Compositions, systems, and methods for introducing POE lubricants into electric (HEV, PHEV, EV) vehicle air conditioning / heating systems, or stationary air conditioning / heating systems, or stationary refrigeration systems, using refrigerants or refrigerant blends with lower GWP or low GWP.

Abstract

To provide compositions, systems and methods for introducing lubricants and additives that are designed to work with environmentally friendly refrigerants into vehicle heat management systems including passenger compartment air conditioning (A / C) systems.SOLUTION: Also disclosed are methods for charging lubricants and specific additives using environmentally desirable (low GWP) refrigerant or refrigerant blend compositions into an environmentally friendly system, such as a system that uses HFO-1234yf.SELECTED DRAWING: None

Description

【Technical Field】 【0001】 The present invention generally relates to compositions, systems, and methods for introducing lubricants and additives designed to function with environmentally friendly refrigerants into conventional, hybrid, plug-in hybrid, or electric vehicle thermal management systems, including passenger compartment air conditioning (A / C) or electric vehicle heat pump systems, or stationary air conditioning or stationary refrigeration systems. More specifically, the present invention relates to methods for filling lubricants and specific additives using environmentally desirable (low GWP) refrigerants or refrigerant blend compositions in environmentally friendly systems such as systems using blends containing HFO-1234yf, HFO-1234ze, HFO-1234ze, HFO-1233zd, HFO-1336mzzZ, HFO-1336mzzE, or these refrigerants or other low GWP refrigerant blend components (i.e., those containing R-32, CO2, etc.). The present invention also relates to methods for filling refrigerants containing lubricants and specific additives for environmental use in environmentally friendly A / C systems such as A / C systems using HFO-1234yf. 【Background Art】 【0002】 Since the mid-1990s, the refrigerant R-134a has been used in automotive air conditioning (A / C) systems for vapor compression cycles. Currently, due to environmental and social pressures, global automotive manufacturers are shifting to HFO-1234yf (2,3,3,3-tetrafluoropropene), a low global warming potential (GWP) refrigerant, as the vehicle A / C refrigerant. In conventional vapor compression A / C systems, to achieve cooling, the A / C compressor circulates the refrigerant through the A / C system. Therefore, the A / C compressor is essential for the operation of the A / C system. The A / C compressor functions as the heart of the A / C system, pumping the working fluid throughout the system. If the A / C compressor does not operate correctly, the A / C system will fail. 【0003】 To function properly, an A / C compressor requires a lubricant with the correct physical parameters (viscosity, moisture content, TAN, etc.). The lubricant must circulate completely throughout the A / C system. The lubricant must be carried by the refrigerant from one part of the system to the next, and the lubricant must be able to carry the refrigerant from one part of the system to another while providing lubrication when it is inside the compressor. Therefore, mutual compatibility between the refrigerant and lubricant across the operating range of the A / C system from 0°C to 40°C is essential for the effective operation of the system. 【0004】 The automotive industry is striving to meet increasingly ambitious environmental targets, and vehicle platforms are changing as a result. Conventional vehicles use gasoline or diesel internal combustion engines (ICE) for propulsion. However, there is a clear shift towards vehicle electrification due to environmental benefits. Automotive OEMs are designing new vehicles that replace all or part of the propulsion needs with electric motors and batteries. Some vehicles still retain ICE and are known as hybrid electric vehicles (HEVs), plug-in hybrid electric vehicles (PHEVs), or mild hybrid electric vehicles (MHEVs). Other vehicles are fully electric and do not have an ICE; these are called full EVs. 【0005】 HEVs, PHEVs, MHEVs, and EVs all use at least one electric motor that replaces the belt-driven pulleys found in gasoline / diesel-powered vehicles. It is known from various publications that polyalkylene glycol (PAG) lubricants cannot be used in HEV / PHEV / MHEV / EV systems. The use of PAG can reduce the insulation resistance of the electric compressor to near zero. More specifically, using a 1% PAG lubricant can reduce the insulation resistance of the electric compressor from over 10 megaohms to less than 1 megaohm. On the other hand, polyol ester or POE type lubricants offer high dielectric properties, thus helping to maintain the integrity of the compressor's electric windings. Original equipment manufacturers (OEMs) typically add A / C lubricants during the initial vehicle A / C filling process. The A / C system may require repair due to a failure of a component affecting the A / C system (such as a ruptured hose or line) or a vehicle accident. Typically, the automotive aftermarket or service industry employs recovery, reuse, refill, i.e., "R / R / R" machines to reinject / replenish refrigerant and lubricant into A / C systems after repairs. However, current R / R / R machines designed for use with HFO-1234yf, based on SAE J2843, particularly section 8.9.5.1 of the above SAE standard (incorporated herein by reference), cannot automatically inject lubricant into the system after repairs using the R / R / R machine. The lubricant must be injected either manually or mechanically. In each of these options, the lubricant is filled into an injector, and then a hose is attached to the underside of the A / C system. The vehicle is started and the A / C system is set to maximum cooling, which also starts the A / C compressor. Once the A / C compressor has started cyclically, the attached injector is switched to the open position, and the lubricant is transported to the A / C system along the hose. 【0006】 This method can also be used, but it is a time-consuming process and requires the use of a manual pump-type mechanism to push the lubricant into the connected hose and advance it to the A / C service port. The lubricant is then drawn into the system by the A / C compressor. It can be difficult to deliver the correct amount of lubricant into the system because the lubricant may adhere to the walls of the hose during the delivery process. [Overview of the project] [Problems that the invention aims to solve] 【0007】 Therefore, in this technical field, there is a need for a quick and convenient way to deliver lubricant into A / C or heating systems without using manual injectors. 【0008】 In this technical field, there is also a need for a quick and convenient method of delivering lubricants into fixed A / C or heating systems or refrigeration systems without using manual injectors or vacuum pumps. 【0009】 For certain applications, it may be advantageous to use a similar delivery process to deliver refrigerants, refrigerants containing lubricants, or refrigerants containing other performance-enhancing additives into a fixed A / C system using this same delivery method. [Means for solving the problem] 【0010】 Certain embodiments of this disclosure solve problems associated with conventional compositions, systems, and methods by providing a low-GWP refrigerant that can be used to inject lubricant into a low-GWP HFO-1234yf automotive A / C system, including use through a typical A / C aftermarket refill hose. In manual injectors or manual pumps, the flow of lubricant is controlled by the viscosity of the lubricant and the suction of the A / C compressor. The method of the present invention uses a refrigerant to deliver lubricant and / or lubricant additive packages into an A / C hose without sticking to the hose, thereby ensuring that more lubricant or lubricant / additive packages are introduced into the A / C system, thereby improving the flow of the material. 