EP0542796B1 - Compositions azeotropes de dichloro-1,1-fluoroethane-1; ethanol; et nitromethane - Google Patents
Compositions azeotropes de dichloro-1,1-fluoroethane-1; ethanol; et nitromethane Download PDFInfo
- Publication number
- EP0542796B1 EP0542796B1 EP91913860A EP91913860A EP0542796B1 EP 0542796 B1 EP0542796 B1 EP 0542796B1 EP 91913860 A EP91913860 A EP 91913860A EP 91913860 A EP91913860 A EP 91913860A EP 0542796 B1 EP0542796 B1 EP 0542796B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- azeotrope
- weight percent
- compositions
- dichloro
- composition
- 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
- 239000000203 mixture Substances 0.000 title claims abstract description 135
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 title claims abstract description 24
- NNEGVZAPOQNLGP-UHFFFAOYSA-N 1,1-dichloro-1-fluoroethane;ethanol Chemical group CCO.CC(F)(Cl)Cl NNEGVZAPOQNLGP-UHFFFAOYSA-N 0.000 title abstract description 6
- 238000004140 cleaning Methods 0.000 claims abstract description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 48
- FRCHKSNAZZFGCA-UHFFFAOYSA-N 1,1-dichloro-1-fluoroethane Chemical compound CC(F)(Cl)Cl FRCHKSNAZZFGCA-UHFFFAOYSA-N 0.000 claims description 36
- 238000000034 method Methods 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 6
- 239000002904 solvent Substances 0.000 abstract description 49
- 238000005108 dry cleaning Methods 0.000 abstract description 3
- 238000005237 degreasing agent Methods 0.000 abstract 1
- 238000009835 boiling Methods 0.000 description 37
- 238000005238 degreasing Methods 0.000 description 17
- OHMHBGPWCHTMQE-UHFFFAOYSA-N 2,2-dichloro-1,1,1-trifluoroethane Chemical compound FC(F)(F)C(Cl)Cl OHMHBGPWCHTMQE-UHFFFAOYSA-N 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 239000013527 degreasing agent Substances 0.000 description 11
- 239000003380 propellant Substances 0.000 description 11
- 239000007788 liquid Substances 0.000 description 10
- 238000004821 distillation Methods 0.000 description 9
- 239000000443 aerosol Substances 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 239000012808 vapor phase Substances 0.000 description 8
- 238000001704 evaporation Methods 0.000 description 7
- 230000008020 evaporation Effects 0.000 description 7
- LVGUZGTVOIAKKC-UHFFFAOYSA-N 1,1,1,2-tetrafluoroethane Chemical compound FCC(F)(F)F LVGUZGTVOIAKKC-UHFFFAOYSA-N 0.000 description 6
- XPDWGBQVDMORPB-UHFFFAOYSA-N Fluoroform Chemical compound FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 description 6
- VOPWNXZWBYDODV-UHFFFAOYSA-N Chlorodifluoromethane Chemical compound FC(F)Cl VOPWNXZWBYDODV-UHFFFAOYSA-N 0.000 description 5
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000012459 cleaning agent Substances 0.000 description 4
- 239000012141 concentrate Substances 0.000 description 4
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 239000002689 soil Substances 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- BOSAWIQFTJIYIS-UHFFFAOYSA-N 1,1,1-trichloro-2,2,2-trifluoroethane Chemical compound FC(F)(F)C(Cl)(Cl)Cl BOSAWIQFTJIYIS-UHFFFAOYSA-N 0.000 description 3
- AJDIZQLSFPQPEY-UHFFFAOYSA-N 1,1,2-Trichlorotrifluoroethane Chemical compound FC(F)(Cl)C(F)(Cl)Cl AJDIZQLSFPQPEY-UHFFFAOYSA-N 0.000 description 3
- NPNPZTNLOVBDOC-UHFFFAOYSA-N 1,1-difluoroethane Chemical compound CC(F)F NPNPZTNLOVBDOC-UHFFFAOYSA-N 0.000 description 3
- DDMOUSALMHHKOS-UHFFFAOYSA-N 1,2-dichloro-1,1,2,2-tetrafluoroethane Chemical compound FC(F)(Cl)C(F)(F)Cl DDMOUSALMHHKOS-UHFFFAOYSA-N 0.000 description 3
