CA2026576C - Hydrochlorofluorocarbon azeotropic or azeotropic-like mixture - Google Patents
Hydrochlorofluorocarbon azeotropic or azeotropic-like mixture Download PDFInfo
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Abstract
A hydrochlorofluorocarbon azeotropic or azeotropic-like mixture comprising at least one member selected from the group consisting of the hydrochlorofluoropropanes 1,1-dichloro-2,2,3,3,3-pentafluoropropane and 1,1-dichloro-2,2,3,3,3-pentafluorpropane, and alcohols having from 1 to 4 carbon atoms. They are useful as a chlorofluorocarbon (CFC) alternative, and particularly as a solvent in cleaning agents.
Description
2~~~ ~°~
1 _ DESCRIPTION
TITLE OF THE TNVE:NTION
HXDROCHLOROFLUOROCARBON AZEO'rROPIC OR
AZEOTROPIC-LTKE MIXTURE
TECHNICAL FIELD
The present invention relates to a novel hydrochlorofluorocarbon azeotropic or azeotropic-like mixture which can be used as a chlorofluorocarbon alternative and which has excellent properties as a solvent and so on.
BACKGROUND ART
Chlorafluorocarbon compounds (hereinafter referred simply as CFCs) have little toxicity and are, in many cases, non-flammable and chemically stable. Various CFCs having different boiling points are available. By virtue of such properties, 1,1,2-trichloro-1,2,2-trifluoroethane (R113) is used as a solvent or a blowing agent;
trichloromonofluoromethane (R11) is used as a blowing agent or a propellant; and dichlorodifluoromethane (R12), is used as a propellant or a refrigerant.
Chemically stable R11, R12 and 8113 have long lifetime in the troposphere and reach the stratosphere, where they will be dissociated by solar radiation tp release chlorine radicals, which initiate a chain reaction with ozone and deplete the ozone layer.
Accordingly, the regulations for limiting the use of such conventional CFCs have been implemented. Therefore, a . CA 02026576 1999-03-18 r research has been actively conducted to develop a CFC
alternative which scarcely depletes the ozone layer.
It is an object of the present invention to provide a mixture containing a novel hydrochlorofluoropropane having 3 carbon atoms, which has various excellent properties equal to conventional CFCs and which is useful as a CFC alternative.
The present invention provides a hydrochlorofluorocarbon azeotropic or azeotropic-like mixture comprising at least one member selected from the group consisting of the hydrochlorofluoropropanes 1,1-dichloro-2,2,3,3,3-pentafluoropropane and 1,1-dichloro-2,2,3,3,3-pentafluorpropane, and at least one member selected from halogenated hydrocarbons having a boiling point of from 20 to 85°C other than the above hydrochlorofluoropropanes, hydrocarbons having a boiling point of from 20 to 85°C, and particularly preferred, alcohols having from 1 to 4 carbon atoms.
The mixture of the present invention is non-flammable or hardly flammable and may take a form of an azeotropic composition or an azeotropic-like composition.
Particularly when used as a solvent, it provides properties equal or superior to conventional 1,1,2-trichlorotrifluoroethane (R113). Therefore, it is very useful as an alternative for 8113. Further, no substantial change in the composition was observed when boiling or evaporating. Therefore, it may be used in the same manner as a conventional single CFC, whereby it has a merit in that no substantial change in the conventional technique is required.
The hydrochlorofluoropropanes of the present invention contain a hydrogen atom, a chlorine atom and a fluorine atom as essential elements. This group broadly includes the following compounds:
CC2FZCF2CHC22 (R224ca) CCQZFCFZCHCQF(R224cb) CF,CFzCHCQ2 (R225ca) CCQFZCFZCHCQF(R225cb) CCQFZCFZCHZCQ(R234cc) CHFZCFZCHCQF(R235ca) CH3CF~ZCCQZF(R243cc) CHFzCF2CHz'CQ (R244ca) CHZCQCFZCH2CQ(R252ca) CHCQZCFZCH3(R252cb) CH3CFZCHZCQ(R262ca) CHFZCFzCCQzF(R225cc) CHCQf~CFzCHCQF(R234ca) CfiFzCFzCHCQz (R234cb) CHzFCFzCC.QzF(R234cd) CF,CFZCH2CQ(R235cb) CCQFzCFzCH2F(R235cc) CHzCQCFzCHCQF (R243~ca) CHaFCFzCHCQz(R243cb) CH2FCF2CHCQF(R244cb) CCQFzCFzCH,(R244cc) CHzFCFzCHzCQ(R253ca) CH, CFz CIiCQF (R253cb) CF,CFZCHCQF~R226ca) CCQF2CFzCHFz~(R226cb) CCQ,CFzCHCQz(R222c) CCQzFCFzCHCQz(R223ca) CCQ,CF2CHCQF(R223cb) CCQ3CF~CliFz (R224cc) CHCQzCFzCIiCQz (R232ca) CCQ,CFzCHZCQ (R232cb) CCQzFCFzCHzCQ(R233cb) CHCQzCFZCHCQF(R233ca) CCQ,CFZCHZF(R233cc) CCQ,CFzCH,(R242cb) CHCQzCFzCHzCQ (R242ca) Among them, of interest are R244ca, R244cb, R235ca, and R243cc, and particularly preferred are R225ca and R225cb.
The halogenated hydrocarbons having a boiling point of from 20 to 85°C other than the hydrochlorofluoropropanes of the formula I, include chlorinated hydrocarbons, fluorinated hydrocarbons and brominated hydrocarbons having from 1 to 4 carbon atoms.
The chlorinated hydrocarbons having from 1 to 4 carbon atoms, include dichloromethane, trichloromethane, trans-1,2-dichloroethylene, cis-1,2-dichloroethylene, 1-chloropropane, 2-chloro-2-methylpropane, 1,1,1-trichloroethane and 1,1-dichloroethane. The fluorinated hydrocarbons include 1,1,2-trichlorotrifluoroethane -- ~ (R113), 1,1,2-trichloro-2,2-difluoroethane (R122), 1,2,2-trichloro-1,2-difluoroethane (R122a), 1,1,1-trichloro-2,2-difluoroethane (R122b), l,l-dichloro-2,2,2-trifluoroethane (R123), 1,2-dichloro-1,1-difluoroethane (R132b), 1,2-dichloro-1-fluoroethane (R141)., 1,1-dichloro-1-fluoroethane (R141b) and trichlorofluoromethane (R11). Likewise, the brominated hydrocarbons include 2-bromopropane as a preferred example.
The hydrocarbons having a boiling point of from 20 to 85°C, include aliphatic, alicyclic and aromatic hydrocarbons. Preferably, they include hydrocarbons having from 5 to 8 carbon atoms such as n-pentane, isopentane, n-hexane, 2,4-dimethylpentane, cyclopentane, 2,2-dimethylbutane, 2-methylpentane, methylcyclopentane, cyclohexan a and 2,3-~dimethylbutane. The hydrocarbons having from 5 to 8 carbon atoms may be a mixture obtained as a petraleum fraction and may preferably be a petroleum fraction containing as the main component at least one member selected from the group consisting of cyclopentane, 2,2-dimethylbutane, 2-methylpentane and 2,3-dimethylbutane.
The azeotropic or azeotropic-like composition of the mixture of the present invention may vary to an extent of t 1.0~ by weight depending upon the purities of the compounds to be mixed or by the influence of measuring error, etc.
To the mixture of the present invention, other components may further be incorporated, as the case requires. For example, when the mixture is used as a solvent, it may contain at least one member selected from the group consisting of hydrocarbons such as neopentane, 3-methylpentane, neohexane, hexane, 3-methylhexane, heptane, isoheptane, 2,3-dimethylpentane, 2,4-dimethylpentane, octane, 2,2,3-trimethylpentane, 2,2,4-trimethylpentane, cyclopentane, methylcyclohexane and ethylcyclohexane; chlorinated hydrocarbons such as 1,1,2-trichloroethane, 1,2-dichloroethane, trichloroethylene and tetrachloroethylene; chlorofluorinated hydrocarbons other than those of the present invention, such as 1,1-dichloro-2,3,3,3-tetrafluoropropene-1, trans-3=chloro-1,1,1,2,4,4,5,5,5-monafluoropentene-2, cis-3-chloro-1,1,1,2,4,4,5,5,5-nonafluoropentene-2, 1,1,1,2,2,5,5,6,6,6-decafluorohexane and tetrachloro-1,2,-difluoroethane; vitro compounds; phenols; amines;
ethers; amylenes; esters; organic phosphites; epoxides;
furans; alcohols; ketones; amides; and triazoles.
The content of such additional components in the mixture of the present invention is not particularly limited, but for the purpose of improving or controlling the solibility or obtaining a suitable boiling point or non-flammability, the content is usually from 0 to. 50~ by weight, preferably from 1 to 40~ by weight. Preferably such incorporation will bring about an azeotropic or azeotropic-like composition. Further, to give the mixture a high level of stabilizing effect, it is effective to incorporate a stabilizer. The content of such additional components is usually from 1 ppm to 10~
by weight, preferably from 10 ppm to 5~ by weight.
Further, the mixture of the present invention may further contain various cleaning assistants, surfactants, emulsifying agents, water, etc.
As the vitro compounds, those represented by the formula R-NOz wherein R is a chain or cyclic hydrocarbon group having from 1 to 6 carbon atoms and containing a saturated or unsaturated bond, may be employed.
Specifically, they include nitromethane, nitroethane, 1-nitropropane, 2-nitropropane and nitrobenzene. More preferred are nit:romethane anck nitroethane.
As the phenols, those represented by the following formulas are preferred:
R R R R
O R' R ~ OR~
R" ~ , R R' COOK
OR' R-~- i R ", ' R ~~ ' R ~~
R R" ~HR
COOR~-R", O
' R
wherein each of R, R', R" and R"' is OH or a chain or cyclic hydrocarbon group having from 1 to 6 carbon atoms and containing a saturated or unsaturated bond.
Specifically, they include phenol, o-cresol, m-cresol, p-cresol, thymol, p-tert-butylphenol, tert-butylcatechol, catechol, isoeugenol, o-methoxyphenol, 4,4'-dihydroxyphenyl-2,2-propane, isoamyl salicylate, benzyl salicylate, methyl salicylate and 2,6-di-t-butyl-p-cresol. More preferred are phenol, 4,4-dihydroxyphenyl-2,2-propane arid 2,6-di-t-butyl-p-cresol.
As the amines, those represented by the following formulas are preferred:
2~~~'~'~~
_ g _ R-P1 (R, ) 2 , (R) z-N (R, ) z , (R) a-NR, R
(R) 3N , RN , 0~ j N-R , R, (R) ZN-R, -N- (R~~) x R-CHN (R, ) Z-R"-N- (R", ) Z
( ) N-R, -NI-I-R"-N- (R", (R) ZN- (R' NI-l) 4-R" , R-NH-R,,.and (R) Z-N-OR' wherein each of R, R', R" and R"' is a hydrogen atom or a chain or cyclic hydrocarbon group having from 1 to 8 carbon atoms and containing a saturated or unsaturated bond.
Specifically, they include pentylamine, hexylamine, diisopropylamine, diisobutylamine, di-n-propylamine, diallylamine, triethylamine, n-methylaniline, pyridine, picoline, morpholine, N-methylmorpholine, triallylamine, allylamine, a-methylbenzylamine, methylamine, , dimethylamine, trimethylamine, ethylamine, diethylamine, propylamine, isopropylamine, sec-butylamine, tert-butylamine, dibutylamine, tributylamine, dipentylamine, tripentylamine, 2-ethylhexylamine, aniline, N,N-dimethylaniline, N,N-diethylaniline, ethylenediamine, propylenediamine, diethylenetriamine, tetraethylenepentamine, benzylamine, dibenzylamine, diphenylamine and diethylhydroxylamine. More preferred are diisopropylamine and diallylamine.
- to -As the ethers, those represented by the Following formulas are preferred:
R
R-0-R~ , 0~ ~ 0 , R-OH-R~ 0~1 , R
HO-R-0-R~ , ~f0-R-0-R~ -0-R'~ , 1-IO-R-OH , R-0- R' -Ctl - R~~ , R-0-R' _0_R" , !-~ J
to R-0-CH - R~ , R-0-R' - (OR~~
~-0 wherein each of R, R' and R" is a chain or cyclic hydrocarbon group having from 1 to 10 carbon atoms and containing a saturated or unsaturated bond.
Specifically, they include 1,4-dioxane, 1,2-butanediol, isopropyl ether, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol methyl ether, ethyl isobutyl ether, ethyl isopentyl ether, ethyl naphthyl ether, ethyl vinyl ether, ethyl phenyl ether, anisole, anethole, ethyl propargyl ether, ethyl propyl ether, ethyl methyl ether, ethylene glycol, methyl glycidyl ether, ethylene glycol diethyl ether, ethylene glycol diphenyl ether, ethylene glycol dimethyl ether, ethylene glycol monophenyl ether, ethylene glycol monobutyl ether, ethylene glycol monobenzyl ether, dipentyl ether, allyl ethyl ether, diisopentyl ether, diallyl ether, butyl - 17. -glycidy7. ether, allyl glycidyl ether, dipropyl ether, ethyl glycidyl ether, vinyl glycidyl ettaer, dimethyl ether, diethyl ether, di-n-propyl ether, dibutyl ether, 1,2-dimethoxyethane, trimethoxyethane, and triethoxyethane. More preferred are 1,4-dioxane, butyl glycidyl ether and 1,2-dimethoxyethane.