【0011】 Using a manual injector or pump can cause lubricant to adhere to the hose lines connected to the A / C system. Using a refrigerant to move the lubricant into the system will certainly introduce more lubricant into the A / C system compared to manual or pump injectors, because the refrigerant carries and transports the lubricant into the A / C system. The lubricant or lubricant / additive and the refrigerant are packaged together in a conventional container (e.g., a can) under conditions that the lubricant and refrigerant are miscible. If the small can is left standing, the refrigerant changes state from a compressed liquefied gas to a refrigerant gas. During this process, the refrigerant, which is miscible with the lubricant, atomizes the lubricant or lubricant / additive mixture and transports the lubricant or lubricant / additive mixture further along the hose and into the A / C system before the lubricant or lubricant / additive mixture can settle on the walls of the A / C refill hose. 【0012】 One aspect of the present invention relates to a composition comprising about 50 to about 80% by weight of a POE lubricant and about 20 to about 50% by weight of a low GWP refrigerant. 【0013】 Another aspect of the present invention relates to a composition comprising about 60 to about 65% by weight of a POE lubricant and about 35 to about 40% by weight of a low GWP refrigerant. 【0014】 Another aspect of the present invention relates to the aforementioned composition further comprising about 1 to about 5% by weight of an acid scavenger. 【0015】 Another aspect of the present invention relates to any of the aforementioned compositions further comprising about 1 to about 5% by weight of a performance enhancer. 【0016】 Further embodiments relate to any of the aforementioned compositions further comprising about 1 to about 10% by weight of a flame suppressant. 【0017】 One aspect of the present invention relates to a container containing any of the aforementioned compositions for use in directly delivering them into a vehicle A / C system. 【0018】 One aspect of the present invention relates to a method for delivering a POE lubricant into a vehicle A / C system using either the aforementioned composition or container. 【0019】 Another aspect of the present invention includes the method described above, and further includes the step of delivering an acid sweeper into a vehicle A / C system. 【0020】 Another aspect of the present invention includes the method described above, and further includes the step of delivering a performance enhancer into a vehicle A / C system. 【0021】 Another aspect of the present invention includes the method described above, and further includes the step of delivering a flame suppressant into a vehicle A / C system. 【0022】 Further aspects of the present invention include the aforementioned method carried out under pressure and temperature conditions in which the lubricant is miscible with the solvent. 【0023】 One aspect of the present invention includes a system, method, and container for delivering any of the aforementioned compositions to an A / C or heating system of an automobile, comprising a container containing the aforementioned compositions, a compressor, a condenser, a dryer, an expansion valve, and an evaporator. 【0024】 Another aspect of the present invention includes a system, method, and container for delivering any of the compositions to a stationary A / C / heating system that includes a container containing the aforementioned composition, a compressor, a condenser, a dryer, an expansion valve, and an evaporator with a capillary tube. 【0025】 And finally, another aspect of the present invention includes a system, method, and container for delivering any of the compositions to a stationary refrigeration system that includes a container containing the aforementioned composition, a compressor, a condenser, a dryer, an expansion valve, a flash tank, and an evaporator. 【0026】 Another aspect of the present invention relates to a composition comprising from about 1 to about 15 weight percent of a POE lubricant and from about 85 to about 99 weight percent of a low GWP refrigerant. 【0027】 Another aspect of the present invention relates to a composition comprising from about 1 to about 10 weight percent of a POE lubricant and from about 90 to about 99 weight percent of a low GWP refrigerant. 【0028】 A further aspect of the present invention relates to a composition comprising from about 1 to about 5 weight percent of a POE lubricant and from about 95 to about 99 weight percent of a low GWP refrigerant. 【0029】 The various aspects and embodiments disclosed herein can be used alone or in various combinations with each other. BRIEF DESCRIPTION OF THE DRAWINGS 【0030】 [Figure 1] Schematic diagram of a system for introducing the composition of the present invention into a conventional A / C vehicle system. [Figure 2] Schematic diagram of a system for introducing the composition of the present invention into an electric vehicle A / C or heating system. <00001​​​​​​[Modes for carrying out the invention] 【0031】 The present invention relates to compositions comprising, or possibly comprising, lubricants and additives, or essentially thereof, lubricants and additives, generally designed to work with environmentally friendly refrigerants. More specifically, the present invention relates to compositions comprising, or essentially comprising, about 50 to about 80% by weight, about 55 to about 70% by weight, or about 60 to about 65% by weight of a POE lubricant, about 0 to about 5% by weight of an additive, and about 20 to about 50% by weight, about 30 to about 45% by weight, or about 35 to about 40% by weight of a low GWP refrigerant or refrigerant blend. 【0032】 The present invention may also relate to compositions comprising, or essentially comprising, about 1 to about 15% by weight, about 1 to about 10% by weight, or about 1 to about 5% by weight of a POE lubricant, about 0 to about 5% by weight of an additive, and about 85 to about 99% by weight, about 90% to about 99% by weight, or about 95% to about 99% by weight of a low GWP refrigerant or refrigerant blend. 【0033】 Lubricant The lubricant used in this composition preferably has sufficient solubility in the vehicle's A / C refrigerant so that it can be reliably returned from the evaporator to the compressor. Furthermore, the lubricant preferably has relatively low viscosity at low temperatures so that it can pass through the evaporator (e.g., a low-temperature evaporator). In one embodiment, the lubricant and the A / C refrigerant are miscible over a wide temperature range. A preferred lubricant may be one or more polyol ester type lubricants (POEs). As used herein, the polyol ester includes compounds containing an ester of a diol or polyol having about 3 to 20 hydroxyl groups and a fatty acid having about 1 to 24 carbon atoms, and is preferably used as a polyol. 【0034】 Esters that can be used as base oils are disclosed, for example, in European Patent Application Publication No. 2 727 980(A1), which is incorporated herein by reference. 【0035】 Examples of diols include ethylene glycol, 1,3-propanediol, propylene glycol, 1,4-butanediol, 1,2-butanediol, 2-methyl-1,3-propanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 2-ethyl-2-methyl-1,3-propanediol, 1,7-heptanediol, 2-methyl-2-propyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, and 1,12-dodecanediol. 【0036】 Examples of the polyols mentioned above include polyhydric alcohols, such as trimethylolethane, trimethylolpropane, trimethylolbutane, di(trimethylolpropane), tri(trimethylolpropane), pentaerythritol, di(pentaerythritol), tri(pentaerythritol), glycerin, polyglycerin (dimers to icosomers of glycerin), 1,3,5-pentanetriol, sorbitol, sorbitan, sorbitol-glycerin condensates, adonitol, arabitol, xylitol, mannitol, etc.; polysaccharides, such as xylose, arabinose, ribose, rhamnose, glucose, fructose, galactose, mannose, sorbose, cellobiose, maltose, isomaltose, trehalose, sucrose, raffinose, gentianose, melegitose, etc.; and their partial etherification products and methyl glucosides. Among these, hindered alcohols, such as neopentyl glycol, trimethylolethane, trimethylolpropane, trimethylolbutane, di(trimethylolpropane), tri(trimethylolpropane), pentaerythritol, di(pentaerythritol), and tri(pentaerythritol), are preferred as polyols. 