Azeotrope-like solvent mixtures exhibiting low global warming potential and methods of use thereof

Abstract

A cleaning solvent mixture comprising an HCFO, for example, 1-chloro-2, 3, 3-trifluoropropene, and a solvent mixture comprising at least one of an organic solvent, an organic solvent, and an organic solvent, trans dichloroethylene; and a high boiling point HFE, such as HFE-7300; the cleaning solvent composition has the application as a non-flammable, low global warming potential, azeotrope-like cleaning solvent composition. The other solvent components may include a surfactant and a co-solvent. A method of removing soils from an article includes contacting the article with a solvent composition, or by contacting with a liquid and / or vapor solvent composition, such as in a conventional vapor degreaser device, in any suitable manner, such as a spray delivered by a propellant gas, and removing the composition from the article.

Description

[0001] Related applications

[0002] This application claims priority to provisional patent application serial number 63 / 487,906, filed on March 2, 2023, entitled "AZEOTROPE-LIKE SOLVENT BLENDS EXHIBITING LOW GLOBAL WARMING POTENTIAL AND METHODS OFUSE", filed in the name of Trenessa Rioux. Technical Background Technical Field

[0003] This invention relates to solvent-based cleaning compositions (sometimes referred to herein as "mixtures") for cleaning various articles (including metals and plastics in metalworking, electronics, and other industries) in industrial processes. These solvent-based cleaning compositions are non-flammable and azeotropic, composed of low global warming potential components that do not deplete the ozone layer, and possess highly efficient cleaning capabilities. The solvent mixtures of this invention can also be used as carrier fluids for lubricants, etc.

[0004] Related technical descriptions

[0005] Solvent mixtures are used in industrial processes to clean a variety of contaminants and residues (hereinafter sometimes referred to as "soil" or "soiling substances"). The electronics industry typically cleans flux, solder paste, adhesives, and coatings from various sources before and after component assembly. Such sources can include one or more materials across a wide range, including metals, ceramics, and synthetic polymer (plastic) substrates and components. Metalworking operations must remove lubricants and soaps, abrasive media, and grease from metal surfaces. Many of these contaminants are difficult to remove from metal surfaces, especially when using non-aqueous cleaning agents.

[0006] Of particular interest are non-flammable solvent mixtures, which provide cleaning solvents that can be safely used in aerosol packaging, as wiping fluids, or in bulk cleaning tanks, such as in vapor degreasing (“VDG”) units. Typically, these cleaning solvents include halogenated compounds that are not inherently flammable, or that can become non-flammable in mixtures with other halogenated compounds. For example, chlorinated hydrocarbons, such as flammable trans-dichloroethylene (TDCE), are known to be used as high-solubility components, along with fluorinated components (used to make the cleaning solvent mixture non-flammable). Furthermore, especially for VDG applications, the cleaning solvent mixture should be an azeotrope or exhibit azeotropic behavior and be non-flammable, and therefore the vapors should also be non-flammable. Therefore, it is highly desirable that the azeotrope does not undergo significant fractionation after distillation, condensation, and remixing as it does in the vapor degreasing unit. That is, in VDG, the component ratios in the boiling tank should be nearly identical to, or at least not drastically different from, the component ratios in the washing tank; or, similarly, the component ratios in the boiling flask and receiver throughout the distillation process.

[0007] The industry seeks to maximize the cleaning power of its products, often defined as the Kauri-Butanol index (“KB value”). A high KB value indicates a high cleaning power of the solvent component or solvent mixture. To achieve a high KB value, the concentration of TDCE or other high-KB components in the blend is as high as possible. However, as the amount of high-KB components in the composition increases, the solvent mixture becomes more difficult to make non-flammable. DuPont has made significant progress in this area with the introduction of an azeotropic blend of 4% by weight methyl perfluoroheptene (MPHE) ether, 0.8% by weight Vertrel XF, and 95.2% by weight TDCE, supplied by Chemours as Opteon SF79. This is currently the highest concentration of TDCE in a commercial product. The product has a KB value of 100. However, the high TDCE concentration has an adverse effect on flammability, meaning that the Opteon SF79 solvent is more flammable than intended.

[0008] US Patent Application Publication US2016 / 0326468 A1, published November 10, 2016 by Robin et al., discloses a composition comprising 0.1 to 8 wt% of methyl perfluoroheptenyl ether, 90 to 99 wt% of trans-1,2-dichloroethylene, and 0.6 to 2 wt% of hydrofluorocarbons (HFCs) selected from a very large group including heptafluorocyclopentane.

[0009] U.S. Patent 10,669,502 to D. Ikeda et al., issued on June 2, 2020, discloses 65-80% TDCE, 5-25% low-boiling-point (40-65°C) HFE and 5-25% high-boiling-point (70-120°C) HFE as a cleaning and carrier fluid composition.

[0010] U.S. Patent 10,828,579 to R. Singh, issued on November 10, 2020, discloses aerosol compositions of trans- and cis-1-chloro-2,3,3-trifluoro-1-propene (HCFO 1233yd E&Z) and a large group of cosolvents.

[0011] U.S. Patent Publication 2022 / 0073804 to H. Mitsuoka, published on March 10, 2022, discloses an azeotrope of TDCE (34.5%) and HCFO1233ydZ (65.5%).

