CN1082089A

CN1082089A - Comprise 1,1,2,2, the refrigerant compositions of-Tetrafluoroethane

Info

Publication number: CN1082089A
Application number: CN 93108526
Authority: CN
Inventors: B·H·迈纳; D·M·佩特龙; D·L·克卢格; B·S·龙格
Original assignee: EI Du Pont de Nemours and Co
Current assignee: EIDP Inc
Priority date: 1992-07-15
Filing date: 1993-07-13
Publication date: 1994-02-16
Also published as: TW336952B; MX9304247A

Abstract

The present invention relates to refrigerant compositions, comprise 1,1,2,2 ,-the Tetrafluoroethane and second component 1,1,1,2,2,3,3-seven fluorine propylene, 1,1,1,2,2-pentafluoropropane, three (trifluoromethyl) amine, five is fluoridized trifluoromethyl sulphur, cyclopropane, is crossed fluorine cyclopropane, fluoroethane, 1,1,1 trifluoro propane, 2,2 ,-difluoropropane, 2-fluoropropane or 1-fluoropropane.The present invention also relates to comprise 1,1,2 of significant quantity, 2-Tetrafluoroethane and a kind of Azeotrope compositions or the Azeotrope-like compositions that form with above-mentioned second component.

Description

Comprise 1,1,2,2, the refrigerant compositions of-Tetrafluoroethane

The present invention relates to comprise 1,1,2, the 2-Tetrafluoroethane is the refrigerant compositions of a component.The present invention also relates to comprise 1,1,2, swelling agent, aerosol propellants, refrigeration agent, heat-transfer material, gaseous dielectric, fire-fighting medium, energy cycle working fluid, polymerisation medium, the particle that the composition binary azeotropic of 2-or the class binary azeotropic, described composition also can be used as sanitising agent, polyolefine and polyurethanes removed the substituting agent of fluid, carrier fluid, grinding buffer reagent and siccative.

Fluoridizing hydro carbons has many purposes, and one of them is as refrigeration agent.This class refrigeration agent comprises Refrigerant 12 (CFC-12) and monochlorodifluoromethane (HCFC-22).

In recent years, pointed out that some drains into the atmospheric hydrocarbon refrigerant meeting reverse influence stratospheric ozone layer of fluoridizing.Though this opinion is not confirmed as yet fully, is just starting the motion of using and producing of control some chloro-fluoro-carbon kind (CFCs) and Hydrochlorofluorocarbons class (HCFCs) under international agreement.

Therefore, having to seek development, and to consume the ozone ability than existing refrigeration agent low, still can reach the refrigeration agent that can accept refrigeration performance simultaneously.Advised replacing CFCs and HCFs with hydrogen fluorohydrocarbon class (HFCs), because HFCs is not chloride, the therefore tool ability that consumes ozone not.

In refrigeration application, refrigeration agent is everlasting operating period through descending column leakage and losing: shaft seal point, coiled pipe connection, weld and disruptive pipeline.In addition, refrigeration agent also may drain in the atmosphere in maintenance refrigeration equipment process.If this refrigeration agent is not a kind of pure component or a kind of azeotropic or Azeotrope-like compositions, this refrigeration agent is when leaking from refrigeration equipment or draining into the atmosphere, and the composition of this refrigeration agent will change, and this can cause refrigeration agent to become flammable or make the refrigeration performance variation.

Therefore, need to use single fluorinated hydrocarbons or comprise one or more a kind of azeotropic or Azeotrope-like compositions of fluoridizing hydro carbons to be used as refrigeration agent.

Fluoridize hydro carbons and also can be used as a kind of sanitising agent or cleaning as the solvent of electronic circuit board.Wish that this sanitising agent is azeotropic or class azeotropic, because in steam deoils operation, for last rinsing cleaning, this sanitising agent usually will be by redistillation and is utilized.

