Note: Descriptions are shown in the official language in which they were submitted.
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PROCESS FOR FORMING A CLEANING COMPOSITION
FIELD
1Q The present invention relates to a process for making a cleaning
composition, and a cleaning composition formed by said process. Specifically,
the present invention relates to a process for making a cleaning composition
containing a polymer, and a cleaning composition containing said polymer
formed by said process. .
BACKGROUND
A cleaning composition, especially a laundry composition, will typically
contain an acidic species present during the production process. For example,
the production process may utilize the acid active form of an anionic
surfactant,
which is neutralized during the production process. While certain anionic
surfactants may be added as a pre-neutralized surfactant, in certain locales,
such a pre-neutralized surfactant is either unavailable, of unreliable
quality, or
excessively expensive. Accordingly, a typical production process adds an acid
active, and neutralizes it therein.
Polymers are commonly added to a cleaning composition to provide soil
dispersion properties, anti-redeposition properties, fabric modification
properties,
etc. Such polymers may, for example, complex with soils to remove them from
clothes, capture soils to reduce redeposition, and bind to fabric to provide a
soft
feel.
One type of polymer which is especially useful in a cleaning composition
is a modified polyamine polymer. Such a modified polyamine polymer typically
provides one or more of the desirable properties discussed above.
Specifically,
such a modified polyamine polymer may provide, for example, improved soil
dispersion, anti-redeposition, and fabric modification properties. The
modified
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polyamine polymer may contain, for example, additional charged or uncharged
groups connected to a polymer backbone.
The desirable properties of these polymers typically depend upon their
molecular weight and the properties of any chemically modified groups attached
thereto. Such polymers, and especially modified polyamine polymers, are
typically expensive, as compared to other detergent ingredients, and are thus
used at relatively low concentrations. However, the properties noted above are
typically concentration-dependent; the greater the concentration of the
polymer,
the greater the desired effect. Thus, it is desirable to add an effective
concentration of the polymer, and yet keep this concentration low enough so as
not to excessively increase the formulations cost of the cleaning composition.
Accordingly, the need remains for a process which incorporates a polymer
into a cleaning composition at a concentration which maintains polymer
properties and performance profiles without increasing formulation costs.
SUMMARY
It has now been found that an acid active present in a detergent
production process may degrade certain polymers, causing them to disintegrate
into lower molecular weight fragments which are significantly less effective
in
providing the desired polymer properties. Such a polymer is therefore
described
herein as an "acid-sensitive polymer." Thus, the present invention relates to
an
improved process for forming a cleaning composition containing an acid active
and an acid-sensitive polymer, which reduces acid-sensitive polymer
degradation
and results in maintained polymer properties and performance profiles without
increasing formulation costs.
The present invention relates to a process for forming a cleaning
composition containing the steps of providing at least one alkaline material
and at
least one acid active, and adding the acid active and the alkaline material to
a
mixer. The acid active is substantially neutralized within the mixer to form a
neutralized detergent active. At least one acid-sensitive polymer is added to
the
neutralized detergent active to form a slurry, and the slurry is formed into a
cleaning composition. A cleaning composition as formed by the above process is
also described herein.
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These and other features, aspects, and advantages of the present
invention will become evident to those skilled in the art from a reading of
the
present disclosure with the appended claims.
DETAILED DESCRIPTION
In accordance with the present invention it has now been found that a
cleaning composition may utilize both an acid active and an acid-sensitive
polymer and yet avoid acid-induced degradation of the acid-sensitive polymer.
As there is no need to add extra acid-sensitive polymer in order to compensate
for expected degradation, this improved process maintains the performance
profile and benefits of the polymer without increasing formulation costs. This
improved process reduces degradation, and therefore improves the effectiveness
of a given amount of acid-sensitive polymer.
All percentages, ratios and proportions herein are by weight of the final
cleaning composition, unless otherwise specified. All temperatures are in
degrees Celsius (°C), unless otherwise specified. All documents cited
are
incorporated herein by reference.
As used herein, the term "alkyl" means a hydrocarbyl moiety which is
straight or branched, saturated or unsaturated. Unless otherwise specified,
alkyl
moieties are preferably saturated or unsaturated with double bonds, preferably
with one or two double bonds. Included in the term "alkyl" is the alkyl
portion of
acyl groups.
The term "substantially neutralized", as used herein indicates that at least
50%, preferably at least 80%, and more preferably at least 85% of the acid
active, by weight, has been neutralized.
In accordance with the present invention, it has been recognized that an
acid active present in a typical cleaning composition production process may
degrade certain polymers, causing them to disintegrate into lower molecular
weight fragments which are significantly less effective. Such a polymer is
therefore described herein as an "acid-sensitive polymer." Without intending
to
be limited by theory, it is believed that an acid active may react with the
acid-
sensitive polymer to cause it to degrade, or otherwise lose its effectiveness
in the
cleaning formulation. For example, an acid active may react with an active
group
on the acid-sensitive polymer to reduce the acid-sensitive polymer's
properties in
the cleaning composition. In another example, an acid active may react with
the
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acid-sensitive polymer's backbone to cause it to hydrolyze and disintegrate
into
smaller fragments which are significantly less effective in a cleaning
composition.