As the amylenes, a-amylene, ~i-amylene, Y-amylene, a-isoamylene and ~3-isoamylene are preferred. More preferred is ~3-amylene.
ZO As the esters, those represented by the following formulas are preferred:
R-C00-R' , R- i 0 , ~ (R' ) 2-N-C00-R' , and IV-R, 15 ~ RO-R' -COOR
wherFin each of R, R' and R" is a hydrogen atom or a chain ox cyclic hydrocarbon group having from 1 to G carbon .
atoms and containing a saturated or unsaturated bond.
20 Specifically, they include methyl acetate, ethyl acetate, propyl acetate, n-butyl acetate, isobutyl acetate, isopropyl acetate, ethyl acrylate, 2-hydroxyethyl methacrylate, methyl acrylate, butyl acrylate, phenyl acrylate, allyl acrylate, caprolactam, 2~ ethyl carbamate, methyl carbamate, and methyl salicylate.
More preferred are methyl acetate and methyl salicylate.
As the organic phosphites, those represented by the 2~~~~~~~
following formula are preferred:
(RO) 3P, (R-R' -0) 3P , (RO) zPOR' , ~ R " OCHZ C (RS) 3P , R' 0~ 4 , R-R' -0 P
R" 3 OHZC\ / CHZO~
to ROP \ ~ C \ ~ POR' , OHZC CHZO
~ OH Z C\ / CH 2 0\
R-R' -OP\ ~ C \ / P0-- R"-R"' , wherein each of R, R', R" and R"' is a hydrogen atom or a saturated or unsaturated chain or cyclic hydrocarbon group having from 1 to 18 carbon atoms. Specifically,, they include triphenolphosphite, tris(nonylphenyl)phosphite, triethylphosphite, tris(2-ethylhexy7.)phosphiLe, tridecylphosphite, tributylphosphite, diphenylmono(2-ethylhexyl)phosphite, diphenylmonodecylphosphite, diphenylmonotridecylphosphite, dilaurylhydrogen ~phosphite, diphenylhydrogen phosphate, tetraphenyldipropylene glycol pentaerythritol tetraphosphite, trilauryltrithiophosphite, - 13 ~-bis(tridecyl)pentaerythritol diphosphite, bis(nonylphenyl)per~taerythritol diphosphite, tristearyl phosphite, distearyl pentaerythritol diphosphite, and tris(2,4-di-tert-butylphenyl)phosphite. More preferred are triphenylphosphite and tributylphosphite.
As the epoxides, those represented by the following formulas are preferred:
RO and XRO
wherein R is a saturated or unsaturated chain or cyclic hydrocarbon group having from 1 to 8 carbon atoms, and X
is a halogen atom.
Specifically, they include 1,2-butylene oxide, epichlorohydrin, propylene oxide, 2,3-butylene oxide and styrene oxide. More preferred are 1,2-butylene oxide and epichlorohydrin.
As the furans, those represented by the following formulas axe preferred:
N - ~ " and 2 o R R R / N 1-!
wherein each of R, R' and R" is a saturated or unsaturated hydrocarbon group having from 1 to 2 carbon atoms.
Specifically they include tetrahydrofuran, n-methylpyrrole, 2-methylpyrrole and 3-methylpyrrole. More preferred is N-methylpyrrole.
'~F ~ "i ; 3 - 14 ' As the alcohols which are mainly used as stabilizers, those presented by the following formulas are preferred:
R-OH, NH2-R-OH, R-O-R'-OH and R-R'-OH
wherein each of R and R' is a saturated or unsaturated chain or cyclic hydrocarbon group having from 1 to 6 carbon atoms.
Specifically, they include, methanol, ethanol, sec-butanol, text-butanol, allylalcohol, benzylalcohol, propanol, isopropanol, tert-amylalcohol, 1-amino-2-propanol, propargylalcohol, isobutanol,~butanol, 3-methyl-pentyn-3-ol, 1-methoxy-2°propanol, 3-methyl-1-butyn-3-ol, 2-methyl-3-butyn-3-ol, pentyl alcohol, hexanol, heptanol and octanol. More preferred axe sec-butanol and propargyl alcohol.
As the ketones and amides, those represented by the following formulas are preferred:
(R) 2co, R-co-R' , (RNCO> 2, ~ coo ~ -R
R-CO-NFI-R' , R-CON- (R' ) 2, ~COON-R' (R) ZNCON (R' ) Z, R-c0\ / R \
. / N-R", and CO\ ~ co R' R
a5 N~ . \ NR", wherein each of R, R', R" and R"' is a hydrogen acorn or a saturated or unsaturated hydrocarbon group having from 1 to 4 carbon atoms. Specifically, they include acetone, methyl ethyl ketone, methyl isobutyl ketone, azodicarbonamide, malefic acid hydrazine, phthalic acid hydrazine, formamide, N-methylformamide, N,N-dimethylformamide, N-methylpropropioneamide, 2-pyrrolidone, N,N,N',N'-tetramethylurea and N-methylpyrrolidone. More preferred are methyl isobutyl ketone and 2-pyrrolidone.
As the triazoles, those presented by the following formulas are preferred:
OH
, R-N3-R' , R-N3-R'--O~i, X-R-N3 "
, I, - R - R , and R -, . ~ ", R-N~-R'-N-R"
wherein each of R, R', R" and R"' is a hydrogen atom or a~
saturated or unsaturated chain or cyclic hydrocarbon group having from 1 to 16 carbon atoms, and X is a halogen atom.
Specifically, they include 2-(2'-hydroxy-5'-methyl-phenyl)benzotr:iazole, 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 1,2,3-benzotriazol2, and 1-[(N,N-bis-2-ethylhexyl)aminomethyl)benzotriazole.
--Mare preferred is 1,2,3-benzotriazole.
The hydrochlorofluorocarbon azeotropic or azeotropic-like mixture of the present invention is useful for various purposes, for example, as a blowing agent and so on, like conventional CFCs. It is particularly useful as a solvent, since it provides a solvency equivalent or superior to conventional 8113. Specific applications as the solvent include a removing agent for flux, grease, oil, wax or ink, a coating solvent, an extracting agent, a cleaning or water-removing agent for various articles made of glass, ceramics, plastic, rubber or metal,.
particularly for semiconductor devices, electronic components, electronic circuit boards, electrical devices, precision machine parts or optical lenses.
Further, it is useful as a resist developer, a resist-removing agent or a buff polishing and cleaning agent.
As a cleaning method, manual wiping, dipping, spraying, shaking, ultrasonic cleaning or vapor cleaning may be employed.
Now, the present invention will be described in further detail with reference to Examples. However, it should be understood that the present invention is by no means restricted by such specific Examples.
EXAMPLES 1 to 152 1,000 g of a mixture as identified in Table 1 was charged in a distillation flask, and using a packed distillation column which contained approximately 20 l~ ._ theoretical plates, distillation was conducted under atmospheric pressure. The fractions thereby obtained were measured by gas chromatography, whereby the presence of an azeotropic composition was found.
On the other hand, the azeotropic-like composition was obtained from the composition after repeating the evaporation and condensation of a mixture as identified in Table 1 for 3 days by an open system cleaning sump.
TEST FOR CLEANING MACHINE OIL
A SUS-304 test piece (25 mm x 30 mm x 2 mm in thickness) was immersed in machine oil (CQ-30, .
manufactured by Nippon Sekiyu K.K.) and then immersed in the azeotropic mixture of the present invention for 5 minutes. The results are shown in Table 1, wherein symbol A-O indicates that the machine oil can be removed satisfactorily at the same level as 8113.
TEST FOR CLEANING FLUX
A single sided printed circuit board (50 mm x 100 mm x 1.6 mm in thickness) was coated with a flux (Tamura F-AL-4, manufactured by Tamura Seisakusho) and heated at 200°C for 2 minutes in a convection oven. Then, it was immersed in the azeotropic mixture of the present invention for one minute. The results are shown in Table 1, in which symbol B- 00 indicates that the flux can be removed satisfactorily at the same level as R113/ethanol - 96.2 wt~/3.8 wt~.
TEST FOR REMOVING WATER
A glass plate (30 mm x 18 mm x 5 mm in thickness) was inunersed in deionized water and then irnmersed in the azeotropic mixture of the present invention for 2U
seconds for removal of water. The glass plate withdrawn, was immersed in dry methanol, whereby the removal of water was determined from the increase of the water content in methanol. The results are shown in Table 1, in which symbol C-UO indicates that the water can be lp removed satisfactorily at the same level as R113/methanol - 93.6 wt~/6.4 wt~.
2265"~
Table 1 Boiling Azeo-Azeo-Charged point tropic-tropic Exam- B.P. composi- of like Test com pies Mixtures (oC) tion Azeo- o cmpo- results P
sit on (wt~) trope sition (wt~) (C) (wt~) R225ca 51.1 30 31 25 5-45 A-1 R141b 32 70 75 55-95 R225ca 51.1 40 42 22-62 A-OO
8113 47.6 60 58 38-78 R225ca 51.1 80 78 58-98 A-OO
3 8122 71.9 20 52 22 2-42 R225ca 51,1 52 42 50 30-70~ A-OO
4 R132b 46.8 48 50 30-70 R225ca 51.1 50 47 27-67 B-Dichloro- 39.8 50 34 53 33-73 methane R225cb 56.1 20 16 1-36 A-OO
R141b 32 80 84 64-99 R225cb 56.1 50 43 33-53 B-OO
7 Dichloro- 39.8 50 36 57 47-67 methane R225cb 56.1 42 39 19-59 A-OO
8 R132b 46.8 58 43 61 41-81 R225cb 56.1 80 78 58-98 A- 00 8122 71.9 20 55 22 2-42 R225cb 56.1 30 32 12-52 A-OO
8113 47.6 70 46 68 48-88 R244ca 54 15 13 1-33 A-OO
11 R141b 32 85 32 87 67-99 R244ca 54 50 38 18-58 A-O
12 Dichloro- 39.8 50 35 62 42-82 B-methane 202fi~7 Table 1 (continued) Boiling Azeo-Charged point Azeo- tropic-tropic Exam- B.P. composi- of like Test pies Mixtures (oC) tion Azeo- compo- compo- results sition (wt~) trope sition (wt~) (oC) (wt~) R244ca 54 80 83 63-99 A-O
13 8122 71.9 20 55 17 1-37 R244ca 54 42 38 18-58 A-O
14 R132b 46.8 58 44 62 42-82 R244ca 54 20 47 26 6-46 A-O
15 8113 47.6 80 74 54-94 R225ca 51.1 70 66 46-98~ A-O
16 Cyclo- 99.3 30 45 34 2-54 pentane R225cb 56.1 58 55 35-98 A-O
17 Cyclo- 49.3 42 47 45 2-65 pentane R244ca 54 50 48 28-98 A-2,2- 49.7 50 50 52 2-72 dimethyl-butane R225cb 56.1 25 21 11-98 A-2 r 2._ 49.7 75 79 2-89 dimethyl-butane R244ca 54 55 50 30-98 A-OO
20 Cyclo- 49.3 45 47 50 2-70 pentane R225ca 51.1 60 56 36-98 A-OO
2,2- 49.7 40 49 44 2-64 dimethyl-butane 202~~'~
_ 21 _.
Table 1 (continued) Roiling Azeo-Ctaargedpoint Azeo- tropic-tropic Exam- B.F. composi-of like Test Mixtures compo-ples (C) tion Azeo- cmpo- results sition (wt~) trope sition (wt~) (C) (wt~) R225ca 51.1 60 66 46-86 A-OO
22 2-bromo- 59.4 40 47 34 14-54 propane R225cb 56.1 60 58 38-78 A-OO
23 2-bromo--59.4 40 49 42 22-62 propane R244ca 54 50~ 55 35-75 A- ~O
24 2-bromo- 59.4 50 48 45 25-65~
propane R244cb 58 60 50 30-70 A-OO
25 2-bromo- 59.4 40 50 50 30-70 propane R235ca 43.9 70 74 54-94 A-OO
26 2-bromo- 59.4 30 42 26 6-46 propane R243cc 60.2 40 50 30-70 A- 00 27 2-bromo- 59.4 60 52 50 30-70 propane ' R225cb 56.1 90 - 50-99 A-O
28 2-methyl-60.3 10 - - 1-50 pentane R244ca 54 90 91 71-99 A-O
29 2-methyl-60.3 10 55 9 1-29 pentane R244cb 58 70 72 52-98 A-0 30 2-methyl-60.3 30 55 28 2-48 pentane 2a~~~~
'fable 1 (continued) Boiling Azeo-Azeo-Charged point tropic-tropic Exam- B.P, composi- of like Test _ ple~ Mixtures (C) Lion Azeo- com compo- results o i sit on (wt~) trope (wt~) sition (C) (wt$) R243cc 60.2 70 74 54-99 A-C>
31 2-methyl-60.3 30 61 26 1-46 pentane R225cb 56.1 ' 80 78 58-98 A- O
2.3- 58.0 20 22 2-42 dimethyl-butane R244ca 54 80 76 56-96~ A-O
2'3 58.0 20 53 24 4-44 33 dimethyl-butane R244cb 58 60 63 43-95 A-~
2.3- 58.0 40 55 37 5-57 34 dimethyl-butane R225ca 51.1 90 - 85-99 A-O
23- 58.0 10 - 1-15 35 dimethyl- - , butane R243cc 60.2 90 - 50-95 A-OO
2'3 58.0 10 - 5-50 36 dimethyl- -butane R225ca 51.1 60 57 37-77 A-trans- 47.7 40 43 23-63 37 1,2- 44 dichloro-ethylene ~0265'~
Table 1 (continued) Boiling Azeo-Charged point Azeo- tropie-tropic Exam- B.P. composi- of like Test _ Ales Mixtures (C) Lion Azeo- com Compo- results o p sit on (wt~) trope (wt~) sition (C) (wt$) R225cb 56.1 50 47 27-67 A-OO
trans- 47.7 50 53 33-73 38 1,2- 46 dichloro-ethylene R244ca 54 50 46 27-66 A-O
trans- 47.7 50 54 34-74 39 1,2- 45 dichloro-ethylene R244cb 58 45 40 20-60 A-O
traps- 47.7 55 60 40-80 40 1,2- 46 dichloro-ethylene R235ca 43.9 70 66 46-86 A-O
traps- 47.7 30 34 14-54 41 1,2- 41 dichloro-ethylene R243cc 60.2 40 42 22-62 A-O
traps- 47.7 60 58 38-78 42 1,2- 45 dichloro-ethylene R225ca 51.1 80 78 58-98 A-O
cis-1,2- 60.6 20 50 22 2-42 dichloro-ethylene 2o~s~~~
Table 1 (continued) F3ai.ling Azeo-Azeo-Charged point tropic-tropic Exam- Fs. composi- of like Test P.
