EP0389133B1 - Azeotropic composition of 2,2-dichloro-1,1,1-trifluoroethane and methanol - Google Patents
Azeotropic composition of 2,2-dichloro-1,1,1-trifluoroethane and methanol Download PDFInfo
- Publication number
- EP0389133B1 EP0389133B1 EP90302267A EP90302267A EP0389133B1 EP 0389133 B1 EP0389133 B1 EP 0389133B1 EP 90302267 A EP90302267 A EP 90302267A EP 90302267 A EP90302267 A EP 90302267A EP 0389133 B1 EP0389133 B1 EP 0389133B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- azeotrope
- composition
- weight percent
- methanol
- trifluoroethane
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G5/00—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents
- C23G5/02—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents using organic solvents
- C23G5/028—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents using organic solvents containing halogenated hydrocarbons
- C23G5/02809—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents using organic solvents containing halogenated hydrocarbons containing chlorine and fluorine
- C23G5/02825—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents using organic solvents containing halogenated hydrocarbons containing chlorine and fluorine containing hydrogen
- C23G5/02829—Ethanes
- C23G5/02838—C2HCl2F3
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/50—Solvents
- C11D7/5036—Azeotropic mixtures containing halogenated solvents
- C11D7/5068—Mixtures of halogenated and non-halogenated solvents
- C11D7/5077—Mixtures of only oxygen-containing solvents
- C11D7/5081—Mixtures of only oxygen-containing solvents the oxygen-containing solvents being alcohols only
Definitions
- Defluxing solvents should have the following characteristics: be low boiling, be nonflammable, have low toxicity and high solvency power so that flux and flux-residues can be removed without damaging the substrate being cleaned.
- an azeotropic mixture gives off vapor which has the same composition as the mixture. Since there is no preferential vaporization of the components, azeotropic mixtures remain constant boiling throughout distillation. In vapor-degreasing operations, this constant boiling aspect of azeotropic mixtures is desirable since the solvent vapor can be condensed back into a mixture with its original composition and then be used for the final rinse. Thus, vapor defluxing and degreasing systems act as a still.
- the solvent composition exhibits a constant boiling point, i.e., is a single material, an azeotrope or is azeotrope-like, fractionation will occur and undesirable solvent distributions will result which could detrimentally affect the safety and efficacy of the cleaning operation.
- EP-A-429,451 discloses azeotrope-like compositions containing 98.9-99% 2,2-dichloro-1,1,1-trifluoroethane, 1.0-1.2% methanol and 0.01% nitromethane, wherein such compositions may be used in processes for cleaning solid surfaces, such as defluxing printed circuits and cleaning metals.
- 4002573 disclose binary constant boiling compositions of 1,2-dichloro-1,1,2-trifluoroethane with trichlorofluoromethane, with diethyl ether and with dischloromethane and also ternary constant boiling compositions comprising 1,2-dichloro-1,1,2-trifluoroethane diethyl ether, and 1,2-dibromo-1,1,2,2-tetrafluoroethane.
- an azeotrope or azeotrope-like compositon which is a binary mixture of 97-99.5 weight percent 2,2-dichloro-1,1,1-trifluoroethane and 0.5-3 weight percent methanol at atmospheric pressure.
- the present invention provids a nonflammable azeotropic composition which is well suited for solvent cleaning applications.
- the fluorinated compound is also known as KCFC-123, in the nomenclature conventional to the chlorofluorocarbon field.
- azeotrope or azeotrope-like composition is meant a constant boiling liquid admixture of two or more substances, which admixture behaves like a single substance in that the vapor, produced by partial evaporation or distillation of the liquid, has substantially the same composition as the liquid, i.e. the admixture distils without substantial change in composition.
- Constant boiling compositions which are characterized as azeotropes or azeotrope-like, exhibit either a maximum or minimum boiling point as compared with that of the non-azeotropic mixtures of the same substances.
- effective amount is defined as the amount of each component of the instant invention admixture which, when combined, results in the formation of the azeotrope or azeotrope-like compositions of the instant invention.
