Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
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Modified Alkoxylated Polyol Compounds
FIELD OF THE INVENTION
This invention relates to modified alkoxylated polyol compounds, methods of
making
modified alkoxylated polyol compounds, and cleaning compositions comprising
the same.
BACKGROUND OF THE INVENTION
Polyol compounds such as sugars like sucrose or maltitose are known as a
sustainable and
readily available raw material. Ethoxyates of maltitol is known, e.g., CAS
503446-80-8. This
material has been widely disclosed as a surfactant for cosmetic and other
personal care
applications such as that discussed in JP 2003-096182. Other known ethoxylated
polyols
include: ethoxylated manitol (CAS 53047-O1-2), ethoxylated inostol (CAS 503446-
79-5),
ethoxylated sorbitol (CAS 53694-15-8). JP 10-081744 discusses the production
of
polyetherpolyols by adding alkylene oxides to saccharide in the presence of
amine catalysts.
However, as "catalyst" implies, the amine catalysts do not become incorporated
into the
polyetherpolyol structure.
Also known are a series of amine terminated ethoxylates known in the trade as
JEFFAMINES~ sold by Huntsman. These are mainly derived from polyethylene
glycol and
mixtures of polyethylene glycol and polypropylene glycol where the glycols are
aminated
directly with ammonia and a catalyst. These are called JEFFAMINE D~ and
JEFFAMINE ED~
series. The most complex mixture of the JEFFAMINES~ series is the T series.
The
JEFFAMINES~ are based on either trimethylolpropane or glycerine and thus have
three
ammonia terminated ethoxy/propoxy branches radiating from the glycerin or
trimethylolpropane
core.
Amination of polyols with ammonia and other amines is further exemplified in
US
5,371,119, but uses modification of the polyol specifically via
epichlorohydrin to form a polyol
bis-halohydrin followed by reaction with ammonia or an amine to form repeating
networks of
amino polyols. This results in formation of a complex polymerized mixture
containing multiple
polyols linked randomly via the reactive halo hydrin. This complex mixture is
not believed to be
of value to formulators of cleaning compositions fox the purpose of providing
cleaning benefits
and is targeted towards forming emulsifiers.
Simple amination ofpolyols are described in WO 01/98388 A1 discussing simple
aminated
polyols, further reacted with aldehydes, in particular formaldehyde, to make
complex polymeric
networks. Included in these complex structures is the ability to have sulfide,
carboxylate, alkyl
esters, alkyl sulphonates, and alkyl phosphates as a functional unit of the
complex structure.
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However, the resulting complex polymeric networks is not believed to be of
value to formulators
of cleaning compositions for the purpose of providing cleaning benefits.
Additionally, it has not
been taught to manipulate these materials in a controlled and specific manner.
Selective
modification of sugar derived polyols to provide modified polyols where the
star like structure is
tuned to meet the needs of detergent formulators is highly desirable.
There also exists a need for materials that are relatively easy to manufacture
from
sustainable and readily available raw materials, which may be broadly tuned to
address specific
performance requirements. .
Stressed conditions also give the additional problem of having anionic
surfactants such as
linear alkylbenzene sulfonates or alkyl sulfates form larger order aggregates.
The aggregation of
the anionic surfactant reduces the amount of the anionic surfactant available
to clean.
There exists a need fox materials that are relatively easy to manufacture from
sustainable
and readily available raw materials, which may be tuned in a controlled and
specific manner to
address specific formulability and performance requirements. A multifunctional
material that
provides cleaning and gives increased surfactant availability by preventing
formation of larger
ordered aggregates of anionic surfactant with free hardness during use is
desired.
Specific performance requirements include providing cleaning of hydrophobic
stains
(grease, oil) to hydrophilic stains (clay) associated with outdoor soils.
Other performance
requirements include used in personal care compositions, such as contact lens
solution, uses in
adhesives, vulcanization of rubbers, use in polyurethane processes, use as dye
additives, use as a
dispersant in agricultural applications, use as dispersants for inks, asphalt
dispersants, surfactant
dissolution aides, in use surfactant solubilizers in presence of calcium and
magnesium among
other performance requirements.
Formulability of some of the current commercial polymers, which provide
cleaning of
outdoor soils, into granular and liquid laundry detergents, hard surface
cleaners, dish cleaning
compositions, personal care compositions as well as oil drilling compositions
continues to
challenge detergent formulators.
SUMMARY OF THE INVENTION
The present invention relates to compounds, processes, cleaning compositions,
and
methods of using said compounds and compositions characterized by comprising a
polyol
compound, the polyol compound comprising at least three hydroxy moieties, at
least one of the
hydroxy moieties further comprising a alkoxy moiety, the alkoxy moiety is
selected from the
group consisting of ethoxy, propoxy, butoxy and mixtures thereof; further
wherein at least one of
the hydroxy moieties further comprise an anionic capping unit.
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The present invention further relates compounds, processes, cleaning
compositions, and
methods of using said compounds and compositions characterized by comprising a
polyol
compound, the polyol compound comprising at least three hydroxy moieties, at
least one of the
hydroxy moieties further comprising a alkoxy moiety, the alkoxy moiety is
selected from the
group consisting of ethoxy, propoxy, butoxy and mixtures thereof; further
wherein at least one of
the hydroxy moieties is replaced by and thus further comprises an anionic
capping unit and at
least one of the hydroxy moieties is substituted by an amine capping unit.
The present invention further relates compounds, processes, cleaning
compositions, and
methods of using said compounds and compositions characterized by comprising a
polyol
compound, the polyol compound comprising at least three hydroxy moieties, at
least one of the
hydroxy moieties further comprising a alkoxy moiety, the alkoxy moiety is
selected from the
group consisting of ethoxy, propoxy, butoxy and mixtures thereof; further
wherein at least one of
the hydroxy moieties is replaced by and thus further comprises an anionic
capping unit and at
least one of the hydroxy moieties is substituted by a quaternary amine capping
unit.
The present invention further relates compounds, processes, cleaning
compositions, and
methods of using said compounds and compositions characterized by comprising a
polyol
compound, the polyol compound comprising at least three hydroxy moieties, at
least one of the
hydroxy moieties further comprising a alkoxy moiety, the alkoxy moiety is
selected from the
group consisting of ethoxy, propoxy, butoxy and mixtures thereof; further
wherein at least one of
the hydroxy moieties is replaced by and thus further comprises an anionic
capping unit, at least
one of the hydroxy moieties is substituted by an amine capping unit and at
least one of the
hydroxy moieties is substituted by a quaternary amine capping unit.
