Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
CA 02845415 2015-04-20
SOLVENT FORMULATIONS COMPRISING AN ACETIC ACID ALKYL ESTER
AND A CARBONATE ESTER, AND OPTIONALLY
A BENZENE-CONTAINING COMPOUND
FII41.41) OF INVENTION
[0001j The present disclosure relates generally to solvent
formulations. More
specifically, the present disclosure relates to solvent compositions that may
be used to
replace methyl ethyl ketone and/or acetone.
BACKCROUND OF THE INVENTION
[0002] Organic solvents, such as methyl ethyl ketone (MEK),ucetone,
xylene and
toluene, and other hydrocarbons or oxygenated solvents are used in a number of
applications. Many of these solvents have toxic and/or environmentally
deleterious
properties. For example, human and animal studies indicate that exposure to
these
chemicals can have detriinental effects on the central nervous system, as well
as on the
hepatic and renal systems. MEK and related ketones are considered carcinogenic
and
developmental toxins, can produce central nervous system effects, and show
hepatic and
renal toxicity (Raymond, 1991, Selywetz, 1995, Spencer 1976, Altenkirch,
1978); and
acetone has been shown to enhance the toxicity of other chemicals through
synergistic
toxic effects (Hewitt 1983, Adams 1986, Freeman 1985). "Hazardous air
pollutants" (or
"HAPs"), also known as toxic air pollutants or air toxies, may cause cancer or
other
serious health effects, such as reproductive effects or birth defects, or
adverse
environmental and ecological effects. HAPs are regulated in many countries.
[0003] Furthermore, many organic solvents are highly volatile and, of the
total
amount released to the environment, a significant percentage eventually enters
the
atmosphere. As such, these solvents have been designated volatile organic
compounds
(or "VOCs") and are regulated. Compounds or solvents having lower volatility
have
been classified as VOC-exempt by many countries.
[0004.1 Methyl acetate (MA) is a carboxylate ester having the formula
CH3COOCH3.
lt is a flammable liquid with a solubility of 25% in water at room temperature
and is not
stable in the presence of strong aqueous bases or aqueous acids. MA is VOC
exempt.
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CA 02845415 2014-03-07
SUMMARY OF THE INVENTION
[0005] The present disclosure provides, in part, a solvent
composition including an
acetic acid alkyl (CI-C4) ester and a carbonate.
[0006] In a first aspect, the disclosure provides a solvent
composition including an
acetate ester in an amount between about 40% v/v and about 95% v/v, where the
acetate
ester is an acetic acid alkyl (C i-C4) ester; a carbonate ester in an amount
between about
5% v/v and about 55% v/v; and, optionally, a benzene-containing compound in an
amount between about 5% and about 15%.
[0007] In alternative embodiments, the acetate ester may be present
in an amount
between about 65% v/v and about 95% v/v; and the carbonate ester may be
present in an
amount between about 5% v/v and about 35% v/v.
[0008] In alternative embodiments, the acetate ester may be present
in an amount
between about 65% v/v and about 75% v/v; the carbonate ester may be present in
an
amount between about 10% v/v and about 30% v/v; and the benzene-containing
compound may be present in an amount between about 5% v/v and about 10% v/v.
[0009] In alternative embodiments,the acetate ester may be methyl
acetate (MA),
ethyl acetate (EA), or tert-butyl acetate (TBAc).
[0010] In alternative embodiments, the carbonate ester may be
dimethyl carbonate
(DMC), or propylene carbonate (PC)).
[0011] In alternative embodiments, the benzene-containing compound, if
present,
may be benzyl alcohol (BA) or parachlorobenzotrifluoride (PCBTF).
[0012] In alternative embodiments, when the acetate ester is MA, the
acetate ester
may be present in an amount between about 65% v/v and about 80% v/v; when the
carbonate ester is DMC, the carbonate ester may be present in an amount
between about
15% v/v and about 25% v/v; and when the benzene-containing compound is BA, the
benzene-containing compound may be present in an amount between about 6.5% v/v
and
10% v/v.
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[0013] In alternative embodiments, the solvent composition may
consist essentially
of MA in an amount of about 72% v/v; DMC in an amount of about 20% v/v; and BA
in
an amount of about 8% v/v.
[0014] In some embodiments, the flash point of the solvent
composition may be at
least -2 C. In an alternative embodiment, the flash point of the solvent
composition may
be about 0 C.
[0015] In some embodiments, the maximum incremental reactivity of the
solvent
composition may be no greater than 0.57. In an alternative embodiment, the
maximum
incremental reactivity of the solvent composition may be about 0.10.
[0016] In some embodiments, the evaporation rate of the solvent composition
may be
at least 1.4. In an alternative embodiment, the evaporation rate of the
solvent
composition may be about 3.62.
[0017] In alternative embodiments, when the acetate ester is MA, the
acetate ester
may be present in an amount between about 65% v/v and about 95% v/v; and, when
the
carbonate ester is DMC, the carbonate ester may be present in an amount
between about
10% v/v and about 30% v/v.
[0018] In alternative embodiments, the solvent composition may
consist essentially
of MA in an amount of about 75% v/v; and DMC in an amount of about 25% v/v.
[0019] In alternative embodiments, when the acetate ester is MA, the
acetate ester
may be present in an amount between about 65% v/v and about 95% v/v; and when
the
carbonate ester is PC, the carbonate ester may be present in an amount between
about
10% v/v and about 30% v/v.
[0020] In alternative embodiments, the solvent composition may
consist essentially
of MA in an amount of about 70% v/v; and PC in an amount of about 30% v/v.
[0021] In alternative embodiments, when the acetate ester is EA, the
acetate ester
may be present in an amount between about 65% v/v and about 95% v/v; and when
the
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carbonate ester is PC, the carbonate ester may be present in an amount between
about
10% v/v and about 30% v/v.
[0022] In alternative embodiments, the solvent composition may
consist essentially
of EA in an amount of about 88% v/v; and PC in an amount of about 12% v/v.
