U.S. patent application number 10/369263 was filed with the patent office on 2004-08-19 for paper products softening compositions.
This patent application is currently assigned to Huntsman petrochemical corporation. Invention is credited to Ashrawi, Samir S., Nguyen, Duy T..
Application Number | 20040159415 10/369263 |
Document ID | / |
Family ID | 32850304 |
Filed Date | 2004-08-19 |
United States Patent
Application |
20040159415 |
Kind Code |
A1 |
Nguyen, Duy T. ; et
al. |
August 19, 2004 |
Paper products softening compositions
Abstract
Provided herein are amphoteric surfactants derived from
ethyleneamines, which surfactants are useful in treating paper,
fibers, textiles, hair, and human skin, to impart
softness-to-the-touch properties thereto.
Inventors: |
Nguyen, Duy T.; (Austin,
TX) ; Ashrawi, Samir S.; (Austin, TX) |
Correspondence
Address: |
Legal Department
Huntsman LLC
P.O. Box 15730
Austin
TX
78761
US
|
Assignee: |
Huntsman petrochemical
corporation
7114 North Lamar Blvd.
Austin
TX
78752
|
Family ID: |
32850304 |
Appl. No.: |
10/369263 |
Filed: |
February 18, 2003 |
Current U.S.
Class: |
162/158 |
Current CPC
Class: |
D21H 21/24 20130101;
C07C 233/35 20130101 |
Class at
Publication: |
162/158 |
International
Class: |
D21F 011/00 |
Claims
I claim:
1) A composition of matter useful for treating paper, textiles, and
human skin comprising an amphoteric surfactant represented by the
formula: 9in which x is any integer selected from the group
consisting of: 4, 5, and 6; R.sub.1 in each occurrence is
independently any alkyl group having between 5 and 25 carbon atoms,
whether straight-chain, branched, cyclic, saturated or unsaturated;
R.sub.2 in each occurrence is independently selected from the group
consisting of: 1) hydrogen; 2) any saturated or unsaturated
aliphatic mono- or di-carboxylic acid moiety having one or more
carboxyl functional groups and having one or more straight-chain or
branched, saturated or un-saturated aliphatic chains containing
from 2 to 20 carbon atoms; 3) a saturated or unsaturated aliphatic
mono sulfonic acid moiety comprising an --SO.sub.3H functional
group and having one or more straight-chain or branched, saturated
or un-saturated aliphatic chains containing from 2 to 20 carbon
atoms; and 4) a radical of the formula: 10 in which R.sub.1 is
defined as above.
2) A composition according to claim 1 wherein R.sub.1 in each
occurrence may be independently derived from a carboxylic having an
unsaturated alkyl carbon bond.
3) A composition according to claim 1 wherein R.sub.2 in each
occurrence is independently derived from an acid selected from the
group consisting of: acrylic acid, maleic anhydride, vinylsulfonic
acid, allylsulfonic acid, 2-methyl vinyl sulfonic acid, and maleic
acid.
4) A composition of matter useful for treating paper, textiles, and
human skin comprising a mixture of at least two components each of
which comprise different amphoteric surfactants which are
represented by the formula: 11in which x is any integer selected
from the group consisting of: 4, 5, and 6; R.sub.1 in each
occurrence is independently any alkyl group having between 5 and 25
carbon atoms, whether straight-chain, branched, cyclic, saturated
or unsaturated; R.sub.2 in each occurrence is independently
selected from the group consisting of: 1) hydrogen; 2) any
saturated or unsaturated aliphatic mono- or di-carboxylic acid
moiety having one or more carboxyl functional groups and having one
or more straight-chain or branched, saturated or unsaturated
aliphatic chains containing from 2 to 20 carbon atoms; 3) a
saturated or unsaturated aliphatic mono sulfonic acid moiety
comprising an --SO.sub.3H functional group and having one or more
straight-chain or branched, saturated or un-saturated aliphatic
chains containing from 2 to 20 carbon atoms; and 4) a radical of
the formula: 12 in which R.sub.1 is defined as above.