- BOUGCJDAQLKBQH-UHFFFAOYSA-N 1-chloro-1,2,2,2-tetrafluoroethane Chemical compound FC(Cl)C(F)(F)F BOUGCJDAQLKBQH-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- PXBRQCKWGAHEHS-UHFFFAOYSA-N dichlorodifluoromethane Chemical compound FC(F)(Cl)Cl PXBRQCKWGAHEHS-UHFFFAOYSA-N 0.000 description 3
- 235000019404 dichlorodifluoromethane Nutrition 0.000 description 3
- UMNKXPULIDJLSU-UHFFFAOYSA-N dichlorofluoromethane Chemical compound FC(Cl)Cl UMNKXPULIDJLSU-UHFFFAOYSA-N 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- CYRMSUTZVYGINF-UHFFFAOYSA-N trichlorofluoromethane Chemical compound FC(Cl)(Cl)Cl CYRMSUTZVYGINF-UHFFFAOYSA-N 0.000 description 3
- VLIDBBNDBSNADN-UHFFFAOYSA-N 1,1-dichloro-2,2-difluoroethane Chemical compound FC(F)C(Cl)Cl VLIDBBNDBSNADN-UHFFFAOYSA-N 0.000 description 2
- BHNZEZWIUMJCGF-UHFFFAOYSA-N 1-chloro-1,1-difluoroethane Chemical compound CC(F)(F)Cl BHNZEZWIUMJCGF-UHFFFAOYSA-N 0.000 description 2
- FWAQVJAOVDYHAF-UHFFFAOYSA-N 1-chloro-1,2,2-trifluoroethane Chemical compound FC(F)C(F)Cl FWAQVJAOVDYHAF-UHFFFAOYSA-N 0.000 description 2
- MSXVEPNJUHWQHW-UHFFFAOYSA-N 2-methylbutan-2-ol Chemical compound CCC(C)(C)O MSXVEPNJUHWQHW-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 239000001273 butane Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- OPOHQUJHFHLJFN-UHFFFAOYSA-N ethanol;nitromethane Chemical compound CCO.C[N+]([O-])=O OPOHQUJHFHLJFN-UHFFFAOYSA-N 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000001282 iso-butane Substances 0.000 description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- HOMDJHGZAAKUQV-UHFFFAOYSA-N 1-(propoxymethoxy)propane Chemical compound CCCOCOCCC HOMDJHGZAAKUQV-UHFFFAOYSA-N 0.000 description 1
- CYXIKYKBLDZZNW-UHFFFAOYSA-N 2-Chloro-1,1,1-trifluoroethane Chemical compound FC(F)(F)CCl CYXIKYKBLDZZNW-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 239000004338 Dichlorodifluoromethane Substances 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- 150000001241 acetals Chemical class 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000000712 assembly Effects 0.000 description 1
- 238000000429 assembly Methods 0.000 description 1
- 239000000926 atmospheric chemistry Substances 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- DLDJFQGPPSQZKI-UHFFFAOYSA-N but-2-yne-1,4-diol Chemical compound OCC#CCO DLDJFQGPPSQZKI-UHFFFAOYSA-N 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- KYKAJFCTULSVSH-UHFFFAOYSA-N chloro(fluoro)methane Chemical compound F[C]Cl KYKAJFCTULSVSH-UHFFFAOYSA-N 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 229940099364 dichlorofluoromethane Drugs 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011067 equilibration Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 235000019256 formaldehyde Nutrition 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- -1 hydrofluorocarbon Chemical compound 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 238000013178 mathematical model Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000001272 nitrous oxide Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 1
- 229940029284 trichlorofluoromethane Drugs 0.000 description 1
- 229940086542 triethylamine Drugs 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
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
- 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
-
- 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
- C23G5/02832—C2H3Cl2F
Definitions
- This invention relates to azeotrope-like mixtures of 1,1-dichloro-1-fluoroethane; ethanol; and nitromethane. These mixtures are useful in a variety of vapor degreasing, cold cleaning and solvent cleaning applications including defluxing.
