COMPOSITION WITH HFC AND HFO

Description

Technical Field

[0001] The present invention relates to a composition comprising HFC and HFO. HFC denotes hydrofluorocarbon, and HFO denotes hydrofluoroolefin.Background Art

[0002] Amid worldwide discussion about global warming as a highly serious issue, the development of environmentally preferable refrigeration and air conditioning equipment have become increasingly important. Refrigerants have an impact on warming, and are greatly involved in the performance of refrigeration and air conditioning equipment; therefore, they play an important role in techniques to reduce emissions of carbon dioxide, which affects to warming.

[0003] In recent years, there have been various proposals for partially fluorinated propene (HFO) having a double bond in the molecule, which has lower global-warming potential (GWP) than conventionally known CFC (chlorofluorocarbon), HCFC (hydrochlorofluorocarbon), and HFC.

[0004] Known examples of HFO include HFO-1234yf (2,3,3,3-tetrafluoropropene) and HFO-1234ze (E- or Z-1,3,3,3-tetrafluoropropene).

[0005] These substances are used singly or in the form of a composition (mixture) for various applications. As such compositions, for example, compositions comprising a mixture of HFC and HFO are known:.

[0006] WO 2010 / 002020 (JP-A-2011-525205) discloses a refrigerant composition comprising 36-50 mass% of 1,1,1,2-tetrafluoroethane (HFC-134a) and 50-64 mass% of 2,3,3,3-tetrafluoropropene (HFO-1234yf).

[0007] WO 2011 / 093521 (JP-A-2013-501820) discloses a refrigerant composition comprising 30-50 mass% of difluoromethane (HFC-32) and 70-50 mass% of 2,3,3,3-tetrafluoropropene (HFO-1234yf).

[0008] WO 2010 / 002014 (JP-A-2011-525204) discloses a refrigerant composition comprising difluoromethane (HFC-32), pentafluoroethane (HFC-125), and 2,3,3,3-tetrafluoropropene (HFO-1234yf), wherein the ratio of HFC-32 / HFC-125 / HFO-1234yf is in a range surrounded by points (0 / 21 / 79 mass%), (16.6 / 25.3 / 58.1 mass%), and (0 / 28.4 / 71.6 mass%) in a ternary diagram of the refrigerant composition, and the composition essentially comprises HFC-32.

[0009] WO 2012 / 151238 (JP-A-2014-514423) discloses a heat transfer composition comprising (a) 20-30 wt.% of HFC-32, (b) 20-30 wt.% of HFC-125, (c) 0-15 wt.% of HFO-1234yf and 10-30 wt.% of HFO-1234ze, and (d) 15-30 wt.% of HFC-134a, with the weight percent being based on the total of the components (a)-(d) in the composition.

[0010] Although CFC and HCFC have lubrication performance, the lubrication performance of a composition comprising a mixture of HFC and HFO is lower than those of CFC and / or HCFC. In particular, when such a composition is used as a refrigerant composition, the lubrication performance as a whole is generally ensured by using a lubricating oil (refrigerant oil) in combination. In this respect, it is desirable to improve the lubrication performance of the composition comprising a mixture of HFC and HFO before a lubricating oil is used in combination. This improvement has become an issue.Summary of InventionTechnical Problem

[0011] An object of the present invention is to provide a composition comprising a mixture of HFC and HFO, and having improved lubrication performance.Solution to Problem

[0012] The present inventor conducted extensive research to achieve the above object, and consequently found that the above object can be achieved by a composition comprising HFC and HFO, and further comprising a specific third component. Thus, the present invention has been completed.

[0013] That is, the present invention relates to a composition comprising (1) HFO-1234ze and optionally HFO-1234yf; (2) HFC-134a and optionally HFC-134; and (3) HCFC-1122, HCFC-124, CFC-1113, and 3,3,3-trifluoropropyne.

[0014] Also, the invention provides the use of the present composition as a refrigerant composition.

[0015] Preferred embodiments of the invention are as defined in the appended dependent claims and / or in the following detailed description.Advantageous Effects of Invention

[0016] The compositions of the present invention have improved lubrication performance because they comprise HFC and HFO, and further comprise a specific third component (at least one of specific chlorine-containing substances and 1,1,1-trifluoropropyne, i.e., at least one of HCFC-1122, HCFC-124, CFC-1113, and 3,3,3-trifluoropropyne). The compositions of the present invention are useful as refrigerant compositions, for example.Brief Description of Drawing

[0017] Fig. 1 is a schematic view of a thrust-type friction and abrasion tester (pin-on-disk type) used in an abrasion test in the Examples and Comparative Examples.Description of Embodiments

[0018] The compositions of the present invention comprise HFC and HFO, and further comprise a specific third component (at least one of specific chlorine-containing substances and 1,1,1-trifluoropropyne, i.e., at least one of HCFC-1122, HCFC-124, CFC-1113, and 3,3,3-trifluoropropyne). The components constituting the composition of the present invention are defined in Table 1. Table 1CodeStructureChemical NameHFC-134aCF 3 CH 2 F1,1,1,2-tetrafluoroethaneHFC-134CF 2 HCF 2 H1,1,2,2-tetrafluoroethaneHFO-1234yfCF 3 CF=CH 2 2,3,3,3-tetrafluoropropeneHFO-1234zeCF 3 CH=CHFE- or Z-1,3,3,3-tetrafluoropropeneHCFC-1122CF 2 =CHCl2,2-difluoro-1-chloroethyleneHCFC-124CF 3 CFClH1,1,1,2-tetrafluoroethaneCFC-1113CF 2 =CClFChlorotrifluoroethylene-CH 3 C=CH3,3,3-trifluoropropyne Composition

