TWI376409B - Fluorinated alkene refrigerant compositions - Google Patents

Description

1376409 IX. Description of the Invention: [Technical Field of the Invention] The present invention relates to a composition for compressing a refrigeration, an air conditioner, and a heat pump system as a refrigerant fluid. [Prior Art] Because of a chlorine-containing refrigerant, such as chlorofluorocarbonization The properties of the (CFC's), hydrogen gas carbides (HCF's) and the like deplete the ozone layer, and thus the use of these compounds as cold beads for air conditioning and cold bed systems is gradually unpopular. Therefore, it is increasingly desirable to use a chlorine-free refrigerant compound that does not deplete the ozone layer, such as hydrofluorocarbons (HFC's), to replace the gas-containing refrigerant to improve the gas-containing refrigeration system. In order for any substituted material to be used in the relevant frozen composition, the material must be miscible with the lubricant used in the compressor. Unfortunately, many non-gas chilled fluids, including HFC's, are traditionally used in CFC's and HFCs, and the types of lubricants used, including, for example, mineral oils, alkyl benzenes or poly(alpha olefins) are insoluble and/or non-soluble. Miscible. In order for the chilled fluid _lubricant combination to function effectively in a compression refrigeration, air conditioning or heat pump system, the lubricant must be sufficiently soluble in the chilled liquid over a wide range of operating temperatures. This solubility reduces the viscosity of the lubricant and allows it to flow more easily through the system. In the absence of this solubility, the lubricant becomes apt to get stuck in the coils of the evaporator of the refrigeration, air conditioning or heat pump system and other system parts and thus reduces the efficiency of the system. Polyalkylene glycol, esterified polyalkylene glycol and polyol ester lubricating oil have been developed as miscible lubricants for HFC frozen liquids. The polyalkylene glycol chilling lubricants are disclosed in U.S. Patent Nos. 4,755,316; 4,971,712 and 4,975,212, 97,170, doc. Polydentate diol vinegar is disclosed in U.S. Patent No. 5, _, 〇28. The polyalkylene glycol and polyalkylene glycol vinegar oils disclosed are miscible in a halothane having one or two carbon atoms and no double bond. Therefore, it has been found that fluids of fluorocarbon matrix are widely used in cold-warming systems. The use of air-conditioning systems and thermal-recording applications, including tempering and cooling; Compressed cold east generally includes changing the refrigerant from a liquid phase to a gas phase via heat absorption at a lower pressure, and then changing from the gas phase to the liquid phase via heat removal at a higher pressure. Although cold; the main purpose of the East is to remove energy at low temperatures, but the main purpose of heat pumping Lu is to add energy at higher temperatures. The heat pump is replaced by heating. The operation of the condenser as a reverse cycle system is alternated with the operation of the freezing evaporator. Technically, new fluids of new fluorocarbon and hydrofluorocarbon matrices are continuously sought to provide alternatives to colddong and heat pump applications. Applicants have learned that the fluoroolefin matrix material (fluoroolefin) is particularly important because of its characteristics that make it an environmentally safer alternative to the currently used halothane (HFC, S). The skunk layer is safe but is suspected of causing global warming. Applicants also understand that HFC's frozen composition substitutes in many cases preferably have specific performance properties that are considered acceptable substitutes, including wettability, chemical stability, low toxicity, non-flammability, lubrication. Agent · Phase 'valley and use efficiency. The final feature is important in many cold image systems, air conditioning systems, and hot Lipu applications, especially when the loss of cold beam thermodynamic performance or energy efficiency may increase the amount of fossil fuels through the increase in electrical energy demand, resulting in two environmental impacts. When it is affected. In addition, the HFC Freezing Composition 97170.doc 1376409 has the advantage of not requiring significant engineering changes to the vapor compression technology and lubricant system currently used in HFC chillers. Flammability is another important property of many applications. In other words, the use of non-flammable compositions is considered important or necessary in many applications including heat transfer applications. Therefore, the use of non-combustible compounds in such compositions is often helpful. As used herein, the term "non-flammable" refers to a compound or composition that is non-flammable as measured according to ASTM Standard E_681, dated 2002, which is incorporated herein by reference. Unfortunately, many other HFcs that may be suitable for use in cryogen compositions are flammable. For example, 'fluorone difluoroethane (HFC-152a) and fluoroolefin U1, trifluoropropene (HF〇-1243zf) are each flammable and therefore cannot be used in many applications. It has been suggested to use a