The present process also reduces undesirable polymerization of the acid
sensitive polymer. Without intending to be limited by theory, it is believed
that
certain acid-sensitive polymers may undesirably form homopolymers or
copolymers when exposed to acid. Such undesirable polymerization may
destroy or reduce the polymer's effectiveness and performance profile in the
final
composition.
Accordingly, the process of the present invention reduces such
undesirable reactions by substantially neutralizing the acid active prior to
adding
the acid-sensitive polymer. Furthermore, this improved process also provides
additional benefits. For example, as the acid-sensitive polymers are typically
expensive, the present invention reduces formulation costs by requiring the
addition of less acid-sensitive polymer to provide the same beneficial
effects.
Conversely, as the beneficial effects of such acid-sensitive polymers aye
typically
dependent upon their concentration in the cleaning composition, the present
process improves the overall effectiveness of a given level of acid-sensitive
polymer.
In the process of the present invention, at least one alkaline material is
provided with which to neutralize the acid active. The alkaline material may
be
any of those useful in a cleaning composition, and especially a laundry
composition. The alkaline material is typically selected from the alkali metal
and
alkali earth metal salts of, for example, carbonate, phosphate, silicate,
layered
silicate, hydroxide, and mixtures thereof.
Preferred examples of the carbonate useful herein include the
bicarbonates and sesquicarbonates, more preferably, sodium carbonate (i.e.,
soda ash), potassium carbonate, and mixtures thereof.
Where permitted, alkali and alkali earth metal phosphates are especially
useful herein as they may serve the dual purpose of acting as an alkaline
material, as well as a builder. If present, the builder may assist in
controlling
mineral hardness and in the removal of particulate soils. Preferred phosphates
useful herein include, but are not limited to, the alkali metal, ammonium and
alkanolammonium salts of polyphosphates (exemplified by the tripolyphosphates,
pyrophosphates, and glassy polymeric meta-phosphates), phosphonates, and
mixtures thereof.
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The alkali metal and alkali earth metal silicate and layered silicate are also
useful herein. Examples of silicate builders are the alkali metal silicates,
particularly those having a Si02:Na20 ratio in the range 1.6:1 to 3.2:1 and
layered silicates, such as the layered sodium silicates described in U.S.
Patent
5 4,664,839, issued May 12, 1987 to Rieck. NaSKS-6 is the trademark for a
crystalline layered silicate marketed by Hoechst (commonly abbreviated herein
as "SKS-6"). NaSKS-6 has the delta-Na2Si05 morphology form of layered
silicate. SKS-6 is a highly preferred layered silicate for use herein, but
other
such layered silicates, such as those having the general formula
NaMSix02x+1 ~yH20 wherein M is sodium or hydrogen, x is a number from 1.9 to
4, preferably 2, and y is a number from 0 to 20, preferably 0 can be used
herein.
Various other layered silicates from Hoechst include NaSKS-5, NaSKS-7 and
NaSKS-11, as the alpha, beta and gamma forms. As noted above, the delta-
Na2Si05 (NaSKS-6 form) is most preferred for use herein. Other silicates may
also be useful such as for example magnesium silicate, which can serve as a
crispening agent in granular formulations, as a stabilizing agent for oxygen
bleaches, and as a component of suds control systems.
The hydroxide useful herein is preferably sodium hydroxide, such as is
used in a caustic neutralization process. Typically, an apueous solution of
caustic sodium hydroxide is added to the mixer, in order to neutralize the
acid
active.
The alkaline material useful herein is typically provided in the cleaning
composition in at least a stoichiometric molar ratio sufficient to completely
neutralize the acid active. Typically, the alkaline material is in
stoichiometric
excess. The stoichiometric molar ratio of alkaline material to acid active is
at
least 1:1, preferably at least 1.2:1. In certain processes, such as
agglomeration
processes, this stoichiometric molar ratio of alkaline material to acid active
may
reach 8:1, or more.
The present process also provides at least one acid active which is added
to the mixer and neutralized by the alkaline material. The acid active useful
herein is typically the acid form of an anionic surfactant.
The anionic surfactant useful herein typically includes the acid forms of
sulfonated surfactants and sulfonated surface-active materials. Especially
useful
herein are the acid forms of conventional C11-C1g alkyl benzene sulfonates.
Such alkyl benzene sulfonates may be either the branched alkyl sulfonates, the
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linear alkyl benzene sulfonates ("LAS"), or mixtures thereof. Typically, the
sulfuric and/or sulfonic acid form of the desired anionic surfactant is
provided.
For example, to provide linear alkyl benzene sulfonate in the final cleaning
composition, linear alkyl benzene sulfonic acid may be provided and
neutralized
in the process herein.
The process herein includes the step of adding the acid active and the
alkaline material to a mixer. The acid active is then substantially
neutralized
within the mixer to form a neutralized detergent active. The types of mixer
useful
herein include both the commercially-available batch-type slurry mixers (also
called a "crutcher"), or any type of liquid mixer. Such mixers may be operated
continuously, for example, in a multi-stage process. The processing described
herein may be performed in a single mixer, or multiple mixers as desired.
