Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
CA 02249587 1998-09-21
WO 97/34972 PCT/US97/03374
FABRTC SOFTENING COMPOUND/COMPOSIT10N
S
TECHNICAL FIELD
The present invention relates to fabric softening compounds and/or
compositions
preferably for use in formulating translucent, or, more preferably, clear,
aqueous.
concentrated, liquid softening compositions useful for softening cloth. It
especially
relates to fabric softening compounds and/or compositions suitable for
formulating textile
softening compositions for use in the rinse cycle of a textile laundering
operation to
1 S provide excellent fabric-softening/static-control benefits, the
compositions being
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°C.
BACKGROUND OF THE IIWENTION
The art discloses 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 S% by weight of a short chain organic acid.
The present invention provides fabric softener actives suitable for
formulating
2S e.g., concentrated, preferably clear, preferably aqueous, liquid textile
treatment
compositions, preferably with low organic solvent level (i.e., below about
40%, by weight
of the composition), 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. Said 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. However, in order to
formulate such
compositions, a fabric softener active is required with a relatively fluid
nature. Such
fabric softener actives can be prepared by using highly unsaturated materials,
but there are
3S many problems associated with such materials, including the fact that they
are subject to
chemical instability and normally are not as effective as saturated materials
for softening.
CA 02249587 1998-09-21
WO 97/34972 PCT/US97/03374
2
SUMMARY OF THE INVENTION
Fabric softener actives for use herein are biodegradable, and contain ester
linkages
in the long hydrophobic chains. They contain both branched and unsaturated
acyl chains.
Specifically, the actives preferably have the formulas:
1.
(R)4-m - N(+) - I(CH2)n - Y- R elm X(-)
(1)
wherein each R substituent is hydrogen or a short chain C1-C6, preferably C1-
C3 alkyl or
hydroxyalkyl group, e.g., methyl (most preferred), ethyl, propyi,
hydroxyethyl, and the
like, benzyl, or mixtures thereof; each m is 2 or 3, preferably 2; 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 R1, plus one when Y is -O-{O)C- or -{R)N-
(O)C-
("YR1 sum"), is C6-022, preferably 012-22~ more preferably 014-020,
(hereinafter, R1
and YR1 are used interchangeably to represent the hydrophobic chain, the R1
chain
lengths in general being even numbered for fatty alcohols and odd for fatty
acids), but no
more than one YR1 sum being less than about 12 and then the other R1, or YR1,
sum is at
least about 16, with each R1 comprising a long chain CS-021 (or C6-022),
preferably
C 10-020 {or Cg-C 1 g) branched alkyl or unsaturated alkyl, most preferably C
12-C 1 g (or
C 11-C 17) branched alkyl, or unsaturated alkyl, the ratio of branched alkyl
to unsaturated
alkyl being from about 95:5 to about 5:95, preferably from about 75:25 to
about 25:75,
more preferably from about 50:50 to about 30:70, and for the unsaturated alkyl
group, the
Iodine Value of the parent fatty acid of this R1 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 (As used herein, the "branched alkyl" groups include those that
contain a
substituent that is hydrophobic, even though they are attached to the main
chain by bonds
that are not carbon to carbon, e.g., by oxygen, as in the alkoxy substituents,
and the Iodine
Value of a "parent" fatty acid, or "corresponding" fatty acid, is used to
define a level of
unsaturation for an R1 groups that is the same as the level of unsaturation
that would be
present in a fatty acid containing the same R1 group. When an individual R1 is
both
branched and unsaturated, it is treated as if it is branched.); and wherein
the counterion,
X-, can be any softener-compatible anion, preferably, chloride, bromide,
methyisulfate,
ethylsulfate, sulfate, and/or nitrate, more preferably chloride;
CA 02249587 1998-09-21
WO 97/34972 PCT/US97/03374
3
'. softener having the formula:
~.- YR1
R3 N(+) C~CH
C H2 YR ~
(?)
wherein each Y, R, R1, and X(-) have the same meanings as before (Such
compounds
include those having the formula:
[CH3J3 N(+)[CH2CH(CH20(O)CR1)O(O)CR1J C1(-)
where -O-(O)CR1 is derived partly from unsaturated, e.g., oleic, fatty acid
and,
preferably, each R is a methyl or ethyl group and preferably each R1 is in the
range of
C 15 to C 1 g with degrees of branching and substitution being present in the
alkyl chains
and partly from a branched chain fatty acid like isostearic acid); and
3. mixtures thereof.
The compositions herein preferably comprise:
A. from about 2% to about 80%, preferably from about 13% to about 75%, more
preferably from about 15% to about 70%, and even more preferably from about
19% to
about 65%, by weight of the composition, of biodegradable fabric softener
active selected
from the group consisting of
1. softener active having the formula:
(R)4-m - N(+) - [(CH2)n - Y- R ~Jm X(-)
(1)
wherein each R substituent is hydrogen or a short chain C1-C6, preferably C1-
C3 alkyl or
- hydroxyalkyl group, e.g., methyl (most preferred), ethyl, propyl,
hydroxyethyl, and the
like, benzyl, or mixtures thereof; each m is 2 or 3, preferably 2; 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 R1, plus one when Y is -O-(O)C- or -(R)N-
(O)C-, is
C6-C22, preferably C12-22~ more preferably C14-C20, but no more than one R1,
or YR1,
CA 02249587 1998-09-21
WO 97/34972 PCT/US97/03374
sum being less than about 12 and then the other R l , or YR 1, sum is at least
about 16, with
each R1 being a long chain CS-C21 (or C6-C~~), preferably Cg-C1g (or C1p-
C2p).or .
more preferably C I 1-C I 7, (or C 1 ~-C 1 g) branched alkyl and unsaturated
alkyl (e.g.,
alkenyl, also referred to sometimes as "alkylene", and including
polyunsaturated alkyl),
~ the ratio of branched alkyl to unsaturated alkyl being from about x:95 to
about 9~:5,
preferably from about 75:25 to about 25:7, more preferably from about 50:50 to
about
30:70, and for the unsaturated alkyl group, the Iodine Value of the parent
fatty acid of this
R1 group is preferably from about 20 to about 140, more preferably from about
SO to
about 130; and most preferably from about 70 to about 115; and wherein the
counterion.
X-, can be any softener-compatible anion, preferably, chloride, bromide,
methylsulfate,
ethylsulfate, sulfate, and/or nitrate, more preferably chloride;
2. softener active having the formula:
~.- YR~
R NC+) CH2CH X~-)
~ CH2 YR ~
(2)
wherein each Y, R, R1, and X(-) have the same meanings as before ; and
3. mixtures thereof.
[In one preferred biodegradable quaternary ammonium fabric softening compound,
C(O)R1 is derived partly from unsaturated fatty acid, e.g., oleic acid, and/or
fatty acids
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;
soybean oil; corn oil; tall oil; rice bran oil; etc. and partly from a
branched chain fatty acid
like isostearic acid.] [As used hereinafter, these biodegradable fabric
softener actives
containing ester linkages are referred to as "DEQA", which includes both
diester, triester,
and monoester compounds containing from one to three, preferably two, long
chain
hydrophobic groups. The corresponding amide softener actives and the mixed
ester-
amide softener actives can also contain from one to three, preferably two,
long chain
hydrophobic groups.]
B. optionally, but preferably, the compositions can also contain less than
about 40%,
preferably from about 10% to about 35%, more preferably from about 12% to
about 2~%,
and even more preferably from about 14% to about 20%, by weight of the
composition of
principal solvent having a ClogP of from about 0.15 to about 0.64, preferably
from about
CA 02249587 1998-09-21
WO 97/34972 PCT/US97/03374
0.2~ to about 0.62. and more preferably from about 0.40 to about 0.60, said
principal
solvent preferably containing insufficient amounts of solvents selected from
the group
consisting of: 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-
ethylhexyl-1,3-diol,
5 and mixtures thereof, when used alone, to provide a clear product,
preferably insufficient
to provide a stable product, more preferabty insufficient to provide a
detectable change in
the physical characteristics of the composition, and especially completely
free thereof,
and the principal solvent preferably being selected from the group disclosed
hereinafter;
C. optionally, but preferably, an effective amount, sufficient to improve
clarity, of
low molecular weight water soluble solvents like ethanol, isopropanol,
propylene glycol,
1,3=propanediol, propylene carbonate, etc., said water soluble solvents being
at a level
that will not form clear compositions by themselves;
D. optionally, but preferably, an effective amount to improve clarity, of
water soluble
calcium and/or magnesium salt, preferably chloride; and
E. the balance being water.
Preferably, the compositions herein are aqueous, translucent or clear,
preferably
clear, compositions containing from about 3% to about 95%, preferably from
about 10%
to about 80%, more preferably from about 30% to about 70%, and even more
preferably
from about 40% to about 60%, water and from about 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 SO%, more preferably more than about 60%, and
even more
preferably more than about 75%, of the total organic solvent present.
The compositions can also be prepared as conventional dispersions of the
fabric
softener active containing from about 2% to about 50%, preferably from about
10% to
about 40%, more preferably from about t 5% to about 30%, of the fabric
softener active.
The compositions can also be prepared as solids, either granular, or attached
to substrates,
as disclosed hereinafter.
The pH of the aqueous compositions should be from about 1 to about 7,
preferably
from about 1.5 to about 5, more preferably from about 2 to about 3.5.
CA 02249587 1998-09-21
WO 97/34972 PCT/US97/03374
b
DETAILED DESCRIPTION OF THE INVENTION
I. FABRIC SOFTENING ACTIVE
The present invention relates to fabric softening actives and compositions
containing, as an essential component, from about 2% to about 80%, preferably
from
about 13% to about 75%, more preferably from about 1 S% to about 70%, and even
more
preferably from about 19% to about 65%, by weight of the composition, of said
fabric
softener actives. said fabric softener actives being selected from the
compounds identif ed
hereinafter, and mixtures thereof.
(A) Diester Ouaternarv Ammonium Fabric Softenin Active
Compound (DEOA)
( 1 ) The first type of DEQA preferably comprises, as the principal active,
compounds of the formula
(R)4-m - N(+) - ~(CH2)n - Y- R ~Jm X(-)
(1)
wherein each R substituent is hydrogen or a short chain C 1-C6, preferably C 1-
C3 alkyl or
hydroxyalkyl group, e.g., methyl (most preferred); ethyl, propyl,
hydroxyethyl, and the
like, benzyl, or mixtures thereof; each m is 2 or 3; each n is from 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 R1, plus one when Y is -O-(O)C- or -(R)N-(O)C-, is C6-
C22,
preferably C 12-22~ more preferably C 14-C20, but no more than one R 1, or YR
1, sum
being less than about 12 and then the other R1, or YR1, sum is at least about
16, with
each Rl being a long chain CS-C21 (or C6-C22), preferably Cg-C 1 g (or Cg-
C20), most
preferably C 11-C 17 (or C 12-C 1 g), branched alkyl and unsaturated alkyl
(including
polyunsaturated alkyl), the ratio of branched alkyl to unsaturated alkyl being
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, and for the unsaturated alkyl
group, the
Iodine Value of Rl of the parent fatty acid of this R1 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 11 S; and wherein the counterion, X-, can be any softener-
compatible anion,
preferably, chloride, bromide, methylsulfate, ethylsulfate, sulfate, and/or
nitrate, more
preferably chloride;
2. softener having the formula:
CA 02249587 1998-09-21
WO 97/34972 PCT/US97/03374
- ~ YR~
R3 N(+) CSC'
C H2 YR ~
(2)
wherein each Y, R, R1, and X(-) have the same meanings as before (Such
compounds
include those having the formula:
[CH3)3 N(+)[CH2CH(CH20(O)CR1)O(O)CR1] C1(-)
where -O(O)CR1 is derived partly from unsaturated, e.g., oleic, fatty acid
and, preferably,
each R is a methyl or ethyl group and preferably each R1 is in the range of
C15 to C19
with degrees of branching and substitution being present in the alkyl chains
and partly
from a branched chain fatty acid like isostearic acid); and
3. mixtures thereof.
The counterion, X(-) 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(-) represents half a group.
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)CR1 which is derived from unsaturated, and polyunsaturated, fatty
acids,
e.g., oleic acid, and/or partially hydrogenated fatty acids, derived from
vegetable oils
andlor 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 DEQA1 to DEQAg.
DEQA6 is prepared from a soy bean fatty acid, DEQA~ is prepared from a
slightly
hydrogenated tallow fatty acid, and DEQAg is prepared from slightly
hydrogenated
canola fatty acids.
CA 02249587 1998-09-21
WO 97/34972 PCT/US97/03374
g
DEQAs prepared with Rl groups that contain branched chains, e.g., from
isostearic
acid. for at least part of the R1 groups comprise the other part of the
mixture. It is also
preferred that the fabric softener active itself comprise compounds containing
mixed
branched-chain and unsaturated Rl groups. The total of active represented by
the
branched chain groups is typically from about S% to about 95%. preferably from
about
25% to about 75%, more preferably from about 35% to about 50%.
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 aIcohols 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.
Branched Chain Fatty Acid 1: 2-n-Heptylundecanoic Acid
0
~ v v
2-n-Heptylundecanoic acid [22890-21-7] is available from TCI America, catalog
number I0281. 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~ Alcohols.
Branched Chain Fatty Acid 2: 2-n-Hexyldecanoic Acid
0
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.
Branched Chain Fatty Acid 3: 2-n-Butyloctanoic Acid
0
CA 02249587 1998-09-21
WO 97/34972 PCT/US97/03374
2-n-Butyloctanoic Acid is available from Union Carbide under the trade name
ISOCARB~ 12 Acid. It can be made by oxidizing the Guerbet alcohol 2-
butyloctanol.
- Branched Chain Fatty Acid .1: 5 7 9-Trimethylnonanoic Acid
0
HO
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.
Branched Chain Fatty Acid 5~ Alpha-alkylated Carboxylic Acids
RR'CHC02H
Alpha substituted acids can be prepared by the C-alkyiation of an enamine
which
is derived from a straight chained aidehyde such as octanal or decanal. The
derived
enamine will form the carbanion on the carbon alpha to the terminal nitrogen.
Reaction of
1 S 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 then be oxidized to the corresponding carboxylic
acid.
Aloha-heptvldecanoic acid
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% HCI. 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.
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 (Cr03/H2S04/H20) in acetone;
Cr03-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.
Branched Chain Fatty Acid 6~ 9- and 10-Alkoxvoctadecanoic Acids Other
Positional
Isomers, and the Corresponding Alkoxvoctadecanols.
CA 02249587 1998-09-21
WO 97/34972 PCT/US97/03374
IO
9- and I O-Methoxvoctadecanoic 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 tent-
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.
9- and 10-Isonropoxyoctadecanoic Acids. The same procedure is used except that
2-propanol is substituted for methanol in the bromination step. This yields
the desired S
and 10-isopropoxyoctadecanoic acids.
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.
Corresponding Fattv Alcohols. The substituted octadecanoic acids are reduced
to
the corresponding octadecanols using borane-THF after the method of Brown, J.
Amer.
Chem. Soc. ( I 970), 92, 1637.
Branched Chain Fatty Acid 7: Phenyloctadecanoic Acid. Alkylphenyloctadecanoic
Acid. and the Corre~ondiJ~ Octadecanols.
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 SOC° 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.
Meth~phenyloctadecanoic Acid. The synthesis is repeated but with toluene
instead of benzene to yield the mixed positional isomers of
methylphenyloctadecanoic
acid.
Correspo~ ndinn 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.
Branched Chain Fatty Acid 8: Phenoxvoctadecanoic Acid.
Hvdroxvnhenvloctadecanoic Acid, and the Corresnondin~ Octadecanols
CA 02249587 2001-07-09
Hvdroxvpherivloctadecanoic Acids. The method of Nakano and Foglia described
in The Journal of the American Oil Chemists Society, (1984),61(3), X69-73 is
used.
About 1:x:6 mole ratio of oleic acid, phenol, and methanesulfonic acid are
allowed to
react at about 2~C° 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 posiaonal isomers of hydroxyphenyloctadecanoic acid.
Phenoxvoctadecanoic 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
hydroxyphenytoctadecanoic
acid. A purified mixture of phenoxyoctadecanoic acid positional isomers is
obtained by
chromatography.
Correst~onding Octadecanols. The substituted octadecanoic acids are reduced to
the corresponding octadecanols using borane-TI-iF after the method of Brown,
J. Amer.
Chem. Soc. ( 1970), 92, 1637.
1 S Branched Chain Fatty Acids 9: Iso~earic Acids,
Isostearic acids are produced from the monomeric acids obtained in the
dimerization of unsaturated C 1 g fatty acids, according to U.S. Pat. No.
2,812,342, issued
Nov. 5, 1957 to R. M. Peters.
Suitable branched fabric softening actives which can be mixed with the above
24 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, andlor
the corresponding branched chain fatty alcohols. Similarly, the branched chain
fatty acids
andlor alcohols can be used with unsaturated fatty acids and/or alcohols to
farm suitable
mixed chain actives. Specific examples of DEQAs containing br~aached chains
disclosed
25 hereinafter as DEQA10-DEQA2~ can be blended with unsaturated DEQAs. DEQA10
.
DEQA12 aye prepared from different commercially available isostearic acids.
As dixloxd hereinbefore, other preferred DEQA's are those that are prepared as
a
single DEQA &vm blends of all the different branched and unsaturated fatty
acids that are
represented (total fatty acid blend), rather than from blebs of mixtures of
separate
30 finished DEQA°s that are prepared from different portions of the
total fatty acid blend.
It is prefenrd that at least a substantial percentage of the fatty acyl groups
are
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
35 from about 5% to about 25%, more preferably from about 10% to about 18%.
Both cis
CA 02249587 1998-09-21
WO 97/34972 PCT/I1S97/03374
i~
and traps isomers can be used, preferably with a cis/trans ratio of from 1:1
to about X0:1.
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 RI group
is the same as the percentage of that same R1 group is to the total RI groups
used to form
all of the softener actives.)
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.
The mixed branched-chain and unsaturated materials are easier to formulate
than
conventional saturated straight 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,
chelants, 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.
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:
each Y is -O-(O)C-, or -C(O)-O-, preferably -O-(O)C-;
m is 2 or 3, preferably 2;
each n is 1 to 4, preferably 2;
each R substituent is a C 1-C6 alkyl, preferably a methyl, ethyl, propyl,
benzyl
groups and mixtures thereof, more preferably a C 1-C3 alkyl group;
each Rl, or YR1, is a saturated Cg-C 14~ preferably a C 12-14 hY~ophobic group
comprising 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
CA 02249587 1998-09-21
WO 97/34972 PCT/US97/03374
13
acyl group. R1+l. when Y is -O-(O)C- or -(R)N-(O)C-.) and the counterion, X-,
is
the same as above. Preferably X- does not include phosphate salts.
The saturated Cg-C 1 ~ fatty acyl groups can be pure derivatives, or can be
mixed
chain lengths.
' S Suitable fatty acid sources for said fatty acyl groups are coco, lauric,
caprylic, and
capric acids.
For C I 2-C 14 (or C I I -C 13 ) hYdrocarbyl groups, the groups are preferably
saturated,
e.g., the IV is preferably less than about 10, preferably less than about 5.
It will be understood that the branched RI 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 I groups maintain their basically . hydrophobic character. The
preferred
compounds can be considered to be biodegradable diester variations of hardened
ditailow
dimethyl ammonium chloride (hereinafter referred to as "DTDMAC"), which is a
widely
used fabric softener.
I5 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 YRI 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 YRI
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
I 1: I . The level of monoester present can be controlled in manufacturing the
DEQA.
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(CH2CH20H)2 is esterified at both hydroxyl
groups with an acid chloride of the formula R1C(O)Cl, to form an amine which
can be
made cationic by acidification (one R is H) to be one type of softener, or
then quaternized
with an alkyl halide, RX, to yield the desired reaction product (wherein R and
RI are as
CA 02249587 2001-07-09
defined hereinbefore). However, it will be appreciated by those skilled in the
chemical
arcs that this reaction sequence allows a broad selection of agents to be
prepared,
Yet another t7EQA softener active that is suitable for the forrrtulation of
the fabric
softening actives and concentrated. clear liquid fabric softener compositions
of the present
invention has the above formula ( 1 ) wherein one FL group is a C 1,.4 hy~xy
alkyl group,
preferably one wherein one R group is a hydroxyethyi group.
(2) The second type of DEQA active has the general forrnul$:
1
R3 N(+) C f-I~C~ ~ X(-)
CH2 yR ~
to (Z)
wherein each Y, R, Rl, and X(') have the same meanitegs as ~fQ~. Such
compounds
include those having the formula:
ICH3.]3 ~~)LCH2CH(CH20(O)CR I )O(O~R 1 ] C I (')
where each R is a methyl or ethyl group and preferably each R t is in the
raage of C 1$ to
C 1 g. Degrees of substitution can be present in the alkyl or unsaturated
alkyl chains_ The
anion X(') in the molecule is the same as in DEQA ( 1 ) above. As used herein,
when the
diester is speciSed, it can include the monoester that is present The amount
of moaoeszer
that can be p~seat is the same as in DEQA ( 1 ). An example of a preferred
DEQA of
formula (2) is the "propyl" ester quaternary ammotuum fabric softentr activo
havi~ the
foauuta I,2-di(scyloxy~.3-trimet6ylam~niQprop~ ~oride, whercia the aryl group
is
the saase as dset of DEQAS, exemptifiod hereinatler as DEQA~.
T~ h~ Qf ~ 8~era1 methods of rucking them are disclosed is U. S.
fiat. No. 4, I3'7,1$0, Naik et al., issued ?aa. 30, 1979 ,
In suitable softer actives ( 1 ) and (2), each R1 is a branched alkyl,
monounsatu~pad unsatu~sted alkyl, or polyunsaturated alkyl group: the actives
containing
mixwres of branched alley and . unsaturated alkyl R 1 grog, ~;~y within the
individual molecules, in the ratios disclosed hereinbefore.
~ DEQ~ ~~ can contain a low level of fancy acid, which can be from
'reacted starting m~rial used to form the DEQA and/or as a by-produM of any
pat:ia!
CA 02249587 1998-09-21
WO 97/34972 PCT/US97/03374
~J~
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 ~%. by weight of the softener active.
Ii. OPIONAL BUT PREFERRED PRINCIPAL SOLVENT SYSTEM
The compositions of the present invention preferably 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°F (about
4.4°C) and are able to recover after storage down to about 20°F
(about 6.7°C).
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 S% 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.
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
CA 02249587 2001-07-09
partition coefficients of the principal solvent ingredients of this invention
are
conveniently given in the form of their logarithm to the base I 0. loge.
The loge of rrtany ingredients has been reported; for example, the Pomona92
database, available froth Daylight Chemical Information Systems, Inc.
(Daylight CIS),
Irvine. California. contains many, along with citations to the original
Literature. However,
the lagP values are toast conveniently calculated by the '.C);,p~p» pmg~, also
available from Daylight CIS. This program also lists experiment IogP values
when they
are available in the Polslona92 database. The "calculated loge" (ClogP) is
determined by
~e ~~~t aPp~b of Hansch and Leo (cf., A. Leo, in Comprehensive Medicinal
I0 Chemistry, Vol. 4, C. Hansch, P. G. Sammens, J_ B. Taylor and C. A.
Ramsden, ~~.. p.
