RU2418027C2 - Coolant or heat carrier composition, method of using said composition, method of cooling or heating, installations containing said composition, method of detecting said composition in installation, foaming agent containing said composition, method of obtaining foam, sprayed composition, method of obtaining aerosol products, method of suppressing flame or extinction, as well as method of treating area with inert gas in order to prevent burning - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: invention relates to a coolant or heat carrier composition which contains an azeotropic or nearly azeotropic component, which contains 1-99 wt % HFC-1234yf and approximately 99-1 wt % HEC-134a and, optionally, at least one compound selected from a group consisting of propane, n-butane, isobutene and dimethyl ether. The coolant or heat carrier composition optionally contains at least one more component selected from lubricant substances, isotopic indicators, compatibility agents, dyes which are fluorescent in UV light, soluble agents, stabilisers, water absorbers and deodorant agents. The composition is used in refrigerator installations, air conditioners and heat pumps, for cooling or heating, as liquid heat carriers, foaming agents, aerosol propellants and agents for suppressing or extinguishing fire.

EFFECT: composition with low global warming potential and low ozone layer depletion potential.

29 cl, 14 ex, 6 ex

Description

CROSS RELATIONS TO RELATED APPLICATIONS

This application claims priority to provisional patent application US 60/658543, filed March 4, 2005, and provisional patent application US 60/710439, filed August 23, 2005, and provisional patent application US 60/732769, filed 1 November 2005

BACKGROUND OF THE INVENTION

1. The technical field

This invention relates to compositions used in refrigeration systems, air conditioners and heat pump systems, where the composition includes a fluoroolefin and at least one other component. Compositions in accordance with this invention are used in the processes of producing cold or heat as liquid heat transfer agents, blowing agents, aerosol propellants and fire fighting agents and fire extinguishers.

2. The level of technology

Over the past few decades, the refrigeration industry has been working on the search for coolers that can replace the ozone layer that reduces chlorofluorocarbons (CFCs) and hydrochlorofluorocarbons (HFCS), which are being phased out in accordance with the Montreal Protocol. The solution for most refrigeration manufacturers is the commercialization of hydrofluorocarbon (HFC) coolers. The new HFC coolers, HFC-134a, the most widely used at present, have zero potential to reduce the ozone layer and, therefore, do not fall under the current instructive cessation of production in accordance with the Montreal Protocol.

Newer environmental regulations may ultimately lead to a global reduction in the production of certain HFC coolers. The automotive industry is currently facing regulations regarding the potential impact of chillers used in automotive air conditioning on global warming. Therefore, in the automotive air-conditioning market, there is a significant ongoing need for new coolers with a reduced impact on global warming. If future regulations are applied even more widely, there will be an increased need for coolers that can be used in all areas of the refrigeration and air conditioning industries.

The currently proposed coolers for HFC-134a include HFC-152a, pure hydrocarbons such as butane or propane, or “natural” coolers such as CO ₂ . Many of these proposed substitutes are toxic, flammable and / or have low energy efficiency. Therefore, a search is underway for new alternative coolers.

The object of this invention are new cooling compositions and compositions of liquid coolants, which have unique characteristics that meet the requirements of low or zero potential to reduce the ozone layer and low potential for global warming compared to modern chillers.

SUMMARY OF THE INVENTION

This invention relates to compositions containing HFC-1225ye and at least one compound selected from the group including:

HFC-1234ze, HFC-1234yf, HFC-1234ye, HFC-1243zf, HFC-32, HFC-125, HFC-134, HFC-134a, HFC-143a, HFC-152a, HFC-161, HFC-227ea, HFC- 236ea, HFC-236fa, HFC-245fa, HFC-365mfc, propane, n-butane, isobutane, 2-methylbutane, n-pentane, cyclopentane, dimethyl ether, CF ₃ SCF ₃ , CO ₂ and CF ₃ I.

This invention also relates to a composition comprising HFC-1234ze and at least one compound selected from the group consisting of: HFC-1234yf, HFC-1234ye, HFC-1243zf, HFC-32, HFC-125, HFC-134, HFC-134a, HFC-143a, HFC-152a, HFC-161, HFC-227ea, HFC-236ea, HFC-236fa, HFC-245fa, HFC-365mfc, propane, n-butane, isobutane, 2-methylbutane, n- pentane, cyclopentane, dimethyl ether, CF ₃ SCF ₃ , CO ₂ and CF ₃ I.

This invention also relates to a composition comprising HFC-1234yf and at least one compound selected from the group consisting of: HFC-1234ye, HFC-1243zf, HFC-32, HFC-125, HFC-134, HFC-134a, HFC-143a, HFC-152a, HFC-161, HFC-227ea, HFC-236ea, HFC-236fa, HFC-245fa, HFC-365mfc, propane, n-butane, isobutane, 2-methylbutane, n-pentane, cyclopentane, dimethyl ether, CF ₃ SCF ₃ , CO ₂ and CF ₃ I.

This invention also relates to compositions containing HFC-1234ye and at least one compound selected from the group consisting of: HFC-1243zf, HFC-32, HFC-125, HFC-134, HFC-134a, HFC-143a, HFC-152a, HFC-161, HFC-227ea, HFC-236ea, HFC-236fa, HFC-245fa, HFC-365mfc, propane, n-butane, isobutane, 2-methylbutane, n-pentane, cyclopentane, dimethyl ether, CF ₃ SCF ₃ , CO ₂ and CF ₃ I.

This invention also relates to compositions containing HFC-1243zf and at least one compound selected from the group consisting of: HFC-32, HFC-125, HFC-134, HFC-134a, HFC-143a, HFC-152a, HFC-161, HFC-227еа, HFC-236еа, HFC-236fa, HFC-245fa, HFC-365mfc, propane, n-butane, isobutane, 2-methylbutane, n-pentane, cyclopentane, dimethyl ether, CF ₃ SCF ₃ , CO ₂ and CF ₃ I.

The present invention also relates to a composition comprising:

(a) at least one lubricant selected from the group consisting of polyhydric alcohol esters, polyalkylene glycol, polyvinyl ethers, mineral oils, alkylbenzenes, synthetic paraffins, synthetic naphthenes and poly (alpha) olefins; and

(b) a composition selected from the group including:

from about 1% of the mass. up to about 99% of the mass. HFC-1225ue and from about 99% of the mass. up to about 1% of the mass. HFC-152a;

from about 1% of the mass. up to about 99% of the mass. HFC-1225ue and from about 99% of the mass. up to about 1% of the mass. HFC-1234yf;

from about 1% of the mass. up to about 99% of the mass. HFC-1225ue and from about 99% of the mass. up to about 1% of the mass. trans-HFC-1234ze;

from about 1% of the mass. up to about 99% of the mass. HFC-1225ue and from about 99% of the mass. up to about 1% of the mass. HFC-1243zf;

from about 1% of the mass. up to about 99% of the mass. trans-HFC-1234ze and from about 99% of the mass. up to about 1% of the mass. HFC-134a;

from about 1% of the mass. up to about 99% of the mass. trans-HFC-1234ze and from about 99% of the mass. up to about 1% of the mass. HFC-152a;

from about 1% of the mass. up to about 99% of the mass. trans-HFC-1234ze and from about 99% of the mass. up to about 1% of the mass. HFC-227ea and

from about 1% of the mass. up to about 99% of the mass. trans-HFC-1234ze and from about 99% of the mass. up to about 1% of the mass. CF ₃ I.

The present invention also relates to a composition comprising:

(a) a cooler or liquid coolant selected from the group including:

from about 1% of the mass. up to about 99% of the mass. HFC-1225ye and from about 99% of the mass. up to about 1% of the mass. HFC-152a;

from about 1% of the mass. up to about 99% of the mass. HFC-1225ye and from about 99% of the mass. up to about 1% of the mass. HFC-1234yf;

from about 1% of the mass. up to about 99% of the mass. HFC-1225ye and from about 99% of the mass. up to about 1% of the mass. trans-HFC-1234ze;

from about 1% of the mass. up to about 99% of the mass. HFC-1225ye and from about 99% of the mass. up to about 1% of the mass. HFC-1243zf;

from about 1% of the mass. up to about 99% of the mass. trans-HFC-1234ze and from about 99% of the mass. up to about 1% of the mass. HFC-134a;

from about 1% of the mass. up to about 99% of the mass. trans-HFC-1234ze and from about 99% of the mass. up to about 1% of the mass. HFC-152a;

from about 1% of the mass. up to about 99% of the mass. trans-HFC-1234ze and from about 99% of the mass. up to about 1% of the mass. HFC-227ea and

from about 1% of the mass. up to about 99% of the mass. trans-HFC-1234ze and from about 99% of the mass. up to about 1% of the mass. CF ₃ I;

and

(b) a compatibility agent selected from the group including:

i) polyoxyalkylene glycol ethers represented by the formula R ¹ [(OR ² ) _x OR ³ ] _y , where: x is an integer from 1 to 3; y is an integer from 1 to 4; R ^{1 is} selected from hydrogen and aliphatic hydrocarbon radicals having from 1 to 6 carbon atoms and y binding sites; R ² selected from aliphatic hydrocarbylene radicals having from 2 to 4 carbon atoms; R ³ selected from hydrogen and aliphatic and alicyclic hydrocarbon radicals having from 1 to 6 carbon atoms; where at least one of R ¹ and R ^{3 is} selected from said hydrocarbon radicals and where said polyoxyalkylene glycol ethers have a molecular weight of from about 100 to about 300 atomic mass units;

ii) amides represented by the formulas R ¹ C (O) NR ² R ³ and cyclo- [R ⁴ CON (R ⁵ ) -], where R ¹ , R ² , R ³ and R ^{5 are} independently selected from aliphatic and alicyclic hydrocarbon radicals having from 1 to 12 carbon atoms and not more than one aromatic radical having from 6 to 12 carbon atoms; R ^{4 is} selected from aliphatic hydrocarbylene radicals having from 3 to 12 carbon atoms; and where these amides have a molecular weight of from about 100 to about 300 atomic units of mass;

iii) ketones represented by the formula R ¹ C (O) R ² , where R ¹ and R ^{2 are} independently selected from aliphatic, alicyclic and aryl hydrocarbon radicals having from 1 to 12 carbon atoms, and where said ketones have a molecular weight of from about 70 up to about 300 atomic units of mass;

iv) nitriles represented by the formula R ¹ CN, where R ^{1 is} selected from aliphatic, alicyclic or aryl hydrocarbon radicals having from 5 to 12 carbon atoms, and where said nitriles have a molecular weight of from about 90 to about 200 atomic mass units;

v) chlorocarbons represented by the formula RCl _x , where x is 1 or 2; R is selected from aliphatic and alicyclic hydrocarbon radicals having from 1 to 12 carbon atoms; and where these chlorocarbons have a molecular weight of from about 100 to about 200 atomic units of mass;

vi) aryl ethers represented by the formula R ¹ OR ² , where R ^{1 is} selected from aryl hydrocarbon radicals having from 6 to 12 carbon atoms; R ² selected from aliphatic hydrocarbon radicals having from 1 to 4 carbon atoms; and wherein said aryl ethers have a molecular weight of from about 100 to about 150 atomic units of mass;

vii) 1,1,1-trifluoroalkanes represented by the formula CF ₃ R ¹ , wherein R ^{1 is} selected from aliphatic and alicyclic hydrocarbon radicals having from about 5 to about 15 carbon atoms;

viii) fluoroethers represented by the formula R ¹ OCF ₂ CF ₂ H, where R ^{1 is} selected from aliphatic, alicyclic and aromatic hydrocarbon radicals having from about 5 to about 15 carbon atoms; or where said fluoroethers are derived from fluoroolefins and polyhydric alcohols, where said fluoroolefins are of type CF ₂ = CXY, where X is hydrogen, chloro or fluoro and Y is chloro, fluoro, CF ₃ or OR _f , where R _f is CF ₃ , C ₂ F ₅ or C ₃ F ₇ and said polyhydric alcohols are linear or branched, where said linear polyhydric alcohols are of type HOCH ₂ (CHOH) _x (CRR ') _y CH ₂ OH, where R and R' are hydrogen, CH ₃ or C ₂ H ₅ , x is an integer from 0 to 4, y is an integer from 0 to 3 and z is either zero or 1, and where these branched polyatomic alcohols are of type C (OH) _t (R) _u (CH ₂ OH) _v [(CH ₂ ) _m CH ₂ OH] _w , where R may be hydrogen, CH ₃ or C ₂ H ₅ , m is an integer from 0 up to 3, t and u are 0 or 1, v and w are integers from 0 to 4, and also where t + u + v + w = 4; and

ix) lactones represented by structures [B], [C] and [D]

where R ₁ -R ₈ independently selected from hydrogen, linear, branched, cyclic, bicyclic, saturated and unsaturated hydrocarbyl radicals; and the molecular weight is from about 100 to about 300 atomic units of mass; and

x) esters represented by the general formula R ¹ CO ₂ R ² where R ¹ and R ^{2 are} independently selected from linear and cyclic, saturated and unsaturated, alkyl and aryl radicals and where said esters have a molecular weight of from about 80 to about 550 atomic mass units.