The acid active useful herein is typically provided at levels of from about
10% to about 65%, preferably from about 12% to about 45%, and more
preferably from about 15% to about 35%, by weight of the final cleaning
composition.
In a preferred embodiment of the process described herein, sodium
silicate is added to the neutralized detergent active prior to adding the acid-
sensitive polymer. Without intending to be limited by theory, it is believed
that
this insures an alkaline environment, so as to further prevent any residual
acid
active form degrading the acid-sensitive polymer.
An acid-sensitive polymer is also provided herein. The acid-sensitive
polymer useful herein reacts with an acid active to reduce the effectiveness
of
the acid-sensitive polymer in the cleaning composition. As noted above, this
reduction of effectiveness may result, for example, from chemical modification
of
the acid-sensitive polymer's active groups, from actual fragmentation of the
acid-
sensitive polymer's backbone, etc. Preferred acid-sensitive polymers useful
herein include soil dispersion polymers, anti-redeposition polymers, and
fabric
conditioning polymers mixtures thereof. More preferred classes of polymers
useful herein include modified polyamine polymers, polyacrylate polymers,
copolymers of acrylic and maieic acids, and mixtures thereof.
Modified polyamine polymers are especially preferred herein as an acid-
sensitive polymer. These polymers have shown a high susceptibility to acid-
induced degradation when added with an acid active in the normal agglomeration
processes. These modified polyamine polymers are even more preferably
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modified polyethyleneimine polymers which comprise either linear or cyclic
backbones. The polyamine backbones can also comprise polyamine branching
chains to a greater or lesser degree. in general, the polyamine backbones
described herein are modified in such a manner that each nitrogen of the
polyamine chain is thereafter described in terms of a unit that is
substituted,
quaternized, oxidized, or combinations thereof.
For the purposes of the present invention the term "modification" is
defined as replacing a backbone -NH hydrogen atom by an E unit (substitution),
quaternizing a backbone nitrogen (quaternized) or oxidizing a backbone
nitrogen
to the N-oxide (oxidized}. The terms "modification" and "substitution" are
used
interchangeably when referring to the process of replacing a hydrogen atom
attached to a backbone nitrogen with an E unit. Quaternization or oxidation
may
take place in some circumstances without substitution, but substitution is
preferably accompanied by oxidation or quaternization of at least one backbone
nitrogen.
The linear or non-cyclic pofyamine backbones that comprise the modifed
polyethyleneimine polymers of the present invention have the general formula:
H B
I I
~H2N-R]n+~-~N-R]m-~N-R]n-NH2
said backbones prior to subsequent modification, comprise primary, secondary
and tertiary amine nitrogens connected by R "linking" units. The cyclic
polyamine
backbones comprising the modified polyethyleneimine polymers of the present
invention have the general formula:
H B R
I I I
1H2N-R]n+~-~N-R]m-~N-R]n-IN-R]k-'NH2
said backbones prior to subsequent modification, comprise primary, secondary
and tertiary amine nitrogens connected by R "linking" units
For the purpose of the present invention, primary amine nitrogens
comprising the backbone or branching chain once modified are defined as V or Z
"terminal" units. For example, when a primary amine moiety, located at the end
of the main polyamine backbone or branching chain having the structure:
H2N-R]-
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is modified according to the present invention, it is thereafter defined as a
V
"terminal" unit, or simply a V unit. However, for the purposes of the present
invention, some or all of the primary amine moieties can remain unmodified
subject to the restrictions further described herein below. These unmodified
primary amine moieties by virtue of their position in the backbone chain
remain
"terminal" units. Likewise, when a primary amine moiety, located at the end of
the main polyamine backbone having the structure:
=NH2
is modified according to the present invention, it is thereafter defined as a
Z
"terminal" unit, or simply a Z unit. This unit can remain unmodified subject
to the
restrictions further described herein below.
In a similar manner, secondary amine nitrogens comprising the backbone
or branching chain once modified are defined as W "backbone" units. For
example, when a secondary amine moiety, the major constituent of the
backbones and branching chains of the present invention, having the structure:
H
is modified according to the present invention, it is thereafter defined as a
W
"backbone" unit, or simply a W unit. However, for the purposes of the present
invention, some or all of the secondary amine moieties can remain unmodified.
These unmodified secondary amine moieties by virtue of their position in the
backbone chain remain "backbone" units.
In a further similar manner, tertiary amine nitrogens comprising the
backbone or branching chain once modified are further referred to as Y
"branching" units. For example, when a tertiary amine moiety, which is a chain
branch point of either the poiyamine backbone or other branching chains or
rings,
wherein B represents a continuation of the chain structure by branching,
having
the structure:
B
-[N-R]-
is modified according to the present invention, it is thereafter defined as a
Y
"branching" unit, or simply a Y unit. However, for the purposes of the present
invention, some or all or the tertiary amine moieties can remain unmodified.
