JP2853900B2 - Azeotrope-like composition of dichloropentafluoropropane and an alkanol having 1 to 4 carbon atoms - Google Patents

Description

This application claims the benefit of US Patent Application No. 418,008, filed October 6, 1989, and US Patent Application No. 417,983, filed October 6, 1989. Is a continuation-in-part application.

FIELD OF THE INVENTION The present invention relates to dichloropentafluoropropane and 1
It relates to an azeotrope-like composition of alkanols having ４4 carbon atoms. These mixtures are useful in various steam degreasing, low temperature cleaning and solvent cleaning applications, including defluxing and dry cleaning.

DESCRIPTION OF RELATED APPLICATIONS Publicly assigned co-pending U.S. Patent Application No. 418,008, filed October 6, 1989, includes 1,1-dichloro-2,2,3,
An azeotrope-like composition of 3,3-pentafluoropropane and an alkanol having 1 to 3 carbon atoms is disclosed.

U.S. Patent Application Serial No. 417,983, filed October 6, 1989, discloses 1,3-dichloro-1,1,2,
An azeotrope-like composition of 2,3-pentafluoropropane and an alkanol having 1 to 3 carbon atoms is disclosed.

BACKGROUND OF THE INVENTION Fluorocarbon-based solvents have been widely used for degreasing solid surfaces, especially complex parts and soils that are difficult to remove, and for other cleaning.

In its simplest form, steam degreasing or solvent cleaning consists of exposing the room temperature object to be cleaned to boiling solvent vapors. The vapors condensed on the object become a clean distilling solvent for washing off fats or other dirt. Finally, the solvent evaporates from the target substance, leaving a target substance containing no residue. This is in contrast to liquid solvents, which leave deposits on the object after rinsing.

Steam degreasing equipment requires high temperatures to improve the cleaning action of solvents, difficult-to-remove dirt, or large numbers of assembly lines that require efficient cleaning of metal parts and assemblies. Used for operation. The conventional operation of a steam degreasing machine is to immerse the parts to be cleaned in a boiling solvent sump, where most of the dirt is removed, and then place the parts in a sump containing fresh distillation solvent at about room temperature. Dipping, and finally exposing the part to solvent vapor on a boiling sump to condense the vapor on the cleaned part. Furthermore, the parts can be sprayed with a distillation solvent and then finally rinsed and cleaned.

Steam degreasing equipment suitable for the operations described above are well known in the art. For example, Sherliker et al., U.S. Pat. No. 3,085,918 discloses a suitable steam degreasing apparatus of this type including a boiling sump, a clean sump, a water separator and other auxiliary equipment.

Cold cleaning is another application that uses multiple solvents. In most low temperature cleaning applications, the dirty parts are immersed in a fluid or wiped off with a solvent-soaked cloth and allowed to air dry.

In recent years, non-toxic flame retardant fluorocarbon solvents such as trichlorotrifluoroethane have been widely used in degreasing applications and other solvent cleaning applications. Trichlorotrifluoroethane has been found to have sufficient solubility in fats, oils, waxes and the like. Therefore, widespread use for cleaning electric motors, compressors, heavy metal parts, precision precision metal parts, printed circuit boards, gyroscopes, guidance equipment, aerospace and missile hardware, aluminum parts, etc. Was found.

The art has focused on azeotropic compositions with a fluorocarbon component as the fluorocarbon component contributes to more desirable properties such as polar function, increased solvency and stabilizers. Azeotropic compositions are desirable because they are not fractionated by boiling. This behavior is desirable because the redistilled material occurs in the steam degreasing unit described above where these solvents are used for a final rinse. For example, a steam degreasing system acts as a still. Thus, if the solvent composition is not essentially constant boiling, fractionation can occur and undesirable solvent distribution can occur, compromising cleaning and processing safety. If the solvent mixture is not an azeotrope or azeotrope-like, the preferential evaporation of the more volatile components of the solvent mixture, which may be less desirable, e.g., less soluble in soil, It will result in a mixture of altered composition that has less inertness to metal, plastic or elastomer components and may have increased flammability and toxicity.

The art is constantly searching for new fluorocarbon-based azeotropes or azeotrope-like mixtures that provide alternatives to new and specific applications for steam degreasing and other cleaning applications. At present, fluorocarbon-based azeotrope-like mixtures are of particular interest because they are considered to be stratosphere-safe alternatives to the currently used fully halogenated chlorofluorocarbons.
Fully halogenated chlorofluorocarbons have been associated with causing environmental problems related to the depletion of the ozone layer that protects the earth. Mathematical models have demonstrated that hydrochlorofluorocarbons, such as dichloropentafluoropropane, have a much lower potential for ozone depletion and global warming than fully halogenated species.

EP-A-347 792 assigned to Asano discloses the use of hydrogen-containing chlorofluoropropanes as solvents. Dichloropentafluoropropane isomers HCFC-224ca, HCFC-225cb and HCFC-225c
c are three examples of the hydrogen-containing chlorofluoropropanes mentioned in this EP patent specification. This document also discloses that when the compound of the present invention is used as a cleaning solvent, the cleaning effect of the solvent is improved.
Hydrocarbons; alcohols such as methanol, ethanol, n-propyl alcohol, isopropyl alcohol and t-butyl alcohol; ketones; chlorinated hydrocarbons; esters; or organic solvents such as aromatic compounds, or surfactants. It states that it may. This document also states that "if azeotropic or pseudo-azeotropic properties exist for the composition obtained by combining the compound of the present invention with another (one) compound, those solvents are referred to as azeotropic conditions or pseudo-azeotropic conditions. It is preferable to use it under boiling conditions ... ". This reference, however, does not teach or suggest the presently claimed binary or ternary compositions of the present invention. More importantly, this document includes the claimed combination of Applicant (or a combination of the other compounds listed therein for the basic solvent composition).
Has no teaching or suggestion that it forms an azeotrope-like composition.