The present invention also relates to a composition comprising:

(a) at least one ultraviolet fluorescent dye selected from the group consisting of naphthalimides, perylene, coumarins, anthracenes, phenanthracenes, xanthenes, thioxanthenes, naphthoxantenes, fluoresceins, derivatives of these dyes, and combinations thereof; and

(b) a composition selected from the group including:

from about 1% of the mass. up to about 99% of the mass. HFC-1225ye and from about 99% of the mass. up to about 1% of the mass. HFC-152a;

from about 1% of the mass. up to about 99% of the mass. HFC-1225ye and from about 99% of the mass. up to about 1% of the mass. HFC-1234yf;

from about 1% of the mass. up to about 99% of the mass. HFC-1225ye and from about 99% of the mass. up to about 1% of the mass. trans-HFC-1234ze;

from about 1% of the mass. up to about 99% of the mass. HFC-1225ye and from about 99% of the mass. up to about 1% of the mass. HFC-1243zf;

from about 1% of the mass. up to about 99% of the mass. trans-HFC-1234ze and from about 99% of the mass. up to about 1% of the mass. HFC-134a;

from about 1% of the mass. up to about 99% of the mass. trans-HFC-1234ze and from about 99% of the mass. up to about 1% of the mass. HFC-152a;

from about 1% of the mass. up to about 99% of the mass. trans-HFC-1234ze and from about 99% of the mass. up to about 1% of the mass. HFC-227ea; and

from about 1% of the mass. up to about 99% of the mass. trans-HFC-1234ze and from about 99% of the mass. up to about 1% of the mass. CF ₃ I.

The present invention also relates to a method for dissolving a cooler or liquid coolant composition in a lubricant for a refrigeration system selected from the group consisting of mineral oils, alkylbenzenes, synthetic paraffins, synthetic naphthenes and poly (alpha) olefins, wherein said method comprises reacting said lubricating agent with the specified composition of the coolant or liquid coolant in the presence of an effective amount of a compatibility agent, where the specified coolant or liquid coolant with erzhit composition selected from the group consisting of:

from about 1% of the mass. up to about 99% of the mass. HFC-1225ye and from about 99% of the mass. up to about 1% of the mass. HFC-152a;

from about 1% of the mass. up to about 99% of the mass. HFC-1225ye and from about 99% of the mass. up to about 1% of the mass. HFC-1234yf;

from about 1% of the mass. up to about 99% of the mass. HFC-1225ye and from about 99% of the mass. up to about 1% of the mass. trans-HFC-1234ze;

from about 1% of the mass. up to about 99% of the mass. HFC-1225ye and from about 99% of the mass. up to about 1% of the mass. HFC-1243zf;

from about 1% of the mass. up to about 99% of the mass. trans-HFC-1234ze and from about 99% of the mass. up to about 1% of the mass. HFC-134a;

from about 1% of the mass. up to about 99% of the mass. trans-HFC-1234ze and from about 99% of the mass. up to about 1% of the mass. HFC-152a;

from about 1% of the mass. up to about 99% of the mass. trans-HFC-1234ze and from about 99% of the mass. up to about 1% of the mass. HFC-227ea and

from about 1% of the mass. up to about 99% of the mass. trans-HFC-1234ze and from about 99% of the mass. up to about 1% of the mass. CF ₃ I;

and

where the specified compatibility agent is selected from the group including:

a) polyoxyalkylene glycol ethers represented by the formula R ¹ [(OR ² ) _x OR ³ ] _y , where: x is an integer from 1 to 3; y is an integer from 1 to 4; R ^{1 is} selected from hydrogen and aliphatic hydrocarbon radicals having from 1 to 6 carbon atoms and y binding sites; R ² selected from aliphatic hydrocarbylene radicals having from 2 to 4 carbon atoms; R ³ selected from hydrogen and aliphatic and alicyclic hydrocarbon radicals having from 1 to 6 carbon atoms; where at least one of R ¹ and R ^{3 is} selected from said hydrocarbon radicals and where said polyoxyalkylene glycol ethers have a molecular weight of from about 100 to about 300 atomic mass units;

b) amides represented by the formulas R ¹ C (O) NR ² R ³ and cyclo- [R ⁴ CON (R ⁵ ) -], where R ¹ , R ² , R ³ and R ^{5 are} independently selected from aliphatic and alicyclic hydrocarbon radicals having from 1 to 12 carbon atoms and not more than one aromatic radical having from 6 to 12 carbon atoms; R ^{4 is} selected from aliphatic hydrocarbylene radicals having from 3 to 12 carbon atoms; and where these amides have a molecular weight of from about 100 to about 300 atomic units of mass;

c) ketones represented by the formula R ¹ C (O) R ² , where R ¹ and R ^{2 are} independently selected from aliphatic, alicyclic and aryl hydrocarbon radicals having from 1 to 12 carbon atoms, and where said ketones have a molecular weight of from about 70 up to about 300 atomic units of mass;

d) nitriles represented by the formula R ¹ CN, where R ^{1 is} selected from aliphatic, alicyclic or aryl hydrocarbon radicals having from 5 to 12 carbon atoms, and where said nitriles have a molecular weight of from about 90 to about 200 atomic mass units;

e) chlorocarbons represented by the formula RCl _x , where x is 1 or 2; R is selected from aliphatic and alicyclic hydrocarbon radicals having from 1 to 12 carbon atoms; and where these chlorocarbons have a molecular weight of from about 100 to about 200 atomic units of mass;

f) aryl ethers represented by the formula R ¹ OR ² , where R ^{1 is} selected from aryl hydrocarbon radicals having from 6 to 12 carbon atoms; R ² selected from aliphatic hydrocarbon radicals having from 1 to 4 carbon atoms; and wherein said aryl ethers have a molecular weight of from about 100 to about 150 atomic units of mass;

g) 1,1,1-trifluoroalkanes represented by the formula CF ₃ R ¹ , wherein R ^{1 is} selected from aliphatic and alicyclic hydrocarbon radicals having from about 5 to about 15 carbon atoms;

h) fluoroethers represented by the formula R ¹ OCF ₂ CF ₂ H, wherein R ^{1 is} selected from aliphatic and alicyclic hydrocarbon radicals having from about 5 to about 15 carbon atoms; or where said fluoroethers are derived from fluoroolefins and polyhydric alcohols, where said fluoroolefins are of type CF ₂ = CXY, where X is hydrogen, chloro or fluoro and Y is chloro, fluoro, CF ₃ or OR _f , where R _f is CF ₃ , C ₂ F ₅ or C ₃ F ₇ ; and said polyols are of type HOCH ₂ CRR '(CH ₂ ) _z (CHOH) _x CH ₂ (CH ₂ OH) _y , where R and R' are hydrogen, CH ₃ or C ₂ H ₅ , x is an integer of 0 to 4, y is an integer from 0 to 3 and z is either zero or 1; and

i) lactones represented by structures [B], [C] and [D]:

where R ₁ -R ₈ independently selected from hydrogen, linear, branched, cyclic, bicyclic, saturated and unsaturated hydrocarbyl radicals; and the molecular weight is from about 100 to about 300 atomic units of mass; and

j) esters represented by the general formula R ¹ CO ₂ R ² where R ¹ and R ^{2 are} independently selected from linear and cyclic, saturated and unsaturated, alkyl and aryl radicals and where said esters have a molecular weight of from about 80 to about 550 atomic mass units.

This invention also relates to a method for replacing high GWP chillers in refrigeration units, air conditioners, or heat pumps, wherein said high GWP chillers are selected from the group consisting of R134a, R22, R123, R11, R245fa, R114, R236fa, R124, R12, R410A , R407C, R417A, R422A, R507A, R502 and R404A, where this method includes the filing of a composition selected from the group including:

from about 1% of the mass. up to about 99% of the mass. HFC-1225ye and from about 99% of the mass. up to about 1% of the mass. HFC-152a;

from about 1% of the mass. up to about 99% of the mass. HFC-1225ye and from about 99% of the mass. up to about 1% of the mass. HFC-1234yf;

from about 1% of the mass. up to about 99% of the mass. HFC-1225ye and from about 99% of the mass. up to about 1% of the mass. trans-HFC-1234ze;

from about 1% of the mass. up to about 99% of the mass. HFC-1225ye and from about 99% of the mass. up to about 1% of the mass. HFC-1243zf;

from about 1% of the mass. up to about 99% of the mass. trans-HFC-1234ze and from about 99% of the mass. up to about 1% of the mass. HFC-134a;

from about 1% of the mass. up to about 99% of the mass. trans-HFC-1234ze and from about 99% of the mass. up to about 1% of the mass. HFC-152a;

from about 1% of the mass. up to about 99% of the mass. trans-HFC-1234ze and from about 99% of the mass. up to about 1% of the mass. HFC-227ea; and

from about 1% of the mass. up to about 99% of the mass. trans-HFC-1234ze and from about 99% of the mass. up to about 1% of the mass. CF ₃ I;

in the specified refrigeration unit, air conditioner or heat pump apparatus in which it is used, used or is expected to use the specified coolers with high GWP.

The present invention also relates to a method for early detection of refrigerant leakage in a refrigeration unit, air conditioner, or heat pump apparatus, wherein said method comprises the use of a non-azeotropic composition in said apparatus and tracking the decrease in cooling capacity.

DETAILED DESCRIPTION OF THE INVENTION

This invention relates to compositions containing at least one fluoroolefin. The compositions of this invention also include at least one additional component, which may be a second fluoroolefin, hydrofluorocarbon (HFC), hydrocarbon, dimethyl ether, bis (trifluoromethyl) sulfide, CF ₃ I or CO ₂ . Fluoroolefin compounds and other components of the compositions in accordance with this invention are listed in table 1.

TABLE 1

The individual components listed in table 1 can be obtained by methods known in the art.

The fluoroolefin compounds used in the compositions of this invention, HFC-1225ye, HFC-1235ze and HFC-1234ye, can exist in the form of isomers or stereoisomers of various configurations. The invention encompasses all individual configurations of isomers, individual stereoisomers, or any combination or mixture thereof. For example, 1,3,3,3-tetrafluoropropene (HFC-1234ze) represents the cis isomer, trans isomer, or any combination or mixture of both isomers in any ratio. Another example is HFC-1225ye, which is a cis isomer, a trans isomer, or any combination or mixture of both isomers in any ratio.

Compositions in accordance with this invention include the following:

HFC-1225ye and at least one compound selected from the group consisting of: HFC-1234ze, HFC-1234yf, HFC-1234ye, HFC-1243zf, HFC-32, HFC-125, HFC-134, HFC-134a, HFC-143a, HFC-152a, HFC-161, HFC-227ea, HFC-236ea, HFC-236fa, HFC-245fa, HFC-365mfc, propane, n-butane, isobutane, 2-methylbutane, n-pentane, cyclopentane, dimethyl ether, CF ₃ SCF ₃ , CO ₂ and CF ₃ I;

HFC-1234ze and at least one compound selected from the group consisting of: HFC-1225ye, HFC-1234yf, HFC-1234ye, HFC-1243zf, HFC-32, HFC-125, HFC-134, HFC-134a, HFC-143a, HFC-152a, HFC-161, HFC-227ea, HFC-236ea, HFC-236fa, HFC-245fa, HFC-365mfc, propane, n-butane, isobutane, 2-methylbutane, n-pentane, cyclopentane, dimethyl ether, CF ₃ SCF ₃ , CO ₂ and CF ₃ I;

HFC-1234yf and at least one compound selected from the group consisting of: HFC-1234ye, HFC-1243zf, HFC-32, HFC-125, HFC-134, HFC-134a, HFC-143a, HFC-152a, HFC-161, HFC-227ea, HFC-236ea, HFC-236fa, HFC-245fa, HFC-365mfc, propane, n-butane, isobutane, 2-methylbutane, n-pentane, cyclopentane, dimethyl ether, CF ₃ SCF ₃ , CO ₂ and CF ₃ I; and

HFC-1243zf and at least one compound selected from the group consisting of: HFC-1234ye, HFC-32, HFC-125, HFC-134, HFC-134a, HFC-143a, HFC-152a, HFC-161, HFC-227ea, HFC-236ea, HFC-236fa, HFC-245fa, HFC-365mfc, propane, n-butane, isobutane, 2-methylbutane, n-pentane, cyclopentane, dimethyl ether, CF ₃ SCF ₃ , CO ₂ and CF ₃ I;

HFC-1234ye and at least one compound selected from the group consisting of: HFC-32, HFC-125, HFC-134, HFC-134a, HFC-143a, HFC-152a, HFC-161, HFC-227ea, HFC-236ea, HFC-236fa, HFC-245fa, HFC-365mfc, propane, n-butane, isobutane, 2-methylbutane, n-pentane, cyclopentane, dimethyl ether, CF ₃ SCF ₃ , CO ₂ and CF ₃ I.

Usually used compositions in accordance with this invention, in which the fluoroolefin is present in an amount of from about 1% of the mass. up to about 99% of the mass., preferably from about 20% of the mass. up to about 99% of the mass., more preferably from about 40% of the mass. up to about 99% of the mass. or even more preferably from about 50% of the mass. up to about 99% of the mass.

