Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
PF0000071030/Wei CA 02851208 2014-04-04
1
Thickener comprising at least one cationic polymer
As originally filed
Description
The present invention relates to a thickener comprising at least one cationic
polymer
and at least one activator, wherein the ratio of activator to cationic polymer
is > 10:100
[% by weight/% by weight]. The cationic polymer is preparable by
polymerization of at
least one water-soluble, ethylenically unsaturated monomer and at least one
ethylenically unsaturated associative monomer. The present invention further
relates to
a process for preparing the inventive thickener and to surfactant-containing
formulations comprising at least one thickener. The invention further provides
for the
use of the surfactant-containing formulations, for example as a softener or as
a liquid
washing composition, and to the use of the thickener, for example as a
viscosity
modifier.
WO 03/102043 relates to aqueous formulations comprising a cationic polymer
prepared from (i) a water-soluble, ethylenically unsaturated monomer or a
monomer
mixture comprising at least one cationic monomer, (ii) at least one
crosslinker in an
amount of more than 50 ppm based on component (i), and (iii) at least one
chain
transfer agent. The aqueous formulations can be used as thickeners in domestic
formulations.
WO 2009/019225 relates to an aqueous dispersion of an alkali-soluble
copolymer, said
dispersion being suitable as an associative thickener. The copolymer comprises
polymerized units of a) at least one ethylenically unsaturated carboxylic
acid, b) at least
one nonionic ethylenically unsaturated surfactant monomer, c) at least one C1-
C2-alkyl
methacrylate and d) at least one C2-C4-alkyl acrylate, where the alkyl chain
length
averaged over the number of alkyl groups of the alkyl acrylate is 2.1 to 4Ø
The
associative thickeners can be prepared by emulsion polymerization. The
associative
thickeners are suitable for use in washing and cleaning compositions.
Liquid Dispersion Polymer (LDP) compositions are disclosed in WO 2005/097834.
These LDP compositions comprise a hydrophilic, water-soluble or swellable
polymer
with a neutralization content of about 25 to about 100%, a nonaqueous carrier
phase
and an oil-in-water surfactant. The hydrophilic, water-soluble or swellable
polymer is
preferably obtained by polymerization, for example of acrylic acid or
methacrylic acid.
The LDP dispersions are suitable for production of microparticulate
thickeners, as
EK10-1030PC
PF0000071030/Wei CA 02851208 2014-04-04
2
used, for example, in aqueous or organic compositions, especially in personal
care or
pharmaceutical formulations.
WO 2010/078959 relates to cationic polymer thickeners consisting of a
crosslinked
water-swellable cationic polymer comprising at least one cationic monomer and
optionally nonionic or anionic monomers, said polymer comprising less than 25%
of
water-soluble polymer chains, based on the total weight of the polymer. The
polymer
also comprises a crosslinker in a concentration of 500 to 5000 ppm relative to
the
polymer. The cationic polymer is prepared by inverse emulsion polymerization.
WO 2010/079100 discloses fabric softener compositions comprising polymers
according to WO 2010/078959.
US 2008/0312343 relates to inverse latex compositions and to the use thereof
as a
thickener and/or emulsifier, for example for production of cosmetic or
pharmaceutical
formulations. The inverse latex compositions comprise at least 50 to 80% by
weight of
at least one linear, branched or crosslinked organic polymer (P), at least 5
to 10% by
weight of a water-in-oil-type emulsifier system, 5 to 45% by weight of at
least one oil
and up to 5% water. The polymer P comprises uncharged monomers and optionally
cationic or anionic monomers. The inverse latex composition may optionally
comprise
up to 5% by weight of an oil-in-water-type emulsifier system. The inverse
latex
compositions can be prepared by inverse emulsion polymerization.
EP-A 172 025 relates to a dispersion in a continuous liquid phase of a
polymer, which
is formed by polymerization of an ethylenically unsaturated monomer comprising
a
hydrophobic group of at least eight carbon atoms and an ethylenically
unsaturated
monomer copolymerizable therewith. The dispersion is stable and essentially
anhydrous, and comprises at least 40% by weight of polymer. In the
polymerization,
the copolymerizable, ethylenically unsaturated monomers used may, for example,
be
anionic monomers. The polymerization can be performed as an inverse emulsion
polymerization.