- This definition includes the amounts of each component, which amounts may vary depending upon the pressure applied to the composition so long as the azeotrope or azeotrope-like compositions continue to exist at the different pressures, but with possible different boiling points. Therefore, effective amount includes the weight percentages of each component of the compositions of the instant invention which form azeotrope or azeotrope-like compositions at pressures other than atmospheric pressure. When the pressure applied to these compositions is adjusted to atmospheric pressure, i.e., 760 mm Hg, these compositions will contain the azeotrope of the instant invention which will boil at the atmospheric boiling point for the true azeotrope described herein.
- Binary mixtures of 97-99.5 weight percent HCFC-123 and 0.5-3 weight percent methanol are characterized as azeotropes or azeotrope-like in that mixtures within this range exhibit a substantially constant boiling point at constant pressure. Being substantially constant boiling, the mixtures do not tend to fractionate to any great extent upon evaporation. After evaporation, only a small difference exists between the composition of the vapor and the composition of the initial liquid phase. This difference is such that the compositions of the vapor and liquid phases are considered substantially identical. Accordingly, any mixture within this range exhibits properties which are characteristic of a true binary azeotrope.
- the binary composition consisting of about 98.8 weight percent HCFC-123, and about 1.2 weight percent methanol has been established, within the accuracy of the fractional distillation method, as a true binary azeotrope, boiling at about 28°C, at substantially atmospheric pressure and is preferred.
- the HCFC-123 of the instant invention may contain minor amounts of HCFC-123a.
- the azeotrope of the present invention permits easy recovery and reuse of the solvent from vapor defluxing and degreasing operations because of its azeotropic nature.
- the azeotropic mixture of this invention can be used in cleaning processes such as described in U.S. Patent No.3,881,949, which is incorporated herein by reference.
- the azeotrope of the instant invention can be prepared by any convenient method including mixing orcom- bining the desired component amounts.
- a preferred method is to weigh the desired component amounts and thereafter combine them in an appropriate container.
- a solution containing 98.8 weight percent HCFC-123 and 1.2 weight percent methanol was prepared in a suitable container and mixed thoroughly. This solution was distilled in a glass distillation apparatus equipped with a Claisen-Vigeraux distillation head. The boiling temperature of this solution remained essentially constant at an uncorrected 27.5°C for the most part of the distillation as shown by the data in Table 2.
- the constant-boiling character of the solution was consistent with the distillation characteristics of an azeotrope or azeotrope-like composition.
- a solution containing 50.0 weight percent HCFC-123 and 50.0 weight percent methanol was prepared in a suitable container and mixed thoroughly. This solution was distilled in a glass distillation apparatus equipped with a Claisen-Vigeraux distillation head.
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Metallurgy (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Detergent Compositions (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
- Manufacturing Of Printed Wiring (AREA)
Abstract
Description
- As modern electronic circuit boards evolve toward increased circuit and component densities, thorough cleaning of the boards after soldering becomes more important. Generally, current industrial processes for soldering electronic components to circuit boards involve coating the entire circuit side of the board with a flux and thereafter passing this coated side of the board over preheaters and through molten solder. The flux cleans the conductive metal parts and promotes solder fusion. Commonly used fluxes consist, for the most part, of rosin, either used alone or with activating additives, such as amine hydrochlorides or oxalic acid derivatives.
- After soldering, which thermally degrades part of the rosin, the remaining flux and flux-residues are often removed from the circuit boards with a heated organic solvent. The requirements for such solvents are very stringent. Defluxing solvents should have the following characteristics: be low boiling, be nonflammable, have low toxicity and high solvency power so that flux and flux-residues can be removed without damaging the substrate being cleaned.
- While boiling temperature, flammability and solvent power characteristics can often be adjusted by mixing different solvents together, the mixtures that are formed are often unsatisfactory because they fractionate to an undesirable degree on boiling while in use. The more volatile components of these mixtures vaporize first, causing the boiling mixtures to continuously change in both composition and boiling temperature. This fractionation is undesirable since it could result in altered solvency properties. The fractionation also makes it virtually impossible to recover and reuse a solvent mixture with the original composition.