The invention also provides compounds listed in table 2.

TABLE 2

It is expected that the most preferred compositions in accordance with this invention, listed in table 2, retain the desired properties and functionality, if the components are present in concentrations, such as listed, ± 2% of the mass. It is expected that compositions containing CO ₂ retain the desired properties and functionality, if CO _{2 is} present in concentrations, such as listed, ± 0.2% of the mass.

Compositions in accordance with this invention can be azeotropic or almost azeotropic compositions. By azeotropic composition is meant a mixture of two or more substances with a constant boiling point, which behaves as a single substance. One way to characterize the azeotropic composition is that the vapor obtained by partial evaporation or distillation of a liquid has the same composition as the liquid from which it is evaporated or distilled, i.e. the mixture is distilled / boils without changing the composition. Compositions with a constant boiling point are characterized as azeotropic, since they exhibit either a maximum or minimum boiling point compared to a non-azeotropic mixture of the same compounds. The azeotropic composition does not fractionate in the refrigeration or air conditioning system during its operation, which may reduce the efficiency of the system. In addition, the azeotropic composition does not fractionate during a leak from a refrigeration or air conditioning system. In a situation where one of the components of the mixture is flammable, fractionation during leakage can lead to the formation of a flammable composition either inside the system or outside the system.

An almost azeotropic composition (also called an "azeotropic composition") is an almost constantly boiling liquid mixture of two or more substances, which behaves almost like a single substance. One way to characterize an almost azeotropic composition is that the vapor obtained by partial evaporation or distillation of a liquid has the same composition as the liquid from which it is evaporated or distilled, i.e. the mixture is distilled / boils without changing the composition. Another way to characterize an almost azeotropic composition is that the vapor pressure at the boiling point and the vapor pressure at the condensation temperature of the composition at a certain temperature are almost the same. In this case, the composition is almost azeotropic if, after removal of 50% of the mass. composition by evaporation or boiling the difference in vapor pressure between the original composition and the composition remaining after removal of 50% of the mass. the original composition is less than about 10%.

Azeotropic compositions in accordance with this invention at a certain temperature are shown in table 3.

TABLE 3

In addition, triple azeotrope compositions were listed in Table 4.

TABLE 4

Almost azeotropic compositions in accordance with this invention at a certain temperature are listed in table 5.

TABLE 5

Also identified triple and almost azeotropic compositions of the highest order containing fluoroolefin are presented in table 6.

TABLE 6

Certain compositions in accordance with this invention are non-azeotropic compositions. Compositions in accordance with this invention falling into the preferred interval in accordance with table 2, but not falling into almost azeotropic intervals in accordance with table 5 and table 6, can be considered non-azeotropic.

Non-azeotropic compositions may have certain advantages over azeotropic or almost azeotropic mixtures. A non-azeotropic composition is a mixture of two or more substances that behaves as a mixture, and not as a single substance. One way to characterize a non-azeotropic composition is that the vapor obtained by partial evaporation or distillation of a liquid has a significantly different composition compared to the liquid from which it is evaporated or distilled, i.e. the mixture is distilled / boils with significant changes in composition. Another way to characterize a non-azeotropic composition is that the vapor pressure at the boiling point and the vapor pressure at the condensation temperature of the composition at a certain temperature are significantly different. In this case, the composition is non-azeotropic, if after removal of 50% of the mass. composition by evaporation or boiling the difference in vapor pressure between the original composition and the composition remaining after removal of 50% of the mass. the original composition is more than about 10%.

Compositions in accordance with this invention can be obtained by any convenient method of combining the desired amounts of the individual components. A preferred method is to weigh the desired amounts of components, followed by combining the components in a suitable vessel. Stirring may be used if desired.

An alternative means of preparing compositions in accordance with this invention may be a method for producing a composite cooler composition, wherein said composite cooler composition comprises a composition in accordance with this invention, wherein said method comprises (i) recovering a volume of one or more components of a cooler composition from at least , one container with a cooler, (ii) removal of impurities to such an extent that it is possible to reuse the specified one or more regenerated com ponenta, (iii) and, optionally, combining all or part of the indicated volume of components with at least one additional cooler composition or component.

A cooler container may be any container that stores a composite cooler composition used in a refrigeration unit, air conditioner, or heat pump unit. The specified container for the cooler may be a refrigeration unit, an air conditioner or a heat pump apparatus in which a mixture of cooler is used. Additionally, the cooler container may be a waste storage container for collecting the regenerated components of the cooler mixture, including, but not limited to, pressure cylinders.

A residual cooler is any amount of a cooler mixture or a component of a cooler mixture that can be removed from the cooler container by any method known to move the cooler mixtures or components of the cooler mixtures.

The impurities may be any components present in the cooler mixture or components of the cooler mixture due to use in a refrigeration unit, air conditioner or heat pump. Such impurities include, but are not limited to, refrigerant system lubricants described above, particles including, but not limited to, metals, metal salts, or elastomer particles that may enter the mixture from a refrigeration unit, air conditioner, or heat pump apparatus, and any other contaminants that could adversely affect the effectiveness of the refrigerant compound composition.

Such contaminants can be removed sufficiently to be able to reuse the coolant mixture or component of the coolant mixture without adversely affecting the performance or equipment that uses the coolant mixture or component of the coolant mixture.

It may be necessary to supply an additional coolant mixture or a component of a coolant mixture to a residual coolant mixture or a component of a coolant mixture to obtain a composition that meets the specifications required for a given product. For example, if the cooler mixture comprises 3 components in a specific weight ratio, it may be necessary to add one or more components in a given amount to restore the composition within the specification.

Compositions in accordance with this invention have zero or low potential to reduce the ozone layer and low potential for global warming (GWP). In addition, the compositions of this invention have less global warming potential than many hydrofluorocarbon coolers currently in use. One aspect of the present invention is a chiller with a global warming potential of less than 1000, less than 500, less than 150, less than 100 or less than 50. Another aspect of the present invention is to reduce the net GWP of chiller mixtures by adding fluoroolefins to said mixtures.

The compositions of this invention can be used as low global warming potential (GWP) substitutes for currently used chillers, including but not limited to R134a (or HFC-134a, 1,1,1,2-tetrafluoroethane ), R22 (or HCFC-22, chlorodifluoromethane), R123 (or HFC-123, 2,2-dichloro-1,1,1-trifluoroethane), R11 (or CFC-11, fluorotrichloromethane), R12 (CFC-12, dichlorodifluoromethane), R245fa (or HFC-245fa, 1,1,1,3,3-pentafluoropropane), R114 (or CFC-114, 1,2-dichloro-1,1,2,2-tetrafluoroethane), R236fa (or HFC-236fa, 1,1,1,3,3,3-hexafluoropropane), R124 (or HCFC-124, 2-chloro-1,1,1,2-tetra fluoroethane), R407C (designation ASHRAE for a mixture of 52% by mass of R134a, 25% by mass of R125 (pentafluoroethane) and 23% by mass of R32 (difluoromethane)), R410A (designation ASHRAE for a mixture of 50% by mass R125 and 50% by mass R32), R417A (designation ASHRAE for a mixture of 46.6% by mass of R125, 50.0% by mass of R134a and 3.4% by mass of n-butane), R422A (designation ASHRAE for a mixture of 85.1% by mass of R125, 11.5% by weight of R134a and 3.4% by weight of isobutane), R404A (designation ASHRAE for a mixture of 44% by weight R125, 52% of the mass. R143a (1,1,1-trifluoroethane) and 4.0% of the mass. R134a) and R507A (designation ASHRAE for a mixture of 50% by weight of R125 and 50% by weight of R143a). In addition, the compositions of this invention can be used as substitutes for R12 (CFC-12, dichlorodifluoromethane) or R502 (ASHRAE designation for a mixture of 51.2% by weight of CFC-115 (chloropentafluoroethane) and 48.8% by weight of HCFCs -22).

Often replacement chillers are most applicable if they can be used in original refrigeration equipment designed for various chillers. Compositions in accordance with this invention can be used as substitutes for the above coolers in the original equipment. In addition, the compositions in accordance with this invention can be used as substitutes for the above coolers in equipment designed for the use of the above coolers.

Compositions in accordance with this invention may also contain a lubricating agent.

Lubricants in accordance with this invention include lubricants for the refrigeration system, i.e. those lubricants suitable for use in refrigeration units, air conditioners or heat pumps. Among these lubricants are those commonly used in compression chillers that use chlorofluorocarbon coolers. Such lubricants and their properties are described in 1990 by ASHRAE Handbook, Refrigeration Systems and Applications, chapter 8, entitled “Lubricants in Refrigeration Systems”, pages 8.1-8.21. Lubricating agents in accordance with this invention may include agents commonly known as “mineral oils” in the field of lubrication of compression refrigeration units. Mineral oils include paraffins (i.e. straight and branched chain saturated hydrocarbons), naphthenes (i.e. cyclic paraffins) and aromatics (i.e. unsaturated cyclic hydrocarbons containing one or more rings having alternating double bonds) ) Lubricating agents in accordance with this invention also include agents commonly known as “synthetic oils” in the field of lubrication of compression refrigeration units. Synthetic oils include alkylaryls (i.e., linear and branched alkyl alkylbenzenes), synthetic paraffins and naphthenes, and poly (alpha-olefins). Representative conventional lubricants in accordance with this invention include the commercially available BVM 100 N (paraffin mineral oil from BVA Oils), Suniso® 3GS and Suniso® 5GS (naphthenic mineral oil from Crompton Co.), Sontex® 372LT (naphthenic mineral oil from Pennzoil ), Calumet® RO-30 (naphthenic mineral oil from Calumet Lubricants), Zerol® 75, Zerol® 150 and Zerol® 500 (linear alkylbenzenes from Shrieve Chemicals) and HAB 22 (branched alkylbenzene from Nippon Oil).

Lubricating agents in accordance with this invention will also include agents designed for use in hydrofluorocarbon coolers and mixed with coolers in accordance with this invention in the conditions of operation of compression refrigeration units, air conditioners or heat pumps. Such lubricants and their properties are described in Synthetic Lubricants and High-Performance Fluids, RLShubkin, editor, Marcel Dekker, 1993. Such lubricants include, but are not limited to, polyhydric alcohol esters such as Castrol® 100 (Castrol, United Kingdom), polyalkylene glycols (PAGs) such as Dow RL-488A (Dow Chemical, Midland, Michigan), and polyvinyl ethers (EPV). These lubricants are readily available from various commercial sources.

The lubricants in accordance with this invention are selected in accordance with these compressor requirements and the environmental conditions to which the lubricant will be subjected. Lubricating agents in accordance with this invention preferably have a kinematic viscosity of at least 5 cSt (centistokes) at a temperature of 40 ° C.

Widely used additives for refrigeration systems can optionally be added to the compositions of this invention, if desired, to improve the lubricity and stability of the system. Such additives are commonly known in the field of refrigeration compressor compressor lubrication and include anti-friction additives, anti-seize lubricants, corrosion and oxidation inhibitors, metal surface deactivators, free radical traps, blowing agents and defoamers, leak detectors and the like. In general, such additives are present only in small amounts relative to the total weight of the lubricating agent composition. They are usually used in concentrations from less than about 0.1% to not more than about 3% for each additive. Such additives are selected based on the specific requirements of the system. Some typical examples of such additives may include, but are not limited to, lubricity improvers, such as alkyl or aryl phosphoric acid esters and thiophosphates. In addition, metal dialkyl dithiophosphates (e.g., zinc dialkyl dithiophosphate or DPDC, Lubrizol 1375) and other members of this series of chemical compounds can be used in the compositions of this invention. Other anti-friction additives include natural product oils and asymmetric polyhydroxy lubricating additives such as Synergol TMS (International Lubricants). Stabilizers such as antioxidants, free radical traps, and water scavengers may also be used. Compounds of this category may include, but are not limited to, butyl-substituted hydroxytoluene (BHT) and epoxides.

Compositions in accordance with this invention may also contain from about 0.01% of the mass. up to about 5% of the mass. additives such as, for example, a stabilizer, a free radical trap and / or an antioxidant. Such additives include, but are not limited to, nitromethane, hindered phenols, hydroxylamines, thiols, phosphites or lactones. Individual additives or combinations thereof may be used.

Compositions in accordance with this invention may also contain from about 0.01% of the mass. up to about 5% of the mass. water absorber (drying agent). Such water scavengers may contain orthoesters, such as trimethyl, triethyl or tripropyl orthoformate.

The compositions of this invention may also contain an isotopic indicator selected from the group consisting of hydrofluorocarbons (HFCs), deuterated hydrocarbons, deuterated hydrofluorocarbons, perfluorocarbons, fluoroethers, brominated compounds, iodinated compounds, alcohols, aldehydes, ketones, nitrous oxide (N ₂ O ) and their combinations. Isotopic indicators are added to the composition in predetermined amounts in order to make it possible to determine any dilution, contamination, or other change in composition, as described in US Patent Application No. 11/062044, filed February 18, 2005.

Typical isotopic indicators for use in the compositions of this invention are listed in Table 7.