The Azeotrope compositions or the Azeotrope-like compositions that contain a kind of fluorinated hydrocarbons also are useful in following situation: at the urethane of airtight vesicle; in the manufacturing of phenolic aldehyde and thermoplastic foam as the air blowing agent; make propelling agent in the aerosol; make heat-transfer material; gaseous dielectric; fire-fighting medium; the energy cycle working fluid; for example be used for heat pump; the situation medium of polyreaction; as remove the particulate fluid from the metallic surface; as carrier fluid; for example can be used for the film of lubricant is placed on the metal parts; perhaps be used for removing the grinding buffer compounds, as the surrogate that removes the siccative that anhydrates from for example jewelry or metal parts, as the demonstration protective material in the custom circuit manufacturing technology from the surfaces such as metal of polishing as grinding buffer reagent; comprise chlorine type developer; and when using with for example 1 or trieline and so on reagent as the stripper of photoresist material.

The present invention relates to find to comprise 1,1,2 that the 2-Tetrafluoroethane is as the refrigerant compositions of a component.Swelling agent, aerosol propellants, refrigeration agent, heat-transfer material, gaseous dielectric, fire-fighting medium, energy cycle working fluid, polymerisation medium, the particle that said composition also can be used as sanitising agent, polyolefine and polyurethanes removed the substituting agent of fluid, carrier fluid, grinding buffer reagent and siccative.And, the present invention relates to find following composition, promptly comprise 1,1,2 of significant quantity, binary azeotropic or Azeotrope-like compositions that 2-Tetrafluoroethane and a kind of second component form.

The present invention relates to 1,1,2,2-Tetrafluoroethane (HFC-134), the composition of boiling point=-19.7 ℃ and at least a following component:

1.1,1,1,2,2,3,3-heptafluoro-propane (HFC-227ca, or CHF2CF2CF3 boiling point-17.0 ℃),

2.1,1,1,2,2-pentafluoropropane (HFC-245cb or CF3CF2CH3, boiling point-17.5 ℃),

3. three (trifluoromethyl) amine (CF3) ₃N, boiling point=-6.5 ℃),

4. five fluoridize fluoroform sulphur (SF5CF3, boiling point=-20.4 ℃),

5. cyclopropane (C3H6, boiling point=32.8 ℃),

6. cross fluorine cyclopropane (C216, or CF2CF2CF(annular), boiling point=-31.5 ℃),

7. fluoroethane (HFC-161, or CH3CFH2, boiling point=-37.7 ℃),

8.1,1,1-trifluoro propane (HFC-263fb, or CH3CH2CF, boiling point=-13.0 ℃),

9.2,2 difluoropropane (HFC-272ca, or CH3CF2CH3, boiling point-0.4 ℃),

10.2-fluoro-propane (HFC-281ea, or CH3CHFCH3, boiling point=-9.4 ℃),

11.1-fluoro-propane (HFC-281fa, or CH3CH2CH2F, boiling point=-2.5 ℃).

HFC-227ca(1,1,1,2,2,3,3-heptafluoro-propane, CAS registration number 2252-84-8) by 2,2,3,3-tetrafluoro propionic acid and SF4 react in the presence of boron trifluoride and make.See people such as Hasek, J.Am.Chem.Soc., V.5, PP.543-551(1960).

HFC-245cb(CAS registration number 1814-88-6) can in the presence of triglyme, react by methyl chloride and cesium fluoride and tetrafluoroethylene and make, see Yale, United States Patent (USP) 3,381,042.

(CF3) ₃N(CAS registration number 432-03-1) by Trimethylamine 99 electrochemical fluorination and making in the presence of anhydrous hydrogen fluoride, sees Kauck and Simons, United States Patent (USP) 2616927.

SF5CF3(CAS registration number 373-80-8) by the electrochemical fluorination preparation of thiocarbamide, see Schmeisser and Huber, Z.Naturforsch., Sect.B, V.21, PP.285-286(1966)

C216(CAS registration number 931-91-9) makes by tetrafluoroethylene photodissociation in the presence of the ethene thinner, see Mastrangelo, United States Patent (USP) 3,228,864.

HFC-263fb(CAS registration number 421-07-8) by 1,1-difluoro propylene and HF make 90-100 ℃ of reaction, see people such as McBee, J.Am.Chem.Soe., V.69, PP.944-947(1947).

