Note: Descriptions are shown in the official language in which they were submitted.
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PROCESS FOR IMPROVING THE ODOR OF COMMERCIAL SOLVENT
USED IN FABRIC SOFTENING COMPOSITIONS
TECHNICAL FIELD
The present invention relates to processes for improving the odor of certain
commercially available solvents and the resulting compositions. Specifically,
processes
for improving the odor of commercially available 2,2,4-trimethyl-1,3-
pentanediol and the
resulting compositions are provided that solve problems that have previously
gone
unnoticed, particularly for clear or translucent liquid fabric softening
compositions.
BACKGROUND OF THE INVENTION
As a well-known compound, 2.2,4-trimethyl-1,3-pentanediol is used in a variety
of contexts. For instance, 2,2,4-trimethyl-1,3-pentanediol has been used in
surface
coating and unsaturated polyester resins, as an intermediate for synthetic
lubricants and
polyurethane elastomers and foams, and as a part of glycol mixtures to improve
rosin
solubility in inks. See KIRK-OTHMER ENCYCLOPEDIA OF CHEMICAL TECHNOLOGY (3d
ed. 1978). As used in such industrial products, the offensive odor typically
associated
with commercially available 2,2,4-trimethyl-1,3-pentanediol does not adversely
affect
the acceptability of such products when incorporated therein, since the
acceptability of
such products does not largely depend on the odor of the product.
It has recently been found that 2,2,4-trimethyl-1,3-pentanediol is a useful
solvent
in consumer products such as fabric softening compositions. See Trinh et al.,
PCT Patent
Application Nos. W09703169-A1 and W09703170-A1, both published on January 30,
1997, said documents being incorporated herein by reference. In consumer
products
such as fabric softeners, the acceptability of the product depends largely on
the pleasant
odor of the product. However, a problem with using 2,2,4-trimethyl-1,3-
pentanediol as a
solvent in consumer products relates to the offensive odor typically
associated with
commercially available 2,2,4-trimethyl-1,3-pentanediol. Consumer products
containing
commercially available 2,2,4-trimethyl-1,3-pentanediol usually suffer from
unacceptable
odor problems which are related to the use of 2,2,4-trimethyl-1,3-pentanediol.
Therefore,
industry, especially the consumer products industry, continues to seek ways in
which to
incorporate commercially available 2,2,4-trimethyl-1,3-pentanediol in consumer
products, particularly fabric softening products, without the products
suffering from
unacceptable odor problems related to the use of 2,2,4-trimethyl-1,3-
pentanediol.
It has now been discovered that commercially available 2,2,4-trimethyl-1,3-
pentanediol can be processed so that its offensive odor is significantly
reduced and so
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that it can be used in a consumer product, especially fabric softening
products, without
imparting an unacceptable odor effect to the product.
SUMMARY OF THE INVENTION
The present invention relates to processes for improving the odor of
commercially available 2,2,4-trimethyl-1,3-pentanediol by reducing the gas
phase
concentrations) of one or more odorant materials typically found in
commercially
available 2,2,4-trimethyl-1,3-pentanediol. The processes utilized in the
present invention
to reduce the gas phase concentrations of odorant materials typicaiiy found in
commercially available 2,2,4-trimethyl-1,3-pentanediol include, but are not
limited to,
reduction, hydrogenation, recrystallization, ion exchange treatment,
fractional
distillation. base treatment, aqueous extraction, vacuum stripping, nitrogen
sparging, and
combinations of the processes described herein.
The present invention also encompasses the compositions resulting from the
processes described herein to remove odorant materials from commercially
available
2,2,4-trimethyl-1,3-pentanediol. Additionally, the present invention relates
to fabric
softening compositions containing commercially available 2,2,4-trimethyl-1,3-
pentanediol which has been processed according to the present invention.
DETAILED DESCRIPTION OF THE INVENTION
I Commercial ~ ~ 4-Trimethyl-1 3-Pentanediol Having Improved Odor
The compound 2,2,4-trimethyl-1,3-pentanediol is commercially available from
the Eastman Chemical Company. As a commercial material, 2,2,4-trimethyl-1,3-
pentanediol typically contains one or more odorant materials which have been
found to
contribute to the offensive odor usually associated with commercially
available 2,2,4-
trimethyl-1,3-pentanediol. Specifically, it has been found that commercially
available
2,2,4-trimethyl-1,3-pentanediol contains one or more odorant materials,
including, but
not limited to: isobutyl aldehyde, isobutyric acid, 2,2,4-trimethyl-3-keto-
pentanol, 2,2,4-
trimethyl-3-keto-pentanol isobutyrate, diisopropyl ketone, 2,2,4-trimethyl-1,3-
pentanediol monoisobutyrate, and mixtures of such odorant materials.
The odorant materials described herein are characterized as having offensive
and/or repulsive odors. Isobutyl aldehyde has been described as having an
"extremely
diffusive, penetrating odor, pungent and - undiluted - unpleasant, sour,
repulsive." See
Steffen Arctander, PERFUME AND FLAVOR CHEMICALS, Vol. I, No. 548 (1969).
Isobutyric acid has been described as having a "powerful, diffusive sour
(acid) odor,
slightly less repulsive and less buttery than n-Butyric acid." See Steffen
Arctander,
PERFUME AND FLAVOR CHEMICALS, Vol. I, No. S50 (1969). Diisopropyl ketone has
been
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described as having a "powerful and diffusive ethereal-fruity, pungent odor."
See Steffen
Arctander, PERFUME AND FLAVOR CHEMICALS, Vol. I, No. 1090 (1969).
The compound 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate is available from
- the Eastman Chemical Company under the trade name Texanol0. This monoester
of
2,2,4-trimethyl-1,3-pentanediol is used as a coalescing aid in flat and
semigloss latex
paint formulations. See KIRK-UTHMER ENCYCLOPEDIA OF CHEMICAL TECHNOLOGY (3d
ed. 1978). A "solvent" odor is typically associated with commercially
available
Texanol~ due to impurities found in the commercial material. However, as a
pure
substance, 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate has a more
acceptable odor
due to its low volatility resulting from its high molecular weight.
It is preferable that the gas phase concentrations) of at least one or more of
these
odorant materials which are found in commercially available 2,2,4-trimethyl-
1,3-
pentanediol be significantly reduced in order to improve the odor of
commercially
available 2,2,4-trimethyl-1,3-pentanediol. As a result of reducing the gas
phase
concentrations of one or more of these odorant materials, consumer products
containing
2,2,4-trimethyl-1,3-pentanediol will typically achieve more acceptable odor
characteristics.
The "gas phase concentration" of odorant material is defined by measuring the
level of odorant material in a head space over a 2,2,4-trimethyl-1,3-
pentanediol sample
containing odorant materials. Chromatograms are generated using a 105 mL head
space
sample over about 2 grams of sample. The head space sample is trapped onto a
solid
absorbent and thermally desorbed onto a column directly via cryofocusing at
about -
100°C. The identification of materials is based on the peaks in the
chromatograms. The
gas phase concentration of each odorant material found in a typical
commercially
available 2,2,4-trimethyl-1,3-pentanediol sample and a typical invention
sample is as
follows:
Approximate Concentration of Head Space Impurities
Chemical Identification Gas chase concentration (~aIL1
Decreased by Commercial Typical Typical Typical
Invention
Sample invention Invention Invention
Sample Sample Sample
#1 #2 #3
Isobutyl aldehyde> 17 0.1 0.1 0.2
Isobutyric acid >8 0.1 <0.1 0.1
2,2,4-Trimethyl-3-keto-> 20 0.2 0.1 0.1
pentanol
2,2,4-Trimethyl-3-keto->2 < 0.1 < 0.1 ~ < 0.1
pentanol isobutyrate
Diisopropyt ketone1 0.1 0.1 <0.1
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2,2,4-Trimethyl-1,3- 1 <0.1 <0.1 <0.1
pentanediol
monoisobutyrate
Increased by Invention
Isobutanol 3 > 17 > 19 > 26
Isobutyl isobutyrate 9 > 10 > 12 > 22
The acceptable gas phase concentrations of each odorant material are as
follows:
isobutyl aldehyde should be less than about 1 ~, preferably less than about
10, more
preferably less than about 5, and most preferably less than about 1 micrograms
per liter
pg/L); isobutyric acid should be less than about 7, preferably less than about
4, and more
preferably less than about 1 micrograms per liter (~g/L); 2,2,4-trimethyl-3-
keto-pentanol
should be less than about 19, preferably less than about 10, and more
preferably less than
about 1 micrograms per liter (~g/L); 2,2,4-trimethyl-3-keto-pentanol
isobutyrate should
be less than about 2, preferably less than about 1.5, and more preferably less
than about 1
micrograms per liter(~g/L); diisopropyl ketone should be less than about 3,
preferably
less than about 2, and more preferably less than about 1 micrograms per liter
(pg/L);
2,2,4-trimethyl-1,3-pentanediol monoisobutyrate should be less than about 3,
preferably
less than about 2, and more preferably less than about 1 micrograms per liter
(~g/L).
These gas phase concentration levels provide better odor than the commercially
available
2,2,4-trimethyl-1,3-pentanediol.
Decreasing the gas phase concentration of the above odorant materials by some
methods result in increasing the gas phase concentration of other materials,
such as
isobutanol and isobutyl isobutyrate. Isobutanol has been described as having a
"[c]hoking, cough-provoking odor unless diluted; then rather mild, chemical,
sweet, yet
harsh." See Steffen Arctander, PERFUME AND FLAVOR CHEMICALS, Vol. I, No. 390
(1969). Isobutyl isobutyrate has an odor described as a "[s]weet-fruity, but
also rather
harsh-Pineapple-like, diffusive-ethereal odor. Fresher, but less
characteristic (a non-
descript fruit type) than the other isomers. Occasionally used in masking
odors for
industrial masking of repulsive odors, phenolic, cresylic, "chemical" odors,
solvent
odors, etch The relatively low boiling point (and high vapor pressure at room
temperature) of this ester makes it particularly suitable for such purposes."
See Steffen
Arctander, PERFUME AND FLAVOR CHEMICALS, Vol. I, No. 415 (1969).
It is especially novel and unobvious to process commercially available 2,2,4-
trimethyl-1,3-pentanediol so that the gas phase concentrations of certain
odorant
materials, such as isobuty! aldehyde and isobutyric acid, are decreased while
the gas
phase concentrations of other materials, such as isobutanol and isobutyl
isobutyrate, are
increased, which surprisingly results in an overall improvement in the odor of
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commercially available 2,2,4-trimethyl-1,3-pentanediol. It is also novel and
unobvious
to process commercially available 2,2,4-trimethyl-1,3-pentanediol as described
herein
and use the 2,2,4-trimethyl-1,3-pentanediol having improved odor in consumer
products,
such as fabric softeners, to achieve a more acceptable product odor.
It is surprising that an increase in the gas phase concentration of
isobutanol, along
with a decrease in the gas phase concentration of odorant materials,
particularly isobutyl
aldehyde and isobutyric acid, will result in an overall improvement in the
odor of
commercially available 2,2,4-trimethyl-1,3-pentanediol. This is especially
unexpected
when one considers the typically offensive odor associated with isobutanol. It
is
theorized, although not wanting to be bound by theory, that the combined
positive effect
of reducing the gas phase concentrations of odorant materials like isobutyl
aldehyde,
isobutyric acid, and diisopropyl ketone, along with a masking effect of
increasing the gas
concentration of isobutyl isobutyrate, will outweigh any negative effect of
increasing the
gas phase concentration of isobutanol, which will result in commercially
available 2,2,4-
trimethyl-1,3-pentanediol having a much improved odor.
It is also theorized, although not wanting to be bound by theory, that it is
important to incorporate the 2,2,4-trimethyl-1,3-pentanediol having improved
odor into a
fabric softening composition having a low pH. This is important because it is
believed
that the low pH of the fabric softening composition reduces the tendency of
any esters,
such as isobutyl isobutyrate, to hydrolyze over time to form isobutyric acid,
which would
negatively impact the odor of the composition.
II. Process for Imnrovin~ the Odor of Commercial 2.2.4-Trimethyl-1 3-
Pentanediol
Reduction is an effective process for improving the odor of commercially
available 2,2,4-trimethyl-1,3-pentanediol. For maximum improvement in odor,
reduction of 2,2,4-trimethyl-I,3-pentanediol can be accomplished by treating
it with
sodium borohydride as a reducing agent. Any of several forms of sodium
borohydride
may be used. For example, sodium borohydride powder, pellets, granules, or
aqueous
solution in combination with a base stabilizing agent, such as sodium
hydroxide can be
used. Potassium borohydride or other metal borohydrides can also be used. The
amount
of sodium borohydride used to reduce commercially available 2,2,4-trimethyl-
1,3-
pentanediol is 0.05% to 5%, preferably 0.2% to 2%, and more preferably 0.5% to
i .5%,
by weight of the 2,2,4-trimethyl-1,3-pentanediol.
Commercially available 2,2,4-trimethyl-1,3-pentanediol can also be reduced by
catalytieally hydrogenating it to improve its odor. Hydrogenation of 2,2,4-
trimethyl-1,3-
pentanediol is preferably accomplished by using hydrogen and a hydrogenation
catalyst,
including, but not limited to, palladium, nickel, copper, platinum, and copper
chromite
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catalysts, or combinations of such catalysts. This can be accomplished in
either a batch
or continuous hydrogenation process. The catalyst can be slurried or used in a
fixed bed.
Other catalytic hydrogenation processes are described in Robert J. Peterson,
HYDROGENATION CATALYSTS ( 1977), incorporated herein by reference.
Recrystallization of commercially available 2,2,4-trimethyl-1,3-pentanediol is
another effective way to remove odorant materials. One preferred
recrystallization
process involves taking up the 2,2,4-trimethyl-1,3-pentanediol in hexane to
form a
solution, optionally treating the solution with activated carbon,
crystallizing the 2,2,4-
trimethyl-1,3-pentanediol from hexane, and then evaporating the hexane
solvent.
Another, more preferred, recrystallization process includes taking up the
2,2,4-trimethyi-
1,3-pentanediol in hexane to form a solution, treating the solution with an an
ion
exchange resin. crystallizing 2.2,4-trimethyl-1.3-pentanediol from hexane,
extracting it
with an aqueous solution, drying it over sodium sulfate, and then evaporating
the hexane
solvent. Other recrystallization processes are discussed in Robert H. Perry &
Cecil H.
Chilton, CHEMICAL ENGINEERS HANDBOOK 17-8 to 17-25 (5th ed. 1973),
incorporated
herein by reference.
The present invention also involves fractionally distilling commercially
available
2,2,4-trimethyl-1,3-pentanediol in order to remove at least one odorant
material. The
fractional distillation can be carried out in either a batch or continuous
feed mode. with
the resulting 2,2,4-trimethyl-1,3-pentanediol taken off as either an overhead
or side
stream. A fractional distillation process typically results in a light
fraction, a middle
fraction, and a heavy fraction. wherein the middle fraction of 2,2,4-trimethyl-
I ,3-
pentanediol has improved odor. The odor of the fractionally distilled 2,2,4-
trimethyl-1,3-
pentanediol can then be further improved by reducing or hydrogenating the
fractionally
distilled 2,2,4-trimethyl-1,3-pentanediol by using the reducing or
hydrogenating agents
described herein. Fractional distillation processes are also described in
Robert H. Perry
& Cecil H. Chilton, CHEMICAL ENGINEERS HANDBOOK 13-I to 13-60 (5th ed. 1973),
incorporated herein by reference.
A base treatment process can also improve the odor of commercially available
2,2,4-trimethyl-1,3-pentanediol. A base treatment process useful for the
present
invention involves adding a solution containing a base, such as sodium
hydroxide,
sodium carbonate. or sodium methoxide at 25%, and a solvent, such as methanol
or
water. to 2,2,4-trimethyl-1,3-pentanediol in order to form an alkaline liquid
mixture. The
alkaline mixture is then heated to reflux the solvent. An acid, such as
hydrochloric acid,
is added to the alkaline mixture to adjust the pH in order to create a neutral
liquid
mixture. The neutral liquid mixture is then fractionally distilled to form a
light fraction,
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a middle fraction, and a heavy fraction. The resulting middle fraction and
heavy fraction
of 2,2,4-trimethyl-1,3-pentanediol have improved odor.
The odor of the 2,2,4-trimethyl-1,3-pentanediol processed according to any of
the
processes described above can be further improved by aqueous extraction(s),
which can
be carried out in either a batch or continuous operation. A counter-current
column can be
utilized for continuous aqueous extractions. Aqueous extraction(s) alone can
improve
the odor of commercially available 2,2,4-trimethyl-1,3-pentanediol, but it is
preferred to
use aqueous extraction(s) in combination with one or more processes described
herein.
Aqueous extration steps) can also incorporate a base, such as sodium hydroxide
or
sodium carbonate, to further improve the odor of commercially available 2,2,4-
trimethyl-
1,3-pentanediol.
Vacuum stripping will also improve the odor of commercially available 2,2,4-
trimethyl-1,3-pentanediol. It is preferred that vacuum stripping be used in
combination
with at least one or more of the processes described herein.
Another process involves nitrogen sparging of molten 2,2,4-trimethyl-1,3-
pentanediol to decrease the gas phase concentration of odorant materials.
While this
process by itself is not as effective as the previously described processes,
nitrogen
sparging can be useful as a final odor-improving step in combination with at
least one or
more of the previously mentioned processes. Nitrogen sparging can aid in the
removal of
solvent odor from a recrystallization process.
The present invention also encompasses improving the odor of commercially
available 2,2,4-trimethyl-I ,3-pentanediol by a combination of the processes
described
herein. Preferred embodiments of the present invention are described in the
Examples
provided hereinafter.
It is preferred that the odorant materials found in commercially available
2,2,4-
trimethyl-1,3-pentanediol not be reduced by alkoxyiation because the
alkoxylated
materials will change the nature of the 2,2,4-trimethyl-1,3-pentanediol. As
described in
PCT Application No. W09703169-AI, incorporated by reference hereinbefore, the
alkoxylation changes the ClogP of the 2,2,4-trimethyl-1,3-pentanediol.
III. Fabric Softening Compositions
A. Other Solvents
The commercially available 2,2,4-trimethyl-1,3-pentanediol having improved
odor of the present invention can be used as a principal solvent in liquid
fabric softening
compositions, as disclosed in PCT Application Nos. W09703169-AI and W09703170-
A1, incorporated by reference hereinbefore. It can also be used in such
compositions as
part of a mixture of other suitable solvents to form a principal solvent
system.
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For the clear fabric softening compositions of the present invention, the
principal
solvent is typically less than about 40%, preferably from about 5% to about
35%, more
preferably from about 10% to about 25%, and even more preferably from about
12% to
about 18%, by weight of the composition. Said principal solvent is selected to
minimize
solvent odor impact in the composition and to provide a iow viscosity to the
final
composition. For example, isopropyl alcohol is not very effective and has a
strong odor.
n-Propyl alcohol is more effective, but also has a distinct odor. Several
butyl aicohols
also have odors but can be used for effective clarity/stability, especially
when used as
part of a principal solvent system to minimize their odor. The alcohols are
also selected
for optimum low temperature stability, that is they are able to form
compositions that are
liquid with acceptable low viscosities and translucent, preferably clear, down
to about
40°F (about 4.4°C) and are able to recover after storage down to
about 20°F (about
6.7°C).
The suitability of any principal solvent for the formulation of the liquid,
concentrated, preferably clear, fabric softener compositions herein with the
requisite
stability is surprisingly selective. Suitable solvents can be selected based
upon their
octanol/water partition coefficient (P). Octanol/water partition coefficient
of a principal
solvent is the ratio between its equilibrium concentration in octanol and in
water. The
partition coefficients of the principal solvent ingredients of this invention
are
conveniently given in the form of their logarithm to the base 10, loge.