It is an object of the present invention to provide new environmentally acceptable azeotrope-like compositions that are useful in various industrial cleaning applications.

Another object of the present invention is to resist azeotrope-like compositions that are liquid at room temperature and that do not fractionate under the conditions of use.

Other objects and advantages of the present invention will become apparent from the following description.

SUMMARY OF THE INVENTION The present invention relates to novel azeotrope-like compositions that are useful in various industrial cleaning applications. In particular, the invention relates to a composition of dichloropentafluoropropane and an alkanol having 1 to 4 carbon atoms, which is essentially constant boiling, environmentally acceptable and remains liquid at room temperature.

DETAILED DESCRIPTION OF THE INVENTION According to the present invention, a novel azeotrope-like composition comprises 82-99.99% by weight of dichloropentafluoropropane and 1%
0.01 to 18% by weight of alkanol having up to 4 carbon atoms
Consisting essentially of dichloropentafluoropropane and an alkanol having 1 to 4 carbon atoms, at 101 kPa at 50.6 ° C. ± 5.
It was found to boil at 6 ° C.

Dichloropentafluoropropane has nine isomers: (1) 2,2-dichloro-1,1,1,3,3-pentafluoropropane (HCFC-225a); (2) 1,2-dichloro -1,2,3,3,3-pentafluoropropane (HCFC-225
ba); (3) 1,2-dichloro-1,1,2,3,3-pentafluoropropane (HCFC-225bb); (4) 1,1-dichloro-2,
2,3,3,3-pentafluoropropane (HCFC-225ca);
(5) 1,3-dichloro-1,1,2,2,3-pentafluoropropane (HCFC-225ca); (6) 1,1-dichloro-1,2,2,3,
3-pentafluoropropane (HCFC-225cc); (7) 1,
2-dichloro-1,1,3,3,3-pentafluoropropane (HC
(8) 1,3-dichloro-1,1,2,3,3-pentafluoropropane (HCFC-225ea); and (9) 1,1-
Dichloro-1,2,3,3,3-pentafluoropropane (HCFC
-225eb). For the purposes of the present invention, dichloropentafluoropropane relates to any isomer or mixture of isomers in any ratio. However, 1,1
-Dichloro-2,2,3,3,3-pentafluoropropane and the 1,3-dichloro-1,1,2,2,3-pentafluoropropane isomer are the preferred isomers.

The dichloropentafluoropropane component of the present invention has sufficient solubility. The alkanol component also has sufficient dissolving power to dissolve polar organics and amine hydrochloride. Therefore, when these components are mixed in an effective amount, an effective azeotropic solvent is obtained.

When the alkanol is methanol, the azeotrope-like composition of the present invention comprises dichloropentafluoropropane 82
It consists essentially of 9797% by weight and 3-18% by weight of methanol and boils at 101 kPa at 47.2 ° C. ± 1.9 ° C.

When the alkanol is ethanol, the azeotrope-like composition of the present invention comprises dichloropenta-fluoropropane
It consists essentially of 86-99% by weight and 1-14% by weight of ethanol and boils at 52.1 ° C. ± 2.2 ° C. at 101 kPa.

When the alkanol is 1-propanol, the azeotrope-like composition of the present invention comprises 96-99.99% by weight of dichloropentafluoropropane and 0.01-4% of 1-propanol.
It consists essentially of weight percent and boils at 53.6 ° C. ± 2.5 ° C. at 101 kPa.

When the alkanol is 2-propanol, the azeotrope-like composition of the present invention comprises 94-99.99% by weight of dichloropentafluoropropane and 0.01-6% of 2-propanol.
It consists essentially of weight percent and boils at 53.6 ° C ± 2.3 ° C at 101 kPa.

When the alkanol is 2-methyl-2-propanol, the azeotrope-like composition of the present invention comprises 98-99.99% by weight of dichloropentafluoropropane and 2-methyl-propanol.
Consisting essentially of 0.01 to 2% by weight of 2-propanol and
Boiling at 53.6 ℃ ± 2.5 ℃ at 101kPa.

When the dichloropentafluoropropane component is 225ca and the alkanol is methanol, the azeotrope-like composition of the present invention comprises 1,1-dichloro-2,2,3,3,3-pentafluoropropane 82-97. Weight% and methanol 3 ~
Consisting essentially of 18% by weight and at 99.3 kPa at 45.4 ° C ± 0.5 ° C
Bring to a boil.

In a further preferred embodiment of the present invention using 225 ca and methanol, the azeotrope-like composition comprises 86-96% by weight of 1,1-dichloro-2,2,3,3,3-pentafluoropropane and 4-4% methanol. Consists essentially of 14% by weight.

In the most preferred embodiment of the present invention using 225 ca and methanol, the azeotrope-like composition comprises 88-96% by weight of 1,1-dichloro-2,2,3,3,3-pentafluoropropane and 4-4% methanol. Consists essentially of 12% by weight.

