JPH06509836A - Azeotrope-like composition of 2-trifluoromethyl-1,1,1,2-tetrafluorobutane and methanol, ethanol or isopropanol - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] 2-trifluoromethyl-1,1,1,2-tetrafluorobutane and the present invention are 2-trifluoromethyl-1,1,1,2-tetrafluorobutane -Azeotrope of trifluoromethyl-1,1,1,2-tetrafluorobutane Concerning mixtures similar to. These mixtures are defluxed (defl, uxin). g) and various steam degreasing, cold cleaning (including dry cleaning) It is useful in cold cleaning and solvent cleaning applications.

Background of the invention Vapor degreasing and solvents with fluorocarbon-based, i.e. based, solvents Cleaning involves degreasing solid surfaces that are difficult to remove dirt, especially complex areas, or otherwise It has found wide application in the cleaning industry.

Vapor degreasing or solvent cleaning, in its simplest method, is a cleaning that is at room temperature. It consists of exposing the object to be treated to a boiling solvent. vapor condensing on the object Qi becomes a clean, distilled solvent that washes away grease and other contaminants. . Once the solvent has finally evaporated from the object, simply wash the object in the liquid solvent No residue is left behind like in the case.

Difficulties in removing stains when high temperatures are required to improve the cleaning action of the solvent cleaning of metal parts and assemblies must be carried out efficiently and quickly. For operation of large assembly lines in case of The process places the parts to be cleaned in a boiling solvent sump that removes most of the dirt. mp), i.e. immersed in a reservoir of solvent, after which the parts are freshly distilled to near room temperature. immersed in a sump containing some solvent, and finally the solvent vapor above a sump of boiling solvent. It consists of IHing the parts. Here, the solvent vapor condenses on the cleaned parts. do.

Note that the parts can also be sprayed with distilled solvent before final cleaning.

Steam desaturation equipment suitable for the above operations is well known in the art. For example, Sherliker et al. in U.S. Pat. No. 3.085.918 boiling solvent sump, cleaning liquid sump, water separator and other auxiliary equipment discloses such a suitable vapor degreasing device consisting of.

Cold cleaning is another application where multiple solvents are used.

In most cold cleaning applications, dirty parts are immersed in a fluid. or similar object is soaked in a solvent and allowed to air dry. .

Fluorocarbon solvents, such as trichlorotrifluoroethane, have recently been used for degreasing, Widely used as an effective non-toxic, non-flammable agent useful in other solvent cleaning applications. It has come to have many uses. Trichlorotrifluoroethane contains grease, oil, It was discovered that it has sufficient dissolving power for wax, camphor, etc. Trichrome Rotrifluoroethane is therefore used in electric motors, compressors, heavy metal parts, precision dense metal parts, printed circuit boards, gyroscopes, guidance devices, spacecraft and missiles It has found wide application in cleaning hardware, aluminum parts, etc.

Azeotrope or azeotrope-like compositions are preferred. Such compositions This is because fractional distillation does not occur when the temperature rises. This behavior occurs when these solvents are used. In the aforementioned vapor degreasing equipment, the redistilled material is used for a final rinse and cleaning. This is desirable because it can be generated. However, this vapor degreasing system is It acts as. If the solvent composition does not exhibit a constant boiling point, i.e. it is azeotrope-like. If not, fractional distillation will occur and undesired solvent distribution will affect cleaning and process safety. It will act to undermine the The more volatile components of the solvent mixture are This is the case when the mixture is not azeotrope-like after evaporation first. ), a greater reduction in the solvency of soils, metals, plastics or Greater reduction in inertness and higher flammability for each component of the lastomer resulting in a mixture of altered composition that would have more undesirable properties such as toxicity. I will do it. This technology can be used to produce the desired fluorine such as trichlorotrifluoroethane. The orocarbon component can be included to provide desired properties, such as functionality with respect to polarity, azeotrope compositions or azeotropes containing components that further provide added solvency and stability; Progress has been made towards compound-like compositions.

This technology is now also new, for special applications, and also for steam degreasing and other cleaning Alternative fluorocarbons, hydrofluorocarbons and hydrogen Search for new azeotrope-like mixtures based on dorochlorofluorocarbons continues to do so. The currently used talolofluorocarbons (CFCs) , containing no or minimal chlorine, considered to be a stratospheric-safe alternative. Contains only fluorocarbons, hydrofluorocarbons and hydrochlorofluorocarbons Of particular interest are azeotrope-like mixtures based on fluorocarbons. Ru. The former CFCs cause environmental problems related to the ozone layer that protects the earth. This is what is speculated to be caused. In the mathematical model, 2-trifluoromethyl -1,1,1,2-tetrafluorobutane (also known as HFC-467 in this technical field) hydrofluorocarbons (known as First, 1. 1. 2-Trichloro-1,2,2-trifluoroethane (CFC -113) compared to lorofluorocarbons, resulting in ozone depletion and greenhouse effect. It is widely accepted that the contribution of global warming to global warming is negligible. .