The loge of many ingredients has been reported; for example, the Pomona92
database, available from Daylight Chemical Information Systems, Ine. (Daylight
CIS),
Irvine, California, contains many, along with citations to the original
literature.
However, the iogP values are most conveniently calculated by the "CLOGP"
program,
also available from Daylight CIS. This program also lists experimental loge
values
when they are available in the Pomona92 database. The "calculated loge"
(ClogP) is
determined by the fragment approach of Hansch and Leo (cf., A. Leo, in
Comprehensive
Medicinal Chemistry, Vol. 4. C. Hansch, P. G. Sammens, J. B. Taylor and C. A.
Ramsden, 'ids., p. 295. Pergamon Press, 1990, incorporated herein by
reference). The
fragment approach is based on the chemical structure of each ingredient, and
takes into
account the numbers and types of atoms, the atom connectivity, and chemical
bonding.
The CIogP values, which are the most reliable and widely used estimates for
this
physicochemical property, are preferably used instead of the experimental loge
values in
the selection of the principal solvent ingredients which are useful in the
present
invention. Other methods that can be used to compute ClogP include, e.g.,
Crippen's
fragmentation method as disclosed in J. Chem. Inf. Comput. Sci., 27, 21
(1987);
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Viswanadhan's fragmentation method as disclose in J. Chem. lnf. Comput. Sci.,
29, 163
( I 989); and Broto's method as disclosed in Eur. 3. Med. Chem. - Chim.
Theor., 19, 71
( 1984).
The principal solvents herein are selected from those having a ClogP of from
about 0.15 to about 0.64, preferably from about 0.25 to about 0.62, and more
preferably
from about 0.40 to about 0.60, said principal solvent preferably being
asymmetric, and
preferably having a melting, or solidification, point that allows it to be
liquid at, or near
room temperature. Solvents that have a low molecular weight and are
biodegradable are
also desirable for some purposes. The more asymmetric solvents appear to be
very
desirable, whereas the highly symmetrical solvents, having a center of
symmetry, such as
1,7-heptanediol, or 1,4-bis(hydroxymethyl)cyclohexane, appear to be unable to
provide
the essentially clear compositions when used alone, even though their CIogP
values fall
in the preferred range. One can select the most suitable principal solvent by
determining
whether a composition containing about 27% di(oleyoyloxyethyl)dimethylammonium
chloride, about 16-20% of principal solvent, and about 4-6% ethanol remains
clear
during storage at about 40°F (about 4.4°C) and recovers from
being frozen at about 0°F
(about -18°C).
When there is an insufficient amount of principal solvent e.g.: 2,2,4-
trimethyl-
1,3-pentanediol having improved odor of the present invention; the ethoxylate,
diethoxylate, or triethoxylate derivatives of 2,2,4-trimethyl-I,3-pentanediol;
2-ethyl-1,3-
hexanediol; and/or 2-ethyl-1,3-hexanediol ethoxylates (I-3) and/or mixtures
thereof, to
provide a clear product, or even to provide a stable product, other solvents
can be added,
preferably I,4-cyclohexanedimethanol.
The typical principal solvent, in addition to 2,2,4-trimethyl-1,3-pentanediol
having improved odor of the present invention, is preferably selected from the
group
consisting of:
I. mono-ols including:
a. n-propanol; and/or
b. ' 2-butanol and/or 2-methyl-2-propanol;
II. hexane diol isomers including: 2,3-butanediol, 2,3-dimethyl-; 1,2-
butanediol, 2,3-
dimethyl-; I,2-butanediol, 3,3-dimethyl-; 2,3-pentanediol, 2-methyl-; 2,3-
pentanediol, 3-
methyl-; 2,3-pentanediol, 4-methyl-; 2,3-hexanediol; 3,4-hexanediol; 1,2-
butanediol, 2-
ethyl-; 1,2-pentanediol, 2-methyl-; 1,2-pentanediol, 3-methyl-; 1,2-
pentanedioh 4-
methyl-; and/or 1,2-hexanediol;
III. heptane diol isomers including: 1,3-propanediol, 2-butyl-;,1,3-
propanediol, 2,2-
diethyl-; 1,3-propanediol, 2-(1-methylpropyl)-; 1,3-propanediol, 2-(2-
methylpropyl)-;
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1,3-propanedioh 2-methyl-2-propyl-; 1,2-butanediol, 2,3,3-trimethyl-; 1,4-
butanediol, 2-
ethyl-2-methyl-; 1,4-butanediol, 2-ethyl-3-methyl-; 1,4-butanediol, 2-propyl-;
1,4-
butanediol, 2-isopropyl-; 1,5-pentanediol, 2,2-dimethyl-; 1,5-pentanedioh 2,3-
dimethyl-;
1,5-pentanediol, 2,4-dimethyl-; I,5-pentanediol, 3,3-dimethyl-; 2,3-
pentancdiol, 2,3-
dimethyl-; 2,3-pentanediol, 2.4-dimethyl-; 2,3-pentanediol, 3,4-dimethyl-; 2,3-
pentanediol, 4,4-dimethyl-; 3,4-pentanediol, 2,3-dimethyl-; I,S-pentanediol, 2-
ethyl-;
1,6-hexanediol, 2-methyl-; 1,6-hexanediol, 3-methyl-; 2,3-hexanediol, 2-methyl-
; 2,3-
hexanediol, 3-methyl-; 2,3-hexanediol, 4-methyl-; 2,3-hexanediol, S-methyl-;
3,4-
hexanediol, 2-methyl-; 3,4-hexanediol, 3-methyl-; 1,3-heptanediol; 1,4-
heptanediol; 1,5-
heptanediol; and/or 1,6-heptanediol;
IV. octane diol isomers including: 1,3-propanediol, 2-(2-methylbutyl)-; 1,3-
propanediol, 2-(1,1-dimethylpropyl)- 1,3-propanediol, 2-(1,2-dimethylpropyl)-;
1,3-
propanediol, 2-(1-ethylpropyl)-; 1,3-propanediol, 2-(1-methylbutyl)-; 1,3-
propanediol, 2-
(2,2-dimethylpropyl)-; 1,3-propanediol. 2-(3-methylbutyl)-; 1,3-propanediol, 2-
butyl-2-
methyl-; 1,3-propanediol, 2-ethyl-2-isopropyl-; 1.3-propanediol, 2-ethyl-2-
propyl-; 1,3-
propanediol, 2-methyl-2-(I-methylpropyl)-; 1,3-propanediol, 2-methyl-2-(2-
methylpropyl)-; 1,3-propanediol, 2-tertiary-butyl-2-methyl-; 1,3-butanediol,
2,2-diethyl-;
1,3-butanediol, 2-(I-methyipropyl)-; 1,3-butanediol, 2-butyl-; 1,3-butanediol,
2-ethyl-
2,3-dimethyl-; 1,3-butanediol, 2-( I , I -dimethylethyl)-; 1,3-butanediol, 2-
(2-
methylpropyl)-; 1,3-butanediol, ?-methyl-2-isopropyl-; 1,3-butanediol, 2-
methyl-2-
propyl-; 1,3-butanediol, 3-methyl-2-isopropyl-; 1,3-butanediol, 3-methyl-2-
propyl-; 1,4-
butanediol. 2,2-diethyl-; 1,4-butanediol, 2-methyl-2-propyl-; 1,4-butanediol,
2-(1-
methylpropyl)-; I ,4-butanediol, 2-ethyl-2,3-dimethyl-; I ,4-butanediol, 2-
ethyl-3,3-
dimethyl-; I ,4-butanediol, 2-( I ,1-dimethylethyl)-; 1,4-butanediol, 2-(2-
methylpropyl)-;
1,4-butanediol, 2-methyl-3-propyl-; 1,4-butanediol, 3-methyl-2-isopropyl-; I,3-
pentanediol, 2,2,3-trimethyl-; 1,3-pentanediol, 2,2,4-trimethyl-; 1,3-
pentanediol, 2,3,4-
trimethyl-; 1,3-pentanediol, 2,4,4-trimethyl-; 1,3-pentanediol, 3,4,4-
trimethyl-; 1,4-
pentanediol, 2,2,3-trimethyl-; 1,4-pentanediol, 2,2,4-trimethyl-; 1,4-
pentanediol, 2,3,3-
trimethyl-; 1,4-pentanediol, 2,3,4-trimethyl-; 1,4-pentanediol, 3,3,4-
trimethyl-; 1,5-
pentanediol, 2,2,3-trimethyl-; I ,S-pentanediol, 2,2,4-trimethyl-; 1,5-
pentanediol, 2,3,3-
trimethyl-; I,5-pentanediol, 2,3,4-trimethyl-; 2,4-pentanediol, 2,3,3-
trimethyl-; 2,4-
pentanediol, 2,3,4-trimethyl-; 1,3-pentanediol, 2-ethyl- 2-methyl-; 1,3-
pentanediol, 2-
ethyl-3-methyl-; 1,3-pentanediol, 2-ethyl-4-methyl-; 1,3-pentanediol, 3-ethyl-
2-methyl-;
1,4-pentanediol, 2-ethyl-2-methyl-; 1,4-pentanediol, 2-ethyl-3-methyl-; 1,4-
pentanediol,
2-ethyl-4-methyl-; 1,4-pentanediol, 3-ethyl-2-methyl-; 1,4-pentanediol, 3-
ethyl-3-
methyl-; I,5-pentanediol, 2-ethyl-2-methyl-; 1,5-pentanediol, 2-ethyl-3-methyl-
; I,5-
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pentanediol, 2-ethyl-4-methyl-; 1,5-pentanediol, 3-ethyl-3-methyl-; 2,4-
pentanediol, 3-
ethyl-2-methyl-; 1,3-pentanediol, 2-isopropyl-; 1,3-pentanediol, 2-propyl-;
1,4-
pentanediol, 2-isopropyl-; 1,4-pentanediol, 2-propyl-; 1,4-pentanediol, 3-
isopropyl-; 1,5-
pentanediol, 2-isopropyl-; 2,4-pentanediol, 3-propyl-; I,3-hexanediol, 2,2-
dimethyl-; 1,3-
hexanediol, 2,3-dimethyl-; 1,3-hexanediol, 2,4-dimethyl-; 1,3-hexanediol, 2,5-
dimethyl-;
I ,3-hexanediol, 3,4-dimethyl-; 1,3-hexanediol, 3,5-dimethyl-; 1,3-hexanediol,
4,5-
dimethyl-; I,4-hexanediol, 2,2-dimethyl-; 1,4-hexanediol, 2,3-dimethyl-; 1,4-
hexanediol,
2,4-dimethyl-; 1,4-hexanediol, 2,5-dimethyl-; 1,4-hexanediol, 3,3-dimethyl-;
1,4-
hexanediol, 3,4-dimethyl-; 1,4-hexanediol, 3,5-dimethyl-; 1,3-hexanediol, 4,4-
dimethyl-;
1,4-hexanediol, 4,5-dimethyl-; 1,4-hexanediol, 5,5-dimethyl-; 1,5-hexanediol,
2,2-
dimethyl-; 1,5-hexanediol, 2,3-dimethyl-; 1,5-hexanediol, 2,4-dimethyl-; 1,5-
hexanediol,
2.5-dimethyl-; 1,5-hexanediol, 3,3-dimethyl-; 1,5-hexanediol, 3,4-dimethyl-;
1,5-
hexanediol, 3,5-dimethyl-; I,5-hexanediol, 4,5-dimethyl-; 1,6-hexanediol, 2,2-
dimethyl-;
1,6-hexanediol, 2,3-dimethyl-; 1,6-hexanediol, 2,4-dimethyl-; 1,6-hexanediol,
2,5-
dimethyl-; 1,6-hexanediol, 3,3-dimethyl-; 1,6-hexanediol, 3,4-dimethyI-; 2,4-
hexanediol,
2,3-dimethyl-; 2,4-hexanediol, 2,4-dimethyl-; 2,4-hexanediol, 2,5-dimethyl-;
2,4-
hexanediol, 3,3-dimethyl-; 2,4-hexanediol, 3,4-dimethyl-; 2,4-hexanediol, 3,5-
dimethyl-;
2,4-hexanediol, 4,5-dimethyl-; 2,4-hexanediol, 5,5-dimethyl-; 2,5-hexanediol,
2,3-
dimethyl-; 2,5-hexanediol, 2,4-dimethyl-; 2,5-hexanediol, 2,5-dimethyl-; 2,5-
hexanediol,
3,3-dimethyl-; 2,5-hexanediol, 3,4-dimethyl-; 2,6-hexanediol, 3,3-dimethyl-;
1,3-
hexanediol, 2-ethyl-; 1,3-hexanediol, 4-ethyl-; 1,4-hexanediol, 2-ethyl-; 1,4-
hexanediol,
4-ethyl-; 1,5-hexanediol, 2-ethyl-; 2,4-hexanediol, 3-ethyl-; 2,4-hexanediol,
4-ethyl-; 2,5-
hexanediol, 3-ethyl-; 1,3-heptanediol, 2-methyl-; 1,3-heptanediol, 3-methyl-;
1,3-
heptanediol, 4-methyl-; 1,3-heptanediol, 5-methyl-; 1,3-heptanediol, 6-methyl-
; 1,4-
heptanediol, 2-methyl-; 1,4-heptanediol, 3-methyl-; 1,4-heptanediol, 4-methyl-
; 1,4-
heptanediol, 5-methyl-; 1,4-heptanediol, 6-methyl-; 1,5-heptanediol, 2-methyl-
; 1,5-
heptanediol, 3-methyl-; 1,5-heptanediol, 4-methyl-; I,5-heptanediol, 5-methyl-
; 1,5-
heptanediol, 6-methyl-; 1,6-heptanediol, 2-methyl-; 1,6-heptanediol, 3-methyl-
; I,6-
heptanediol, 4-methyl-; 1,6-heptanediol, 5-methyl-; 1,6-heptanediol, 6-methyl-
; 2,4-
heptanediol, 2-methyl-; 2,4-heptanediol, 3-methyl-; 2,4-heptanediol, 4-methyl-
; 2,4-
heptanediol, 5-methyl-; 2,4-heptanediol, 6-methyl-; 2,5-heptanediol, 2-methyl-
; 2,5-
heptanediol, 3-methyl-; 2,5-heptanediol, 4-methyl-; 2,5-heptanediol, 5-methyl-
; 2,5-
heptanediol, 6-methyl-; 2,6-heptanedioi, 2-methyl-; 2,6-heptanediol, 3-methyl-
; 2,6-
heptanediol, 4-methyl-; 3,4-heptanediol, 3-methyl-; 3,5-heptanediol, 2-methyl-
; 3,5-
heptanediol, 3-methyl-; 3,5-heptanediol, 4-methyl-; 2,4-octanedioh 2,5-
octanediol; 2,6-
octanediol; 2,7-octanediol; 3,5-octanediol; and/or 3,6-octanediol;
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V. nonane diol isomers including: 2,4-pentanediol, 2,3,3,4-tetramethyl-; 2,4-
pentanediol, 3-tertiarybutyl-; 2,4-hexanediol, 2,5,5-trimethyl-; 2,4-
hexanediol, 3,3,4-
trimethyl-; 2,4-hexanediol, 3.3,5-trimethyl-; 2,4-hexanediol, 3,5,5-trimethyl-
; 2,4-
hexanediol, 4,5,5-trimethyi-; 2,5-hexanediol, 3,3,4-trimethyl-; and/or 2,5-
hexanediol,
3,3,5-trimethyl-;
VI. glyceryl ethers and/or di(hydroxyalkyl)ethers including: 1,2-propanediol,
3-(n-
pentyloxy)-; 1,2-propanediol, 3-(2-pentyloxy)-; 1,2-propanediol, 3-(3-
pentyloxy)-; 1,2-
propanediol, 3-(2-methyl-1-butyloxy)-; 1,2-propanediol, 3-(iso-amyloxy)-; 1,2-
propanediol, 3-(3-methyl-2-butyloxy)-; 1,2-propanediol, 3-(cyclohexyloxy)-;
1,2-
propanediol, 3-(I-cyclohex-I-enyloxy)-; 1,3-propanediol, 2-(pentyloxy)-; 1,3-
propanediol, 2-{2-pentyloxy)-; 1,3-propanediol, 2-(3-pentyloxy)-; 1,3-
propanediol, 2-(2-
methyl-I-butyloxy)-; I_3-propanediol. 2-(iso-amyloxy)-; 1,3-propanediol, 2-(3-
methyl-2-
butyloxyj-; 1,3-propanediol, 2-(cyclohexyloxy)-; 1,3-propanediol, 2-(1-
cyclohex-1-
enyloxy)-; 1,2-propanediol, 3-(butyloxy)-, triethoxylated; 1,2-propanediol, 3-
(butyloxy)-,
tetraethoxylated; 1,2-propanediol, 3-(butyloxy)-, pentaethoxylated; 1,2-
propanediol, 3-
(butyloxy)-, hexaethoxylated: 1,2-propanediol. 3-{butyloxy)-,
heptaethoxylated; 1,2-
propanediol, 3-(butyloxy)-, octaethoxylated; 1,2-propanediol, 3-{butyloxy)-,
nonaethoxylated; 1,2-propanediol, 3-(butyloxy)-, monopropoxylated; 1,2-
propanediol, 3-
(butyloxy)-, dibutyleneoxylated; 1,2-propanediol, 3-(butyloxy)-,
tributyleneoxylated;
1,2-propanediol, 3-phenyloxy-; 1,2-propanediol, 3-benzyloxy-; I ,2-
propanediol, 3-(2-
phenylethyloxy)-; 1,2-propanediol, 3-(I-phenyl-2-propanyloxy)-; 1,3-
propanediol, 2-
phenyloxy-; 1,3-propanediol. 2-(m-cresyloxy)-; 1,3-propanediol, 2-{p-
cresyloxy)-; 1.3-
propanediol, -benzyloxy-; 1,3-propanediol, 2-(2-phenylethyloxy}-; 1,3-
propanediol, 2-(1-
phenylethyloxy)-; bis(2-hydroxybutyl)ether; and/or bis(2-
hydroxycyclopentyl)ether:
VII. saturated and unsaturated alicyclic diols and their derivatives
including:
(a) the saturated diols and their derivatives, including:
1-isopropyl-1,2-cyclobutanediol; 3-ethyl-4-methyl-1,2-cyclobutanediol; 3-
propyl-1.2-
cyclobutanediol; 3-isopropyl-1,2-cyclobutanediol; 1-ethyl-1,2-
cyclopentanediol; 1,2-
dimethyl-lt2-cyclopentanediol; 1,4-dimethyl-1,2-cyclopentanediol; 2,4,5-
trimethyl-1,3-
cyciopentanediol; 3,3-dimethyl-1,2-cyclopentanediol; 3,4-dimethyl-1,2-
cyclopentanediol; 3,5-dimethyl-1.2-cyclopentanediol; 3-ethyl-1,2-
