EP0494975B1 - Azeotropähnliche zusammensetzungen von 1,3-dichlor-1,1,2,2,3-pentafluorpropan und 2-methyl-2-propanol - Google Patents

Azeotropähnliche zusammensetzungen von 1,3-dichlor-1,1,2,2,3-pentafluorpropan und 2-methyl-2-propanol Download PDF

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Publication number
EP0494975B1
EP0494975B1 EP90915683A EP90915683A EP0494975B1 EP 0494975 B1 EP0494975 B1 EP 0494975B1 EP 90915683 A EP90915683 A EP 90915683A EP 90915683 A EP90915683 A EP 90915683A EP 0494975 B1 EP0494975 B1 EP 0494975B1
Authority
EP
European Patent Office
Prior art keywords
azeotrope
compositions
dichloro
pentafluoropropane
boiling
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
Application number
EP90915683A
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English (en)
French (fr)
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EP0494975A1 (de
Inventor
Hillel Magid
David Paul Wilson
Dennis M. Lavery
Richard M. Hollister
Richard E. Eibeck
Michael Van Der Puy
Rajat Basu
Ellen Louise Swan
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Honeywell International Inc
Original Assignee
AlliedSignal Inc
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority claimed from US07/526,748 external-priority patent/US5124065A/en
Application filed by AlliedSignal Inc filed Critical AlliedSignal Inc
Priority to AT90915683T priority Critical patent/ATE101194T1/de
Publication of EP0494975A1 publication Critical patent/EP0494975A1/de
Application granted granted Critical
Publication of EP0494975B1 publication Critical patent/EP0494975B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • 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
    • 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
    • C23G5/02841—Propanes
    • C23G5/02851—C2HCl2F5