5) A composition according to claim 4 wherein one of the components
of said mixture has the structure: 13in which R in each occurrence
is independently any alkyl group having between 5 and 25 carbon
atoms, whether straight-chain, branched, cyclic, saturated or
unsaturated.
6) A composition according to claim 5 in which the carboxylic acid
appendage on the nitrogen atom is derived from acrylic acid.
7) A composition according to claim 4 wherein one of the components
of said mixture has the structure: 14in which R in each occurrence
is independently any alkyl group having between 5 and 25 carbon
atoms, whether straight-chain, branched, cyclic, saturated or
unsaturated, and in which L is any alkyl group having any number of
carbon atoms between about 2 and about 20, whether straight-chain,
branched, or cyclic.
8) A composition according to claim 4 wherein said mixture
comprises: a) a first amphoteric surfactant, having a value for x
of 4; b) a second amphoteric surfactant, having a value for x of 5;
c) a third amphoteric surfactant, having a value for x of 6, said
first amphoteric surfactant being present in any amount between
8.0% and 20.0%; said second amphoteric surfactant being present in
any amount between 25.0% and 45.0%; and said third amphoteric
surfactant being present in any amount between 35.0% and 60.0%,
wherein said percentages are calculated on a weight basis with
respect to all of the amphoteric surfactants present which are
defined by said formula.
9) A process for treating a substrate comprising the steps of: a)
providing an aqueous composition that comprises an amphoteric
surfactant according to claim 1; and b) contacting said substrate
with said aqueous composition.
10) A process according to claim 9 wherein the concentration of
said amphoteric surfactant is any concentration between 0.10% and
5.00% by weight based upon the total weight of said aqueous
composition.
11) A process for treating a substrate comprising the steps of: a)
providing an aqueous composition that comprises an amphoteric
surfactant according to claim 4; and b) contacting said substrate
with said aqueous composition.
12) A process according to claim 11 wherein the concentration of
said amphoteric surfactant is any concentration between 0.10% and
5.00% by weight based upon the total weight of said aqueous
composition.
13) A process for treating a substrate comprising the steps of: a)
providing an aqueous composition that comprises an amphoteric
surfactant according to claim 7; and b) contacting said substrate
with said aqueous composition.
14) A process according to claim 13 wherein the concentration of
said amphoteric surfactant is any concentration between 0.10% and
5.00% by weight based upon the total weight of said aqueous
composition.
Description
TECHNICAL FIELD
[0001] This invention relates to compositions useful for treating
various surfaces including fibers, textiles, paper, hair, and human
skin. More particularly, it relates to compositions and methods for
treating metal, paper, and textiles which compositions comprise an
amphoteric surfactant derived from ethyleneamines, long-chain fatty
acids, and acrylic acid. According to one preferred form of the
invention the ethyleneamine used as a raw material from which the
surfactant is derived is tetraethylenepentamine.
BACKGROUND
[0002] U.S. Pat. No. 5,322,630 provides a method of acidizing a
subterranean formation with an acqueous acid solution wherein the
acid solution contains corrosion inhibiting amounts of an amine
derivative prepared by reacting an unsaturated carboxylic acid with
(a) fatty amine or polyamine, or (b) a fatty amido amine or
polyamine, or (c) a fatty imidazoline amine or polyamine. The
derivative is characterized by the absence of primary amino groups,
and preferably contains only tertiary amino groups. Disclosed
therein are amphoteric derivatives of a broad range of fatty
polyamines, fatty amidoamines, fatty imidazolines and polyamines
which are disclosed as being useful as oilfield corrosion
inhibitors.
[0003] U.S. Pat. Nos. 6,004,914; 6,200,938; and 6,369,007 teach
amphoteric derivatives of aliphatic polyamines, such as
diethylenetriamine or triethylenetetramine reacted with long chain
fatty acids, esters or triglycerides from various natural or
synthetic sources are effective in the softening/texture
modification of substrates such as paper, textiles, human skin
surfaces and hair tresses, as well as in applications for metal
working and lubrication. The polyamines are first reacted with
fatty acids, esters or triglycerides derived from various animal,
vegetable or synthetic sources ranging in molecular distribution
from butyric through erucic acids (e.g. milkfat, soy bean oil,
rapeseed oil) to form polyamines or imidazolines; they are then
further reacted with unsaturated or halogenated carboxylic acids,
carboxylated epoxy compounds or acid anhydrides (e.g. acrylic acid,
itaconic acid, chloroacetic acid, maleic anhydrides octadecenyl
anhydride) to form the various amphoteric structures.