cyclopentanediol; 4,4-
dimethyl-1,2-cyclopentanediol; 4-ethyl- I ,2-cyciopentanediol; I , I -
bis(hydroxymethyl)cyclohexane; 1,2-bis(hydroxymethyl)cyclohexane; 1,2-dimethyl-
1,3-
cyclohexanediol; 1,3-bis(hydroxymethyl)cyclohexane; 1,3-dimethyl-1,3-
cyclohexanediol; 1,6-dimethyl-1,3-cyclohexanediol; 1-hydroxy-
cyclohexaneethanol; I-
hydroxy-cyclohexanemethanol; I-ethyl-1,3-cyclohexanediol; 1-methyl-1,2-
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cyclohexanediol; 2,2-dimethyl-1,3-cyclohexanediol; 2,3-dimethyl-1,4-
cyclohexanediol;
2,4-dimethyl-1,3-cyclohexanediol; 2,5-dimethyl-1,3-cyclohexanediol; 2,6-
dimethyi-1,4-
cyclohexanediol; 2-ethyl-1,3-cyclohexanediol; 2-hydroxycyclohexaneethanol; 2-
hydroxyethyl-1-cyclohexanol; 2-hydroxymethylcyclohexanol; 3-hydroxyethyl-1-
cyclohexanol; 3-hydroxycyclohexaneethanol; 3-hydroxymethylcyclohexanol; 3-
methyl-
1,2-cyclohexanediol; 4,4-dimethyl-1,3-cyclohexanediol; 4,5-dimethyl-1,3-
cyclohexanediol; 4,6-dimethyl-1,3-cyclohexanediol; 4-ethyl-1,3-
cyclohexanediol; 4-
hydroxyethyl-I-cyclohexanol; 4-hydroxymethylcyclohexanol; 4-methyl-1,2-
cyclohexanediol; 5,5-dimethyl-I,3-cyclohexanediol; 5-ethyl-I,3-
cyclohexanediol; 1,2-
cycloheptanediol; 2-methyl-1,3-cycloheptanediol; 2-methyl-1,4-
cycloheptanediol; 4-
methyl-1,3-cycloheptanediol; 5-methyl-1,3-cycloheptanediol; 5-methyl-1,4-
cycloheptanediol; 6-methyl-1,4-cycloheptanediol; ; 1,3-cyclooctanediol; 1,4-
cyclooctanediol; I,5-cyclooctanediol; 1,2-cyclohexanediol, diethoxylate; 1,2-
cyclohexanediol, triethoxylate; I,2-cyclohexanediol, tetraethoxylate; 1,2-
cyclohexanediol, pentaethoxylate; 1,2-cyclohexanediol, hexaethoxylate; 1,2-
cyclohexanediol, heptaethoxylate; 1,2-cyclohexanediol, octaethoxylate; 1,2-
cyclohexanediol, nonaethoxylate; 1,2-cyclohexanediol, monopropoxylate; 1,2-
cyclohexanediol, monobutylenoxylate; 1,2-cyclohexanediol, dibutylenoxylate;
and/or
I,2-cyclohexanediol, tributylenoxylate; and
(b). the unsaturated alicyclic diols including: 1,2-cyclobutanediol, 1-ethenyl-
2-ethyl-; 3-
cyclobutene-1,2-diol, 1,2,3,4-tetramethyl-; 3-cyclobutene-1,2-diol, 3,4-
diethyl-; 3-
cyclobutene-1,2-diol, 3-(1,1-dimethylethyl)-; 3-cyclobutene-1,2-diol, 3-butyl-
; 1,2-
cyclopentanediol, 1,2-dimethyl-4-methylene-; 1,2-cyclopentanediol, 1-ethyl-3-
methylene-; 1,2-cyclopentanediol, 4-{1-propenyl); 3-cyclopentene-1,2-diol, 1-
ethyl-3-
methyl-; 1,2-cyclohexanediol, 1-ethenyl-; 1,2-cyclohexanediol, 1-methyl-3-
methylene-;
1,2-cyclohexanediol, 1-methyl-4-methylene-; 1,2-cyclohexanediol, 3-ethenyl-;
1,2-
cyclohexanediol, 4-ethenyl-; 3-cyclohexene-1,2-diol, 2,6-dimethyl-; 3-
cyclohexene-1,2-
diol, 6,6-dimethyl-; 4-cyciohexene-1,2-diol, 3,6-dimethyl-; 4-cyclohexene-1,2-
diol, 4,5-
dimethyl-; 3-cyclooctene-1,2-diol; 4-cyclooctene-1,2-diol; and/or 5-
cyclooctene-1,2-diol;
VIII. Alkoxylated derivatives of C3_g diols [In the following disclosure, "EO"
means
polyethoxylates, i.e., -(CH2CH20)nH; Me-En means methyl-capped polyethoxylates
-
(CH2CH20)nCH3 ; "2(Me-En)" means 2 Me-En groups needed; "PO" means
polypropoxylates, -(CH(CH3)CH20)nH ; "BO" means polybutyleneoxy groups,
(CH(CH2CH3)CH20)nH ; and "n-BO" means poly(n-butyleneoxy) or
poly(tetramethylene)oxy groups -(CH2CH2CH2CH20)nH. The use of the term "(Cx)"
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herein refers to the number of carbon atoms in the base material which is
alkoxylated.J
including:
I. 1,2-propanediol 2(Me-EI_4); 1,2-propanediol P04; 1,2-propanediol, 2-
methyl- (Me-E4_Ip): 1,2-propanediol, 2-methyl- 2(Me-EI); 1,2-propanediol. 2-
methyl-
P03; 1,2-propanediol, 2-methyl- BOI; 1,3-propanediol 2(Me-E6_g); 1,3-
propanediol
POS_6; 1,3-propanediol, 2,2-diethyl- EI_~; 1,3-propanediol, 2,2-diethyl- POI;
1,3-
propanediol, 2,2-diethyl- n-BO I _2; 1,3-propanediol, 2,2-dimethyl- 2(Me E I
_2); 1,3-
propanediol, 2,2-dimethyl- P03_4; 1,3-propanediol, 2-(I-methylpropyl)- E1_~;
1,3-
propanediol, 2-( I-methylpropyl)- POI ; 1,3-propanediol, 2-( 1-methylpropyl)-
n-BOI _2;
1,3-propanediol, 2-{2-methylpropyl)- E I _~; I ,3-propanediol, 2-(2-
methylpropyl)- POI ;
1,3-propanediol, 2-(2-methylpropyl)- n-BOI_~; 1,3-propanediol, 2-ethyl- (Me
E6_10)
1,3-propanediol, 2-ethyl- 2(Me E I ); 1,3-propanediol, 2-ethyl- P03; 1,3-
propanediol, 2-
ethyl-2-methyl- (Me E I _6); 1,3-propanediol, 2-ethyl-2-methyl- P02; I ,3-
propanediol, 2-
ethyl-2-methyl- BOI ; 1,3-propanediol, 2-isopropyl- (Me E1 _6); 1,3-
propanediol, 2-
isopropyl- P02; 1,3-propanediol, 2-isopropyl- BO I ; I ,3-propanediol, 2-
methyl- 2(Me
E2_5); 1,3-propanediol, 2-methyl- P04_5; 1,3-propanediol, 2-methyl- B02; 1,3-
propanediol, 2-methyl-2-isopropyl- E2-9; 1,3-propanediol, 2-methyl-2-isopropyl-
POI;
1,3-propanediol, 2-methyl-2-isopropyl- n-BOI_3; 1,3-propanediol, 2-methyl-2-
propyl-
EI _7; I ,3-propanediol, 2-methyl-2-propyl- POI ; I ,3-propanediol, 2-methyl-2-
propyl- n-
BOI _2; 1,3-propanediol, 2-propyl- (Me E I _4); 1,3-propanediol, 2-propyl-
P02; I ,3-
propanediol, 2-propyl- BOI;
2. 1.2-butanediol (Me E2_g); 1.2-butanediol P02-3; 1.2-butanediol BOI;
1,2-butanediol, 2,3-dimethyl- E 1 _H; I .2-butanediol. 2.3-dimethyl- n-BOI _2;
I ,2-
butanediol, 2-ethyl- E I _3; 1,2-butanediol, 2-ethyl- n-BO I ; 1,2-butanediol,
2-methyl- (Me
E I _2); 1,2-butanediol, 2-methyl- PO I ; I ,2-butanediol, 3,3-dimethyl- E I
_6; 1,2-
butanediol, 3,3-dimethyl- n-BOI_2; 1,2-butanediol, 3-methyl- (Me EI_2); 1,2-
butanediol,
3-methyl- POI; 1,3-butanediol 2(Me E3_6); 1,3-butanediol POS; 1,3-butanediol
B02;
1,3-butanediol, 2,2,3-trimethyl- (Me EI_3); 1,3-butanediol, 2,2,3-trimethyl-
POI_2; 1,3-
butanedioI;~2,2-dimethyl- (Me E3_g); 1,3-butanediol, 2,2-dimethyl- P03; 1,3-
butanediol,
2,3-dimethyl- (Me E3_g); 1,3-butanediol, 2,3-dimethyl- P03; 1,3-butanediol, 2-
ethyl-
(Me EI_6); 1.3-butanediol, 2-ethyl- P02_3; 1,3-butanediol, 2-ethyl- BOI; 1,3-
butanediol,
2-ethyl-2-methyl- (Me EI); 1,3-butanediol, 2-ethyl-2-methyl- POI; 1,3-
butanediol, 2-
ethyl-2-methyl- n-B02_4; 1,3-butanediol, 2-ethyl-3-methyl- (Me EI); 1,3-
butanediol, 2-
ethyl-3-methyl- POI ; 1,3-butanediol, 2-ethyl-3-methyl- n-B02_4; 1,3-
butanediol, 2-
isopropyl- (Me E I ); I ,3-butanediol, 2-isopropyl- PO I ; I ,3-butan~diol, 2-
isopropyl- n-
B02_4; 1,3-butanediol, 2-methyl- 2(Me El_3); 1,3-butanediol, 2-methyl- P04;
I,3-
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-I 5-
butanediol, 2-propyl- E2_9; 1,3-butanediol, 2-propyl- POI; 1,3-butanediol, 2-
propyl- n-
BOI_3; 1,3-butanediol, 3-methyl- 2(Me EI_3); 1,3-butanediol, 3-methyl- P04;
1,4-
butanediol 2(Me E2_4); I ,4-butanediol P04_5; I ,4-butanediol B02; 1,4-
butanediol,
2,2,3-trimethyl- E2_9; 1,4-butanediol, 2,2,3-trimethyl- POI; 1,4-butanediol,
2,2,3-
trimethyl- n-BOI_3; 1,4-butanediol, 2,2-dimethyl- (Me EI_6); 1,4-butanediol,
2,2-
dimethyl- P02; I ,4-butanediol, 2,2-dimethyl- BO I ; 1,4-butanediol, 2,3-
dimethyl- (Me
E I _6); 1,4-butanediol, 2,3-dimethyl- P02; I ,4-butanediol, 2,3-dimethyl- BO
I ; 1,4-
butanediol, 2-ethyl- (Me EI_4); 1,4-butanediol, 2-ethyl- P02; 1,4-butanediol,
2-ethyl-
BO I ; I ,4-butanediol, 2-ethyl-2-methyl- E I _~; 1,4-butanediol, 2-ethyl-2-
methyl- PO I ;
1,4-butanediol, 2-ethyl-2-methyl- n-BO I _2; I,4-butanediol, 2-ethyl-3-methyl-
E I _~; 1,4-
butanediol, 2-ethyl-3-methyl- PO I ; I ,4-butanediol, 2-ethyl-3-methyl- n-BO I
_2; 1,4-
butanediol, 2-isopropyl- E I _~; I ,4-butanediol, 2-isopropyl- PO I ; I ,4-
butanediol, 2-
isopropyl- n-BOI_2; 1,4-butanediol, 2-methyl- (Me E6_10); 1,4-butanediol, 2-
methyl-
2(Me E I ); I ,4-butanediol, 2-methyl- P03; 1,4-butanediol, 2-methyl- BOI ;
1,4-
butanediol, 2-propyl- E I _5; I ,4-butanediol, 2-propyl- n-BO I _2; 1,4-
butanediol, 3-ethyl-
1-methyl- E2_9; 1,4-butanediol, 3-ethyl-1-methyl- POI; 1,4-butanediol, 3-ethyl-
I-
methyI- n-BOI_3; 2,3-butanediol (Me E6_IO); 2,3-butanediol 2(Me EI); 2,3-
butanediol
P03_4; 2,3-butanediol BOI; 2,3-butanediol, 2,3-dimethyl- E3_9; 2,3-butanediol,
2,3-
dimethyl- POI; 2,3-butanediol, 2,3-dimethyl- n-BOI_3; 2,3-butanediol, 2-methyl-
(Me
EI_5); 2,3-butanediol, 2-methyl- P02; 2,3-butanediol, 2-methyl- BOI;
3. 1,2-pentanediol E3_I0; 1,2-pentanediol, POI; 1,2-pentanediol, n-B02_3;
1,2-pentanediol, 2-methyl E I _3; 1,2-pentanediol, 2-methyl n-BO I ; I ,2-
pentanediol, 2-
methyl BOI; 1,2-pentanediol, 3-methyl EI_3; 1,2-pentanediol, 3-methyl n-BOI;
1,2-
pentanediol, 4-methyl E I _3; 1,2-pentanediol, 4-methyl n-BO I ; 1,3-
pentanediol 2(Me-E I _
2); 1,3-pentanediol P03_4; 1,3-pentanediol, 2,2-dimethyl- (Me-EI); 1,3-
pentanediol, 2,2-
dimethyl- POI; 1,3-pentanediol, 2,2-dimethyl- n-B02_4; 1,3-pentanediol, 2,3-
dimethyl-
(Me-EI); 1,3-pentanediol, 2,3-dimethyl- POI; 1,3-pentanediol, 2,3-dimethyl- n-
B02_4;
I ,3-pentanediol, 2,4-dimethyl- (Me-E I ); I ,3-pentanediol, 2,4-dimethyl- PO
I ; 1,3-
pentanediol', 2,4-dimethyl- n-B02_4; 1,3-pentanediol, 2-ethyl- E2_9; 1,3-
pentanediol, 2-
ethyl- POI; 1,3-pentanediol, 2-ethyl- n-BOI_3; 1,3-pentanediol, 2-methyl- 2(Me-
EI-6);
1,3-pentanediol, 2-methyl- P02_3; 1,3-pentanediol, 2-methyl- BOI; 1,3-
pentanediol, 3,4-
dimethyl- (Me-EI); 1,3-pentanediol, 3,4-dimethyl- POI; 1,3-pentanediol, 3,4-
dimethyl-
n-B02_4; 1,3-pentanediol, 3-methyl- {Me-EI_6); 1,3-pentanediol, 3-methyl-
P02_3; 1,3-
pentanediol, 3-methyl- BOI; 1,3-pentanedioI, 4,4-dimethyl- (Me-EI); 1,3-
pentanediol,
4,4-dimethyl- POI; 1,3-pentanediol, 4,4-dimethyl- n-B02_4; 1,3-pentanediol, 4-
methyl-
(Me-EI_6); 1,3-pentanediol, 4-methyl- P02_3; 1,3-pentanediol, 4-methyl- BOI;
1,4-
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pentanediol, 2(Me-E1_2); 1,4-pentanediol P03_4; 1,4-pentanediol, 2,2-dimethyl-
(Me-
EI); 1,4-pentanediol, 2,2-dimethyl- POI; 1,4-pentanediol, 2,2-dimethyl- n-
B02_4; 1,4-
pentanediol, 2,3-dimethyl- (Me-E I ); 1,4-pentanediol, 2,3-dimethyl- PO I ; I
,4-
pentanediol, 2,3-dimethyl- n-B02_4; 1,4-pentanediol, 2,4-dimethyl- (Me-EI);
1,4-
pentanediol, 2,4-dimethyl- POI; 1,4-pentanediol, 2,4-dimethyl- n-B02_4; 1,4-
pentanediol, 2-methyl- (Me-E I _6); I ,4-pentanediol, 2-methyl- P02_3; 1,4-
pentanediol, 2-
methyl- BOI; 1,4-pentanediol, 3,3-dimethyl- (Me-EI); 1,4-pentanediol, 3,3-
dimethyl-
POI; 1,4-pentanediol, 3,3-dimethyl- n-B02-4; 1,4-pentanedioi, 3,4-dimethyl-
(Me-EI);
1,4-pentanediol, 3,4-dimethyl- POI; 1,4-pentanediol, 3,4-dimethyl- n-B02_4;
1,4-
pentanediol, 3-methyl- 2(Me-EI_6); 1,4-pentanediol, 3-methyl- P02_3; 1,4-
pentanediol,
3-methyl- BOI; 1,4-pentanediol, 4-methyl- 2(Me-EI_6); 1,4-pentanediol, 4-
methyl-
PO~_3; 1,4-pentanediol, 4-methyl- BOI; 1,5-pentanediol, (Me-E4_10); 1,5-
pentanediol
2(Me-EI); 1,5-pentanediol P03; 1,5-pentanediol, 2,2-dimethyl- EI_~; 1,5-
pentanediol,
2,2-dimethyl- POI ; 1,5-pentanediol, 2 2-dimethyl- n-BOI _2; 1,5-pentanediol,
2,3-
dimethyl- EI_~; 1,5-pentanediol, 2,3-dimethyl- POI; 1,5-pentanediol, 2,3-
dimethyl- n-
BOI_2; 1,5-pentanediol, 2,4-dimethyl- EI_~; 1,5-pentanediol, 2,4-dimethyl-
POI; 1,5-
pentanediol, 2,4-dimethyl- n-BOI_2; 1,5-pentanediol, 2-ethyl- El_5; 1,5-
pentanediol, 2-
ethyl- n-BOI_2; 1,5-pentanediol, 2-methyl- (Me-EI_4); 1,5-pentanediol, 2-
methyl- P02;
1,5-pentanediol, 3,3-dimethyl- E I _~; 1,5-pentanediol, 3,3-dimethyl- PO I ;
1,5-
pentanediol, 3,3-dimethyl- n-BO I _2; I ,5-pentanediol, 3-methyl- (Me-E I _4);
1,5-
pentanediol, 3-methyl- PO~; ~,3-pentanediol, (Me-E I _3); 2,3-pentanediol,
P02; 2,3-
pentanediol. 2-methyl- E I _~; 2,3-pentanediol, 2-methyl- PO I ; 2,3-
pentanediol, 2-methyl-
n-BOI_2; ~,3-pentanediol. 3-methyl- EI_~; 2,3-pentanediol, 3-methyl- POI; 2,3-
pentanediol, 3-methyl- n-BOI_2; '',3-pentanediol, 4-methyl- EI_~; 2,3-
pentanediol, 4-
methyl- POI; 2,3-pentanediol, 4-methyl- n-BOI_2; 2,4-pentanediol, 2(Me-EI-4);
2,4-
pentanediol P04; 2,4-pentanediol. 2,3-dimethyl- (Me-EI_4); 2,4-pentanediol,
2,3-
dimethyl- P02; 2,4-pentanediol, 2,4-dimethyl- (Me-EI-4); 2,4-pentanediol, 2,4-
dimethyl- P02; 2,4-pentanediol, 2-methyl- (Me-E5_10); 2,4-pentanediol, 2-
methyl- P03;
2,4-pentanediol, 3,3-dimethyl- (Me-EI_4); 2,4-pentanediol, 3,3-dimethyl- P02;
2,4-
pentanediol, 3-methyl- (Me-E5_Ip); 2,4-pentanediol, 3-methyl- P03;
4. 1,3-hexanedioi (Me-EI_5); 1,3-hexanediol P02; 1,3-hexanediol BOI; 1,3-
hexanediol, 2-methyl- E2_9; 1,3-hexanediol, 2-methyl- POI; 1,3-hexanediol, 2-
methyl-
n-BO I _3; 1,3-hexanediol, 2-methyl- BO I ; 1,3-hexanediol, 3-methyl- E2_9;
1,3-
hexanediol, 3-methyl- POI; 1,3-hexanediol, 3-methyl- n-BOI_3; 1,3-hexanediol,
4-
methyl- E2_9; 1,3- .hexanediol, 4-methyl- POI; 1,3-hexanediol, 4-methyl- n-
BOI_3; 1,3-
hexanediol. 5-methyl- E2_9; 1,3-hexanediol, 5-methyl- POI; 1,3-hexanediol, 5-
methyl-
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n-BO1_3; 1,4-hexanediol (Me-EI_5); 1,4-hexanediol P02; 1,4-hexanediol BOI; 1,4-
hexanediol, 2-methyl- E2_9; 1,4-hexanediol, 2-methyl- POI; 1,4-hexanediol, 2-
methyl-
n-BO 1 _3; 1,4-hexanediol, 3-methyl- E2_9; 1,4-hexanediol, 3-methyl- PO ~ ;
1,4-
