U.S. patent application number 11/044560 was filed with the patent office on 2005-09-15 for concentrated, stable, translucent or clear, fabric softening compositions including chelants.
This patent application is currently assigned to The Procter & Gamble Company. Invention is credited to Declercq, Marc Johan, Demeyere, Hugo Jean Marie, Hartman, Frederick Anthony, Severns, John Cort, Wahl, Errol Hoffman, Waite, Scott William, Ward, Alice Marie.
Application Number | 20050202998 11/044560 |
Document ID | / |
Family ID | 34912780 |
Filed Date | 2005-09-15 |
United States Patent
Application |
20050202998 |
Kind Code |
A1 |
Wahl, Errol Hoffman ; et
al. |
September 15, 2005 |
Concentrated, stable, translucent or clear, fabric softening
compositions including chelants
Abstract
Clear or translucent fabric softening compositions having a
biodegradable fabric softening active and an added chelating agent
are disclosed. The biodegradable fabric softening active preferably
has the formula: 1 wherein each R substituent is hydrogen or a
short chain C.sub.1-C.sub.6, preferably C.sub.1-C.sub.3 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 1 to about 4, preferably 2; each Y is
--O--(O)C--, --(R)N--(O)C--, --C(O)--N(R)--, or --C(O)--O--,
preferably --O--(O)C--; the sum of carbons in each R.sup.1, plus
one when Y is --O--(O)C-- or --(R)N--(O)--, is C.sub.6-C.sub.22,
preferably C.sub.12-22, more preferably C.sub.14-C.sub.20, but no
more than one R.sup.1 or YR.sup.1 sum being less than about 12 and
then the other R.sup.1 or YR.sup.1 sum is at least about 16, with
each R.sup.1 being a long chain C.sub.5-C.sub.21 (or
C.sub.6-C.sub.22), preferably C.sub.9-C.sub.19 (or
C.sub.9-C.sub.20), most preferably C.sub.11-C.sub.17 (or
C.sub.12-C.sub.18), straight, branched, unsaturated or
polyunsatruated alkyl, the average Iodine Value of the parent fatty
acid of the R.sup.1 being from about 20 to about 140. The chelating
agent is preferably diaminetriaminepentaacetic acid. The
compositions display excellant clarity with a percentage haze in
the transmission mode of a Hunter Color analysis of less than 90%,
preferably less than 50%.
Inventors: |
Wahl, Errol Hoffman;
(Cincinnati, OH) ; Severns, John Cort; (West
Chester, OH) ; Waite, Scott William; (Cincinnati,
OH) ; Hartman, Frederick Anthony; (Cincinnati,
OH) ; Demeyere, Hugo Jean Marie; (Merchtem, BE)
; Declercq, Marc Johan; (Strombeek-Bever, BE) ;
Ward, Alice Marie; (Hattiesburg, MS) |
Correspondence
Address: |
THE PROCTER & GAMBLE COMPANY
INTELLECTUAL PROPERTY DIVISION
WINTON HILL TECHNICAL CENTER - BOX 161
6110 CENTER HILL AVENUE
CINCINNATI
OH
45224
US
|
Assignee: |
The Procter & Gamble
Company
|
Family ID: |
34912780 |
Appl. No.: |
11/044560 |
Filed: |
January 27, 2005 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
11044560 |
Jan 27, 2005 |
|
|
|
08864875 |
May 20, 1997 |
|
|
|
08864875 |
May 20, 1997 |
|
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PCT/US96/11572 |
Jul 11, 1996 |
|
|
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Current U.S.
Class: |
510/515 |
Current CPC
Class: |
C11D 1/62 20130101; C11D
1/645 20130101; C11D 3/0015 20130101 |
Class at
Publication: |
510/515 |
International
Class: |
D06L 001/00 |
Claims
What is claimed is:
1. A fabric softening composition comprising: A. from about 2% to
about 80%, by weight of the composition, of a fabric softener
active; B. from about 0.001% to about 10% by weight of the
composition of a chelating material, wherein the chelating material
comprises diethylenetriaminepentaacetic acid (DTPA): C. wherein the
composition has a percentage haze in transmision mode of a Hunter
Color analysis of less than about 90.
2. The composition of claim 1, wherein said percentage haze in
transmision mode of a Hunter Color analysis is less than about
50%.
3. The composition of claim 2, wherein said percentage haze in
transmision mode of a Hunter Color analysis is less than about
25%.
4. The composition of claim 1, wherein the DTPA is at least 0.75%
by weight of the composition.
5. The composition of claim 2, wherein the wherein the DTPA is at
least 0.75% by weight of the composition.
6. The composition of claim 3, wherein the DTPA is at least 0.75%
by weight of the composition.
7. A fabric softening composition comprising: A. from about 2% to
about 80%, by weight of the composition, of a fabric softener
active; B. from about 2.5% to about 10% by weight of the
composition of a chelating material, wherein the chelating material
is chosen from at least one of the following:
diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic
acid, ethylenediamine-N,N'-disuccinnic acid,
diethylenetriamine-N,N,N',N",N"-pentakis(methane phosphonic acid),
nitrilotriacetic acid, or a mixture thereof; C. wherein the
composition has a percentage haze in transmision mode of a Hunter
Color analysis of less than about 90.
8. The composition of claim 7, wherein said percentage haze in
transmision mode of a Hunter Color analysis is less than about
50%.
9. The composition of claim 8, wherein said percentage haze in
transmision mode of a Hunter Color analysis is less than about
25%.
10. A method of softening fabric comprising the step of contacting
fabric with the composition according to claim 1.
11. A method of softening fabric comprising the step of contacting
fabric with the composition according to claim 7.
12. The composition of claim 1, further comprising from about
0.001% to about 5% by weight of the composition of a cellulase
enzyme.
13. The composition of claim 7, further comprising from about
0.001% to about 5% by weight of the composition of a cellulase
enzyme.
14. A clear or translucent composition comprising a fabric
softening active and diethylenetriaminepentaacetic acid.
15. The composition of claim 14 further comprising a perfume.
Description
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This application is a continuation of U.S. application Ser.
No. 08/864,875 filed May 20, 1997, which is a continuation of U.S.
Ser. No. 96/11572 filed Jul. 11, 1996, which claims priority to
U.S. application Ser. No. 08/621,019 filed Mar. 22, 1996, which
claims priority to U.S. Provisional Application No. 60/001,057
filed Jul. 11, 1995
TECHNICAL FIELD
[0002] The present invention relates to translucent or clear,
aqueous, concentrated, liquid softening compositions which include
chelants. It especially relates to softening compositions for use
in the rinse cycle of a laundering operation to provide excellent
fabric-softening/static-co- ntrol benefits. The compositions are
characterized by, e.g., reduced staining of fabric, excellent water
dispersibility, rewettability, and/or storage and viscosity
stability at sub-normal temperatures, i.e., temperatures below
normal room temperature, e.g., 25.degree. C.
BACKGROUND OF THE INVENTION
[0003] The art discloses problems associated with formulating and
preparing translucent or clear, concentrated fabric conditioning
formulations. For example, European Patent Application No. 404,471,
Machin et al., published Dec. 27, 1990, teaches isotropic liquid
softening compositions with at least 20% by weight softener and at
least 5% by weight of a short chain organic acid.
[0004] Fabric softening compositions containing high solvent levels
are known in the art. However, softener agglomerates can form and
can deposit on clothes which can result in staining and reduced
softening performance. Also, compositions may thicken and/or
precipitate at lower temperatures, i.e., at about 40.degree. F.
(about 4.degree. C.) to about 65.degree. F. (about 18.degree. C.).
These compositions can also be costly for the consumer due to the
high solvent levels associated with making a concentrated, clear
product.
[0005] The present invention provides concentrated aqueous liquid
fabric softening compositions with low organic solvent level (i.e.,
below about 40%, by weight of the composition) and a chelating
agent, that have improved stability (i.e., remain clear or
translucent and do not precipitate, gel, thicken, or solidify) at
normal, i.e., room temperatures and sub-normal temperatures under
prolonged storage conditions. The compositions also provide reduced
staining of fabrics, good cold water dispersibility, together with
excellent softening, anti-static and fabric rewettability
characteristics, as well as reduced dispenser residue buildup and
excellent freeze-thaw recovery.
BACKGROUND ART
[0006] U.S. Pat. No. 3,756,950 discloses the addition of chelants
to fabric softening compositions to prevent yellowing of fabrics
treated with the compositions. U.S. Pat. No. 5,399,272 discloses
clear liquid fabric softening compositions. U.S. Pat. No. 5,525,245
also discloses clear liquid fabric softening compositions.
SUMMARY OF THE INVENTION
[0007] Accordingly to a first embodiment of the present invention,
a clear or translucent fabric softening composition is provided.
The composition comprises:
[0008] A. from about 2% to about 80%, by weight of the composition,
of a biodegradable fabric softener active selected from the group
consisting of:
[0009] i. a compound having the formula: 2
[0010] wherein each R substituent is hydrogen or a short chain
C.sub.1-C.sub.6, preferably C.sub.1-C.sub.3 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 1 to about 4, preferably 2; each Y is --O--(O)C--,
--(R)N--(O)C--, --C(O)--N(R)--, or --C(O)--O--, preferably
--O--(O)C--; the sum of carbons in each R.sup.1, plus one when Y is
--O--(O)C-- or --(R)N--(O)C--, is C.sub.6-C.sub.22, preferably
C.sub.12-22, more preferably C.sub.14-C.sub.20, but no more than
one R.sup.1 or YR.sup.1 sum being less than about 12 and then the
other R.sup.1 or YR.sup.1 sum is at least about 16, with each
R.sup.1 being a long chain C.sub.5-C.sub.21 (or C.sub.6-C.sub.22),
preferably C.sub.9-C.sub.19 (or C.sub.9-C.sub.20), most preferably
C.sub.11-C.sub.17 (or C.sub.12-C.sub.18), straight, branched,
unsaturated or polyunsaturated alkyl, the average Iodine Value of
the parent fatty acid of the R.sup.1 being from about 20 to about
140;
[0011] ii. a compound having the formula: 3
[0012] wherein each Y, R, R.sup.1, and X.sup.(-) have the same
meanings as before; and
[0013] iii. mixtures thereof;
[0014] B. less than about 40%, by weight of the composition of a
principal solvent having a ClogP of from about 0.15 to about
0.64;
[0015] C. from about 0.001% to about 10% by weight of the
composition of a chelating material;
[0016] D. optionally, an effective amount, sufficient to improve
clarity, of low molecular weight water soluble solvents selected
from the group consisting of: ethanol, isopropanol, propylene
glycol, 1,3-propanediol, propylene carbonate, and mixtures thereof,
the water soluble solvents being at a level that will not form
clear compositions by themselves; and
[0017] E. the balance being water.
[0018] Each R.sup.1 in the fabric softening active may comprise a
long chain C.sub.5-C.sub.21 branched alkyl or unsaturated alkyl,
optionally substituted. Optionally, the ratio of branched alkyl to
unsaturated alkyl being from about 5:95 to about 95:5, and for the
unsaturated alkyl group, the average Iodine Value of the parent
fatty acid of this R.sup.1 group is from about 20 to about 140.
Again optionally, the composition contains from about 15% to about
70% of the softener active, wherein, in the softener active, each R
substituent is hydrogen or a short chain C.sub.1-C.sub.3 alkyl or
hydroxyalkyl group; each n is 2; each Y is --O--(O)C--; the sum of
carbons in each R.sup.1 plus one is C.sub.12-C.sub.22 , and R.sup.1
is branched alkyl or unsaturated alkyl, the ratio of branched alkyl
to unsaturated alkyl being from about 75:25 to about 25:75, and for
the unsaturated alkyl group, the average Iodine Value of the parent
fatty acid of this R.sup.1 group is from about 50 to about 130; and
wherein the counterion, X.sup.-, is selected from the group
consisting of: chloride, bromide, methylsulfate, ethylsulfate,
sulfate, and nitrate.
[0019] Optionally, each R substituent is hydrogen or a short chain
C.sub.1-C.sub.3 alkyl or hydroxyalkyl group; each n is 2; the sum
of carbons in each R.sup.1 plus one is C.sub.12-C.sub.20; and the
counterion, X.sup.-, is selected from the group consisting of:
chloride, bromide, methylsulfate, ethylsulfate, sulfate, and
nitrate, still more preferably each R substituent is selected from
the group consisting of: methyl, ethyl, propyl, hydroxyethyl, and
benzyl; each m is 2; each n is 2; the sum of carbons in each
R.sup.1, plus one is C.sub.14-C.sub.20, with each R.sup.1 being a
long chain C.sub.13-C.sub.19 branched alkyl or unsaturated alkyl,
the ratio of branched alkyl to unsaturated alkyl being from about
50:50 to about 30:70; for the unsaturated alkyl group, the Iodine
Value of the parent fatty acid of this R.sup.1 group is from about
70 to about 115; and wherein the counterion, X.sup.-, is
chloride.
[0020] Also, the level of fabric softening active containing
polyunsaturated alkylene groups is optionally at least about 3% by
weight of the total softener active present and the average Iodine
Value of the parent fatty acid of the R.sup.1 group is from about
60 to about 140.
[0021] The chelant in said composition may be selected from the
group consisting of diethylenetriaminepentaacetic acid,
ethylenediaminetetraace- tic acid, ethylenediamine-N,N'-disuccinnic
acid, diethylenetriamine-N,N,N'- ,N",N"-pentakis(methane phosphonic
acid), nitrilotriacetic acid and mixtures thereof with
diethylenetriaminepentaacetic acid being the most preferred.
Preferably, the composition includes from about 0.01% to about 5%
by weight of the composition of said chelant and/or from about 4%
to about 50%, most preferably from about 10% to about 40% of the
fabric softener active.
[0022] According to a second embodiment of the present invention, a
clear or translucent fabric softening composition is provided. The
composition comprises:
[0023] A. from about 2% to about 80%, by weight of the composition,
of biodegradable fabric softener active;
[0024] B. less than about 40%, by weight of the composition of a
principal solvent having a ClogP of from about 0.15 to about
0.64;
[0025] C. from about 0.001% to about 10% by weight of the
composition of a chelating material to improve color and clarity of
the composition; and
[0026] E. the balance being water;
[0027] wherein the composition has a percentage haze in transmision
mode of a Hunter Color analysis of less than about 90.
[0028] Preferably, the percentage haze in transmision mode of a
Hunter Color analysis is less than about 50% and most preferably
less than about 25%. The chelant may be preferably selected from
the group consisting of diethylenetriaminepentaacetic acid,
ethylenediaminetetraacetic acid, ethylenediamine-N,N'-disuccinnic
acid, diethylenetriamine-N,N,N',N",N"-pe- ntakis(methane phosphonic
acid), nitrilotriacetic acid and mixtures thereof with
diethylenetriaminepentaacetic acid being the most preferred. The
fabric softening active may be defined as above.
[0029] Preferably, the compositions herein are aqueous, translucent
or clear, most preferably clear, compositions containing from about
3% to about 95%, preferably from about 5% to about 80%, more
preferably from about 15% to about 70%, and even more preferably
from about 40% to about 60%, water and from about 3% to about 40%,
preferably from about 10% to about 35%, more preferably from about
12% to about 25%, and even more preferably from about 14% to about
20%, of the above principal alcohol solvent B. These preferred
products (compositions) are not translucent or clear without
principal solvent B. The amount of principal solvent B. required 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.
[0030] The principal solvents are desirably kept to the lowest
levels that provide acceptable stability/clarity in the present
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 level) is needed
to attain product clarity. Inversely, the less the water content,
the less principal solvent (relative to the softener) is needed.
Thus, at low water levels of from about 5% 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 ratio is
preferably from about 30:70 to about 55:45, more preferably from
about 35:65 to about 45:55. At higher water levels, the softener to
principal solvent ratios should be even higher.
[0031] The pH of the compositions should preferably be from about 1
to about 7, preferably from about 1.5 to about 5, more preferably
from about 2 to about 3.5.
DETAILED DESCRIPTION OF THE INVENTION
[0032] I. Fabric Softening Active
[0033] The present invention contains as an essential component
from about 2% to about 80%, preferably from about 13% to about 75%,
more preferably from about 17% to about 70%, and even more
preferably from about 19% to about 65% by weight of the
composition, of a fabric softener active selected from the
compounds identified hereinafter, and mixtures thereof.
[0034] (A) Diester Quatemary Ammonium Fabric Softening Active
Compound (DEQA)
[0035] (1) The first type of DEQA preferably comprises, as the
principal active, compounds of the formula 4
[0036] wherein each R substituent is hydrogen or a short chain
C.sub.1-C.sub.6, preferably C.sub.1-C.sub.3 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, preferably 2; each Y is --O--(O)C--,
--(R)N--(O)C--, --C(O)--N(R)--, or --C(O)--O--, preferably
--O--(O)C--; the sum of carbons in each R.sup.1, plus one when Y is
--O--(O)C-- or --(R)N--(O)C--, is C.sub.6-C.sub.22, preferably
C.sub.12-22, more preferably C.sub.14-C.sub.20, but no more than
one R.sup.1 or YR.sup.1 sum being less than about 12 and then the
other R.sup.1 or YR.sup.1 sum is at least about 16, with each
R.sup.1 being a long chain C.sub.5-C.sub.21 (or C.sub.6-C.sub.22),
preferably C.sub.9-C.sub.19 (or C.sub.9-C.sub.20), most preferably
C.sub.11-C.sub.17 (or C.sub.12-C.sub.18), straight, branched,
unsaturated or polyunsaturated alkyl.
[0037] R.sup.1 may be branched alkyl and unsaturated alkyl
(including polyunsaturated alkyl), wherein the ratio of branched
alkyl to unsaturated alkyl is from about 5:95 to about 95:5,
preferably from about 75:25 to about 25:75, more preferably from
about 50:50 to about 30:70, especially 35:65.
[0038] Optionally, the softener active may contain alkyl,
monounsaturated alkylene, and polyunsaturated alkylene groups, with
the softener active containing polyunsaturated alkylene groups
being at least about 3%, preferably at least about 5%, more
preferably at least about 10%, and even more preferably at least
about 15%, by weight of the total softener active present. (As used
herein, the "percent of softener active" containing a given R.sup.1
group is based upon taking a percentage of the total active based
upon the percentage that the given R.sup.1 group is, of the total
R.sup.1 groups present.)
[0039] The Iodine Value of the parent fatty acid of the R.sup.1
group is preferably from about 20 to about 140, more preferably
from about 50 to about 130; and most preferably from about 70 to
about 115; and wherein the counterion, X.sup.-, can be any
softener-compatible anion, preferably, chloride, bromide,
methylsulfate, ethylsulfate, sulfate, and/or nitrate, more
preferably chloride.
[0040] Alternatively, the fabric softening actives prepared
according to the present invention may have the formula: 5
[0041] wherein each Y, R, R.sup.1, and X.sup.(-) have the same
meanings as before. Such compounds include those having the
formula:
[CH.sub.3].sub.3
N.sup.(+)[CH.sub.2CH(CH.sub.2O(O)CR.sup.1)O(O)CR.sup.1]Cl-
.sup.(-)
[0042] where --O(O)CR.sup.1 is derived partly from unsaturated,
e.g., oleic, fatty acid and, preferably, each R is a methyl or
ethyl group and preferably each R.sup.1 is in the range of C.sub.15
to C.sub.19 with degrees of branching and substitution being
present in the alkyl chains.
[0043] Mixtures of actives of formula (1) and (2) may also be
prepared.
[0044] The counterion, X.sup.(-) above, can be any
softener-compatible anion, preferably the anion of a strong acid,
for example, chloride, bromide, methylsulfate, ethylsulfate,
sulfate, nitrate and the like, more preferably chloride. The anion
can also, but less preferably, carry a double charge in which case
X.sup.(-) represents half a group.
[0045] The fabric softener active can comprise mixtures of
compounds containing, respectively, branched and unsaturated
compounds. Preferred biodegradable quaternary ammonium fabric
softening compounds useful in preparing such mixtures can contain
the group --O--(O)CR.sup.1 which is derived from unsaturated, and
polyunsaturated, fatty acids, e.g., oleic acid, and/or partially
hydrogenated fatty acids, derived from 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. Mixtures of unsaturated fatty acids,
and mixtures of DEQAs that are derived from different unsaturated
fatty acids can be used, and are preferred. Non-limiting examples
of DEQAs prepared from preferred unsaturated fatty acids are
disclosed hereinafter as DEQA.sup.1 to DEQA.sup.8.
[0046] DEQA.sup.6 is prepared from a soy bean fatty acid,
DEQA.sup.7 is prepared from a slightly hydrogenated tallow fatty
acid, and DEQA.sup.8 is prepared from slightly hydrogenated canola
fatty acids.
[0047] DEQAs prepared with R.sup.1 groups that contain branched
chains, e.g., from isostearic acid, for at least part of the
R.sup.1 groups comprise the other part of the mixture. It is also
an option that the fabric softener active itself comprise compounds
containing mixed branched-chain and unsaturated R.sup.1 groups. The
total of active represented by the branched chain groups is
typically from about 5% to about 95%, preferably from about 25% to
about 75%, more preferably from about 35% to about 50%.
[0048] Suitable branched chain fatty acids that can be used to
prepare branched, or mixed branched alkyl and unsaturated alkyl
DEQAs, can be prepared by a variety of methods. The corresponding
branched chain fatty alcohols can be prepared by reduction of the
branched chain fatty acids by standard reactions, e.g., using
borane-THF after the method of Brown, J. Amer. Chem. Soc. (1970),
92, 1637, incorporated herein by reference. The following are
non-limiting examples of branched chain fatty acids.
[0049] Branched Chain Fatty Acid 1: 2-n-Heptylundecanoic Acid 6
[0050] 2-n-Heptylundecanoic acid [22890-21-7] is available from TCI
America, catalog number IO281. It can be made by oxidizing the
Guerbet alcohol 2-heptylundecanol which is, in turn, the aldol
condensation product of nonanal. Guerbet alcohols are available
commercially from Condea under the trade name ISOFOL.RTM.
Alcohols.
[0051] Branched Chain Fatty Acid 2: 2-n-Hexyldecanoic Acid 7
[0052] 2-n-Heptylundecanoic acid [25354-97-6] is available from TCI
America, catalog number H0507. It can be made by oxidizing the
Guerbet alcohol 2-hexyldecanol which is, in turn, the aldol
condensation product of octanal.
[0053] Branched Chain Fatty Acid 3: 2-n-Butyloctanoic Acid 8
[0054] 2-n-Butyloctanoic Acid is available from Union Carbide under
the trade name ISOCARB.RTM. 12 Acid. It can be made by oxidizing
the Guerbet alcohol 2-butyloctanol.
[0055] Branched Chain Fatty Acid 4: 5,7,9-Trimethylnonanoic Acid
9
[0056] 5,7,9-Trimethylnonanoic acid and 3,5,7,9-tetramethylnonanoic
acid are made by the Union Camp Corporation using the oxo process
described by N. E. Lawson, et. al. in J. Am. Oil. Chem. Soc. 1981,
58, 59.
[0057] Branched Chain Fatty Acid 5: Alpha-alkylated Carboxylic
Acids
RR'CHCO.sub.2H
[0058] Alpha substituted acids can be prepared by the C-alkylation
of an enamine which is derived from a straight chained aldehyde
such as octanal or decanal. The derived enamine will form the
carbanion on the carbon alpha to the terminal nitrogen. Reaction of
the enamine anion with an alkyl bromide, in the presence of a
catalytic amount of NaI, will give the branched chain enamine which
upon hydrolysis gives the alpha alkylated aldehyde. The aldehyde
can the be oxidized to the corresponding carboxylic acid.
[0059] Alpha-Heptyldecanoic Acid
[0060] Decanal (aldehyde) can be reacted with an excess of a cyclic
amine such as pyrrolidine, by heating at reflux in toluene in the
presence of a trace amount of p-toluene sulfonic acid. As the amine
condenses with the aldehyde, water is formed and can be removed by
reflux through a water trap. After the theoretical amount of water
has been removed, heptylbromide and sodium iodide can be added an
the alkylation completed in the same solvent system. Following
alkylation (overnight), the reaction mixture is poured over ice and
made acidic with 20% HCl. This hydrolysis converts the alkylated
enamine to the alpha-heptyl decanal. The product can be isolated by
separation, washing, then drying, of the solvent layer and
subsequent removal of the solvent by vacuum distillation.
[0061] The isolated branched aldehyde can then be converted to the
desired carboxylic acid by oxidation in an appropriate solvent
system. Examples of oxidizing agents are; aqueous potassium
permanganate; The Jones Reagent
(CrO.sub.3/H.sub.2SO.sub.4/H.sub.2O) in acetone; CrO.sub.3-acetic
acid,etc. Separation of the desired alpha-heptyldecanoic acid from
the oxidizing medium will be facilitated by the high molecular
weight of the acid.
[0062] Branched Chain Fatty Acid 6: 9 and 10-Alkoxyoctadecanoic
Acids, Other Positional Isomers, and the Corresponding
Alkoxyoctadecanols
[0063] 9 and 10-Methoxyoctadecanoic Acids. The method of Siouffi
et. al. described in Chemistry and Physics of Lipids, (1972), 8(2),
91-101 is followed. About 5 g portion of methyl oleate is dissolved
in about 8 g of methanol and treated with tert-butyl hypobromite to
give the mixed methoxybromo derivatives. These are isolated and
debrominated with Rany catalyst and the crude acid is isolated
after acidification. Hydrogenation of olefinic components in the
crude acid is conducted in cyclohexane using platinum oxide. This
produces the crude mixture of the desired 9 and
10-methoxyoctadecanoic acids.
[0064] 9 and 10-Isopropoxyoctadecanoic Acids. The same procedure is
used except that 2-propanol is substituted for methanol in the
bromination step. This yields the desired 9 and
10-isopropoxyoctadecanoic acids.
[0065] Positional Isomers of Alkoxyoctadecanoic Acids: The same
procedure is used except that oleic acid is first isomerized to a
mixture of unsaturated acids by heating with methanesulfonic acid.
The alkoxybromination-reduction sequence in this case leads to
mixtures of additional positional isomers of alkoxyoctadecanoic
acids.
[0066] Corresponding Fatty Alcohols. The substituted octadecanoic
acids are reduced to the corresponding octadecanols using
borane-THF after the method of Brown, J. Amer. Chem. Soc. (1970),
92, 1637.
[0067] Branched Chain Fatty Acid 7: Phenyloctadecanoic Acid,
Alkylphenyloctadecanoic Acid, and the Corresponding
Octadecanols
[0068] Phenyloctadecanoic Acid. The method of Nakano and Foglia
described in The Journal of the American Oil Chemists Society,
(1984),61(3), 569-73 is used. About 5 g portion of oleic acid and
about 6.91 g of benzene are treated dropwise with about 10.2 g of
methanesulfonic acid at about 50 C..degree. and then allowed to
stir for about 6 hours. The reaction mixture is added to water and
extracted with diethyl ether. Removal of the solvents by vacuum
stripping gives the crude mixture of positional isomers of
phenyloctadecanoic acid.
[0069] Methylphenyloctadecanoic Acid. The synthesis is repeated but
with toluene instead of benzene to yield the mixed positional
isomers of methylphenyloctadecanoic acid.
[0070] Corresponding Octadecanols. The substituted octadecanoic
acids are reduced to the corresponding octadecanols using
borane-THF after the method of Brown, J. Amer. Chem. Soc. (1970),
92, 1637.
[0071] Branched Chain Fatty Acid 8: Phenoxyoctadecanoic Acid,
Hydroxyphenyloctadecanoic Acid, and the Corresponding
Octadecanols
[0072] Hydroxyphenyloctadecanoic Acids. The method of Nakano and
Foglia described in The Journal of the American Oil Chemists
Society, (1984),61(3), 569-73 is used. About 1:5:6 mole ratio of
oleic acid, phenol, and methanesulfonic acid are allowed to react
at about 25 C..degree. for about 48 hours. The reaction mixture is
added to water and extracted with ether. The extract is stripped of
solvent and phenol to give the desired crude mixed positional
isomers of hydroxyphenyloctadecanoic acid.
[0073] Phenoxyoctadecanoic Acids. The reaction is repeated with
about 1:5:2 mole ratio of oleic acid, phenol, and methanesulfonic
acid. The isolated crude product is predominantly
phenoxyoctadecanoic acid, but also contains
hydroxyphenyloctadecanoic acid. A purified mixture of
phenoxyoctadecanoic acid positional isomers is obtained by
chromatography.
[0074] Corresponding Octadecanols. The substituted octadecanoic
acids are reduced to the corresponding octadecanols using
borane-THF after the method of Brown, J. Amer. Chem. Soc. (1970),
92, 1637.
[0075] Branched Chain Fatty Acids 9: Isostearic Acids
[0076] Isostearic acids are produced from the monomeric acids
obtained in the dimerization of unsaturated C.sub.18 fatty acids,
according to U.S. Pat. No. 2,812,342, issued Nov. 5, 1957 to R. M.
Peters, incorporated herein by reference.
[0077] Suitable branched fabric softening actives which can be
mixed with the above described unsaturated fabric softening actives
(DEQAs) to form the fabric softening actives of this invention can
be formed using the above branched chain fatty acids, and/or the
corresponding branched chain fatty alcohols. Similarly, the
branched chain fatty acids and/or alcohols can be used with
unsaturated fatty acids and/or alcohols to form suitable mixed
chain actives.
[0078] As disclosed hereinbefore, other preferred DEQA's are those
that are prepared as a single DEQA from blends of all the different
branched and unsaturated fatty acids that are represented (total
fatty acid blend), rather than from blends of mixtures of separate
finished DEQA's that are prepared from different portions of the
total fatty acid blend.
[0079] At least a substantial percentage of the fatty acyl groups
may be unsaturated, e.g., from about 25% to 70%, preferably from
about 50% to about 65%. Polyunsaturated fatty acid groups can be
used. The total level of active containing polyunsaturated fatty
acyl groups (TPU) can be from about 3% to about 30%, preferably
from about 5% to about 25%, more preferably from about 10% to about
18%. Both cis and trans isomers can be used, preferably 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. (As used herein, the "percent of softener active"
containing a given R.sup.1 group is the same as the percentage of
that same R.sup.1 group is to the total R.sup.1 groups used to form
all of the softener actives.)
[0080] The unsaturated, including the polyunsaturated, fatty acyl
groups, discussed hereinbefore and hereinafter, surprisingly
provide effective softening when used with the branched chain fatty
acyl groups, and also provide good rewetting characteristics, good
antistatic characteristics, and especially, superior recovery after
freezing and thawing.
[0081] The mixed branched-chain and unsaturated materials are
easier to formulate than conventional saturated branched chain
fabric softener actives. They can be used to form concentrated
premixes that maintain their low viscosity and are therefore easier
to process, e.g., pump, mix, etc. These materials with only the low
amount of solvent that 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 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. The use of branched chain fatty acyl
groups improves the resistance to degradation while maintaining
fluidity and improving softening.
[0082] The present invention can also contain some medium-chain
biodegradable quaternary ammonium fabric softening compound, DEQA,
having the above formula (1) and/or formula (2), below,
wherein:
[0083] each Y is --O--(O)C--, or --C(O)--O--, preferably
--O--(O)C--;
[0084] m is 2 or 3, preferably 2;
[0085] each n is 1 to 4, preferably 2;
[0086] each R substituent is a C.sub.1-C.sub.6 alkyl, preferably a
methyl, ethyl, propyl, benzyl groups and mixtures thereof, more
preferably a C.sub.1-C.sub.3 alkyl group;
[0087] each R.sup.1, or YR.sup.1, is a saturated C.sub.8-C.sub.14,
preferably a C.sub.12-14 hydrocarbyl, or substituted hydrocarbyl
substituent (the IV is preferably about 10 or less, more preferably
less than about 5), (The sum of the carbons in the acyl group,
R.sup.1+1, when Y is --O--(O)C-- or --(R)N--(O)C--.) and the
counterion, X.sup.-, is the same as above.