295, Pergaman Press, i 990 !. The fragment approach is
based on the chemical structure of each ingredient, and takes into account the
nt,tmbers
and types of atoms, the atom connectivity, and cheruicad bonding. 'these CIogP
vaIu~es,
which are the most reliable and widely used estimates for this physicochemical
property,
acre preferably used instead of the expe:imen~ IogP values in the selection of
the
principal solvent ingredients which are useful in the present invention. Other
methods
chat can be used to compute ClogP include; e.g., Crippen's fragznentacion
method as
disclosed in J. Chew. irtf. Comput_ Sci., 27, 21 ( 1 X87); Viswanadl>en~s
&agmentaiion
method as disclose in J. Cheat. Inf. Cotnput. Sri., 29, 163 ( 1989); arid
8roto's method as
disclosed in Eur. J. Med. Chew - Clzun. Theor., 19, 71 (1984). The principal
solvents
him ~ ~l~ ~'°m ~~ having a ClogP of from about O. I S ro about 0.64,
preferably front about 0.25 to about 0.62, and more preferably from about 0.40
to about
0.60, said pri~ci~ solvent preferably being at Ieast somewhat asyr~~c, and
preferably having a melting, or solidification, point that allows it to be
liquid at. or near
2$ ~ ~. that have a low aaolecular weight and are biodegradable are
~ d~b~e for some ~pOSe~ T~ ire metric solvents appear to be very
~ whaees the highly syaametrical s4lve~ such as I,7 ~di, or I,4~
bis(hyd~Yl) ~~, wlticb have a ~ of ~, to lx unable
to provide the esseatist clear c~pvsitions when used alone, even though their
ClogP
values fall in the preferttd range.
T~ pmt p~n~pal solvents can be ideated by the appearance of the
so#ta~r vesicles, as obecrv~d via ~roge~c e1mipy of tlx compositions that
have been diluted to the ,~o~~on used in the rinse. '>;'h~ dilute compositions
aPP~r to have dispersioaR of fabric soRener that exhibit a mort uailarnellar
appearance
tfaa conve:atioual fabric soRmer compositions. The closer to tint-lamellar thr
CA 02249587 1998-09-21
WO 97/34972 PCT/US97/03374
11
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
S compositions, especially when the perfume is added to the compositions at.
or near, room
temperature.
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.
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;
146452-48-4; 123807-34-1; 123807-33-0; 123807-32-9; and 123807-31-8.
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.
CA 02249587 1998-09-21
WO 97/34972 PCT/US97/03374
l~
TABLE I
MONO-OLS
CAS No.
n propanol 71_3_8
CAS No.
2-butanol 15892-23-6
2-methyl-2-propanol 7~-65-0
Inoperable Isomer
2-methyl-1-propanoT 78-83-1
TABLE II
C6 DIOLS
Operable Isomers CAS No.
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
1,3 pentanediol, 3-methyl- 63521-37-9
2,3 pentanediol. .!-methyl- 7795-79-1
1, 3-hexanediol 617-30-1
3, :t-hexanediol 922-17-8
1,2-butanediol, 2-ethyl- 66553-16-0
1,2-pentanediol, 2-methyl- 20667-OS-4
1,2-pentanediol, 3-methyl- 159623-53-7
1,2-pentanediol, 4-methyl- 72110-08-8
1,Z-heaanediol 6920-22-5
Inoperable Isomers
1,3-propanediol, 2-ethyl-2-methyl-
1,3-propanediol, 2-isopropyl-
1,3-propanediol, 2-propyi-
1,3-butanediol, 2,2-dimethyl-
1,3-butanediol, 2,3-dimethyl-
1,3-butanediol, 2-ethyi-
1,4-butanediol, 2,2-dimethyl-
1,4-butanediol, 2,3-dimethyl-
CA 02249587 1998-09-21
WO 97/34972 PCT/US97/03374
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
CA 02249587 1998-09-21
WO 97/34972 PCT/US97/03374
TABLE III
C7 DIOLS
Operable Isomers CAS No.
1,3-propanediol, 2-butyl- 2612-26-2
1,3-propanediol, 2.2-diethyl- 115-76-4
1,3-propanediol, 2-(1-methylpropyl)-33673-
O 1-7
1,3-propanediol, 2-(2-methylpropyl)-26462-
2 0-8
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-
9 8-4
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-
7 1-8
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-
0 7-9
1,5-heptanediol 60096-09-5
1,6-heptanediol 13175-27-4
CA 02249587 1998-09-21
WO 97/34972 PCT/US97/03374
Preferred Isomers
1.3 propanediol. ~-butyl- 2612-26-2
l , -1-butanediol. 2 propyl- 62946-68-3
l,~ pentanediol. 2-ethyl- 14189-13-0
2. 3 pentanediol, 2, 3-dimethyl-693 I -70-0
2.3 pentanediol. ?.-t-dimethyl- 66225-53-4
2.3 pentanediol. 3.-1-dimethyl- 3716.x-0=t-8
2.3 pentanediol, -!.-l-dimethyl-89851-45-6
I0 3.-l pentanediol, 2.3-dimethyl-Method B
l,6-hexanediol, 2-methyl- 25258-92-8
l,6-hexanediol, 3-methyl- 4089-71-8
1. 3-heptanediol 2343 3-04-7
I , -l-heptanediol 40646-07-9
1, S-heptanediol 60096-09-5
I , 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
I,4-butanediol, 3-ethyl-1-methyl-
1,2-pentanediol, 2,3-dimethyl-
1,2-pentanediol, 2,4-dimethyl-
I,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-
CA 02249587 1998-09-21
WO 97/349?2 PCT/US97/03374
~1..
1,3-pentanediol, 2,4-dimethyl-
1.3-pentanediol. 2-ethyl-
I,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-pentanedioI, 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
CA 02249587 1998-09-21
WO 97/34972 PCT/US97/03374
*** 146432-31-9; 146432-30-8; 146432-49-~: 146432-48-4;
123807-34-l; 123807-33-0: 123807-3?-9: 123807-31-8;
and mirtures thereof.
TABLE IV
OCTANEDIOL ISOMERS
PROPANEDIOL DERIVATIVES
Chemical Name CAS No.
Operable Isomers
1,3-propanediol, 2-(2-methylbutyl)- 87194-40-9
1,3-propanediol, 2-(l,l-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-24765-35-7
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, Z-(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
CA 02249587 1998-09-21
WO 97/34972 PCT/US97/03374
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 S I ,4-butanediol, 2-( 1-methylpropyl)-Method H
1,4-butanediol, 2-ethyl-2,3-dimethyl-Method F
1,4-butanediol, 2-ethyl-3,3-dimethyi-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-(I-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-(l,l-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
l,~-butanediol, 2-ethyl-2,3-dimethyl-Method F
1, ~l-butanediol, 2-ethyl-3, 3-dimethyl-Method F
1, 4-butanediol. 2-(1,1-dimethylethyl)-36976-70-2
l,=f-butanediol, 3-methyl-2-isopropyl-99799-24-3
CA 02249587 1998-09-21
WO 97/34972 PCT/US97/03374
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-tl-imethyl-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
I,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
CA 02249587 1998-09-21
WO 97134972 PCT/US97103374
Preferred Isomers
1.3 pentanediol. 2. 2, 3-trimethyl-3>j 12_3-I-0
1. 3 pentanediol. 2. 2, -l-trimethyl-I -h~-19_-1
1.3 pentanediol, 2.3..1-trimethyl-I 1661-l-13-2
!, 3 pentanediol, 2. -1. -l-trimethyl-I 09387-36-2
l.3 pentanediol, 3..1.-t-trimethyl-81756-.SO-S
1, .1 pentanediol, 2, 2. 3-trimethyl-Method H
l,-I pentanediol, 2,2,,t-trimethyl-80861-10-,t
l,=I pentanediol. Z.3.3-trimethyl-Method F
I , ~1 pentanediol, 2, 3. -1-trimethyl-92310-7.1-.f
I , :f pentanediol, 3, 3. -I-trimethyl-16-166-3~-6
I , S pentanediol, 2. 2, 3-trimethyl-Method A
I , ~ pentanediol, 2. 2, -I-trimethyl-3-16.i-I ~-3
1 S I , 5 pentanediol, 2, 3, Method A
3-trimethyl-
2,:1 pentanediol, 2,3.-l-trimethyl-2-1892-,i1-2
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
I,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-OS-7
CA 02249587 1998-09-21
WO 97/34972 PCT/US97/03374
~1
1,4-pentanediol. 2-ethyl-2-methyl-Method H
I ,-t-pentanediol. 2-ethyl-3-methyl-iVIethod F
1.4-pentanediol. 2-ethyl-4-methyl-Method G
I,4-pentanediol. 3-ethyl-2-methyl-Method F
1,4-pentanediol, 3-ethyl-3-methyl-Method F
I,5-pentanediol, 2-ethyl-2-methyl-Method F
1,~-pentanediol, 2-ethyl-3-methyl-54886-83-8
I,5-pentanediol. 2-ethyl-4-methyl-Method F
I,5-pentanediol, 3-ethyl-3-methyl-57740-
I 2-2
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-I48904-97-6
1,3-pentanediol, 3-ethyl-2-methyl-55661-OS-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
CA 02249587 1998-09-21
WO 97/34972 PCT/US97/03374
1.4-pentanediol. 2-propyl- Method H
1.4-pentanediol. 3-isopropyl- Method H
1.~-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-pentanedioI, 3-isopropyl-
DIMETHYLHEXANEDIOL ISOMERS
Operable Isomers
1,3-hexanediol, 2,2-dimethyl- 22006-96-8
1,3-hexanedioi, 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-hexanedioi, 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-hexanedioi, 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
CA 02249587 1998-09-21
WO 97/34972 PCT/US97/03374
1.5-hexanediol. 2.'_'-dimethyl- iVlethod A
1,5-hexanediol, 2.3-dimethyl- 62718-OS-2
1.5-hexanediol. 2.4-dimethyl- 73455-82-0
1,5-hexanediol. 2.5-dimethyl- 58510-
2 8-4
1,5-hexanediol. 3.3-dimethyl- 41736-99-6
I,5-hexanedioi, 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- 424I2-51-1
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
I,3-heaanediol, 2,2-dimethyl- 22006-96-8
1,3-heaanediol, 2,3-dimethyl- Method D
1,3-he=anediol, 2,4-dimethyl- 78122-99-3
I,3-hexanediol, 2,5-dimethyl-Method C
1,3-heaanediol, 3,4-dimethyl- Method D
1,3-heaanediol, 3,5-dimethyl- Method D
1,3-heaanediol, 4,4-dimethyl- Method C
1,3-hexanediol, 4,5-dimethyl- Method C
1,4-hesanediol, 2,2-dimethyl-Method H
1,4-heaanediol, 2,3-dimethyl- Method F
1,4-hexanediol, 2,4-dimethyl- Method G
1,4-heasnediol, 2,5-dimethyt- 22417-60-3
1,4-hexanediol, 3,3-dimethyl- Method F
CA 02249587 1998-09-21
WO 97/34972 PCT/US97/03374
1,4-hexanediol, 3,4-dimethyi- 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
S 1,5-hexanediol, 2,2-dimethyl- Method A
1,5-hexanediol, 2,3-dimethyl- 62718-OS-2
1,5-hexaaediol, 2,4-dimethyl- 73455-82-0
1,5-hexanediol, 2,5-dimethyl- 58S 10-28-4
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-
I,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,S-dimethyl-
2S I,2-hexanediol, S,S-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, S,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
CA 02249587 1998-09-21
WO 97/34972 PCT/US97/o3374
31
More Preferred Isomers
1,3-hexanediol, 2-ethyl- 94-96-2
1,3-hexanediol, -1-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-ethvl-
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- I094I7-38-1
1,3-heptanediol, 3-methyl- 165326-88-5
1,3-heptanediol, 4-methyl- Method C
1,3-heptanediol, 5-methyl- Method D
I,3-heptanediol, 6-methyl- Method C
1,4-heptanediol, 2-methyl- 15966-03-7
I,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
I,5-heptanediol, 2-methyl- 141605-00-7
1,5-heptanediol, 3-methyl- Method A
I,5-heptanediol, 4-methyl- Method A
1,5-heptanediol, 5-methyl- 99799-26-5
CA 02249587 1998-09-21
WO 97/34972 PCT/US97/03374
1.5-heptanediol. 6-methyl- 57740-00-8
1.6-heptanediol. ?-methyl- 132148-22-2
1,6-heptanediol. 3-methyl- Method G
i,6-heptanediol, 4-methyl- 156307-84-~
1.6-heptanediol, ~-methyl- Method A
1,6-heptanediol, 6-methyl- 5392-
5 7-4
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-
3 8-4
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-heptanediot, 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
CA 02249587 1998-09-21
WO 97/34972 PC"T/US97/03374
1,6-heptanediol, 5-methyl- Method A
1,6-heptanediol, 6-methyl- 5392-~7-4
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-heptaaediol, 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- S I 916-46-2
2,6-heptanediol, 2-methyl- 73304-48-0
2,6-heptanediol, 3-methyl- 29915-96-6
2,6-heptanediol, 4-methyl- 106257-69-b
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
CA 02249587 1998-09-21
WO 97/34972 PCT/US97/03374
More Preferred Isomers
2,.I-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-~5-5
3,6-octanediol 24434-09-1
Inoperable Isomers
1,2-octanediol 1117-86-8
1,3-octanediol 23433-OS-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
TABLE V
NONANEDIOL ISOMERS
Chemical Name CAS No.
Preferred Isomers
2,4-pentanedioi, 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
CA 02249587 1998-09-21
WO 97/34972 PCT/US97/03374
2,4-hexanediol. 2.3,x-trimethyl-, erythro- 26344-20-7
2.4-hexanediol. ?.3.~-trimethyl-, threo- 26343-49-7
1,3-propanediol. 2-butyl-2-ethy (- 115-84-4
2,4-hexanediol, ?.3,~-trimethyl-. threo- 26343-49-7
TABLE 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
More Preferred Monoglvceroi Ethers
and Derivatives CAS No.
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)-
I,2-propanediol, 3-(cyclohexyloxy)-
1,2-propanediol, 3-(1-cyclohex-I-enyloxy)-
1,3-propanediol, 2-(pentyloxy)-
1,3-propanediol, 2-(2-pentyloxy~
1,3-propanediol, 2-(3-pentyloxy)-
1,3-propanediol, 2-(2-methyl-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-(butyloay)-, pentaethoxylated
1,2~propanediol, 3-(butyloxy)-, hexaethoxylated
1,2-propanediol, 3-(butyloay)-, heptaethoxylsted
1,2-propanediol, 3-(butyloryr, octaethoxylated
I,2-propanediol, 3-(butyioxy)-, nonaethoxylated
1,2-propanediol, 3-(butyloxy)-, monopropoxylated
1,2-propanediol, 3-(butyloxy)-, dibutyleneoxylated
1,2-propanediol, 3-(butyloxy)-, tributyleneoxylated
More Preferred Di(hydroxvalhyl) Ethers
bis(2-hydroxybutyl) ether
bis(2-hydroxycyclopentyl) ether
CA 02249587 1998-09-21
WO 97/34972 PCT/US97/03374
Inoperable Monoglvcerol Ethers
1.2-propanedioI, 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-ethylhexyioxy)-
1,2-propanediol, 3-(cyclopentyloxy)-
1,2-propanediol, 3-(1-cyclohex-2-enyloxy)-
1,3-propanediol, 2-(1-cyclohex-2-enyloxy)-
AROMATIC GLYCERYL ETIiERS
Operable Aromatic Glycery! Ethers
1,2-propanediol, 3-phenyloxy-
1,2-propanedioi, 3-benzyloxy-
1,2-propanediol, 3-(2-phenylethyloxy)-
1,2-propanediol, 3-(1-phenyl-2-propanyloxy)-
1,3-propanediol, 2-phenyioxy-
1,3-propanediol, 2-(m-cresyioxy)-
1,3-propanediol, 2-(p-cresyloxy)-
1,3-propanediol, 2-benzyioxy-
1,3-propanediol, 2-(2-phenylethyloxy)-
1,3-propanediol, 2-(I-phenylethyloxy)-
Preferred Aromatic Glyceryl Ethers
1, 2 propanediol, 3 phenyloxy-
1,2 propanediol, 3-benzyloxy-
1,2 propa»ediol, 3-(2 phenylethyloxy)-
1, 3 propanediol, 2-(m-cresyloxy)-
3 5 1, 3 propa»ediol, 2-(p-cresyl oxy)-
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-phenylethylory)-
1,3-propanediol, 2-(m-cresyloxy)-
CA 02249587 1998-09-21
WO 97/34972 PCT/US97/03374
37
1,3-propanediol, 2-(p-cresyloxy)-
I,3-propanediol, 2-(2-phenylethyloxy)-
TABLE VII
ALICYCLIC DIOLS AND DERIVATIVES
Chemical Name CAS No.
Preferred Cylic Diols and Derivatives
IO
1-isopropyl-l, Z-cyclobutanediol 59895-32-8
3-ethyl--~-methyl-l.2-cyclobutanediol
3 propyl-l,2-cyclobutanediol
3-isopropyl-I , 2-cyclobutanediol 42113-90-6
I -ethyl-l, 2-cyclopentanediol 67396-I 7-2
I , 2-dimethyl-1, 2-cyclopentanediol33046-20-7
1, .~-dimethyl-l, 2-cyclopentanediol89794-56-9
2, -l, 5-trimethyl-I , 3-cyclopentanediol
3, 3-dimethyl-1, 2-cyclopentanediol89794-57-0
3,-l-dimethyl-1, 2-cyclopentanediol70051-69-3
3, 5-dimethyl-l, 2-cyclopentanediol89794-58-1
3-ethyl-l, 2-cyclopentanediol
.l. -l-dimethyl-I , 2-cyclopentanediol70197-54-5
4-ethyl-1,2-cyclopentanediol
1,1-bis(hydroxymethyl)cyclohexane2658-60-8
1. 2-bis(hydroxymethyl)cyclohexane76155-27-6
I , 2-dimethyl-1, 3-cyclohexanediol53023-07-7
I , 3-bis(hydroxymethyl)cyclohexane13022-98-5
l, 3-dimethyl-l, 3-cyclohexanediol128749-93-9
1, 6-dimethyl-1, 3-cyclohexanediol164713-I 6-0
1-hydroxy-cyclohexaneethanol 40894-I 7-S
I -hydroxy-cyclohexanemethanol 15753-47-6
3 5 1-ethyl-1, 3-cyclohexanediol 10601-18-0
I -methyl-1, 2-cyclohexanediol 52718-65-7
2, 2-dimethyl-1, 3-cyclohexanediol114693-83-3
2, 3-dimethyl-1, 4-cyclohexanediol70156-82-0
2, 4-dimethyl-1, 3-cyclohexanediol
2, 5-dimethyl-1, 3-cyclohexanediol
2, 6-dimethyl-I , 4-cyclohexanediol34958-42-4
2-ethyl-1, 3-cyclohexanediol 15 ~ 433-88-8
2-hydroxycyclohexaneethanol 2-1682-42-6
Z-hydroxyethyl-l -cyclohexanol
CA 02249587 1998-09-21
WO 97/34972 PCT/US97/03374
3d
2-hydroxvmethylcvclohexanol 89794-
- - 52-S
3-hydroxvethvl-I -cirlohexanol
3-hydroxycyclohexaneethanol 86~ 76-87-6
3-hydroxymethvlcvclohexanol
3-methyl-1.2-cyclohexanediol 23.177-91-0
-l, -l-dimethyl-I , 3-cyclohexanediolI ,203-.i 0-0
4, 5-dimethyl-1, 3-cyclohexanediol
-1. b-dimethyl-l, 3-cyclohexanediol16066-66-3
:l-ethyl-1, 3-cyclohexanediol
-1-hydroxyethyl-I-cyclohexanol
4-hydroxymethylcyclohexanol 33893-85-3
4-methyl-1, 2-cyclohexanediol 23832-27-I
S, ~-dimethyl-1. 3-cyclohexanediol~ 1335-83-2
5-ethyl-I, 3-cyclohexanediol
1, 2-cycl oheptanediol 108268-28-6
2-methyl-I , 3-cycloheptanediol 1013 75-80-8
2-methyl-1, 4-cycloheptanediol
4-methyl-1, 3-cycloheptanediol
5-methyl-l,3-cycloheptanediol
5-methyl-I , -l-cycloheptanediol 90201-OD-6
6-methyl-I , -f-cycloheptanediol
1, 3-cyclooctanediol 101935-36-8
1, 4-cyclooctanediol 73982-04-4
1, ~-cyclooctanediol 23418-82-8
1,2-cyclohexanediol, diethoxylate
1,2-cyclohexanediol, triethoxylate
1,2-cyclohexanediol, tetraethoxylate
1, 2-cyclohexanediol, pentaethoxylate
l,2-cyclohexanediol, hexaethoxylate
1, 2-cyclohexanediol, heptaethoxylate
l, 2-cyclohexanediol, octaethoxylate
1,2-cyclohexanediol, nonaethoxylate
1,2-cyclohexanediol, monopropoxylate
1,2-cyclohexanediol, monobutylenoxylate
1,2-cyclohexanediol, dibutylenoxylate
1,2-cyclohexanediol, tributylenoxylate
CA 02249587 1998-09-21
WO 97/34972 PCT/US97/03374
Chemical Name CAS No.
More Preferred Cvlic 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-b
1-ethyl-1,2-cyclopentanedioi 67396-17-2
I 0 1,2-dimethyl-1,2-cyclopentanediol33046-20-7
1,4-dimethyl-I,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-I,2-cyclopentanediol 89794-58-1
15 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
20 1,2-bis(hydroxymethyl)cyclohexane76155-27-6
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-cycIohexanediol 52718-65-7
25 3-hydroxymethylcyclohexanol
3-methyl-1,2-cyclohexanediol 23477-91-0
4,4-dimethyl-I,3-cyclohexanediol 14203-50-0
4,5-dimethyl-1,3-cyclohexanediol
4,6-dimethyl-1,3-cyclohexanediol 16066-66-3
30 4-ethyl-1,3-cycloheaanediol
4-hydroryethyl-1-cyclohexanol
4-hydrorymethylryclohexanol 33893-85-5
4-methyl-1,2-cycloheaanediol 23832-27-1
3 5 1,2-cycioheptanediol 108268-28-6
1,2-cyclohexanediol, pentaethoxylate
1,2-cycloheaanediol, heaaethoxylate
1,2-cyciohexanediol, heptaethoxylate
40 1,2-cyclohexanediol, octaethoxylate
1,2-cyclohexanediol, nonaethoxylate
1,2-cyclohexanediol, monopropoxylate
1,2-cyclohexanediol, dibutylenoxylate
CA 02249587 1998-09-21
WO 97/34972 PCT/US97/03374
The unsaturated alicyclic diols include the following known unsaturated
alicyclic
diols:
Operable Unsaturated Alicvclic Diols
Chemical Name CAS No.