hexanediol, 3-methyl- n-BO1_3; 1,4-hexanediol, 4-methyl- E2_g; 1,4-hexanediol,
4-
methyl- POI ; 1,4-hexanedioi, 4-methyl- n-BOI _3; 1,4-hexanediol, 5-methyl-
E2_9; 1,4-
hexanediol, 5-methyl- POI; 1,4-hexanediol, 5-methyl- n-BOI_3; 1,5-hexanediol
(Me-E1_
5); 1,5-hexanediol P02; 1,5-hexanediol BOI; 1,5-hexanediol, 2-methyl- E2_9;
1,5-
hexanediol, 2-methyl- POI; 1,5-hexanediol, 2-methyl- n-BOl_3; 1,5-hexanediol,
3-
methyl- E2_9; 1,5-hexanediol, 3-methyl- POI; 1,5-hexanediol, 3-methyl- n-
BO1_3; 1,5-
hexanediol, 4-methyl- E2_9; 1,5-hexanediol, 4-methyl- POI; 1,5-hexanediol, 4-
methyl-
n-BO 1 _3; I ,5-hexanediol, 5-methyl- E2_9; 1,5-hexanediol, 5-methyl- PO I ;
1,5-
hexanediol, 5-methyl- n-BO I _~; I ,6-hexanediol (Me-E I _2); I ,6-hexanediol
POI _2; 1,6-
hexanediol n-B04; 1,6-hexanediol, 2-methyl- EI_5; 1,6-hexanediol, 2-methyl- n-
BOI_2;
1,6-hexanediol, 3-methyl- E I _5; I ,6-hexanedioi, 3-methyl- n-BO 1 _2; 2,3-
hexanediol E I _
5; 2,3-hexanediol n-BOI; 2,3-hexanediol BOI; 2,4-hexanediol (Me-E3_g); 2,4-
hexanediol P03; 2,4-hexanediol, 2-methyl- (Me-E I _2); 2,4-hexanediol 2-methyl-
POI _2;
2,4-hexanediol, 3-methyl- (Me-E I _2); 2,4-hexanediol 3-methyl- PO I _2; 2,4-
hexanediol,
4-methyl- (Me-E I _2); 2,4-hexanediol 4-methyl- POI _2; 2,4-hexanediol, 5-
methyl- (Me-
EI _2}; 2,4-hexanediol 5-methyl- POI _2; 2,5-hexanediol (Me-E3_g); 2,5-
hexanediol P03;
2,5-hexanediol, 2-methyl- (Me-E I _2); 2,5-hexanediol 2-methyl- POI _2; 2,5-
hexanediol,
3-methyl- (Me-EI _2); 2,5-hexanediol 3-methyl- POI _2; 3,4-hexanediol EOI _5;
3,4-
hexanediol n-BO I ; 3,4-hexanediol BO I ;
5. I ,3-heptanediol E I _7; 1,3-heptanediol PO I ; I ,3-heptanediol n-BO I _2;
1,4-heptanediol EI_7; 1,4-heptanediol PO I; 1,4-heptanediol n-BOI_2; 1,5-
heptanediol
EI_7; 1,5-heptanediol POI; 1,5-heptanediol n-BOI_2; 1,6-heptanediol EI_7; 1,6-
heptanediol POI ; 1,6-heptanediol n-BO I _2; I ,7-heptanediol E I _2; 1,7-
heptanediol n-
BOI; 2,4-heptanediol E3_10; 2,4-heptanediol (Me-EI); 2,4-heptanediol POI; 2,4-
heptanediol n-B03; 2,5-heptanediol E3_10; 2,5-heptanediol (Me-EI); 2,5-
heptanediol
POI; 2,5-heptanediol n-B03; 2,6-heptanediol E3_I0; 2,6-heptanediol (Me-EI);
2,6-
heptanediol POI; 2,6-heptanediol n-B03; 3,5-heptanediol E3_10; 3,5-heptanediol
(Me-
EI); 3,5-heptanediol POI; 3,5-heptanediol n-B03;
6. 1,3-butanediol, 3-methyl-2-isopropyl- POI; 2,4-pentanediol, 2,3,3-
trimethyl- POI; 1,3-butanediol, 2,2-diethyl- E2_5; 2,4-hexanediol, 2,3-
dimethyl- E2_5;
2,4-hexanediol, 2,4-dimethyl- E2_5; 2,4-hexanediol, 2,5-dimethyl- E2_5; 2,4-
hexanediol,
3,3-dimethyl- E2_5; 2,4-hexanediol, 3,4-dimethyl- E2_5; 2,4-hexanediol, 3,5-
dimethyl-
E2_5; 2,4-hexanediol, 4,5-dimethyl- E2_5; 2,4-hexanediol, 5,5-dimethyl- E2_5;
2,5-
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hexanediol, 2,3-dimethyl- E2_5; 2,5-hexanediol, 2,4-dimethyl- E2_5; 2,5-
hexanediol, 2,5-
dimethyl- E2-5; 2,5-hexanediol, 3,3-dimethyl- E2_5; 2,5-hexanediol, 3,4-
dimethyl- E2_5;
3,5-heptanediol, 3-methyl- E2_5; 1,3-butanediol, 2,2-diethyl- n-BO1_2; 2,4-
hexanediol,
~,3-dimethyl- n-BOl _2; ~,4-hexanediol, 2,4-dimethyl- n-BO 1 _2; 2,4-
hexanediol, 2,5-
dimethyl- n-BOl _2; 2,4-hexanediol, 3,3-dimethyl- n-BOl _2; 2,4-hexanediol,
3,4-
dimethyl- n-BO 1 _2; 2,4-hexanediol. 3,5-dimethyl- n-BOl _2; 2,4-hexanediol,
4,5-
dimethyl- n-BOl _2; 2,4-hexanediol, 5,5-dimethyl-, n-BOl _2; 2,5-hexanediol,
2,3-
dimethyl- n-BOl _2; 2,5-hexanediol, 2.4-dimethyl- n-BO1 _2; 2,5-hexanediol,
2,5-
dimethyl- n-BOl _2; 2,5-hexanediol, 3,3-dimethyl- n-BOl _2; 2,5-hexanediol,
3,4-
dimethyl- n-BOl_2; 3,5-heptanediol, 3-methyl- n-BOl_2; 1,3-propanediol, 2-(1,2-
dimethylpropyl)- n-BOl ; 1,3-butanediol, 2-ethyl-2,3-dimethyl- n-BOl ; 1,3-
butanediol,
2-methyl-2-isopropyl- n-BOl ; 1.4-butanediol. 3-methyl-2-isopropyl- n-BOl ;
1,3-
pentanediol, 2,2,3-trimethyl- n-BOI; 1,3-pentanediol, 2,2,4-trimethyl- n-BOI;
1,3-
pentanediol, 2,4,4-trimethyl- n-BO l ; 1,3-pentanediol, 3,4,4-trimethyl- n-BOl
; 1,4-
pentanediol, 2,2,3-trimethyl- n-BOI; 1,4-pentanediol, 2,2,4-trimethyl- n-BO1;
1,4-
pentanediol, 2,3,3-trimethyl- n-BOI; 1,4-pentanediol, 2,3,4-trimethyl- n-BO1;
1,4-
pentanediol, 3,3,4-trimethyl- n-BOI; ~,4-pentanediol, 2,3,4-trimethyl- n-BO1;
2,4-
hexanediol, 4-ethyl- n-BOI; ~,4-heptanediol, 2-methyl- n-BOI; 2,4-heptanediol,
3-
methyl- n-BO1; 2,4-heptanediol, 4-methyl- n-BO1; 2,4-heptanediol, 5-methyl- n-
BOI;
2,4-heptanediol, 6-methyl- n-BOI; 2,5-heptanediol. 2-methyl- n-BOl; 2,5-
heptanediol,
3-methyl- n-BOl ; 2,5-heptanediol, 4-methyl- n-BOl ; 2,5-heptanediol, 5-methyl-
n-BO l ;
2,5-heptanediol, 6-methyl- n-BO ~ ; 2,6-heptanediol, 2-methyl- n-BO 1; 2,6-
heptanediol,
3-methyl- n-BOl ; 2,6-heptanediol. 4-methyl- n-BO l ; 3,5-heptanediol, 2-
methyl- n-BOl ;
1,3-propanediol, 2-(1,2-dimethylpropyl)- E1_3; 1,3-butanediol, 2-ethyl-2,3-
dimethyl- El_
3; 1,3-butanediol, 2-methyl-2-isopropyl- El_3; 1,4-butanediol, 3-methyl-2-
isopropyl- El_
1,3-pentanediol, 2,2,3-trimethyl- El_3; 1,3-pentanediol, 2,2,4-trimethyl-
El_3; 1,3-
pentanediol, 2,4,4-trimethyl- E 1-3; 1,3-pentanediol, 3,4,4-trimethyl- E 1-3;
1,4-
pentanediol, 2,2,3-trimethyl- El_3; 1,4-pentanediol, 2,2,4-trimethyl- E1_3;
1,4-
pentanedio'l, 2,3,3-trimethyl- E 1-3; 1,4-pentanediol, 2,3,4-trimethyl- E 1
_3; 1,4-
pentanediol, 3,3,4-trimethyl- E1_3; 2,4-pentanediol, 2,3,4-trimethyl- E1_3;
2,4-
hexanediol, 4-ethyl- E1_3; 2,4-heptanediol. 2-methyl- El_3; 2,4-heptanediol, 3-
methyl-
E 1 _3; 2,4-heptanediol, 4-methyl- E ~ -3; 2,4-heptanediol, 5-methyl- E 1 _3;
2,4-heptanediol,
6-methyl- E1_3; 2,5-heptanediol, 2-methyl- El-3; 2,5-heptanediol, 3-methyl-
El_3; 2,5-
heptanediol, 4-methyl- EI_3; 2,5-heptanediol, 5-methyl- El_3; 2,5-heptanediol,
6-
methyl- E1_3; 2,6-heptanediol, 2-methyl- E1_3; 2,6-heptanediol,,3-methyl-
E1_3; 2,6-
heptanediol, 4-methyl- El_3; and/or 3,5-heptanedioh 2-methyl- El_3; and
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7. mixtures thereof;
IX. aromatic diols including: I-phenyl-1,2-ethanediol; 1-phenyl-1,2-
propanediol; 2-
phenyl-1,2-propanediol; 3-phenyl-1,2-propanediol; I-(3-methylphenyl)-1,3-
propanediol;
I-(4-methylphenyl)-1,3-propanediol; 2-methyl-1-phenyl-1,3-propanediol; I-
phenyl-1,3-
butanediol; 3-phenyl-1,3-butanediol; I-phenyl-1,4-butanediol; 2-phenyl-1,4-
butanediol;
and/or 1-phenyl-2,3-butanediol;
X. principal solvents which are homologs, or analogs, of the above structures
where
one, or more, CH2 groups are added while, for each CH2 group added, two
hydrogen
atoms are removed from adjacent carbon atoms in the molecule to form one
carbon-
carbon double bond, thus holding the number of hydrogen atoms in the molecule
constant, including the following:
1,3-Propanediol, 2,2-di-2-propenyl-; 1,3-Propanediol, 2-( 1-pentenyl)-; 1,3-
Propanediol,
2-(2-methyl-2-propenyl)-2-(2-propenyl)-; 1,3-Propanediol, 2-(3-methyl-I-
butenyl)-; 1,3-
Propanediol, 2-(4-pentenyl)-; 1,3-Propanediol, 2-ethyl-2-(2-methyl-2-propenyl)-
; 1,3-
Propanediol, 2-ethyl-2-(2-propenyl)-; 1,3-Propanediol, 2-methyl-2-(3-methyl-3-
butenyl)-
1,3-Butanediol, 2,2-diallyl-; 1,3-Butanediol, 2-(1-ethyl-I-propenyl)-; 1,3-
Butanediol, 2-
(2-butenyl)-2-methyl-; 1,3-Butanediol, 2-(3-methyl-2-butenyl)-; 1,3-
Butanediol, 2-ethyl-
2-(2-propenyl)-; 1,3-Butanediol, 2-methyl-2-(I-methyl-2-propenyl)-; 1,4-
Butanediol,
2,3-bis(I-methylethylidene)-; 1,4-Butanedioi, 2-(3-methyl-2-butenyl)-3-
methylene-; 2-
Butene-1,4-diol, 2-(1,1-dimethylpropyl)-; 2-Butene-1,4-diol, 2-(I-
methylpropyl)-; 2-
Butene-1,4-diol, 2-butyl-; 1,3-Pentanediol, 2-ethenyl-3-ethyl-; 1,3-
Pentanediol, 2-
ethenyl-4,4-dimethyl-; 1,4-Pentanediol, 3-methyl-2-(2-propenyl)-; I,5-
Pentanediol, 2-(I-
propenyl)-; I,5-Pentanediol, 2-(2-propenyl)-; I,5-Pentanediol, 2-ethylidene-3-
methyl-;
I,S-Pentanediol, 2-propylidene-; 2,4-Pentanediol, 3-ethylidene-2,4-dimethyl-;
4-Pentene-
1,3-diol, 2-(1,1-dimethylethyl)-; 4-Pentene-1,3-diol, 2-ethyl-2,3-dimethyl-;
1,4-
Hexanediol, 4-ethyl-2-methylene-; 1,5-Hexadiene-3,4-diol, 2,3,5-trimethyl-;
1,5-
Hexadiene-3,4-diol, S-ethyl-3-methyl-; 1,5-Hexanediol, 2-(1-methylethenyl)-;
1,6-
Hexanediol, 2-ethenyl-; I-Rexene-3,4-diol, 5,5-dimethyl-; 1-Rexene-3,4-diol,
5,5-
dimethyl-;' 2-Rexene-I,5-diol, 4-ethenyl-2,5-dimethyl-; 3-Rexene-1,6-diol, 2-
ethenyl-
2,5-dimethyl-; 3-Rexene-1,6-diol, 2-ethyl-; 3-Rexene-1,6-diol, 3,4-dimethyl-;
4-Hexene-
2,3-diol, 2,5-dimethyl-; 4-Rexene-2,3-diol, 3,4-dimethyl-; 5-Rexene-1,3-diol,
3-(2-
propenyl)-; 5-Rexene-2,3-diol, 2,3-dimethyl-; 5-Rexene-2,3-diol, 3,4-dimethyl-
; 5-
Hexene-2,3-diol, 3,5-dimethyl-; 5-Rexene-2,4-diol, 3-ethenyl-2,5-dimethyl-;
1,4-
Heptanediol, 6-methyl-5-methylene-; 1,5-Heptadiene-3,4-diol, 2,3-dimethyl-;
1,5-
Heptadiene-3,4-diol, 2,5-dimethyl-; 1,5-Heptadiene-3,4-diol, _3,5-dimethyl-;
1,7-
Heptanediol, 2,6-bis(methylene)-; 1,7-Heptanediol, 4-methylene-; I-Heptene-3,5-
diol,
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2,4-dimethyl-; I-Heptene-3,5-diol, '',6-dimethyl-; I-Heptene-3,5-diol, 3-
ethenyl-5-
methyl; I-Heptene-3,5-diol, 6,6-dimethyl-; 2,4-Heptadiene-2,6-diol, 4,6-
dimethyl-; 2,5-
Heptadiene-1,7-diol, 4,4-dimethyl-; ~,6-Heptadiene-1,4-diol, 2,5,5-trimethyl-;
2-
Heptene-1,4-diol, 5,6-dimethyl-; 2-Heptene-1,5-diol, 5-ethyl-; 2-Heptene-i,7-
diol, 2-
methyl-; 3-Heptene-1,5-diol, 4,6-dimethyl-; 3-Heptene-1,7-diol, 3-methyl-6-
methylene-
3-Heptene-2,5-diol, 2,4-dimethyl-; 3-Heptene-2.5-diol, 2,5-dimethyl-; 3-
Heptene-2,6-
diol, 2,6-dimethyl-; 3-Heptene-2,6-diol, 4,6-dimethyl-; 5-Heptene-1,3-diol,
2,4-dimethyl-
5-Heptene-1,3-diol, 3,6-dimethyl-; 5-Heptene-l,4-diol, 2,6-dimethyl-; 5-
Heptene-1,4
diol, 3,6-dimethyl-; 5-Heptene-2,4-diol, 2,3-dimethyl-; 6- Heptene-1,3-diol,
2,2-dimethyl
6-Heptene-1,4-diol. 4-(2-propenyl)-; 6-Heptene-1,4-diol. 5,6-dimethyl-; 6-
Heptene-1,5
diol, 2.4-dimethyl-; 6-Heptene-1,5-diol. 2-ethylidene-6-methyl-; 6-Heptene-2,4-
diol, 4-
(2-propenyl)-; 6-Heptene-2,4-diol. 5.5-dimethyl-; 6-Heptene-2,5-diol, 4.6-
dimethyl-; 6-
Heptene-2,5-diol, 5-ethenyl-4-methyl-; I ,3-Octanediol, 2-methylene-; 1,6-
Octadiene-3,5-
dioi, 2,6-dimethyl-; 1,6-Octadiene-3,5-diol. 3,7-dimethyl-; 1,7-Octadiene-3,6-
diol, 2,b-
dimethyl-; 1,7-Octadiene-3,6-diol, 2.7-dimethyl-; 1,7-Octadiene-3,6-diol, 3,6-
dimethyl-;
I-Octene-3,6-diol, 3-ethenyl-; 2,4,6-Octatriene-1,8-diol, 2,7-dimethyl-; 2,4-
Octadiene-
1,7-diol, 3,7-dimethyl-; 2.5-Octadiene-1,7-diol, 2,6-dimethyl-; 2,5-Octadiene-
1,7-diol,
3,7-dimethyl-; 2,6-Octadiene-1.4-diol, 3,7-dimethyl- (Rosiridol); 2,6-
Octadiene-1,8-diol,
2-methyl-; 2,7-Octadiene-1,4-diol, 3,7-dimethyl-; 2,7-Octadiene-1,5-diol, 2,6-
dimethyl-;
2,7-Octadiene-1,6-diol, 2,6-dimethyl- (8-Hydroxylinalool); 2,7-Octadiene-1,6-
diol, 2,7-
dimethyl-; 2-Octene-1,4-diol; 2-Octene-1,7-diol; 2-Octene-1,7-diol, ''-methyl-
6-
methylene-; 3,5-Octadiene-1,7-diol. 3.7-dimethyl-; 3,5-Octadiene-2,7-diol, 2,7-
dimethyl-
3,5-Octanediol, 4-methylene-; 3,7-Octadiene-1,6-diol, 2,6-dimethyl-; 3,7-
Octadiene-
2,5-diol, 2,7-dimethyl-; 3,7-Octadiene-2,6-diol, 2,6-dimethyi-; 3-Octene-1,5-
diol, 4-
methyl-; 3-Octene-1,5-diol, 5-methyl-; 4,6-Octadiene-1,3-diol, 2,2-dimethyl-;
4,7-
Octadiene-2,3-diol, 2,6-dimethyl-; 4,7-Octadiene-2,6-diol, 2,6-dimethyl-; 4-
Octene-1,6-
diol, 7-methyl-; 2,7-bis(methylene)-; 2-methylene-; 5,?-Octadiene-1,4-diol,
2,7-
dimethyl-; 5,7-Octadiene-1,4-diol, 7-methyl-; 5-Octene-1,3-diol; 6-Octene-1,3-
diol, 7-
methyl-; 62~ctene-1,4-diol, 7-methyl-; 6-Octene-I,5-diol; 6-Octene-1,5-diol, 7-
methyl-;
6-Octene-3,5-diol, 2-methyl-; 6-Octene-3,5-diol, 4-methyl-; 7-Octene-1,3-diol,
2-methyl-
7-Octene-1,3-diol, 4-methyl-; 7-Octene-1,3-diol, 7-methyl-; 7-Octene-I,5-diol;
7
Octene-1,6-diol; 7-Octene-1,6-diol, 5-methyl-; 7-Octene-2,4-diol, 2-methyl-6-
methylene
7-Octene-2,5-diol, 7-methyl-; 7-Octene-3,5-diol, 2-methyl-; I-Nonene-3,5-diol;
i
Nonene-3,7-diol; 3-Nonene-2,5-diol; 4,6-Nonadiene-1,3-diol, 8-methyl-; 4-
Nonene-2,8-
diol; 6,8-Nonadiene-1,5-diol; 7-Nonene-2,4-diol; 8-Nonene-2,4-diol; 8-Nonene-
2,5-diol;
1,9-Decadiene-3,8-diol; and/or 1,9-Decadiene-4,6-diol; and
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XI. mixtures thereof;
The clear fabric softening compositions described herein can optionally, but
preferably, contain:
( 1 ) an effective amount, sufficient to improve clarity, of low molecular
weight
water soluble solvents like ethanol, isopropanol, propylene glycol, 1,3-
propanediol,
propylene carbonate, etc., said water soluble solvents being at a level that
will not form
clear compositions by themselves;
(2) optionally, but preferably, fiom 0% to about 1 S%, preferably from about
0.1% to about 8%, and more preferably from about 0.2% to about 5%, of perfume;
(3) optionally, from 0% to about 2%, preferably from about 0.01% to about
0.2%, and more preferably from about 0.035% to about 0.1 %, of stabilizer; and
(4) optionally, an effective amount to improve clarity, of water soluble
calcium and/or magnesium salt, preferably chloride.