[0088] Preferably X.sup.- does not include phosphate salts.
[0089] The saturated C.sub.8-C.sub.14 fatty acyl groups can be pure
derivatives, or can be mixed chain lengths.
[0090] Suitable fatty acid sources for said fatty acyl groups are
coco, lauric, caprylic, and capric acids.
[0091] For C.sub.12-C.sub.14 (or C.sub.11-C.sub.13) hydrocarbyl
groups, the groups are preferably saturated, e.g., the IV is
preferably less than about 10, preferably less than about 5.
[0092] It will be understood that the branched R and R.sup.1
substituents can contain various groups such as alkoxyl groups
which act as branching, and a small percentage can be straight, so
long as the R.sup.1 groups maintain their basically hydrophobic
character. The preferred compounds can be considered to be
biodegradable diester variations of hardened ditallow dimethyl
ammonium chloride (hereinafter referred to as "DTDMAC"), which is a
widely used fabric softener.
[0093] 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., one YR.sup.1 group is either --OH, or
--C(O)OH, and, for Formula 1., m is 2. The corresponding diamide
and/or mixed ester-amide can also include the active with one long
chain hydrophobic group, e.g., one YR.sup.1 group is either --N(R)H
, or --C(O)OH. In the following, any disclosure, e.g., levels, for
the monoester actives is also applicable to the monoamide actives.
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%. However, under high, anionic
detergent surfactant or detergent builder carry-over conditions,
some monoester can be preferred. The overall ratios of diester to
monoester are from about 100:1 to about 2:1, preferably from about
50:1 to about 5:1, more preferably from about 13:1 to about 8:1.
Under high detergent carry-over conditions, the di/monoester ratio
is preferably about 11:1. The level of monoester present can be
controlled in manufacturing the DEQA.
[0094] The above compounds, as exemplified hereinafter, used as the
biodegradable quaternized ester-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(CH.sub.2CH.sub.2OH).sub.2 is esterified at
both hydroxyl groups with an acid chloride of the formula
R.sup.1C(O)Cl, then quatemized with an alkyl halide, RX, to yield
the desired reaction product (wherein R and R.sup.1 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.
[0095] Yet another DEQA softener active that is suitable for the
formulation of the fabric softening actives and concentrated, clear
liquid fabric softener compositions of the present invention has
the above formula (1) wherein one R group is a C.sub.1-4 hydroxy
alkyl group, preferably one wherein one R group is a hydroxyethyl
group.
[0096] (2) The second type of DEQA active has the general formula:
10
[0097] wherein each Y, R, R.sup.1, and X.sup.(-) have the same
meanings as before. Such compounds include those having the
formula:
[CH.sub.3].sub.3N.sup.(+)[CH.sub.2CH(CH.sub.2O(O)CR.sup.1)O(O)CR.sup.1]Cl.-
sup.(-)
[0098] where each R is a methyl or ethyl group and preferably each
R.sup.1 is in the range of C.sub.15 to C.sub.19. Degrees of
substitution can be present in the alkyl or unsaturated alkyl
chains. The anion X.sup.(-) in the molecule is the same as in DEQA
(1) above. 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). 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, wherein the
acyl group is the same as that of DEQA.sup.5.
[0099] 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.
[0100] In suitable softener actives (1) and (2), each R.sup.1 may
be an alkyl, branched alkyl, monounsaturated unsaturated alkyl, or
polyunsaturated alkyl group. The actives may contain mixtures of
branched alkyl and unsaturated alkyl R.sup.1 groups, especially
within the individual molecules, in the ratios disclosed
hereinbefore.
[0101] The DEQAs herein can contain a low level of fatty acid,
which can be from unreacted starting material used to form the DEQA
and/or as a by-product of any partial degradation (hydrolysis) of
the softener active in the finished composition. It is preferred
that the level of free fatty acid be low, preferably below about
10%, and more preferably below about 5%, by weight of the softener
active.
[0102] II. Principal Solvent System
[0103] The compositions of the present invention comprise less than
about 40%, preferably from about 10% to about 35%, more preferably
from about 12% to about 25%, and even more preferably from about
14% to about 20%, of the principal solvent, by weight of the
composition. Said principal solvent is selected to minimize solvent
odor impact in the composition and to provide a low 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 alcohols
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.degree. F. (about 4.4.degree.
C.) and are able to recover after storage down to about 20.degree.
F. (about 6.7.degree. C.).
[0104] 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, logP.
[0105] The logP of many ingredients has been reported; for example,
the Pomona92 database, available from Daylight Chemical Information
Systems, Inc. (Daylight CIS), Irvine, Calif., contains many, along
with citations to the original literature. However, the logP values
are most conveniently calculated by the "CLOGP" program, also
available from Daylight CIS. This program also lists experimental
logP values when they are available in the Pomona92 database. The
"calculated logP" (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,
Eds., 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 ClogP values, which are the most reliable and widely used
estimates for this physicochemical property, are preferably used
instead of the experimental logP 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); Viswanadhan's fragmentation method as
disclose in J. Chem. Inf. Comput. Sci., 29, 163 (1989); and Broto's
method as disclosed in Eur. J. Med. Chem.-Chim. Theor., 19, 71
(1984).
[0106] 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 ClogP 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.degree. F. (about 4.4.degree. C.) and recovers
from being frozen at about 0.degree. F. (about -18.degree. C.).
[0107] The most preferred principal solvents can be identified by
the appearance of the freeze-dried dilute treatment compositions
used to treat fabrics. These dilute compositions appear to have
dispersions of fabric softener that exhibit a more uni-lamellar
appearance than conventional fabric softener compositions. The
closer to uni-lamellar the appearance, the better the compositions
seem to perform. These compositions provide surprisingly good
fabric softening as compared to similar compositions prepared in
the conventional way with the same fabric softener active. The
compositions also inherently provide improved perfume deposition as
compared to conventional fabric softening compositions, especially
when the perfume is added to the compositions at, or near, room
temperature.
[0108] Operable principal solvents are listed below under various
listings, e.g., aliphatic and/or alicyclic diols with a given
number of carbon atoms; monols; derivatives of glycerine;
alkoxylates of diols; and mixtures of all of the above. The
preferred principal solvents are in italics and the most preferred
principal solvents are in bold type. The reference numbers are the
Chemical Abstracts Service Registry numbers (CAS No.) for those
compounds that have such a number. Novel compounds have a method
identified, described hereinafter, that can be used to prepare the
compounds. Some inoperable principal solvents are also listed below
for comparison purposes. The inoperable principal solvents,
however, can be used in mixtures with operable principal solvents.
Operable principal solvents can be used to make concentrated fabric
softener compositions that meet the stability/clarity requirements
set forth herein.
[0109] Many diol principal solvents that have the same chemical
formula can exist as many stereoisomers and/or optical isomers.
Each isomer is normally assigned with a different CAS No. For
examples, different isomers of 4-methyl-2,3-hexanediol are assigned
to at least the following CAS Nos: 146452-51-9; 146452-50-8;
146452-49-5; 14645248-4; 123807-34-1; 123807-33-0; 123807-32-9; and
123807-31-8.
[0110] In the following listings, for simplicity, each chemical
formula is listed with only one CAS No. This disclosure is only for
exemplification and is sufficient to allow the practice of the
invention. The disclosure is not limiting. Therefore, it is
understood that other isomers with other CAS Nos, and their
mixtures, are also included. By the same token, when a CAS No.
represents a molecule which contains some particular isotopes,
e.g., deuterium, tritium, carbon-13, etc., it is understood that
materials which contain naturally distributed isotopes are also
included, and vice versa.
1TABLE I MONO-OLS CAS No. n-propanol 71-23-8 2-butanol 15892-23-6
2-methyl-2-propanol 75-65-0 Inoperable Isomer 2-methyl-1-propanol
78-83-1
[0111]
2TABLE II C6 DIOLS CAS No. Operable Isomers 2,3-butanediol,
2,3-dimethyl- 76-09-5 1,2-butanediol, 2,3-dimethyl- 66553-15-9
1,2-butanediol, 3,3-dimethyl- 59562-82-2 2,3-pentanediol, 2-methyl-
7795-80-4 2,3-pentanediol, 3-methyl- 63521-37-9 2,3-pentanediol,
4-methyl- 7795-79-1 2,3-hexanediol 617-30-1 3,4-hexanediol 922-17-8
1,2-butanediol, 2-ethyl- 66553-16-0 1,2-pentanediol, 2-methyl-
20667-05-4 1,2-pentanediol, 3-methyl- 159623-53-7 1,2-pentanediol,
4-methyl- 72110-08-8 1,2-hexanediol 6920-22-5 Inoperable Isomers
1,3-propanediol, 2-ethyl-2-methyl- 1,3-propanediol, 2-isopropyl-
1,3-propanediol, 2-propyl- 1,3-butanediol, 2,2-dimethyl-
1,3-butanediol, 2,3-dimethyl- 1,3-butanediol, 2-ethyl-
1,4-butanediol, 2,2-dimethyl- 1,4-butanediol, 2,3-dimethyl-
1,4-butanediol, 2-ethyl- 1,3-pentanediol, 2-methyl-
1,3-pentanediol, 3-methyl- 1,3-pentanediol, 4-methyl-
1,4-pentanediol, 2-methyl- 1,4-pentanediol, 3-methyl-
1,4-pentanediol, 4-methyl- 1,5-pentanediol, 2-methyl-
1,5-pentanediol, 3-methyl- 2,4-pentanediol, 2-methyl-
2,4-pentanediol, 3-methyl- 1,3-hexanediol 1,4-hexanediol
1,5-hexanediol 1,6-hexanediol 2,4-hexanediol 2,5-hexanediol
[0112]
3TABLE III C7 DIOLS CAS No. Operable Isomers 1,3-propanediol,
2-butyl- 2612-26-2 1,3-propanediol, 2,2-diethyl- 115-76-4
1,3-propanediol, 2-(1-methylpropyl)- 33673-01-7 1,3-propanediol,
2-(2-methylpropyl)- 26462-20-8 1,3-propanediol, 2-methyl-2-propyl-
78-26-2 1,2-butanediol, 2,3,3-trimethyl- Method B 1,4-butanediol,
2-ethyl-2-methyl- 76651-98-4 1,4-butanediol, 2-ethyl-3-methyl-
66225-34-1 1,4-butanediol, 2-propyl- 62946-68-3 1,4-butanediol,
2-isopropyl- 39497-66-0 1,5-pentanediol, 2,2-dimethyl- 3121-82-2
1,5-pentanediol, 2,3-dimethyl- 81554-20-3 1,5-pentanediol,
2,4-dimethyl- 2121-69-9 1,5-pentanediol, 3,3-dimethyl- 53120-74-4
2,3-pentanediol, 2,3-dimethyl- 6931-70-0 2,3-pentanediol,
2,4-dimethyl- 66225-53-4 2,3-pentanediol, 3,4-dimethyl- 37164-04-8
2,3-pentanediol, 4,4-dimethyl- 89851-45-6 3,4-pentanediol,
2,3-dimethyl- Method B 1,5-pentanediol, 2-ethyl- 14189-13-0
1,6-hexanediol, 2-methyl- 25258-92-8 1,6-hexanediol, 3-methyl-
4089-71-8 2,3-hexanediol, 2-methyl- 59215-55-3 2,3-hexanediol,
3-methyl- 139093-40-6 2,3-hexanediol, 4-methyl- *** 2,3-hexanediol,
5-methyl- Method B 3,4-hexanediol, 2-methyl- Method B
3,4-hexanediol, 3-methyl- 18938-47-1 1,3-heptanediol 23433-04-7
1,4-heptanediol 40646-07-9 1,5-heptanediol 60096-09-5
1,6-heptanediol 13175-27-4 Preferred Isomers 1,3-propanediol,
2-butyl- 2612-26-2 1,4-butanediol, 2-propyl- 62946-68-3
1,5-pentanediol, 2-ethyl- 14189-13-0 2,3-pentanediol, 2,3-dimethyl-
6931-70-0 2,3-pentanediol, 2,4-dimethyl- 66225-53-4
2,3-pentanediol, 3,4-dimethyl- 37164-04-8 2,3-pentanediol,
4,4-dimethyl- 89851-45-6 3,4-pentanediol, 2,3-dimethyl- Method B
1,6-hexanediol, 2-methyl- 25258-92-8 1,6-hexanediol, 3-methyl-
4089-71-8 1,3-heptanediol 23433-04-7 1,4-heptanediol 40646-07-9
1,5-heptanediol 60096-09-5 1,6-heptanediol 13175-27-4 More
Preferred Isomers 2,3-pentanediol, 2,3-dimethyl- 6931-70-0
2,3-pentanediol, 2,4-dimethyl- 66225-53-4 2,3-pentanediol,
3,4-dimethyl- 37164-04-8 2,3-pentanediol, 4,4-dimethyl- 89851-45-6
3,4-pentanediol, 2,3-dimethyl- Method B Inoperable Isomers
1,3-propanediol, 2-methyl-2-isopropyl- 1,2-butanediol,
2-ethyl-3-methyl- 1,3-butanediol, 2,2,3-trimethyl- 1,3-butanediol,
2-ethyl-2-methyl- 1,3-butanediol, 2-ethyl-3-methyl- 1,3-butanediol,
2-isopropyl- 1,3-butanediol, 2-propyl- 1,4-butanediol,
2,2,3-trimethyl 1,4-butanediol, 3-ethyl-1-methyl- 1,2-pentanediol,
2,3-dimethyl- 1,2-pentanediol, 2,4-dimethyl- 1,2-pentanediol,
3,3-dimethyl- 1,2-pentanediol, 3,4-dimethyl- 1,2-pentanediol,
4,4-dimethyl- 1,2-pentanediol, 2-ethyl- 1,3-pentanediol,
2,2-dimethyl- 1,3-pentanediol, 2,3-dimethyl- 1,3-pentanediol,
2,4-dimethyl- 1,3-pentanediol, 2-ethyl- 1,3-pentanediol,
3,4-dimethyl- 1,3-pentanediol, 4,4-dimethyl- 1,4-pentanediol,
2,2-dimethyl- 1,4-pentanediol, 2,3-dimethyl- 1,4-pentanediol,
2,4-dimethyl- 1,4-pentanediol, 3,3-dimethyl- 1,4-pentanediol,
3,4-dimethyl- 2,4-pentanediol, 2,3-dimethyl- 2,4-pentanediol,
2,4-dimethyl- 2,4-pentanediol, 3,3-dimethyl- 1,2-hexanediol,
2-methyl- 1,2-hexanediol, 3-methyl- 1,2-hexanediol, 4-methyl-
1,2-hexanediol, 5-methyl- 1,3-hexanediol, 2-methyl- 1,3-hexanediol,
3-methyl- 1,3-hexanediol, 4-methyl- 1,3-hexanediol, 5-methyl-
1,4-hexanediol, 2-methyl- 1,4-hexanediol, 3-methyl- 1,4-hexanediol,
4-methyl- 1,4-hexanediol, 5-methyl- 1,5-hexanediol, 2-methyl-
1,5-hexanediol, 3-methyl- 1,5-hexanediol, 4-methyl- 1,5-hexanediol,
5-methyl- 2,4-hexanediol, 2-methyl- 2,4-hexanediol, 3-methyl-
2,4-hexanediol, 4-methyl- 2,4-hexanediol, 5-methyl- 2,5-hexanediol,
2-methyl- 2,5-hexanediol, 3-methyl- 1,2-heptanediol 2,3-heptanediol
2,4-heptanediol 2,5-heptanediol 2,6-heptanediol 3,4-heptanediol
1,7-heptanediol 3,5-heptanediol ***146452-51-9; 146452-50-8;
146452-49-5; 146452-48-4; 123807-34-1; 123807-33-0; 123807-32-9;
123807-31-8; and mixtures thereof.
[0113]
4TABLE IV OCTANEDIOL ISOMERS Chemical Name CAS No. PROPANEDIOL
DERIVATIVES Operable Isomers 1,3-propanediol, 2-(2-methylbutyl)-
87194-40-9 1,3-propanediol, 2-(1,1-dimethylpropyl)- Method D
1,3-propanediol, 2-(1,2-dimethylpropyl)- Method D 1,3-propanediol,
2-(1-ethylpropyl)- 25462-28-6 1,3-propanediol, 2-(1-methylbutyl)-
22131-29-9 1,3-propanediol, 2-(2,2-dimethylpropyl)- Method D
1,3-propanediol, 2-(3-methylbutyl)- 25462-27-5 1,3-propanediol,
2-butyl-2-methyl- 3121-83-3 1,3-propanediol, 2-ethyl-2-isopropyl-
24765-55-7 1,3-propanediol, 2-ethyl-2-propyl- 25450-88-8
1,3-propanediol, 2-methyl-2-(1-methylpropyl)- 813-60-5
1,3-propanediol, 2-methyl-2-(2-methylpropyl)- 25462-42-4
1,3-propanediol, 2-tertiary-butyl-2-methyl- 25462-45-7 More
Preferred Isomers 1,3-propanediol, 2-(1,1-dimethylpropyl)- Method D
1,3-propanediol, 2-(1,2-dimethylpropyl)- Method D 1,3-propanediol,
2-(1-ethylpropyl)- 25462-28-6 1,3-propanediol,
2-(2,2-dimethylpropyl)- Method D 1,3-propanediol,
2-ethyl-2-isopropyl- 24765-55-7 1,3-propanediol,
2-methyl-2-(1-methylpropyl)- 813-60-5 1,3-propanediol,
2-methyl-2-(2-methylpropyl)- 25462-42-4 1,3-propanediol,
2-tertiary-butyl-2-methyl- 25462-45-7 Inoperable Isomers
1,3-propanediol, 2-pentyl- BUTANEDIOL DERIVATIVES Operable Isomers
1,3-butanediol, 2,2-diethyl- 99799-77-6 1,3-butanediol,
2-(1-methylpropyl)- Method C 1,3-butanediol, 2-butyl- 83988-22-1
1,3-butanediol, 2-ethyl-2,3-dimethyl- Method D 1,3-butanediol,
2-(1,1-dimethylethyl)- 67271-58-3 1,3-butanediol,
2-(2-methylpropyl)- Method C 1,3-butanediol, 2-methyl-2-isopropyl-
Method C 1,3-butanediol, 2-methyl-2-propyl- 99799-79-8
1,3-butanediol, 3-methyl-2-isopropyl- Method C 1,3-butanediol,
3-methyl-2-propyl- Method D 1,4-butanediol, 2,2-diethyl- Method H
1,4-butanediol, 2-methyl-2-propyl- Method H 1,4-butanediol,
2-(1-methylpropyl)- Method H 1,4-butanediol, 2-ethyl-2,3-dimethyl-
Method F 1,4-butanediol, 2-ethyl-3,3-dimethyl- Method F
1,4-butanediol, 2-(1,1-dimethylethyl)- 36976-70-2 1,4-butanediol,
2-(2-methylpropyl)- Method F 1,4-butanediol, 2-methyl-3-propyl-
90951-76-1 1,4-butanediol, 3-methyl-2-isopropyl- 99799-24-3
Preferred Isomers 1,3-butanediol, 2,2-diethyl- 99799-77-6
1,3-butanediol, 2-(1-methylpropyl)- Method C 1,3-butanediol,
2-butyl- 83988-22-1 1,3-butanediol, 2-ethyl-2,3-dimethyl- Method D
1,3-butanediol, 2-(1,1-dimethylethyl)- 67271-58-3 1,3-butanediol,
2-(2-methylpropyl)- Method C 1,3-butanediol, 2-methyl-2-isopropyl-
Method C 1,3-butanediol, 2-methyl-2-propyl- 99799-79-8
1,3-butanediol, 3-methyl-2-propyl- Method D 1,4-butanediol,
2,2-diethyl- Method H 1,4-butanediol, 2-ethyl-2,3-dimethyl- Method
F 1,4-butanediol, 2-ethyl-3,3-dimethyl- Method F 1,4-butanediol,
2-(1,1-dimethylethyl)- 36976-70-2 1,4-butanediol,
3-methyl-2-isopropyl- 99799-24-3 More Preferred Isomers
1,3-butanediol, 2-(1-methylpropyl)- Method C 1,3-butanediol,
2-(2-methylpropyl)- Method C 1,3-butanediol, 2-butyl- 83988-22-1
1,3-butanediol, 2-methyl-2-propyl- 99799-79-8 1,3-butanediol,
3-methyl-2-propyl- Method D 1,4-butanediol, 2,2-diethyl- Method H
1,4-butanediol, 2-ethyl-2,3-dimethyl- Method F 1,4-butanediol,
2-ethyl-3,3-dimethyl- Method F 1,4-butanediol,
2-(1,1-dimethylethyl)- 36976-70-2 Inoperable Isomers
1,4-butanediol, 2-butyl- 1,2-butanediol, 2-ethyl-3,3-dimethyl-
1,4-butanediol, 2-methyl-2-isopropyl- 1,2-butanediol,
3-methyl-2-isopropyl- 1,4-butanediol, 2,2,3,3-tetramethyl-
TRIMETHYLPENTANEDIOL ISOMERS Operable Isomers 1,3-pentanediol,
2,2,3-trimethyl- 35512-54-0 1,3-pentanediol, 2,2,4-trimethyl-
144-19-4 1,3-pentanediol, 2,3,4-trimethyl- 116614-13-2
1,3-pentanediol, 2,4,4-trimethyl- 109387-36-2 1,3-pentanediol,
3,4,4-trimethyl- 81756-50-5 1,4-pentanediol, 2,2,3-trimethyl-
Method H 1,4-pentanediol, 2,2,4-trimethyl- 80864-10-4
1,4-pentanediol, 2,3,3-trimethyl- Method H 1,4-pentanediol,
2,3,4-trimethyl- 92340-74-4 1,4-pentanediol, 3,3,4-trimethyl-
16466-35-6 1,5-pentanediol, 2,2,3-trimethyl- Method F
1,5-pentanediol, 2,2,4-trimethyl- 3465-14-3 1,5-pentanediol,
2,3,3-trimethyl- Method A 1,5-pentanediol, 2,3,4-trimethyl-
85373-83-7 2,4-pentanediol, 2,3,3-trimethyl- 24892-51-1
2,4-pentanediol, 2,3,4-trimethyl- 24892-52-2 Preferred Isomers
1,3-pentanediol, 2,2,3-trimethyl- 35512-54-0 1,3-pentanediol,
2,2,4-trimethyl- 144-19-4 1,3-pentanediol, 2,3,4-trimethyl-
116614-13-2 1,3-pentanediol, 2,4,4-trimethyl- 109387-36-2
1,3-pentanediol, 3,4,4-trimethyl- 81756-50-5 1,4-pentanediol,
2,2,3-trimethyl- Method H 1,4-pentanediol, 2,2,4-trimethyl-
80864-10-4 1,4-pentanediol, 2,3,3-trimethyl- Method F
1,4-pentanediol, 2,3,4-trimethyl- 92340-74-4 1,4-pentanediol,
3,3,4-trimethyl- 16466-35-6 1,5-pentanediol, 2,2,3-trimethyl-
Method A 1,5-pentanediol, 2,2,4-trimethyl- 3465-14-3
1,5-pentanediol, 2,3,3-trimethyl- Method A 2,4-pentanediol,
2,3,4-trimethyl- 24892-52-2 More Preferred Iomers 1,3-pentanediol,
2,3,4-trimethyl- 116614-13-2 1,4-pentanediol, 2,3,4-trimethyl-
92340-74-4 1,5-pentanediol, 2,2,3-trimethyl- Method A
1,5-pentanediol, 2,2,4-trimethyl- 3465-14-3 1,5-pentanediol,
2,3,3-trimethyl- Method A Inoperable Isomers 1,2-pentanediol,
2,3,3-trimethyl- 1,2-pentanediol, 2,3,4-trimethyl- 1,2-pentanediol,
2,4,4-trimethyl- 1,2-pentanediol, 3,3,4-trimethyl- 1,2-pentanediol,
3,4,4-trimethyl- 2,3-pentanediol, 2,3,4-trimethyl- 2,3-pentanediol,
2,4,4-trimethyl- 2,3-pentanediol, 3,4,4-trimethyl-
ETHYLMETHYLPENTANEDIOL ISOMERS Operable Isomers 1,3-pentanediol,
2-ethyl-2-methyl- Method C 1,3-pentanediol, 2-ethyl-3-methyl-
Method D 1,3-pentanediol, 2-ethyl-4-methyl- 148904-97-6
1,3-pentanediol, 3-ethyl-2-methyl- 55661-05-7 1,4-pentanediol,
2-ethyl-2-methyl- Method H 1,4-pentanediol, 2-ethyl-3-methyl-
Method F 1,4-pentanediol, 2-ethyl-4-methyl- Method G
1,4-pentanediol, 3-ethyl-2-methyl- Method F 1,4-pentanediol,
3-ethyl-3-methyl- Method F 1,5-pentanediol, 2-ethyl-2-methyl-
Method F 1,5-pentanediol, 2-ethyl-3-methyl- 54886-83-8
1,5-pentanediol, 2-ethyl-4-methyl- Method F 1,5-pentanediol,
3-ethyl-3-methyl- 57740-12-2 2,4-pentanediol, 3-ethyl-2-methyl-
Method G More Preferred Isomers 1,3-pentanediol, 2-ethyl-2-methyl-
Method C 1,3-pentanediol, 2-ethyl-3-methyl- Method D
1,3-pentanediol, 2-ethyl-4-methyl- 148904-97-6 1,3-pentanediol,
3-ethyl-2-methyl- 55661-05-7 1,4-pentanediol, 2-ethyl-2-methyl-
Method H 1,4-pentanediol, 2-ethyl-3-methyl- Method F
1,4-pentanediol, 2-ethyl-4-methyl- Method G 1,5-pentanediol,
3-ethyl-3-methyl- 57740-12-2 2,4-pentanediol, 3-ethyl-2-methyl-
Method G Inoperable Isomers 1,2-pentanediol, 2-ethyl-3-methyl-
1,2-pentanediol, 2-ethyl-4-methyl- 1,2-pentanediol,
3-ethyl-2-methyl- 1,2-pentanediol, 3-ethyl-3-methyl-
1,2-pentanediol, 3-ethyl-4-methyl- 1,3-pentanediol,
3-ethyl-4-methyl- 1,4-pentanediol, 3-ethyl-4-methyl-
1,5-pentanediol, 3-ethyl-2-methyl- 2,3-pentanediol,
3-ethyl-2-methyl- 2,3-pentanediol, 3-ethyl-4-methyl-
2,4-pentanediol, 3-ethyl-3-methyl- PROPYLPENTANEDIOL ISOMERS
Operable Isomers 1,3-pentanediol, 2-isopropyl- Method D
1,3-pentanediol, 2-propyl- Method C 1,4-pentanediol, 2-isopropyl-
Method H 1,4-pentanediol, 2-propyl- Method H 1,4-pentanediol,
3-isopropyl- Method H 1,5-pentanediol, 2-isopropyl- 90951-89-6
2,4-pentanediol, 3-propyl- Method C More Preferred Isomers
1,3-pentanediol, 2-isopropyl- Method D 1,3-pentanediol, 2-propyl-
Method C 1,4-pentanediol, 2-isopropyl- Method H 1,4-pentanediol,
2-propyl- Method H 1,4-pentanediol, 3-isopropyl- Method H
2,4-pentanediol, 3-propyl- Method C Inoperable Isomers
1,2-pentanediol, 2-propyl- 1,2-pentanediol, 2-isopropyl-
1,4-pentanediol, 3-propyl- 1,5-pentanediol, 2-propyl-
2,4-pentanediol, 3-isopropyl- DIMETHYLHEXANEDIOL ISOMERS Operable
Isomers 1,3-hexanediol, 2,2-dimethyl- 22006-96-8 1,3-hexanediol,
2,3-dimethyl- Method D 1,3-hexanediol, 2,4-dimethyl- 78122-99-3
1,3-hexanediol, 2,5-dimethyl- Method C 1,3-hexanediol,
3,4-dimethyl- Method D 1,3-hexanediol, 3,5-dimethyl- Method D
1,3-hexanediol, 4,4-dimethyl- Method C 1,3-hexanediol,