1.2-Cyclobutanediol.l-ethenyl-2-ethyl- 58016-14-I
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-I,2-diol, 3-butyl- 142543-SS-3
1,2-Cyclopentanediol, 1,2-dimethyl-4-methylene-103150-02-3
1,2-Cyciopentanediol, I-ethyl-3-methylene- 90314-52-6
1,2-Cyclopentanediol, 4-(1-propenyl) 128I73-45-5
3-Cyclopentene-1,2-diol, 1-ethyl-3-methyl- 903I4-43-5
1,2-Cyclohexanediol, 1-ethenyl- 134134-16-0
1,2-Cyclohexanediol, I-methyl-3-methylene-98204-78-S
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-I,2-diol 124791-61-3
5-Cyclooctene-1,2-diol 117468-07-2
Inoperable Unsaturated C~rclic Diols
1,2-Cyclopentanediol, I-(1-methylethenyl)- 61447-83-4
1,2-PropanedioI, 1-cyclopentyl- 55383-20-5
1,3-Cyclopentanediol, 2-(1-methylethylidene)- 65651-46-9
1,3-Propanediol, 2-(1-cycIopenten-1-yl)- 77192-43-9
1,3-Propanediol, 2-(2-cyclopenten-1-yl)- 25462-31-1
1,2-Ethanediol, 1-(1-cyclohexen-I-yl)- 151674-61-2
1,2-Ethanediol, 1-(3-cyclohexen-I-yl) 64011-53-6
2-Cyclohexene-1,4-diol, 5,5-dimethyl- 147274-SS-3
4-Cyclohexene-1,3-diol, 3,6-dimethyl- 127716-90-9
CA 02249587 1998-09-21
WO 97/34972 PCT/US97/03374
1.3-Cycloheptanediol. 2-methylene- 132292-67-2
5-Cyc loheptene- I .3-diol. 1-methyl- 160813-33-2
5-Cycloheptene-1.3-diol, ~-methyl- 160813-32-1
2-Cyclooctene-1,4-diol 3 7996-40-0
TABLE VIII
C3C~DIOL ALKOXYLATED DERIVATIVES
In the following tables, "EO" means polyethoxylates, i.e., -(CH2CH20)nH; Me-
En means methyl-capped polyethoxylates -(CH2CH20)nCH3 ; "2(Me-En)" means 2 Me-
En groups needed; "PO" means polypropoxylates, -(CH(CH3)CH20)nH ; "BO" means
polybutyleneoxy groups, (CH(CH2CH3)CH20)nH ; and "n-BO" means poly(n-
butyleneoxy) or poly(tetramethylene)oxy groups -(CH2CH2CH2CH20)nH. The
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.
TABLE VIVA
Base
Material
Base Materisl(a)CAS No. EO's l(Me-En)2(Me-En)PO's n-BO'sBO's
(d) (~) (d) (e) (0
1,2-propanediot57-55-6 1_4
(C3)
3-4 4
1,2-propanediol,558-43-0 4-10 l
2-methyl- (C4) 8-10 1 3
1,3-propanediol(C3)504-63-2 6-8 5-6
8 6
1,3-propanediol,115-76-41-7 1-2
2,2-diethyl- 7 1 2
(C7)
1,3-propanediol,l26-30-7 3~
2,2-dimethyl- ~ 1-2 4
(CS)
1,3-propanediol,33673-O1-71-7 I-2
2-(1-
methylpropyl~ 4-7 1 2
(C7)
1,3-propanediol,26462-20-81-7 1-2
2-(2-
methylpropyl~ 4-7 1 2
(C7)
I,3-propanediol,2612-29-5 6-l0
2-ethyl- {CS) 9-10 1 3
1,3-propanediol,2-77-84-9 1-6
ethyl-2-methyl- 3-6 2 1
(C6)
1,3-propanediol,2612-27-3 1-6
2-isopropyl- 3-6 2 1
(C6)
CA 02249587 1998-09-21
WO 97/34972 PCT/US97/03374
~z
1.3-propanediol,2163-42-0 ~_; ;t-~
2-methyl- (C4) 4-5 5 2
1.3-propanedioi.2-2109-23-12-9 1-~
methyl-2-isopropyl- 6-9 I 2-3
(C7)
1,3-propanediol,2-78-26-2 1-7
methyl-2-propyl- 4-7 I 2
(C7)
I ,3-propanediol,26 t
2-28-4 1
2_propyl- (C6) I-4 2
,_, -,-.,_,__~.,.
i am mumvm m muma~cu dllCUXylaieCl groups In tnls and tolloW ng 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~CH20) groups in the
polyethoxylated derivative.
(c) The numbers in this column are average numbers of (CH2CH20) groups in the
one
methyl-capped polyethoxylate substituant in each derivative.
(d) The numbers in this column are average numbers of (CH2CH20) groups in each
of
the two methyl-capped polyethoxylate substituants in each derivative.
(e) The numbers in this column are average numbers of (CH{CH3)CH20) groups in
the
polypropoxylated derivative.
(f) The numbers in this column are average numbers of (CH2CH2CH2CH20) groups
in
the polytetramethyleneoxylated derivative.
(g) The numbers in this column are average numbers of (CH(CH2CH3)CH20) groups
in
the polybutoxylated derivative.
TABLE VIIIB
Base
Material
Base Material(a)CAS No. EO's I(Me-En)2(Me-En)PO's n-BO'sBO's
(b) (e) (d) (e) ~~ (8)
1,2-butanediol(C4)584-03-2 2-8
6-8 2-3 I
1,2-butanediol,66553-IS-91-6 1-2
2,3-dimethyl- 2-5 I
(C6)
I,2-butanediol,66553-16-0
2-ethyl- (C6) I-3 I
1,2-butanediol,41051-72-3
2-methyl- (CS) I-2 1
1,2-butanediol,59562-82-21-6 1-2
3,3-dimethyl- 2-5 I
(C6)
1,2-butanediol,50468-22-9
3-methyl- (CS) I-2 1
1,3-butanediol107-88-0 3-6 5
(C4)
5-6 2
CA 02249587 1998-09-21
WO 97/34972 PCT/US97/03374
1,3-butanediol.163~t3-7~-?
2,
2.3-trimethvl- I-3
(C7)
1,3-butanediol.2,76-;~-7 3_g
2-dimethyl- ~g
(C6)
1,3-butanediol,24893-3~--I 3-g
2,3-dimethyl- ~g
(C6) -
1.3-butanediol,66553-i7-1 1-6
2-ethyl- (C6) 4-6 2 I
to
3
1,3-butanediol,Method 2-4
2- C
ethyl-2-methyl- 1 1 3
(C7)
1,3-butanediol,68799-03-I 2-4
2-
ethyl-3-methyl- I 1 I
(C7) 3
1,3-butanediot,66567-04-2 2-4
2-isopropyl- 1 1 3
(C7)
1,3-butanediol,684-84-4 1-3
2-methyl- (CS) 2-3 4
1,3-butanediol,66567-03-12-9 1-3
2-propy!- (C7) 6-8 1 2-3
1,3-butanediol,2568-33-4 1-3
3-methyl- (CS) 2-3 4
1,4-butanedioi(C4)I10-63-4 2-4 4-5 2
3-4 4-5
1,4-butanediol,162108-60-32-9 1-3
2,
2,3-trimethvl- 6-9 I 2-3
(C7)
l,4-butanediol,32812-23-0 I-6
2,2-dimeihyl- 3-6 2 1
(C6)
1,4-butanediol,57716-80-0 I-6
2,3-dimethyl- 3-6 2 1
(C6)
l,4-butanediol,57716-79-7 I
2-ethyl- (C6) 1_4
1,4-butanediol,76651-98-41-7 1-2
2-
ethyl-2-methyl- 4-7 1 2
(C7)
l,4-butanediol,66225-34-1I-7 1-2
2-
ethyl-3-methyl- 4-7 1 2
(C7)
1,4-butanediol,39497-66-0I-7 I-2
2-isopropyl- 4-7 1 2
(C7)
l,4-butanediol,2938-98-9 6-10 I
2-methyl- (CS) 9-10 1 3
1,4-butanediol,62946-68-31-5 1-2
2-propyl- (C7) 2-g 1
1,4-butanediol,Method 2-9 I-3
3- F
ethyl-I-methyl- 6-8 1 2-3
(C7)
2,3-butanediol513-85-9 6-10 l
(C4)
9-10 I 3-4
2,3-butanediol,76-09-5 3-9 1-3
2,3-dimethyl- 7-9 1 2-3
(C6)
CA 02249587 1998-09-21
WO 97/34972 PCT/US97/03374
44
2.3-butanediol, 5396-.i8-7 ~-5
2-methv(- (CS) 2-5 2 1
(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 (CH2CH~0) groups in the
polyethoxylated derivative. "
(c) The numbers in this column are average numbers of (CH~CH~O) groups in the
one
methyl-capped polyethoxylate substituant in each derivative.
(d) The numbers in this column are average numbers of (CH2CH20) groups in each
of
the two methyl-capped polyethoxylate substituants in each derivative.
(e) The numbers in this column are average numbers of (CH(CH3)CH~O) groups in
the
polypropoxylated derivative.
(fJ The numbers in this column are average numbers of (CH2CH2CH2CH20) groups
in
the polytetramethyleneoxylated derivative.
(g) The numbers in this column are average numbers of (CH(CH~CH3)CH~O) groups
in
the polybutoxylated derivative.
TABLE VIIIC
Base
Material
Base Material(a)CAS No. EO's 1(Me-En)2(Me-En)PO's n-BO'sBO's
(b) (~) (d) (e) (~ (a)
1,2-pentanediol5343-92-0 3-10 2-3
(CS) 7-10 1 3
1,2-pentanediol,20667-OS-4
2-methyl- 1-3 1
(C6)
1,2-pentanediol,159623-53-7
3-methyl- 1-3 1
(C6)
1,2-pentanediol,72110-08-8
4-methyl-
(C6)
1,3-pentanediol3174-67-2
(CS) 1-2 3-4
1,3-pentanediol,2157-31-5 2-4
2,2-dimethyl- 1 1 3
(C7)
1,3-pentanediol,66225-52-3 2-4
2,3-dimethyl- 1 1 3
(C7)
1,3-pentanediol,60712-38-1 2-4
2,4-dimethyl- 1 1 3
(C7)
1,3-pentanediol,29887-11-42-9 I-3
2-ethyl- (C7) 6-8 1 2-3
1,3-pentanediol,149-31-S I-6 1
2-methyl- 4-6 2-3
(C6)
1,3-pentanediol,129851-50-9 2-4
3,4-dimethyl- 1 1 3
(C7)
CA 02249587 1998-09-21
WO 97/34972 PCT/US97/03374
1:3-pentanediol,33879-72-0 1-6 1
3-methyl- 4-6 2-3
(C6)
1.3-pentanediol.3048-l6-3 2-4
4..~-dimethvl- 1 1 3
(C7)
l.3-pentanediol,X4876-99-2 I_6 l
4-methyl- 4-6 2-3
(C6)
1,4-pentanediol626-95-9
(CS) 1-2 3-4
1,4-pentanediol,Method 2-4
F
2.2-dimethyl- 1 1 3
(C7)
1,4-pentanediol,Method 2-4
F
2.3-dimethyl- 1 1 3
(C7)
1,4-pentanediol,Method _ 2-4
F
2,4-dimethyl- 1 1 3
(C7)
1.4-pentanediol,6287- l7-8 i _6 1
2-methyl- 4-6 Z-3
(C6)
i,4-pentanediol,81887-62-9 2-4
3.3-dimethyl- 1 1 3
(C7)
1,4-pentanediol,63521-36-8 2-4
3,4-dimethyl- 1 1 3
(C7)
1,4-pentanediol,26787-63-3 I-6 1
3-methyl- 4-6 2-3
(C6)
1,4-pentanediol,1462-10-8 1-6 1
4-methyl- 4-6 2-3
(C6)
1,5-pentanediol111-29-5 4-10
(CS) 8-10 1 3
1,5-pentanediol,3121-82-2 I-7 i-2
2,2-dimethyl- 4-7 1 2
(C7)
1,5-pentanediol,81554-20-3i-7 1-2
2,3-dimethyl- 4-7 1 2
(C7}
1,5-pentanediol,2121-69-9 I-7 1-2
2,4-dimethyl- 4-7 1 2
(C7)
1,5-pentanediol,14189-13-01-5 1-2
2-ethyl- (C7) 2-g 1
1,5-pentanediol,42856-62-2
2-methyl- 1-4 2
(C6}
1,5-pentanediol,53120-74-41-7 I-2
3.3-dimethyl- 4-7 1 2
(C7)
1,5-pentanediol,4457-71-0
3-methyl- 1-4
(C6)
2,3-pentanediol42027-23-6
(CS) 1_3 2
2,3-pentanediol,7795-80-4 I-7 1-2
2-methyl- 4-7 1 2
(C6)
2,3-pentanediol,63521-37-91-7 I-2
3-methyl- 4-7 1 2
(C6)
CA 02249587 1998-09-21
WO 97/34972 PCT/US97/03374
~ib
2.3-pentanediol,7795-79-11-7 1-2
4-methyl- (C6) .i-7 1 2
2.4-pentanediol625-69-4 1_.~
(CS) 2-4 4
2,4-pentanediol,24893-39-8 1-4
2,3-dimethyl- 2-4 2
(C7)
2,4-pentanediol,24892-49-7 1-4
2,4-dimethvl- 2-4 2
(C7)
2,4-pentanediol,107-41-5 5-10
2-methyl- (C6) g_lp 3
2,4-pentanediol,24892-50-0 1-4
3.3-dimethyl- 2-4 2
(C7)
2,4-pentanediol,Method 5-10
H
3-methyl- (C6) g_lp 3
(a) The numb ' d' d
f lk
er o tn tcate a oxylated groups tn thts 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 (CH2CH20) groups in the
S polyethoxylated derivative.
(c) The numbers in this column are average numbers of (CH2CH20) groups in the
one
methyl-capped polyethoxylate substituant in each derivative.
(d) The numbers in this column are average numbers of (CH2CH20) groups in each
of
the two methyl-capped polyethoxylate substituants in each derivative.
(e) The numbers in this column are average numbers of (CH(CH3)CH~O) groups in
the
polypropoxylated derivative.
(fj The numbers in this column are average numbers of (CH2CH2CH2CH20) groups
in
the polytetramethyleneoxylated derivative.
(g) The numbers in this column are average numbers of (CH(CH~CH3)CH20) groups
in
the polybutoxylated derivative.
TABLE VIIID
B~e
Material
Base Material(a) CAS No. EO's 1(Me-En)PO's n-BO'sBO's
- (b) (c) (e) (
1,3-hexanediol (C6) 21531-91-9 1-5
2-5 2 1
1,3-hexanediol, 2-methyl-66072-21-72-9 1-3 1
(C7) 6-8 1 2-3
1,3-hexanediol, 3-methyl-Method 2-9 1-3
D
(C7) b-8 1 2-3
1,3-hexanediol, 4-methyl-Method 2-9 1-3
C
(C7) 6-8 1 2-3
1,3-hexanediol, 5-methyl-109863-14-12-9 1-3
(C7) 6-8 1 2-3
CA 02249587 1998-09-21
WO 97/34972 PCT/US97/03374
1.-l-hexanedioi 16-13?_53_-l
(C6)
2-5 2
I .-l-heranediol. Method 2-9 I _3
?-methyl- F
(C7 ) 6-8 1 2-3
1,4-heYanediol, 6622-36-3 2-9 I-3
3-methyl-
(C7) 6-8 1 2-3
1.4-hexanediol.4-methyl-40646-OS-02-9 1-3
(C7) 6-8 1 2-3
I.-1-hexanediol, 38624-36-12-9 1-3
5-methyl-
(C7) 6-8 1 2-3
1,5-hexanediol (C6)928-~0-~ 1-S
2-5 2
1,5-hexanediol, Method 2-9 1_3
2-methyl- F
(C7) 6-8 1 2-3
1,5-hexanediol, Method 2-9 1-3
3-methyl- F'
(C7) 6-8 1 2-3
I,5-hexanediol, 66225-37-42-9 1-3
4-methyl-
(C7) 6-8 1 2-3
I,5-hexanediol, 1462-11-9 2-9 I-3
S-methyl-
(C7) 6-8 1 Z-3
1,6-hexanediol(C6) 629-I1-8
1-2 1-2 4
1,6-hexanediol, 25258-92-81-S 1-2
2-methyl-
(C7)
2-5
1,6-hexanediol, 4089-71-8 I-5 1-2
3-methyl-
(C7) 2-5 1
2,3-hexanediol (C6)617-30-1 1-S 1-2
2-5
2,4-hexanediol(C6) 19780-90-6 3-g
5-8 3
2,4-hexanediol, 66225-35-2
2-methyl-
(C7) 1-1 1-2
2,4-hexanediol, 116530-79-1
3-methyl-
(C7) 1-2 1-2
2,4-hexanediol, 38836-25-8
4-methyl-
(C7) 1-2 1-2
2,4-hexanediol, 54877-00-8
5-methyl-
(C7) 1-2 1-2
2,5-hexanediol (C6)2935-44-6 3-g
5-8 3
2,5-hexanediol, 29044-06-2
2-methyl-
(C7) 1-2 1-2
2,5-hexanediol, Method
3-methyl- H
(C7) 1-2 1-2
3,4-hexanediol (C6)922-17-8 I-5
2-5
CA 02249587 1998-09-21
WO 97/34972 PCT/US97/03374
N$
(a) The number of indicated alkotylated 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~_CH~O) groups in the
polyethoxylated derivative. '
(c) The numbers in this column are average numbers of (CH2CH20) groups in the
one
methyl-capped polyethoxylate substituant in each derivative.
(e) The numbers in this column are average numbers of (CH(CH3)CH20) groups in
the
polypropoxylated derivative.
(f) The numbers in this column are average numbers of (CH2CH2CH2CH~0) groups
in
the polytetramethyleneoxylated derivative. '
(g) The numbers in this column are average numbers of (CH(CH2CH3)CH20) groups
in
the polybutoxylated derivative.
15, TABLE VIIIE
Base
Material
Base Material(a) CAS No. EO's I(Me-En)PO'sn-BO's
(b) (c) (e)
1,3-heptanediol 23433-04-71-7 1-2
(C7)
3-6 I 2
1,4-heptanediol 40646-07-91-7 I-2
{C7)
3-6 1 2
I,5-heptanediol 60096-09-51-7 I-2
(C7)
3-6 I 2
1,6-heptanediot 13175-27-4I-7 I-2
(C7)
3-6 I 2
1,7-heptanediol 629-30-I
(C7)
1-2 I
2,4-heptanediol(C7)20748-86-I3-10
7-10 1 I 3
2,5-heptanediol(C7)70444-25-63-10
7-10 1 I 3
2,6-heptanediol 5969-12-03-10
(C7)
7-10 1 I 3
3,5-heptanediol(C7)86632-40-83-10
7-IO 1 1 3
(a) The number of groups le, the
indicated alkoxylated in generic
this
Table
are
ail
operab
limits being listed ose pe and
on the f rst line, that listed
and th are
preferred
are
in
bold
ty
on the second line.
(b) The numbers in this column are average numbers of (CH2CH20) groups in the
polyethoxylated derivative.
(c) The numbers in this column are average numbers of (CH2CH20) groups in the
one
methyl-capped polyethoxylate substituant in each derivative.
CA 02249587 1998-09-21
WO 97/34972 PCT/US97/03374
NR
(e) The numbers in this column are average numbers of (CH(CH~)CH~O) groups in
the
polypropoxylated derivative.
(~ The numbers in this column are average numbers of (CH2CH2CH2CH20) groups in
the polytetramethyleneoxylated derivative.
Table IX
AROMATIC DIOLS
Suitable aromatic diols include:
Chemical Name CAS No.
Operable Aromatic Diols
1-phenyl-1,2-ethanedioi 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-S
1-(3-methylphenyl)-1,3-propanediol 51699-43-S
1-(4-methylphenyl~-1,3-propanediol 159266-06-5
2-methyl-1-phenyl-1,3-propanediol139068-60-3
1-phenyl-1,3-butanediol 118100-60-0
3-phenyl-1,3-butanediol 68330-54-1
1-phenyl-1.4-butanediol 13 6173-88-1
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-l,2 propanediol 1855-09-0
2 phenyl-1,2 propanediol 87760-50-7
3 pherryl-1,2 propanediol 17131-14-S
1-(3-methylpherryl)-1,3 propanediol 51699-43-5
I -(4-methylpherryl)-1, 3 propanediol159266-06-S
2-methyl-I phenyl-1,3 propanediol139068-60-3
1 phenyl-1,3-butanediol 118100-60-0
3 phenyl-1,3-butanediol 68330-54-1
1 phenyl-1,~-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
CA 02249587 1998-09-21
WO 97/34972 PCT/US97/03374
1-(3-methylphenyl)-1,3-propanediol 51699-43-S
1-(-1-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
S 1-phenyl-1,.I-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 I 57008-SS-4
3-phenyl-1,2-butanediol 141505-72-8
4-phenyl-1,2-butanediol 14361 S-31-0
1S 2-phenyl-I,3-butanediol 103941-94-2
4-phenyl-1,3-butanedioi 81096-91-~
2-phenyl-2,3-butanediol 138432-94-7
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
CH2 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:
2S TABLE X
EXAMPLES OF UNSATURATED COMPOUNDS
Operable Unsaturated Diols
I,3-Propanediol, 2,2-di-2-propenyl- 55038-13-6
1,3-Propanediol, 2-(I-pentenyl)- 138436-i8-7
1,3-Propanediol, 2-(2-methyl-2-propenyl)-2-(2-propenyl)-121887-76-1
1,3-Propanediol, 2-(3-methyl-1-butenyl)- 138.436-17-6
1,3-Propanediol, 2-(4-pentenyl)- 73012-46-1
1,3-Propanediol, 2-ethyl-2-(2-methyl-2-propenyl)-91367-61-2
3S 1,3-Propanediol, 2-ethyl-2-(2-propenyl)- 27606-26-4
1,3-Propanediol, 2-methyl-2-(3-methyl-3-butenyl)-132130-9S-1
1,3-Butanediol, 2.2-diallyl- 103985-49-S
1,3-Butanediol, 2-(1-ethyl-I-propenyl)- 116103-35-b
1,3-Butanediol, 2-(2-butenyl)-2-methyl- 92207-83-~
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-(.I-methyl-2-propenyl)-I4158S-58-2
CA 02249587 1998-09-21
WO 97/34972 PCT/US97/03374
5)
1.4-Butanediol, ?.3-bis(1-methylethylidene)-5217-63-6
1.4-Butanediol. ?-(3-methyl-2-butenyl)-3-methylene-115895-78-8
2-Butene-1.4-diol. 2-( 1,1-dimethylpropyl)-911 ~4-O 1-7
2-Butene-1.4-diol. 2-( 1-methylpropyl)- 911 ~4-00-6
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-
4 4-2
1.5-Pentanediol, 2-(2-propenyl)- 134757-O1-0
1,5-Pentanediol, 2-ethylidene-3-methyl- 42178-93-8
1,5-Pentanedioh 2-propylidene- 58203-50-2
2,4-Pentanediol. 3-ethylidene-2,4-dimethyl-88610-19-9
4-Pentene-1,3-diol, 2-( I ,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
I,6-Hexanediol, 2-ethenyl- 66747-3I-7
1-Rexene-3,4-dioi, 5,5-dimethyl- 169736-29-2
1-Rexene-3,4-diol, 5,5-dimethyl- 120191-04-0
2-Rexene-1,5-diol, 4-ethenyi-2,5-dimethyl-70101-76-7
3-Rexene-1,6-dioI, 2-ethenyl-2,5-dimethyl-I 12763-52-7
3-Rexene-1,6-diol, 2-ethyl- 84143-45-3
3-Rexene-1,6-diol, 3,4-dimethyl- 125032-66-8
4-Rexene-2,3-diol, 2,5-dimethyl- 13295-61-9
4-Rexene-2,3-diol, 3,4-dimethyl- 135367-17-8
5-Rexene-1,3-diol, 3-(2-propenyl)- 74693-24-6
5-Rexene-2,3-diol, 2,3-dimethyl- 154386-00-2
5-Rexene-2,3-diol, 3,4-dimethyl- 135096-13-8
5-Rexene-2,3-diol, 3,5-dimethyl- 134626-63-4
5-Rexene-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-S1-7
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
CA 02249587 1998-09-21
WO 97/34972 PCT/US97/03374
5a.