Mixtures campo-les (C) Lion Azeo- compo- results p sition (wt~) trope sition (wt~) (C) (wt~) R225cb 56.1 70 69 59-79 A-OO
cis-1,2- 60.6 30 53 31 21-41 dichloro-ethylene R244ca 54 70 67 47-87 A-OO
cis-1,2- 60.6 30 51 33 13-53 dichloro-ethylene R244cb 58 60 59 39-79 A-OO
cis-1,2- 60.6 40 54 41 21-61 dichloro-ethylene R235ca 43.9 90 94 74-99 A-OO
cis-1,2- 60.6 10 45 6 1-26 dichloro-ethylene R243cc 60.2 60 58 38-78 A- 00 cis-1,2- 60.6 40 52 42 22-62 dichloro-ethylene R244cb 58 10 12 2-32 A-~
8113 47.6 90 88 68-98 R235ca 43.9 60 56 36-76 A-OO
50 8113 47.6 40 42 44 24-64 IR244cb 58 30 33 13-53 A-OO
51 Dichloro-39.8 70 36 67 47-87 methane ' R235ca 43.9 50 53 33-73 A-OO
52 Dichloro-39.8 50 32 47 27-67 methane ~'~~a'~
25 __ Table 1 (continued) Boiling Azeo-Charged point Azeo- tropic-.
tropzc Exam- B.P. composi--of like Test com ples Mixtures (C) tion Azeo- o compo- results p -sition (wt$) trope (wt$) sition (C) (wt$) R243cc 60.2 50 30 10-50 A-OO
53 Dichloro-39.8 50 38 70 50-90 methane R244cb 58 40 43 23-99 A-OO
54 Cyclo- 49.3 60 48 57 1-77 pentane R235ca 43.9 80 77 67-99 A-OO
55 Cycla- 49.3 20 42 23 1-33 pentane R243cc 60.2 25 30 10-99 A-UO
56 Cyclo- 49.3 75 49 70 1-90 pentane R244cb 58 40 34 14-99 A-O
2r2- 49.7 60 50 66 1-86 57 dimethyl-butane R235ca 43.9 80 81 61-99 A-O
2.2 49.7 20 43 19 1-39 58 dimethyl-butane R244cb 58 80 75 55-95 A-OO
59 8122 71.9 20 58 25 5-45 R244cb 58 30 29 9-49 A-OO
60 R132b 46.8 70 45 71 51-91 R235ca 43.9 20 14 1-34 A-O
61 8123 27.1 8 28 86 66-99 R235ca 43.9 20 57 37-77 A-O
62 R132b 46.8 80 39 43 23-63 _ 26 _.
Tab7.e 1 (continued) Boiling Azeo-Charged point Azeo- tropic-tropic Exam- B.P. composi- of like Test Mixtures compo-ples (C) tion Azeo- sition cmpo- results (wt~) trope (wt~) sition (C) (wt~) R235ca 43,9 30 34 14-54 A-OO
63 R141b 32 70 30 66 46-86 R243cc 60.2 80 77 57-97 A-~
64 8122 71.9 ,20 60 23 3-43 R243cc 60.2 20 24 4-44 A-OO
65 R132b 46.8 80 46 76 56-96 R225ca 51.1 90 95 75-99~ A-~
66 8141 75.7 ZO 52 5 1-25 R225cb 56.1 90 89 69-99 A-UO
67 8141 75.7 10 56 11 1-31 R244cb 58 85 90 70-99 A-O
68 8141 75.7 15 5~ 10 1-30 R225ca 51.1 97 94.6 75-99 B-O
69 Methanol 64.5 3 46 5.4 1-25 C-O
R225cb 56.1 97 95.6 74-99.5 70 Ethanol 78.3 3 53.8 4.4 0.5-26 C-O
R225cb 56.1 97 97.9 77-99 A-O
71 Iso- 82.4 3 54.9 2.1 1-23 B- O
propanol C-O
R225cb 56.1 95 93.3 74-99 72 Methanol 64 5 47.2 6.7 1-26 . C-O
R225ca 51.1 90 94.8 14-98 A-O
73 R225cb 56.1 5 50 2.7 1-85 B-O
Ethanol 78.3 5 2.5 1-16 C-O
2026~~b Table 1 (continued]
Boiling Azeo-Azeo-Charged point tropic-tropic Exam- B.P. composi-of like Test Mixtures compo-ples (C) tion Azeo- sition compo- results (wt~) trope sition (wt~) (C) (wt~) R225ca 51.1 89 89.8 14-98 A-OO
74 R225cb 56.1 6 46 5.6 1-85 B-O
Methanol 64.7 5 4.6 1-16 C-O
A-~
R225ca 51.1 98.5 97.3 75-99.5_ B
75 Ethanol 78.3 1.5 50 2.7 0.5-25 C-OO
R225ca 51,1 76-99 A-OO
76 Tso- 82.4 - - - 1-24 B--UO
~
propanol C-O
R225ca 51.1 35 38 15-61 A-O
8113 47.6 15 15 8-44 B-OO
77 Dichloro-39.8 50 - 47 34-70 methane R225cb 56.1 25 26 6-37 A-OO
78 8113 47.6 35 - 35 22-52 R132b 46.8 40 39 27-51 R225ca 51.1 3S 32 22-55 A-OO
79 8113 47.6 25 - 29 10-46 R132b 46.8 40 39 21-55 R225cb 56.1 25 26 8-38 A-OO
8113 47.6 25 24 8-47 B-OO
80 Dichloro-39.8 50 - 50 34-63 methane R244ca 54 25 25 6-33 A-OO
8113 47,6 20 19 9-41 B-OO
81 Dichloro-39.8 55 - 56 43-68 methane R244ca 54 20 19 4-39 A-Oo 82 8113 47.6 30 - 32 6-53 R132b 46.8 50 49 30-67 202~W
Table 1 (continued) Boiling Azeo-Azeo-Charged point tropic-tropic Exam- B.P. composi-of like Test Mixtures compo-ples (C) Lion Azeo- compo- results sition (wt~) trope sition (wt~) (C) (wt~) R225ca 51.1 40 41 28-52 A-OO
8113 47.6 20 22 7-39 B-O
trans- 47.7 40 37 25-48 1,2-dichloro-ethylene R244ca 54 30 25 8-36 A-OO
8113 47.6 60 62 48-85. B-OO
84 2-bromo- 59.4 10 - 13 3-28 propane R225ca 51.1 40 42 29-60 A-OO
8113 47.6 50 47 11-61 B-OO
85 2-bromo- 59.4 10 - 11 3-29 propane R244ca 54 20 22 4-38 A- 00 8113 47.6 60 58 40-77 B-OO
86 cis-1,2- 60.6 20 - 20 9-32 dichloro-ethylene ' R225ca 56.1 35 32 19'43 A-OO
8113 47.6 50 53 39-60 B-CJ
87 cis-1,2- 60.6 15 - 15 8-22 dichloro-ethylene R225ca 51.1 40 42 25-54 A-~
8113 47.6 45 45 38-58 B-O
88 cis-1,2- 60.6 15 - 13 8-22 dichloro-ethylene ' ~~D26~~
'i'able 1 (CUI7tlnued) Boiling Azeo-Azeo-Charged point tropic-tropic Exam- B.P. composi-of like Test Mixtures compo-ples (C) Lion Azeo- cmpo- results sition (wt~) trope (wt~) sition (C) (wt~) R244ca 54 35 34 5-95 A-8113 47.6 22 20 4-60 B- ~O
trans- 47.7 48 46 26-59 8g -1,2-dichloro-ethylene R225cb 56.1 35 36 27-51 A- oU
8113 47.6 25 27 6-44 B-OO
.
trans- 47.7 40 37 29-48 1,2-dichloro-ethylene R225cb 56.1 35 34 22-43 A- 00 8113 47.6 55 56 38-68 B-OO
91 2-bromo- 59.4 10 - 10 3-26 propane R225cb 56.1 35 34 20-53 A-OO
8113 47.6 55 55 8-72 92 Cyclo- 49.3 10 - 11 1-40 pentane -R225ca 51.1 40 41 28-65 A-O
8113 47.6 50 52 13-68 93 Cyclo- 49.3 10 - 7 2-35 pentane R244ca 54 25 23 17-46 A- 00 8113 47.6 70 71 8-77 94 2,2- 49.7 5 - 6 2-56 dimethyl-butane Table 1 (continued) Boiling Azeo-Charged point Azeo- tropic-tropic Exam- B.P. composi-of like Test Mixtures com o-ples (C) tion Azeo- p compo- results sition (wt~) trope sition (wt~) (C) (wt~) R225ca 51.1 50 52 42-61 A- 00 8113 47.6 20 16 7-55 B-O
1-chloro- 46.6 30 32 2-43 propane R225cb 56.1 40 42 23-44 A-O
8113 47.6 30 27 8-70 B-OO
1-chloro- 46.6 30 31 2-47 propane R244ca 54 20 22 4-33 A-OO
8113 47.6 60 57 41-78 B-OO
97 2-chloro- 50.7 20 - 21 8-31 2-methyl-propane R244ca 54 30 27 5-45 A-OO
R113 47.6 50 50 9-74 ~8 -Cyclo- 49.3 20 23 12-46 pentane R225ca 51.1 45 40 28-56 A- 00 8113 47.6 50 55 12-64 B-OO
99 2-chloro- 50.7 5 - 5 2-32 2-methyl-propane R225cb 56.1 30 31 17-38 A-OO
8113 47.6 60 58 41-75 B- n0 100 2-chloro- 50.7 10 - 11 2-21 2-methyl-propane R224ca 54 35 36 9-39 A-OO
8113 47.6 20 19 9-84 B-OO
1-chloro- 46.6 45 45 2-60 propane 20265' Table 1 (continued) Boiling Azeo-Azeo-Charged point tropic-tropic Exam- B.P. composi- o~ like Test ples Mixtures (oC) tion Azeo- compo-compo- results sition (wt~) trope sition (wt~) (C) (wt~) R225ca 51.1 90 90 36-97 A-O
R225cb 56.1 5 7 1-51 2-methyl-60.3 5 3 1-16 pentane R225ca 51.1185 88 6-94 A-O
R225cb 56.1 10 8 1-83 103 2,3- 58.0 5 - 4 1-26 dimethyl-butane R225ca 51.1 50 50 6-67 A-~
R225cb 56.1 10 12 4-67 B-O
104 2-chloro-50.7 40 - 38 1-58 2-methyl-propane R225ca 51.1 ~ 40 41 7-56 A-O
R225cb 56.1 15 14 7-61 B-O
( 105 1-chloro-46.6 45 - 45 1-54 propane R225ca 51.1 55 54 6-66 A-O
R225cb 56.1 10 10 5-64 B-O
2-bromo- 59.4 35 36 10-48 propane R225ca 51.1 60 58 6-70 A-O
R225cb 56.1 10 12 4-74 B-O
107 cis-1,2- 60.6 30 - 30 10-38 dichloro-ethylene Table 1 (continued) Boiling Azeo-Azeo-Charged point tropic-tropic Exam- B.P. composi- of like Test Mixtures compo-ples (C) tion Azeo- Sition cmpo- results (wt~) trope sition (wt~) (C) (wt~) R225ca 51.1 40 42 8-57 A- 00 R225cb 56.1 15 13 6-54 B-OO
trans- 47.7 45 45 10-59 1,2-dichloro-ethylene R225ca 51.1 80 80 40-89 A-O
109 R225cb 56.1 10 - 8 2-37 B-~
.