[0012] U.S. Provisional Patent Application Serial No. 63 / 351969 (Attorney's File MCC0125US) discloses an azeotropic solvent mixture of 70-95.7% TDCE, 3.8-15% heptafluorocyclopentane, and 0.5-15% 1-chloro-2,3,3-trifluoro-1-propene.

[0013] In addition to maximizing cleaning power and reducing flammability, the industry is also seeking cleaning products with minimal environmental impact. Ideally, cleaning products should have zero ozone depletion potential and negligible global warming potential.

[0014] Hydrochlorofluorocarbons (HCFCs) with high ozone-depleting potential have been replaced by non-ozone-depleting HFCs. Many HFCs are also being replaced today due to their high global warming potential. For example, HFC-43-10mee, commonly known as Vertrel XF, has a global warming potential (“GWP”) of 1640.

[0015] The Global Warming Potential (GWP) is established to compare the impact of different gases on global warming. Specifically, it is a measure of how much energy one ton of a gas will absorb relative to one ton of carbon dioxide (CO2) emissions over a given time period. The higher the GWP, the greater the degree to which a given gas contributes to global warming during that period, compared to CO2. A 100-year timeframe is commonly used for GWP. GWP provides a universal unit of measurement, allowing analysts to estimate emissions of different gases. Hydrofluoroethers (HFE), hydrofluoroolefins (HFO), and hydrochlorofluoroolefins (HCFO) have relatively low GWPs and are therefore preferred ingredients in cleaning products. Summary of the Invention

[0016] This invention relates to clean solvent compositions exhibiting azeotropic behavior with low flammability and low global warming potential. This azeotropic behavior enables the effective use of these solvent compositions (sometimes referred to herein as solvent mixtures or blends) in vapor degreasing operations. The clean solvent compositions of this invention exhibit substantially no fractionation or only limited fractionation during distillation, which is important for efficient and safe operation of clean processes and for the safety of various solvent packaging such as bulk solvents, solvent aerosols, wipes, and pump sprays. The solvent compositions of this invention can also be used in other applications, such as as carrier fluids for lubricants or other materials, for example, in the application of lubricants in manufacturing operations.

[0017] This invention provides a solvent mixture comprising about 40% to about 90% by weight of trans-dichloroethylene, monochlorotrifluoropropylene, hydrofluoroether, and optionally C1 to C3 alcohol. One or two of a suitable surfactant and a suitable cosolvent may be added in an amount that does not significantly and adversely affect the non-flammability, azeotropic properties, and effective cleaning ability of the solvent mixture.

[0018] For example, one embodiment of the solvent mixture of the present invention comprises 59-80% trans-dichloroethylene; 11-23% monochlorotrifluoropropylene, such as one or more described in column 5, lines 1-17 of U.S. Patent 10,828,579; 5-20% high-boiling hydrofluoroether (HFE) as described in claim 2 of U.S. Patent 10,669,502; and 0-5% C1-C3 alcohol. In some embodiments, the solvent mixture of the present invention may contain other components, such as surfactants and co-solvents described below, as well as other components in amounts and characteristics that maintain the azeotropic, low global warming potential, and cleaning efficacy properties of the solvent mixture. Alternatively, the solvent mixture of the present invention may be limited to (“consisting of”) only the claimed components or the claimed components plus components that do not affect the essential characteristics of the invention (“consisting of substantially”).

[0019] Monochlorotrifluoropropylene can be selected from, for example, the group consisting of: trans-CF3CH═CC1H(1233zdE); cis-CF3CH═CCIH(1233zdZ); trans-CHF2CF═CCIH(1233ydE); cis-CHF2CF═CCIH(1233ydZ); trans-CHF2CH═CC1F(1233zbE); cis-CHF2CH═CC1F(1233zbZ); trans-CHF2C One or more of the following: C1═CHF(1233xeE); cisCHF2CC1═CHF(1233xeZ); CH2FCC1═CF2(1233x0); transCHFC1CF═CFH(1233yeE); cisCHFC1CF═CFH(1233yeZ); CH2C1CF═CF2(1233yc); CF2C1CF═CH2(1233xf); and two or more of these.

[0020] For example, hydrofluoroethers may be selected from the group consisting of: ethyl nonafluorobutyl ether, 1,1,2,3,3,3-hexafluoropropyl-2,2,2-trifluoroethyl ether, 1,1,2,2-tetrafluoroethyl-2,2,3,3,3-pentafluoropropyl ether, 1,1-difluoroethyl-2,2,3,3-tetrafluoropropyl ether, 1,1,2,3,3,3-hexafluoropropyl-2,2,3,3,3-pentafluoropropyl ether, 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether, 1,1,2,3,3,3-hexafluoropropyl-2,2,3,3-tetrafluoropropyl ether, and 3-methoxy-4-trifluoromethyl-1,1,1,2,2,3,4,5,5,5-decafluoropentane, or two or more of these groups.

[0021] Other aspects of this application provide solvent compositions exhibiting azeotropic properties, comprising:

[0022] Approximately 71 to approximately 75% by weight of trans-dichloroethylene (TDCE), and approximately 15 to approximately 19% by weight of 1-chloroethylene

[0023] -2,3,3-trifluoro-1-propene (AS300) and about 7 to about 10% by weight of 3-methoxy-4-trifluoromethyl

[0024] -1,1,1,2,2,3,4,5,5,5-Decafluoropentane (HFE-7300);

[0025] About 85 to about 95% by weight of trans-dichloroethylene (TDCE), about 1 to about 5% by weight of 1-chloro-2,3,3-trifluoro-1-propene (AS300) and about 1 to about 5% by weight of 3-methoxy-4-trifluoromethyl-1,1,1,2,2,3,4,5,5,5-decafluoropentane (HFE-7300);

[0026] About 90% by weight trans-dichloroethylene (TDCE), about 5% by weight 1-chloro-2,3,3-trifluoro-1-propene (AS300) and about 5% by weight 3-methoxy-4-trifluoromethyl-1,1,1,2,2,3,4,5,5,5-decafluoropentane (HFE-7300).