higher carbon number fluoroolefin, i.e., a fluorine-substituted olefin having at least five carbon atoms as a refrigerant. U.S. Patent No. 4,788,352 to Smutny is directed to the manufacture of fluorinated compounds having at least some degree of unsaturation. The Smutny patent recognizes such higher carbon number olefins as known as refrigerants, insecticides, The utility of electrofluids, heat transfer fluids, solvents, and intermediates of various chemical reactions. Although the fluorinated olefins described in Smutny have a certain degree of utility in heat transfer applications, it is believed that such compounds also have specific disadvantages. For example, these Some of the compounds in the compound are susceptible to damage to the substrate, particularly for general-purpose plastics such as acrylic resins and AB S resins. Moreover, because of the potential toxicity of higher carbon number dilute hydrocarbon compounds, such compounds are described in Smutny. It is also not suitable for specific applications' which makes this toxicity possible as 97l70.doc 丄:

The result of the insecticide activity described in SmUtny. Moreover, the boiling point of such compounds is so high that they can be used in specific applications as a cold; east agent. It is therefore appreciated that many applications, including vapor compression heating and cooling systems, may be useful to avoid the need for a set of sigma, particularly fluid transfer compositions, of one or more of the above disadvantages. In addition, the applicant is also sure to be. In the midday application, there is still a need to be safer than HFC, s in the environment, with fluorocarbonization that is class or better to the thermodynamic performance properties of the refrigerant, and compatible with existing systems. And a frozen liquid of a hydrofluorocarbon substrate. SUMMARY OF THE INVENTION The present inventors have discovered that the above needs and other needs are met by a composition comprising one or more C3 or C4 gas-lean, preferably a compound having the formula τ: xcfzr3_z(i) wherein X is 0 : 2 or (: 3 not 35 and, substituted or unsubstituted, the ruler is independently Cl, Br, 1 or Η, and Z is 1 to 3. The invention preferably also comprises one or more lubrications The invention is in combination with one or more compounds of the invention. The invention also provides methods and systems for utilizing the heat transfer compositions of the invention. [Embodiment] The present invention relates to compositions comprising at least one fluoroolefin, wherein the sulphur Containing 3 to 4 carbon atoms and at least one carbon-carbon double bond. For convenience, the fluoroolefin compound of the present invention sometimes refers to a hydrofluoroolefin or "HF〇s" herein, although the HFOs of the present invention are expected Two carbon-carbon double bonds may be included, but such compounds 97170.doc 1376409 are not considered to be preferred compounds. As described above, the compositions of the present invention comprise one or more compounds according to the formula. In a preferred embodiment, the compositions comprise Compound of the formula :: π

(Π) wherein each R is independently Cl, F, Br, I or Η; R' is (CR2)nY; Υ is CRFZ, and n is 〇 or 1. In a particular embodiment of the high preference, γ is ch, η 疋Ο ' and at least one of the remaining r' is F. The Applicant generally believes that the above-mentioned formula and formula π compounds are generally effective and effective in heat transfer applications, particularly on compressed refrigerant compositions. However, it has been surprisingly and unexpectedly discovered that certain compounds having a structure according to the above formula exhibit an extremely low degree of toxicity compared to other such compounds. As can be readily appreciated, this finding has potentially great advantages and benefits for the cryogen composition as well as any and all formulations that satisfy the above formula, but otherwise would incorporate a combination of highly toxic compounds. More specifically, it is believed that the degree of very low toxicity is related to the compound of the formula π, and it is preferred that the oxime is CF3, wherein at least one of the unsaturated terminal carbons is ruthenium and at least one of the remaining ruthenium is F. Also believe in all of these compounds. It is effective to constitute and stereoisomers and advantageously has low toxicity. In a particular embodiment of the high preference, particularly in a particular embodiment comprising the above described low toxicity compound, η is zero. Thus, in certain preferred embodiments, the compositions of the present invention comprise one or more compounds selected from the group consisting of trifluoropropene (HFC-1243), tetrafluoropropene (HF〇-1234), pentafluoropropylene 97170 .doc 1376409 (HFO-1225) and a group consisting of combinations of these compounds. The trans isomer (4) is near-claw and the cis isomer has a boiling point of nearly +9 ι. This trans isomer is particularly useful as a cryogen and as an aerosol propellant. It is excellent that the compound of the present invention is a tetrafluoropropene and pentafluoropropene compound having an unsaturated terminal carbon having not