- Vapor degreasing and solvent cleaning with fluorocarbon based solvents have found widespread use in industry 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 behind no residue as would be the case where the object is simply washed in liquid solvent.
- 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.
- the soiled part is either immersed in the fluid or wiped with rags or similar objects soaked in solvents and allowed to air dry.
- Fluorocarbon solvents such as trichlorotrifluoroethane
- 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 and missile hardware, aluminum parts and the like.
- azeotrope or azeotrope-like compositions including the desired fluorocarbon components such as trichlorotrifluoroethane which include components which contribute additionally desired characteristics, such as polar functionality, increased solvency power, and stabilizers.
- Azeotropic or azeotrope-like 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.
- solvent composition exhibits a constant boiling point, i.e., is azeotrope-like, 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 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.
- hydrochlorofluorocarbons such as 1,1-dichloro-1-fluoroethane (HCFC-141b)
- HCFC-141b 1,1-dichloro-1-fluoroethane
- HCFC-141b is known to be useful as a solvent.
- HCFC-141b has a boiling point of about 32°C.
- Aerosol products utilize a propellant gas or mixture of propellant gases, preferably in a liquified gas rather than a compressed gas state, to generate sufficient pressure to expel the active ingredients, i.e. product concentrates such as solvents, from the container upon opening of the aerosol valve.
- the propellants may be in direct contact with the solvent, as in most conventional aerosol systems, or may be isolated from the solvent, as in barrier-type aerosol systems.
- Kokai Patent Publication 136,982 published May 30, 1989 discloses a buff-grinding cleaning agent of 25 weight percent ethanol and 75 weight percent of an azeotropic composition of 25 weight percent 1,1-dichloro-1-fluoroethane and 50 weight percent 1,1-dichloro-2,2,2-trifluoroethane.
- Kokai Patent Publication 137,253, published May 30, 1989 discloses a resist developing agent of 25 weight percent ethanol and 75 weight percent of an azeotropic composition of 25 weight percent 1,1-dichloro-1-fluoroethane and 50 weight percent 1,1-dichloro-2,2,2-trifluoroethane.
- Kokai Patent Publication 137,259 discloses a resist separating agent of 15 weight percent ethanol, 10 weight percent alkyl benzene sulfonic acid, and 75 weight percent of an azeotropic composition of 25 weight percent 1,1-dichloro-1-fluoroethane and 50 weight percent 1,1-dichloro-2,2,2-trifluoroethane.
- Kokai Patent Publication 138,300 discloses a flux cleaning agent of 25 weight percent methanol and 75 weight percent of an azeotropic composition of 25 weight percent 1,1-dichloro-1-fluoroethane and 50 weight percent 1,1-dichloro-2,2,2-trifluoroethane.
- Kokai Patent Publication 139,104 discloses a solvent of 5 weight percent trichloroethylene, 20 weight percent ethanol, and 75 weight percent of an azeotropic composition of 25 weight percent 1,1-dichloro-1-fluoroethane and 75 weight percent 1,1-dichloro-2,2,2-trifluoroethane.
- Kokai Patent Publication 139,861 published June 1, 1989, discloses a dry-cleaning agent of 25 weight percent ethanol and 75 weight percent of an azeotropic composition of 25 weight percent 1,1-dichloro-1-fluoroethane and 75 weight percent 1,1-dichloro-2,2,2-trifluoroethane.
- Another object of the invention is to provide novel environmentally acceptable solvents for use in the aforementioned applications.