TABLE 7

The compounds listed in table 7 are available commercially (from companies selling chemicals) or can be obtained by methods known in the art.

Individual isotopic indicators can be used in combination with cooling / heating fluid in the compositions of this invention, or several isotopic indicators can be combined in any proportion to produce a mixture of isotopic indicators. A mixture of isotopic indicators may contain several isotopic indicators from one class of compounds or several isotopic indicators from different classes of compounds. For example, a mixture of isotopic indicators may contain 2 or more deuterated hydrofluorocarbons or one deuterated hydrofluorocarbon in combination with one or more perfluorocarbons.

In addition, some of the compounds of table 7 exist in the form of many isomers, structural or optical. Individual isomers or multiple isomers of the same compound can be used in any proportion to obtain an isotopic indicator. Further, single or multiple isomers of a given compound can be combined in any proportion with any number of other compounds to produce a mixture of isotopic indicators.

An isotopic indicator or a mixture of isotopic indicators may be present in the compositions in a total concentration of from about 50 parts per million (ppm) to about 1000 ppm. Preferably, an isotopic indicator or a mixture of isotopic indicators is present in a total concentration of from about 50 ppm. up to about 500 ppm, and more preferably, an isotopic indicator or a mixture of isotopic indicators is present in a total concentration of from about 100 ppm. up to about 300 ppm

The compositions of this invention may also contain a compatibility agent selected from the group consisting of polyoxyalkylene glycol ethers, amides, nitriles, ketones, chlorocarbons, esters, lactones, aryl ethers, fluoroethers and 1,1,1-trifluoroalkanes. The compatibility agent is used to improve the solubility of hydrofluorocarbon coolers in conventional lubricants for refrigeration systems. Lubricants for refrigeration systems are needed to lubricate the compressor of a refrigeration unit, air conditioner or heat pump. The lubricant must move through the apparatus with a cooler, in particular, it must return from the non-compression zones to the compressor in order to again act as a lubricant and prevent breakdown of the compressor.

Hydrofluorocarbon chillers are generally not compatible with conventional refrigerant lubricants such as mineral oils, alkylbenzenes, synthetic paraffins, synthetic naphthenes and poly (alpha) olefins. Many substitute lubricants have been proposed, however polyalkylene glycols, polyhydric alcohol esters and polyvinyl ethers, proposed for use with hydrofluorocarbon coolers, are expensive and readily absorb water. Water in a refrigeration unit, air conditioner, or heat pump can lead to corrosion and the formation of particles that can clog hair tubes and other small holes in the system, resulting in a breakdown of the system. In addition, costly and lengthy flushing procedures are required in existing equipment to replace a lubricant. Therefore, it is advisable to continue to use the original lubricant, if possible.

The compatibility agents of the invention improve the solubility of hydrofluorocarbon coolers in conventional lubricants for refrigeration systems, thereby improving the return of oil to the compressor.

Polyoxyalkylene glycol ether compatibility agents in accordance with this invention are represented by the formula R ¹ [(OR ² ) _x OR ³ ] _y , where: x is an integer from 1 to 3; y is an integer from 1 to 4; R ^{1 is} selected from hydrogen and aliphatic hydrocarbon radicals having from 1 to 6 carbon atoms and y binding sites; R ² selected from aliphatic hydrocarbylene radicals having from 2 to 4 carbon atoms; R ³ selected from hydrogen and aliphatic and alicyclic hydrocarbon radicals having from 1 to 6 carbon atoms; at least one of R ¹ and R ^{3 is} selected from said hydrocarbon radicals; and wherein said polyoxyalkylene glycol ethers have a molecular weight of from about 100 to about 300 atomic units. In this description, binding sites mean sites of radicals capable of forming covalent bonds with other radicals. Hydrocarbylene radicals mean divalent hydrocarbon radicals. In accordance with this invention, preferred polyoxyalkylene glycol ether compatibility agents are represented by the formula R ¹ [(OR ² ) _x OR ³ ] _y : x is preferably 1-2; y is preferably 1; R ¹ and R ^{3 are} preferably independently selected from hydrogen and aliphatic hydrocarbon radicals having from 1 to 4 carbon atoms; R ^{2 is} preferably selected from aliphatic hydrocarbylene radicals having from 2 to 3 carbon atoms, most preferably 3 carbon atoms; the molecular weight of the polyoxyalkylene glycol ether is preferably from about 100 to about 250 atomic units of mass, most preferably from about 125 to about 250 atomic units of mass. R ¹ and R ³ hydrocarbon radicals having from 1 to 6 carbon atoms may be linear, branched or cyclic. Representative R ¹ and R ³ hydrocarbon radicals include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, tert-pentyl, cyclopentyl and cyclohexyl. Where the free hydroxyl radicals of polyoxyalkylene glycol ether compatibility agents may not be compatible with certain materials of the design of a compressor refrigeration unit (e.g. Mylar®), R ¹ and R ³ are preferably aliphatic hydrocarbon radicals having from 1 to 4 carbon atoms, the most preferably 1 carbon atom. R ² aliphatic hydrocarbylene radicals having from 2 to 4 carbon atoms form repeating oxyalkylene radicals - (OR ² ) _x , which include oxyethylene radicals, oxypropylene radicals and oxybutylene radicals. The oxyalkylene radicals containing R ² in one molecule of the polyoxyalkylene glycol ether compatibility agent may be the same, or the same molecule may contain different R ² oxyalkylene groups. The polyoxyalkylene glycol ether ether compatibility agents of the present invention preferably contain at least one hydroxypropylene radical. If R ¹ is an aliphatic or alicyclic hydrocarbon radical having from 1 to 6 carbon atoms and y binding sites, the radical may be linear, branched or cyclic. Representative R ¹ aliphatic hydrocarbon radicals having two binding sites include, for example, an ethylene radical, a propylene radical, a butylene radical, a pentylene radical, a hexylene radical, a cyclopentylene radical, and a cyclohexylene radical. Typical R ¹ aliphatic hydrocarbon radicals having three or four binding sites include residues derived from polyalcohols such as trimethylolpropane, glycerol, pentaerythritol, 1,2,3-trihydroxycyclohexane and 1,3,5-trihydroxycyclohexane, removing their hydroxyl radicals.

Representative polyoxyalkylene glycol ether compatibility agents include, but are not limited to, CH ₃ OCH ₂ CH (CH ₃ ) O (H or CH ₃ ) (methyl (or dimethyl) propylene glycol ether), CH ₃ O [CH ₂ CH (CH ₃ ) O] ₂ (H or CH ₃ ) (dipropylene glycol methyl (or dimethyl) ether), CH ₃ O [CH ₂ CH (CH ₃ ) O] ₃ (H or CH ₃ ) (tripropylene glycol methyl (or dimethyl) ether) , C ₂ H ₅ OCH ₂ CH (CH ₃ ) O (H or C ₂ H ₅ ) (ethyl (or diethyl) propylene glycol ether), C ₂ H ₅ O [CH ₂ CH (CH ₃ ) O] ₂ (H or C ₂ H ₅ ) (dipropylene glycol ethyl (or diethyl) ether), C ₂ H ₅ O [CH ₂ CH (CH ₃ ) O] ₃ (H or C ₂ H ₅ ) (ethyl (and whether diethyl) tripropylene glycol ether), C ₃ H ₇ OCH ₂ CH (CH ₃ ) O (H or C ₃ H ₇ ) (n-propyl (or di-n-propyl) propylene glycol ether), C ₃ H ₇ O [CH ₂ CH (CH ₃ ) O] ₂ (H or C ₃ H ₇ ) (dipropylene glycol n-propyl (or di-n-propyl) ether), C ₃ H ₇ O [CH ₂ CH (CH ₃ ) O] ₃ ( H or C ₃ H ₇ ) (n-propyl (or di-n-propyl) tripropylene glycol ether), C ₄ H ₉ OCH ₂ CH (CH ₃ ) OH (n-butyl propylene glycol ether), C ₄ H ₉ O [CH ₂ CH (CH ₃ ) O] ₂ (H or C ₄ H ₉ ) (n-butyl (or di-n-butyl) ether of dipropylene glycol), C ₄ H ₉ O [CH ₂ CH (CH ₃ ) O] ₃ ( H or C ₄ H ₉ ) (n-butyl (or di-n-butyl) ether of tripropylene glycol), (CH ₃ ) ₃ COS ₂ CH (CH ₃ ) OH (propylene glycol tert-butyl ether), (CH ₃ ) ₃ CO [CH ₂ CH (CH ₃ ) O] ₂ (H or (CH ₃ ) ₃ ) (tert-butyl (or di-tert dipropylene glycol-butyl ether), (CH ₃ ) ₃ CO [CH ₂ CH (CH ₃ ) O] ₃ (H or (CH ₃ ) ₃ ) (tert-butyl (or di-tert-butyl) tripropylene glycol ether), С ₅ H ₁₁ OCH ₂ CH (CH ₃ ) OH (n-pentyl ether of propylene glycol), C ₄ H ₉ OCH ₂ CH (C ₂ H ₅ ) OH (n-butyl ether of butylene glycol), C ₄ H ₉ O [CH ₂ CH (C ₂ H ₅ ) O] ₂ H (dibutylene glycol n-butyl ether), trimethylolpropane tri-n-butyl ether (C ₂ H ₅ C (CH ₂ O (CH ₂ ) ₃ CH ₃ ) ₃ ) and di-n- trimethylolpropane butyl ether (C ₂ H ₅ C (CH ₂ O (CH ₂ ) ₃ CH ₃ ) ₂ CH ₂ OH).

Amide compatibility agents in accordance with this invention include those represented by the formulas R ¹ C (O) NR ² R ³ and cyclo- [R ⁴ C (O) N (R ⁵ ) -], where R ¹ , R ² , R ³ and R ^{5 are} independently selected from aliphatic and alicyclic hydrocarbon radicals having from 1 to 12 carbon atoms; R ^{4 is} selected from aliphatic hydrocarbylene radicals having from 3 to 12 carbon atoms; and where these amides have a molecular weight of from about 100 to about 300 atomic units of mass. The molecular weight of these amides is preferably from about 160 to about 250 atomic units of mass. R ¹ , R ² , R ³ and R ⁵ may optionally include substituted hydrocarbon radicals, i.e., radicals containing non-hydrocarbon substituents selected from halogens (e.g. fluorine, chlorine) and alkoxides (e.g. methoxy). R ¹ , R ² , R ³ and R ⁵ may optionally include heteroatom-substituted hydrocarbon radicals, i.e., radicals that contain nitrogen (aza), oxygen (oxa) or sulfur (thia) atoms in a radical chain, usually consisting of carbon atoms. In general, no more than three non-hydrocarbon substituents and heteroatoms, preferably no more than one, can be present for every 10 carbon atoms in R ^1-3 , and the presence of such non-hydrocarbon substituents and heteroatoms should be taken into account when applying the above molecular weight restrictions. Preferred amide compatibility agents are composed of carbon, hydrogen, nitrogen and oxygen. Typical R ¹ , R ² , R ³ and R ⁵ aliphatic and alicyclic hydrocarbon radicals include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, tert-pentyl, cyclopentyl, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and their configuration isomers. Preferred variants of the amide compatibility agents include those in which R ⁴ in the above formula, cyclo- [R ⁴ CON (R ⁵ ) -] can be represented by a hydrocarbylene radical (CR ⁶ R ⁷ ) _n , in other words, which have the formula cyclo- [ (CR ⁶ R ⁷ ) _n C (O) N (R ⁵ ) -], where: the above molecular weight values are applied; n is an integer from 3 to 5; R ⁵ is a saturated hydrocarbon radical containing from 1 to 12 carbon atoms; R ⁶ and R ^{7 are} independently selected (for each n) according to the rules suggested above for the selection of R ^1-3 . In the lactams represented by the formula cyclo - [(CR ⁶ R ⁷ ) _n C (O) N (R ⁵ ) -], all R ⁶ and R ⁷ are preferably hydrogen or contain one saturated hydrocarbon radical among n methylene units, and R ⁵ is a saturated hydrocarbon radical containing from 3 to 12 carbon atoms. For example, 1- (saturated hydrocarbon radical) -5-methylpyrrolidin-2-ones.

Representative amide compatibility agents include, but are not limited to: 1-octylpyrrolidin-2-one, 1-decylpyrrolidin-2-one, 1-octyl-5-methylpyrrolidin-2-one, 1-butylcaprolactam, 1-cyclohexylpyrrolidin-2-one , 1-butyl-5-methylpiperid-2-one, 1-pentyl-5-methylpiperid-2-one, 1-hexylcaprolactam, 1-hexyl-5-methylpyrrolidin-2-one, 5-methyl-1-pentylpiperid-2 -one, 1,3-dimethylpiperid-2-one, 1-methylcaprolactam, 1-butylpyrrolidin-2-one, 1,5-dimethylpiperid-2-one, 1-decyl-5-methylpyrrolidin-2-one, 1-dodecylpyrrolide -2-one, N, N-dibutylformamide and N, N-diisopropylacetamide.