In a preferred embodiment of the invention using 225 ca and methanol, the azeotrope-like composition comprises 89-95% by weight of 1,1-dichloro-2,2,3,3,3-pentafluoropropane.
And 5 to 11% by weight of methanol.

When the dichloropentafluoropropane component is 225ca and the alkanol is methanol, the azeotrope-like composition of the present invention comprises 1,1-dichloro-2,2,3,3,3-pentafluoropropane 92-99. Wt% and ethanol 1
Consisting essentially of 8% by weight and at 99.3 kPa at 50.0 ° C. ± 0.5 ° C.
Bring to a boil.

In a preferred embodiment using 225 ca and ethanol, the azeotrope-like composition of the present invention comprises 94-99% by weight of 1,1-dichloro-2,2,3,3,3-pentafluoropropane.
And 1-6% by weight of ethanol.

In a further preferred embodiment using 225 ca and ethanol, the azeotrope-like composition of the present invention comprises 1,1-dichloro-2,2,3,3,3-pentafluoropropane 94-98.5.
Consist essentially of 1.5% by weight of ethanol and 1.5-6% by weight of ethanol.

When the dichloropentafluoropropane component is 225ca and the alkanol is 2-propanol, the azeotrope-like composition of the present invention comprises 1,1-dichloro-2,2,3,3,3
-96-99.99% by weight of pentafluoropropane and 2-
Consisting essentially of 0.01-4% by weight of propanol and 99.3%
Boiling at 51.0 ℃ ± 0.3 ℃ at kPa.

In a preferred embodiment using 225ca and 2-propanol, the azeotrope-like composition of the present invention comprises 1,1-
Dichloro-2,2,3,3,3-pentafluoropropane 97.5-9
Consists essentially of 9.99% by weight and 0.01-2.5% by weight of 2-propanol.

In a further preferred embodiment using 225ca and 2-propanol, the azeotrope-like composition of the present invention comprises
1-dichloro-2,2,3,3,3-pentafluoropropane 98-
It consists essentially of 99.99% by weight and 0.01 to 2% by weight of 2-propanol.

When the dichloropentafluoropropane component is 225cb and the alkanol is methanol, the azeotrope-like composition of the present invention comprises 82-97% by weight of 1,3-dichloro-1.1,2.2,3-pentafluoropropane and methanol 3 ~
Consists essentially of 18% by weight and at 97.8 kPa at 47.9 ° C ± 0.8 ° C
Bring to a boil.

In a preferred embodiment using 225 cb and methanol, the azeotrope-like composition of the present invention comprises 84-96% by weight of 1,3-dichloro-1,1,2,2,3-pentafluoropropane.
And 4-16% by weight of methanol.

In a further preferred embodiment using 225cb and methanol, the azeotrope-like composition of the present invention comprises 1,3-dichloro-1,1,2,2,3-pentafluoropropane 86 to about 96
Consist essentially of 4% by weight and 4-14% by weight of methanol.

In a most preferred embodiment using 225cb and methanol, the azeotrope-like composition of the present invention comprises 88-95% by weight of 1,3-dichloro-1,1,2,2,3-pentafluoropropane and 5 to 5% of methanol. Consists essentially of 12% by weight.

When the dichloropentafluoropropane component is 225cb and the alkanol is ethanol, the azeotrope-like composition of the present invention comprises 86-97% by weight of 1,3-dichloro-1.1,2.2,3-pentafluoropropane and ethanol 3 ~
Consists essentially of 14% by weight and at 58.1 ° C ± 0.4 ° C at 98.1kPa
Bring to a boil.

In a preferred embodiment using 225 cb and ethanol, the azeotrope-like composition of the present invention comprises 88-97% by weight of 1,3-dichloro-1,1,2,2,3-pentafluoropropane.
And 3 to 12% by weight of ethanol.

In the most preferred embodiment using 225cb and ethanol, the azeotrope-like composition of the present invention comprises 89-97% by weight of 1,3-dichloro-1,1,2,2,3-pentafluoropropane and 3-97% by weight of ethanol. Consists essentially of 11% by weight.

When the dichloropentafluoropropane component is 225cb and the alkanol is 1-propanol, the azeotrope-like composition of the present invention comprises 1,3-dichloro-1.1,2.2,3
96 to 99.99% by weight of pentafluoropropane and 1-
Consisting essentially of 0.01-4% by weight of propanol and 99.3%
Boiling at 55.5 ℃ ± 0.2 ℃ at kPa.

In a preferred embodiment using 225cb and 1-propanol, the azeotrope-like composition of the present invention comprises 1,3-
Dichloro-1,1,2,2,3-pentafluoropropane 97-99.
It consists essentially of 99% by weight and 0.01 to 3% by weight of 1-propanol.

In a most preferred embodiment using 225cb and 1-propanol, the azeotrope-like composition of the present invention comprises
3-dichloro-1,1,2,2,3-pentafluoropropane 98 ~
It consists essentially of 99.99% by weight and 0.01 to 2% by weight of 1-propanol.

When the dichloropentafluoropropane component is 225cb and the alkanol is 2-propanol, the azeotrope-like composition of the present invention comprises 1,3-dichloro-1.1,2.2,3
-Consisting essentially of 94-99% by weight of pentafluoropropane and 1-6% by weight of 2-propanol and 5 at 98.9 kPa
Boiling at 5.0 ℃ ± 0.3 ℃.