1-Heptene-3.~-diol. 3-ethenyl-s-methyl 61841-10-9
I -Heptene-3,~-diol. 6.6-dimethyl- 109788-O 1-4
2.4-Heptadiene-2.6-diol. 4,6-dimethyl- I 02605-95-8
2,5-Heptadiene-1.7-diol. 4.4-dimethyl- 162816-19-5
2.6-Heptadiene-1,4-diol, 2.5,x-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-I,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-I,3-diol, 2,4-dimethyl- 123363-69-9
5-Heptene-I,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-I
6-Heptene-1,3-dial, 2,2-dimethyl- 140192-39-8
6-Heptene-I,4-diol, 4-(2-propenyl)- 1727-87-3
6-Heptene-I,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-I
6-Heptene-2,5-diol, 5-ethenyl-4-methyl- 65757-3I-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-dioi, 3,6-dimethyl- 31354-73-1
1-Octene-3,6-diol, 3-ethenyl- 65757-34-8
2,4,6-Octatriene-I,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- 101391-01-9
(Rosiridol)
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
CA 02249587 1998-09-21
WO 97/34972 PCT/US97/03374
2.7-Octadiene-1.6-diol. 2.6-dimethyl- (8-Hydroxylinalool)103619-06-3
2.7-Octadiene-I.6-diol, 2.7-dimethyl- 60250-14-8
2-Octene-1.4-diol 40735-I~-7
2-Octene-1.7-diol 73 842-9~-2
2-Octene-1,7-diol, 2-methyl-6-methylene- 91140-16-8
3.~-Octadiene-1,7-diol, 3.7-dimethyl- 62875-09-6
3,5-Octadiene-2,7-diol, 2.7-dimethyl- 7177-18-6
3,~-Octanediol, 4-methylene- 143233-15-2
3,7-Octadiene-1,6-diol, 2.6-dimethyl- 127446-29-1
i0 3,7-Octadiene-2,~-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-O1-6
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, S-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 i 65746-84-9
4,6-Nonadiene-1,3-diol, 8-methyl- 124099-52-1
4-Nonene-2, 8-diol 154600-80-3
6, 8-Nonadiene-1, S-diol 1085 86-03-4
CA 02249587 1998-09-21
WO 97/34972 PCT/US97/03374
7-Nonene-2.4-diol 30625-41-3
8-Nonene-2.4-diol 1 I 9785-59-0
8-Nonene-2.~-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--t9-S
1, 3-Butanediol, 2-(1-ethyl-I propenyl)- 116103-3S-6
1,3-Butanediol, 2-(2-butenyl)-2-methyl- 92207-83-S
1.3-Butanediol, 2-(3-methyl-2-butenyl)- 98955-19-2
1,3-Butanediol, 2-ethyl-2-(2 propenyl)- 122761-93-7
I , 3-Butanediol, 2-methyl-2-(I -methyl-2!-I1 S8S-S8-2
propenyl)-
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,-t-dimethyl-143447-08-9
I , 4-Pentanediol, 3-methyl-2-(2 propenyl)-139301-86-3
-!-Pentene-1,3-diol, 2-(1, I-dimethylethyl)-109788-04-7
4-Pentene-1, 3-diol, 2-ethyl-2, 3-dimethyl-90676-97--1
1, 4-Hexanediol, 4-ethyl-2-methylene- 66950-87-6
1, S-Hexadiene-3. -1-diol, 2, 3, S-trimethyl-18984-03-7
l,S-Hexanediol, 2-(I-methylethenyl)- 96802-18-S
2-Hexene-1, S-diol, 4-ethenyl-2, S-dimethyl-70101-76-7
1,4-Heptanediol, 6-methyl-S-methylene- 100590-29-2
2. 4-Heptadiene-2, 6-diol, 4, 6-dimethyl-102605-9S-8
2, 6-Heptadiene-I , 4-diol, 2, S, S-trimethyl-I 15346-30-0
2-Heptene-I, 4-diol, S, 6-dimethyl- 103867-76-I
3-Heptene-I , S-diol, 4, 6 dimethyl- 1-17028-4S-3
S-Heptene-I, 3-diol, 2, 4-dimethyl- 123363-69-9
S-Heptene-1, 3-diol, 3. 6-dimethyl- 96924-S2-6
S-Heptene-1,4-diol, 2,6-dimethyl- 106777-98-4
S-Heptene-I , 4-diol, 3, 6-dimethyl- ! 06777-99-S
6-Heptene-1,3-diol, 2,2-dimethyl- 140192-39-8
6-Heptene-1, 4-diol, S, 6-dimethyl- 1523.14-16-6
6-Heptene-1, S-diol, 2, 4-dimethyl- 74231-27-9
6-Heptene-1, S-diol, 2-ethylidene-6-methyl-91139-73-0
6-Heptene-2, 4-diol, 4-(2 propenyl)- 101536-7S-8
1-Octene-3, 6-diol, 3-ethenyl- 65757-34-8
2, 4, 6-Octatriene-1, 8-diol, 2, 7-dimethyl- 162648-63-7
CA 02249587 1998-09-21
WO 97/34972 PCT/US97/03374
2. 5-Octadiene-1, 7 -diol. 2, b-dimethyl- 911-!0-07-7
2.5-Octadiene-I, 7-diol, 3.7-dimethyl- 117935-59-8
2, b-Octadiene-I. -l-diol, 3. 7-dimethyl- (Rosiridol)101391-Ol
-9
2,b-Octadiene-1,8-diol, 2-methyl- I-19112-02-7
2, 7-Octadiene-1. -1-diol. 3. 7-dimethyl- 91 I.IO-08-8
l, 7-Octadiene-1. 5-diol, 2, b-dimethyl- 911,10-09-9
2.7-Octadiene-I,b-diol, 2.b-dimethyl- (8-Hydroxylinalool)103619-06-3
2, 7-Octadiene-l, b-diol. 2, 7-dimethyl- 60250-14-8
2-Octene-I. 7-diol, 2-methyl-b-methylene- 911.10-I
b-8
3.5-Octadiene-2, 7-diol, 2, 7-dimethyl- 7177-l8-6
3, 5-Octanediol, ,~-methylene- 143233-15-2
3, 7-Octadiene-I, b-diol, 2, b-dimethyl- 127:146-29-I
4-Octene-I, 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, .1-diol, 2-methyl-b-methylene- 72-146-81-2
7-Octene-2, 5-diol. 7-methyl- 152344-l2-2
7-Octene-3.5-diol, 2-methyl- 98753-85-6
1-Nonene-3. 5-diol 119554-56-2
I -Nonene-3. 7-diol 23866-97-9
3-Nonene-2, 5-diol 165 7.16-84-9
4-Nonene-2, 8-diol 154600-80-3
6.8-Nonadiene-I , 5-diol 108586-03-4
7-Nonene-2,4-diol 30625-41-3
8-Nonene-2, -f-diol I 19785-5 9-0
8-Nonene-2, 5-diol 132381-58-9
1, 9-Decadiene-3, 8-diol 103984-04-9
CA 02249587 1998-09-21
WO 97/34972 PCTNS97/03374
5b
1, 9-Decadiene--1. 6-diol 13883j-67-3
and
XI. mixtures thereof.
There are no CI-2 mono-ols that provide a clear concentrated fabric softener
compositions in the context of this invention. There is only one C3 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°C, or allowing it to
recover upon rewatming
to room temperature, although its boiling point is undesirably low. Of the C4
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~_6 mono-
ols that
provide clear products except for unsaturated mon-ols as described above and
hereinafter.
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.
For example, for the 1,2-alkanediol principal solvent series having the
general
formula HO-CH2-CHOH-(CH2)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 CIogP 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, l,~-
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).
CA 02249587 1998-09-21
WO 97/34972 PCT/US97/03374
There are no C3-CS diols that provide a clear concentrated composition in the
context of this invention.
Although there are many C6 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.
There are more possible C~ 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-;
I,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-; I,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-pentanedioI,
4,4-dimethyl
and 3,4-pentanediol, 2,3-dimethyl-.
Similarly, there are even more Cg diol isomers, but only the listed ones
provide
clear products and the preferred ones are: I,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,I-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-; I,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-
pentanedioI, 2,2,4-
trimethyl-; 1,5-pentanediol, 2,3,3-trimethyl-; 2,4-pentanediol, 2,3,4-
trimethyl-; 1,3-
CA 02249587 1998-09-21
WO 97/34972 PCT/US97/03374
pentanediol. 2-ethyl-2-methyl-; 1.3-pentanediol, 2-ethyl-3-methyl-; 1,3-
pentanediol, ?-
ethyl-4-methyl-; 1.3-pentanediol, 3-ethyl-2-methyl-; I.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.~-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-hexanedioI, 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-dimethylpropyi)-
; 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-;
CA 02249587 1998-09-21
WO 97/34972 PCT/US97/03374
1.3-butanediol, 2-(I-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-ethvl-
3,3-dimethyl-; 1.4-butanediol, 2-(1,1-dimethylethyl)-; 1,3-pentanediol, 2,3,4-
trimethyl-;
1,5-pentanediol, 2,2.3-trimethyl-; I,~-pentanediol, 2,2,4-trimethyl-; I,~-
pentanediol,
2,3,3-trimethyl-; 1,3-pentanediol, ?-ethyl-2-methyl-; I,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-;
I,5-pentanediol, 3-ethyl-3-methyl-; 2,4-pentanediol, 3-ethyl-2-methyl-; 1,3-
pentanediol,
2-isopropyl-; I,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-; I,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-dimethyi-; 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,~-
hexanediol, 2,2-dimethyl-; I,5-hexanediol, 2,3-dimethyl-; I,5-hexanediol, 2,4-
dimethyl-;
1,5-hexanediol, 2,5-dimethyl-; 1,5-hexanediol, 3,3-dimethyl-; I,5-hexanediol,
3,4-
dimethyl-; I,5-hexanediol, 3,5-dimethyl-; I,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-; I,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-; I,5-hepianediol, 3-methyl-; I,5-heptanediol, 4-methyl-
; I,5-
heptanediol, S-methyl-; 1,5-heptanediol, 6-methyl-; 1,6-heptanediol, 2-methyl-
; 1,6-
heptanediol, 3-methyl-; 1,6-heptanediol, 4-methyl-; I,b-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,~-
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-
CA 02249587 1998-09-21
WO 97/34972 PCT/US97/03374
bb
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.
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-I,3-diols, i.e., a mixture of 8-carbon-I,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-
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-pentanediol 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.
The formulatability, and other properties, such as odor, fluidity, melting
point
lowering, etc., of some C6-g diols listed above in Tables II-IV which are not
preferred,
can be improved by polyalkoxylation. Also, some of the C3_5 diols which are
alkoxylated are preferred. Preferred alkoxylated derivatives of the above C3-g
diols [In
the following disclosure, "EO" means polyethoxylates, "En" means -(CH2CH20)nH;
Me-En means methyl-capped polyethoxylates -(CH2CH20)nCH3 ; "2(Me-En)" means 2
Me-En groups needed; "PO" means polypropoxylates, -(CH(CH3)CH20)nH ; "BO"
means polybutyleneoxy groups, (CH(CH2CH3)CH20)nH ; and "n-BO" means poly(n-
butyleneoxy) groups -(CH2CH2CH2CH20)nH.] include:
I. 1,2-propanediol (C3) 2(Me-E3~); 1,2-propanediol (C3) P04; 1,2-propanediol,
2-
methyl- (C4) (Me-Eg-IO); 1,2-propanediol, 2-methyl- (C4) 2(Me-EI); 1,2-
propanediol, 2-
methyl- (C4} P03; 1,3-propanediol (C3) 2(Me-Eg); I,3-propanediol (C3) P06; I,3-
propanediol, 2,2-diethyl- (C7) E4_7; 1,3-propanediol, 2,2-diethyl- (C7) POI;
I,3-
propanediol, 2,2-diethyl- (C7) n-B02; I,3-propanediol, 2,2-dimethyl- (CS) 2(Me
EI-2)~
1,3-propanediol, 2,2-dimethyl- (CS) P04; 1,3-propanediol, 2-{I-methylpropyl}-
(C7) E4-
7; 1,3-propanediol, 2-{I-methylpropyl)- (C7) PO1; 1,3-propanediol, 2-(I-
methylpropyl)-
(C7) n-B02; 1,3-propanediol, 2-(2-methylpropyl}- (C7) E4-7; I,3-propanediol, 2-
(2-
methylpropyl)- (C7) POI; 1,3-propanediol, 2-(2-methylpropyl}- (C7) n-B02; 1,3-
propanediol, 2-ethyl- (CS) (Me E9_10)~ I,3-propanediol, 2-ethyl- (CS) 2(Me
EI); 1,3-
propanediol, 2-ethyl- (CS) P03; I,3-propanediol, 2-ethyl-2-methyl- (C6) (Me
E3_6); 1,3-
propanediol, 2-ethyl-2-methyl- (C6} P02; 1,3-propanediol, 2-ethyl-2-methyl-
(C6) BOI;
1,3-propanediol, 2-isopropyl- (C6) (Me E3-6); I,3-propanediol, 2-isopropyl-
(C6) P02:
CA 02249587 1998-09-21
WO 97/34972 PCT/US97/03374
iol
1.3-propanediol, 2-isopropyl- (C6) BOI; 1.3-propanediol, 2-methyl- (C4) 2(Me
E4_5);
1.3-propanediol. 2-methyl- (C4) POS; 1.3-propanediol, 2-methyl- (C4) B02; 1.3-
propanediol, 2-methyl-2-isopropyl- (C7) E6_9; 1,3-propanediol, 2-methyl-2-
isopropyl-
(C7) POI; 1,3-propanediol, 2-methyl-2-isopropyl- (C7) n-B02_3; 1,3-
propanediol, 2-
methyl-2-propyl- (C7) E4_~; 1,3-propanediol, 2-methyl-2-propyl- (C7) POI; 1,3-
propanediol, 2-methyl-2-propyl- (C7) n-B02; 1,3-propanediol, 2-propyl- (C6)
(Me EI_4);
1,3-propanediol, 2-propyl- (C6) P02;
2. I.2-butanediol (C4) (Me E6_g); 1,2-butanediol (C4) P02_3; 1,2-butanediol
(C4)
BOI; 1,2-butanediol, 2,3-dimethyl- (C6) E2_5; 1,2-butanediol, 2,3-dimethyl-
(C6) n-BOI;
1,2-butanediol, 2-ethyl- (C6) EI_3; 1,2-butanediol, 2-ethyl- (C6) n-BOI; 1,2-
butanediol,
2-methyl- (CS) (Me EI_2); 1,2-butanediol, 2-methyl- (CS) POI; 1,2-butanediol,
3,3
dimethyl- (C6) E2_~; 1,2-butanediol, 3,3-dimethyl- (C6) n-BOI; I,2-butanediol,
3-
methyl- (CS) (Me EI_2); 1,2-butanediol, 3-methyl- (CS) PO1; 1,3-butanediol
(C4) 2(Me
ES_6); 1,3-butanediol (C4) B02; 1,3-butanediol, 2,2,3-trimethyl- (C7) (Me
EI_3); I,3-
butanediol, 2,2.3-trimethyl- (C7) P02; I,3-butanediol, 2,2-dimethyi- (C6) (Me
E6_g); 1,3-
butanedioI, 2,2-dimethyl- (C6) P03; 1,3-butanediol, 2,3-dimethyl- (C6) (Me
E6_g); I,3-
butanediol, 2,3-dimethyl- (C6) P03; I,3-butanediol, 2-ethyl- (C6) (Me E4_6);
1,3-
butanediol, 2-ethyl- (C6) P02_3; 1,3-butanediol, 2-ethyl- (C6) BOI; 1,3-
butanediol, 2-
ethyl--2-methyl- (C7) (Me EI); 1,3-butanediol, 2-ethyl-2-methyl- (C7) POI; 1,3-
butanediol, 2-ethyl-2-methyl- (C7) n-B03; I,3-butanediol, 2-ethyl-3-methyl-
(C7) (Me
E1); 1,3-butanediol, 2-ethyl-3-methyl- (C7) PO1; 1,3-butanediol, 2-ethyl-3-
methyl- (C7)
n-B03; 1,3-butanediol, 2-isopropyl- (C7) (Me EI); 1,3-butanediol, 2-isopropyl-
(C7)
PO1; 1,3-butanediol, 2-isopropyl- (C7) n-B03; 1,3-butanediol, 2-methyl- (CS)
2(Me E2_
3); 1,3-butanediol, 2-methyl- (CS) P04; 1,3-butanediol, 2-propyl- (C7) E6_g;
1,3-
butanediol, 2-propyl- (C7) POI; 1,3-butanediol, 2-propyl- (C7) n-B02_3; 1,3-
butanediol,
3-methyl- (CS) 2(Me E2_3); 1,3-butanediol, 3-methyl- (CS) P04; 1,4-butanediol
(C4)
2(Me E3~); 1,4-butanediol (C4) P04_S; 1,4-butanediol, 2,2,3-trimethyl- (C7)
E6_9; 1,4-
butanediol, 2,2,3-trimethyl- (C7) PO1; 1,4-butanediol, 2,2,3-trimethyl- (C7) n-
B02_3;
1,4-butanediol, 2,2-dimethyl- (C6) (Me E3_6); 1,4-butanediol, 2,2-dimethyl-
(C6) P02;
1,4-butanediol, 2,2-dimethyl- (C6) BOI; 1,4-butanediol, 2,3-dimethyl- (C6) (Me
E3_6);
1,4-butanedioi, 2,3-dimethyl- (C6) P02; 1,4-butanediol, 2,3-dimethyl- (C6)
BOI; 1,4-
butanediol, 2-ethyl- (C6) (Me E1~); 1,4-butanediol, 2-ethyl- (C6) P02; 1,4-
butanediol,
2-ethyl-2-methyl- (C7) E4_~; 1,4-butanediol, 2-ethyl-2-methyl- (C7) POI; 1,4-
butanediol,
2-ethyl-2-methyl- (C7) n-B02; 1,4-butanediol, 2-ethyl-3-methyl- (C7) E4_7; 1,4-
butanediol, 2-ethyl-3-methyl- (C7) POI; I,4-butanediol, 2-ethyl-3-methyl- (C7)
n-B02;
CA 02249587 1998-09-21
WO 97/34972 PCT/US97/03374
1.4-butanediol. 2-isopropyl- (C7) E4_7; 1,4-butanediol. 2-isopropyl- (C7) POI;
1,4-
butanediol, 2-isopropyl- (C7) n-B02; I,4-butanediol. '?-methyl- (C~) (Me
E9_10); 1.4-
butanediol. ?-methyl- (CS) 2(Me EI); 1,4-butanediol, 2-methyl- (C~) P03; 1.4-
butanediol. 2-propyl- (C7) E2_5; 1,4-butanediol, 2-propyl- (C7) n-BOI; 1.4-
butanediol. i-
~ ethyl-I-methyl- (C7) E6_g; 1,4-butanediol, 3-ethyl-I-methyl- (C7) POI; 1,4-
butanediol,
3-ethyl-I-methyl- (C7) n-BO~_3; 2.3-butanediol (C4) (Me E9_IO); 2,3-butanediol
(C4)
2(Me EI); 2,3-butanediol (C4) P03_,~; 2,3-butanediol, 2,3-dimethyl- (C6) E7_9;
2,3
butanediol, 2,3-dimethyl- (C6) POI; 2,3-butanediol, 2,3-dimethyl- (C6) B02_3;
'',3
butanediol, 2-methyl- (CS) (Me E2_5); 2,3-butanediol, 2-methyl- (CS) P02; 2.3
butanediol, 2-methyl- (CS) BOI;
3. 1,2-pentanediol (CS) E~_I0; 1,2-pentanediol, (CS) POI; 1,2-pentanediol,
(CS) n-B03; 1,2-pentanediol, 2-methyl (C6) E1_3; 1,2-pentanediol, 2-methyl
(C6) n-
BOI; 1,2-pentanediol, 3-methyl (C6) E1_3; 1,2-pentanediol, 3-methyl (C6) n-
BOI; 1,2-
pentanediol, 4-methyl (C6) EI_3; 1,2-pentanediol, 4-methyl (C6) n-BOI; 1,3-
pentanediol
(CS) 2(Me-EI_2); 1,3-pentanediol (CS) P03~; 1,3-pentanediol, 2,2-dimethyl-
(C7) (Me-
EI); 1,3-pentanediol, 2,2-dimethyl- (C7) PO1; 1,3-pentanediol, 2,2-dimethyl-
(C7) n-
B03; I,3-pentanediol, 2,3-dimethyl- (C7) (Me-EI); 1,3-pentanediol, 2,3-
dimethyl- (C7)
POI; 1,3-pentanediol, 2,3-dimethyl- (C7) n-B03; 1,3-pentanediol, 2,4-dimethyl-
(C7)
(Me-EI); 1,3-pentanediol, 2,4-dimethyl- (C7) POI; 1,3-pentanediol, 2,4-
dimethyl- (C7)
n-B03; I,3-pentanediol, 2-ethyl- {C7) E6_g; 1,3-pentanediol, 2-ethyl- (C7)
POI; 1,3-
pentanediol, 2-ethyl- (C7) n-B02_3; 1,3-pentanediol, 2-methyl- (C6) 2(Me-
E4_6); 1,3-
pentanediol, 2-methyl- (C6) P02_3; 1,3-pentanediol, 3,4-dimethyl- (C7) (Me-
EI); 1,3-
pentanediol, 3,4-dimethyl- (C7) POI; 1,3-pentanediol; 3,4-dimethyl- (C7) n-
B03; 1,3-
pentanediol, 3-methyl- (Cf>) 2(Me-E4_6); 1,3-pentanedioi, 3-methyl- (C6)
P02_3; 1,3-
pentanediol, 4,4-dimethyl- (C7) (Me-EI); 1,3-pentanediol, 4,4-dimethyl- (C7)
POI; 1,3-
pentanediol, 4,4-dimethyl- (C7) n-B03; 1,3-pentanediol, 4-methyl- (C6) 2(Me-
E4_6); 1,3-
pentanediol, 4-methyl- (C6) P02_3; 1,4-pentanediol, (CS) 2(Me-EI_2); 1,4-