[0023] In alternative embodiments, when the acetate ester is TBAc, the
acetate ester
may be present in an amount between about 65% v/v and about 95% v/v; and when
the
carbonate ester is PC, the carbonate ester may be present in an amount between
about
10% v/v and about 30% v/v.
[0024] In alternative embodiments, the solvent composition may
consist essentially
of: TBAc in an amount of about 65% v/v and PC in an amount of about 35% v/v;
TBAc
in an amount of about 55% v/v and PC in an amount of about 45% v/v; or TBAc in
an
amount of about 75% v/v and PC in an amount of about 25% v/v.
[0025] In alternative embodiments, when the acetate ester is TBAc,
the acetate ester
may be present in an amount between about 65% v/v and about 80% v/v; when the
carbonate ester is DMC, the carbonate ester may be present in an amount
between about
15% v/v and about 25% v/v; and when the benzene-containing compound is BA, the
benzene-containing compound may be present in an amount between about 6.5% v/v
and
10% v/v.
[0026] In alternative embodiments, the solvent composition may
consist essentially
of TBAc in an amount of about 40% v/v; PC in an amount of about 52% v/v; and
BA in
an amount of about 8%.
[0027] In some embodiments, the solvent composition may be
substantially
anhydrous.
[0028] In some embodiments, the solvent composition may be a low
toxicity solvent
composition.
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[0029] In another aspect, the disclosure provides a kit include a
solvent composition
as described herein together with instructions for use as a methyl ethyl
ketone (MEK) or
acetone replacement.
[0030] In some embodiments, a solvent composition as described herein
may be used
as a MEK and/or acetone replacement.
[0031] In some embodiments, a solvent composition as described herein
may be
used, without limitation, in: paints, varnish, fiberglass and/or gelcoat
manufacturing;
paint and varnish removers; coatings; inks; adhesives; hard surface cleaners;
household
dyes; tints; insecticides; laundry starches; lubricating greases and oils;
automotive
chemicals; markers; nail polish and polish remover; shoe polish; undercoats;
waterproofing compounds; particleboard; surface preparation; general and heavy
duty
degreasing; laboratory and equipment wipe solvents; general purpose surface
wipe
cleaners; or paint gun and/or paint line cleaners.
[0032] In some embodiments, a solvent composition as described herein
may be
used, without limitation, in: dissolution and processing of acrylic polymers;
the
production of resins; or formulation or removal of nail polish. The resins may
be, without
limitation, acrylic resins, urethane resins, alkyd resins, phenolic resins,
polyaspartic
urethane resins, epoxy resins, saturated or unsaturated polyester resins. The
nail polish
may be, without limitation, a nitrocellulose-based nail polish, methacrylated
monomer-
based nail polish, oligonucleotide ("ligomer")-based nail polish, a UV cure
nail polish or
a LED cure nail polish.
[0033] In some embodiments, a solvent composition as described herein
may be
used, without limitation, in: cleaning and/or removing wax, paint, varnish
and/or
coatings; cleaning fiberglass; cleaning gelcoat; cleaning and/or removing inks
and/or
markers; cleaning and/or removing dyes; cleaning excess oils and/or grease;
cleaning nail
polish; cleaning shoe polish; cleaning brakes and/or contacts; cleaning and/or
removing
adhesives; paint formulations and cleaning; ink and marker formulations and
cleaning;
precision cleaning applications; cleaning hard surfaces; aerospace cleaning
applications;
and/or general cleaning and degreasing applications.
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[0034] In an alternative embodiment, a solvent composition as
described herein may
consist essentially of methyl acetate in an amount of about 72% v/v; dimethyl
carbonate
in an amount of about 20% v/v; and benzyl alcohol in an amount of about 8%
v/v. In
some embodiments, such a solvent composition may be used as a MEK replacement.
In
some embodiments, such a solvent composition may be used, without limitation,
in
dissolution and processing of acrylic polymers; the production of resins (such
as acrylic
resins, urethane resins, alkyd resins, phenolic resins, polyaspartic urethane
resins, epoxy
resins, saturated or unsaturated polyester resins); formulation or removal of
nail polish
(such as nitrocellulose-based nail polish, methacrylated monomer-based nail
polish,
oligonucleotide ("ligomer")-based nail polish, a UV cure nail polish or a LED
cure nail
polish); or fiberglass and/or gelcoat manufacturing; or waterproofing
compounds. In
some embodiments, such a solvent composition may be used, without limitation,
in
paints, varnish, fiberglass and gelcoat manufacturing, paint and varnish
removers,
coatings, inks, adhesives, hard surface cleaners, household dyes, tints,
insecticides,
laundry starches, lubricating greases and oils, automotive chemicals, markers,
nail polish
and polish remover, shoe polish, undercoats, waterproofing compounds,
particleboard,
surface preparation, general and heavy duty degreasing, laboratory and
equipment wipe
solvent, general purpose surface wipe cleaner and/or paint gun and paint line
cleaner.
[0035] In another aspect, the disclosure provides a method of making
a MEK or
acetone replacement composition by: providing an acetate ester in an amount
between
about 40% v/v and about 95% v/v, the acetate ester being an acetic acid alkyl
(C i-C4)
ester; a carbonate ester in an amount between about 5% v/v and about 55% v/v;
and,
optionally, a benzene-containing compound in an amount between about 5% and
about
15%; and combining the acetate ester, carbonate ester and benzene-containing
compound,
if present, to form a homogeneous blend.
[0036] In another aspect, the disclosure provides a method of making
a MEK or
acetone replacement composition by providing methyl acetate in an amount
between
about 65% v/v (or about 61.95 wt%) and about 80% v/v (or about 77.79 wt%);
dimethyl
carbonate in an amount between about 15% v/v (or about 16.76 wt%) and about
25% v/v;
(or about 27.38 wt%) and benzyl alcohol in an amount between about 6.5% v/v
(or about
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7.06 wt%) and 10% v/v (or about 10.67 wt%); and combining the methyl acetate,
dimethyl carbonate and benzyl alcohol to form a homogeneous blend.