[0027] Approximately 59 to 70% by weight of trans-dichloroethylene (TDCE), and approximately 10 to 25% by weight of 1-chloroethylene.

[0028] -2,3,3-trifluoro-1-propene (AS300) and about 11 to about 18% by weight of 3-methoxy-4-trifluoromethyl

[0029] -1,1,1,2,2,3,4,5,5,5-decafluoropentane (HFE-7300) and about 1 to about 5 by weight of ethanol;

[0030] Approximately 63% by weight trans-dichloroethylene (TDCE), approximately 20% by weight 1-chloro-2,3,3-trifluoro-1-propene (AS300), approximately 15% by weight 3-methoxy-4-trifluoromethyl-1,1,1,2,2,3,4,5,5,5-decafluoropentane (HFE-7300), and approximately 2% by weight ethanol;

[0031] About 40 to about 60% by weight of trans-dichloroethylene (TDCE), about 15 to about 40% by weight of 1,1,2,2-tetrafluoroethyl-2,2,2-triethyl ether (AE3000), and about 10 to about 25% by weight of 1,1,1,2,3,3-hexafluoro-3-methoxypropane (HFE-356).

[0032] Approximately 40 to 60% by weight of trans-dichloroethylene (TDCE), and approximately 11 to 21% by weight of 1-chloroethylene.

[0033] -2,3,3-trifluoro-1-propene (AS300) and about 20 to about 40% by weight of 1,1,1,2,3,3-hexafluoro-3-methoxypropane (HFE-356); and

[0034] It contains approximately 53% by weight trans-dichloroethylene (TDCE), approximately 11% by weight 1-chloro-2,3,3-trifluoro-1-propene (AS300), and approximately 36% by weight 1,1,1,2,3,3-hexafluoro-3-methoxypropane (HFE-356).

[0035] The method aspect of the present invention provides a method for removing contaminants from metal, ceramic, and synthetic polymer articles, comprising: contacting one or more articles with a solvent composition exhibiting azeotropic properties as disclosed herein, and removing the solvent composition from the articles.

[0036] This invention overcomes or at least improves upon the problems of prior art, such as U.S. Patent 10,669,502. This is achieved by using monochlorotrifluoropropylene (HCFO) instead of the low-boiling-point hydrofluoroether specified in U.S. Patent 10,669,502, thus maintaining the concentration of TDCE while significantly increasing the KB value due to the inherently higher KB value of HCFO. Furthermore, the superior flame-retardant properties of HCFO allow for the optional introduction of C1-C3 alcohols into the solvent blends of this invention, which further increases the KB value of the blend without making it flammable, while keeping the TDCE at a low weight percentage. This can be crucial in applications such as removing highly polar / ionic contaminants from so-called "clean-free" fluxes used in the electronics industry. When seeking compatibility with plastic substrates, a lower percentage of TDCE is sometimes necessary because higher TDCE levels can negatively impact the compatibility of the plastic substrate.

[0037] One embodiment of the cleaning solvent composition of the present invention comprises about 59 to about 70 wt% trans-dichloroethylene (TDCE), about 10 to about 25 wt% 1-chloro-2,3,3-trifluoro-1-propene (AS300), about 11 to about 18 wt% 3-methoxy-4-trifluoromethyl-1,1,1,2,2,3,4,5,5,5-decafluoropentane (HFE-7300), and about 1 to about 5 wt% ethanol. The KB value of this mixture is 99.

[0038] A second embodiment of the cleaning solvent composition of the present invention comprises about 70 to about 80 wt% trans-dichloroethylene (TDCE), about 11 to about 21 wt% 1-chloro-2,3,3-trifluoro-1-propene (AS300), and about 5 to about 15 wt% 3-methoxy-4-trifluoromethyl-1,1,1,2,2,3,4,5,5,5-decafluoropentane (HFE-7300). The KB value of this mixture is 99.

[0039] A third embodiment of the cleaning solvent composition of the present invention comprises about 40 to about 60 wt% trans-dichloroethylene (TDCE), about 11 to about 21 wt% 1-chloro-2,3,3-trifluoro-1-propene (AS300), and about 20 to about 40 wt% 1,1,1,2,3,3-hexafluoro-3-methoxypropane (HFE-356). The KB value of this mixture is 57.

[0040] A fourth embodiment of the cleaning solvent composition of the present invention comprises about 40 to about 60 wt% trans-dichloroethylene (TDCE), about 15 to about 40 wt% 1,1,2,2-tetrafluoroethyl-2,2,2-triethyl ether (AE3000), and about 10 to about 25 wt% 1,1,1,2,3,3-hexafluoro-3-methoxypropane (HFE-356). The KB value of this mixture is 58.