These unmodified tertiary amine moieties by virtue of their position in the
backbone chain remain "branching" units. The R units associated with the V, W
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and Y unit nitrogens which serve to connect the polyamine nitrogens, are
described herein below.
The final modified structure of the modified polyethyleneimine polymers of
the present invention can be therefore represented by the general formula:
V(n+1 )WmYnZ
for linear modified polyethyleneimine polymers and by the general formula:
V(n_k+1 )WmYnY,kZ
for cyclic modified polyethyleneimine polymers . For the case of modified
polyethyleneimine polymers comprising rings, a Y' unit of the formula:
serves as a branch point for a backbone or branch ring. For every Y' unit
there is
a Y unit having the formula:
B
I
-[N-R]
that will form the connection point of the ring to the main polymer chain or
branch. In the unique case where the backbone is a complete ring, the
polyamine backbone has the formula:
H B
I I
[H2N-R~n+~-[N-R~m-[NIR~n'
therefore comprising no Z terminal unit and having the formula:
Vn-kwmYnY~k
wherein k is the number of ring forming branching units. Preferably the
polyamine
backbones of the present invention comprise no rings.
In the case of non-cyclic modified polyethyleneimine polymers, the ratio of
the index n to the index m relates to the relative degree of branching. A
fully
non-branched linear modified polyethyleneimine polymer according to the
present invention has the formula:
VWmZ
that is, n is equal to 0. The greater the value of n (the lower the ratio of m
to n),
the greater the degree of branching in the molecule. Typically the value for m
ranges from a minimum value of 4 to about 400, however larger values of m,
especially when the value of the index n is very low or nearly 0, are also
preferred.
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Each polyamine nitrogen whether primary, secondary or tertiary, once
modified according to the present invention, is further defined as being a
member
of one of three general classes; simple substituted, quaternized or oxidized.
Those polyamine nitrogen units not modified are classed into V, W, Y, or Z
units
5 depending on whether they are primary, secondary or tertiary nitrogens. That
is
unmodified primary amine nitrogens are V or Z units, unmodified secondary
amine nitrogens are W units and unmodified tertiary amine nitrogens are Y
units
for the purposes of the present invention.
Modified primary amine moieties are defined as V "terminal" units having
10 one of three forms:
a) simple substituted units having the structure:
E- N-I~-
b) quaternized units having the structure:
X
E ~R-
E
wherein X is a suitable counter ion providing charge balance; and
c) oxidized units having the structure:
O
E-~-R-
Modified secondary amine moieties are defined as W "backbone" units
having one of three forms:
a) simple substituted units having the structure:
-N-F~-
b) quaternized units having the structure:
X
-N=R-
E
wherein X is a suitable counter ion providing charge balance; and
c) oxidized units having the structure:
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-N_ F~
Modified tertiary amine moieties are defined as Y "branching" units having
one of three forms:
a) unmodified units having the structure:
-N-F~
I
b) quaternized units having the structure:
X
-N=R-
wherein X is a suitable counter ion providing charge balance; and
c) oxidized units having the structure:
Certain modified primary amine moieties are defined as Z "terminal" units
having one of three forms:
a) simple substituted units having the structure:
- N-E
b) quaternized units having the structure:
E
-I~E
wherein X is a suitable counter ion providing charge balance; and
c) oxidized units having the structure:
E
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When any position on a nitrogen is unsubstituted of unmodified, it is
understood that hydrogen will substitute for E. For example, a primary amine
unit comprising one E unit in the form of a hydroxyethyl moiety is a V
terminal
unit having the formula:
(HOCH2CH2)HN-.
For the purposes of the present invention there are two types of chain
terminating units, the V and Z units. The Z "terminal" unit derives from a
terminal
primary amino moiety of the structure -NH2. Non-cyclic polyamine backbones
according to the present invention comprise only one Z unit whereas cyclic
polyamines can comprise no Z units. The Z "terminal" unit can be substituted
with any of the E units described further herein below, except when the Z unit
is
modified to form an N-oxide. In the case where the Z unit nitrogen is oxidized
to
an N-oxide, the nitrogen must be modified and therefore E cannot be a
hydrogen.