European Patent Publication No. 431.458 published on June 12, 1991 is 1.1° 2, 3. 4. Teach a mixture of 4-hexafluorobutane and ethanol ing.

U.S. Patent No. 5.023.010 describes 1. 1. 1. 2. 3. 3- Teach an azeotrope of hexafluoro-3-methquine propane and methanol There is. U.S. Pat. No. 5,035,830 discloses that hexafluoropropylene/e Azeotropes of tyrene cyclic dimers and methanol or ethanol are taught.

U.S. Patent No. 5.064.559 describes 1. 1. 1. 2. 3. 4. 4. 5. 5. 5-decafluoropentane and methanol or ethanol teaches an azeotrope of.

U.S. Pat. No. 5,073,291 describes 1,4-dihydroperfluorobutane. and methanol.

U.S. Patent No. 5.073.288 and U.S. Patent No. 5.073.290 are 1°1 , 1. 2. 2. 3. 5. 5. 0-nonafluoro-4-trifluoro Lomethylpenkun or 1. 1. 1. 2. 2. 5. 5. 5-octa The combination of fluoro-4-trifluoromethylbencune and methanol or ethanol Component-based azeotrope-like compositions are taught.

U.S. Pat. No. 4,842,764 describes 1,1-dichloro-1-fluoroethyl discloses an azeotrope-like composition of methanol and methanol. U.S. Patent No. 4,970 ．． No. 013 specifies 2,3-dichloro-1,1,1,3,3-pentafluoropolymer. An azeotrope of lopane and methanol is disclosed. U.S. Patent No. 4.　986゜ No. 928 specifies 1-chloro-1,2,2-1-lifluorocyclobutane and meta discloses an azeotrope with nol. Commonly Assigned U.S. Patent No. 4, No. 988.455 discloses 1,1-dichloro-1,2,2-1-lifluoropropropylene. Azeotrope-like compositions of bread and methanol are disclosed.

U.S. Patent No. 5,023,010 describes 1. 1. 1. 2. 3. 3- Discloses an azeotrope of hexafluoro-3-methquine propane and methanol There is. Japanese Unexamined Patent Publication No. 1986-98699 published on April 17, 1989 is 1,1-di Composition of azeotrope of chloro-2,2,2-trifluoroethane and methanol is disclosed. Japanese Unexamined Patent Publication No. 64-304194 published on December 7, 1989 is the azeotrope of 1-chloro-2,2,3,3-tetrafluoropropane and methanol A mixture is disclosed.

Detailed description of the invention Addressing the need for alternatives to chlorofluorocarbon solvents in this technology field The solution of the present inventor is 2-trifluoromethyl-1,1,1,2-tetrafluoro butane and methanol, ethanol or isopropanol, and as an optional ingredient By a mixture comprising nitromethane. Also, 2-trifluoromethyl-1° 1, 1. 2-tetrafluorobutane and methanol, ethanol or isopropylene A novel azeotrope-like mixture comprising Patul and optionally nitromethane A composition with a constant boiling point has been discovered.

Preferably, the novel azeotrope-like composition comprises an effective amount of 2-trifluoromethyl -1,1,1,2-tetrafluorobutane and methanol, ethanol or isopropyl and optionally nitromethane. As used herein The term “effective amount” refers to the amount of effect each ingredient has when combined with the other ingredient. means the amount of each component thereof in which the azeotrope-like composition of the present invention is formed.

These azeotrope-like compositions contain from about 64 to about 99.0% by weight of 2-trifluoromethane. Chil-1,1,1,2-tetrafluorobutane and about 0.5 to about 36% by weight ethyl alcohol or isopropanol and about 0 to about 1% by weight nitromethane.

When methanol is present, this new azeotrope-like composition has an 5% by weight of 2-trifluoromethyl-1,1,1,2-tetrafluorobutane and It comprises from about 0.5% to about 30% by weight methanol.

The azeotrope-like compositions of the present invention are advantageous for the following reasons. That is, 2-trifluoro Lomethyl-1,1,1,2-tetrafluorobutane contributes to ozone depletion. It is a negligible reagent and its boiling point is 37°C. methanol, ethanol The olefin and isopropanol components have good solvent properties. However, these Combining effective amounts of the components results in an efficient azeotrope-like solvent.