more than one F substituent, in particular: ruthenium, 3, 3, 3 4 tetrapropyl propylene (Qing-(2) called; 2 , 3,3,3_tetrapropene propylene (HF〇i234yf) and 1,2,3,3,3-pentafluoropropene (HFO-1225ye) and any and all stereoisomers of each of these compounds. Such compounds have been found to have extremely severe low toxicity levels when exposed to inhalation in mice and rats. On the other hand, it has been found that very high levels of toxicity may be associated with certain modifications that may be used with the compositions of the present invention. A compound, that is, a compound having more than one F on the terminally unsaturated carbon or having at least one of the terminal unsaturated carbons. For example, if the mice and rats are exposed to inhalation, 1,1 has been found. , 3,3,3_pentafluoropropene (HFO-1225ZC) exhibits an unacceptably high degree of toxicity. Preferred compounds of the invention, namely HF〇_1225 and HF〇_1234, are known materials and are listed in the chemical summary database. HF〇_1225 is a commercially available product, such as that available from Syntex Chemical Company. In addition, the method is generally The above is described in the patent literature for the manufacture of fluoroolefins. For example, a process for the production of fluoropropene, such as CF3CH=Ch2, by catalytic gas phase fluorination of various saturated and unsaturated halogen-containing C3 compounds is described in U.S. Patent No. 2,889,379; And U.S. Patent No. 5,532,419, the disclosure of which is hereby incorporated by reference in its entirety in its entirety in the entire disclosure of the disclosure of the disclosure of the entire disclosure of the disclosure of the disclosure of the disclosure of the disclosure of the disclosure of the disclosure of the disclosure of A gas phase catalytic process for olefins, and is also incorporated herein by way of reference. EP 974, 571 discloses the use of 1,1,1,3,3-pentafluoropropanone at higher temperatures ( HFC-245fa) is contacted with a catalyzed catalyst in the gas phase or in a liquid phase with an alcohol solution of KOH, NaOH, *Ca(OH) 2 or Mg(〇H) 2 to prepare U'l,3- A method of preparing a tetrafluoropropene. Moreover, the method of preparing a compound according to the present invention is generally directed to a US Patent Application Serial No. 3,789 (26,267, USA), entitled " To describe, the case is also incorporated herein by reference. For many important reasons, it is believed that the compositions of the present invention have advantageous properties. For example, based at least in part on mathematical models, applicants believe that the present invention will have no substantial negative impact on atmospheric chemistry, as compared to some other cryptic species. 'The contribution to the skunk layer consumption is negligible. Therefore, the preferred embodiment of the present invention has the advantage of not substantially causing ozone layer consumption. Compared to many of the currently used hydrofluorescence, the preferred composition is substantially Will not cause global warming. Although it is contemplated that the compositions of the present invention may comprise a wide range of levels of a compound of the invention 'but generally the present invention. The composition of the composition preferably comprises at least about 50% by weight of the composition, preferably at least about 7 Torr. The weight % is based on the illusion compound 'excellent line, according to the celery compound. Preferably, the preferred composition for use as a blowing agent in accordance with the present invention is at least about 5% by weight, based on the amount of the compound, based on the amount of the compound, preferably at least about 5% by weight. The compositions of the present invention may comprise other components for the purpose of increasing or providing certain functions of the compositions of the present invention or, in some cases, reducing the cost of the compositions. For example, the cold chiller compositions according to the present invention, particularly those compositions for the gas 97170.doc 1376409 phase compression system, comprise a lubricant in an amount generally comprising about 30 weight percent of the composition. Further, to about 50% by weight of the β, the composition of the present invention may also contain a compatibilizing agent such as propane for the purpose of assisting the phase and solubility of the lubricant. Such compatibilizers, including propane, butane and pentane, are preferably present in an amount of about 0.5% by weight of the composition. Up to about 5% by weight. A combination of a surfactant and a solubilizing agent may also be added to the compositions of the present invention to aid in the solubility of the oil, as disclosed in U.S. Patent No. 6,5,837, the disclosure of which is incorporated herein by reference. Conventional cold; East lubricants such as hydrofluorocarbon (HFC) refrigerants used in refrigerators for polyol esters (p〇Es), polyalkylene glycol oxime (PAGs) and esterified polyalkylene glycol systems 0 can be used with the cryogen compositions of the present invention. Methods and Systems The compositions of the present invention are useful in a variety of related