Note: Descriptions are shown in the official language in which they were submitted.
CA 02377342 2001-12-24
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CONCENTRATED SURFACTANT BLENDS
1. Field of the Invention
The present invention relates generally to anionic surfactant compositions
and, more
particularly, to concentrated liquid mixtures of anionic and nonionic
surfactants.
Specifically, this invention relates to concentrated liquid surfactant
compositions containing
~o anionic and nonionic surfactants that may have relatively low viscosity
and/or that may be
substantially isotropic.
2. Description of Related Art
Multiple surfactants in formulated laundry detergents are often employed. For
example, anionic surfactants have been found to give good performance on polar
or
~s particulate types of soils and help to prevent soil redeposition. In
addition, anionic
surfactants may be used to control formulation viscosity. Nonionic surfactants
have been
found to give good detergency on nonpolar soils and may be used to impart
electrolyte or
hard water tolerance.
Typical anionic surfactants used in laundry include, but are not limited to,
linear alkyl
zo benzene sulfonates, alkyl sulfates, ether sulfates, secondary alkyl
sulfates, a,-olefin sulfonate,
phosphate esters, sulfosuccinates, isethionates, carboxylates, etc. Most of
these surfactants
are typically sold in the form of a sodium salt.
One common type of anionic surfactant, linear alkylbenzene sulfonate ("LAS"),
is
widely used in commercial cleanser products due to its effectiveness as a
detergent, ease of
zs biodegradation, and relative low cost. Typically, linear alkylbenzene
sulfonates are produced
via sulfonation of linear alkylbenzene intermediates.
Linear alkylbenzene is typically manufactured on an industrial scale using one
of
three commercial processes which differ from one another primarily by virtue
of the catalyst
system employed. In this regard, one process employs an aluminum trichloride
catalyst,
1
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another process uses a hydrogen fluoride catalyst while the third process uses
solid alkylation
catalyst. The three processes result in linear alkylbenzene products with
different phenyl
isomer distributions. For example, a typical phenyl isomer distribution for
products of the
aluminum trichloride process is about 30% 2-phenyl isomer and about 22% 3-
phenyl isomer.
s In contrast, a typical phenyl isomer distribution for products of the
hydrogen fluoride process
is about 20% 2-phenyl isomer and about 20% 3-phenyl isomer, although reported
values may
differ. The product of the aluminum trichloride process, which is relatively
high in 2-phenyl
isomer content, is often referred to as "high 2-phenyl" linear alkylbenzene,
whereas the
product of the hydrogen fluoride process, which is relatively low in 2-phenyl
isomer content,
io is often referred to as "low 2-phenyl" linear alkylbenzene.
The sulfonates of linear alkylbenzenes are known to exhibit different physical
properties depending upon the position of the aromatic group on the alkyl
chain. Therefore,
high 2-phenyl linear alkylbenzene sulfonates have physical properties that
differ from low 2-
phenyl linear alkylbenzene sulfonates. For example, high 2-phenyl linear
alkylbenzene
is sulfonates typically have a higher solubility in aqueous media than do low
2-phenyl linear
alkylbenzene sulfonates. Furthermore, an aqueous solution comprising a high 2-
phenyl linear
alkylbenzene sulfonate may exhibit a higher viscosity than an aqueous solution
comprising a
low 2-phenyl linear alkylbenzene sulfonate. In cases where maximum solubility
of linear
alkylbenzene sulfonate in an aqueous detergent formulation is of concern, a
product
2o containing a relatively high percentage of compounds in which the aromatic
substituent is in
the 2 or 3 position and a correspondingly smaller percentage of isomers in
which the aromatic
substituent is positioned centrally with respect to the alkyl chain may be
advantageous.
Hydrotropes, such as sodium xylene sulfonate, may be added to improve
solubility of
low 2-phenyl linear alkylbenzene sulfonates. As used herein, the term
"hydrotrope" is
is defined to be a compound that has the property of increasing the aqueous
solubility of various
slightly soluble organic chemicals.
In general, anionic surfactants are sold in the form of sodium, potassium or
amine
salts. The salts tend to be solid materials at room temperature, so they are
typically sold as
aqueous solutions. Because of gel phase formation, surfactant concentrations
between about
30 20% and about 40% by weight of total weight of a surfactant solution are
typically employed.
Above concentrations of about 40% active surfactant, anionic surfactant
solutions typically
form viscous gels or pastes. To reduce viscosity, solvents such as ethanol or
isopropanol may
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be added. However, such components are volatile organic components ("VOCs")
and tend to
form flammable mixtures.
In a further effort to form surfactant compositions having higher activities
and lower
viscosities, various other additives have been conventionally employed,
including alkyl
s polyglycosides and alkalide metal chlorides. However, such compositions also
include water
and amphoteric surfactant, thus limiting the activity of the surfactant
mixture. In still other
cases, compositions including concentrated lamellar or other types of liquid
crystals have
been employed. However, such compositions are typically not isotropic at room
temperature
and have activities limited to about 70%.
io SUMMARY OF THE INVENTION
Disclosed herein are improved surfactant compositions. Surprisingly,
substantially
isotropic and substantially non-flammable concentrated liquid surfactant
compositions may
be formulated from anionic and nonionic surfactants. The disclosed liquid
surfactant
compositions may be advantageously employed for a number of uses, including in
the
~s formulation of any surfactant or detergent composition in which one or more
anionic
surfactants are present as a surfactant component. Examples of such
compositions include,
but are not limited to, heavy duty laundry detergents, herbicide emulsifiers,
hard surface
cleaners, bathroom cleaners, all purpose cleaners, dishwashing detergents, car
wash
detergents, janitorial cleaners, light duty liquid detergents, etc. The
disclosed concentrated
zo liquid surfactant blends may be useful in the formulation of other
compositions as well
including, but not limited to, those used in coating applications, emulsion
polymerization,
pigment dispersions, wetting agents and the like.
In the disclosed compositions, concentrated liquid surfactant mixtures
containing one
or more anionic surfactants may be formulated using one or more nonionic
surfactants as a
zs solvent system. In one embodiment, the disclosed liquid surfactant
compositions contain
substantially no water, although water may be present in other embodiments, if
so desired.
Using this approach, substantially isotropic liquid surfactant mixtures having
relatively low
viscosity at up to about 100% active surfactant content may be surprisingly
prepared.
Advantageously, such compositions avoid the use of flammable solvents and
reduce the
3o amount of water which must be shipped with a surfactant product.
Furthermore, the
disclosed compositions may be formulated to achieve one or more of these
advantageous
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properties without the use of volatile organic compounds ("VOCs"), and thus
may be referred
to as substantially VOC free or as containing substantially no VOCs. In
addition, another
embodiment of the disclosed compositions contains substantially no liquid
crystal
constituents, and thus may be described as being substantially liquid crystal
free. Still
s further, another embodiment of the disclosed compositions contains
substantially no
microemulsion constituents, and thus may be described as being substantially
microemulsion
free.
As used herein, relatively low viscosities include any viscosity lower than a
viscosity
of a comparable liquid anionic surfactant solution consisting of no other
additional
~o ingredients (i.e., no ingredients other than water and electrolyte), and
lacking the disclosed
mixture of nonionic and anionic surfactants. In one embodiment, the disclosed
concentrated
liquid surfactant compositions may be advantageously formulated to have
viscosities at 25°C
of less than about 2000 centipoise (cps), alternatively less than about 1500
cps, alternatively
less than about 1000 cps, alternatively less than about 800 cps, alternatively
less than about
is 600 cps. In an alternate embodiment, viscosity of the disclosed liquid
compositions at 25°C
may range from about 2000 cps to about 5000 cps, alternatively from about 1500
cps to about
2000 cps, alternatively from about 1000 cps to about 1500 cps, and
alternatively from about
500 cps to about 800 cps.
In one respect, disclosed is a liquid surfactant composition, including at
least one
zo anionic surfactant and at least one nonionic surfactant. The liquid
surfactant composition
may have an active surfactant content of greater than 40% by weight of the
total weight of the
composition, may be substantially isotropic at a temperature of about
25°C, and may contain
substantially no volatile organic components.
In another respect, disclosed is a liquid surfactant composition, including at
least one
is anionic surfactant and at least one nonionic surfactant. The anionic
surfactant may be at least
one of alkyl benzene sulfonate, alkyl sulfate, alcohol sulfate, ether sulfate,
secondary alkyl
sulfate, oc-olefin sulfonate, phosphate ester, sulfosuccinate, isethionate,
carboxylate, or a
mixture thereof; and the nonionic surfactant may be at least one of
nonylphenol ethoxylate,
alcohol ethoxylate, EO-PO block copolymer, or a mixture thereof. The liquid
surfactant
so composition may have an active surfactant content of greater than 40% by
weight of the total
weight of the composition, may be substantially isotropic at a temperature of
about 25°C,
may have a pH of greater than about 7, may have a viscosity of less than about
2000
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centipoise at 25°C, may be substantially non-flammable, and may contain
substantially no
volatile organic components.