[0041] A fifth embodiment of the cleaning solvent composition of the present invention comprises about 85 to about 95 wt% trans-dichloroethylene (TDCE), about 1 to about 5 wt% 1-chloro-2,3,3-trifluoro-1-propene (AS300), and about 1 to about 5 wt% 3-methoxy-4-trifluoromethyl-1,1,1,2,2,3,4,5,5,5-decafluoropentane (HFE-7300). The KB value of this mixture is 115.

[0042] Another embodiment of the cleaning solvent composition of the present invention includes any of the above embodiments, wherein a surfactant is added at a concentration of about 0.1 to about 3% by weight. Suitable surfactants include, but are not limited to, RhodafacRS-710 (80-90% polyoxyethylene tridecyl ether phosphate [CAS#9046-01-9], 15-20% alcohol ethoxylate [CAS#78330-21-9], 1-5% phosphoric acid [CAS#7664-38-2], <1% water [CAS#7732-18-5]), Tergitol 15-S-3 (C12-14 secondary ethoxylated alcohol), and Steposol (N,N-dimethyl-9-decanoic acid, [MET10U]).

[0043] Another embodiment of the cleaning solvent composition of the present invention comprises any of the solvent mixtures described above, with the addition of a co-solvent, the amount of which is about 1 to about 50% by weight of the other components in the solvent mixture. This embodiment of the present invention is hereinafter referred to as a "high co-solvent mixture". In this embodiment, the boiling tank of the vapor degreasing apparatus is provided with the high co-solvent mixture, and the co-solvent is not distilled into the washing tank. Suitable co-solvents include, but are not limited to, Steposol (N,N-dimethyl-9-decanoic acid, [MET10U]), Rhodafac RS-710 (80-90% polyoxyethylene tridecyl ether phosphate [CAS#9046-01-9], 15-20% alcohol ethoxylate [CAS#78330-21-9], 1-5% phosphoric acid [CAS#7664-38-2], <1% water [CAS#7732-18-5]), benzyl alcohol, and hexanediol.

[0044] Unless otherwise specified or clear from the context, all percentages of a given component, whether expressed as “wt%”, “weight%”, “weight percentage” or otherwise, are weight percentages of the component in the solvent mixture based on the total weight of the solvent mixture.

[0045] As used herein, the term "quasi-azeotropic" or similar meaning used in relation to the clean solvent mixtures of the present invention refers to a solvent mixture that, while it may not possess perfect azeotropic properties (although some mixtures of the present invention may be), exhibits minimal or limited compositional change after repeated distillation steps, i.e., no more than 20% by weight of the initial amount of each component in the mixture during at least 5 hours of continuous distillation (evaporation and condensation). Generally, the term "quasi-azeotropic composition" refers to an azeotropic or substantially azeotropic liquid mixture of two or more substances that behaves as or nearly as a single substance upon distillation. That is, the vapor produced by distilling the liquid has at least substantially the same composition as the liquid from which it was distilled (within the 20% by weight variation described above). In other words, there is no substantial change in composition when the mixture is distilled. Furthermore, quasi-azeotropic compositions can be characterized by boiling points lower than the boiling points of each pure component in the composition.

[0046] To illustrate the azeotropic behavior of one embodiment of the solvent mixture of the present invention, see Example 5 below. The TDCE component was initially present in an amount of 75% by weight of the mixture, and even after the ninth stage of fractionation, when the remaining mixture was only 24% by weight of the initial amount, TDCE was present in an amount of 75.44% by weight. The weight percentage of TDCE removed by fractionation was calculated as follows: (75.44-75) / 75 x 100 = 0.58% by weight. This illustrates the azeotropic behavior of the solvent mixture.

[0047] The solvent compositions of the present invention may contain other components, such as surfactants and cosolvents as described above, provided that the type and amount of these other components do not significantly and adversely affect the low global warming potential, azeotropic properties, or cleaning efficacy of the composition. That is, the solvent mixtures of the present invention may contain, consist of, or be substantially composed of the specified components. In some cases, the solvent mixture may consist of only specific components, except for trace impurities found in commercially available ingredients used to prepare the solvent mixtures of the present invention. Propellants may be used to transport the solvent compositions of the present invention. Because such propellants evaporate, they do not affect the low global warming potential, azeotropic properties, or cleaning efficacy of the solvent composition. Attached Figure Description

[0048] Figure 1This is a front view of a benchtop simulation of a standard 2-sump vapor degreaser, which includes a double-sphere assembly for obtaining the double-sphere distillation data described below; and

[0049] As shown in the figure Figure 2-11 This is a graph showing the changes in the concentration of solvent mixture components identified during double-ball distillation or fractionation. Detailed Implementation

[0050] The following abbreviations, trademarks, and product names have the following meanings, whether used in the singular or plural form.

[0051] “TDCE” or “Trans”. Trans dichloroethylene. Chemical Abstracts Service number (“CAS#”) 156-60-5.

[0052] “XF”. Hydrofluorocarbon compound, 2,3-dihydrodecafluoropentane (HFC 43-10me) [trade name VertrelXF]. CAS#1384-95-42.

[0053] "AS300" is a specific mixture of the cis and trans geometric isomers of 1-chloro-2,3,3-trifluoropropene, produced by >

[0054] Composed of 89% (Z)-1-chloro-2,3,3-trifluoropropene and <10% (E)-1-chloro-2,3,3-trifluoropropene, by AGC, Inc.

[0055] Chemicals Company offers it under the trade name "Amolea AS300".

[0056] “SF33”. Hydrofluoroolefin, (Z)-1,1,1,4,4,4-hexafluoro-2-butene; Chemours Company’s trade name Opteon SF33. CAS#692-49-9.