SUMMARY OF THE INVENTION
[0004] The present invention relates to amphoteric surfactants that
are useful in various applications including paper softener, fabric
softener, metal working and lubrication. An amphoteric surfactant
of the present invention may be made by reacting tetraethylene
pentamine ("TEPA") with 2.5 to 3.0 moles of a fatty acid to form an
intermediate amide compound which is then converted to an
amphoteric compound by reacting it with 1 to 2 moles of an
unsaturated acid species selected from the group consisting of:
maleic acid, maleic anhydride, vinyl sulfonic acid, 2-methyl vinyl
sulfonic acid, allylsulfonic acid, and acrylic acid. Thus, the
present invention concerns compositions of matter useful for
treating paper, textiles, and human skin comprising an amphoteric
surfactant represented by the formula: 1
[0005] in which x is any integer selected from the group consisting
of 4, 5, and 6; R.sub.1 in each occurrence is independently any
alkyl group having between 5 and 25 carbon atoms, whether
straight-chain, branched, cyclic, saturated or unsaturated; R.sub.2
in each occurrence is independently selected from the group
consisting of: 1) hydrogen; 2) any saturated or unsaturated
aliphatic mono- or di-carboxylic acid moiety having one or more
carboxyl functional groups and having one or more straight-chain or
branched, saturated or un-saturated aliphatic chains containing
from 2 to 20 carbon atoms; 3) any saturated or unsaturated
aliphatic mono sulfonic acid moiety having one or more --SO.sub.3H
functional groups and having one or more straight-chain or
branched, saturated or un-saturated aliphatic chains containing
from 2 to 20 carbon atoms; and 4) a radical of the formula: 2
[0006] in which R.sub.1 has the same meaning as that ascribed to it
above.
[0007] According to another embodiment, a composition according to
the invention comprises a mixture of at least two components each
of which comprise different amphoteric surfactants which are
represented by the formula: 3
[0008] in which R.sub.1 in each occurrence is independently any
alkyl group having between 5 and 25 carbon atoms, whether
straight-chain, branched, cyclic, saturated or unsaturated; R.sub.2
in each occurrence is independently selected from the group
consisting of: 1) hydrogen; 2) any saturated or unsaturated
aliphatic mono- or di-carboxylic acid moiety having one or more
carboxyl functional groups and having one or more straight-chain or
branched, saturated or un-saturated aliphatic chains containing
from 2 to 20 carbon atoms; 3) any saturated or unsaturated
aliphatic mono sulfonic acid moiety having one or more --SO.sub.3H
functional groups and having one or more straight-chain or
branched, saturated or un-saturated aliphatic chains containing
from 2 to 20 carbon atoms; and 4) a radical of the formula: 4
[0009] in which R.sub.1 has the same meaning as that ascribed to it
above. According to yet a further embodiment, the above-described
mixture comprises:
[0010] a) a first amphoteric surfactant, having a value for x of
4;
[0011] b) a second amphoteric surfactant, having a value for x of
5;
[0012] c) a third amphoteric surfactant, having a value for x of
6,
[0013] with the first amphoteric surfactant being present in any
amount between 8.0% and 20.0%; the second amphoteric surfactant
being present in any amount between 25.0% and 45.0%; and the third
amphoteric surfactant being present in any amount between 35.0% and
60.0%, with all percentages being calculated on a weight basis with
respect to all of the amphoteric surfactants present which are
defined by the above formula.