In yet another respect, disclosed is a method for preparing a liquid
surfactant
composition, including combining at least one nonionic surfactant with at
least one anionic
s surfactant to solubilize the anionic surfactant and to form a liquid
surfactant composition.
The liquid surfactant composition may have an active surfactant content of
greater than 40%
by weight of the total weight of the composition, may be substantially
isotropic at a
temperature of about 25°C, may be substantially non-flammable and may
contain
substantially no volatile organic components.
io
DETAILED DESCRIPTION OF ILLUSTRATIVE EMBODIMENTS
As used herein, the indefinite articles "a" and "an" connote "one or more."
When individual active surfactant content values are expressed herein for a
surfactant
composition as a percentage of the surfactant actives by weight, it refers to
the weight of a
~s given surfactant active expressed as a percentage of the total weight of
all surfactants actives
present in the given composition, excluding any non-surfactant components. For
those
compositions made up of 100% active surfactant materials, the weight
percentage of a given
component expressed as a percentage of surfactant actives would be the same as
the weight
percentage expressed as a percentage of the total weight of the composition.
zo In the following description, Tables 1-12 are referred to with regard to
specific
commercial and exemplary components which may be employed in various
combinations in
the formulation of the disclosed surfactant compositions. With benefit of this
disclosure it
will be understood by those of skill in the art that any of the specific
compounds, and/or
combinations thereof, disclosed in these tables may be employed to the extent
they are
is suitable for use in any of the embodiments disclosed herein, whether
otherwise specifically
referred to or not.
In the formulation of the disclosed liquid surfactant compositions, one or
more
nonionic surfactants may be combined with salts and/or acids of anionic
surfactants to form
concentrated surfactant compositions. As used herein, the "active surfactant
content" of a
CA 02377342 2001-12-24
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surfactant composition refers to the total weight percentage of surfactant
(anionic, nonionic,
and cationic) present in a particular composition. The "active detergent
content" of a
surfactant composition refers to the total weight percentage of surfactants
and other
detergent-active components, such as hydrotropes. A surfactant composition
having an
s active detergent content of greater than 80% is referred to herein as "high
active." However,
advantages may also be achieved with the disclosed compositions by providing
substantially
isotropic surfactant compositions having active detergent contents of less
than 80%. As used
herein, "isotropic" means a solution exhibiting non-birefringement under a
polarized
microscope at the specified temperature.
~o In the practice of one embodiment of the disclosed method and compositions,
suitable
nonionic surfactants include any nonionic surfactant material that is a liquid
at a desired
temperature (such as anticipated temperature of shipping, storage and/or use).
For example,
selected suitable nonionic surfactants may be liquid at room temperature and
include, for
example, such surfactants which exist in a liquid form within a temperature
range of at least
is from about 10°C to about 40°C, alternatively of at least from
about 20°C to about 30°C, and
alternatively at least about 25°C, with it being understood that the
individual surfactants may
optionally be liquid at temperature values outside these values as well. It
will be understood
with benefit of this disclosure that nonionic surfactants which are also
liquid at lower and/or
greater temperatures than room temperature, or alternatively the temperatures
of these ranges
zo are also suitable.
Suitable nonionic surfactants include, but are not limited to, alkyl phenol
ethoxylates
(including nonylphenol ethoxylates), alcohol ethoxylates, tallow amine and
ether amine
ethoxylates, ethylene oxide/propylene oxide ("EO-PO") block copolymers,
alcohol EO-PO
adducts, mixtures thereof, etc. Specific examples include, but are not limited
to, nonylphenol
zs ethoxylates such as "SURFONIC N-95TM" (having molecular weight of about
638) available
from Huntsman and linear alcohol ethoxylates such as "SURFONIC L-24-7TM"
available
from Huntsman, and ethoxylated alkyl amines such as Surfonic~ T-15 also
available from
Huntsman Corporation. Other specific examples include, but are not limited to,
nonionic
surfactants commercially available from Huntsman Corporation, Witco, and
Stepan, as
3o described below.
Specific examples of suitable nonionic surfactants available from Huntsman
Corporation include, but are not limited to, surfactants listed in Table 1.
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Table 1 - Examples of Nonionic Surfactants Available from Huntsman
ALCOHOL ETHOXYLATES
Linear Alcohol L-series Biodegradation, Surfonic~ L610-3,
Surfonic
Ethoxylates L108/85-5, Surfonic L1270-2, Surfonic L12/85-2,
Surfonic
L12-2.6, Surfonic L12-6, Surfonic L12-8,
Surfonic L24-1.3,
Surfonic L24-2, Surfonic L24-3, Surfonic
L24-4, Surfonic
L24-4.4, Surfonic L24-5, Surfonic L24-7,
Surfonic L24-9,
Surfonic L24-12, Surfonic L24-17, Surfonic
L24-22, Surfonic
L46-7, Surfonic L68-18, Surfonic HF-055
Branched Alcohol Surfonic AE-2, Surfonic DA-4, Surfonic
DA-6, Surfonic EH-2,
Ethoxylates Surfonic TDA-3B, Surfonic TDA-6, Surfonic
TDA-8, Surfonic
TDA-8/90, Surfonic TDA-8.4, Surfonic TDA-9,
Surfonic
TDA-11, Surfonic DDA-3, Surfonic DDA-6,
Surfonic DDA-8,
Surfonic DDA-12
ALKYLPHENOL ETHOXYLATES
Nonylphenol Surfonic N-Series Biodegradation, Surfonic
N-10, Surfonic N-
Ethoxylates 31.5, Surfonic N-40, Surfonic N-60, Surfonic
N-70, Surfonic
N-80, Surfonic N-85, Surfonic N-95, Surfonic
N-100, Surfonic
N-102, Surfonic N-110, Surfonic N-120,
Surfonic N-150,
Surfonic NB-158, Surfonic NB-189, Surfonic
N-200, Surfonic
N-300, Surfonic NB-307, Surfonic N-400,
Surfonic NB-407,
Surfonic N-500, Surfonic NB-507, Surfonic
N-550, Surfonic
NB-557, Surfonic N-700, Surfonic N-800,
Surfonic N-1000,
Surfonic NB-1007
Octylphenol Surfonic OP-15, Surfonic OP-35, Surfonic
OP-50, Surfonic
Ethoxylates OP-70, Surfonic OP-100, Surfonic OP-120,
Surfonic OPB-
167, Surfonic OPB-307, Surfonic OP-400,
Surfonic OPB-407,
Surfonic OPB-707
Dodecylphenol Surfonic DDP-40, Surfonic DDP-SO (draft),
Surfonic DDP-60,
Ethoxylates Surfonic DDP-70 (draft), Surfonic DDP-80
(draft), Surfonic
DDP-90, Surfonic DDP-100 (draft), Surfonic
DDP-110 (draft),
Surfonic DDP-120 (draft), Surfonic DDP-140
(draft)
Dinonylphenol Surfonic DNP-15 (draft), Surfonic DNP-20
(draft), Surfonic
Ethoxylates DNP-40 (draft), Surfonic DNP-70 (draft),
Surfonic DNP-80
(draft), Surfonic DNP-100 (draft), Surfonic
DNP-140 (draft),
Surfonic DNP-180 (draft), Surfonic DNP-240
(draft), Surfonic
DNP-490 (draft), Surfonic DNP-550 (draft),
Surfonic DNP-
700 (draft), Surfonic DNP-1000 (draft),
Surfonic DNP-1500
(draft)
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ALCOHOL OR ALKY LPHENOL ALKOXYLATES (EO/PO)
Surfonic LF-17, Surfonic LF-18, Surfonic
LF-37, Surfonic LF-
40, Surfonic LF-41, Surfonic LF-47, Surfonic
LF-50, Surfonic
LF-68, Surfonic LF-0312, Surfonic JL-80X,
Surfonic JL-SOX-
B1, Surfonic JL-25X, Surfonic P-l, Surfonic
P-3, Surfonic P-5,
Surfonic P-6, Defoamer PM, Surfonic L4-29X
EO/PO BLOCK COPO LYMERS
Surfonic POA-L42, Surfonic POA-L44, Surfonic
POA-L61,
Surfonic POA-L62, Surfonic POA-L62LF, Surfonic
POA-L64,
Surfonic POA-L81, Surfonic POA-L101, Surfonic
POA-2582,
Surfonic POA-LFl, Surfonic POA-LF2, Surfonic
POA-LFS
POGOL PEGS
Pogol 200, Pogol 300, Pogol 400, Pogol
500, Pogol 600, Pogol
900, Pogol 1000, Pogol 1005, Pogol 1450,
Pogol 1457
Examples of suitable nonionic surfactants also include products available from
Witco.
