U.S. patent application number 09/783702 was filed with the patent office on 2001-08-30 for azeotrope-like compositions and their use.
This patent application is currently assigned to 3M Innovative Properties Company. Invention is credited to Flynn, Richard M., Milbrath, Dean S., Owens, John G., Vitcak, Daniel R., Yanome, Hideto.
Application Number | 20010018408 09/783702 |
Document ID | / |
Family ID | 23756664 |
Filed Date | 2001-08-30 |
United States Patent
Application |
20010018408 |
Kind Code |
A1 |
Flynn, Richard M. ; et
al. |
August 30, 2001 |
Azeotrope-like compositions and their use
Abstract
The invention provides azeotrope-like compositions consisting
essentially of R.sub.fOC.sub.2H.sub.5, where R.sub.f is a branched
or straight chain perfluoroalkyl group having 4 carbon atoms, and
an organic solvent selected from the group consisting of: straight
chain, branched chain and cyclic alkanes having 6 to 8 carbon
atoms; esters having 4 carbon atoms; ketones having 4 carbon atoms;
disiloxanes having 6 carbon atoms; cyclic and acyclic ethers having
4 to 6 carbon atoms; chlorinated alkanes having 3 to 4 carbon atoms
and chlorinated alkenes having 2 carbon atoms. The compositions are
useful for cleaning, as solvents or carriers for coating and as
heat transfer materials.
Inventors: |
Flynn, Richard M.;
(Mahtomedi, MN) ; Milbrath, Dean S.; (Stillwater,
MN) ; Owens, John G.; (Woodbury, MN) ; Vitcak,
Daniel R.; (Cottage Grove, MN) ; Yanome, Hideto;
(Sagamihara, JP) |
Correspondence
Address: |
Office of Intellectual Property Counsel
3M Innovative Properties Company
PO Box 33427
St. Paul
MN
55133-3427
US
|
Assignee: |
3M Innovative Properties
Company
|
Family ID: |
23756664 |
Appl. No.: |
09/783702 |
Filed: |
February 14, 2001 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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09783702 |
Feb 14, 2001 |
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09429508 |
Oct 28, 1999 |
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6235700 |
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09429508 |
Oct 28, 1999 |
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09130236 |
Aug 6, 1998 |
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6063748 |
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09130236 |
Aug 6, 1998 |
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08649743 |
May 15, 1996 |
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5814595 |
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08649743 |
May 15, 1996 |
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08442399 |
May 16, 1995 |
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Current U.S.
Class: |
510/177 ;
510/415; 510/506 |
Current CPC
Class: |
C11D 7/28 20130101; C23G
5/032 20130101; C09K 2205/132 20130101; C11D 7/5077 20130101; C09K
2205/11 20130101; C11D 7/264 20130101; C09K 5/04 20130101; C11D
7/263 20130101; C09K 2205/102 20130101; C11D 7/261 20130101; C09K
2205/108 20130101; C11D 7/266 20130101; C11D 7/5063 20130101; C09D
7/20 20180101; C09K 2205/114 20130101; C09K 5/045 20130101; C11D
7/5095 20130101; C09K 2205/32 20130101; C09K 2205/122 20130101;
C11D 7/32 20130101; C09K 2205/112 20130101; C11D 7/24 20130101;
C11D 7/5072 20130101; C11D 7/267 20130101 |
Class at
Publication: |
510/177 ;
510/415; 510/506 |
International
Class: |
C11D 001/00; C11D
017/00; C11D 017/08 |
Claims
We claim:
1. A process for depositing a coating on a substrate surface
comprising the step of applying to at least a portion of at least
one surface of the substrate a liquid coating composition
comprising: (A) an azeotrope-like composition including (a)
perfluorobutyl ethyl ether, consisting essentially of
perfluoro-n-butyl ethyl ether and perfluoroisobutyl ethyl ether and
mixtures thereof, and (b) organic solvent; and (B) at least one
coating material which is soluble or dispersible in the
azeotrope-like composition wherein the composition is selected from
the group consisting of: (i) compositions consisting essentially of
about 89 to 38 weight percent of the ether and about 11 to 62
weight percent 1-chlorobutane that boil at about 68.degree. to
70.degree. C. at 736 torr; (ii) compositions consisting essentially
of about 94 to 71 weight percent of the ether and about 6 to 29
weight percent 1,2-dichloropropane that boil at about 73.degree. to
75.degree. C. at 738 torr; (iii) compositions consisting
essentially of about 76 to 40 weight percent of the ether and about
24 to 60 weight percent 2,2-dichloropropane that boil at about
65.degree. to 67.degree. C. at 731 torr; (iv) compositions
consisting essentially of about 46 to 4 weight percent of the ether
and about 54 to 96 weight percent trans-1,2-dichloroethylene that
boil at about 43.degree. to 45.degree. C. at 729 torr; (v)
compositions consisting essentially of about 95 to 68 weight
percent of the ether and about 5 to 32 weight percent
2,3-dichloro-1-propene that boil at about 72.degree. to 74.degree.
C. at 735 torr; and (vi) compositions consisting essentially of
about 78 to 21 weight percent of the ether and about 22 to 79
weight percent 1-bromopropane that boil at about 62.degree. to
64.degree. C. at 725 torr. (vii) compositions consisting
essentially of about 94 to 35 weight percent of the ether and about
6 to 65 weight percent methanol that boil at about 52 to 54.degree.
C. at 720 torr; (viii) compositions consisting essentially of about
94 to 55 weight percent of the ether and about 6 to 45 weight
percent ethanol that boil at about 61 to 63.degree. C. at 722
torr.
2. The process of claim 1 wherein said azeotrope-like composition
consists essentially of about 18 weight percent perfluoro-n-butyl
ethyl ether, and about 82 weight percent perfluoroisobutyl ethyl
ether, and one organic solvent, and is selected from the group
consisting of: (i) compositions consisting essentially of the ether
and 1-chlorobutane, the compositions, when fractionally distilled,
form a distillate fraction that is an azeotrope that consists
essentially of about 72 weight percent of the ether and about 28
percent of the 1-chlorobutane and boils at about 69.degree. C. at
about 740 torr; (ii) compositions consisting essentially of the
ether and 1,2-dichloropropane, the compositions, when fractionally
distilled, form a distillate fraction that is an azeotrope that
consists essentially of about 87 weight percent of the ether and
about 13 percent of the 1,2-dichloropropane and boils at about
73.degree. C. at about 732 torr; (iii) compositions consisting
essentially of the ether and 2,2-dichloropropane, the compositions,
when fractionally distilled, form a distillate fraction that is an
azeotrope that consists essentially of about 62 weight percent of
the ether and about 38 percent of the 2,2-dichloropropane and boils
at about 65.degree. C. at about 740 torr; (iv) compositions
consisting essentially of the ether and trans-1,2-dichloroethylene,
the compositions, when fractionally distilled, form a distillate
fraction that is an azeotrope that consists essentially of about 31
weight percent of the ether and about 69 percent of the
trans-1,2-dichloroethylene and boils at about 45.degree. C. at
about 731 torr; and (v) compositions consisting essentially of the
ether and 1-bromopropane, the compositions, when fractionally
distilled, form a distillate fraction that is an azeotrope that
consists essentially of about 56 weight percent of the ether and
about 44 percent of the 1-bromopropane and boils at about
63.degree. C. at about 730 torr; (vi) compositions consisting
essentially of the ether and methanol, wherein the compositions,
when fractionally distilled, form a distillate fraction that is an
azeotrope consisting essentially of about 84 weight percent of the
ether and 16 percent of the methanol that boils at about 53.degree.
C. at about 731 torr; (vii) compositions consisting essentially of
the ether and ethanol, wherein the compositions, when fractionally
distilled, form a distillate fraction that is an azeotrope
consisting essentially of about 88 weight percent of the ether and
about 12 percent of the ethanol that boils at about 62.degree. C.
at about 731 torr; (viii) compositions consisting essentially of
the ether and 2-propanol, wherein the compositions, when
fractionally distilled, form a distillate fraction that is an
azeotrope consisting essentially of about 87 weight percent of the
ether and about 13 percent of the 2-propanol that boils at about
65.degree. C. at about 731 torr; (ix) compositions consisting
essentially of the ether and t-butanol, wherein the compositions,
when fractionally distilled, form a distillate fraction that is an
azeotrope consisting essentially of about 84 weight percent of the
ether and about 16 percent of the t-butanol that boils at about
67.degree. C. at about 741 torr; wherein the concentrations of the
ether and the organic solvent in the azeotrope-like composition
differ from the concentrations of such components in the
corresponding azeotrope by no more than ten percent.