The modified polyethyleneimine polymers of the present invention
comprise backbone R "linking" units that serve to connect the nitrogen atoms
of
the backbone. R units comprise units that for the purposes of the present
invention are referred to as "hydrocarbyl R" units and "oxy R" units. The
"hydrocarbyl" R units are C2-C12 alkylene, C4-C12 alkenylene, Cg-C12
hydroxyalkylene wherein the hydroxyl moiety may take any position on the R
unit
chain except the carbon atoms directly connected to the polyamine backbone
nitrogens; C4-C12 dihydroxyalkylene wherein the hydroxyl moieties may occupy
any two of the carbon atoms of the R unit chain except those carbon atoms
directly connected to the polyamine backbone nitrogens; Cg-C12 dialkylarylene
which for the purpose of the present invention are arylene moieties having two
alkyl substituent groups as part of the linking chain. For example, a
dialkylarylene unit has the formula:
o r -~~"~ ~ ~ ~a'~r-
although the unit need not be 1,4-substituted, but can also be 1,2 or 1,3
substituted C2-C12 alkylene, preferably ethylene, 1,2-propylene, and mixtures
thereof, more preferably ethylene. The "oxy" R units comprise
(R1 O)xRb(OR1 )x-, -CH2CH(OR2)CH20)z(R1 O)yR1 (OCH2CH(OR2)CH2)w-, _
CH2CH(OR2)CH2-, -(R10)xR1-, and mixtures thereof. Preferred R units are
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C2-C12 alkylene, C3-C12 hydroxyalkylene, C4-C12 dihydroxyalkylene, Cg-C12
dialkylarylene, -(R10)xR1-, -CH2CH(OR2)CH2-, -
(CH2CH(OH)CH20)Z(R1 O)yR1 (OCH2CH-(OH)CH2)w-, -(R1 O)xR5(OR1 )x-,
more preferred R units are C2-C12 alkylene, Cg-C12 hydroxy-alkylene, C4-C12
dihydroxyalkylene, -(R10)xR1-, -(R10)xR5(OR1)x-,
(CH2CH(OH)CH20)Z(R1 O)yR1 (OCH2CH-(OH)CH2)w-, and mixtures thereof,
even more preferred R units are C2-C12 alkylene, Cg hydroxyalkylene, and
mixtures thereof, most preferred are C2-C6 alkylene. The most preferred
backbones of the present invention comprise at least 50% R units that are
ethylene.
R1 units are C2-Cg alkylene, and mixtures thereof, preferably ethylene.
R2 is hydrogen, and -(R1 O)xB, preferably hydrogen.
R3 is C1-C1g alkyl, C7-C12 arylalkylene, C~-C12 alkyl substituted aryl,
Cg-C12 aryl, and mixtures thereof , preferably C1-C12 alkyl, C7-C12
arylalkylene, more preferably C 1-C 12 alkyl, most preferably methyl. R3 units
serve as part of E units described herein below.
R4 is C1-C12 alkylene, C4-C12 alkenylene, Cg-C12 arylalkylene, Cg-C10
arylene, preferably C1-C10 alkylene, Cg-C12 arylalkylene, more preferably C2-
Cg alkylene, most preferably ethylene or butylene.
R5 is C1-C12 alkylene, C3-C12 hydroxyalkyfene, C4-C12
dihydroxyalkylene, Cg-C12 dialkylarylene, -C{O)-, -C(O)NHR6NHC{O)-,
C(O)(R4)rC(O)-, -R1 (OR1 )-, -CH2CH(OH)CH20(R1 O)yR1 OCH2CH(OH)CH2-, -
C(O){R4)rC(O)-, -CH2CH(OH)CH2-, R5 is preferably ethylene, -C(O)-, -
C(O)NHR6NHC(O)-, -R1(OR1)-, -CH2CH(OH)CH2-, -
CH2CH(OH)CH20{R10)yR10CH2CH-(OH)CH2-, more preferably -
CH2CH(OH)CH2-.
R6 is C2-C12 alkylene or Cg-C12 arylene.
The preferred "oxy" R units are further defined in terms of the R1, R2, and
R5 units. Preferred "oxy" R units comprise the preferred R1, R2, and R5 units.
The preferred modified polyethyleneimine polymers of the present invention
comprise at least 50% R1 units that are ethylene. Preferred R1, R2, and R5
units are combined with the "'oxy" R units to yield the preferred "oxy" R
units in
the following manner.
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i) Substituting more preferred R5 into -(CH2CH20)xR5(OCH2CH2)x-
yields -(CH2CH20)xCH2CHOHCH2(OCH2CH2)x-.
ii) Substituting preferred R1 and R2 into -(CH2CH(OR2)CH20)z
(R10)yRlO(CH2CH(OR2)CH2)N,- yields -(CH2CH(OH)CH20)r
(CH2CH20)yCH2CH20(CH2CH(OH)CH2)w-.
iii) Substituting preferred R2 into -CHZCH(OR2)CH2- yields
-CH2CH(OH)CH2-.
E units are selected from the group consisting of hydrogen, C1-C22 alkyl,
C3-C22 alkenyl, C7-C22 arylalkyl, CZ-C22 hydroxyalkyl, -(CH2)pC02M,
(CH2)qSOgM, -CH(CH2C02M)C02M, -(CH2)pPOgM, -(R10)mB, -C(O)R3,
preferably hydrogen, C2-CZ2 hydroxyalkylene, benzyl, C1-C22 alkylene, -
(R10)mB, -C(O)R3, -(CH2)pC02M, -(CH2)qSOgM, -CH(CH2CO2M)C02M, more
preferably C1-C22 alkylene, -(R10)xB, -C(O)R3, -(CH2)pC02M, -(CH2)qSOgM,
-CH(CH2C02M)C02M, most preferably C1-C22 alkylene, -(R10)xB, and -
C(O)R3. When no modification or substitution is made on a nitrogen then
hydrogen atom will remain as the moiety representing E.