Such products include, for example, WITCONOLTM linear ethoxylated alcohols,
s DESONICTM alkylphenol ethoxylates, WITCAMIDE~ and VAR.AMIDETM amide ether
condensates, and VARONICTM coco and tallow amine ethoxylates. Some specific
examples
of such surfactants are listed in Table 2. Other nonionic materials include,
but are not limited
to, alcohol ethoxylates ("AE"), nonylphenol ethoxylates ("NPE"), ethoxylated
mono and
diglycerides, ethoxylated amines, amides, amine oxides and specialty blends.
io
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Table 2 - Examples of Amphoteric and Nonionic Surfactants Available from Witco
AMPHOTERIC AND
NONIONIC SURFACTANTS
Product Tradename Description
REWOTERIC AMB 12P Cocoamidopropyl Dimethyl Betaine
REWOTERIC AM B Cocoamidopropyl Dimethyl Betaine
14
REWOTERIC AM 2C Disodium Coco Amphodiacetate
2
REWOTERIC AM TEG Tallow Glycinate
REWOTERIC AM CAS Cocoamidopropyl Hydroxy Sultaine
REWOTERIC AM Coco Amphopropionate
KSF40
REWOTERIC AMV Sodium Capryloamphoacetate
WITCAMIDE 128T Cocoamide DEA
WITCONOL 12-3 C12/C15 Alcohol Ethoxylate (3E0)
WITCONOL 12-7 C 12/C 15 Alcohol Ethoxylate (7E0)
WITCONOL 12-6 C12/C14 Alcohol Ethoxylate (6E0)
DESONIC 9N Nonylphenol + 9 EO
VARONIC K-205 PEG 5 Cocamine
VARONIC K-210 PEG 10 Cocamine
VARONIC T-210 PEG 10 Tallow Amine
VARONICK T-215 PEG 15 Tallow Amine
Specific examples of suitable nonionic surfactants available from Stepan
include, but
are not limited to, surfactants listed in Table 3.
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Table 3 - Examples of Nonionic Surfactants Available from Stepan
ALKOXYLATES
MAKON 4 Nonlyl Phenol Ethoxylate100 LiquidDetergents and emulsifiers
MAKON 6 Nonlyl Phenol Ethoxylate100 Liquiddiffering in ethylene
oxide
MAKON 8 Nonlyl Phenol Ehtoxylate100 Liquidcontent. Makon 4
is the
MAKON 10 Nonlyl Phenol Ehtoxylate100 Liquidmost oil-soluble.
Makon
MAKON 12 Nonlyl Phenol Ehtoxylate100 Liquid12 is the least
oil soluble.
MAKON Octyl Phenol Ethoxylate100 LiquidEmulsifier, detergent
OP-9 dispersant, and
wetting
agent.
MAKON Polyalkoxylated 100 LiquidNon-foaming wetting
Amide
agents for mechanical
MAKON Polyalkoxylated 100 Liquiddishwash detergents
Aliphatic and
NF-12 Base metal cleaning.
AMIDOX PEG-6 Lauramide 100 Solid Emulsifiers, detergents,
L-
wetting agents that
have
AMIDOX PEG-6 Cocamide 100 Liquidsome of the properties
C- of
both alkanolamides
and
nonionic type surfactants.
BIO-SOFT Alkoxylated Alcohol100 LiquidEmulsifiers and
detergents
EA-8 differing in ethylene
oxide
BIO-SOFT Alkoxylated Alcohol100 Liquidcontent.
EA-10
NEUTRONY Nonyl Phenol Ethoxylate100 LiquidDetergent and emulsifier
X 656 for hard surface
detergents.
In one embodiment, an amount of nonionic surfactant sufficient to solubilize
the
anionic surfactant may be employed. For achieving lower relative viscosities,
a weight
s amount of nonionic surfactant greater than anionic surfactant may be
employed, although this
is not necessary to achieve the benefit of the disclosed methods and
compositions. For
example, in one embodiment a weight ratio of nonionic surfactant to anionic
surfactant may
range from about 10:1 to about 1:10, alternatively from about 10:1 to about
5:1, alternatively
from about 1:10 to about 1:5, alternatively from about 1:1 to about 3:1, and
in one particular
io embodiment may be about 3:1, although ratios outside these given ranges are
also possible.
In alternative embodiments of the disclosed liquid surfactant compositions,
nonionic
surfactants may be present in an amount of from about A% to about B% by weight
of total
weight of surfactant composition while at the same time anionic surfactants
may be present
in an amount of from about C% to about D% by weight of total weight of
surfactant
is composition; where for each respective embodiment the value of A may be
selected from the
CA 02377342 2001-12-24
WO 01/00758 PCT/US00/17690
range of values of from 35 to 79, and a corresponding value of B may be
selected from the
range of values of from 36 to 80 with the proviso that A is less than B for a
given
embodiment; and where for each respective embodiment the value of C may be
selected from
the range of values of from 5 to 39, and a corresponding value of D may be
selected from the
s range of values of from 6 to 40 with the proviso that C is less than D for a
given embodiment.
For example, in an embodiment where A= 60, B=80, C= 20 and D = 40, a
surfactant
composition including an amount of nonionic surfactants of from about 60% to
about 80%
by weight of the total weight of the composition, and an amount of anionic
surfactant of from
about 20% to about 40% by weight of the total weight of the composition would
be
io represented. Similarly, in an embodiment where A= 35, B=80, C= 15 and D =
40, a
surfactant composition including an amount of nonionic surfactants of from
about 35% to
about 80% by weight of the total weight of the composition, and an amount of
anionic
surfactant of from about 15% to about 40% by weight of the total weight of the
composition
would be represented. It will be understood with benefit of this disclosure,
that in any of the
is above-given embodiments where the total of nonionic surfactant content and
anionic
surfactant content is less than 100%, then the balance of the surfactant
composition may be
made up of other non-surfactant components described elsewhere herein (e.g.,
water,
hydrotrope, etc.). Using the possible values of A, B, C and D, amount of such
other
components in a surfactant composition may vary from 0 to about 60% by weight
of the total
zo weight of the composition. Thus, where nonionic surfactant content is about
80% by weight
of the total weight of the composition and anionic surfactant content is about
15% by weight
of the total weight of the composition, then the content of non-surfactant
component may be
about 5% by weight of the total weight of the composition.
In separate respective and alternative embodiments, nonionic surfactant or a
mixture
zs of nonionic surfactants may be present to solubilize an anionic surfactant
or mixture of
anionic surfactants in a surfactant composition in an amount of from about x%
to about y% of
the surfactant actives by weight, where for each respective embodiment the
value of x may be
selected from the range of values of from 9 to 90, and a corresponding value
of y may be
selected from the range of values of from 11 to 91 with the proviso that x is
less than y for a
3o given embodiment. For example, in an embodiment where x= 50 and y= 66, a
surfactant
composition including an amount of nonionic surfactants of from about 50% to
about 66% of
the surfactant actives by weight would be represented. In such embodiments,
anionic
surfactants may make up the balance of surfactant actives, and the overall
active surfactant
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WO 01/00758 PCT/US00/17690
content (i.e., total of nonionic surfactants content and anionic surfactants
content) of a given
surfactant composition may be as expressed elsewhere herein.
In one embodiment, suitable anionic surfactants may be characterized as having
pKa
values less than 7, although anionic surfactants having other pKa values are
also suitable.
s Examples of suitable anionic surfactants include, but are not limited to,
linear and/or
branched chain alkylbenzene sulfonates, alkyl sulfates, alcohol sulfates,
ether sulfates,
secondary alkyl sulfates, a-olefin sulfonates, phosphate esters,
sulfosuccinates, isethionates,
carboxylates, mixtures thereof, etc. Most of these surfactants are typically
sold in the form of
a sodium salt.
~o In one exemplary embodiment, one or more alkylbenzene sulfonate/s may be
employed as anionic surfactants. In this regard, alkylbenzene sulfonate
compounds having
varying molecular weights, alkyl chain length and alkyl chain phenyl location
combination
may be employed. Examples of such compounds may be found in U.S. Patent No.
3,776,962; U.S. Patent No. 5,152,933; U.S. Patent No. 5,167,872; Drazd, Joseph
C. and
is Wilma Gonnan, "Formulating Characteristics of High and Low 2-Phenyl Linear
Alkylbenzene Sulfonates in Liquid Detergents," JADCS, 65(3):398-404, March
1988;
Sweeney, W. A. and A. C. Olson, "Performance of Straight-Chain Alkylbenzene
Sulfonates
(LAS) in Heavy-Duty Detergents," JAOCS, 41:815-822, December 1964.; Drazd,
Joseph C.,
"An Introduction to Light Duty (Dishwashing) Liquids Part I. Raw Materials,"
Chemical
Zo Times & Trends, 29-58, January 1985; Cohen, L. et al., "Influence of 2-
Phenyl Alkane and
Tetralin Content on Solubility and Viscosity of Linear Alkylbenzene
Sulfonate," JAOCS,
72(1):115-122, 1995; Smith, Dewey L., "Impact of Composition on the
Performance of
Sodium Linear Alkylbenzenesulfonate (NaLAS)," JAOCS, 74(7):837-845, 1997; van
Os, N.