DETAILED DESCRIPTION OF THE INVENTION
There exists a need for materials that are relatively easy to manufacture from
sustainable
and readily available raw materials, which may be broadly tuned to address
specific formidability
and performance requirements.
Polyol compounds such as sugar based materials and polyethylene/polypropylene
glycol
materials axe sustainable and readily available raw materials that lend
themselves to be broadly
tuned to address specific formulability and performance requirements. As used
herein "tune"
means having the ability to manipulate the chemical structure of the polyol
compounds to achieve
distinguishing chemical functionality. For example, an alkoxylated polyol
compound modified
by comprising an anionic capping unit is a tuned structure giving desired
characteristics for
specific formulability and performance requirements. Another example, an
allcoxylated polyol
compound modified by comprising an anionic capping unit and amine capping unit
is a tuned
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structure giving desired characteristics. Another example is when an
alkoxylated polyol
compound is modified by comprising an anionic capping unit and a quaternary
amine capping
unit, is a tuned structure giving desired characteristics. Finally another
example may contain both
elements of the two examples, thus containing an anionic capping unit and an
amine and
quaternary amine capping unit.
The polyol compounds useful in the present invention comprises at least three
hydroxy
moieties, preferably more than three hydroxy moieties. Most preferably six or
more hydroxy
moieties. At least one of the hydroxy moieties further comprising a alkoxy
moiety, the alkoxy
moiety is selected from the group consisting of ethoxy (E0), propoxy (PO),
butoxy (BO) and
mixtures thereof preferably ethoxy and propoxy moieties, more preferably
ethoxy moieties. The
average degree of alkoxylation is from about 1 to about 100, preferably from
about 4 to about 60,
more preferably from about 10 to about 40. Alkoxylation is preferably block
alkoxylation.
The polyol compounds useful in the present invention further have at least one
of the
alkoxy moieties comprising at least one anionic capping unit. Further
modifications or tuning of
the compound may occur, but one anionic capping unit must be present in the
compound of the
present invention. One embodiment comprises more than one hydroxy moiety
further comprising
an alkoxy moiety having an anionic capping unit. For example formula (I):
O(EO)xH O(EO)XS03Na+
Na+
+Na 03
+Na 03Sx(OE)O O(EO)XS03Na+
formula (I)
wherein x of formula (I) is from about 1 to about 100, or such as from about
10 to about 40.
Suitable anionic capping unit include sulfate, sulfosuccinate, succinate,
maleate,
phosphate, phthalate, sulfocarboxylate, sulfodicarboxylate, propanesultone,
1,2-disulfopropanol,
sulfopropylamine, sulphonate, monocarboxylate, methylene carboxylate, ethylene
carboxylate,
carbonates, mellitic, pyromellitic, sulfophenol, sulfocatechol,
disulfocatechol, tartrate, citrate,
acrylate, methacrylate, poly acrylate, poly acrylate-maleate copolymer, and
mixtures thereof.
Preferably the anionic capping units are sulfate, sulfosuccinate, succinate,
maleate, sulfonate,
methylene carboxylate and ethylene carboxylate.
Suitable polyol compounds for starting materials for use in the present
invention include
maltitol, sucrose, xylitol, glycerol, pentaerythitol, glucose, maltose,
matotriose, maltodextrin,
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maltopentose, maltohexose, isomaltulose, sorbitol, poly vinyl alcohol,
partially hydrolyzed
polyvinylacetate, xylan reduced maltotriose, reduced maltodextrins,
polyethylene glycol,
polypropylene glycol, polyglycerol, diglycerol ether and mixtures thereof.
Good examples
include the polyol compound being selected as sorbitol, maltitol, sucrose,
xylan, polyethylene
glycol, polypropylene glycol and mixtures thereof. Another group for the
polyol compound is
sorbitol, maltitol, sucrose, xylan, and mixtures thereof.
Tuning of the polyol compounds can be derived from one or more modifications,
dependant upon the desired formidability and performance requirements. Tuning
requires anionic
modifications and can include incorporating a cationic or zwitterionic charge
modifications to the
polyol compounds.
In one embodiment of the present invention, at least one hydroxy moiety
comprises an
alkoxy moiety, wherein the alkoxy moiety further comprises at least one
anionic capping unit.
In another embodiment of the present invention, at least one hydroxy moiety
comprises
an alkoxy moiety, wherein the alkoxy moiety further comprises more than one
anionic capping
unit, wherein at least one anionic capping unit, but less than all anionic
capping units, is then
selectively substituted by a amine capping unit. The amine capping unit is
selected from a
primary amine containing capping unit, a secondary amine containing capping
unit, a tertiary
amine containing capping unit, and mixtures thereof.
Suitable primary amines for the primary amine containing capping unit include
monoamines, diamine, triamine, polyamines, and mixtures thereof. Suitable
secondary amines for
the secondary amine containing capping unit include monoamines, diamine,
triamine, polyamines,
and mixtures thereof. Suitable tertiary amines for the tertiary amine
containing capping unit
include monoamines, diamine, triamine, polyamines, and mixtures thereof.
Suitable monoamines, diamines, triamines or polyamines for use in the present
invention
include ammonia, methyl amine, dimethylamine, ethylene diamine,
dimethylaminopropylamine,
bis dimethylaminopropylamine (bis DMAPA), hexemethylene diamine, benzylamine,
isoquinoline, ethylamine, diethylamine, dodecylamine, tallow
triethylenediamine, mono
substituted rnonoamine, monosubstituted diamine, monosubstituted podyamine,
disubstituted
monoamine, disubstiuted diamine, disubstituted polyamine, trisubstituted
triamine, tri-substituted
polyamine, multisubstituted polyamine comprising more than three substitutions
provided at least
one nitrogen contains a hydrogen, and mixtures thereof.
In another embodiment of the 'present invention, at least one of nitrogens in
the amine
capping unit is quaternized. As used herein "quaternized" means that the amine
capping unit is
given a positive charge through quaternization or protonization of the amine
capping unit. For
example, bis-DMAPA contains three nitrogens, only one of the nitrogens need be
quaternized.
However, it is preferred to have all nitrogens quaternized on any given amine
capping unit.
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The tuning or modification may be combined depending upon the desired
formulability
and performance requirements. Non-limiting examples of modified polyol
compounds of the
present invention include:
+ +
(CHz)zN(CHs)z(CHz)sN(CH3)a
~3
formula (II)wherein x of formula (I) is from about 1 to about 100; and such as
from about 10 to
about 40.