4,5-dimethyl- Method C 1,4-hexanediol, 2,2-dimethyl- Method F
1,4-hexanediol, 2,3-dimethyl- Method F 1,4-hexanediol,
2,4-dimethyl- Method G 1,4-hexanediol, 2,5-dimethyl- 22417-60-3
1,4-hexanediol, 3,3-dimethyl- Method F 1,4-hexanediol,
3,4-dimethyl- Method E 1,4-hexanediol, 3,5-dimethyl- Method H
1,4-hexanediol, 4,5-dimethyl- Method E 1,4-hexanediol,
5,5-dimethyl- 38624-38-3 1,5-hexanediol, 2,2-dimethyl- Method A
1,5-hexanediol, 2,3-dimethyl- 62718-05-2 1,5-hexanediol,
2,4-dimethyl- 73455-82-0 1,5-hexanediol, 2,5-dimethyl- 58510-28-4
1,5-hexanediol, 3,3-dimethyl- 41736-99-6 1,5-hexanediol,
3,4-dimethyl- Method A 1,5-hexanediol, 3,5-dimethyl- Method G
1,5-hexanediol, 4,5-dimethyl- Method F 1,6-hexanediol,
2,2-dimethyl- 13622-91-8 1,6-hexanediol, 2,3-dimethyl- Method F
1,6-hexanediol, 2,4-dimethyl- Method F 1,6-hexanediol,
2,5-dimethyl- 49623-11-2 1,6-hexanediol, 3,3-dimethyl- Method F
1,6-hexanediol, 3,4-dimethyl- 65363-45-3 2,4-hexanediol,
2,3-dimethyl- 26344-17-2 2,4-hexanediol, 2,4-dimethyl- 29649-22-7
2,4-hexanediol, 2,5-dimethyl- 3899-89-6 2,4-hexanediol,
3,3-dimethyl- 42412-51-1 2,4-hexanediol, 3,4-dimethyl- 90951-83-0
2,4-hexanediol, 3,5-dimethyl- 159300-34-2 2,4-hexanediol,
4,5-dimethyl- Method D 2,4-hexanediol, 5,5-dimethyl- 108505-10-8
2,5-hexanediol, 2,3-dimethyl- Method G 2,5-hexanediol,
2,4-dimethyl- Method G 2,5-hexanediol, 2,5-dimethyl- 110-03-2
2,5-hexanediol, 3,3-dimethyl- Method H 2,5-hexanediol,
3,4-dimethyl- 99799-30-1 2,6-hexanediol, 3,3-dimethyl- Method A
More Preferred Isomers 1,3-hexanediol, 2,2-dimethyl- 22006-96-8
1,3-hexanediol, 2,3-dimethyl- Method D 1,3-hexanediol,
2,4-dimethyl- 78122-99-3 1,3-hexanediol, 2,5-dimethyl- Method C
1,3-hexanediol, 3,4-dimethyl- Method D 1,3-hexanediol,
3,5-dimethyl- Method D 1,3-hexanediol, 4,4-dimethyl- Method C
1,3-hexanediol, 4,5-dimethyl- Method C 1,4-hexanediol,
2,2-dimethyl- Method H 1,4-hexanediol, 2,3-dimethyl- Method F
1,4-hexanediol, 2,4-dimethyl- Method G 1,4-hexanediol,
2,5-dimethyl- 22417-60-3 1,4-hexanediol, 3,3-dimethyl- Method F
1,4-hexanediol, 3,4-dimethyl- Method E 1,4-hexanediol,
3,5-dimethyl- Method H 1,4-hexanediol, 4,5-dimethyl- Method E
1,4-hexanediol, 5,5-dimethyl- 38624-38-3 1,5-hexanediol,
2,2-dimethyl- Method A 1,5-hexanediol, 2,3-dimethyl- 62718-05-2
1,5-hexanediol, 2,4-dimethyl- 73455-82-0 1,5-hexanediol,
2,5-dimethyl- 58510-28-4 1,5-hexanediol, 3,3-dimethyl- 41736-99-6
1,5-hexanediol, 3,4-dimethyl- Method A 1,5-hexanediol,
3,5-dimethyl- Method G 1,5-hexanediol, 4,5-dimethyl- Method F
2,6-hexanediol, 3,3-dimethyl- Method A Inoperable Isomers
1,2-hexanediol, 2,3-dimethyl- 1,2-hexanediol, 2,4-dimethyl-
1,2-hexanediol, 2,5-dimethyl- 1,2-hexanediol, 3,3-dimethyl-
1,2-hexanediol, 3,4-dimethyl- 1,2-hexanediol, 3,5-dimethyl-
1,2-hexanediol, 4,4-dimethyl- 1,2-hexanediol, 4,5-dimethyl-
1,2-hexanediol, 5,5-dimethyl- 2,3-hexanediol, 2,3-dimethyl-
2,3-hexanediol, 2,4-dimethyl- 2,3-hexanediol, 2,5-dimethyl-
2,3-hexanediol, 3,4-dimethyl- 2,3-hexanediol, 3,5-dimethyl-
2,3-hexanediol, 4,4-dimethyl- 2,3-hexanediol, 4,5-dimethyl-
2,3-hexanediol, 5,5-dimethyl- 3,4-hexanediol, 2,2-dimethyl-
3,4-hexanediol, 2,3-dimethyl- 3,4-hexanediol, 2,4-dimethyl-
3,4-hexanediol, 2,5-dimethyl- 3,4-hexanediol, 3,4-dimethyl-
ETHYLHEXANEDIOL ISOMERS More Preferred Isomers 1,3-hexanediol,
2-ethyl- 94-96-2 1,3-hexanediol, 4-ethyl- Method C 1,4-hexanediol,
2-ethyl- 148904-97-6 1,4-hexanediol, 4-ethyl- 1113-00-4
1,5-hexanediol, 2-ethyl- 58374-34-8 2,4-hexanediol, 3-ethyl- Method
C 2,4-hexanediol, 4-ethyl- 33683-47-5 2,5-hexanediol, 3-ethyl-
Method F Inoperable Isomers 1,5-hexanediol, 4-ethyl-
1,6-hexanediol, 2-ethyl- 1,4-hexanediol, 3-ethyl- 1,5-hexanediol,
3-ethyl- 1,6-hexanediol, 3-ethyl- 1,2-hexanediol, 2-ethyl-
1,2-hexanediol, 3-ethyl- 1,2-hexanediol, 4-ethyl 2,3-hexanediol,
3-ethyl- 2,3-hexanediol, 4-ethyl- 3,4-hexanediol, 3-ethyl-
1,3-hexanediol, 3-ethyl- METHYLHEPTANEDIOL ISOMERS Operable Isomers
1,3-heptanediol, 2-methyl- 109417-38-1 1,3-heptanediol, 3-methyl-
165326-88-5 1,3-heptanediol, 4-methyl- Method C 1,3-heptanediol,
5-methyl- Method D 1,3-heptanediol, 6-methyl- Method C
1,4-heptanediol, 2-methyl- 15966-03-7 1,4-heptanediol, 3-methyl-
7748-38-1 1,4-heptanediol, 4-methyl- 72473-94-0 1,4-heptanediol,
5-methyl- 63003-04-3 1,4-heptanediol, 6-methyl- 99799-25-4
1,5-heptanediol, 2-methyl- 141605-00-7 1,5-heptanediol, 3-methyl-
Method A 1,5-heptanediol, 4-methyl- Method A 1,5-heptanediol,
5-methyl- 99799-26-5 1,5-heptanediol, 6-methyl- 57740-00-8
1,6-heptanediol, 2-methyl- 132148-22-2 1,6-heptanediol, 3-methyl-
Method G 1,6-heptanediol, 4-methyl- 156307-84-5 1,6-heptanediol,
5-methyl- Method A 1,6-heptanediol, 6-methyl- 5392-57-4
2,4-heptanediol, 2-methyl- 38836-26-9 2,4-heptanediol, 3-methyl-
6964-04-1 2,4-heptanediol, 4-methyl- 165326-87-4 2,4-heptanediol,
5-methyl- Method C 2,4-heptanediol, 6-methyl- 79356-95-9
2,5-heptanediol, 2-methyl- 141605-02-9 2,5-heptanediol, 3-methyl-
Method G 2,5-heptanediol, 4-methyl- 156407-38-4 2,5-heptanediol,
5-methyl- 148843-72-5 2,5-heptanediol, 6-methyl- 51916-46-2
2,6-heptanediol, 2-methyl- 73304-48-0 2,6-heptanediol, 3-methyl-
29915-96-6 2,6-heptanediol, 4-methyl- 106257-69-6 3,4-heptanediol,
3-methyl- 18938-50-6 3,5-heptanediol, 2-methyl- Method C
3,5-heptanediol, 3-methyl- 99799-27-6 3,5-heptanediol, 4-methyl-
156407-37-3 More Preferred Isomers 1,3-heptanediol, 2-methyl-
109417-38-1 1,3-heptanediol, 3-methyl- 165326-88-5 1,3-heptanediol,
4-methyl- Method C 1,3-heptanediol, 5-methyl- Method D
1,3-heptanediol, 6-methyl- Method C 1,4-heptanediol, 2-methyl-
15966-03-7 1,4-heptanediol, 3-methyl- 7748-38-1 1,4-heptanediol,
4-methyl- 72473-94-0 1,4-heptanediol, 5-methyl- 63003-04-3
1,4-heptanediol, 6-methyl- 99799-25-4 1,5-heptanediol, 2-methyl-
141605-00-7 1,5-heptanediol, 3-methyl- Method A 1,5-heptanediol,
4-methyl- Method A 1,5-heptanediol, 5-methyl- 99799-26-5
1,5-heptanediol, 6-methyl- 57740-00-8 1,6-heptanediol, 2-methyl-
132148-22-2 1,6-heptanediol, 3-methyl- Method G 1,6-heptanediol,
4-methyl- 156307-84-5 1,6-heptanediol, 5-methyl- Method A
1,6-heptanediol, 6-methyl- 5392-57-4 2,4-heptanediol, 2-methyl-
38836-26-9 2,4-heptanediol, 3-methyl- 6964-04-1 2,4-heptanediol,
4-methyl- 165326-87-4 2,4-heptanediol, 5-methyl- Method C
2,4-heptanediol, 6-methyl- 79356-95-9 2,5-heptanediol, 2-methyl-
141605-02-9 2,5-heptanediol, 3-methyl- Method H 2,5-heptanediol,
4-methyl- 156407-38-4
2,5-heptanediol, 5-methyl- 148843-72-5 2,5-heptanediol, 6-methyl-
51916-46-2 2,6-heptanediol, 2-methyl- 73304-48-0 2,6-heptanediol,
3-methyl- 29915-96-6 2,6-heptanediol, 4-methyl- 106257-69-6
3,4-heptanediol, 3-methyl- 18938-50-6 3,5-heptanediol, 2-methyl-
Method C 3,5-heptanediol, 4-methyl- 156407-37-3 Inoperable Isomers
1,7-heptanediol, 2-methyl- 1,7-heptanediol, 3-methyl-
1,7-heptanediol, 4-methyl- 2,3-heptanediol, 2-methyl-
2,3-heptanediol, 3-methyl- 2,3-heptanediol, 4-methyl-
2,3-heptanediol, 5-methyl- 2,3-heptanediol, 6-methyl-
3,4-heptanediol, 2-methyl- 3,4-heptanediol, 4-methyl-
3,4-heptanediol, 5-methyl- 3,4-heptanediol, 6-methyl-
1,2-heptanediol, 2-methyl- 1,2-heptanediol, 3-methyl-
1,2-heptanediol, 4-methyl- 1,2-heptanediol, 5-methyl-
1,2-heptanediol, 6-methyl- OCTANEDIOL ISOMERS More Preferred
Isomers 2,4-octanediol 90162-24-6 2,5-octanediol 4527-78-0
2,6-octanediol Method A 2,7-octanediol 19686-96-5 3,5-octanediol
24892-55-5 3,6-octanediol 24434-09-1 Inoperable Isomers
1,2-octanediol 1117-86-8 1,3-octanediol 23433-05-8 1,4-octanediol
51916-47-3 1,5-octanediol 2736-67-6 1,6-octanediol 4060-76-6
1,7-octanediol 13175-32-1 1,8-octanediol 629-41-4 2,3-octanediol
e.g., 98464-24-5 3,4-octanediol e.g., 99799-31-2 3,5-octanediol
e.g., 129025-63-4
[0114]
5TABLE V NONANEDIOL ISOMERS Chemical Name CAS No. Preferred Isomers
2,4-pentanediol, 2,3,3,4-tetramethyl- 19424-43-2 Operable Isomers
2,4-pentanediol, 3-tertiarybutyl- 142205-14-9 2,4-hexanediol,
2,5,5-trimethyl- 97460-08-7 2,4-hexanediol, 3,3,4-trimethyl- Method
D 2,4-hexanediol, 3,3,5-trimethyl- 27122-58-3 2,4-hexanediol,
3,5,5-trimethyl- Method D 2,4-hexanediol, 4,5,5-trimethyl- Method D
2,5-hexanediol, 3,3,4-trimethyl- Method H 2,5-hexanediol,
3,3,5-trimethyl- Method G Inoperable Isomers There are over 500
inoperable isomers including the following: 2,4-hexanediol,
2,4,5-trimethyl- 36587-81-2 2,4-hexanediol, 2,3,5-trimethyl-,
erythro- 26344-20-7 2,4-hexanediol, 2,3,5-trimethyl-, threo-
26343-49-7 1,3-propanediol, 2-butyl-2-ethyl- 115-84-4
2,4-hexanediol, 2,3,5-trimethyl-, threo- 26343-49-7
[0115]
6TABLE VI ALKYL GLYCERYL ETHERS, DI(HYDROXYALKYL) ETHERS, AND ARYL
GLYCERYL ETHERS Preferred Monoglycerol Ethers and Derivatives
1,2-propanediol, 3-(butyloxy)-, triethoxylated 1,2-propanediol,
3-(butyloxy)-, tetraethoxylated CAS No. More Preferred Monoglycerol
Ethers and Derivatives 1,2-propanediol, 3-(n-pentyloxy)- 22636-32-4
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-(1-cyclohex-1-enyloxy)- 1,3-propanediol, 2-(pentyloxy)-
1,3-propanediol, 2-(2-pentyloxy)- 1,3-propanediol, 2-(3-pentyloxy)-
1,3-propanediol, 2-(2-methyl-1-butyloxy)- 1,3-propanediol,
2-(iso-amyloxy)- 1,3-propanediol, 2-(3-methyl-2-butyloxy)-
1,3-propanediol, 2-(cyclohexyloxy)- 1,3-propanediol,
2-(1-cyclohex-1-enyloxy)- 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 More Preferred Di(hydroxyalkyl)
Ethers bis(2-hydroxybutyl) ether bis(2-hydroxycyclopentyl) ether
Inoperable Monoglycerol Ethers 1,2-propanediol, 3-ethyloxy-
1,2-propanediol, 3-propyloxy- 1,2-propanediol, 3-isopropyloxy-
1,2-propanediol, 3-butyloxy- 1,2-propanediol, 3-isobutyloxy-
1,2-propanediol, 3-tert-butyloxy- 1,2-propanediol, 3-octyloxy-
1,2-propanediol, 3-(2-ethylhexyloxy)- 1,2-propanediol,
3-(cyclopentyloxy)- 1,2-propanediol, 3-(1-cyclohex-2-enyloxy)-
1,3-propanediol, 2-(1-cyclohex-2-enyloxy)- AROMATIC GLYCERYL ETHERS
Operable Aromatic Glyceryl Ethers 1,2-propanediol, 3-phenyloxy-
1,2-propanediol, 3-benzyloxy- 1,2-propanediol,
3-(2-phenylethyloxy)- 1,2-propanediol, 3-(1-phenyl-2-propanyloxy)-
- 1,3-propanediol, 2-phenyloxy- 1,3-propanediol, 2-(m-cresyloxy)-
1,3-propanediol, 2-(p-cresyloxy)- 1,3-propanediol, 2-benzyloxy-
1,3-propanediol, 2-(2-phenylethyloxy)- 1,3-propanediol,
2-(1-phenylethyloxy)- Preferred Aromatic Glyceryl Ethers
1,2-propanediol, 3-phenyloxy- 1,2-propanediol, 3-benzyloxy-
1,2-propanediol, 3-(2-phenylethyloxy)- 1,3-propanediol,
2-(m-cresyloxy)- 1,3-propanediol, 2-(p-cresyloxy)- 1,3-propanediol,
2-benzyloxy- 1,3-propanediol, 2-(2-phenylethyloxy)- Preferred
Aromatic Glyceryl Ethers 1,2-propanediol, 3-phenyloxy-
1,2-propanediol, 3-benzyloxy- 1,2-propanediol,
3-(2-phenylethyloxy)- 1,3-propanediol, 2-(m-cresyloxy)-
1,3-propanediol, 2-(p-cresyloxy)- 1,3-propanediol,
2-(2-phenylethyloxy)-
[0116]
7TABLE VII ALICYCLIC DIOLS AND DERIVATIVES Chemical Name CAS No.
Preferred Cylic Diols and Derivatives
1-isopropyl-1,2-cyclobutanediol 59895-32-8
3-ethyl-4-methyl-1,2-cyclobutanediol 3-propyl-1,2-cyclobutanediol
3-isopropyl-1,2-cyclobutanediol 42113-90-6
1-ethyl-1,2-cyclopentanediol 67396-17-2 1,2-dimethyl-1,2-cyclopen-
tanediol 33046-20-7 1,4-dimethyl-1,2-cyclopentanediol 89794-56-9
2,4,5-trimethyl-1,3-cyclopentanediol
3,3-dimethyl-1,2-cyclopentanediol 89794-57-0
3,4-dimethyl-1,2-cyclopentanediol 70051-69-3
3,5-dimethyl-1,2-cyclopentanediol 89794-58-1
3-ethyl-1,2-cyclopentanediol 4,4-dimethyl-1,2-cyclopentanediol
70197-54-5 4-ethyl-1,2-cyclopentanediol
1,1-bis(hydroxymethyl)cyclohexane 2658-60-8
1,2-bis(hydroxymethyl)cyclohexane 76155-27-6
1,2-dimethyl-1,3-cyclohexanediol 53023-07-7
1,3-bis(hydroxymethyl)cyclohexane 13022-98-5
1,3-dimethyl-1,3-cyclohexanediol 128749-93-9
1,6-dimethyl-1,3-cyclohexanediol 164713-16-0
1-hydroxy-cyclohexaneethanol 40894-17-5 1-hydroxy-cyclohexanemeth-
anol 15753-47-6 1-ethyl-1,3-cyclohexanediol 10601-18-0
1-methyl-1,2-cyclohexanediol 52718-65-7 2,2-dimethyl-1,3-cyclohex-
anediol 114693-83-3 2,3-dimethyl-1,4-cyclohexanediol 70156-82-0
2,4-dimethyl-1,3-cyclohexanediol 2,5-dimethyl-1,3-cyclohexan- ediol
2,6-dimethyl-1,4-cyclohexanediol 34958-42-4
2-ethyl-1,3-cyclohexanediol 155433-88-8 2-hydroxycyclohexaneethan-
ol 24682-42-6 2-hydroxyethyl-1-cyclohexanol
2-hydroxymethylcyclohexanol 89794-52-5 3-hydroxyethyl-1-cyclohexa-
nol 3-hydroxycyclohexaneethanol 86576-87-6
3-hydroxymethylcyclohexanol 3-methyl-1,2-cyclohexanediol 23477-91-0
4,4-dimethyl-1,3-cyclohexanediol 14203-50-0
4,5-dimethyl-1,3-cyclohexanediol 4,6-dimethyl-1,3-cyclohexanediol
16066-66-3 4-ethyl-1,3-cyclohexanediol
4-hydroxyethyl-1-cyclohexanol 4-hydroxymethylcyclohexanol
33893-85-5 4-methyl-1,2-cyclohexanediol 23832-27-1
5,5-dimethyl-1,3-cyclohexanediol 51335-83-2
5-ethyl-1,3-cyclohexanediol 1,2-cycloheptanediol 108268-28-6
2-methyl-1,3-cycloheptanediol 101375-80-8
2-methyl-1,4-cycloheptanediol 4-methyl-1,3-cycloheptanediol
5-methyl-1,3-cycloheptanediol 5-methyl-1,4-cycloheptanediol
90201-00-6 6-methyl-1,4-cycloheptanediol 1,3-cyclooctanediol
101935-36-8 1,4-cyclooctanediol 73982-04-4 1,5-cyclooctanediol
23418-82-8 1,2-cyclohexanediol, diethoxylate 1,2-cyclohexanediol,
triethoxylate 1,2-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 1,2-cyclohexanediol, tributylenoxylate More
Preferred Cylic Diols and Derivatives
1-isopropyl-1,2-cyclobutanediol 59895-32-8
3-ethyl-4-methyl-1,2-cyclobutanediol 3-propyl-1,2-cyclobutanedio- l
3-isopropyl-1,2-cyclobutanediol 42113-90-6
1-ethyl-1,2-cyclopentanediol 67396-17-2 1,2-dimethyl-1,2-cyclopen-
tanediol 33046-20-7 1,4-dimethyl-1,2-cyclopentanediol 89794-56-9
3,3-dimethyl-1,2-cyclopentanediol 89794-57-0
3,4-dimethyl-1,2-cyclopentanediol 70051-69-3
3,5-dimethyl-1,2-cyclopentanediol 89794-58-1
3-ethyl-1,2-cyclopentanediol 4,4-dimethyl-1,2-cyclopentanediol
70197-54-5 4-ethyl-1,2-cyclopentanediol
1,1-bis(hydroxymethyl)cyclohexane 2658-60-8
1,2-bis(hydroxymethyl)cyclohexane 76155-27-6
1,2-dimethyl-1,3-cyclohexanediol 53023-07-7
1,3-bis(hydroxymethyl)cyclohexane 13022-98-5
1-hydroxy-cyclohexanemethanol 15753-47-6 1-methyl-1,2-cyclohexane-
diol 52718-65-7 3-hydroxymethylcyclohexanol
3-methyl-1,2-cyclohexanediol 23477-91-0 4,4-dimethyl-1,3-cyclohex-
anediol 14203-50-0 4,5-dimethyl-1,3-cyclohexanediol
4,6-dimethyl-1,3-cyclohexanediol 16066-66-3
4-ethyl-1,3-cyclohexanediol 4-hydroxyethyl-1-cyclohexanol
4-hydroxymethylcyclohexanol 33893-85-5 4-methyl-1,2-cyclohexanedi-
ol 23832-27-1 1,2-cycloheptanediol 108268-28-6 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,
dibutylenoxylate The unsaturated alicyclic diols include the
following known unsaturated alicyclic diols: Operable Unsaturated
Alicyclic Diols 1,2-Cyclobutanediol, 1-ethenyl-2-ethyl- 58016-14-1
3-Cyclobutene-1,2-diol, 1,2,3,4-tetramethyl- 90112-64-4
3-Cyclobutene-1,2-diol, 3,4-diethyl- 142543-60-0
3-Cyclobutene-1,2-diol, 3-(1,1-dimethylethyl)- 142543-56-4
3-Cyclobutene-1,2-diol, 3-butyl- 142543-55-3 1,2-Cyclopentanediol,
1,2-dimethyl-4-methylene- 103150-02-3 1,2-Cyclopentanediol,
1-ethyl-3-methylene- 90314-52-6 1,2-Cyclopentanediol,
4-(1-propenyl) 128173-45-5 3-Cyclopentene-1,2-diol,
1-ethyl-3-methyl- 90314-43-5 1,2-Cyclohexanediol, 1-ethenyl-
134134-16-0 1,2-Cyclohexanediol, 1-methyl-3-methylene- 98204-78-5
1,2-Cyclohexanediol, 1-methyl-4-methylene- 133358-53-9
1,2-Cyclohexanediol, 3-ethenyl- 55310-51-5 1,2-Cyclohexanediol,
4-ethenyl- 85905-16-4 3-Cyclohexene-1,2-diol, 2,6-dimethyl-
81969-75-7 3-Cyclohexene-1,2-diol, 6,6-dimethyl- 61875-93-2
4-Cyclohexene-1,2-diol, 3,6-dimethyl- 156808-73-0
4-Cyclohexene-1,2-diol, 4,5-dimethyl- 154351-54-9
3-Cyclooctene-1,2-diol 170211-27-5 4-Cyclooctene-1,2-diol
124791-61-3 5-Cyclooctene-1,2-diol 117468-07-2 Inoperable
Unsaturated Cyclic Diols 1,2-Cyclopentanediol, 1-(1-methylethenyl)-
61447-83-4 1,2-Propanediol, 1-cyclopentyl- 55383-20-5
1,3-Cyclopentanediol, 2-(1-methylethylidene)- 65651-46-9
1,3-Propanediol, 2-(1-cyclopenten-1-yl)- 77192-43-9
1,3-Propanediol, 2-(2-cyclopenten-1-yl)- 25462-31-1 1,2-Ethanediol,
1-(1-cyclohexen-1-yl)- 151674-61-2 1,2-Ethanediol,
1-(3-cyclohexen-1-yl) 64011-53-6 2-Cyclohexene-1,4-diol,
5,5-dimethyl- 147274-55-3 4-Cyclohexene-1,3-diol, 3,6-dimethyl-
127716-90-9 1,3-Cycloheptanediol, 2-methylene- 132292-67-2
5-Cycloheptene-1,3-diol, 1-methyl- 160813-33-2
5-Cycloheptene-1,3-diol, 5-methyl- 160813-32-1
2-Cyclooctene-1,4-diol 37996-40-0
TABLE VIII
C.sub.3C.sub.7Diol Alkoxylated Derivatives
[0117] In the following tables, "EO" means polyethoxylates, i.e.,
--(CH.sub.2CH.sub.2O).sub.nH; Me-E.sub.n means methyl-capped
polyethoxylates --(CH.sub.2CH.sub.2O).sub.nCH.sub.3; "2(Me-En)"
means 2 Me-En groups needed; "PO" means polypropoxylates,
--(CH(CH.sub.3)CH.sub.2- O).sub.nH; "BO" means polybutyleneoxy
groups, --(CH(CH.sub.2CH.sub.3)CH.su- b.2O).sub.nH; and "n-BO"
means poly(n-butyleneoxy) or poly(tetramethylene)oxy groups
--(CH.sub.2CH.sub.2CH.sub.2CH.sub.2O).sub.- nH. The indicated
alkoxylated derivatives are all operable and those that are
preferred are in bold type and listed on the second line.
Non-limiting, typical synthesis methods to prepare the alkoxylated
derivatives are given hereinafter.
8TABLE VIIIA Base Material EO's 1(Me-En) 2(Me-En) PO's n-BO's BO's
Base Material.sup.(a) CAS No. (b) (c) (d) (e) (f) (g)
1,2-propanediol 57-55-6 1-4 (C3) 3-4 4 1,2-propanediol, 558-43-0
4-10 1 2-methyl-(C4) 8-10 1 3 1,3-propanediol 504-63-2 6-8 5-6 (C3)
8 6 1,3-propanediol, 115-76-4 1-7 1-2 2,2-diethyl-(C7) 4-7 1 2
1,3-propanediol, 126-30-7 3-4 2,2-dimethyl-(C5) 1-2 4
1,3-propanediol, 2- 33673-01-7 1-7 1-2 (1-methylpropyl)- 4-7 1 2
(C7) 1,3-propanediol, 2- 26462-20-8 1-7 1-2 (2-methylpropyl)- 4-7 1
2 (C7) 1,3-propanediol, 2612-29-5 6-10 2-ethyl-(C5) 9-10 1 3
1,3-propanediol, 2- 77-84-9 1-6 ethyl-2-methyl-(C6) 3-6 2 1
1,3-propanediol, 2612-27-3 1-6 2-isopropyl-(C6) 3-6 2 1
1,3-propanediol, 2163-42-0 2-5 4-5 2-methyl-(C4) 4-5 5 2
1,3-propanediol, 2- 2109-23-1 2-9 1-3 methyl-2-isopropyl- 6-9 1 2-3
(C7) 1,3-propanediol, 2- 78-26-2 1-7 1-2 methyl-2-propyl- 4-7 1 2
(C7) 1,3-propanediol, 2612-28-4 1 2-propyl-(C6) 1-4 2 .sup.(a)The
number of indicated alkoxylated groups in this and following Tables
VIII are all operable, the generic limits being listed on the first
line, and those that are preferred are in bold type and listed on
the second line. (b) The numbers in this column are average numbers
of (CH.sub.2CH.sub.2O) groups in the polyethoxylated derivative.
(c) The numbers in this column are average numbers of
(CH.sub.2CH.sub.2O) groups in the one methyl-capped polyethoxylate
substituant in each derivative. (d) The numbers in this column are
average numbers of (CH.sub.2CH.sub.2O) groups in each of the two
methyl-capped polyethoxylate substituants in each derivative. (e)
The numbers in this column are average numbers of
(CH(CH.sub.3)CH.sub.2O) groups in the polypropoxylated derivative.
(f) The numbers in this column are average numbers of
(CH.sub.2CH.sub.2CH.sub.2CH.sub.2O) groups in the
polytetramethyleneoxyla- ted derivative. (g) The numbers in this
column are average numbers of (CH(CH.sub.2CH.sub.3)CH.sub.2O)
groups in the polybutoxylated derivative.
[0118]
9TABLE VIIIB Base Material EO's 1(Me-En) 2(Me-En) PO's n-BO's BO's
Base Material.sup.(a) CAS No. (b) (c) (d) (e) (f) (g)
1,2-butanediol (C4) 584-03-2 2-8 6-8 2-3 1 1,2-butanediol,
66553-15-9 1-6 1-2 2,3-dimethyl-(C6) 2-5 1 1,2-butanediol,
66553-16-0 2-ethyl-(C6) 1-3 1 1,2-butanediol, 41051-72-3
2-methyl-(C5) 1-2 1 1,2-butanediol, 59562-82-2 1-6 1-2
3,3-dimethyl-(C6) 2-5 1 1,2-butanediol, 50468-22-9 3-methyl-(C5)
1-2 1 1,3-butanediol (C4) 107-88-0 3-6 5 5-6 2 1,3-butanediol, 2,
16343-75-2 1-2 2,3-trimethyl-(C7) 1-3 2 1,3-butanediol, 2, 76-35-7
3-8 2-dimethyl-(C6) 6-8 3 1,3-butanediol, 24893-35-4 3-8
2,3-dimethyl-(C6) 6-8 3 1,3-butanediol, 66553-17-1 1-6 2-ethyl-(C6)
4-6 2 to 3 1 1,3-butanediol, 2- Method C 2-4 ethyl-2-methyl-(C7) 1
1 3 1,3-butanediol, 2- 68799-03-1 2-4 ethyl-3-methyl-(C7) 1 1 3
1,3-butanediol, 66567-04-2 2-4 2-isopropyl-(C7) 1 1 3
1,3-butanediol, 684-84-4 1-3 2-methyl-(C5) 2-3 4 1,3-butanediol,
66567-03-1 2-9 1-3 2-propyl-(C7) 6-8 1 2-3 1,3-butanediol,
2568-33-4 1-3 3-methyl-(C5) 2-3 4 1,4-butanediol(C4) 110-63-4 2-4
4-5 2 3-4 4-5 1,4-butanediol, 2, 162108-60-3 2-9 1-3
2,3-trimethyl-(C7) 6-9 1 2-3 1,4-butanediol, 32812-23-0 1-6
2,2-dimethyl-(C6) 3-6 2 1 1,4-butanediol, 57716-80-0 1-6
2,3-dimethyl-(C6) 3-6 2 1 1,4-butanediol, 57716-79-7 1 2-ethyl-(C6)
1-4 2 1,4-butanediol, 2- 76651-98-4 1-7 1-2 ethyl-2-methyl-(C7) 4-7
1 2 1,4-butanediol, 2- 66225-34-1 1-7 1-2 ethyl-3-methyl-(C7) 4-7 1
2 1,4-butanediol, 39497-66-0 1-7 1-2 2-isopropyl-(C7) 4-7 1 2
1,4-butanediol, 2938-98-9 6-10 1 2-methyl-(C5) 9-10 1 3
1,4-butanediol, 62946-68-3 1-5 1-2 2-propyl-(C7) 2-5 1
1,4-butanediol, 3- Method F 2-9 1-3 ethyl-1-methyl-(C7) 6-8 1 2-3
2,3-butanediol (C4) 513-85-9 6-10 1 9-10 1 3-4 2,3-butanediol,
76-09-5 3-9 1-3 2,3-dimethyl-(C6) 7-9 1 2-3 2,3-butanediol,
5396-58-7 1-5 2-methyl-(C5) 2-5 2 1 .sup.(a)The number of indicated
alkoxylated groups in this Table are all operable, the generic
limits being listed on the first line, and those that are preferred
are in bold type and listed on the second line. (b) The numbers in
this column are average numbers of (CH.sub.2CH.sub.2O) groups in
the polyethoxylated derivative. (c) The numbers in this column are
average numbers of (CH.sub.2CH.sub.2O) groups in the one
methyl-capped polyethoxylate substituant in each derivative. (d)
The numbers in this column are average numbers of
(CH.sub.2CH.sub.2O) groups in each of the two methyl-capped
polyethoxylate substituants in each derivative. (e) The numbers in
this column are average numbers of (CH(CH.sub.3)CH.sub.2O) groups
in the polypropoxylated derivative. (f) The numbers in this column
are average numbers of (CH.sub.2CH.sub.2CH.sub.2CH.sub.2O) groups
in the polytetramethyleneoxylated derivative. (g) The numbers in
this column are average numbers of (CH(CH.sub.2CH.sub.3)CH.sub-
.2O) groups in the polybutoxylated derivative.