The balance of the composition is typically water.
Preferably, the fabric softening compositions herein are aqueous, translucent
or
clear, preferably clear, compositions containing from about 3% to about 95%,
preferably
from about 10% to about 80%, more preferably from about 30% to about 70%, and
even
more preferably from about 40% to about 60%, water and from about 5% to about
40%,
preferably from about 7% to about 35%, more preferably from about 10% to about
25%,
and even more preferably from about 12% to about 18%, of the above principal
alcohol
solvent. These preferred products (compositions) are not translucent or clear
without the
principal solvent. The amount of principal solvent used to make the
compositions
translucent or clear is preferably more than 50%, more preferably more than
about 60%,
and even more preferably more than about 75%, of the total organic solvent
present.
The principal solvents are desirably kept to the lowest levels that provide
acceptable stability/clarity in the present fabric softening compositions. The
presence of
water exerts an important effect on the need for the principal solvents to
achieve clarity
of these compositions. The higher the water content, the higher the principal
solvent
level (relative to the softener active level) is needed to attain product
clarity. Inversely,
the less the water content, the less principal solvent (relative to the
softener active) is
needed. Thus, at low water levels of from about 3% to about 15%, the softener
active-to-
principal solvent weight ratio is preferably from about 55:45 to about 85:15,
more
preferably from about 60:40 to about 80:20. At water levels of from about 15%
to about
70%, the softener active-to-principal solvent weight ratio is preferably from
about 45:55
to about 70:30, more preferably from about 55:45 to about 70:30. But at high
water
levels of from about 70% to about 80%, the softener active-to-principal
solvent weight
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ratio is preferably from about 30:70 to about 55:4, more preferably from about
35:65 to
about 45:55. At higher water levels, the softener active to principal solvent
ratios should
be even higher.
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B. Fabric Softenin~ Active
An essential component in the fabric softening compositions described herein
is,
from about 15% to about 50%, preferably from about 16% to about 35%, more
preferably from about 17% to about 30%, by weight of the composition, of a
biodegradable fabric softener active selected from the compounds identified
hereinafter,
and mixtures thereof. The fabric softener active used can be highly
unsaturated and/or
branched and is preferably biodegradable. The unsaturated compounds should
have at
least about 3%, e.g., from about 3% to about 30%, of softener active
containing
polyunsaturated groups. Normally, one would not want polyunsaturated groups in
actives, since they tend to be much more unstable than even monounsaturated
groups.
The presence of these highly unsaturated materials makes it highly desirable,
and for the
higher levels of polyunsaturation, essential, that the highly unsaturated
and/or branched
fabric softening actives and/or compositions herein contain antibacterial
agents,
antioxidants, and/or reducing materials, to protect the actives from
degradation. The
long chain hydrocabon groups can also comprise branched chains, e.g., from
isostearic
acid, for at least part of the groups. The total of active represented by the
branched chain
groups, when they are present, is typically from about 1 % to about I 00%,
preferably
from about 10% to about 70%, more preferably from about 20% to about 50%.
Diester Ouaternary Ammonium Fabric Softeni~ Active Compound (DEOA~
( 1 ) The first type of DEQA preferably comprises, as the principal active,
compounds of the formula
~R)4-m - NC+) - WH2)n - Y- R elm X{-)
(1)
wherein each R substituent is a short chain C1-C6, preferably CI-C3 alkyl or
hydroxyalkyl group, e.g., methyl (most preferred), ethyl, propyl,
hydroxyethyl, and the
like, benzyl or mixtures thereof; each m is 2 or 3; each n is from I to about
4; each Y is
-O-(O)C-, -C(O)-O-, -(R)N-(O)C, or -C(O)-N(R)-; the sum of carbons in each R1,
plus
one when Y is -O-{O)C- or -(R)N-(O)C-, is C I 2-C22, preferably C 14-C20, with
each R 1
being a hydrocarbyl, or substituted hydrocarbyl group, including straight and
branched
chain alkyls. Preferably, the softener active contains alkyl, monounsaturated
alkylene,
and polyunsaturated alkylene groups, with the softener active containing
polyunsaturated
alkylene groups being at least about 3%, e.g., from about 3% to about 30%, by
weight of
the total softener active present. (As used herein, the "percent of softener
active"
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containing a given R1 group is based upon taking a percentage of the total
active based
upon the percentage that the given R1 group is, of the total R1 groups
present.)
The Iodine Value (hereinafter referred to as IV) of the parent fatty acids of
these
R1 group is preferably from about 60 to about 140, more preferably from about
70 to
about 130; and even more preferably from about 7~ to about 115, on the
average. It is
believed that the actives which comprise unsaturated R1 groups are preferably
from
about 50% to about 100%, more preferably from about 55% to about 95°ra,
and even
more preferably from about 60% to about 90%, by weight of the total active
present. The
actives containing polyunsaturated R1 groups are at least about 3%, preferably
at least
about ~%, and more preferably at least about 10%, and yet more preferably at
least about
15%, by weight, of the total actives present. These polyunsaturated groups are
necessary
to provide optimum viscosity stability, especially after freezing and thawing.
The higher
the level of polyunsaturated R1 groups in the actives, the lower the level of
actives which
comprise unsaturated R1 groups can be.
The counterion, X(-~ above, can be any softener-compatible anion, preferably
the
anion of a strong acid, for example, chloride, bromide, methylsulfate,
sulfate, nitrate and
the like. and more preferably chloride.
These biodegradable quaternary ammonium fabric softening compounds
preferably contain the group C(O)R1 which is derived, primarily from
unsaturated fatty
acids, e.g., oleic acid, the preferred polyunsaturated fatty acids, and/or
saturated fatty
acids, and/or partially hydrogenated fatty acids from natural sources, e.g.,
derived from
animal fats, vegetable oils and/or partially hydrogenated vegetable oils, such
as, canola
oil, safflower oil, peanut oil, sunflower oil, corn oil, soybean oil, tall
oil, rice bran oil,
etc. In other preferred embodiments, the fatty acids have the following
approximate
distributions:
Fatty Acyl Group DE A1 DEOA~ DEOA3 DE A4 DEQA~
C 12 trace trace 0 0 0
C14 3 3 0 0 0
C16 ~ 4 4 5 5 5
C18 0 0 ~ 6 6
C14:1 3 3 0 0 0
C16:1 11 7 0 0 3
C 18:1 74 73 71 68 67
C18:2 4 8 8 11 11
C18:3 0 1 1 2 2
C20:1 0 0 2 2 2
C20 and 0 0 2 0
up
Unknowns 0 0 6 6 7
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Total 99 99 100 100 102
IV 86-90 88-95 99 100 95
cis/trans (C 18:1 ) 20-30 20-30 4 S 5
TPU 4 9 10 13 13
Nonlimiting examples of DEQA's are as follows:
Fatty Acyl DEOA 10 DEOA 11
Group
C14 0 1
C16 11 25
C 18 4 20
C14:1 0 0
C16:1 1 0
C18:1 27 45
C18:2 50 6
C18:3 7 0
Unknowns 0 3
Total 100 100
IV 125-138 56
cis/trans Not 7
(C 18:1 )
Available
TPU 57 6
DEQA10 is prepared from a soy bean fatty acid, and DEQA11 is prepared from a
slightly
hydrogenated tallow fatty acid.
It is preferred that at least a majority of the fatty acyl groups are
unsaturated, e.g.,
from about 50% to 100%, preferably from about 55% to about 95%, more
preferably
from about 60% to about 90%, and that the total level of active containing
polyunsaturated fatty acyl groups (TPU) be from about 3% to about 30%,
preferably
from about 5% to about 25%, more preferably from about 10% to about 18%. The
cis/trans r4tio for the unsaturated fatty acyl groups is important, with a
cis/trans ratio of
from 1:1 to about 50:1, the minimum being 1:1, preferably at least 3:1, and
more
preferably from about 4:1 to about 20:1.
The unsaturated, including the preferred polyunsaturated, fatty acyl groups
surprisingly provide effective softening, but also provide better rewetting
characteristics,
good antistatic characteristics, and superior recovery after freezing and
thawing.
The highly unsaturated materials are also easier to formulate into
concentrated
premixes that maintain their low viscosity and are therefore easier to
process; e.g., pump,
mixing, etc. These highly unsaturated materials with only a low amount of
solvent that
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normally is associated with such materials, i.e., from about 5% to about 20%,
preferably
from about 8% to about 25%, more preferably from about 10% to about 20%,
weight of
the total softener/solvent mixture, are also easier to formulate into
concentrated, stable
dispersion compositions of the present invention, even at ambient
temperatures. This
ability to process the actives at low temperatures is especially important for
the
polyunsaturated groups, since it mimimizes degradation. Additional protection
against
degradation can be provided when the compounds and softener compositions
contain
effective antioxidants and/or reducing agents, as disclosed hereinafter.
It will be understood that substituents R and R1 can optionally be substituted
with
various groups such as alkoxyl or hydroxyl groups, so long as the R1 groups
maintain
their basically hydrophobic character. The preferred compounds can be
considered to be
biodegradable diester variations of ditallow dimethyl ammonium chloride (
hereinafter
referred to as "DTDMAC"), which is a widely used fabric softener. A preferred
long
chain DEQA is the DEQA prepared from sources containing high levels of
polyunsaturation, i.e., N,N-di(acyl-oxyethyl)-N,N-dimethyl ammonium chloride,
where
the acyl is derived from fatty acids containing sufficient polyunsaturation.
As used herein, when the diester is specified, it can include the monoester
that is
present. Preferably, at least about 80% of the DEQA is in the diester form,
and from 0%
to about 20% can be DEQA monoester (e.g., in formula (1), m is 2 and one YR1
group is
either "H" or "-C-(O)-OH"). For softening, under no/low detergent carry-over
laundry
conditions the percentage of monoester should be as low as possible,
preferably no more
than about 5%. 1-Iowever, under high, anionic detergent surfactant or
detergent builder
carry-over conditions, some monoester or monoamide can be preferred. The
overall
ratios of diester to monoester, or diamide to monoamide, are from about 100:1
to about
2:1, preferably from about 50:1 to about 5:1, more preferably from about I 3:1
to about
8: i . Under high detergent carry-over conditions, the di/monoester ratio i5
preferably
about 11:1. The level of monoester, or monoamide, present can be controlled in
manufacturing the DEQA.
The above compounds, used as the biodegradable quaternized ester-amine, or
amido-amine, softening material in the practice of this invention, can be
prepared using
standard reaction chemistry. In one synthesis of a di-ester variation of
DTDMAC, an
amine of the formula RN(CH2CH20H)2 is esterified at both hydroxyl groups with
an
acid chloride of the formula R1C(O)C1, then quaternized with an alkyl halide,
RX, to
yield the desired reaction product (wherein R and R1 are as defined
hereinbefore).
However, it will be appreciated by those skilled in the chemical arts that
this reaction
sequence allows a broad selection of agents to be prepared.
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Yet another DEQA softener active that is suitable for the formulation of the
concentrated, liquid fabric softener compositions of the present invention,
has the above
formula ( 1 ) wherein one R group is a C 1 _4 hydroxy alkyl group, or
polyalkoxy group,
preferably one wherein one R group is a hydroxyethyi group. An example of such
a
hydroxyethyl ester active is di(acyloxyethyl)(2-hydroxyethyl)methyl ammonium
methyl
sulfate, where the acyl is derived from the fatty acids described
hereinbefore. Another
example of this type of DEQA is derived from the same fatty acid as that of
DEQAl, and
is denoted hereinafter as DEQAB.
(2) A second type of DEQA active has the general formula:
R 1-Y C HZ ~ + (-)
CHCH2N( )R3 X
1
R -Y~
(2)
wherein each Y, R, Rl, and X(-) have the same meanings as before. Such
compounds
include those having the formula:
[CH3]3 N(+)[CH2CH(CH20C[O]Rl)OC(O)Rl] C1(')
where each R is a methyl or ethyl group and preferably each R 1 is in the
range of C 15 to
C 1 g. As used herein, when the diester is specified, it can include the
monoester that is
present. The amount of monoester that can be present is the same as in DEQA (
1 ).
These types of agents and general methods of making them are disclosed in U.S.
Pat. No. 4,137,180, Naik et al., issued Jan. 30, 1979, which is incorporated
herein by
reference. An example of a preferred DEQA of formula (2) is the "propyl" ester
quaternary ammonium fabric softener active having the formula 1,2-di(acyloxy)-
3
trimethylammoniopropane chloride, where the acyl is the same as that of DEQAS,
and is
a
denoted hereinafter as DEQA9.
(3) a third type of DEQA softener active has the general formula:
[RC(O)OC2H4]nN+(Rl)m X_
wherein each R in a compound is a C6-C22 hydrocarbyl group, preferably having
an IV
from about 70 to about 140 based upon the IV of the equivalent fatty acid with
the
cis/trans ratio preferably being as described hereinafter, n is a number from
1 to three on
the weight average in any mixture of compounds, each R1 in a compound is a C 1
_3 alkyl
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or hydroxy alkyl group, the total of n and the number of RI groups that are
hydroxyethyl
groups equaling 3, n+m equaling 4, and X is a softener compatible anion,
preferably
methyl sulfate. Preferably the cisarans isomer ratio of the fatty acid (of the
C 18: I
component) is at least about 1:1, preferably about 2:1, more preferably 3:1,
and even
more preferably about 4: I , or higher.
Preferred biodegradable fabric softener compounds of the third type of DIJQA
softener active described hereinbefore comprise quaternary ammonium salt, the
quaternized ammonium salt being a quaternized product of condensation between:
a)-a fraction of saturated or unsaturated, linear or branched fatty acids, or
of derivatives
of said acids, said fatty acids or derivatives each possessing a hydrocarbon
chain in
which the number of atoms is between ~ and 21. and
b)-triethanolamine,
characterized in that said condensation product has an acid value, measured by
titration
of the condensation product with a standard KOH solution against a
phenolphthalein
indicator, of less than about 6.5.
The acid value is preferably less than or equal to about 5, more preferably
less
than about 3. Indeed, the lower the AV, the better softness softness
performance is
obtained.
The acid value is determined by titration of the condensation product with a
standard KOH solution against a phenolphthalein indicator according to
ISO#t53402. The
AV is expressed as mg KOI-I/g of the condensation product.
For optimum softness benefit. it is preferred that the reactants are present
in a
molar ratio of fatty acid fraction to triethanolamine of from about I :1 to
about 2.5:1.
It has also been found that the optimum softness performance is also affected
by
the detergent carry-over laundry conditions, and more especially by the
presence of the
anionic surfactant in the solution in which the softening composition is used.
Indeed, the
presence of anionic surfactant that is usually carried over from the wash will
interact with
the softener compound, thereby reducing its performance. Thus, depending on
usage
r
conditions, the mole ratio of fatty acid/ triethanolamine can be critical.
Accordingly,
where no rinse occurs between the wash cycle and the rinse cycle containing
the
softening compound, a high amount of anionic surfactant will be carried over
in the rinse
cycle containing the softening compound. In this instance, it has been found
that a fatty
acid fraction/triethanolamine mole ratio of about 1.4:1 to about 1.8:1 is
preferred. By
high amount of anionic surfactant, it is meant that the presence of anionic in
the rinse
cycle at a level such that the molar ratio anionic surfactant/cationic
softener compound of
the invention is at least about 1/10.
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Thus, according to another aspect of the invention, there is provided a method
of
treating fabrics which comprises the step of contacting the fabrics in an
aqueous medium
containing the softener compound of the invention or softening composition
thereof
wherein the fatty acid /triethanolamine mole ratio in the softener compound is
from about
1.4:1 to about 1.8:1, preferably about 1.5:1 and the aqueous medium comprises
a molar
ratio of anionic surfactant to said softener compound of the invention of at
least about
1:10.
Where, on the other hand, an intermediate rinse cycle occurs between the wash
and the later rinse cycle, less anionic surfactant, i.e. less than about 1:10
of a molar ratio
anionic surfactant to cationic compound of the invention, will then be carried
over.
Accordingly, it has been found that a fatty acid / triethanolamine mole ratio
of about
1.8:1 to about 2.2:1 is then preferred. Accordingly, in another aspect of the
invention,
there is provided a method of treating fabrics which comprises the step of
contacting the
fabrics in an aqueous medium containing the softener compound of the invention
or
softening composition thereof wherein the fatty acid/triethanolamine mole
ratio in the
softener compound is from about 1.8:1 to about 2:1, preferably about 2.0:1 and
the
aqueous medium comprises a molar ratio of anionic surfactant to said softener
compound
of the invention of less than about 1:10.
In a preferred embodiment of the invention, the fatty acid fraction and the
triethanolamine are present in a molar ratio of from about 1:1 to about 2.5:1.
The DEQA actives described hereinabove can contain a low level of the fatty
acids which can be unreacted starting material and/or by-product of any
partial
degradation, e.g., hydrolysis, of the softener actives in the finished
compositions. It is
preferred that the level of free fatty acid be low, preferably below about
10%, more
preferably below about S%, by weight of the softener active.
Other, less biodegradable fabric softeners that can also be used herein, at
least in
part, are disclosed, at least generically, for the basic structures, in U.S.
Pat. Nos.
3,861,870, Edwards and Diehl; 4,308,151, Cambre; 3,886,075, Bernardino;
4,233,164,
r
Davis; 4,401,578, Verbruggen; 3,974,076, Wiersema and Rieke; and 4,237,016,
Rudkin,
Clint, and Young, all of said patents being incorporated herein by reference.
Other fabric softening agents are further disclosed in U.S. Pat. No.
4,661,269,
issued April 28, 1987, to Toan Trinh, Errol H. Wahl, Donald M. Swartley and
Ronald L.
Hemingway, said patent being incorporated herein by reference.
Other primary fabric softener actives that can be used in the fabric softening
compositions described herein are those that are highly unsaturated versions
of the
traditional softener actives, i.e., di-long chain alkyl nitrogen derivatives,
normally
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cationic materials, such as dialkyldimethylammonium chloride and imidazolinium
compounds as described hereinafter. As discussed in more detail hereinbefore
and
hereinafter, more biodegradable fabric softener compounds can be present.