+ +
+ + O(EOya(CHz)zN(CH3)z(CHz)~(CHs)3
+ +
O (EO)~ 4(CH~ZN(CH3~(CI~)3N(CH3)3
_ ~ 8 Cl
~~h5s~3 N3+
5H O ~O(~hsS03'Na
~(EO), sS03'Na
formula (III)
~'3S~.s(~E~'~~ r~ ~ ~ $ Cl
+ +
~~~~~15~U3
formula (IV)
Process of Making
The present invention also relates to a process fox making the compound of the
present
invention. The process for making the compound of the present invention
comprises the optional
step of alkoxylating a polyol compound comprising at least three hydroxy
moieties such that the
average degree of alkoxylation of at least one hydroxy moiety is between about
1 and about 100;
and such as from about 4 to about 60; further such as from about 10 to about
40; to form an
alkoxylated polyol comprising at least one alkoxy moiety. Alternatively, an
alkoxylated polyol,
such as CAS 52625-13-5, a propoxylated sorbitol or sorbitol polyoxy ethylene
ether available
+ +
~fECh, afCI-~~~~fGI~~N(CFi~?~
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from Lipo Chemicals Inc., may be used as the starting material of the present
invention. If the
average degree of alkoxylation is not a desired level, an alkoxylation step
may be used to achieve
the desired degree of alkoxylation from about 1 to about 100, and such as from
about 4 to about
60; further such as from about 10 to about 40. Next, the process comprises the
step of reacting at
least one alkoxy moiety of the compound with an anionic capping unit to form
an anionic
alkoxylated polyol, although more anionic capping units may be selected.
In one embodiment the process comprises another step of substituting at least
one anionic
capping unit of the anionic alkoxylated polyol with an amine capping unit to
form an anionic
aminated alkoxylated polyol. In this process only certain anionic capping
units may be
substituted such as sulfate, phosphate and carbonate. The process may further
comprise the step
of quaternizing at least one of the nitrogens in the amine capping of the
anionic aminated
alkoxylated polyol to form a zwitterionic alkoxylated polyol. Quaternization
can be performed on
any of the anionic aminated alkoxylated polyols. In one embodiment, the
process comprises the
step of alkoxylating some or most of the hydroxy moieties of the polyol such
that the degree of
alkoxylation is from about 1 to about 100; and such as from about 4 to about
60, further such as
from about 10 to about 40; to form an alkoxylated polyol. The process further
comprises the step
of reacting the alkoxy moiety of the alkoxylated polyol with at least one
anionic capping unit
containing as least one of the following anionic groups; sulfate, phosphate
and carbonate; to form
an anionic alkoxylated polyol. The process may partially or completely react
the alkoxy moiety
of the alkoxylated polyol with an anionic capping unit. It is also understood
that anionic capping
units other than sulfate, phosphate or carbonate may also be present in the
anionic alkoxylated
polyol. Preferably all alkoxy moieties comprise an anionic capping unit.
Optionally, the process comprises the step of substituting the anionic capping
unit with an
amine capping unit selected from sulfate, phosphate and carbonate and mixtures
thereof, to form
an aminated anionic alkoxylated polyol (scheme I below). The substitution of
the anionic capping
units present with an amine capping unit may be partial or complete.
Preferably the subsitution of
the anionic capping unit with the amine capping unit is partial forming an
anionic aminated
alkoxylated polyol.
Optionally, the process also comprises the process of providing an aminated
alkoxylated
polyol by direct amination of the alkoxylated polyol using catalytic amination
(scheme II below)
Optionally, the process may further comprise the step of quaternizing at least
one of the
nitrogens of the amine capping unit of the anionic aminated alkoxylated polyol
forming a
zwitterionic alkoxylated polyol. The quaternization of the amine capping unit
of the anionic
aminated alkoxylated polyol may be partial or complete. In one embodiment, the
quaternization
is partial. In another embodiment, the quaternization is complete. The
quaternization of the
nitrogens of the amine capping unit may be partial or complete, preferably
complete. A
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nonlimiting synthesis scheme is exemplified in Synthesis Scheme I and
Synthesis Scheme II
below:
Synthesis Scheme I Anionic aminated alkoxylated polyol
H(OE)x0
off off 6 times x EO o(EO),~H
OH O(EO)XH
STEP 1 H Base Catalyst H(oE)xo
OH OH H(OE)x0 O(EO)xH
H(OE)x0 +Na 05S(OE)x0 p(EO)KS03Na+
p(~7hH
6 ClS03H o(EO)~SO,Na+
STEP 2 H(pE)x0 ~~)xH ~ +Na 03S(OE)X
CHZCIz
Na035(OE~ EO SO Na
H(OE)x0 O(HO)xH
+Na03S(OE)XO O(EO)~.S03Na+ 3 (CH3)2NH (CHy~NCHzCHZ(OE)x.~0 O(EO)nSO3Na+
STEP 3 +Na'03S(OE)n O(EO)xS03Na+ ~ O(EO)K_iCHZCHZN(CHy)z
Na OgS(OE)x
~ Heatl Pressure ~
+Na03S(OE~ ~EO)xS03Na+ ' 3 OSO Na+ (Cf~~NCH2CH2(OE)x_~~O)"SD3Na+
3
(CI~)zNCHZCHz(OE~_i0 ~)%S~Na'
(CHy)3NCH2CH2(OE~_~ O
EO)KSO~
3 (CH30)ZS02. k
STEP 4 EO)x_~CHpCHyN(CH3)Z EO)x.~CHZCH2N(CH~)~
+Na-03S(OB)x ~ b,s(OE)xo
(CH3)7NCH2CH2(OE~_i o(EO)xs~Na+ Heat/H20 (CHy)3+CHzCHa(OE~n
a EO)xSOJ
The process rnay comprise optionally Step 1, Step 2, and optionally, Step 3
and 4. The
step to providing the anionic aminated alkoxylated polyol via a neucleophilic
substitution of
sulfate moieties by an amine capping unit should be noted. This is a
nonlimiting example as
phosphate or carbonate groups may also be used for substitution by an amine
capping unit.