The ketone compatibility agents in accordance with this invention are represented by the formula R ¹ C (O) R ² , where R ¹ and R ^{2 are} independently selected from aliphatic, alicyclic and aryl hydrocarbon radicals having from 1 to 12 carbon atoms, and where said ketones have a molecular a mass of from about 70 to about 300 atomic units of mass. R ¹ and R ² in said ketones are preferably independently selected from aliphatic and alicyclic hydrocarbon radicals having from 1 to 9 carbon atoms. The molecular weight of such ketones is preferably from about 100 to about 200 atomic units of mass. R ¹ and R ² together can form a hydrocarbylene radical bound and forming a five-, six- or seven-membered ring cyclic ketone, for example cyclopentanone, cyclohexanone and cycloheptanone. R ¹ and R ² may optionally include substituted hydrocarbon radicals, i.e., radicals containing non-hydrocarbon substituents selected from halogens (e.g. fluorine, chlorine) and alkoxides (e.g. methoxy). R ¹ and R ² may optionally include heteroatom-substituted hydrocarbon radicals, i.e., radicals that contain nitrogen (aza), oxygen (keto, oxa) or sulfur (thia) atoms in a radical chain, usually consisting of carbon atoms. In general, no more than three non-hydrocarbon substituents and heteroatoms, preferably no more than one, can be present for every 10 carbon atoms in R ¹ and R ² , and the presence of such non-hydrocarbon substituents and heteroatoms should be taken into account when applying the above molecular weight restrictions. Typical R ¹ and R ² aliphatic, alicyclic and aryl hydrocarbon radicals in the general formula R ¹ C (O) R ² include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl , tert-pentyl, cyclopentyl, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and their configuration isomers, as well as phenyl, benzyl, cumenyl, mesityl, tolyl, xylyl and phenethyl.

Representative ketone compatibility agents include, but are not limited to, 2-butanone, 2-pentanone, acetophenone, butyrophenone, hexanophenone, cyclohexanone, cycloheptanone, 2-heptanone, 3-heptanone, 5-methyl-2-hexanone, 2-octanone, 3 -octanone, diisobutylketone, 4-ethylcyclohexanone, 2-nonanone, 5-nonanone, 2-decanone, 4-decanone, 2-decalon, 2-tridecanone, dihexyl ketone and dicyclohexyl ketone.

The nitrile compatibility agents in accordance with this invention are represented by the formula R ¹ CN, where R ^{1 is} selected from aliphatic, alicyclic or aryl hydrocarbon radicals having from 5 to 12 carbon atoms, and where said nitriles have a molecular weight of from about 90 to about 200 atomic units masses. R ¹ in these nitrile compatibility agents is preferably selected from aliphatic and alicyclic hydrocarbon radicals having from 8 to 10 carbon atoms. The molecular weight of these nitrile compatibility agents is preferably from about 120 to about 140 atomic units of mass. R ¹ may optionally include substituted hydrocarbon radicals, i.e., radicals containing non-hydrocarbon substituents selected from halogens (e.g. fluorine, chlorine) and alkoxides (e.g. methoxy). R ¹ may optionally include heteroatom-substituted hydrocarbon radicals, i.e., radicals that contain nitrogen (aza), oxygen (keto, oxa) or sulfur (thia) atoms in a radical chain, usually consisting of carbon atoms. In general, no more than three non-hydrocarbon substituents and heteroatoms, preferably no more than one, can be present for every 10 carbon atoms in R ¹ , and the presence of such non-hydrocarbon substituents and heteroatoms should be taken into account when applying the above molecular weight restrictions. Typical R ¹ aliphatic, alicyclic and aryl hydrocarbon radicals in the general formula R ¹ CN include pentyl, isopentyl, neopentyl, tert-pentyl, cyclopentyl, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and their configuration isomers, as well benzyl, cumenyl, mesityl, tolyl, xylyl and phenethyl.

Representative nitrile compatibility agents include, but are not limited to: 1-cyanopentane, 2,2-dimethyl-4-cyanopentane, 1-cyanohexane, 1-cyanoheptane, 1-cyano-octane, 2-cyano-octane, 1-cyanononane, 1-cyano-decane, 2 -cyanodecane, 1-cyanoundecane and 1-cyanododecane.

The chlorocarbon compatibility agents of the present invention include chlorocarbons represented by the formula RCl _x , where x is selected from the integers 1 or 2; R is selected from aliphatic and alicyclic hydrocarbon radicals having from 1 to 12 carbon atoms; and where these chlorocarbons have a molecular weight of from about 100 to about 200 atomic units of mass. The molecular weight of said compatibility chlorocarbon agents is preferably from about 120 to about 150 atomic units of mass. Typical R aliphatic and alicyclic radicals in the formula RCl _x include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, tert-pentyl, cyclopentyl, cyclohexyl, heptyl, octyl, nonyl , decyl, undecyl, dodecyl and their configurational isomers.

Representative chloro carbon compatibility agents include, but are not limited to: 3- (chloromethyl) pentane, 3-chloro-3-methylpentane, 1-chlorhexane, 1,6-dichlorohexane, 1-chlorheptane, 1-chloroctane, 1-chlorononan, 1- chlordecane and 1,1,1-trichlorodecane.

The ester compatibility agents of the present invention include esters represented by the general formula R ¹ CO ₂ R ² , where R ¹ and R ^{2 are} independently selected from linear and cyclic, saturated and unsaturated, alkyl and aryl radicals. Preferred esters consist mainly of elements C, H and O, have a molecular weight of from about 80 to about 550 atomic units of mass.

Specific esters include, but are not limited to: (CH _{3) 2} CHCH ₂ OOS (CH _{2) 2-4} CH ₂ OCOCH _{(CH3) 2} (diisobutyl dibasic ester), ethyl hexanoate, ethylheptanoate, n-butyl propionate, n propyl propionate, ethyl benzoate, di-n-propyl phthalate, ethoxyethyl ester of benzoic acid, dipropyl carbonate, Exxate 700 (commercial C ₇ alkyl acetate), Exxate 800 (commercial C ₈ alkyl acetate), dibutyl phthalate and tert-butyl acetate.

Lactone compatibility agents in accordance with this invention include lactones represented by structures [A], [B] and [C]:

These lactones contain a functional group —CO ₂ - in a ring of six (A) or, preferably, five atoms (B), where for structures [A] and [B] R ₁ -R _{8 are} independently selected from hydrogen or linear, branched, cyclic, bicyclic, saturated and unsaturated hydrocarbyl radicals. Each R ₁ -R ₈ may be associated with the formation of a ring with another R ₁ -R ₈ . The lactone may have an exocyclic alkylidene group, as in structure [C], where R ₁ -R _{6 are} independently selected from hydrogen or linear, branched, cyclic, bicyclic, saturated and unsaturated hydrocarbyl radicals. Each R ₁ -R ₆ may be associated with the formation of a ring with another R ₁ -R ₆ . Lactone compatibility agents have a molecular weight of from about 100 to about 300 atomic mass units, preferably from about 80 to about 200 atomic mass units.

Representative lactone compatibility agents include, but are not limited to, the compounds shown in table 8.

TABLE 8

Lactone compatibility agents typically have a kinematic viscosity of less than 7 centistokes at 40 ° C. For example, gamma-undecalactone has a kinematic viscosity of 5.4 centistokes and cis- (3-hexyl-5-methyl) dihydrofuran-2-one has a kinematic viscosity of 4.5 centistokes at a temperature of 40 ° C both. Compatibility lactone agents may be commercially available or prepared by methods described in US patent application 10/910495, filed August 3, 2004, incorporated herein by reference.

Aryl ether compatibility agents in accordance with this invention include aryl ethers represented by the formula R ¹ OR ² , wherein: R ^{1 is} selected from aryl hydrocarbon radicals having from 6 to 12 carbon atoms; R ² selected from aliphatic hydrocarbon radicals having from 1 to 4 carbon atoms; and wherein said aryl ethers have a molecular weight of from about 100 to about 150 atomic units of mass. Typical R ¹ aryl radicals in the general formula R ¹ OR ² include phenyl, biphenyl, cumenyl, mesityl, tolyl, xylyl, naphthyl and pyridyl. Representative R ² aliphatic hydrocarbon radicals in the general formula R ¹ OR ² include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl and tert-butyl. Representative aromatic etheric compatibility agents include, but are not limited to: methylphenyl ether (anisole), 1,3-dimethyloxybenzene, ethylphenyl ether, and butylphenyl ether.

Compatibility fluoroether agents according to the invention include those represented by the formula R ¹ OCF ₂ CF ₂ H, wherein R ^{1 is} selected from aliphatic, alicyclic and aromatic hydrocarbon radicals having from about 5 to about 15 carbon atoms, preferably primary, linear, saturated alkyl radicals. Representative compatibility fluoroether agents include, but are not limited to: C ₈ H ₁₇ OCF ₂ CF ₂ H and C ₆ H ₁₃ OCF ₂ CF ₂ H. It should be noted that if the cooler is a fluoroether, then the compatibilizer cannot be the same fluoro ether.

Compatibility fluoroether agents may also include ethers derived from fluoroolefins and polyols. Fluoroolefins can be of type CF ₂ = CXY, where X is hydrogen, chlorine or fluorine and Y is chlorine, fluorine, CF ₃ or OR _f , where R _f is CF ₃ , C ₂ F ₅ or C ₃ F ₇ . Representative fluoroolefins include tetrafluoroethylene, chlorotrifluoroethylene, hexafluoropropylene, and perfluoromethyl vinyl ether. Polyhydric alcohols can be linear or branched. Linear polyols can be of the type HOCH ₂ (CHOH) _x (CRR ') _y CH ₂ OH, where R and R' are hydrogen, or CH ₃ , or C ₂ H ₅ , and where x is an integer from 0 to 4, and y is an integer from 0 to 4. Branched polyhydric alcohols may be of type C (OH) _t (R) _u (CH ₂ OH) _v [(CH ₂ ) _m CH ₂ OH] _w , where R may be hydrogen, CH ₃ or C ₂ H ₅ , m is an integer from 0 to 3, t and u are 0 or 1, v and w are integers from 0 to 4, and also where t + u + v + w = 4. Representative polyols include trimethylol propane, pentaerythritol, butanediol and ethylene glycol.

The 1,1,1-trifluoroalkane compatibility agents of the present invention include 1,1,1-trifluoroalkanes represented by the formula CF ₃ R ¹ , wherein R ^{1 is} selected from aliphatic and alicyclic hydrocarbon radicals having from about 5 to about 15 carbon atoms , preferably, primary, linear, saturated alkyl radicals. Representative 1,1,1-trifluoroalkane compatibility agents include, but are not limited to: 1,1,1-trifluorohexane and 1,1,1-trifluorododecane.

By an effective amount of a compatibilizing agent is meant that amount of a compatibilizing agent that effectively dissolves the lubricant in the composition, thereby ensuring adequate oil return to optimize the operation of the refrigeration unit, air conditioner, or heat pump.

Compositions in accordance with this invention usually contain from about 0.1 to about 40 wt. -%, preferably from about 0.2 to about 20 wt. -%, and most preferably from about 0.3 to about 10% of the mass. compatibility agent in the compositions in accordance with this invention.

This invention also relates to a method for dissolving a cooler or a heat transfer fluid containing compositions according to this invention in a lubricant for a refrigeration system selected from the group consisting of mineral oils, alkylbenzenes, synthetic paraffins, synthetic naphthenes and poly (alpha) olefins, where said method comprising reacting said lubricant with said composition in the presence of an effective amount of a compatibilizing agent, wherein said compatibilizing agent is selected dissolved from the group consisting of simple polyoxyalkylene glycol ethers, amides, nitriles, ketones, chlorocarbons, esters, lactones, aryl ethers, and 1,1,1-ftoefiry triftoralkany.

The present invention also relates to a method for improving the return of oil to a compressor in a compressor refrigeration unit, air conditioner, or heat pump apparatus, wherein said method comprises the use of a composition comprising a compatibility agent in said apparatus.

Compositions in accordance with this invention may also contain an ultraviolet (UV) dye and, optionally, a dissolving agent. UV dye is a useful component for detecting leaks in a composition, allowing a person to see the fluorescence of the dye in the composition at or around the leak in a refrigeration unit, air conditioner, or heat pump. One skilled in the art can see the dye fluorescence in ultraviolet light. Solvents may be necessary due to the poor solubility of such UV dyes in some compositions.

By "ultraviolet" dye is meant a composition that fluoresces in UV light, which absorbs light in the ultraviolet or "near" ultraviolet range of the electromagnetic spectrum. The fluorescence emitted by a UV fluorescent dye can be determined by irradiation with UV light, which emits radiation with a wavelength ranging from 10 nanometers to 750 nanometers. Therefore, if a composition containing such a UV-fluorescent dye leaks at a given location in a refrigeration unit, air conditioner or heat pump apparatus, fluorescence can be detected at the point of leakage. Such UV fluorescent dyes include, but are not limited to, naphthalimides, perylene, coumarins, anthracenes, phenanthracenes, xanthenes, thioxanthenes, naphthoxantenes, fluoresceins and their derivatives or combinations thereof.