Definitions

  • This invention relates to azeotrope-like mixtures of 1,3-dichloro-1,1,2,2,3-pentafluoropropane and 2-methyl-2-propanol. These mixtures are useful in a variety of vapor degreasing, cold cleaning, and solvent cleaning applications including defluxing and dry cleaning.
  • Fluorocarbon based solvents have been used extensively for the degreasing and otherwise cleaning of solid surfaces, especially intricate parts and difficult to remove soils.
  • vapor degreasing or solvent cleaning consists of exposing a room temperature object to be cleaned to the vapors of a boiling solvent. Vapors condensing on the object provide clean distilled solvent to wash away grease or other contamination. Final evaporation of solvent from the object leaves the object free of residue. This is contrasted with liquid solvents which leave deposits on the object after rinsing.
  • a vapor degreaser is used for difficult to remove soils where elevated temperature is necessary to improve the cleaning action of the solvent, or for large volume assembly line operations where the cleaning of metal parts and assemblies must be done efficiently.
  • the conventional operation of a vapor degreaser consists of immersing the part to be cleaned in a sump of boiling solvent which removes the bulk of the soil, thereafter immersing the part in a sump containing freshly distilled solvent near room temperature, and finally exposing the part to solvent vapors over the boiling sump which condense on the cleaned part.
  • the part can also be sprayed with distilled solvent before final rinsing.
  • Vapor degreasers suitable in the above-described operations are well known in the art.
  • Sherliker et al. in U.S. Patent 3,085,918 disclose such suitable vapor degreasers comprising a boiling sump, a clean sump, a water separator, and other ancillary equipment.
  • Cold cleaning is another application where a number of solvents are used. In most cold cleaning applications, the soiled part is either immersed in the fluid or wiped with cloths soaked in solvents and allowed to air dry.
  • Trichlorotrifluoroethane has been found to have satisfactory solvent power for greases, oils, waxes and the like. It has therefore found widespread use for cleaning electric motors, compressors, heavy metal parts, delicate precision metal parts, printed circuit boards, gyroscopes, guidance systems, aerospace missile hardware and aluminum parts.
  • azeotropic compositions having fluorocarbon components because the fluorocarbon components contribute additionally desired characteristics, like polar functionality, increased solvency power, and stabilizers.
  • Azeotropic compositions are desired because they do not fractionate upon boiling. This behavior is desirable because in the previously described vapor degreasing equipment with which these solvents are employed, redistilled material is generated for final rinse-cleaning. Thus, the vapor degreasing system acts as a still. Therefore, unless the solvent composition is essentially constant boiling, fractionation will occur and undesirable solvent distribution may act to upset the cleaning and safety of processing.
  • Preferential evaporation of the more volatile components of the solvent mixtures which would be the case if they were not an azeotrope or azeotrope-like, would result in mixtures with changed compositions which may have less desirable properties, such as lower solvency towards soils, less inertness towards metal, plastic or elastomer components, and increased flammability and toxicity.
  • fluorocarbon-based azeotrope-like mixtures are of particular interest because they are considered to be stratospherically safe substitutes for presently used fully halogenated chlorofluorocarbons. The latter have been implicated in causing environmental problems associated with the depletion of the earth's protective ozone layer.
  • Mathematical models have substantiated that hydrochlorofluorocarbons, like dichloropentafluoropropane, have a much lower ozone depletion potential and global warming potential than the fully halogenated species.
  • EP-A-347 924 to Asano discloses the use of hydrogen-containing chlorofluoropropanes as solvents.
  • Dichloropentafluoropropane isomers HCFC-224ca, HCFC-225cb and HCFC-225cc are among the hydrogen-containing chlorofluoropropanes listed.
  • the reference also provides that when the compounds of the invention are used as cleaning solvents, an organic solvent such as a hydrocarbon, an alcohol like methanol, ethanol, n-propyl alcohol, isopropyl alcohol and tert-butyl alcohol, a ketone, a chlorinated hydrocarbon, an ester or an aromatic compound or a surfactant may be incorporated to improve the cleaning effects of the solvent.
  • the reference also provides, "When azeotropy or pseudozaeotropy exists with a composition obtained by the combination of the compound of the present invention with [an]other compound, it is preferred to use them under an azeotropic or pseudozaeotropic condition."
  • This reference does not, however, teach or suggest the instant binary or ternary compositions applicants are claiming. More importantly, there is no teaching or suggestion in reference that applicants' claimed combinations (or the combination of any other compound listed in the reference to the basic solvent compositions) will result in the formation of an azeotrope-like composition.
  • the present invention provides azeotrope-like compositions consisting essentially of from 98 to 99.99 weight percent 1,3-dichloro-1,1,2,2,3-pentafluoro-propane and from 0.01 to 2 weight percent 2-methyl-2-propanol, and boiling at 55.7°C + 0.2°C at 99.87 KPa (749.1 mm Hg).
  • the present invention also provides a method of cleaning a solid surface comprising treating said surface with an azeotrope-like composition as defined above.
  • Dichloropentafluoropropane exists in nine isomeric forms: (1) 2,2-dichloro-1,1,1,3,3-pentafluoropropane (HCFC-225a); (2) 1,2-dichloro-1,2,3,3,3-pentafluoropropane (HCFC-225ba); (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-225cb); (6) 1,1-dichloro-1,2,2,3,3-pentafluoropropane (HCFC-225cc); (7) 1,2-dichloro-1,1,3,3,3-pentafluoropropane (HCFC-225d); (8) 1,3-dichloro-1,1,2,3,
  • the dichloropentafluoropropane component of the invention has good solvent properties.
  • the 2-methyl-2-propanol component also has good solvent capabilities; dissolving polar organic materials and amine hydrochlorides. Thus, when these components are combined in effective amounts, an efficient azeotropic solvent results.
  • compositions within the indicated ranges, as well as certain compositions outside the indicated ranges, are azeotrope-like, as defined more particularly below.
  • thermodynamic state of a fluid is defined by four variables: pressure, temperature, liquid composition and vapor composition, or P-T-X-Y, respectively.
  • An azeotrope is a unique characteristic of a system of two or more components where X and Y are equal at a stated P and T. In practice, this means that the components of a mixture cannot be separated during distillation, and therefore are useful in vapor phase solvent cleaning as described above.
  • azeotrope-like composition is intended to mean that the composition behaves like a true azeotrope in terms of its constant-boiling characteristics or tendency not to fractionate upon boiling or evaporation. Such compositions may or may not be a true azeotrope.
  • the composition of the vapor formed during boiling or evaporation is identical or substantially identical to the original liquid composition.
  • the liquid composition if it changes at all, changes only minimally. This is contrasted with non-azeotrope-like compositions in which the liquid composition changes substantially during boiling or evaporation.
  • one way to determine whether a candidate mixture is "azeotrope-like" within the meaning of this invention is to distill a sample thereof under conditions (i.e. resolution - number of plates) which would be expected to separate the mixture into its separate components. If the mixture is non-azeotropic or non-azeotrope-like, the mixture will fractionate, i.e., separate into its various components with the lowest boiling component distilling off first, and so on. If the mixture is azeotrope-like, some finite amount of a first distillation cut will be obtained which contains all of the mixture components and which is constant boiling or behaves as a single substance.
  • azeotrope-like compositions there is a range of compositions containing the same components in varying proportions which are azeotrope-like. All such compositions are intended to be covered by the term azeotrope-like as used herein.
  • azeotrope-like As an example, it is well known that at different pressures, the composition of a given azeotrope will vary at least slightly as does the boiling point of the composition.
  • an azeotrope of A and B represents a unique type of relationship but with a variable composition depending on temperature and/or pressure. As is readily understood by persons skilled in the art, the boiling point of the azeotrope will vary with the pressure.
  • the azeotrope-like compositions of the invention may be used to clean solid surfaces by treating said surfaces with said compositions in any manner well known in the art such as by dipping or spraying or use of conventional degreasing apparatus.
  • the azeotrope-like compositions discussed herein are useful as solvents for a variety of cleaning applications including vapor degreasing, defluxing, cold cleaning, dry cleaning, dewatering, decontamination, spot cleaning, aerosol propelled rework, extraction, particle removal, and surfactant cleaning applications. These azeotrope-like compositions are also useful as blowing agents, Rankine cycle and absorption refrigerants, and power fluids.
  • the dichloropentafluoropropane and alkanol components of the invention are known materials. Preferably, they should be used in sufficiently high purity so as to avoid the introduction of adverse influences upon the solvent or constant boiling properties of the system.
  • Part B Synthesis of 1,1,2,2,3-pentafluoropropane.
  • a 500 ml flask was equipped with a mechanical stirrer and a Vigreaux distillation column, which in turn was connected to a dry-ice trap, and maintained under a nitrogen atmosphere.
  • the flask was charged with 400 ml N-methylpyrrolidone, 145 gm (0.507 mol) 2,2,3,3-tetrafluoropropyl-p-toluenesulfonate (produced in Part A above), and 87 gm (1.5 mol) spray-dried KF.
  • the mixture was then heated to 190-200°C for 3.25 hours during which time 61 gm volatile product distilled into the cold trap (90% crude yield). Upon distillation, the fraction boiling at 25-28°C was collected.
  • Part C Synthesis of 1,1,3-trichloro-1,2,2,3,3-pentafluoropropane.
  • a 22 liter flask was evacuated and charged with 20.7 gm (0.154 mol) 1,1,2,2,3-pentafluoro-propane (produced in Part B above) and 0.6 mol chlorine. It was irradiated 100 minutes with a 450 W Hanovia Hg lamp at a distance of about 7.6 cm. The flask was then cooled in an ice bath, nitrogen being added as necessary to maintain 1 atm (101 kPa). Liquid in the flask was removed via 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 totaled 31.2 g (85%), the GC purity being 99.7%. The product from several runs was combined and distilled to provide a material having b.p. 73.5-74°C.
  • Part D Synthesis of 1,3-dichloro-1,1,2,2,3-pentafluoropropane. 106.6 gm (0.45 mol) of 1,1,3-trichloro-1,2,2,3,3-pentafluoropropane (produced in Part C above) and 300 gm (5 mol) isopropanol were stirred under an inert atmosphere and irradiated 4.5 hours with a 450 W Hanovia Hg lamp at a distance of 5-7.6 cm. The acidic reaction mixture was then poured into 1.5 liters ice water.
  • compositions may include additional components which form new azeotrope-like compositions. Any such compositions are considered to be within the scope of the present invention as long as the compositions are constant-boiling or essentially constant-boiling and contain all of the essential components described herein.
  • Inhibitors may be added to the present azeotrope-like compositions to inhibit decomposition of the compositions; react with undesirable decomposition products of the compositions; and/or prevent corrosion of metal surfaces.
  • Any or all of the following classes of inhibitors may be employed in the invention: epoxy compounds such as propylene oxide; nitroalkanes such as nitromethane; ethers such as 1-4-dioxane; unsaturated compounds such as 1,4-butyne diol; acetals or ketals such as dipropoxy methane; ketones such as methyl ethyl ketone; alcohols such as tertiary amyl alcohol; esters such as triphenyl phosphite; and amines such as triethyl amine.
  • Other suitable inhibitors will readily occur to those skilled in the art.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Detergent Compositions (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Manufacturing Of Printed Wiring (AREA)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
  • Extraction Or Liquid Replacement (AREA)