Synthesis Scheme II:
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H(OE~O EO
off OH 6 times x EO « )'~
OH O(EO)TI-I
STEP 1 H H(OE~p
Base Catalyst
OH OH H(OE~O O(EO),~H
H(OE~O p(~~H
NH3 HZNCH2CHz(OE~.iO p EO H
STEP 2 «HO~H > ( )x
H(OE~O See US 5003107 (EO)x.,CH2cHZNH2
H(OE~
H(pE~p o(EO~H or US 23139289A1
by Huntsman for HZNCH2CHz(OE~_~~O)xH
procedure to reapply
HZNCHzCHz(OE)x.ip O(EO)xH (CHs)aNCHZCHZ(pE)x.i0 O(EO)XH
+
O(EO)x_~CHZCHZNHZ 9 (CH30)ZSO2. O(EO)x_~CHZCHZN(CH3)3
STEP 3 H(OE~ ---~ H(OE~
HZNCHZCHZ(OE~_~ EO)xH base (pH3hNCHxCHz(OE)x_~ Ep)xH
+
+ 9 CH30S03Na
(CH3)3NCHZCH2(OE~.iO p(EO)xH
+ +
O(EO)X_iCH2CHZN(CH3)3 Transsulfation (cH,),NCHzcHz(oEk_,o ~~xs~.
STEP 4 H(pE)x HZ~ EO)x,~CFizCH2N(CH~)3
(CH3)yNCHZCH2(OE~_~ Ep)xH -O~S(OE)x0
+ Heat
(CH~)~+CH2CHz(OE~_~ O(~)xSO;
+ 9 CH30S03Na
Scheme II is distinguished from Scheme I in two areas; (1) direct substitution
of the terminal
hydroxy moieties is accomplished by catalytic oxidationlreduction using metal
catalysts and
hydrogen; (2) sulfation is carried out after amination and quatemization by
transulfation as
disclosed in LTS 6,452,035. A zwitterionic alkoxylated polyol of the same
composition may be
prepared by either Scheme I or Scheme II above. One of skill in the art will
recognized that other
amine capping units may be used, including but not limited to ammonia or
dimethylaminopropylamine.
A specific description of the process of the present invention is described in
more detail
below.
Ethoxylation of Polyol
Ethoxylation of the polyol, such as sorbitol, may be completed by any known
technique,
such as that described in EP 174436 A1 Propoxylation and butoxylation may also
be completed
by known techniques.
Add sorbitol (17.5g, 0.0962 mol) to an autoclave, purge the autoclave with
nitrogen, heat
sorbitol to 110-120°C; autoclave stirred and apply vacuum to about 20
mmHg.
Vacuum is continuously applied while the autoclave is cooled to about 110-
120° C. while
introducing 6.2g of a 25% sodium methoxide in methanol solution (0.0288 moles,
to achieve a
5% catalyst loading based upon hydroxy moieties). The methanol from the
methoxide solution is
removed from the autoclave under vacuum. A device is used to monitor the power
consumed by
the agitator. The agitator power is monitored along with the temperature and
pressure. Agitator
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power and temperature values gradually increase as methanol is removed from
the autoclave and
the viscosity of the mixture increases and stabilizes in about 1.5 hours
indicating that most of the
methanol has been removed. The mixture is further heated and agitated under
vacuum for an
additional 30 minutes.
Vacuum is removed and the autoclave is cooled to or kept at 110° C.
while it is being
charged with nitrogen to 1725 kPa (250 psia) and then vented to ambient
pressure. The autoclave
is charged to 1380 kPa (200 psia) with nitrogen. Ethylene oxide is added to
the autoclave
incrementally while closely monitoring the autoclave pressure, temperature,
and ethylene oxide
flow rate while maintaining the temperature between 110 and 120° C. and
limiting any
temperature increases due to reaction exotherm. After the addition of 483g of
ethylene oxide
(10.97 mol, resulting in a total of 19 moles of ethylene oxide per mol of OH),
the temperature is
increased to I20° C. and the mixture stirred for an additional 2 hours.
The reaction mixture is then collected into a 22 L three neck round bottomed
flask purged
with nitrogen. The strong alkali catalyst is neutralized by slow addition of
2.8g methanesulfonic
acid (0.00288 moles) with heating (110° C.) and mechanical stirring.
The reaction mixture is then
purged of residual ethylene oxide and deodorized by sparging an inert gas
(argon or nitrogen) into
the mixture through a gas dispersion frit while agitating and heating the
mixture to 120° C. for 1
hour. The final reaction product, approximately SOOg, is cooled slightly, and
poured into a glass
container purged with nitrogen for storage.
Alternatively, polyol may be purchased with a degree of alkoxylation that is
at or below
that desired, such as CAS S262S-13-S, a propoxylated sorbitol or sorbitol
polyoxy ethylene ether
available from Lipo Chemicals Inc. Wherein the desired degree of alkoxylation
is achieved by
the processes known and/or described above.
Sulfation of Sorbitol EO,~d (Average of 19 EO moieties per hydroxy moiety)
Weigh into a SOOmI Erlenmeyer flask Sorbitol El4 (299.7g, O.OS8 mol) and
methylene
chloride (300g) ("the solution") . Equip the flask with a magnetic stirring
bar and stir until
complete dissolution. Place the flask in an ice bath until the solution
reaches about 10°C. Stir
vigorous while slowing pouring chlorosulfonic acid (48.3g, 0.415 mol) over the
period of about S
minutes to form a reaction solution. Stir the reaction solution in the ice
bath for 1.5 hours.
Place a solution of sodium methoxide (197g of 2S% in methanol) in SOg of
methylene
chloride in a IL Erlenmeyer flask ("base solution") and chill in an ice bath
until the temperature
of the solution reaches about 10°C. Stir the base solution vigorous
using a magnetic stirring bar.
Slowly pour the reaction solution into the base solution over a period of
about 3 minutes. A mild
exotherm should be observed. The resulting solution becomes milky as salts
form. After addition
is complete, measure the pH to be about 12. Add to this resulting solution
about 100 ml of
distilled water, and transfer the resulting emulsion to a 1L round bottom
flask and use a rotary
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evaporator at 50°C to strip, in portions, to obtain a clear solution.
Transfer the clear solution to a
Kulgelrohr apparatus. At 60°C and 133 Pa (lmm Hg) strip the solution to
yield 366g of off white
waxy solid, 90% active (10% salts).
Carbon NMR spectrum (500 MHz; pulse sequence: s2pul, solvent D20; relax. delay
0.300 sec, pulse 45.0; acq. time 1.090 sec) shows an absence of alcohol groups
at about 60ppm
and the emergence of a new peak at about 67ppm consistent with formation of
the end group
sulfate. Proton NMR spectrum (500 MHz or 300 MHz; pulse sequence: s2pul,
solvent DzO;
relax. delay 1.000 sec, pulse 45.0; acq. time 2.345 sec) shows a new peak at
about 4ppm which
was integrated against the ethoxy group protons at about 3.Sppm and is
consistent with the
molecule having 6 end group sulfates.