The solvent agents of the invention include at least one compound selected from the group consisting of hydrocarbons, hydrocarbon ethers, polyoxyalkylene glycol ethers, amides, nitriles, ketones, chlorocarbons, esters, lactones, aryl ethers, fluoroethers and 1,1,1-trifluoroalkanes. Solvents based on polyoxyalkylene glycol ethers, amides, nitriles, ketones, chlorocarbons, esters, lactones, aryl ethers, fluoroethers and 1,1,1-trifluoroalkanes are described above as compatibility agents for use with conventional refrigeration system lubricants.

Hydrocarbon dissolving agents in accordance with this invention include hydrocarbons, including straight, branched or cyclic alkanes or alkenes containing 5 or less carbon atoms and only hydrogen in the absence of other functional groups. Representative hydrocarbon solvents include propane, propylene, cyclopropane, n-butane, isobutane, 2-methylbutane and n-pentane. It should be noted that if the composition contains a hydrocarbon, then the solvent may not be the same hydrocarbon.

The hydrocarbon ether solvents of the present invention include ethers containing only carbon, hydrogen and oxygen, such as dimethyl ether (DME).

Solvent agents in accordance with this invention may be present as a single compound or may be present as a mixture of more than one solvent agent. Mixtures of solvent agents may contain two solvent agents from one class of compounds, for example two lactones, or two solvent agents from two different classes of compounds, for example, lactone and polyoxyalkylene glycol ether.

In compositions in accordance with this invention, containing a cooler and fluorescent in UV dye or containing a liquid coolant and fluorescent in UV dye, from about 0.001% of the mass. up to about 1.0% of the mass. the composition is a UV dye, preferably from about 0.005% of the mass. up to about 0.5% of the mass., and most preferably, from about 0.01% of the mass. up to about 0.25% of the mass.

Solvent agents, such as ketones, may have an unpleasant odor, which can be masked by the addition of an odor suppressant or perfume. Typical examples of odor suppressants or fragrances may include commercially available Evergreen, Fresh Lemon, Cherry, Cinnamon, Peppermint, Flower or Orange Peel, as well as d-limonene and pinene. Such odor suppressing agents can be used in concentrations from about 0.001% to not more than about 15% of the mass. in relation to the total weight of the odor-concealing agent and the dissolving agent.

The solubility of these UV-fluorescent dyes in accordance with this invention may be poor. Therefore, the methods of introducing such dyes into refrigeration units, air conditioners or heat pumps are inconvenient, expensive and time consuming. US patent No. RE 36951 describes a method in which powder dye, solid granules or a dye suspension are used that can be incorporated into a component of a refrigeration unit, air conditioner or heat pump apparatus. Since the cooler and lubricant circulate through the apparatus, the dye is dissolved or dispersed and passed through the apparatus. Many other methods of introducing dye into refrigeration units or air conditioners are described in the literature.

Ideally, the UV fluorescent dye can be dissolved in the cooler itself, thereby not requiring any special method of introduction into the refrigeration unit, air conditioner or heat pump. This invention relates to compositions comprising a fluorescent in UV dye, which can be introduced into the system as a solution in a cooler. Compositions in accordance with this invention allow the storage and transportation of compositions containing dyes, even at low temperatures while maintaining the dye in solution.

In compositions in accordance with this invention containing a coolant, fluorescent in UV dye and a dissolving agent or containing a liquid coolant, fluorescent in UV agent and a dissolving agent, from about 1 to about 50 wt. -%, preferably from about 2 to about 25% of the mass ., most preferably, from about 5 to about 15% of the mass. from the combined composition is a solvent agent. In the compositions in accordance with this invention, fluorescent in UV dye is present in a concentration of from about 0.001% of the mass. up to about 1.0 wt. -%, preferably from 0.005% of the mass. up to about 0.5% of the mass., most preferably from 0.01% of the mass. up to about 0.25% of the mass.

The present invention also relates to a method of using compositions also containing a dye fluorescent in ultraviolet and, optionally, a dissolving agent, in refrigeration units, air conditioners and heat pump apparatuses. The method includes introducing the composition into a refrigeration unit, air conditioner or heat pump apparatus. This can be accomplished by dissolving the UV dye fluorescent in the composition in the presence of a dissolving agent and introducing the resulting composition into the apparatus. Alternatively, this can be accomplished by combining the solvent and the UV dye fluorescent in the UV and introducing the resulting composition into a refrigeration unit or conditioner containing a coolant and / or liquid coolant. The resulting composition can be used in refrigeration units, air conditioners or heat pumps.

The present invention also relates to a method for using compositions containing ultraviolet fluorescent dye to detect leaks. The presence of dye in the composition allows you to determine the leakage of the cooler in the refrigeration unit, air conditioner or heat pump. Leak detection helps to pay attention to, solve a problem or prevent the ineffective operation of the device or system or equipment breakdown. Leak detection also helps retain the chemicals used in the apparatus.

The method includes the use of a composition containing a coolant, ultraviolet fluorescent dye described above, and, optionally, a solvent agent described above, in a refrigeration unit, air conditioner or heat pump apparatus, and the use of suitable means for determining a coolant containing ultraviolet fluorescent dye. Suitable means for determining the dye include, but are not limited to, ultraviolet lamps, often referred to as "invisible light" or "blue light". Such ultraviolet lamps are commercially available from a variety of sources specifically designed for this purpose. As soon as a composition containing dye fluorescent in ultraviolet is introduced into a refrigeration unit, air conditioner or heat pump apparatus and begins to circulate in the system, leakage can be determined by illuminating the apparatus with the indicated UV lamp and observing the dye fluorescence near any leakage site.

This invention also relates to a method for replacing a high GWP cooler in refrigeration units, air conditioners, or heat pumps, wherein said high GWP cooler is selected from the group consisting of R134a, R22, R245fa, R114, R236fa, R124, R410A, R407C, R417A, R422A , R507A and R404A, wherein said method comprises feeding the composition of the invention to said refrigeration unit, air conditioner or heat pump apparatus in which it is used or which is designed to use said high GWP cooler.

Steam compressor refrigeration, air conditioning, or heat pump systems include an evaporator, compressor, condenser, and expansion device. In the vapor compression cycle at many stages, the cooler is reused, providing a cooling effect at one stage and a heating effect at another stage. The cycle can be briefly described as follows. The liquid cooler enters the evaporator through an expansion device, and the liquid cooler boils in the evaporator at low temperature to produce gas and create cold. Gas at low pressure enters the compressor, in which the gas is compressed with increasing pressure and temperature. A gaseous cooler at a higher pressure (compressed) is then fed to a condenser in which the cooler condenses and releases heat to the environment. The cooler returns to the expansion device through which the liquid expands from the high pressure level in the condenser to the low pressure level in the evaporator, thereby repeating the cycle.

As used herein, the terms “mobile refrigeration units” or “mobile air conditioners” refer to any refrigeration unit or air conditioner integrated in a vehicle for use on roads, railways, sea or air. In addition, apparatuses intended for cooling or air conditioning in systems independent of any moving means, known as systems for "mixed transport" are included in this invention. Such systems for multimodal transportation include “containers” (combined for transportation by sea / on land), as well as “swap bodies” (combined for transportation by road and rail). This invention is especially useful for refrigeration units and air conditioners for automobile vehicles, such as automobile air conditioners or refrigeration equipment for automobile vehicles.

This invention also relates to a method for producing cooling, comprising evaporating the compositions in accordance with this invention next to the object to be cooled, followed by condensation of these compositions.

This invention also relates to a method for producing heat, comprising condensing the compositions in accordance with this invention next to a heated object, followed by evaporation of these compositions.

This invention also relates to refrigeration units, air conditioners, and heat pump apparatuses comprising a composition in accordance with this invention, wherein said composition contains at least one fluoroolefin.

This invention also relates to mobile air conditioners containing a composition in accordance with this invention, where the composition contains at least one fluoroolefin.

The present invention also relates to a method for early detection of leakage in refrigeration units, air conditioners or heat pump apparatuses, wherein said method comprises the use of a non-azeotropic composition in said apparatuses and monitoring the decrease in cooling capacity. Non-azeotropic compositions are fractionated by leakage from a refrigeration unit, air conditioner, or heat pump apparatus, and a component with a lower boiling point (with a higher vapor pressure) is the first to leave the apparatus. When this happens, if the component with a lower boiling point in this composition provides the main freezing power, there will be a noticeable decrease in power and, thus, the performance of the apparatus. In automotive air conditioning systems, for example, passengers in a car can detect a decrease in system cooling capacity. Such a decrease in cooling capacity can be interpreted as a cooler leak and is a signal that the system needs to be repaired.

This invention also relates to a method of using the compositions in accordance with this invention as liquid heat transfer compositions, wherein said method comprises transferring said composition from a heat source to a heat sink.

Liquid heat carriers are used to transfer, supply or remove heat from one space, room, object or body to another space, room, object or body by radiation, heat conduction or convection. The liquid coolant can function as a secondary cooler, being a means for transferring cold (or heat) from a remote refrigeration (or heating) system. In some systems, the heat transfer fluid may remain unchanged during the transfer process (i.e., not evaporate or condense). Alternatively, liquid coolants can be used in evaporative cooling processes.

A heat source can be defined as any space, room, object or body from which it is desirable to transfer, supply or remove heat. Examples of heat sources can be spaces (open or closed) that require freezing or cooling, such as refrigerators or freezers in supermarkets, spaces in buildings that require air conditioning, or passenger compartments in cars that require air conditioning. A heat sink can be any space, room, object, or body that can absorb heat. A vapor compressor refrigeration unit is one example of such a heat sink.

In another embodiment, the present invention relates to foaming compositions containing compositions containing fluoroolefin described above for use in the production of foam. In other embodiments, the invention relates to foaming compositions, preferably polyurethane and polyisocyanate foaming compositions, and a method for producing foams. Such foaming options include one or more of the compositions of the invention containing a fluoroolefin as a foaming agent in expandable compositions, wherein the compositions preferably include one or more additional components capable of reacting and foaming under suitable conditions to form a foam or a cellular structure any methods well known in the art, such as those described in "Polyurethanes Chemistry and Technology," Volumes I and II, Saunders and Frisch, 1962, John Wiley and Sons, New York, NY, which includes When incorporated herein by reference, they can be used or adapted for use as foaming options in accordance with this invention.

This invention also relates to a method for producing foam, comprising: (a) adding a fluoroolefin-containing composition in accordance with this invention to a foaming composition; and (b) reacting the foaming composition under conditions effective to produce foam.

Another embodiment of the invention relates to the use of the fluoroolefin-containing compositions described above as propellants in sprayable compositions. In addition, the present invention relates to sprayable compositions containing the above-described fluoroolefin compositions. An active ingredient sprayable with inert ingredients, solvents and other materials may also be present in the sprayable composition. Preferably, the sprayable composition is an aerosol. Suitable sprayable active materials include, but are not limited to, cosmetics, such as deodorants, perfumes, hair sprays, cleaners, and polishing agents, as well as medical products, such as anti-asthma medicines and anti-odor agents.

This invention also relates to a method for producing aerosol products, comprising the step of adding a composition containing a fluoroolefin, such as described above, to the active ingredients in an aerosol container, where the composition acts as a propellant.

Another aspect of the present invention relates to flame suppression methods, wherein said methods comprise reacting the flame with a liquid containing a fluoroolefin composition according to the invention. Any means of reacting the flame with the composition may be used. For example, the fluoroolefin-containing composition of the invention may be sprayed, poured, and so forth into a flame, or at least a portion of the flame may be flooded with a flame arrestor. In the light of the person presented here, a person skilled in the art can easily adapt many conventional apparatuses and methods for suppressing flame for use in accordance with this invention.

In another embodiment, methods of extinguishing or suppressing fire by full flooding methods are provided, including using an agent containing a composition comprising a fluoroolefin in accordance with this invention; placing the agent in a discharge device under pressure and dumping the agent into the area to extinguish or suppress fire in this area. Another embodiment relates to methods for treating a site to prevent fire or explosion, comprising obtaining an agent containing a composition comprising a fluoroolefin in accordance with this invention; placing the agent in a pressure relief device and discharging the agent to a site to prevent fire or explosion.

The term "extinction" is usually used to mean the complete destruction of fire; while “suppression” is often used to denote a reduction, but not necessarily complete destruction, fire or explosion. As used herein, the terms “blanking” and “suppressing” are used interchangeably. There are four main types of halocarbon protection against fire and explosion. (1) In extinguishing and / or suppression of flames by full flooding, the agent is discharged into the space to achieve a concentration sufficient to extinguish or suppress the existing fire. Full flooding includes the protection of enclosed spaces that are potentially occupied by people, such as computer rooms, as well as specialized, often unoccupied spaces, such as niches for aircraft engines and motor compartments in vehicles. (2) In flowing means, the agent is fed directly into the fire or into the ignition area. This is usually achieved by using wheeled or portable units with manual control. The second method used in flowing means includes a “localized” system that ejects an agent in the direction of fire from one or more fixed nozzles. Localized systems can be activated either manually or automatically. (3) In suppressing an explosion, the fluoroolefin-containing composition of the invention is discharged to suppress an explosion that has already been initiated. The term "suppression" is usually used in this area, since the explosion is usually self-limiting. However, the use of this term does not necessarily mean that the explosion is not destroyed by the agent. A detector is typically used in the art to detect the expansion of the explosion cloud, and the agent is immediately used to suppress the explosion. Explosion suppression is used primarily, but not only, in the defense industry. (4) In an inert gas treatment, the fluoroolefin-containing composition of the invention is dumped into the space to prevent explosion or fire. Often systems are used that are identical to those used to extinguish or suppress flames with a full flood. Hazardous conditions (eg, hazardous concentrations of flammable or explosive gases) are usually determined and the fluoroolefin-containing composition of the invention is discharged to prevent explosion or fire until the conditions are safe.