M. et al., "Alkylarenesulphonates: The Effect of Chemical Structure on Physico-
chemical
is Properties," Tenside Surf. Det., 29(3):175-189, 1992; Moreno, A. et al.,
"Influence of
Structure and Counterions on Physicochemical Properties of Linear Alkylbenzene
Sulfonates," JAOCS, 67(8):547-552, August 1990; Matheson, K. Lee and Ted P.
Matson,
"Effect of Carbon Chain and Phenyl Isomer Distribution on Use Properties of
Linear
Alkylbenzene Sulfonate: A Comparison of 'High' and 'Low' 2-Phenyl LAS
Homologs,"
so JAOCS, 60(9):1693-1698, September 1983; Cox, Michael F. and Dewey L. Smith,
"Effect of
LAB composition on LAS Performance," INFORM, 8(1):19-24, January 1997; U.S.
Patent
Application Serial No. 08/598,692 filed on February 8, 1996, U.S. Patent
Application Serial
12
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Number 09/141,660 filed on August 28, 1998, and U.S. Patent Application Serial
Number
09/143,177 filed on August 28, 1998; all of the foregoing references being
incorporated
herein by reference in their entirety.
In one embodiment, alkylbenzene sulfonate compounds used in accordance with
the
s disclosed compositions and methods and having the characteristics described
herein include
those having a linear alkyl group. Typically linear alkyl chain lengths are
between about 8
and about 16 carbon atoms, although greater and lesser lengths are possible.
One specific low 2-phenyl alkylbenzene sulfonate composition is a sulfonate
prepared
from a linear alkyl benzene known as ALKYLATE 225TM (commercially available
from
~o Huntsman Specialty Chemicals Corporation). Other examples of suitable
linear
alkylbenzenes for preparing linear alkyl benzene sulfonates include, but are
not limited to,
ALKYLATE 215TM, ALKYLATE 229TM, ALKYLATE H230LTM, and ALKYLATE
H230HTM (also available from Huntsman Specialty Chemicals Corporation).
Suitable
processes for sulfonating such linear alkyl benzenes include, but are not
limited to, those
is employing an air/S03 sulfonator or chlorosulfonic acid.
Examples of other suitable anionic surfactants include, but are not limited
to, alkyl
sulfates, ether sulfates, secondary alkyl sulfates, a,-olefin sulfonates,
xylene sulfonates,
alcohol sulfates, phosphate esters, napthalene sulfonates, sulfosuccinates,
isethionates,
carboxylates, etc.
2o Specific examples of other suitable anionic surfactants include, but are
not limited to,
the surfactants listed in Table 4 and available from Huntsman Corporation,
Houston, Texas.
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Table 4 - Ezamples of Anionic Surfactants Available from Huntsman
Anionic Surfactant Type Product Name
DETERGENT Nonasol LD-50, Nonasol N4SS,
Sulfonic
SULFATES/SULFONATES Acid LS, Surfonic SB-N4AS~,
Surfonic
SNS-60~, Surfonic SNS-40~
PHOSPHATE ESTERS AgphosTM 7140, Surfonic PE-1168,
Surfonic PE-1178~, Surfonic
PE~,
Surfonic PE-1218~, Surfonic
PE-2188~,
Surfonic PE-2208~, Surfonic
PE-2258~,
Surfonic PE-JV-OS-015~, Surfonic
PE-BP-2~, Surfonic PE-25/97~
SULFONATES SXS-40, PSA, XSA-80, XSA-90,
XSA-95
SULFOSUCCINATES Surfonic DOS-40; Surfonic
DOS-60;
Surfonic DOS-70E; Surfonic
DOS-70MS;
Surfonic DOS-75; Surfonic
DOS-75PG
~ ISETHIONATE ~ Surfonic SI
Still other specific examples of suitable anionic surfactants include, but are
not
limited to, the surfactants listed in Table 5 available from Witco
Corporation, Greenwich,
CT.
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Table 5 - Ezamples of Anionic Surfactants Available from Witco
PRODUCT DESCRIPTION
WITCONATETM Alkylbenzene, Alpha Olefin, and Xylene
Sulfonates
WITCO~ Alkylbenzene Sulfonic Acid and Slurries
WITCOLATETM Alcohol Sulfates and Ether Sulfates
EMPHOSTM Phosphate Esters
PETRO~ Naphthalene Sulfonate Hydrotopes
EMCOL~ Speciality Anionic Surfactants
Witco Workhorse Linear Alkyl Benzene Sulfonates (LAS);
Surfactants/HydrotropesAlcohol Sulfates
Anionics (AS); Alcohol Ether Sulfates (AES),
Alpha Olefin
Sulfonates (AOS), Sodium Xylene Sulfonate
(SXS)
Witco Specialty Sulfosuccinates, Ether Carboxylates,
Surfactants/HydrotropesNaphthalene
Anionics Sulfonates, Phosphate Esters
WITCONATE 90 Flakes Sodium Alkylbenzene Sulfonate
WITCONATE Slurries Sodium Alkylbenzene Sulfonate
WITCONATE 1298SA Sodium Alkylbenzene Sulfonic Acid
WITCONATE 45 Liquid Sodium Alkylbenzene Sulfonate & SXS
WITCONATE 60T Liq. TEA-Dodecylbenzene Sulfonate
WITCOLATE WAC-LA Sodium Lauryl Sulfate
WITCOLATE A Powder Sodium Lauryl Sulfate
EMCOL 4161 L Sodium oleylalkanolamido sulfosuccinate
WITCOLATE SE-5 Sodium Pareth-25 (Ether) Sulfate (3E0)
WITCOLATE LES-60C Sodium Lauryl Ether Sulfate (3E0)
WITCOLATE AE-3 Ammonium Pareth-25 (Ether) Sulfate
WITCOLATE LES-60a Ammonium Laureth (Ether) Sulfate
WITCOLATE ES-370 Sodium Lauryl Ether Sulfate (3E0)
WITCOLATE AOS Sodium Alpha Olefin Sulfonate
WITCOLATE AOK Sodium Alpha Olefin Sulfonate
WITCONATE 93 S Isopropylamine of Dodecylbenzene Sulfonate
WITCONATE P-1059 Isopropylamine of Dodecylbenzene Sulfonate
EMCOL CNP 110 Alkylaryl Ethoxylated Carboxylate
EMCOL CLA 40 C12-14 Ethoxylated Carboxylic Acid
WITCONATE SXS Liq. Sodium Xylene Sulfonate
WITCONATE SXS FL Sodium Xylene Sulfonate
WITCONATE NAS-8 Sodium Octyl Sulfonate
PETRO BA Sodium Alkyl Naphthalene Sulfonate
PETRO BAF Sodium Alkyl Naphthalene Sulfonate
Ether Carboxylate Emcol CNP-40, Emcol CNP-60, Emcol CNP-100,
Anionic Emcol
Surfactant CNP-110, Emcol CNP-120, Emcol CLA-40,
Emcol CBA-
50, Emcol CBA-60, Emcol CBA-100,
Structure:
O
RO-(CH2CH20)NCHz.- C/
~ OH
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PRODUCT DESCRIPTION
RO = nonylphenol, DO/tetradecanol, tridecanol,
ethylhexanol
n=3,4,5,6or10
Still other specific examples of anionic surfactants include, but are not
limited to, the
surfactants listed in Table 6 and available from Stepan Company.