DETAILED DESCRIPTION
[0014] An amphoteric surfactant of the present invention is
exemplified by the use of TEPA as a raw material, and other
amphoteric surfactants according to the invention are readily
prepared using the same general procedure but with ethyleneamines
such as pentaethylenehexamine, hexaethyleneheptamine,
heptaethyleneoctamine, etc. An amphoteric surfactant according to
the invention may be prepared by first reacting TEPA as a starting
material with 2.5 to 3 moles fatty acids, to form an intermediate
substituted TEPA polyamide. According to one preferred form of the
invention, 3 moles of fatty acid are reacted with 1 mole of TEPA to
yield the triamide. According to a preferred form of the invention,
the polyamide is subsequently reacted with 1 to 2 moles of an
unsaturated acid species such as acrylic acid or vinylsulfonic acid
to form an amphoteric surfactant. According to one preferred form
of the invention, 2 moles of acrylic acid are reacted with one mole
of polyamide, which is preferably a triamide. The resulting
amphoteric compounds are useful as softeners for tissue paper,
fabrics, hair and skin. The resulting amphoteric compounds are also
useful as lubricants in metalworking.
[0015] The general reaction scheme for producing an amphoteric
surfactant useful in accordance with the present invention is set
forth below: 5
[0016] In reaction (I), one mole of tetraethylenepentamine is
caused to be reacted with three moles of the mono-carboxylic acid
in which R may be any C.sub.1 through C.sub.25 alkyl group, whether
straight-chain, branched, cyclic, saturated or unsaturated. In the
case of unsaturated carboxylic acids used as reactant with TEPA,
the present invention contemplates the use of both cis- and
trans-isomers. According to one preferred form of the invention,
the reactant carboxylic acid is oleic acid, although any other
carboxylic acid having between about 7 and 25 carbon atoms may be
used, or mixtures thereof. The product of the reaction between
three moles of the carboxylic acid and TEPA is the triamide shown
in formula (II): 6
[0017] in which the R portion is supplied by the oleic acid.
[0018] This structure represents the predominant product of such
reaction according to the invention. In practice, a mixture of
positional isomers is formed with the carboxylic acid residue being
substituted upon the various possible positions of substitution
having an active hydrogen atom at which the acid function of the
carboxylic acid is capable of reacting, as is known to those
skilled in the art. When fewer than three moles of acid are reacted
per mole of TEPA, the resulting product is a mixture of isomers
substituted at the first and second; first and third; first and
fourth; first and fifth; second and third; and second and fourth
positions. The present invention embraces all such positional
isomers and mixtures thereof.
[0019] Subsequent reaction of the polyamide shown in formula (II)
with an unsaturated acid, such as, but not limited to, acrylic acid
according to the formula (III): 7
[0020] yields an amphoteric surfactant according to the invention,
as described generally by formula (0) previously shown, and shown
structurally in formula (IV): 8
[0021] for the case where one mole of acrylic acid is reacted. When
an unsaturated sulfonate such as vinylsulfonic acid or
allylsulfonic acid is employed, the carboxylic acid group in the
above structure is replaced by the group --SO.sub.3H thus providing
an amphoteric surfactant with a sulfonate anionic portion. The
structure above represents the predominant product of such reaction
according to the invention. In practice, a mixture of positional
isomers is formed with the acrylic residue being substituted upon
the various possible positions of substitution having an active
hydrogen atom at which the unsaturated function of the acrylic acid
is capable of reacting, as is known to those skilled in the art.
When more than one mole of acrylic or other unsaturated carboxylic
or sulfonic acid is reacted, more than one of the possible
positions is substituted. The present invention embraces all such
positional isomers. Monomers other than acrylic acid may of course
be employed in the role just described for acrylic acid, including
unsaturated acid species selected from the group consisting of
maleic acid, maleic anhydride, vinyl sulfonic acid, 2-methyl vinyl
sulfonic acid, and allylsulfonic acid.
[0022] According to one preferred form of the invention, oleic acid
is reacted with TEPA at 144.degree. C. for about 6-10 hours and is
subsequently reacted with acrylic acid in the presence of propylene
glycol or polyethylene glycol at about 105.degree. C. for about 8
hours, or until the reaction is complete. The structures of the
reaction product are easily confirmed using NMR and IR
spectroscopy.
[0023] The following examples are illustrative of the present
invention and should not be construed as being delimitive thereof
in any way. In general, any polyalkylene polyamine can be reacted
with a fatty acid to yield an amide which is subsequently reacted
with acrylic acid to yield an amphoteric surfactants useful in
treating hair, skin, paper, textiles and fibers according to the
invention.