[0037] Other aspects and features of the present disclosure will
become apparent to
those ordinarily skilled in the art upon review of the following description
of specific
examples in conjunction with the accompanying figures.
BRIEF DESCRIPTION OF THE DRAWINGS
[0038] These and other features of the invention will become more
apparent from the
following description in which reference is made to the appended drawings
wherein:
[0039] FIGURE 1 is a representation of the different components of
the Hansen
Solubility Parameters: Dispersion, Polar and Hydrogen bonding for various
solvents. The
size of the spheres correspond to the hydrogen bonding component.
[0040] FIGURE 2 shows initial blends from 1 to 20. Blends A, E and F
correspond
to Formulations 1, 3 and 2 respectively.
[0041] FIGURE 3 is a graph comparing the evaporation rate of
Formulation 1
(squares) with that of MEK (diamonds).
DETAILED DESCRIPTION
[0042] The present disclosure provides, in part, a solvent
composition including an
acetic acid alkyl (Ci-C4) ester (referred to herein as "acetate ester"), such
as methyl
acetate (MA), ethyl acetate (EA), or tert-butyl acetate (TBAc)) and a
carbonate ester
(e.g., dimethyl carbonate (DMC), or propylene carbonate (PC)).
[0043] By "acetate ester," as used herein, is meant an acetic acid
alkyl (C1-C4) ester
having the formula CH3CO2R, where R is CI-Ca alkyl. "Alkyl" refers to a
straight or
branched hydrocarbon chain group consisting solely of carbon and hydrogen
atoms,
containing no unsaturation and including, for example, from one to four carbon
atoms,
such as 1, 2, 3, or 4 carbon atoms.
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[0044] In some embodiments, the acetate ester may be present in the
solvent
composition in any amount between about 40% v/v to about 95% v/v, or 65% v/v
to
about 95% v/v, or any amount between about 65% v/v to about 70% v/v, or any
amount
between about 70% v/v to about 75% v/v, or any amount between about 75% v/v to
about
80% v/v, or any amount between about 80% v/v to about 85% v/v, or any amount
between about 85% v/v to about 90% v/v, or any amount between about 90% v/v to
about
95% v/v, or any value in between, for example, 40%, 45%, 50%, 55%, 60%, 65%,
70%
v/v, 75% v/v, 80% v/v, 85% v/v, 90%, 95% v/v, etc.
[0045] In some embodiments, the acetate ester may be MA, which may
be present in
the solvent composition in any amount between about 40% v/v to about 95% v/v,
or any
amount between about 60% v/v or 65% v/v to about 95% v/v, or any amount
between
about 65% v/v to about 70% v/v, or any amount between about 70% v/v to about
75%
v/v, or any amount between about 75% v/v to about 80% v/v, or any amount
between
about 80% v/v to about 85% v/v, or any amount between about 85% v/v to about
90%
v/v, or any amount between about 90% v/v to about 95% v/v, or any value in
between,
for example, 70% v/v, 75% v/v, 80% v/v, 85% v/v, 90% v/v, etc.
[0046] In some embodiments, the acetate ester may be EA, which may
be present in
the solvent composition in any amount between about 40% v/v to about 95% v/v,
or any
amount between about 65% v/v to about 95% v/v, or any amount between about 65%
v/v
to about 70% v/v, or any amount between about 70% v/v to about 75% v/v, or any
amount between about 75% v/v to about 80% v/v, or any amount between about 80%
v/v
to about 85% v/v, or any amount between about 85% v/v to about 90% v/v, or any
amount between about 90% v/v to about 95% v/v, or any value in between, for
example,
70% v/v, 75% v/v, 80% v/v, 85% v/v, 90% v/v, etc.
[0047] In some embodiments, the acetate ester may be TBAc, which may be
present
in the solvent composition in any amount between about 40% v/v to about 95%
v/v, or
any amount between about 65% v/v to about 95% v/v, or any amount between about
65%
v/v to about 70% v/v, or any amount between about 70% v/v to about 75% v/v, or
any
amount between about 75% v/v to about 80% v/v, or any amount between about 80%
v/v
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to about 85% v/v, or any amount between about 85% v/v to about 90% v/v, or any
amount between about 90% v/v to about 95% v/v, or any value in between, for
example,
70% v/v, 75% v/v, 80% v/v, 85% v/v, 90% v/v, etc.
[0048] In some embodiments, the carbonate ester may be present in the
solvent
composition in any amount between about 5% v/v to about 55% v/v, or any amount
between about 5% v/v to about 35% v/v, in any amount between about 10% v/v to
about
30% v/v, or any value in between, for example, 10% v/v, 15% v/v, 20% v/v, 25%
v/v,
30% v/v, 40% v/v, 45% v/v, etc.
[0049] In some embodiments, the carbonate ester may be PC, which may
be present
in the solvent composition in any amount between about 5% v/v to about 35%
v/v, or in
any amount between about 10% v/v to about 30% v/v, or any value in between,
for
example, 10% v/v, 11% v/v, 12% v/v, 13% v/v, 14% v/v, 15% v/v, 20% v/v, 25%
v/v, 30% v/v, etc.
[0050] In some embodiments, the carbonate ester may be DMC, which may
be
present in the solvent composition in any amount between about 5% v/v to about
55%
v/v, or in any amount between about 10% v/v to about 30% v/v, or any value in
between,
for example, 10% v/v, 15% v/v, 20% v/v, 25% v/v, 30% v/v, 40% v/v, 45% v/v,
52%
v/v, etc.
[0051] In further embodiments, the solvent composition may
additionally include a
non-toxic or low-toxicity benzene-containing compound, such as benzyl alcohol
(BA) or
parachlorobenzotrifluoride (PCBTF). In some embodiments, the benzyl alcohol
(BA) or
parachlorobenzotrifluoride (PCBTF) may be in an amount between about 5% v/v
and
about 15% v/v, or any value in between, for example, 5% v/v, 6% v/v, 7% v/v,
8% v/v,
9% v/v, 10% v/v, 11% v/v, 12% v/v, 13% v/v, 14% v/v, 15% v/v, etc.