HFC-272ca(CAS registration number 420-45-1) by 2, the 2-propylene dichloride is fluoridized with SbF3 and is made, and sees Henne and Renoll, J.Am.Chem.Soc.V.59, PP.2434-2436(1937).

HFC-161(CAS registration number 353-36-6), the HFC-281ea(isopropyl fluoride, CAS registration number 420-26-8), with HFC-281fa(n-propyl fluorine, CAS registration number 460-13-9) by hydrogen fluoride respectively with ethene, propylene and cyclopropane prepared in reaction, see Grosse and Lin, J.Org.Chem, V.3, PP.26-32(1938).

Following composition can be used as refrigeration agent.

Table 1

Composition number

1 1-99wt%HFC-134 1-99Wt%HFC-227ca

2 1-99wt%HFC-134 1-99wt%HFC-245cb

3 5-95wt%HFC-134 5-95wt%(CF3)3N

4 1-99wt%HFC-134 1-99wt%SF5CF3

5 5-95wt%HFC-134 5-95wt% cyclopropane

6 1-99wt%HFC-134 1-99wt%C216

7 1-95wt%HFC-134 5-99wt%HFC-161

8 5-99wt%HFC-134 1-95wt%HFC-263fb

9 5-99wt%HFC-134 1-95wt%HFC-272ca

10 5-99wt%HFC-134 1-95wt%HFC-281ea

11 5-99wt%HFC-134 1-95wt%HFC-281fa

The present invention also relates to find azeotropic or class azeotropic composition, said composition contains HFC-134 and a kind of second component of significant quantity, and wherein second component is HFC-227ca, HFC-245cb, (CF3) N, SF5CF3, cyclopropane, C216, HFC-161, HFC-263fb, HFC-272ca, HFC-281ea and HFC-281fa.

" azeotropic " composition means the azeotropic liquid mixture of two or more materials, and its behavior resembles a kind of one matter.One of method that characterizes a kind of azeotropic component is that promptly mixture distillation liquid/phegma has identical composition, changes and form with steam and this liquid of this liquid portion evaporation or distillation generation.The feature of azeotropic composition is an azeotropic because compare with the zeotrope of same composition, they or show maximum boiling point or show minimum boiling point.

" class azeotropic " composition means the azeotropic of two or more materials or the liquid mixture of substantially constant boiling, its behavior resembles a kind of one matter, one of method that characterizes a kind of Azeotrope-like compositions is steam and this liquid with this liquid portion evaporation or distillation generation, be that mixture distillation liquid/phegma has substantially the same composition, do not change and form.

Have recognized that in this area, a kind of azeotropic or class azeotropic composition are if after the composition of 50wt% is removed with evaporation or boiling, original composition and remove the original composition of 50wt% after poor between the vapour pressure of remaining composition, when weighing, for less than 10% with absolute units.Implication with absolute units is to measure with the pressure unit of knowing in this area, as pound/square inch, normal atmosphere, crust, holder, every square centimeter of dyne, mmhg, inch of water and other suitable term.

Therefore, what comprise among the present invention is the HFC-134 of significant quantity and a kind of composition of second component, wherein second component is HFC-227ca, HFC-245cb, (CF3) 3N, SF5CF3, cyclopropane, C216, HFC-161, HFC-263fb, HFC-272ca, HFC-281ea or HFC-281fa, boiled off or seethe with excitement at former composition like this and vapor away after 50wt% produces remaining composition, the difference of vapour pressure is 10% or littler between former composition and the remaining set compound.

The present invention's azeotropic, azeotropic or class azeotropic composition basically comprises following (all compositions are measured) in the time of 25 ℃:

1.1-99, better 50-90, preferably 69.8wt%HFC-134; 1-99,

Better 10-50, preferably 30.2wt%HFC-227ca.

2.1-99, better 30-80, preferably 54.2wt%HFC-134; 1-99,

Better 20-70, preferably 45.8wt%HFC-245cb.