In a preferred embodiment using 225cb and 2-propanol, the azeotrope-like composition of the present invention comprises 1,3-
Dichloro-1,1,2,2,3-pentafluoropropane 95-98.
It consists essentially of 5% by weight and 1.5-5% by weight of 2-propanol.

In a most preferred embodiment using 225cb and 2-propanol, the azeotrope-like composition of the present invention comprises
3-dichloro-1,1,2,2,3-pentafluoropropane 95.5
Consist essentially of 998.5% by weight and 1.5-4.5% by weight of 2-propanol.

When the dichloropentafluoropropane component is 225 cb and the alkanol is 2-methyl-2-propanol, the azeotrope-like composition of the present invention comprises 1,3-dichloro-1.1,2.2,3-pentafluoropropane 98 999.99% by weight and 0.01 to 2% by weight of 2-methyl-2-propanol
And boils at 59.6 ° C ± 0.2 ° C at 99.6 kPa.

The exact or true azeotrope-like composition was not determined, but was confirmed to be within the ranges shown. Regardless of where the true azeotrope is present, all compositions within the indicated range as well as certain compositions outside the indicated range are azeotrope-like as defined in more detail below. .

From basic principles, the fluid dynamics state is determined by four variables: pressure, temperature, liquid composition and vapor composition,
That is, each is defined by PTXY. An azeotrope is a unique feature of systems having two or more components where X and Y are constant P and T. actually,
This means that the components of the mixture do not separate during distillation and are therefore useful in the vapor phase solvent washing described above.

For the purpose of this discussion, an azeotrope-like composition is intended to mean that the composition behaves like a true azeotrope with respect to its constant boiling properties or properties that are not fractionated by boiling or evaporation. It is. Such compositions may or may not be a true azeotrope. For example, in such a composition, the composition of the vapor generated upon boiling or evaporation is the same or substantially the same as the original liquid composition. Thus, the liquid composition upon boiling or evaporation changes, if at all, only minimally. This is in contrast to non-azeotropic compositions in which the liquid composition changes substantially upon boiling or evaporation.

Thus, one method of determining whether a candidate mixture is "azeotrope-like" within the meaning of the invention is to subject those samples to conditions under which the mixture is expected to separate into its separated components. (Ie, decomposition, plate number). If the mixture is non-azeotropic or non-azeotrope-like, the mixture is fractionated, i.e., separated into its various components, including the lowest-boiling component that is distilled off first. If the mixture is azeotrope-like, a certain amount of the first distillation cut is obtained, which contains all the components of the mixture and either has a constant boiling point or behaves as a single substance. This phenomenon cannot occur if the mixture is not azeotrope-like, ie is not part of an azeotropic system. If the degree of fractionation of the candidate mixture is too great, a composition closer to the true azeotrope must be selected to minimize fractionation. Of course, distillation of the azeotrope-like composition as in a steam degreasing unit tends to produce and concentrate a true azeotrope.

From the foregoing, another characteristic of an azeotrope-like composition is that there is a range of compositions that contain the same components that are azeotrope-like in various ratios. All such compositions are included in the term azeotrope-like, as used herein. As an example, it is well known that at various pressures, the composition of a given azeotrope changes at least slightly, as does the boiling point of the composition. For example, azeotropes of A and B exhibit a unique type of relationship, but their composition is likely to change with temperature and / or pressure. Therefore, another way to define an azeotrope-like within the meaning of the present invention is that such a mixture may be boiled in the range of ± 5.6 ° C (101 kPa) with a boiling point of 50.6 ° C disclosed herein. It is to show that As will be readily appreciated by those skilled in the art, the boiling point of an azeotrope will vary with pressure.

In an operational embodiment of the present invention, the azeotrope-like composition of the present invention may be used in the art, such as by dipping or spraying a solid surface with the above composition or using a conventional degreasing device. It can be used to clean the surface by treating it with any known method.

As mentioned above, the azeotrope-like compositions discussed herein include steam degreasing, defusing agents, low temperature cleaning, dry cleaning, dehydration, decontamination, spot cleaning, aerosol spray regeneration, extraction, particle removal. And as a solvent for various cleaning applications, including surfactant cleaning applications. These azeotrope-like compositions are further useful as blowing agents, Rankine cycle and absorption refrigerants, and power fluids.

The dichloropentafluoropropane and alkanol components of the present invention are known materials. Preferably, they should be used in sufficiently high purity so that they are not adversely affected by the constant boiling characteristics of the solvent or system.

Commercially available alkanols can be used in the present invention. Most dichloropentafluoropropane isomers, such as the preferred HCFC-225ca isomer, are not commercially available in large quantities, and thus, until they become commercially available, May be produced by performing the organic synthesis disclosed in the above. For example, 1,1-dichloro-2,2,3,3,3-pentafluoropropane is obtained by reacting 2,2,3,3,3-pentafluorol-propanol and p-toluenesulfonate chloride with each other. It can be made by producing 2,2,3,3,3-pentafluoropropyl-p-toluenesulfonate. Next, N-methylpyrrolidone, lithium chloride and 2,2,3,3,3-pentafluoropropyl-p-toluenesulfonate are reacted with each other to give 1-chloro-2,2,3,3,
Produces 3-pentafluoropropane. Finally, chlorine and 1-chloro-2,2,3,3,3-pentafluoropropane are reacted with each other to produce 1,1-dichloro-2,2,3,3,3-pentafluoropropane. A detailed synthesis method is described in Example 1.