[0052] In some embodiments, a solvent composition according to the present
disclosure includes methyl acetate in an amount between about 65% v/v (about
58.95
wt%) and about 95% v/v (about 93.63wt%) and propylene carbonate in an amount
between about 5% v/v (6.37wt%) and about 35% v/v (41.04wt %).
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[0053] In some embodiments, a solvent composition according to the
present
disclosure includes about 88% v/v (about 85.01 wt %) methyl acetate and about
12% v/v
(about 14.99 wt %) polypropylene carbonate.
[0054] In some embodiments, a solvent composition according to the
present
disclosure includes about 70% v/v (about 64.34 wt%) methyl acetate and about
30% v/v
(about 35.65 wt %) polypropylene carbonate.
[0055] In some embodiments, a solvent composition according to the
present
disclosure includes methyl acetate in an amount between about 60% v/v (about
56.78 wt
%) and about 85% v/v (about 83.25 wt%), dimethyl carbonate in an amount
between
about 10% v/v (about 11.25 wt%) and about 30% v/v (about 32.62 wt%) and benzyl
alcohol in an amount between about 5% v/v (about 5.48 wt% ) and about 10% v/v
(about
10.6 wt%).
[0056] In some embodiments, a solvent composition according to the
present
disclosure includes about 72 % v/v (about 69.27 wt%) methyl acetate, about 20%
v/v
(22.11 wt%) dimethyl carbonate, and about 8% (about 8.62 wt%) benzyl alcohol.
[0057] In some embodiments, a solvent composition according to the
present
disclosure includes methyl acetate in an amount between about 65% v/v (or
about 61.95
wt%) and about 80% v/v (or about 77.79 wt%); dimethyl carbonate in an amount
between about 15% v/v (or about 16.76 wt%) and about 25% v/v; (or about 27.38
wt%)
and benzyl alcohol in an amount between about 6.5% v/v (or about 7.06 wt%) and
10%
v/v (or about 10.67 wt%).
[0058] In some embodiments, a solvent composition according to the
present
disclosure includes methyl acetate in an amount between about 65% v/v (or
about 61.95
wt%) and about 78.5% v/v (or about 76.20 wt%); dimethyl carbonate in an amount
between about 15% v/v (or about 16.76 wt%) and about 25% v/v; (or about 27.38
wt%)
and benzyl alcohol in an amount between about 6.5% v/v (or about 7.06 wt%) and
about
10% v/v (or about 10.67 wt%) .
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[0059] It is to be understood that varying the concentration of a
reagent in a
composition will generally require a corresponding adjustment (increase or
decrease) in
the amount of the other reagents in the composition.
[0060] In some embodiments, a solvent composition according to the
present
disclosure includes an acetate ester, such as MA. EA, or TBAc, in combination
with
additional reagents to increase dispersion and decrease hydrogen bonding
and/or to
decrease the polarity of the composition. For example, a solvent composition
that
resembles the behaviour of MEK or acetone as a solvent may be formulated using
mathematical models to predict the solubility profile of solvent blends.
Accordingly, in
some embodiments, a solvent composition according to the present disclosure
may be
formulated according to Hansen solubility parameters (HSP) (Hansen, 1999) and
may
have: a dispersion parameter (8D) between about 7.7 and about 8.5; a polarity
parameter
(8P) between about 4 and about 5.2; and a hydrogen bonding parameter (6H)
between
about 3.0 and about 3.6. Such parameters result in a Hansen Solubility
Parameter (6 MPa)
of about 9.0 to about 10.4, where 62 = 6D2 6p2 6"2.
Accordingly, in some
embodiments, a solvent composition according to the present disclosure may
have a
dispersion parameter higher than that of MA (7.58). In some embodiments, a
solvent
composition according to the present disclosure includes a composition with
HSP values
similar to those of MEK. In some embodiments, a solvent composition according
to the
present disclosure includes a composition in which 6P and 6H values are
similar to those
of MEK.
[0061] In alternative embodiments, a solvent composition according to
the present
disclosure may have: a dispersion parameter (6D) between about 7.5 and about
8; a
polarity parameter (613) between about 3 and about 4; and a hydrogen bonding
parameter
(8H) between about 3.2 and about 4. Such parameters result in a Hansen
Solubility
Parameter (8 MPa) of about 8.68 to about 9.79, where 62 = 6D2 + 6132 + 6H2. In
some
embodiments, a solvent composition according to the present disclosure
includes a
composition with HSP values similar to those of acetone. In some embodiments,
a
solvent composition according to the present disclosure includes a composition
in which
6P and SH values are similar to those of acetone.
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[0062] Table 1 shows the Hansen Solubility Parameters for various
compounds and
compositions and Figure 1 shows a three-dimensional representation of many of
these
compounds.
Table 1: Hansen Solubility parameters of blends, single components, MEK and
acetone
1 hildebrand = 1 call/2 cm-3/2 = 0.48888 MPa1/2 (1S)= 2.4542*10^-2 kcal/mol
1/2 A^-3/2
SD SP 611 (hydrogen
________________________ (1V1Pa) (dispersion) (polarity) bonding)
PC
13.32216199 9.8
8.8 2
PCBTF 8.8 2.9 1.9
DMC 9.896969233 8.5 4.7 1.9
-
TBA 7.765307463 7 1.7 = 2.9
Ethyl acetate 8.8 = 7.7 2.3 3.5
Methyl acetate 9.147961522 7.58 3.52 3.72
Formulation 1 = 9.435396725 7.896 3.7444 3.558
Formulation 2 9.547972082 7.8464 4 1536 3.5136
Formulation 3 10.25238566 8.2682 5.1568 3.1868
MEK 9.1 I 7,82 I 4.4 I 2.49
Acetone 9.928746144 7.7 5.2 3.5
[0063] In some embodiments, the carbonate ester may be used to
increase the
dispersion and decrease the hydrogen bonding of the composition. Without being
bound
to any particular theory, the carbonate ester may be used to modify the
solubility and
solvency parameters of the acetate ester to, for example and adjust the
evaporation rate to
that approximating MEK.