methods and systems, including heat transfer fluids, such as refrigeration, air conditioning, and heat pumps, which can be used as methods and systems for transferring heat. The refrigerant used in the system. Preferably, the heat transfer method generally comprises providing a composition of the invention and transferring heat to or from the composition by phase change of the composition. For example, the process of the present invention provides for cooling by absorbing the heat of the fluid or article, preferably by condensing - a cold comprising the composition of the present invention; and then evaporating the refrigerant in the vicinity of the object or fluid to be cooled. In many such methods, the step of compressing the refrigerant vapor, typically by means of a rotary compressor or the like, is also included in the cold; Then, after this step, an intercooling step is sometimes followed to remove the heat added to the cryogen composition of the present invention by at least a partial compression step. Then, in this intermediate cooling step 97170.doc 12 1376409, it is preferred to subsequently reduce the pressure of the cooled high pressure refrigerant vapor by a slight equilibration to condense at least a portion of the vapor into a relatively cold liquid phase. In this embodiment, the reduced temperature refrigerant liquid is then vaporized by heat transferred from the object or fluid to be cooled. In another embodiment of the method of the invention, the composition of the invention may be used in a method of producing heat comprising chilling a cryogen comprising the composition in the vicinity of a liquid or object to be heated, followed by evaporating the cryogen. Such a method, as mentioned above, is often the reverse cycle of the above refrigeration cycle. According to a feature of the invention, a method of producing refrigeration is by condensing a mixture of 2 to 5 carbon atoms and at least one but not more than 2 double bonds of fluoroolefin, and then evaporating at the vicinity of the object to be cooled. The fluoroolefin is provided in a manner. Preferred are fluoroolefins having 3 carbon atoms and one double bond. Because the heat pump system is simply cold; the opposite of the East system, therefore, according to another feature of this month, it is possible to provide a condensation by containing 2 to 5 carbon atoms and at least (10) but not exceeding by heating near the object. The method of heating is carried out in such a manner that two double bonds of olefins and thus the fluoroolefin are evaporated. Preferably, it is also a fluoroolefin β containing 3 carbon atoms and 1 double bond.

The polyglycol diol used in the system, wherein the organic lubricant wire is supplied from the surface of the cold bundle, the air conditioner and the heat polyalkylene glycol, the polyalkylene glycol ester and the polyol ester lubricant. 97170.doc -13- 1^/0409 In certain preferred embodiments, the lubricant of the present invention is an organic compound containing carbon, hydrogen and oxygen, and the ratio of oxygen to carbon in the organic compound is sufficient to provide a degree to The miscibility of the fluoroolefin provides a liquid phase when about t to 5% by weight of the lubricant is added to the refrigerant fluid. Preferably, the mixture has a liquid phase in the presence of from 1 to 20% by weight of the lubricant in the mixture. The best system mixture is a liquid phase in the proportion of all mixture components. Preferably, such solubility or miscibility occurs at least one temperature from about _4 〇 β (: to 7 〇 t > c is preferably present throughout the temperature range. As used herein, the term "freezing system" Means any line or device that provides cooling using a frozen liquid or cold bead or any part or portion of such a system or device. Such refrigeration systems include, for example, air conditioners, refrigerators, freezers, transport refrigeration systems, commercial refrigeration systems And the like. The present invention replaces HFC,s, which is suspected of causing global warming, although it is safe for the ozone layer. At least some of the preferred HF〇,s according to the present invention have only minimal equipment changes. Substituting the physical characteristics of the HFCs. Suitable for use in the diol diol lubricants used in the present invention, generally comprising about 5 to 5 oximes of an oxygen-extended repeating unit, wherein the oxyalkylene repeating unit comprises from 1 to 5 carbons. The polymorphic diol may be a straight or branched chain and may be a homopolymer or copolymer of 2, 3 or more oxygen-extended ethyl, oxypropyl, oxybutyl or oxopentyl or a composition of any ratio thereof. The alkanediol comprises at least 50% oxygen exudyl. The composition according to the invention may comprise one or more polyhonodiol as a full agent, one or more polyalkylene diesters as a lubricant, one or more as a lubricant Polyol vinegar or one or more polyalkylene glycols, one or more polyglycol diols S are intended to be a mixture with _ or a plurality of polyols. 