【0037】 The number of carbon atoms in a fatty acid is not particularly limited, but generally, fatty acids having 1 to 24 carbon atoms are used. Among fatty acids having 1 to 24 carbon atoms, from the viewpoint of lubrication properties, fatty acids having 3 or more carbon atoms are preferred, fatty acids having 4 or more carbon atoms are more preferred, fatty acids having 5 or more carbon atoms are even more preferred, and fatty acids having 10 or more carbon atoms are most preferred. Furthermore, from the viewpoint of compatibility with refrigerants, fatty acids having 18 or fewer carbon atoms are preferred, fatty acids having 12 or fewer carbon atoms are more preferred, and fatty acids having 9 or fewer carbon atoms are even more preferred. 【0038】 Furthermore, the fatty acid may be either a straight-chain fatty acid or a branched-chain fatty acid. From the viewpoint of lubrication properties, a straight-chain fatty acid is preferred, while from the viewpoint of hydrolysis stability, a branched-chain fatty acid is preferred. Furthermore, the fatty acid may be either a saturated fatty acid or an unsaturated fatty acid. 【0039】 Specifically, examples of the above fatty acids include straight-chain or branched-chain fatty acids, such as pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, heptadecanoic acid, octadecanoic acid, nonadecanoic acid, eicosanic acid, oleic acid, etc.; and so-called neoacids, which have quaternary carbon atoms. More specifically, preferred examples include valeric acid (n-pentanoic acid), caproic acid (n-hexanoic acid), enanthic acid (n-heptanoic acid), caprylic acid (n-octanoic acid), pelargonic acid (n-nonanoic acid), capric acid (n-decanoic acid), oleic acid (cis-9-octadecanoic acid), isopentanoic acid (3-methylbutanoic acid), 2-methylhexanoic acid, 2-ethylpentanoic acid, 2-ethylhexanoic acid, and 3,5,5-trimethylhexanoic acid. Incidentally, polyol esters may be partial esters in which the hydroxyl groups of the polyol are not completely esterified; complete esters in which all hydroxyl groups are esterified; or mixtures of partial and complete esters, with complete esters being preferred. 【0040】 In polyol esters, from the viewpoint of superior hydrolysis stability, esters of hindered alcohols, such as neopentyl glycol, trimethylolethane, trimethylolpropane, trimethylolbutane, di(trimethylolpropane), tri(trimethylolpropane), pentaerythritol, di(pentaerythritol), and tri(pentaerythritol), are more preferred, and esters of neopentyl glycol, trimethylolethane, trimethylolpropane, trimethylolbutane, or pentaerythritol are even more preferred; from the viewpoint of particularly excellent compatibility with refrigerants and hydrolysis stability, pentaerythritol esters are most preferred. 【0041】 Preferred specific examples of polyol esters include: diesters of neopentyl glycol with one or more fatty acids selected from valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, oleic acid, isopentanoic acid, 2-methylhexanoic acid, 2-ethylpentanoic acid, 2-ethylhexanoic acid, and 3,5,5-trimethylhexanoic acid; triesters of trimethylolethane with one or more fatty acids selected from valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, oleic acid, isopentanoic acid, 2-methylhexanoic acid, 2-ethylpentanoic acid, 2-ethylhexanoic acid, and 3,5,5-trimethylhexanoic acid; and trimethylolpropane with valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, oleic acid, isopentanoic acid, 2- Examples include triesters of methylhexanoic acid, 2-ethylpentanoic acid, 2-ethylhexanoic acid, and 3,5,5-trimethylhexanoic acid with one or more fatty acids selected from these; triesters of trimethylolbutane with one or more fatty acids selected from valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, oleic acid, isopentanoic acid, 2-methylhexanoic acid, 2-ethylpentanoic acid, 2-ethylhexanoic acid, and 3,5,5-trimethylhexanoic acid; and tetraesters of pentaerythritol with one or more fatty acids selected from valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, oleic acid, isopentanoic acid, 2-methylhexanoic acid, 2-ethylpentanoic acid, 2-ethylhexanoic acid, and 3,5,5-trimethylhexanoic acid. 【0042】 Incidentally, esters with two or more fatty acids may also be mixtures of two or more esters of one fatty acid and a polyol, and esters of such mixed fatty acids and polyols. In particular, esters of mixed fatty acids and polyols are superior in low-temperature properties and compatibility with refrigerants. 【0043】 In a preferred embodiment, the lubricant is soluble in the refrigerant of the vehicle A / C system at temperatures in the range of about 0°C to about 100°C, more preferably in the range of about 0°C to about 40°C, and more specifically in the range of 5°C to 40°C. In another embodiment, high-temperature solubility is undesirable because attempts to retain the lubricant in the compressor are not preferred. In this embodiment, the lubricant is soluble at temperatures above about 70°C, more preferably above about 80°C, and most preferably in the range of 90 to 95°C. 【0044】 Lubricants used for air conditioning applications in electric vehicles may have a kinematic viscosity of 75–110 cSt, ideally about 80–100 cSt, and most specifically 85–95 cSt (measured at 40°C according to ASTM D445). However, it should be noted that, without limiting the present invention, other lubricant viscosities may be mentioned depending on the needs of the A / C compressor in electric vehicles. 【0045】 Table 1 shows preferred characteristics of automotive lubricants for use with the compositions of the present invention. 【0046】 [Table 1] 【0047】 Furthermore, the POE lubricant used in this composition should have material compatibility with elastomers and plastics used in typical vehicle A / C systems. The POE lubricant used should have good material compatibility with, for example, Neoprene WRT (polychloroprene / 2,3-dichloro-1,3-butadiene copolymer), HNBR (hydrogenated nitrile butadiene rubber), NBR (nitrile butadiene rubber), EPDM (ethylene propylene diene monomer), silicone, and butyl rubber, as measured by ASHRAE 97:2007 "Sealed Glass Tube Method to Test the Chemical Stability of Materials for Use within Refrigerant Systems" at 100°C for two weeks. Similarly, the POE lubricant used should have good material compatibility with plastic materials, namely polyester, nylon, epoxy, polyethylene, terephthalate, and polyimide, when measured at 100°C for two weeks according to ASHRAE 97:2007 "Sealed Glass Tube Method to Test the Chemical Stability of Materials for Use within Refrigerant Systems". Plastics and elastomers with the above POE lubricant and HFO-1234yf should have a gain of less than about 10% by weight, less than about 8% by weight, or less than about 7% by weight, or a linear swelling of less than about 10%, less than about 8%, or less than about 7%, or a hardness change of less than about 10%, less than about 8%, or less than about 7%, when measured by durometer. Ideally, when measured by durometer, plastics and elastomers have a gain of less than 10% by weight in at least two properties, or a linear swelling of less than 10%, or a hardness change of about 10%, preferably less than 10% for all three properties. 【0048】 Several POE lubricants were found to possess the necessary miscibility with certain low-GWP refrigerants, namely HFO-1234yf (available from The Chemours Company as Optone™ refrigerant), the desired lubricant viscosity over the desired temperature range, and the desired elastomer / plastic material compatibility. Specifically, POE is commercially known as automotive POE lubricants and is known by the following trademarks: “ND-11” and “SE-10Y”. Acceptable POE lubricants for stationary applications were “Emkarate RL 32 3MAF”, “Emkarate RL32H”, and “Solest 35”. 【0049】 refrigerant The refrigerant portion of the compositions of the present invention includes at least one hydrofluoroolefin, more commonly known as an HFO-type refrigerant, but is not limited to any particular HFO refrigerant. Hydrofluoroolefins have low global warming potential (GWP) and zero ozone depletion potential (ODP). The Intergovernmental Panel on Climate Change (IPCC) regularly investigates and establishes GWP for fluorocarbons. The hydrofluoroolefin refrigerants embodied in the present invention have a GWP of less than about 100 GWP, but typically have a GWP of less than 10, or even as low as 1 GWP. A particularly useful hydrofluoroolefin is HFO-1234yf, which exhibits a GWP of less than 1 according to the UN IPCC Fifth Assessment Report (AR5). 