EXAMPLE 1
Preparation of TEPA+3 Moles Oleic Acid (TEPA Triamide)
[0024] 505.8 grams (1.8 moles) of oleic acid is charged to a 1 L
round bottom flask equipped with a mechanical stirrer and nitrogen
purge. 113.6 grams (0.60 moles) tetraethylene pentamine ("TEPA") is
slowly added with stirring under nitrogen at such a rate that the
temperature is not permitted to exceed 120.degree. C. Following the
addition the temperature of the contents of the flask are
maintained at 120.degree. C. for 30 minutes, after which time the
heat is increased to cause the reactor contents to reach
144.degree. C., at which temperature the reactor contents are
maintained for 6 hours further. Condensate is collected in a
Dean-Stark trap (theoretical=32.4 ml). The reaction is considered
to be complete when the acid number is below 10 meq/gram (acid
numbers referred to in this specification are measured by titrating
an aqueous sample using aqueous base which is about 0.1 N to a
phenolphthalein end point and calculating the acid number using the
relation:
meq/gram=((B).times.(N).times.56.1)/(weight of sample in grams)
[0025] in which B=the total number of milliliters of base used;
and
[0026] N=the Normality of the base used.
[0027] The resulting product is a waxy solid at room temperature.
Total yield=93.0% of theoretical, as determined by NMR and IR
spectra. The resulting product is a waxy solid at room temperature.
Total yield=93.0% of theoretical, as determined by NMR and IR
spectra.
EXAMPLE 2
Preparation of TEPA Triamide Amphoteric Surfactant
[0028] To a 3-neck 1 L round bottom flask equipped with a
mechanical stirrer, nitrogen purge, and addition funnel is charged
130.6 grams of propylene glycol and 98.3 grams (0.1 moles) of the
oleic acid triamide of TEPA prepared from example 1 above. The
contents of the flask are heated with stirring to 90.degree. C.
until the contents became homogeneous. 7.2 grams (0.1 mole) of
acrylic acid are added slowly, and the contents of the flask are
maintained at 105.degree. C. for 3 hours. Alternatively, the
reaction may be terminated when at least 90% of the acrylic acid
has reacted, as determined by quantitative IR spectroscopy.
EXAMPLE 3
Preparation of Ethyleneamine E-100+3 Moles TOFA (E-100
Triamide)
[0029] Ethyleneamine E-100 (Huntsman Corp.) is a mixture of
tetraethylenepentamine (10-15% TEPA), pentaethylenehexamine (33-38%
PEHA) and hexaethyleneheptamine (45-54% HEHA). 516.4 grams of tall
oil fatty acid ("TOFA") is charged to a 1 L round bottom flask.
under nitrogen purge. 162.6 grams of Ethylenamine E-100 is slowly
added with stirring under nitrogen, the temperature being kept
below 120.degree. C. throughout the addition. Following the
addition, the temperature of the contents of the flask is
maintained at 120.degree. C. for 30 minutes. Then the temperature
is increased to 144.degree. C. and maintained at 144.degree. C. for
an additional six hours. The reaction is considered to be complete
when the acid number is below 10.
EXAMPLE 4
Preparation of Ethyleneamine E-100 Triamide Amphoteric
Surfactant
[0030] To a 3-neck 1 L round bottom flask equipped with a
mechanical stirrer, nitrogen purge, and addition funnel is charged
120.6 grams of propylene glycol and 98.3 grams (0.1 moles) of the
oleic acid triamide of TEPA prepared from example 3 above. The
contents of the flask are heated with stirring to 90.degree. C.
until the contents became homogeneous. 6.5 grams (0.090 mole) of
acrylic acid are added slowly, and the contents of the flask are
maintained at 105.degree. C. for 3 hours. Alternatively, the
reaction may be terminated when at least 90% of the acrylic acid
has reacted, as determined by quantitative IR spectroscopy.