[0119]
10TABLE VIIIC Base Material EO's 1(Me-En) 2(Me-En) PO's n-BO's BO's
Base Material.sup.(a) CAS No. (b) (c) (d) (e) (f) (g)
1,2-pentanediol 5343-92-0 3-10 2-3 (C5) 7-10 1 3 1,2-pentanediol,
20667-05-4 2-methyl-(C6) 1-3 1 1,2-pentanediol, 159623-53-7
3-methyl-(C6) 1-3 1 1,2-pentanediol, 72110-08-8 4-methyl-(C6) 1-3 1
1,3-pentanediol 3174-67-2 (C5) 1-2 3-4 1,3-pentanediol, 2157-31-5
2-4 2,2-dimethyl-(C7) 1 1 3 1,3-pentanediol, 66225-52-3 2-4
2,3-dimethyl-(C7) 1 1 3 1,3-pentanediol, 60712-38-1 2-4
2,4-dimethyl-(C7) 1 1 3 1,3-pentanediol, 29887-11-4 2-9 1-3
2-ethyl-(C7) 6-8 1 2-3 1,3-pentanediol, 149-31-5 1-6 1
2-methyl-(C6) 4-6 2-3 1,3-pentanediol, 129851-50-9 2-4
3,4-dimethyl-(C7) 1 1 3 1,3-pentanediol, 33879-72-0 1-6 1
3-methyl-(C6) 4-6 2-3 1,3-pentanediol, 30458-16-3 2-4
4,4-dimethyl-(C7) 1 1 3 1,3-pentanediol, 54876-99-2 1-6 1
4-methyl-(C6) 4-6 2-3 1,4-pentanediol 626-95-9 (C5) 1-2 3-4
1,4-pentanediol, Method F 2-4 2,2-dimethyl-(C7) 1 1 3
1,4-pentanediol, Method F 2-4 2,3-dimethyl-(C7) 1 1 3
1,4-pentanediol, Method F 2-4 2,4-dimethyl-(C7) 1 1 3
1,4-pentanediol, 6287-17-8 1-6 1 2-methyl-(C6) 4-6 2-3
1,4-pentanediol, 81887-62-9 2-4 3,3-dimethyl-(C7) 1 1 3
1,4-pentanediol, 63521-36-8 2-4 3,4-dimethyl-(C7) 1 1 3
1,4-pentanediol, 26787-63-3 1-6 1 3-methyl-(C6) 4-6 2-3
1,4-pentanediol, 1462-10-8 1-6 1 4-methyl-(C6) 4-6 2-3
1,5-pentanediol 111-29-5 4-10 (C5) 8-10 1 3 1,5-pentanediol,
3121-82-2 1-7 1-2 2,2-dimethyl-(C7) 4-7 1 2 1,5-pentanediol,
81554-20-3 1-7 1-2 2,3-dimethyl-(C7) 4-7 1 2 1,5-pentanediol,
2121-69-9 1-7 1-2 2,4-dimethyl-(C7) 4-7 1 2 1,5-pentanediol,
14189-13-0 1-5 1-2 2-ethyl-(C7) 2-5 1 1,5-pentanediol, 42856-62-2
2-methyl-(C6) 1-4 2 1,5-pentanediol, 53120-74-4 1-7 1-2
3,3-dimethyl-(C7) 4-7 1 2 1,5-pentanediol, 4457-71-0 3-methyl-(C6)
1-4 2 2,3-pentanediol 42027-23-6 (C5) 1-3 2 2,3-pentanediol,
7795-80-4 1-7 1-2 2-methyl-(C6) 4-7 1 2 2,3-pentanediol, 63521-37-9
1-7 1-2 3-methyl-(C6) 4-7 1 2 2,3-pentanediol, 7795-79-1 1-7 1-2
4-methyl-(C6) 4-7 1 2 2,4-pentanediol 625-69-4 1-4 (C5) 2-4 4
2,4-pentanediol, 24893-39-8 1-4 2,3-dimethyl-(C7) 2-4 2
2,4-pentanediol, 24892-49-7 1-4 2,4-dimethyl-(C7) 2-4 2
2,4-pentanediol, 107-41-5 5-10 2-methyl-(C6) 8-10 3
2,4-pentanediol, 24892-50-0 1-4 3,3-dimethyl-(C7) 2-4 2
2,4-pentanediol, Method H 5-10 3-methyl-(C6) 8-10 3 .sup.(a)The
number of indicated alkoxylated groups in this Table are all
operable, the generic limits being listed on the first line, and
those that are preferred are in bold type and listed on the second
line. (b) The numbers in this column are average numbers of
(CH.sub.2CH.sub.2O) groups in the polyethoxylated derivative. (c)
The numbers in this column are average numbers of
(CH.sub.2CH.sub.2O) groups in the one methyl-capped polyethoxylate
substituant in each derivative. (d) The numbers in this column are
average numbers of (CH.sub.2CH.sub.2O) groups in each of the two
methyl-capped polyethoxylate substituants in each derivative. (e)
The numbers in this column are average numbers of
(CH(CH.sub.3)CH.sub.2O) groups in the polypropoxylated derivative.
(f) The numbers in this column are average numbers of
(CH.sub.2CH.sub.2CH.sub.2CH.sub.2O) groups in the
polytetramethyleneoxylated derivative. (g) The numbers in this
column are average numbers of (CH(CH.sub.2CH.sub.3)CH.sub.2O)
groups in the polybutoxylated derivative.
[0120]
11TABLE VIIID Base Material EO's 1(Me-En) PO's n-BO's BO's Base
Material.sup.(a) CAS No. (b) (c) (e) (f) (g) 1,3-hexanediol (C6)
21531-91-9 1-5 2-5 2 1 1,3-hexanediol, 2-methyl- 66072-21-7 2-9 1-3
1 (C7) 6-8 1 2-3 1,3-hexanediol, 3-methyl- Method D 2-9 1-3 (C7)
6-8 1 2-3 1,3-hexanediol, 4-methyl- Method C 2-9 1-3 (C7) 6-8 1 2-3
1,3-hexanediol, 5-methyl- 109863-14-1 2-9 1-3 (C7) 6-8 1 2-3
1,4-hexanediol (C6) 16432-53-4 1-5 2-5 2 1 1,4-hexanediol,
2-methyl- Method F 2-9 1-3 (C7) 6-8 1 2-3 1,4-hexanediol, 3-methyl-
66225-36-3 2-9 1-3 (C7) 6-8 1 2-3 1,4-hexanediol, 4-methyl-
40646-08-0 2-9 1-3 (C7) 6-8 1 2-3 1,4-hexanediol, 5-methyl-
38624-36-1 2-9 1-3 (C7) 6-8 1 2-3 1,5-hexanediol (C6) 928-40-5 1-5
2-5 2 1 1,5-hexanediol, 2-methyl- Method F 2-9 1-3 (C7) 6-8 1 2-3
1,5-hexanediol, 3-methyl- Method F 2-9 1-3 (C7) 6-8 1 2-3
1,5-hexanediol, 4-methyl- 66225-37-4 2-9 1-3 (C7) 6-8 1 2-3
1,5-hexanediol, 5-methyl- 1462-11-9 2-9 1-3 (C7) 6-8 1 2-3
1,6-hexanediol (C6) 629-11-8 1-2 1-2 4 1,6-hexanediol, 2-methyl-
25258-92-8 1-5 1-2 (C7) 2-5 1 1,6-hexanediol, 3-methyl- 4089-71-8
1-5 1-2 (C7) 2-5 1 2,3-hexanediol (C6) 617-30-1 1-5 1-2 2-5 1
2,4-hexanediol (C6) 19780-90-6 3-8 5-8 3 2,4-hexanediol, 2-methyl-
66225-35-2 (C7) 1-2 1-2 2,4-hexanediol, 3-methyl- 116530-79-1 (C7)
1-2 1-2 2,4-hexanediol, 4-methyl- 38836-25-8 (C7) 1-2 1-2
2,4-hexanediol, 5-methyl- 54877-00-8 (C7) 1-2 1-2 2,5-hexanediol
(C6) 2935-44-6 3-8 5-8 3 2,5-hexanediol, 2-methyl- 29044-06-2 (C7)
1-2 1-2 2,5-hexanediol, 3-methyl- Method H (C7) 1-2 1-2
3,4-hexanediol (C6) 922-17-8 1-5 2-5 1 .sup.(a)The number of
indicated alkoxylated groups in this Table are all operable, the
generic limits being listed on the first line, and those that are
preferred are in bold type and listed on the second line. (b) The
numbers in this column are average numbers of (CH.sub.2CH.sub.2O)
groups in the polyethoxylated derivative. (c) The numbers in this
column are average numbers of (CH.sub.2CH.sub.2O) groups in the one
methyl-capped polyethoxylate substituant in each derivative. (e)
The numbers in this column are average numbers of
(CH(CH.sub.3)CH.sub.2O) groups in the polypropoxylated derivative.
(f) The numbers in this column are average numbers of
(CH.sub.2CH.sub.2CH.sub.2CH.sub.2O) groups in the
polytetramethyleneoxylated derivative. (g) The numbers in this
column are average numbers of (CH(CH.sub.2CH.sub.3)CH.sub.2O)
groups in the polybutoxylated derivative.
[0121]
12TABLE VIIIE Base Material EO's 1(Me-En) PO's n-BO's Base
Material.sup.(a) CAS No. (b) (c) (e) (f) 1,3-heptanediol (C7)
23433-04-7 1-7 1-2 3-6 1 2 1,4-heptanediol (C7) 40646-07-9 1-7 1-2
3-6 1 2 1,5-heptanediol (C7) 60096-09-5 1-7 1-2 3-6 1 2
1,6-heptanediol (C7) 13175-27-4 1-7 1-2 3-6 1 2 1,7-heptanediol
(C7) 629-30-1 1-2 1 2,4-heptanediol (C7) 20748-86-1 3-10 7-10 1 1 3
2,5-heptanediol (C7) 70444-25-6 3-10 7-10 1 1 3 2,6-heptanediol
(C7) 5969-12-0 3-10 7-10 1 1 3 3,5-heptanediol (C7) 86632-40-8 3-10
7-10 1 1 3 .sup.(a)The number of indicated alkoxylated groups in
this Table are all operable, the generic limits being listed on the
first line, and those that are preferred are in bold type and
listed on the second line. (b) The numbers in this column are
average numbers of (CH.sub.2CH.sub.2O) groups in the
polyethoxylated derivative. (c) The numbers in this column are
average numbers of (CH.sub.2CH.sub.2O) groups in the one
methyl-capped polyethoxylate substituant in each derivative. (e)
The numbers in this column are average numbers of
(CH(CH.sub.3)CH.sub.2O) groups in the polypropoxylated derivative.
(f) The numbers in this column are average numbers of
(CH.sub.2CH.sub.2CH.sub.2CH.sub.2O) groups in the
polytetramethyleneoxylated derivative.
[0122]
13TABLE IX AROMATIC DIOLS Suitable aromatic diols include: Chemical
Name CAS No. Operable Aromatic Diols 1-phenyl-1,2-ethanediol
93-56-1 1-phenyl-1,2-propanediol 1855-09-0 2-phenyl-1,2-propanediol
87760-50-7 3-phenyl-1,2-propanediol 17131-14-5
1-(3-methylphenyl)-1,3-propanediol 51699-43-5
1-(4-methylphenyl)-1,3-propanediol 159266-06-5
2-methyl-1-phenyl-1,3-propanediol 139068-60-3
1-phenyl-1,3-butanediol 118100-60-0 3-phenyl-1,3-butanediol
68330-54-1 1-phenyl-1,4-butanediol 136173-88-1
2-phenyl-1,4-butanediol 95840-73-6 1-phenyl-2,3-butanediol
169437-68-7 Preferred Aromatic Diols 1-phenyl-1,2-ethanediol
93-56-1 1-phenyl-1,2-propanediol 1855-09-0 2-phenyl-1,2-propanediol
87760-50-7 3-phenyl-1,2-propanediol 17131-14-5
1-(3-methylphenyl)-1,3-propan- ediol 51699-43-5
1-(4-methylphenyl)-1,3-propanediol 159266-06-5
2-methyl-1-phenyl-1,3-propanediol 139068-60-3
1-phenyl-1,3-butanediol 118100-60-0 3-phenyl-1,3-butanediol
68330-54-1 1-phenyl-1,4-butanediol 136173-88-1 More Preferred
Aromatic Diols 1-phenyl-1,2-propanediol 1855-09-0
2-phenyl-1,2-propanediol 87760-50-7 3-phenyl-1,2-propanediol
17131-14-5 1-(3-methylphenyl)-1,3-propanediol 51699-43-5
1-(4-methylphenyl)-1,3-propanediol 159266-06-5
2-methyl-1-phenyl-1,3-propanediol 139068-60-3
3-phenyl-1,3-butanediol 68330-54-1 1-phenyl-1,4-butanediol
136173-88-1 Inoperable Aromatic Diols 1-phenyl-1,3-propanediol
2-phenyl-1,3-propanediol 1-phenyl-1,2-butanediol 154902-08-6
2-phenyl-1,2-butanediol 157008-55-4 3-phenyl-1,2-butanediol
141505-72-8 4-phenyl-1,2-butanediol 143615-31-0
2-phenyl-1,3-butanediol 103941-94-2 4-phenyl-1,3-butanediol
81096-91-5 2-phenyl-2,3-butanediol 138432-94-7
[0123] X. principal solvents which are homologs, or analogs, of the
above structures where the total number of hydrogen atoms is
increased by the addition of one, or more additional CH.sub.2
groups, the total number of hydrogen atoms being kept at the same
number by introducing double bonds, are also useful with examples
including the following known compounds:
14TABLE X EXAMPLES OF UNSATURATED COMPOUNDS Operable Unsaturated
Diols 1,3-Propanediol, 2,2-di-2-propenyl- 55038-13-6
1,3-Propanediol, 2-(1-pentenyl)- 138436-18-7 1,3-Propanediol,
2-(2-methyl-2-propenyl)-2-(2-propenyl- )- 121887-76-1
1,3-Propanediol, 2-(3-methyl-1-butenyl)- 138436-17-6
1,3-Propanediol, 2-(4-pentenyl)- 73012-46-1 1,3-Propanediol,
2-ethyl-2-(2-methyl-2-propenyl)- 91367-61-2 1,3-Propanediol,
2-ethyl-2-(2-propenyl)- 27606-26-4 1,3-Propanediol,
2-methyl-2-(3-methyl-3-butenyl)- 132130-95-1 1,3-Butanediol,
2,2-diallyl- 103985-49-5 1,3-Butanediol, 2-(1-ethyl-1-propenyl)-
116103-35-6 1,3-Butanediol, 2-(2-butenyl)-2-methyl- 92207-83-5
1,3-Butanediol, 2-(3-methyl-2-butenyl)- 98955-19-2 1,3-Butanediol,
2-ethyl-2-(2-propenyl)- 122761-93-7 1,3-Butanediol,
2-methyl-2-(1-methyl-2-propenyl)- 141585-58-2 1,4-Butanediol,
2,3-bis(1-methylethylidene)- 52127-63-6 1,4-Butanediol,
2-(3-methyl-2-butenyl)-3-methylene- 115895-78-8 2-Butene-1,4-diol,
2-(1,1-dimethylpropyl)- 91154-01-7 2-Butene-1,4-diol,
2-(1-methylpropyl)- 91154-00-6 2-Butene-1,4-diol, 2-butyl-
153943-66-9 1,3-Pentanediol, 2-ethenyl-3-ethyl- 104683-37-6
1,3-Pentanediol, 2-ethenyl-4,4-dimethyl- 143447-08-9
1,4-Pentanediol, 3-methyl-2-(2-propenyl)- 139301-86-3
1,5-Pentanediol, 2-(1-propenyl)- 84143-44-2 1,5-Pentanediol,
2-(2-propenyl)- 134757-01-0 1,5-Pentanediol, 2-ethylidene-3-methyl-
42178-93-8 1,5-Pentanediol, 2-propylidene- 58203-50-2
2,4-Pentanediol, 3-ethylidene-2,4-dimethyl- 88610-19-9
4-Pentene-1,3-diol, 2-(1,1-dimethylethyl)- 109788-04-7
4-Pentene-1,3-diol, 2-ethyl-2,3-dimethyl- 90676-97-4
1,4-Hexanediol, 4-ethyl-2-methylene- 66950-87-6
1,5-Hexadiene-3,4-diol, 2,3,5-trimethyl- 18984-03-7
1,5-Hexadiene-3,4-diol, 5-ethyl-3-methyl- 18927-12-3
1,5-Hexanediol, 2-(1-methylethenyl)- 96802-18-5 1,6-Hexanediol,
2-ethenyl- 66747-31-7 1-Hexene-3,4-diol, 5,5-dimethyl- 169736-29-2
1-Hexene-3,4-diol, 5,5-dimethyl- 120191-04-0 2-Hexene-1,5-diol,
4-ethenyl-2,5-dimethyl- 70101-76-7 3-Hexene-1,6-diol,
2-ethenyl-2,5-dimethyl- 112763-52-7 3-Hexene-1,6-diol, 2-ethyl-
84143-45-3 3-Hexene-1,6-diol, 3,4-dimethyl- 125032-66-8
4-Hexene-2,3-diol, 2,5-dimethyl- 13295-61-9 4-Hexene-2,3-diol,
3,4-dimethyl- 135367-17-8 5-Hexene-1,3-diol, 3-(2-propenyl)-
74693-24-6 5-Hexene-2,3-diol, 2,3-dimethyl- 154386-00-2
5-Hexene-2,3-diol, 3,4-dimethyl- 135096-13-8 5-Hexene-2,3-diol,
3,5-dimethyl- 134626-63-4 5-Hexene-2,4-diol,
3-ethenyl-2,5-dimethyl- 155751-24-9 1,4-Heptanediol,
6-methyl-5-methylene- 100590-29-2 1,5-Heptadiene-3,4-diol,
2,3-dimethyl- 18927-06-5 1,5-Heptadiene-3,4-diol, 2,5-dimethyl-
22607-16-5 1,5-Heptadiene-3,4-diol, 3,5-dimethyl- 18938-51-7
1,7-Heptanediol, 2,6-bis(methylene)- 139618-24-9 1,7-Heptanediol,
4-methylene- 71370-08-6 1-Heptene-3,5-diol, 2,4-dimethyl-
155932-77-7 1-Heptene-3,5-diol, 2,6-dimethyl- 132157-35-8
1-Heptene-3,5-diol, 3-ethenyl-5-methyl 61841-10-9
1-Heptene-3,5-diol, 6,6-dimethyl- 109788-01-4
2,4-Heptadiene-2,6-diol, 4,6-dimethyl- 102605-95-8
2,5-Heptadiene-1,7-diol, 4,4-dimethyl- 162816-19-5
2,6-Heptadiene-1,4-diol, 2,5,5-trimethyl- 115346-30-0
2-Heptene-1,4-diol, 5,6-dimethyl- 103867-76-1 2-Heptene-1,5-diol,
5-ethyl- 104683-39-8 2-Heptene-1,7-diol, 2-methyl- 74868-68-1
3-Heptene-1,5-diol, 4,6-dimethyl- 147028-45-3 3-Heptene-1,7-diol,
3-methyl-6-methylene- 109750-55-2 3-Heptene-2,5-diol, 2,4-dimethyl-
98955-40-9 3-Heptene-2,5-diol, 2,5-dimethyl- 24459-23-2
3-Heptene-2,6-diol, 2,6-dimethyl- 160524-66-3 3-Heptene-2,6-diol,
4,6-dimethyl- 59502-66-8 5-Heptene-1,3-diol, 2,4-dimethyl-
123363-69-9 5-Heptene-1,3-diol, 3,6-dimethyl- 96924-52-6
5-Heptene-1,4-diol, 2,6-dimethyl- 106777-98-4 5-Heptene-1,4-diol,
3,6-dimethyl- 106777-99-5 5-Heptene-2,4-diol, 2,3-dimethyl-
104651-56-1 6-Heptene-1,3-diol, 2,2-dimethyl- 140192-39-8
6-Heptene-1,4-diol, 4-(2-propenyl)- 1727-87-3 6-Heptene-1,4-diol,
5,6-dimethyl- 152344-16-6 6-Heptene-1,5-diol, 2,4-dimethyl-
74231-27-9 6-Heptene-1,5-diol, 2-ethylidene-6-methyl- 91139-73-0
6-Heptene-2,4-diol, 4-(2-propenyl)- 101536-75-8 6-Heptene-2,4-diol,
5,5-dimethyl- 98753-77-6 6-Heptene-2,5-diol, 4,6-dimethyl-
134876-94-1 6-Heptene-2,5-diol, 5-ethenyl-4-methyl- 65757-31-5
1,3-Octanediol, 2-methylene- 108086-78-8 1,6-Octadiene-3,5-diol,
2,6-dimethyl- 91140-06-6 1,6-Octadiene-3,5-diol, 3,7-dimethyl-
75654-19-2 1,7-Octadiene-3,6-diol, 2,6-dimethyl- 51276-33-6
1,7-Octadiene-3,6-diol, 2,7-dimethyl- 26947-10-4
1,7-Octadiene-3,6-diol, 3,6-dimethyl- 31354-73-1 1-Octene-3,6-diol,
3-ethenyl- 65757-34-8 2,4,6-Octatriene-1,8-diol- , 2,7-dimethyl-
162648-63-7 2,4-Octadiene-1,7-diol, 3,7-dimethyl- 136054-24-5
2,5-Octadiene-1,7-diol, 2,6-dimethyl- 91140-07-7
2,5-Octadiene-1,7-diol, 3,7-dimethyl- 117935-59-8
2,6-Octadiene-1,4-diol, 3,7-dimethyl-(Rosiridol) 101391-01-9
2,6-Octadiene-1,8-diol, 2-methyl- 149112-02-7
2,7-Octadiene-1,4-diol, 3,7-dimethyl- 91140-08-8
2,7-Octadiene-1,5-diol, 2,6-dimethyl- 91140-09-9
2,7-Octadiene-1,6-diol, 2,6-dimethyl-(8-Hydroxylinalool)
103619-06-3 2,7-Octadiene-1,6-diol, 2,7-dimethyl- 60250-14-8
2-Octene-1,4-diol 40735-15-7 2-Octene-1,7-diol 73842-95-2
2-Octene-1,7-diol, 2-methyl-6-methylene- 91140-16-8
3,5-Octadiene-1,7-diol, 3,7-dimethyl- 62875-09-6
3,5-Octadiene-2,7-diol, 2,7-dimethyl- 7177-18-6 3,5-Octanediol,
4-methylene- 143233-15-2 3,7-Octadiene-1,6-diol, 2,6-dimethyl-
127446-29-1 3,7-Octadiene-2,5-diol, 2,7-dimethyl- 171436-39-8
3,7-Octadiene-2,6-diol, 2,6-dimethyl- 150283-67-3
3-Octene-1,5-diol, 4-methyl- 147028-43-1 3-Octene-1,5-diol,
5-methyl- 19764-77-3 4,6-Octadiene-1,3-diol, 2,2-dimethyl-
39824-01-6 4,7-Octadiene-2,3-diol, 2,6-dimethyl- 51117-38-5
4,7-Octadiene-2,6-diol, 2,6-dimethyl- 59076-71-0 4-Octene-1,6-diol,
7-methyl- 84538-24-9 4-Octene-1,8-diol, 2,7-bis(methylene)-
109750-56-3 4-Octene-1,8-diol, 2-methylene- 109750-58-5
5,7-Octadiene-1,4-diol, 2,7-dimethyl- 105676-78-6
5,7-Octadiene-1,4-diol, 7-methyl- 105676-80-0 5-Octene-1,3-diol
130272-38-7 6-Octene-1,3-diol, 7-methyl- 110971-19-2
6-Octene-1,4-diol, 7-methyl- 152715-87-2 6-Octene-1,5-diol
145623-79-6 6-Octene-1,5-diol, 7-methyl- 116214-61-0
6-Octene-3,5-diol, 2-methyl- 65534-66-9 6-Octene-3,5-diol,
4-methyl- 156414-25-4 7-Octene-1,3-diol, 2-methyl- 155295-38-8
7-Octene-1,3-diol, 4-methyl- 142459-25-4 7-Octene-1,3-diol,
7-methyl- 132130-96-2 7-Octene-1,5-diol 7310-51-2 7-Octene-1,6-diol
159099-43-1 7-Octene-1,6-diol, 5-methyl- 144880-56-8
7-Octene-2,4-diol, 2-methyl-6-methylene- 72446-81-2
7-Octene-2,5-diol, 7-methyl- 152344-12-2 7-Octene-3,5-diol,
2-methyl- 98753-85-6 1-Nonene-3,5-diol 119554-56-2
1-Nonene-3,7-diol 23866-97-9 3-Nonene-2,5-diol 165746-84-9
4,6-Nonadiene-1,3-diol, 8-methyl- 124099-52-1 4-Nonene-2,8-diol
154600-80-3 6,8-Nonadiene-1,5-diol 108586-03-4 7-Nonene-2,4-diol
30625-41-3 8-Nonene-2,4-diol 119785-59-0 8-Nonene-2,5-diol
132381-58-9 1,9-Decadiene-3,8-diol 103984-04-9
1,9-Decadiene-4,6-diol 138835-67-3 Preferred Unsaturated Diols
1,3-Butanediol, 2,2-diallyl- 103985-49-5 1,3-Butanediol,
2-(1-ethyl-1-propenyl)- 116103-35-6 1,3-Butanediol,
2-(2-butenyl)-2-methyl- 92207-83-5 1,3-Butanediol,
2-(3-methyl-2-butenyl)- 98955-19-2 1,3-Butanediol,
2-ethyl-2-(2-propenyl)- 122761-93-7 1,3-Butanediol,
2-methyl-2-(1-methyl-2-propenyl)- 141585-58-2 1,4-Butanediol,
2,3-bis(1-methylethylidene)- 52127-63-6 1,3-Pentanediol,
2-ethenyl-3-ethyl- 104683-37-6 1,3-Pentanediol,
2-ethenyl-4,4-dimethyl- 143447-08-9 1,4-Pentanediol,
3-methyl-2-(2-propenyl)- 139301-86-3 4-Pentene-1,3-diol,
2-(1,1-dimethylethyl)- 109788-04-7 4-Pentene-1,3-diol,
2-ethyl-2,3-dimethyl- 90676-97-4 1,4-Hexanediol,
4-ethyl-2-methylene- 66950-87-6 1,5-Hexadiene-3,4-diol,
2,3,5-trimethyl- 18984-03-7 1,5-Hexanediol,2-(1-methylethenyl)-
96802-18-5 2-Hexene-1,5-diol, 4-ethenyl-2,5-dimethyl- 70101-76-7
1,4-Heptanediol, 6-methyl-5-methylene- 100590-29-2
2,4-Heptadiene-2,6-diol, 4,6-dimethyl- 102605-95-8
2,6-Heptadiene-1,4-diol, 2,5,5-trimethyl- 115346-30-0
2-Heptene-1,4-diol, 5,6-dimethyl- 103867-76-1 3-Heptene-1,5-diol,
4,6-dimethyl- 147028-45-3 5-Heptene-1,3-diol, 2,4-dimethyl-
123363-69-9 5-Heptene-1,3-diol, 3,6-dimethyl- 96924-52-6
5-Heptene-1,4-diol, 2,6-dimethyl- 106777-98-4 5-Heptene-1,4-diol,
3,6-dimethyl- 106777-99-5 6-Heptene-1,3-diol, 2,2-dimethyl-
140192-39-8 6-Heptene-1,4-diol, 5,6-dimethyl- 152344-16-6
6-Heptene-1,5-diol, 2,4-dimethyl- 74231-27-9 6-Heptene-1,5-diol,
2-ethylidene-6-methyl- 91139-73-0 6-Heptene-2,4-diol,
4-(2-propenyl)- 101536-75-8 1-Octene-3,6-diol, 3-ethenyl-
65757-34-8 2,4,6-Octatriene-1,8-diol, 2,7-dimethyl- 162648-63-7
2,5-Octadiene-1,7-diol, 2,6-dimethyl- 91140-07-7
2,5-Octadiene-1,7-diol, 3,7-dimethyl- 117935-59-8
2,6-Octadiene-1,4-diol, 3,7-dimethyl-(Rosiridol) 101391-01-9
2,6-Octadiene-1,8-diol, 2-methyl- 149112-02-7
2,7-Octadiene-1,4-diol, 3,7-dimethyl- 91140-08-8
2,7-Octadiene-1,5-diol, 2,6-dimethyl- 91140-09-9
2,7-Octadiene-1,6-diol, 2,6-dimethyl-(8-Hydroxylinalool)
103619-06-3 2,7-Octadiene-1,6-diol, 2,7-dimethyl- 60250-14-8
2-Octene-1,7-diol, 2-methyl-6-methylene- 91140-16-8
3,5-Octadiene-2,7-diol, 2,7-dimethyl- 7177-18-6 3,5-Octanediol,
4-methylene- 143233-15-2 3,7-Octadiene-1,6-diol, 2,6-dimethyl-
127446-29-1 4-Octene-1,8-diol, 2-methylene- 109750-58-5
6-Octene-3,5-diol, 2-methyl- 65534-66-9 6-Octene-3,5-diol,
4-methyl- 156414-25-4 7-Octene-2,4-diol, 2-methyl-6-methylene-
72446-81-2 7-Octene-2,5-diol, 7-methyl- 152344-12-2
7-Octene-3,5-diol, 2-methyl- 98753-85-6 1-Nonene-3,5-diol
119554-56-2 1-Nonene-3,7-diol 23866-97-9 3-Nonene-2,5-diol
165746-84-9 4-Nonene-2,8-diol 154600-80-3 6,8-Nonadiene-1,5-diol
108586-03-4 7-Nonene-2,4-diol 30625-41-3 8-Nonene-2,4-diol
119785-59-0 8-Nonene-2,5-diol 132381-58-9 1,9-Decadiene-3,8-diol
103984-04-9 1,9-Decadiene-4,6-diol 138835-67-3 ; and XI. mixtures
thereof.
[0124] There are no C.sub.1-2 mono-ols that provide a clear
concentrated fabric softener compositions in the context of this
invention. There is only one C.sub.3 mono-ol, n-propanol, that
provides acceptable performance in terms of forming a clear product
and either keeping it clear to a temperature of about 20.degree.
C., or allowing it to recover upon rewarming to room temperature.
Of the C.sub.4 mono-ols, only 2-butanol and 2-methyl-2-propanol
provide very good performance, but 2-methyl-2-propanol has a
boiling point that is undesirably low. There are no C.sub.5-6
mono-ols that provide clear products except for unsaturated
mono-ols as described above and hereinafter.
[0125] It is found that some principal solvents which have two
hydroxyl groups in their chemical formulas are suitable for use in
the formulation of the liquid concentrated, clear fabric softener
compositions of this invention. It is discovered that the
suitability of each principal solvent is surprisingly very
selective, dependent on the number of carbon atoms, the isomeric
configuration of the molecules having the same number of carbon
atoms, the degree of unsaturation, etc. Principal solvents with
similar solubility characteristics to the principal solvents above
and possessing at least some asymmetry will provide the same
benefit. It is discovered that the suitable principal solvents have
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.
[0126] For example, for the 1,2-alkanediol principal solvent series
having the general formula HO--CH.sub.2--CHOH--(CH.sub.2).sub.n--H,
with n being from 1 to 8, only 1,2-hexanediol (n=4), which has a
ClogP value of about 0.53, which is within the effective ClogP
range of from about 0.15 to about 0.64, is a good principal
solvent, and is within the claim of this invention, while the
others, e.g., 1,2-propanediol, 1,2-butanediol, 1,2-pentanediol,
1,2-octanediol, 1,2-decanediol, having ClogP values outside the
effective 0.15-0.64 range, are not. Furthermore, of the hexanediol
isomers, again, the 1,2-hexanediol is a good principal solvent,
while many other isomers such as 1,3-hexanediol, 1,4-hexanediol,
1,5-hexanediol, 1,6-hexanediol, 2,4-hexanediol, and 2,5-hexanediol,
having ClogP values outside the effective 0.15-0.64 range, are not.
These are illustrated by the Examples and Comparative Examples I-A
and I-B (vide infra).
[0127] There are no C.sub.3-C.sub.5 diols that provide a clear
concentrated composition in the context of this invention.
[0128] Although there are many C.sub.6 diols that are possible
isomers, only the ones listed above are suitable for making clear
products and only: 1,2-butanediol, 2,3-dimethyl-; 1,2-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-pentanediol, 4-methyl-;
and 1,2-hexanediol are preferred, of which the most preferred are:
1,2-butanediol, 2-ethyl-; 1,2-pentanediol, 2-methyl-;
1,2-pentanediol, 3-methyl-; 1,2-pentanediol, 4-methyl-; and
1,2-hexanediol.
[0129] There are more possible C.sub.7 diol isomers, but only the
listed ones provide clear products and the preferred ones are:
1,3-butanediol, 2-butyl-; 1,4-butanediol, 2-propyl-;
1,5-pentanediol, 2-ethyl-; 2,3-pentanediol, 2,3-dimethyl-;
2,3-pentanediol, 2,4-dimethyl-; 2,3-pentanediol, 4,4-dimethyl-;
3,4-pentanediol, 2,3-dimethyl-; 1,6-hexanediol, 2-methyl-;
1,6-hexanediol, 3-methyl-; 1,3-heptanediol; 1,4-heptanediol;
1,5-heptanediol; 1,6-heptanediol; of which the most preferred are:
2,3-pentanediol, 2,3-dimethyl-; 2,3-pentanediol, 2,4-dimethyl-;
2,3-pentanediol, 3,4-dimethyl-; 2,3-pentanediol, 4,4-dimethyl-; and
3,4-pentanediol, 2,3-dimethyl-.