Claims (4)

  1. Azeotrop-ähnliche Zusammensetzung, welche im wesentlichen aus 98-99,99 Gewichtsprozent 1,3-dichloro-1,1,2,2,3-Pentafluoropropan und 0,01-2 Gewichtsprozent 2-Methyl-2-Propanol besteht, und deren Siedepunkt bei 99,87 KPa (749,1 mm Hg) bei 55,7°C ± 0,2°C liegt.
  2. Azetrop-ähnliche Zusammensetzung nach Anspruch 1, dadurch gekennzeichnet, dass eine wirkungsvolle Menge eines Inhibators in dieser Zusammensetzung vorhanden ist.
  3. Azetrop-ähnliche Zusammensetzung nach Anspruch 2, dadurch gekennzeichnet, dass dieser Inhibitor unter Epoxyverbindungen, Nitroalkanen, Ether, Azetalen, Ketalen, Ketonen, Alkoholen, Estern une Aminen ausgewählt ist.
  4. Verfahren zum Reinigen einer Feststoffoberfläche durch Behandlung dieser Oberfläche mit einer Azetrop-ähnlichen Zusammensetzung nach irgendeinem der Ansprüche 1 bis 3.
EP90915683A 1989-10-06 1990-09-20 Azeotropähnliche zusammensetzungen von 1,3-dichlor-1,1,2,2,3-pentafluorpropan und 2-methyl-2-propanol Expired - Lifetime EP0494975B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT90915683T ATE101194T1 (de) 1989-10-06 1990-09-20 Azeotropaehnliche zusammensetzungen von 1,3dichlor-1,1,2,2,3-pentafluorpropan und 2-methyl-2-propanol.