- novel mixtures comprising from 95.5 to 99.49 weight percent of 1,1-dichloro-1-fluoroethane; from 0.5 to 3.5 weight percent of ethanol; and from 0.01 to 1.0 weight percent of nitromethane which boil at 32.8°C ⁇ 0.5°C at 760 mm Hg (101 kPa).
- the azeotrope-like compositions of the invention comprise from 96.1 to 99.05 weight percent of 1,1-dichloro-1-fluoroethane; from 0.9 to 3.0 weight percent of ethanol; and from 0.05 to 0.9 weight percent of nitromethane.
- the azeotrope-like compositions of the invention comprise from 97.1 to 98.75 weight percent of 1,1-dichloro-1-fluoroethane; from 1.2 to 2.0 weight percent of ethanol; and from 0.05 to 0.9 weight percent of nitromethane.
- azeotrope-like is used herein for the mixtures of the invention because in the claimed proportions, the compositions of 1,1-dichloro-1-fluoroethane, ethanol, and nitromethane are constant-boiling or essentially constant-boiling and for some reason, which is not fully understood, remain or hang together in a vapor degreaser.
- compositions within the indicated ranges, as well as certain compositions outside the indicated ranges, are azeotrope-like, as defined more particularly below.
- compositions with 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 the 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 an azeotrope, i.e. has constant-boiling characteristics or a tendency not to fractionate upon boiling or evaporation.
- 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 to a minimal or negligible extent. This is to be contrasted with non-azeotrope-like compositions in which during boiling or evaporation, the liquid composition changes to a substantial degree.
- 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-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. This phenomenon cannot occur if the mixture is not azeotrope-like, i.e. it does not behave like an azeotrope. Of course, upon distillation of an azeotrope-like composition such as in a vapor degreaser, the true azeotrope will form and tend to concentrate.
- azeotrope-like compositions there is a range of compositions containing the same components in varying proportions which are azeotrope-like or constant-boiling. All such compositions are intended to be covered by the term azeotrope-like or constant-boiling as used herein.
- azeotrope-like or constant-boiling As an example, it is well known that at differing pressures, the composition of a given azeotrope-like composition will vary at least slightly as does the boiling point of the composition.
- an azeotrope-like composition of A and B represents a unique type of relationship but with a variable composition depending on temperature and/or pressure.
- the mixtures boil within ⁇ 0.5°C (at 760 mm Hg (101 kPa)) of the 32.8°C boiling point.
- the boiling point of the azeotrope-like composition will vary with the pressure.
- azeotrope-like compositions of the invention are useful as solvents in a variety of vapor degreasing, cold cleaning and solvent cleaning applications including defluxing.
- 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 to the art such as by dipping or spraying or use of conventional degreasing apparatus.
- the azeotrope-like compositions are used to clean solid surfaces by spraying the surfaces with the compositions
- the azeotrope-like compositions are sprayed onto the surfaces by using a propellant.
- the propellant is selected from the group consisting of hydrocarbons, chlorofluorocarbons, hydrochlorofluorocarbon, hydrofluorocarbon, dimethyl ether, carbon dioxide, nitrogen, nitrous oxide, methylene oxide, air, and mixtures thereof.
- Useful hydrocarbon propellants include isobutane, butane, propane, and mixtures thereof; commercially available isobutane, butane, and propane may be used in the present invention.
- Useful chlorofluorocarbon propellants include trichlorofluoromethane (known in the art as CFC-11), dichlorodifluoromethane (known in the art as CFC-12), 1,1,2-trichloro-1,2,2-trifluoroethane (known in the art as CFC-113), and 1,2-dichloro-1,1,2,2-tetrafluoroethane (known in the art as CFC-114); commercially available CFC-11, CFC-12, CFC-113, and CFC-114 may be used in the present invention.
- Useful hydrochlorofluorocarbon propellants include dichlorofluoromethane (known in the art as HCFC-21), chlorodifluoromethane (known in the art as HCFC-22), 1-chloro-1,2,2,2-tetrafluoroethane (known in the art as HCFC-124), 1,1-dichloro-2,2-difluoroethane (known in the art as HCFC-132a), 1-chloro-2,2,2-trifluoroethane (known in the art as HCFC-133), and l-chloro-1,1-difluoroethane (known in the art as HCFC-142b); commercially available HCFC-21, HCFC-22, and HCFC-142b may be used in the present invention.