Synthesis of 2,2-dichloro-1,1,1,3,3-pentafluoropropane (225a). This compound has 1,1,1-trichloro-
A solution of 2,2,2-trifluoromethane in dimethylformamide and chlorotrimethylsilane are reacted in the presence of zinc to give 1- (trimethylsiloxy) -2,2-dichloro-3,
It can be prepared by producing 3,3-trifluoro-N, N-dimethylpropylamine. 1- (trimethylsiloxy) -2,2-dichloro-3,3,3-trifluoro-N, N-dimethylpropylamine is reacted with sulfuric acid to give 2,2-dichloro-3,3,3-trifluoro Produces propionaldehyde. Next, 2,2-dichloro-3,3,3-trifluoropropionaldehyde is reacted with sulfur tetrafluoride to produce 2,2-dichloro-1,1,1,3,3-pentafluoropropane. .

Synthesis of 1,2-dichloro-1,2,3,3,3-pentafluoropropane (225ba). This isomer is called Palet
a) et al., Bull. Soc. Chim. Fr., (6) 920-4 (1986).

Synthesis of 1,2-dichloro-1,1,2,3,3-pentafluoropropane (225bb). Synthetic method of this isomer, M. Hauptschein and LABigelow, J. Am. Chem. Soc., (73) 1428-30
(1951). The synthesis of this compound is further described by AHFainberg and WTMill Jr.
er, Jr.), J. Am. Chem. Soc., (79) 4170-4, (1957).

Synthesis of 1,3-dichloro-1,1,2,2,3-pentafluoropropane (255cb). The synthesis of this compound involves four steps.

Component A: Synthesis of 2,2,3,3-tetrafluoropropyl-p-toluenesulfonate. 406 g (3.08 mol) of 2,2,3,3-tetrafluoropropanol, 613 g (3.22 mol) of tosyl chloride and 1200 ml of water) were heated to 50 ° C. with mechanical stirring. Sodium hydroxide in water 560ml (139.7g, 3.5m
l) was added at such a rate that the temperature was kept below 65 ° C. After the addition was complete, the mixture was stirred at 50 ° C. until the pH of the aqueous phase was 6. Cool the mixture and methylene chloride
Extracted in 1.5 liters. 200 m aqueous ammonia
l, washed twice with 350 ml of water, dried over magnesium sulfate and distilled to give 697.2 g (79%) of a viscous oil.

Part B: Synthesis of 1,1,2,2,3-pentafluoropropane. 50
In a 0 ml flask, add a mechanical stirrer and Vigreau
x) A distillation column was attached, which in turn was connected to a dry ice trap and kept under a nitrogen atmosphere. The flask was charged with 400 ml of N-methylpyrrolidone, 145 g (0.507 mol) of 2,2,3,3-tetrafluoropropyl-p-toluenesulfonate (prepared in Part A above) and 87 g (1.5 mol) of spray-dried KF. Was. Next, mix the mixture with 190-2
Heat to 00 ° C for 3.25 hours, during which time volatile products 61
g was distilled in a cold trap (crude yield 90%). During the distillation, a fraction boiling at 25-28 ° C. was collected.

Part C: Synthesis of 1,1,3-trichloro-1,2,2,3,3-pentafluoropropane. Evacuate the 22 liter flask,
20.7 g (0.154 mol) of 1,1,2,2,3-pentafluoropropane (prepared in part B above) and 0.6 mol of chlorine were charged. It was then illuminated with a 450 W Hanovia Hg lamp at a distance of about 7.6 cm for 100 minutes. The flask was then cooled in an ice bath and maintained at 1 atmosphere (101 kPa) with the addition of nitrogen as needed. The liquid in the flask was removed with a syringe. The flask was connected to a dry ice trap and evacuated slowly (15-30 minutes). The contents of the dry ice trap and the initial liquid phase total 31.2 g (8
5%), and the gas chromatography purity was 99.7%. The products from several distillations were combined and distilled to give a material with a bp of 73.5-74 ° C.

Part D: Synthesis of 1,3-dichloro-1,1,2,2,3-pentafluoropropane. 106.6 g of 1,1,3-trichloro-1,2,2,3,3-pentafluoropropane (prepared in part C above)
(0.45 mol) and 300 g (5 mol) of isopropanol were stirred under an inert atmosphere and irradiated with a 450 W Hanovia Hg lamp at a distance of 5 to 7.6 cm for 4.5 hours. Next, the acidic reaction mixture was poured into 1.5 liter of ice water. The organic layer was separated, washed twice with 50 ml of water, dried over calcium sulfate and distilled to yield 50.5 g (55%) of C1CF2CF2C1F with a bp of 54.5-56 ° C. 1H−
NMR (CDC13): concentrated at ddd at 6.43 ppm, JH-CF = 4
7Hz, JH-CC-Fa = 12Hz, JH-CC-Fb = 2Hz
Met.