[0130] Similarly, there are even more C.sub.8 diol isomers, but
only the listed ones provide clear products and the preferred ones
are: 1,3-propanediol, 2-(1,1-dimethylpropyl)-; 1,3-propanediol,
2-(1,2-dimethylpropyl)-; 1,3-propanediol, 2-(1-ethylpropyl)-;
1,3-propanediol, 2-(2,2-dimethylpropyl)-; 1,3-propanediol,
2-ethyl-2-isopropyl-; 1,3-propanediol,
2-methyl-2-(1-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-(1-methylpropyl)-; 1,3-butanediol, 2-butyl-;
1,3-butanediol, 2-ethyl-2,3-dimethyl-; 1,3-butanediol,
2-(1,1-dimethylethyl)-; 1,3-butanediol, 2-(2-methylpropyl)-;
1,3-butanediol, 2-methyl-2-propyl-; 1,3-butanediol,
2-methyl-2-isopropyl-; 1,3-butanediol, 3-methyl-2-propyl-;
1,4-butanediol, 2,2-diethyl-; 1,4-butanediol,
2-ethyl-2,3-dimethyl-; 1,4-butanediol, 2-ethyl-3,3-dimethyl-;
1,4-butanediol, 2-(1,1-dimethylethyl)-; 1,4-butanediol,
3-methyl-2-isopropyl-; 1,3-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-; 1,5-pentanediol,
2,2,4-trimethyl-; 1,5-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-; 1,5-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-;
2,4-pentanediol, 3-propyl-; 1,3-hexanediol, 2,2-dimethyl-;
1,3-hexanediol, 2,3-dimethyl-; 1,3-hexanediol, 2,4-dimethyl-;
1,3-hexanediol, 2,5-dimethyl-; 1,3-hexanediol, 3,4-dimethyl-;
1,3-hexanediol, 3,5-dimethyl-; 1,3-hexanediol, 4,4-dimethyl-;
1,3-hexanediol, 4,5-dimethyl-; 1,4-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-;
1,4-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-; 1,5-hexanediol, 4,5-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-; 1,5-heptanediol, 5-methyl-;
1,5-heptanediol, 6-methyl-; 1,6-heptanediol, 2-methyl-;
1,6-heptanediol, 3-methyl-; 1,6-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-heptanediol, 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, 4-methyl-;
2,4-octanediol; 2,5-octanediol; 2,6-octanediol; 2,7-octanediol;
3,5-octanediol; and/or 3,6-octanediol of which the following are
the most preferred: 1,3-propanediol, 2-(1,1-dimethylpropyl)-;
1,3-propanediol, 2-(1,2-dimethylpropyl)-; 1,3-propanediol,
2-(1-ethylpropyl)-; 1,3-propanediol, 2-(2,2-dimethylpropyl)-;
1,3-propanediol, 2-ethyl-2-isopropyl-; 1,3-propanediol,
2-methyl-2-(1-methylpropyl)-; 1,3-propanediol,
2-methyl-2-(2-methylpropyl)-; 1,3-propanediol,
2-tertiary-butyl-2-methyl-- ; 1,3-butanediol, 2-(1-methylpropyl)-;
1,3-butanediol, 2-(2-methylpropyl)-; 1,3-butanediol, 2-butyl-;
1,3-butanediol, 2-methyl-2-propyl-; 1,3-butanediol,
3-methyl-2-propyl-; 1,4-butanediol, 2,2-diethyl-; 1,4-butanediol,
2-ethyl-2,3-dimethyl-; 1,4-butanediol, 2-ethyl-3,3-dimethyl-;
1,4-butanediol, 2-(1,1-dimethylethyl)-; 1,3-pentanediol,
2,3,4-trimethyl-; 1,5-pentanediol, 2,2,3-trimethyl-;
1,5-pentanediol, 2,2,4-trimethyl-; 1,5-pentanediol,
2,3,3-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-;
1,5-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-; 2,4-pentanediol,
3-propyl-; 1,3-hexanediol, 2,2-dimethyl-; 1,3-hexanediol,
2,3-dimethyl-; 1,3-hexanediol, 2,4-dimethyl-; 1,3-hexanediol,
2,5-dimethyl-; 1,3-hexanediol, 3,4-dimethyl-; 1,3-hexanediol,
3,5-dimethyl-; 1,3-hexanediol, 4,4-dimethyl-; 1,3-hexanediol,
4,5-dimethyl-; 1,4-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-; 1,4-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-; 1,5-hexanediol, 4,5-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-;
1,5-heptanediol, 5-methyl-; 1,5-heptanediol, 6-methyl-;
1,6-heptanediol, 2-methyl-; 1,6-heptanediol, 3-methyl-;
1,6-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-heptanediol, 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, 4-methyl-; 2,4-octanediol; 2,5-octanediol;
2,6-octanediol; 2,7-octanediol; 3,5-octanediol; and/or
3,6-octanediol.
[0131] Preferred mixtures of eight-carbon-atom-1,3 diols can be
formed by the condensation of mixtures of butyraldehyde,
isobutyraldehyde and/or methyl ethyl ketone (2-butanone), so long
as there are at least two of these reactants in the reaction
mixture, in the presence of highly alkaline catalyst followed by
conversion by hydrogenation to form a mixture of
eight-carbon-1,3-diols, i.e., a mixture of 8-carbon-1,3-diols
primarily consisting of: 2,2,4-trimethyl-1,3-pentanediol;
2-ethyl-1,3-hexanediol; 2,2-dimethyl-1,3-hexanediol;
2-ethyl-4-methyl-1,3-pentandiol; 2-ethyl-3-methyl-1,3-pentanediol;
3,5-octanediol; 2,2-dimethyl-2,4-hexanediol;
2-methyl-3,5-heptanediol; and/or 3-methyl-3,5-heptanediol, the
level of 2,2,4-trimethyl-1,3-pentane- diol being less than half of
any mixture, possibly along with other minor isomers resulting from
condensation on the methylene group of 2-butanone, when it is
present, instead of on the methyl group.
[0132] The formulatability, and other properties, such as odor,
fluidity, melting point lowering, etc., of some C.sub.6-8 diols
listed above in Tables II-IV which are not preferred, can be
improved by polyalkoxylation. Also, some of the C.sub.3-5 diols
which are alkoxylated are preferred. Preferred alkoxylated
derivatives of the above C.sub.3-8 diols [In the following
disclosure, "EO" means polyethoxylates, "E.sub.n" means
--(CH.sub.2CH.sub.2O).sub.nH; Me-E.sub.n means methyl-capped
polyethoxylates --(CH.sub.2CH.sub.2O).sub.nCH.sub.3; "2(Me-En)"
means 2 Me-En groups needed; "PO" means polypropoxylates,
--(CH(CH.sub.3)CH.sub.2- O).sub.nH ; "BO" means polybutyleneoxy
groups, (CH(CH.sub.2CH.sub.3)CH.sub- .2O).sub.nH ; and "n-BO" means
poly(n-butyleneoxy) groups
--(CH.sub.2CH.sub.2CH.sub.2CH.sub.2O).sub.nH.] include:
[0133] 1. 1,2-propanediol (C3) 2(Me-E.sub.3-4); 1,2-propanediol
(C3) PO.sub.4; 1,2-propanediol, 2-methyl-(C4) (Me-E.sub.8-10);
1,2-propanediol, 2-methyl-(C4) 2(Me-E.sub.1); 1,2-propanediol,
2-methyl-(C4) PO.sub.3; 1,3-propanediol (C3) 2(Me-E.sub.8);
1,3-propanediol (C3) PO.sub.6; 1,3-propanediol, 2,2-diethyl-(C7)
E.sub.4-7; 1,3-propanediol, 2,2-diethyl-(C7) PO1; 1,3-propanediol,
2,2-diethyl-(C7) n-BO.sub.2; 1,3-propanediol, 2,2-dimethyl-(C5)
2(Me E.sub.1-2); 1,3-propanediol, 2,2-dimethyl-(C5) PO.sub.4;
1,3-propanediol, 2-(1-methylpropyl)-(C7) E.sub.4-7;
1,3-propanediol, 2-(1-methylpropyl)-(C7) PO.sub.1; 1,3-propanediol,
2-(1-methylpropyl)-(C7) n-BO.sub.2; 1,3-propanediol,
2-(2-methylpropyl)-(C7) E.sub.4-7; 1,3-propanediol,
2-(2-methylpropyl)-(C7) PO.sub.1; 1,3-propanediol,
2-(2-methylpropyl)-(C7) n-BO.sub.2; 1,3-propanediol, 2-ethyl-(C5)
(Me E.sub.9-10); 1,3-propanediol, 2-ethyl-(C5) 2(Me E.sub.1);
1,3-propanediol, 2-ethyl-(C5) PO.sub.3; 1,3-propanediol,
2-ethyl-2-methyl-(C6) (Me E.sub.3-6); 1,3-propanediol,
2-ethyl-2-methyl-(C6) PO.sub.2; 1,3-propanediol,
2-ethyl-2-methyl-(C6) BO.sub.1; 1,3-propanediol, 2-isopropyl-(C6)
(Me E.sub.3-6); 1,3-propanediol, 2-isopropyl-(C6) PO.sub.2;
1,3-propanediol, 2-isopropyl-(C6) BO.sub.1; 1,3-propanediol,
2-methyl-(C4) 2(Me E.sub.4-5); 1,3-propanediol, 2-methyl-(C4)
PO.sub.5; 1,3-propanediol, 2-methyl-(C4) BO.sub.2; 1,3-propanediol,
2-methyl-2-isopropyl-(C7) E.sub.6-9; 1,3-propanediol,
2-methyl-2-isopropyl-(C7) PO.sub.1; 1,3-propanediol,
2-methyl-2-isopropyl-(C7) n-BO.sub.2-3; 1,3-propanediol,
2-methyl-2-propyl-(C7) E.sub.4-7; 1,3-propanediol,
2-methyl-2-propyl-(C7) PO.sub.1; 1,3-propanediol,
2-methyl-2-propyl-(C7) n-BO.sub.2; 1,3-propanediol, 2-propyl-(C6)
(Me E.sub.1-4); 1,3-propanediol, 2-propyl-(C6) PO.sub.2;
[0134] 2. 1,2-butanediol (C4) (Me E.sub.6-8); 1,2-butanediol (C4)
PO.sub.2-3; 1,2-butanediol (C4) BO.sub.1; 1,2-butanediol,
2,3-dimethyl-(C6) E.sub.2-5; 1,2-butanediol, 2,3-dimethyl-(C6)
n-BO.sub.1; 1,2-butanediol, 2-ethyl-(C6) E.sub.1-3; 1,2-butanediol,
2-ethyl-(C6) n-BO.sub.1; 1,2-butanediol, 2-methyl-(C5) (Me E1-2);
1,2-butanediol, 2-methyl-(C5) PO.sub.1; 1,2-butanediol,
3,3-dimethyl-(C6) E.sub.2-5; 1,2-butanediol, 3,3-dimethyl-(C6)
n-BO.sub.1; 1,2-butanediol, 3-methyl-(C5) (Me E.sub.1-2);
1,2-butanediol, 3-methyl-(C5) PO.sub.1; 1,3-butanediol (C4) 2(Me
E.sub.5-6); 1,3-butanediol (C4) BO.sub.2; 1,3-butanediol,
2,2,3-trimethyl-(C7) (Me E.sub.1-3); 1,3-butanediol,
2,2,3-trimethyl-(C7) PO.sub.2; 1,3-butanediol, 2,2-dimethyl-(C6)
(Me E.sub.6-8); 1,3-butanediol, 2,2-dimethyl-(C6) PO.sub.3;
1,3-butanediol, 2,3-dimethyl-(C6) (Me E.sub.6-8); 1,3-butanediol,
2,3-dimethyl-(C6) PO.sub.3; 1,3-butanediol, 2-ethyl-(C6) (Me
E.sub.4-6); 1,3-butanediol, 2-ethyl-(C6) PO.sub.2-3;
1,3-butanediol, 2-ethyl-(C6) BO.sub.1; 1,3-butanediol,
2-ethyl-2-methyl-(C7) (Me E.sub.1); 1,3-butanediol,
2-ethyl-2-methyl-(C7) PO.sub.1; 1,3-butanediol,
2-ethyl-2-methyl-(C7) n-BO.sub.3; 1,3-butanediol,
2-ethyl-3-methyl-(C7) (Me E.sub.1); 1,3-butanediol,
2-ethyl-3-methyl-(C7) PO.sub.1; 1,3-butanediol,
2-ethyl-3-methyl-(C7) n-BO.sub.3; 1,3-butanediol, 2-isopropyl-(C7)
(Me E.sub.1); 1,3-butanediol, 2-isopropyl-(C7) PO.sub.1;
1,3-butanediol, 2-isopropyl-(C7) n-BO.sub.3; 1,3-butanediol,
2-methyl-(C5) 2(Me E.sub.2-3); 1,3-butanediol, 2-methyl-(C5)
PO.sub.4; 1,3-butanediol, 2-propyl-(C7) E.sub.6-8; 1,3-butanediol,
2-propyl-(C7) PO.sub.1; 1,3-butanediol, 2-propyl-(C7) n-BO.sub.2-3;
1,3-butanediol, 3-methyl-(C5) 2(Me E.sub.2-3); 1,3-butanediol,
3-methyl-(C5) PO.sub.4; 1,4-butanediol (C4) 2(Me E.sub.3-4);
1,4-butanediol (C4) PO.sub.4-5; 1,4-butanediol,
2,2,3-trimethyl-(C7) E.sub.6-9; 1,4-butanediol,
2,2,3-trimethyl-(C7) PO.sub.1; 1,4-butanediol, 2,2,3-trimethyl-(C7)
n-BO.sub.2-3; 1,4-butanediol, 2,2-dimethyl-(C6) (Me E.sub.3-6);
1,4-butanediol, 2,2-dimethyl-(C6) PO.sub.2; 1,4-butanediol,
2,2-dimethyl-(C6) BO.sub.1; 1,4-butanediol, 2,3-dimethyl-(C6) (Me
E.sub.3-6); 1,4-butanediol, 2,3-dimethyl-(C6) PO.sub.2;
1,4-butanediol, 2,3-dimethyl-(C6) BO.sub.1; 1,4-butanediol,
2-ethyl-(C6) (Me E.sub.1-4); 1,4-butanediol, 2-ethyl-(C6) PO.sub.2;
1,4-butanediol, 2-ethyl-2-methyl-(C7) E.sub.4-7; 1,4-butanediol,
2-ethyl-2-methyl-(C7) PO.sub.1; 1,4-butanediol,
2-ethyl-2-methyl-(C7) n-BO.sub.2; 1,4-butanediol,
2-ethyl-3-methyl-(C7) E.sub.4-7; 1,4-butanediol,
2-ethyl-3-methyl-(C7) PO.sub.1; 1,4-butanediol,
2-ethyl-3-methyl-(C7) n-BO.sub.2; 1,4-butanediol, 2-isopropyl-(C7)
E.sub.4-7; 1,4-butanediol, 2-isopropyl-(C7) PO.sub.1;
1,4-butanediol, 2-isopropyl-(C7) n-BO.sub.2; 1,4-butanediol,
2-methyl-(C5) (Me E.sub.9-10); 1,4-butanediol, 2-methyl-(C5) 2(Me
E.sub.1); 1,4-butanediol, 2-methyl-(C5) PO.sub.3; 1,4-butanediol,
2-propyl-(C7) E.sub.2-5; 1,4-butanediol, 2-propyl-(C7) n-BO.sub.1;
1,4-butanediol, 3-ethyl-1-methyl-(C7) E.sub.6-8; 1,4-butanediol,
3-ethyl-1-methyl-(C7) PO.sub.1; 1,4-butanediol,
3-ethyl-1-methyl-(C7) n-BO.sub.2-3; 2,3-butanediol (C4) (Me
E.sub.9-10); 2,3-butanediol (C4) 2(Me E.sub.1); 2,3-butanediol (C4)
PO.sub.3-4; 2,3-butanediol, 2,3-dimethyl-(C6) E.sub.7-9;
2,3-butanediol, 2,3-dimethyl-(C6) PO.sub.1; 2,3-butanediol,
2,3-dimethyl-(C6) BO.sub.2-3; 2,3-butanediol, 2-methyl-(C5) (Me
E.sub.2-5); 2,3-butanediol, 2-methyl-(C5) PO.sub.2; 2,3-butanediol,
2-methyl-(C5) BO.sub.1;
[0135] 3. 1,2-pentanediol (C5) E.sub.7-10; 1,2-pentanediol, (C5)
PO.sub.1; 1,2-pentanediol, (C5) n-BO.sub.3; 1,2-pentanediol,
2-methyl (C6) E.sub.1-3; 1,2-pentanediol, 2-methyl (C6) n-BO.sub.1;
1,2-pentanediol, 3-methyl (C6) E.sub.1-3; 1,2-pentanediol, 3-methyl
(C6) n-BO.sub.1; 1,2-pentanediol, 4-methyl (C6) E.sub.1-3;
1,2-pentanediol, 4-methyl (C6) n-BO.sub.1; 1,3-pentanediol (C5)
2(Me-E.sub.1-2); 1,3-pentanediol (C5) PO.sub.3-4; 1,3-pentanediol,
2,2-dimethyl-(C7) (Me-E.sub.1); 1,3-pentanediol, 2,2-dimethyl-(C7)
PO.sub.1; 1,3-pentanediol, 2,2-dimethyl-(C7) n-BO.sub.3;
1,3-pentanediol, 2,3-dimethyl-(C7) (Me-E.sub.1); 1,3-pentanediol,
2,3-dimethyl-(C7) PO.sub.1; 1,3-pentanediol, 2,3-dimethyl-(C7)
n-BO.sub.3; 1,3-pentanediol, 2,4-dimethyl-(C7) (Me-E.sub.1);
1,3-pentanediol, 2,4-dimethyl-(C7) PO.sub.1; 1,3-pentanediol,
2,4-dimethyl-(C7) n-BO.sub.3; 1,3-pentanediol, 2-ethyl-(C7)
E.sub.6-8; 1,3-pentanediol, 2-ethyl-(C7) PO.sub.1; 1,3-pentanediol,
2-ethyl-(C7) n-BO.sub.2-3; 1,3-pentanediol, 2-methyl-(C6)
2(Me-E.sub.4-6); 1,3-pentanediol, 2-methyl-(C6) PO.sub.2-3;
1,3-pentanediol, 3,4-dimethyl-(C7) (Me-E.sub.1); 1,3-pentanediol,
3,4-dimethyl-(C7) PO.sub.1; 1,3-pentanediol, 3,4-dimethyl-(C7)
n-BO.sub.3; 1,3-pentanediol, 3-methyl-(C6) 2(Me-E.sub.4-6);
1,3-pentanediol, 3-methyl-(C6) PO.sub.2-3; 1,3-pentanediol,
4,4-dimethyl-(C7) (Me-E.sub.1); 1,3-pentanediol, 4,4-dimethyl-(C7)
PO.sub.1; 1,3-pentanediol, 4,4-dimethyl-(C7) n-BO.sub.3;
1,3-pentanediol, 4-methyl-(C6) 2(Me-E.sub.4-6); 1,3-pentanediol,
4-methyl-(C6) PO.sub.2-3; 1,4-pentanediol, (C5) 2(Me-E.sub.1-2);
1,4-pentanediol (C5) PO.sub.3-4; 1,4-pentanediol, 2,2-dimethyl-(C7)
(Me-E.sub.1); 1,4-pentanediol, 2,2-dimethyl-(C7) PO.sub.1;
1,4-pentanediol, 2,2-dimethyl-(C7) n-BO.sub.3; 1,4-pentanediol,
2,3-dimethyl-(C7) (Me-E.sub.1); 1,4-pentanediol, 2,3-dimethyl-(C7)
PO.sub.1; 1,4-pentanediol, 2,3-dimethyl-(C7) n-BO.sub.3;
1,4-pentanediol, 2,4-dimethyl-(C7) (Me-E.sub.1); 1,4-pentanediol,
2,4-dimethyl-(C7) PO.sub.1; 1,4-pentanediol, 2,4-dimethyl-(C7)
n-BO.sub.3; 1,4-pentanediol, 2-methyl-(C6) (Me-E.sub.4-6);
1,4-pentanediol, 2-methyl-(C6) PO.sub.2-3; 1,4-pentanediol,
3,3-dimethyl-(C7) (Me-E.sub.1); 1,4-pentanediol, 3,3-dimethyl-(C7)
PO.sub.1; 1,4-pentanediol, 3,3-dimethyl-(C7) n-BO.sub.3;
1,4-pentanediol, 3,4-dimethyl-(C7) (Me-E.sub.1); 1,4-pentanediol,
3,4-dimethyl-(C7) PO.sub.1; 1,4-pentanediol, 3,4-dimethyl-(C7)
n-BO.sub.3; 1,4-pentanediol, 3-methyl-(C6) 2(Me-E.sub.4-6);
1,4-pentanediol, 3-methyl-(C6) PO.sub.2-3; 1,4-pentanediol,
4-methyl-(C6) 2(Me-E.sub.4-6); 1,4-pentanediol, 4-methyl-(C6)
PO.sub.2-3; 1,5-pentanediol, (C5) (Me-E.sub.8-10); 1,5-pentanediol
(C5) 2(Me-E.sub.1); 1,5-pentanediol (C5) PO.sub.3; 1,5-pentanediol,
2,2-dimethyl-(C7) E.sub.4-7; 1,5-pentanediol, 2,2-dimethyl-(C7)
PO.sub.1; 1,5-pentanediol, 2,2-dimethyl-(C7) n-BO.sub.2;
1,5-pentanediol, 2,3-dimethyl-(C7) E.sub.4-7; 1,5-pentanediol,
2,3-dimethyl-(C7) PO.sub.1; 1,5-pentanediol, 2,3-dimethyl-(C7)
n-BO.sub.2; 1,5-pentanediol, 2,4-dimethyl-(C7) E.sub.4-7;
1,5-pentanediol, 2,4-dimethyl-(C7) PO.sub.1; 1,5-pentanediol,
2,4-dimethyl-(C7) n-BO.sub.2; 1,5-pentanediol, 2-ethyl-(C7)
E.sub.2-5; 1,5-pentanediol, 2-ethyl-(C7) n-BO.sub.1;
1,5-pentanediol, 2-methyl-(C6) (Me-E.sub.1-4); 1,5-pentanediol,
2-methyl-(C6) PO.sub.2; 1,5-pentanediol, 3,3-dimethyl-(C7)
E.sub.4-7; 1,5-pentanediol, 3,3-dimethyl-(C7) PO.sub.1;
1,5-pentanediol, 3,3-dimethyl-(C7) n-BO.sub.2; 1,5-pentanediol,
3-methyl-(C6) (Me-E.sub.1-4); 1,5-pentanediol, 3-methyl-(C6)
PO.sub.2; 2,3-pentanediol, (C5) (Me-E.sub.1-3); 2,3-pentanediol,
(C5) PO.sub.2; 2,3-pentanediol, 2-methyl-(C6) E.sub.4-7;
2,3-pentanediol, 2-methyl-(C6) PO.sub.1; 2,3-pentanediol,
2-methyl-(C6) n-BO.sub.2; 2,3-pentanediol, 3-methyl-(C6) E.sub.4-7;
2,3-pentanediol, 3-methyl-(C6) PO.sub.1; 2,3-pentanediol,
3-methyl-(C6) n-BO.sub.2; 2,3-pentanediol, 4-methyl-(C6) E.sub.4-7;
2,3-pentanediol, 4-methyl-(C6) PO.sub.1; 2,3-pentanediol,
4-methyl-(C6) n-BO.sub.2; 2,4-pentanediol, (C5) 2(Me-E.sub.2-4);
2,4-pentanediol (C5) PO.sub.4; 2,4-pentanediol, 2,3-dimethyl-(C7)
(Me-E.sub.2-4); 2,4-pentanediol, 2,3-dimethyl-(C7) PO.sub.2;
2,4-pentanediol, 2,4-dimethyl-(C7) (Me-E.sub.2-4); 2,4-pentanediol,
2,4-dimethyl-(C7) PO.sub.2; 2,4-pentanediol, 2-methyl-(C7)
(Me-E.sub.8-10); 2,4-pentanediol, 2-methyl-(C7) PO.sub.3;
2,4-pentanediol, 3,3-dimethyl-(C7) (Me-E.sub.2-4); 2,4-pentanediol,
3,3-dimethyl-(C7) PO.sub.2; 2,4-pentanediol, 3-methyl-(C6)
(Me-E.sub.8-10); 2,4-pentanediol, 3-methyl-(C6) PO.sub.3;
[0136] 4. 1,3-hexanediol (C6) (Me-E.sub.2-5); 1,3-hexanediol (C6)
PO.sub.2; 1,3-hexanediol (C6) BO.sub.1; 1,3-hexanediol,
2-methyl-(C7) E.sub.6-8; 1,3-hexanediol, 2-methyl-(C7) PO.sub.1;
1,3-hexanediol, 2-methyl-(C7) n-BO.sub.2-3; 1,3-hexanediol,
3-methyl-(C7) E.sub.6-8; 1,3-hexanediol, 3-methyl-(C7) PO.sub.1;
1,3-hexanediol, 3-methyl-(C7) n-BO.sub.2-3; 1,3-hexanediol,
4-methyl-(C7) E.sub.6-8; 1,3-hexanediol, 4-methyl-(C7) PO.sub.1;
1,3-hexanediol, 4-methyl-(C7) n-BO.sub.2-3; 1,3-hexanediol,
5-methyl-(C7) E.sub.6-8; 1,3-hexanediol, 5-methyl-(C7) PO.sub.1;
1,3-hexanediol, 5-methyl-(C7) n-BO.sub.2-3; 1,4-hexanediol (C6)
(Me-E.sub.2-5); 1,4-hexanediol (C6) PO.sub.2; 1,4-hexanediol (C6)
BO.sub.1; 1,4-hexanediol, 2-methyl-(C7) E.sub.6-8; 1,4-hexanediol,
2-methyl-(C7) PO.sub.1; 1,4-hexanediol, 2-methyl-(C7) n-BO.sub.2-3;
1,4-hexanediol, 3-methyl-(C7) E.sub.6-8; 1,4-hexanediol,
3-methyl-(C7) PO.sub.1; 1,4-hexanediol, 3-methyl-(C7) n-BO.sub.2-3;
1,4-hexanediol, 4-methyl-(C7) E.sub.6-8; 1,4-hexanediol,
4-methyl-(C7) PO.sub.1; 1,4-hexanediol, 4-methyl-(C7) n-BO.sub.2-3;
1,4-hexanediol, 5-methyl-(C7) E.sub.6-8; 1,4-hexanediol,
5-methyl-(C7) PO.sub.1; 1,4-hexanediol, 5-methyl-(C7) n-BO.sub.2-3;
1,5-hexanediol (C6) (Me-E.sub.2-5); 1,5-hexanediol (C6) PO.sub.2;
1,5-hexanediol (C6) BO.sub.1; 1,5-hexanediol, 2-methyl-(C7)
E.sub.6-8; 1,5-hexanediol, 2-methyl-(C7) PO.sub.1; 1,5-hexanediol,
2-methyl-(C7) n-BO.sub.2-3; 1,5-hexanediol, 3-methyl-(C7)
E.sub.6-8; 1,5-hexanediol, 3-methyl-(C7) PO.sub.1; 1,5-hexanediol,
3-methyl-(C7) n-BO.sub.2-3; 1,5-hexanediol, 4-methyl-(C7)
E.sub.6-8; 1,5-hexanediol, 4-methyl-(C7) PO.sub.1; 1,5-hexanediol,
4-methyl-(C7) n-BO.sub.2-3; 1,5-hexanediol, 5-methyl-(C7)
E.sub.6-8; 1,5-hexanediol, 5-methyl-(C7) PO.sub.1; 1,5-hexanediol,
5-methyl-(C7) n-BO.sub.2-3; 1,6-hexanediol (C6) (Me-E.sub.1-2);
1,6- hexanediol (C6) PO.sub.1-2; 1,6-hexanediol (C6) n-BO.sub.4;
1,6-hexanediol, 2-methyl-(C7) E.sub.2-5; 1,6-hexanediol,
2-methyl-(C7) n-BO.sub.1; 1,6-hexanediol, 3-methyl-(C7) E.sub.2-5;
1,6-hexanediol, 3-methyl-(C7) n-BO.sub.1; 2,3-hexanediol (C6)
E.sub.2-5; 2,3-hexanediol (C6) n-BO.sub.1; 2,4-hexanediol (C6)
(Me-E.sub.5-8); 2,4-hexanediol (C6) PO.sub.3; 2,4-hexanediol,
2-methyl-(C7) (Me-E.sub.1-2); 2,4-hexanediol 2-methyl-(C7)
PO.sub.1-2; 2,4-hexanediol, 3-methyl-(C7) (Me-E.sub.1-2);
2,4-hexanediol 3-methyl-(C7) PO.sub.1-2; 2,4-hexanediol,
4-methyl-(C7) (Me-E.sub.1-2); 2,4-hexanediol 4-methyl-(C7)
PO.sub.1-2; 2,4-hexanediol, 5-methyl-(C7) (Me-E.sub.1-2);
2,4-hexanediol 5-methyl-(C7) PO.sub.1-2; 2,5-hexanediol (C6)
(Me-E.sub.5-8); 2,5-hexanediol (C6) PO.sub.3; 2,5-hexanediol,
2-methyl-(C7) (Me-E.sub.1-2); 2,5-hexanediol 2-methyl-(C7)
PO.sub.1-2; 2,5-hexanediol, 3-methyl-(C7) (Me-E.sub.1-2);
2,5-hexanediol 3-methyl-(C7) PO.sub.1-2; 3,4-hexanediol (C6)
EO.sub.2-5; 3,4-hexanediol (C6) n-BO.sub.1;
[0137] 5. 1,3-heptanediol (C7) E.sub.3-6; 1,3-heptanediol (C7)
PO.sub.1; 1,3-heptanediol (C7) n-BO.sub.2; 1,4-heptanediol (C7)
E.sub.3-6; 1,4-heptanediol (C7) PO.sub.1; 1,4-heptanediol (C7)
n-BO.sub.2; 1,5-heptanediol (C7) E.sub.3-6; 1,5-heptanediol (C7)
PO.sub.1; 1,5-heptanediol (C7) n-BO.sub.2; 1,6-heptanediol (C7)
E.sub.3-6; 1,6-heptanediol (C7) PO.sub.1; 1,6-heptanediol (C7)
n-BO.sub.2; 1,7-heptanediol (C7) E.sub.1-2; 1,7-heptanediol (C7)
n-BO.sub.1; 2,4-heptanediol (C7) E.sub.7-10; 2,4-heptanediol (C7)
(Me-E.sub.1); 2,4-heptanediol (C7) PO.sub.1; 2,4-heptanediol (C7)
n-BO.sub.3; 2,5-heptanediol (C7) E.sub.7-10; 2,5-heptanediol (C7)
(Me-E.sub.1); 2,5-heptanediol (C7) PO.sub.1; 2,5-heptanediol (C7)
n-BO.sub.3; 2,6-heptanediol (C7) E.sub.7-10; 2,6-heptanediol (C7)
(Me-E.sub.1); 2,6-heptanediol (C7) PO.sub.1; 2,6-heptanediol (C7)
n-BO.sub.3; 3,5-heptanediol (C7) E.sub.7-10; 3,5-heptanediol (C7)
(Me-E.sub.1); 3,5-heptanediol (C7) PO.sub.1; 3,5-heptanediol (C7)
n-BO.sub.3;
[0138] 6. 1,3-butanediol, 3-methyl-2-isopropyl-(C8) PO.sub.1;
2,4-pentanediol, 2,3,3-trimethyl-(C8) PO.sub.1; 1,3-butanediol,
2,2-diethyl-(C8) E.sub.2-5; 2,4-hexanediol, 2,3-dimethyl-(C8)
E.sub.2-5; 2,4-hexanediol, 2,4-dimethyl-(C8) E.sub.2-5;
2,4-hexanediol, 2,5-dimethyl-(C8) E.sub.2-5; 2,4-hexanediol,
3,3-dimethyl-(C8) E.sub.2-5; 2,4-hexanediol, 3,4-dimethyl-(C8)
E.sub.2-5; 2,4-hexanediol, 3,5-dimethyl-(C8) E.sub.2-5;
2,4-hexanediol, 4,5-dimethyl-(C8) E.sub.2-5; 2,4-hexanediol,
5,5-dimethyl-(C8) E.sub.2-5; 2,5-hexanediol, 2,3-dimethyl-(C8)
E.sub.2-5; 2,5-hexanediol, 2,4-dimethyl-(C8) E.sub.2-5;
2,5-hexanediol, 2,5-dimethyl-(C8) E.sub.2-5; 2,5-hexanediol,
3,3-dimethyl-(C8) E.sub.2-5; 2,5-hexanediol, 3,4-dimethyl-(C8)
E.sub.2-5; 3,5-heptanediol, 3-methyl-(C8) E.sub.2-5;
1,3-butanediol, 2,2-diethyl-(C8) n-BO.sub.1-2; 2,4-hexanediol,
2,3-dimethyl-(C8) n-BO.sub.1-2; 2,4-hexanediol, 2,4-dimethyl-(C8)
n-BO.sub.1-2; 2,4-hexanediol, 2,5-dimethyl-(C8) n-BO.sub.1-2;
2,4-hexanediol, 3,3-dimethyl-(C8) n-BO.sub.1-2; 2,4-hexanediol,
3,4-dimethyl-(C8) n-BO.sub.1-2; 2,4-hexanediol, 3,5-dimethyl-(C8)
n-BO.sub.1-2; 2,4-hexanediol, 4,5-dimethyl-(C8) n-BO.sub.1-2;
2,4-hexanediol, 5,5-dimethyl-, n-BO.sub.1-2; 2,5-hexanediol,
2,3-dimethyl-(C8) n-BO.sub.1-2; 2,5-hexanediol, 2,4-dimethyl-(C8)
n-BO.sub.1-2; 2,5-hexanediol, 2,5-dimethyl-(C8) n-BO.sub.1-2;
2,5-hexanediol, 3,3-dimethyl-(C8) n-BO.sub.1-2; 2,5-hexanediol,
3,4-dimethyl-(C8) n-BO.sub.1-2; 3,5-heptanediol, 3-methyl-(C8)
n-BO.sub.1-2; 1,3-propanediol, 2-(1,2-dimethylpropyl)-(C8)
n-BO.sub.1; 1,3-butanediol, 2-ethyl-2,3-dimethyl-(C8) n-BO.sub.1;
1,3-butanediol, 2-methyl-2-isopropyl-(C8) n-BO.sub.1;
1,4-butanediol, 3-methyl-2-isopropyl-(C8) n-BO.sub.1;
1,3-pentanediol, 2,2,3-trimethyl-(C8) n-BO.sub.1; 1,3-pentanediol,
2,2,4-trimethyl-(C8) n-BO.sub.1; 1,3-pentanediol,
2,4,4-trimethyl-(C8) n-BO.sub.1; 1,3-pentanediol,
3,4,4-trimethyl-(C8) n-BO.sub.1; 1,4-pentanediol,
2,2,3-trimethyl-(C8) n-BO.sub.1; 1,4-pentanediol,
2,2,4-trimethyl-(C8) n-BO.sub.1; 1,4-pentanediol,
2,3,3-trimethyl-(C8) n-BO.sub.1; 1,4-pentanediol,
2,3,4-trimethyl-(C8) n-BO.sub.1; 1,4-pentanediol,
3,3,4-trimethyl-(C8) n-BO.sub.1; 2,4-pentanediol,
2,3,4-trimethyl-(C8) n-BO.sub.1; 2,4-hexanediol, 4-ethyl-(C8)
n-BO.sub.1; 2,4-heptanediol, 2-methyl-(C8) n-BO.sub.1;
2,4-heptanediol, 3-methyl-(C8) n-BO.sub.1; 2,4-heptanediol,
4-methyl-(C8) n-BO.sub.1; 2,4-heptanediol, 5-methyl-(C8)
n-BO.sub.1; 2,4-heptanediol, 6-methyl-(C8) n-BO.sub.1;
2,5-heptanediol, 2-methyl-(C8) n-BO.sub.1; 2,5-heptanediol,
3-methyl-(C8) n-BO.sub.1; 2,5-heptanediol, 4-methyl-(C8)
n-BO.sub.1; 2,5-heptanediol, 5-methyl-(C8) n-BO.sub.1;
2,5-heptanediol, 6-methyl-(C8) n-BO.sub.1; 2,6-heptanediol,
2-methyl-(C8) n-BO.sub.1; 2,6-heptanediol, 3-methyl-(C8)
n-BO.sub.1; 2,6-heptanediol, 4-methyl-(C8) n-BO.sub.1;
3,5-heptanediol, 2-methyl-(C8) n-BO.sub.1; 1,3-propanediol,
2-(1,2-dimethylpropyl)-(C8) E.sub.1-3; 1,3-butanediol,
2ethyl-2,3-dimethyl-(C8) E.sub.1-3; 1,3-butanediol,
2-methyl-2-isopropyl-(C8) E.sub.1-3; 1,4-butanediol,
3-methyl-2-isopropyl-(C8) E.sub.1-3; 1,3-pentanediol,
2,2,3-trimethyl-(C8) E.sub.1-3; 1,3-pentanediol,
2,2,4-trimethyl-(C8) E.sub.1-3; 1,3-pentanediol,
2,4,4-trimethyl-(C8) E.sub.1-3; 1,3-pentanediol,
3,4,4-trimethyl-(C8) E.sub.1-3; 1,4-pentanediol,
2,2,3-trimethyl-(C8) E.sub.1-3; 1,4-pentanediol,
2,2,4-trimethyl-(C8) E.sub.1-3; 1,4-pentanediol,
2,3,3-trimethyl-(C8) E.sub.1-3; 1,4-pentanediol,
2,3,4-trimethyl-(C8) E.sub.1-3; 1,4-pentanediol,
3,3,4-trimethyl-(C8) E.sub.1-3; 2,4-pentanediol,
2,3,4-trimethyl-(C8) E.sub.1-3; 2,4-hexanediol, 4-ethyl-(C8)
E.sub.1-3; 2,4-heptanediol, 2-methyl-(C8) E.sub.1-3;
2,4-heptanediol, 3-methyl-(C8) E.sub.1-3; 2,4-heptanediol,
4-methyl-(C8) E.sub.1-3; 2,4-heptanediol, 5-methyl-(C8) E.sub.1-3;
2,4-heptanediol, 6-methyl-(C8) E.sub.1-3; 2,5-heptanediol,
2-methyl-(C8) E.sub.1-3; 2,5-heptanediol, 3-methyl-(C8) E.sub.1-3;
2,5-heptanediol, 4-methyl-(C8) E.sub.1-3; 2,5-heptanediol,
5-methyl-(C8) E.sub.1-3; 2,5-heptanediol, 6-methyl-(C8) E.sub.1-3;
2,6-heptanediol, 2-methyl-(C8) E.sub.1-3; 2,6-heptanediol,
3-methyl-(C8) E.sub.1-3; 2,6-heptanediol, 4-methyl-(C8) E.sub.1-3;
and/or 3,5-heptanediol, 2-methyl-(C8) E.sub.1-3; and
[0139] 7. mixtures thereof.