Example 2: Amination of Sorbitol EO"n Hexasulfate Of Example 1
Weigh into a 200m1 glass liner sorbitol EO"4 hexasulfate (61.3g of 90% active,
0.0095 mol) and
3-(dimethylamino)propylamine ("DMAPA" 18.5g, 0.181 mol). Heat the liner in a
rocking
autoclave at 152 kPa (150 prig) under nitrogen until the temperature reaches
165°C and hold at
165°C for 2 hours. Cool to room temperature (20 - 25°C). Take
the material up in 150 ml of
methylene chloride and centrifuge to separate the salts. Transfer the
supernatant to a SOOmI round
bottom flask and strip the supernatant on a rotary evaporator at SO°C
until most (less than 5 mL)
of the solvent is removed. Heat on a Kugelrohr apparatus at 120°C and
133 Pa (lmm Hg) for 30
minutes to remove excess amine to afford 47.8g of brown hard solid. Proton NMR
(500 MHz or
300 MHz; pulse sequence: s2pul, solvent D20; relax. delay 0.300 sec, pulse
45.0; acq. time 3.744
sec) indicated about 3 sulfates and about 2 DMAPA per molecule.
Examine 3: Quaternization of Amine Containing Sulfate Of Example 2
Dissolve an aminated Sorbitol EO,Ia in 100g of methylene chloride in a SOOmI
round
bottom flask equipped with a magnestic stirring bar and chill in an ice bath
until the temperature
reaches 10°C. Adjust the solution to a pH 12 with sodium methoxide (25%
solution in methanol).
Add to the solution methyl iodide (lS.Og, 0.106mo1). Stopper the flask and
stir the solution
overnight (about 14 hours). Strip the solution on a Kugelrohr apparatus at
50°C and 133 Pa (lmm
Hg) to afford 66g of tacky brown solid. Proton NMR (500 MHz or 300 MHz; pulse
sequence:
s2pul, solvent D20; relax. delay 1.000 sec, pulse 45.0; acq. time 2.345 sec)
indicated that all
nitrogens in the amine capping unit were fully quaternized.
Cleanin Compositions
The present invention further relates to a cleaning composition comprising the
modified
alkoxylated polyol compound of the present invention. The cleaning
compositions can be in any
conventional form, namely, in the form of a liquid, powder, granules,
agglomerate, paste, tablet,
pouches, bar, gel, types delivered in dual-compartment containers, spray or
foam detergents,
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12
premoistened wipes (i.e., the cleaning composition in combination with a
nonwoven material such
as that discussed in US 6,121,165, Mackey, et al.), dry wipes (i.e., the
cleaning composition in
combination with a nonwoven materials, such as that discussed in US 5,980,931,
Fowler, et al.)
activated with water by a consumer, and other homogeneous or multiphase
consumer cleaning
product forms.
In addition to cleaning compositions, the compounds of the present invention
may be also
suitable for use or incorporation into industrial cleaners (i.e. floor
cleaners). Often these cleaning
compositions will additionally comprise surfactants and other cleaning adjunct
ingredients,
discussed in more detail below. In one embodiment, the cleaning composition of
the present
invention is a liquid or solid laundry detergent composition.
In another embodiment, the cleaning composition of the present invention is a
hard surface
cleaning composition, preferably wherein the hard surface cleaning composition
impregnates a
nonwoven substrate. As used herein "impregnate" means that the hard surface
cleaning
composition is placed in contact with a nonwoven substrate such that at least
a portion of the
nonwoven substrate is penetrated by the hard surface cleaning composition,
preferably the hard
surface cleaning composition saturates the nonwoven substrate.
In another embodiment the cleaning composition is a liquid dish cleaning
composition, such
as liquid hand dishwashing compositions, solid automatic dishwashing cleaning
compositions,
liquid automatic dishwashing cleaning compositions, and tab/unit does forms of
automatic
dishwashing cleaning compositions.
The cleaning composition may also be utilized in car care compositions, for
cleaning various
surfaces such as hard wood, tile, ceramic, plastic, leather, metal, glass.
This cleaning composition
could be also designed to be used in a personal care composition such as
shampoo composition,
body wash, liquid or solid soap and other cleaning composition in which
surfactant comes into
contact with free hardness and in all compositions that require hardness
tolerant surfactant system,
such as oil drilling compositions.
Modified Alkoxylated Pol~ol Com ounds
The cleaning composition of the present invention may comprise from about
0.005% to
about 30%, and such as from about 0.01% to about 10%, further such as from
about 0.05% to
about 5% by weight of the cleaning composition of a modified polyol compound
as described
herein.
Surfactants - The cleaning composition of the present invention may comprise a
surfactant or
surfactant system comprising surfactants selected from nonionic, anionic,
cationic, ampholytic,
zwitterionic, semi-polar nonionic surfactants; and other adjuncts such as
alkyl alcohols, or
mixtures thereof. The cleaning composition of the present invention further
comprises from about
from about 0.01% to about 90%, and such as from about 0.01% to about 80%,
further such as
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13
from about 0.05% to about 50%, more further such as from about 0.05% to about
40% by weight
of the cleaning composition of a surfactant system having one or more
surfactants.
Anionic Surfactants
Nonlimiting examples of anionic surfactants useful herein include: C8-C,8
alkyl benzene
sulfonates (LAS); Clo-Czo primary, branched-chain and random alkyl sulfates
(AS); C,o-Cis
secondary (2,3) alkyl sulfates; C,o-C,$ alkyl alkoxy sulfates (AExS) wherein x
is from 1-30; C,o-
Ci$ alkyl alkoxy carboxylates comprising 1-5 ethoxy units; mid-chain branched
alkyl sulfates as
discussed in US 6,020,303 and US 6,060,443; mid-chain branched alkyl alkoxy
sulfates as
discussed in US 6,008,181 and US 6,020,303; modified alkylbenzene sulfonate
(MLAS) as
discussed in WO 99/05243, WO 99/05242 and WO 99/05244; methyl ester sulfonate
(MES); and
alpha-olefin sulfonate (AOS).
Nonionic Surfactants
Non-limiting examples of nonionic surfactants include: ClZ-C,8 alkyl
ethoxylates, such as,
NEODOL~ nonionic surfactants from Shell; C6-C,2 alkyl phenol alkoxylates
wherein the
alkoxylate units are a mixture of ethyleneoxy and propyleneoxy units; C,2-C18
alcohol and C6-C,Z
alkyl phenol condensates with ethylene oxide/propylene oxide block alkyl
polyamine ethoxylates
such as PLURONIC~ from BASF; C,4-Czz mid-chain branched alcohols, BA, as
discussed in US
6,150,322; C,4-C22 mid-chain branched alkyl alkoxylates, BAEx, wherein x 1-30,
as discussed in
US 6,153,577, US 6,020,303 and US 6,093,856; Alkylpolysaccharides as discussed
in U.S.