8122 71.9 10 12 3-23 R225ca 51.1 80 84 44-92 A-O
110 R225cb 56.1 10 - 8 2-41 B-O
8141 75.7 10 8 1-17 R225ca 51.1 35 36 6-44 A-O
111 R225cb 56.1 10 - 11 4-44 B-O
R132b 46.8 55 53 44-73 R225ca 56.1 25 20 8-31 A-O
R141b 32 65 67 36-88 B-112 Dichloro- 39.8 10 - 13 3-38 , methane R225ca 51.1 30 26 8-41 A- OO
R141b 32 60 62 32-84 B-~
113 Dichloro- 39.8 10 - 12 3-31 methane R225ca 51.1 15 12 6-33 A-O
114 R141b 32 5 - 7 2-33 B-O
8123 27.1 80 81 44-86 R225ca 51.1 30 33 5-47 A-O
115 R225cb 56.1 10 - 9 3-42 8113 47.6 60 58 5-79 1 1 ~ i L 1 r r n Table 1 (continued) Boiling Azeo-Azeo-Charged point tropic-tropic Exam- B.P. composi- of like Test Mixtures compo-ples (C) tion Azeo- sition compo- results (wt~) trope sition (wt~) (C) (wt$) R225ca 51.1 25 25 9-49 A-Oo R225cb 56.1 Z1 21 8-39 B- 00 116 Dichloro-39.8 55 - 54 5-70 methane R244ca 54 15 16 6-31 A-OO
R141b 32 70 68 38-90 B-O
117 Dichloro-39.8 15 - 16 3-40 methane R244ca 54 20 21 5-58 A- 00 R225cb 56.1 40 42 7-66 B-O
118 2-bromo- 59.4 40 - 37 5-54 propane R244ca 54 30 31 4-58 A-R225cb 56.1 40 35 7-71 B-O
119 cis-1,2- 60.6 30 - 34 4-43 dichloro-ethylene R244ca 54 15 15 8-58 A-O
R225cb 56.1 40 39 9-65 B- ~O
120 1-chloro-46.6 45 - 46 5-71 propane R244ca 54 ZO 22 7-55 A-O
R225cb 56.1 30 32 8-56 B-O
121 2-chloro-50.7 50 - 46 5-74 2-methyl-propane R244ca 54 60 62 29-87 A-O
R225cb 56.1 20 20 6-68 122 2,3- 58 20 - 18 2-29 dimethyl-butane ~0~~~~
Table 1 (continued) Boiling Azeo-Charged point Azeo- tropic-tropic Exam- B.P. composi- of like Test Mixtures compo-ples (C) Lion Azeo- compo- results sition (wt~) trope (wt~) sition (C) (wt~) R244ca 54 20 18 5-42 A-OO
123 R225cb 56.1 20 - 24 7-50 B-~
R132b 46.8 60 58 41-80 R244ca 54 30 30 5-55 A-OO
R225cb 56.1 25 26 8-57 B-OO
trans- 47.7 45 44 5--61 1,2-dichloro-ethylene R244ca 54 25 25 8-56 A-OO
R225cb 56.1 30 32 9-55 125 Cyclo- 49.3 45 - 45 5-69 pentane R244ca 54 20 17 7-35 A-O
R225cb 56.1 20 24 9-42 B-o0 126 Dichloro-39.8 60 - 59 45-73 methane R244ca 54 40 39 7-61 A-OO
R225ca 51.1 20 19 8-71 127 2,2- 49.7 40 - 42 5-72 dimethyl-butane R244ca 54 10 12 5-41 A-OO
R225ca 51.1 30 34 9-48 B-OD
128 Dichloro-39.8 60 - 54 40-73 methane R244ca 54 10 9 2-37 A-OO
l29 R225ca 51.1 40 - 40 7-50 B-OO
R132b 46.8 ~ 50 51 35-72 ~o~~~~
Table 1 (continued) Boiling Azeo-Charged point Azeo- tropic-tropic Exam- B.P. composi- of like Test Mixtures compo-ples (C) Lion Azeo- compo- results .
sition (wt~) trope sition (wt~) (C) (wt~) R244ca 54 25 24 3-49 A-~
130 R225ca 51.1 70 - 70 47-95 B-~
8141 75.7 5 6 0.1-17 R244ca 54 10 11 5-S5 A-CC~
R225ca 51.1 55 55 9-67 131 Cyclo- 49.3 35 - 34 3-53 pentane R244ca 54 20 21 3-59 A-OO
~
132 R225ca 51.1 70 - 70 36-93 B-Oo 8122 71.9 10 9 1-22 R244ca 54 10 11 3-69 A-OO
R225ca 51.1 50 47 8-78 B-OO
trans- 47.7 40 42 3-54 1,2-dichloro-ethylene R244ca 54 8 10 3-59 A-OO
R225ca 51.1 62 60 7-75 B-O
134 cis-1,2- 60.6 30 - 30 3-38 dichloro-ethylene R244ca 54 10 8 3-58 A-OO
R225ca 51.1 60 58 6-71 B-~
135 2-bromo- 59.4 30 - 34 3-44 propane R244ca 54 45 47 22-86 A-O
136 R225cb 56.1 45 - ~ 47 6-72 B-OO
8141 75.7 10 6 1-21 ~026~~
Table 1 (COIltlnued) Bailing Azeo Charged point Azeo- tropic-tropic Exam- B.P. compasi- of like Test Mixtures compo-ples (C) tion Azeo- compo- results sition (wt~) trope sition (wt$) (C) (wt$) R225ca 51.1 50 48 10-88 A-OO
R225cb 56.1 10 15 8-70 137 Cyclo- 49.3 40 - 37 3-58 pentane R244ca 54 50 45 8-83 A-~
138 R225cb 56.1 40 - 45 6-84 B-OO
8122 71.9 10 10 3-28 R244ca 54 30 29 3-84 A-~
~
R225ca 51.1 65 67 13-94 139 2,3- 58 5 - 4 0.1-19 dimethyl-butane R244ca 54 10 11 3-98 A-OO
R225ca 51.1 50 48 7-62 B-O
140 1-chloro-46.6 40 - 41 3-56 propane R244ca 54 10 10 3-56 A-R225ca 51.1 60 54 6-72 B-O
141 2-chloro-50.7 30 - 36 3-54 2-methyl-propane R244ca 54 45 42 7-76 A-O
R225cb 56.1 10 14 8-62 142 2, 2- 49 45 - 44 3-73 .7 dimethyl-butane 20~~~~
Table 1 (continued) Boiling Azeo-Charged point Azeo- tropic-tropic Exam- B.P. composi- of like Test ples Mixtures (oC) tion Azeo- compo- compo- results sition (wt~) trope sition (wt~) (~C) (wt~) R244ca 54 76-99 A-O
143 Methanol 64.'7- - - 1-24 B-O
R244ca 54 77-99 A-OO
144 Ethanol 78.3 - - - 1-23 B-OO
R244ca 54 79-99 A- n0 145 Iso- 82.4 - - - 1-21 B-O
propanol R225ca 51.1 50-80 146 R244ca 54 - - - 10-40 A-OO
Ethanol 78.3 . 1-ZO B- 00 R225cb 56.1 40-80 147 R224ca S4 - - - 10-50 A-OO
Ethanol 78.3 1-ZO B-Oo R225ca 51.1 5-99 R225cb 56.1 3-99 A- 00 148 R244ca 54 - - - 1-69 H-OO
Ethanol 78.3 1-35 R225ca 51.1 50-80 A-1o0 149 R244ca 54 - - - 10-40 B-OO
Methanol G4.7 1-10 R225cb 56.1 40-80 A-150 R244ca 54 - - - 10-50 H-OO
Methanol 64.7 1-10 R225ca 51.1 5-99 A- 00 R225cb 56.1 3-99 B- 00 151 R244ca 54 - - - 1-69 Methanol 64.7 1-35 202G~°~
Table 1 (cont.i.nued) Boiling Azeo-Chargec~ point Azeo- tropic-tropic Exam- B.F. composi- o like Test Mixtures compo-ples (C) tion Azeo- sitioncmpo- results (wt~) trope sition (wt~) (C) (wt$) R225ca 51.1 1-98 A-OO
R22~cb 56.1 1-98 B-OO
Iso- 82.4 1-16 ~propanol 2026~'~
REFERENCE EXAMPLES
For the purpose of ascertaining the effects of the azeotropic-like mixture of the present invention for stabilization, the following test was applied to the mixture as identified in Table 2.
In accordance with JIS K1600, a metal test piece was placed in both the liquid phase portion and the gas phase portion of the stabilized mixture as identified in Table 2, and after 48 hours, the state of corrosion of the test piece was inspected. The results are shown in Table 2.
Azeotropic-like mixture AA: R225ca/R225cb/methanol = 47 wt~/47 wt$/6 wt~
Stabilizer NM: Nitromethane PH: Phenol DIPA: Diisopropylamine DO: 1,4-Dioxane Am: j3-Amylene MeA: Methyl acetate TPH: Triphenylphosphite B0: 1,2-Buthyleneoxide DME: 1,2-Dimethoxyethane MP: N-methylpyrrole s-Bu: sec-Butanol MIBK: Methyl isobutyl ketone ECH: Epichlorohydrin i-Bu: Isobutanol BHT: 2,6-Di-t-butyl-o-cresol BTA: 1,2,3-Benzotriazole Appearance of test piece O : No corrosion O : No substantial corrosion 0 : Corrosion slightly observed X: Substantial corrosion observed.
Table 2 Cor Reference rosion of test piece Stabilized mixture (wt~) Examples Fe Cu Ag AA01 AA(99.5)/PH(0.5) O O O
AA02 AA(99.5)/DIPA(0.5) ~ O O
AA03 AA(99.5)/Am(0.5) O O O
AA04 AA(99.5)/TPH(0.5) O O O
AA05 AA(99.5)/MP(0.5) ~ O O
AA06 AA(99.5)/BTA(0.5) O O O
AA07 AA(99)/NM(1) O O O
AA08 AA(99)/DO(1) O O O
AA09 AA(99)/MeA(1) O O O
AA10 AA(99)/B0(1) O O O
AAIl AA(99)/DME(1) O O
AA12 AA(99)/s-Bu(1) OO O O
AA13 AA(99)/MIBK(1) AA14 AA(99)/ECH(1) O O O
AA15 AA(98.5)/NM(1)/BTA(0.5) O O ~ ' AA16 ~(975)/NM(1)/BO(1)/ Op OO O
BHT(0.5) AA17 ~(97)/NM(1)/BO(1)/ Oo O
BHT(0.5/BTA(0.5) X18 AA(96)/NM(1)/BTA(0.5)/
BO(1)/i-Bu(1)/BHT(0.5) Compara-tive AA(100) Example INDUSTRIAL APPLICABILITY
The hydrochlorofluorocarbon azeotropic or azeotropic-like mixture of th a present invention is non-flammable or hardly flammable and has excellent properties equal or superior to conventional CFCs. Further, the mixture shows no substantial change in the composition during boiling and evaporating, since it has an azeotropic composition or an azeotropic-like composition, and it can be used in the same manner as a conventional single CFC
and thus has a merit that it requires no substantial change of the conventional technique. Further, it. is excellent in the properties for dissolving and removing a flux or oil like 8113 which is commonly used as a - solvent, and thus it is useful as a cleaning agent which may be an alternative for 8113.
1 _ DESCRIPTION
TITLE OF THE TNVE:NTION
HXDROCHLOROFLUOROCARBON AZEO'rROPIC OR
AZEOTROPIC-LTKE MIXTURE
TECHNICAL FIELD
The present invention relates to a novel hydrochlorofluorocarbon azeotropic or azeotropic-like mixture which can be used as a chlorofluorocarbon alternative and which has excellent properties as a solvent and so on.
BACKGROUND ART
Chlorafluorocarbon compounds (hereinafter referred simply as CFCs) have little toxicity and are, in many cases, non-flammable and chemically stable. Various CFCs having different boiling points are available. By virtue of such properties, 1,1,2-trichloro-1,2,2-trifluoroethane (R113) is used as a solvent or a blowing agent;
trichloromonofluoromethane (R11) is used as a blowing agent or a propellant; and dichlorodifluoromethane (R12), is used as a propellant or a refrigerant.
Chemically stable R11, R12 and 8113 have long lifetime in the troposphere and reach the stratosphere, where they will be dissociated by solar radiation tp release chlorine radicals, which initiate a chain reaction with ozone and deplete the ozone layer.
Accordingly, the regulations for limiting the use of such conventional CFCs have been implemented. Therefore, a . CA 02026576 1999-03-18 r research has been actively conducted to develop a CFC
alternative which scarcely depletes the ozone layer.
It is an object of the present invention to provide a mixture containing a novel hydrochlorofluoropropane having 3 carbon atoms, which has various excellent properties equal to conventional CFCs and which is useful as a CFC alternative.
The present invention provides a hydrochlorofluorocarbon azeotropic or azeotropic-like mixture comprising at least one member selected from the group consisting of the hydrochlorofluoropropanes 1,1-dichloro-2,2,3,3,3-pentafluoropropane and 1,1-dichloro-2,2,3,3,3-pentafluorpropane, and at least one member selected from halogenated hydrocarbons having a boiling point of from 20 to 85°C other than the above hydrochlorofluoropropanes, hydrocarbons having a boiling point of from 20 to 85°C, and particularly preferred, alcohols having from 1 to 4 carbon atoms.
The mixture of the present invention is non-flammable or hardly flammable and may take a form of an azeotropic composition or an azeotropic-like composition.
Particularly when used as a solvent, it provides properties equal or superior to conventional 1,1,2-trichlorotrifluoroethane (R113). Therefore, it is very useful as an alternative for 8113. Further, no substantial change in the composition was observed when boiling or evaporating. Therefore, it may be used in the same manner as a conventional single CFC, whereby it has a merit in that no substantial change in the conventional technique is required.