[0057] “HFX-110”. Methyl perfluoroheptenyl ether; Trade name HFX-110. CAS#Proprietary.

[0058] "HFC" refers to, for example, 2,3-dihydrodecafluoropentane (HFC 43-10mee) and heptafluorocyclopentane.

[0059] “HFCP”. 1,1,2,2,3,3,4-Hepenocyclopentane. Trade name: Zeorora. CAS#15290-77-4.

[0060] “HFE”. Hydrofluoroether, such as 3-methoxy-4-trifluoromethyl-1,1,1,2,2,3,4,5,5,5-decafluoropentane CAS#132182-92-4 (HFE-7300).

[0061] “ SFR”. 67% trans-dichloroethylene, 18% 2,3-dihydrodecafluoropentane (HFC 43-10mee);

[0062] A mixture of 12% heptafluorocyclopentane and 3% methanol. The substance has a boiling point of 106°F (41.1°C) and is available from Chemours Corporation in Wilmington, Delaware.

[0063] "Opteon SF79" is a mixture of 95.2% trans-dichloroethylene, 4.0% methyl perfluorohepten ether (HFX-110), and 0.8% 2,3-dihydrodecafluoropentane (HFC 43-10mee). The substance has a boiling point of 121°F.

[0064] (49.4℃), available from Chemours Corporation in Wilmington, Delaware.

[0065] "Opteon SF80" is a mixture of 95.2% trans-dichloroethylene, 4.0% methyl perfluorohepten ether (HFX-110), and 0.8% (Z)-1,1,1,4,4,4-hexafluoro-2-butene (Opteon SF33). The substance has a boiling point of 121°F (49.4°C) and is available from Chemours Corporation in Wilmington, Delaware.

[0066] “EtOH”. Ethanol.

[0067] “MeOH”. Methanol.

[0068] Figure 1 A laboratory glassware 10 is shown, comprising a boiling ball 12 having a neck 12a protruding into a washing ball 14. An opening 12b is formed in the neck 12a within the washing ball 14. A condenser 16 is mounted at the outlet end 14a of the washing ball 14 and includes a cooling coil 18 disposed within the condenser 16. A cold water inlet 18a is connected to a cooling water source (not shown), and a cold water outlet 18b is connected to a drain (not shown). The boiling ball 12 is mounted on a heated fireplace mantle 20.

[0069] In use, the solvent composition to be tested is introduced into boiling ball 12 and heated to boil the solvent composition and generate vapor. The vapor rises to cleaning ball 14 and then enters condenser 16 as indicated by arrow V1. The vapor condenses by contact with cooling coil 18 and flows into cleaning ball 14 as indicated by arrow C1. When the condensate collected in cleaning ball 14 reaches the level of orifice 12b, the overflow solvent flows back into boiling ball 12 as indicated by arrow C2.

[0070] Standard test procedures The test was conducted in a standard twin-tank steam degreaser, or using... Figure 1 The simulation was conducted on a benchtop using a "double-sphere" apparatus of the type shown, which has a standard solvent distillation head with a collection bottle and a sampling port on a boiling flask. Figure 1 (Not shown in the image). Gas chromatography analysis of samples from different locations and times was performed using an Agilent Corporation DB-200 capillary column (trifluoropropylmethyldimethylsiloxane stationary phase) and an FID detector. The following examples report the results of tests performed according to this standard test procedure.

[0071] Comparative Example 1. Distillation in a steam degreaser SFR.

[0072]

[0073] It can be seen that although this solvent mixture essentially maintains an azeotropic behavior, its vapor composition changes rapidly and significantly. The TDCE ratio between the boiling tank and the rinsing tank changed by more than 10% compared to the original value (from 67.7 wt% to 78.2 wt%).

[0074] Comparative Example 2. Distillation of Opteon SF79

[0075]

[0076] As can be seen, the weight percentage of Vertrel XF in the mixture between the "boiling" and "washing" bottles also changed significantly. Most notably, the Vertrel XF used to improve the non-flammability of the mixture was almost completely consumed in the boiling flask early in the distillation process.

[0077] Comparative Example 3. Distillation of Opteon SF80

[0078]

[0079] It can be seen that this product mixture also altered the ratio between the "boiling" and "washing" bottles. Most notably, the SF33 used to improve the non-flammability of the mixture was almost completely depleted in the boiling tank.

[0080] Example 4. The mixture 25-68-2 (one embodiment of the present invention) was fractionated, and the results are listed in Table 1 below.

[0081] Table 125-68-2 Fractionation Data

[0082] distillate HF-7300 TDCE EtOH AS300 Distillation temperature (°C) Top temperature (°C) % Remaining Solvent initial concentration 15 63 2 20 100％ 1 11.96 65.06 2.91 20.07 46 45.5 91％ 2 11.53 64.50 3.57 20.33 46 45.5 83％ 3 12.06 66.35 2.42 19.16 47 45.7 74％ 4 12.22 66.12 2.33 19.31 47 45.8 65％ 5 12.46 65.89 2.18 19.44 47 45.9 55％ 6 12.64 65.77 2.00 19.58 47 45.9 44％ 7 12.96 65.46 1.74 19.82 47 46.1 34％ 8 13.46 65.10 1.36 20.06 47 46.2 24％ 9 14.05 64.66 0.93 20.33 47 44.4 14％ 10 15.16 63.67 0.43 20.72 47 46.7 6％ % component difference -1.07 -1.06 78.50 -3.60

[0083] Figure 2 The data in Table 1 is illustrated in a chart.