E units do not comprise hydrogen atom when the V, W or Z units are
oxidized, that is the nitrogens are N-oxides. For example, the backbone chain
or
branching chains do not comprise units of the following structure:
-N-R or H-N--R or -N-H
2o H H H
Additionally, E units do not comprise carbonyl moieties directly bonded to
a nitrogen atom when the V, W or Z units are oxidized, that is, the nitrogens
are
N-oxides. According to the present invention, the E unit -C(O)R3 moiety is not
bonded to an N-oxide modified nitrogen, that is, there are no N-oxide amides
having the structure:
O ~ ~ O
-N-R or R3-~-N-R or -N-~-R3
~O
or combinations thereof.
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B is hydrogen, C1-Cg alkyl, -(CH2)qS03M, -(CH2)pC02M, -(CH2)q-
(CHS03M)CH2S03M, -(CH2)q(CHS02M)CH2S03M, -(CH2)pP03M, -P03M,
preferably hydrogen, -(CH2)qS03M, -(CH2)q(CHS03M)CH2S03M, -(CH2)q-
(CHS02M)CH2S03M, more preferably hydrogen or -(CH2)qS03M.
5 M is hydrogen or a water soluble cation in sufficient amount to satisfy
charge balance. For example, a sodium cation equally satisfies -(CH2)pC02M,
and -(CH2)qS03M, thereby resulting in -(CH2)pC02Na, and -
(CH2)qS03Na moieties. More than one monovalent cation, (sodium, potassium,
etc.) can be combined to satisfy the required chemical charge balance.
10 However, more than one anionic group may be charge balanced by a divalent
cation, or more than one monovalent cation may be necessary to satisfy the
charge requirements of a poly-anionic radical. For example, a -(CH2)pP03M
moiety substituted with sodium atoms has the formula -(CH2)pP03Na3. Divalent
cations such as calcium (Ca2+) or magnesium (Mg2+) may be substituted for or
15 combined with other suitable monovalent water soluble cations. Preferred
cations are sodium and potassium, more preferred is sodium.
X is a water soluble anion such as chlorine (CI-), bromine (Br) and iodine
(I-) or X can be any negatively charged radical such as sulfate (S042-) and
methosulfate (CH3S03-).
The formula indices have the following values: p has the value from 1 to 6,
q has the value from 0 to 6; r has the value 0 or 1; w has the value 0 or 1, x
has
the value from 1 to 100; y has the value from 0 to 100; z has the value 0 or
1; m
has the value from 4 to about 400, n has the value from 0 to about 200; m + n
has the value of at least 5.
The preferred modified polyethyleneimine polymers of the present
invention comprise polyamine backbones wherein less than about 50% of the R
groups comprise "oxy" R units, preferably less than about 20% , more
preferably
less than 5%, most preferably the R units comprise no "oxy" R units.
The most preferred modified polyethyleneimine polymers which comprise
no "oxy" R units comprise polyamine backbones wherein less than 50% of the R
groups comprise more than 3 carbon atoms. For example, ethylene, 1,2
propylene, and 1,3-propylene comprise 3 or less carbon atoms and are the
preferred "hydrocarbyl" R units. That is when backbone R units are C2-C12
alkylene, preferred is C2-C3 alkylene, most preferred is ethylene.
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The modified polyethyleneimine polymers of the present invention
comprise modified homogeneous and non-homogeneous polyamine backbones,
wherein 100% or less of the -NH units are modified. For the purpose of the
present invention the term "homogeneous polyamine backbone" is defined as a
polyamine backbone having R units that are the same (i.e., all ethylene).
However, this sameness definition does not exclude polyamines that comprise
other extraneous units comprising the polymer backbone which are present due
to an artifact of the chosen method of chemical synthesis. For example, it is
known to those skilled in the art that ethanolamine may be used as an
"initiator"
in the synthesis of polyethyleneimines, therefore a sample of
polyethyleneimine
that comprises one hydroxyethyi moiety resulting from the polymerization
"initiator" would be considered to comprise a homogeneous polyamine backbone
for the purposes of the present invention. A polyamine backbone comprising all
ethylene R units wherein no branching Y units are present is a homogeneous
backbone. A polyamine backbone comprising all ethylene R units is a
homogeneous backbone regardless of the degree of branching or the number of
cyclic branches present.
For the purposes of the present invention the term "non-homogeneous
polymer backbone" refers to polyamine backbones that are a composite of
various R unit lengths and R unit types. For example, a non-homogeneous
backbone comprises R units that are a mixture of ethylene and 1,2-propylene
units. For the purposes of the present invention a mixture of "hydrocarbyl"
and
"oxy" R units is not necessary to provide a non-homogeneous backbone. The
proper manipulation of these "R unit chain lengths" provides the formulator
with
the ability to modify the solubility and fabric substantivity of the modified
polyethyleneimine polymers of the present invention.
Preferred modified polyethyleneimine polymers of the present invention
comprise homogeneous polyamine backbones that are totally or partially
substituted by polyethyleneoxy moieties, totally or partially quaternized
amines,
nitrogens totally or partially oxidized to N-oxides, and mixtures thereof.