pentanediol
(CS) P03~; 1,4-pentanediol, 2,2-dimethyl- (C7) (Me-EI); 1,4-pentanediol, 2,2-
dimethyl-
(C7) POI; 1,4-pentanediol, 2,2-dimethyl- (C7) n-B03; 1,4-pentanediol, 2,3-
dimethyl-
(C7) (Me-EI); 1,4-pentanediol, 2,3-dimethyl- (C7) POI; 1,4-pentanediol, 2,3-
dimethyl-
(C7) n-B03; 1,4-pentanediol, 2,4-dimethyl- (C7) (Me-EI); 1,4-pentanediol, 2,4-
dimethyl-
(C7) POI; 1,4-pentanediol, 2,4-dimethyl- (C7) n-B03; 1,4-pentanediol, 2-methyl-
(C6)
(Me-E4_6); 1,4-pentanediol, 2-methyl- (C6) P02_3; 1,4-pentanediol, 3,3-
dimethyl- (C7)
(Me-EI); 1,4-pentanediol, 3,3-dimethyl- (C7) POI; 1,4-pentanediol, 3,3-
dimethyl- (C7)
n-B03; 1,4-pentanediol, 3,4-dimethyl- (C7) (Me-EI); 1,4-pentanediol, 3,4-
dimethyl- (C7)
CA 02249587 1998-09-21
WO 97/34972 PCT/US97/03374
POI ; 1.4-pentanediol, 3,.1~-dimethyl- (C7) n-B03; I ,4-pentanediol, 3-methyl-
(C6) 2(Me-
E4_6); 1.4-pentanediol, 3-methyl- (C6) P02_;; 1,4-pentanedio(; 4-methyl- (C6)
2(Me-E4_
); 1,4-pentanediol, 4-methyl- (C6) P02_3; 1.~-pentanediol. (CS) (Me-Eg_IO);
1,5
pentanediol (C~) 2(Me-EI); 1,5-pentanediol (C~) P03; I,5-pentanediol, 2,2-
dimethyl
(C7) E4_7; I,S-pentanediol. 2,2-dimethyl- (C7) POI; I,~-pentanedioI, 2,2-
dimethyl- (C7)
n-B02; I,5-pentanedioi, 2.3-dimethyl- (C7) E4_~; I,5-pentanediol, 2,3-dimethyl-
(C7)
POI; I,5-pentanediol, 2,3-dimethyl- (C7) n-B02; I,5-pentanediol, 2,4-dimethyi-
(C7) E4_
~; 1,5-pentanedioi, 2,4-dimethyl- (C7) POI; 1,5-pentanediol, 2,4-dimethyl-
(C7) n-B02;
1,5-pentanediol, 2-ethyl- (C7) E2_5; I,5-pentanediol, 2-ethyl- (C7) n-BOI; I,~-
pentanediol, 2-methyl- (C6) (Me-E1_4); 1,5-pentanediol, 2-methyl- (C6) P02;
I,5-
pentanediol, 3,3-dimethyl- (C7) E4_~; I,~-pentanediol, 3,3-dimethyl- (C7) POI;
I,5-
pentanediol, 3,3-dimethyl- (C7) n-B02; I,5-pentanediol, 3-methyl- (C6) (Me-
EI_4); I,5-
pentanediol, 3-methyl- (C6) P02; 2,3-pentanediol, (C~) (Me-E1_3); 2,3-
pentanediol, (CS)
P02; 2,3-pentanediol, 2-methyl- (C6) E4_~; 2,3-pentanediol, 2-methyl- (C6)
PO1; 2,3-
pentanediol, 2-methyl- (C6) n-B02; 2,3-pentanediol, 3-methyl- (C6) E4_~; 2,3-
pentanediol, 3-methyl- (C6) PO1; 2,3-pentanediol, 3-methyl- (C6) n-B02; 2,3-
pentanediol, 4-methyl- (C6) E4_~; 2,3-pentanediol, 4-methyl- (C6) POI; 2,3-
pentanediol,
4-methyl- (C6) n-B02; 2,4-pentanediol, (CS) 2(Me-E2_4); 2,4-pentanediol (CS)
P04; 2,4-
pentanediol, 2,3-dimethyl- (C7) (Me-E2~); 2,4-pentanediol, 2,3-dimethyl- (C7)
P02;
2,4-pentanediol, 2,4-dimethyl- (C7) (Me-E2-4); 2,4-pentanediol, 2,4-dimethyl-
(C7} P02;
2,4-pentanediol, 2-methyl- (C7) (Me-Eg_10); 2,4-pentanediol, 2-methyl- (C7)
P03; 2,4-
pentanediol, 3,3-dimethyl- (C7) (Me-E2~); 2,4-pentanediol, 3,3-dimethyl- (C7)
P02;
2,4-pentanediol, 3-methyl- (C6) (Me-Eg_IO); 2,4-pentanediol, 3-methyl- (C6)
P03;
4. 1,3-hexanediol (C6) (Me-E2_5); 1,3-hexanediol (C6) P02; 1,3-hexanediol
(C6) BO1; 1,3-hexanediol, 2-methyl- (C7) E6_g; 1,3-hexanediol, 2-methyl- (C7)
POI;
1,3-hexanediol, 2-methyl- (C7) n-B02_3; 1,3-hexanediol, 3-methyl- (C7) E6_g;
1,3
hexanediol, 3-methyl- (C7) POI; 1,3-hexanediol, 3-methyl- (C7) n-B02_3; 1,3
hexanediol, 4-methyl- (C7) E6_g; 1,3-hexanediol, 4-methyl- (C7) POI; 1,3-
hexanediol, 4
methyl- (C7) n-B02_3; 1,3-hexanediol, 5-methyl- (C7) E6_g; 1,3-hexanediol, S-
methyl
(C7) PO1; 1,3-hexanediol, 5-methyl- (C7) n-B02_3; 1,4-hexanediol (C6) (Me-
E2_5); 1,4-
hexanediol (C6) P02; 1,4-hexanediol {C6) BOI; 1,4-hexanedioI, 2-methyl- (C7)
E6_g;
1,4-hexanediol, 2-methyl- (C7) PO1; I,4-hexanediol, 2-methyl- (C7) n-B02_3;
1,4-
hexanediol, 3-methyl- (C7} E6_g; 1,4-hexanediol, 3-methyl- (C7) POI; 1,4-
hexanediol, 3-
methyl- (C7) n-B02_3; 1,4-hexanediol; 4-methyl- (C7) E6_g; 1,4-hexanediol, 4-
methyl-
(C7) POI; 1,4-hexanediol, 4-methyl- (C7) n-B02_3; 1,4-hexanediol, 5-methyl-
(C7) E6_
CA 02249587 1998-09-21
WO 97/34972 PCT/US97/03374
g; 1,4-hexanediol. ~-methyl- (C7) POI; 1,4-hexanediol, ~-methyl- (C7) n-BO~_3;
1,~-
hexanediol (C6) (Me-E~_5); 1.~-hexanediol (C6) PO~; I,5-hexanediol (C6) BOI;
I,5-
hexanediol. 2-methyl- (C7) E6_g; 1,~-hexanediol, 2-methyl- (C7) POI; I,5-
hexanediol. 2-
methyl- (C7) n-BO~_3; 1,~-hexanediol, 3-methyl- (C7) E6_g; I,5-hexanediol, 3-
methvl-
{C7) POI; 1,~-hexanediol, 3-methyl- (C7) n-B02_3; 1.~-hexanediol, 4-methyl-
(C7) E6_
g; 1,5-hexanediol, 4-methyl- (C7) POI; I,5-hexanediol, 4-methyl- {C7) n-BO~_3;
l,~-
hexanediol, ~-methyl- (C7) E6_g; I,5-hexanediol, ~-methyl- (C7) POI; I,5-
hexanediol, 5-
methyl- (C7) n-B02_3; 1,6-hexanediol (C6) (Me-EI_2); 1,6-hexanediol (C6)
POI_2; 1,6-
hexanediol (C6} n-B04; 1,6-hexanediol, 2-methyl- (C7) E2_5; 1,6-hexanediol, 2-
methyl-
(C7) n-BOI; 1,6-hexanediol, 3-methyl- (C7) E2_5; 1,6-hexanediol, 3-methyl-
(C7) n-
BOI; 2,3-hexanediol (C6) E2_5; 2,3-hexanediol (C6) n-BOI; 2,4-hexanediol (C6)
(Me-
ES_g); 2,4-hexanediol (C6) P03; 2,4-hexanediol, 2-methyl- (C7) (Me-E I _2);
2,4-
hexanediol 2-methyl- (C7) POI_2; 2,4-hexanediol, 3-methyl- (C7) (Me-EI_2); 2,4-
hexanediol 3-methyl- (C7) PO1_2; 2,4-hexanediol, 4-methyl- (C7) (Me-EI_2); 2,4-
hexanediol 4-methyl- (C7) POI _2; 2,4-hexanediol, 5-methyl- (C7) (Me-E I _2);
2,4-
hexanediol 5-methyl- (C7) PO1_2; 2,5-hexanediol (C6) (Me-ES_g); 2,5-hexanediol
(C6)
P03; 2,5-hexanediol, 2-methyl- (C7) (Me-EI_2); 2,5-hexanediol 2-methyl- (C7)
POI_2;
2,5-hexanediol, 3-methyl- (C7) (Me-E I _2); 2,5-hexanediol 3-methyl- (C?) PO I
_2; 3,4-
hexanediol (C6) E02_S; 3,4-hexanediol (C6) n-BOI;
5. 1,3-heptanediol (C7) E3_6; 1,3-heptanediol (C7) POI; 1,3-heptanediol
(C7) n-B02; 1,4-heptanediol (C7) E3_6; 1,4-heptanediol (C7) POI; 1,4-
heptanediol (C7}
n-B02; 1,5-heptanediol (C7) E3_6; 1,5-heptanediol (C7) POI; 1,5-heptanediol
(C7) n-
B02; 1,6-heptanediol (C7) E3_6; 1,6-heptanediol (C7) POI; 1,6-heptanediol (C7)
n-B02;
1,7-heptanediol (C7) E1_2; 1,7-heptanediol (C7) n-BOI; 2,4-heptanediol (C7)
E?_I0; 2,4-
heptanediol (C7) (Me-EI); 2,4-heptanediol (C7) POI; 2,4-heptanediol (C7) n-
B03; 2,5-
heptanediol (C7) E7_I0; 2,5-heptanediol (C7) (Me-EI); 2,5-heptanediol (C7)
POI; 2,5-
heptanediol (C7) n-B03; 2,6-heptanediol (C7) E7_I0; 2,6-heptanediol (C7) (Me-
EI); 2,6-
heptanediol (C7) POI; 2,6-heptanediol (C7) n-B03; 3,5-heptanediol (C7) E?-I0;
3,5-
heptanediol (C7) (Me-EI); 3,5-heptanediol (C7) POI; 3,5-heptanediol (C7) n-
B03;
6. 1,3-butanediol, 3-methyl-2-isopropyl- (C8) POI; 2,4-pentanediol, 2,3,3-
trimethyl- (C8) POI; 1,3-butanediol, 2,2-diethyl- (C8) E2_5; 2,4-hexanediol,
2,3-
dimethyl- (C8) E2_5; 2,4-hexanediol, 2,4-dimethyl- (C8) E2_5; 2,4-hexanediol,
2,5-
dimethyl- (C8) E2_S; 2,4-hexanediol, 3,3-dimethyl- (C8) E2_~; 2,4-hexanediol,
3,4-
dimethyl- (C8) E2_5; 2,4-hexanediol, 3,5-dimethyl- (C8) E2_5; 2,4-hexanediol,
4,5-
dimethyl- (C8) E2_5; 2,4-hexanediol, 5,5-dimethyl- (C8) E2_5; 2,5-hexanediol,
2,3-
CA 02249587 1998-09-21
WO 97/34972 PCT/US97/03374
~0''5
dimethyl- (C8) E~_5; 2,5-hexanediol. 2.4-dimethyl- (C8) E~_~; 2,5-hexanediol,
2,5-
dimethyl- (C8) E~_~; 2,5-hexanediol, 3,3-dimethyl- (C8) E~-~; 2,5-hexanediol,
3,4-
dimethyl- (C8) E~_5; 3.5-heptanediol, 3-methyl- (C8) E2_5; 1,3-butanediol. 2.2-
diethvl-
(C8) n-BOl_2; 2,4-hexanediol, 2.3-dimethyl- (C8) n-BO1_2; 2,4-hexanediol, 2,4-
dimethyl- (C8) n-BOl_2; 2,4-hexanediol, 2.5-dimethyl- (C8} n-BOI_2; 2.4-
hexanediol,
3,3-dimethyl- (C8) n-BOI _~; 2,4-hexanediol, 3,4-dimethyl- (C8) n-BOI _~; 2,4-
hexanediol, 3,5-dimethyl- (C8) n-BOI_2; 2,4-hexanediol, 4,5-dirnethyl- (C8) n-
BOI-2~
2,4-hexanediol, 5,5-dimethyl-, n-BO1_2; 2,5-hexanediol, 2,3-dimethyl- (C8) n-
BOl_2;
2,5-hexanediol, 2,4-dimethyl- (C8) n-BOl _2; 2,5-hexanediol, 2,5-dimethyl-
(C8) n-BOI _
2; 2,5-hexanediol, 3,3-dimethyl- (C8) n-BOl_2; 2,5-hexanediol, 3,4-dimethyl-
(C8) n-
BOI_2; 3,5-heptanediol, 3-methyl- (C8) n-BOl_2; 1,3-propanediol, 2-(1,2-
dimethylpropyl)- (C8) n-BOI; 1,3-butanediol, 2-ethyl-2,3-dimethyl- (C8) n-BOI;
1,3-
butanediol, 2-methyl-2-isopropyl- (C8) n-BOI; 1,4-butanedioI, 3-methyl-2-
isopropyl-
(C8) n-BOI; 1,3-pentanediol, 2,2,3-trimethyl- (C8) n-BOI; 1,3-pentanediol,
2,2,4-
trimethyl- (C8) n-BOI; 1,3-pentanediol, 2,4,4-trimethyl- (C8) n-BOI; 1,3-
pentanediol,
3,4,4-trimethyl- (C8) n-BOI; 1,4-pentanediol, 2,2,3-trimethyl- (C8) n-BOI; 1,4-
pentanediol, 2,2,4-trimethyl- (C8) n-BOI; 1,4-pentanediol, 2,3,3-trimethyl-
(C8) n-BOI;
1,4-pentanediol, 2,3,4-trimethyl- (C8) n-BOI; 1,4-pentanediol, 3,3,4-trimethyl-
(C8) n-
BOI; 2,4-pentanediol, 2,3,4-trimethyl- (C8) n-BOI; 2,4-hexanediol, 4-ethyl-
(C8) n-BOI;
2,4-heptanediol, 2-methyl- (C8) n-BOl ; 2,4-heptanediol, 3-methyl- (C8) n-BO l
; 2,4-
heptanediol, 4-methyl- (C8) n-BOI; 2,4-heptanediol, 5-methyl- (C8) n-BOI; 2,4-
heptanediol, 6-methyl- (C8) n-BOI; 2,5-heptanediol, 2-methyl- (C8) n-BOI; 2,5-
heptanediol, 3-methyl- (C8) n-BOI ; 2,5-heptanediol, 4-methyl- (C8) n-BOI ;
2,5-
heptanediol, 5-methyl- (C8) n-BOI; 2,5-heptanediol, 6-methyl- (C8) n-BOI; 2,6-
heptanediol, 2-methyl- (C8) n-BOI ; 2,6-heptanediol, 3-methyl- (C8) n-BO I ;
2,6-
heptanediol, 4-methyl- (C8) n-BOI; 3,5-heptanediol, 2-methyl- (C8) n-BOI; 1,3-
propanediol, 2-(1,2-dimethylpropyl)- (C8) El_3; 1,3-butanediol, 2-ethyl-2,3-
dimethyl-
(C8) El_3; 1,3-butanediol, 2-methyl-2-isopropyl- (C8) EI_3; l,4-butanediol, 3-
methyl-2-
isopropyl- (C8) E l _3; 1,3-pentanediol, 2,2,3-trimethyl- (C8) E 1 _3; 1,3-
pentanediol, 2,2,4-
trimethyl- (C8) EI_3; I,3-pentanediol, 2,4,4-trimethyl- (C8) El_3; 1,3-
pentanediol, 3,4,4-
trimethyl- (C8) El_3; 1,4-pentanediol, 2,2,3-trimethyl- (C8) El_3; 1,4-
pentanediol, 2,2,4-
trimethyl- (C8) El_3; 1,4-pentanediol, 2,3,3-trimethyl- (C8) EI_3; 1,4-
pentanediol, 2,3,4-
trimethyl- (C8) EI_3; 1,4-pentanediol, 3,3,4-trimethyl- (C8) EI_3; 2,4-
pentanediol, 2,3,4-
trimethyl- (C8) EI_3; 2,4-hexanediol, 4-ethyl- (C8) EI_3; 2,4-heptanediol, 2-
methyl- (C8)
E 1 _3; 2,4-heptanediol, 3-methyl- (C8) E I _3; 2,4-heptanediol, 4-methyl-
(C8) E 1 _3; 2,4-
CA 02249587 1998-09-21
WO 97/34972 PCT/US97/03374
how
heptanediol. 6-methyl- (C8) E 1 _;; 2.4-heptanediol, 6-methyl- (C8) E 1 _3;
2,5-heptanediol,
2-methyl- (C8) EI_;; 2.~-heptanediol, 3-methyl- (C8) E1_3; 2.~-heptanediol, 4-
methyl-
(C8) E 1 _;; 2.~-heptanediol, 5-methyl- (C8) E 1 _3; 2,~-heptanediol, 6-methyl-
(C8) E 1 _3;
2.6-heptanediol, 2-methyl- (C8) E 1 _3; 2,6-heptanediol, 3-methyl- (C8) E 1
_~; 2,6-
~ heptanediol, 4-methyl- (C8) E 1 _3; and/or 3,5-heptanediol, 2-methyl- (C8) E
1 _3; and
7. mixtures thereof.
Of the nonane isomers, only 2,4-pentadiol, 2,3,3,4-tetramethyl- is highly
preferred.
In addition to the aliphatic diol principal solvents, and some of their
alkoxvlated
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 HOCH2-CHOH-CH2-O-R, wherein R is from C2 to C8 alkyl, only monopentyl
ethers with the formula HOCH2-CHOH-CH2-O-CSH11 (3-pentyloxy-1,2-propanediol),
wherein the CSH11 group comprises different pentyl isomers, have ClogP values
within
the preferred CiogP 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.
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.
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.
CA 02249587 1998-09-21
WO 97/34972 PCT/US97/03374
(o?
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-I-butyloxy)-; 1,2-propanediol, 3-(iso-amyloxy)-; 1,2-
~ propanediol, 3-(3-methyl-2-butyloxy)-; 1,2-propanediol, 3-(cyclohexyloxy)-:
1,2-
propanediol, 3-(I-cyclohex-I-enyloxy)-; I,3-propanediol, 2-(pentyloxy)-; I,3-
propanediol, 2-(2-pentyloxy}-; 1,3-propanediol, 2-(3-pentyloxy)-; 1,3-
propanediol, 2-(2-
methyl-I-butyloxy)-; 1,3-propanediol, 2-(iso-amyloxy)-; 1,3-propanediol, 2-(3-
methyl-2-
butyloxy)-; 1,3-propanediol, 2-(cyclohexyioxy)-; 1,3-propanediol, 2-(I-
cyclohex-1-
enyloxy)-; 1,2-propanediol, 3-(butyloxy)-, pentaethoxylated; 1,2-propanediol,
3-
(butyloxy)-, hexaethoxylated; I,2-propanediol, 3-(butyloxy)-,
heptaethoxylated; I,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-propanedioI, 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;
An illustrative and non-limiting example of synthesis methods to prepare the
preferred alkyl and aryl monoglyceryl ethers is given hereinafter.
The alicyclic diols and their derivatives that are preferred include: ( 1 )
the saturated
diols and their derivatives including: 1-isopropyl-1,2-cyclobutanediol; 3-
ethyl-4-methyl-
1,2-cyclobutanediol; 3-propyl-1,2-cyclobutanediol; 3-isopropyl-1,2-
cyclobutanediol; 1-
ethyl-1,2-cyclopentanediol; 1,2-dimethyl-1,2-cyclopentanediol; 1,4-dimethyl-
1,2-
cyclopentanedioI; 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; I ,1-bis(hydroxymethyl)cyclohexane; I .2-
bis(hydroxymethyl)cyclohexane; 1,2-dimethyl-1,3-cyclohexanediol; I,3-
bis(hydroxymethyl)cyclohexane; I,3-dimethyl-I,3-cyclohexanediol; 1,6-dimethyl-
1,3-
CA 02249587 1998-09-21
WO 97/34972 PCT/US97/03374
~0~
cyclohexanediol; I-hydroxy-cyclohexaneethanol; I-hydroxy-cyclohexanemethanol;
1-
ethyl-1,3-cyclohexanediol; I-methyl-1,2-cyclohexanediol; 2,~-dimethyl-1,3-
cyclohexanediol; 2,3-dimethyl-I,4-cyclohexanediol; 2,4-dimethyl-1.3-
cyclohexanediol;
2,~-dimethyl-I,3-cyclohexanediol; 2.6-dimethyl-1,4-cyclohexanediol; ?-ethyl-
1,3-
cyclohexanediol; 2-hydroxycyclohexaneethanol; 2-hydroxyethyl-I-cyclohexanol; 2-
hydroxymethylcyclohexanol; 3-hydroxyethyl-1-cyclohexanol; ;-
hydroxycyclohexaneethanol; 3-hydroxymethylcyclohexanol; 3-methyl-I?-
cyclohexanediol; 4.4-dimethyl-I,3-Cyclohexanediol; 4,5-dimethyl-1,3-
cyclohexanediol;
4,6-dimethyl-I,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-I,3-cyclohexanediol; 1,2-
cycloheptanediol; 2-
methyl-1,3-cycloheptanediol; 2-methyl-1,4-cycloheptanediol; 4-methyl-1,3-
cycloheptanediol; 5-methyl-1,3-cycloheptanediol; 5-methyl-1,4-
cycloheptanediol; 6-
methyl-1,4-cycloheptanediol; ; 1,3-cyclooctanediol; 1,4-cyclooctanediol; 1,5-
cyclooctanediol; 1,2-cyclohexanediol, diethoxylate; 1,2-cyclohexanediol,
triethoxylate;
I,2-cyclohexanediol, tetraethoxylate; 1,2-cyclohexanediol, pentaethoxylate;
1,2-
cyclohexanediol, hexaethoxylate; I,2-cyclohexanediol, heptaethoxylate; 1,2-
cyciohexanediol, octaethoxylate; 1,2-cyclohexanediol, nonaethoxylate; 1,2-
cyclohexanediol, monopropoxylate; 1,2-cyclohexanediol, monobutylenoxylate; 1,2-
cyclohexanediol, dibutylenoxylate; and/or I,2-cyclohexanediol,
tributylenoxylate. The
most preferred saturated alicyclic diols and their derivatives are: I-
isopropyl-I,2-
cyclobutanediol; 3-ethyl-4-methyl-1,2-cyclobutanediol; 3-propyl-1,2-
cyclobutanediol; 3-
isopropyl-1,2-cyclobutanediol; 1-ethyl-1,2-cyclopentanedioI; 1,2-dimethyl-1,2-
cyclopentanediol; I,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-cyciopentanediol; 4-ethyl-1,2-
cyclopentanediol; I,I-
bis(hydroxymethylxyclohexane; 1,2-bis(hydroxymethylkyclohexane; I,2-dimethyl-
1,3-
cyclohexanediol; 1,3-bis(hydroxymethyl)cyclohexane; I-hydroxy-
cyclohexanemethanol;
1-methyl-1,2-cyclohexanediol; 3-hydroxymethylcyclohexanol; 3-methyl-1,2-
cyclohexanediol; 4,4-dimethyl-1,3-cyclohexanediol; 4,5-dimethyl-I,3-
cyclohexanediol;
4,b-dimethyl-1,3-cyclohexanediol; 4-ethyl-I,3-cyclohexanediol; 4-hydroxyethyl-
1-
cyclohexanol; 4-hydroxymethylcyclohexanol; 4-methyl-1,2-cyclohexanediol; I,2-
cycloheptanediol; ; 1,2-cyclohexanediol, pentaethoxylate; 1,2-cyclohexanediol,
hexaethoxylate; 1,2-cyclohexanediol, heptaethoxylate; 1,2-cyclohexanediol,
CA 02249587 1998-09-21
WO 97/34972 PCT/US97/03374
octaethoxylate; 1,2-cyclohexanediol, nonaethoxylate; 1,2-cyclohexanediol,
monopropoxylate: and/or 1,2-cyclohexanediol, dibutylenoxylate.
Preferred aromatic diols include: I-phenyl-1,2-ethanediol; 1-phenyl-1.2-
propanediol; 2-phenyl-1,2-propanediol; 3-phenyl-1,2-propanediol; I-(3-
methylphenyl)
1,3-propanediol; 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; I-(3-methylphenyl)-1,3-propanediol; I-(4-methylphenyl)-1,3-
propanediol;
2-methyl-1-phenyl-1,3-propanediol; and/or 1-phenyl-1,4-butanediol are the most
preferred.