[0084] Example 4 shows that, prior to a 20% change in ethanol concentration, this embodiment of the invention maintained azeotropic-like characteristics in approximately 70% of the fractionation process. This is within the safe operating parameters for vapor defatting.

[0085] The composition of the 25-68-2 distillate in fraction 5 is rounded to the nearest integer.

[0086] 13% HFE-7300

[0087] 67% TDCE

[0088] 2% EtOH

[0089] 20% AS300

[0090] No detectable flashes were found in the ASTM D56 flash point test of fractions 1-5.

[0091] Similarly, the double-ball distillation of solvent mixture 25-68-2 also demonstrated the azeotropic behavior of the mixture, as shown in Table 2 below. The composition of the mixture did not change slightly until the turnover was 6. (The term "turnover" refers to the volume of the washing tank per distillation cycle.) Double-ball distillation is very similar to efficient vapor degreasing operations.

[0092] Table 2 25-68-2 Double-sphere distillation

[0093]

[0094] Table 2 25-68-2 Double-sphere distillation (continued)

[0095] distillate Turnover Boiling temperature Steam temperature initial concentration 0 1 1 47 46.5 2 2 47 46.5 3 3 47 46.5 4 4 47 46.5 5 5 47 46.5 6 6 47 46.5 % component difference

[0096] Figure 3 The data in Table 2 is illustrated in a chart.

[0097] The Kb value of Example 4 is 99, indicating good solvation and thus effective cleaning.

[0098] Example 5. As shown in Table 3, mixture 25-74-1 (an embodiment of the present invention) was fractionated. The fraction distilled to 76% indicates the azeotropic properties of this solvent mixture.

[0099] Table 3 25-74-1 Fractionation

[0100] distillate HFE-7300 TDCE AS300 Distillation temperature (°C) Top temperature (°C) % Remaining Solvent initial mixture 9 75 16 100％ 1 9.73 71.77 18.48 48 46.8 92％ 2 9.69 72.15 18.14 48 46.8 84％ 3 9.69 72.37 17.93 49 46.9 76％ 4 9.70 72.55 17.73 49 46.9 68％ 5 9.67 72.82 17.50 49 46.9 60％ 6 9.60 73.22 17.16 49 46.9 52％ 7 9.52 73.68 16.79 49 47 43％ 8 9.39 74.24 16.36 49 46.9 33％ 9 8.99 75.44 15.56 49 47 24％ % component difference 0.11 -0.59 2.75

[0101] Figure 4 The data in Table 3 is illustrated in a chart.

[0102] The results of the double-sphere fractionation of solvent mixture 25-74-1 are listed in Table 4.

[0103] Table 4

[0104]

[0105] Figure 5 The data in Table 4 is illustrated in a chart.

[0106] Even after 8 cycles, the dual-ball data remained virtually unchanged (Kb = 99), supporting effective steam degreasing and cleaning performance.

[0107] Examples 6 and 7 below are based on a medium TDCE content level (<60 wt% TDCE). A medium TDCE level may be required when plastic substrate compatibility is needed, i.e., if the plastic surface of the substrate will not degrade.

[0108] Example 6, solvent mixture 25-64-3 has the following components in initial amounts:

[0109] HFE 356:36.wt%

[0110] TDCE 52.8wt%

[0111] AS300 11.2wt%

[0112] Fractional distillation of the mixture yielded the following results.

[0113] Fractionation in Table 525-64-3

[0114] distillate HFE-356 Trans AS300 Distillation temperature (°C) Top temperature (°C) % Remaining Solvent initial mixture 36 52.8 11.2 100％ 1 36.38 52.60 11.02 45 43.2 92％ 2 40.58 54.25 14.65 45 43.6 85％ 3 40.08 51.67 8.23 45 43.6 76％ 4 39.74 51.69 8.55 45 43.7 68％ 5 39.31 51.80 8.87 45 43.9 60％ 6 38.70 51.99 9.29 45 43.9 52％ 7 38.17 52.09 9.72 45 43.9 44％ 8 37.37 52.25 10.36 45 44 35％ 9 36.05 52.67 11.27 45 44 27％ 10 34.32 53.15 12.51 45 44.2 18％ % component difference -4.67 0.66 11.70

[0115] The fact that the component ratio changed by less than 20% in 80% distillation clearly indicates that it is an azeotropic mixture.

[0116] Figure 6 The data in Table 5 is illustrated in a chart.

[0117] Double-sphere distillation of solvent mixture 25-64-3 showed that even at a turnover rate of 8, the component ratios changed only slightly, indicating that the mixture is an azeotropic solvent.

[0118] Double-sphere distillation (Table 625-64-3)

[0119]

[0120] Figure 7 The data in Table 6 is illustrated in a chart.

[0121] The solvent mixture of Example 6 has a KB value of 57 and has been tested to be non-flammable.

[0122] Example 7 Fractionation of Formula 25-65-1

[0123] This formulation contains two low-boiling-point HFE solvent components. HFE 356 and AE3000 (1,1,2,2-tetrafluoroethyl-2,2,2-triethyl ether) each have a boiling point of approximately 54°C.