3. The process of claim 1 wherein said azeotrope-like composition
consists essentially of about 95 weight percent perfluoro-n-butyl
ethyl ether, and about 5 weight percent perfluoroisobutyl ethyl
ether, and one organic solvent, and is selected from the group
consisting of: (i) compositions consisting essentially the ether
and 1-chlorobutane, the compositions, when fractionally distilled,
form a distillate fraction that is an azeotrope that consists
essentially of about 74 weight percent of the ether and about 26
percent of the 1-chlorobutane and boils at about 69.degree. C. at
about 730 torr; (ii) compositions consisting essentially of the
ether and 1,2-dichloropropane, the compositions, when fractionally
distilled, form a distillate fraction that is an azeotrope that
consists essentially of about 84 weight percent of the ether and
about 16 percent of the 1,2-dichloropropane and boils at about
74.degree. C. at about 730 torr; (iii) compositions consisting
essentially of the ether and 2,2-dichloropropane, the compositions,
when fractionally distilled, form a distillate fraction that is an
azeotrope that consists essentially of about 55 weight percent of
the ether and about 45 percent of the 2,2-dichloropropane and boils
at about 66.degree. C. at about 729 torr; (iv) compositions
consisting essentially of the ether and trans-1,2-dichloroethylene,
the compositions, when fractionally distilled, form a distillate
fraction that is an azeotrope that consists essentially of about 37
weight percent of the ether and about 63 percent of the
trans-1,2-dichloroethylene and boils at about 46.degree. C. at
about 731 torr; and (v) compositions consisting essentially of the
ether and 2,3-dichloro- 1-propene, the compositions, when
fractionally distilled, form a distillate fraction that is an
azeotrope that consists essentially of about 82 weight percent of
the ether and about 18 percent of the 2,3-dichloro-1-propene and
boils at about 73.degree. C. at about 725 torr; wherein the
concentrations of the ether and the organic solvent in the
azeotrope-like composition differ from the concentrations of such
components in the corresponding azeotrope by no more than about ten
percent.
4. An azeotrope-like composition according to claim 1 wherein the
concentrations of the ether and the organic solvent in the
azeotrope-like composition differ from the concentrations of such
components in the corresponding azeotrope by no more than five
percent.
5. An azeotrope-like composition according to claim 4 wherein the
azeotrope-like composition is an azeotrope.
6. A process for removing contaminants from the surface of a
substrate comprising the step of contacting the substrate with one
or more of the azeotrope-like compositions including (a)
perfluorobutyl methyl ether, consisting essentially of
perfluoro-n-butyl methyl ether and perfluoroisobutyl methyl ether
and mixtures thereof, and (b) organic solvent,; until the
contaminants are dissolved, dispersed or displaced in or by the
azeotrope-like composition, and removing the azeotrope-like
composition containing the dissolved, dispersed or displaced
contaminants from the surface of the substrate, which composition
is selected from the group consisting of: wherein the composition
is selected from the group consisting of: (i) compositions
consisting essentially of about 89 to 38 weight percent of the
ether and about 11 to 62 weight percent 1-chlorobutane that boil at
about 68.degree. to 70.degree. C. at 736 torr; (ii) compositions
consisting essentially of about 94 to 71 weight percent of the
ether and about 6 to 29 weight percent 1,2-dichloropropane that
boil at about 73.degree. to 75.degree. C. at 738 torr; (iii)
compositions consisting essentially of about 76 to 40 weight
percent of the ether and about 24 to 60 weight percent
2,2-dichloropropane that boil at about 65.degree. to 67.degree. C.
at 731 torr; (iv) compositions consisting essentially of about 46
to 4 weight percent of the ether and about 54 to 96 weight percent
trans-1,2-dichloroethylene that boil at about 43.degree. to
45.degree. C. at 729 torr; (v) compositions consisting essentially
of about 95 to 68 weight percent of the ether and about 5 to 32
weight percent 2,3-dichloro-1-propene that boil at about 72.degree.
to 74.degree. C. at 735 torr; and (vi) compositions consisting
essentially of about 78 to 21 weight percent of the ether and about
22 to 79 weight percent 1-bromopropane that boil at about
62.degree. to 64.degree. C. at 725 torr. (vii) compositions
consisting essentially of about 94 to 35 weight percent of the
ether and about 6 to 65 weight percent methanol that boil at about
52 to 54.degree. C. at 720 torr; (viii) compositions consisting
essentially of about 94 to 55 weight percent of the ether and about
6 to 45 weight percent ethanol that boil at about 61 to 63.degree.
C. at 722 torr.
7. The process of claim 6 wherein said azeotrope-like composition
consists essentially of about 18 weight percent perfluoro-n-butyl
ethyl ether, and about 82 weight percent perfluoroisobutyl ethyl
ether, and one organic solvent, and is selected from the group
consisting of: (i) compositions consisting essentially of the ether
and 1-chlorobutane, the compositions, when fractionally distilled,
form a distillate fraction that is an azeotrope that consists
essentially of about 72 weight percent of the ether and about 28
percent of the 1-chlorobutane and boils at about 69.degree. C. at
about 740 torr; (ii) compositions consisting essentially of the
ether and 1,2-dichloropropane, the compositions, when fractionally
distilled, form a distillate fraction that is an azeotrope that
consists essentially of about 87 weight percent of the ether and
about 13 percent of the 1,2-dichloropropane and boils at about
73.degree. C. at about 732 torr; (iii) compositions consisting
essentially of the ether and 2,2-dichloropropane, the compositions,
when fractionally distilled, form a distillate fraction that is an
azeotrope that consists essentially of about 62 weight percent of
the ether and about 38 percent of the 2,2-dichloropropane and boils
at about 65.degree. C. at about 740 torr; (iv) compositions
consisting essentially of the ether and trans-1,2-dichloroethylene,
the compositions, when fractionally distilled, form a distillate
fraction that is an azeotrope that consists essentially of about 31
weight percent of the ether and about 69 percent of the
trans-1,2-dichloroethylene and boils at about 45.degree. C. at
about 731 torr; and (v) compositions consisting essentially of the
ether and 1-bromopropane, the compositions, when fractionally
distilled, form a distillate fraction that is an azeotrope that
consists essentially of about 56 weight percent of the ether and
about 44 percent of the 1-bromopropane and boils at about
63.degree. C. at about 730 torr; (vi) compositions consisting
essentially of the ether and methanol, wherein the compositions,
when fractionally distilled, form a distillate fraction that is an
azeotrope consisting essentially of about 84 weight percent of the
ether and 16 percent of the methanol that boils at about 53.degree.
C. at about 731 torr; (vii) compositions consisting essentially of
the ether and ethanol, wherein the compositions, when fractionally
distilled, form a distillate fraction that is an azeotrope
consisting essentially of about 88 weight percent of the ether and
about 12 percent of the ethanol that boils at about 62.degree. C.
at about 731 torr; (viii) compositions consisting essentially of
the ether and 2-propanol, wherein the compositions, when
fractionally distilled, form a distillate fraction that is an
azeotrope consisting essentially of about 87 weight percent of the
ether and about 13 percent of the 2-propanol that boils at about
65.degree. C. at about 731 torr; (ix) compositions consisting
essentially of the ether and t-butanol, wherein the compositions,
when fractionally distilled, form a distillate fraction that is an
azeotrope consisting essentially of about 84 weight percent of the
ether and about 16 percent of the t-butanol that boils at about
67.degree. C. at about 741 torr; wherein the concentrations of the
ether and the organic solvent in the azeotrope-like composition
differ from the concentrations of such components in the
corresponding azeotrope by no more than ten percent.