[0064] In some embodiments, the benzene-containing compound, such as
benzyl
alcohol, may be used to decrease the polarity of the composition. In
alternative
embodiments the benzene-containing compound, such as benzyl alcohol, may be
used to
improve the capacity of the composition to, for example, remove/dissolve epoxy
based
coatings.
[0065] In some embodiments, a solvent composition according to the
present
disclosure may include reagents that are not classified as hazardous air
pollutants
(HAPs), as environmentally hazardous, or as ozone-depleting (VOCs). In some
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embodiments, a solvent composition according to the present disclosure may
include
reagents declared exempt by the National Pollutant Release Inventory (NPRI).
[0066] In some embodiments, a solvent composition according to the
present
disclosure may include compounds or reagents that are VOC-exempt. By "VOC-
exempt" is meant a compound or reagent that has reduced photochemical
reactivity (i.e.,
does not contribute to ozone formation) and has been classified as such by at
least one
governmental agency, such as the Environmental Protection Agency (EPA) of the
United
States of America or Environment Canada. Such compositions are useful in
reducing
VOC emissions. MA and PCBTF are presently VOC-exempt.
[0067] A compound's maximum incremental reactivity (MIR) value is a measure
of
the compound's ability to generate ozone due to photochemical degradation. The
lower
the MIR value, the less ozone (and, accordingly, the less smog) that is
generated by the
compound. In some embodiments, a solvent composition according to the present
disclosure may have a MIR value lower than acetone (MIR 0.43) or MEK (MIR
1.49), or
both. In alternative embodiments, compositions according to the present
disclosure may
have a MIR value similar to methyl acetate (MIR 0.07). In some embodiments,
compositions with low MIR values are useful in aerosol or coating
applications.
Compositions according to the present disclosure that have suitably low MIR
values can,
in some embodiments, be mixed with aerosol and coating formulations. The MIR
values
of the resultant mixtures can be calculated and assessed for their ability to
meet reactivity
standards, such as those established by the Environmental Protection Agency
(EPA) of
the U.S.A.
[0068] In some embodiments, a solvent composition according to the
present
disclosure may have low volatility (or high flash point).
[0069] In some embodiments, a solvent composition according to the present
disclosure has a higher flash point than acetone (-20 C) or MEK (-9 C) or MA (-
4 C). In
some embodiments, a solvent composition according to the present disclosure
has a flash
= point of greater than 0 C, as determined by, for example, Catoire, 2006.
In some
embodiments, a solvent composition according to the present disclosure has a
flash point
13
CA 02845415 2014-03-07
of greater than 5 C, as determined by, for example, Catoire, 2006. In some
embodiments,
a solvent composition according to the present disclosure has a flash point of
greater than
37 C, as determined by, for example, Catoire, 2006. In some embodiments,
compositions
with a flash point value of greater than 37 C are considered non-flammable and
are
therefore useful in applications where flammability is a concern although
solvent
compositions with lower flash points may be used for a variety of industrial
applications.
[0070] In some embodiments, a solvent composition according to the
present
disclosure may have low toxicity as determined, for example by one or more of
oral
LD50 on rats, biodegradability, teratogenicity, carcinogenicity and/or hepatic
and renal
toxicity measurements, which can be determined using standard methods. In some
embodiments, a solvent composition according to the present disclosure may
contain
reagents classified as non-carcinogenic.
[0071] In some embodiments, a solvent composition according to the
present
disclosure may not contain substantial amounts of benzene (C6H6). In some
embodiments, a solvent composition according to the present disclosure may be
substantially free of benzene.
[0072] In some embodiments, a solvent composition according to the
present
disclosure may have an evaporation rate approximating that of MEK at ambient
or room
temperatures. Evaporation rates can be expressed relative to the evaporation
of n-butyl
acetate (=1), as a standard. In alternative embodiments, a solvent composition
according
to the present disclosure may have an evaporation rate about 1, 1.5 or 2 times
faster than
MEK at ambient or room temperatures.
[0073] In some embodiments, a solvent composition according to the
present
disclosure does not leave a residue after evaporation to dryness at, for
example, ambient
or room temperature.
[0074] In some embodiments, a solvent composition according to the
present
disclosure may be substantially anhydrous, for example, containing less than
0.02 wt%
14
CA 02845415 2014-03-07
water. In alternative embodiments, a solvent composition according to the
present
disclosure may contain less than 550 ppm of water.
[0075] In some embodiments, a solvent composition according to the
present
disclosure may be substantially immiscible with water.
[0076] In some embodiments, a solvent composition according to the present
disclosure has a purity of, for example, at least 99.5%, for example, at least
99.6%,
99.7%, 99.8%, 99.9%, or 100%. In alternative embodiments, the acetate ester
(such as
MA, EA or TBAc), may have a purity of, for example, at least 99.5%. In
alternative
embodiments, the carbonate ester, may have a purity of, for example, at least
99.5%.
[0077] In some embodiments, a solvent composition according to the present
disclosure may be biodegradable. For example, in some embodiments, solvent
compositions according to the present disclosure may be readily biodegradable
to CO2
and water.
[0078] In some embodiments, a solvent composition according to the
present
disclosure may have a high loading capacity, as determined for example by
measurements of peak widths at differing loading levels.
[0079] In some embodiments, a solvent composition according to the
present
disclosure may have improved flow characteristics, for example, when compared
to
and/or acetone.
[0080] In some embodiments, a solvent composition according to the present
disclosure may have low viscosity. For example, a solvent composition
according to the
present disclosure can be 10 - 25% more efficient in viscosity reduction than
and/or
acetone.