However,
not all backbone amine nitrogens must be modified in the same manner, the
choice of modification being left to the specific needs of the formulator. The
degree of ethoxylation is also determined by the specific requirements of the
formulator.
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The preferred polyamines that comprise the backbone of the compounds
of the present invention are generally polyalkyleneamines (PAA's),
polyalkyleneimines (PAI's), preferably polyethyleneamine (PEA's),
polyethyleneimines (PEI's), or PEA's or PEI's connected by moieties having
longer R units than the parent PAA's, PAI's, PEA's or PEI's. A common
polyalkyleneamine (PAA) is tetrabutylenepentamine. PEA's are obtained by
reactions involving ammonia and ethylene dichloride, followed by fractional
distillation. The common PEA's obtained are triethylenetetramine (TETA) and
teraethylenepentamine {TEPA). Above the pentamines, i.e., the hexamines,
heptamines, octamines and possibly nonamines, the cogenerically derived
mixture does not appear to separate by distillation and can include other
materials such as cyclic amines and particularly piperazines. There can also
be
present cyclic amines with side chains in which nitrogen atoms appear. See
U.S.
Patent 2,792,372, Dickinson, issued May 14, 1957, which describes the
preparation of PEA's.
Preferred amine polymer backbones comprise R units that are C2 alkylene
(ethylene) units, also known as polyethyleneimines (PEI's). Preferred PEI's
have
at least moderate branching, that is the ratio of m to n is less than 4:1,
however
PEI's having a ratio of m to n of about 2:1 are most preferred. Preferred
backbones, prior to modification have the general formula:
H B
I I
[HZN-CH2CH2]n+~-[N-CH2CH2],n-[N-CH2CH2]n-NH2
wherein m and n are the same as defined herein above. Preferred PEI's, prior
to
modification, will have a molecular weight greater than about 200 Daltons.
The relative proportions of primary, secondary and tertiary amine units in
the polyamine backbone, especially in the case of PEI's, will vary, depending
on
the manner of preparation. Each hydrogen atom attached to each nitrogen atom
of the polyamine backbone chain represents a potential site for subsequent
substitution, quaternization or oxidation.
These modified polyethyleneimine polymers can be prepared, for
example, by polymerizing ethyleneimine in the presence of a catalyst such as
carbon dioxide, sodium bisulfate, sulfuric acid, hydrogen peroxide,
hydrochloric
acid, acetic acid, etc. Specific methods for preparing these polyamine
backbones are disclosed in U.S. Patent 2,182,306, Ulrich et al., issued
December 5, 1939; U.S. Patent 3,033,746, Mayle et al., issued May 8, 1962;
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U.S. Patent 2,208,095, Esselmann et al., issued July 16, 1940; U.S. Patent
2,806,839, Crowther, issued September 17, 1957; and U.S. Patent 2,553,696,
Wilson, issued May 21, 1951; all herein incorporated by reference.
Examples of modified polyethyleneimine polymers of the present invention
comprising PEI's, are illustrated in Formulas I - IV:
Formula I depicts a modified polyethyleneimine polymer comprising a PEI
backbone wherein all substitutable nitrogens are modified by replacement of
hydrogen with a polyoxyalkyleneoxy unit, -(CH2CH20)7H, having the formula:
~H(O~z~z~lz
'NJ H(~z~z)mN~NI(CHzCH20),H]z
~~z~0)~H ~ (~~zOI,H
[H(O~d"~z),]zN~N~N~ ~~l ~N'~~'~Nt~~(~z~z0),~z
~~z~OOH ~~yz0),H ~ (QizCHzO),H
]~"~(~z~t)~]z~ ~N~~H(~zCHzO),H]Z
l~,i K(~Z~zo),Hlz
Formula I
This is an example of a modified polyethyleneimine polymer that is fully
modified
by one type of moiety.
Formula II depicts a modified polyethyleneimine polymer comprising a PEI
backbone wherein all substitutable primary amine nitrogens are modified by
replacement of hydrogen with. a polyoxyalkyleneoxy unit, -(CH2CH20)7H, the
molecule is then modified by subsequent oxidation of all oxidizable primary
and
secondary nitrogens to N-oxides, said modified polyethyleneimine polymer
having the formula:
0 0
Ihl(~CHz)~zN ~I(CHZCHzOhHlz O(CHZOCHzO)eH
~N~ O~N~~~f(GiiCHzO)~H]z
H(~"~~a"~z)e "''O O(CHICHzOJe~ 0(CH CH O
O ~ z z )~
O
]H(~a"~z1~1 ~Nw/'~ W/'~~~~ ~~H(a"~za"~z0),HJz
x
ChizCHzO)BH N O(GizCHzO)BH
O O
]H(~2~~]2~ ~N~~(~z~20)~H]z
M(ChtzCH20)~H]z
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Formula II
Formula III depicts ,a modified polyethyleneimine polymer comprising a
PEI backbone wherein all backbone hydrogen atoms are substituted and some
backbone amine units are quaternized. The substituents are polyoxyalkyleneoxy
units, -(CH2CH20)~H, or methyl groups. The modified PEI soil release polymer
has the formula:
II..I(~z~z)nzN N(~z0"IzO~rH CH
J cr /'~(~ ~
A1 ~ ~ A1~1/~(~2~2 -'7H
~3 ,~3
IH(p0"~O-Iz~rlzN~~~'/''~'N~N~N~N~.,/~N~~+~'/~'N~ ~~')2
CI' ~ ~ [ Cr ~~,.,,
CI' + 1CH
' +CI-
IH(~~~')z~ ~N~ v. _~_
N(~s)z
Formula III
Formula IV depicts a modified polyethyleneimine polymer comprising a
PEI backbone wherein the backbone nitrogens are modified by substitution (i.e.