8. The process of claim 6 wherein said azeotrope-like composition
consists essentially of about 95 weight percent perfluoro-n-butyl
ethyl ether, and about 5 weight percent perfluoroisobutyl ethyl
ether, and one organic solvent, and is selected from the group
consisting of: (i) compositions consisting essentially the ether
and 1-chlorobutane, the compositions, when fractionally distilled,
form a distillate fraction that is an azeotrope that consists
essentially of about 74 weight percent of the ether and about 26
percent of the 1-chlorobutane and boils at about 69.degree. C. at
about 730 torr; (ii) compositions consisting essentially of the
ether and 1,2-dichloropropane, the compositions, when fractionally
distilled, form a distillate fraction that is an azeotrope that
consists essentially of about 84 weight percent of the ether and
about 16 percent of the 1,2-dichloropropane and boils at about
74.degree. C. at about 730 torr; (iii) compositions consisting
essentially of the ether and 2,2-dichloropropane, the compositions,
when fractionally distilled, form a distillate fraction that is an
azeotrope that consists essentially of about 55 weight percent of
the ether and about 45 percent of the 2,2-dichloropropane and boils
at about 66.degree. C. at about 729 torr; (iv) compositions
consisting essentially of the ether and trans-1,2-dichloroethylene,
the compositions, when fractionally distilled, form a distillate
fraction that is an azeotrope that consists essentially of about 37
weight percent of the ether and about 63 percent of the
trans-1,2-dichloroethylene and boils at about 46.degree. C. at
about 731 torr; and (v) compositions consisting essentially of the
ether and 2,3-dichloro-1-propene, the compositions, when
fractionally distilled, form a distillate fraction that is an
azeotrope that consists essentially of about 82 weight percent of
the ether and about 18 percent of the 2,3-dichloro-1-propene and
boils at about 73.degree. C. at about 725 torr; wherein the
concentrations of the ether and the organic solvent in the
azeotrope-like composition differ from the concentrations of such
components in the corresponding azeotrope by no more than about ten
percent.
9. An azeotrope-like composition according to claim 6 wherein the
concentrations of the ether and the organic solvent in the
azeotrope-like composition differ from the concentrations of such
components in the corresponding azeotrope by no more than five
percent.
10. An azeotrope-like composition according to claim 8 wherein the
azeotrope-like composition is an azeotrope.
Description
CROSS-REFERENCE TO RELATED APPLICATION
[0001] This application is a division of U.S. patent application
Ser. No. 09/429,508, filed on Oct. 28, 1999; which is a division of
U.S. patent application Ser. No. 09/130,236, filed on Aug. 6, 1998;
which is a division of U.S. patent application Ser. No. 08/649,743,
filed on May 15, 1998; which was a continuation-in-part of U.S.
patent application Ser. No. 08/442,399, filed on May 16, 1995, now
abandoned.
FIELD OF THE INVENTION
[0002] The invention relates to azeotropes and methods of using
azeotropes to clean substrates, deposit coatings and transfer
thermal energy.
BACKGROUND
[0003] Chlorofluorocarbons (CFCs) and hydrochlorofluorocarbons
(HCFCs) have been used in a wide variety of solvent applications
such as drying, cleaning (e.g., the removal of flux residues from
printed circuit boards), and vapor degreasing. Such materials have
also been used in refrigeration and heat transfer processes. While
these materials were initially believed to be environmentally
benign, they have now been linked to ozone depletion. According to
the Montreal Protocol and its attendant amendments, production and
use of CFCs must be discontinued (see, e.g., P. S. Zurer, "Looming
Ban on Production of CFCs, Halons Spurs Switch to Substitutes,"
Chemical & Engineering News, page 12, Nov. 15, 1993). The
characteristics sought in replacements, in addition to low ozone
depletion potential, typically have included boiling point ranges
suitable for a variety of solvent cleaning applications, low
flammability, and low toxicity. Solvent replacements also should
have the ability to dissolve both hydrocarbon-based and
fluorocarbon-based soils. Preferably, substitutes will also be low
in toxicity, have no flash points (as measured by ASTM D3278-89),
have acceptable stability for use in cleaning applications, and
have short atmospheric lifetimes and low global warming
potentials.
[0004] Certain perfluorinated (PFCs) and highly fluorinated
hydrofluorocarbon (HFCs) materials have also been evaluated as CFC
and HCFC replacements in solvent applications. While these
compounds are generally sufficiently chemically stable, nontoxic
and nonflammable to be used in solvent applications, PFCs tend to
persist in the atmosphere, and PFCs and HFCs are generally less
effective than CFCs and HCFCs for dissolving or dispersing
hydrocarbon materials. Also, mixtures of PFCs or HFCs with
hydrocarbons tend to be better solvents and dispersants for
hydrocarbons than PFCs or HFCs alone.
[0005] Many azeotropes possess properties that make them useful
solvents. For example, azeotropes have a constant boiling point,
which avoids boiling temperature drift during processing and use.
In addition, when a volume of an azeotrope is used as a solvent,
the properties of the solvent remain constant because the
composition of the solvent does not change. Azeotropes that are
used as solvents also can be recovered conveniently by
distillation.
[0006] There currently is a need for azeotrope or azeotrope-like
compositions that can replace CFC- and HCFC-containing solvents.
Preferably these compositions would be non-flammable, have good
solvent power, cause no damage to the ozone layer and have a
relatively short atmospheric lifetime so that they do not
significantly contribute to global warming.
SUMMARY
[0007] In one aspect, the invention provides azeotrope-like
compositions consisting essentially of a hydrofluorocarbon ether
and organic solvent. The hydrofluorocarbon ether is represented by
the general formula R.sub.fOC.sub.2H.sub.5, where R.sub.f is a
branched or straight chain perfluoroalkyl group having 4 carbon
atoms and the organic solvent is selected from the group consisting
of: straight chain, branched chain and cyclic alkanes containing 6
to 8 carbon atoms, esters containing 4 carbon atoms, ketones
containing 4 carbon atoms, siloxanes containing 6 carbon atoms,
cyclic and acyclic ethers containing 4 to 6 carbon atoms,
chlorinated alkanes containing 3 to 4 carbon atoms, chlorinated
alkenes having 2 to 3 carbon atoms, alcohols containing one to four
carbon atoms, fluorinated alcohols having 3 carbon atoms,
1-bromopropane and acetonitrile. While the concentrations of the
hydrofluorocarbon ether and organic solvent included in an
azeotrope-like composition may vary somewhat from the
concentrations found in the azeotrope formed between them and
remain a composition within the scope of this invention, the
boiling points of the azeotrope-like compositions will be
substantially the same as those of their corresponding azeotropes.
Preferably, the azeotrope-like compositions boil at ambient
pressure at temperatures that are within about 1.degree. C. of the
temperatures at which their corresponding azeotropes boil at the
same pressure.
[0008] In another aspect, the invention provides a method of
cleaning objects by contacting the object to be cleaned with one or
more of the azeotrope-like compositions of this invention or the
vapor of such compositions until undesirable contaminants or soils
on the object are dissolved, dispersed or displaced and rinsed
away.
[0009] In yet another aspect, the invention also provides a method
of coating substrates using the azeotrope-like compositions as
solvents or carriers for the coating material. The process
comprises the step of applying to at least a portion of at least
one surface of a substrate a liquid coating composition comprising:
(a) an azeotrope-like composition, and (b) at least one coating
material which is soluble or dispersible in the azeotrope-like
composition. Preferably, the process further comprises the step of
removing the azeotrope-like composition from the liquid coating
composition, for example, by evaporation.
[0010] The invention also provides coating compositions comprising
an azeotrope-like composition and coating material which are useful
in the aforementioned coating process.
[0011] In yet another aspect, the invention provides a method of
transferring thermal energy using the azeotrope-like compositions
as heat transfer fluids.
DETAILED DESCRIPTION
[0012] The azeotrope-like compositions are mixtures of
hydrofluorocarbon ether and organic solvent which, if fractionally
distilled, produce a distillate fraction that is an azeotrope of
the hydrofluorocarbon ether and organic solvent.
[0013] The azeotrope-like compositions boil at temperatures that
are essentially the same as the boiling points of their
corresponding azeotropes. Preferably, the boiling point of an
azeotrope-like composition at ambient pressure is within about
1.degree. C. of the boiling point of its azeotrope measured at the
same pressure. More preferably, the azeotrope-like compositions
will boil at temperatures that are within about 0.5.degree. C. of
the boiling points of their corresponding azeotropes measured at
the same pressure.