[0081] In some embodiments, a solvent composition according to the
present
disclosure may have improved solvency, relative to for example, MEK and/or
acetone.
This may, in some embodiments, permit the use of less solvent when compared to
compositions containing MEK and/or acetone. In some embodiments, solvent
CA 02845415 2014-03-07
compositions according to the present disclosure may have a solvency
approximating that
of MEK and/or acetone.
[0082] In some embodiments, a solvent composition according to the
present
disclosure may have a specific gravity of about 0.96 g/ml.
[0083] In some embodiments, a solvent composition according to the present
disclosure may have performance characteristics approximating that of MEK
and/or
acetone, as described herein or known in the art.
[0084] In some embodiments, a solvent composition according to the
present
disclosure may be recycled through distillation at an appropriate temperature
(for
example, above the boiling point of 70 C (158 F).
[0085] In some embodiments, a solvent composition according to the
present
disclosure may have a mild odor. In some embodiments, compositions according
to the
present disclosure may include reagents that do not have an unpleasant and/or
strong
odor.
[0086] In some embodiments, a solvent composition according to the present
disclosure may be useful in replacing MEK, MEK blends, acetone, and/or acetone
blends.
The compositions can be used, for example, as a solvent in various
applications.
Examples of contemplated applications include, without limitation:
reformulation of an
aerosol to meet a reactivity limit while maintaining performance properties
and reducing
the formation of tropospheric ozone; dissolution of a resin; use as a paint
thinner; use as a
paint remover; use as a cleaner; use as a degreaser; and use an adhesive
remover.
[0087] In some embodiments, a solvent composition according to the
present
disclosure may be useful in the manufacturing and formulation of paints,
coatings,
polymers, inks, adhesives, personal care products, as well as in industrial,
commercial
cleaning/de-greasing applications.
[0088] In some embodiments, a solvent composition according to the
present
disclosure may be useful in paints and coating formulations and/or cleaning,
paint and/or
16
CA 02845415 2014-03-07
varnish removers, ink and/or marker formulations and/or cleaning, adhesive
formulations
and/or cleaning and/or removal, gelcoat formulations and/or cleaning,
fiberglass
manufacturing, hard surface cleaners, undercoat formulation and/or cleaning,
waterproofing compounds, household dyes and/or tints, laundry starches and
shoe
polishes, nail polish and/or nail polish removers, general aerospace cleaning,
lubricating
oils and/or greases, automotive chemicals and cleaners, etc.
[0089] In some embodiments, a solvent composition according to the
present
disclosure may be useful as a surface preparation and/or precision cleaner,
general
purpose surface wipe cleaner (for example, prior to painting), general and/or
heavy duty
degreaser, laboratory and equipment wipe solvent, brake and/or contact
cleaner, paint gun
and paint line cleaner, etc.
[0090] In some embodiments, a solvent composition according to the
present
disclosure may be useful as a chemical intermediate, a dewaxing agent in for
example
lubricant base oil production, etc.
[0091] In some embodiments, a solvent composition according to the present
disclosure may be useful in the production and cleaning of magnetic tapes,
[0092] In some embodiments, a solvent composition according to the
present
disclosure may be useful as a solvent for fats, oils, waxes, etc.
[0093] In some embodiments, a solvent composition according to the
present
disclosure may be useful in the formulation and production of resins.
[0094] In some embodiments, a solvent composition according to the
present
disclosure may be useful in the formulation of high solids coatings, which may
for
example, be useful in reducing emissions from coating operations.
[0095] In some embodiments, a solvent composition according to the
present
disclosure may be useful as a diluents in the production of lacquers for
automotive/furniture finishes, adhesives for PVC pipes, resin thinners and
clean-up
operations, reaction/extraction solvent for pharmaceuticals, etc.
17
CA 02845415 2014-03-07
[0096] In some embodiments, a solvent composition according to the
present
disclosure may be useful in the production of cyanoacrylate adhesives. In
alternative
embodiments, a solvent composition according to the present disclosure may be
useful to
remove cyanoacrylate adhesives from a variety of surfaces, substrates, human
tissue or
skin, etc.
[0097] In some embodiments, a solvent composition according to the
present
disclosure may be useful in the production of cosmetics, included but not
limited to
perfumes and/or nail polish, such as nitrocellulose-based nail polish,
methylacrylated
monomer-based nail polish, oligonucleotide ("ligomer")-based nail polish, etc.
In
alternative embodiments, a solvent composition according to the present
disclosure may
be useful to remove these types of nail polish and/or leave the nail bed stain
and residue-
free as well as prepare the nail for the application of any of the above nail
polishes.
[0098] In some embodiments, the compositions do not cause paints to
curdle or leave
an oily residue after evaporation.
[0099] In some embodiments, Formulation 1 may be used in dissolution and
processing of acrylic polymers.
[00100] In some embodiments, Formulation 1 may be used in the production of
resins,
such as acrylic resins, urethane resins, alkyd resins, phenolic resins,
polyaspartic urethane
resins, epoxy resins, saturated and/or unsaturated polyester resins, etc.
[00101] In some embodiments, Formulation 1 may be used in formulation or
removal
of nail polish, such as nitrocellulose-based nail polish, methacrylated
monomer-based
nail polish, oligonucleotide ("ligomer")-based nail polish, etc. In some
embodiments,
Formulation 1 may be used in UV cure and/or LED cure nail polish.
[00102] In some embodiments, Formulation 1 may be used in fiberglass and/or
gelcoat
manufacturing.
[00103] In some embodiments, Formulation 1 may be used in may be used in
waterproofing compounds.
18
CA 02845415 2014-03-07
[00104] In some embodiments. Formulation 1 may be used as a replacement for
MEK
in epoxy formulas.
[00105] In some embodiments, Formulation 1 may be used to replace MEK in 2K
polyurethane formulas if it contains no hydroxol groups capable of reacting
with
isocyanate cross-linkers and if the water content is below 500 ppm In some
embodiments, Formulation 1 may be used in 2 k polyurethane systems in either
the
polyol and/or isocyanate portions of the system.