The hydrochlorofluoropropanes of the present invention contain a hydrogen atom, a chlorine atom and a fluorine atom as essential elements. This group broadly includes the following compounds:
CC2FZCF2CHC22 (R224ca) CCQZFCFZCHCQF(R224cb) CF,CFzCHCQ2 (R225ca) CCQFZCFZCHCQF(R225cb) CCQFZCFZCHZCQ(R234cc) CHFZCFZCHCQF(R235ca) CH3CF~ZCCQZF(R243cc) CHFzCF2CHz'CQ (R244ca) CHZCQCFZCH2CQ(R252ca) CHCQZCFZCH3(R252cb) CH3CFZCHZCQ(R262ca) CHFZCFzCCQzF(R225cc) CHCQf~CFzCHCQF(R234ca) CfiFzCFzCHCQz (R234cb) CHzFCFzCC.QzF(R234cd) CF,CFZCH2CQ(R235cb) CCQFzCFzCH2F(R235cc) CHzCQCFzCHCQF (R243~ca) CHaFCFzCHCQz(R243cb) CH2FCF2CHCQF(R244cb) CCQFzCFzCH,(R244cc) CHzFCFzCHzCQ(R253ca) CH, CFz CIiCQF (R253cb) CF,CFZCHCQF~R226ca) CCQF2CFzCHFz~(R226cb) CCQ,CFzCHCQz(R222c) CCQzFCFzCHCQz(R223ca) CCQ,CF2CHCQF(R223cb) CCQ3CF~CliFz (R224cc) CHCQzCFzCIiCQz (R232ca) CCQ,CFzCHZCQ (R232cb) CCQzFCFzCHzCQ(R233cb) CHCQzCFZCHCQF(R233ca) CCQ,CFZCHZF(R233cc) CCQ,CFzCH,(R242cb) CHCQzCFzCHzCQ (R242ca) Among them, of interest are R244ca, R244cb, R235ca, and R243cc, and particularly preferred are R225ca and R225cb.
The halogenated hydrocarbons having a boiling point of from 20 to 85°C other than the hydrochlorofluoropropanes of the formula I, include chlorinated hydrocarbons, fluorinated hydrocarbons and brominated hydrocarbons having from 1 to 4 carbon atoms.
The chlorinated hydrocarbons having from 1 to 4 carbon atoms, include dichloromethane, trichloromethane, trans-1,2-dichloroethylene, cis-1,2-dichloroethylene, 1-chloropropane, 2-chloro-2-methylpropane, 1,1,1-trichloroethane and 1,1-dichloroethane. The fluorinated hydrocarbons include 1,1,2-trichlorotrifluoroethane -- ~ (R113), 1,1,2-trichloro-2,2-difluoroethane (R122), 1,2,2-trichloro-1,2-difluoroethane (R122a), 1,1,1-trichloro-2,2-difluoroethane (R122b), l,l-dichloro-2,2,2-trifluoroethane (R123), 1,2-dichloro-1,1-difluoroethane (R132b), 1,2-dichloro-1-fluoroethane (R141)., 1,1-dichloro-1-fluoroethane (R141b) and trichlorofluoromethane (R11). Likewise, the brominated hydrocarbons include 2-bromopropane as a preferred example.
The hydrocarbons having a boiling point of from 20 to 85°C, include aliphatic, alicyclic and aromatic hydrocarbons. Preferably, they include hydrocarbons having from 5 to 8 carbon atoms such as n-pentane, isopentane, n-hexane, 2,4-dimethylpentane, cyclopentane, 2,2-dimethylbutane, 2-methylpentane, methylcyclopentane, cyclohexan a and 2,3-~dimethylbutane. The hydrocarbons having from 5 to 8 carbon atoms may be a mixture obtained as a petraleum fraction and may preferably be a petroleum fraction containing as the main component at least one member selected from the group consisting of cyclopentane, 2,2-dimethylbutane, 2-methylpentane and 2,3-dimethylbutane.
The azeotropic or azeotropic-like composition of the mixture of the present invention may vary to an extent of t 1.0~ by weight depending upon the purities of the compounds to be mixed or by the influence of measuring error, etc.
To the mixture of the present invention, other components may further be incorporated, as the case requires. For example, when the mixture is used as a solvent, it may contain at least one member selected from the group consisting of hydrocarbons such as neopentane, 3-methylpentane, neohexane, hexane, 3-methylhexane, heptane, isoheptane, 2,3-dimethylpentane, 2,4-dimethylpentane, octane, 2,2,3-trimethylpentane, 2,2,4-trimethylpentane, cyclopentane, methylcyclohexane and ethylcyclohexane; chlorinated hydrocarbons such as 1,1,2-trichloroethane, 1,2-dichloroethane, trichloroethylene and tetrachloroethylene; chlorofluorinated hydrocarbons other than those of the present invention, such as 1,1-dichloro-2,3,3,3-tetrafluoropropene-1, trans-3=chloro-1,1,1,2,4,4,5,5,5-monafluoropentene-2, cis-3-chloro-1,1,1,2,4,4,5,5,5-nonafluoropentene-2, 1,1,1,2,2,5,5,6,6,6-decafluorohexane and tetrachloro-1,2,-difluoroethane; vitro compounds; phenols; amines;
ethers; amylenes; esters; organic phosphites; epoxides;
furans; alcohols; ketones; amides; and triazoles.
The content of such additional components in the mixture of the present invention is not particularly limited, but for the purpose of improving or controlling the solibility or obtaining a suitable boiling point or non-flammability, the content is usually from 0 to. 50~ by weight, preferably from 1 to 40~ by weight. Preferably such incorporation will bring about an azeotropic or azeotropic-like composition. Further, to give the mixture a high level of stabilizing effect, it is effective to incorporate a stabilizer. The content of such additional components is usually from 1 ppm to 10~
by weight, preferably from 10 ppm to 5~ by weight.
Further, the mixture of the present invention may further contain various cleaning assistants, surfactants, emulsifying agents, water, etc.
As the vitro compounds, those represented by the formula R-NOz wherein R is a chain or cyclic hydrocarbon group having from 1 to 6 carbon atoms and containing a saturated or unsaturated bond, may be employed.
Specifically, they include nitromethane, nitroethane, 1-nitropropane, 2-nitropropane and nitrobenzene. More preferred are nit:romethane anck nitroethane.
As the phenols, those represented by the following formulas are preferred:
R R R R
O R' R ~ OR~
R" ~ , R R' COOK
OR' R-~- i R ", ' R ~~ ' R ~~
R R" ~HR
COOR~-R", O
' R
wherein each of R, R', R" and R"' is OH or a chain or cyclic hydrocarbon group having from 1 to 6 carbon atoms and containing a saturated or unsaturated bond.
Specifically, they include phenol, o-cresol, m-cresol, p-cresol, thymol, p-tert-butylphenol, tert-butylcatechol, catechol, isoeugenol, o-methoxyphenol, 4,4'-dihydroxyphenyl-2,2-propane, isoamyl salicylate, benzyl salicylate, methyl salicylate and 2,6-di-t-butyl-p-cresol. More preferred are phenol, 4,4-dihydroxyphenyl-2,2-propane arid 2,6-di-t-butyl-p-cresol.
As the amines, those represented by the following formulas are preferred:
2~~~'~'~~
_ g _ R-P1 (R, ) 2 , (R) z-N (R, ) z , (R) a-NR, R
(R) 3N , RN , 0~ j N-R , R, (R) ZN-R, -N- (R~~) x R-CHN (R, ) Z-R"-N- (R", ) Z
( ) N-R, -NI-I-R"-N- (R", (R) ZN- (R' NI-l) 4-R" , R-NH-R,,.and (R) Z-N-OR' wherein each of R, R', R" and R"' is a hydrogen atom or a chain or cyclic hydrocarbon group having from 1 to 8 carbon atoms and containing a saturated or unsaturated bond.
Specifically, they include pentylamine, hexylamine, diisopropylamine, diisobutylamine, di-n-propylamine, diallylamine, triethylamine, n-methylaniline, pyridine, picoline, morpholine, N-methylmorpholine, triallylamine, allylamine, a-methylbenzylamine, methylamine, , dimethylamine, trimethylamine, ethylamine, diethylamine, propylamine, isopropylamine, sec-butylamine, tert-butylamine, dibutylamine, tributylamine, dipentylamine, tripentylamine, 2-ethylhexylamine, aniline, N,N-dimethylaniline, N,N-diethylaniline, ethylenediamine, propylenediamine, diethylenetriamine, tetraethylenepentamine, benzylamine, dibenzylamine, diphenylamine and diethylhydroxylamine. More preferred are diisopropylamine and diallylamine.
- to -As the ethers, those represented by the Following formulas are preferred:
R
R-0-R~ , 0~ ~ 0 , R-OH-R~ 0~1 , R
HO-R-0-R~ , ~f0-R-0-R~ -0-R'~ , 1-IO-R-OH , R-0- R' -Ctl - R~~ , R-0-R' _0_R" , !-~ J
to R-0-CH - R~ , R-0-R' - (OR~~
~-0 wherein each of R, R' and R" is a chain or cyclic hydrocarbon group having from 1 to 10 carbon atoms and containing a saturated or unsaturated bond.
Specifically, they include 1,4-dioxane, 1,2-butanediol, isopropyl ether, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol methyl ether, ethyl isobutyl ether, ethyl isopentyl ether, ethyl naphthyl ether, ethyl vinyl ether, ethyl phenyl ether, anisole, anethole, ethyl propargyl ether, ethyl propyl ether, ethyl methyl ether, ethylene glycol, methyl glycidyl ether, ethylene glycol diethyl ether, ethylene glycol diphenyl ether, ethylene glycol dimethyl ether, ethylene glycol monophenyl ether, ethylene glycol monobutyl ether, ethylene glycol monobenzyl ether, dipentyl ether, allyl ethyl ether, diisopentyl ether, diallyl ether, butyl - 17. -glycidy7. ether, allyl glycidyl ether, dipropyl ether, ethyl glycidyl ether, vinyl glycidyl ettaer, dimethyl ether, diethyl ether, di-n-propyl ether, dibutyl ether, 1,2-dimethoxyethane, trimethoxyethane, and triethoxyethane. More preferred are 1,4-dioxane, butyl glycidyl ether and 1,2-dimethoxyethane.
As the amylenes, a-amylene, ~i-amylene, Y-amylene, a-isoamylene and ~3-isoamylene are preferred. More preferred is ~3-amylene.
ZO As the esters, those represented by the following formulas are preferred:
R-C00-R' , R- i 0 , ~ (R' ) 2-N-C00-R' , and IV-R, 15 ~ RO-R' -COOR
wherFin each of R, R' and R" is a hydrogen atom or a chain ox cyclic hydrocarbon group having from 1 to G carbon .
atoms and containing a saturated or unsaturated bond.
20 Specifically, they include methyl acetate, ethyl acetate, propyl acetate, n-butyl acetate, isobutyl acetate, isopropyl acetate, ethyl acrylate, 2-hydroxyethyl methacrylate, methyl acrylate, butyl acrylate, phenyl acrylate, allyl acrylate, caprolactam, 2~ ethyl carbamate, methyl carbamate, and methyl salicylate.
More preferred are methyl acetate and methyl salicylate.
As the organic phosphites, those represented by the 2~~~~~~~
following formula are preferred:
(RO) 3P, (R-R' -0) 3P , (RO) zPOR' , ~ R " OCHZ C (RS) 3P , R' 0~ 4 , R-R' -0 P
R" 3 OHZC\ / CHZO~
to ROP \ ~ C \ ~ POR' , OHZC CHZO
~ OH Z C\ / CH 2 0\
R-R' -OP\ ~ C \ / P0-- R"-R"' , wherein each of R, R', R" and R"' is a hydrogen atom or a saturated or unsaturated chain or cyclic hydrocarbon group having from 1 to 18 carbon atoms. Specifically,, they include triphenolphosphite, tris(nonylphenyl)phosphite, triethylphosphite, tris(2-ethylhexy7.)phosphiLe, tridecylphosphite, tributylphosphite, diphenylmono(2-ethylhexyl)phosphite, diphenylmonodecylphosphite, diphenylmonotridecylphosphite, dilaurylhydrogen ~phosphite, diphenylhydrogen phosphate, tetraphenyldipropylene glycol pentaerythritol tetraphosphite, trilauryltrithiophosphite, - 13 ~-bis(tridecyl)pentaerythritol diphosphite, bis(nonylphenyl)per~taerythritol diphosphite, tristearyl phosphite, distearyl pentaerythritol diphosphite, and tris(2,4-di-tert-butylphenyl)phosphite. More preferred are triphenylphosphite and tributylphosphite.
As the epoxides, those represented by the following formulas are preferred:
RO and XRO
wherein R is a saturated or unsaturated chain or cyclic hydrocarbon group having from 1 to 8 carbon atoms, and X
is a halogen atom.
Specifically, they include 1,2-butylene oxide, epichlorohydrin, propylene oxide, 2,3-butylene oxide and styrene oxide. More preferred are 1,2-butylene oxide and epichlorohydrin.
As the furans, those represented by the following formulas axe preferred:
N - ~ " and 2 o R R R / N 1-!
wherein each of R, R' and R" is a saturated or unsaturated hydrocarbon group having from 1 to 2 carbon atoms.
Specifically they include tetrahydrofuran, n-methylpyrrole, 2-methylpyrrole and 3-methylpyrrole. More preferred is N-methylpyrrole.
'~F ~ "i ; 3 - 14 ' As the alcohols which are mainly used as stabilizers, those presented by the following formulas are preferred:
R-OH, NH2-R-OH, R-O-R'-OH and R-R'-OH
wherein each of R and R' is a saturated or unsaturated chain or cyclic hydrocarbon group having from 1 to 6 carbon atoms.
Specifically, they include, methanol, ethanol, sec-butanol, text-butanol, allylalcohol, benzylalcohol, propanol, isopropanol, tert-amylalcohol, 1-amino-2-propanol, propargylalcohol, isobutanol,~butanol, 3-methyl-pentyn-3-ol, 1-methoxy-2°propanol, 3-methyl-1-butyn-3-ol, 2-methyl-3-butyn-3-ol, pentyl alcohol, hexanol, heptanol and octanol. More preferred axe sec-butanol and propargyl alcohol.