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Table 6 - Ezamples of Anionic Surfactants Available from Stepan
Product Chemical Description
ALPHA SULFO METHYL ESTERS
Alpha-Step ML-40~ Sodium methyl 2-sulfolaurate
and
disodium 2-sulfolaurate
Alpha-Step MC-48~ Sodium methyl 2-sulfo C12-C,g
ester and
disodium 2-sulfo C~2-C1g fatty
acid salt
ALKYLBENZENE SULFONATES
Bio-Soft D-40~ Sodium alkylbenzene sulfonate,
linear
Bio-Soft D-62~ Sodium alkylbenzene sulfonate,
linear
Bio-Soft N-300~ TEA-Dodecylbenzene sulfonate
NACCONOL 40G~ Sodium alkylbenzene sulfonate,
linear
NACCONOL 90G~ Sodium alkylbenzene sulfonate,
linear
Ninate 401 ~ Calcium alkylbenzene sulfonate,
branched
Bio-Soft N-411~ Amine alkylbenzene sulfonate,
linear
SULFONIC ACIDS
Bio-Soft S-100~ Alkylbenzene sulfonic acid,
linear
Bio-Soft S-126~ Alkylbenzene sulfonic acid,
linear
Stepantan H-100~ Alkylbenzene sulfonic acid,
branched
HYDROTROPES
Stepanate SXS~ Sodium xylene sulfonate
Stepanate AXS~ Ammonium xylene sulfonate
Stepanate SCS~ Sodium cumene sulfonate
PHOSPHATE ESTERS
Cedephos FA-600~ Alkyl ether phosphate
Stepfac 8170~ Alkylaryl ether phosphate
SPECL4LTIES
Bio-Terge PAS-8S~ Sodium alkane sulfonate
ALKYL SULFATES
Stepanol WA-extra~ Sodium lauryl sulfate
Stepanol WAC~ Sodium lauryl sulfate
Stepanol WA-special~ Sodium lauryl sulfate
Stepanol ME-dry~ Sodium lauryl sulfate
Stepanol AM~ Ammonium lauryl sulfate
Stepanol AM-V~ Ammonium lauryl sulfate
ALKYL ETHER SULFATES
Steol 4N~ Sodium laureth sulfate
Steol CS-460~ Sodium laureth sulfate
Steol CA-460~ Ammonium laureth sulfate
Steol KS-460~ Sodium laureth sulfate, modified
Steol KA-460~ Ammonium laureth sulfate,
modified
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It will be understood with benefit of this disclosure by those of skill in the
art that the
foregoing examples of anionic surfactants are exemplary only, and that other
anionic
surfactants meeting the criteria set forth herein may also be employed.
In the practice of the disclosed method and compositions, an anionic
surfactant (such
s as an alkylbenzene sulfonate) may include any counterion or cation suitable
for neutralization
or salt formation with selected anionic surfactands. In one embodiment a
counterion or
canon is typically ammonium or substituted ammonium. In this regard, a
substituted
ammonium may include, but is not limited to, monoethanol ammonium, diethanol
ammonium, triethanol ammonium, or a mixture thereof. In another embodiment,
such a
~o counterion or cation may be an alkali metal, an alkaline earth metal, or a
mixture thereof.
Examples of alkali metals include, but are not limited to, lithium, sodium,
potassium, cesium,
or a mixture thereof. Examples of alkaline earth metals include, but are not
limited to,
magnesium, calcium, strontium, barium, or a mixture thereof.
Amounts of anionic surfactant relative to nonionic surfactant have been
described
~s above. In addition to nonionic and anionic surfactants, embodiments of the
disclosed
surfactant compositions may also include a wide variety of other optional
ingredients if so
desired. Such ingredients are further described herein. It will be understood
that the
previously given ratios of nonionic to anionic surfactant are suitable whether
or not additional
optional ingredients are employed. Thus, high active surfactant compositions
may be
zo formulated from anionic surfactants and nonionic surfactants in relative
amounts as described
elsewhere herein and with the addition of other optional ingredients, if so
desired. In cases
where optional additional ingredients are present, activity of a surfactant
composition may
fall with the activity ranges described elsewhere herein. In those cases where
no additional
components are employed, active surfactant content of a surfactant composition
may be
zs advantageously about 100%.
In one embodiment, optional detergent enhancement additives may be employed.
Examples of such enhancers include, but are not limited to, ethoxylated amine
surfactants
and/or ethoxylated ether amine surfactants. Further information on ethoxylated
amine and
ethoxylated ether amine enhancers may be found in United States Provisional
Patent
so Application Serial Number 60/115,408 filed on January 11, 1999 and entitled
"CONCENTRATED LIQUID DETERGENT COMPOSITION"; United States Provisional
Patent Application Serial Number 60/139,441 filed on June 15, 1999 and
entitled
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"SURFACTANT COMPOSITIONS CONTAINING ALKOXYLATED AMINES"; and
United States Patent Application Serial Number 09/479,436, filed on January 7,
2000, and
entitled "SURFACTANT COMPOSITIONS CONTAINING ALKOXYLAT'ED AMINES,"
each of which are incorporated herein by reference.
s In still another embodiment, nonionic surfactants which are solid at a
desired
temperature (such as anticipated temperature of shipping, storage and/or use).
More
specifically, nonionic surfactants may be employed that exist in a solid form
at room
temperature, alternatively within a temperature range of at least from about
10°C to about
40°C, alternatively at least from about 20°C to about
30°C, and alternatively at about 25°C.
io For example, one or more nonionic surfactants that exist as a solid at room
temperature may
be employed by adding sufficient liquefies or liquefying compound, such as
propylene glycol
or polyethylene glycol to liquefy the material.
If so desired, in another embodiment solid anionic surfactants (e.g., ether
sulfates,
etc.) may be dissolved or otherwise mixed with a polar solvent suitable for
solvating the
is surfactant (e.g., water, etc.), prior to combination with other liquid
components of a liquid
surfactant composition (e.g., liquid nonionic surfactant solution, etc.).
Examples of suitable liquefying compounds include water soluble glycols such
as
polyethylene glycols, ethylene glycol, propylene glycol and ethylene glycol
mixture,
mixtures thereof, etc. Exemplary suitable polyethylene glycol compounds
include, but are
Zo not limited to, polyethylene glycol compounds having a molecular weight of
between about
100 and about 1000, alternatively between 200 and about 2000. Specific
examples include
one or more polyethylene glycol solubility enhancers having between about 1
and about 20,
alternatively between about 3 and about 6 ethylene glycol monomers joined by
ether
linkages. Specific examples of such polyethylene glycol compounds include, but
are not
is limited to, propylene glycol and/or polyethylene glycol products marketed
by Huntsman
Chemical Corporation under the trade name POGOLTM. In the case of POGOLTM
compounds, the numeric designation indicates the average molecular weight of
the
polyethylene glycol compounds. Specific examples include, but are not limited
to, POGOL
200, POGOL 300, POGOL 400, POGOL 500, POGOL 600, POGOL 900, POGOL 1000,
3o POGOL 1005, POGOL 1450, and POGOL 1457, available from Huntsman Chemical
Corporation. In one embodiment, an amount of liquefies compound sufficient to
obtain a
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relatively low viscosity liquid is employed (e.g., equal to or less than about
1000 centipoise),
although greater or lesser amounts are also possible.
In the practice of the disclosed compositions and methods, a liquefying
compound
may be present in an amount of from about 1 % to about 20% by weight of total
weight of
s composition, alternatively from about 5% to about 10% by weight of total
weight of
composition. Such liquefying compounds may be employed with solid nonionic
surfactants
such as Surfonic~ N-200 or Surfonic~ L46-12, or mixtures thereof. In such
compositions,
the solid nonionic surfactants are typically employed in the same weight ratio
relative to
anionic surfactants previously described. For example incorporation of about
10% by weight
io propylene glycol liquefier with anionic surfactant and nonionic surfactant
that is solid at
room temperature would result in an about 90% active surfactant composition.
In one embodiment, the disclosed anionic surfactant/nonionic surfactant
compositions, high active concentrated surfactant compositions may have an
active surfactant
content of greater than 40% by weight of total composition weight,
alternatively from about
is 40% to about 100%, and alternatively may be equivalent to each and every
individual integer
represented between 41% and about 100%, including about 100% by weight of
total
composition weight. Further, in other exemplary embodiments, possible active
surfactant
content ranges of the disclosed surfactant compositions may be expressed as
being from
about X% to about Y% by weight of total composition, wherein X is a number
from 41 to 99,
Zo and wherein Y is a number from 42 to 100, with the proviso that for any
given combination
of X and Y, Y is greater than X. For example, in one embodiment where X has a
value of 45
and Y has a value of 65, the active surfactant content range of the surfactant
composition is
from about 45% to about 65%.
In still other exemplary embodiments, the disclosed surfactant compositions
may be
is formulated to have an active detergent content of greater than 50% by
weight of total
composition, alternatively greater than 60% by weight of total composition,
alternatively
greater than 70% by weight of total composition, alternatively greater than
78% by weight of
total composition, alternatively greater than 80% by weight of total
composition, alternatively
greater than or equal to about 80% by weight of total composition;
alternatively greater than
30 85% by weight of total composition weight, alternatively greater than 90%
by weight of total
composition, alternatively greater than about 95% by weight of total
composition, with it
CA 02377342 2001-12-24
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being understood that the upper limit of these given ranges is 100% by weight
of total
composition weight.