- On the other hand, an azeotropic mixture gives off vapor which has the same composition as the mixture. Since there is no preferential vaporization of the components, azeotropic mixtures remain constant boiling throughout distillation. In vapor-degreasing operations, this constant boiling aspect of azeotropic mixtures is desirable since the solvent vapor can be condensed back into a mixture with its original composition and then be used for the final rinse. Thus, vapor defluxing and degreasing systems act as a still. Unless the solvent composition exhibits a constant boiling point, i.e., is a single material, an azeotrope or is azeotrope-like, fractionation will occur and undesirable solvent distributions will result which could detrimentally affect the safety and efficacy of the cleaning operation.
- Unfortunately, as recognized in the art, it is not possible to predict the formation of azeotropes. This fact obviously complicates the search for new azeotropic compositions which have application in the field. Nevertheless, there is a constant effort in the art to discover new azeotropes or azeotrope-like compositions which have improved solvency characteristics and particularly greater versatility in solvency power.
- EP-A-429,451 discloses azeotrope-like compositions containing 98.9-99% 2,2-dichloro-1,1,1-trifluoroethane, 1.0-1.2% methanol and 0.01% nitromethane, wherein such compositions may be used in processes for cleaning solid surfaces, such as defluxing printed circuits and cleaning metals. US-A-3940342 and No. 4002573 disclose binary constant boiling compositions of 1,2-dichloro-1,1,2-trifluoroethane with trichlorofluoromethane, with diethyl ether and with dischloromethane and also ternary constant boiling compositions comprising 1,2-dichloro-1,1,2-trifluoroethane diethyl ether, and 1,2-dibromo-1,1,2,2-tetrafluoroethane.
- According to the present invention there is provided an azeotrope or azeotrope-like compositon which is a binary mixture of 97-99.5 weight percent 2,2-dichloro-1,1,1-trifluoroethane and 0.5-3 weight percent methanol at atmospheric pressure.
- The present invention provids a nonflammable azeotropic composition which is well suited for solvent cleaning applications.
- The composition of the present invention consists of an admixture of effective amounts of 97-99.5 weight percent 2,2-dichloro-1,1,1-trifluoroethane (CHCIZ-CF3, boiling point = 27.9°C) and 0.5-3 weight percent methanol (CHaOH, boiling point = 65.0°C) to form an azeotrope or azeotrope-like mixture. The fluorinated compound is also known as KCFC-123, in the nomenclature conventional to the chlorofluorocarbon field.
- By azeotrope or azeotrope-like composition is meant a constant boiling liquid admixture of two or more substances, which admixture behaves like a single substance in that the vapor, produced by partial evaporation or distillation of the liquid, has substantially the same composition as the liquid, i.e. the admixture distils without substantial change in composition. Constant boiling compositions, which are characterized as azeotropes or azeotrope-like, exhibit either a maximum or minimum boiling point as compared with that of the non-azeotropic mixtures of the same substances.
- For purposes of this invention, effective amount is defined as the amount of each component of the instant invention admixture which, when combined, results in the formation of the azeotrope or azeotrope-like compositions of the instant invention. This definition includes the amounts of each component, which amounts may vary depending upon the pressure applied to the composition so long as the azeotrope or azeotrope-like compositions continue to exist at the different pressures, but with possible different boiling points. Therefore, effective amount includes the weight percentages of each component of the compositions of the instant invention which form azeotrope or azeotrope-like compositions at pressures other than atmospheric pressure. When the pressure applied to these compositions is adjusted to atmospheric pressure, i.e., 760 mm Hg, these compositions will contain the azeotrope of the instant invention which will boil at the atmospheric boiling point for the true azeotrope described herein.
- It is possible to fingerprint, in effect, a constant boiling admixture which may appear under many guises, depending upon the conditions chosen, by any of several criteria:
- * The composition can be defined as an azeotrope of A, B, C, (and D...) since the very term "azeotrope" is at once both definitive and limitative, and requires that effective amounts of A, B, C (and D...) form this unique composition of matter which is a constant boiling admixture.
- * It is well known by those skilled in the art that, at different pressures, the composition of a given azeotrope will vary at least to some degree, and changes in pressure will also change, at least to some degree, the boiling point temperature. Thus an azeotrope of A, B, C (and D...) represents a unique type of relationship butwith a variable composition which depends on temperature and/or pressure. Therefore, compositional ranges, rather than fixed compositions, are often used to define azeotropes.