[0014] The concentrations of the hydrofluorocarbon ether and
organic solvent in a particular azeotrope-like composition may vary
substantially from the amounts contained in the composition's
corresponding azeotrope, and the magnitude of such permissible
variation depends upon the organic solvent used to make the
composition. Preferably, the concentrations of hydrofluorocarbon
ether and organic solvent in an azeotrope-like composition vary no
more than about ten percent from the concentrations of such
components contained in the azeotrope formed between them at
ambient pressure. More preferably, the concentrations are within
about five percent of those contained in the azeotrope. Most
preferably, the azeotropic composition contains essentially the
same concentrations of the ether and solvent as are contained in
the azeotrope formed between them at ambient pressure. Where the
concentrations of ether and organic solvent in an azeotrope-like
composition differ from the concentrations contained in the
corresponding azeotrope, the preferred compositions contain a
concentration of the ether that is in excess of the ether's
concentration in the azeotrope. Such compositions are likely to be
less flammable than azeotrope-like compositions in which the
organic solvent is present in a concentration that is in excess of
its concentration in the azeotrope. The most preferred compositions
will exhibit no significant change in the solvent power of the
composition over time.
[0015] The azeotrope-like compositions of this invention may also
contain, in addition to the hydrofluorocarbon ether and organic
solvent, small amounts of other compounds which do not interfere in
the formation of the azeotrope. For example, small amounts of
surfactants may be present in the azeotrope-like compositions of
the invention to improve the dispersibility or solubility of
materials, such as water, soils or coating materials (e.g.,
perfluoropolyether lubricants and fluoropolymers), in the
azeotrope-like composition. Azeotropes or azeotrope-like
compositions containing as a component 1,2-trans-dichloroethylene
preferably also contain about 0.25 to 1 weight percent of
nitromethane and about 0.05 to 0.4 weight percent of epoxy butane
to prevent degradation of the 1,2-trans-dichloroethylene. Most
preferably, such compositions will contain about 0.5 weight percent
nitromethane and 0.1 weight percent of the epoxy butane.
[0016] The characteristics of azeotropes are discussed in detail in
Merchant, U.S. Pat. No. 5,064,560 (see, in particular, col. 4,
lines 7-48).
[0017] The hydrofluorocarbon ether useful in the invention can be
represented by the following general formula:
[0018] R.sub.f--O--C.sub.2H.sub.5 (I)
[0019] where, in the above formula, R.sub.f is selected from the
group consisting of linear or branched perfluoroalkyl groups having
4 carbon atoms. The ether may be a mixture of ethers having linear
or branched perfluoroalkyl R.sub.f groups. For example,
perfluorobutyl ethyl ether containing about 95 perfluro-n-butyl
ethyl ether and 5 weight percent perfluoroisobutyl ethyl ether and
perfluorobutyl ethyl ether containing about 15 to 35 wieght percent
perfluoroisobutyl ethyl ether and 85 to 65 weight percent
perfluoro-n-butyl ethyl ether are also useful in this
invention.
[0020] The hydrofluorocarbon ether can be prepared by alkylation
of: CF.sub.3CF.sub.2CF.sub.2CF.sub.2O.sup.-,
CF.sub.3CF(CF.sub.3)CF.sub.2O.su- p.-,
C.sub.2F.sub.5C(CF.sub.3)FO.sup.-, C(CF.sub.3).sub.3O.sup.- and
mixtures thereof. The aforementioned perfluoroalkoxides can be
prepared by reaction of: CF.sub.3CF.sub.2CF.sub.2C(O)F,
CF.sub.3CF(CF.sub.3)C(O)F and C.sub.2F.sub.5C(O)CF.sub.3, and
mixtures thereof, with any suitable source of anhydrous fluoride
ion such as anhydrous alkali metal fluoride (e.g., potassium
fluoride or cesium fluoride) or anhydrous silver fluoride in an
anhydrous polar, aprotic solvent in the presence of a quaternary
ammonium compound such as "ADOGEN 464" available from the Aldrich
Chemical Company. The perfluoroalkoxide, C(CF.sub.3).sub.3O.sup.--
, can be prepared by reacting C(CF.sub.3).sub.3OH with a base such
as KOH in an anhydrous polar, aprotic solvent in the presence of a
quaternary ammonium compound. General preparative methods for the
ethers are also described in French Patent No. 2,287,432 and German
Patent No. 1,294,949.
[0021] Suitable alkylating agents for use in the preparation
include dialkyl sulfates (e.g., diethyl sulfate), alkyl halides
(e.g., ethyl iodide), alkyl p-toluenesulfonates (e.g., ethyl
p-toluenesulfonate), alkyl perfluoroalkanesulfonates (e.g., ethyl
perfluoromethanesulfonate), and the like. Suitable polar, aprotic
solvents include acyclic ethers such as diethyl ether, ethylene
glycol dimethyl ether, and diethylene glycol dimethyl ether;
carboxylic acid esters such as methyl formate, ethyl formate,
methyl acetate, diethyl carbonate, propylene carbonate, and
ethylene carbonate; alkyl nitriles such as acetonitrile; alkyl
amides such as N,N-dimethylformamide, N,N-diethylformamide, and
N-methylpyrrolidone; alkyl sulfoxides such as dimethyl sulfoxide;
alkyl sulfones such as dimethylsulfone, tetramethylene sulfone, and
other sulfolanes; oxazolidones such as N-methyl-2-oxazolidone; and
mixtures thereof.
[0022] Perfluorinated acyl fluorides (for use in preparing the
hydrofluorocarbon ether) can be prepared by electrochemical
fluorination (ECF) of the corresponding hydrocarbon carboxylic acid
(or a derivative thereof), using either anhydrous hydrogen fluoride
(Simons ECF) or KF.2HF (Phillips ECF) as the electrolyte.
Perfluorinated acyl fluorides and perfluorinated ketones can also
be prepared by dissociation of perfluorinated carboxylic acid
esters (which can be prepared from the corresponding hydrocarbon or
partially-fluorinated carboxylic acid esters by direct fluorination
with fluorine gas). Dissociation can be achieved by contacting the
perfluorinated ester with a source of fluoride ion under reacting
conditions (see the methods described in U.S. Pat. No. 3,900,372
(Childs) and U.S. Pat. No. 5,466,877 (Moore)), or by combining the
ester with at least one initiating reagent selected from the group
consisting of gaseous, non-hydroxylic nucleophiles; liquid,
non-hydroxylic nucleophiles; and mixtures of at least one
non-hydroxylic nucleophile (gaseous, liquid, or solid) and at least
one solvent which is inert to acylating agents.
[0023] Initiating reagents which can be employed in the
dissociation are those gaseous or liquid, non-hydroxylic
nucleophiles and mixtures of gaseous, liquid, or solid,
non-hydroxylic nucleophile(s) and solvent (hereinafter termed
"solvent mixtures") which are capable of nucleophilic reaction with
perfluorinated esters. The presence of small amounts of hydroxylic
nucleophiles can be tolerated. Suitable gaseous or liquid,
non-hydroxylic nucleophiles include dialkylamines, trialkylamines,
carboxamides, alkyl sulfoxides, amine oxides, oxazolidones,
pyridines, and the like, and mixtures thereof. Suitable
non-hydroxylic nucleophiles for use in solvent mixtures include
such gaseous or liquid, non-hydroxylic nucleophiles, as well as
solid, non-hydroxylic nucleophiles, e.g., fluoride, cyanide,
cyanate, iodide, chloride, bromide, acetate, mercaptide, alkoxide,
thiocyanate, azide, trimethylsilyl difluoride, bisulfite, and
bifluoride anions, which can be utilized in the form of alkali
metal, ammonium, alkyl-substituted ammonium (mono-, di-, tri-, or
tetra-substituted), or quaternary phosphonium salts, and mixtures
thereof. Such salts are in general commercially available but, if
desired, can be prepared by known methods, e.g., those described by
M. C. Sneed and R. C. Brasted in Comprehensive Inorganic Chemistry,
Volume Six (The Alkali Metals), pages 61-64, D. Van Nostrand
Company, Inc., New York (1957), and by H. Kobler et al. in Justus
Liebigs Ann. Chem., 1978, 1937. 1,4-diazabicyclo[2.2.2] octane and
the like are also suitable solid nucleophiles.
[0024] The hydrofluorocarbon ethers used to prepare the
azeotrope-like compositions of this invention do not deplete the
ozone in the earth's atmosphere and have surprisingly short
atmospheric lifetimes thereby minimizing their impact on global
warming. Reported in Table 1, is an atmospheric lifetime for the
hydrofluorocarbon ether which was calculated using the technique
described in Y. Tang, Atmospheric Fate of Various Fluorocarbons, M.