Synthesis of 1,1-dichloro-1,2,2,3,3-pentafluoropropane (225 cc). This compound is prepared by reacting 2,2,3,3-tetrafluoro-1-propanol and p-toluenesulfonate chloride to form 2,2,3,3-tetrafluoropropyl-p-toluenesulfonate. Can be manufactured. Next, 2,2,3,3-tetrafluoropropyl-p-toluenesulfonate was reacted with potassium fluoride in N-methylpyrrolidone to give 1,1,2,2,3-
Produces pentafluoropropane. Then, 1,1,2,2,3
Reacting pentafluoropropane with chlorine to produce 1,1-dichloro-1,2,2,3,3-pentafluoropropane.

Synthesis of 1,2-dichloro-1,1,3,3,3-pentafluoropropane (225d). This isomer is available from PCR Inc. of Gainesville, Florida (P.
CR Incorporated). Alternatively, the compound can be made by adding equimolar amounts of 1,1,1,3,3-pentafluoropropane and chlorine gas to an air-purged borosilicate glass flask. Next, the flask is irradiated with a mercury lamp. Upon completion of the irradiation, the contents of the flask are cooled. The product obtained is 1,2-dichloro-1,1,3,3,3-pentafluoropropane.

Synthesis of 1,3-dichloro-1,1,2,3,3-pentafluoropropane (225ea). This compound reacts trifluoroethylene with dichlorotrifluoromethane to give 1,3-dichloro-1,1,2,3,3-pentafluoropropane and 1,1
-Can be produced by producing dichloro-1,2,3,3,3-pentafluoropropane. 1,3-Dichloro-1,1,2,3,3-pentafluoropropane is separated from its isomers using fractional distillation and / or dispersive gas chromatography.

Synthesis of 1,1-dichloro-1,2,3,3,3-pentafluoropropane (225eb). This compound reacts trifluoroethylene with dichlorodifluoromethane to give 1,3-dichloro-1,1,2,3,3-pentafluoropropane and 1,1-
It can be produced by producing dichloro-1,2,3,3,3-pentafluoropropane. 1,1-Dichloro-1,2,3,3,3-pentafluoropropane is separated from its isomers using fractional distillation and / or preparative gas chromatography. Alternatively, 225eb may be prepared by the synthetic method disclosed in Au Pareta et al., Bull. Soc. Chim. Fr., (6) 920-4 (1986). 1,1-Dichloro-1,2,3,3,3-pentafluoropropane can be separated from its two isomers using fractional distillation and / or preparative gas chromatography.

It should be understood that the present compositions can include additional components that form new azeotrope-like compositions. All such compositions are considered to be within the scope of the present invention, as long as the composition is constant boiling or essentially constant boiling and includes all of the essential components described herein. Can be

Inhibitors can be added to the present azeotrope-like composition to inhibit decomposition of the composition, ie, react with unwanted decomposition products of the composition; and / or prevent corrosion of metal surfaces. Any or all of the following types of inhibitors can be used in the present invention: epoxy compounds, such as propylene oxide; nitroalkanes,
For example, nitromethane; ethers, such as 1-4-dioxane; unsaturated compounds, such as 1,4-butynediol; acetals or ketals, such as dipropoxymethane;
Ketones such as methyl ethyl ketone; alcohols such as tertiary amyl alcohol; esters such as triphenyl phosphite; and amines such as triethylamine. Other suitable inhibitors are readily apparent to one skilled in the art.

By describing the present invention in detail and with reference to their preferred embodiments, it is apparent that modifications and variations are possible without departing from the scope of the invention as defined in the appended claims.

The present invention is more fully illustrated by the following non-limiting examples.

Example 1 This example relates to the preparation of 1,1-dichloro-2,2,3,3,3-pentafluoropropane (225ca), a preferred dichloropentafluoropropane component of the present invention.

Component A: Synthesis of 2,2,3,3,3-pentafluoro-propyl-p-toluenesulfonate. In water at 25 ° C., p-toluenesulfonate chloride (400.66 g, 2.10 mol) is added to 2,2,3,
3,3-Pentafluoro-1-propanol (300.8 g) was added. The mixture was heated to 50 ° C. in a 5 liter three-neck separatory funnel with mechanical stirring. Sodium hydroxide in water 383 ml (92.56 g, 2.31 mol)
(6 molar solution) was added to the reaction mixture from another separatory funnel for 2.5
The temperature was added dropwise over time keeping the temperature below 55 ° C. At the completion of this addition, if the pH of the aqueous phase was about 6, the organic phase was drained from the flask while still warm and cooled to 25 ° C. The crude product was recrystallized from petroleum ether to give 2,2,3,3,3-pentafluoro-propyl-
500.7 g (1.65 mol, 82.3%) of white needle crystals of p-toluenesulfonate (mp 47.0-52.5 ° C.) were obtained. 1H-NM
R: 2.45ppm (S, 3H), 4.38ppm (t.2H, J = 12Hz), 7.35ppm
(D, 2H, J = 6 Hz); 19F-NMR: +83.9 ppm (S, 3F), +123.
2 (t, 2F, J = 12 Hz), analyzed from CFC13.