97170.doc 1376409 Suitable diols include U.S. Patent No. 4,97i Polyalkylene glycol having a hydroxyl group at each end as disclosed in U.S. Patent No. 4,755,316, the disclosure of each of each of each of The end is a trans-glycol, but other suitable & HFO/T*1, the monthly agent comprises one or two terminal hydroxyl terminated polyalkylene glycol. The hydroxyl group may contain [... Alkyl groups, alkyl groups of 1 to 10 carbon atoms containing a hetero atom such as nitrogen, fluoroalkyl groups and the like described in U.S. Patent No. 4,975,2, the disclosure of which is incorporated herein by reference. In this context, when the dialkyl alkane hydroxy group is end-capped, the same type can be used. End capping groups of two different types of combinations. One or two hydroxyl groups may also be blocked by the formation of an ester with a carboxylic acid as disclosed in U.S. Patent No. 5, No. 8, No. 28, also discloses the disclosure of the same. The contents of this patent are incorporated herein by reference. The lubricating oil of this patent is a polyol ester and a polyalkylene glycol ester. The carboxylic acid can also be fluorinated. When both ends of the polyalkylene glycol are blocked, Or both ends may be blocked by an ester, or one end may be blocked by an ester and the other end may be unblocked or may be passed through a terminal of the above alkyl, heteroalkyl or fluoroalkyl group. Lubricants include Goodwrench refrigeration oil from General Motors' HFC-134a system and MOPAR-56 from Daimler-Chrysler Corporation, an ethylene-based double-terminated polyalkylene glycol. Commercially available polyalkylene glycol esters include Mobil EAL 22cc available from Exxon-Mobil and s〇iest 12 from PPI Engineering Services. A wide variety of polyalkylene glycol lubricants are also commercially available from d〇w Chemical Company. In a preferred embodiment, the viscosity of the lubricant of the present invention at about 37 ° C is from about 1 to 1000 centipoise, more preferably from about 10 to about 2 centipoise, 97170.doc -15 - 1376409 Excellent from about 30 to about 15 centipoise.

In addition to HFO cold; east agent and slip agent, the composition according to the present invention may contain other additives or materials of the type used by cold, air conditioning and hot Lipu compositions to enhance their properties. For example, the compositions also include extreme pressure and anti-wear additives, oxidizing agents and thermal stability improvers, pour point and mist suppressors, defoamers, other HFO soluble lubricants and the like. An example of such an additive is disclosed in U.S. Patent No. 5,254,28, the disclosure of which is incorporated herein by reference. The composition of the present invention may further comprise a quantitative mineral oil lubricant, wherein the mineral oil lubricant is dissolved or miscible in other cases, but the addition of the pre-F〇 When the combination of glycol vinegar or polyol vinegar is at least partially miscible or partially soluble. Generally, this amount is up to about 5-20 weights. As disclosed in U.S. Patent No. 6,516,837, a surfactant may also be added to mix the mineral oil with a polyglycol diol, a 抆-龄 此 + + & $ 沉 沉 曰 兀 兀 及 及 及 及 及The disclosure of this disclosure is incorporated herein by reference.

The cold group I of the present invention can be introduced into a compressed cold bead, air conditioner or heat pump system using any of a wide variety of methods in this month. For example, the one-fourth method includes connecting a cold-to-cold container to the low pressure side of the cold feed system and opening the cold line compressor to cool the east composition into the system. In such a specific case, the cold-cure container can be placed on the balance to monitor entry and read.

The amount of cold green compound in the system. The feed is stopped when the required amount of the cold composition has been introduced into the system. Or a wide range of feeding tools known to those skilled in the art are available from commercial companies. Therefore, under the above-mentioned disclosure of the inner valley, the skilled person can easily introduce the HFO refrigerant and the 97170.doc-16 air conditioning and heat pump system of the present invention into the compression cold shower without the need to pass the frozen composition. More experiments. The example of the 'but does not limit its scope. The following examples are provided to illustrate the objective of the present invention. The coefficient of performance (COP) is a generally accepted measure of the performance of a cold body agent, and in particular can be used to represent the relative dynamic efficiency of a coldener in a particular heating or cooling cycle. Where the particular cycle system comprises the cold; the evaporation or continuation of the agent. In cold-finish engineering, this term refers to the ratio of energy applied to the dust-reducing machine by the action of cold beads when compressing the vapor. The capacity of the cold agent represents the volumetric efficiency of the cold ice agent and provides a measure of the ability of the compressor to extract heat for assuming a volumetric flow rate of the refrigerant. In other words, to provide a specific compressor, a higher capacity cold coolant will supply more cooling or heating capacity... a way to estimate the cold (IV) I under certain operating conditions is to use standard refrigeration cycle analysis techniques (see, for example, Rc Downing, Handbook of Fluorocarbon Coolant, Chapter 3, Prentice_HaU, 1988) Estimated from the thermodynamic properties of a cold pack. A refrigeration/air conditioning cycle system is provided in which a slight isosceles compression and a compressor inlet temperature of about 50 are scared, and the temperature of the condenser is about 150. F and the temperature of the evaporator is about -35 °F. Take the COP value! (10), the capacity value is i 〇〇 and the discharge temperature is based on HFGM34a, and c 〇 p of several compositions of the present invention are measured in the temperature range of the condenser and the evaporator and recorded in Table 1 below. 