[00106] In some embodiments, Formulation 9 may be used as a replacement for
MEK
and/or acetone in, for example, cleaning or other applications. In some
embodiments,
Formulation 9 may be used as a replacement for MEK and/or acetone in precision
cleaning applications, surface preparation, cleaning hard surfaces, laboratory
and/or
equipment wipe solvents, and/or general cleaning and degreasing.
[00107] In some embodiments, Formulation 9 may be useful in aerospace cleaning
applications.
[00108] In some embodiments, Formulation 9 may be useful in preparing surfaces
prior to, for example, painting, due to its ability to evaporate quickly and
leave no or
minimal surface residue.
[00109] In some embodiments, Formulation 9 may be useful in paint formulations
and
cleaning, ink and marker formulations and cleaning, hard surface cleaning,
lubricating
greases and oils, automotive chemicals, nail polish and polish remover.
[00110] In some embodiments, Formulation 9 may be useful in or to: clean
and/or
remove wax, paint, varnish and/or coatings, clean fiberglass, clean gelcoat,
clean and/or
remove inks and/or markers, clean and/or remove dyes, clean excess oils and/or
grease,
clean nail polish, clean shoe polish, clean brakes and/or contacts, clean
and/or remove
adhesives.
[00111] In alternative embodiments, Formulation 9 is not used in the
preparation of
formulations.
19
CA 02845415 2014-03-07
[00112] It is to be understood that a solvent composition according to the
present
disclosure can be used in a variety of applications in which MEK and/or
acetone is
traditionally used, and can be used to replace the MEK and/or acetone in such
applications. Accordingly, it is to be understood that the ultimate amounts of
a solvent
composition according to the present disclosure may vary depending on the
ultimate use
and final composition of the product in which the solvent composition
according to the
present disclosure is being used.
EXAMPLE 1
[00113] Candidate compounds were selected using a number of environmental
criteria,
such as low flammability, safety, low VOC or VOC exempt status, and
sustainable
sourcing.
[00114] Candidate compounds were also selected based on their physicochemical
properties as, for example, determined from various chemical databases, such
as
CHEMnetBASE or Chemspider. Candidates with relatively high flash points, low
toxicity and low vapor pressures, when compared with MEK, acetone, n-methyl
pirrolidine (NMP) and methyl n-propyl ketone (MPK), etc. were selected for
further
testing.
[00115] The selected compounds were subsequently combined in different initial
blends (Table 2). The blends or formulations described herein were selected
through
standardized performance tests on fresh and cured epoxy and urethane resins
and MEK-
based paints. Double blinded standardized performance tests were conducted to
identify
blends for further testing. The capacity of the blends to properly dissolve 2
adhesives,
three epoxy-based coatings and one MEK-based paint was assessed on fresh and
cured
samples. The odor of the blends was also tested.
CA 02845415 2014-03-07
a
44 V t
..., - .., ... :.-..1 =iii. ,,- z t, , ..% :.-
- -1 % t v,tt. . ,
1 40 0 60 ..
2 60 40
3 40 60
4 60 40
5 60 40
2.--
6 60 40
7 60 _ 40 ,
8 40 20 40 ,
9 60 20 20
=
10 20 " 20 60
11 , 20 80
-
l'' 40 60
13- 20 80
14- 40 60
15 20 80
16 40 60
-
17 20 80
18 40 604
19 30 70 1
20 30 70
2130 30 = 40 _
_ ,
_
A 10 50 40
B = , 20 15 65
C
(Formulation
3) 30 70 1
,
i D 10 90 !
E
; (Formulation i
2) 12 88 i
i F
1 (Formulation .. ..,
i 1) 8 72
,. 20
Table 2
[00116] Blends were also tested as cleaners, paint removers, degreasers and
adhesive
removers. (Figure 2).
[00117] Blends 3 and 4 were discarded due to their poor performance in these
tests.
Blends C, E and F correspond to Formulations 3, 2, and 1, respectively, as
described
herein.
21
CA 02845415 2014-03-07
EXAMPLE 2
[00118] A solvent composition (Formulation 1) was prepared by mixing the
following:
72% (v/v) or 69.27 wt% methyl acetate? 99% purity (CAS # 79-20-9)
20% (v/v) or 22.11 wt% dimethyl carbonate? 99.50% (CAS # 616-38-6)
8% (v/v) or 8.62% wt% benzyl alcohol,? 99.90% purity (CAS # 100-51-6)
[00119] In Formulation 1, dimethyl carbonate was used to increase the
dispersion and
decrease the hydrogen bonding of the blend, while benzyl alcohol was used to
lower the
polarity.
[00120] Formulation 1 has a MIR value of 0.46 and a predicted flash point of
about
7.5 C.
[00121] Formulation 1 has an evaporation rate = 3.6 (MEK = 3.8).
EXAMPLE 3
[00122] A solvent composition (Formulation 2) was prepared by mixing the
following:
88% (v/v) or 85.01 wt% methyl acetate? 99% purity (CAS # 79-20-9)
12% (v/v) or 14.99 wt% propylene carbonate? 99.5% purity (CAS # 108-32-7)
[00123] Formulation 2 has an MIR value of 0.09 and a predicted flash point of
about
9 C.
[00124] Formulation 2 was able to dissolve MEK-based paints and resins
successfully.
EXAMPLE 4
[00125] A solvent composition (Formulation 3) was prepared by mixing the
following:
70% (v/v) or 64.34 wt% methyl acetate? 99% purity (CAS # 79-20-9)
30% (v/v) or 35.65 wt% propylene carbonate? 99.5% purity (CAS # 108-32-7)
[00126] Formulation 3 has a MIR value of 0.12, and a flash point of about 39 C
(<37 C).