Examples of
such fabric softeners can be found in U.S. Pat. Nos. 3,408,361, Mannheimer,
issued
Oct. 29, 1968; 4,709,045. Kubo et al., issued Nov. 24, 1987; 4,233.451, Pracht
et al.,
issued Nov. 11, 1980; 4,127,489, Pracht et al., issued Nov. 28, 1979;
3,689,424, Berg et
al., issued Sept. 5, 1972; 4,128,485, Baumann et al., issued Dec. ~, 1978;
4,161,604,
Elster et al., issued July 17, 1979; 4,189,593, Wechsler et al., issued Feb. I
9, 1980; and
4,339,391, Hoffman et al., issued July 13, 1982, said patents being
incorporated herein
by reference.
Accordingly, the fabric softener actives used in the present invention can
also
comprise a majority of compounds as follows:
(4) softener active having the formula:
R4_m - Ny) - R 1 m A-
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wherein each m is 2 or 3, each R1 is a C6-C22, preferably C14-C20, but no more
than
one being less than about C 12 and then the other is at least about 16,
hydrocarbyl, or
substituted hydrocarbyl substituent, preferably C 10-C20 alkyl or alkenyl
(unsaturated
alkyl, including polyunsaturated alkyl, also referred to sometimes as
"alkylene"), most
preferably C 12-C 1 g alkyl or alkenyl, and where the Iodine Value of a fatty
acid
containing this Rl group is from about 70 to about 140, more preferably from
about 80
to about 130; and most preferably from about 90 to about 115 with a cis/trans
ratio of
from about 1:1 to about 50:1, the minimum being 1:1, preferably from about 2:1
to about
40:1, more preferably from about 3:1 to about 30:1, and even more preferably
from about
4:1 to about 20:1; each R1 can also preferably be a branched chain C14-C22
alkyl group,
preferably a branched chain C 16-C 1 g group; each R is H or a short chain C 1-
C6,
preferably C1-C3 alkyl or hydroxyalkyl group, e.g., methyl (most preferred),
ethyl,
propyl, hydroxyethyl, and the like, benzyl, or (R2 O)2-4I-I; and A- is a
softener
compatible anion, preferably, chloride, bromide, methylsulfate, ethylsulfate,
sulfate, and
nitrate, more preferably chloride and methyl sulfate;
(5) softener active having the formula:
N C-2
R1 C I A _
O
1 ~ N+ CH2
R C G R2~ \
R
wherein each R, R1, and A' have the definitions given above; each R2 is a C1_6
alkylene
group, preferably an ethylene group; and G is an oxygen atom or an -NR- group,
(6) softener active having the formula:
R'-C N-CH2
O N-CHz
Rt-C-G_ Rz~
wherein R 1, R2 and G are defined as above;
(7) reaction products of substantially unsaturated and/or branched chain
higher fatty acids with dialkylenetriamines in, e.g., a molecular ratio of
about 2:1, said
reaction products containing compounds of the formula:
R1~(O~-NH-RZ-NH-R3 NH--C(O}-R1
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wherein R l , R2 are defined as above, and each R3 is a C 1 _6 alkylene group,
preferably
an ethylene group;
(8) softener active having the formula:
[R1--C(O~NR-R' N(R)2-R3-NR-C:(U)--Rl]+ A-
wherein R, R 1, R2, R3 and A- are defined as above;
(9) the reaction product of substantially unsaturated and/or branched chain
higher fatty acid with hydroxyalkylalkylenediamines in a molecular ratio of
about 2:1,
said reaction products containing compounds of the formula:
Rl-C(O)-NH-R2-N(R30H)-C(O)-R1
wherein R1, R2 and R3 are defined as above;
( 10) softener active having the formula:
R R
N-R~-N
N ~N ~AO
Ri R~
wherein R, R1, R2, and A- are defined as above; and
{ 11 ) mixtures thereof.
Examples of Compound (4) are dialkylenedimethylammonium salts such as
dicanoladimethylammonium chloride, dicanoladimethylammonium methylsulfate,
di(partially hydrogenated soybean, cis/trans ratio of about
4:1)dimethylammonium
chloride, dioleyldimethylammonium chloride. Dioleyldimethylammonium chloride
and
di(canola)dimethylammonium chloride are preferred. An example of commercially
available dialkylenedimethylammonium salts usable in the present invention is
dioleyldimethylammonium chloride available from Witco Corporation .under the
trade
name Adogen~ 472.
An example of Compound (5) is 1-methyl-1-oleylamidoethyl-2-
oleylimidazolinium methylsulfate wherein R1 is an acyclic aliphatic C 15-C 17
hydrocarbon group, R2 is an ethylene group, G is a NH group, RS is a methyl
group and
A- is a methyl sulfate anion, available commercially from the Witco
Corporation under
the trade name Varisoft~ 3690.
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An example of Compound (6) is 1-oleylamidoethyl-2-oleylimidazoline wherein R1
is an acyclic aliphatic C 15-C 17 hydrocarbon group, R2 is an ethylene group,
and G is a
NH group.
An example of Compound {7) is reaction products of oleic acids with
diethylenetriamine in a molecular ratio of about 2:1, said reaction product
mixture
containing N,N"-dioleoyldiethylenetriamine with the formula:
R 1-C(O)-NH-Cl-12CH2-Nl-1-CH2CH2-NH-C(O)-R 1
wherein R1-C(O) is oleoyl group of a commercially available oleic acid derived
from a
vegetable or animal source, such as Emersol~ 223LL or Emersol~ 7021, available
from
Henkel Corporation. and R2 and R3 are divalent ethylene groups.
An example of Compound (8) is a difatty amidoamine based softener having the
formula:
[R1-C(O)-NH-CH2CH2-N(CH3)(CH2CH20H)-CH2CH2-NH-C(O)-R1]+ CH3S04-
wherein R1-C(O) is oleoyl group, available commercially from the Witco
Corporation
under the trade name Varisoft~ 222LT.
An example of Compound (9) is reaction products of oleic acids with N-2-
hydroxyethylethylenediamine in a molecular ratio of about 2:1, said reaction
product
mixture containing a compound of the formula:
R1-C(O)-NH-CH2CH2-N(CH2CH20H)-C(O)-R1
wherein R1-C(O) is oleoyl group of a commercially available oleic acid derived
from a
vegetable or animal source, such as Emersoln 223LL or Emersol~ 7021, available
from
Henkel Corporation.
An example of Compound ( 10) is the diquaternary compound having the formula:
CH3 CH3~
N-CH2CH2-N
2CH3S040
N~ ~N
Rt R1
wherein R1 is derived from oleic acid, and the compound is available from
Witco
Company.
The above individual fabric softener actives can be used individually or as
mixtures.
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One type of optional but highly desirable cationic compound which can be used
in
combination with the above softener actives are compounds containing one long
chain
acyclic Cg-C~~ hydrocarbon group, selected from the group consisting of:
( 12) acyclic quaternary ammonium salts having the formula:
~Rl N(RS)~_R61+ A_
wherein R~ and R~' are C 1-C4 alkyl or hydroxyalkyl groups, and Rl and A- are
defined
as herein above,
( 13) substituted imidazolinium salts having the formula:
O
N-CH~
Rl-Cv I AO
N-CHI
R~~ ~ H
wherein R~ is hydrogen or a Cl-C4 saturated alkyl or hydroxyalkyl group. and
Rl and
A- are defined as herein above;
( 14) substituted imidazolinium salts having the formula:
O
Rt-CN-CH2 Ao
N-CI-h
HO-R'- ~ ~ Rs
wherein R~ is a Cl-C4 alkyl or hydroxyalkyl group, and Rl, R~, and A' are as
defined
above;
(15) alkylpyridinium salts having the formula:
O
R4-N O A
wherein R4 is an acyclic aliphatic Cg-C2~ hydrocarbon group and A- is an
anion; and
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( 16) alkanamide alkylene pyridinium salts having the formula:
O O
R~-C-NH-R'--N O AO
wherein R l , R2 and A- are defined as herein above; and mixtures thereof.
Examples of Compound (12) are the monoalkenyltrimethylammonium salts such
as monooleyltrimethylammonium chloride, monocanolatrimethylammonium chloride,
and soyatrimethylammonium chloride. Monooleyltrimethylammonium chloride and
monocanolatrimethylammonium chloride are preferred. Other examples of Compound
(12) are soyatrimethylammonium chloride available from Witco Corporation under
the
trade name Adogen~ 415, erucyltrimethylammonium chloride wherein R1 is a C22
hydrocarbyl group derived from a natural source; soyadimethylethylammonium
ethylsulfate wherein R 1 is a C 16-C 1 g hydrocarbon group, RS is a methyl
group, R6 is an
ethyl group, and A' is an ethylsulfate anion; and methyl bis(2-
hydroxyethyl)oleylammonium chloride wherein R I is a C 1 g hydrocarbyl group,
RS is a
2-hydroxyethyl group and R6 is a methyl group.
An example of Compound (14) is 1-ethyl-1-(2-hydroxyethyl)-2-
isoheptadecylimidazolinium ethylsulfate wherein R1 is a C1~ hydrocarbyl group,
R2 is
an ethylene group, RS is an ethyl group, and A- is an ethylsulfate anion.
[In preferred quaternary ammonium fabric softening compounds, and especially
DEQAs, -(O)CR1 is derived from unsaturated fatty acid, e.g., oleic acid,
and/or fatty
acids and/or partially hydrogenated fatty acids, derived from animal fats,
vegetable oils
and/or partially hydrogenated vegetable oils, such as: canola oil; safflower
oil; peanut oil;
sunflower oil; soybean oil; corn oil; tall oil; rice bran oil; etc.] [As used
herein,
biodegradable fabric softener actives containing ester linkages are referred
to as
"DEQA", which includes both diester, triester, and monoester compounds
containing
r
from one to three, preferably two, long chain hydrophobic groups. The
corresponding
amide softener actives and the mixed ester-amide softener actives can also
contain from
one to three, preferably two, long chain hydrophobic groups. These fabric
softener
actives have the characteristic that they can be processed by conventional
mixing means
at ambient temperature, at least in the presence of about 15% of solvent C. as
disclosed
herein.]
Anion A
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In the cationic nitrogenous salts herein, the anion A- , which is any softener
compatible anion, provides electrical neutrality. Most often, the anion used
to provide
electrical neutrality in these salts is from a strong acid, especially a
halide, such as
chloride, bromide, or iodide. However, other anions can be used, such as
methylsulfate,
ethylsulfate, acetate, formate. sulfate, carbonate, and the Like. Chloride and
methylsulfate are preferred herein as anion A.
C. Optional Ingredients
1. Perfume
The fabric softening compositions of the present invention can contain any
softener compatible perfume. Preferred perfumes are disclosed in U.S. Pat.
5,500,138,
Bacon et al., issued March 19. 1996, said patent being incorporated herein by
reference.
Perfume is optionally present at a level of from about 0% to about 10%,
preferably from
about 0.1% to about 5%, more preferably from about 0.2% to about 3%, by weight
of the
finished composition. It is an advantage of the use of this invention, that
the perfume
preferably can be added in the premix to simplify the preparation of the
finished
dispersion compositions and to improve fabric deposition of said perfume. The
premix
can be added to water containing the requisite amount of acid, preferably
mineral acid,
more preferably HC1. to create the finished composition as discussed
hereinafter.
~. Stabilizers
Stabilizers are highly desirable. and even essential, in the fabric softening
compositions, and, optionally, the raw materials, of the present invention.
The term
"stabilizer," as used herein, includes antioxidants and reductive agents.
These agents are
present at a level of fiom 0% to about 2%, preferably from about 0.01 % to
about 0.2%,
more preferably from about 0.035% to about 0.1% for antioxidants, and more
preferably
from about 0.01% to about 0.2% for reductive agents, in the final composition.
For the
premix, the levels are adjusted, depending on the concentrations of the
softener active in
the premix and the finished composition. These assure good odor stability
under long
term storage conditions. Antioxidants and reductive agent stabilizers are
especially
critical for unscented or low scent products (no or low perfume).
Examples of antioxidants that can be added to the fabric softening
compositions of
this invention include a mixture of ascorbic acid, ascorbic palmitate, propyl
gallate,
available from Eastman Chemical Products, Inc., under the trade names TenoxO
PG and
Tenox~ S-1; a mixture of BHT (butylated hydroxytoluene), BHA (butylated
hydroxyanisole), propyl gallate, and citric acid, available from Eastman
Chemical
Products, Inc., .under the trade name Tenox~-6; butylated hydroxytoluene,
available
from UOP Process Division under the trade name Sustane~ BHT; tertiary
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butylhydroquinone, Eastman Chemical Products, Inc., as Tenox~ TBHQ; natural
tocopherols, Eastman Chemical Products, Inc., as Tenox~ GT-1/GT-2; and
butylated
hydroxyanisole, Eastman Chemical Products, Inc., as BHA; long chain esters (Cg-
C22)
of gallic acid, e.g., dodecyl gallate; IrganoxC~ 1010; Irganox~ 1035; Irganox~
B 1171;
Irganox0 1425; Irganox~ 3114; Irganoxc~ 3125; and mixtures thereof; preferably
Irganox~ 3125, Irganox~ 1425, Irganox~ 3114, and mixtures thereof; more
preferably
Irganox~ 3125 alone or mixed with citric acid and/or other chelators such as
isopropyl
citrate, Dequest0 2010, available from Monsanto with a chemical name of 1-
hydroxyethylidene-1, 1-diphosphonic acid (etidronic acid), and TironU,
available from
Kodak with a chemical name of 4,5-dihydroxy-m-benzene-sulfonic acid/sodium
salt, and
DTPA~, available from Aldrich with a chemical name of
diethylenetriaminepentaacetic
acid.
3. Brighteners
The fabric softening compositions herein can also optionally contain from
about
0.005% to 5% by weight of certain types of hydrophilic optical brighteners
which also
provide a dye transfer inhibition action. If used, the fabric softening
compositions herein
will preferably comprise from about 0.001 % to 1 % by weight of such optical
brighteners.
The hydrophilic optical brighteners useful in the present invention are those
having the structural formula:
R~~ R2
~N H H NO
NOON O ~ ~ O N OO N
ON H H NO
R2 S03M S~3M R~
wherein R1 is selected from anilino, N-2-bis-hydroxyethyl and NH-2-
hydroxyethyl; R2
is selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methylamino,
morphilino,
chloro and amino; and M is a salt-forming cation such as sodium or potassium.
When in the above formula, R1 is anilino, R2 is N-2-bis-hydroxyethyl and M is
a
r
cation such as sodium, the brightener is 4,4',-bis[(4-anilino-6-(N-2-bis-
hydroxyethyl)-s-
triazine-2-yl)amino]-2,2'-stilbenedisulfonic acid and disodium salt. This
particular
brightener species is commercially marketed under the tradename Tinopal-LTNPA-
GX~
by Ciba-Geigy Corporation. Tinopal-UNPA-GX is the preferred hydrophilic
optical
brightener useful in the fabric softening compositions herein.
When in the above formula, R1 is anilino, R2 is N-2-hydroxyethyl-N-2-
methylamino and M is a cation such as sodium, the brightener is 4,4'-bis[(4-
anilino-6-(N-
2-hydroxyethyl-N-methylamino)-s-triazine-2-yl)amino]2,2'-stilbenedisulfonic
acid
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disodium salt. This particular brightener species is commercially marketed
under the
tradename Tinopal SBM-GX~J by Ciba-Geigy Corporation.
When in the above formula, RI is anilino, R2 is morphilino and M is a canon
such as sodium, the brightener is 4,4'-bis[(4-anilino-6-morphilino-s-triazine-
2-
yl)amino]2,2'-stilbenedisulfonic acid. sodium salt. This particular brightener
species is
commercially marketed under the tradename Tinopal AMS-GX~ by Ciba Geigy
Corporation.
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4. Dispersibilit Aids
The fabric softening compositions of the present invention can optionally
contain
dispersibility aids, e.g., those selected from the group consisting of mono-
long chain
alkyl cationic quaternary ammonium compounds, mono-long chain alkyl amine
oxides,
and mixtures thereof, to assist in the formation of the finished fabric
softening
compositions. When said dispersibility aid is present , it is typically
present at a total
level of from about 2% to about 25%, preferably from about 3% to about 17%,
more
preferably from about 4% to about 15%, and even more preferably from 5% to
about
13% by weight of the composition. These materials can either be added as part
of the
active softener raw material, (I), or added as a separate component. The total
level of
dispersibility aid includes any amount that may be present as part of
component (I).
a. Mono-Alkyl Cationic Quaternary Ammonium Compound
When the mono-alkyl cationic quaternary ammonium compound is present, it is
typically present at a level of from about 2% to about 25%, preferably from
about 3% to
about 17%, more preferably from about 4% to about 15%, and even more
preferably
from S% to about 13% by weight of the composition, the total mono-alkyl
cationic
quaternary ammonium compound being at least at an effective level.
Such mono-alkyl cationic quaternary ammonium compounds useful in the present
invention are, preferably, quaternary ammonium salts of the general formula:
~R4N+(R5)3~ X_
wherein R4 is Cg-C22 alkyl or alkenyl group, preferably C 10-C 1 g alkyl or
alkenyl
group; more preferably C 10-C 14 or C 16-C 1 g alkyl or alkenyl group;
each RS is a C 1-C6 alkyl or substituted alkyl group (e.g., hydroxy alkyl),
preferably C 1-
C3 alkyl group, e.g., methyl (most preferred), ethyl, propyl, and the like, a
benzyl group,
hydrogen, a polyethoxylated chain with from about 2 to about 20 oxyethylene
units,
preferably from about 2.5 to about 13 oxyethylene units, more preferably from
about 3 to
about 10 oXyethylene units, and mixtures thereof; and
X- is as defined hereinbefore for (Formula (I)).
Especially preferred dispersibility aids are monolauryl trimethyl ammonium
chloride and monotallow trimethyl ammonium chloride available from Witco under
the
trade name Varisoft~ 471 and monooleyl trimethyl ammonium chloride available
from
Witco under the tradename Varisoft~ 417.
The R4 group can also be attached to the cationic nitrogen atom through a
group
containing one, or more, ester, amide, ether, amine, etc., linking groups
which can be
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desirable for increased concentratability of component (I), etc. Such linking
groups are
preferably within from about one to about three carbon atoms of the nitrogen
atom.
Mono-alkyl cationic quaternary ammonium compounds also include Cg-C2~
alkyl choline esters. The preferred dispersibility aids of this type have the
formula:
R1C(O)-O-CH~CH~N+(R)3 X-
wherein R 1, R and X- are as defined previously.
Highly preferred dispersibility aids include C 1 ~-C 14 coco choline ester and
C 16-
C 1 g tallow choline ester.
Suitable biodegradable single-long-chain alkyl dispersibility aids containing
an
ester linkage in the long chains are described in U.S. Pat. No. 4.840,738,
Hardy and
Walley, issued June 20, 1989, said patent being incorporated herein by
reference.
When the dispersibility aid comprises alkyl choline esters, preferably the
dispersion compositions also contain a small amount, preferably from about 2%
to about
5% by weight of the composition, of organic acid. Organic acids are described
in
European Patent Application No. 404,471, Machin et al., published on Dec. ?7,
1990,
supra, which is herein incorporated by reference. Preferably the organic acid
is selected
from the group consisting of glycolic acid. acetic acid, citric acid, and
mixtures thereof.