S. Thesis, Massachusetts Institute of Technology (1993). The
results of this calculation are presented in Table 1 under the
heading "Atmospheric Lifetime (years)". The atmospheric lifetimes
of the hydrofluorocarbon ether and its corresponding
hydrofluorocarbon alkane were also calculated using a correlation
developed between the highest occupied molecular orbital energy and
the known atmospheric lifetimes of hydrofluorocarbons and
hydrofluorocarbon ethers that is similar to a correlation described
by Cooper et al. in Atmos. Environ. 26A, 7, 1331(1992). These
values are reported in Table 1 under the heading "Estimated
Atmospheric Lifetime." The global warming potential of the
hydrofluorocarbon ether was calculated using the equation described
in the Intergovernmental Panel's Climate Change: The IPCC
Scientific Assessment, Cambridge University Press (1990). The
results of the calculation are presented in Table 1 under the
heading "Global Warming Potential". It is apparent from the data in
Table 1 that the hydrofluorocarbon ether has a relatively short
estimated atmospheric lifetime and a relatively small global
warming potential. Surprisingly, the hydrofluorocarbon ether also
has a significantly shorter estimated atmospheric lifetime than its
corresponding hydrofluorocarbon alkane.
1TABLE 1 Estimated Atmospheric Atmospheric Global Warming Lifetime
Lifetime Potential Compound (years) (years) (100 year ITH)
C.sub.4F.sub.9--C.sub.2H.sub.5 2.0 -- -- C.sub.4F.sub.9--O--C.sub.-
2H.sub.5 0.5 1.2 70
[0025] Typical organic solvents useful in this invention include
straight chain, branched chain and cyclic alkanes containing 6 to 8
carbon atoms (e.g., hexane, heptane, cyclohexane,
methylcyclohexane, heptane and isooctane); esters containing 4
carbon atoms (e.g., methyl propionate and ethyl acetate); ketones
containing 4 carbon atoms (e.g., methyl ethyl ketone); siloxanes
containing 6 carbon atoms (e.g., hexamethyldisiloxane); cyclic and
acyclic ethers containing 4 to 6 carbon atoms (e.g., t-amyl methyl
ether, 1,4-dioxane, tetrahydrofuran, tetrahydropyran and
1,2-dimethoxyethane); chlorinated alkanes containing 3 to 4 carbon
atoms (e.g., 1,2-dichloropropane, 2,2-dichloropropane and
1-chlorobutane); chlorinated alkenes having 2 to 3 carbon atoms
(e.g., trans-1,2-dichloroethylene and 2,3-dichloro-1-propene);
alcohols containing one to four carbon atoms (e.g., methanol,
ethanol, 2-propanol, 1-propanol and t-butanol); fluorinated
alcohols having 3 carbon atoms (e.g., pentafluoro-1-propanol and
hexafluoro-2-propanol); 1-bromopropane; and acetonitrile.
[0026] Preferably, the azeotrope-like compositions are homogeneous.
That is, they form a single phase under ambient conditions, i.e.,
at room temperature and atmospheric pressure.
[0027] The azeotrope-like compositions are prepared by mixing the
desired amounts of hydrofluorocarbon ether, organic solvent and any
other minor components such as surfactants together using
conventional mixing means.
[0028] The cleaning process of the invention can be carried out by
contacting a contaminated substrate with one of the azeotrope-like
compositions of this invention until the contaminants on the
substrate are dissolved, dispersed or displaced in or by the
azeotrope-like composition and then removing (for example by
rinsing the substrate with fresh, uncontaminated azeotrope-like
composition or by removing a substrate immersed in an
azeotrope-like composition from the bath and permitting the
contaminated azeotrope-like composition to flow off of the
substrate) the azeotrope-like composition containing the dissolved,
dispersed or displaced contaminant from the substrate. The
azeotrope-like composition can be used in either the vapor or the
liquid state (or both), and any of the known techniques for
"contacting" a substrate can be utilized. For example, the liquid
azeotrope-like composition can be sprayed or brushed onto the
substrate, the vaporous azeotrope-like composition can be blown
across the substrate, or the substrate can be immersed in either a
vaporous or a liquid azeotrope-like composition. Elevated
temperatures, ultrasonic energy, and/or agitation can be used to
facilitate the cleaning. Various different solvent cleaning
techniques are described by B. N. Ellis in Cleaning and
Contamination of Electronics Components and Assemblies,
Electrochemical Publications Limited, Ayr, Scotland, pages 182-94
(1986).
[0029] Both organic and inorganic substrates can be cleaned by the
process of the invention. Representative examples of the substrates
include metals; ceramics; glass; polymers such as: polycarbonate,
polystyrene and acrylonitrile-butadiene-styrene copolymer; natural
fibers (and fabrics derived therefrom) such as: cotton, silk,
linen, wool, ramie; fur; leather and suede; synthetic fibers (and
fabrics derived therefrom) such as: polyester, rayon, acrylics,
nylon, polyolefin, acetates, triacetates and blends thereof;
fabrics comprising a blend of natural and synthetic fibers; and
composites of the foregoing materials. The process is especially
useful in the precision cleaning of electronic components (e.g.,
circuit boards), optical or magnetic media, and medical devices and
medical articles such as syringes, surgical equipment, implantable
devices and prosthesis.
[0030] The cleaning process of the invention can be used to
dissolve or remove most contaminants from the surface of a
substrate. For example, materials such as light hydrocarbon
contaminants; higher molecular weight hydrocarbon contaminants such
as mineral oils, greases, cutting and stamping oils and waxes;
fluorocarbon contaminants such as perfluoropolyethers,
bromotrifluoroethylene oligomers (gyroscope fluids), and
chiorotrifluoroethylene oligomers (hydraulic fluids, lubricants);
silicone oils and greases; solder fluxes; particulates; and other
contaminants encountered in precision, electronic, metal, and
medical device cleaning can be removed. The process is particularly
useful for the removal of hydrocarbon contaminants (especially,
light hydrocarbon oils), fluorocarbon contaminants, particulates,
and water (as described in the next paragraph).
[0031] To displace or remove water from substrate surfaces, the
cleaning process of the invention can be carried out as described
in U.S. Pat. No. 5,125,978 (Flynn et al.) by contacting the surface
of an article with an azeotrope-like composition which preferably
contains a non-ionic fluoroaliphatic surface active agent. The wet
article is immersed in the liquid azeotrope-like composition and
agitated therein, the displaced water is separated from the
azeotrope-like composition, and the resulting water-free article is
removed from the liquid azeotrope-like composition. Further
description of the process and the articles which can be treated
are found in U.S. Pat. No. 5,125,978 and the process can also be
carried out as described in U.S. Pat. No. 3,903,012
(Brandreth).
[0032] The azeotrope-like compositions can also be used in coating
deposition applications, where the azeotrope-like composition
functions as a carrier for a coating material to enable deposition
of the material on the surface of a substrate. The invention thus
also provides a coating composition comprising the azeotrope-like
composition and a process for depositing a coating on a substrate
surface using the azeotrope-like composition. The process comprises
the step of applying to at least a portion of at least one surface
of a substrate a coating of a liquid coating composition comprising
(a) an azeotrope-like composition, and (b) at least one coating
material which is soluble or dispersible in the azeotrope-like
composition. The coating composition can further comprise one or
more additives (e.g., surfactants, coloring agents, stabilizers,
anti-oxidants, flame retardants, and the like). Preferably, the
process further comprises the step of removing the azeotrope-like
composition from the deposited coating by, e.g., allowing
evaporation (which can be aided by the application of, e.g., heat
or vacuum).
[0033] The coating materials which can be deposited by the process
include pigments, lubricants, stabilizers, adhesives,
anti-oxidants, dyes, polymers, pharmaceuticals, release agents,
inorganic oxides, and the like, and combinations thereof. Preferred
materials include perfluoropolyether, hydrocarbon, and silicone
lubricants; amorphous copolymers of tetrafluoroethylene;
polytetrafluoroethylene; and combinations thereof. Representative
examples of materials suitable for use in the process include
titanium dioxide, iron oxides, magnesium oxide,
perfluoropolyethers, polysiloxanes, stearic acid, acrylic
adhesives, polytetrafluoroethylene, amorphous copolymers of
tetrafluoroethylene, and combinations thereof. Any of the
substrates described above (for cleaning applications) can be
coated via the process of the invention. The process can be
particularly useful for coating magnetic hard disks or electrical
connectors with perfluoropolyether lubricants or medical devices
with silicone lubricants.