As the ketones and amides, those represented by the following formulas are preferred:
(R) 2co, R-co-R' , (RNCO> 2, ~ coo ~ -R
R-CO-NFI-R' , R-CON- (R' ) 2, ~COON-R' (R) ZNCON (R' ) Z, R-c0\ / R \
. / N-R", and CO\ ~ co R' R
a5 N~ . \ NR", wherein each of R, R', R" and R"' is a hydrogen acorn or a saturated or unsaturated hydrocarbon group having from 1 to 4 carbon atoms. Specifically, they include acetone, methyl ethyl ketone, methyl isobutyl ketone, azodicarbonamide, malefic acid hydrazine, phthalic acid hydrazine, formamide, N-methylformamide, N,N-dimethylformamide, N-methylpropropioneamide, 2-pyrrolidone, N,N,N',N'-tetramethylurea and N-methylpyrrolidone. More preferred are methyl isobutyl ketone and 2-pyrrolidone.
As the triazoles, those presented by the following formulas are preferred:
OH
, R-N3-R' , R-N3-R'--O~i, X-R-N3 "
, I, - R - R , and R -, . ~ ", R-N~-R'-N-R"
wherein each of R, R', R" and R"' is a hydrogen atom or a~
saturated or unsaturated chain or cyclic hydrocarbon group having from 1 to 16 carbon atoms, and X is a halogen atom.
Specifically, they include 2-(2'-hydroxy-5'-methyl-phenyl)benzotr:iazole, 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 1,2,3-benzotriazol2, and 1-[(N,N-bis-2-ethylhexyl)aminomethyl)benzotriazole.
--Mare preferred is 1,2,3-benzotriazole.
The hydrochlorofluorocarbon azeotropic or azeotropic-like mixture of the present invention is useful for various purposes, for example, as a blowing agent and so on, like conventional CFCs. It is particularly useful as a solvent, since it provides a solvency equivalent or superior to conventional 8113. Specific applications as the solvent include a removing agent for flux, grease, oil, wax or ink, a coating solvent, an extracting agent, a cleaning or water-removing agent for various articles made of glass, ceramics, plastic, rubber or metal,.
particularly for semiconductor devices, electronic components, electronic circuit boards, electrical devices, precision machine parts or optical lenses.
Further, it is useful as a resist developer, a resist-removing agent or a buff polishing and cleaning agent.
As a cleaning method, manual wiping, dipping, spraying, shaking, ultrasonic cleaning or vapor cleaning may be employed.
Now, the present invention will be described in further detail with reference to Examples. However, it should be understood that the present invention is by no means restricted by such specific Examples.
EXAMPLES 1 to 152 1,000 g of a mixture as identified in Table 1 was charged in a distillation flask, and using a packed distillation column which contained approximately 20 l~ ._ theoretical plates, distillation was conducted under atmospheric pressure. The fractions thereby obtained were measured by gas chromatography, whereby the presence of an azeotropic composition was found.
On the other hand, the azeotropic-like composition was obtained from the composition after repeating the evaporation and condensation of a mixture as identified in Table 1 for 3 days by an open system cleaning sump.
TEST FOR CLEANING MACHINE OIL
A SUS-304 test piece (25 mm x 30 mm x 2 mm in thickness) was immersed in machine oil (CQ-30, .
manufactured by Nippon Sekiyu K.K.) and then immersed in the azeotropic mixture of the present invention for 5 minutes. The results are shown in Table 1, wherein symbol A-O indicates that the machine oil can be removed satisfactorily at the same level as 8113.
TEST FOR CLEANING FLUX
A single sided printed circuit board (50 mm x 100 mm x 1.6 mm in thickness) was coated with a flux (Tamura F-AL-4, manufactured by Tamura Seisakusho) and heated at 200°C for 2 minutes in a convection oven. Then, it was immersed in the azeotropic mixture of the present invention for one minute. The results are shown in Table 1, in which symbol B- 00 indicates that the flux can be removed satisfactorily at the same level as R113/ethanol - 96.2 wt~/3.8 wt~.
TEST FOR REMOVING WATER
A glass plate (30 mm x 18 mm x 5 mm in thickness) was inunersed in deionized water and then irnmersed in the azeotropic mixture of the present invention for 2U
seconds for removal of water. The glass plate withdrawn, was immersed in dry methanol, whereby the removal of water was determined from the increase of the water content in methanol. The results are shown in Table 1, in which symbol C-UO indicates that the water can be lp removed satisfactorily at the same level as R113/methanol - 93.6 wt~/6.4 wt~.
2265"~
Table 1 Boiling Azeo-Azeo-Charged point tropic-tropic Exam- B.P. composi- of like Test com pies Mixtures (oC) tion Azeo- o cmpo- results P
sit on (wt~) trope sition (wt~) (C) (wt~) R225ca 51.1 30 31 25 5-45 A-1 R141b 32 70 75 55-95 R225ca 51.1 40 42 22-62 A-OO
8113 47.6 60 58 38-78 R225ca 51.1 80 78 58-98 A-OO
3 8122 71.9 20 52 22 2-42 R225ca 51,1 52 42 50 30-70~ A-OO
4 R132b 46.8 48 50 30-70 R225ca 51.1 50 47 27-67 B-Dichloro- 39.8 50 34 53 33-73 methane R225cb 56.1 20 16 1-36 A-OO
R141b 32 80 84 64-99 R225cb 56.1 50 43 33-53 B-OO
7 Dichloro- 39.8 50 36 57 47-67 methane R225cb 56.1 42 39 19-59 A-OO
8 R132b 46.8 58 43 61 41-81 R225cb 56.1 80 78 58-98 A- 00 8122 71.9 20 55 22 2-42 R225cb 56.1 30 32 12-52 A-OO
8113 47.6 70 46 68 48-88 R244ca 54 15 13 1-33 A-OO
11 R141b 32 85 32 87 67-99 R244ca 54 50 38 18-58 A-O
12 Dichloro- 39.8 50 35 62 42-82 B-methane 202fi~7 Table 1 (continued) Boiling Azeo-Charged point Azeo- tropic-tropic Exam- B.P. composi- of like Test pies Mixtures (oC) tion Azeo- compo- compo- results sition (wt~) trope sition (wt~) (oC) (wt~) R244ca 54 80 83 63-99 A-O
13 8122 71.9 20 55 17 1-37 R244ca 54 42 38 18-58 A-O
14 R132b 46.8 58 44 62 42-82 R244ca 54 20 47 26 6-46 A-O
15 8113 47.6 80 74 54-94 R225ca 51.1 70 66 46-98~ A-O
16 Cyclo- 99.3 30 45 34 2-54 pentane R225cb 56.1 58 55 35-98 A-O
17 Cyclo- 49.3 42 47 45 2-65 pentane R244ca 54 50 48 28-98 A-2,2- 49.7 50 50 52 2-72 dimethyl-butane R225cb 56.1 25 21 11-98 A-2 r 2._ 49.7 75 79 2-89 dimethyl-butane R244ca 54 55 50 30-98 A-OO
20 Cyclo- 49.3 45 47 50 2-70 pentane R225ca 51.1 60 56 36-98 A-OO
2,2- 49.7 40 49 44 2-64 dimethyl-butane 202~~'~
_ 21 _.
Table 1 (continued) Roiling Azeo-Ctaargedpoint Azeo- tropic-tropic Exam- B.F. composi-of like Test Mixtures compo-ples (C) tion Azeo- cmpo- results sition (wt~) trope sition (wt~) (C) (wt~) R225ca 51.1 60 66 46-86 A-OO
22 2-bromo- 59.4 40 47 34 14-54 propane R225cb 56.1 60 58 38-78 A-OO
23 2-bromo--59.4 40 49 42 22-62 propane R244ca 54 50~ 55 35-75 A- ~O
24 2-bromo- 59.4 50 48 45 25-65~
propane R244cb 58 60 50 30-70 A-OO
25 2-bromo- 59.4 40 50 50 30-70 propane R235ca 43.9 70 74 54-94 A-OO
26 2-bromo- 59.4 30 42 26 6-46 propane R243cc 60.2 40 50 30-70 A- 00 27 2-bromo- 59.4 60 52 50 30-70 propane ' R225cb 56.1 90 - 50-99 A-O
28 2-methyl-60.3 10 - - 1-50 pentane R244ca 54 90 91 71-99 A-O
29 2-methyl-60.3 10 55 9 1-29 pentane R244cb 58 70 72 52-98 A-0 30 2-methyl-60.3 30 55 28 2-48 pentane 2a~~~~
'fable 1 (continued) Boiling Azeo-Azeo-Charged point tropic-tropic Exam- B.P, composi- of like Test _ ple~ Mixtures (C) Lion Azeo- com compo- results o i sit on (wt~) trope (wt~) sition (C) (wt$) R243cc 60.2 70 74 54-99 A-C>
31 2-methyl-60.3 30 61 26 1-46 pentane R225cb 56.1 ' 80 78 58-98 A- O
2.3- 58.0 20 22 2-42 dimethyl-butane R244ca 54 80 76 56-96~ A-O
2'3 58.0 20 53 24 4-44 33 dimethyl-butane R244cb 58 60 63 43-95 A-~
2.3- 58.0 40 55 37 5-57 34 dimethyl-butane R225ca 51.1 90 - 85-99 A-O
23- 58.0 10 - 1-15 35 dimethyl- - , butane R243cc 60.2 90 - 50-95 A-OO
2'3 58.0 10 - 5-50 36 dimethyl- -butane R225ca 51.1 60 57 37-77 A-trans- 47.7 40 43 23-63 37 1,2- 44 dichloro-ethylene ~0265'~
Table 1 (continued) Boiling Azeo-Charged point Azeo- tropie-tropic Exam- B.P. composi- of like Test _ Ales Mixtures (C) Lion Azeo- com Compo- results o p sit on (wt~) trope (wt~) sition (C) (wt$) R225cb 56.1 50 47 27-67 A-OO
trans- 47.7 50 53 33-73 38 1,2- 46 dichloro-ethylene R244ca 54 50 46 27-66 A-O
trans- 47.7 50 54 34-74 39 1,2- 45 dichloro-ethylene R244cb 58 45 40 20-60 A-O
traps- 47.7 55 60 40-80 40 1,2- 46 dichloro-ethylene R235ca 43.9 70 66 46-86 A-O
traps- 47.7 30 34 14-54 41 1,2- 41 dichloro-ethylene R243cc 60.2 40 42 22-62 A-O
traps- 47.7 60 58 38-78 42 1,2- 45 dichloro-ethylene R225ca 51.1 80 78 58-98 A-O
cis-1,2- 60.6 20 50 22 2-42 dichloro-ethylene 2o~s~~~
Table 1 (continued) F3ai.ling Azeo-Azeo-Charged point tropic-tropic Exam- Fs. composi- of like Test P.
Mixtures campo-les (C) Lion Azeo- compo- results p sition (wt~) trope sition (wt~) (C) (wt~) R225cb 56.1 70 69 59-79 A-OO
cis-1,2- 60.6 30 53 31 21-41 dichloro-ethylene R244ca 54 70 67 47-87 A-OO
cis-1,2- 60.6 30 51 33 13-53 dichloro-ethylene R244cb 58 60 59 39-79 A-OO
cis-1,2- 60.6 40 54 41 21-61 dichloro-ethylene R235ca 43.9 90 94 74-99 A-OO
cis-1,2- 60.6 10 45 6 1-26 dichloro-ethylene R243cc 60.2 60 58 38-78 A- 00 cis-1,2- 60.6 40 52 42 22-62 dichloro-ethylene R244cb 58 10 12 2-32 A-~
8113 47.6 90 88 68-98 R235ca 43.9 60 56 36-76 A-OO
50 8113 47.6 40 42 44 24-64 IR244cb 58 30 33 13-53 A-OO
51 Dichloro-39.8 70 36 67 47-87 methane ' R235ca 43.9 50 53 33-73 A-OO
52 Dichloro-39.8 50 32 47 27-67 methane ~'~~a'~
25 __ Table 1 (continued) Boiling Azeo-Charged point Azeo- tropic-.