- HCFC-124 may be prepared by a known process such as that taught by U.S. Patent 4,843,181
- HCFC-133 may be prepared by a known process such as that taught by U.S
- Useful hydrofluorocarbon propellants include trifluoromethane (known in the art as HFC-23), 1,1,1,2-tetrafluoroethane (known in the art as HFC-134a), and 1,1-difluoroethane (known in the art as HFC-152a); commercially available HFC-23 and HFC-152a may be used in the present invention. Until HFC-134a becomes available in commercial quantities, HFC-134a may be made by a known method such as that disclosed by U.S. Patent 4,851,595. More preferred propellants include hydrochlorofluorocarbons, hydrofluorocarbons, and mixtures thereof. The most preferred propellants include chlorodifluoromethane and 1,1,1,2-tetrafluoroethane.
- the 1,1-dichloro-1-fluoroethane; ethanol; and nitromethane components of the novel solvent azeotrope-like compositions of the invention are known materials.
- the materials should be used in sufficiently high purity so as to avoid the introduction of adverse influences upon the desired properties or constant-boiling properties of the system.
- a vapor phase degreasing machine was charged with a preferred mixture in accordance with the invention, comprising about 98.5 weight percent of HCFC-141b, about 1.2 weight percent of ethanol, and about 0.3 weight percent of nitromethane.
- the mixture was evaluated for its constant boiling or non-segregating characteristics.
- the vapor phase degreasing machine utilized was a small water-cooled, three-sump vapor phase degreaser which represents a type of system configuration comparable to machine types in the field today which would present the most rigorous test of solvent segregating behavior.
- the degreaser employed to demonstrate the invention contained two overflowing rinse-sumps and a boil-sump.
- the boil-sump and the still were electrically heated, and each contained a low-level shut-off switch.
- Solvent vapors in both the degreaser and the still were condensed on water-cooled stainless-steel coils.
- the still was fed by gravity from the boil-sump. Condensate from the still was returned to the first rinse-sump, also by gravity.
- the capacity of the unit was approximately 5.68 litre (1.5 gallons).
- This degreaser was very similar to degreasers which are commonly used in commercial establishments.
- the solvent charge was brought to reflux and the compositions in the condensate sump containing the clear condensate from the still, the work sump containing the overflow from the condensate sump, the boil sump where the overflow from the work sump is brought to the mixture boiling points, and the still were determined with a Perkin Elmer Sigma 3 gas chromatograph.
- the temperature of the liquid in all the sumps was monitored with thermocouple temperature sensing devices accurate to ⁇ 0.2°C. Refluxing was continued for about 30 hours and boil and condensate sump compositions were monitored throughout this time.
- a mixture was considered constant-boiling or non-segregating if the maximum concentration difference between sumps for any mixture component was ⁇ 2 sigma around the mean value.
- Sigma is a standard deviation unit and it is our experience from many observations of vapor degreaser performance that commercial "azeotrope-like" vapor phase degreasing solvents exhibit at least a ⁇ 2 sigma variation in composition with time and yet produce very satisfactory non-segregating cleaning behavior.
- Example 1 was repeated except that the vapor phase degreasing machine was charged with another preferred mixture in accordance with the invention, comprising about 97.7 weight percent of HCFC-141b, about 2.0 weight percent of ethanol, and about 0.3 weight percent of nitromethane.
- a 5-plate Oldershaw distillation column with a cold water condensed automatic liquid dividing head was used for this example.
- the distillation column was charged with HCFC-141b, ethanol, and nitromethane in the amounts indicated in Table III below for the starting material.
- Each composition was heated under total reflux for about an hour to ensure equilibration.
- a reflux ratio of 5:1 was employed for this particular distillation.