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
CH2 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-I-propenyl)-; 1,3-
butanediol, 2-(2-
butenyl)-2-methyl-; 1,3-butanediol, 2-(3-methyl-2-butenyl)-; 1,3-butanediol, 2-
ethyl-2-(2-
propenyl)-; 1,3-butanediol, 2-methyl-2-(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-; I,5-hexanediol, 2-(1-
methylethenyl}-; 2-hexene-I,S-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-I,4-diol, 5,6-dimethyl-; 3-heptene-1,5-diol, 4,6-
dimethyl-; S-
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-I,5-diol, 2,4-dimethyl-; 6-heptene-
I,5-diol, 2-
ethylidene-6-methyl-; 6-heptene-2,4-diol, 4-(2-propenyl)-; I-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-
CA 02249587 1998-09-21
WO 97/34972 PCT/US97/03374
~b
3,~-diol, 4-methyl-; 7-octene-2,4-diol, 2-methyl-6-methylene-; 7-octene-2,~-
diol, 7-
methyl-; 7-octene-3.~-diol, 2-methyl-: 1-nonene-3,~-diol; 1-nonene-3,7-diol; 3-
nonene-
2,~-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-decadiene-4,6-
diol.
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; I,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.
When several derivatives of the same diol with different aikyleneoxy 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
I S 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
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., CH2) 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, CH2 groups are added while,
for each
CH2 group added, two hydrogen atoms are removed from adjacent carbon atoms in
the
molecule to form one carbon-carbon double bond, thus holding the number of
hydrogen
atoms in the molecule constant with respect to the chemical formula of the
"parent"
saturated principal solvent. This is due to a surprising fact that adding a -
CH2- 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 CIogP value by about a similar amount, viz., about 0.48, thus about
compensating for
the -CH2- addition. Therefore one goes from a preferred saturated principal
solvent to the
CA 02249587 1998-09-21
WO 97/34972 PCT/US97/03374
'T l
preferred higher molecular weight unsaturated analogs/homologs containing at
least one
more carbon atom by inserting one double bond for each additional CH2 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 range. The following are some illustrative examples:
2.2-Dimethyl-6-heptene-I,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 CH2
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.
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 CH2
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.
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 CH2
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.
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 CH2
group and a double bond to either of the following preferred C8-diol principal
solvents: 3
ethyi-2-methyl-1,3-pentanediol or 2-ethyl-3-methyl-1,3-pentanediol.
3,6-Dimethyl-S-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 CH2
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.
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 CH2
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.
4-Methyl-6-octene-3,5-diol (CAS No. 156414-25-4) is a preferred C9-diol
principal solvent and can be considered to be derived by appropriately adding
a CH2
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.
Rosiridol (CAS No. 101391-O1-9) and isorosirido! (CAS No. 149252-15-3) are
two isomers of 3,7-dimethyI-2,6-octadiene-1,4-diol, and are preferred C10-diol
principal
CA 02249587 1998-09-21
WO 97/34972 PCTNS97/03374
~z
solvents. They can be considered to be derived by appropriately adding two CH2
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-I,3-hexanediol; or 3,5-dimethyl-1,4-hexanediol.
8-Hydroxylinalool (CAS No. 103619-06-3, 2,6-dimethyl-2,7-octadiene-1,6-diol)
is a prefer ed C 10-diol principal solvent and can be considered to be derived
by
appropriately adding two CH2 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.
2,7-Dimethyl-3,7-octadiene-2,5-diol (CAS No. I 71436-39-8) is a preferred C 10
diol principal solvent and can be considered to be derived by appropriately
adding two
CH2 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.
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 CH2
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.
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. 160429-40-
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; S-methyl-2,4-hexanediol; or
2,4-
dimethyl-1,3-pentanediol; and 2,6-dimethyi-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-I,2-heptanediol; 6-methyl-1,2-
heptanediol; or 2,5-dimethyl-1,2-hexanediol.
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, CH2 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
CA 02249587 1998-09-21
WO 97/34972 PCT/US97/03374
~3
preferred unsaturated 6,6-dimethyl-1-heptene-3.S-diol (CAS No. 109788-O1-4)
having no
adjacent hydroxyl groups can be considered to be derived from the inoperable
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.S-diol is derived from
either 2-
S methyl-3,S-heptanediol or S,S-dimethyl-2,4-hexanediol which are both
preferred principal
solvents and do not have adjacent hydroxyl groups. Conversely. inserting CH2
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-S-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-S-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
1S 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,S-
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. Le., in general, the relationship is more reliable when the
distance/relationship of
the two hydroxy groups is maintained. Le., 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.
It has been discovered that the use of these specific principal alcohol
solvents can
2S 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.
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
3S principal solvent level (relative to the softener level) is needed to
attain product clarity.
CA 02249587 1998-09-21
WO 97/34972 PCT/US97/03374
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:~~
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.
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 processabiiity of the softener
compositions.
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 solvents)
of this
invention is still present in the liquid concentrated, clear fabric softener
composition. An
effective amount of the principal solvents) 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 solvents) 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.
CA 02249587 1998-09-21
WO 97134972 PCT/US97/03374
'~ 5
For example, even though 1.2-pentanediol, 1.3-octanediol, and hydroxy pivalyl
hydroxy pivalate (hereinafter, HPHP) having the following formula:
HO-CH2-C(CH3)2-CH2-O-CO-C(CH3)2_CH2-OH (CAS # 1115-20-4)
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.
Some of the secondary solvents that can be used are those listed as inoperable
hereinbefore and hereinafter, as well as some parent, non-alkoxylated solvents
disclosed
in Tables VIIIA-VIIIE.
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°C, more preferably by at least about
10°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.
Alkvl Lactates
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.
These principal solvents all provide the unobvious benefit described
hereinbefore.
III. OPTIONAL INGREDIENTS
(A) Low molecular weight water soluble solvents can also be used at levels of
of from 0% to about 12%, preferably from about 1% to about 10%, more
preferably from
CA 02249587 1998-09-21
WO 97/34972 PCT/US97/03374
about ?% 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 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.
(B) Bri~ghteners
The compositions herein can also optionally contain from about 0.005% to 5% by
weight of certain types of hydrophilic optical brighteners which also provide
a dye
transfer inhibition action. If used, the compositions herein will preferably
comprise from
about 0.001 % to 1 % by weight of such optical brighteners.
The hydrophilic optical brighteners useful in the present invention are those
having the structural formula:
R~ RZ
N H H N
N O>-N ~ C=C ~ N--CO N
/ N H H N
R2 S03M S~3M Rt
wherein R1 is selected from anilino, N-2-bis-hydroxyethyl and NH-2-
hydroxyethyl; R2 is
selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methylamino,
morphilino,
chloro and amino; and M is a salt-forming canon such as sodium or potassium.
When in the above formula, R1 is anilino, R2 is N-2-bis-hydroxyethyl and M is
a
cation such as sodium, the brightener is 4,4',-bis[(4-anilino-6-(N-2-bis-
hydroxyethyl)-s-
triazine-2-yl)amino]-2,2'-stilbenedisulfonic acid and disodium salt. This
particular
brightener species is commercially marketed under the tradename Tinopal-LTNPA-
GX~
by Ciba-Geigy Corporation. Tinopal-L1NPA-GX is the preferred hydrophilic
optical
brightener useful in the rinse added compositions herein.
When in the above formula, R1 is anilino, R2 is N-2-hydroxyethyl-N-2-
methylamino and M is a cation such as sodium, the brightener is 4,4'-bis[(4-
anilino-6-(N-
2-hydroxyethyl-N-methylamino)-s-triazine-2-yl)amino]2,2'-stilbenedisulfonic
acid
disodium salt. This particular brightener species is commercially marketed
under the
tradename Tinopal SBM-GX~ by Ciba-Geigy Corporation.
CA 02249587 2001-07-09
When in the above formula, RI is aniiino, R~ is morphilino and M is a cation
such
as sodium, the brightener is .~,4'-bis[(4-aniIino-6-morphilino-s-triazine-2-
yl)amino)2.?'-
stilbenedisulfonic acid, sodium salt. This particular brightener species is
commercially
marketed under the tradename Tinopal AMS-GX~ by Ciba Geigy Corporation.
(C) Dispersibilitv Aids
(3) Optional ViscositvlDisnersibilitv Modifiers
lteiatively concentrated compositions containing both saturated and
unsaturated
diester quaternary ammonium compounds can be prepared that are stable without
the
addition of concentration aids. However, the compositions of the present
iavernion may
require organic and/or inorganic concentration aids to go to even higher
concentrations
and/or to meet higher stability standards depending on the other ingredients.
These
concentration aids which typically can be viscosity modifiers may be needed,
or
preferred, for ensuring stability under extreme conditions when particular
softener active
levels are used. The surfactant concentration aids are typically selected from
the group
consisting of ( 1 ) single long chain alkyl cationic surfactants; (2) nonionic
surfactants; (3)
amine oxides; (4) fatty acids; and (5) mixtures thereof. These aids are
described in
U.S. Patent No. 5,545,340 Wahl, et al, issued August 13, 1996.
When said dispersibility aids are present , the total levei is from about 2%
to about
25%, preferably from about 3°/, to about 17%, more preferably from
about 4% to about
15%, and even more preferably from 5% to about 13% by weight of the
composition.
These materials can either be added as part of the active soRener raw
material, (I), e.g.,
the mono-long chain alkyl cationic surfactant and/or the fatty acid which are
reactants
used to form the biodegradable fabric softener active as discussed
hereinbefore, or added
as a sepa~e compozzart. The total level of dispersibility aid includes any
amount that
~Y ~ pmt as part of cx~mponent (n.
1 ) CYI Cationic ~tIBIeln3lV mm~tL~
When the mono-alkyl cationic quaternary ammonium compound is present, it is
typically present at a level of from .about 2% to about 25%, preferably from
about 3% to
about 17%, more preferably from about 4% to about 15%, and even more
preferably from
5% to about 13% by weight of the composition, the total mono-alkyl cationic
quaternary
ammonium compound being at least at an effective level.
Such mono-alkyi cationic quaternary ammonium compounds useful in the present
invention are, preferably, quaternary ammonium salts of the general formula:
~4N+(RS)3~ X.
CA 02249587 2001-07-09
wherein
R~ is Cg-C22 alkyl or aIkenyl group, preferably C l0-C I g alkyl or alkenyl
group; more
preferably C 1 p-C 1 ~ or C 16-C 1 g alkyl or alkenyl group;
each R~ is a C 1-C6 alkyl or substituted alkyl group (e.g., hydroxy alkyl),
preferably C 1-
C3 alkyl group, e.g., methyl (most preferred), ethyl, propyl, and the like, a
benzyl group,
hydrogen, a polyethoxylated chain with from about 2 to about 20 oxyethylene
units.
preferably from about 2.5 to about 13 oxyethylene units, more preferably from
about 3 to
about 10 oxyethyIene units, and mixtures thereof; and
X- is as defined hereinbefore for (Formula (I)).
Especially preferred dispersibility aids are monolauryl trimethyl ammonium
chloride and monotallow trimethyl ammonium chloride available from Witco under
the
trade name Varisoft~ 471 and monooIeyl trimethyl ammonium chloride available
from
Witco under the tradename VarisoR~ 417.
The R4 group can also be attached to the cationic nitrogen atom through a
group
containing one, or more, ester, amide, ether, amine, ete., linking groups
which can be
desirable for increased concentratability of component (n, etc. Such linking
groups are
preferably within from about one to about three carbon atoms of the nitrogen
atom.
Mono-alkyl cationic quaternary ammonium compounds also include Cg-C22 alkyl
choline esters. "fhe preferred dispersibility aids of this type have the
formula:
R1C(O)-O-CH2CH2N+(R)3 X~
wherein R1, R and X- are as defined previously.
Highly preferred dispersibility aids include C 12-C 14 corn choline ester and
C 16-
C 1 g tallow choline ester.
Suitable biodegradable single-long-chain alkyl dispersibiliry aids containing
an
ester- linica~e is the long chains are described in U.S. Pat: No. 4,840,738,
Hardy and
Wallet', issued lone 20,1989.
What the dispersibility aid comprises alkyl choline esters, preferably the
compositions also contain a small amount, preferably from about 2% to about 5%
by
weight of the composition, of organic acid Organic acids are described in
European
Patent Application No. 404,471, Machin et al., published oa Dec. 27, 1990,
supra,
Preferably the organic acid is selected from the group
consisting of glycolic acid, acetic acid, citric acid, and mixtures thereof.
Ethoxylated quaternary ammonium compounds which can serve as the
dispersibility aid include ethylbis(polytthoxy ethanol)alkylammonium
ethyl~sulfate with
17 moles of ethylene oxide, available under the trade name Variquat~ 66 from
Sherex
CA 02249587 1998-09-21
WO 97/34972 PCT/US97/03374
7R
Chemical Company; polyethylene glycol ( 1 ~) oleammonium chloride, available
under the
trade name Ethoquad~ 0/2~ from Akzo; and polyethylene glycol ( 15) cocomonium
chloride. available under the trade name Ethoquad~ C/25 from Akzo.
Although the main function of the dispersibility aid is to increase the
dispersibility
of the ester softener, preferably the dispersibility aids of the present
invention also have
some softening properties to boost softening performance of the composition.
Therefore,
preferably the compositions of the present invention are essentially free of
non
nitrogenous ethoxylated nonionic dispersibility aids which will decrease the
overall
softening performance of the compositions.
Also, quaternary compounds having only a single long alkyl chain, can protect
the
cationic softener from interacting with anionic surfactants and/or detergent
builders that
are carried over into the rinse from the wash solution.
(2) Amine Oxides
Suitable amine oxides include those with one alkyl or hydroxyalkyl moiety of
about 8 to about 22 carbon atoms, preferably from about 10 to about 18 carbon
atoms,
more preferably from about 8 to about 14 carbon atoms, and two alkyl moieties
selected
from the group consisting of alkyl groups and hydroxyalkyl groups with about 1
to about
3 carbon atoms.
Examples include dimethyloctylamine oxide, diethyldecylamine oxide, bis-(2-
hydroxyethyl)dodecyi-amine oxide, dimethyldodecylamine oxide, dipropyl-
tetradecylamine oxide, methylethylhexadecylamine oxide, dimethyl-2-
hydroxyoctadecylamine oxide, and coconut fatty alkyl dimethylamine oxide.
(D) Stabilizers
Stabilizers can be present in the compositions of the present invention. The
term
"stabilizer," as used herein, includes antioxidants and reductive agents.
These agents are
present at a level of from 0% to about 2%, preferably from about 0.01 % to
about 0.2%,
more preferably from about 0.035% to about 0.1% for antioxidants, and more
preferably
from about 0.01 % to about 0.2% for reductive agents. These assure good odor
stability
under long term storage conditions. Antioxidants and reductive agent
stabilizers are
especially critical for unscented or low scent products (no or low perfume).
Examples of antioxidants that can be added to the compositions of this
invention
include a mixture of ascorbic acid, ascorbic palmitate, propyl gallate,
available from
Eastman Chemical Products, Inc., under the trade names Tenox~ PG and Tenox~ S-
1; a
mixture of BHT (butylated hydroxytoluene), BHA (butylated hydroxyanisole),
propyl
gallate, and citric acid, available from Eastman Chemical Products, Inc.,
under the trade
CA 02249587 1998-09-21
WO 97/34972 PCT/US97/03374
name Tenox:~-6; butylated hydroxytoluene. available from UOP Process Division
under
the trade name Sustane~ BHT; tertiary butylhydroquinone, Eastman Chemical
Products.
Inc.. as Tenor TBHQ; natural tocopherols, Eastman Chemical Products, Inc., as
Tenor GT-1/GT-2; and butylated hydroxyanisole, Eastman Chemical Products,
Inc., as
BHA; long chain esters (Cg-C22) of gallic acid, e.g., dodecyl gallate;
Irganox~ 1010;
Irganox~ 1035; Irganox~ B 1171; Irganox~ 1425; Irganox~ 3114; Irganox~ 3125;
and
mixtures thereof; preferably Irganox~ 3125, Irganox~ 1425, Irganox~ 3114, and
mixtures thereof; more preferably Irganox~ 3125 alone or mixed with citric
acid and/or
other chelators such as isopropyl citrate, Dequest~ 2010, available from
Monsanto with a
chemical name of 1-hydroxyethylidene-l, 1-diphosphonic acid (etidronic acid),
and
Tiron~, available from Kodak with a chemical name of 4,5-dihydroxy-m-benzene-
sulfonic acid/sodium salt, and DTPA~, available from Aldrich with a chemical
name of
diethylenetriaminepentaacetic acid.
The chemical names and CAS numbers for some of the above stabilizers which can
be used in the compositions of the present invention are listed in Table I
below.
(E) Soil Release Agent
In the present invention, an optional soil release agent can be added. The
addition
of the soil release agent can occur in combination with the premix, in
combination with
the acid/water seat, before or after electrolyte addition, or after the final
composition is
made. The softening composition prepared by the process of the present
invention herein
can contain from 0% to about 10%, preferably from 0.2% to about 5%, of a soil
release
agent. Preferably, such a soil release agent is a polymer. Polymeric soil
release agents
useful in the present invention include copolymeric blocks of terephthalate
and
polyethylene oxide or polypropylene oxide, and the like.
A preferred soil release agent is a copolymer having blocks of terephthalate
and
polyethylene oxide. More specifically, these polymers are comprised of
repeating units of
ethylene terephthalate and polyethylene oxide terephthalate at a molar ratio
of ethylene
terephthalate units to polyethylene oxide terephthalate units of from 25:75 to
about 35:65,
said polyethylene oxide terephthalate containing polyethylene oxide blocks
having
molecular weights of from about 300 to about 2000. The molecular weight of
this
polymeric soil release agent is in the range of from about 5,000 to about
55,000.
Another preferred polymeric soil release agent is a crystallizabie polyester
with
repeat units of ethylene terephthalate units containing from about 10% to
about 1 S% by
weight of ethylene terephthalate units together with from about 10% to about
SO% by
weight of polyoxyethylene terephthalate units, derived from a polyoxyethylene
glycol of
CA 02249587 1998-09-21
WO 97/34972 PCTNS97/03374
81
average molecular weight of from about 300 to about 6.000, and the molar ratio
of
ethylene terephthalate units to polyoxyethylene terephthalate units in the
crystallizable
polymeric compound is between 2:1 and 6:1. Examples of this polymer include
the
commercially available materials Zelcon 4780~ (from Dupont) and Milease T~
(from
~ ICI).
Highly preferred soil release agents are polymers of the generic formula:
O
X- OCH CH O-O-R14 CI ~-OR15 O 14-
( 2 2)p( )u(O-C-R OC O)(CH2CH20-)~-X
in which each X can be a suitable capping group, with each X typically being
selected
from the group consisting of H, and alkyl or acyl groups containing from about
1 to about
4 carbon atoms. p is selected for water solubility and generally is from about
6 to about
I13, preferably from about 20 to about 50. a is critical to formulation in a
liquid
composition having a relatively high ionic strength. There should be very
little material
in which a is greater than 10. Furthermore, there should be at least 20%,
preferably at
least 40%, of material in which a ranges from about 3 to about 5.
The R14 moieties are essentially 1,4-phenylene moieties. As used herein, the
term
"the R 14 moieties are essentially 1,4-phenylene moieties" refers to compounds
where the
R14 moieties consist entirely of 1,4-phenylene moieties, or are partially
substituted with
other arylene or alkarylene moieties, alkylene moieties, alkenylene moieties,
or mixtures
thereof. Arylene and alkarylene moieties which can be partially substituted
for 1,4-
phenyiene include 1,3-phenylene, 1,2-phenylene, 1,8-naphthylene, 1,4-
naphthylene, 2,~-
biphenylene, 4,4-biphenylene, and mixtures thereof. Alkylene and alkenylene
moieties
which can be partially substituted include 1,2-propylene, 1,4-butylene, 1,5-
pentylene, 1,6-
hexamethylene, 1,7-heptamethylene, 1,8-octamethylene, 1,4-cyclohexylene, and
mixtures
thereof.
For the RI4 moieties, the degree of partial substitution with moieties other
than
1,4-phenylene should be such that the soil release properties of the compound
are not
adversely affected to any great extent. Generally the degree of partial
substitution which
can be tolerated will depend upon the backbone length of the compound, i.e.,
longer
backbones can have greater partial substitution for 1,4-phenylene moieties.
Usually.
compounds where the R14 comprise from about 50% to about 100% 1,4-phenylene
moieties (from 0% to about 50% moieties other than 1,4-phenylene) have
adequate soil
release activity. For example, polyesters made according to the present
invention with a
CA 02249587 2001-07-09
-X0:60 mole ratio of isophthalic ( 1.3-phenylene) to terephthalic ( l .4-
phenylene) acid have
adequate soil release activity. However, because most polyesters used in fiber
making
comprise ethylene terephthalate units, it is usually desirable to minimize the
degree of
partial substitution with moieties other than 1,4-phenylene For best soil
release activity.
Preferably, the R14 moieties consist entirely of (i.e., comprise I00%) 1.4-
phenylene
moieties. i.e., each R14 moiety is I,4-phenylene.
For the R 1 ~ moieties, suitable ethylene or substituted ethylene moieties
include
ethylene, 1,2-propylene, i,2-butylene. 1,2-hexylene, 3-methoxy-1,2-propylene,
and
mixtures thereof. Preferably, the R1~ moieties are essentially ethylene
moieties, 1,2-
propylene moieties, or mixtures thereof. Inclusion of a greater percentage of
ethylene
moieties tends to improve the soil release activity of compounds.
Surprisingly, inclusion
of a greater percentage of 1,2-propylene moieties tends to improve the water
solubility of
compounds.
Therefore, the use of 1,2-propylene moieties or a similar branched equivalent
is
desirable for incorporation of any substantial part of the soil release
component in the
liquid fabric softener compositions. Preferably, from about 75% to about 100%,
are 1,2
propylene moieties.
The value for each p is at least about 6, and preferably is at least about 10.
The
value for each n usually ranges from about I2 to about I 13. Typically the
value for each
p is in the range of from about 12 to about 43.
A more complete disclosure of soil release agents is contained in U.S. Pat.
Nos.:
4,661,267, Decker, Konig, Straathof, and Gosselink, issued Apr. 28, 1987;
4,7I1,730,
Gosselink and Diehl, isstxd Dec. 8, 1987; 4,749,596, Evens, Huntington,
Stcwart, Wolf,
and Zimmerer, issued Jeme 7, 1988; 4,818,569, Trinh, Gosselink, and Rattinger,
issued
April 4, 1989; 4,877,896, Maldonado, Trinh, and Gosselink, issued pct, 31,
1989;
4,956,447, f~oaselink et al., issues Sept. ! 1, 1990; and 4,976,879,
Maldonado, Trinh, and
Gosselink, issued Dac 11, 1990.
These soil release agents can also act as scum dispersaats.
(~ Scum Dis~ ant
In the present inveation, the premix can be combined with an optional scum
dispersaat, other than the soil release agent, and heated to a temperature at
or above the
melting points) of the components.
The preferred scum dispersants heroin are .formed by highly ethoxylating
hydrophobic materials, The hydrophobic material can be a fatty alcohol, fatty
acid, fatty
CA 02249587 1998-09-21
WO 97/34972 PCT/US97/03374
83
amine, fatty acid amide, amine oxide, quaternary ammonium compound, or the
hydrophobic moieties used to form soil release polymers. The preferred scum
dispersants
are highly ethoxylated, e.g., more than about 17, preferably more than about
25, more
preferably more than about 40, moles of ethylene oxide per molecule on the
average, with
the polyethylene oxide portion being from about 76% to about 97%, preferably
from
about 81 % to about 94%, of the total molecular weight.