3.27-84, better 40-70, preferably 56.4wt%HFC-134; 16-73,

Better 30-60, preferably 43.6wt%(CF3) 3N.

4.1-99, better 10-70, preferably 35.9wt%HFC-134; 1-99,

Better 30-90, preferably 64.1wt%SF5CF3.

5.32-79, better 40-70, preferably 55.5wt%HFC-134; 21-68,

Better 30-60, preferably 44.5wt% cyclopropane.

6.1-99, better 10-50, preferably 29.2wt%HFC-134; 1-99,

Better 50-90, preferably 70.8wt%FC-C216.

7.1-84, better 1-50, preferably 11.3wt%HFC-134; 16-99,

Better 50-99, preferably 88.7wt%HFC-161.

8.31-99, better 50-90, preferably 67.2wt%HFC-134; 1-69,

Better 10-50, preferably 32.8wt%HFC-263fb.

9.51-99, better 70-99, preferably 84.0wt%HFC-134; 1-49,

Better 1-30, preferably 16.0wt%HFC-272ca.

10.48-99, better 70-99, preferably 84.7wt%HFC-134; 1-52,

Better 1-30, preferably 15.3wt%HFC-281ea.

11.58-99, better 80-99, preferably 93.8wt%HFC-134; 1-42,

Better 1-20, preferably 6.2wt%HFC-281fa.

For purpose of the present invention, " significant quantity " is defined as each component of the present composition, the amount when forming azeotropic or Azeotrope-like compositions when combining.This definition comprises the quantity of each component, and this quantity can change along with being added in the pressure on the composition, as long as azeotropic or Azeotrope-like compositions continue to exist with this different pressures, but may the boiling point difference.

Therefore, significant quantity for example comprises each component of the composition of the present invention of can weight percentage expressing, under the temperature and pressure beyond describing, forms the consumption of azeotropic or class azeotropic composition here.

For the purpose of discussing, azeotropic or azeotropic implication are also represented azeotropic or azeotropic basically basically.In other words, implication in these terms is included is not only above-mentioned genuine azeotrope, and comprise and contain other composition that these identical components exist in varing proportions, and belong to identical azeotropic system part, be those suitable compositions of Azeotrope-like in nature.As being fully recognized that in this area, the composition that contains with the azeotrope same composition has a scope, it not only shows suitable basically character for refrigeration and other application facet, and can not have in the azeotropic feature or when seething with excitement aspect the isolating tendency, also show and the genuine suitable basically character of Azeotrope compositions.

In fact, it is possible characterizing a kind of constant boiling mixture with following any standard, and this constant boiling mixture can various outward appearances occur, and depends on selected condition.

* this composition may be defined as A, B, C(and D ...) azeotrope, because this term " azeotrope " mean immediately it be determine and be restricted, and to this be that the unique material of azeotropic composition is formed, need the A of significant quantity, B, C(and D ...).

* those skilled in the art knows, and under different pressures, the composition of given azeotrope can change in to a certain degree at least, and pressure change also makes boiling temperature change at least to a certain extent.Therefore, A, B, C(and D ...) a kind of azeotrope represented a kind of relation of unique types, can become along with temperature and/or pressure but form.So, compositing range commonly used, rather than form with fixed and to define azeotrope.

* said composition may be defined as A, B, C(and D ...) specific weight percentage relation or molecular fraction relation, recognize that simultaneously these specific values only point out a kind of specific relation, and in fact, by A, B, C(and D ...) a series of this relation of representative, in fact for a kind of given but be stressed influence and the azeotrope that changes exists.

* A, B, C(and D ...) a kind of characterizing method of azeotrope can be, it is the azeotrope of feature that said composition is defined as with the boiling point under the certain pressure, therefore forming the feature that provides evaluation with a kind of concrete numeral can reasonably limit the scope of the invention, it only is subjected to the restriction of used analytical instrument, and has the accuracy of used analytical instrument.

Azeotrope of the present invention or class are boiled composition can be by any method easily, comprise that mixing required amount prepares.Preferable methods is the amount that weighs up each required component, in suitable containers they is mixed then.