Preferred azeotrope-like compositions based on methanol are shown in Table 1 below.

In Table ■, 2-trifluoromethyl-1,1,1,2-tetrafluorobuta It is abbreviated as HFC-467.

Table I Preferred, More preferred, Most preferred Boiling point ('C), component range (wt%) Range (wt%) Range (wt%) (760mmHg) RFC-46775-978 0-9696-9433,5±1.0 methanol 3-25 4-20 6-1 4 Nitromethano 0 0 0 Preferred azeotrope-like compositions based on ethanol are shown in Table II below.

In Table II, 2-trifluoromethyl-1,1,1,2-tetrafluorob Tan is abbreviated as HFC-46.7.

Table TI Preferred, More preferred, Most preferred Boiling point (0C) component range (wt%) range Range (wt%) Range (wt%) (760mm) Ig) RFC-4676499,5 79,5-9984,6-98,536,5±0.5 Ethano-φ0.5-36 1-20.5 1.5-15.4 Nitromekuno O-10-0゜50-0. Preferred azeotrope-like compositions based on 4 isopropanol are shown in the table below. Shown in I. In Table III, 2-trifluoromethyl-1,1,1,2-tet Rahfluorobutane is abbreviated as RFC-467.

Table III Preferred, More preferred, Most preferred Boiling point ('C) component range (wt%) range Range (weight%) Range (weight%) (760mmHg) HFC-46771,5-9 9,578,3-9982,9-98,639,1±0゜5 isopropanol 0.5 28.5 1 -21.7 1,4 17. Nitromethane 0-1 0-0.5 0-0.4 Compositions within the above range as well as those outside the above range All specific compositions are azeotrope-like, as defined in more detail below. Ru.

The exact azeotrope compositions have not been determined, but they fall within the ranges mentioned above. has been confirmed. The above range, regardless of where the true azeotrope exists , as well as compositions outside the above ranges, all of which are defined in more detail below. It is like an azeotrope.

As used herein, the term "azeotrope-like composition" refers to the composition behaves like an azeotrope, i.e. has certain boiling properties, i.e. boils or evaporates. It means having a tendency not to be fractionated. However, such a group In chemical products, the composition of the vapor formed during boiling or evaporation is the same as the original liquid composition. The same or substantially the same. Therefore, the liquid composition changes during boiling or steaming. Even if it does, it will only change to a minimal or negligible extent. this is , a non-azeotropic mixture in which the liquid composition changes to a substantial degree during boiling or vaporization. This is in contrast to the composition. As is readily understood by those skilled in the art, azeotropic mixtures The boiling point of the solid composition changes with pressure.

The azeotrope-like composition of the present invention can be used in combination with defluxing and dry cleaning. As a solvent in various steam degreasing, cold cleaning and solvent cleaning applications. Useful.

In one process embodiment of the invention, the azeotrope-like composition of the invention is applied to the surface of a substrate. by treating the surface with this composition by any method known in the art. , for example by dipping or spraying, or by substantially removing the contaminant. Dissolving contaminants from the substrate surface by use of conventional degreasing equipment that removes or dissolves contaminants. or can be used to remove contaminants.

2-trifluoromethyl-1,1,1,2-tetone of the azeotrope-like composition of the present invention Lafluorobutane is a commercially available 4-iodo-2-trifluoromethyl- By reacting 1,1,1,2-tetrafluorobutane with zinc and hydrochloric acid, It can be manufactured using Methanol in novel solvent azeotrope-like compositions of the present invention , ethanol, isopropanol and nitromethane are known substances. can be obtained commercially.

The invention will be explained more fully in the following non-limiting examples.

Example 1 This example shows the production of 2-trifluoromethyl-1,1,1,2-tetrafluorobutane. Regarding.

500 ml flask with mechanical stirrer, distillation column and take-off head 4-iodo-2-trifluoromethyl-1,1,1,2-tetrafluor, which is commercially available in 15 grams of orobutane (046 mol), 28.5 grams of fine zinc powder (045 mol) mol) and 230 ml of 10% hydrochloric acid were added. This mixture was stirred and 'C and distillate (boiling point 37-39°C) 7.4 grams (80% yield) ) were collected. IHNMR (CDC13): 2.1 (m, 2H), 1.2 (t, 3H) l) l) m.