by -(CH2CH20)7H or methyl), quaternized, oxidized to N-oxides or combinations
thereof. The resulting modified polyethyleneimine polymer has the formula:
II.I(~"Iz~z),lzN N ~zCH20~,H CH
N O'~, . ~,I~I(CHzCHz O)~H
°r
CI-(; CHI O ~ ~ ~ CH3 O
IH(~~z~rlxN~+r~N~y~N~N~N~~~N~~~')z
CI' ~ O n ~ Cr ~3
Cr _O.,I
' +CI-
(H(~~~7)z ~N~N(~~3
~N(~~z
Formula IV
In the above examples, not all nitrogens of a unit class comprise the same
modification. The present invention allows the formulator to have a portion of
the
secondary amine nitrogens ethoxylated while having other secondary amine
nitrogens oxidized to N-oxides. This also applies to the primary amine
nitrogens,
in that the formulator may choose to modify all or a portion of the primary
amine
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nitrogens with one or more substituents prior to oxidation or quaternization.
Any
possible combination of E groups can be substituted on the primary and
secondary amine nitrogens, except for the restrictions described herein above.
The acid-sensitive polymer useful herein is typically provided at levels of
5 from about 0.05% to about 15%, preferably from about 0.1 % to about 10%, and
more preferably from about 0.2% to about 7%, by weight of the cleaning
composition. If the acid-sensitive polymer herein is a modified
polyethyleneimine
polymer, it is typically provided at levels of from about 0.05% to about 2%,
preferably from about 0.1 % to about 1 %, and more preferably from about 0.2%
to
10 about 0.8%, by weight of the cleaning composition.
In a preferred embodiment of the present invention, a carrier is provided,
in which the acid-sensitive polymer is dispersed to form a premix. Because the
acid-sensitive polymer is typically either a solid or a viscous liquid, and
because
of the typically low concentration at which the acid-sensitive polymer is
used, a
15 carrier is usually required in order to evenly disperse the acid-sensitive
polymer
throughout the neutralized detergent active. The carrier is typically a
liquid, and
may either serve only as a carrier, or may serve a dual purpose. As the acid
sensitive polymer is to be dispersed therein to form the premix, the carrier
is
preferably non-acidic, such as water. Aiso useful herein is a non-aqueous
20 carrier, or a basic carrier.
Enough carrier must be provided such that the acid-sensitive polymer is
easily dispersed, preferably dissolved, therein to form the premix. The weight
ratio of carrier to acid-sensitive polymer in the premix is typically at least
about
1:1, preferably from about 1:1 to about 8:1.
The acid-sensitive polymer or, in a preferred embodiment, the premix
containing the acid-sensitive polymer, is added to the neutralized detergent
active to form a slurry. This typically takes place within a mixer or
apparatus
which homogenizes the slurry. The mixer may be the same mixer used in the
previous neutralization step, or a different mixer. The slurry is then formed
into a
cleaning composition by, for example, spray drying, or agglomeration processes
known in the art.
In a preferred process, the slurry is formed into spray-dried granules in a
conventional spray drying tower operated at an inlet temperature range of from
about 180°C to about 450°C. Such a known apparatus operates by
spraying the
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slurry via nozzles into a counter-current (or co-current) stream of hot air
which
dries the slurry and ultimately forms porous spray-dried granules.
Examples of the invention are set forth hereinafter by way of illustration
and are not intended to be in any way limiting of the invention.
EXAMPLE 1
A cleaning composition is formed according to the following process.
About 20-25% acid active corresponding to the acid form of LAS is provided.
About 1.2 times the stoichiometrically-required amount of dilute caustic
hydroxide
solution is provided to neutralize the acid active. The acid active and the
alkaline
material are added to a mixer, and neutralized therein to form a neutralized
detergent active. About 8% silicate is also added to the neutralized detergent
active. An acid-sensitive polymer (a modified polyethyleneimine polymer,
having
a backbone of MW 1800 and a degree of ethoxylation of about 7) is provided and
mixed with water at a weight ratio of about 1:1 to about 8:1 to form a premix.
The
premix is then added to the mixer, where it is mixed for about 10 seconds to
form
a slurry. Other detergent ingredients, such as phosphate, sulfate, etc. are
also
added at this point.
The slurry is then dumped into a drop tank and pumped at a pressure of
from 40-70 bar, through a pressure nozzle in a spray tower to form spray-dried
granules. The spray tower employs counter-current airflow with an inlet
temperature of about 320-350 °C.