Ethoxylated quaternary ammonium compounds which can serve as the
dispersibility aid include ethylbis(polyethoxy ethanol)alkylammonium ethyl-
sulfate with
17 moles of ethylene oxide, available under the trade name Variquat~ 66 from
Sherex
Chemical Company: polyethylene glycol ( 15) oleammonium chloride, available
under
the trade name Ethoquad'~ 0/25 from Akzo; and polyethylene glycol (15)
cocomonium
chloride, available under the trade name Ethoquad~ C/25 from Akzo.
Although the main function of the dispersibility aid is to increase the
dispersibility of the ester softener, preferably the dispersibility aids of
the present
invention also have some softening properties to boost softening performance
of the
composition. Therefore, preferably the fabric softening compositions of the
present
invention are essentially free of non-nitrogenous ethoxylated nonionic
dispersibility aids
which will decrease the overall softening performance of the fabric softening
compositions.
Also, quaternary compounds having only a single long alkyl chain, can protect
the cationic softener from interacting with anionic surfactants and/or
detergent builders
that are earned over into the rinse from the wash solution.
b. Amine Oxides
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Suitable amine oxides include those with one alkyl or hydroxyalkyl moiety of
about 8 to about 22 carbon atoms, preferably from about 1 U to about 18 carbon
atoms,
more preferably from about 8 to about I4 carbon atoms, and two alkyl moieties
selected
tiom the group consisting of alkyl groups and hydroxyalkyl groups with about 1
to about
3 carbon atoms.
Examples include dimethyloctylamine oxide, diethyldecylamine oxide, bis-(2-
hydroxyethyl)dodecyl-amine oxide, dimethyldodecylamine oxide, dipropyl-
tetradecylamine oxide, methylethylhexadecylamine oxide, dimethyl-2-
hydroxyoctadecylamine oxide, and coconut fatty alkyl dimethylamine oxide.
5. Soil Release Agent
In the present invention, an optional soil release agent can be added,
especially to
the finished fabric softening compositions. The addition of the soil release
agent can
occur in combination with a premix, in combination with the acid/water seat,
before or
after electrolyte addition, or after the final composition is made. The
finished softening
composition prepared by the process of the present invention herein can
contain from 0%
to about 10%, preferably from 0.2% to about S%, of a soil release agent. The
concentration in the premix is adjusted to provide the desired end
concentration.
Preferably, such a soil release agent is a polymer. Polymeric soil release
agents useful in
the present invention include copolymeric blocks of terephthalate and
polyethylene oxide
or polypropylene oxide, and the like.
A preferred soil release agent is a copolymer having blocks of terephthalate
and
polyethylene oxide. More specifically, these polymers are comprised of
repeating units
of ethylene terephthalate and polyethylene oxide terephthalate at a molar
ratio of
ethylene terephthalate units to polyethylene oxide terephthalate units of from
25:75 to
about 35:65, said polyethylene oxide terephthalate containing polyethylene
oxide blocks
having molecuiar weights of from about 300 to about 2000. The molecular weight
of
this polymeric soil release agent is in the range of from about 5,000 to about
55,000.
Another preferred polymeric soil release agent is a crystallizable polyester
with
repeat units of ethylene terephthalate units containing from about 10% to
about 15% by
weight of ethylene terephthaiate units together with from about 10% to about
50% by
weight of polyoxyethylene terephthalate units, derived from a polyoxyethylene
glycol of
average molecular weight of from about 300 to about 6,000, and the molar ratio
of
ethylene terephthalate units to polyoxyethylene terephthalate units in the
crystallizable
polymeric compound is between 2:1 and 6:1. Examples of this polymer include
the
commercially available materials ZeIcon 4780~ (from Dupont) and Milease T~
(from
ICI).
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Highly preferred soil release agents are polymers of the generic formula:
O
14 II 15 I 14_ II -X
X-{OCH2CH2)p(O-C-R C -OR )u(O-~-R OC-O)(CH2CH20-)n
in which each X can be a suitable capping group, with each X typically being
selected
from the group consisting of I-I, and alkyl or acyl groups containing from
about 1 to
about 4 carbon atoms. p is selected for water solubility and generally is from
about 6 to
about I 13, preferably from about 20 to about 50. a is critical to formulation
in a liquid
composition having a relatively high ionic strength. There should be very
little material
in which a is greater than 10. Furthermore, there should be at least 20%,
preferably at
least 40%. of material in which a ranges from about 3 to about S.
The RI4 moieties are essentially 1,4-phenylene moieties. As used herein, the
term "the RI4 moieties are essentially 1,4-phenylene moieties" refers to
compounds
where the R14 moieties consist entirely of 1,4-phenylene moieties, or are
partially
substituted with other arylene or alkarylene moieties, alkylene moieties,
alkenylene
moieties, or mixtures thereof. Arylene and alkarylene moieties which can be
partially
substituted for 1,4-phenylene include 1,3-phenylene, 1,2-phenylene, 1,8-
naphthylene,
I,4-naphthylene, 2,2-biphenylene, 4,4-biphenylene, and mixtures thereof.
Alkylene and
alkenylene moieties which can be partially substituted include 1,2-propylene,
1,4-
butylene, 1,5-pentylene, 1,6-hexamethylene, 1,7-heptamethylene, 1,8-
octamethylene,
1,4-cyclohexylene, and mixtures thereof.
For the R14 moieties, the degree of partial substitution with moieties other
than
1,4-phenylene should be such that the soil release properties of the compound
are not
adversely affected to any great extent. Generally the degree of partial
substitution which
can be tolerated will depend upon the backbone length of the compound, i.e.,
longer
backbones can have greater partial substitution for 1,4-phenylene moieties.
Usually,
compounds where the R14 comprise from about 50% to about 100% 1,4-phenylene
moieties (from 0% to about SO% moieties other than 1,4-phenylene) have
adequate soil
release activity. For example, polyesters made according to the present
invention with a
40:60 mole ratio of isophthalic (1,3-phenylene) to terephthalic (1,4-
phenylene} acid have
adequate soil release activity. However, because most polyesters used in fiber
making
comprise ethylene terephthalate units, it is usually desirable to minimize the
degree of
partial substitution with moieties other than 1,4-phenylene for best soil
release activity.
Preferably, the RI4 moieties consist entirely of (i.e., comprise 100%) I ,4-
phenylene
moieties, i.e., each RI4 moiety is 1,4-phenylene.
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For the R15 moieties, suitable ethylene or substituted ethylene moieties
include
ethylene, 1,2-propylene, 1,2-butylene, 1,2-hexylene, 3-methoxy-1,2-propylene,
and
mixtures thereof. Preferably, the R15 moieties are essentially ethylene
moieties, 1,2-
propylene moieties, or mixtures thereof. Inclusion of a greater percentage of
ethylene
moieties tends to improve the soil release activity of compounds.
Surprisingly, inclusion
of a greater percentage of 1,2-propylene moieties tends to improve the water
solubility of
compounds.
Therefore, the use of 1,2-propylene moieties or a similar branched equivalent
is
desirable for incorporation of any substantial part of the soil release
component in the
liquid fabric softener compositions. Preferably, from about 75% to about 100%,
are 1,2-
propylene moieties.
The value for each p is at least about 6, and preferably is at least about 10.
The
value for each n usually ranges from about 12 to about 113. Typically the
value for each
p is in the range of from about 12 to about 43.
A more complete disclosure of soil release agents is contained in U.S. Pat.
Nos.:
4,661,267, Decker, Konig, Straathof, and Gosselink, issued Apr. 28, 1987;
4,711,730,
Gosselink and Diehl, issued Dec. 8, 1987; 4,749,596, Evans, Huntington,
Stewart, Wolf,
and Zimmerer, issued June 7, 1988; 4,818,569, Trinh, Gosselink, and Rattinger,
issued
April 4, 1989; 4,877,896, Maldonado, Trinh, and Gosselink, issued Oct. 31,
1989;
4,956,447, Gosselink et al., issued Sept. 11, 1990; and 4,976,879, Maldonado,
Trinh,
and Gosselink, issued Dec. 11, 1990, all of said patents being incorporated
herein by
reference.
These soil release agents can also act as scum dispersants.
6. Scum Dispersant
In the present invention, the fabric softening compositions can also contain
an
optional scum dispersant, other than the soil release agent, and heated to a
temperature at
or above the melting points) of the components. Scum dispersants are desirable
components of the finished fabric softening compositions herein.
The' preferred scum dispersants herein are formed by highly ethoxylating
hydrophobic materials. The hydrophobic material can be a fatty alcohol, fatty
acid, fatty
amine, fatty acid amide, amine oxide, quaternary ammonium compound, or the
hydrophobic moieties used to form soil release polymers. The preferred scum
dispersants are highly ethoxyiated, e.g., more than about 17, preferably more
than about
25, more preferably more than about 40, moles of ethylene oxide per molecule
on the
average, with the polyethylene oxide portion being from about 76% to about
97%,
preferably from about 81 % to about 94%, of the total molecular weight.
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The Ieve1 of scum dispersant is sufficient to keep the scum at an acceptable,
preferably unnoticeable to the consumer, level under the conditions of use,
but not
enough to adversely affect softening. For some purposes it is desirable that
the scum is
nonexistent. Depending on the amount of anionic or nonionic detergent, etc.,
used in the
wash cycle of a typical laundering process, the efficiency of the rinsing
steps prior to the
introduction of the dispersion compositions herein, and the water hardness,
the amount of
anionic or nonionic detergent surfactant and detergency builder (especially
phosphates
and zeolites) entrapped in the fabric (laundry) will vary. Normally, the
minimum amount
of scum dispersant should be used to avoid adversely affecting softening
properties.
Typically scum dispersion requires at least about 2%, preferably at least
about 4% (at
least 6% and preferably at least 10% for maximum scum avoidance) based upon
the level
of softener active. However, at levels of about 10% (relative to the softener
material) or
more, one risks loss of softening efficacy of the product especially when the
fabrics
contain high proportions of nonionic surfactant which has been absorbed during
the
washing operation.
Preferred scum dispersants are: Brij 700~' Varonic U-250~; Genapol T-500~,
Genapol T-800~; Plurafac A-79~; and Neodol 2S-SO~.
7. Bactericides
Examples of bactericides used in the fabric softening compositions of this
invention include glutaraldehyde, formaldehyde, ?-bromo-2-nitro-propane-1,3-
diol sold
by Inolex Chemicals. located in Philadelphia, Pennsylvania, under the trade
name
Bronopol~. and a mixture of S-chloro-2-methyl-4-isothiazoline-3-one and 2-
methyl-4-
isothiazoline-3-one sold by Rohm and Haas Company under the trade name Kathon
CG/ICP~. Typical levels of bactericides used in the present dispersion
compositions arc
from about 1 to about 1,000 ppm by weight of the agent.
8. Chelatin~ Agents
The finished dispersion compositions and processes herein can optionally
employ
one or more copper and/or nickel chelating agents ("cheiators"). Such water-
soluble
chelating agents can be selected from the group consisting of amino
carboxylates, amino
phosphonates, polyfunctionally-substituted aromatic chelating agents and
mixtures
thereof, all as hereinafter defined. The whiteness and/or brightness of
fabrics are
substantially improved or restored by such chelating agents and the stability
of the
materials in the dispersion compositions are improved.
Amino carboxylates useful as chelating agents herein include
ethylenediaminetetraacetates (EDTA), N-hydroxyethylethylenediaminetriacetates,
nitrilotriacetates (NTA), ethylenediamine tetraproprionates, ethylenediamine-
N,N'-
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diglutamates, 2-hyroxypropylenediamine-N,N'-disuccinates,
triethylenetetraaminehexacetates, diethylenetriaminepentaacetates (DETPA), and
ethanoldiglycines, including their water-soluble salts such as the alkali
metal,
ammonium, and substituted ammonium salts thereof and mixtures thereof.
Amino phosphonates are also suitable for use as chelating agents in the
dispersion
compositions of the invention when at least low levels of total phosphorus are
permitted
in detergent dispersion compositions, and include ethylenediaminetetrakis
(methylenephosphonates), diethylenetriamine-N,N,N',N",N"-pentakis(methane
phosphonate) (DETMP) and 1-hydroxyethane-1.1-diphosphonate (HEDP). Preferably,
these amino phosphonates to not contain alkyl or alkenyl groups with more than
about 6
carbon atoms.
The chelating agents are typically used in the present rinse process at levels
from
about 2 ppm to about 25 ppm, for periods fiom i minute up to several hours'
soaking.
The preferred EDDS chelator used herein (also known as ethylenediamine-N,N'-
disuccinate) is the material described in U.S. Patent 4,704,233, cited
hereinabove, and
has the formula (shown in free acid form):
H-N -C H~-C H2-N -H
CHI CH CH CH2
COOH COOH COOH COOH
As disclosed in the patent, EDDS can be prepared using malefic anhydride and
ethylenediamine. The preferred biodegradable [S,S] isomer of EDDS can be
prepared by
reacting L-aspartic acid with 1.2-dibromoethane. The EDDS has advantages over
other
chelators in that it is effective for chelating both copper and nickel
rations, is available in
a biodegradable form, and does not contain phosphorus. The EDDS employed
herein as
a chelator is typically in its salt form, i.e., wherein one or more of the
four acidic
hydrogens are replaced by a water-soluble ration M, such as sodium, potassium,
ammonium, triethanolammonium, and the like. As noted before, the EDDS chelator
is
also typically used in the present rinse process at levels from about .2 ppm
to about
25 ppm for periods from 1 minute up to several hours' soaking. At certain pH's
the
EDDS is preferably used in combination with zinc rations.
As can be seen from the foregoing, a wide variety of chelators can be used
herein.
Indeed, simple polycarboxylates such as citrate, oxydisuccinate, and the like,
can also be
used, although such chelators are not as effective as the amino carboxylates
and
phosphonates, on a weight basis. Accordingly, usage levels may be adjusted to
take into
account differing degrees of chelating effectiveness. The chelators herein
will preferably
have a stability constant (of the fully ionized chelator) for copper ions of
at least about 5,
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preferably at least about 7. Typically, the chelators will comprise from about
0.5% to
about 10%, more preferably from about 0.75% to about 5%, by weight of the
dispersion
compositions herein. Preferred chelators include DETMP, DETPA, NTA, EDDS and
mixtures thereof.
9 Optional Viscosity/Dispersibility Modifiers
Relatively concentrated fabric softening compositions containing the
unsaturated
diester quaternary ammonium compounds herein can be prepared that are stable
without
the addition of concentration aids. However, the fabric softening compositions
of the
present invention may require organic and/or inorganic concentration aids to
go to even
higher concentrations and/or to meet higher stability standards depending on
the other
ingredients. These concentration aids which typically can be viscosity
modifiers may be
needed, or preferred, for ensuring stability under extreme conditions when
particular
softener active levels are used. The surfactant concentration aids are
typically selected
from the group consisting of (1) single long chain alkyl cationic surfactants;
{2) nonionic
surfactants; (3) amine oxides; (4) fatty acids; and (5) mixtures thereof.
These aids are
described in P&G Copending Application Serial No. 081461,207, filed June 5,
1995,
Wahl et al., specifically on page 14, line 12 to page 20, line 12, which is
herein
incorporated by reference.
10. Chlorine Scaven~~l.,ers
Chlorine is used in many parts of the world to sanitize water. To ensure that
the
water is safe, a small residual amount, typically about 1 to 2 parts per
million (ppm), of
chlorine is left in the water. At least about 10% of U.S. households has about
2 ppm or
more of chlorine in its tap water at some time. It has been found that this
small amount
of chlorine in the tap water can also contribute to fading or color changes of
some fabric
dyes. Thus, chlorine-induced fading of fabric colors over time can result from
the
presence of residual chlorine in the rinse water. Accordingly, in addition to
the chelator,
the present invention preferably also employs a chlorine scavenger. Moreover,
the use of
such chlorine scavengers provides a secondary benefit due to their ability to
eliminate or
reduce the chlorine odor on fabrics.
Chlorine scavengers are materials that react with chlorine, or with chlorine-
generating materials, such as hypochlorite, to eliminate or reduce the
bleaching activity
of the chlorine materials. For color fidelity purposes, it is generally
suitable to
incorporate enough chlorine scavenger to neutralize about l-10 ppm chlorine in
rinse
water, typically to neutralize at least about 1 ppm in rinse water. For the
additional
elimination or reduction of fabric chlorine odor resulting from the use of a
chlorine
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bleach in the wash, the compositions should contain enough chlorine scavenger
to
neutralize at least about 10 ppm in rinse water.
Such compositions according to the present invention provide about 0.1 ppm to
about 40 ppm, preferably from about 0.2 ppm to about 20 ppm, and more
preferably
from about 0.3 ppm to about 10 ppm of chlorine scavenger to an average rinse
bath.
Suitable levels of chlorine scavengers in the compositions of the present
invention range
from about 0.01% to about 10%, preferably from about 0.02% to about 5%, most
preferably from about 0.03% to about 4%, by weight of total composition. If
both the
cation and the anion of the scavenger react with chlorine, which is desirable,
the level
may be adjusted to react with an equivalent amount of available chlorine.
Non-limiting examples of chlorine scavengers include primary and secondary
amines, including primary and secondary fatty amines; ammonium salts, e.g.,
chloride,
sulfate; amine-functional polymers; amino acid homopolymers with amino groups
and
their salts, such as polyarginine, polylysine, polyhistidine; amino acid
copolymers with
amino groups and their salts; amino acids and their salts, preferably those
having more
than one amino group per molecule, such as arginine, histidine, not including
lysine
reducing anions such as sulfite, bisulfate, thiosulfate, nitrite; antioxidants
such as
ascorbate, carbamate, phenols; and mixtures thereof. Ammonium chloride is a
preferred
inexpensive chlorine scavenger for use herein.
Other useful chlorine scavengers include water-soluble, low molecular weight
primary and secondary amines of low volatility, e.g., monoethanolamine,
diethanolamine, tris(hydroxymethyl)aminomethane, hexamethylenetetramine.
Suitable
amine-functional chlorine scavenger polymers include: water-soluble
polyethyleneimines, polyamines, polyvinylamines, polyamineamides and
poiyacrylamides. The preferred polymers are polyethyleneimines, the
polyamines, and
polyamineamides. Preferred poiyethyleneimines have a molecular weight of less
than
about 2000, more preferably from about 200 to about 1500.
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11. Dye Transfer Inhibitors
The compositions of the present invention may also include one or more
materials
effective for inhibiting the transfer of dyes from one fabric to another
during the rinsing
process. Generally, such dye transfer inhibiting agents include polyvinyl
pyrrolidone
polymers, polyamine N-oxide polymers, copolymers of N-vinylpyrroiidone and N-
vinylimidazole, manganese phthalocyanine, peroxidases, and mixtures thereof.
If used,
these agents typically comprise from about 0.01% to about 10% by weight of the
composition, preferably from about 0.01 % to about 5%, and more preferably
from about
0.05% to about 2%.
More specifically, the polyamine N-oxide polymers preferred for use herein
contain units having the following structural formula: R-Ax-Z; wherein Z is a
polymerizable unit to which an N-O group can be attached or the N-O group can
form
part of the polymerizable unit or the N-O group can be attached to both units;
A is one of
the following structures: -NC(O)-, -C(O)O-, -S-, -O-, -N=; x is 0 or 1; and R
is aliphatic,
ethoxylated aliphatics, aromatics, heterocyclic or alicyclic groups or any
combination
thereof to which the nitrogen of the N-O group can be attached or the N-O
group is part
of these groups. Preferred polyamine N-oxides are those wherein R is a
heterocyclic
group such as pyridine, pyrrole, imidazole, pyrrolidine, piperidine and
derivatives
thereo f.
The N-O group can be represented by the following general structures:
O O
I I
~R~)x- i WR2)y; =NWRt)x
~R3)z
wherein R1, R~, R3 are aliphatic, aromatic, heterocyclic or alicyclic groups
or
combinations thereof; x, y and z are 0 or 1; and the nitrogen of the N-O group
can be
attached or form part of any of the aforementioned groups. The amine oxide
unit of the
polyamine N-oxides has a pKa <10, preferably pKa <7, more preferred pKa <6.