97170.doc 1376409 Table 1 | Refrigerant composition relative COP Relative capacity discharge temperature 1 HFO 1225ye 1.02 0.76 158 HFO trans-1234ze 1.04 0.70 165 HFO cis-1234ze 1.13 0.36 155 HFO 1234yf 0.98 1.10 168 This example shows some Preferred compounds for use with the compositions of the present invention each have a better energy efficiency than HFC-134a (1.02, 1.04 and 1.13 each compared to 1 Torr) and utilize a compressor of the present cryogen composition A more favorable discharge temperature will be produced (compared to 175, each of which is 158, 165 and 1 55) 'because this result will likely cause less maintenance problems. Example 2 The miscibility of HFO-l225ye and HFO-1234ze with various frozen lubricants was tested. The lubricants to be tested are mineral oil (C3), alkylbenzene (Zer〇l 15〇), ester oil (Mobil EAL 22cc and Solest 120), polyalkylene glycol (PAG) oil (134 & system of Goodwrench refrigeration oil) And poly (α_ dilute hydrocarbon) oil (CP-6〇〇5_丨〇〇). For each of the refrigerant/oil compositions, three compositions, i.e., 5, 2 Torr, and 5% by weight of lubricating oil were tested, each of which was a test compound of the present invention. The lubricant composition is placed in a thick-walled glass tube. The pomelo emptys the air in these tubes, adds the cryogen compound according to the invention, and then seals the tubes. The tubes are then placed in an air bath environment, the temperature of which varies from about _ thief to 7 (TC. at about 1 (rc spacing, visual observation of the presence of the tube contents or multiple liquid phases. It was observed that the mixture was recorded as immiscible in the case of exceeding the liquid phase. The mixture was recorded as miscible. The medium-liquid phase only accounted for a very small volume in the case where only one liquid phase was observed. Two liquid phases were observed, but in this case, the mixture was recorded as part 97170.doc -18-1376409 miscible. All tested proportions of polyalkylene glycol and ester oil lubricants were determined over the entire temperature range. To be miscible, except for the mixture of HFO-1225ye and polyalkylene glycol, the refrigerant mixture was found to be immiscible in the temperature range of -50 ° C to -30 ° C and at -20 ° C to Partially miscible at 50 ° C. The cryogen/PAG is miscible at 50% by weight of PAG in the refrigerant and at 60 ° C. It is from 5 wt % lubricant to 50 in the refrigerant. Weight % lubricant and miscible at 70 ° C. Example 3 When used with refrigeration and air conditioning systems When in contact, the compatibility of the refrigerant compounds and compositions of the present invention with PAG lubricants is tested at 350 ° C, which is far more severe than found in many refrigeration and air conditioning applications. Aluminum, copper and steel The sheets were placed in a thick-walled glass tube. 2 grams of oil was added to the tubes. The air in the tubes was then evacuated and 1 gram of cryogen was added. The tubes were placed in a 350 °F oven for one week and visually observed. End of exposure period The tubes were removed. The procedure was followed for the following oils and compositions of the compounds of the invention: a) HFC-1234ze and GM Goodwrench PAG oil b) HFC-1243zf and GM Goodwrench PAG oil c) HFC-1234ze and MOPAR-56 PAG Oil d) HFC-1243zf and MOPAR-56 PAG oil e) HFC-1225ye and MOPAR-56PAG oil. In all cases, there is minimal change in the appearance of the tube contents. This means that 97170.doc -19- 1376409 shows that the present invention is cold; the agent compounds and compositions are found in the cold, air-conditioned air conditioners, steels and copper, and the like, or among these types of systems. The hydrazine used together with the composition is stable when it is contacted with J/reading oil type. Comparative example As Example 3, aluminum, copper and steel sheets are added to the thick-walled glass tube with mineral oil and cfc_i2 at 350°. Heat under C - week. & At the end of the dew period, f is out of this tube and visually observed. It was observed that the liquid contents turned black, indicating that the contents of the tube were severely decomposed. To date, CFC-12 and mineral oil have become the preferred combination of many refrigerant systems and methods. Thus, the stability of the cold-reinforcing agent compounds and compositions of the present invention with many commonly used lubricating oils is significantly superior to the widely used prior art cold bed-lubricating oil compositions.