[0124] Table 7

[0125] distillate HFE356 AE3000 TDCE ethanol Distillation temperature (°C) Top temperature (°C) % Remaining Solvent initial mixture 20 26.5 50.5 3 100％ 1 19.61 27.87 49.55 2.95 43 41.4 93％ 2 18.66 29.62 49.30 2.4 43 41.5 85％ 3 18.85 29.39 49.29 2.45 43 41.9 77％ 4 19.04 29.15 49.28 2.51 43 41.8 69％ 5 19.22 28.93 49.29 2.54 43 41.9 61％ 6 19.43 28.62 49.33 2.59 43 41.9 53％ 7 19.67 28.29 49.37 2.65 43 41.9 46％ 8 19.88 27.96 49.44 2.71 43 42 38％ 9 20.18 27.53 49.49 2.78 43 42.2 30％ 10 20.53 26.94 49.62 2.89 43 42.2 23％ % component difference 5.10 -2.30 -1.05 3.67

[0126] Figure 8 The data in Table 7 is illustrated in a chart.

[0127] Table 8

[0128] Table 8 shows the results of double-sphere distillation of mixture 25-65-1.

[0129]

[0130] Table 8 (continued)

[0131] Table 8 shows the results of double-sphere distillation of mixture 25-65-1.

[0132] boiling steam Turnover temperature temperature initial mixture 1 1 43 42.1 2 2 43 42 3 3 43 41.9 4 4 42 41.9 5 5 43 42 6 6 43 42 7 7 43 42 8 8 43 41.9 9 9 43 41.9 % component difference

[0133] The Kb value of mixture 25-65-1 is 58, and it has been tested to be non-flammable.

[0134] Figure 9 The data in Table 8 is illustrated in a chart.

[0135] Example 8 Fractionation of 18-119-5

[0136] Table 9

[0137] Table 9 shows that the fractionation of this implementation scheme consists of a high-concentration mixture of trans-dichloroethylene (TDCE) with high-boiling-point HFE and HFCO.

[0138] distillate 7300％ TDCE% AS300% Bottom temperature (°C) Top temperature (°C) % Remaining Solvent 0 4.98 90.07 4.95 47.7 51 100％ 1 9.09 84.06 6.85 47.70 52 91％ 2 7.96 85.64 6.40 47.9 52 82％ 3 6.84 87.22 5.94 48.00 52 74％ 4 6.72 87.40 5.88 48.00 52 65％ 5 6.11 88.25 5.64 48.00 52 56％ 6 4.60 90.39 5.01 48.10 52 48％ 7 4.11 91.11 4.78 48.20 52 39％ 8 2.40 93.73 3.87 48.50 52 29％ 9 1.65 95.02 3.33 48.60 52 21％ 10 0.68 96.91 2.41 487.70 52 14％

[0139] Table 10

[0140] Table 10 shows the double-sphere distillation of mixture 18-119-5.

[0141]

[0142] Figure 10 The data in Table 10 is illustrated in a chart.

[0143] Mixture 18-119-5 is non-flammable with a KB value of 115.

[0144] Table 11 shows the series of mixture 25-68-2 in a steam degreaser for 4 days.

[0145]

[0146] Table 11 (continued)

[0147]

[0148] Figure 11 The data in Table 11 is illustrated in a chart.

[0149] Although the invention has been described in detail with reference to specific embodiments thereof, these embodiments are exemplary and not restrictive.

Claims

1. A solvent composition comprising about 40 wt% to about 90 wt% of trans-dichloroethylene, monochlorotrifluoropropylene, hydrofluoroether, and optionally C1 to C3 alcohol.

2. The solvent composition according to claim 1, wherein the monochlorotrifluoropropylene is selected from the group consisting of: trans-CF3CH═CC1H(1233zdE); cis-CF3CH═CCIH(1233zdZ); trans-CHF2CF═CCIH(1233ydE); cis-CHF2CF═CCIH(1233ydZ); trans-CHF2CH═CC1F(1233zbE); cis-CHF2CH═CC1F(1233zbE); 233zbZ); trans CHF2CC1═CHF(1233xeE); cis CHF2CC1═CHF(1233xeZ); CH2FCC1═CF2(1233x0); trans CHFC1CF═CFH(1233yeE); cis CHFC1CF═CFH(1233yeZ); CH2C1CF═CF2(1233yc); CF2C1CF═CH2(1233xf) are one or more of these.

3. The solvent composition according to claim 1, wherein the hydrofluoroether is selected from the group consisting of: ethyl nonafluorobutyl ether, 1,1,2,3,3,3-hexafluoropropyl-2,2,2-trifluoroethyl ether, 1,1,2,2-tetrafluoroethyl-2,2,3,3,3-pentafluoropropyl ether, 1,1-difluoroethyl-2,2,3,3-tetrafluoropropyl ether, 1,1,2,3,3,3-hexafluoropropyl-2,2,3,3,3-pentafluoropropyl ether, 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether, 1,1,2,3,3,3-hexafluoropropyl-2,2,3,3-tetrafluoropropyl ether, and 3-methoxy-4-trifluoromethyl-1,1,1,2,2,3,4,5,5,5-decafluoropentane, or one or more thereof.