Provide explanation specific examples of the present invention below, unless otherwise indicated, all percentage ratios by weight.Should be appreciated that these examples as just illustration purpose, are not to limit the scope of the invention by any way.

Example 1 is studied mutually

Under 25 ℃ normal temperature, to studies show that mutually of following composition, following composition is an azeotrope, forms in these compositions to change, and has measured its vapour pressure.

The composition vapour pressure

psia(kPa)

1 69.8wt%HFC-134 30.2wt%HFC-227ca 77.8(537)

2 54.2wt%HFC-134 45.8wt%HFC-245cb 89.7(619)

3 56.4wt%HFC-134 43.6wt%(CF ₃) ₃N 92.3(636)

4 35.9wt%HFC-134 64.1wt%SF ₅CF ₃94.8(653)

5 55.5wt%HFC-134 44.5wt% cyclopropane 147.4 (1016)

6 29.2wt%HFC-134 70.8wt%C216 103.9(716)

7 11.3wt%HFC-134 88.7wt%HFC-161 130.5(900)

8 67.2wt%HFC-134 32.8wt%HFC-263fb 87.3(602)

9 84.0wt%HFC-134 16.0wt%HFC-272ca 80.3(554)

10 84.7wt%HFC-134 15.3wt%HFC-281ea 81.6(563)

11 93.8wt%HFC-134 6.2wt%HFC-281fa 76.9(530)

Vapour leakage is to the influence of vapour pressure during 2 25 ℃ of examples

In the time of 25 ℃,, measure the vapour pressure of composition with a container splendid attire starting composition.Allow said composition release in container, keeping temperature is 25 ℃, is removed until the 50wt% of starting composition, at this moment measures the vapour pressure of staying the composition in the container, and the result is summarized as follows.