4,565,647 Llenado, issued January 26, 1986; specifically alkylpolyglycosides
as discussed in US
4,483,780 and LTS 4,483,779; Polyhydroxy fatty acid amides (GS-base) as
discussed in US
5,332,528; and ether capped poly(oxyalkylated) alcohol surfactants as
discussed in US 6,482,994
and WO 01/42408.
Cationic Surfactants
Non-limiting examples of anionic surfactants include: the quaternary ammonium
surfactants, which can have up to 26 carbon atoms include: alkoxylate
quaternary ammonium
(AQA) surfactants as discussed in US 6,136,769; dimethyl hydroxyethyl
quaternary ammonium
as discussed in 6,004,922; polyamine cationic surfactants as discussed in WO
98/35002, WO
98/35003, WO 98/35004, WO 98/35005, and WO 98135006; cationic ester
surfactants as
discussed in US Patents Nos 4,228,042, 4,239,660 4,260,529 and US 6,022,844;
and amino
surfactants as discussed in US 6,221,825 and WO 00/47708, specifically amido
propyldimethyl
amine (APA).
Zwitterionic Surfactants
Non-limiting examples of zwitterionic surfactants include: derivatives of
secondary and
tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or
derivatives of
quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds.
See U.S.
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14
Patent No. 3,929,678 to Laughlin et al., issued December 30, 1975 at column
19, line 38 through
column 22, line 48, for examples of zwitterionic surfactants; betaine,
including alkyl dimethyl
betaine and cocodimethyl amidopropyl betaine, C$ to Cl8 ( Clz to C~$) amine
oxides and sulfo and
hydroxy betaines, such as N-alkyl-N,N-dimethylammino-1-propane sulfonate where
the alkyl
group can be Cg to C,B, Clo to C,4.
Ampholytic Surfactants
Non-limiting examples of ampholytic surfactants include: aliphatic derivatives
of
secondary or tertiary amines, or aliphatic derivatives of heterocyclic
secondary and tertiary
amines in which the aliphatic radical can be straight- or branched-chain. One
of the aliphatic
substituents contains at least about 8 carbon atoms, typically from about 8 to
about 18 carbon
atoms, and at least one contains an anionic water-solubilizing group, e.g.
carboxy, sulfonate,
sulfate. See U.S. Patent No. 3,929,678 to Laughlin et al., issued December 30,
1975 at column 19,
lines 18-35, for examples of arnpholytic surfactants.
Semi-Polar Nonionic Surfactants
Non-limiting examples of semi-polar nonionic surfactants include: water-
soluble amine oxides
containing one alkyl moiety of from about 10 to about 18 carbon atoms and 2
moieties selected
from the group consisting of alkyl groups and hydroxyalkyl groups containing
from about 1 to
about 3 carbon atoms; water-soluble phosphine oxides containing one alkyl
moiety of from about
to about 18 carbon atoms and 2 moieties selected from the group consisting of
alkyl groups
and hydroxyalkyl groups containing from about 1 to about 3 carbon atoms; and
water-soluble
sulfoxides containing one alkyl moiety of from about 10 to about 18 carbon
atoms and a moiety
selected from the group consisting of alkyl and hydroxyalkyl moieties of from
about 1 to about 3
carbon atoms. See WO 01/32816, US 4,681,704, and US 4,133,779.
Gemini Surfactants
Gemini Surfactants are compounds having at least two hydrophobic groups and at
least
two hydrophilic groups per molecule have been introduced. These have become
known as
"gemini surfactants" in the literature, e.g., Chemtech, March 1993, pp 30-33,
and J. American
Chemical Soc., 115, 10083-10090 (1993) and the references cited therein.
Cleaning Adtunct Materials
In general, a cleaning adjunct is any material required to transform a
cleaning
composition containing only the minimum essential ingredients into a cleaning
composition
useful for laundry, hard surface, personal care, consumer, commercial and/or
industrial cleaning
purposes. In certain embodiments, cleaning adjuncts are easily recognizable to
those of skill in
the art as being absolutely characteristic of cleaning products, especially of
cleaning products
intended for direct use by a consumer in a domestic environment.
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The precise nature of these additional components, and levels of incorporation
thereof,
will depend on the physical form of the cleaning composition and the nature of
the cleaning
operation for which it is to be used.
The cleaning adjunct ingredients if used with bleach should have good
stability therewith.
Certain embodiments of cleaning compositions herein should be boron-free
and/or phosphate-free
as required by legislation. Levels of cleaning adjuncts are from about
0.00001% to about 99.9%,
and such as from about 0.0001% to about 50% by weight of the cleaning
compositions. Use
levels of the overall cleaning compositions can vary widely depending on the
intended
application, ranging for example from a few ppm in solution to so-called
"direct application" of
the neat cleaning composition to the surface to be cleaned.
Quite typically, cleaning compositions herein such as laundry detergents,
laundry
detergent additives, hard surface cleaners, synthetic and soap-based laundry
bars, fabric softeners
and fabric treatment liquids, solids and treatment articles of all kinds will
require several adjuncts,
though certain simply formulated products, such as bleach additives, may
require only, for
example, an oxygen bleaching agent and a surfactant as described herein. A
comprehensive list of
suitable laundry or cleaning adjunct materials can be found in WO 99/05242.
Common cleaning adjuncts include builders, enzymes, polymers not discussed
above,
bleaches, bleach activators, catalytic materials and the like excluding any
materials already
defined hereinabove. Other cleaning adjuncts herein can include suds boosters,
suds suppressors
(antifoams) and the like, diverse active ingredients or specialized materials
such as dispersant
polymers (e.g., from BASF Corp. or Rohm & Haas) other than those described
above, color
speckles, silvercare, anti-tarnish and/or anti-corrosion agents, dyes,
fillers, germicides, alkalinity
sources, hydrotropes, anti-oxidants, enzyme stabilizing agents, pro-perfumes,
perfumes,
solubilizing agents, carriers, processing aids, pigments, and, for liquid
formulations, solvents,
chelating agents, dye transfer inhibiting agents, dispersants, brighteners,
suds suppressors, dyes,
structure elasticizing agents, fabric softeners, anti-abrasion agents,
hydrotropes, processing aids,
and other fabric care agents, surface and skin care agents. Suitable examples
of such other
cleaning adjuncts and levels of use are found in U.S. Patent Nos. 5,576,282,
6,306,812 B1 and
6,326,348 B 1.