97170.doc 20·

Claims (1)

Η年1376409 修修(3⁄4)本本10, the scope of application for patent: 093132902 Patent application Chinese patent application scope replacement (January 101) 1. A liquid combination for compressing refrigeration, air conditioning or heat pump systems The composition comprises: (A) a fluoroolefin having the following structure: R \=C-R 丨R (II) wherein each R is independently Cl, F, Br, I or ruthenium; and R' is CRF2; (B) - an effective amount of a substantially miscible organic lubricant that provides lubrication - which effectively provides a degree of miscibility with the fluoroolefin, such that when up to 5% by weight of the organic lubricant is added to the fluoroolefin, The mixture has a liquid phase at a temperature of at least -4 (TC and +7 (TC), wherein the organic lubricant comprises a polyalkylene glycol, the polyalkylene glycol is at least 2 oxygen-extended ethyl, oxygen-extended A homopolymer of propyl, oxobutyl or oxopentyl. 2. The composition of claim 1 wherein when up to 5% by weight of the organic lubricant is added to the fluoroolefin, the mixture has a liquid phase 3. The composition of claim 2, wherein up to 2% by weight of the organic lubricant plus When the fluorocarbon is added, the mixture has a liquid phase. 4. The composition of claim 3, wherein the mixture has a liquid phase at all ratios of the fluoroolefin to the organic lubricant. The composition of the composition, wherein the mixture has a liquid phase in the temperature range of _4 〇 < t to +7 。. 6. The composition of claim 1, wherein the fluoroolefin comprises i'3, 3' 3· tetrafluoropropene. 97170-1010117.doc 丄:)/0斗: The composition of claim 1 wherein the organic lubricant comprises a polyalkylene glycol. The composition of the month 7 is wherein the polyalkylene glycol A composition having at least one terminal group according to item 8, wherein the terminal group of the polyalkylene glycol is a hydroxyl group. The composition of the item 7 wherein the polyalkylene glycol has at least one alkyl group end group 11. The composition of claim 10, wherein at least one of the terminal alkyl groups of the polyalkylene glycol comprises at least one hetero atom. 12. The composition of claim 11, wherein the polyalkylene glycol has at least one ruthenium end group. 13. The item 1 έ , I, and the σ substance, wherein the organic lubricant comprises a polyalkylene glycol. 14. The composition of claim 1, wherein the organic lubricant comprises a polyol ester. 15. The composition of claim R, wherein the fluoroolefin comprises % trifluoropropene. 16·如#求项! The composition' additionally comprises a hydrocarbon lubricant which is inherently miscible with the olefin and the organic lubricant. 17. The composition of claim 16 additionally comprising a surfactant for dissolving the hydrocarbon lubricant and the organic lubricant in an amount effective to form a substantially biomiscible blend. A method of producing a cold bundle effect comprising condensing a refrigerant composition comprising fluoroolefin having the following structure: 97170-1010117.doc • 2 · 1376409 PR > JR· R (Π) wherein each R system is independently a , F, Br, WH; and r^crF2, and thereafter evaporating the cryogen composition in the vicinity of the object to be cooled, wherein an organic lubricant effective to provide a riding action is added to the cold binder composition, and The organic lubricant is effective to provide a degree of miscibility with the fluorocarbon, such that when up to 5% by weight of the organic lubricant is added to the fluoroolefin, the refrigerant composition is at least one of _4 Torr. 〇 and +7〇. (at a temperature of - liquid phase, wherein the organic lubricant comprises a polyalkylene glycol, the polyalkylene glycol being at least 2 oxygen-extended ethyl, oxypropyl, oxybutyl or oxopentyl 19. The method of claim 18, wherein the fluorocarbon comprises u,3,3·tetrafluoropropene. The fluoroolefin comprises a method of claim 18, wherein the method of claim 18, wherein the freezing method is carried out in a compression refrigeration system, wherein the method of claim 18 is The method of claim 18, wherein the refrigerant composition has a liquid phase when up to 2% by weight of the organic lubricant is added to the olefin. The method of claim 23, wherein The refrigerant composition has a liquid phase at all ratios of the fluoroolefin to the organic lubricant. The method of claim 18, wherein the refrigerant composition is at -40 (: to +70 ° C) A liquid phase in the temperature range. 97170-1010117.doc 1376409 26, the method of claim 18, wherein in addition A hydrocarbon lubricant in which a fluoroolefin is miscible with the organic lubricant is added to the refrigerant composition. 