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
US41798389A 1989-10-06 1989-10-06
US41800889A 1989-10-06 1989-10-06
US417983 1989-10-06
US418008 1989-10-06
US526748 1990-05-22
US07/526,748 US5124065A (en) 1989-10-06 1990-05-22 Azeotrope-like compositions of dichloropentafluoropropane and an alkanol having 1-4 carbon atoms

Publications (2)

Publication Number Publication Date
EP0494975A1 EP0494975A1 (de) 1992-07-22
EP0494975B1 true EP0494975B1 (de) 1994-02-02

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EP90915683A Expired - Lifetime EP0494975B1 (de) 1989-10-06 1990-09-20 Azeotropähnliche zusammensetzungen von 1,3-dichlor-1,1,2,2,3-pentafluorpropan und 2-methyl-2-propanol

Country Status (11)

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EP (1) EP0494975B1 (de)
JP (1) JP2853900B2 (de)
AU (1) AU641700B2 (de)
BR (1) BR9007715A (de)
CA (1) CA2067218A1 (de)
DE (1) DE69006508T2 (de)
ES (1) ES2062560T3 (de)
IE (1) IE64912B1 (de)
MY (1) MY107105A (de)
NO (1) NO178438C (de)
WO (1) WO1991005035A1 (de)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU623748B2 (en) * 1989-02-01 1992-05-21 Asahi Glass Company Limited Hydrochlorofluorocarbon azeotropic or azeotropic-like mixture
US5320683A (en) * 1989-02-06 1994-06-14 Asahi Glass Company Ltd. Azeotropic or azeotropic-like composition of hydrochlorofluoropropane
FR2661918B1 (fr) * 1990-05-10 1992-07-17 Atochem Composition nettoyante a base de 1,1,1,2,2-pentafluoro-3,3-dichloro-propane et de methyl tert-butyl ether.
US5104565A (en) * 1990-06-25 1992-04-14 Allied-Signal Inc. Azeotrope-like compositions of dichloropentafluoropropane, 2-propanol and a hydrocarbon containing six carbon atoms
AU9177891A (en) * 1990-12-18 1992-07-22 Allied-Signal Inc. Azeotrope-like compositions of dichloropentafluoropropane, an alkanol having 1-3 carbon atoms and 2-methyl-2-propanol
KR20120073330A (ko) * 2004-02-24 2012-07-04 아사히 가라스 가부시키가이샤 물기 제거 방법 및 물기 제거 장치

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1321375A (en) * 1971-03-03 1973-06-27 Ici Ltd Solvent compositions
CZ279988B6 (cs) * 1988-06-22 1995-09-13 Asahi Glass Company Ltd. Čisticí prostředek a jeho použití
DK0381216T3 (da) * 1989-02-01 1996-05-13 Asahi Glass Co Ltd Azeotrop eller azeotroplignende chlorfluorcarbonhydridblanding
JP2734624B2 (ja) * 1989-04-26 1998-04-02 旭硝子株式会社 弗素化炭化水素系共沸様組成物
JP2737246B2 (ja) * 1989-05-26 1998-04-08 旭硝子株式会社 弗素化炭化水素系共沸組成物
JP2734623B2 (ja) * 1989-04-26 1998-04-02 旭硝子株式会社 弗素化炭化水素系共沸様組成物
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

Also Published As

Publication number Publication date
NO921254D0 (no) 1992-03-31
ES2062560T3 (es) 1994-12-16
AU6547890A (en) 1991-04-28
IE64912B1 (en) 1995-09-20
MY107105A (en) 1995-09-30
NO921254L (no) 1992-03-31
BR9007715A (pt) 1992-07-07
JPH05500979A (ja) 1993-02-25
WO1991005035A1 (en) 1991-04-18
DE69006508D1 (de) 1994-03-17
NO178438B (no) 1995-12-18
IE903207A1 (en) 1991-04-10
JP2853900B2 (ja) 1999-02-03
DE69006508T2 (de) 1994-05-26
AU641700B2 (en) 1993-09-30
NO178438C (no) 1996-03-27
CA2067218A1 (en) 1991-04-07
EP0494975A1 (de) 1992-07-22

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