Method of Use
The present invention includes a method for cleaning a surface or fabric. Such
method
includes the steps of contacting a modified alkoxylated polyol compound of the
present invention
or an embodiment of the cleaning composition comprising the modified
alkoxylated polyol
compound of the present invention, in neat form or diluted in a wash liquor,
with at least a portion
of a surface or fabric then optionally rinsing such surface or fabric.
Preferably the surface or
fabric is subjected to a washing step prior to the aforementioned optional
rinsing step. For
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purposes of the present invention, washing includes but is not limited to,
scrubbing, and
mechanical agitation.
As will be appreciated by one skilled in the art, the cleaning compositions of
the present
invention are ideally suited for use in home care (hard surface cleaning
compositions), personal
care and/or laundry applications. Accordingly, the present invention includes
a method for
cleaning a surface and/or laundering a fabric. The method comprises the steps
of contacting a
surface and/or fabric to be cleaned/laundered with the modified alkoxylated
polyol compound or a
cleaning composition comprising the modified alkoxylated polyol compound. The
surface may
comprise most any hard surface being found in a typical home such as hard
wood, tile, ceramic,
plastic, leather, metal, glass, or may consist of a cleaning surfaces in a
personal care product such
as hair and skin. The surface may also include dishes, glasses, and other
cooking surfaces. The
fabric may comprise most any fabric capable of being laundered in normal
consumer use
conditions.
The cleaning composition solution pH is chosen to be the most complimentary to
a
surface to be cleaned spanning broad range of pH, from about 5 to about 11.
For personal care
such as skin and hair cleaning pH of such composition preferably has a pH from
about 5 to about
8 for laundry cleaning compositions pH of from about 8 to about 10. The
compositions are
preferably employed at concentrations of from about 200 ppm to about 10,000
ppm in solution.
The water temperatures preferably range from about 5 °C to about
100 °C.
For use in laundry cleaning compositions, the compositions are preferably
employed at
concentrations from about 200 ppm to about 10000 ppm in solution (or wash
liquor). The water
temperatures preferably range from about 5°C to about 60°C. The
water to fabric ratio is
preferably from about 1:1 to about 20:1.
The present invention included a method for cleaning a surface or fabric. Such
method
includes the step of contacting a nonwoven substrate impregnated with an
embodiment of the
cleaning composition of the present invention, and contacting the nonwoven
substrate with at
least a portion of a surface and/or fabric. The method may further comprise a
washing step. For
purposes of the present invention, washing includes but is not limited to,
scrubbing, and
mechanical agitation. The method may further comprise a rinsing step.
As used herein "nonwoven substrate" can comprise any conventionally fashioned
nonwoven sheet or web having suitable basis weight, caliper (thickness),
absorbency and strength
characteristics. Examples of suitable commercially available nonwoven
substrates include those
marketed under the tradename SONTAR.A~ by DuPont and POLYWEB RO by James River
Corp.
As will be appreciated by one skilled in the art, the cleaning compositions of
the present
invention are ideally suited for use in hard surface applications.
Accordingly, the present
invention includes a method for cleaning hard surfaces. The method comprises
the steps of
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contacting a hard surface to be cleaned with a hard surface solution or
nonwoven substrate
impregnated with an embodiment of the cleaning composition of the present
invention. The
method of use comprises the steps of contacting the cleaning composition with
at least a portion
of the nonwoven substrate, then contacting a hard surface by the hand of a
user or by the use of an
implement to which the nonwoven substrate attaches.
As will be appreciated by one skilled in the art, the cleaning compositions of
the present
invention are ideally suited for use in liquid dish cleaning compositions. The
method for using a
liquid dish composition of the present invention comprises the steps of
contacting soiled dishes
with an effective amount, typically from about 0.5 m1. to about 20 ml. (per 25
dishes being
treated) of the liquid dish cleaning composition of the present invention
diluted in water. Suitable
examples may be seen below in Table 5.
Generally, from about 0.01 ml, to about 150 ml. of a liquid dish cleaning
composition of the
invention is combined with from about 2000 ml. to about 20000 ml of water in a
sink having a
volumetric capacity in the range of from about 1000 ml. to about 20000 ml..
The soiled dishes
are immersed in the sink containing the diluted compositions then obtained,
where contacting the
soiled surface of the dish with a cloth, sponge, or similar article cleans
them. The cloth, sponge,
or similar article may be immersed in the detergent composition and water
mixture prior to being
contacted with the dish surface, and is typically contacted with the dish
surface for a period of
time ranged from about 1 to about 10 seconds. The contacting of cloth, sponge,
or similar article
to the dish surface is preferably accompanied by a concurrent scrubbing of the
dish surface.
Another method of use will comprise immersing the soiled dishes into a water
bath
without any liquid dish cleaning composition. A device for absorbing liquid
dish cleaning
composition, such as a sponge, is placed directly into a separate quantity of
undiluted liquid dish
cleaning composition for a period of time typically ranging from about 1 to
about 5 seconds. The
absorbing device, and consequently the undiluted liquid dish cleaning
composition, is then
contacted individually to the surface of each of the soiled dishes to remove
said soiling. The
absorbing device is typically contacted with each dish surface for a period of
time range from
about 1 to about 10 seconds. The contacting of the absorbing device to the
dish surface is
preferably accompanied by concurrent scrubbing.
As will be appreciated by one skilled in the art, the cleaning compositions of
the present
invention are also suited for use in personal cleaning care applications.
Accordingly, the present
invention includes a method for cleaning skin or hair. The method comprises
the steps of
contacting a skin / hair to be cleaned with a cleaning solution or nonwoven
substrate impregnated
with an embodiment of the cleaning compositions discussed herein. The method
of use of the
nonwoven substrate when contacting skin and hair may be by the hand of a user
or by the use of
an implement to which the nonwoven substrate attaches.
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Other Compositions
Other compositions that comprise the compound of the present invention may be
used in
personal care compositions, such as contact lens solution, used as adhesives,
in the vulcanization
of rubbers, used in polyurethane manufacturing processes, used in dye
compositions, used as an
ink composition, used as a dispersant in agricultural applications, such as a
dispersant in an
antifungal composition, among other compositions.
Formulations
Table 1-Li u id Laundr Cleaninompositions
C
A
Ingredients [% by wt.]
Linear 10-15
alkylbenzenesulfonate
Clz_~s alcohol 1-5
ethoxy
(1.l-2.5) sulfate
Ciz-i3 alcohol 1-5
ethoxylate ~~_9~
cocodimethyl 0.1-1
amine
oxide
fatty acid 1-5
citric acid 1-5
Polymer c' 0.5-3
hydroxylated 5-20
castor
oil (structurant)
Vi~ater, perfumes,ad 100
dyes, and other
trace
components
polymer according to any one of Examples 1-3 and formula I-IVof the present
application.