Advantageously, the disclosed surfactant compositions may also be formulated
to be
substantially isotropic over a temperature range of from about 0°C to
about 50°C,
s alternatively from about 5°C to about 40°C, alternatively from
about 10°C to about 40°C,
alternatively from about 20°C to about 30°C, and alternatively
at about 25°C, it being
understood that such a composition may also be substantially isotropic at
greater and/or lesser
temperature values outside these ranges. Such a surfactant composition may
also be
substantially non-flammable. Such a surfactant composition may also be
fonmulated to be
~o substantially VOC free (i.e., meaning having substantially no volatile
organic components),
while at the same time possessing these advantageous properties. As used
herein, VOCs
include, but are not limited to, volatile solvents, ethanol, isopropanol,
benzyl alcohol, etc.
If desired, neutralization of anionic surfactants in the disclosed surfactant
compositions may be accomplished with the addition of a basic compound.
Examples of
~s such optional neutralizing compounds include, but are not limited to,
alkanolamines (e.g.,
monoethanolamine ("MEA"), diethanolamine ("DEA"), triethanolamine ("TEA"),
etc.), alkyl
amines (e.g., isopropylamine, 2-(2-aminoethoxy)ethanol (HUNTSMAN "DGA"),
etc.),
ammonium hydroxide, NaOH, KOH, and mixtures thereof. Amounts of neutralizing
compound may be any amount suitable for partially or completely neutralizing
an anionic
zo surfactant acid. In one embodiment, an amount of neutralizing compound
sufficient to
neutralize from about 75% to about 90%, alternatively about 75%, of the
anionic surfactant is
employed, although greater or lesser amounts are also possible. In another
embodiment,
neutralizing compound may be present in a surfactant composition in an amount
of from
about 0% to about 9% by weight of total composition weight, alternatively in
an amount of
is about 25% by weight of total composition weight, although greater or lesser
amounts may
also be present. When so present, a neutralizing compound may be considered as
part of the
anionic surfactant content of the surfactant composition.
In the formulation of the disclosed surfactant compositions, anionic and
nonionic
surfactant components may be combined in any manner suitable to solubilize the
anionic
3o surfactant components in the nonionic surfactant components to achieve
compositions
having surfactant activity values as described elsewhere herein. For example,
in one
embodiment, appropriate amounts of un-neutralized anionic surfactantls (e.g.,
LAS Acid, the
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sour ester of ether sulfate, etc.) and neutralizing agents (e.g.,
monoethanolamine ("MEA"),
NaOH, etc.) may be added to a nonionic surfactant or mixture of nonionic
surfactants. Once
the so-formed surfactant mixture achieves relatively constant temperature, it
may be allowed
to cool to form a substantially isotropic composition.
s In one exemplary embodiment, a surfactant concentrate composition may be
formulated by dissolving from about 15% by weight to about 19% by weight of
total weight
of surfactant composition of tallow amine ethoxylate salt LAS (e.g., HUNTSMAN
"ALKYLATE 229"), from about 15% by weight to about 19% by weight of total
weight of
surfactant composition of HUNTSMAN "SURFONIC T-15", from about 0.5% by weight
to
io about 5% by weight of total weight of surfactant composition of MEA
neutralizing
compound and from about 18% to about 22% by weight of total weight of
surfactant
composition of water, into from about 33% by weight to about 37% by weight of
total
surfactant composition of HUNTSMAN "SURFONIC~ N-95" and from about 6% by
weight
to about 10% by weight of total weight of surfactant composition of POGOL 300.
The
~s components of such a blend may be adjusted to create a surfactant blend
having desired
characteristics, such as activity and/or pH, by for example varying the amount
of LAS
anionic surfactant relative to MEA neutralizing compound (e.g., in one
embodiment to have a
pH of from about 7.75 to about 8.75, although greater and lesser values are
possible). For
example, a surfactant concentrate composition known as "SURFONIC HDL-10" from
zo HUNTSMAN CORPORATION may be formulated by dissolving about 17.4% by weight
of
total weight of surfactant composition of HUNTSMAN "ALKYLATE 229", about 17.4%
by
weight of total weight of surfactant composition of HUNTSMAN "SURFONIC T-15",
about
2.4% by weight of total weight of surfactant composition of MEA neutralizing
compound and
about 20% by weight of total weight of surfactant composition of water, into
about 34.8% by
zs weight of total surfactant composition of HUNTSMAN "SURFONIC~ N-95" about
8% by
weight of total weight of surfactant composition of POGOL 300 to make a
relatively low
viscosity, and about 80% active detergent content blend having a pH of about
8.24 (see
Example 1).
In another exemplary embodiment, a surfactant concentrate composition may be
so formulated by dissolving from about 23% by weight to about 27% by weight of
total weight
of surfactant composition of the MEA salt of LAS (e.g., "ALKYLATE 229"), into
from
about 73% by weight to about 77% by weight of total surfactant composition of
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HUNTSMAN "SURFONIC~ N-95" to make an about 100% active blend. The components
of such a blend may be adjusted to create a surfactant blend having desired
characteristics,
such as activity and/or pH, by for example varying the amount of LAS anionic
surfactant
relative to MEA neutralizing compound used to form the MEA salt of LAS (e.g.,
in one
s embodiment to have a pH of from about 9.25 to about 10.25, although greater
and lesser
values are possible). For example, a surfactant concentrate composition known
as
"SURFONIC HDL-30" from HUNTSMAN CORPORATION may be formulated by
dissolving about 25% by weight of total weight of surfactant composition of
the MEA salt of
LAS (e.g., HUNTSMAN "ALKYLATE 229") in about 75% by weight of total surfactant
~o composition of HUNTSMAN "SURFONIC~ N-95" to make to make a relatively low
viscosity, and about 100% active surfactant content blend having a pH of about
9.79 (see
Example 2).
It will be understood with benefit of this disclosure that the preceding two
embodiments are exemplary only, and that activity values, pH values,
number/identity and/or
is amounts of components may be varied as so desired, including outside the
ranges given
above for one or more of these parameters to achieve substantially isotropic,
relatively low
viscosity, liquid surfactant compositions having substantially no VOC content.
If desired, alkoxylated amine surfactants may be combined with nonionic
surfactants
and salts or acids of anionic surfactants to, for example, form salts between
the ethoxylated
Zo amine surfactants and the anionic surfactants. Such salts may be formed,
for example; via
exchange of amine and sodium cations. In one exemplary embodiment, sufficient
alkoxylated amine may be employed in conjunction with the neutralization
compound to
neutralize about 25% of the anionic surfactant. A range of alkoxylated amine
surfactants
may be used to form the salt. Suitable alkoxylated amines include any
ethoxylated amines
Zs capable of forming a water soluble salt with an anionic surfactant.
Examples include
primary, secondary and tertiary alkoxylated amines, ethoxylate ether amines,
as well as
mixtures thereof. When so desired, alkoxylated amine surfactants may be
combined with
salts or acids of anionic surfactants to form salts between the ethoxylated
amine surfactants
and the anionic surfactants. Such salts may be formed, for example, via
exchange of amine
3o and sodium cations.
In one embodiment, suitable tertiary alkoxylated amine surfactants consist of
a
hydrocarbon tail attached to a nitrogen atom. The nitrogen atom has been
alkoxylated to give
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tertiary amine. The tertiary amine is capable of abstracting a proton from a
strong acid to
form a salt. The following structure illustrates such a salt formed between an
LAS acid and a
tertiary ethoxylated amine:
1
~3
~+
H-(O C H2C HZ)-N-(C H2C H20)-H
n-x
s wherein: R = straight or branched alkyl group having from about 8 to about
22
carbon atoms;
n = total moles of ethoxylation and is from about 2 to about 30; and
x = from about 1 to about 29.
In one particular example of this embodiment, an ethoxylated amine may be a
tertiary
io tallow amine ethoxylate in which R = straight or branched alkyl group
having from about 16
to about 18 carbon atoms; n = from about 5 to about 20; and x = from about 4
to about 19.
Still other examples of suitable ethoxylated tertiary amines include
ethoxylated
tertiary amines having some propylene oxide or other alkoxide content. For
example, "R" in
the previously given tertiary ethoxylated amine formula may be an alkyl group
as defined
is above, or alternatively, a combination of an alkyl group as defined above
and an alkoxide
group, with the alkyl group being bound to the nitrogen atom. In another
example, "R" in the
preceding tertiary amine formula may be a combination of an alkyl group as
defined above
and an alkylaryl, with the alkyl group being bound to the nitrogen atom. In
yet another
embodiment, an alkoxylated tertiary amine may be of the above formula, with
the exception
Zo that one or more of the x and/or (n-x) ethylene oxide groups may be
replaced with one or
more propylene oxide groups, other alkylene oxide groups, or mixtures thereof.