Any polymer backbone can be used as long as the amine oxide polymer formed is
water-soluble and has dye transfer inhibiting properties. Examples of suitable
polymeric
backbones are polyvinyls, polyalkylenes, polyesters, polyethers, polyamide.
polyimides,
polyacrylates and mixtures thereof. These polymers include random or block
copolymers
where one monomer type is an amine N-oxide and the other monomer type is an N-
oxide.
The amine N-oxide polymers typically have a ratio of amine to the amine N-
oxide of 10:1
to 1:1,000,000. However, the number of amine oxide groups present in the
polyamine
oxide polymer can be varied by appropriate copolymerization or by an
appropriate degree
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of N-oxidation. The polyamine oxides can be obtained in almost any degree of
polymerization. Typically, the average molecular weight is within the range of
500 to
1,000,000; more preferred 1,000 to 500,000; most preferred 5,000 to 100,000.
This
preferred class of materials can be referred to as "PVNO".
The most preferred polyamine N-oxide useful in the rinse added compositions
and
processes herein is poly(4-vinylpyridine-N-oxide) which as an average
molecular weight
of about 50,000 and an amine to amine N-oxide ratio of about 1:4.
Copolymers of N-vinylpyrrolidone and N-vinylimidazole polymers (referred to as
a class as "PVPVI") are also preferred for use herein. Preferably the PVPVI
has an
average molecular weight range from 5,000 to 1,000,000, more preferably from
5,000 to
200,000, and most preferably from 10,000 to 20,000. (The average molecular
weight
range is determined by light scattering as described in Barth, ei al.,
Chemical Analysis,
Vol 113. "Modern Methods of Polymer Characterization", the disclosures of
which are
incorporated herein by reference.) The PVPVI copolymers typically have a molar
ratio of
N-vinylimidazole to N-vinylpyrrolidone from 1:1 to 0.2:1, more preferably from
0.8:1 to
0.3:1, most preferably from 0.6:1 to 0.4:1. These copolymers can be either
linear or
branched.
The present compositions also may employ a polyvinylpyrrolidone ("PVP")
having an average molecular weight of from about 5,000 to about 400,000,
preferably
from about 5,000 to about 200,000, and more preferably from about 5,000 to
about
50,000. PVP's are known to persons skilled in the detergent field; see, for
example, EP-
A-262,897 and EP-A-256,696, incorporated herein by reference. Compositions
containing PVP can also contain polyethylene glycol ("PEG") having an average
molecular weight from about 500 to about 100,000, preferably from about 1,000
to about
10,000. Preferably, the ratio of PEG to PVP on a ppm basis delivered in wash
solutions
is from about 2:1 to about 50:1, and more preferably from about 3:1 to about
10:1.
The compositions herein may also optionally contain from about 0.005% to 5%
by weight of certain types of hydrophilic optical brighteners which also
provide a dye
transfer inhibition action. If used, the compositions herein will preferably
comprise from
about 0.001 % to 1 % by weight of such optical brighteners.
The hydrophilic optical brighteners useful in the present invention are those
having the structural formula:
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R~ Rz
~N H H . N
N ~~--N ~ C C ~ N--~O N
~N H H N
R., S03M S03M R~
wherein R1 is selected from anilino, N-2-bis-hydroxyethyl and NI-I-2-
hydroxyethyl; R2 is
selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methylamino,
morphilino,
chloro and amino; and M is a salt-forming canon such as sodium or potassium.
When in the above formula, Rl is anilino, R~ is N-2-bis-hydroxyethyl and M is
a
cation such as sodium, the brightener is 4.4',-bis[(4-anilino-6-(N-2-bis-
hydroxyethyl)-s-
triazine-2-yl)amino]-2 2'-stilbenedisulfonic acid and disodium salt. This
particular
brightener species is commercially marketed under the tradename Tinopal-LJNPA-
GX by
Ciba-Geigy Corporation. Tinopal-UNPA-GX is the preferred hydrophilic optical
brightener useful in the rinse added compositions herein.
When in the above formula, RI is anilino, R2 is N-2-hydroxyethyl-N-2-
methylamino and M is a cation such as sodium, the brightener is 4,4'-bis[(4-
anilino-6-(N-
2-hydroxyethyl-N-methylamino)-s-triazine-2-yl)amino]2,?'-stilbenedisulfonic
acid
disodium salt. This particular brightener species is commercially marketed
under the
tradename Tinopal SBM-GX by Ciba-Geigy Corporation.
When in the above formula, R1 is anilino, R~ is morphilino and M is a cation
such as sodium, the brightener is 4,4'-bis[(4-anilino-6-morphilino-s-triazine-
2-
yl)amino]2,2'-stilbenedisulfonic acid, sodium salt. This particular brightener
species is
commercially marketed under the tradename Tinopal AMS-GX by Ciba Geigy
Corporation.
The specific optical brightener species selected for use in the present
invention
provide especially effective dye transfer inhibition performance benefits when
used in
combination with the selected polymeric dye transfer inhibiting agents
hereinbefore
described. The combination of such selected polymeric materials (e.g., PVNO
and/or
PVPVI) with such selected optical brighteners (e.g., Tinopal L1NPA-GX, Tinopal
SBM-
GX and/or Tinopal AMS-GX) provides significantly better dye transfer
inhibition in
aqueous solutions than does either of these two components when used alone.
Without
being bound by theory, it is believed that such brighteners work this way
because they
have high affinity for fabrics in the aqueous solution and therefore deposit
relatively
quick on fabrics. The extent to which brighteners deposit on fabrics in
solution can be
defined by a parameter called the "exhaustion coefficient". The exhaustion
coefficient is
in general as the ratio of a) the brightener material deposited on fabric to
b) the initial
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brightener concentration in the wash liquor. Brighteners with relatively high
exhaustion
coefficients are the most suitable for inhibiting dye transfer in the context
of the present
invention.
Of course, it will be appreciated that other, conventional optical brightener
types
of compounds can optionally also be used in the present compositions to
provide
conventional fabric "brightness" benefits, rather than a true dye transfer
inhibiting effect.
12. Other Optional Ingredients
The finished dispersion compositions of the present invention can include
optional components conventionally used in textile treatment dispersion
compositions,
for example: colorants; preservatives; surfactants; anti-shrinkage agents;
fabric crisping
agents; spotting agents; germicides; fungicides; anti-oxidants such as
butylated hydroxy
toluene, anti-corrosion agents. and the like.
Particularly preferred ingredients include water soluble calcium and/or
magnesium compounds, which provide additional stability. The chloride salts
are
preferred, but acetate, nitrate, etc. salts can be used. The level of said
calcium and/or
magnesium salts is from 0% to about 2%, preferably from about 0.05% to about
0.5%,
more preferably from about 0.1 % to about 0.25%. These materials are desirably
added to
the water and/or acid (water seat) used to prepare the finished dispersion
compositions to
help adjust the finished viscosity.
The present invention can also include other compatible ingredients, including
those as disclosed in copending applications Serial Nos.: 08/372,068, filed
January 12,
1995, Rusche, et al.; 08/372,490, filed January 12, 1995, Shaw, et al.; and
08/277,558,
filed July 19, 1994, Hartman, et al., incorporated herein by reference.
The following examples illustrate the processes and resulting compositions of
the
present invention, but are not intended to be limiting thereof. All parts,
percentages,
proportions, and ratios herein are by weight unless otherwise specified and
all numerical
values are approximations based upon normal confidence limits.
EXAMPLE 1
About 25 grams of commercially available 2,2,4-trimethyl-1,3-pentanediol are
placed in a 100 mL beaker set up on a hot plate with a magnetic stirrer. The
2,2,4-
trimethyl-1,3-pentanediol is heated to about 65°C and, once it becomes
liquid, it is stirred
using a magnetic stir bar. About 0.25 g of sodium borohydride powder is then
gradually
added to the beaker over an approximate 10 minute period. The sodium
borohydride
dissolves within about 5 minutes. Stirring is continued for an additional hour
before
allowing the treated 2,2,4-trimethyl-1,3-pentanediol to cool to room
temperature. The
resulting 2,2,4-trimethyl-1,3-pentanediol has a low, unobjectionable odor.
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EXAMPLE 2
About 150 grams of melted (liquid) commercially available 2,2,4-trimethyl-1,3-
pentanediol are placed in a 300 mL Parr autoclave fitted with a mechanical
stirrer,
external electric heater, thermocouple, pressure gauge and hydrogen supply
line. About
0.75 grams of 10% palladium-on-carbon catalyst is added to the liquid 2,2,4-
trimethyl-
1,3-pentanediol. The autoclave is sealed and stirring is initiated. The
autoclave is then
thoroughly purged with hydrogen. About 200 psig hydrogen pressure is then
applied to
the autoclave. The contents of the autoclave are then heated to about
65°C. The
hydrogen pressure is then adjusted and held at about 300 prig for six hours.
After
approximately six hours, the autoclave is cooled and vented. The palladium-on-
carbon
catalyst is then immediately filtered from the liquid 2,2,4-trimethyl-1,3-
pentanediol. The
resulting 2,2,4-trimethyl-I.3-pentanediol has low, unoffensive odor.
EXAMPLE 3
About 150 grams of melted (liquid) commercially available 2,2,4-trimethyl-1,3-
pentanediol is placed in a 300 mL Pan autoclave fitted with a mechanical
stirrer, external
electric heater, thermocouple, pressure gauge and hydrogen supply line. About
0.08
grams of Raney nickel catalyst is added to the liquid 2,2,4-trimethyl-1,3-
pentanediol.
The autoclave is sealed and stirring is initiated. The autoclave is then
thoroughly purged
with hydrogen. About 200 psig hydrogen pressure is then applied to the
autoclave. The
contents of the autoclave are then heated to about 65°C. The hydrogen
pressure is then
adjusted and held at about 300 psig for six hours. After approximately six
hours, the
autoclave is cooled and vented. The Raney nickel catalyst is then immediately
filtered
from the liquid 2,2,4-trimethyl-1,3-pentanediol. The resulting 2,2,4-trimethyl-
1,3-
pentanediol has low, unoffensive odor.
EXAMPLE 4
About 41.25 grams of commercially available 2,2,4-trimethyl-1,3-pentanediol
are
placed in a 400 mL beaker. About 100 mL of water are added to the beaker, and
the
contents of the beaker are heated on a steam bath until the 2,2,4-trimethyl-
1,3-
pentanedio'I is dissolved and a solution is formed. The solution is stirred
vigorously to
form a cloudy solution, which eventually separates into 2 layers, the top
layer being
2,2,4-trimethyl-1,3-pentanediol and the bottom Layer being water. The top
layer is
decanted into about 50 mL of hexane to form a new solution. About 23 grams of
activated charcoal are added to the new solution while the solution is still
hot. The
solution is then filtered while still hot using Whatman 40 paper. The filtered
solution is
then allowed to cool to room temperature. The filtered solution is then
further cooled to
a few degrees below room temperature by placing it in a refrigerator.
Approximately 20
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minutes after large crystals are formed, the hexane is decanted off the
crystals into a
second 400 mL beaker. The crystals are then rinsed with a few mLs of hexane
and added
to the second beaker. After approximately 20 minutes, more crystals are formed
in the
second beaker. The hexane is decanted off those crystals into a third beaker.
The
crystals in the first two beakers are then dissolved in about 50 mL of hexane
by heating,
and allowed to cool to room temperature to form crystals. The hexane is
decanted from
the resulting crystals. The residual hexane is then removed by freeze drying.
The
resulting 2,2,4-trimethyl-1,3-pentanediol has low, unobjectionable odor.
EXAMPLE 5
About 2500 grams of commercially available 2,2,4-trimethyl-1,3-pentanediol are
placed in a 5 liter, 3-neck flask fitted with a heating mantle, thermometer, 5
sieve tray
distillation column and hot water condenser. A few boiling stones are added to
the flask.
A vacuum is then applied to reduce the pressure in the flask to about 0.5
mmHg. The
contents of the flask are then heated using the heating mantle. The first
condensate is
observed when the pot temperature reaches approximately 102°C, with a
vapor
temperature of about 81 °C. Approximately 450 grams of distillate are
initially collected,
which is referred to as the light fraction. Collection of a middle fraction is
initiated when
the pot temperature is approximately 120°C, with a vapor temperature of
about 104°C
and a pressure of about 2.4 mmHg. The collection of the middle fraction is
terminated
after collecting about 1560 grams of distillate. The flask is then cooled and
the
remaining heavy fraction is decanted. The 2,2,4-trimethyl-1,3-pentanediol
middle
fraction has a low, unobjectionable odor, while the odor of the light and
heavy fractions
are pungent.
EXAMPLE 6
About 200 grams of commercially available 2,2,4-trimethyl-1,3-pentanediol is
placed in a 500 mL 3-neck flask fitted with a heating mantle, reflux condenser
and
thermometer. The 2,2,4-trimethyl-1,3-pentanediol is then heated to
approximately 90°C
to melt (liquify) the 2,2,4-trimethyl-1,3-pentanediol. A few boiling stones
are added,
along withrabout 3.4 grams of a 25% sodium methoxide (in methanol) solution
and about
20 grams of methanol. The mixture is then heated to ~80°C in order to
reflux the
methanol. After an hour at reflux temperature, hydrochloric acid is added
gradually to
adjust the pH of the mixture to approximately 7. The neutralized mixture is
then
fractionally distilled according to Example 5. The distillation yields a
middle fraction
and a heavy fraction of 2,2,4-trimethyl-1,3-pentanediol that have low,
unobjectionable
odor, and a light fraction of 2,2,4-trimethyl-1,3-pentanediol that has an
intense, offensive
odor.
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EXAMPLE 7
About 2500 grams of commercially available 2,2,4-trimethyl-1,3-pentanediol are
fractionally distilled according to Example 5. About 20 grams of the middle
distillation
fraction are treated with about 0.20 grams of sodium borohydride according to
Example
I . The odor of the middle distillate fraction from Example 5 is further
improved.
EXAMPLE 8
About 2500 grams of commercially available 2,2,4-trimethyl-1,3-pentanediol are
fractionally distilled according to Example 5. About 150 grams of the middle
distillation
fraction are then catalytically hydrogenated in a 300 mL Parr autoclave
according to
Example 2 or 3. The odor of the middle distillate fraction from Example 5 is
further
improved.
EXAMPLE 9
About 25 grams of commercially available 2,2,4-trimethyl-1,3-pentanediol are
treated with sodium borohydride according to Example I. Using a separatory
funnel, a
portion of the borohydride treated 2,2,4-trimethyl-1,3-pentanediol is
extracted twice with
an equal volume of a hot (~80°C) 0.1 N hydrochloric acid solution, then
once with an
equal volume of hot {~80°C) deionized water. The resulting 2,2,4-
trimethyl-1,3-
pentanediol contains about 11 % moisture and has improved odor versus the
borohydride
treated 2.2,4-trimethyl-1,3-pentanediol of Example 1.
EXAMPLE 10
About 2500 grams of commercially available 2,2,4-trimethyl-1,3-pentanediol are
fractionally distilled according to Example 5. About 25 grams of the middle
distillation
fraction are then reduced by treating it with sodium borohydride according to
Example 1.
The odor of the middle distillate fraction from Example 5 is further improved.
EXAMPLE 11
About I50 grams of commercially available 2,2,4-trimethyl-1,3-pentanediol is
hydrogenated according to Example 2 or 3. Using a separatory funnel, a portion
of the
hydrogenated 2,2,4-trimethyl-I,3-pentanediol is extracted 3 successive times
with an
equal volume of hot (~80°C) deionized water, using fresh water each
time. The resulting
2,2,4-trimethyl-1,3-pentanediol contains about ll% moisture and has improved
odor
versus the hydrogenated 2,2,4-trimethyl-1,3-pentanediol of Example 2 or 3.
EXAMPLE 12
About 150 grams of melted (liquid) commercially available 2,2,4-trimethyl-1,3-
pentanediol is catalytically hydrogenated according to Example 2 or 3. Using a
separatory funnel, a portion of the catalytically hydrogenated 2,2,4-trimethyl-
1,3-
pentanediol is extracted 3 successive times with an equal volume of hot
(~80°C)
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deionized water, using fresh water each time. The resulting 2,2,4-trimethyl-
1,3-
pentanediol contains about 11% moisture and has improved odor versus the
catalytically
hydrogenated 2,2,4-trimethyl-1,3-pentanediol of Example 2 or 3.
The following non-limiting Examples A, B, C, D and E show clear, or
translucent, liquid fabric softening products with acceptable viscosity,
containing the
commercially available 2,2,4-trimethyl-1,3-pentanediol having improved odor
according
to the present invention.
EXAMPLES A. B, C, D and E
In the following fabric softening compositions, the abbreviated component
identifications have the following meanings:
FSA1 : N,N-di(acyl-oxyethyl)-N,N-dimethylammonium
(Fabric Softening Active) chloride, wherein the fatty acyl group is derived
from canola oil
FSA2 : N,N-di(acyl-oxyethyl)-N,N-
(Fabric Softening Active) methylhydroxyethylammonium methyl sulfate,
wherein the fatty acyl group is derived from
canola oil
TMPD : Commercial 2,2,4-trimethyl-1,3-pentanediol
having improved odor according to the present
invention
CHDM : 1,4 cyclohexanedimethanol
The compositions in Examples A, B, C, D and E below are made by first
preparing an oil seat of fabric softener active at ambient temperature. The
fabric softener
active can be heated, if necessary, to melting if the softener active is not
fluid at room
temperature. The fabric softener active is mixed using an IKA RW 25~ mixer for
about
2 to about 5 minutes at about I50 rpm. Separately, an acid/water seat is
prepared by
mixing the HC1 with deionized (DI) water at ambient temperature. If the fabric
softener
active andfor the principal solvents) are not fluid at room temperature and
need to be
heated, the acid/water seat should also be heated to a suitable temperature,
e.g., about
100°F (about 38°C) and maintaining said temperature with a water
bath. The principal
solvents) (melted at suitable temperatures if their melting points are above
room
temperature) are added to the fabric softener premix and said premix is mixed
for about 5
minutes. The acid/water seat is then added to the fabric softener premix and
mixed for
about 20 to about 30 minutes or until the composition is clear and
homogeneous. The
composition is allowed to air cool to ambient temperature.
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A B C D E
FSAI 30 - - 26 34.7
FSA2 - 25 28 - -
Ethanol 2.6 2.2 2.5 2.3 3.1
Hexylene glycol - 2.2 2.5 2.3 3.1
1,2 Hexanediol - 12 5 - -
TMPD 12 5 9 1 S 18
CHDM 5 - - 5 6
HCl 0.02 0.02 0.02 0.02 0.03
Perfume 2.0 1.5 2.0 2.0 2.5
Dye 5 ppm 20 ppm 5 ppm 5 ppm 5 ppm
Demineralized Balance Balance BalanceBalance Balance
water
For commercial purposes, the above compositions in Examples A, B, C, D and E
are introduced into containers, specifically bottles, and more specifically
clear bottles
(although translucent bottles can be used), made from polypropylene (although
glass,
oriented polyethylene, etc., can be substituted), the bottle having a light
blue tint to
compensate for any yellow color that is present, or that may develop during
storage
(although, for short times, and perfectly clear products, clear containers
with no tint, or
other tints, can be used), and having an ultraviolet light absorber in the
bottle to
minimize the effects of ultraviolet light on the materials inside, especially
the highly
unsaturated actives (the absorbers can also be on the surface). The overall
effect of the
clarity and the container being to demonstrate the clarity of the
compositions, thus
assuring the consumer of the quality of the product. The clarity and odor of
the fabric
softener are critical to acceptance, especially when higher levels of the
fabric softener are
present.
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