[0140] Of the nonane isomers, only 2,4-pentadiol,
2,3,3,4-tetramethyl- is highly preferred.
[0141] In addition to the aliphatic diol principal solvents, and
some of their alkoxylated derivatives, discussed hereinbefore and
hereinafter, some specific diol ethers are also found to be
suitable principal solvents for the formulation of liquid
concentrated, clear fabric softener compositions of the present
invention. Similar to the aliphatic diol principal solvents, it is
discovered that the suitability of each principal solvent is very
selective, depending, e.g., on the number of carbon atoms in the
specific diol ether molecules. For example, as given in Table VI,
for the glyceryl ether series having the formula
HOCH.sub.2--CHOH--CH.sub.2--O--R, wherein R is from C2 to C8 alkyl,
only monopentyl ethers with the formula
HOCH.sub.2--CHOH--CH.sub.2--O--C.sub.5- H.sub.11
(3-pentyloxy-1,2-propanediol), wherein the C.sub.5H.sub.11 group
comprises different pentyl isomers, have ClogP values within the
preferred ClogP values of from about 0.25 to about 0.62 and are
suitable for the formulation of liquid concentrated, clear fabric
softeners of the present invention. These are illustrated by the
Examples and Comparative Examples XXXIIA-7 to XXXIIA-7F. It is also
found that the cyclohexyl derivative, but not the cyclopentyl
derivative, is suitable. Similarly, selectivity is exhibited in the
selection of aryl glyceryl ethers. Of the many possible aromatic
groups, only a few phenol derivatives are suitable.
[0142] The same narrow selectivity is also found for the
di(hydroxyalkyl) ethers. It is discovered that bis(2-hydroxybutyl)
ether, but not bis(2-hydroxypentyl) ether, is suitable. For the
di(cyclic hydroxyalkyl) analogs, the bis(2-hydroxycyclopentyl)
ether is suitable, but not the bis(2-hydroxycyclohexyl) ether.
Non-limiting examples of synthesis methods for the preparation of
some preferred di(hydroxyalkyl) ethers are given hereinafter.
[0143] The butyl monoglycerol ether (also named
3-butyloxy-1,2-propanediol- ) is not well suited to form liquid
concentrated, clear fabric softeners of the present invention.
However, its polyethoxylated derivatives, preferably from about
triethoxylated to about nonaethoxylated, more preferably from
pentaethoxylated to octaethoxylated, are suitable principal
solvents, as given in Table VI.
[0144] All of the preferred alkyl glyceryl ethers and/or
di(hydroxyalkyl)ethers that have been identified are given in Table
VI and the most preferred are: 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-(1-cyclohex-1-enyloxy)-; 1,3-propanediol,
2-(pentyloxy)-; 1,3-propanediol, 2-(2-pentyloxy)-; 1,3-propanediol,
2-(3-pentyloxy)-; 1,3-propanediol, 2-(2-methyl-1-butyloxy)-;
1,3-propanediol, 2-(iso-amyloxy)-; 1,3-propanediol,
2-(3-methyl-2-butyloxy)-; 1,3-propanediol, 2-(cyclohexyloxy)-;
1,3-propanediol, 2-(1-cyclohex-1-enyloxy)-; 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; and/or 1,2-propanediol, 3-(butyloxy)-,
tributyleneoxylated. Preferred aromatic glyceryl ethers include:
1,2-propanediol, 3-phenyloxy-; 1,2-propanediol, 3-benzyloxy-;
1,2-propanediol, 3-(2-phenylethyloxy)-; 1,2-propanediol,
1,3-propanediol, 2-(m-cresyloxy)-; 1,3-propanediol,
2-(p-cresyloxy)-; 1,3-propanediol, 2-benzyloxy-; 1,3-propanediol,
2-(2-phenylethyloxy)-; and mixtures thereof. The more preferred
aromatic glyceryl ethers include: 1,2-propanediol, 3-phenyloxy-;
1,2-propanediol, 3-benzyloxy-; 1,2-propanediol,
3-(2-phenylethyloxy)-; 1,2-propanediol, 1,3-propanediol,
2-(m-cresyloxy)-; 1,3-propanediol, 2-(p-cresyloxy)-;
1,3-propanediol, 2-(2-phenylethyloxy)-; and mixtures thereof. The
most preferred di(hydroxyalkyl)ethers include:
bis(2-hydroxybutyl)ether; and bis(2-hydroxycyclopentyl)ether;
[0145] An illustrative and non-limiting example of synthesis
methods to prepare the preferred alkyl and aryl monoglyceryl ethers
is given hereinafter.
[0146] The alicyclic diols and their derivatives that are preferred
include: (1) the saturated diols and their derivatives including:
1-isopropyl-1,2-cyclobutanediol;
3-ethyl4-methyl-1,2-cyclobutanediol; 3-propyl-1,2-cyclobutanediol;
3-isopropyl-1,2-cyclobutanediol; 1-ethyl-1,2-cyclopentanediol;
1,2-dimethyl-1,2-cyclopentanediol;
1,4-dimethyl-1,2-cyclopentanediol;
2,4,5-trimethyl-1,3-cyclopentanediol;
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-1,2-cyclopentanediol;
1,1-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; 1-hydroxy-cyclohexanemethanol;
1-ethyl-1,3-cyclohexanediol; 1-methyl-1,2-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-dimethyl-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-1-cyclohexanol;
4-hydroxymethylcyclohexanol; 4-methyl-1,2-cyclohexanediol;
5,5-dimethyl-1,3-cyclohexanediol; 5-ethyl-1,3-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; 1,5-cyclooctanediol; 1,2-cyclohexanediol,
diethoxylate; 1,2-cyclohexanediol, triethoxylate;
1,2-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
1,2-cyclohexanediol, tributylenoxylate. The most preferred
saturated alicyclic diols and their derivatives are:
1-isopropyl-1,2-cyclobutanedio- l;
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-1,2-cyclopentanediol;
1,4-dimethyl-1,2-cyclopentanediol;
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-1,2-cyclopentanediol;
1,1-bis(hydroxymethyl)cyclohexane;
1,2-bis(hydroxymethyl)cyclohexane;
1,2-dimethyl-1,3-cyclohexanediol;
1,3-bis(hydroxymethyl)cyclohexane; 1-hydroxy-cyclohexanemethanol;
1-methyl-1,2-cyclohexanediol; 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-1-cyclohexanol;
4-hydroxymethylcyclohexanol; 4-methyl-1,2-cyclohexanediol;
1,2-cycloheptanediol; 1,2-cyclohexanediol, pentaethoxylate;
1,2-cyclohexanediol, hexaethoxylate; 1,2-cyclohexanediol,
heptaethoxylate; 1,2-cyclohexanediol, octaethoxylate;
1,2-cyclohexanediol, nonaethoxylate; 1,2-cyclohexanediol,
monopropoxylate; and/or 1,2-cyclohexanediol, dibutylenoxylate.
[0147] Preferred aromatic diols include: 1-phenyl-1,2-ethanediol;
1-phenyl-1,2-propanediol; 2-phenyl-1,2-propanediol;
3-phenyl-1,2-propanediol; 1-(3-methylphenyl)-1,3-propanediol;
1-(4-methylphenyl)-1,3-propanediol;
2-methyl-1-phenyl-1,3-propanediol; 1-phenyl-1,3-butanediol;
3-phenyl-1,3-butanediol; and/or 1-phenyl-1,4-butanediol, of which,
1-phenyl-1,2-propanediol; 2-phenyl-1,2-propanediol;
3-phenyl-1,2-propanediol; 1-(3-methylphenyl)-1,3-propanediol;
1-(4-methylphenyl)-1,3-propanediol;
2-methyl-1-phenyl-1,3-propanediol; and/or 1-phenyl-1,4-butanediol
are the most preferred.
[0148] As discussed hereinbefore, all of the unsaturated materials
that are related to the other preferred principal solvents herein
by the same relationship, i.e., having one more CH.sub.2 group than
the corresponding saturated principal solvent will also be
preferred. However, the specific preferred unsaturated diol
principal solvents are: 1,3-butanediol, 2,2-diallyl-;
1,3-butanediol, 2-(1-ethyl-1-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-(1-methyl-2-propenyl)-; 1,4-butanediol,
2,3-bis(1-methylethylidene)-; 1,3-pentanediol, 2-ethenyl-3-ethyl-;
1,3-pentanediol, 2-ethenyl-4,4-dimethyl-; 1,4-pentanediol,
3-methyl-2-(2-propenyl)-; 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-hexanediol, 2-(1-methylethenyl)-;
2-hexene-1,5-diol, 4-ethenyl-2,5-dimethyl-; 1,4-heptanediol,
6-methyl-5-methylene-; 2,4-heptadiene-2,6-diol, 4,6-dimethyl-;
2,6-heptadiene-1,4-diol, 2,5,5-trimethyl-; 2-heptene-1,4-diol,
5,6-dimethyl-; 3-heptene-1,5-diol, 4,6-dimethyl-;
5-heptene-1,3-diol, 2,4-dimethyl-; 5-heptene-1,3-diol,
3,6-dimethyl-; 5-heptene-1,4-diol, 2,6-dimethyl-;
5-heptene-1,4-diol, 3,6-dimethyl-; 6-heptene-1,3-diol,
2,2-dimethyl-; 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)-;
1-octene-3,6-diol, 3-ethenyl-; 2,4,6-octatriene-1,8-diol,
2,7-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-1,7-diol, 2-methyl-6-methylene-;
3,5-octadiene-2,7-diol, 2,7-dimethyl-; 3,5-octanediol,
4-methylene-; 3,7-octadiene-1,6-diol, 2,6-dimethyl-;
4-octene-1,8-diol, 2-methylene-; 6-octene-3,5-diol, 2-methyl-;
6-octene-3,5-diol, 4-methyl-; 7-octene-2,4-diol,
2-methyl-6-methylene-; 7-octene-2,5-diol, 7-methyl-;
7-octene-3,5-diol, 2-methyl-; 1-nonene-3,5-diol; 1-nonene-3,7-diol;
nonene-2,5-diol; 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-decadiene4,6-diol.
[0149] Said principal alcohol solvent can also preferably be
selected from the group consisting of: 2,5-dimethyl-2,5-hexanediol;
2-ethyl-1,3-hexanediol; 2-methyl-2-propyl-1,3-propanediol;
1,2-hexanediol; and mixtures thereof. More preferably said
principal alcohol solvent is selected from the group consisting of
2-ethyl-1,3-hexanediol; 2-methyl-2-propyl-1,3-propanediol;
1,2-hexanediol; and mixtures thereof. Even more preferably, said
principal alcohol solvent is selected from the groups consisting of
2-ethyl-1,3-hexanediol; 1,2-hexanediol; and mixtures thereof.
[0150] When several derivatives of the same diol with different
alkyleneoxy groups can be used, e.g., 2-methyl-2,3-butanediol
having 3 to 5 ethyleneoxy groups, or 2 propyleneoxy groups, or 1
butyleneoxy group, it is preferred to use the derivative with the
lowest number of groups, i.e., in this case, the derivative with
one butyleneoxy group. However, when only about one to about four
ethyleneoxy groups are needed to provide good formulatability, such
derivatives are also preferred.
Unsaturated Diols
[0151] It is found surprisingly that there is a clear similarity
between the acceptability (formulatability) of a saturated diol and
its unsaturated homologs, or analogs, having higher molecular
weights. The unsaturated homologs/analogs have the same
formulatability as the parent saturated principal solvent with the
condition that the unsaturated principal solvents have one
additional methylene (viz., CH.sub.2) group for each double bond in
the chemical formula. In other words, there is an apparent
"addition rule" in that for each good saturated principal solvent
of this invention, which is suitable for the formulation of clear,
concentrated fabric softener compositions, there are suitable
unsaturated principal solvents where one, or more, CH.sub.2 groups
are added while, for each CH.sub.2 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 with respect to the chemical formula
of the "parent" saturated principal solvent. This is due to a
surprising fact that adding a --CH.sub.2-- group to a solvent
chemical formula has an effect of increasing its ClogP value by
about 0.53, while removing two adjacent hydrogen atoms to form a
double bond has an effect of decreasing its ClogP value by about a
similar amount, viz., about 0.48, thus about compensating for the
--CH.sub.2-- addition. Therefore one goes from a preferred
saturated principal solvent to the preferred higher molecular
weight unsaturated analogs/homologs containing at least one more
carbon atom by inserting one double bond for each additional
CH.sub.2 group, and thus the total number of hydrogen atoms is kept
the same as in the parent saturated principal solvent, as long as
the ClogP value of the new solvent remains within the effective
0.15-0.64, preferably from about 0.25 to about 0.62, and more
preferably from about 0.40 to about 0.60, range. The following are
some illustrative examples:
[0152] 2,2-Dimethyl-6-heptene-1,3-diol (CAS No. 140192-39-8) is a
preferred C9-diol principal solvent and can be considered to be
derived by appropriately adding a CH.sub.2 group and a double bond
to either of the following preferred C8-diol principal solvents:
2-methyl-1,3-heptanediol or 2,2-dimethyl-1,3-hexanediol.
[0153] 2,4-Dimethyl-5-heptene-1,3-diol (CAS No. 123363-69-9) is a
preferred C9-diol principal solvent and can be considered to be
derived by appropriately adding a CH.sub.2 group and a double bond
to either of the following preferred C8-diol principal solvents:
2-methyl-1,3-heptanediol or 2,4-dimethyl-1,3-hexanediol.
[0154] 2-(1-Ethyl-1-propenyl)-1,3-butanediol (CAS No. 116103-35-6)
is a preferred C9-diol principal solvent and can be considered to
be derived by appropriately adding a CH.sub.2 group and a double
bond to either of the following preferred C8-diol principal
solvents: 2-(1-ethylpropyl)-1,3-propanediol or
2-(1-methylpropyl)-1,3-butanediol.
[0155] 2-Ethenyl-3-ethyl-1,3-pentanediol (CAS No. 104683-37-6) is a
preferred C9-diol principal solvent and can be considered to be
derived by appropriately adding a CH.sub.2 group and a double bond
to either of the following preferred C8-diol principal solvents:
3-ethyl-2-methyl-1,3-pentanediol or
2-ethyl-3-methyl-1,3-pentanediol.
[0156] 3,6-Dimethyl-5-heptene-1,4-diol (e.g., CAS No. 106777-99-5)
is a preferred C9-diol principal solvent and can be considered to
be derived by appropriately adding a CH.sub.2 group and a double
bond to any of the following preferred C8-diol principal solvents:
3-methyl-1,4-heptanediol; 6-methyl-1,4-heptanediol; or
3,5-dimethyl-1,4-hexanediol.
[0157] 5,6-Dimethyl-6-heptene-1,4-diol (e.g., CAS No. 152344-16-6)
is a preferred C9-diol principal solvent and can be considered to
be derived by appropriately adding a CH.sub.2 group and a double
bond to any of the following preferred C8-diol principal solvents:
5-methyl-1,4-heptanediol; 6-methyl-1,4-heptanediol; or
4,5-dimethyl-1,3-hexanediol.
[0158] 4-Methyl-6-octene-3,5-diol (CAS No. 156414-254) is a
preferred C9-diol principal solvent and can be considered to be
derived by appropriately adding a CH.sub.2 group and a double bond
to any of the following preferred C8-diol principal solvents:
3,5-octanediol, 3-methyl-2,4-heptanediol or
4-methyl-3,5-heptanediol.
[0159] Rosiridol (CAS No. 101391-01-9) and isorosiridol (CAS No.
149252-15-3) are two isomers of
3,7-dimethyl-2,6-octadiene-1,4-diol, and are preferred C10-diol
principal solvents. They can be considered to be derived by
appropriately adding two CH.sub.2 groups and two double bonds to
any of the following preferred C8-diol principal solvents:
2-methyl-1,3-heptanediol; 6-methyl-1,3-heptanediol;
3-methyl-1,4-heptanediol; 6-methyl-1,4-heptanediol;
2,5-dimethyl-1,3-hexanediol; or 3,5-dimethyl-1,4-hexanediol.
[0160] 8-Hydroxylinalool (CAS No. 103619-06-3,
2,6-dimethyl-2,7-octadiene-- 1,6-diol) is a preferred C10-diol
principal solvent and can be considered to be derived by
appropriately adding two CH.sub.2 groups and two double bonds to
any of the following preferred C8-diol principal solvents:
2-methyl-1,5-heptanediol; 5-methyl-1,5-heptanediol;
2-methyl-1,6-heptanediol; 6-methyl-1,6-heptanediol; or
2,4-dimethyl-1,4-hexanediol.
[0161] 2,7-Dimethyl-3,7-octadiene-2,5-diol (CAS No. 171436-39-8) is
a preferred C10-diol principal solvent and can be considered to be
derived by appropriately adding two CH.sub.2 group and two double
bond to any of the following preferred C8-diol principal solvents:
2,5-octanediol; 6-methyl-1,4-heptanediol; 2-methyl-2,4-heptanediol;
6-methyl-2,4-heptanediol; 2-methyl-2,5-heptanediol;
6-methyl-2,5-heptanediol; and 2,5-dimethyl-2,4-hexanediol.
[0162] 4-Butyl-2-butene-1,4-diol (CAS No. 153943-66-9) is a
preferred C8-diol principal solvent and can be considered to be
derived by appropriately adding a CH.sub.2 group and a double bond
to any of the following preferred C7-diol principal solvents:
2-propyl-1,4-butanediol or 2-butyl-1,3-propanediol.
[0163] By the same token, there are cases where a higher molecular
weight unsaturated homolog which is derived from a poor, inoperable
saturated solvent is itself a poor solvent. For example,
3,5-dimethyl-5-hexene-2,4-- diol (e.g., CAS No. 16042940-3) is a
poor unsaturated C8 solvent, and can be considered to be derived
from the following poor saturated C7 solvents:
3-methyl-2,4-hexanediol; 5-methyl-2,4-hexanediol; or
2,4-dimethyl-1,3-pentanediol; and 2,6-dimethyl-5-heptene-1,2-diol
(e.g., CAS No. 141505-71-7) is a poor unsaturated C9 solvent, and
can be considered to be derived from the following poor saturated
C8 solvents: 2-methyl-1,2-heptanediol; 6-methyl-1,2-heptanediol; or
2,5-dimethyl-1,2-hexanediol.
[0164] It is also found, surprisingly, that there is an exception
to the above addition rule, in which saturated principal solvents
always have unsaturated analogs/homologs with the same degree of
acceptability. The exception relates to saturated diol principal
solvents having the two hydroxyl groups situated on two adjacent
carbon atoms. In some cases, but not always, inserting one, or
more, CH.sub.2 groups between the two adjacent hydroxyl groups of a
poor solvent results in a higher molecular weight unsaturated
homolog which is more suitable for the clear, concentrated fabric
softener formulation. For example, the preferred unsaturated
6,6-dimethyl-1-heptene-3,5-diol (CAS No. 109788-01-4) having no
adjacent hydroxyl groups can be considered to be derived from the
inoperable 2,2-dimethyl-3,4-hexanediol which has adjacent hydroxyl
groups. In this case, it is more reliable to consider that the
6,6-dimethyl-1-heptene-3,5-diol is derived from either
2-methyl-3,5-heptanediol or 5,5-dimethyl-2,4-hexanediol which are
both preferred principal solvents and do not have adjacent hydroxyl
groups. Conversely, inserting CH.sub.2 groups between the adjacent
hydroxyl groups of a preferred principal solvent can result in an
inoperable higher molecular weight unsaturated diol solvent. For
example, the inoperable unsaturated 2,4-dimethyl-5-hexene-2,4-diol
(CAS No. 87604-24-8) having no adjacent hydroxyl groups can be
considered to be derived from the preferred
2,3-dimethyl-2,3-pentanediol which has adjacent hydroxyl groups. In
this case, it is more reliably to derive the inoperable unsaturated
2,4-dimethyl-5-hexene-2,4-diol from either 2-methyl-2,4-hexanediol
or 4-methyl-2,4-hexanediol which are both inoperable solvents and
do not have adjacent hydroxyl groups. There are also cases where an
inoperable unsaturated solvent having no adjacent hydroxyl groups
can be considered to be derived from an inoperable solvent which
has adjacent hydroxyl groups, such as the pair
4,5-dimethyl-6-hexene-1,3-diol and 3,4-dimethyl-1,2-pentanediol.
Therefore, in order to deduce the formulatability of an unsaturated
solvent having no adjacent hydroxyl groups, one should start from a
low molecular weight saturated homolog also not having adjacent
hydroxyl groups. I.e., in general, the relationship is more
reliable when the distance/relationship of the two hydroxy groups
is maintained. I.e., it is reliable to start from a saturated
solvent with adjacent hydroxyl groups to deduce the formulatability
of the higher molecular weight unsaturated homologs also having
adjacent hydroxyl groups.
[0165] It has been discovered that the use of these specific
principal alcohol solvents can produce clear, low viscosity, stable
fabric softener compositions at surprisingly low principal solvent
levels, i.e., less than about 40%, by weight of the composition. It
has also been discovered that the use of the principal alcohol
solvents can produce highly concentrated fabric softener
compositions, that are stable and can be diluted, e.g. from about
2:1 to about 10:1, to produce compositions with lower levels of
fabric softener that are still stable.
[0166] As previously discussed, the principal solvents are
desirably kept to the lowest levels that are feasible in the
present compositions for obtaining translucency or clarity. 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 level) is needed to attain product
clarity. Inversely, the less the water content, the less principal
solvent (relative to the softener) is needed. Thus, at low water
levels of from about 5% 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 ratio is preferably
from about 30:70 to about 55:45, more preferably from about 35:65
to about 45:55. At even higher water levels, the softener to
principal solvent ratios should also be even higher.
[0167] Mixtures of the above principal solvents are particularly
preferred, since one of the problems associated with large amounts
of solvents is safety. Mixtures decrease the amount of any one
material that is present. Odor and flammability can also be
mimimized by use of mixtures, especially when one of the principal
solvents is volatile and/or has an odor, which is more likely for
low molecular weight materials. Suitable solvents that can be used
at levels that would not be sufficient to produce a clear product
are 2,2,4-trimethyl-1,3-pentane diol; the ethoxylate, diethoxylate,
or triethoxylate derivatives of 2,2,4-trimethyl-1,3-pentane diol;
and/or 2-ethyl-1,3-hexanediol. For the purposes of this invention,
these solvents should only be used at levels that will not provide
a stable, or clear product. Preferred mixtures are those where the
majority of the solvent is one, or more, that have been identified
hereinbefore as most preferred. The use of mixtures of solvents is
also preferred, especially when one, or more, of the preferred
principal solvents are solid at room temperature. In this case, the
mixtures are fluid, or have lower melting points, thus improving
processability of the softener compositions.
[0168] It is also discovered that it is possible to substitute for
part of a principal solvent or a mixture of principal solvents of
this invention with a secondary solvent, or a mixture of secondary
solvents, which by themselves are not operable as a principal
solvent of this invention, as long as an effective amount of the
operable principal solvent(s) of this invention is still present in
the liquid concentrated, clear fabric softener composition. An
effective amount of the principal solvent(s) of this invention is
at least greater than about 5%, preferably more than about 7%, more
preferably more than about 10% of the composition, when at least
about 15% of the softener active is also present. The substitute
solvent(s) can be used at any level, but preferably about equal to,
or less than, the amount of operable principal solvent, as defined
hereinbefore, that is present in the fabric softener
composition.
[0169] For example, even though 1,2-pentanediol, 1,3-octanediol,
and hydroxy pivalyl hydroxy pivalate (hereinafter, HPHP) having the
following formula:
HO--CH.sub.2--C(CH.sub.3).sub.2--CH.sub.2--O--CO--C(CH.sub.3).sub.2--CH.su-
b.2--OH (CAS# 1115-20-4)
[0170] are inoperable solvents according to this invention,
mixtures of these solvents with the principal solvent, e.g., with
the preferred 1,2-hexanediol principal solvent, wherein the
1,2-hexanediol principal solvent is present at effective levels,
also provide liquid concentrated, clear fabric softener
compositions.
[0171] The principal solvent can be used to either make a
composition translucent or clear, or can be used to reduce the
temperature at which the composition is translucent or clear. Thus
the invention also comprises the method of adding the principal
solvent, at the previously indicated levels, to a composition that
is not translucent, or clear, or which has a temperature where
instability occurs that is too high, to make the composition
translucent or clear, or, when the composition is clear, e.g., at
ambient temperature, or down to a specific temperature, to reduce
the temperature at which instability occurs, preferably by at least
about 5.degree. C., more preferably by at least about 10.degree. C.