- * The composition can be defined as a particular weight percent relationship or mole percent relationship of A, B, C (and D...), while recognizing that such specific values point out only one particular such relationship and that in actuality, a series of such relationships, represented by A, B, C (and D...) actually exist for a given azeotrope, varied by the influence of pressure.
- * An azeotrope of A, B, C (and D...) can be characterized by defining the composition as an azeotrope characterized by a boiling point at a given pressure, thus giving identifying characteristics without unduly limiting the scope of the invention by a specific numerical composition, which is limited by and is only as accurate as the analytical equipment available.
- Binary mixtures of 97-99.5 weight percent HCFC-123 and 0.5-3 weight percent methanol are characterized as azeotropes or azeotrope-like in that mixtures within this range exhibit a substantially constant boiling point at constant pressure. Being substantially constant boiling, the mixtures do not tend to fractionate to any great extent upon evaporation. After evaporation, only a small difference exists between the composition of the vapor and the composition of the initial liquid phase. This difference is such that the compositions of the vapor and liquid phases are considered substantially identical. Accordingly, any mixture within this range exhibits properties which are characteristic of a true binary azeotrope.
- The binary composition consisting of about 98.8 weight percent HCFC-123, and about 1.2 weight percent methanol has been established, within the accuracy of the fractional distillation method, as a true binary azeotrope, boiling at about 28°C, at substantially atmospheric pressure and is preferred.
- The HCFC-123 of the instant invention may contain minor amounts of HCFC-123a.
- The azeotrope of the present invention permits easy recovery and reuse of the solvent from vapor defluxing and degreasing operations because of its azeotropic nature. As an example, the azeotropic mixture of this invention can be used in cleaning processes such as described in U.S. Patent No.3,881,949, which is incorporated herein by reference.
- The azeotrope of the instant invention can be prepared by any convenient method including mixing orcom- bining the desired component amounts. A preferred method is to weigh the desired component amounts and thereafter combine them in an appropriate container.
- A sample of HCFC-123 was placed in a glass flask equipped with a reflux condenser and brought to a boil. Small amounts of methanol were incrementally added to the boiling HCFC-123 to form a refluxing mixture of changing composition. The boiling temperature of this mixture was found to first decrease when methanol was initially added and then increase when the methanol concentration of the mixture exceeded 1.2 weight percent, forming a minimum boiling point of 27.6°C at the composition of 98.8 weight percent HCFC-123 and 1.2 weight percent methanol. The data for this distillation are shown in Table 1.
-
- A solution containing 98.8 weight percent HCFC-123 and 1.2 weight percent methanol was prepared in a suitable container and mixed thoroughly. This solution was distilled in a glass distillation apparatus equipped with a Claisen-Vigeraux distillation head. The boiling temperature of this solution remained essentially constant at an uncorrected 27.5°C for the most part of the distillation as shown by the data in Table 2.
-
- A solution containing 50.0 weight percent HCFC-123 and 50.0 weight percent methanol was prepared in a suitable container and mixed thoroughly. This solution was distilled in a glass distillation apparatus equipped with a Claisen-Vigeraux distillation head.
- Since the solution was rich in methanol, when distilled it was expected to boil off the HCFC-123/methanol azeotrope first and then the excess methanol when HCFC-123 became exhausted. Gas chromotographic analyses of the incrementally pooled distillate verified that the composition of the minimum boiling first-distillates contained 1.0-1.8 weight percent methanol and 99.0-98.2 weight percent HCFC-123, affirming the existence and the composition of the azeotrope. The date are listed in Table 3.