The extinguishing method can be carried out by feeding the composition to a closed area surrounding the fire. Any known delivery methods may be used, provided that a sufficient amount of the composition is supplied to the closed area at a sufficient interval. For example, the composition may be delivered in a stream, i.e. using conventional portable (or fixed) fire extinguishing devices; fogging or flooding, i.e. feeding the composition (using a suitable pipe, valves and control devices) into a closed area surrounding the fire. The compositions may optionally be combined with an inert propellant, for example nitrogen, argon, glycidyl azide decomposition products or carbon dioxide, to increase the rate of discharge of the composition from the used flow or flooding equipment.

Preferably, the extinguishing process includes feeding the fluoroolefin-containing composition of the invention to a fire or flame in an amount sufficient to extinguish the fire or flame. One skilled in the art will understand that the amount of flame suppression agent needed to extinguish a particular flame depends on the nature and extent of the hazard source. If a flame suppression agent is supplied by flooding, combustion chamber test data are used to determine the amount or concentration of flame suppression agent required to extinguish a particular type and size of flame.

Laboratory tests to determine the effective concentration range of compositions containing fluoroolefin when used in combination with flame-extinguishing agents or flame suppressants when the flame is completely flooded or extinguished using an inert gas are described, for example, in US Pat. No. 5,759,430, which is incorporated herein by reference .

EXAMPLES

EXAMPLE 1

Steam Leak Exposure

The initial composition is loaded into the vessel at a temperature of either -25 ° C, or, if indicated specifically, 25 ° C, and the initial vapor pressure of the composition is measured. Compositions allow to flow out of the vessel, keeping the temperature constant, until 50% of the mass flows out. from the original composition, after which the vapor pressure of the composition remaining in the vessel is measured. The results are shown in table 9.

TABLE 9

For compositions in accordance with this invention, the difference in vapor pressure between the original composition and the composition remaining after removal of 50 wt. -%, is less than 10%. This shows that the compositions in accordance with this invention can be azeotropic or almost azeotropic.

EXAMPLE 2

Cooling data

Table 10 shows the performance of various cooler compositions in accordance with this invention compared to HFC-134a. Table 10 App. Pressure means evaporator pressure, Cond. Pressure means condenser pressure, comp. Nag. T means discharge temperature in the compressor, COP means energy efficiency and POWER. means power. Data is based on the following conditions.

Evaporator temperature 40.0 ° F (4.4 ° C) Condenser temperature 130.0 ° F (54.4 ° C) Subcooling temperature 10.0 ° F (5.5 ° C) Return gas temperature 60.0 ° F (15.6 ° C) Compressor performance one hundred%

Note: overheating is taken into account when calculating cooling capacity.

TABLE 10

Some compositions have even greater energy efficiency (COP) than HFC-134a, while having lower discharge pressure and discharge temperature. The power of the compositions in accordance with this invention is also comparable to R134a, which means that they can be replacement coolers for R134a in refrigeration units and air conditioners, in particular in mobile air conditioners. Hydrocarbon containing compositions can also improve oil solubility for conventional mineral oil and alkylbenzene lubricants.

EXAMPLE 3

Cooling data

Table 11 shows the performance of various cooler compositions in accordance with this invention compared to R404A and R422A. Table 11 App. Pressure means evaporator pressure, Cond. Pressure means condenser pressure, comp. Nag. T means the discharge temperature in the compressor, EER means energy efficiency and POWER means power. Data is based on the following conditions.

Evaporator temperature -17.8 ° C Condenser temperature 46.1 ° C Subcooling temperature 5.5 ° C Return gas temperature 15.6 ° C Compressor performance 70%

Note: overheating is taken into account when calculating cooling capacity.

TABLE 11

Some compositions have energy efficiency (COP) comparable to the top rates of R404A and R422A. The discharge temperature is also lower than that of the R404A and R507A. The power of the compositions in accordance with this invention is also comparable with R404A, R507A and R422A, which means that they can be replacement coolers in refrigeration units and air conditioners. Hydrocarbon containing compositions can also improve oil solubility for conventional mineral oil and alkylbenzene lubricants.

EXAMPLE 4

Cooling data

Table 12 shows the performance of the various cooler compositions in accordance with this invention compared to HCFC-22, R410A, R407C and R417A. Table 12 App. Pressure means evaporator pressure, Cond. Pressure means condenser pressure, comp. Nag. T means the discharge temperature in the compressor, EER means energy efficiency and POWER. means power. Data is based on the following conditions.

Evaporator temperature 4.4 ° C Condenser temperature 54.4 ° C Subcooling temperature 5.5 ° C Return gas temperature 15.6 ° C Compressor performance one hundred%

Note: overheating is taken into account when calculating cooling capacity.

TABLE 12

Some compositions have an energy efficiency (EER) comparable to the upper rates R22, R407C, R417A and R410A, while having low discharge temperatures. The power of the compositions in accordance with this invention is also comparable with R22, R407C and R417A, which means that they can be replacement coolers in refrigeration units and air conditioners. Hydrocarbon containing compositions can also improve oil solubility for conventional mineral oil and alkylbenzene lubricants.

EXAMPLE 5

Cooling data

Table 13 shows the performance of various cooler compositions in accordance with this invention compared to HCFC-22 and R410A. Table 13 App. Pressure means evaporator pressure, Cond. Pressure means condenser pressure, comp. Nag. T means the discharge temperature in the compressor, EER means energy efficiency and POWER. means power. Data is based on the following conditions.

Evaporator temperature 4 ° C Condenser temperature 43 ° C Subcooling temperature 6 ° C Return gas temperature 18 ° C Compressor performance 70%

Note: overheating is taken into account when calculating cooling capacity.

TABLE 13

The compositions have an energy efficiency (EER) comparable to R22 and R410A, while having acceptable discharge temperatures. The power of the compositions in accordance with this invention is also comparable to R22, which means that they can be replacement coolers in refrigeration units and air conditioners.

EXAMPLE 6

Flammability

Flammable compounds can be identified using ASTM (American Society for Testing Materials) test E681-01 with an electronic ignition source. Such tests for flammability performed for HFC-1234yf, HFC-1225ye and blends according to the invention at a pressure of 101 kPa (14.7 lb / d ^2), a temperature of 100 ° C (212 ° F) and a relative humidity of 50% at various concentrations in air to determine the lower flammability limit (LEL) and the upper flammability limit (ERW). The results are presented in table 14.

TABLE 14

The results show that although HFC-1234yf is highly flammable, the addition of HFC-1225ye reduces flammability. Therefore, compositions containing from about 1% of the mass. up to about 40% of the mass. HFC-1234yf and from about 99% of the mass. up to about 51% of the mass. HFC-1225ye are preferred.

Claims (29)

1. The composition of the cooler or coolant containing an azeotropic or almost azeotropic component containing from about 1 wt.% To about 99 wt.% HFC-1234yf and from about 99 wt.% To about 1 wt.% HFC-134a, and optionally at least one compound selected from the group consisting of propane, n-butane, isobutane and dimethyl ether; the specified composition of the cooler or coolant optionally contains at least one more component selected from lubricants, isotopic indicators, compatibility agents, ultraviolet fluorescent dyes, solvents, stabilizers, water absorbents and odor suppressing agents. 2. The composition according to claim 1, containing at least one compound selected from the group consisting of propane, n-butane, isobutane and dimethyl ether. 3. The composition according to claim 2, where the azeotropic or almost azeotropic component is selected from the group consisting of:
about 1 wt.% to about 80 wt.% HFC-1234yf, about 1 wt.% to about 80 wt.% HFC-134a and about 19 wt.% to about 98 wt.% propane;
about 1 wt.% to about 98 wt.% HFC-1234yf, about 1 wt.% to about 98 wt.% HFC-134a and about 1 wt.% to about 30 wt.% n-butane;
about 1 wt.% to about 98 wt.% HFC-1234yf, about 1 wt.% to about 98 wt.% HFC-134a and about 1 wt.% to about 30 wt.% isobutane; and
about 1 wt.% to about 98 wt.% HFC-1234yf, about 1 wt.% to about 98 wt.% HFC-134a and about 1 wt.% to about 40 wt.% dimethyl ether. 4. The composition according to claim 3, where the specified azeotropic component is selected from the group consisting of:
about 70.4 wt.% HFC-1234yf and about 29.6 wt.% HFC-134a having a vapor pressure of about 18.4 psia (127 kPa) at a temperature of about -25 ° C;
about 60.3 wt.% HFC-1234yf, about 35.2 wt.% HFC-134a, and about 4.5 wt.% n-butane having a vapor pressure of about 18.58 psia (128 kPa) at a temperature of about - 25 ° C; and
about 24.0 wt.% HFC-1234yf, about 67.9 wt.% HFC-134a, and about 8.1 wt.% dimethyl ether having a vapor pressure of about 17.21 psia (110 kPa) at a temperature of about -25 ° C. 5. The composition according to claim 1, containing from about 30 wt.% To about 99 wt.% HFC-1234yf and from about 70 wt.% To about 1 wt.% HFC-134a. 6. The composition according to claim 1, containing about 90 wt.% HFC-1234yf and about 10 wt.% HFC-134a. 7. The composition according to claim 1, comprising an azeotropic component containing 70.4 wt.% HFC-1234yf and 29.6 wt.% HFC-134a, having a vapor pressure of about 18.4 psia (127 kPa) at a temperature of about -25 ° C. 8. The composition according to claim 1, containing a lubricant selected from the group consisting of esters of polyhydric alcohols, polyalkylene glycols, polyvinyl ethers, mineral oil, alkylbenzenes, synthetic paraffins, synthetic naphthenes and poly (alpha) olefins. 9. The composition according to claim 1, containing an isotopic indicator selected from the group consisting of hydrofluorocarbons, deuterated hydrocarbons, deuterated hydrofluorocarbons, perfluorocarbons, fluoroethers, brominated compounds, iodinated compounds, alcohols, aldehydes, ketones, nitrous oxide (N ₂ O) and their combinations. 10. The composition according to claim 9, containing an isotopic indicator selected from the group consisting of CD ₃ CD ₃ , CD ₃ CD ₂ CD ₃ , CD ₂ F ₂ , CF ₃ CD ₂ CF ₃ , CD ₂ FCF ₃ , CD ₃ CF ₃ , CDF ₂ CF ₃ , CF ₃ CDFCF ₃ , CF ₃ CF ₂ CDF ₂ , CDF ₂ CDF ₂ , CF ₃ CF ₂ CD ₃ , CF ₃ CD ₂ CH ₃ , CF ₂ CH ₂ CD ₃ , CF ₃ CF ₃ , cyclo-CF ₂ CF ₂ CF ₂ -, CF ₃ CF ₂ CF ₃ , cyclo-CF ₂ CF ₂ CF ₂ CF ₂ -, CF ₃ CF ₂ CF ₂ CF ₃ , CF ₃ CF (CF ₃ ) ₂ , cyclo-CF (CF ₃ ) CF ₂ CF (CF ₃ ) CF ₂ -, trans-cyclo-CF ₂ CF (CF ₃ ) CF (CF ₃ ) CF ₂ -, cis-cyclo-CF ₂ CF (CF ₃ ) CF (CF ₃ ) CF ₂ -, CF ₃ OCHF ₂ , CF ₃ OCH ₂ F, CF ₃ OCH ₃ , CF ₃ OCHFCF ₃ , CF ₃ OCH ₂ CF ₃ , CF ₃ OCH ₂ CHF ₂ , CF ₃ CH ₂ OCHF ₂ , CH ₃ OCF ₂ CF ₃ , CH ₃ CF ₂ OCF ₃ , CF ₃ CF ₂ CF ₂ OCHFCF ₃ , CF ₃ CF ₂ CF ₂ OCF (CF ₃ ) CF ₂ OCHFCF ₃ , CHF ₃ , CH ₂ FCH ₃ , CHF ₂ CH ₃ , CHF ₂ CHF ₂ , CF ₃ CHFCF ₃ , CF ₃ CF ₂ CHF ₂ , CF ₃ CF ₂ CH ₂ F, CHF ₂ CHFCF ₃ , CF ₃ CH ₂ CF ₃ , CF ₃ CF ₂ CH ₃ , CF ₃ CH ₂ CHF ₂ , CHF ₂ CF ₂ CH ₃ , CF ₃ CHFCH ₃ , CF ₃ CH ₂ CH ₃ , CH ₃ CF ₂ CH ₃ , CH ₃ CHFCH ₃ , CH ₂ FCH ₂ CH ₃ , CHF ₂ CF ₂ CF ₂ CF ₃ , (CF ₃ ) ₂ CHCF ₃ , CF ₃ CH ₂ CF ₂ CF ₃ , CHF ₂ CF ₂ CF ₂ CHF ₂ , CH ₃ CF ₂ CF ₂ CF ₃ , CF ₃ CHFCHFCF ₂ CF ₃ , perfluoromethylcyclopentane, perfluoromethylcyclohexane, perfluorodimethylcyclohexane (ortho , meta or para) perftoretiltsiklogesana, perfluoroindan, perftortrimetiltsiklogesana and its isomers perftorizopropiltsiklogeksana, cis-perfluorodecalin, trans-perfluorodecalin, cis- or trans-isomers thereof and perftormetildekalina, CH ₃ Br, CH ₂ FBr, CHF ₂ Br, CHFBr ₂ CHBr ₃ , CH ₂ BrCH ₃ , CHBr = CH ₂ , CH ₂ BrCH ₂ Br, CFBr = CHF, CF ₃ I, CHF ₂ I, CH ₂ FI, CF ₂ ICH ₂ F, CF ₂ ICHF ₂ , CF ₂ ICF ₂ I, C ₆ F ₅ I, ethanol, n-propanol, isopropanol, acetone, n-propanal, n-butanal, methyl ethyl ketone, nitrous oxide and combinations thereof. 11. The composition according to claim 1, containing a compatibility agent selected from the group consisting of:
a) polyoxyalkylene glycol ethers represented by the formula R ¹ [(OR ² ) _x OR ³ ] _y , where x is an integer from 1 to 3; y is an integer from 1 to 4; R ¹ selected from hydrogen and aliphatic hydrocarbon radicals having from 1 to 6 carbon atoms and at the binding sites; R ² selected from aliphatic hydrocarbylene radicals having from 2 to 4 carbon atoms; R ³ selected from hydrogen and aliphatic and alicyclic hydrocarbon radicals having from 1 to 6 carbon atoms; where at least one of R ¹ and R ^{3 is} selected from said hydrocarbon radicals; and wherein said polyoxyalkylene glycol ethers have a molecular weight of from about 100 to about 300 atomic units of mass;
b) amides represented by the formulas R ¹ C (O) NR ² R ³ and cyclo- [R ⁴ CON (R ⁵ ) -], where R ¹ , R ² , R ³ and R ^{5 are} independently selected from aliphatic and alicyclic hydrocarbon radicals having from 1 to 12 carbon atoms and not more than one aromatic radical having from 6 to 12 carbon atoms; R ^{4 is} selected from aliphatic hydrocarbylene radicals having from 3 to 12 carbon atoms; and where these amides have a molecular weight of from about 100 to about 300 atomic units of mass;
c) ketones represented by the formula R ¹ C (O) R ² , where R ¹ and R ^{2 are} independently selected from aliphatic, alicyclic and aryl hydrocarbon radicals having from 1 to 12 carbon atoms, and where said ketones have a molecular weight of from about 70 up to about 300 atomic units of mass;
d) nitriles represented by the formula R ¹ CN, where R ^{1 is} selected from aliphatic, alicyclic or aryl hydrocarbon radicals having from 5 to 12 carbon atoms, and where said nitriles have a molecular weight of from about 90 to about 200 atomic mass units;
e) chlorocarbons represented by the formula RCl _x , where x is 1 or 2; R is selected from aliphatic and alicyclic hydrocarbon radicals having from 1 to 12 carbon atoms; and where these chlorocarbons have a molecular weight of from about 100 to about 200 atomic units of mass;
f) aryl ethers represented by the formula R ¹ OR ² ,
where R ¹ selected from aryl hydrocarbon radicals having from 6 to 12 carbon atoms; R ² selected from aliphatic hydrocarbon radicals having from 1 to 4 carbon atoms; and wherein said aryl ethers have a molecular weight of from about 100 to about 150 atomic units of mass;
g) 1,1,1-trifluoroalkanes represented by the formula CF ₃ R ¹ , wherein R ^{1 is} selected from aliphatic and alicyclic hydrocarbon radicals having from about 5 to about 15 carbon atoms;
h) fluoroethers represented by the formula R ¹ OCF ₂ CF ₂ H, where R ^{1 is} selected from aliphatic, alicyclic and aromatic hydrocarbon radicals having from about 5 to about 15 carbon atoms; or where said fluoroethers are derived from fluoroolefins and polyols, where said fluoroolefins are of type CF ₂ = CXY, where X is hydrogen, chloro or fluoro, and Y is chloro, fluoro, CF ₃ or OR _f , where R _f is CF ₃ , C ₂ F ₅ or C ₃ F ₇ ; and said polyhydric alcohols are linear or branched, where said linear polyhydric alcohols are of type HOCH ₂ (CHOH) _x (CRR ′) _y CH ₂ OH, where R and R ′ are hydrogen, CH ₃ or C ₂ H ₅ , x is an integer a number from 0 to 4, y is an integer from 0 to 3, and z is either zero or 1, and where these branched polyhydric alcohols are of type C (OH) _t (R) _u (CH ₂ OH) _v [(CH ₂ ) _m CH ₂ OH] _w , where R can be hydrogen, CH ₃ or C ₂ H ₅ , m is an integer from 0 to 3, t and u are 0 or 1, v and w are integers from 0 to 4 , and also where t + u + v + w = 4; and
i) lactones represented by structures [B], [C] and [D]:

where R ¹ -R ⁸ independently selected from hydrogen, linear, branched, cyclic, bicyclic, saturated and unsaturated hydrocarbyl radicals; and the molecular weight is from about 100 to about 300 atomic units of mass; and
j) esters represented by the general formula R ¹ CO ₂ R ² where R ¹ and R ^{2 are} independently selected from linear and cyclic, saturated and unsaturated, alkyl and aryl radicals; and wherein said esters have a molecular weight of from about 80 to about 550 atomic units of mass. 12. The composition according to claim 1, where the ultraviolet fluorescent dye is selected from the group comprising naphthalimides, perylene, coumarins, anthracenes, phenanthracenes, xanthenes, thioxanthenes, naphthoxantenes, fluoresceins, derivatives of these dyes, and combinations thereof. 13. The composition according to item 12, containing at least one solvent agent selected from the group consisting of hydrocarbons, dimethyl ether, ethers of polyoxyalkylene glycol, amides, ketones, nitriles, chlorocarbons, esters, lactones, aryl ethers, hydrofluoroethers and 1,1,1-trifluoroalkanes. 14. The composition according to item 13, where the specified solvent agent is selected from the group consisting of:
a) polyoxyalkylene glycol ethers represented by the formula R ¹ [(OR ² ) _x OR ³ ] _y , where x is an integer from 1 to 3; y is an integer from 1 to 4; R ¹ selected from hydrogen and aliphatic hydrocarbon radicals having from 1 to 6 carbon atoms and at the binding sites; R ² selected from aliphatic hydrocarbylene radicals having from 2 to 4 carbon atoms; R ³ selected from hydrogen and aliphatic and alicyclic hydrocarbon radicals having from 1 to 6 carbon atoms; where at least one of R ¹ and R ^{3 is} selected from said hydrocarbon radicals; and wherein said polyoxyalkylene glycol ethers have a molecular weight of from about 100 to about 300 atomic units of mass;
b) amides represented by the formulas R ¹ C (O) NR ² R ³ and cyclo- [R ⁴ CON (R ⁵ ) -], where R ¹ , R ² , R ³ and R ^{5 are} independently selected from aliphatic and alicyclic hydrocarbon radicals having from 1 to 12 carbon atoms and not more than one aromatic radical having from 6 to 12 carbon atoms; R ^{4 is} selected from aliphatic hydrocarbylene radicals having from 3 to 12 carbon atoms; and where these amides have a molecular weight of from about 100 to about 300 atomic units of mass;
c) ketones represented by the formula R ¹ C (O) R ² , where R ¹ and R ^{2 are} independently selected from aliphatic, alicyclic and aryl hydrocarbon radicals having from 1 to 12 carbon atoms, and where said ketones have a molecular weight of from about 70 up to about 300 atomic units of mass;
d) nitriles represented by the formula R ¹ CN, where R ^{1 is} selected from aliphatic, alicyclic or aryl hydrocarbon radicals having from 5 to 12 carbon atoms, and where said nitriles have a molecular weight of from about 90 to about 200 atomic mass units;
e) chlorocarbons represented by the formula RCl _x , where x is 1 or 2; R is selected from aliphatic and alicyclic hydrocarbon radicals having from 1 to 12 carbon atoms; and where these chlorocarbons have a molecular weight of from about 100 to about 200 atomic units of mass;
f) aryl ethers represented by the formula R ¹ OR ² , where R ^{1 is} selected from aryl hydrocarbon radicals having from 6 to 12 carbon atoms; R ² selected from aliphatic hydrocarbon radicals having from 1 to 4 carbon atoms; and wherein said aryl ethers have a molecular weight of from about 100 to about 150 atomic units of mass;
g) 1,1,1-trifluoroalkanes represented by the formula CF ₃ R ¹ , wherein R ^{1 is} selected from aliphatic and alicyclic hydrocarbon radicals having from about 5 to about 15 carbon atoms;
h) fluoroethers represented by the formula R ¹ OCF ₂ CF ₂ H, where R ^{1 is} selected from aliphatic, alicyclic and aromatic hydrocarbon radicals having from about 5 to about 15 carbon atoms; or where said fluoroethers are derived from fluoroolefins and polyols, where said fluoroolefins are of type CF ₂ = CXY, where X is hydrogen, chloro or fluoro, and Y is chloro, fluoro, CF ₃ or OR _f , where R _f is CF ₃ , C ₂ F ₅ or C ₃ F ₇ ; and said polyols are
linear or branched, wherein said linear polyols are of type HOCH ₂ (CHOH) _x (CRR ′) _y CH ₂ OH, where R and R ′ are hydrogen, CH ₃ or C ₂ H ₅ , x is an integer from 0 to 4 , y is an integer from 0 to 3, and z is either zero or 1, and where these branched polyhydric alcohols are of type C (OH) _t (R) _u (CH ₂ OH) _v [(CH ₂ ) _m CH ₂ OH] _w , where R can be hydrogen, CH ₃ or C ₂ H ₅ , m is an integer from 0 to 3, t and u are 0 or 1, v and w are integers from 0 to 4, and where t + u + v + w = 4; and
i) lactones represented by structures [B], [C] and [D]:

where R ¹ -R ⁸ independently selected from hydrogen, linear, branched, cyclic, bicyclic, saturated and unsaturated hydrocarbyl radicals; and the molecular weight is from about 100 to about 300 atomic units of mass; and
j) esters represented by the general formula R ¹ CO ₂ R ² where R ¹ and R ^{2 are} independently selected from linear and cyclic, saturated and unsaturated, alkyl and aryl radicals; and wherein said esters have a molecular weight of from about 80 to about 550 atomic units of mass. 15. The composition according to claim 1, containing a stabilizer, a water absorber or an odor suppressing agent. 16. The composition of claim 15, wherein said stabilizer is selected from the group consisting of nitromethane, hindered phenols, hydroxylamines, thiols, phosphites and lactones. 17. The cooling method, where the specified method includes evaporation, the composition according to any one of claims 1 to 7 near the object to be cooled, followed by condensation of the specified composition. 18. A heating method, wherein said method comprises condensing said composition according to any one of claims 1 to 7 near an object to be heated, followed by evaporation of said composition. 19. The method for detecting a composition according to item 12 in a compressor refrigeration unit, air conditioner or heat pump apparatus, wherein said method comprises supplying said composition to said apparatus and using suitable means to determine said composition at a leak point or near a leak point in said apparatus. 20. The method of applying the composition according to any one of claims 1 to 7 as a liquid coolant, where the method includes transferring said composition from a heat source to a heat sink. 21. Refrigeration units, air conditioners or heat pumps containing the composition according to any one of claims 1 to 7. 22. Refrigeration units, air conditioners or heat pumps according to item 21, including mobile or stationary air conditioners. 23. Foaming agent containing the composition according to any one of claims 1 to 7. 24. A method of producing foam, including:
(a) adding to the foamable composition a composition according to any one of claims 1 to 4; and
(b) the interaction of the expandable composition under conditions effective to obtain a foam. 25. A sprayable composition comprising a composition according to any one of claims 1 to 7. 26. A method for producing aerosol products, comprising the step of adding a composition according to any one of claims 1 to 7 to the active ingredients in an aerosol container, where the composition acts as a propellant. 27. A method of suppressing a flame, comprising reacting a flame with a liquid containing a composition according to any one of claims 1 to 7. 28. A method of extinguishing or suppressing a flame by complete flooding, including:
(a) obtaining an agent containing a composition according to any one of claims 1 to 7;
(b) placing the agent in a pressure relief device; and
(c) discharging the agent to a site to extinguish or suppress fire in that area. 29. A method of treating a site with an inert gas to prevent fire or explosion, including:
(a) obtaining an agent containing a composition according to any one of claims 1 to 7;
(b) placing the agent in a pressure relief device; and
(c) discharging the agent to a site to prevent fire or explosion.