Refrigeration 0wt% has evaporated 50wt% and has evaporated the % steam

Composition psia (kPa) psia (kPa) presses variation

HFC-134/HFC-227ca

99.0/1.0 76.2(525) 76.2(525) 0

90.0/10.0 77.1(532) 77.0(531) 0.1

69.8/30.2 77.8(537) 77.8(537) 0

50.0/50.0 77.1(532) 76.9(530) 0.3

1.0/99.0 64.3(443) 64.2(443) 0.2

HFC-134/HFC-245cb

99.0/1.0 77.0(531) 76.4(527) 0.8

80.0/20.0 86.6(597) 84.4(582) 2.5

54.2/45.8 89.7(618) 89.7(618) 0

30.0/70.0 86.9(599) 84.7(584) 2.5

1.0/99.0 68.6(473) 67.9(468) 1.0

HFC-134/(CF ₃) ₃N

84.0/16.0 89.5(617) 80.7(557) 9.8

70.0/30.0 91.8(633) 90.5(624) 1.4

56.4/43.6 92.3(636) 92.3(636) 0

40.0/60.0 91.3(629) 89.5(617) 2.0

27.0/73.0 88.1(607) 79.6(549) 9.6

HFC-134/SF ₅CF ₃

99.0/1.0 76.9(530) 76.3(526) 0.8

70.0/30.0 90.2(622) 87.0(600) 3.5

35.9/64.1 94.8(654) 94.8(654) 0

10.0/90.0 89.3(616) 87.7(605) 1.8

1.0/99.0 82.2(567) 81.8(564) 0.5

The HFC-134/ cyclopropane

79.0/21.0 142.9(985) 128.9(889) 9.8

70.0/30.0 146.2(1008) 143.0(986) 2.2

55.5/44.5 147.4(1016) 147.4(1016) 0

40.0/60.0 146.8(1012) 144.8(998) 1.4

32.0/68.0 146.0(1007) 133.0(917) 8.9

HFC-134/C216

99.0/1.0 77.1(532) 76.4(527) 0.9

50.0/50.0 101.7(701) 100.3(692) 1.4

29.2/70.8 103.9(716) 103.9(716) 0

10.0/90.0 100.8(695) 100.0(689) 0.8

1.0/99.0 95.8(661) 95.6(659) 0.2

HFC-134/HFC-161

84.0/16.0 105.7(729) 95.2(656) 9.9

50.0/50.0 125.9(868) 123.8(854) 1.7

11.3/88.7 130.5(900) 130.5(900) 0

1.0/99.0 130.2(898) 130.2(898) 0

HFC-134/HFC-263fb

31.0/69.0 81.2(560) 73.4(506) 9.6

50.0/50.0 86.0(593) 84.5(583) 1.7

67.2/32.8 87.3(602) 87.3(602) 0

90.0/10.0 83.3(574) 81.0(558) 2.8

99.0/1.0 77.1(532) 76.5(527) 0.8

HFC-134/HFC-272ca

51.0/49.0 75.6(521) 68.4(472) 9.5

70.0/30.0 79.2(546) 78.0(538) 1.5

84.0/16.0 80.3(554) 80.3(554) 0

99.0/1.0 76.8(530) 76.5(527) 0.4

HFC-134/HFC-281ea

48.0/52.0 74.0(510) 66.7(460) 9.9

70.0/30.0 80.0(552) 78.6(542) 1.7

84.7/15.3 81.6(563) 81.6(563) 0

99.0/1.0 77.1(532) 76.7(529) 0.5

HFC-134/HFC-281fa

58.0/42.0 68.9(475) 62.2(429) 9.7

80.0/20.0 75.1(518) 74.0(510) 1.5

93.8/6.2 76.9(530) 76.9(530) 0

99.0/1.0 76.4(527) 76.3(526) 0.1

The result of this example shows that these compositions are that azeotropic or class are boiled because after the former composition of 50wt% is removed, the remaining set compound in the time of 25 ℃ vapour pressure and the vapour pressure of former composition differ in about 10%.

Example 3 refrigerant performances

Following table shows the performance of refrigeration agent of the present invention.Data are based on following condition:

7.2 ℃ of evaporator temperatures (45.0)

54.4 ℃ of condenser temperatures (130.0)

46.1 ℃ of supercooling temperatures (115.0)

Return 18.3 ℃ of gas temperatures (65.0)

Compressor efficiency is 75%.

Novel composition of the present invention comprises azeotropic or class azeotropic composition, can be used for producing refrigeration, and method is with the said composition condensation, is treating to evaporate this condensation product around the cold object then.This novel composition also can be used for producing heat, and method is near this refrigeration agent of condensation heated material, evaporates this refrigeration agent then.

Except that being used for refrigeration, new azeotropic of the present invention or basically azeotropic composition also be of value to swelling agent and energy cycle working fluid as aerosol propellants, heat-transfer material, gaseous dielectric, fire-fighting medium, polyolefine and polyurethanes.

Additive composition

Can also add other component in above-mentioned azeotropic or the class azeotropic composition, as:

The fat of boiling point between-60-+30 ℃ belongs to hydrocarbon,

The hydrogen fluorine carbon alkane of boiling point between-60-+30 ℃,

The hydrofluoropropane of boiling point between-60-+30 ℃,

The hydro carbons ester of boiling point between-60-+30 ℃,

The Hydrochlorofluorocarbons of boiling point between-60-+30 ℃,

The hydrogen fluorohydrocarbon of boiling point between-60-+30 ℃,

The hydrogen chlorocarbon of boiling point between-60-+30 ℃,

Chlorination carbon and cross fluorinated compound, and do not change the character of composition basically, comprise its azeotropic behavior.The example of these components comprises:

Compound molecule formula boiling point, ℃

HC-290 CH3?CH2?CH3 -42

HCFC-124 CHCl?FCF3 -12

FC-600 CH3?CH2?CH2?CH3 0

Various additives also can add in the novel composition of the present invention for various purposes as lubricant, anticorrosive agent, stablizer, dyestuff and other suitable material, as long as they do not have disadvantageous effect to the predetermined application of said composition.Preferred lubricant comprises that molecular weight is greater than 250 ester class.