- Approximately 50 percent of the original charges were collected in four similar-sized overhead fractions.
- the compositions of these fractions were analyzed using gas chromatography. The averages of the distillate fractions and the overhead temperatures are quite constant within the uncertainty associated with determining the compositions, indicating that the mixtures are constant-boiling or azeotrope-like.
- Performance studies are conducted to evaluate the solvent properties of the azeotrope-like compositions of the invention. Specifically, metal coupons are cleaned using the present azeotrope-like composition of Example 1 as solvent. The metal coupons are soiled with various types of oils and heated to 93°C so as to partially simulate the temperature attained while machining and grinding in the presence of these oils.
- the metal coupons thus treated were degreased in a simulated vapor phase degreaser machine. Condenser coils are kept around the lip of a cylindrical vessel to condense the solvent vapor which then drips down to the vessel. The metal coupons are held in the solvent vapor and rinsed for a period of 15 seconds to 2 minutes depending upon the oils selected.
- the cleaning performance of the azeotrope-like compositions is determined by visual observation of the coupons.
- the azeotrope-like composition of Example 1 is effective as a solvent.
- Example 4 is repeated using the azeotrope-like composition of Example 2.
- the azeotrope-like composition of Example 2 is effective as a solvent.
- Example 4 is repeated using the azeotrope-like composition of Example 3.
- the azeotrope-like composition of Example 3 is effective as a solvent.
- a 177.5 cm 3 (six-ounce) three-piece aerosol can is used.
- the azeotrope-like composition of Example 1 is weighed into a tared aerosol can. After purging the can with tetrafluoroethane in order to displace the air within the container, a valve is mechanically crimped onto the can. Liquid chlorodifluoromethane is then added through the valve utilizing pressure burettes.
- a printed circuit board having an area of 244.85 cm 2 (37.95 square inches)and densely populated with dip sockets, resistors, and capacitors is precleaned by rinsing with isopropanol before wave soldering.
- the board is then fluxed and wave soldered using a Hollis TDL wave solder machine.
- the printed circuit board is then spray cleaned using the aerosol can having the azeotrope-like composition therein.
- the cleanliness of the board is tested visually and also using an Omega-meter which measured the ionic contamination of the board.
- the azeotrope-like composition of Example 1 is particularly useful as a solvent for spray cleaning applications.
- Example 7 is repeated except that the azeotrope-like composition of Example 2 is used.
- the azeotrope-like composition of Example 2 is particularly useful as a solvent for spray cleaning applications.
- Example 7 is repeated except that the azeotrope-like composition of Example 3 is used.
- the azeotrope-like composition of Example 3 is particularly useful as a solvent for spray cleaning applications.
- 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; 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)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Detergent Compositions (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Manufacturing Of Printed Wiring (AREA)
Claims (6)
- Compositions de type azéotrope comprenant de 95,5 à 99,49% en poids de 1,1-dichloro-1-fluoroéthane, de 0,5 à 3,5% en poids d'éthanol et de 0,01 à 1% en poids de nitrométhane de point d'ébullition 32,8°C ± 0,5°C à 760 mm de Hg (101 kPa).
- Compositions de type azéotrope selon la revendication 1, comprenant de 96,1 à 99,05% en poids dudit 1,1-dichloro-1-fluoroéthane, de 0,9 à 3% en poids dudit éthanol et de 0,05 à 0,9% en poids dudit nitrométhane.
- Compositions de type azéotrope selon la revendication 1, comprenant de 97,1 à 98,75% en poids dudit 1,1-dichloro-1-fluoroéthane, de 1,2 à 2% en poids dudit éthanol et de 0,05 à 0,9% en poids dudit nitrométhane.
- Procédé de nettoyage d'une surface solide, qui comprend le traitement de ladite surface avec ladite composition de type azéotrope selon la revendication 1.
- Procédé de nettoyage d'une surface solide, qui comprend le traitement de ladite surface avec ladite composition de type azéotrope selon la revendication 2.