These examples include, but are not limited to, ethoxylated amines of the
"SURFONIC~" series available from Huntsman including, but not limited to, T-5,
T-10, T-
15, T-20, T-2, and T-50, wherein the numerical suffix indicates moles of
ethoxylation per
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molecule. Other examples of suitable ethoxylated tertiary amines include, but
are not limited
to, Varonic T-215 available from Witco Corporation, Greenwich, CT and
compositions
available from Akzo Nobel. Other examples of suitable ethoxylate tertiary
amines include
ethoxylated tertiary amines having some propylene oxide or other alkoxide
content. For
s example "R" in the previously given tertiary ethoxylated amine formula may
be an alkyl
group as defined above, or alternatively, a combination of an alkyl group as
defined above
and an alkoxide group, with the alkyl group being bound to the nitrogen atom.
In another
example, "R" in the preceding tertiary amine formula may be a combination of
an alkyl group
as defined above and an alkylaryl, with the alkyl group being bound to the
nitrogen atom. In
~o yet another embodiment, an alkoxylated tertiary amine may be of the above
formula, with the
exception that one or more of the x and/or (n-x) ethylene oxide groups may be
replaced with
one or more propylene oxide groups, other alkylene oxide groups, or mixtures
thereof.
Specific examples of suitable ethoxylated tertiary amines may also be found in
Table
7.
~s Table 7 - Examples of Ethozylated Tertiary Amines Available from Huntsman
Trademark Product Theoretical Total Amine
Molecular Weight(meq/g)
SURFONIC~ T-2 350 2.75 - 3.10
T-5 490 1.96 - 2.13
T-10 710 1.37 - 1.49
T-12 798 1.23 - 1.28
T-15 908 1.05-1.12
T-20 1150 0.89 - 0.94
T-SO 2470 .39 - .42
As shown in Table 7, specific examples of suitable ethoxylated amines include,
but
are not limited to, ethoxylated amines of the "SURFONIC~ " series available
from
2o Huntsman including, but not limited to, T-2, T-5, T-10, T-15, T-20, and T-
S0, wherein the
numerical suffix indicates moles of ethoxylation per molecule. These tallow-
amine-
ethoxylates are of the type that may be represented by the formula:
H-(OCH2CH2)- i -(CH2CH20) _H
R
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wherein: R = straight or branched alkyl group having from about 16 to about 18
carbon atoms;
n = moles of ethoxylation and is equivalent to the numerical suffix
following the "T" (i. e., 2, 5, 10, 15, 20, 50, etc. ); and
s x and (n-x) represent number of ethylene oxide groups in separate
chains on the molecule.
Examples of other suitable alkoxylated tertiary amines may be found in Table
8.
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Table 8 - Examples of Other Alkozylated Tertiary Amines Available from Akzo
Nobel
Trademark Product Chemical DescriptionEquivalent Weight
(Minimum/Maximum)
"ETHOMEEN" C/12 Ethoxylated (2) 280/300
Ethoxylated Amines Cocoalkylamine
C/15 Ethoxylated (5) 410/435
Cocoalkylamine
C/20 Ethoxylated (10) 620/660
Cocoalkylamine
C/25 Ethoxylated (15) 830/890
Cocoalkylamine
O/12 Ethoxylated (2) 343/363
oleylamine
O/15 Ethoxylated (5) 470/495
oleylamine
T/12 Ethoxylated (2) 340/360
tallowalkylamine
T/15 Ethoxylated (5) 470/495
tallowalkylamine
T/25 Ethoxylated (15) 890/950
tallowallcylamine
S/12 Ethoxylated (2) 342%362
soyaalkylamine
S/15 Ethoxylated (S) 470/495
soyaalkylamine
S/20 Ethoxylated (1) 685/725
soyaalkylamine
S/25 Ethoxylated (15) 895/955
soyaalkylamine
18/12 Ethoxylated (2) 350/370
octadecylamine
18/15 Ethoxylated (5) 480%505
octadecylamine
18/20 Ethoxylated (10) 690/730
octadecylamine
18/25 Ethoxylated (15) 900/960
octadecylamine
18/60 Ethoxylated (50) 2370/2570
octadecylamine
"ETHODUOMEEN" T/13 Ethoxylated (3) 220/250
N-
Ethoxylated Diamines tallow-1,3-
diaminopropane
T/20 Ethoxylated (10) 375/405
N-
tallow-1,3-
diaminopropane
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Trademark Product Chemical DescriptionEquivalent Weight
(Minimum/Magimum)
T/25 Ethoxylated (15) 485/515
N-
tallow-1,3-
diaminopropane
"PROPROMEEN" C/12 N-cocoalkyl-1,1'-308/318
Propoxylated Amines iminobis-2-propanol
O/12 N-oleyl-1,1'-iminobis-371/391
2-propanol
T/12 N-tallowalkyl-1,1'-373/383
iminobis-2-propanol
Other examples of specific suitable ethoxylated tertiary amines include, but
are not
limited to, Varonic T-215 available from Witco Corporation, Greenwich, CT and
compositions available from Akzo Nobel.
s Other suitable alkoxylated secondary amines include, but are not limited to,
ethoxylated amines having the following formula:
R-N (CH2CH20)-H
x
wherein: R = straight or branched alkyl group having from about 8 to about 22
carbon atoms;
~o x = from about 1 to about 30.
In one particular example of this embodiment, an ethoxylated amine may be a
secondary tallow amine ethoxylate in which R = straight or branched alkyl
group having from
about 16 to about 18 carbon atoms; and x = from about 5 to about 20.
In general, the secondary amine ethoxylates are present in small amount in the
tertiary
is amine ethoxylates and may not be sold separately as commercial products.
Other suitable alkoxylated secondary amines include, but are not limited to,
ethoxylated primary amines having the following formula:
H2 N-(CHZCH20)-H
X
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wherein: x = from about 1 to about 30.
In one particular example of this embodiment, a primary ethoxylated amine may
be
one in which x = from about 2 to about 20. Examples include, but are not
limited to,
s DIGLYCOLAMINETM" available from Huntsman (2-(2-aminoethoxy) ethanol).
It will be understood with benefit of this disclosure by those of skill in the
art that
specific types and molecular weights of amines may be selected to fit
particular purposes.
For example, relatively shorter chain tertiary amine ethoxylates, like
Huntsman T-2 and T-5,
may be used to improve mineral oil detergency (e.g., motor oil, grease, etc.),
while relatively
~o longer chain tertiary amine ethoxylates, like Huntsman T-10 and T-15, may
be used to
improve trigylceride detergency (e.g., cooking oils, fats, etc.).
Alkoxylated ether amines (such as ethoxylated ether amine) surfactants may
also be
used, and include those having the following formula:
H3 (CH CH O)-H
R-(-OCH- H-)-N~ 2 2 x
y (CH2CH20)-H
n-x
i s wherein: R = straight or branched alkyl group having from about 8 to about
22
carbon atoms;
n = total moles of ethoxylation and is from about 2 to about 30;
x = from about 1 to about 29; and
y=1to30.
2o In one particular example of this embodiment, an ethoxylated amine may be a
tertiary
tallow amine ethoxylate in which R = straight or branched alkyl group having
from about 12
to about 14 carbon atoms; n = from about 5 to about 20; x = from about 4 to
about 19; and y
= 1 to about 20.
Specific examples of suitable alkoxylated ether amines (such as ethoxylated
ether
is amines) etc., may be found in Tables 9 and 10. Such amines may be primary,
secondary or
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tertiary ethoxylated ether amines. Examples include, but are not limited to,
ethoxylated ether
amines of the "Surfonic PEATM" series available from Huntsman Corporation
including, but
not limited to, "Surfonic PEA-25TM" ethoxylated linear polyetheramine, wherein
the two
digits of the numerical suffix indicates the moles of propoxylation and
ethoxylation per
s molecule respectively. As shown in Table 10, other examples of suitable
ethoxylated ether
amines include, but are not limited to, E-17-S available from Tomah Products,
Milton, WI.
Table 9 - Ezamples of Ethozylated Ether Amines Available from Huntsman
Trademark Product Molecular Total Amine
Weight (meq/g)
SURFO1VIC~ PEA-25 547 1.69-1.96
As shown in Table 9, specific examples of suitable ethoxylated ether amines
include,
io but are not limited to, an ethoxylated ether amine of the "SURFO1VIC~ "
series available
from Huntsman known as "PEA-25", wherein the numerical suffices indicate moles
of
propoxylation and ethoxylation, respectively, per molecule. These ethoxylated
amines are of
the type that may be represented by the formula:
H3
,(CH2CH20)-H
R-(-OCH2 H-)-N~ x
y (CH2CH20)-H
n-x
wherein: R = straight or branched alkyl group having from about 12 to about 14
carbon atoms;
n = total moles of ethoxylation and is equivalent to the second
numerical suffix (5 for "PEA-25");
Zo y = total moles of propoxylation and is equivalent to the first numerical
suffix (2 for "PEA-25"); and
x and (n-x) represent number of ethylene oxide groups in separate
chains on the molecule.