【0050】 The Global Warming Potential (GWP) is an index used to estimate the relative contribution of one kilogram of atmospheric emissions of a particular greenhouse gas to global warming, compared to one kilogram of carbon dioxide emissions. GWP can be calculated for various time periods and reflects the atmospheric lifetime effect of a given gas. A GWP over a 100-year period is a commonly referenced value. For mixtures, a weighted average can be calculated based on the individual GWPs for each component. 【0051】 Leck et al. (U.S. Patent Application Publication No. 2007 / 0187639, paragraph 10, incorporated herein by reference) further enumerate examples of unsaturated fluorocarbon refrigerants that may be used as fluoroolefins in the present invention. As described in paragraph 10 of Leck et al., typical unsaturated fluorocarbon refrigerants or heat storage fluids include 1,2,3,3,3-pentafluoro-1-propene, 1,1,3,3,3-pentafluoro-1-propene, 1,1,2,3,3-pentafluoro-1-propene, 1,2,3,3-tetrafluoro-1-propene, 2,3,3,3-tetrafluoro-1-propene, 1,3,3,3-tetrafluoro-1-propene, 1,1,2,3-tetrafluoro-1-propene, 1,1,3,3- Tetrafluoro-1-propene, 1,2,3,3-tetrafluoro-1-propene, 2,3,3-trifluoro-1-propene, 3,3,3-trifluoro-1-propene, 1,1,2-trifluoro-1-propene, 1,1,3-trifluoro-1-propene, 1,2,3-trifluoro-1-propene, 1,3,3-trifluoro-1-propene, 1,1,1,2,3,4,4,4-octafluoro-2-butene, 1,1,2,3,3,4,4,4-octafluoro-1-butene, 1,1, 1,2,4,4,4-heptafluoro-2-butene, 1,2,3,3,4,4,4-heptafluoro-1-butene, 1,1,1,2,3,4,4-heptafluoro-2-butene, 1,3,3,3-tetrafluoro-2-(trifluoromethyl-2-propene, 1,1,3,3,4,4,4-heptafluoro-1-butene, 1,1,2,3,3,4,4-heptafluoro-1-butene, 1,1,2,3,3,4,4-heptafluoro-1-butene, 2,3,3,4,4,4-hexafluoro-1 -butene, 1,1,1,4,4,4-hexafluoro-2-butene, 1,3,3,4,4,4-hexafluoro-1-butene, 1,2,3,4,4,4-hexafluoro-1-butene, 1,2,3,3,4,4-hexafluoro-1-butene, 1,1,2,3,4,4-hexafluoro-2-butene, 1,1,1,2,3,4-hexafluoro-2-butene, 1,1,1,3,4,4-hexafluoro-2-butene, 1,1,2,3,3,4-Hexafluoro-1-butene, 1,1,2,3,4,4-Hexafluoro-1-butene, 3,3,3-Trifluoro-2-(trifluoromethyl)-1-propene, 1,1,1,2,4-Pentafluoro-2-butene, 1,1,1,3,4-Pentafluoro-2-butene, 3,3,4,4,4-Pentafluoro-1-butene, 1,1,1,4,4-Pentafluoro-2-butene, 1,1,1,2,3-Pentafluoro-2-butene, 2,3,3,4,4-Pentafluoro-1-butene, 1,1,2,4,4-Pentafluoro-2-butene, 1, 1,2,3,3-Pentafluoro-1-butene, 1,1,2,3,4-Pentafluoro-2-butene, 1,2,3,3,4-Pentafluoro-1-butene, 1,1,3,3,3-Pentafluoro-2-methyl-1-propene, 2-(Difluoromethyl)-3,3,3-Trifluoro-1-propene, 3,3,4,4-Tetrafluoro-1-butene, 1,1,3,3-Tetrafluoro-2-methyl-1-propene, 1,3,3,3-Tetrafluoro-2-methyl-1-propene, 2-(Difluoromethyl)-3,3-Difluoro-1-propene, 1,1, 1,2-tetrafluoro-2-butene, 1,1,1,3-tetrafluoro-2-butene, 1,1,1,2,3,4,4,5,5,5-decafluoro-2-pentene, 1,1,2,3,3,4,4,5,5,5-decafluoro-1-pentene, 1,1,1,4,4,4-hexafluoro-2-(trifluoromethyl)-2-butene, 1,1,1,2,4,4,5,5,5-nonafluoro-2-pentene, 1,1,1,3,4,4,5,5,5-nonafluoro-2-pentene, 1,2,3,3,4,4,5,5,5-nonafluoro-1-pentene, 1,1 ,3,3,4,4,5,5,5-nonafluoro-1-pentene, 1,1,2,3,3,4,4,5,5-nonafluoro-1-pentene, 1,1,2,3,4,4,5,5,5-nonafluoro-2-pentene, 1,1,1,12,3,4,4,5,5-nonafluoro-2-pentene, 1,1,1,2,3,4,5,5,5-nonafluoro-2-pentene, 1,2,3,4,4,4-hexafluoro-3(trifluoromethyl)-1-butene, 1,1,2,4,4,4-hexafluoro-3-(trifluoromethyl)-1-butene, 1,1,1,4,4,4-Hexafluoro-3-(trifluoromethyl)-2-butene, 1,1,3,4,4,4-Hexafluoro-3-(trifluoromethyl)-1-butene, 2,3,3,4,4,5,5,5-Octafluoro-1-pentene, 1,2,3,3,4,4,5,5-Octafluoro-1-pentene, 3,3,4,4,4-Pentafluoro-2-(trifluoromethyl)-1-butene, 1,1,4,4,4-Pentafluoro-3-(trifluoromethyl)-1-butene, 1,3,4,4,4-Pentafluoro-3-(trifluoromethyl)-1-butene, 1 1,4,4,4-pentafluoro-2-(trifluoromethyl)-1-butene, 1,1,1,4,4,5,5,5-octafluoro-2-pentene, 3,4,4,4-tetrafluoro-3-(trifluoromethyl)-1-butene, 3,3,4,4,5,5,5-heptafluoro-1-pentene, 2,3,3,4,4,5,5-heptafluoro-1-pentene, 1,1,3,3,5,5,5-heptafluoro-1-pentene, 1,1,1,2,4,4,4-heptafluoro-3-methyl2-butene, 2,4,4,4-tetrafluoro-3-(trifluoromethyl)-1-butene Oromethyl)-1-butene, 1,4,4,4-tetrafluoro-3-(trifluoromethyl)-1-butene, 1,4,4,4-tetrafluoro-3-(trifluoromethyl)-2-butene, 2,4,4,4-tetrafluoro-3-(trifluoromethyl)-2-butene, 3-(trifluoromethyl)-4,4,4-trifluoro-2-butene, 3,4,4,5,5,5-hexafluoro-2-pentene, 1,1,1,4,4,4-hexafluoro-2-methyl-2-butene, 3,3,4,5,5,5-hexafluoro-1-pentene, 4,4,4- Lifluoro-2-(trifluoromethyl)-1-butene, 1,1,2,3,3,4,4,5,5,6,6,6-dodecafluoro-1-hexene, 1,1,1,2,2,3,4,5,5,6,6,6-dodecafluoro-3-hexene, 1,1,1,4,4,4-hexafluoro-2,3-bis(trifluoromethyl)-2-butene, 1,1,1,4,4,5,5,5-octafluoro-2trifluoromethyl-2-pentene, 1,1,1,3,4,5,5,5-octafluoro-4-(trifluoromethyl)-2-pentene, 1,1,1,4,5,5,5-Heptafluoro-4(trifluoromethyl)-2-pentene, 1,1,1,4,4,5,5,6,6,6-Decafluoro-2-hexene, 1,1,1,2,2,5,5,6,6,6-Decafluoro-3-hexene, 3,3,4,4,5,5,6,6,6-Nonafluoro-1-hexene, 4,4,4-Trifluoro-3,3-Bis(trifluoromethyl)-1-butene, 1,1,1,4,4,4-Hexafluoro-3-methyl-2-(trifluoromethyl)-2-butene, 2,3,3,5,5,5-Hexafluoro-4-(trifluoromethyl)-1 -Pentene, 1,1,1,2,4,4,5,5,5-nonafluoro-3-methyl-2-pentene, 1,1,1,5,5,5-hexafluoro-4(trifluoromethyl)-2-pentene, 3,4,4,5,5,6,6,6-octafluoro-2-hexene, 3,3,4,4,5,5,6,6-octafluoro-2-hexene, 1,1,1,4,4-pentafluoro-2-(trifluoromethyl)-2-pentene, 4,4,5,5,5-pentafluoro-2-(trifluoromethyl)-1-pentene, 3,3,4,4,5,5,5-heptafluoro-2- Methyl-1-pentene, 1,1,1,2,3,4,4,5,5,6,6,7,7,7-tetradecafluoro-2-heptene, 1,1,1,2,2,3,4,5,5,6,6,7,7,7-tetradecafluoro-2-heptene, 1,1,1,3,4,4,5,5,6,6,7,7,7-tridecafluoro-2-heptene, 1,1,1,2,4,4,5,5,6,6,7,7,7-tridecafluoro-2-heptene, 1,1,1,2,2,4,5,5,6,6,7,7,7-tridecafluoro-3-heptene, 1,1,1,2,2,3,5,5,6,6,7 ,7,7-tridecafluoro-3-heptene, 4,4,5,5,6,6,6-heptafluoro-2-hexene, 4,4,5,5,6,6,6-heptafluoro-1-hexene, 1,1,1,2,2,3,4-heptafluoro-3-hexene, 4,5,5,5-tetrafluoro-4-(trifluoromethyl)-1-pentene, 1,1,1,2,5,5,5-heptafluoro-4-methyl-2-pentene, 1,1,1,3-tetrafluoro-2-(trifluoromethyl)-2-pentene, 1,2,3,3,4,4-hexafluorocyclobutene, 3,3,4,Examples include 4-tetrafluorocyclobutene, 3,3,4,4,5,5-hexafluorocyclopentene, 1,2,3,3,4,4,5,5-octafluorocyclopentene, 1,2,3,3,4,4,5,5,6,6-decafluorocyclohexene, 1,1,1,2,3,4,5,5,5-nonafluoro-4-(trifluoromethyl)-2-pentene, pentafluoroethyl trifluorovinyl ether, trifluoromethyl trifluorovinyl ether; or any combination thereof. 【0052】 Furthermore, there may be one or more non-low GWP refrigerant components, including a refrigerant portion. Minor et al. (U.S. Patent Application Publication 2007 / 0289317, incorporated herein by reference) further enumerate examples of saturated and unsaturated fluorocarbon refrigerants that may be used as fluoroalkanes in the present invention. As described in paragraph 81 of Minor et al., typical hydrofluorocarbons may be represented by the formula CxH2x+2_yFy or CxH2x_yFy (wherein x may be equal to 3 to 8 and y may be equal to 1 to 17). Hydrofluorocarbons may be linear, branched, or cyclic saturated or unsaturated compounds having about 3 to 8 carbon atoms. While not limiting, as described in paragraphs 47-78 of Minor et al., exemplary fluoroalkanes that may be used include: 1,1,2,2,3-pentafluoropropane; 1,1,1,3,3-pentafluoropropane; 1,1,3-trifluoropropane; 1,1,3-trifluoropropane; 1,3-difluoropropane; 2-(difluoromethyl)-1,1,1,2,3,3-hexafluoropropane; 1,1,2,2,3,3,4,4-octafluorobutane; 1,1,1,2,2,4-hexafluorobutane; 1,1,1,3,3-pentafluoropropane; Examples include ruolobutane; 1,1-difluorobutane; 1,3-difluoro-2-methylpropane; 1,2-difluoro-2-methylpropane; 1,2-difluorobutane; 1,3-difluorobutane; 1,4-difluorobutane; 2,3-difluorobutane; 1,1,1,2,3,3,4,4-octafluoro-2-(trifluoromethyl)butane; 1,1,1,2,2,3,3,4,4,5,5-undecafluoropentane; 1,1,1,2,2,3,4,5,5,5-decafluoropentane; and 1,1,1,2,2,3,3,5,5,5-decafluoropentane. 【0053】 The refrigerant or refrigerant blend portion of the above invention has a GWP of less than 300, specifically less than 150 GWP, more specifically less than 75 GWP, and ideally less than 5 GWP. It is possible to use the refrigerant in such a way that GWP < 1. 