[0034] To form a coating composition, the components of the
composition (i.e., the azeotrope-like composition, the coating
material(s), and any additive(s) utilized) can be combined by any
conventional mixing technique used for dissolving, dispersing, or
emulsifying coating materials, e.g., by mechanical agitation,
ultrasonic agitation, manual agitation, and the like. The
azeotrope-like composition and the coating material(s) can be
combined in any ratio depending upon the desired thickness of the
coating, but the coating material(s) preferably constitute from
about 0.1 to about 10 weight percent of the coating composition for
most coating applications.
[0035] The deposition process of the invention can be carried out
by applying the coating composition to a substrate by any
conventional technique. For example, the composition can be brushed
or sprayed (e.g., as an aerosol) onto the substrate, or the
substrate can be spin-coated. Preferably, the substrate is coated
by immersion in the composition. hmmersion can be carried out at
any suitable temperature and can be maintained for any convenient
length of time. If the substrate is a tubing, such as a catheter,
and it is desired to ensure that the composition coats the lumen
wall, it may be advantageous to draw the composition into the lumen
by the application of reduced pressure.
[0036] After a coating is applied to a substrate, the
azeotrope-like composition can be removed from the deposited
coating by evaporation. If desired, the rate of evaporation can be
accelerated by application of reduced pressure or mild heat. The
coating can be of any convenient thickness, and, in practice, the
thickness will be determined by such factors as the viscosity of
the coating material, the temperature at which the coating is
applied, and the rate of withdrawal (if immersion is utilized).
[0037] Objects and advantages of this invention are further
illustrated by the following examples, but the particular materials
and amounts thereof recited in these examples, as well as other
conditions and details, should not be construed to unduly limit
this invention.
EXAMPLES
EXAMPLES 1-2
[0038] The preparation and identification of the azeotrope-like
compositions of this invention are described in the following
Examples.
[0039] Preparation of Ether "A"
[0040] Ether "A", used to prepare the azeotrope-like compositions
and azeotropes of the following Examples was prepared as
follows.
[0041] A 20 gallon Hastalloy C. reactor, equipped with a stirrer
and a cooling system, was charged with spray-dried potassium
fluoride (7.0 kg, 120.3 mole). The reactor was sealed, and the
pressure inside the reactor was reduced to less than 100 torr.
Anhydrous dimethyl formamide (22.5 kg) was then added to the
reactor, and the reactor was cooled to below 0.degree. C. with
constant agitation. Heptafluorobutyryl fluoride (22.5 kg of 58%
purity, 60.6 mole) was added to the reactor contents. When the
temperature of the reactor reached -20.degree. C., diethyl sulfate
(18.6 kg, 120.8 mole) was added to the reactor over a period of
approximately two hours. The resulting mixture was then held for 16
hours with continued agitation, was raised to 50.degree. C. for an
additional four hours to facilitate complete reaction, and was
cooled to 20.degree. C. Then, volatile material (primarily
perfluorooxacyclopentane present in the starting heptafluorobutyryl
fluoride) was vented from the reactor over a three-hour period. The
reactor was then resealed, and water (6.0 kg) was added slowly to
the reactor. After the exothermic reaction of the water with
unreacted perfluorobutyryl fluoride subsided, the reactor was
cooled to 25.degree. C., and the reactor contents were stirred for
30 minutes. The reactor pressure was carefully vented, and the
lower organic phase of the resulting product was removed to afford
17.3 kg of material which was 73% C.sub.4F.sub.9OC.sub.2H.sub.5.
Analysis revealed the product to be approximately 95 wt. %
perfluoro-n-butyl ethyl ether and 5 wt. % perfluoro-isobutyl ethyl
ether. The product identity was confirmed by GCMS and by .sup.1H,
.sup.19F NMR and IR and boiled at 76.2.degree. C. at 739.6
torr.
[0042] Preparation of Ether "B"
[0043] Into a 100 gallon Hastalloy C. reactor with a stirrer and a
cooling system was charged 21.8 kg (375.2 mole) of spray-dried
potassium fluoride. The reactor was sealed and the pressure inside
the reactor was reduced to less than 100 torr. Anhydrous diglyme
(139.4 kg), triethylamine (5.44 kg, 53.9 mole), ADOGEN 464.TM.
(1.54 kg, 3.33 mole), diethyl sulfate (62.6 kg, 406 mole) were
added to the reactor followed by perfluoroisobutyryl fluoride (86.3
kg of 80% acid fluoride content, 319.6 mole). The resulting mixture
was then held at 60.degree. C. for 18 hours with continued
agitation, raised to 85.degree. C., then water (20 kg) and 45%
aqueous potassium hydroxide (25.4 kg, 203.9 mole) was added to the
reaction mixture. After stirring for approximately 30 minutes, the
reactor was cooled to 43.degree. C. and an additional 136.2 kg of
water was added, followed by 48% aqueous hydrogen fluoride (4.08
kg, 98.1 mole) to obtain a final pH of 7 to 8. The product was
separated from the reaction mixture by distillation to obtain 74.0
kg of crude product which was further purified by a second
distillation. The process provided a product that was approximately
82 wt. % perfluoro-isobutyl ethyl ether and 18 wt. %
perfluoro-n-butyl ethyl ether, which boiled at about 75.0.degree.
C. at 739.3 torr. The product identity was confirmed by CGMS,
.sup.1H and .sup.19FNMR and IR.
EXAMPLES 3-30
[0044] Preparation and Identification of Azeotrope Compositions:
Ebulliometer Method
[0045] The azeotropes of this invention were initially identified
by screening mixtures of hydrofluorocarbon ether and various
organic solvents using an ebulliometer or boiling point apparatus
(specifically a Model MBP-100 available from Cal-Glass for
Research, Inc., Costa Mesa Calif.). The lower boiling component of
the test mixtures (typically an amount of 25 to 30 mLs) was added
to the boiling point apparatus, heated and allowed to equilibrate
to its boiling point (typically about 30 minutes). After
equilibration, the boiling point was recorded, a 1.0 mL aliquot of
the higher boiling component was added to the apparatus and the
resulting mixture was allowed to equilibrate for about 30 minutes
at which time the boiling point was recorded. The test continued
basically as described above, with additions to the test mixture of
1.0 mL of the higher boiling point component every 30 minutes until
15 to 20 mLs of the higher boiling point component had been added.
The presence of an azeotrope was noted when the test mixture
exhibited a lower boiling point than the boiling point of the
lowest boiling component of the test mixture. The compositions
corresponding to the aforementioned boiling points were determined.
The composition (volume %) of the organic solvent in the
composition was then plotted as a function of boiling point. The
azeotrope-like compositions boiling at temperatures within about
1.degree. C. of the respective azeotrope boiling point were then
identified from the plot and this compositional data (on a weight %
basis) as well as the boiling point range corresponding to the
compositions (expressed as the difference between the composition
boiling point and the azeotrope boiling point) are presented in
Table 2.
[0046] The organic solvents used to prepare the azeotrope-like
compositions described in these Examples were purchased
commercially from the Aldrich Chemical and Fluka Chemical
Companies.