- Procédé de nettoyage d'une surface solide, qui comprend le traitement de ladite surface avec ladite composition de type azéotrope selon la revendication 3.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US56552290A | 1990-08-09 | 1990-08-09 | |
US565522 | 1990-08-09 | ||
PCT/US1991/004842 WO1992002666A1 (fr) | 1990-08-09 | 1991-07-10 | Compositions azeotropes de dichloro-1,1-fluoroethane-1; ethanol; et nitromethane |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0542796A1 EP0542796A1 (fr) | 1993-05-26 |
EP0542796B1 true EP0542796B1 (fr) | 1996-09-25 |
Family
ID=24258998
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP91913860A Expired - Lifetime EP0542796B1 (fr) | 1990-08-09 | 1991-07-10 | Compositions azeotropes de dichloro-1,1-fluoroethane-1; ethanol; et nitromethane |
Country Status (10)
Country | Link |
---|---|
EP (1) | EP0542796B1 (fr) |
JP (1) | JPH05508880A (fr) |
KR (1) | KR930701583A (fr) |
AT (1) | ATE143419T1 (fr) |
AU (1) | AU8288891A (fr) |
CA (1) | CA2087847A1 (fr) |
DE (1) | DE69122396D1 (fr) |
ES (1) | ES2091936T3 (fr) |
MX (1) | MX9100409A (fr) |
WO (1) | WO1992002666A1 (fr) |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS62124198A (ja) * | 1985-11-26 | 1987-06-05 | 旭化成株式会社 | 溶剤組成物 |
US5246617A (en) * | 1988-01-20 | 1993-09-21 | E. I. Du Pont De Nemours And Company | Azeotropic compositions of 1,1-dichloro-1-fluoroethane and methanol/ethanol |
KR960015228B1 (ko) * | 1988-05-03 | 1996-11-04 | 알라이드-시그날 인코포레이티드 | 1, 1-디클로로-1-플루오로에탄/메탄올계 공비성조성물 |
US4836947A (en) * | 1988-06-09 | 1989-06-06 | Allied-Signal Inc. | Azeotrope-like compositions of 1,1-dichloro-1-fluoroethane and ethanol |
US4863630A (en) * | 1989-03-29 | 1989-09-05 | Allied-Signal Inc. | Azeotrope-like compositions of 1,1-dichloro-1-fluoroethane, dichlorotrifluoroethane and ethanol |
-
1991
- 1991-07-10 AT AT91913860T patent/ATE143419T1/de not_active IP Right Cessation
- 1991-07-10 ES ES91913860T patent/ES2091936T3/es not_active Expired - Lifetime
- 1991-07-10 AU AU82888/91A patent/AU8288891A/en not_active Abandoned
- 1991-07-10 WO PCT/US1991/004842 patent/WO1992002666A1/fr active IP Right Grant
- 1991-07-10 KR KR1019930700340A patent/KR930701583A/ko not_active Application Discontinuation
- 1991-07-10 CA CA002087847A patent/CA2087847A1/fr not_active Abandoned
- 1991-07-10 EP EP91913860A patent/EP0542796B1/fr not_active Expired - Lifetime
- 1991-07-10 DE DE69122396T patent/DE69122396D1/de not_active Expired - Lifetime
- 1991-07-10 JP JP91512931A patent/JPH05508880A/ja active Pending
- 1991-07-29 MX MX9100409A patent/MX9100409A/es unknown
Also Published As
Publication number | Publication date |
---|---|
DE69122396D1 (de) | 1996-10-31 |
EP0542796A1 (fr) | 1993-05-26 |
KR930701583A (ko) | 1993-06-12 |
ATE143419T1 (de) | 1996-10-15 |
MX9100409A (es) | 1992-04-01 |
JPH05508880A (ja) | 1993-12-09 |
CA2087847A1 (fr) | 1992-02-10 |
ES2091936T3 (es) | 1996-11-16 |
AU8288891A (en) | 1992-03-02 |
WO1992002666A1 (fr) | 1992-02-20 |
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