【0054】 The refrigerant portion of the above blend has a minimum ignition energy (MIE) of at least 300 MJ / kg, preferably greater than 1,000 MJ / kg, more specifically between 1,000 MJ / kg and 5,000 MJ, and even more specifically at least 5,000 MJ / kg, as measured by ASTM E-582. The heat of combustion, calculated according to American Society of Heating, Refrigeration and Air-conditioning Engineers (ASHRAE) Standard 34, must be less than 19,000 kJ / kg, more specifically between 8 and 12 kJ / kg, and even more specifically between 9.5 and 11.5 kJ / kg. The lower flammability limit of the refrigerant portion at 21°C may actually be non-flammable, as measured by ASTM E-681. Alternatively, if the refrigerant portion has a flammability limit, the lower flammability limit may be at least 5 vol% as measured by ASTM E-681, more specifically at least 6 vol%, and even more specifically at least 6.2 vol%. 【0055】 The resulting composition, i.e., the lubricant and refrigerant referred to herein, can be “added” to the A / C system, and advantageously, because it is relatively low in corrosiveness, the resulting corrosion experienced by the metal (e.g., aluminum, copper, or iron) that is part of the A / C system in contact with the composition is relatively minimal. Furthermore, after testing at 175°C for 14 days, there was no tarnishing of the steel, no metal coupon film or visible corrosion, and no precipitates or aggregates formed during the test. 【0056】 The relatively low corrosiveness of the lubricant / refrigerant composition is advantageous, as the refrigerant composition portion may exhibit one or any combination of the following properties: The total acid number (TAN) after aging at 175°C for 14 days according to ASHRAE 97:2007 "Sealed Glass Tube Method to Test the Chemical Stability of Materials for Use within Refrigerant Systems" is less than 3.3 mgKOH / g, less than 1.5 mgKOH / g, and specifically less than 1.0 mgKOH / g, as measured according to ASTM D664-01. For aluminum, copper, and carbon steel metal strips, the total halide concentration (e.g., fluoride ion concentration) after aging at 175°C for 14 days according to ASHRAE 97:2007 "Sealed Glass Tube Method to Test the Chemical Stability of Materials for Use within Refrigerant Systems" is less than approximately 100 ppm, preferably less than 50 ppm, and ideally less than 10 ppm. In aluminum, copper, and iron metal strips, the total organic acid concentration after aging at 175°C for 14 days according to ASHRAE 97:2007 "Sealed Glass Tube Method to Test the Chemical Stability of Materials for Use within Refrigerant Systems" was less than approximately 300 ppm, as measured by ion chromatography. 【0057】 Additives that can improve the lifespan of the refrigerant and A / C, as well as the durability of the compressor, are desirable. In one aspect of the present invention, a composition containing the refrigerant of the present invention is used to introduce a lubricant and other additives, such as a) an acid scavenger, b) a performance enhancer, and c) a flame suppressant into an A / C system. 【0058】 Acid remover The acid scavenger may include a siloxane, an activated aromatic compound, or a combination of both. Serrano et al. (paragraph 38), incorporated herein by reference, disclose that the siloxane may be any molecule having a siloxy functional group. The siloxane may include an alkylsiloxane, an arylsiloxane, or a siloxane containing a mixture of aryl and alkyl substituents. For example, the siloxane may be an alkylsiloxane, including a dialkylsiloxane or a polydialkylsiloxane. Preferred siloxanes include groups having an oxygen atom bonded to two silicon atoms, i.e., a structure: SiiOiSi. For example, the siloxane may be a siloxane of formula IV: R1[Si(R2R3)4O]nSi(R2R3)R4 (wherein n is 1 or more). The siloxane of formula IV has n preferably 2 or more, more preferably 3 or more (e.g., about 4 or more). The siloxane of formula IV has n which is preferably about 30 or less, more preferably about 12 or less, and most preferably about 7 or less. Preferably, the R4 group is an aryl group or an alkyl group. Preferably, the R2 group is an aryl group or an alkyl group, or a mixture thereof. Preferably, the R3 group is an aryl group or an alkyl group, or a mixture thereof. Preferably, the R4 group is an aryl group or an alkyl group. Preferably, R1, R2, R3, R4, or any combination thereof is not hydrogen. The R2 groups in the molecule may be the same or different. Preferably, the R2 groups in the molecule are the same. The R2 group in the molecule may be the same or different from the R3 group. Preferably, the R2 and R3 groups in the molecule are the same. A preferred siloxane is the siloxane of formula IV in which R1, R2, R3, R4, R5, or any combination thereof is a methyl, ethyl, propyl, or butyl group, or any combination thereof. Examples of siloxanes that may be used include hexamethyldisiloxane, polydimethylsiloxane, polymethylphenylsiloxane, dodecamethylpentasiloxane, decamethylcyclopentasiloxane, decamethyltetrasiloxane, octamethyltrisiloxane, or any combination thereof. 【0059】 By reference to paragraph

[0039] of Serrano et al., in one aspect of the present invention, it should be noted that the siloxane is an alkylsiloxane containing about 1 to about 12 carbon atoms, for example, hexamethyldisiloxane. Alternatively, the siloxane may also be a polymer such as a polydialkylsiloxane in which the alkyl group is methyl, ethyl, propyl, butyl, or any combination thereof. Preferred polydialkylsiloxanes have a molecular weight of about 100 to about 10,000. Very preferred siloxanes include hexamethyldisiloxane, polydimethylsiloxane, and combinations thereof. The siloxane may essentially consist of polydimethylsiloxane, hexamethyldisiloxane, or combinations thereof. 【0060】 Activated aromatic compounds may be any aromatic molecule or a mixture thereof that has been activated for a Friedel-Crafts addition reaction. An aromatic molecule activated for a Friedel-Crafts addition reaction is defined as any aromatic molecule that can undergo addition with a mineral acid. In particular, it is any aromatic molecule that can undergo addition with a mineral acid in the application environment (AC system) or during the thermal stabilization test of ASHRAE 97:2007 "Sealed Glass Tube Method to Test the Chemical Stability of Materials for Use within Refrigerant Systems". Such molecules or compounds are typically activated by substituting a hydrogen atom of the aromatic ring with one of the following groups: NH2, NHR, NRz, ADH, AD, NHCOCH3, NHCOR, 4OCH3, OR, CH3, 4C2H5, R, or C6H5 (wherein R is a hydrocarbon (preferably a hydrocarbon containing about 1 to about 100 carbon atoms)). The activated aromatic molecule may be an alcohol or ether in which an oxygen atom (i.e., an oxygen atom of an alcohol or ether group) is directly bonded to the aromatic group. The activated aromatic molecule may be an amine in which a nitrogen atom (i.e., the nitrogen atom of the amine group) is directly bonded to the aromatic group. As an example, the activated aromatic molecule may have the formula ArXRn (wherein X is O (i.e., oxygen) or N (i.e., nitrogen); n:1 when X:O, and n:2 when x:N; Ar is an aromatic group (i.e., the group C6H5); R may be H or a carbon-containing group; when n:2, the R groups may be the same or different). For example, R may be H (i.e., hydrogen), Ar, an alkyl group, or any combination thereof. Exemplary activated aromatic molecules that may be used in the refrigerant compositions taught herein include diphenyl oxide (i.e., diphenyl ether), methylphenyl ether (e.g., anisole), ethylphenyl ether, butylphenyl ether, or any combination thereof. A very preferred aromatic molecule activated for Friedel-Crafts addition reactions is diphenyl oxide. 【0061】 From paragraph