2TABLE 2 Boiling Conc. Conc. Temp. Organic Solvent: Solvent Ether
Range Pressure Ex. Ether (wt %) (wt %) (.degree. C.) (torr) 3
Hexane: Ether A 27.8-75.5 82.2-24.5 61.8 723 4 Heptane: Ether A
2.5-21.9 97.5-78.1 73.3 711.4 5 Isooctane: 1.5-17.2 98.5-82.8 74.9
732.6 Ether A 6 Cyclohexane: 12.0-47.1 88.0-52.9 66.7 730.5 Ether A
7 Methylcyclo- 2.2-26.4 97.8-73.6 73.3 733.2 hexane: Ether A 8
t-Amyl methyl 2.2-35.0 97.8-65.0 74.5 736.6 ether: Ether A 9
Tetrahydrofuran: 26.7-80.6 73.3-19.4 61.4 734.2 Ether A 10
Tetrahyronyran: 2.5-30.9 97.5-69.18 73.8 731.9 Ether A 11
1,4-Dioxane: 1.5-17.8 98.5-82.2 74.7 735.7 Ether A 12
1,2-Dimethoxy- 4.4-42.5 95.6-57.5 73.7 733.1 ethane: Ether A 13
Ethyl Acetae: 11.4-66.7 88.6-33.3 71.0 740.1 Ether A 14 Methyl
11.6-62.3 88.4-37.8 71.3 737.4 Propionate: Ether A 15 Methyl Ethyl
9.0-34.2 91.0-65.8 71.0 729.6 Ketone: Ether A 16 Methanol: 6.4-64.9
93.6-35.1 52.6 720.5 Ether A 17 Ethanol: Ether A 5.7-45.2 94.3-54.8
61.7 722.2 18 2-Pronanol: 6.3-19.8 93.7-80.2 63.7 729.2 Ether A 19
1-Propanol: 4.7-30.6 95.3-69.4 69.8 732.6 Ether A 20 t-Butanol:
7.0-38.9 93.0-61.1 67.3 735.6 Ether A 21 Pentafluoro-1- 15.7-54.3
84.3-45.7 67.9 735.2 Pronanol: Ether 22 Hexafluoro-2- 62.6-98.2
37.4-1.8 56.6 735.7 Pronanol: Ether 23 Hexamethyl 2.2-15.8
97.8-84.2 75.1 738.1 Disiloxane: Ether 24 1-Chlorobutane: 11.3-61.5
88.7-38.5 69.1 735.7 Ether A 25 1,2-Dichloro- 6.4-29.4 93.6-70.6
73.8 737.6 propane: Ether A 26 2,2-Dichloro- 23.6-60.0* 76.4-40.0*
66.4 730.8 propane: Ether A 27 trans-1.2- 53.9-95.5 46.1-4.5 43.8
728.7 28 2,3-Dichloro-1- 5.1-32.1 94.9-67.9 72.8 735.2 Propene:
Ether 29 1-Bromopropane: 22.0-79.1 78.0-20.9 63.2 725 Ether A 30
Acetonitrile: 6.4-55.0 93.6-45.0 65.4 739 Ether A *Estimated value
based upon symmetrical Boiling Point Curve.
EXAMPLES 31-72
[0047] Preparation and Characterization of the Azeotrope-like
Compositions by the Distillation Method
[0048] Mixtures of hydrofluorocarbon ether and organic solvents
which exhibited a ng point depression in the Ebulliometer Method
were evaluated again to more sely determine the composition of the
azeotrope. Mixtures of the hydrofluorocarbon the organic solvent of
interest were prepared and distilled in a concentric tube llation
column (Model 9333 from Ace Glass, Vineland N.J.). The distillation
allowed to equilibrate at total reflux for at least 60 minutes. In
each distillation, six successive distillate samples, each
approximately 5 percent by volume of the total liquid charge, were
taken while operating the column at a liquid reflux ratio of 20 to
1. The composition of the distillate samples were then analyzed
using an HP-5890 Series II Plus Gas Chromatograph with a 30 m HP-5
(cross-linked 5% phenyl methyl silicone gum stationary phase,
available from Hewlett Packard Co.), NUKOL (available from Supelco
Inc.), or STABILWAX DA (available from Altech Associates) capillary
column and a flame ionization detector. The boiling points of the
distillate were measured using a thermocouple which was accurate to
about 1.degree. C. The compositional data, boiling points and
ambient pressures at which the boiling points were measured are
reported in Table 3.
[0049] The azeotropes were also tested for flammability by placing
a small aliquot of the azeotrope in an open aluminum dish and
holding a flame source in contact with the vapor of the azeotrope
above the dish. Flame propagation across the vapor indicated that
the azeotrope was flammable. The flammability data is presented in
Table 3 under the heading "Flammability".
3TABLE 3 Ether Organic Conc. Solvent Boiling Ambient Organic
Solvent: (wt. Conc. Point Pressure Flamm- Ex. Ether %) (wt %)
(.degree. C.) (torr) able 31 Hexane: Ether A 59.7 40.3 61.5 734.1
Yes 32 Heptane: Ether A 92.5 7.5 73.2 737.7 Yes 33 Heptane: Ether B
89.7 10.3 72.8 737.7 Yes 34 Isooctane: 91.0 9.0 74.0 735.2 Yes
Ether A 35 Isooctane: 90.9 9.1 73.9 738.4 Yes Ether B 36
Cyclohexane: 66.5 33.5 65.8 727.7 Yes Ether A 37 Cyclohexane: 74.5
25.5 65.7 731.1 Yes Ether B 38 Methylcyclo- 88.6 11.4 73.3 737.7
Yes hexane: Ether A 39 Methylcyclo 90.6 9.4 73.0 739.1 Yes hexane:
Ether B 40 t-Amyl methyl 85.4 14.6 73.7 737.7 Yes Ether: Ether A 41
t-Amyl methyl 85.2 14.8 72.9 729.4 Yes Ether:Ether B 42
Tetrahydrofuran: 55.4 44.6 62.3 741.0 Yes Ether A 43
Tetrahydrofuran: 52.6 47.4 61.6 727.3 Yes Ether B 44
Tetrahydropyran: 83.3 16.7 76.7 742.1 Yes Ether A 45 1,4-Dioxane:
91.8 8.2 76.0 740.9 Yes Ether A 46 1,2-Dimethoxy- 82.2 17.8 73.0
736.6 Yes ethane: Ether A 47 1,2-Dimethoxy- 81.9 18.1 73.2 740.9
Yes ethane: Ether B 48 Ethyl Acetate: 68.2 31.8 69.8 736.5 Yes
Ether A 49 Ethyl Acetate: 69.3 30.7 69.7 729.4 Yes Ether B 50
Methyl Prop- 73.0 27.0 70.8 736.6 Yes ionate: Ether A 51 Methyl
Ethyl 86.2 13.8 70.2 734.0 Yes Ketone: Ether A 52 Methyl Ethyl 78.9
21.1 70.0 733.3 Yes Ketone: Ether B 53 Methanol: 84.5 15.5 52.3
733.2 Yes Ether B 54 Ethanol: Ether B 88.0 12.0 61.3 734.1 Yes 55
2-Propanol: 87.1 12.9 64.9 734.5 Yes Ether B 56 t-Butanol: 83.7
16.3 67.3 744.2 Yes Ether B 57 Pentafluoro-1- 75.3 24.7 66.6 730.5
Yes Propanol: Ether B 58 Hexafluoro-2- 34.7 65.3 56.0 731.2 No
Propanol: Ether B 59 Hexamethyl 90.6 9.4 74.2 734.0 Yes Disiloxane:
Ether A 60 Hexamethyl 89.6 10.4 74.0 743.8 Yes Disiloxane: Ether B
61 1-Chlorobutane: 74.2 25.8 67.9 730.1 Yes Ether A 62
1-Chlorobutane: 71.9 28.1 67.7 727.3 Yes Ether B 63 1,2-Dichloro-
83.6 16.4 73.0 740.3 No propane: Ether A 64 1,2-Dichioro- 86.8 13.2
72.9 745.8 No propane: Ether B 65 2,2-Dichloro- 54.9 45.1 67.1
738.7 Yes propane: Ether A 66 2,2-Dichloro- 67.7 38.3 65.6 743.8
Yes propane: Ether B 67 trans-1,2- 37.3 62.7 44.5 740.6 No
Dichloroethylene Ether A 68 trans-1,2- 31.2 68.8 44.8 737.5 No
Dichloroethylene: Ether B 69 2,3-Dichloro-1- 81.6 18.4 72.8 739.1
Yes Propene: Ether A 70 1-Bromopropane: 55.0 44.0 62.1 733.5 Yes
Ether B 71 Acetonitrile: 83.0 17.0 65.2 736.2 Yes Ether A 72
Acetonitrile: 85.4 14.6 63.9 733.7 Yes Ether B
EXAMPLES 73-114
[0050] A number of the azeotrope-like compositions were tested for
their ability to dissolve hydrocarbons of increasing molecular
weight according to the procedure described in U.S. Pat. No.
5,275,669 (Van Der Puy et al.), the description of which is
incorporated herein by reference. The data shown in Table 4 was
obtained by determining the largest normal hydrocarbon alkane which
was soluble in a particular azeotrope-like composition at a level
of 50 volume percent. The hydrocarbon solubilities in the
azeotrope-like compositions were measured at both room temperature
and the boiling points of the azeotrope-like compositions. The data
is reported in Table 4. The numbers in Table 4 under the headings
"Hydrocarbon @ RT" and "Hydrocarbon @ BP" correspond to the number
of carbon atoms in the largest hydrocarbon n-alkane that was
soluble in each of the azeotrope-like compositions at room
temperature and the boiling point of the azeotrope-like
composition, respectively.