[0019] The present composition comprises HFC and HFO, wherein the composition comprises: (1) HFO-1234ze and optionally HFO-1234yf as the HFO; (2) HFC-134a and optionally HFC-134 as the HFC; and (3) HCFC-1122, HCFC-124, CFC-1113, and 3,3,3-trifluoropropyne as a third component.

[0020] Compared with a composition comprising only a combination of HFC and HFO mentioned above, the present composition has improved lubrication performance because it comprises, in addition to the combination of HFC and HFO mentioned above, at least one of HCFC-1122, HCFC-124, CFC-1113, and 1,1,1-trifluoropropyne as a third component.

[0021] HFO-1234yf and HFO-1234ze may be used singly or mixed at any ratio for use. When HFO-1234yf and HFO-1234ze are mixed, it is preferable that the HFO-1234yf content is 1-99 mass%, and the HFO-1234ze content is 99-1 mass%, when the total amount of the HFOs is 100 mass%.

[0022] The third component includes HCFC-1122, HCFC-124, CFC-1113, and 3,3,3-trifluoropropyne. The content of each of these third components is not limited; however, among the third components, the CFC-1113 content is preferably higher.

[0023] The total amount of HFC and HFO is preferably ≥ 95 mass% when the total amount of the HFC, the HFO, and the third component (HCFC-1122, HCFC-124, CFC-1113, and 3,3,3-trifluoropropyne) is 100 mass%. In other words, the content of the third component is preferably < 5 mass%. Although the lubrication performance is maintained even when the content of the third component is ≥ 5 mass%, < 5 mass% is preferred in order to maintain the properties of the mixture composition of HFC and HFO.

[0024] The present composition has improved lubrication performance because it comprises HFC and HFO, and further comprises a specific third component (HCFC-1122, HCFC-124, CFC-1113, and 3,3,3-trifluoropropyne).

[0025] The present composition can be used for various applications, such as refrigerant compositions, aerosol propellants, foaming agents, blowing agents, solvents, cleaning agents, dispersion media, displacement drying agents, buffing abrasive agents, polymerization media, swelling agents, and fire suppression agents.

[0026] Among these applications, the composition of the present invention can be particularly suitably used as refrigerant composition because it has improved lubrication performance. For example, the present composition can be suitably used in various refrigerators, such as car air conditioners, vending machine refrigerators, commercial and home air conditioners, gas heat pumps (GHPs), and electrical heat pumps (EHPs). When used as a refrigerant composition, the present composition may further contain a refrigerant oil, if necessary. The refrigerant oil content, when used, is preferably 10-50 mass% of the refrigerant composition.Examples

[0027] The present invention is described in detail below with reference to Examples and Comparative Examples.

[0028] In the Examples and the Comparative Examples, the lubrication performance of each composition was evaluated from the results of an abrasion test and a baking test. The methods of the abrasion test and the baking test are as described below.Abrasion test

[0029] Using a thrust-type friction and abrasion tester (pin-on-disk type: see Fig. 1), abrasion loss was measured by the abrasion test using each composition.Baking test

[0030] Baking load was measured by the baking test using each composition, in which a rod (shaft material) was pressed to a rotating disk (bearing material) while applying a load. The baking load was evaluated as a relative value when the baking load in the Comparative Example was regarded as 100.Example 1 and Comparative Example 1

[0031] The compositions of Example 1 and Comparative Example 1 were prepared according to the formulations shown in Table 2. Table 2Example 1Comparative Example 1HFC-134a + HFC134 (60 mass%)99.5 mass%100 mass%HFO-1234yf (39.5 mass%)HCFC-1122 (0.3 mass%)0.5 mass%-HCFC-124 (0.1 mass%)CFC-1113 (0.05 mass%)1,1,1-trifluoropropyne (0.05 mass%)

[0032] Table 3 below shows the test results. Table 3Example 1Comparative Example 1Abrasion test (abrasion loss)4.0 µm4.3 µmBaking test (load)107100

[0033] The results of Table 3 revealed that the lubrication performance was improved by adding a third component.

Claims

1. A composition comprising: (1) HFO-1234ze and optionally HFO-1234yf; (2) HFC-134a and optionally HFC-134; and (3) HCFC-1122, HCFC-124, CFC-1113, and 3,3,3-trifluoropropyne.

2. The composition of claim 1, wherein the total amount of (1) and (2) is ≥ 95 mass%, based on the total amount of (1) - (3).

3. The composition of claim 1 or 2, which is a refrigerant composition.

4. The composition of any of claims 1-3, which further comprises a refrigerant oil in an amount of 10-50 mass% in the composition.

5. Use of a composition as defined in any of claims 1-4 as a refrigerant composition.