[0045] of Serrano et al., incorporated by reference, the acid scavenger (e.g., activated aromatic molecules, siloxanes, or both) may be present at any concentration, resulting in a relatively low total acid value, a relatively low total halide concentration, a relatively low total organic acid concentration, or any combination thereof. Preferably, the acid scavenger is present at a concentration of more than about 0.0050% by weight, more preferably more than about 0.05% by weight, and even more preferably more than about 0.1% by weight (e.g., more than about 0.5% by weight) based on the total weight of the refrigerant composition. Preferably, the acid scavenger is present at a concentration of less than about 3% by weight, more preferably less than about 2.5% by weight, and most preferably less than about 2% by weight (e.g., less than about 1.8% by weight) based on the total weight of the refrigerant composition. 【0062】 Further examples of acid scavengers that may be included in the refrigerant composition, and are preferably excluded from the refrigerant composition, include those described by Kaneko (U.S. Patent Application No. 11 / 575,256, published as U.S. Patent Application Publication No. 2007 / 0290164, paragraph 42, expressly incorporated herein by reference), such as one or more epoxy compounds such as phenyl glycidyl ethers, alkyl glycidyl ethers, alkylene glycol glycidyl ethers, cyclohexene oxides, otren oxides, or epoxidized soybean lubricants, and those described by Singh et al. (U.S. Patent Application No. 11 / 250,219, published as U.S. Patent Application Publication No. 2006 / 0116310, paragraphs 34-42, expressly incorporated herein by reference). 【0063】 Performance enhancer Preferred additives include those described in U.S. Patents No. 5,152,926 and No. 4,755,316, which are incorporated herein by reference. Particularly preferred extreme pressure additives include mixtures of (A) tolyltriazole or a substituted derivative thereof, (B) an amine (e.g., Jeffamine M-600), and (C)(i) an ethoxylated phosphate ester (e.g., Antara LP-700), or (ii) a phosphate alcohol (e.g., ZELEC 3337), or (iii) zinc dialkyldithiophosphate (e.g., Lubrizol 5139, 5604, 5178, or 5186), or (iv) mercaptobenzothiazole, or (v) a 2,5-dimercapto-1,3,4-triadianazole derivative (e.g., Curvan 826), or a mixture thereof. Further examples of additives that may be used are given in U.S. Patent No. 5,976,399 (Schnur, 5:12–6:51, incorporated herein by reference). 【0064】 The acid value is measured in mgKOH / g units according to ASTM D664-01. The total halide concentration, fluoride ion concentration, and total organic acid concentration are measured by ion chromatography. The chemical stability of the refrigerant system is measured according to ASHRAE 97:2007 "Sealed Glass Tube Method to Test the Chemical Stability of Materials for Use within Refrigerant Systems". The viscosity of the lubricant is tested at 40°C according to ASTM D-445. 【0065】 Mouli et al. (International Publication No. 2008 / 027595) teach the use of alkylsilanes as stabilizers in refrigerant compositions containing fluoroolefins. In certain refrigerant compositions, phosphates, phosphates, epoxides, and phenolic additives are also used. These are described, for example, by Kaneko (U.S. Patent Application No. 11 / 575,256, published as U.S. Patent Application Publication No. 2007 / 0290164) and Singh et al. (U.S. Patent Application No. 11 / 250,219, published as U.S. Patent Application Publication No. 2006 / 0116310). All of these aforementioned applications are expressly incorporated herein by reference. 【0066】 Flame suppressant Preferred flame suppressants include those described herein by reference in the patent application "Compositions containing fluorine substituted olefins" Canadian Patent No. 2557873(A1)," as well as fluorinated products such as HFC-125 and / or Krytox® lubricants, similarly incorporated herein by reference in the patent application "Compositions comprising fluoroolefins and uses thereof" International Publication No. 2009018117(A1). 【0067】 Miscibility / Package Stability When used as the primary refrigerant for vehicle A / C systems, HFO-1234yf is generally found to be compatible with polyol esters or POE-type lubricants. However, in certain environments, not all POE lubricants possess the necessary miscibility range, thermal stability, material compatibility, and moisture levels, among other characteristics, that make them suitable for use with HFO-1234yf in automotive A / C systems. Therefore, the compositions of the present invention are substantially free of POE lubricants that do not possess the aforementioned characteristics. "Substantially free" means that when a composition of the present invention contains HFO-1234yf, the composition contains less than 5% by weight, typically less than 3% by weight, and in some cases less than 0.5% by weight, of the following POEs: Dow RL244, Zerol 150, and 3GS. The amount of lubricant typically used in A / C or refrigeration systems ranges from about 5% to about 10% by weight of the refrigerant. For example, 600g of refrigerant is used for filling, and 60g of lubricant is used (90 wt% refrigerant / 10 wt% lubricant). However, since refrigerant is used to move the lubricant into the system, the amount of POE lubricant used in combination with the refrigerant is relatively large, approximately 50-80 wt% lubricant / 20-50 wt% refrigerant (for example, about 60-65 wt% lubricant). 【0068】 The main component of the composition of the present invention may include a lubricant, but the trace component(s) may include a refrigerant having some small amount (0-5 wt%) of additives that improve the desired performance characteristics. That is, the refrigerant is used to transport or move the liquid lubricant and additives into the A / C system. 【0069】 Lubricants and refrigerants must be miscible over a much wider range due to storage and usage conditions. Many cities on Earth experience temperatures exceeding 37.5°C. Furthermore, lubricant / refrigerant compositions are expected to be stored in relatively hot warehouses or used in hot garages where temperatures may reach 37.5°C for periods exceeding 70 days. 【0070】 Furthermore, it is possible that the product may be used in winter after a major vehicle system failure, such as a head-on collision. Therefore, the lubricant / refrigerant should be stored in a low-temperature warehouse and only brought into the garage during maintenance. The lubricant / refrigerant composition is stable at temperatures of approximately -20, -30, -40, and even -50°C, which should help in storing the composition at -20°C for longer periods, such as 5 days. 【0071】 It is remarkable that the compositions of the present invention maintain miscibility over a wide range of temperature and pressure conditions (for example, a 20-50 wt% refrigerant / 50-80 wt% lubricant composition that is miscible over a temperature range of -18°C to 37°C at a pressure of 160 kPa to 945 kPa in a sealed container). The miscibility of POE lubricant / refrigerant is tested by loading a predetermined amount of lubricant and refrigerant (see table below) into a sealed tube using the ASHRAE 97:2007 "Sealed Glass Tube Method to Test the Chemical Stability of Materials for Use within Refrigerant Systems" method. The sealed tube is then placed in a water bath to determine whether the mixture is miscible over a certain temperature range. The test is performed in two segments, with a 24-hour period between segments to allow the tube to return to room temperature before starting the next segment. The cold segment starts at room temperature, slowly decreasing the temperature by 5°C increments to -50°C, holding each temperature for 10 minutes, and recording visual findings at each holding temperature. The hot segment begins at room temperature, and the temperature is slowly increased in 5°C increments to 90°C or the critical temperature of the refrigerant being tested, with each temperature held for 10 minutes, and visual observations recorded at each holding temperature. 【0072】 The thermal stability of POE lubricant / refrigerant compositions was evaluated using ASHRAE 97:2007, "Sealed Glass Tube Method to Test the Chemical Stability of Materials for Use within Refrigerant Systems." The lubricant / refrigerant systems were placed in sealed tubes containing metal (Al, Cu, carbon steel) coupons and maintained at 175°C for two weeks. The results demonstrated that the POE lubricant / low-GWP refrigerant was thermally stable at high temperatures, indicating that the composition should not decompose during storage. There was no tarnishing of the steel, no metal film or visible corrosion, and no fluoride ion formation or acid formation. No precipitates or aggregates formed during the test. The color of the refrigerant / lubricant system remained unchanged. 