC-227ea), CF3CH2CF3 (HFC-236fa), CHF2CH2CF3 (HFC-245fa), CHF2CF2CF2H (H_FC-338pcc) and CF3CHFCHFCF2CF3 (HFC-43-1 Ornee).

8. The composition of claim 1, characterized in that the halogenated hydrocarbon is selected from the group consisting of azeotropic and azeotrope compositions such as: HCFC-22, HFC-152a, and HCFC-124; HFC-125, HFC-143a, and HFC-134a; HFC-32, HFC-125, HFC-134a; HCFC-22, HFC-143a and HFC-125; HCFC-22, HCFC-124, HCFC-142b; HFC-32 and HFC-125; and HFC-125 and HFC-143a.

9. The composition of claim 1, characterized in that it further comprises from 0 to 10 weight percent of at least one C3 to C5 hydrocarbon.

10. The composition of claim 1, characterized in that the polymeric oil return agent contains at least about 10 weight percent of fluorine.

11. The composition of claim 1, characterized in that the polymeric oil return agent has an average molecular weight number of at least about 3,000.

12. The composition of claim 1, characterized in that the polymeric oil return agent has an average molecular weight number of at least about 6,000.

13. The composition of claim 1, characterized in that the polymeric oil return agent has an average number of molecular weight of at least about 10,000.

14. The composition of claim 1, characterized in that the polymeric oil return agent is a polymer comprising at least one monomer represented by the formula CH2 = C (R1) C02R2, wherein R1 is selected from hydrogen, Ci and C2 alkyl radicals and R2 is selected from radicals Ci to C20 and radicals -CH2CH2-CXF (2X + D, where x is from 2 to 24.

15. A process for producing refrigeration, characterized in that it comprises evaporating a composition of claim 1 in the vicinity of a body to be cooled.

16. A process for producing heat, characterized in that it comprises condensing a composition of claim 1 in the vicinity of a body to be heated.