tropzc Exam- B.P. composi--of like Test com ples Mixtures (C) tion Azeo- o compo- results p -sition (wt$) trope (wt$) sition (C) (wt$) R243cc 60.2 50 30 10-50 A-OO
53 Dichloro-39.8 50 38 70 50-90 methane R244cb 58 40 43 23-99 A-OO
54 Cyclo- 49.3 60 48 57 1-77 pentane R235ca 43.9 80 77 67-99 A-OO
55 Cycla- 49.3 20 42 23 1-33 pentane R243cc 60.2 25 30 10-99 A-UO
56 Cyclo- 49.3 75 49 70 1-90 pentane R244cb 58 40 34 14-99 A-O
2r2- 49.7 60 50 66 1-86 57 dimethyl-butane R235ca 43.9 80 81 61-99 A-O
2.2 49.7 20 43 19 1-39 58 dimethyl-butane R244cb 58 80 75 55-95 A-OO
59 8122 71.9 20 58 25 5-45 R244cb 58 30 29 9-49 A-OO
60 R132b 46.8 70 45 71 51-91 R235ca 43.9 20 14 1-34 A-O
61 8123 27.1 8 28 86 66-99 R235ca 43.9 20 57 37-77 A-O
62 R132b 46.8 80 39 43 23-63 _ 26 _.
Tab7.e 1 (continued) Boiling Azeo-Charged point Azeo- tropic-tropic Exam- B.P. composi- of like Test Mixtures compo-ples (C) tion Azeo- sition cmpo- results (wt~) trope (wt~) sition (C) (wt~) R235ca 43,9 30 34 14-54 A-OO
63 R141b 32 70 30 66 46-86 R243cc 60.2 80 77 57-97 A-~
64 8122 71.9 ,20 60 23 3-43 R243cc 60.2 20 24 4-44 A-OO
65 R132b 46.8 80 46 76 56-96 R225ca 51.1 90 95 75-99~ A-~
66 8141 75.7 ZO 52 5 1-25 R225cb 56.1 90 89 69-99 A-UO
67 8141 75.7 10 56 11 1-31 R244cb 58 85 90 70-99 A-O
68 8141 75.7 15 5~ 10 1-30 R225ca 51.1 97 94.6 75-99 B-O
69 Methanol 64.5 3 46 5.4 1-25 C-O
R225cb 56.1 97 95.6 74-99.5 70 Ethanol 78.3 3 53.8 4.4 0.5-26 C-O
R225cb 56.1 97 97.9 77-99 A-O
71 Iso- 82.4 3 54.9 2.1 1-23 B- O
propanol C-O
R225cb 56.1 95 93.3 74-99 72 Methanol 64 5 47.2 6.7 1-26 . C-O
R225ca 51.1 90 94.8 14-98 A-O
73 R225cb 56.1 5 50 2.7 1-85 B-O
Ethanol 78.3 5 2.5 1-16 C-O
2026~~b Table 1 (continued]
Boiling Azeo-Azeo-Charged point tropic-tropic Exam- B.P. composi-of like Test Mixtures compo-ples (C) tion Azeo- sition compo- results (wt~) trope sition (wt~) (C) (wt~) R225ca 51.1 89 89.8 14-98 A-OO
74 R225cb 56.1 6 46 5.6 1-85 B-O
Methanol 64.7 5 4.6 1-16 C-O
A-~
R225ca 51.1 98.5 97.3 75-99.5_ B
75 Ethanol 78.3 1.5 50 2.7 0.5-25 C-OO
R225ca 51,1 76-99 A-OO
76 Tso- 82.4 - - - 1-24 B--UO
~
propanol C-O
R225ca 51.1 35 38 15-61 A-O
8113 47.6 15 15 8-44 B-OO
77 Dichloro-39.8 50 - 47 34-70 methane R225cb 56.1 25 26 6-37 A-OO
78 8113 47.6 35 - 35 22-52 R132b 46.8 40 39 27-51 R225ca 51.1 3S 32 22-55 A-OO
79 8113 47.6 25 - 29 10-46 R132b 46.8 40 39 21-55 R225cb 56.1 25 26 8-38 A-OO
8113 47.6 25 24 8-47 B-OO
80 Dichloro-39.8 50 - 50 34-63 methane R244ca 54 25 25 6-33 A-OO
8113 47,6 20 19 9-41 B-OO
81 Dichloro-39.8 55 - 56 43-68 methane R244ca 54 20 19 4-39 A-Oo 82 8113 47.6 30 - 32 6-53 R132b 46.8 50 49 30-67 202~W
Table 1 (continued) Boiling Azeo-Azeo-Charged point tropic-tropic Exam- B.P. composi-of like Test Mixtures compo-ples (C) Lion Azeo- compo- results sition (wt~) trope sition (wt~) (C) (wt~) R225ca 51.1 40 41 28-52 A-OO
8113 47.6 20 22 7-39 B-O
trans- 47.7 40 37 25-48 1,2-dichloro-ethylene R244ca 54 30 25 8-36 A-OO
8113 47.6 60 62 48-85. B-OO
84 2-bromo- 59.4 10 - 13 3-28 propane R225ca 51.1 40 42 29-60 A-OO
8113 47.6 50 47 11-61 B-OO
85 2-bromo- 59.4 10 - 11 3-29 propane R244ca 54 20 22 4-38 A- 00 8113 47.6 60 58 40-77 B-OO
86 cis-1,2- 60.6 20 - 20 9-32 dichloro-ethylene ' R225ca 56.1 35 32 19'43 A-OO
8113 47.6 50 53 39-60 B-CJ
87 cis-1,2- 60.6 15 - 15 8-22 dichloro-ethylene R225ca 51.1 40 42 25-54 A-~
8113 47.6 45 45 38-58 B-O
88 cis-1,2- 60.6 15 - 13 8-22 dichloro-ethylene ' ~~D26~~
'i'able 1 (CUI7tlnued) Boiling Azeo-Azeo-Charged point tropic-tropic Exam- B.P. composi-of like Test Mixtures compo-ples (C) Lion Azeo- cmpo- results sition (wt~) trope (wt~) sition (C) (wt~) R244ca 54 35 34 5-95 A-8113 47.6 22 20 4-60 B- ~O
trans- 47.7 48 46 26-59 8g -1,2-dichloro-ethylene R225cb 56.1 35 36 27-51 A- oU
8113 47.6 25 27 6-44 B-OO
.
trans- 47.7 40 37 29-48 1,2-dichloro-ethylene R225cb 56.1 35 34 22-43 A- 00 8113 47.6 55 56 38-68 B-OO
91 2-bromo- 59.4 10 - 10 3-26 propane R225cb 56.1 35 34 20-53 A-OO
8113 47.6 55 55 8-72 92 Cyclo- 49.3 10 - 11 1-40 pentane -R225ca 51.1 40 41 28-65 A-O
8113 47.6 50 52 13-68 93 Cyclo- 49.3 10 - 7 2-35 pentane R244ca 54 25 23 17-46 A- 00 8113 47.6 70 71 8-77 94 2,2- 49.7 5 - 6 2-56 dimethyl-butane Table 1 (continued) Boiling Azeo-Charged point Azeo- tropic-tropic Exam- B.P. composi-of like Test Mixtures com o-ples (C) tion Azeo- p compo- results sition (wt~) trope sition (wt~) (C) (wt~) R225ca 51.1 50 52 42-61 A- 00 8113 47.6 20 16 7-55 B-O
1-chloro- 46.6 30 32 2-43 propane R225cb 56.1 40 42 23-44 A-O
8113 47.6 30 27 8-70 B-OO
1-chloro- 46.6 30 31 2-47 propane R244ca 54 20 22 4-33 A-OO
8113 47.6 60 57 41-78 B-OO
97 2-chloro- 50.7 20 - 21 8-31 2-methyl-propane R244ca 54 30 27 5-45 A-OO
R113 47.6 50 50 9-74 ~8 -Cyclo- 49.3 20 23 12-46 pentane R225ca 51.1 45 40 28-56 A- 00 8113 47.6 50 55 12-64 B-OO
99 2-chloro- 50.7 5 - 5 2-32 2-methyl-propane R225cb 56.1 30 31 17-38 A-OO
8113 47.6 60 58 41-75 B- n0 100 2-chloro- 50.7 10 - 11 2-21 2-methyl-propane R224ca 54 35 36 9-39 A-OO
8113 47.6 20 19 9-84 B-OO
1-chloro- 46.6 45 45 2-60 propane 20265' Table 1 (continued) Boiling Azeo-Azeo-Charged point tropic-tropic Exam- B.P. composi- o~ like Test ples Mixtures (oC) tion Azeo- compo-compo- results sition (wt~) trope sition (wt~) (C) (wt~) R225ca 51.1 90 90 36-97 A-O
R225cb 56.1 5 7 1-51 2-methyl-60.3 5 3 1-16 pentane R225ca 51.1185 88 6-94 A-O
R225cb 56.1 10 8 1-83 103 2,3- 58.0 5 - 4 1-26 dimethyl-butane R225ca 51.1 50 50 6-67 A-~
R225cb 56.1 10 12 4-67 B-O
104 2-chloro-50.7 40 - 38 1-58 2-methyl-propane R225ca 51.1 ~ 40 41 7-56 A-O
R225cb 56.1 15 14 7-61 B-O
( 105 1-chloro-46.6 45 - 45 1-54 propane R225ca 51.1 55 54 6-66 A-O
R225cb 56.1 10 10 5-64 B-O
2-bromo- 59.4 35 36 10-48 propane R225ca 51.1 60 58 6-70 A-O
R225cb 56.1 10 12 4-74 B-O
107 cis-1,2- 60.6 30 - 30 10-38 dichloro-ethylene Table 1 (continued) Boiling Azeo-Azeo-Charged point tropic-tropic Exam- B.P. composi- of like Test Mixtures compo-ples (C) tion Azeo- Sition cmpo- results (wt~) trope sition (wt~) (C) (wt~) R225ca 51.1 40 42 8-57 A- 00 R225cb 56.1 15 13 6-54 B-OO
trans- 47.7 45 45 10-59 1,2-dichloro-ethylene R225ca 51.1 80 80 40-89 A-O
109 R225cb 56.1 10 - 8 2-37 B-~
.
8122 71.9 10 12 3-23 R225ca 51.1 80 84 44-92 A-O
110 R225cb 56.1 10 - 8 2-41 B-O
8141 75.7 10 8 1-17 R225ca 51.1 35 36 6-44 A-O
111 R225cb 56.1 10 - 11 4-44 B-O
R132b 46.8 55 53 44-73 R225ca 56.1 25 20 8-31 A-O
R141b 32 65 67 36-88 B-112 Dichloro- 39.8 10 - 13 3-38 , methane R225ca 51.1 30 26 8-41 A- OO
R141b 32 60 62 32-84 B-~
113 Dichloro- 39.8 10 - 12 3-31 methane R225ca 51.1 15 12 6-33 A-O
114 R141b 32 5 - 7 2-33 B-O
8123 27.1 80 81 44-86 R225ca 51.1 30 33 5-47 A-O
115 R225cb 56.1 10 - 9 3-42 8113 47.6 60 58 5-79 1 1 ~ i L 1 r r n Table 1 (continued) Boiling Azeo-Azeo-Charged point tropic-tropic Exam- B.P. composi- of like Test Mixtures compo-ples (C) tion Azeo- sition compo- results (wt~) trope sition (wt~) (C) (wt$) R225ca 51.1 25 25 9-49 A-Oo R225cb 56.1 Z1 21 8-39 B- 00 116 Dichloro-39.8 55 - 54 5-70 methane R244ca 54 15 16 6-31 A-OO
R141b 32 70 68 38-90 B-O
117 Dichloro-39.8 15 - 16 3-40 methane R244ca 54 20 21 5-58 A- 00 R225cb 56.1 40 42 7-66 B-O
118 2-bromo- 59.4 40 - 37 5-54 propane R244ca 54 30 31 4-58 A-R225cb 56.1 40 35 7-71 B-O
119 cis-1,2- 60.6 30 - 34 4-43 dichloro-ethylene R244ca 54 15 15 8-58 A-O
R225cb 56.1 40 39 9-65 B- ~O
120 1-chloro-46.6 45 - 46 5-71 propane R244ca 54 ZO 22 7-55 A-O
R225cb 56.1 30 32 8-56 B-O
121 2-chloro-50.7 50 - 46 5-74 2-methyl-propane R244ca 54 60 62 29-87 A-O
R225cb 56.1 20 20 6-68 122 2,3- 58 20 - 18 2-29 dimethyl-butane ~0~~~~
Table 1 (continued) Boiling Azeo-Charged point Azeo- tropic-tropic Exam- B.P. composi- of like Test Mixtures compo-ples (C) Lion Azeo- compo- results sition (wt~) trope (wt~) sition (C) (wt~) R244ca 54 20 18 5-42 A-OO
123 R225cb 56.1 20 - 24 7-50 B-~
R132b 46.8 60 58 41-80 R244ca 54 30 30 5-55 A-OO
R225cb 56.1 25 26 8-57 B-OO
trans- 47.7 45 44 5--61 1,2-dichloro-ethylene R244ca 54 25 25 8-56 A-OO
R225cb 56.1 30 32 9-55 125 Cyclo- 49.3 45 - 45 5-69 pentane R244ca 54 20 17 7-35 A-O
R225cb 56.1 20 24 9-42 B-o0 126 Dichloro-39.8 60 - 59 45-73 methane R244ca 54 40 39 7-61 A-OO
R225ca 51.1 20 19 8-71 127 2,2- 49.7 40 - 42 5-72 dimethyl-butane R244ca 54 10 12 5-41 A-OO
R225ca 51.1 30 34 9-48 B-OD
128 Dichloro-39.8 60 - 54 40-73 methane R244ca 54 10 9 2-37 A-OO
l29 R225ca 51.1 40 - 40 7-50 B-OO
R132b 46.8 ~ 50 51 35-72 ~o~~~~
Table 1 (continued) Boiling Azeo-Charged point Azeo- tropic-tropic Exam- B.P. composi- of like Test Mixtures compo-ples (C) Lion Azeo- compo- results .