Part B: Synthesis of 1-chloro-2,2,3,3,3-pentafluoropropane. In a 1 liter flask equipped with a thermometer, a Vigreux column and a distillation receiver head was added 2,2,3,3,3-pentafluoropropane (produced in Part A above).
248.5 g (0.82 mol) of p-toluenesulfonate, 375 ml of N-methylpropylidone and 46.7 g of lithium chloride (1.1
Mol). The mixture was then heated with stirring to 140 ° C., at which point the product began to distill off. Stirring and heating were continued until the pot temperature reached 198 ° C., at which point no more distillate was collected. The crude product was redistilled and the product (bp 27.5-28
C) 107.2 g (78%). 1H-NMR: 3.81 ppm (t, J =
13.5 Hz); 19F-NMR: 83.5 and 119.8 ppm, analyzed from CFC13.

Part C: Synthesis of 1,1-dichloro-2,2,3,3,3-pentafluoropropane. Chlorine (289 ml / min) and 1-chloro-2,2,3,3,3-pentafluoro-propane (prepared in Part B above) (1.72 g / min) were added to a 2.54 cm × 5.08 cm Monel. The reactor was fed simultaneously at 300 ° C. 184 g of crude product,
The operation was repeated until collected in the cold trap in the reactor. After washing the crude product with 6 mol of sodium hydroxide and drying over sodium sulphate, it is distilled to give 69.2 g of starting material and 1,1-dichloro-2,2,3,3,3
46.8 g of pentafluoropropane (bp 48-50.5 ° C.) were obtained. 1H-NMR: 5.9 (t, J = 7.5 Hz) ppm; 19F-NMR: 79.4
(3F) and 119.8 (2F) ppm, analyzed from CFC13.

Example 2 The composition range in which 225ca and methanol exhibited a constant boiling point behavior was determined. This was achieved by placing a measured amount of 225 ca into a boiling point riser. The boiling point riser consisted of a heated sample where the HCFC-225ca was boiled. The upper part of the boiling point riser connected to the sump was cooled, thereby acting as a cooler for boiling steam and allowing the system to operate at full reflux. HCFC-22
After boiling 5ca at atmospheric pressure, a measured amount of methanol was titrated into a boiling point elevator. The change in boiling point was measured using a platinum-resistant thermometer.

Depending on the results, 82 to 97/3 to 18, respectively, preferably 89
9595/522511% by weight of a composition of 225ca / methanol,
It is considered to exhibit a constant boiling point behavior at 101 kPa and 45.4 ° C ± 0.5 ° C.

Examples 3 to 9 The azeotropic properties of the dichloropentafluoropropane components and alkanols listed in Table I were studied. This is done by placing the selected dichloropentafluoropropane isomer in a boiling point elevator, boiling it, adding a measured amount of alkanol, and finally, recording the temperature of the successively boiling mixture. went. The range in which the composition has a constant boiling point is shown in the table.

Examples 10-18 The azeotropic properties of the dichloropentafluoropropane components and methanol listed in Table II were investigated by repeating the experiments outlined in Examples 3-9 above. In each case, the lowest boiling point for the composition curve is believed to indicate that a constant boiling composition forms between each dichloropentafluoropropane component and methanol.

Table II Dichloropentafluoropropane component 2,2-dichloro-1,1,1,3,3-pentafluoropropane (225a) 1,2-dichloro-1,2,3,3,3-pentafluoropropane (225ba ) 1,2-dichloro-1,1,2,3,3-pentafluoropropane (225bb) 1,1-dichloro-1,2,2,3,3-pentafluoropropane (225cc) 1,2-dichloro -1,1,3,3,3-pentafluoropropane (225d) 1,3-dichloro-1,1,2,3,3-pentafluoropropane (225ea) 1,1-dichloro-1,2,3 1,3,3-pentafluoropropane (225eb) 1,1-dichloro-2,2,3,3,3-pentafluoropropane
/ 1,3-Dichloro-1,1,2,2,3-pentafluoropropane (mixture of 225ca / cb) 1,1-dichloro-1,2,2,3,3,3-pentafluoropropane / 1 , 3-Dichloro-1,1,2,2,3-pentafluoropropane (mixture of 25 eb / cb) Examples 19 to 27 The azeotropic properties of the dichloropentafluoropropane components listed in Table II and ethanol were By repeating the experiments outlined in Examples 3-9. In each case, the lowest boiling point for the composition curve is believed to indicate that a constant boiling composition forms between each dichloropentafluoropropane component and ethanol.

Examples 28-36 The azeotropic properties of the dichloropentafluoropropane components listed in Table II and 2-propanol were studied by repeating the experiments outlined in Examples 3-9 above. In each case, the lowest boiling point for the composition curve is believed to indicate that a constant boiling composition forms between each dichloropentafluoropropane component and 1-propanol.

Examples 37-46 The azeotropic properties of the dichloropentafluoropropane isomers listed in Table III and 1-propanol were determined using Examples 3 to
This was examined by repeating the experiment outlined in Section 9.
In each case, the lowest boiling point for the composition curve is believed to indicate that a constant boiling composition is formed between each dichloropentafluoropropane isomer and 1-propanol.