22
CA 02845415 2014-03-07
EXAMPLE 5
[00127] A solvent composition (Formulation 4) was prepared by mixing the
following:
88% (v/v) or 85.01 wt% ethyl acetate
12% (v/v) or 14.99 wt% propylene carbonate
EXAMPLE 6
[00128] A solvent composition (Formulation 5) was prepared by mixing the
following:
40% (v/v) or 35.12 wt% tert-butyl acetate
52% (v/v) or 56.42 wt%dimethyl carbonate
8% (v/v) or 8.46 wt%benzyl alcohol
EXAMPLE 7
[00129] A solvent composition (Formulation 6) was prepared by mixing the
following:
65% (v/v) or 57.18 wt% tert-butyl acetate
35% (v/v) or 42.82 wt% propylene carbonate
EXAMPLE 8
[00130] A solvent composition (Formulation 7) was prepared by mixing the
following:
55% (v/v) or 46.78 wt% tert-butyl acetate
45% (v/v) or 53.22 wt% propylene carbonate
EXAMPLE 9
[00131] A solvent composition (Formulation 8) was prepared by mixing the
following:
75% (v/v) or 68.33 wt% tert-butyl acetate
25% (v/v) or 31.67 wt% propylene carbonate
23
CA 02845415 2015-04-20
EXAMPLE 10
[00132] A solvent composition (Formulation 9) was prepared by mixing the
following:
75% or 72.30 wt% Methyl Acetate
25% or 27.69 wt% Dimethyl Carbonate
[00133] Formulation 9 has a predicted flash point of about 7 C to about 10
C.
[00134] The physical/chemical Characteristics of Formulation 9 were as
follows:
Appearance Clear, slightly yellow liquid.
Colour (APHA, Max) 10
Odour Mild fruity, acid
Flash Point 9 C (48 F) TCC
Density 0.965g/m1 (8.05 lb/gal)
Volatility 100%
Specific Gravity (@ 25 C) 0.965
Acidity (Wt % as Acetic Acid, Max) 0.10
Water Content (Wt %) <0.005% max
Purity (Wt % Min) 99.90
Viscosity (cps@20 C) 0.98
Vapor density (air=1) 2.93
Initial Boiling 70 C (158 F)
Vapour Pressure (mm Hg@ 25 C) 39.8
Solubility in water 3.64 g / 100 ml
Evaporation Rate (n-Butyl Acetate= 1) 3.59
VOC/NPRI Exempt (Most Jurisdictions)
EXAMPLE 11
[00135] Formulation 1 was evaluated as a replacement for MEK in an epoxy-
polyamide
clear formulation. The evaporation rate of Formulation 1 was compared with
MEK, as shown
in Fig. 3.
24
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[00136] Two epoxy clear formulas were prepared as follows:
32031-1 32031-2
Part A
DER 662 Solid Epoxy Resin 438.92 438.92
Xylene 146.31 146.30
Methyl Ethyl Ketone 292.61
Formulation 1 292.62
Total 877.84 877.84
Part B
Ancamide 2060 Polyamide 101.29 99.30
Weight Solids, % 55.17 55.17
Volume Solids, % 46.81 49.85
Specific Gravity 0.979 1.043
Viscosity: Part A 50.6 KU 52.7 KU
Mixed Viscosity: 52.1 KU 55.3 KU
[00137] Formulation 1 was found to have a lower, milder odor compared to MEK.
The evaporation rate of Formulation 1 was 4.17, which is similar to the
published MEK
ER 4Ø In the epoxy formula tested, Formulation 1 has slightly less solvent
power than
MEK. Substitution of the MEK with Formulation 1 resulted in a minor 2 ¨ 3 KU
increase in viscosity.
References:
Adams, N., Goulding, K. H. & Dobbs, A. J. (1986). Effect of acetone on the
toxicity of four chemicals to Selenastrum capricornutum. Bull. Environ.
Contam.
Toxicol., 36, 254-9.
Freeman JJ, Hayes EP. (1985) Acetone potentiation of acute acetonitrile
toxicity
in rats. Journal of Toxicology and Environmental Health 15:609-621.
CA 02845415 2014-03-07
Hewitt, W. R., and Plaa, G. L. (1983). Dose dependent modification of 1,1-
dichloroethylene toxicity by acetone. Toxicol. Lett. 16, 145-152.
Catoire, L., Paulmier, S., (2006) Estimation of closed cup flash points of
combustible solvent blends. Journal of Physical and Chemical Reference Data
35, 9-14.
C. M. Hansen, (1999) 'Hansen Solubility Parameters: A User's Handbook'. CRC
Press LLC, New York.
Raymond, P., & Plaa, G. L. (1995). Ketone potentiation of haloalkane induced
hepato and nephrotoxicity. II. implication of monooxygenases. Journal of
Toxicology and
Environmental Health, Part A Current Issues, 46(3), 317-328.
Schwetz, B. A., Mast, T. J., Weigel, R. J., Dill, J. A., & Morrissey, R. E.
(1991). Developmental toxicity of inhaled methyl ethyl ketone in Swiss mice.
Fundamental and applied toxicology, 16(4), 742-748.
Spencer, P. S., & Schaumburg, H. H. (1976). Feline nervous system response to
chronic intoxication with commercial grades of methyl< i> n</i>-butyl ketone,
methyl<
i> iso</i> butyl ketone, and methyl ethyl ketone. Toxicology and Applied
Pharmacology,
37(2), 301-311.
Altenkirch, H., Stoltenburg, G., & Wagner, H. M. (1978). Experimental
studies on hydrocarbon neuropathies induced by methyl-ethyl-ketone (MEK).
Journal of
neurology, 219(3), 159-170.
[00138} In the preceding description, for purposes of explanation, numerous
details are
set forth in order to provide a thorough understanding of the examples.
However, it will
be apparent to one skilled in the art that these specific details are not
required.
[00139] The above-described examples are intended to be exemplary only.
Alterations, modifications and variations can be effected to the particular
examples by
those of skill in the art without departing from the scope, which is defined
by the claims
appended hereto.
26