The principal advantage of the principal solvent is that it
provides the maximum advantage for a given weight of solvent. It is
understood that "solvent", as used herein, refers to the effect of
the principal solvent and not to its physical form at a given
temperature, since some of the principal solvents are solids at
ambient temperature.
[0172] Alkyl Lactates
[0173] Some alkyl lactate esters, e.g., ethyl lactate and isopropyl
lactate have ClogP values within the effective range of from about
0.15 to about 0.64, and can form liquid concentrated, clear fabric
softener compositions with the fabric softener actives of this
invention, but need to be used at a slightly higher level than the
more effective diol solvents like 1,2-hexanediol. They can also be
used to substitute for part of other principal solvents of this
invention to form liquid concentrated, clear fabric softener
compositions. This is illustrated in Example I-C.
Novel Compounds
[0174] Several of the above principal solvents are novel compounds
including: 1,2-butanediol, 2,3,3-trimethyl-; 3,4-pentanediol,
2,3-dimethyl-; 2,3-hexanediol, 4-methyl-; 2,3-hexanediol,
5-methyl-; 3,4-hexanediol, 2-methyl-; 3,4-pentanediol,
2,3-dimethyl-; 1,3-propanediol, 2-(1,1-dimethylpropyl)-;
1,3-propanediol, 2-(1,2-dimethylpropyl)-; 1,3-propanediol,
2-(2,2-dimethylpropyl)-; 1,3-butanediol, 2-(1-methylpropyl)-;
1,3-butanediol, 2-ethyl-2,3-dimethyl-; 1,3-butanediol,
2-(2-methylpropyl)-; 1,3-butanediol, 2-methyl-2-isopropyl-;
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)-;
1,4-butanediol, 2-ethyl-2,3-dimethyl-; 1,4-butanediol,
2-ethyl-3,3-dimethyl-; 1,4-butanediol, 2-(2-methylpropyl)-;
1,4-pentanediol, 2,2,3-trimethyl-; 1,4-pentanediol,
2,3,3-trimethyl-; 1,5-pentanediol, 2,2,3-trimethyl-;
1,5-pentanediol, 2,3,3-trimethyl-; 1,3-pentanediol,
2-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-; 1,5-pentanediol,
2-ethyl-2-methyl-; 1,5-pentanediol, 2-ethyl-4-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-;
2,4-pentanediol, 3-propyl-; 1,3-hexanediol, 2,3-dimethyl-;
1,3-hexanediol, 2,5-dimethyl-; 1,3-hexanediol, 3,4-dimethyl-;
1,3-hexanediol, 3,5-dimethyl-; 1,3-hexanediol, 4,5-dimethyl-;
1,4-hexanediol, 2,2-dimethyl-; 1,4-hexanediol, 2,3-dimethyl-;
1,4-hexanediol, 2,4-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-;
1,5-hexanediol, 2,2-dimethyl-; 1,5-hexanediol, 3,4-dimethyl-;
1,5-hexanediol, 3,5-dimethyl-; 1,5-hexanediol, 4,5-dimethyl-;
1,6-hexanediol, 2,3-dimethyl-; 1,6-hexanediol, 2,4-dimethyl-;
1,6-hexanediol, 3,3-dimethyl-; 2,4-hexanediol, 4,5-dimethyl-;
2,5-hexanediol, 2,3-dimethyl-; 2,5-hexanediol, 2,4-dimethyl-;
2,5-hexanediol, 3,3-dimethyl-; 2,6-hexanediol, 3,3-dimethyl-;
1,3-hexanediol, 4-ethyl-; 2,4-hexanediol, 3-ethyl-; 2,5-hexanediol,
3-ethyl-; 1,3-heptanediol, 4-methyl-; 1,3-heptanediol, 5-methyl-;
1,3-heptanediol, 6-methyl-; 1,5-heptanediol, 3-methyl-;
1,5-heptanediol, 4-methyl-; 1,6-heptanediol, 3-methyl-;
1,6-heptanediol, 5-methyl-; 2,4-heptanediol, 5-methyl-;
2,5-heptanediol, 3-methyl-; 3,5-heptanediol, 2-methyl-;
2,6-octanediol; 2,4-hexanediol, 3,3,4-trimethyl-; 2,4-hexanediol,
3,5,5-trimethyl-; 2,4-hexanediol, 4,5,5-trimethyl-; 2,5-hexanediol,
3,3,4-trimethyl-; 2,5-hexanediol, 3,3,5-trimethyl-;
1,2-propanediol, 3-(butyloxy)-, triethoxylated; 1,2-propanediol,
3-(butyloxy)-, tetraethoxylated; 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-(1-cyclohex-1-enyloxy)-;
1,3-propanediol, 2-(pentyloxy)-; 1,3-propanediol, 2-(2-pentyloxy)-;
1,3-propanediol, 2-(3-pentyloxy)-; 1,3-propanediol,
2-(2-methyl-1-butyloxy)-; 1,3-propanediol, 2-(iso-amyloxy)-;
1,3-propanediol, 2-(3-methyl-2-butyloxy)-; 1,3-propanediol,
2-(cyclohexyloxy)-; 1,3-propanediol, 2-(1-cyclohex-1-enyloxy)-;
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;
bis(2-hydroxybutyl) ether; and bis(2-hydroxycyclopentyl) ether.
[0175] III. Chelating Agents
[0176] The compositions of the present invention all include one or
more chelating agents such as copper and/or nickel chelating agents
("chelators"). The chelating agents of the present invention are
added to aid in the reduction of color forming bodies thereby
aiding the clarity of the clear or translucent composition and to
reduce malodor. While not wishing to be bound by theory, it is
believed that the addition of a chelating agent reduces or
minimizes the presence of color forming bodies which may be present
in the fabric softening active. In addition, the presence of a
chelating agent minimizes or reduces any malodor which may be
associated with the fabric softening active.
[0177] Accordingly, the compositions of the present invention
include the presence of a chelating agent as an essential component
of the composition. The chelating agent may be present in the
composition in the range of from about 0.001% to about 10% by
weight of the composition. More preferably the chelant is present
in the range of from about 0.01% to about 5% and most preferably in
the range of from about 0.01% to about 3% by weight of the
composition.
[0178] 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 and all preferably in their
acidic form. Amino carboxylates useful as chelating agents herein
include ethylenedi-aminetetraacetates acid (EDTA),
N-hydroxyethylethylenediaminet- riacetates acid,
nitrilotri-acetates (NTA), ethylenediamine tetraproprionates,
ethylenediamine-N,N'-diglutamates,
2-hyroxypropylenediamine-N,N'-disuccinates,
triethylenetetraaminehexaceta- tes, diethylenetriaminepentaacetates
(DETPA) such as diethylenetriaminepentacetic acid (DTPA), and
ethanoldiglycines, including their water-soluble salts such as the
alkali metal, ammonium, and substituted ammonium salts thereof and
mixtures thereof.
[0179] Amino phosphonates are also suitable for use as chelating
agents in the compositions of the invention when at least low
levels of total phosphorus are permitted in detergent compositions,
and include ethylenediaminetetrakis (methylenephosphonates),
diethylenetriamine-N,N,N- ',N",N"-pentakis(methane phosphonate)
(DETMP) and 1-hydroxyethane-1,1-diph- osphonate (HEDP). Preferably,
these amino phosphonates to not contain alkyl or alkenyl groups
with more than about 6 carbon atoms.
[0180] The chelating agents are 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.
[0181] The EDDS chelator which may be used herein (also known as
ethylenediamine-N,N'-disuccinate) is the material described in U.S.
Pat. No. 4,704,233, cited hereinabove, and has the formula (shown
in free acid form): 11
[0182] As disclosed in the patent, EDDS can be prepared using
maleic anhydride and ethylenediamine. The biodegradable [S,S]
isomer of EDDS can be prepared by reacting L-aspartic acid with
1,2-dibromoethane. 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 cation 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 may be used in combination with zinc cations.
[0183] As can be seen from the foregoing, a wide variety of
chelators may be used herein. Indeed, simple polycarboxylates such
as citrate, oxydisuccinate, and the like, may 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, 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
compositions herein. Preferred chelators include DETMP, DETPA,
DTPA, NTA, EDDS and mixtures thereof with DTPA being the most
preferred.
[0184] Clarity of the Composition
[0185] Compositions of the present invention comprise liquid rinse
added fabric softening compositions which are clear or translucent.
By clear compositions, it is intended that the compositions of the
present invention are preferably substantially free of significant
color such that the compositions generally appear as clear as
water. Of course one of ordinary skill in the art will recognize
that a small amount of color may be present in the compositions of
the present invention. In such instances, the compositions of the
present invention will appear clear when packaged in a suitable
container of an offset color shade so that the color of the
composition is offset and the composition appears clear when viewed
through the container.
[0186] The color or clarity of the present invention may be
measured via a Hunter Color analysis. A Hunter Color analysis is
well known to one of ordinary skill in the art. The analysis is
performed on a Hunter Lab ColorQuest Instrument available from
Hunter Labs of Reston, Va. The Hunter Lab ColorQuest Instrument can
perform two separate measurements for the purposes of measuring the
color or clarity of the compositions of the present invention, a
CIELAB color measurement and a measurement of the percentage (%) of
Haze in the solution in the transmission mode of the instrument.
Both measurements are run on the Hunter Lab ColorQuest Instrument
using the total transmission mode. The settings for the instrument
are 0.25" area view, 0.25" port size, UV filter out, no UV lamp,
deionized water as the standard and a 30 mm cell.
[0187] CIELAB is a scale used to measure the color of solutions.
One of ordinary skill in the art is familiar with the CIELAB scale.
A Color difference measurement involves measuring the composition
at the point of intial mixing and then measuring the color of the
composition after a set period of time under specified conditions.
The difference between the initial point in time and final point in
time is then the CIELAB color difference. For the compositions of
the present invention, it is preferable that the clear compositions
have a CIELAB color difference of about 5 or less from initial to
10 days storage at 120.degree. F., more preferably of about 1 or
less and most preferably of about 0.1 or less.
[0188] Percentage haze in the transmission mode measures the amount
of haze, i.e the clarity of the compositions. Preferably, the
compositions of the present invention have a percent haze in the
transmission mode of a Hunter Color analysis of about 90% or less,
more preferably of about 50% or less and most preferably of about
25% or less.
[0189] IV. Optional Ingredients
[0190] (A) Low molecular weight water soluble solvents can also be
used at levels of from 0% to about 12%, preferably from about 1% to
about 10%, more preferably from about 2% to about 8%. The water
soluble solvents cannot provide a clear product at the same low
levels of the principal solvents described hereinbefore but can
provide clear product when the principal solvent is not sufficient
to provide a completely clear product. The presence of these water
soluble solvents is therefore highly desirable. Such solvents
include: ethanol; isopropanol; 1,2-propanediol; 1,3-propanediol;
propylene carbonate; etc. but do not include any of the principal
solvents (B). These water soluble solvents have a greater affinity
for water in the presence of hydrophobic materials like the
softener active than the principal solvents.
[0191] (J) Other Optional Ingredients
[0192] Other optional ingredients useful in compositions of the
present invention include, but are not limited to, dye transfer
inhibiting agents, polymeric dispersing agents, soil release
agents, scum dispersants, suds suppressors, optical brighteners or
other brightening or whitening agents, dye fixing agents, light
fading protection agents, oxygen bleach protection agents, fabric
softening clay, anti-static agents, carriers, hydrotropes,
processing aids, dyes or pigments, bactericides, colorants,
perfumes, preservatives, opacifiers, anti-shrinkage agents,
anti-wrinkle agents, fabric crisping agents, spotting agents,
germicides, fungicides, anti-corrosion agents, and the like.
[0193] Particularly preferred optional 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%.
[0194] Enzymes
[0195] The compositions herein can optionally employ one or more
enzymes such as lipases, proteases, cellulase, amylases and
peroxidases. A preferred enzyme for use herein is a cellulase
enzyme. Indeed, this type of enzyme will further provide a color
care benefit to the treated fabric. Cellulases usable herein
include both bacterial and fungal types, preferably having a pH
optimum between 5 and 9.5. U.S. Pat. No. 4,435,307, Barbesgoard et
al, Mar. 6, 1984, discloses suitable fungal cellulases from
Humicola insolens or Humicola strain DSM1800 or a cellulase
212-producing fungus belonging to the genus Aeromonas, and
cellulase extracted from the hepatopancreas of a marine mollusk,
Dolabella Auricula Solander. Suitable cellulases are also disclosed
in GB-A-2.075.028; GB-A-2.095.275 and DE-OS-2.247.832.
CAREZYME.RTM. and CELLUZYME.RTM. (Novo) are especially useful.
Other suitable cellulases are also disclosed in WO 91/17243 to
Novo, WO 96/34092, WO 96/34945 and EP-A-0,739,982.
[0196] In practical terms for current commercial preparations,
typical amounts are up to about 5 mg by weight, more typically 0.01
mg to 3 mg, of active enzyme per gram of the composition. Stated
otherwise, the compositions herein will typically comprise from
0.001% to 5%, preferably 0.01%-1% by weight of a commercial enzyme
preparation. In the particular cases where activity of the enzyme
preparation can be defined otherwise such as with cellulases,
corresponding activity units are preferred (e.g. CEVU or cellulase
Equivalent Viscosity Units). For instance, the compositions of the
present invention can contain cellulase enzymes at a level
equivalent to an activity from about 0.5 to 1000 CEVU/gram of
composition. Cellulase enzyme preparations used for the purpose of
formulating the compositions of this invention typically have an
activity comprised between 1,000 and 10,000 CEVU/gram in liquid
form, around 1,000 CEVU/gram in solid form.
[0197] The present invention can also include other compatible
ingredients, including those as disclosed in copending applications
Ser. No. 08/372,068, filed Jan. 12, 1995, Rusche, et al.; Ser. No.
08/372,490, filed Jan. 12, 1995, Shaw, et al.; and Ser. No.
08/277,558, filed Jul. 19, 1994, Hartman, et al., incorporated
herein by reference.
Preparation of Principal Solvents
Preparation of Diol Principal Solvents
[0198] Many synthesis methods can be used to prepare the diol
principal solvents of this invention. The appropriate method is
selected for each specific structural requirement of each principal
solvent. Futhermore, most principal solvents can also be prepared
by more than one method. Therefore, the methods cited herein for
each specific principal solvent are for illustrative purposes only
and should not be considered as limiting.
[0199] Method A
[0200] Preparation of 1,5-, 1,6-, and 1,7-Diols
[0201] Method 1
[0202] This synthesis method is a general preparation of
.alpha.,.omega.-type diols derived from substituted cyclic alkenes.
Examples of cyclic alkenes are the alkylated isomers of
cyclopentene, cyclohexene, and cycloheptene. The general formula of
useful alkylated cyclic alkenes is 12
[0203] wherein each R is H, or C.sub.1-C.sub.4-alkyl, and where x
is 3, 4, or 5.
[0204] Cyclic alkenes may be converted to the terminal diols by a
three step reaction sequence.
[0205] Step 1 is the reaction of the cyclic alkene with ozone
(O.sub.3) in a solvent such as anhydrous ethyl acetate to form the
intermediate ozonide. In Step 2 the ozonide is reduced by, e.g.,
palladium catalyst/H.sub.2 to the dialdehyde which is then
converted in Step 3 to the target diol by borohydride
reduction.
[0206] The 1,2-diols are generally prepared by direct hydroxylation
of the appropriate substituted olefins. Example: 13
[0207] wherein each R is H, alkyl, etc.
[0208] In a typical reaction the alkene is reacted with hydrogen
peroxide (30%) and a catalytic amount of osmium tetroxide in
t-butyl alcohol or other suitable solvent. The reaction is cooled
to about 0.degree. C. and allowed to run overnight. Unreacted
compounds and solvent are removed by distillation and the desired
1,2-diol isolated by distillation or crystallization.
[0209] Method 2
[0210] An alternate method is the conversion of the olefin to the
epoxide by the reaction of m-chloroperbenzoic acid, or peracetic
acid, in a solvent such as methylene chloride at temperatures below
about 25.degree. C. The epoxide generated by this chemistry is then
opened to the diol by, e.g., hydrolysis with dilute sulfuric acid.
Step 3 to the target diol by borohydride reduction.
[0211] Method 3
[0212] An alternate method for the preparation of these compounds
is by direct hydroxylation of the cyclic alkene with hydrogen
peroxide and a catalytic amount of osmium tetroxide. The reaction
yields the cyclic diol which is then converted to the open chain
dialdehyde by periodate or lead tetraacetate. The dialdehyde is
then reduced with borohydride as in Method 1, to give the desired
1,5- or 1,6-diols, etc.
[0213] Method B
[0214] Preparation of 1,2 Diols
[0215] Method 1
[0216] Method C
[0217] Preparation of 1,3-Diols
[0218] Acylation of Enamines
[0219] This preparation is for the general type of 1,3-diols and
accommodates a variety of structural features. Enamines are formed
from both ketones and aldehydes which react with acid chlorides to
form the acylated product. The acylated amine derivative is
hydrolyzed back to its acylated carbonyl compound which is the
1,3-dicarbonyl precursor to the desired 1,3-diol. The diol is
generated by borohydride reduction of the 1,3-dicarbonyl
compound.
[0220] Thus acetaldehyde (aldehydes) may be reacted with a
secondary amine, preferably cyclic amines such as pyrrolidine or
morpholine, by heating at reflux in a solvent such as toluene and
with a catalytic amount of p-toluene sulfonic acid. As the amine
reacts (condenses) with the carbonyl compound, water is produced
and is removed, e.g., by reflux through a water trap. After the
theoretical amount of water has been removed, the reaction mixture
is stripped, e.g., under vacuum, to remove the solvent, if desired
(the acylation can be done in the same solvent systems in most
cases).
[0221] The anhydrous crude enamine containing some excess amine is
reacted with the appropriate acid chloride at about 20.degree. C.
to give the acylated enamine. This reaction is usually allowed to
stir overnight at room temperature. The total reaction mixture is
then poured over crushed ice, stirred, and the mixture made acidic
with 20% HCl. This treatment hydrolyzes the enamine to the acylated
dicarbonyl compound. This intermediate is then isolated by
extraction and distillation to remove low boiling impurities, then
reduced by sodium borohydride to the desired 1,3-diol.
[0222] Method D
[0223] Preparation of 1,4 Diols, by Aldol Condensation and
Reduction
[0224] The typical reactions involve one or more aldehydes, one or
more ketones, and mixtures thereof, which have at least one
alpha-hydrogen atom on the carbon atom next to the carbonyl group.
Typical examples of some reactants and some potential final
products are as follows
2
R--CH.sub.2--CHO.fwdarw.HO--CH.sub.2--CH(R)--CHOH--CH.sub.2--R
R--CH.sub.2--CHO+R'--CH.sub.2--CHO.fwdarw.HO--CH.sub.2--CH(R)--CHOH--CH.su-
b.2--R+HO--CH.sub.2--CH(R')--CHOH--CH.sub.2--R'+HO--CH.sub.2--CH(R')--CHOH-
--CH.sub.2--R+HO--CH.sub.2--CH(R)--CHOH--CH.sub.2--R'
R--CH.sub.2--CHO+R'--CO--CH.sub.3.fwdarw.HO--CH.sub.2--CH(R)--CHOH--CH.sub-
.2--R+R--CH.sub.2--CHOH CH.sub.2--CHOH--R'
[0225] The aldehyde, ketone, or mixture thereof which is to be
condensed is placed in an autoclave under an inert atmosphere with
a solvent such as butanol or with a phase transfer medium such as
polyethylene glycol. When a mixed condensation such as with a
ketone and an aldehyde is the target, typically the two reactants
are used in about 1:1 mole ratio. A catalytic amount of strongly
alkaline catalyst such as sodium methoxide is added, typically
about 0.5-10 mole % of the reactants. The autoclave is sealed, and
the mixture is heated at about 35-100.degree. C. until most of the
original reactants have been converted, usually about 5 minutes to
about 3 hours. The crude mixture is neutralized and the carbonyl
functions present are reduced by hydrogenation over Raney Ni at
about 100.degree. C. and about 50 atm for about 1 hour. Volatile
components are removed by distillation and the desired diol
principal solvents are obtained by vacuum distillation.
[0226] More information about this preparation process is disclosed
in Synthesis, (3), 164-5 (1975), A. Pochini and R. Ungaro; PCT Int.
Appl. WO 9,507,254, Kulmala et al, 16 Mar. 1995; Japan Pat. Appl.
No. 40,333, Sato et al, Feb. 9, 1990; Japan Pat. Appl. No. 299,240,
Sato et al, Dec. 4, 1989; Eur. Pat. Appl. No. 367,743, Ankner et
al, May 9, 1990; all of said article and patents being incorporated
herein by reference.
ILLUSTRATIVE EXAMPLES
[0227] Condensation of Butyraldehyde and/or Isobutyraldehyde and
Conversion to Form Eight-Carbon-1,3-Diols
[0228] A portion of n-butanol (about 148 g, about 2 mole, Aldrich)
in a 500 ml, 3-neck, round-bottom flask equipped with a stirring
bar, internal thermometer, condenser, and connection for blanketing
with a nitrogen atmosphere is treated with sodium metal (about 2.3
g, about 0.1 mole, Aldrich) until the sodium has all dissolved.
Then, a mixture of butyraldehyde (about 72 g, about 1 mole,
Aldrich) and isobutyraldehyde (about 72 g, about 1 mole, Aldrich)
is added and the system is held at about 40.degree. C. until most
of the original aldehydes have undergone reaction. The base
catalyst is neutralized by careful addition of sulfuric acid, any
salts are removed by filtration, and the solution is hydrogenated
over Raney Ni at about 100.degree. C. at about 50 atm of pressure
for about 1 hour to yield a mixture of 8-carbon, 1,3-diols. The
butanol solvent and any isobutanol formed during the hydrogenation
are removed by distillation to yield the eight-carbon-1,3-diol
mixture of: 2,2,4-trimethyl-1,3-pentanediol;
2-ethyl-1,3-hexanediol; 2,2-dimethyl-1,3-hexanediol; and
2-ethyl4-methyl-1,3-pentanediol. Optionally, this mixture is
further purified by vacuum distillation, or by decolorization with
activated charcoal. The recovered solvent is used for further
batches of diol production.
[0229] When only butyraldehyde is used in the reaction, the major
product obtained is 2-ethyl-1,3-hexanediol.
[0230] When only isobutyraldehyde is used in the reaction, the
major product obtained is 2,2,4-trimethyl-1,3-pentanediol.
[0231] Mixed Condensation of Butyraldehyde and Methyl Ethyl Ketone
and Conversion to Form a Mixture of Eight-Carbon-1,3-Diols
[0232] Condition A. A portion of n-butanol (about 148 g, about 2
mole, Aldrich) in a 500 ml, 3-neck, round-bottom flask equipped
with a stirring bar, internal thermometer, condenser, and
connection for blanketing with a nitrogen atmosphere is treated
with sodium metal (about 2.3 g, about 0.1 mole, Aldrich) until the
sodium has all dissolved. Then, a mixture of butyraldehyde (about
72 g, about 1 mole, Aldrich) and 2-butanone (about 72 g, about 1
mole, Aldrich) is added and the system is held at about 40.degree.
C. until most of the original butyraldehyde has undergone reaction.
The base catalyst is neutralized by careful addition of sulfuric
acid and any salts are removed by filtration. Optionally, unreacted
starting materials are removed by distillation along with the
reaction solvent. The mixture containing the condensation products
is hydrogenated over Raney Ni at about 100.degree. C. and about 50
atm. for about 1 hour to yield a mixture of 8-carbon-1,3-diols
including 2-ethyl-1,3-hexanediol, 2-ethyl-3-methyl-1,3-pentanediol,
3,5-octanediol; 3-methyl-3,5-heptanediol; and lesser amounts of
other 1,3-diol isomers, e.g., 3-methyl-2,4-heptanediol and
3,4-dimethyl-2,4-hexanediol. The crude diol mixture can be further
purified by fractional distillation.
[0233] Condition B. The above reaction is repeated except that
about 2 moles of butyraldehyde are used for each one mole of
2-butanone. This results in a reaction product with a higher
proportion of diols resulting from self-condensation of the
aldehyde (i.e., 2-ethyl-1,3-hexanediol), and from mixed
condensation of aldehyde and 2-butanone (e.g.,
2-ethyl-3-methyl-1,3-pentanediol and 3,5-octanediol), and a smaller
proportion of those diols resulting from self-condensation of
2-butanone (e.g., 3-methyl-3,5-heptanediol and
3,4-dimethyl-2,4-hexanediol).
[0234] Condition C. The above condensation is repeated except that
about one mole of 2-butanone is placed in the reaction vessel with
the solvent and catalyst and about one mole of butyraldehyde is
gradually added. Conditions are adjusted such that the
self-condensation rate of 2-butanone is slow and the more reactive
carbonyl of the aldehyde reacts promptly upon addition. This
results in a reaction product with a higher proportion of the diols
resulting from the condensation of 2-butanone with butyraldehyde
and from self-condensation of 2-butanone and a smaller proportion
of the diol resulting from self-condensation of butyraldehyde.
[0235] Condition D. The above condensation C. is repeated under low
temperature conditions. About 1.0 mole portion of 2-butanone is
dissolved in about 5 volumes of dry tetrahydrofuran. The solution
is cooled to about -78.degree. C., and about 0.95 mole of potassium
hydride is added in portions. After the hydrogen evolution has
ceased, the solution is held for about one hour to allow for
equilibration to the more stable enolate and then one mole of
n-butyraldehyde is added slowly with good stirring while
maintaining the temperature at about -78.degree. C. After addition
is complete, the solution is allowed to gradually warm to room
temperature and is neutralized by careful addition of sulfuric
acid. Salts are removed by filtration. Optionally, unreacted
starting materials are removed by distillation along with the
reaction solvent. The mixture containing the condensation products
is hydrogenated over Raney Ni at about 100.degree. C. and about 50
atm. for about 1 hour to yield predominantly the diol resulting
from the condensation of the enolate of 2-butanone with
butyraldehyde, 3,5-octanediol. Purification is optionally
accomplished by distillation.
[0236] Mixed Condensation of Isobutyraldehyde and Methyl Ethyl
Ketone and Conversion to Form a Mixture of
Eight-Carbon-1,3-Diols
[0237] The reaction of Condition A above is repeated except that
the butyraldehyde is replaced by isobutyraldehyde. The condensation
and reduction proceed analogously, and the final diol products are
mainly 2,2,4-trimethyl-1,3-pentanediol;
2,2,3-trimethyl-1,3-pentanediol; 2-methyl-3,5-heptanediol; and
3-methyl-3,5-heptanediol.
[0238] Mixed Condensation of Butyraldehyde, Isobutyraldehyde and
Methyl Ethyl Ketone and Conversion to Form a Mixture of
Eight-Carbon-1,3-Diols
[0239] The reaction of Condition A above is repeated, except that
about one mole each of butyraldehyde, isobutyraldehyde, and
2-butanone are used. The condensation and reduction proceed
analogously to yield a mixture of 8-carbon-1,3-diols primarily
consisting of: 2,2,4-trimethyl-1,3-pentanediol;
2-ethyl-1,3-hexanediol; 2,2-dimethyl-1,3-hexanediol;
2-ethyl-4-methyl-1,3-pentanediol; 2-ethyl-3-methyl-1,3-pentanediol;
3,5-octanediol; 2,2,3-trimethyl-1,3-pen- tanediol;
2-methyl-3,5-heptanediol; and 3-methyl-3,5-heptanediol, along with
other minor isomers resulting from condensation on the methylene of
2-butanone instead of the methyl.
[0240] The mixtures prepared by the condensation of butyraldehyde,
isobutyraldehyde, and/or methyl ethyl ketone, preferably have no
more than about 90%, preferably no more than about 80%, more
preferably no more than about 70%, even more preferably no more
than about 60%, and most preferably no more than about 50%, by
weight of any one specific compound. Also, the reaction mixtures
should not contain more than about 95%, preferably no more than
about 90%, more preferably no more than about 85%, and most
preferably no more than about 80%, by weight, of butyraldehyde or
isobutyraldehyde.
[0241] Method E
[0242] Preparation of 1,4 Diols, by the Addition of Acetylide to
Carbonyl Compounds
[0243] Dimetallic acetylides Na.sup.+-:C.ident.C:.sup.31 Na.sup.+
react with aldehydes or ketones to form unsaturated alcohols, e.g.,
14
[0244] The resulting acetylenic diol is then reduced to the alkene
or completely reduced to the saturated diol. The reaction can also
be done by using an about 18% slurry of mono-sodium acetylide with
the carbonyl compound to form the acetylenic alcohol which can be
converted to the sodium salt and reacted with another mole of
carbonyl compound to give the unsaturated 1,4- diol. Where mixed
carbonyl compounds are used with the diacetylides, diol mixtures
will result. Where the mono-acetylide is used, specific structures
can be made in higher yields.
Illustrative Example: Preparation of 6-Methyl-2,5-heptanediol
[0245] A sodium acetylide (about 18% in xylene) slurry is reacted
with isobutryaldehyde to form the acetylenic alcohol
(CH.sub.3).sub.2CH--CHO+NaC.ident.CH.fwdarw.(CH.sub.3).sub.2CH--CHOH--C.id-
ent.C--H
[0246] The acetylenic (ethynyl) alcohol is converted with base to
the sodium acetylide R--CHOH--C.ident.CNa which is then reacted
with a mole of acetaldehyde to give the ethynyl diol
R--CHOH--C.ident.C--CHOH--R'. This compound,
(CH.sub.3).sub.2CH--CHOH--C.ident.C--CHOH--CH3, can be isolated as
the unsaturated diol, if desired, reduced by catalytic
hydrogenation to the corresponding material containing a double
bond in place of the acetylenic bond, or further reduced by
catalytic hydrogenation to the saturated 1,4-diol.
[0247] Method F
[0248] Preparation of Substituted Diols Derived from Cyclic
Anhydrides, Lactones and Esters of Dicarboxylic Acids
[0249] This method of preparation is for the synthesis of diols,
especially several 1,4-diols, which are derived from dicarboxylic
acid anhydrides, diesters and lactones, but not limited to the
1,4-diols or four-carbon diacids.
[0250] These types of diols are generally synthesized by the
reduction of the parent anhydride, lactone or diester with sodium
bis(2-methoxyethoxy)aluminum hydride (Red-Al) as the reducing
agent. This reducing agent is commercially available as a 3.1 molar
solution in toluene and delivers one mole of hydrogen per mole of
reagent. Diesters and cyclic anhydrides require about 3 moles of
Red-Al per mole of substrate. Using an alkyl substituted succinic
anhydride to illustrate this method, the typical reduction is
carried out as follows. 15
[0251] The anhydride is first dissolved in anhydrous toluene and
placed in a reaction vessel equipped with dropping funnel,
mechanical stirrer, thermometer and a reflux condenser connected to
calcium chloride and soda lime tubes to exclude moisture and carbon
dioxide. The reducing agent, in toluene, is placed in the dropping
funnel and is added slowly to the stirred anhydride solution. The
reaction is exothermic and the temperature is allowed to reach
about 80.degree. C. It is maintained at about 80.degree. C. during
the remaining addition time and for about two hours following
addition.
[0252] The reaction mixture is then allowed to cool back to room
temperature. Next, the mixture is added to a stirred aqueous HCl
solution (about 20% concentration) which is cooled in an ice bath,
and the temperature is maintained at about 20 to 30.degree. C.
After acidification the mixture is separated in a separatory funnel
and the organic layer washed with a dilute salt solution until
neutral to pH paper. The neutral diol solution is dried over
anhydrous magnesium sulfate, filtered, then stripped under vacuum
to yield the desired 1,4-diol.
[0253] Method G
[0254] Preparation of Diols with One or Both Alcohol Functions
Being Secondary or Tertiary
[0255] This is a general method to prepare substituted diols from
lactones and/or diesters by alkylation of the carboxyl group(s)
using methyl magnesium bromide (Grignard reagent) or alkyl lithium
compounds usually methyl lithium, e.g., 16
[0256] This type of alkylation can be extended to diesters. An
excess of methylating reagent will generate diols where both
alcohol groups are tertiary.