Table III Dichloropentafluoropropane isomers 2,2-dichloro-1,1,1,3,3-pentafluoropropane (225a) 1,2-dichloro-1,2,3,3,3-pentafluoropropane ( 225ba) 1,2-dichloro-1,1,2,3,3-pentafluoropropane (225bb) 1,1-dichloro-2,2,3,3,3-pentafluoropropane (225ca) 1,1- Dichloro-1,2,2,3,3-pentafluoropropane (225cc) 1,2-Dichloro-1,1,3,3,3-pentafluoropropane (225d) 1,3-Dichloro-1,1,1 2,3,3-pentafluoropropane (225ea) 1,1-dichloro-1,2,3,3,3-pentafluoropropane (225eb) 1,1-dichloro-2,2,3,3,3- Pentafluoropropane
/ 1,3-Dichloro-1,1,2,2,3-pentafluoropropane (mixture of 225ca / cb) 1,1-dichloro-1,2,2,3,3,3-pentafluoropropane / 1 , 3-Dichloro-1,1,2,2,3-pentafluoropropane (mixture of 25 eb / cb) Examples 47-57 The dichloropentafluoropropane isomers listed in Table III and 2-methyl-2-propanol Was studied by repeating the experiments outlined in Examples 3-9 above. In each case, the lowest boiling point for the composition curve is believed to indicate that a constant boiling composition is formed between each dichloropentafluoropropane component and 2-methyl-2-propanol.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI C07C 31/02 C07C 31/02 C09K 3/00 111 C09K 3/00 111 3/30 3/30 5/04 5/04 C23G 5 / 028 C23G 5/028 D06L 1/02 D06L 1/02 H05K 3/26 H05K 3/26 (31) Priority claim number 526,748 (32) Priority date May 22, 1990 (33) Priority claim country United States (US) (72) Inventor Wilson, David Paul 14051, New York, USA, Waxing Court, East Anhurst 118 (72) Inventor Lovely, Dennis M. 14141, New York, USA, Springville, Boston, USA State Road 10310 (72) Inventor Hollister, Richard M. America United States 14214, Buffalo, Inglewood Ave. 221 (72) Inventor Abeck, Richard E. United States of America 14127, Orchard Park, Pine Terrace 23, New York 23 (72) Inventor Van der Pui, Michael United States of America 14227 New York, Cheektowaga, Joanne Lane 32 (72) Inventor Bass, Rajat, United States 14221, New York, Williamsville, Shetland Drive 167 (72) Inventor Swan, Ellen Louise 14131, New York, United States of America 14131, Lansomville, Dickerson・ Load 4584 (56) References JP-A-2-311430 (JP, A) JP-A-2-286631 (JP, A) JP-A-2-286630 (JP, A) (58) Fields studied (Int .Cl. ⁶ , DB name) C11D 7/50 C07C 19/10 C09K 5/04

Claims (11)

(57) [Claims] (1) Dichloropentafluoropropane 82 to 99.9
An azeotrope-like composition consisting essentially of 9% by weight and 0.01 to 18% by weight of an alkanol having 1 to 4 carbon atoms, wherein the azeotrope-like component of said composition is dichloropentafluoropropane and Alkanols having 1 to 4 carbon atoms, provided that dichloropentafluoropropane is 1,1-dichloro-2,2,3,3,3-pentafluoropropane or 1,3-dichloro-1,1,2, Said azeotrope-like composition comprising 2,3-pentafluoropropane, methanol, ethanol and 2-propanol being excluded from the alkanol) and boiling at 101 kPa at 50.6 ° C. ± 5.6 ° C. 2. The composition of claim 1, wherein the composition is 1,3-dichloro-1,1,2,
96 to 99.99% by weight of 2,3-pentafluoropropane and 1
-Consisting essentially of 0.01 to 4% by weight of propanol and 9
2. An azeotrope-like composition according to claim 1, which boils at about 55.5 ° C. at 9.3 kPa. 3. The composition according to claim 1, wherein said composition is 55.5 ° C. ± 0.2 ° C. at 99.3 kPa.
3. The azeotrope-like composition according to claim 2, wherein the composition boils at a boiling point. 4. The composition of claim 1, wherein the composition comprises 1,3-dichloro-1,1,2,
97 to 99.99% by weight of 2,3-pentafluoropropane and 1
3. An azeotrope-like composition according to claim 2, consisting essentially of 0.01 to 3% by weight of propanol. 5. The composition of claim 1, wherein said composition is 1,3-dichloro-1,1,2,
98 to 99.99% by weight of 2,3-pentafluoropropane and 1
3. An azeotrope-like composition according to claim 2, consisting essentially of 0.01 to 2% by weight of propanol. 6. The composition of claim 1, wherein the composition is 1,3-dichloro-1,1,2,
98 to 99.99% by weight of 2,3-pentafluoropropane and 2
-Methyl-2-propanol consisting essentially of 0.01 to 2% by weight and boiling at 59.6C at 99.6 kPa.
Item 10. An azeotrope-like composition according to item 7. 7. The composition according to claim 5, wherein the composition is at 99.6 kPa at about 55.7 ° C. ± 0.2.
7. An azeotrope-like composition according to claim 6, which boils at a temperature of ℃. 8. The method of claim 1, wherein the dichloropentafluoropropane is 1,1-dichloro-2,2,3,3,3-pentafluoropropane and 1,3-dichloro-1,1,2,2,3-pentafluoropropane. An azeotrope-like composition according to claim 1, which is a mixture of fluoropropanes. 9. An azeotrope-like composition according to claim 1 wherein an effective amount of an inhibitor is optionally present in said composition. 10. An azeotrope-like composition according to claim 9, wherein said inhibitor is selected from the group consisting of epoxy compounds, nitroalkanes, ethers, acetals, ketals, ketones, alcohols, esters and amines. Composition. 11. A method for cleaning a solid surface, comprising treating the solid surface with an azeotrope-like composition according to claim 1.