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Table 10 - Ezamples of Ethoaylated Ether Amines Available from Tomah
Product Chemical DescriptionMolecular Minimum
Weight Amine Value
E-14-2 Bis-(2-hydroxyethyl)310 175
isodecyloxypropyl
amine
E-14-5 Poly (5) oxyethylene445 123
isodecyloxypropyl
amine
E-17-2 Bis-(2-hydroxyethyl)345 155
isotridecyloxypropyl
amine
E-17-5 Poly (5) oxyethylene485 112
isotridecyloxypropyl
amine
E-19-2 Bis-(2-hydroxyethyl)350 150
C~2%Cls
alkyloxypropyll amine
E-22-2 Bis-(2-hydroxyethyl)450 120
Octadecyloxypropyl
amine
In one embodiment, an amount of ethoxylated amine and/or ethoxylated ether
amine
sufficient to neutralize the acid functionality of the anionic surfactant may
be employed,
s although greater or lesser amounts are also possible.
Other optional components which may be employed include, but are not limited
to,
amphoteric surfactants. Typically amphoteric surfactants are supplied in
aqueous solution,
and therefore, with benefit of this disclosure, those of skill in the art will
understand that
suitable amounts of amphoteric surfactants may be combined with other
surfactants disclosed
~o herein to result in surfactant compositions having the desired active
surfactant content as
described elsewhere herein. Examples of suitable amphoteric surfactants may be
found in
U.S. Patent No. 5,242,615, which is incorporated herein by reference. Specific
examples
include, but are not limited to, coco dimethylbetaine, coco
amidopropylbetaine, coco amino
propionic acid, etc. Other specific examples include those disclosed elsewhere
herein.
~s In the formulation and practice of the disclosed compositions and methods,
a viscosity
modifier may be employed suitable to prevent gel phase formation upon
dilution. Examples
of suitable modifiers compounds include polyethylene glycols, ethylene glycol,
propylene
glycol, and mixtures thereof. Examples of suitable polyethylene glycol
compounds include,
but are not limited to, polyethylene glycol compounds having a molecular
weight of between
2o about 100 and about 1000, alternatively between 200 and about 400. Specific
examples
include one or more polyethylene glycol solubility enhancers having between
about 1 and
about 20, altennatively between about 3 and about 6 ethylene glycol monomers
joined by
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ether linkages. Specific examples of such polyethylene glycol compounds
include, but are
not limited to, polyethylene glycol products marketed by Huntsman Chemical
Corporation
under the trade name POGOLTM, and POGOL 300. In the case of POGOLT"'
compounds, the
numeric designation indicates the average molecular weight of the polyethylene
glycol
s compounds. In one embodiment, an amount of viscosity modifier compound
sufficient to
obtain a low viscosity liquid is employed, although greater or lesser amounts
are also
possible.
In another embodiment, by employing one or more water soluble glycols (e.g.,
propylene glycol, one or more water soluble polyethylene glycols, a mixture
thereof, etc.), a
~o surfactant composition may be formulated to exist as a single or
substantially homogenous
liquid phase (without segregation) at about 40°F using other components
described elsewhere
herein, but with substantially no water. In such an embodiment, one or more
water soluble
glycols may be present to substantially prevent separation or segregation of a
composition at,
for example, ambient temperatures. Such a formulation may be less corrosive
than aqueous
is solutions and may allow shipping of a composition having substantially no
excess weight due
to water content.
In one particular embodiment, a surfactant concentrate composition may be
formulated by blending together the components listed in Table 11.
Table 11
Concentration Range Component
(by weight of solution)
about 8% to about LAS Acid
35%
up to about 9% Monoethanolamine
up to about 15% Pogol 300
about 8% to about Surfonic T-15
35%
About 15% to about Surfonic N-95*
55%
About 10% to about Water
55%
2o
* -- "SURFONIC N-95" is a nonylphenol ethoxylate available from HUNTSMAN
CORPORATION
having 9.5 moles of ethoxylation and the following formula: C9H,9-C6H4-O-
(EO)9.5-H (where "E0" represents
a mole of ethoxylation).
Although one particular combination of components and weight percentages
thereof
is has been listed in Table 11, it will be understood with benefit of this
disclosure that other
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combinations, other components, as well as other weight percentages (including
outside those
ranges listed in Table 11 ), may be employed in the practice of the disclosed
compositions.
Furthermore, although two particular combinations of components are described
above, it will be understood with benefit of the disclosure that other
combinations, and other
s components, may be employed in the practice of the disclosed compositions.
With benefit of this disclosure, the disclosed concentrated surfactant
compositions
may be employed for a wide variety of uses, including in the formulation of
other
compositions by the addition of other components known to those of skill in
the art. As such,
the disclosed compositions may also be diluted with one or more solvents, as
so needed to fit
~o particular end uses.
In other embodiments, the disclosed compositions may achieve reduced shipping
weights and/or provide advantageous handling properties (such as for example
in pumping,
spraying, mixing, etc.) with little or no dilution. Furthermore, the disclosed
concentrated
surfactant compositions may be used directly with little or no dilution, for
example as for use
~s in an industrial laundry setting where concentrated surfactant composition
(including up to
100% active surfactant content composition) is metered into a washing machine
directly.
EXAMPLES
The following examples are illustrative and should not be construed as
limiting the
scope of the invention or claims thereof.
2o Example 1- High Active Detergent Composition (80% Active Detergent Content)
In this example, a surfactant concentrate is made by blending together the
components
listed in Table 12. A concentrated detergent was prepared by dissolving 8% by
weight
polyethylene glycol in 34.8% by weight Surfonic~ N-95. To this was added 17.4%
by
weight Surfonic~ T-15, 17.4% by weight LAS acid, 2.4% by weight MEA and 20% by
zs weight water. The resulting material was a honey-colored fluid liquid
having an active
detergent content of about 80%. The LAS acid employed was made by sulfonation
of
"ALKYLATE 229TM." "ALKYLATE 229" is a refined mixture of homologs of linear
monalkylbenzene prepared by alkylation with hydrogen fluoride catalyst and
ranging in alkyl
chain length between 10 and 14 (average 12.6), and having an average molecular
weight of
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between about 250 and about 256. Sulfonation typically increases the molecular
weight of a
compound by about 80.
Table 12
Concentration Range Component
(by weight of solution)
17.4% LAS Acid - prepared by
air/S03
sulfonation of Huntsman
"ALKYLATE 229TM"
2.4% Monoethanolamine ("MEA")
8% Pogol 300
17.4% Surfonic~ T-15
34.8% Surfonic~ N-95
20% Water
s The physical properties of the blend are shown in Table 13. The solution was
isotropic at room temperature (about 25° C).
Table 13
Characteristic Value
pH (1%) 8.24
Solids 79.8
Viscosity (cps) 521
Color (Gardner) 6
Advantageously, the blend may be diluted with water with no gel phase
formation.
~o Although one order of component addition is described above, any other
order of
addition suitable for combination of the components to form a concentrated
surfactant liquid
composition as described elsewhere herein may be employed. For example, the
following
sequence of component addition may be used: 1) water; 2) "POGOL 300"
hydrotrope; 3)
"SURFONIC N-95" nonionic surfactant; 4) "ALKYLATE 229" LAS acid; 5) MEA
is neutralizing compound; and 6) "SURFONIC T-15" nonionic surfactant.
Example 2 -100% Active Surfactant Content Composition
In this example, a concentrated surfactant composition blend was prepared by
dissolving 18.5% by weight of the "ALKYLATE 229"-based LAS acid used in
Example 1 in
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75% by weight Surfonic~ N-95. The salt of LAS was prepared by adding 6.5% by
weight
MEA. The resulting material was a honey-colored, fluid liquid having an active
surfactant
content of 100%, a pH (1%) of 9.79, and a viscosity of 753 cps. Observation of
the sample
under a polarized microscope showed no birefringence at room temperature
(about 25°C).
s While the invention may be adaptable to various modifications and
alternative forms,
specific embodiments have been shown by way of example and described herein.
However,
it should be understood that the invention is not intended to be limited to
the particular forms
disclosed. Rather, the invention is to cover all modifications, equivalents,
and alternatives
falling within the spirit and scope of the invention as defined by the
appended claims.
~o Moreover, the different aspects of the disclosed compositions and methods
may be utilized in
various combinations and/or independently. Thus the invention is not limited
to only those
combinations shown herein, but rather may include other combinations.
It will be understood with benefit of this disclosure that in structures where
x and (n-
x) are given herein to represent number of ethylene oxide groups in separate
chains on a
is molecule, values of x and n may vary (for example, within the ranges
given), to give a wide
range of numerical distributions of ethylene oxide in separate chains of a
molecule.
However, in one embodiment, n and n-x may be substantially equal (or very
close in value),
representing a substantially symmetrical or normal distribution of number of
ethylene oxide
groups between two separate chains of a molecule.