Claims (6)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AT90302267T ATE88766T1 (en) | 1989-03-23 | 1990-03-02 | AZEOTROPIC COMPOSITION OF 2,2-DICHLORO-1,1,1-TRIFLUORETHANE AND METHANOL. |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US32771889A | 1989-03-23 | 1989-03-23 | |
US327718 | 1989-03-23 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0389133A1 EP0389133A1 (en) | 1990-09-26 |
EP0389133B1 true EP0389133B1 (en) | 1993-04-28 |
Family
ID=23277741
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP90302267A Expired - Lifetime EP0389133B1 (en) | 1989-03-23 | 1990-03-02 | Azeotropic composition of 2,2-dichloro-1,1,1-trifluoroethane and methanol |
Country Status (9)
Country | Link |
---|---|
EP (1) | EP0389133B1 (en) |
JP (1) | JPH02292400A (en) |
KR (1) | KR900014642A (en) |
CN (1) | CN1045818A (en) |
AT (1) | ATE88766T1 (en) |
AU (1) | AU632016B2 (en) |
BR (1) | BR9001354A (en) |
CA (1) | CA2012445A1 (en) |
DE (1) | DE69001455D1 (en) |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5066417A (en) * | 1989-07-20 | 1991-11-19 | E. I. Du Pont De Nemours And Company | Binary azeotropic compositions of 2,2-dichloro-1,2-difluoroethane with methanol, ethanol, or trans-1,2-dichloroethylene |
US4961869A (en) * | 1989-08-03 | 1990-10-09 | E. I. Du Pont De Nemours And Company | Ternary azeotropic compositions of 2,3-dichloro-1,1,1,3,3-pentafluoropropane with trans-1,2-dichloroethylene and methanol |
US5026497A (en) * | 1990-03-12 | 1991-06-25 | E. I. Du Pont De Nemours And Company | Azeotropic compositions of perfluoro-1,2-dimethylcyclobutane with methanol and 1,1-dichloro-1-fluoroethane or dichlorotrifluoroethane |
BE1005163A3 (en) * | 1991-08-01 | 1993-05-11 | Solvay | Composition containing fluorinated ether and use thereof. |
BE1005181A3 (en) * | 1991-08-19 | 1993-05-18 | Solvay | Composition containing a fluorinated ether and use thereof. |
CN104294305B (en) * | 2014-09-30 | 2016-06-29 | 江苏中容铜业有限公司 | Copper detergent capable of being rapidly prepared |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0429451A1 (en) * | 1988-04-04 | 1991-06-05 | Allied Signal Inc | Azeotropähnliche bestandteile von dichlortrifluoräthan, methanol und nitromethan. |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4070299A (en) * | 1975-08-29 | 1978-01-24 | Phillips Petroleum Company | Azeotropic compositions |
US4816176A (en) * | 1988-04-04 | 1989-03-28 | Allied-Signal Inc. | Azeotrope-like compositions of dichlorotrifluoroethane, methanol and nitromethane |
US4812256A (en) * | 1988-04-20 | 1989-03-14 | E. I. Du Pont De Nemours And Company | Azeotropic compositions of 1,1-difluoro-1,2,2-trichloroethane and methanol, ethanol, isopropanol or n-propanol |
-
1990
- 1990-03-02 EP EP90302267A patent/EP0389133B1/en not_active Expired - Lifetime
- 1990-03-02 AT AT90302267T patent/ATE88766T1/en not_active IP Right Cessation
- 1990-03-02 DE DE9090302267T patent/DE69001455D1/en not_active Expired - Lifetime
- 1990-03-16 CA CA002012445A patent/CA2012445A1/en not_active Abandoned
- 1990-03-22 AU AU52123/90A patent/AU632016B2/en not_active Ceased
- 1990-03-22 BR BR909001354A patent/BR9001354A/en not_active Application Discontinuation
- 1990-03-22 KR KR1019900003901A patent/KR900014642A/en not_active Application Discontinuation
- 1990-03-23 CN CN90101578A patent/CN1045818A/en active Pending
- 1990-03-23 JP JP2075364A patent/JPH02292400A/en active Pending
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0429451A1 (en) * | 1988-04-04 | 1991-06-05 | Allied Signal Inc | Azeotropähnliche bestandteile von dichlortrifluoräthan, methanol und nitromethan. |
Also Published As
Publication number | Publication date |
---|---|
CA2012445A1 (en) | 1990-09-23 |
AU632016B2 (en) | 1992-12-10 |
ATE88766T1 (en) | 1993-05-15 |
AU5212390A (en) | 1990-09-27 |
EP0389133A1 (en) | 1990-09-26 |
CN1045818A (en) | 1990-10-03 |
DE69001455D1 (en) | 1993-06-03 |
JPH02292400A (en) | 1990-12-03 |
BR9001354A (en) | 1991-04-02 |
KR900014642A (en) | 1990-10-24 |
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