[0257] Method H
[0258] Preparation of Substituted 1,3- , 1,4- and 1,5-Diols
[0259] This method is a general preparation of some 1,3-, 1,4- and
1,5-diols which utilizes the chemistry outlined in Method A-1 and
Method A-2. The variation here is the use of a cyclic alkadienes in
place of the cycloalkenes described in Methods A. The general
formula for the starting materials is 17
[0260] wherein each R is H, or C.sub.1-C.sub.4-alkyl and wherein x
is 1, 2 or 3.
[0261] The reactions are those of Methods A with the variation of
having one mole of ethylene glycol generated for each mole of the
desired diol principal solvent formed, e.g., the following
preparation of 2,2-dimethyl-1,4-haxanediol from
1-ethyl-5,5-dimethyl-1,3-cyclohexanediol (CAS No. 79419-18-4):
18
Preparation of Polyethoxylated Derivatives
[0262] The polyethoxylated derivatives of diol principal solvents
are typically prepared in a high-pressure reactor under a nitrogen
atmosphere. A suitable amount of ethylene oxide is added to a
mixture of a diol solvent and potassium hydroxide at high
temperature (from about 80.degree. C. to about 170.degree. C.). The
amount of ethylene oxide is calculated relative to the amount of
the diol solvent in order to add the right number of ethylene oxide
groups per molecule of diol. When the reaction is completed, e.g.,
after about 1 hour, residual unreacted ethylene oxide is removed by
vacuum.
Illustrative Example: Preparation of Tetraethoxylated
3,3-Dimethyl-1,2-butanediol
[0263] To a 2-liter Parr reactor that is equipped for temperature
control, is charged with about 354 grams (about 3.0 moles) of
3,3-dimethyl-1,2-butanediol and about 0.54 grams of potassium
hydroxide. The reactor is sparged with nitrogen and evacuated three
times to a pressure of about 30 mm Hg. The reactor is then filled
again with nitrogen to atmospheric pressure, and heated to about
130.degree. C. The pressure of the reactor is then adjusted to
slightly below the atmospheric pressure by applying a slight
vacuum. Ethylene oxide (about 528 grams, about 12.0 moles) is added
over one hour while controlling the temperature to about
130.degree. C. After about an additional one hour reaction time,
the contents are cooled to about 90.degree. C. and a vacuum is
pulled to remove any residual ethylene oxide.
Preparation of Methyl-Capped Polyethoxylated Derivatives
[0264] Methyl-capped polyethoxylated derivatives of diols are
typically prepared either by reacting a methoxypoly(ethoxy)ethyl
chloride (i.e.,
CH.sub.3O--(CH.sub.2CH.sub.2O).sub.n--CH.sub.2CH.sub.2--Cl) of the
desired chain length with the selected diol, or by reacting a
methyl-capped polyethylene glycol (i.e.,
CH.sub.3O--(CH.sub.2CH.sub.2O).s- ub.n--CH.sub.2CH.sub.2--OH) of
the desired chain length with the epoxy precursor of the diol, or a
combination of these methods.
Illustrative Examples: Synthesis of
(CH.sub.3).sub.2C(OH)CH(CH.sub.3)(OCH.- sub.2CH.sub.2).sub.4
OCH.sub.3, the Methyl-Capped Tetraethoxylated Derivative of
2-methyl-2,3-butanediol
[0265] To a 1-liter, three-neck round bottom flask equipped with a
magnetic stirbar, condenser, thermometer, and temperature
controller (Thermowatch I.sup.2R).RTM. is added tetraethylene
glycol methyl ether (about 208 grams, about 1.0 mole) and sodium
metal (Aldrich, about 2.3 grams, about 0.10 mole), and the mixture
is heated to about 100.degree. C. under argon. After the sodium
dissolves, 2-methyl-2,3-epoxybutane (about 86 grams, about 1.0
mole) is added and the solution is stirred overnight under argon at
about 120.degree. C. A .sup.13C-NMR (dmso-d.sub.6) shows that the
reaction is complete by the disappearance of the epoxide peaks. The
reaction mixture is cooled, poured into an equal volume of water,
neutralized with 6 N HCl, saturated with sodium chloride, and
extracted twice with dichloromethane. The combined dichloromethane
layers are dried over sodium sulfate and solvent is stripped to
yield the desired polyether alcohol in crude form. Optionally,
purification is accomplished by fractional vacuum distillation.
[0266] Synthesis of Methoxytriethoxyethyl Chloride
[0267] To a 1-liter, three-neck round bottom flask equipped with a
magnetic stirring bar, condenser, and temperature controller
(Thermowatch, I.sup.2R) is added tetraethylene glycol methyl ether
(about 208 grams, about 1.0 mole ) under argon. Thionyl chloride
(about 256.0 grams, about 2.15 moles) is added dropwise with good
stirring over about 3 hours, keeping the temperature in the
50-60.degree. C. range. The reaction mixture is then heated
overnight at about 55.degree. C. A .sup.13C-NMR (D.sub.2O) is taken
which shows only a small peak at .about.60 ppm for unreacted
alcohol and a sizable peak at .about.43.5 ppm representing
chlorinated product (--CH.sub.2Cl). Saturated sodium chloride
solution is slowly added to the material until the thionyl chloride
is destroyed. The material is taken up in about 300 ml of saturated
sodium chloride solution and extracted with about 500 ml of
methylene chloride. The organic layer is dried and solvent is
stripped on a rotary evaporator to yield crude methoxyethoxyethyl
chloride. Optionally, purification is accomplished by fractional
vacuum distillation.
Synthesis of
C.sub.2H.sub.5CH(OH)CH(CH.sub.3)CH.sub.2(OCH.sub.2CH.sub.2).s-
ub.4OCH.sub.3, the Methyl-Capped Tetraethoxylated Derivative of
2-Methyl-1,3-pentanediol
[0268] The alcohol, C.sub.2H.sub.5CH(OH)CH(CH.sub.3)CH.sub.2OH
(about 116 grams, about 1.0 mole), is placed in a 1-liter,
three-neck round bottom flask equipped with a magnetic stirring
bar, condenser, and temperature controller (Thermowatch.RTM.,
I.sup.2R) along with about 100 ml of tetrahydrofuran as solvent. To
this solution, sodium hydride (about 32 grams, about 1.24 moles) is
added in portions and the system is held at reflux until gas
evolution ceases. Methoxytriethoxyethyl chloride (about 242 grams,
about 1.2 moles, prepared as above) is added and the system is held
at reflux for about 48 hours. The reaction mixture is cooled to
room temperature and water is cautiously added dropwise with
stirring to decompose excess hydride. The tetrahydrofuran is
stripped off on a rotary evaporator. The crude product is dissolved
in about 400 ml of water and enough sodium chloride is dissolved in
the water to bring it nearly to the saturation level. The mixture
is then extracted twice with about 300 ml portions of
dichloromethane. The combined dichloromethane layers are dried over
sodium sulfate and the solvent is then stripped on a rotary
evaporator to yield the crude product. Optionally, purification is
accomplished by further stripping of unreacted starting materials
and low MW by-products by utilizing a kugelrohr apparatus at about
150.degree. C. under vacuum. Optionally, further purification is
accomplished by vacuum distillation to yield the title
polyether.
Preparation of Polypropoxylated Derivatives
[0269] A three neck, round bottom flask is equipped with a magnetic
stir bar, a solid CO.sub.2-cooled condenser, an addition funnel, a
thermometer, and a temperature control device (Therm-O-Watch, I2R).
The system is swept free of air by a stream of nitrogen and then is
equipped for blanketing the reaction mixture with a nitrogen
atmosphere. To the reaction flask is added the dry alcohol or diol
to be propoxylated. About 0.1-5 mole % of sodium metal is added
cautiously to the reaction vessel in portions with heating if
necessary to get all the sodium to react. The reaction mixture is
then heated to about 80-130.degree. C. and propylene oxide
(Aldrich) is added dropwise from the dropping funnel at a rate to
maintain a small amount of reflux from the solid CO.sub.2-cooled
condenser. Addition of propylene oxide is continued until the
desired amount has been added for the target degree of
propoxylation. Heating is continued until all reflux of propylene
oxide ceases and the temperature is maintained for about an
additional hour to ensure complete reaction. The reaction mixture
is then cooled to room temperature and is neutralized by careful
addition of a convenient acid such as methanesulfonic acid. Any
salts are removed by filtration to give the desired propoxylated
product. The average degree of propoxylation is typically confirmed
by integration of the .sup.1H-NMR spectrum.
Preparation of Polybutoxylated Derivatives
[0270] A three neck, round bottom flask is equipped with a magnetic
stir bar, a solid CO.sub.2-cooled condenser, an addition funnel, a
thermometer, and a temperature control device (Therm-O-Watch, I2R).
The system is swept free of air by a stream of nitrogen and then is
equipped for blanketing the reaction mixture with a nitrogen
atmosphere. To the reaction flask is added the dry alcohol or diol
to be butoxylated. About 0.1-5 mole % of sodium metal is added
cautiously to the reaction vessel in portions with heating if
necessary to get all the sodium to react. The reaction mixture is
then heated to about 80-130.degree. C. and .alpha.-butylene oxide
(Aldrich) is added dropwise from the dropping funnel at a rate to
maintain a small amount of reflux from the solid CO.sub.2-cooled
condenser. Addition of butylene oxide is continued until the
desired amount has been added for the target degree of
butoxylation. Heating is continued until all reflux of butylene
oxide ceases and the temperature is maintained for about an
additional one to two hours to ensure complete reaction. The
reaction mixture is then cooled to room temperature and is
neutralized by careful addition of a convenient acid such as
methanesulfonic acid. Any salts are removed by filtration to give
the desired butoxylated product. The average degree of butoxylation
is typically confirmed by integration of the .sup.1H-NMR
spectrum.
Preparation of Polytetramethyleneoxylated Derivatives
[0271] A dry portion of about 0.1 mole of the desired alcohol or
diol starting material is placed in a 3-neck, round bottom flask
equipped with magnetic stirrer, condenser, internal thermometer and
an argon blanketing system. If the desired average degree of
"tetramethyleneoxylation" is about one per hydroxyl group, about
0.11 moles of 2-(4-chlorobutoxy)tetra- hydropyran (ICI) is added
per mole of alcohol function. A solvent is added if necessary such
as dry tetrahydrofuran, dioxane or dimethylformamide. Then sodium
hydride (about 5 mole % excess relative to the chloro compound) is
added in small portions with good stirring while maintaining a
temperature of about 30-120.degree. C. After all the hydride has
reacted, the temperature is maintained until all of the alcohol
groups have been alkylated, usually about 4-24 hours. After the
reaction is complete, it is cooled and the excess hydride is
decomposed by careful addition of methanol in small portions. Then
about an equal volume of water is added and the pH is adjusted to
about 2 with sulfuric acid. After warming to about 40.degree. C.
and holding it there for about 15 minutes to hydrolyze the
tetrahydropyranyl protecting group, the reaction mixture is
neutralized with sodium hydroxide and the solvents are stripped on
a rotary evaporator. The residue is taken up in ether or methylene
chloride and salts are removed by filtration. Stripping yields the
crude tetramethyleneoxylated alcohol or diol. Further purification
may be accomplished by vacuum distillation. If a final average
degree of tetramethyleneoxylation of less than one is desired, a
correspondingly lesser amount of chloro compound and hydride are
used. For average degrees of tetramethyleneoxylation greater than
one, the entire process is repeated in cycles until the buildup
reaches the target level.
Preparation of Alkyl and Aryl Monoglyceryl Ethers
[0272] A convenient method to prepare alkyl and/or aryl
monoglycerol ethers consists of first preparing the corresponding
alkyl glycidyl ether precursor. This is then converted to a ketal,
which is then hydrolyzed to the monoglyceryl ether (diol).
Following is the illustrative example of the preparation of the
preferred n-pentyl monoglycerol ether, (i.e.,
3-(pentyloxy)-1,2-propanediol)
n-C.sub.5H.sub.11--O--CHOH--CH.sub.2OH.
[0273] Preparation of 3-(pentyloxy)-1,2-propanediol
[0274] A 3-neck, 2-liter round bottomed reaction flask (equipped
with overhead stirrer, cold water condenser, mercury thermometer
and addition funnel) are charged with about 546 g of aqueous NaOH
(about 50% concentration) and about 38.5 g of tetrabutylammonium
hydrogen sulfate (PTC, phase transfer catalyst). The content of the
flask is stirred to achieve dissolution and then about 200 g of
1-pentanol is added along with about 400 ml hexanes (a mixture of
isomers, with about 85% n-hexane). Into the addition funnel is
charged about 418 g of epichlorohydrin which is slowly added
(dropwise) to the stirring reaction mix. The temperature gradually
rises to about 68.degree. C. due to the reaction exotherm. The
reaction is allowed to continue for about 1 hr after complete
addition of the epichlorohydrin (no additional heat).
[0275] The crude reaction mix is diluted with about 500 ml of warm
water, stirred gently and then the aqueous layer is settled and
removed. The hexane layer is mixed diluted again with about 1 liter
of warm water and the pH of the mix is adjusted to about 6.5 by the
addition of dilute aqueous sulfuric acid. The water layer is again
separated and discarded and the hexane layer is then washed 3 times
with fresh water. The hexane layer is then separated and evaporated
to dryness via a rotary evaporator to obtain the crude n-pentyl
glycidyl ether.
[0276] Acetonation (Conversion to the Ketal)
[0277] A 3-neck, 2 liter round bottomed flask (equipped with an
overhead stirrer, cold water condenser, mercury thermometer and
addition funnel) is charged with about 1 liter of acetone. To the
acetone is added about 1 ml of SnCl.sub.4 with stirring. Into an
addition funnel positioned over the reaction flask is added about
200 g of the just prepared n-pentyl glycidyl ether. The glycidyl
ether is added very slowly to the stirring acetone solution (the
rate is adjusted to control the exotherm). The reaction is allowed
to proceed for about 1 hr after complete addition of the glycidyl
ether (maximum temperature about 52.degree. C.).
[0278] Hydrolysis
[0279] The apparatus is converted for distillation and a heating
mantle and temperature controller are added. The crude reaction mix
is concentrated via distillation of about 600 ml of acetone. To the
cooled concentrated solution are added about 1 liter of aqueous
sulfuric acid (about 20% concentration) and about 500 ml of
hexanes. The content of the flask is then heated to about
50.degree. C. with stirring (the apparatus is adjusted to collect
and separate the liberated acetone). The hydrolysis reaction is
continued until TLC (Thin Layer Chromatography) analysis confirms
the completion of reaction.
[0280] The crude reaction mix is cooled and the aqueous layer is
separated and discarded. The organic layer is then diluted with
about 1 liter of warm water and the pH is adjusted to about 7 by
the addition of dilute aqueous NaOH (1N). The aqueous layer is
again separated and the organic phase is washed 3 times with fresh
water. The organic phase is then separated and evaporated via a
rotary evaporator. The residue is then diluted with fresh hexanes
and the desired product is extracted into methanol/water solution
(about 70/30 weight ratio). The methanol/water solution is again
evaporated to dryness via a rotary evaporator (with additional
methanol added to facilitate the water evaporation). The residue is
then filtered hot through glass microfiber filter paper to obtain
the n-pentyl monoglycerol ether.
Preparation of Di(Hydroxyalkyl) Ethers
[0281] Synthesis of bis(2-hydroxybutyl) ether
[0282] A 500 ml, three neck, round bottom flask equipped with
magnetic stirrer, internal thermometer, addition funnel, condenser,
argon supply, and heating mantle, is flushed with argon. Then
1,2-butanediol (about 270 g, about 3 moles, Aldrich) is added and
sodium metal (about 1.2 g, about 0.05 moles, Aldrich) is added and
the sodium is allowed to dissolve. Then the reaction mixture is
heated to about 100.degree. C. and epoxybutane (about 71 g. about 1
mole, Aldrich) is added dropwise with stirring. Heating is
continued until the reflux of epoxybutane has ceased and heating is
continued for an additional hour to drive the conversion to
completion. The reaction mixture is neutralized with sulfuric acid,
the salts are removed by filtration, and the liquid is fractionally
distilled under vacuum to recover the excess butanediol. The
desired ether is obtained as a residue. Optionally, it is purified
by further vacuum distillation.
[0283] Synthesis of bis(2-hydroxycyclopentyl) ether
[0284] A 1-liter, three neck, round bottom flask equipped with
magnetic stirrer, internal thermometer, addition funnel, condenser,
argon supply, and heating mantle, is flushed with argon. Then
1,2-cyclopentanediol (about 306 g, about 3 moles, Aldrich) is added
and boron trifluoride diethyl etherate (about 0.14 g, about 0.01
moles, cis-trans isomer mixture, Aldrich) is added. Then the
reaction mixture is held at about 10-40.degree. C. as cyclopentene
oxide (about 84 g. about 1 mole, Aldrich) is added dropwise with
stirring until all the cyclopentene oxide has reacted. The reaction
mixture is neutralized with sodium hydroxide, and the liquid is
fractionally distilled under vacuum to recover the excess
cyclopentanediol. The desired ether is obtained as a residue.
Optionally, it is purified by further vacuum distillation.
[0285] The above disclosed methods are illustrative only, for
purposes of assisting those skilled in the art in the practice of
the invention, and are not limiting.
[0286] All percentages, ratios and proportions herein are by
weight, unless otherwise specified. All documents cited are, in
relevant part, incorporated herein by reference.
[0287] The following are non-limiting examples of the present
invention:
[0288] The following Examples show clear, or translucent, products
with acceptable viscosities.
[0289] The compositions in the Examples below are made by first
preparing an oil seat of DEQA softener active at ambient
temperature. The softener active can be heated to melting at, e.g.,
about 130-150.degree. F. (about 55-66.degree. C.), if the softener
active is not fluid at room temperature. The softener active is
mixed using an IKA RW 25.RTM. mixer for about 2 to about 5 minutes
at about 150 rpm. Separately, an acid/water seat is prepared by
mixing the HCl with deionized (DI) water at ambient temperature.
Chelant is then added to the water seat. If the softener active
and/or the principal solvent(s) 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.degree. F. (about
38.degree. C.) and maintaining said temperature with a water bath.
The principal solvent(s) (melted at suitable temperatures if their
melting points are above room temperature) are added to the
softener premix and said premix is mixed for about 5 minutes. The
acid/water seat is then added to the 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.
[0290] The following are suitable N,N-di(fatty
acyl-oxyethyl)-N,N-dimethyl ammonium chloride fabric softening
actives (DEQA's), with approximate distributions of fatty acyl
groups given, that are used hereinafter for preparing the following
compositions.
15 Fatty Acyl Group DEQA.sup.1 DEQA.sup.2 DEQA.sup.3 DEQA.sup.4
DEQA.sup.5 C12 trace trace 0 0 0 C14 3 3 0 0 0 C16 4 4 5 5 5 C18 0
0 5 6 6 C14:1 3 3 0 0 C16:1 11 7 0 0 3 C18:1 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 up 0 0 2 0 0
Unknowns 0 0 6 6 7 Total 99 99 100 100 102 IV 86-90 88-95 99 100 95
cis/trans 20-30 20-30 4 5 5 TPU 4 9 10 13 13 TPU = Total
polyunsaturated fatty acyl groups, by weight.
[0291]
16 Fatty Acyl Group DEQA.sup.6 DEQA.sup.7 DEQA.sup.8 C14 0 1 0 C16
11 25 5 C18 4 20 14 C14:1 0 0 0 C16:1 1 0 1 C18:1 27 45 74 C18:2 50
6 3 C18:3 7 0 0 Other 0 3 3 Total 100 100 100 IV 125-138 56 Not
Available cis/trans (C18:1) Not Available 7 Not Available TPU 57 6
Not Available
[0292]
17 1 2 3 4 5 6 7 8 Component Wt. % Wt. % Wt. % Wt. % Wt. % Wt. %
Wt. % Wt. % DEQA.sup.1 26.6 43.2 -- 26.6 -- 26.6 26.6 26.6
DEQA.sup.6 -- -- 27.5 -- 27.5 -- -- -- Ethanol 6 10 5.1 6 3.1 6 4 6
2-Ethyl-1,3- 8 -- -- 8 9 8 9 -- hexanediol 1,2-Hexanediol 8 20 16 8
9 8 9 16 DTPA 0.01 0.01 0.1 0.1 2.5 2.5 0.1 0.01 HCl (pH 2-3.5)
0.005 0.005 0.005 0.005 0.005 0.005 0.005 0.005 Perfume -- -- -- --
-- 1.0 -- -- Kathon -- -- 3 ppm 3 ppm -- -- -- -- DI Water Bal.
Bal. Bal. Bal. Bal. Bal. Bal. Bal. DEQA.sup.6
N,N-di(coco-oyl-oxyethyl)-N,N-dimethyl ammonium chloride. ClogP
values of 2-ethyl-1,3-hexanediol and 1,2-hexanediol are 0.60 and
0.53, respectively, and are within the preferred ClogP range. The
above Examples show clear, or translucent, products with acceptable
viscosities.
Example IA
[0293]
18 Comparative Comparative Comparative Comparative Comparative
Comparative 8 8A 8B 8C 8D 8E 8F Component Wt. % Wt. % Wt. % Wt. %
Wt. % Wt. % Wt. % DEQA.sup.1 26.6 26.6 26.6 26.6 26.6 26.6 26.6
1,2-Hexanediol 16 -- -- -- -- -- -- 1,2- -- 16 -- -- -- -- --
Propanediol 1,2-Butanediol -- -- 16 -- -- -- -- 1,2-Pentanediol --
-- -- 16 -- -- -- 1,2- -- -- -- -- 16 -- -- Heptanediol
1,2-Octanediol -- -- -- -- -- 16 -- 1,2-Decanediol -- -- -- -- --
-- 16 Ethanol 6 6 6 6 6 6 6 HCl (pH 2-3.5) 0.005 0.005 0.005 0.005
0.005 0.005 0.005 DI Water Bal. Bal. Bal. Bal. Bal. Bal. Bal.
[0294] All 1,2-alkanediols in Example IA, except 1,2-hexanediol,
have ClogP values outside the effective 0.15 to 0.64 range. Only
the composition of Example 1-8, containing 1,2-hexanediol, is a
clear composition with acceptable viscosities both at room
temperature and at about 40.degree. F. (about 4.degree. C.);
compositions of Comparative Examples I-8A to I-8F are not clear
and/or do not have acceptable viscosities.
Example IB
[0295]
19 Comparative Comparative Comparative Comparative Comparative
Comparative 8 8G 8H 8I 8J 8K 8L Component Wt. % Wt. % Wt. % Wt. %
Wt. % Wt. % Wt. % DEQA.sup.1 26.6 26.6 26.6 26.6 26.6 26.6 26.6
1,2- 16 -- -- -- -- -- -- Hexanediol 1,3- -- 16 -- -- -- -- --
Hexanediol 1,4- -- -- 16 -- -- -- -- Hexanediol 1,5- -- -- -- 16 --
-- -- Hexanediol 1,6- -- -- -- -- 16 -- -- Hexanediol 2,4- -- -- --
-- -- 16 -- Hexanediol 2,5- -- -- -- -- -- -- 16 Hexanediol Ethanol
6 6 6 6 6 6 6 HCl (pH 2-3.5) 0.005 0.005 0.005 0.005 0.005 0.005
0.005 DI Water Bal. Bal. Bal. Bal. Bal. Bal. Bal.
[0296] All hexanediol isomers in Example IB, except 1,2-hexanediol,
have ClogP values outside the effective 0.15 to 0.64 range. Only
the composition of Example 1-8, containing 1,2-hexanediol, is a
clear composition with acceptable viscosities both at room
temperature and at about 40.degree. F. (about 4.degree. C.);
compositions of Comparative Examples I-8G to I-8L are not clear
and/or do not have acceptable viscosities.
Example I-C
[0297]
20 Compar- ative 8 8M 8N 8O 8P 8Q Component Wt. % Wt. % Wt. % Wt. %
Wt. % Wt. % DEQA.sup.1 26.6 26.6 26.6 26.6 26.6 26.6 1,2- 16 9.2 13
9 9 -- Hexanediol 1,2- -- 6.8 2 -- -- 6.8 Pentanediol 1,2- -- -- 1
-- -- 9.2 Octanediol Ethyl lactate -- -- -- 9 -- -- Isopropyl -- --
-- -- 9 -- lactate Ethanol 6 6 6 6 6 6 HCl 0.005 0.005 0.005 0.005
0.005 0.005 (pH 2-3.5) DI Water Bal. Bal. Bal. Bal. Bal. Bal.
[0298] The compositions of Example I-8, I-8M, and I-8N which
contain effective levels of the preferred 1,2-hexanediol principal
solvent are clear compositions with acceptable viscosities both at
room temperature and at about 40.degree. F. (about 4.degree. C.).
The compositions of Example 1-8O and I-8P which contain effective
levels of the preferred 1,2-hexanediol principal solvent are clear
compositions with acceptable viscosities at room temperature, and
are clear at about 40.degree. F. (about 4.degree. C.) with a small
layer which is separated on top, but recover and become clear when
brought back to room temperature. The compositions of Comparative
Examples I-8Q which does not contain an effective amount of the
preferred 1,2-hexanediol is not clear and/or does not have
acceptable viscosities.
Example II
[0299]
21 1 2 3 4 5 6 7 Component Wt. % Wt. % Wt. % Wt. % Wt. % Wt. % Wt.
% DEQA.sup.1 -- 26.6 -- 20.0 20.0 26.6 -- DEQA.sup.6 27.5 -- 27.5
6.8 6.8 -- 27.5 Ethanol 5.1 6 5.1 3.8 -- 4 5.1 Isopropanol -- -- --
-- -- 2 -- 2-Ethyl-1,3-hexanediol -- -- -- 16 18 -- --
1,2-Hexanediol 16 -- -- -- -- 16 -- 2,5-Dimethyl-2,5- -- -- -- --
-- -- 16 hexanediol 2-Methyl,-2-propyl-1,3- -- 16 16 -- -- -- --
propanediol DTPA 0.01 0.05 0.09 0.1 0.01 0.1 0.05 HCl (pH about
2-3.5) 0.005 0.005 0.005 0.005 0.005 0.005 0.005 DI Water Bal. Bal.
Bal. Bal. Bal. Bal. Bal.
Example III
[0300]
22 1 2 3 4 5 6 7 Component Wt. % Wt. % Wt. % Wt. % Wt. % Wt. % Wt.
% DEQA.sup.1 -- 26.6 -- 26.6 26.6 26.6 -- DEQA.sup.2 26 -- 26 -- --
-- 26 Ethanol 5.1 6 5.1 3.8 -- 4 5.1 Isopropanol -- -- -- -- -- 2
-- n-Propanol 18 -- -- -- -- -- -- 2-Butanol -- 16 -- -- -- -- --
2-methyl-1-propanol -- -- 18 -- -- 2 -- 2-methyl-2-propanol -- --
-- 20 -- -- -- 2,3-butanediol, 2,3- -- -- -- -- 18 -- -- dimethyl-
1,2-butanediol, 2,3- -- -- -- -- -- 16 -- dimethyl- 1,2-butanediol,
3,3- -- -- -- -- -- -- 18 dimethyl- DTPA 0.1 0.1 2.5 0.01 0.01 2.5
0.1 CaCl.sub.2 -- 0.25 -- -- -- -- -- HCl (pH about 2-3.5) 0.005
0.005 0.005 0.005 0.005 0.005 0.005 DI Water Bal. Bal. Bal. Bal.
Bal. Bal. Bal.
Example IV
[0301] A clear fabric softener having the following composition was
prepared and measured for clarity. The clarity was measured on a
Hunter Lab ColorQuest Instrument in the total transmission mode
with a 0.25" area view, a 0.25" port size, the UV filter out, no UV
lamp, deionized water as the standard and a 30 mm cell. The
composition had a CIELAB difference from initial to 10 days storage
at 120.degree. F. of 0.04 with DTPA and 20.37 without DTPA. The
percetage haze of the composition in the transmission mode when
DTPA is included is 1.51%.
23 Component Wt. % DEQA 26.00 Ethanol 2.00 Hexylene Glycol 2.00 1,2
Hexanediol 17.00 HCl (1N) 0.25 Kathon (1.5%) 0.02 DTPA 0.01
Deionized Water 52.72
Processing Aspects
[0302] The principal solvents B. and some mixtures of principal
solvents B. and secondary solvents, as disclosed hereinbefore,
allow the preparation of premixes comprising the softener active A.
(from about 55% to about 85%, preferably from about 60% to about
80%, more preferably from about 65% to about 75%, by weight of the
premix); the principal solvent B. (from about 10% to about 30%,
preferably from about 13% to about 25%, more preferably from about
15% to about 20%, by weight of the premix); and optionally, the
water soluble solvent C (from about 5% to about 20%, preferably
from about 5% to about 17%, more preferably from about 5% to about
15%, by weight of the premix). The principal solvents B. can
optionally be replaced by a mixture of an effective amount of
principal solvents B. and some inoperable solvents, as disclosed
hereinbefore. These premixes contain the desired amount of fabric
softening active A. and sufficient principal solvent B., and,
optionally, solvent C., to give the premix the desired viscosity
for the desired temperature range. Typical viscosities suitable for
processing are less than about 1000 cps, preferably less than about
500 cps, more preferably less than about 300 cps. Use of low
temperatures improves safety, by minimizing solvent vaporization,
minimizes the degradation and/or loss of materials such as the
biodegradable fabric softener active, perfumes, etc., and reduces
the need for heating, thus saving on the expenses for processing.
The result is improved environmental impact and safety from the
manufacturing operation.
[0303] Examples of premixes and processes using them include
premixes which typically contain from about 55% to about 85%,
preferably from about 60% to about 80%, more preferably from about
65% to about 75%, of fabric softener active A., as exemplified with
DEQA.sup.1 and DEQA.sup.8 in the Examples hereinafter, mixed with
from about 10% to about 30%, preferably from about 13% to about
25%, more preferably from about 15% to about 20%, of principal
solvent such as 1,2-hexanediol, and from about 5% to about 20%,
preferably from about 5% to about 15%, of water soluble solvent C.
like ethanol and/or isopropanol.
[0304] When the DEQA.sup.1, containing about 13% ethanol, as
disclosed hereinafter, is used as the fabric softening active, and
1,2-hexanediol is used as the principal solvent, the temperatures
at which the premix is clear and/or liquid for various levels of
principal solvent are as follows:
[0305] about 25% 1,2-hexanediol=clear below about -5.degree. C.,
liquid below about -10.degree. C.
[0306] about 17% 1,2-hexanediol=clear down to about 0.degree. C.,
liquid down to about -10.degree. C.
[0307] about 0% 1,2-hexanediol=clear down to about 17.degree. C.,
liquid down to about 0.degree. C.
[0308] These premixes can be used to formulate finished
compositions in processes comprising the steps of:
[0309] 1. Make premix of fabric softening active, e.g., about 72%
DEQA.sup.1 , about 11% ethanol, and about 17% principal solvent,
e.g., 1,2-hexanediol, let cool to ambient temperature.
[0310] 2. Mix perfume in the premix.
[0311] 3. Make up water seat of water, chelant and HCl at ambient
temperature.
[0312] 4. Add premix to water under good agitation.
[0313] 5. Trim with CaCl.sub.2 solution to desired viscosity.
[0314] 6. Add dye solution to get desired colour.
[0315] The fabric softening actives (DEQAs); the principal solvents
B.; and, optionally, the water soluble solvents, can be formulated
as premixes which can be used to prepare the following
compositions.
[0316] For commercial purposes, the above compositions 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 may have a
light blue tint to compensate for any yellow color that is present,
or that may develop during storage. For short times, and perfectly
clear products, clear containers with no tint, or other tints, can
be used. The bottles may also have 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.
* * * * *