The level of scum dispersant is sufficient to keep the scum at an acceptable,
preferably unnoticeable to the consumer, level under the conditions of use,
but not enough
to adversely affect softening. For some purposes it is desirable that the scum
is
nonexistent. Depending on the amount of anionic or nonionic detergent, etc.,
used in the
wash cycle of a typical laundering process, the efficiency of the rinsing
steps prior to the
introduction of the compositions herein, and the water hardness, the amount of
anionic or
nonionic detergent surfactant and detergency builder (especially phosphates
and zeolites)
entrapped in the fabric {laundry) will vary. Normally, the minimum amount of
scum
dispersant should be used to avoid adversely affecting softening properties.
Typically
scum dispersion requires at least about 2%, preferably at least about 4% (at
least 6% and
preferably at least 10% for maximum scum avoidance) based upon the level of
softener
active. However, at levels of about 10% (relative to the softener material) or
more, one
risks loss of softening efficacy of the product especially when the fabrics
contain high
proportions of nonionic surfactant which has been absorbed during the washing
operation.
Preferred scum dispersants are: Brij 700~; Varonic U-250~; Genapol T-500~,
Genapol T-800~; Plurafac A-79~; and Neodol 25-50~.
(G) Bactericides
Examples of bactericides used in the compositions of this invention include
glutaraldehyde, formaldehyde, 2-bromo-2-vitro-propane-1,3-diol sold by Inolex
Chemicals, located in Philadelphia, Pennsylvania, under the trade name
Bronopol~, and a
mixture of 5-chloro-2-methyl-4-isothiazoline-3-one and 2-methyl-4-
isothiazoline-3-one
sold by Rohm and Haas Company under the trade name Kathon about 1 to about
1,000
ppm by weight of the agent.
(H) Perfume
The present invention can contain any softener compatible perfume.
Suitable perfumes are disclosed in U.S. Pat. 5,500,138, Bacon et al., issued
March
19, 1996, said patent being incorporated herein by reference.
As used herein, perfume includes fragrant substance or mixture of
substances including natural (i.e., obtained by extraction of flowers, herbs,
leaves,
CA 02249587 1998-09-21
WO 97/34972 PG"T/US97/03374
roots, barks, wood. blossoms or plants), artificial (i.e., a mixture of
different nature
oils or oil constituents) and synthetic (i.e., synthetically produced)
odoriferous
substances. Such materials are often accompanied by auxiliary materials, such
as
fixatives, extenders, stabilizers and solvents. These auxiliaries are also
included
within the meaning of "perfume", as used herein. Typically, perfumes are
complex
mixtures of a plurality of organic compounds.
Examples of perfume ingredients useful in the perfumes of the present
invention compositions include, but are not limited to, hexyl cinnamic
aldehyde;
amyl cinnamic aldehyde; amyl salicylate; hexyl salicylate; terpineol; 3,7-
dimethyl-
cis-2,6-octadien-1-ol; 2,6-dimethyl-2-octanol; 2,6-dimethyl-7-octen-2-ol; 3,7-
dimethyl-3-octanol; 3,7-dimethyl-trans-2,6-octadien-1-oI; 3,7-dimethyl-6-octen-
1-
ol; 3,7-dimethyI-1-octanol; 2-methyl-3-(para-tert-butylphenyl)-
propionaldehyde; 4-
(4-hydroxy-4-methylpentyl)-3-cyclohexene-1-carboxaldehyde; tricyclodecenyl
propionate; tricyclodecenyl acetate; anisaldehyde; 2-methyl-2-(para-iso-
propylphenyl)-propionaldehyde; ethyl-3-methyl-3-phenyl glycidate; 4-(para-
hydroxyphenyl)-butan-2-one; 1-(2,6,6-trimethyl-2-cyclohexen-1-yl}-2-buten-1-
one;
para-methoxyacetophenone; para-methoxy-alpha-phenylpropene; methyl-2-n-hexyl-
3-oxo-cyclopentane carboxylate; undecalactone gamma.
Additional examples of fragrance materials include, but are not limited to,
orange oil; lemon oil; grapefruit oil; bergamot oil; clove oil; dodecalactone
gamma;
methyl-2-(2-pentyl-3-oxo-cyclopentyl) acetate; beta-naphthol methylether;
methyl
beta-naphthylketone; coumarin; decylaldehyde; benzaidehyde; 4-tert
butylcycIohexyl acetate; alpha,alpha-dimethylphenethyl acetate;
methylphenylcarbinyl acetate; Schiffs base of 4-(4-hydroxy-4-methyipentyl)-3
cyclohexene-1-carboxaldehyde and methyl anthranilate; cyclic ethyleneglycol
diester of tridecandioic acid; 3,7-dimethyl-2,6-octadiene-1-nitrite; ionone
ganurla
methyl; ionone alpha; ionone beta; petitgrain; methyl cedrylone; 7-acetyl-
1,2,3,4,5,6,7,8-octahydro-1,1,6,7-tetramethyl-naphthalene; ionone methyl;
methyl-
1,6,10-trimethyl-2,5,9-cyclododecatrien-1-yl ketone; 7-acetyl-1,1,3,4,4,6-
hexamethyl tetralin; 4-acetyl-6-tert-butyl-l,l-dimethyl indane; benzophenone;
6-
acetyl-1,1,2,3,3,5-hexamethyl indane; 5-acetyl-3-isopropyl-1,1,2,6-tetramethyl
indane; 1-dodecanal; 7-hydroxy-3,7-dimethyl octanal; 10-undecen-1-al; iso-
hexenyl
cyclohexyl carboxaldehyde; fonmyl tricyclodecan; cyclopentadecanolide; 16-
hydroxy-9-hexadecenoic acid lactone; 1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-
hexamethylcyclopenta-gamma-2-benzopyrane; ambroxane; dodecahydro-3a,6,6,9a-
CA 02249587 1998-09-21
WO 97/34972 PCT/US97/03374
~5
tetramethylnaphtho-[2,1 b]furan: cedrol; S-(2,2.3-trimethylcyclopent-3-enyl)-3-
methylpentan-2-ol; 2-ethyl-4-(2,2,3-trimethyl-3-cyclopenten-1-yl)-2-buten-1-
ol;
caryophyllene alcohol: cedryl acetate; para-tent-butylcyclohexyl acetate;
patchouli;
olibanum resinoid; labdanum; vetivert; copaiba balsam; fir balsam; and
S condensation products of: hydroxycitronellal and methyl anthranilate;
hydroxycitronellal and indol; phenyl acetaldehyde and indol; 4-(4-hydroxy-4-
methyl
pentyl)-3-cyclohexene-1-carboxaldehyde and methyl anthranilate.
More examples of perfume components are geraniol; geranyl acetate;
linalool; linalyl acetate; tetrahydrolinalool; citronellol; citronellyl
acetate;
dihydromyrcenol; dihydromyrcenyl acetate; tetrahydromyrcenol; terpinyl
acetate;
nopol; nopyl acetate; 2-phenylethanol; 2-phenyiethyl acetate; benzyl alcohol;
benzyl
acetate; benzyl salicylate; benzyl benzoate; styrallyl acetate;
dimethylbenzylcarbinol; trichloromethylphenylcarbinyl methyiphenylcarbinyl
acetate; isononyl acetate; vetiveryl acetate; vetiverol; 2-methyl-3-(p-tert-
butylphenyl)-propanal; 2-methyl-3-(p-isopropylphenyl)-propanal; 3-(p-tert-
butylphenyl)-propanal; 4-(4-methyl-3-pentenyl)-3-cyclohexenecarbaldehyde; 4-
acetoxy-3-pentyltetrahydropyran; methyl dihydrojasmonate; 2-n-
heptylcyclopentanone; 3-methyl-2-pentyl-cyclopentanone; n-decanal; n-
dodecanal;
9-decenol-l; phenoxyethyl isobutyrate; phenylacetaldehyde dimethylacetal;
phenylacetaldehyde diethyiacetal; geranonitrile; citronelionitrile; cedryl
acetal; 3-
isocamphylcyclohexanol; cedryl methylether; isolongifolanone; aubepine
nitrite;
aubepine; heliotropine; eugenol; vanillin; diphenyl oxide; hydroxycitronellal
ionones; methyl ionones; isomethyl ionomes; irones; cis-3-hexenol and esters
thereof; indane musk fragrances; tetralin musk fragrances; isochroman musk
fragrances; macrocyclic ketones; macrolactone musk fragrances; ethylene
brassylate.
The perfumes useful in the present invention compositions are substantially
free of halogenated materials and nitromusks.
Suitable solvents, diluents or carriers for perfumes ingredients mentioned
above are for examples, ethanol, isopropanol, diethylene glycol, monoethyl
ether,
dipropylene glycol, diethyl phthalate, triethyl citrate, etc. The amount of
such
solvents, diluents or carriers incorporated in the perfiunes is preferably
kept to the
minimum needed to provide a homogeneous perfume solution.
Perfume can be present at a level of from 0% to about 10%, preferably from
about 0.1% to about 5%, and more preferably from about 0.2% to about 3%, by
CA 02249587 1998-09-21
WO 97/34972 PCT/US97/03374
glo
weight of the finished composition. Fabric softener compositions of the
present
invention provide improved fabric perfume deposition.
(I) Chelatin~~A;~nts
The compositions and processes herein can optionally employ one or more copper
and/or nickel chelating agents ("chelators"). Such water-soluble chelating
agents can be
selected from the group consisting of amino carboxylates, amino phosphonates,
polyfunctionally-substituted aromatic chelating agents and mixtures thereof,
all as
hereinafter defined. The whiteness and/or brightness of fabrics are
substantially improved
or restored by such chelating agents and the stability of the materials in the
compositions
are improved.
Amino carboxylates useful as chelating agents herein include ethylenedi-
aminetetraacetates (EDTA), N-hydroxyethylethylenediaminetriacetates,
nitrilotriacetates
(NTA), ethylenediamine tetraproprionates, ethylenediamine-N,N'-diglutamates, 2-
hyroxypropylenediamine-N,N'-disuccinates, triethylenetetraaminehexacetates,
I S diethylenetriaminepentaacetates (DETPA), and ethanoldiglycines, including
their water-
soluble salts such as the alkali metal, ammonium, and substituted ammonium
salts thereof
and mixtures thereof.
Amino phosphonates are also suitable for use as chelating agents in the
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-diphosphonate (HEDP). Preferably, these amino phosphonates
to not
contain alkyl or alkenyl groups with more than about 6 carbon atoms.
The chelating agents are typically used in the present rinse process at levels
from
about 2 ppm to about 25 ppm, for periods from 1 minute up to several hours'
soaking.
The preferred EDDS chelator used herein (also known as ethylenediamine-N,N'-
disuccinate) is the material described in U.S. Patent 4,704,233, cited
hereinabove, and has
the formula (shown in free acid form):
H-N-CH2-CH2-N-H
CHZ CH CH CH2
COOH COOH COOH COOH
As disclosed in the patent, EDDS can be prepared using malefic anhydride and
ethylenediamine. The preferred biodegradable [S,S] isomer of EDDS can be
prepared by
reacting L-aspartic acid with 1,2-dibromoethane. The EDDS has advantages over
other
chelators in that it is effective for chelating both copper and nickel canons,
is available in
CA 02249587 2001-07-09
g?
a biodegradable form. and does not contain phosphorus. The EDDS employed
herein as a
chelator is typically in its salt form. i.e.. wherein one or more of the four
acidic hydrogens
are replaced by a water-soluble canon M, such, as sodium, pot~si~. ~onium.
triethanolammonium. and the like. As noted before, the EDDS chelator is also
typically
used in the present rinse process at levels from about 2 ppm to about 25 ppm
for periods
from 1 minute up to several hours' soaking. At certain pH's the EDDS is
preferably used
in combination with zinc cations.
As can be seen from the foregoing, a wide variety of chelators can be used
herein.
Indeed, simple polycarboxylates such as citrate,. oxydisuccinate, and the
like, can also be
used, although such chelators are not as effective as the amino carboxylates
and
phosphonates, on a weight basis.. Accordingly, usage levels may be adjusted to
take into
account differing degrees of chelating effectiveness. The chelators herein
will preferably
have a stability constant (of the fully ionized chelator) for copper ions of
at least about 5,
preferably at least about 7: Typically, the chelators will comprise from about
0.3% to
about 10%; more preferably from about 0.75% to about 3°/a, by weight of
the
compositions herein. Preferred cheiators include DETMP, DETPA, NTA, EDDS and
mixtures thereof.
(J) Other Optional Ingredients
The present invention can include optional components conventionally used in
textile treannent compositions, for example: colorants; preservatives;
surfactants; anti
shrinkage agents; fabric crisping agents; spotting agents; germicides;
fungicides; anti
oxidants such as butylated hydraxy toluene, anti-corrosion agents, and the
like.
Particularly preferred ingredients include water soluble calcium and/or
magnesium
compounds, which provide additional stability.. The chloride salts are
preferred, but
acetate, nitrate, cte. salts can be used The level of said calcium andlor
magnesium salts is
from 0'yfi ~o about 2'/0, preferably from about 0.03% to about 0.5%, more
preferably from
about 0.1'X to about 0.23'X°.
The pe~aent invention can also include other compatible ingccdients, including
those as disclosed in copendiag applications Serial Nos.: 081372,068, filed
January 12,
1993, Rusche, et al.; 081372,490, filed January 12, 1995, Shaw, et al.; and
081277,558,
filed July 19,1994, Haroman, ~ a1.
Solid Comp'ositloas
1. Solid l2articulate com~~ttioas
As discussed hereinbefore, the invention also comprises solid particulate
composition comprising:
CA 02249587 2001-07-09
8$
t.~) from about ~0% to about 95%, preferably from about 60% to about 90%,
of said biodegradable fabric softening active;
tB) optionally, from 0% to about 30%, preferably from about 3% to about
1 ~%. of dispersibility modifier; and
(D) from 0% to about 10% of a pH modifier.
Optional ~H Modifier
Since the biodegradable ester fabric softener actives are somewhat labile to
hydrolysis , it is preferable to include optional pH modifiers in the solid
particulate
composition to which water is to be added, to form stable dilute or
concentrated liquid
softener compositions. Said stable liquid compositions should have a pH (neat)
of from
about 2 to about 5, preferably from about 2 to about 4.5, more preferably from
about 2 to
about 4.
The pH can be adjusted by incorporating a solid, water soluble Bronsted acid.
I S Examples of suitable Bronsted acids include inorganic mineral acids, such
as boric acid,
sodium bisulfate, potassium bisulfate, sodium phosphate monobasic, potassium
phosphate monobasic, and mixtures thereof; organic acids, such as citric acid,
fumaric
acid, malefic acid, malic acid, tannic acid, gluconic acid, glutamic acid,
tartaric acid.
glycoiic acid, chloroacetic acid, phenoxyacetie acid, 1,2,3,4-butane
tetracarboxylic acid.
benzene sulfonic acid, benzene phosphoric acid, ortho-toiuene sulfonic acid,
para-toluene
sulfonic acid, phenol sulfonic acid, naphthalene sulfonic acid, oxalic acid,
I,2,4.5-
pyromeilitic acid, 1,2,4-trimellitic acid, adipic acid, benzoic acid,
phenylacedc acid,
salicylic acid, succinic acid, and mixtures thereof; and mixtures of mineral
inorganic
acids and organic acids. Preferred pH modifiers are citric acid,. gluconic
acid, tartaric
acid, 1,2,3,4.butaa~e tetracarboxylic acid, maIic acid, and mixtures thereof.
Y, materials that can form solid clathrates such as cyclodextrins and/or
zeolites, e~., can be used as adjuvants in the solid particulate composition
as host carriers
of cone liquid acids and/or anhydrides, such as acetic acid, HCI, sulfiuic
acid,
phosphoric acid, nitric acid, carbonic acid, ete. An example of such solid
clatherates is
carbon dioxide adsorbed in zeolite A, as disclosed in U.S. Patent 3,888,998,
Whyte and
Samps, issued Juae 10, 1975 and U.S. Patent 4,007,134, Liepe and Japikse,
issued Feb. 8,
1977. Examples of inclusion
complexes of phosphoric acid, sulfuric acid, and nitric acid, and process for
their
preparation are disclosed in U.S. Pat. No. 4.365,06I, issued Dec. 21, 1982 to
Szejtli et al.
CA 02249587 1998-09-21
WO 97/34972 PCT/US97/03374
When used, the pH modifier is typically used at a level of from about 0.01 %
to
about 10%, preferably from about 0.1 % to about 5%, by weight of the
composition.
Preparation of Solid Particulate Granular Fabric Softener
The granules can be formed by preparing a melt, solidifying it by cooling, and
then grinding and sieving to the desired size. In a three-component mixture,
e.g.,
nonionic surfactant, single-long-chain cationic, and DEQA, it is more
preferred, when
forming the granules, to pre-mix the nonionic surfactant and the more soluble
single-long-chain alkyl cationic compound before mixing in a melt of the
diester
quaternary ammonium cationic compound.
It is highly preferred that the primary particles of the granules have a
diameter of
from about 50 to about 1,000, preferably from about 50 to about 400, more
preferably
from about 50 to about 200, microns. The granules can comprise smaller and
larger
particles, but preferably from about 85% to about 95%, more preferably from
about 95%
to about 100%, are within the indicated ranges. Smaller and larger particles
do not
provide optimum emulsions/dispersions when added to water. Other methods of
preparing the primary particles can be used including spray cooling of the
melt. The
primary particles can be agglomerated to form a dust-free, non-tacky, free-
Bowing
powder. The agglomeration can take place in a conventional agglomeration unit
(i.e.,
Zig-Zag Blender, Lodige) by means of a water-soluble binder. Examples of
water-soluble binders useful in the above agglomeration process include
glycerol,
polyethylene glycols, polymers such as PVA, polyaciylates, and natural
polymers such as
sugars.
The flowability of the granules can be improved by treating the surface of the
granules with flow improvers such as clay, silica or zeolite particles, water-
soluble
inorganic salts, starch, etc.
Method of Use
Water can be added to the particulate, solid, granular compositions to form
dilute
or concentrated liquid softener compositions for later addition to the rinse
cycle of the
laundry process with a concentration of said biodegradable cationic softening
compound
of from about 0.5% to about 50%, preferably from about 1% to about 35%, more
preferably from about 4% to about 32%,. The particulate, rinse-added solid
composition
( 1 ) can also be used directly in the rinse bath to provide adequate usage
concentration
(e.g., from about 10 to about 1,000 ppm, preferably from about 50 to about 500
ppm, of
total softener active ingredient). The liquid compositions can be added to the
rinse to
provide the same usage concentrations.
CA 02249587 1998-09-21
WO 97/34972 PCT/US97/03374
The water temperature for preparation should be from about 20°C to
about 90°C,
preferably from about 25°C to about 80°C. Single-long-chain
alkyl cationic surfactants
as the viscosity/dispersibility modifier at a level of from 0% to about 15%,
preferably
from about 3% to about 15%, more preferably from about ~% to about 15%, by
weight of
the composition, are preferred for the solid composition. Nonionic surfactants
at a level
of from about 5% to about 20%, preferably from about 8% to about 15%, as well
as
mixtures of these agents can also serve effectively as the
viscosity/dispersibility modifier.
The emulsified/dispersed particles, formed when the said granules are added to
water to form aqueous concentrates, typically have an average particle size of
less than
about 10 microns, preferably less than about 2 microns, and more preferably
from about
0.2 to about 2 microns, in order that effective deposition onto fabrics is
achieved. The
term "average particle size," in the context of this specification, means a
number average
particle size, i.e., more than 50% of the particles have a diameter less than
the specified
size.
I S Particle size for the emulsified/dispersed particles is determined using,
e.g., a
Malvern particle size analyzer.
Depending upon the particular selection of nonionic and cationic surfactant,
it
may be desirable in certain cases, when using the solids to prepare the
liquid, to employ
an efficient means for dispersing and emulsifying the particles (e.g.,
blender).
Solid particulate compositions used to make liquid compositions can,
optionally,
contain electrolytes, perfume, antifoam agents, flow aids (e.g., silica), dye,
preservatives,
andlor other optional ingredients described hereinbefore.
The benefits of adding water to the particulate solid composition to form
aqueous
compositions to be added later to the rinse bath include the ability to
transport less weight
thereby making shipping more economical, and the ability to form liquid
compositions
similar to those that are normally sold to consumers, e.g., those that are
described herein,
with lower energy input (i.e., less shear and/or lower temperature).
Furthermore, the
particulate granular solid fabric softener compositions, when sold directly to
the
consumers, have less packaging requirements and smaller, more disposable
containers.
The consumers will then add the compositions to available, more permanent,
containers,
and add water to pre-dilute the compositions, which are then ready for use in
the rinse
bath, just like the liquid compositions herein. The liquid form is easier to
handle, since it
simplifies measuring and dispensing.
CA 02249587 2001-07-09
'_'. Drver Activated comDOSitions
The present invention also relates to improved solid dryer-activated fabric
softener
compositions which are either (A) incorporated into articles of manufacture,
e.g., on a
substrate. or, are (B) in the form of particles similar to those disclosed
above. (including,
where appropriate, agglomerates, pellets, and tablets of said particles). Such
compositions typically contain from about 10% to about 95% of fabric softening
agent.
A. Substrate Articles
In preferred embodiments, the present invention encompasses articles of
manufacture.
Representative articles are those that are adapted for use to provide unique
perfume
I O benefits and to soften fabrics in an automatic laundry dryer, of the types
disclosed in U.S.
Pat. Nos.: 3,989.631 Marsan, issued Nov. 2, 1976; 4,OSS,248, Macsan, issued
Oct. 2s,
1977; 4,073,996. 8edenk et al., issued Feb. 14, 1978; 4,022,938, Zaki et al.,
issued May
10, 1977; 4,764.289, Trinh, issued Aug. 16, 1988; 4,808,086, Evaas et al.,
issued Feb.
28,1989; 4,103.047, Zaki et al., issued July 2s, 1978; 3,736,bb8, Dillarstone,
issued June
i 5 5, 1973; 3,701,202, Compa et al:, issued Oct. 31,1972; 3,634,947, Furgai,
issued Jan. 18,
1972; 3.633,s38, Hoeflin, issued Jan. 11, 1972; and 3,43s,s37, Rumsey, issued
Apr. I,
1969; and 4,000,340, Murphy et al., issued Dec. 28, 1976.
Typical articles of manufacture of this type include articles comprising:
20 I. a fabric conditioning composition comprising from about 30% to about 95%
of normally solid, dryer softenable fabric softening agent comprising said
biodegradable fabric softening active; and
II. a dispensing means which provi~ for release of an effective amount of said
composition including an e~'ective amount of ii, sufficient to provide odor
2s control, to fabrics in an automatic laundry dryer at automatic la
uadry dryer
_ .. og ~p~~ ~.g.~ ~m about 35oC to llsoC.
W6e~t the disp~ing means is a flexible substrate, e.g., in sheet
configuration, the
fabric conditioning composition is relessably axed on the substrate to peovide
a weight
ratio of conditioning composition to dry substrate ranging from about 10:1 to
about O.s:l,
30 preferably from about s:l to about 1:1.
The solid fabric softener compositions herein can include cationic and
nonionic
fabric soRener actives used in combination with each other.
CA 02249587 1998-09-21
WO 97/34972 PCT/US97/03374
Ra
PREPARATION OF PRINCIPAL SOLVENTS
PREPARATION OF DIOL PRINCIPAL SOLVENTS
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.
METHOD A
Preparation of 1,5-,1,6-, and 1,7-Diols
Method 1
This synthesis method is a general preparation of a,c~-type diols derived from
substituted cyclic alkenes. Examples of cyclic alkenes are the alkylated
isomers of
cyclopentene, cyclohexene, and cycioheptene. The general formula of useful
alkylated
cyclic alkenes is
~R
C
(CR2~c II
C
~ \R
wherein each R is H, or C 1-C4-alkyl, and where x is 3, 4, or 5.