[0051] The data in Table 4 shows that hydrocarbon alkanes are very
soluble in the azeotrope-like compositions of this invention, and
so the azeotrope-like compositions are excellent solvents for the
cleaning process of this invention. These compositions will also be
effective as solvents for depositing hydrocarbon coatings, e.g.,
coatings of lubricant, onto substrate surfaces.
4TABLE 4 Hydrocarbon Hydrocarbon Ether Organic @ RT (# @ BP Boiling
Organic Solvent: Conc. Solvent carbon (# carbon Point Pressure Ex.
Ether (wt%) Conc. (wt%) atoms) atoms) (.degree. C.) (torr) 73
Hexane: Ether A 59.7 40.3 21 24 62.3 725.1 74 Heptane: Ether 92.5
7.5 13 18 74.3 728.6 A 75 Heptane: Ether 89.7 10.3 13 20 73.7 738.9
B 76 Isooctane: Ether 91.0 9.0 13 19 75.2 728.6 A 77 Isooctane:
Ether 90.9 9.1 13 20 74.3 736.1 B 78 Cyclohexane: 66.5 33.5 15
>24 66.9 724.2 Ether A 79 Cyclohexane: 74.5 25.5 14 24-28 66.6
735.4 Ether B 80 Methylcyclohexane: 88.6 11.4 13 19 74.3 738.7
Ether A 81 Methylcyclohexane: 90.6 9.4 13 19 74.5 736.7 Ether B 82
t-Amylmethyl 85.4 14.6 15 21 74.4 738.4 Ether: Ether A 83
t-Amylmethyl 85.2 14.8 15 22 74 735.2 Ether: Ether B 84
Tetrahydrofuran: 55.4 44.6 21 >24 62.8 731.8 Ether A 85
Tetrahydrofuran: 52.6 47.4 20 28-32 61.9 727.3 Ether B 86
Tetrahyclropyran 83.3 17.7 15 23 72.4 724.8 Ether A 87 1,4-Dioxane:
91.8 8.2 14 19 73.7 725.8 Ether A 88 1,2- 82.2 17.8 16 22 74.3
728.6 Dimethoxyethane: Ether A 89 1,2- 81.9 18.1 16 23 73.7 736.8
Dimethoxyethane: Ether B 90 Ethyl Acetate: 68.2 31.8 19 >24 70.7
730.6 Ether A 91 Ethyl Acetate: 69.3 30.7 18 24 to 28 70.7 739.0
Ether B 92 Methyl 73.0 27.0 18 >24 71.4 732.5 Propionate: Ether
A 93 Methyl Ethyl 86.2 13.8 15 >17 71.7 732.5 Ketone: Ether A 94
Methyl Ethyl 78.9 21.2 17 24 to 28 70.8 734.2 Ketone: Ether B 95
Methanol: Ether 84.5 15.5 11 14 52.8 730.6 B 96 Ethanol. Ether B
88.0 12.0 13 20 65.3 730.9 97 2-Propanol: 87.1 12.9 14 20 65.3
730.9 Ether B 98 t-Butanol: Ether 83.7 16.3 15 22 67.5 733.8 B 99
Pentafluoro-1- 75.3 24.7 9 13 67.6 733.8 Propanol: Ether B 100
Hexafluoro-2- 34.7 65.3 5 8 56.9 733.6 Propanol: Ether B 101
Hexamethyl 90.6 9.4 13 18 75.7 731.9 Disiloxane: Ether A 102
Hexamethyl 89.6 10.4 13 20 75.1 738.5 Disiloxane: Ether B 103
1-Chlorobutane: 74.2 25.8 18 >24 69.2 729.8 Ether A 104
1-Chlorobutane: 71.9 28.1 18 24 to 28 68.9 740.3 Ether B 105 1,2-
83.6 16.4 15 19 73.9 729.6 Dichloropropane Ether A 106 1,2- 86.8
13.2 14 20 72.9 731.9 Dichloropropane Ether B 107 2,2- 54.9 45.1 21
>24 65.7 729.4 Dichloropropane Ether A 108 2,2- 61.7 38.3 19
>28 65.3 739.6 Dichloropropane Ether B 109 trans-1,2- 37.3 62.7
22 >24 45.7 730.6 Dichloroethylene: Ether A 110 trans-1,2- 31.2
68.8 22 >28 45.2 730.5 Dichloroethylene: Ether B 111
2,3-Dichloro-1- 81.6 18.4 14 21 73.0 724.6 propene: Ether A 112 1-
56.0 44.0 19 24 to 28 62.9 730.0 Bromopropane: Ether B 113
Acetonitrile: 83.0 17.0 9 14 63.8 726.7 Ether A 114 Acetonitrile:
85.4 14.6 10 16 64.2 740.5 Ether B
EXAMPLE 115
[0052] The following Example illustrates that azeotrope-like
compositions can be used for dry cleaning fabrics.
[0053] A cleaning solution was prepared using an azeotrope-like
composition prepared from 37 weight percent Ether A and 63 weight
percent trans-1,2-dichloroethylene, and 1 volume percent of SECAPUR
PERFECT, a dry cleaning detergent available from Buesing and Fasch
GmbH of Oldenburg, Germany, and 0.1 volume percent water.
[0054] 15.times.15 cm swatches of a 70/30 percent polyester/wool
blend fabric and a 65/35 percent polyester/cotton blend twill
fabric were stained by applying, at three different sites on each
fabric swatch, three drops of corn oil, three drops of mineral oil
and three drops of dirty motor oil. The oil stains were then driven
into the fabric swatches by placing a 11.2 kg (5 pound) weight over
the swatches for 1 minute and the stains were then allowed to
further set for about 1 hour.
[0055] After the stains were set, the fabric swatches were cleaned
in the cleaning solution by agitating the swatches in about 500 mL
of cleaning solution for about 15 minutes. The swatches were then
removed, air dried and evaluated for any remaining stain using a
Chromometer.TM. CR-300 from Minolta Camera Company of Japan. The
.DELTA.E measurements for the cleaned fabrics were only slightly
greater than the unstained fabric or about 0.0 to 0.32 thus
illustrating that the cleaning solution made of the azeotrope-like
composition is an effective dry cleaning agent.
EXAMPLE 116
[0056] Ether B can also be made according to the following
procedures. Perfluoroisobutyryl fluoride, was prepared by
electrochemically fluorinating isobutyric anhydride (>99% pure)
in a Simons ECF cell of the type described in U.S. Pat. No.
2,713,593 (Brice et al. ) and in Preparation, Properties and
Industrial Applications of Organofluorine Compounds, R. E. Banks,
ed., John Wiley and sons, New York, 1982, pp. 19 to 43 to form a
perfluoroisobutyryl fluoride product containing approximately 56
wt. % perfluoroisobutyryl fluoride, 24 wt. % perfluoro-n-butyryl
fluoride and 20 wt. % percent perfluorinated, inert products.
[0057] A 600 mL stainless steel Parr pressure reactor was charged
with spray-dried potassium fluoride (1.10 mole equivalents relative
to perfluoroisobutyryl fluoride), anhydrous diglyme (1.0 weight
equivalent relative to perfluoroisobutyryl fluoride), Adogen.TM.464
(0.0065 mole equivalents relative to perfluoroisobutyryl fluoride,
purified by dissolving in diglyme, followed by fractional
distillation to remove isopropanol) and tribenzylamine (0.03 mole
equivalents relative to perfluoroisobutyryl fluoride). The vessel
was sealed, cooled with dry ice, charged with perfluoroisobutyryl
fluoride then allowed to warm to room temperature with stirring.
Diethyl sulfate (1.30 mole equivalents relative to
perfluoroisobutyryl fluoride) was then charged to the reactor under
pressure and the reactor held at 25.degree. C. for 30 minutes,
heated to 40.degree. C. for an additional two hours, then heated at
60.degree. C. for an additional 18 hours.
[0058] The reactor was then charged with aqueous potassium
hydroxide (60 g of 45 wt % and 50 g water) to neutralize any
unreacted diethyl sulfate and stirred for 30 minutes at 85.degree.
C. until the solution pH was greater than 13. Excess aqueous
hydrogen fluoride (48 wt % concentration) was added to the solution
until the pH was 7-8, and the product 1-ethoxy nonafluoroisobutane
fraction was distilled from the reaction mixture. The distillate
was washed with water to remove small amounts of ethanol, then
fractionally distilled to further purify the desired product.
[0059] Various modifications and alterations of this invention will
be apparent to those skilled in the art without departing from the
scope and spirit of this invention.
* * * * *