sition (wt~) trope sition (wt~) (C) (wt~) R244ca 54 25 24 3-49 A-~
130 R225ca 51.1 70 - 70 47-95 B-~
8141 75.7 5 6 0.1-17 R244ca 54 10 11 5-S5 A-CC~
R225ca 51.1 55 55 9-67 131 Cyclo- 49.3 35 - 34 3-53 pentane R244ca 54 20 21 3-59 A-OO
~
132 R225ca 51.1 70 - 70 36-93 B-Oo 8122 71.9 10 9 1-22 R244ca 54 10 11 3-69 A-OO
R225ca 51.1 50 47 8-78 B-OO
trans- 47.7 40 42 3-54 1,2-dichloro-ethylene R244ca 54 8 10 3-59 A-OO
R225ca 51.1 62 60 7-75 B-O
134 cis-1,2- 60.6 30 - 30 3-38 dichloro-ethylene R244ca 54 10 8 3-58 A-OO
R225ca 51.1 60 58 6-71 B-~
135 2-bromo- 59.4 30 - 34 3-44 propane R244ca 54 45 47 22-86 A-O
136 R225cb 56.1 45 - ~ 47 6-72 B-OO
8141 75.7 10 6 1-21 ~026~~
Table 1 (COIltlnued) Bailing Azeo Charged point Azeo- tropic-tropic Exam- B.P. compasi- of like Test Mixtures compo-ples (C) tion Azeo- compo- results sition (wt~) trope sition (wt$) (C) (wt$) R225ca 51.1 50 48 10-88 A-OO
R225cb 56.1 10 15 8-70 137 Cyclo- 49.3 40 - 37 3-58 pentane R244ca 54 50 45 8-83 A-~
138 R225cb 56.1 40 - 45 6-84 B-OO
8122 71.9 10 10 3-28 R244ca 54 30 29 3-84 A-~
~
R225ca 51.1 65 67 13-94 139 2,3- 58 5 - 4 0.1-19 dimethyl-butane R244ca 54 10 11 3-98 A-OO
R225ca 51.1 50 48 7-62 B-O
140 1-chloro-46.6 40 - 41 3-56 propane R244ca 54 10 10 3-56 A-R225ca 51.1 60 54 6-72 B-O
141 2-chloro-50.7 30 - 36 3-54 2-methyl-propane R244ca 54 45 42 7-76 A-O
R225cb 56.1 10 14 8-62 142 2, 2- 49 45 - 44 3-73 .7 dimethyl-butane 20~~~~
Table 1 (continued) Boiling Azeo-Charged point Azeo- tropic-tropic Exam- B.P. composi- of like Test ples Mixtures (oC) tion Azeo- compo- compo- results sition (wt~) trope sition (wt~) (~C) (wt~) R244ca 54 76-99 A-O
143 Methanol 64.'7- - - 1-24 B-O
R244ca 54 77-99 A-OO
144 Ethanol 78.3 - - - 1-23 B-OO
R244ca 54 79-99 A- n0 145 Iso- 82.4 - - - 1-21 B-O
propanol R225ca 51.1 50-80 146 R244ca 54 - - - 10-40 A-OO
Ethanol 78.3 . 1-ZO B- 00 R225cb 56.1 40-80 147 R224ca S4 - - - 10-50 A-OO
Ethanol 78.3 1-ZO B-Oo R225ca 51.1 5-99 R225cb 56.1 3-99 A- 00 148 R244ca 54 - - - 1-69 H-OO
Ethanol 78.3 1-35 R225ca 51.1 50-80 A-1o0 149 R244ca 54 - - - 10-40 B-OO
Methanol G4.7 1-10 R225cb 56.1 40-80 A-150 R244ca 54 - - - 10-50 H-OO
Methanol 64.7 1-10 R225ca 51.1 5-99 A- 00 R225cb 56.1 3-99 B- 00 151 R244ca 54 - - - 1-69 Methanol 64.7 1-35 202G~°~
Table 1 (cont.i.nued) Boiling Azeo-Chargec~ point Azeo- tropic-tropic Exam- B.F. composi- o like Test Mixtures compo-ples (C) tion Azeo- sitioncmpo- results (wt~) trope sition (wt~) (C) (wt$) R225ca 51.1 1-98 A-OO
R22~cb 56.1 1-98 B-OO
Iso- 82.4 1-16 ~propanol 2026~'~
REFERENCE EXAMPLES
For the purpose of ascertaining the effects of the azeotropic-like mixture of the present invention for stabilization, the following test was applied to the mixture as identified in Table 2.
In accordance with JIS K1600, a metal test piece was placed in both the liquid phase portion and the gas phase portion of the stabilized mixture as identified in Table 2, and after 48 hours, the state of corrosion of the test piece was inspected. The results are shown in Table 2.
Azeotropic-like mixture AA: R225ca/R225cb/methanol = 47 wt~/47 wt$/6 wt~
Stabilizer NM: Nitromethane PH: Phenol DIPA: Diisopropylamine DO: 1,4-Dioxane Am: j3-Amylene MeA: Methyl acetate TPH: Triphenylphosphite B0: 1,2-Buthyleneoxide DME: 1,2-Dimethoxyethane MP: N-methylpyrrole s-Bu: sec-Butanol MIBK: Methyl isobutyl ketone ECH: Epichlorohydrin i-Bu: Isobutanol BHT: 2,6-Di-t-butyl-o-cresol BTA: 1,2,3-Benzotriazole Appearance of test piece O : No corrosion O : No substantial corrosion 0 : Corrosion slightly observed X: Substantial corrosion observed.
Table 2 Cor Reference rosion of test piece Stabilized mixture (wt~) Examples Fe Cu Ag AA01 AA(99.5)/PH(0.5) O O O
AA02 AA(99.5)/DIPA(0.5) ~ O O
AA03 AA(99.5)/Am(0.5) O O O
AA04 AA(99.5)/TPH(0.5) O O O
AA05 AA(99.5)/MP(0.5) ~ O O
AA06 AA(99.5)/BTA(0.5) O O O
AA07 AA(99)/NM(1) O O O
AA08 AA(99)/DO(1) O O O
AA09 AA(99)/MeA(1) O O O
AA10 AA(99)/B0(1) O O O
AAIl AA(99)/DME(1) O O
AA12 AA(99)/s-Bu(1) OO O O
AA13 AA(99)/MIBK(1) AA14 AA(99)/ECH(1) O O O
AA15 AA(98.5)/NM(1)/BTA(0.5) O O ~ ' AA16 ~(975)/NM(1)/BO(1)/ Op OO O
BHT(0.5) AA17 ~(97)/NM(1)/BO(1)/ Oo O
BHT(0.5/BTA(0.5) X18 AA(96)/NM(1)/BTA(0.5)/
BO(1)/i-Bu(1)/BHT(0.5) Compara-tive AA(100) Example INDUSTRIAL APPLICABILITY
The hydrochlorofluorocarbon azeotropic or azeotropic-like mixture of th a present invention is non-flammable or hardly flammable and has excellent properties equal or superior to conventional CFCs. Further, the mixture shows no substantial change in the composition during boiling and evaporating, since it has an azeotropic composition or an azeotropic-like composition, and it can be used in the same manner as a conventional single CFC
and thus has a merit that it requires no substantial change of the conventional technique. Further, it. is excellent in the properties for dissolving and removing a flux or oil like 8113 which is commonly used as a - solvent, and thus it is useful as a cleaning agent which may be an alternative for 8113.
Claims (4)
1. A hydrochlorofluorocarbon azeotropic-like mixture consisting essentially of:
from 75 to 99 weight percent 1,1-dichloro-2,2,3,3,3-pentafluoropropane and from 1 to 25 weight percent methanol, which boils at about 46° C. at atmospheric pressure; or from 75 to 99.5 weight percent 1,1-dichloro-2,2,3,3,3-pentafluoropropane and from 0.5 to 25 weight percent ethanol, which boils at about 50° C. at atmospheric pressure; or from 74 to 99 weight percent 1,3-dichloro-1,1,2,2,3-pentafluoropropane and from 1 to 26 weight percent methanol, which boils at about 47.2° C. at atmospheric pressure; or from 74 to 99.5 weight percent 1,3-dichloro-1,1,2,2,3-pentafluoropropane and from 0.5 to 26 weight percent ethanol, which boils at about 53.8° C. at atmospheric pressure; or from 77 to 99 weight percent 1,3-dichloro-1,1,2,2,3-pentafluoropropane and from 1 to 23 weight percent isopropanol, which boils at about 54.9° C. at atmospheric pressure;
wherein the components of each azeotropic-like composition consist of either 1,1-dichloro-2,2,3,3,3-pentafluoropropane or 1,3-dichloro-1,1,2,2,3-pentafluoropropane, and either methanol, ethanol or isopropanol.
from 75 to 99 weight percent 1,1-dichloro-2,2,3,3,3-pentafluoropropane and from 1 to 25 weight percent methanol, which boils at about 46° C. at atmospheric pressure; or from 75 to 99.5 weight percent 1,1-dichloro-2,2,3,3,3-pentafluoropropane and from 0.5 to 25 weight percent ethanol, which boils at about 50° C. at atmospheric pressure; or from 74 to 99 weight percent 1,3-dichloro-1,1,2,2,3-pentafluoropropane and from 1 to 26 weight percent methanol, which boils at about 47.2° C. at atmospheric pressure; or from 74 to 99.5 weight percent 1,3-dichloro-1,1,2,2,3-pentafluoropropane and from 0.5 to 26 weight percent ethanol, which boils at about 53.8° C. at atmospheric pressure; or from 77 to 99 weight percent 1,3-dichloro-1,1,2,2,3-pentafluoropropane and from 1 to 23 weight percent isopropanol, which boils at about 54.9° C. at atmospheric pressure;
wherein the components of each azeotropic-like composition consist of either 1,1-dichloro-2,2,3,3,3-pentafluoropropane or 1,3-dichloro-1,1,2,2,3-pentafluoropropane, and either methanol, ethanol or isopropanol.
2. A hydrochlorofluorocarbon azeotropic mixture consisting essentially of:
94.6 weight percent 1,1-dichloro-2,2,3,3,3-pentafluoropropane and 5.4 weight percent methanol, which boils at 46° C. at atmospheric pressure; or 97.3 weight percent 1,1-dichloro-2,2,3,3,3-pentafluoropropane and 2.7 weight percent ethanol, which boils at 50° C. at atmospheric pressure; or 93.3 weight percent 1,3-dichloro-1,1,2,2,3-pentafluoropropane and 6.7 weight percent methanol which boils at 47.2° C. at atmospheric pressure; or 95.6 weight percent 1,3-dichloro-1,1,2,2,3-pentafluoropropane and 4.4 weight percent ethanol, which boils at 53.8° C, at atmospheric pressure; or 97.9 weight percent 1,3-dichloro-1,1,2,2,3-pentafluoropropane and 2.1 weight percent isopropanol, which boils at 54.9° C. at atmospheric pressure;
wherein the components of each azeotropic composition consist of either 1,1-dichloro-2,2,3,3,3-pentafluoropropane or 1,3-dichloro-1,1,2,2,3-pentafluoropropane, and either methanol, ethanol or isopropanol.
94.6 weight percent 1,1-dichloro-2,2,3,3,3-pentafluoropropane and 5.4 weight percent methanol, which boils at 46° C. at atmospheric pressure; or 97.3 weight percent 1,1-dichloro-2,2,3,3,3-pentafluoropropane and 2.7 weight percent ethanol, which boils at 50° C. at atmospheric pressure; or 93.3 weight percent 1,3-dichloro-1,1,2,2,3-pentafluoropropane and 6.7 weight percent methanol which boils at 47.2° C. at atmospheric pressure; or 95.6 weight percent 1,3-dichloro-1,1,2,2,3-pentafluoropropane and 4.4 weight percent ethanol, which boils at 53.8° C, at atmospheric pressure; or 97.9 weight percent 1,3-dichloro-1,1,2,2,3-pentafluoropropane and 2.1 weight percent isopropanol, which boils at 54.9° C. at atmospheric pressure;
wherein the components of each azeotropic composition consist of either 1,1-dichloro-2,2,3,3,3-pentafluoropropane or 1,3-dichloro-1,1,2,2,3-pentafluoropropane, and either methanol, ethanol or isopropanol.
3. An azeotropic composition consisting essentially of CF3CF2CHCl2 (225ca), CClF2CF2CHClF (225cb) and methanol, in amounts by weight of 89.8 percent, 5.6 percent and 4.6 percent, respectively, which boils at about 46° C. at atmospheric pressure.
4. An azeotropic composition consisting essentially of CF2CF2CHCl2 (225ca), CClF2CF2CHClF (225cb) and ethanol, in amounts by weight of 94.8 percent, 2.7 percent and 2.5 percent, respectively, which boils at about 50° C. at atmospheric pressure.
Applications Claiming Priority (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1-20883 | 1989-02-01 | ||
| JP1-20887 | 1989-02-01 | ||
| JP1-20888 | 1989-02-01 | ||
| JP1020888A JPH0798762B2 (en) | 1989-02-01 | 1989-02-01 | Fluorinated hydrocarbon-based azeotropes and azeotrope-like mixtures |
| JP1020883A JPH02202827A (en) | 1989-02-01 | 1989-02-01 | 1,1-dichloro-2,2,3,3,3-pentafluoropropane-based azeotrope and azeotropy-like mixture |
| JP1020887A JP2692230B2 (en) | 1989-02-01 | 1989-02-01 | Fluorinated hydrocarbon azeotropes and azeotrope-like compositions |
| PCT/JP1990/000119 WO1990008814A1 (en) | 1989-02-01 | 1990-02-01 | Hydrochlorofluorocarbon azeotropic or azeotropic-like mixture |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2026576A1 CA2026576A1 (en) | 1990-08-02 |
| CA2026576C true CA2026576C (en) | 2000-10-17 |
Family
ID=27283207
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002026576A Expired - Lifetime CA2026576C (en) | 1989-02-01 | 1990-02-01 | Hydrochlorofluorocarbon azeotropic or azeotropic-like mixture |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA2026576C (en) |
-
1990
- 1990-02-01 CA CA002026576A patent/CA2026576C/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| CA2026576A1 (en) | 1990-08-02 |
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| JPH0834996A (en) | Mixed solvent composition | |
| JPH05339181A (en) | Stabilized solvent composition | |
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