27. The method of claim 26, wherein the method further comprises dissolving the hydrocarbon lubricant with the fluoroolefin and the organic lubricant. The surfactant is added to the cryogen composition in an amount that forms an essentially miscible blend. 28. A method of producing heat comprising condensing a fluoroolefin comprising a structure having the structure below in the vicinity of the object to be heated Heat transfer composition: R C—R· \=ι (Π) wherein each R is independently c, F, Br, coffee; Μ, is crF2, and then the heat transfer composition is evaporated, wherein the organic lubrication is effective to provide lubrication The agent is added to the heat transfer composition, and the organic lubricant is effective to provide a degree of miscibility with the fluorocarbon, and thus up to 5 weight. /. When the organic lubricant is added to the fluoroolefin, the heat transfer composition has a liquid phase at a temperature of at least -4 〇t and +7 〇t, and wherein the organic lubricant comprises a diol diol. The polyglycol diol is a homopolymer of at least two oxygen-extended ethyl groups, oxygen-extended propyl groups, oxygen-extended butyl groups or oxo-pentyl groups. 29. The method of claim 28, wherein the fluorocarbon comprises tetrafluoropropene. 30. The method of claim 28, wherein the fluorocarbon comprises 3 3 3 trifluoropropene. The method of claim 28, wherein the heat transfer composition has a liquid phase when the organic substance is added in an amount of the organic substance. 97170-1010117.doc -4- 1376409 33. The method of claim 28 wherein the heat transfer composition is at _4 〇 to +7 〇. There is a liquid phase in the temperature range of 〇. 34. The method of claim 28, wherein a hydrocarbon lubricant substantially miscible with the fluoroolefin and the organic lubricant is additionally added to the heat transfer composition. 35. The method of claim 34, wherein the hydrocarbon lubricant and the surfactant of the fluoroolefin and the organic lubricant are additionally added to the heat in an amount effective to form an intrinsically miscible blend. In the composition. 36. Use of a liquid composition in a cryo-system, wherein the liquid composition comprises: (A) fluoroolefin having the following structure: Wherein each R is independently Cl, F, Br, I or hydrazine; and R, (Β) - an effective amount of a compoundable agent which provides a lubricating effect, which effectively provides a degree of mixing with the fluoroolefin and R1 Is crf2; and miscible organic lubrication-miscibility, so when it is miscible with the fluoroolefin, the mixture-liquid phase, up to 5 weights of at least one j up to 5% by weight of the organic lubricant When the fluoroolefin is added, When the olefin is added, the mixture has a liquid phase. 37. The use of claim 36, when the fluoroolefin is added, the thirst 97170-1010117.doc 1376409 3 8. The use of claim 37, wherein up to 20% by weight of the organic lubricant is added to the fluoroolefin, The mixture has a liquid phase. 39. The use of claim 38, wherein the mixture has a liquid phase at all ratios of the fluoroolefin to the organic lubricant. 40. The use of claim 36, wherein the mixture has a liquid phase at a temperature ranging from -40 °C to +70 °C. 41. The use of claim 36 wherein the fluoroolefin comprises 1,3,3,3_tetrafluoropropene. 42. The use of claim 36, wherein the organic lubricant comprises a polyalkylene glycol. 43. The use of claim 42 wherein the polyglycol diol has at least one terminal via group β. 44. The use of claim 43 wherein the two terminal groups of the polyalcoholic acid are hydroxyl 0 45. The use of item 42, wherein the polyalkylene glycol has at least one alkyl terminal group" The use of claim 45, wherein at least one terminal alkyl group of the polyalkylene glycol comprises at least one hetero atom. 47. The use of claim 46, wherein the polyalkylene glycol has at least one fluoroalkyl end group. 48. The use of claim 36, wherein the organic lubricant comprises a polyalkylene glycol ester. 49. The use of claim 36, wherein the organic lubricant comprises a polyol ester 50. The use of claim 36, The gas is thin and contains 3 3 3 tripropylene. 51. The use of claim 36, additionally comprising - a hydrocarbon lubricant which is substantially miscible with the olefin and the organic lubricant. Fluoride 52. The use of claim 51 additionally comprises a surfactant for dissolving the hydrocarbon lubricant 97170-1010117.doc -6 - 1376409 and the organic lubricant, the amount of which is effective to form an essentially miscible Soluble blend. 97170-1010117.doc