【0073】 It was an unexpected result that lubricants previously described as "miscible with HFO-1234yf" did not exhibit miscibility across the entire miscibility range. Specifically, POE is referred to as 86cSt type POE lubricant and is known by the following trademarks, namely "ND-11" and "SE-10Y". The acceptable POE lubricants for fixed applications were "Emkarate RL32-3MAF", "Emkarate RL32H", and "Solest 35". 【0074】 While not bound by theory or explanation, it is believed that as the refrigerant concentration increases and becomes the main component of the composition, the miscibility range of the lubricant / lubricant mixture changes. For example, 30% by weight lubricant / 70% by weight refrigerant is the limit for use in an A / C system, but it does not have sufficient miscibility to use the refrigerant to move the lubricant into the system. 【0075】 Conventional POE lubricants used with R-134a (Zerol 150 and 3GS) do not have the same miscibility range as R-1234yf (unsaturated low-GWP refrigerant). Therefore, not all POE lubricants are useful for low-GWP systems. 【0076】 Table 2 shows examples of low-GWP refrigerant / POE lubricant compositions and their miscibility ranges. In the table, the top of the table indicates the product's application in A / C systems, and the bottom of the table indicates the manufacturing and storage temperatures (in the table, "M" means miscibility and "N" means immiscibility). 【0077】 [Table 2] 【0078】 One aspect of the present invention relates to a method for introducing a lubricant into an A / C system. The method of the present invention uses a refrigerant to transport the lubricant and / or lubricant additive package into the A / C hose without substantially adhering to the hose, thereby ensuring that more lubricant or lubricant / additive package is introduced into the A / C system (for example, using a manual injector or manual pump may cause the lubricant to adhere to the hose line connected to the A / C system). Using a refrigerant to move the lubricant into the system ensures that more lubricant is introduced into the A / C system compared to manual or pump injectors because the refrigerant carries and transports the lubricant into the A / C system. The lubricant or lubricant / additive and the refrigerant are packaged together in a conventional container or can under the condition that the lubricant and refrigerant are miscible. If the small container is left standing, the refrigerant changes state from a compressed liquefied gas to a refrigerant gas. During this process, the refrigerant, which is miscible with the lubricant, atomizes the lubricant or lubricant / additive mixture and further transports the lubricant or lubricant / additive mixture along the hose and into the A / C system before there is a possibility that the lubricant or lubricant / additive mixture will settle on the wall of the A / C refill hose. 【0079】 In one aspect of the present invention, the composition of the present invention (lubricant or lubricant / additive and refrigerant) can be packaged in a small, sealed container that is typically 8 ounces or less, more typically 3 to 6 ounces, and more specifically 3 to 4 ounces. 【0080】 In one embodiment, the composition of the present invention may be packaged in a small container having a perforated or self-sealing can lid that can be connected to the vehicle's A / C system using a typical aftermarket refrigerant refill hose. 【0081】 In one embodiment, the fitting used in the can lid should be left-hand threaded and conform to a male CGA166 type connection, because the product is intended for use in low-GWP A / C systems containing HFO-1234yf. The type of hose used to transport the product from the can to the vehicle's A / C system should conform to the SAE J2888 standard for construction. The hose should have two different fittings. One end of the A / C refill hose should have either a puncture needle or a plunger-type mechanism, sometimes called a can tap, that can connect to a small can and release the product inside the container. The fitting connected to the can is a female CGA166 type fitting. The other end of the refill hose should have a designated SAE J639 low-side quick-connect coupler for HFO-1234yf and must be able to connect to the vehicle's A / C system through a low-side service port. 【0082】 In another aspect of the present invention, the composition of the present invention (lubricant or lubricant / additive and refrigerant) can be packaged in a small sealed container, typically 8 to 12 ounces or less. The composition of the present invention should be packaged in a small can having a perforated or self-sealing can lid that can be connected to a fixed system using a typical aftermarket refrigerant refill hose. The fittings used in the can lid should be left-hand threaded and fit a male CGA164 type connection if the product is intended for use in low GWP A / C systems used in flammable refrigerant systems. The fittings used in the can lid should be left-hand threaded and fit a male CGA165 type connection if the product is intended for use in low GWP A / C systems used in non-flammable refrigerant systems. 【0083】 To deliver the composition of the present invention into the A / C system, first, the can containing the lubricant or lubricant / additive and refrigerant should be thoroughly shaken. The vehicle engine should be started, and then the A / C system should be set to maximum cooling. Next, the aftermarket refill hose should be attached to the can as described above. The other end of the hose should be connected to the low-side service port of the vehicle's A / C system. When ready to begin dispensing the product, the contents of the can should be released using a needle or plunger mechanism. The can should be gently shaken from side to side to help release the contents. This process should take approximately 10-15 minutes. 【0084】 This composition can be used to add a lubricant or lubricant / additive to an A / C system at temperatures of approximately 0°C to approximately 40°C, more specifically, at temperatures of approximately 10°C and approximately 35°C, and even more specifically, at temperatures of approximately 15°C to approximately 30°C. The composition of the present invention can be stored at temperatures of a minimum of approximately -20°C and a maximum of approximately 40 to approximately 45°C, but is typically stored at temperatures of approximately 10 to approximately 35°C, more specifically, at temperatures of approximately 15 to approximately 30°C. Typically, when connected to an A / C system, the composition of the present invention is delivered to the A / C system at a pressure of approximately 315 kPa to approximately 435 kPa, or more specifically, approximately 330 kPa to approximately 410 kPa, or even more specifically, approximately 360 kPa to approximately 400 kPa. 【0085】 Another aspect of the present invention relates to a system for introducing the composition of the present invention into a thermal management system, such as an A / C system of an automobile. Referring here to Figure 1, Figure 1 shows a system (100) for introducing a lubricant into an A / C system of an automobile using the composition of the present invention. The system for delivering the composition of the present invention to an A / C system of an automobile includes a container (110) containing the composition, a compressor (120), a condenser (130), a dryer (140), an expansion valve (150), and an evaporator (160). The system (100) further includes a low-side service port (170) and a high-side service port (180). The container (110) or can containing the composition of the present invention is connected to the low-side service port (170) of the compressor (120) via a hose (190). The hose (190) and line (195) connecting the compressor, condenser, dryer, expansion valve, and evaporator are constructed and assembled using materials and methods known in the art. 