Example 2 15ml round heated with an electric heating mantle containing a magnetic stirring bar A micro-boiling point measuring device consisting of 20 flasks ometer) was used. 2-trifluoromethyl- Add 3 milliliters of 1,1,1,2-tetrafluorobutane and several microliters. Measure methanol in small increments with an automatic fringe that can be injected in liter increments. Added. Temperature was measured using a platinum resistance thermometer and pressure was measured using a barometer. did. Approximate corrections were made to the boiling point to obtain the boiling point at 760 mmHg.

The following Table IV shows 2-trifluoromethyl-1,1,1,2-tetrafluorobutane to 760 mmHg (101 kPa) for various mixtures of and methanol. It shows the corrected boiling point measurement. As shown in Table IV, methanol From about 6.5% by weight to about 25% by weight, the boiling point of the composition changes by only 19C. It was. Therefore, the composition behaves as a constant boiling point composition over this range.

(CFC)2CFCEI2C[13 Boiling point (℃) of methanol, parts, weight % Number of parts, weight% @760mm 1'1g (101kPa) 100.00 0 37 ．． 0 97.28 2.72 36.3 95.72 4.28 35.1 94.70 5.30 34.6 93.71 6.29 34.1 92.00 8°00 33.0 90.00 10.00 32.8 86.70 13.30 32.6 75.40 24.60 32.8 Example 3 In this example, the minimum point of the boiling point versus composition curve is 2-trifluoromethyl-1,1,1,2- 88.7% by weight of tetrafluorobutane (hereinafter referred to as HFC-467) and ethano This means that the azeotrope appears in the region of 113% by weight. This clarifies that it is produced depending on the composition.

15ml round bottom 20 including magnetic stirring bar and heated with electric heating mantle A micro boiling point measuring device consisting of a flask was used. The boiling point measuring device has a low boiling point. Add 2.5 ml of the first substance, RFC-467, and place it in a microliquid. Measure and add ethanol in small increments with an automatic fringe that can be injected in liters. added. Temperature was measured using a platinum resistance thermometer and pressure was measured using a barometer.

Approximate corrections were made to the boiling point to obtain the boiling point at 760 mmHg.

The boiling points of various mixtures of HFC-467 and ethanol were measured and 760 m Corrected to mHg (101 kPa). The extrapolation operation of the obtained data is performed using ethanol. It is shown that the lowest boiling point appears in the region of about 1.5 to about 18% by weight. lowest boiling point The best estimate for the point location is 11.3% ethanol by weight, but However, these mixtures are heated at temperatures below 03°C in the ethanol range of 5 to 35% by weight. Boil at a constant temperature inside. The lowest boiling azeotrope therefore exists in this composition range. It is shown that

From the above example, it can be seen that further constant boiling or essentially constant boiling mixtures of the same components can be used using this technique. Anyone skilled in the art can easily confirm this using the above method. readily obvious. Well-characterized outer limits of compositional range boiling at constant temperature No attempt was made to define it. However, anyone skilled in this technical field is an easy way to ascertain constant boiling or essentially constant boiling mixtures containing the same components. Repeat Example 3 except using isopropanol (90% purity) instead of tanol. Ta. HFC-467, a substance with a lower boiling point, is first introduced into the micro boiling point measuring device. It holds approximately 2.8ml and can be injected in microliter increments. The isopropanol was measured and added in small increments using an automatic fringe. HFC-467 The boiling point of various mixtures of and isopropanol was measured and was found to be 760 mmHg. (101 kPa). Extrapolation of these data is performed using the isoproper tool. It is shown that the lowest boiling point appears in the region of about 1.4 to about 17.7% by weight. lowest The best estimate for the location of the boiling point is 8% by weight of isopropanol; However, these mixtures contain isopropanol in the range of 0.5 to 27.5% by weight. Boils at a constant temperature up to 0.3℃. The lowest boiling azeotrope therefore has this composition It is shown that it exists within the range.

The azeotrope-like compositions of the present invention can suppress the decomposition of these compositions and reacts with undesirable decomposition products of metals and/or prevents corrosion of metal surfaces. Inhibitors or inhibitors may also be added. any of the following group of inhibitors or All can be used in the present invention. Al having 4 to 7 carbon atoms canol, nitroalkane with 2 to 3 carbon atoms, nitroalkane with 2 to 7 carbon atoms 1,2-epoxy/alkanes with 1,2-epoxy/alkanes, phosphites with 12-30 carbon atoms esters, ethers with 3 or 4 carbon atoms, ethers with 4 to 6 carbon atoms unsaturated compounds with 4 to 7 carbon atoms, acetals with 3 to 5 carbon atoms Ketones with atoms and amines with 6 to 8 carbon atoms. Other suitable inns Inhibitors will readily occur to those skilled in the art.