Softness Tests for Tissue Paper
[0031] One important aspect of tissue paper for use in personal
care such as facial tissue and bathroom tissue is the softness of
such papers. In order to evaluate the effect of a compound
according to the present invention, several test solutions were
made up as follows:
[0032] Sample 1: 48% (TEPA+3 moles oleic acid+2 moles acrylic acid)
52% propylene glycol.
[0033] Sample 2: 48% (TEPA+2.5 moles oleic acid+1.5 moles acrylic
acid) 52% propylene glycol.
[0034] Sample 3: 48% (TEPA+2 moles oleic acid+2 moles acrylic acid)
52% propylene glycol.
[0035] Sample 4: 48% (TEPA+2 moles oleic acid+1 moles acrylic acid)
52% propylene glycol.
[0036] Sample 5: 48% (TEPA+3 moles oleic acid+1 moles acrylic acid)
52% propylene glycol.
[0037] Sample 6: 70% of sample 1 mixed with 30% of SURFONIC.RTM.
E-400 MO ("monooleate").
[0038] Sample 7: 70% of sample 2 mixed with 30% of SURFONIC.RTM.
E-400 MO.
[0039] Sample 8: 70% of sample 3 mixed with 30% of SURFONIC.RTM.
E-400 MO.
[0040] Sample 9: 70% of sample 4 mixed with 30% of SURFONIC.RTM.
E-400 MO.
[0041] Sample 10: 70% of sample 5 mixed with 30% of SURFONIC.RTM.
E-400 MO.
[0042] Sample 11: pure SUFRONIC.RTM. E-400 MO (SURFONIC.RTM.
products are available from Huntsman Corporation)
[0043] Control 1: 48% (diethylenetetramine "DETA"+2 moles TOFA
(tall oil fatty acid)+1 mole acrylic acid)+52% propylene
glycol.
[0044] Control 2: 70% of control 1+30% SUFRONIC.RTM. E-400 MO.
[0045] In the above samples, the terminology reminiscent of
"(TEPA+2 moles oleic acid+2 moles acrylic acid)" means the
amphoteric surfactant produced by reacting TEPA with 2 moles of
oleic acid, and subsequently reacting the product thereof with 2
moles of acrylic acid. The various compositions descried above in
samples 1-5 were prepared by simple mixing of the specified amount
of glycol and amphoteric surfactant. Similarly, for examples 6-10
the specified amounts of materials were blended together.
SUFRONIC.RTM. E-400 MO is an ethoxylated oleic acid surfactant
available from Huntsman Company LLC of Houston, Tex.
[0046] Solutions for treating tissue paper were prepared by making
up a 1.0% solution of each of the above samples in water.
Evaluations of the effect of each solution were made by immersing a
swatch of untreated tissue in each of the 1.0% aqueous solutions
containing the material in the samples above. The treated tissue
swatches were held in the solution for one minute, and withdrawn.
The treated tissue swatches were then dried in an oven at
25.degree. C. The tissues so treated were evaluated for their
softness to the touch by several members of our research staff and
each given a rating based on the scale: 0=poor/harsh texture;
1=fair; 2=good; 3=very good; 4=excellent/very soft texture. The
results of the softness testing is tabulated in the table I
below:
1TABLE I softness feel test results Sample ID Softness DI Water 0
Sample 6 2.4 Sample 7 2.4 Sample 8 1.2 Sample 9 1.8 Sample 10 3.8
Sample 11 1.4 Sample 5 4.0 Control 1 2.5 Control 2 2.4
[0047] Sample 6 and sample 7 are comparable to the prior art;
however, sample 10 and sample 5 are superior to the prior art. In
the graph below is the surface response curve for the above
samples. It can be seen from the contour plot below of the softness
test results that the maximum performance occurs with 3 moles of
oleic acid and 1 mole of acrylic acid:
[0048] Consideration must be given to the fact that although this
invention has been described and disclosed in relation to certain
preferred embodiments, obvious equivalent modifications and
alterations thereof will become apparent to one of ordinary skill
in this art upon reading and understanding this specification and
the claims appended hereto. Accordingly, the presently disclosed
invention is intended to cover all such modifications and
alterations, and is limited only by the scope of the claims which
follow.
* * * * *