【0086】 Referring now to Figure 2, which shows another embodiment of the present invention, including a system (200) for introducing the composition of the present invention into the A / C system of an electric vehicle. This system for introducing the lubricant composition includes a container (210) containing the composition, an electric compressor (220), a condenser (230), a dryer (240), an expansion valve (250) or an orifice tube (251), and an evaporator (260). The system (200) further includes a low-side service port (270) and a high-side service port (280). The container (210) of the composition of the present invention is connected to the low-side service port (270) of the electric compressor (220) via a hose (290). The hose (290) and line (295) shown in Figure 2 are constructed and assembled using materials and methods known in the art. 【0087】 Referring next to Figure 3, Figure 3 shows a further embodiment of the present invention, including a system (300) for introducing the composition of the present invention into a fixed residential heating / cooling system. This system (300) for introducing the lubricant composition includes a container (310) containing the composition, a compressor / condenser (320) located outside (330) the dwelling, and an evaporator / capillary (340) located inside (350) the dwelling. The container (310) is connected via a hose (370) to a low-side service port (360) of the compressor / condenser (320). The compressor / condenser (320) further includes a high-side service port (380). The hose (370) and line (390) shown in Figure 3 are constructed and assembled using materials and methods known in the art. 【0088】 Referring now to Figure 4, which illustrates another embodiment of the present invention, comprising a commercial fixed-type cooling system (400). This system (400) for introducing a lubricant composition comprises a container (410) containing the composition, a compressor (420), a rooftop condenser (430), a flash tank (440), and a defined refrigerated area (450) (e.g., a refrigerated display cabinet) within a commercial structure (460). The container (410) is connected via a hose (480) to a low-side service port (470) of the compressor (420), which can be located away from the defined refrigerated area (450). The hose (480) and line (490) shown in Figure 4 are constructed and assembled using materials and methods known in the art. 【0089】 When used in the present invention, the terms “comprises,” “comprising,” “includes,” “including,” “has,” “having,” or any other variations thereof are intended to encompass non-exclusive inclusion. For example, a composition, process, method, article, or apparatus containing the elements listed is not necessarily limited to those elements alone, but may include other elements not expressly listed, or other elements inherent in such a composition, process, method, article, or apparatus. Furthermore, unless expressly stated otherwise, “or” means comprehensive or not exclusive or. For example, condition A or B is satisfied by any one of the following: A is true (or exists) and B is false (or does not exist), A is false (or does not exist) and B is true (or exists), and both A and B are true (or exist). 【0090】 The transitional phrase "consisting of" excludes any unspecified elements, processes, or components. In the context of claims, with the exception of impurities normally associated with materials, such phrase excludes the inclusion of materials other than those enumerated from the claims. When the phrase "consisting of" appears in a clause of the claim rather than immediately following the preamble, it limits the elements to those specified in that clause only, and does not exclude other elements from the claims as a whole. 【0091】 The transitional phrase “essentially from” is used to define compositions and methods that include materials, processes, features, components, or elements in addition to those literally disclosed, provided that these additionally included materials, processes, features, components, or elements substantially influence the basic and novel features(s) of the claimed invention, particularly the modes of action for achieving any of the desired results of the processes of the invention. The term “essentially from” occupies an intermediate position between “includes” and “consists of.” 【0092】 If applicants define an invention or a part thereof using non-restrictive terms such as "including," it should be readily understood that (unless otherwise specified) such descriptions should be interpreted to include inventions that essentially consist of or comprise the terms "essentially comprised of" or "consist of." 【0093】 Furthermore, the use of "a" or "an" is employed to describe the elements and components described herein. This is merely for convenience and to give a general sense of the scope of the invention. This description should be interpreted as including one or at least one, and the singular form also includes the plural form unless it is evident that it has a different meaning. 【0094】 While specific aspects, embodiments, and principles have been described above, this specification is provided for illustrative purposes only and is not intended to limit the scope of the present invention or the appended claims.

Claims

[Claim 1] A composition comprising 50 to 80% by weight of a polyol ester (POE) lubricant and 20 to 50% by weight of a refrigerant containing HFO-1234yf, wherein the lubricant is miscible with the refrigerant over a temperature range of -18°C to 37°C at a pressure of 160 kPa to 945 kPa in a sealed container, as measured using ASHRAE 97:2007, the lubricant has a kinematic viscosity of 75 to 110 cSt as measured at 40°C according to ASTM D445 and a total acid number of 0.1 mg KOH / g or less as measured according to ASTM D974, and the refrigerant has a GWP of less than 300. [Claim 2] The composition according to claim 1, further comprising 1 to 5% by weight of an acid scavenging agent. [Claim 3] The composition according to claim 2, wherein the acid-cleansing agent comprises at least one element selected from the group consisting of hexamethyldisiloxane, polydimethylsiloxane, polymethylphenylsiloxane, dodecamethylpentasiloxane, decamethylcyclopentasiloxane, decamethyltetrasiloxane, or octamethyltrisiloxane. [Claim 4] A container comprising the composition according to claim 1, configured to deliver the composition to the air conditioning system of a vehicle. [Claim 5] The container according to claim 4, wherein the pressure inside the container is 160 kPa to 945 kPa. [Claim 6] The container according to claim 4, wherein the container is a sealed container and has a capacity of 8 to 12 ounces or less. [Claim 7] The container according to claim 4, wherein the container has a perforated can lid or a self-sealing can lid that can be connected to the vehicle's air conditioning system using an aftermarket refrigerant refill hose. [Claim 8] The container according to claim 4, wherein the container has a left-hand threaded fitting on its lid that is compatible with a male CGA166 type connection, and the container is configured for use in a low GWP A / C system containing HFO-1234yf. [Claim 9] Use of the container according to claim 4 for directly delivering the composition into the air conditioning system of a vehicle. [Claim 10] The use according to claim 9, wherein the container is part of a system for delivering the composition to the air conditioning system of the vehicle. [Claim 11] The use according to claim 10, wherein the air conditioning system of the vehicle includes an electric compressor, a condenser, a dryer, an expansion valve, and an evaporator. [Claim 12] The use according to claim 9, wherein the composition is delivered to the air conditioning system under pressure and temperature conditions in which the POE lubricant is miscible with the refrigerant. [Claim 13] The use according to claim 12, wherein the composition is delivered to the air conditioning system at a pressure of 315 kPa to 435 kPa. [Claim 14] The use according to claim 12, wherein the composition is delivered to the air conditioning system at a temperature of 18°C ​​to 37°C. [Claim 15] A system for delivering the composition to a vehicle air conditioning system, comprising the container described in claim 4.

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