Inhibitors may be used alone or in any proportion May be used in combination. Typically, the maximum amount based on the total weight of the azeotrope-like composition is Up to about 2% of the inhibitor could be used.

The azeotrope-like compositions of the present invention can be applied by spraying the compositions onto a solid surface. When used to clean those solid surfaces, azeotrope-like compositions are Preferably, the surfaces are sprayed with an agent. Propellant is hydrocarbon, chlorophyll fluorocarbon, hydrochlorofluorocarbon, hydrofluorocarbon, difluorocarbon, Methyl ether, carbon dioxide, nitrogen, nitrous oxide, methylene oxide, air and Preferably, it is selected from the group consisting of mixtures thereof.

Although the present invention has been described in detail above with reference to preferred embodiments, the present invention includes the attached claims. Various modifications and changes may be made without departing from the scope of the invention as defined herein. It is clear that this is possible.

Continuation of front page (81) Designated countries EP (AT, BE, CH, DE.

DK, ES, FR, GB, GR, IE, IT, LU, MC, NL, SE), 0A (BF, BJ, CF, CG, CI, CM, GA, GN, ML, MR, SN, TD, TG), AU, BB, BG, BR, CA, C3, F I, HU.

JP, KP, KR, LK, MG, MN, MW, No, PL, R O,RU,5D (72) Inventor: Basu, Rajat Saboula, New York, USA 1 4075. Williamsville, Shedland Road (72) Inventor Van - Dar Bui, Michael, New York, USA 14227. cheek toe - Wagga, Joanne Lane 32 (72) Inventor Hollister, Richard Marville, New York, United States 14214. buffalo, angle wood avenue

Claims (1)

[Claims] 1.2-trifluoromethyl-1,1,1,2-tetrafluorobutane from about 64 to about 99.5% by weight and about 0.5 to about 36% by weight of ethanol or isopropanol and an azeotrope-like composition comprising from 0 to about 1% by weight of nitromethane; Boiling at about 36.5° C. at 2.760 mmHg, as claimed in claim 1. azeotrope-like composition of. 3.2-Trifluoromethyl-1,1,1,2-tetrafluorobutane approx. 79. 5 to about 99.5% by weight, about 1 to about 20.5% by weight of ethanol, and about nitromethane. consisting essentially of 0 to about 0.5% by weight at about 36.5°C at 760 mmHg. 2. The azeotrope-like composition of claim 1, which boils. 4.2-Trifluoromethyl-1,1,1,2-tetrafluorobutane approx. 71. 5 to about 99.5% by weight and about 0.5 to about 28.5% by weight of isopropanol and nitrate. consisting essentially of about 0 to about 1% by weight lomethane, about 38% at 760 mmHg. 2. The azeotrope-like composition of claim 1, which boils at 1<0>C. 5.2-Trifluoromethyl-1,1,1,2-tetrafluorobutane approx. 82. 9 to about 98.6% by weight and about 1.4 to about 17.1% by weight of isopropanol and nitrate. consisting essentially of about 0 to about 0.4% by weight lomethane, about 3% at 760mmHg 8. The azeotrope-like composition of claim 1 boiling at 1<0>C. 6.2-trifluoromethyl-1,1,1,2-tetrafluorobutane about 70~ an azeotrope comprising about 99.5% by weight and about 0.5 to about 30% methanol; Similar composition. Boiling at about 33.5±about 1.0° C. at 7.760 mmHg. The azeotrope-like composition according to item 1. 8.2-Trifluoromethyl-1,1,1,2-tetrafluorobutane about 75~ Claim 2 comprising about 97% by weight and about 3 to about 25% methanol. The azeotrope-like composition described in . 9. Alkanols with 4 to 7 carbon atoms, di-alkanols with 2 to 3 carbon atoms troalkanes, 1,2-epoxyalkanes with 2 to 7 carbon atoms, 12 to Phosphite esters with 30 carbon atoms, 3 or 4 carbon atoms unsaturated compounds with 4 to 6 carbon atoms, 4 to 7 carbon atoms acetals with 3 to 5 carbon atoms and 6 to 8 carbon atoms further comprising an inhibitor selected from the group consisting of amines having a The azeotrope-like composition according to any one of items 1 to 8. 10. The azeotrope-like composition according to any one of claims 1 to 8 is used as a solvent. to dissolve or remove contaminants from the surface of a substrate comprising the step of using How to leave.