Table 2 Low Sudsin ularundtCleaning Compositions
Gran La
B C D
Wt% Wt% wt%
C1,_,z Linear alkyl
benzene 7 5.1 10.2
sul honate
C~z-is tallow alk 1 1 1
1 sulfate
C,4-is alk 1 ethox 3.2 3.2 3.2
late EO=7
APA~ 0.940,681.36
silicate builderz 4.05- -
Zeolite A3 16.65- -
Carbonate4 14.04- -
Citric Acid Anh drous2.932.932.93
acrylic acid/maleic 0.97
acid 0.970.97
co of mers
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19
Pol mer6 1-5 1-5 1-5
Percarbonate 12.816.1813.25
tetraace leth lenediamine3.645.923.95
1-hydroxyethyidene-
l , l - 0.180.180.18
di hos honic acid
S,S-(ethylenediamine
N,N'- 0.2 0.2 0.2
disuccinic acid)
M S04 0.420.420.42
ENZYMES' % article 1.261.261.26
MINORS (perfume, Ad Ad Ad
dyes, suds 100 100 100
stabilizers
I Ca-so amido propyl dimethyl amine
Z Amorphous Sodium Silicate (Si02:Na20; 2.0 ratio) 3 Hydrated Sodium
Aluminosilicate of formula
NaI2(A102Si02)12~ 27H20 having a primary particle size in the range from 0.1
to 10 micrometers
4Anhydrous sodium carbonate with a particle size between 200~m and 900~m
4:1 acrylic acid/maleic acid, average molecular weigh about 70,000 or 6:4
acrylic acid/maleic acid,
average molecular weight about 10,000)
~ polymer accordin to any one of Examples I-3 or formula I-IV of the present
invention
~ one or more enzymes such as:
Protease - Proteolytic enzyme, having 3.3% by weight of active enzyme, sold by
NOVO Industries A/S
under the tradename SAVINASE~; Proteolytic enzyme, having 4% by weight of
active enzyme, as
described in WO 95/10591, sold by Genencor Int. Inc.
Alcalase- Proteolytic enzyme, having 5.3% by weight of active enzyme, sold by
NOVO Industries A/S
Cellulase - Cellulytic enzyme, having 0.23% by weight of active enzyme, sold
by NOVO Industries A/S
under the tradename CAREZYME~.
Amylase - Amylolytic enzyme, having 1.6% by weight of active enzyme, sold by
NOVO Industries A/S
under the fradename TERMAMYL 120T~; Amylolytic enzyme, as disclosed in PCT/
US9703635.
Lipase - Lipolytic enzyme, having 2.0% by weight of active enzyme, sold by
NOVO Industries A/S under
the tradename LIPOLASE~; Lipolytic enzyme, having 2.0% by weight of active
enzyme, sold by NOVO
Industries A/S under the tradename LIPOLASE ULTRA.
Endolase - Endoglucanase enzyme, having 1.5% by weight of active enzyme, sold
by NOVO Industries
A/S.
TableranularLaundCleaning Compositions
3
G
E F G H
wt% wt% wt% wt%
Clo_,z
linear 13.4- 15.2-
alkyl 15.0 17.2 2.7 2.7
sul honate
Csz-sa
alkyl
ethoxylate.8 .8 .0 .0
EO=9
Builders 18 -- -- --
Se uestrantz-- 17 -- --
enz me 0.35 0.40 -- --
Pol mer3 1-2 1-2 1 1
Carboxy
Methyl
Cellulose.2 .2 .5 -
suds
su ressor40.01 0.01 -- --
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Pol ac 0.80 0.8 0.5
later
buffer 4.0 2.0 6.0 6.0
Carbonate 11.0 15.0 8.0 8.0
bri htener0.08 0.08 0.03 0.03
Sodium 65.0 65.0
Sulfate 34.83 32.339 9
Water and Ad Ad Ad Ad
minors 100 100 100 100
I sodium tripolyphosphate
Zeolite A: Hydrated Sodium Aluminosilicate of formula Nal2(A102Si02)12~ 2~H20
having a primary
particle size in the range from 0.1 to 10 micrometers
3. An modified alkoxylated polyol compound according to Examples 1-3 and
formula I-IV of the present
application
4. suds suppressor
5 Mw=4500
Table 4 Hard Surfa ce Cleanin
Com ositions
Moor cleaningfloor cleaning
ipe solutionolution
I J
Wt% wt%
C, I alcohol ethoxylate
EO=5 0.03 0.03
Sodium C8 Sulfonate0.01 0.01
Propylene Glycol
n-Butyl 2 2
Ether
2-Phenox ethanol 0.05 0.05
Ethanol 3
Pol mere 0.015 0.015
2-Dimethylamino-2-methyl-
2- ro anol DMAMP 0.01 0.01
erfume 0.01-0.060.01-0.06
Suds su ressor2 0.003 0.003
2-methyl-4-isothaizolin-3 --
one 0.015
+ chloro derivative
Water and minors Ad 100 Ad 100
~
polymer according to Examples 1-3 and formula I-IVof the present application.
Z such as Dow Corning AF Emulsion or polydimethyl siloxane
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21
Table 5 Liauid Dishwashing Cleaning Composition
K L M
C,z-,3 alcohol ethox late sulfate 26 23 24
EO=0.6
Amine Oxide 5.8 5.8 5.8
C8_,z alcohol ethox late EO=8 2 2 2
Ethanol 2 2 2
Sodium cumene sulfonate 1.80 1.80 1.80
NaCI 1,4 1.4 1.4
M Clz 0.2 0.2 0.2
Suds Booster' 0.2 0.2 0.2
Pol merz 0.8 0.8 0.8
Water & other trace components (i.e.,dye,ad ad ad
perfume, 100 100 100
diamine, etc.
' as described in US 6,645,925 Bl
2 a polymer according to Examples 1- 3 and formula I-IVof the present
invention.
All documents cited in the Detailed Description of the Invention are, are, in
relevant part,
incorporated herein by reference; the citation of any document is not to be
construed as an
admission that it is prior art with respect to the present invention.
While particular embodiments of the present invention have been illustrated
and
described, it would be obvious to those skilled in the art that various other
changes and
modifications can be made without departing from the spirit and scope of the
invention. It is
therefore intended to cover in the appended claims all such changes and
modifications that are
within the scope of this invention.