Cyclic alkenes may be converted to the terminal diols by a three step reaction
sequence.
Step 1 is the reaction of the cyclic alkene with ozone (03) 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 /H2 to the dialdehyde which is then
converted in Step
3 to the target diol by borohydride reduction.
The 1,2- diols are generally prepared by direct hydroxylation of the
appropriate
substituted olefins. Example:
RFC CSR
wherein each R is H, alkyl, etc.
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°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.
CA 02249587 1998-09-21
WO 97/34972 PCT/US97/03374
Method 2 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°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.
Method 3
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 l, to give the desired I,5- or 1,6- diols, etc.
METHOD B
Preparation of 1,2 Diols
Method 1
METHOD C
Preparation of 1,3-Diols
Acylation of Enamines
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 I,3-dicarbonyl
precursor
to the desired 1,3-diol. The diol is generated by borohydride reduction of the
1,3-
dicarbonyl compound.
Thus acetaldehyde (aldehydes) may be reacted with a secondary amine,
preferably
cyclic amines such as pyrrolidine or morpholine, by heating at reflex 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
reflex 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).
The anhydrous crude enamine containing some excess amine is reacted with the
appropriate acid chloride at about 20°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% HCI.
This
treatment hydrolyzes the enamine to the acylated dicarbonyI compound. This
CA 02249587 2001-07-09
intermediate is then isolated by extraction and distillation to remove low
boiling
impurities. then reduced by sodium borohydride to the desired 1.3- diol.
METHOD D
Preparation of l,~i Diols, by Aldol Condensation and Reduction
The typical reactions involve one or more aldehydes, one or more ketones, and
mixtures thereof, which have at feast 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-CH2-CHO -~ HO-CH2-CH(R~CHOH-CH2-R
R-CH2-CHO + R'-CHZ-CHO --> HO-CH2-CH(RrCHOH-CHI-R +
HO-CH2-CH(R'}-CHOH-CH2-R' + '
HO-CH2-CH(R')-CHOH-CH2-R +
1 S HO-CH2-CH(R)~CHOH-CH2-R'
R-CH2-CHO + R'-CO-CH3 .-+ HO-CH2-CH(R)-CHOH-CH2-R +
R-CH2-CHOH CH2-CHOH-R'
The aldehyde, ketone, or mixture thereof which is to be condensed is placed in
as
autoclave under an inert atmosphere with a solvent such as butanoi or with a
phase
transfer medium such as polyethylene glycol. When a mixed condensation such as
with a
ketone and an aIdehyde 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 tnole% of the reactants. The autoclave is
sealed, and the
mixture is heated at about 35-100°C until most of the original
reactants have been
converted, usually about 5 minutes to about 3 hour, 'The crude mixture is
neutralized and
the fimctions prG~cnt are reduced by hydrogenation over Raney Ni at about
100°
C and abouE 50 atm for about 1 hour. Volatile components are removed by
distillation
and the d~irai diol principal solvents are obtained by vacuum distillation.
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, Kulmaia
et al,
16 Mar. 1995; Japan Pat Appl. No. 40,333, Sato et al, 9 Feb. 1990; Japan Pat.
Appl. No.
299,240, Sato et al, 4 Dec. 1989; Eur. Pat Appl. No. 367,743, Ankaer et al, 9
May 1990.
CA 02249587 1998-09-21
WO 97/34972 PCT/US97/03374
~°~J
Illustrative Examples:
Condensation of Butyraldehyde and/or Isobutyraldehyde and Conversion to Form
Eight-Carbon-1,3-Diols
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°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°C at about 50 atm of pressure for about 1 hour to
yield a mixture of
8-carbon,l,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-ethyl-4-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.
When only butyraldehyde is used in the reaction, the major product obtained is
2-
ethyl-1,3-hexanediol.
When only isobutyraldehyde is used in the reaction, the major product obtained
is
2,2,4-trimethyl-1,3-pentanediol.
Mixed Condensation of Butyraldehyde and Methyl Ethyl Ketone and Conversion to
Form a Miiture of Eight-Carbon-1,3-Diols
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 bas, 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 I
mole, Aldrich) is added and the system is held at about 40°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°C and
about 50 atm. for about 1 hour to yield a mixture of 8-carbon-I,3-diols
including 2-ethyl-
CA 02249587 1998-09-21
WO 97/34972 PCT/US97/03374
a~
1,3-hexanediol, 2-ethyl-3-methyl-1,3-pentanediol, 3.~-octanediol; 3-methyl-3,~-
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.
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).
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 thediol resulting
from self
condensation of butyraldehyde.
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°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°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°C and about 50 atm. for about 1 hour to
yield predominantly
the dial resulting from the condensation of the enolate of 2-butanone with
butyraldehyde,
3,5-octanediol. Purification is optionally accomplished by distillation.
CA 02249587 1998-09-21
WO 97/34972 PCT/US97/03374
4~
Mixed Condensation of Isobutyraldehyde and Methyl Ethyl Ketone and Conversion
to Form a Mixture of Eight-Carbon-1,3-Diols
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,~-heptanediol; and 3-methyl-3,5-heptanediol.
Mixed Condensation of Butyraldehyde, Isobutyraldehyde aad Methyl Ethyl Ketone
and Conversion to Form a Mixture of Eight-Carbon-1,3-Diois
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-pentanediol; 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.
The mixtures prepared by the condensation of butyraIdehyde, 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.
METHOD E
Preparation of 1,4 Diols, by the Addition of Acetylide to Carbonyl Compounds
Dimetallic acetylides Na+ -:C=_C:- Na+ react with aldehydes or ketones to form
unsaturated alcohols, e.g.,
OH OH
2 R-CO-CH3 T NaC=CNa--~ R-C-C=C-C-R
I I
CH3 CH3
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
CA 02249587 1998-09-21
WO 97/34972 PCT/US97/03374
qg
diacetylides, dioI 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
A sodium acetylide (about 18% in xylene) slurry is reacted with
isobutryaldehyde
to form the acetylenic alcohol
(CH3)2CH-CHO + NaC-_-_-CH -~ (CH3)2CH-CHOH-C--_C-H
The acetylenic (ethynyl) alcohol is converted with base to the sodium
acetylide R-
CHOH-C_--CNa which is then reacted with a mole of acetaldehyde to give the
ethynyl
diol R-CHOH-C_--C-CHOH-R'. This compound, (CH3)2CH-CHOH-C--_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.
METHOD F
Preparation of Substituted Diols Derived from Cyclic Anhydrides, Lactones and
Esters of Dicarboxylic Acids
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.
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-A1 per mole of substrate. Using
an alkyl
substituted succinic anhydride to illustrate this method, the typical
reduction is carried out
as follows.
O OH
R \ R
O + Red-A1 --~ + H20
O
OH
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
CA 02249587 1998-09-21
WO 97/34972 PCT/IJS97l03374
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°C. It is maintained at about
80°C during the
remaining addition time and for about two hours following addition.
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°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.
METHOD G
Preparation of Diols with One or Both Alcohol Functions Being Secondary or
Tertiary
This is a general method to prepare substituted diols from lactones and/or
diesters
by alkylation of the carboxyl groups) using methyl magnesium bromide (Grignard
reagent) or alkyl lithium compounds usually methyl lithium, e.g.,
OH
O ~ C._CH3
(CRS . 0 (CR~ CH3
O + 2CH3 --
~-CHZ CHz-OH
This type of alkylation can be extended to diesters. An excess of methylating
reagent will generate diols where both alcohol groups are tertiary.
METHOD H
Preparation of Suhstituted 1,3- ,1,4- and 1,5-Diols
This method is a general preparation of some 1,3-, 1,4- and I,5-diols which
utilizes the chemistry outlined in Method A-I 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
R
I
/'-C~C~H
(C R2hc I
~C~C~H
I
R
CA 02249587 1998-09-21
WO 97/34972 PCT/US97/03374
IvD
wherein each R is H, or C 1-C4-alkyl and wherein x is 1, 2 or 3.
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-
dimethyl-1,3
cyclohexanediol (CAS No. 79419-18-4):
CH3
CH3-C~C~ C CH H3 CSC OH IOH
CH2
CwC~C ~C-OH I H1
CZHS CZHS OH
PREPARATION OF POLYETHOXYLATED DERIVATIVES
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°C to about 170°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
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°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°C. After about an additional
one hour reaction
time, the contents are cooled to about 90°C and a vacuum is pulled to
remove any residual
ethylene oxide.
PREPARATION OF METHYL-CAPPED POLYETHOXYLATED DERIVATIVES
Methyl-capped polyethoxylated derivatives of diols are typically prepared
either
by reacting a methoxypoly(ethoxy)ethyl chloride (i.e., CH30-(CH2CH20)n-CH2CH2
Cl) of the desired chain length with the selected diol, or by reacting a
methyl-capped
CA 02249587 1998-09-21
WO 97/34972 PCT/US97/03374
polyethylene glycol (i.e., CH30-(CH~CH~O)n-CH2CH2-OH) of the desired chain
length
with the epoxy precursor of the diol, or a combination of these methods.
Illustrative Examples: Synthesis of (CH3)2C(OH)CH(CH3)(OCH2CH2)~ OCH3, the
methyl-capped tetraethoxylated derivative of 2-methyl-2,3-butanediol.
To a I -liter, three-neck round bottom flask equipped with a magnetic stirbar,
condenser, thermometer, and temperature controller (Thermowatch I2R)~ 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°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°C.
A 13C-NMR (dmso-d6) 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 HCI, 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.
Synthesis of Methoxytriethoxyethyl Chloride
To a 1-liter, three-neck round bottom flask equipped with a magnetic stirring
bar,
condenser, and temperature controller (Thermowatch, I2R) 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 SO-60°C range. The reaction mixture is
then heated
overnight at about 55°C. A 13C-NMR (D20) is taken which shows only a
small peak at
~60ppm for unreacted alcohol and a sizable peak at --43.Sppm representing
chlorinated
product (-CH2C1). 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 C2HSCH(OH)CH(CH3)CHZ(OCH2CH2)40CH3, the Methyl-Capped
Tetraethoxylated Derivative of 2-Methyl-1,3-pentanediol.
The alcohol, C2HSCH(OH)CH(CH3)CH20H (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~, I2R) along with about 100
ml of
CA 02249587 1998-09-21
WO 97/34972 PCT/US97/03374
lna
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 reflex until gas
evolution ceases.
Methoxytriethoxyethyl chloride (about 242 grams, about 1.2 moles, prepared as
above) is
added and the system is held at reflex for about 48 hours. The reaction
mixture is cooled
S 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 mi 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°C under vacuum. Optionally, further purification is
accomplished by
vacuum distillation to yield the title polyether.
PREPARATION OF POLYPROPOXYLATED DERIVATIVES
A three neck, round bottom flask is equipped with a magnetic stir bar, a solid
C02-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. I -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°C and propylene oxide (Aldrich) is added dropwise from the dropping
funnel at a rate
to maintain a small amount of relax from the solid C02-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 reflex 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 f ltration to give the desired propoxyiated product. The average
degree of
propoxylation is typically confirmed by integration of the 1H-NMR spectrum.
PREPARATION OF POLYBUTOXYLATED DERIVATIVES
A three neck, round bottom flask is equipped with a magnetic stir bar, a solid
C02-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
CA 02249587 1998-09-21
WO 97/34972 PCT/US97/03374
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-S 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°C and a-butylene oxide (Aldrich) is added dropwise from the
dropping funnel at a
rate to maintain a small amount of reflex from the solid C02-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 reflex 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 I H-NMR spectrum.
PREPARATION OF POLYTETRAMETHYLENEOXYLATED DERIVATIVES
I S 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 O.I1 moles of
2-(4-
chlorobutoxy)tetrahydropyran (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°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°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
CA 02249587 1998-09-21
WO 97/34972 PGT/US97/03374
IOy.
greater than one. the entire process is repeated in cycles until the buildup
reaches the
target level.
PREPARATION OF ALKYL AND ARYL MONOGLYCERYL ETHERS
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-CSH11-O-CHOH-CH20H.
Preparation of 3-(pentyloxy)-1,2-propanediol
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°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).
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.
Acetonation lConversion to the Ketal)
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 SnCl4 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
3~ 52°C).
CA 02249587 1998-09-21
WO 97/34972 PCT/US97/03374
ID5
Hvdrolvsis
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 S00 ml of hexanes. The
content of the
flask is then heated to about 50°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.
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 ( 1 N). 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 methanoUwater 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
Synthesis of bis(2-hydroaybutyl) ether
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 2708, 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°C and
epoxybutane (about
71 g. about 1 mole, Aldrich) is added dropwise with stirring. Heating is
continued until
the reflex 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.
Synthesis of bis(2-hydroxycyclopentyl) ether
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
CA 02249587 1998-09-21
WO 97/34972 PCT/US97/03374
lo(p
and boron trifluoride diethyl etherate (about 0.14 g, about 0.01 moles, cis-
traps isomer
mixture, Aldrich) is added. Then the reaction mixture is held at about 10-
40°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.
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.
In the specification and examples herein, all percentages, ratios and parts
are by
weight unless otherwise specified and all numerical limits are normal
approximations.
All documents cited are, in relevant part, incorporated herein by reference.
The following are non-limiting examples of the present invention:
The following are suitable N,N-di(unsaturated 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.
Fatty Acyl
Group DEQA DEQA2 DEQA3 DEQA4 DEQAS
1
C 12 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
C 18:1 74 73 71 68 67
C18:2 4 8 8 11 11
C 18:3 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 S 5
TPU 4 9 10 13 13
TPU = Total polyunsaturated , by
fatty weight.
acyl
groups
CA 02249587 1998-09-21
WO 97/34972 PCT/US97/03374
~u~
Fattv Acv 1 Groun DE A6 DEOA~ pEQA8
C 14 O 1 00
C16 11 25
C18 4 20 14
C14:1 0 0 0
C16:1 1 0 1
C 18:1 27 45 74
C 18:2 50 6 3
C 18:3 7 0 0
Other 0 3 3
Total 100 100 100
IV 125-138 56 Not Available
cis/trans (C 18:1 ) Not Available 7 Not Available
TPU 57 6 Not Available
The following are suitable N,N-di(branched chain 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.
Fattv Acvl Grou p DEQA 10 DEOA 11 DEOA 12
Isomyristic aci d -- 1-2 ---
Myristic acid 7-11 0.5-1 --
Isopalmitic acid 6-7 6-7 1-3
Palmitic acid 4-5 6-7 --
Isostearic 70-76 80-82 60-66
acid
Stearic acid -- 2-3 8-10
Isooleic acid -- -- 13-17
Oleic acid -- -- 6-12
IV 3 2 7-12
Softener
Actives DEOA 13 DE~A 14 DEOA Z 5 DEQA 16
Fatty Acyl Branched Branched Branched Branched
Group fatty fatty acidfatty acid 3 fatty acid
acid 2 4
1
CA 02249587 1998-09-21
WO 97/34972 PCT/US97/03374
!vg
Softener
Actives DEOA 1 ~ pEpp 18 pE~A 19 pE~A?0
Fatty Acyl a-Heptyl 9- and 10- 9- and 10- Methoxyocta
Group decanoic acid Methoxy Isopropoxy- decanoic acid
octadecanoic octadecanoic isomeric
acids acids mixture
Softener
Actives DEQAZ 1 pEQA22 pEpA23
Fatty Acyl Phenyl Methylphenyl- Phenoxyoctadecanoic
Group octadecanoic octadecanoic acids acid
acid
Softener
Active pEOA24 pEpA25
Fatty Acyl 65:35 Mixture of fatty acids 65:35 Mixture of fatty acids
Group used to make DEQA2 and used to make DEQAB and
DEQA 10 DEQA 10
The following Examples show clear, or translucent, products with acceptable
viscosities.
The compositions in the Examples below are made by first preparing a softener
premix by blending at room temperature the appropriate branched DEQA and
unsaturated
DEQA actives. The softener actives can be heated to melting at, e.g., about
130-150°F
(about 55-66°C), if the softener actives) is not fluid at room
temperature. The softener
active is mixed using an IKA RW 25~ 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 room temperature. If the softener actives and/or the principal
solvents) are not
fluid at room temperature and need to be heated, the acid/water seat should
also be heated
to about 100°F (about 38°C) and maintaining said temperature
with a water bath. The
principal solvents) (melted at suitable temperatures if their melting points
are above
room temperature) are added to the 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, if necessary.
CA 02249587 1998-09-21
WO 97/34972 PCT/US97/03374
»9
EXAMPLES
1
TO
6
Ex. Ex. Ex. Ex. Ex. Ex.
1 2 3 4 ~ 6
Ingredients Wt.% Wt.% Wt.% Wt.% Wt.% Wt.%
DEQA2 (85% activein 19.9 -- 15.3 -- 32.5 --
ethanol)
DEQAB (85% activein -- 19.9 -- 15.3 -- 32.5
ethanol)
DEQA10 (85% activein 10.7 10.7 15.3 15.3 17.5 17.5
ethanol )
Ethanol -- -- 2 2 2 2
1,2-Hexanediol 18 18 18 18 28 28
Perfume 1.2 1.2 1 1.35 1.3 1.3
HCl (pH 2-3.5) 0.005 0.005 0.005 0.005 0.005 0.005
Distilled Water Bal. Bal. Bal. Bal. Bal. Bal.
EXAMPLES
7
TO
12
Ex.7 Ex.8 Ex.9 Ex.lO Ex.ll Ex.
l2
Ingredients Wt.% Wt.% Wt.% Wt.% Wt.% Wt.%
DEQA2 (85% activein 19.9 -- -- __ 32 __
ethanol)
DEQAB (85% activein -- -- 19.9 19 -- 19
ethanol)
DEQA11 (85% activein 10.7 -- -- -_ _- __
ethanol)
DEQA12 (85% activein -- 28 -- -- __ --
ethanol)
DEQA 13 (85% activein -- -- 5.4 -- -- __
ethanol)
DEQA14 (85% activein -- -- 5.4 -- -- __
ethanol)
DEQA15 (85% activein -_ __ _ 5 9 __
ethanol)
DEQA16 (85% activein -- -- -- 6 9 --
ethanol)
DEQA 18 (85% activein -- -- -- -_ __
ethanol)
DEQA19 (85% activein -- -- -- -_ --
ethanol)
1.2-Hexanediol 18 15 18 18 28 18
Ethanol __ 1 __ __ __ 1
Perfume 1.2 1 1.2 1.35 2 1.3
CA 02249587 1998-09-21
WO 97/34972 PCT/US97/03374
~ 1t7
HCl (pH 2-3.5) 0.00 0.00 0.00 0.00 0.005 0.00
Distilled Water Bal. Bat. Bal. Bal. Bal. Bal.
EXAMPLES
13
TO
18
Ex. Ex. Ex.lS Ex. Ex. Ex.
l3 l4 l6 l7 l8
Ingredients Wt.% Wt.% Wt.% Wt.% Wt.% Wt
%
DEQA 1 (85% activein 19.9 -- -- 19.9 .
ethanol )
DEQA6 (85% active in -- 17 __ __ _-
--
ethanol)
DEQAB (85% active in -- -- 19.9 -- __
__
ethanol)
DEQA9 (85% active in -- 19.9 19.9
ethanol)
DEQA I 0 (85% activein -- 6.8 7 7 7 7
ethanol)
DEQA11 (85% activein 5.3 -- ~ __ __ __
ethanol)
DEQA20 (85% activein 5.3 -- -_ __ __ __
ethanol)
DEQA21 (85% activein -- 6.8 -- __ __ __
ethanol)
DEQA22 (85% activein -- -_ 3,7 __ __ __
ethanol)
DEQA23 (85% activein __ __ __ 3.7 __ __
ethanol)
DEQA24 (85% activein -- -_ __ __ 3.7 __
ethanol)
DEQA25 (85% activein __ __ __ __ __ 3.7
ethanol)
1,2-Hexanediol 9 9 18 18 18 9
2-Ethyl-1,3-hexanediol 8 -_ __ __ g
2,2,4-Trimethyl-1,3- -- 9 __ __
pentanedioi
Ethanol 2 __ __ __ __ __
Perfume 1.2 1.2 1.2 1.2 1.2 I
.2
HCl (pH 2-3.5) 0.005 0.005 0.005 0.005 0.005 0.005
Distilled Water Hal. Bal. Bal. Bal. Bal. Bal.
CA 02249587 1998-09-21
WO 97/34972 PCT/US97/03374
EXAMPLES 19 - 21
Ex. l9 Ex.20 Ex.3
Ingredients Wt.% Wt.% Wt.%
DEQA24 (8~% active in 30 -- 1
ethanol) ~
DEQA2~ (85% active in -- 30 1
ethanol) S
1.2-Hexanediol 18 18 18
HC1 (pH 2-3.~) 0.005 0.005 0.005
Distilled Water Bal. Bal. Bal.
The above Examples show clear, or translucent, products with acceptable
viscosities.
The compositions of Examples 22 are made at ambient temperature by the
following process:
1. Prepare the water seat containing HCI.
2. Separately, mix perfume and Tenox antioxidant to the diester softener
active.
3. Add the diester active blend into the water seat with mixing.
4. Add about I O-20% of the CaCl2 solution at approximately halfway through
the diester
addition.
5. Add the remainder of the CaCl2 solution after the diester addition is
complete with
mixing.
EXAMPLES 22 TO 27
Ex.22 Ex.23 Ex.24 Ex.25 Ex.26 Ex.27
Ingredients Wt.% Wt.% Wt.% Wt.% t.% Wt.%
W
DEQA2 (85% active 18 -- 15 -- -- _-
in
ethanol)
DEQAB (85% active -- 18 -- 12 -- --
in
ethanol)
DEQA 10 (85% active 9.2 9.2 15 12 -- --
in
ethanol)
DEQA24 (85% active __ __ __ __ 20.8 __
in
ethanol)
DEQA25 (85% active -- -- -- -- __ 2g
in
ethanol)
Perfume 1.35 1.35 1.35 1.35 1.35 1.35
Tenox 6 0.04 0.04 0.04 0.04 0.04 0.04
CaCl2 (25% solution)2 2 2 2 2 2
HC11N 0.30 0.30 0.30 0.30 0.30 0.30
Distilled Water Bal. Bal. Bal. Bal. Bal. Bal.
CA 02249587 1998-09-21
WO 97/34972 PCT/US97/03374
~ ,Z.
The above Examples show dispersion compositions with good stability and
performance.
PROCESSING ASPECTS
S 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. Additional protection for
the
softener active can be provided by adding, e.g., chelant such as
ethylenediaminepentaacetic acid, during preparation of the active. The result
is improved
environmental impact and safety from the manufacturing operation.
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 in
the above Examples, mixed with from about 10% to about 30%, preferably from
about
13% to about 25%, more preferably from about I S% 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.
These premixes can be used to formulate finished compositions in processes
comprising the steps of
1. Make premix of fabric softening active, about 11 % ethanol, and about 17%
principal
solvent, let cool to ambient temperature.
CA 02249587 1998-09-21
WO 97/34972 PCT/US97/03374
113
?. Mix perfume in the premix.
3. Make up water seat of water and HCl at ambient temperature. Optionally add
chelant.
4. Add premix to water under good agitation.
5. Trim with CaCh solution to desired viscosity.
6. Add dye solution to get desired colour.
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 above compositions.
For commercial purposes, the above clear 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 having a light blue tint to compensate
for any yellow
color that is present, or that may develop during storage (although, for short
times, and
perfectly clear products, clear containers with no tint, or other tints, can
be used), and
having an ultraviolet light absorber in the bottle to minimize the effects of
ultraviolet light
on the materials inside, especially the highly unsaturated actives (the
absorbers can also
be on the surface). The overall effect of the clarity and the container being
to demonstrate
the clarity of the compositions, thus assuring the consumer of the quality of
the product.