4. The solvent composition according to claim 2, wherein the hydrofluoroether is selected from the group consisting of: ethyl nonafluorobutyl ether, 1,1,2,3,3,3-hexafluoropropyl-2,2,2-trifluoroethyl ether, 1,1,2,2-tetrafluoroethyl-2,2,3,3,3-pentafluoropropyl ether, 1,1-difluoroethyl-2,2,3,3-tetrafluoropropyl ether, 1,1,2,3,3,3-hexafluoropropyl-2,2,3,3,3-pentafluoropropyl ether, 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether, 1,1,2,3,3,3-hexafluoropropyl-2,2,3,3-tetrafluoropropyl ether, and 3-methoxy-4-trifluoromethyl-1,1,1,2,2,3,4,5,5,5-decafluoropentane, or one or more thereof.

5. The solvent composition according to claim 1, comprising about 59 to about 70 wt% of trans-dichloroethylene (TDCE), about 10 to about 25 wt% of 1-chloro-2,3,3-trifluoro-1-propene (AS300), about 11 to about 18 wt% of 3-methoxy-4-trifluoromethyl-1,1,1,2,2,3,4,5,5,5-decafluoropentane (HFE-7300), and about 1 to about 5 wt% of ethanol.

6. The solvent composition according to claim 1, comprising about 70 to about 80 wt% of trans-dichloroethylene (TDCE), about 11 to about 21 wt% of 1-chloro-2,3,3-trifluoro-1-propene (AS300), and about 5 to about 15 wt% of 3-methoxy-4-trifluoromethyl-1,1,1,2,2,3,4,5,5,5-decafluoropentane (HFE-7300).

7. The solvent composition according to claim 1, comprising about 40 to about 60 wt% of trans-dichloroethylene (TDCE), about 11 to about 21 wt% of 1-chloro-2,3,3-trifluoro-1-propene (AS300), and about 20 to about 40 wt% of 1,1,1,2,3,3-hexafluoro-3-methoxypropane (HFE-356).

8. The solvent composition according to claim 1, comprising about 40 to about 60 wt% of trans-dichloroethylene (TDCE), about 15 to about 40 wt% of 1,1,2,2-tetrafluoroethyl-2,2,2-triethyl ether (AE3000), and about 10 to about 25 wt% of 1,1,1,2,3,3-hexafluoro-3-methoxypropane (HFE-356).

9. The solvent composition according to claim 3, further comprising a surfactant at a concentration of about 0.1 to about 3 wt%.

10. The solvent composition of claim 3, further comprising about 1 to about 50 wt% of a cosolvent of all other components of the solvent composition.

11. A solvent composition exhibiting azeotropic properties and comprising about 71 to about 75 wt% of trans-dichloroethylene (TDCE), about 15 to about 19 wt% of 1-chloro-2,3,3-trifluoro-1-propene (AS300), and about 7 to about 10 wt% of 3-methoxy-4-trifluoromethyl-1,1,1,2,2,3,4,5,5,5-decafluoropentane (HFE-7300).

12. The composition according to claim 11, comprising about 85 to about 95 wt% of trans-dichloroethylene (TDCE), about 1 to about 5 wt% of 1-chloro-2,3,3-trifluoro-1-propene (AS300), and about 1 to about 5 wt% of 3-methoxy-4-trifluoromethyl-1,1,1,2,2,3,4,5,5,5-decafluoropentane (HFE-7300).

13. The composition according to claim 11, comprising about 90 wt% trans-dichloroethylene (TDCE), about 5 wt% 1-chloro-2,3,3-trifluoro-1-propene (AS300), and about 5 wt% 3-methoxy-4-trifluoromethyl-1,1,1,2,2,3,4,5,5,5-decafluoropentane (HFE-7300).

14. The composition of claim 11, comprising about 59 to about 70 wt% of trans-dichloroethylene (TDCE), about 10 to about 25 wt% of 1-chloro-2,3,3-trifluoro-1-propene (AS300), about 11 to about 18 wt% of 3-methoxy-4-trifluoromethyl-1,1,1,2,2,3,4,5,5,5-decafluoropentane (HFE-7300), and about 1 to about 5 wt% of ethanol.

15. The composition according to claim 11, comprising about 63 wt% trans-dichloroethylene (TDCE), about 20 wt% 1-chloro-2,3,3-trifluoro-1-propene (AS300), about 15 wt% 3-methoxy-4-trifluoromethyl-1,1,1,2,2,3,4,5,5,5-decafluoropentane (HFE-7300), and about 2 wt% ethanol.

16. A solvent composition exhibiting azeotropic properties and comprising about 40 to about 60 wt% of trans-dichloroethylene (TDCE), about 15 to about 40 wt% of 1,1,2,2-tetrafluoroethyl-2,2,2-triethyl ether (AE3000), and about 10 to about 25 wt% of 1,1,1,2,3,3-hexafluoro-3-methoxypropane (HFE-356).

17. The composition of claim 16, comprising about 40 to about 60 wt% of trans-dichloroethylene (TDCE), about 11 to about 21 wt% of 1-chloro-2,3,3-trifluoro-1-propene (AS300), and about 20 to about 40 wt% of 1,1,1,2,3,3-hexafluoro-3-methoxypropane (HFE-356).

18. The composition according to claim 16, comprising about 53 wt% trans-dichloroethylene (TDCE), about 11 wt% 1-chloro-2,3,3-trifluoro-1-propene (AS300), and about 36 wt% 1,1,1,2,3,3-hexafluoro-3-methoxypropane (HFE-356).

19. A method for removing contaminants from metal, ceramic, and synthetic polymer articles, comprising: Contact one or more articles with the solvent composition of any one of claims 3, 10, 11, 12, 13, 14, 15, 16, 17 or 18, and remove the composition from one or more articles.

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