Claims

1, a kind of refrigerant compositions comprises 1,1,2,2-Tetrafluoroethane and 1,1,1,2,2,3,3-heptafluoro-propane, 1,1,1,2,2-pentafluoropropane, three (trifluoromethyl) amine, five is fluoridized trifluoromethyl sulphur, cyclopropane, is crossed fluorine cyclopropane, fluoroethane, 1,1,1-trifluoro propane, 2,2-difluoropropane, 2-fluoropropane or 1-fluoropropane.

2,1,1 of significant quantity, 2,2-Tetrafluoroethane and second kind of a kind of Azeotrope compositions or Azeotrope-like compositions that component forms, wherein said second component is 1,1,1,2,2,3,3-heptafluoro-propane, 1,1,1,2,2-pentafluoropropane, three (trifluoromethyl) amine, five is fluoridized trifluoromethyl sulphur, cyclopropane, is crossed fluorine cyclopropane, fluoroethane, 1,1,1-trifluoro propane, 2,2-difluoropropane, 2-fluoropropane or 1-fluoropropane.

3, the Azeotrope compositions of claim 2 or Azeotrope-like compositions, described composition comprises:

1-99wt%1,1,2,2-Tetrafluoroethane and 1-99wt%1,1,1,2,2,3,3-heptafluoro-propane;

1-99wt%1,1,2,2-Tetrafluoroethane and 1-99wt%1,1,1,2,2-pentafluoropropane;

27-84wt%1,1,2,2-Tetrafluoroethane and 16-73wt% three (trifluoromethyl) amine;

1-99wt%1,1,2,2-Tetrafluoroethane and 1-99wt% five fluoridize trifluoromethyl sulphur;

32-79wt%1,1,2,2-Tetrafluoroethane and 21-68wt% cyclopropane;

1-99wt%1,1,2,2-Tetrafluoroethane and 1-99wt% cross the fluorine cyclopropane;

1-84wt%1,1,2,2-Tetrafluoroethane and 16-99wt% fluoroethane;

31-99wt%1,1,2,2-Tetrafluoroethane and 1-69wt%1,1,1-trifluoro propane;

51-99wt%1,1,2,2-Tetrafluoroethane and 1-49wt%2,2-difluoropropane;

48-99wt%1,1,2,2-Tetrafluoroethane and 1-52wt%2-fluoro-propane;

Or 58-99wt%1,1,2,2-Tetrafluoroethane and 1-42wt%1-fluoro-propane.

4, the Azeotrope compositions of claim 2 or Azeotrope-like compositions, described composition comprises:

50-90wt%1,1,2,2-Tetrafluoroethane and 10-50wt%1,1,1,2,2,3,3-heptafluoro-propane;

30-80wt%1,1,2,2-Tetrafluoroethane and 20-70wt%1,1,1,2,2-pentafluoropropane;

40-70wt%1,1,2,2-Tetrafluoroethane and 30-60wt% three (trifluoromethyl) amine;

10-70wt%1,1,2,2-Tetrafluoroethane and 30-90wt% five fluoridize trifluoromethyl sulphur;

40-70wt%1,1,2,2-Tetrafluoroethane and 30-60wt% cyclopropane;

10-50wt%1,1,2,2-Tetrafluoroethane and 50-90wt% cross the fluorine cyclopropane;

1-50wt%1,1,2,2-Tetrafluoroethane and 50-90wt% fluoroethane;

50-90wt%1,1,2,2-Tetrafluoroethane and 10-50wt%1,1,1-trifluoro propane;

70-99wt%1,1,2,2-Tetrafluoroethane and 1-30wt%2,2-difluoropropane;

70-99wt%1,1,2,2-Tetrafluoroethane and 1-30wt%2-fluoro-propane;

Or 80-99wt%1,1,2,2-Tetrafluoroethane and 1-20wt%1-fluoro-propane.

5, a kind of method that produces refrigeration comprises the arbitrary composition condensation with claim 1-4, evaporates said composition then around object to be cooled.

6, a kind of method that produces heat comprises the arbitrary composition condensation around heated material with claim 1-4, evaporates said composition then around heated material.