EP-A 172 724 relates to polymers which are prepared by copolymerization of a)
an
ethylenically unsaturated monomer comprising a hydrophobic group with at least
eight
carbon atoms and b) water-soluble ethylenically unsaturated monomers. All
monomers
are soluble as a mixture in water, and the polymer is prepared by inverse
emulsion
polymerization. The polymer particles have a dry size of <4 pm. The monomer
components b) used may be anionic monomers such as acrylic acid in the form of
the
free acid or as a water-soluble salt, and nonionic monomers such as
acrylamide.
EK10-1030PC as originally filed"
PF0000071030/Wei CA 02851208 2014-04-04
3
EP-A 172 723 relates to a process for flocculating a suspension using a water-
soluble,
essentially linear polymer with a "single point intrinsic viscosity" of > 3.
The polymer is a
copolymer of two or more ethylenically unsaturated monomers comprising at
least
0.5% by weight of a monomer, comprising hydrophobic groups. The polymer may
also
be a cationic polymer.
The problem underlying the present invention consists in the provision of
novel
thickeners. The object is achieved by the inventive thickeners comprising
i) at least one cationic polymer preparable by polymerization of
a) at least one water-soluble ethylenically unsaturated monomer comprising at
least one cationic monomer, optionally at least one anionic monomer and/or
optionally at least one nonionic monomer,
b) at least one ethylenically unsaturated associative monomer,
c) optionally at least one crosslinker,
d) optionally at least one chain transfer agent,
ii) at least one activator,
where the ratio of activator to cationic polymer is > 10 to 100 FA by weight /
% by
weight].
The inventive thickeners are notable in that they possess advantageous
properties with
regard to deposition, shear dilution, stabilization and/or viscosity
(thickening).
Deposition is understood to mean the deposition of the active ingredients of,
for
example, a fabric softener on a fiber during a washing operation. Applied to
the present
invention, this means that, for example, an inventive thickener comprising at
least one
cationic polymer (active ingredient) is present in a fabric softener and the
fabric
softener is used during or after the washing operation. The inventive
thickeners
promote this deposition of the active ingredient during or after the washing
operation to
a considerable degree. Particularly good properties with regard to deposition
can be
achieved when cationic polymers based on at least one associative monomer, a
cationic monomer and a nonionic monomer such as acrylamide are used.
In the assessment of shear dilution, it is important that the thickener or the
corresponding fabric softener, in its ground state, is viscous and thick,
while it is thin in
the course of stirring. The improved shear dilution has a positive effect on
the lifetime
and properties of pumps in the production of the fabric softener, promotes
convenient
dosage for the consumer and promotes the residue-free use of the fabric
softener,
EK10-1030PC as originally filed"
PF0000071030/VVei CA 02851208 2014-04-04
4
especially in the washing machines which possess an automatic dosage device.
The
inventive thickeners increase the stability of the thickener per se and that
of the
corresponding formulation. The settling or creaming of particles is
effectively
prevented, irrespective of whether they are within the order of magnitude of
nanometers, micrometers or millimeters. This is contributed to by the
advantageous
yield point of the inventive thickeners. They also have the advantage that any
redispersion required and thickening are achieved very rapidly.
Inventive thickeners in which a mixture of at least two activators is present,
at least one
activator having a high HLB value and at least one activator having a low HLB
value,
are associated with an additional advantage. The combination of such an
activator
mixture with cationic polymers comprising at least one ethylenically
unsaturated
associative monomer unit leads to spontaneous phase inversion (within seconds)
in the
case of dilution of a thickener with water, without any requirement for
additional energy
input, for example in the form of stirring.
Another advantage in the case of the inventive thickeners is that the ratio of
associative
monomer to the overall polymer is relatively low. In the case of use of the
thickener in
surfactant-containing formulations, the effect of the associative monomers is
optimal
even in amounts of approx. 0.5% by weight (based on the polymer).
When the inventive thickeners are prepared by inverse emulsion polymerization
in
which the temperature is kept constant at at least 40 C, good uniformity of
distribution
of the associative monomer units in the cationic polymer can be observed.
Especially in
the case of small use amounts of, for example, 0.1 to 1% by weight of
associative
monomers, this is advantageous with regard to the overall abovementioned
rheological
properties such as thickening, shear dilution, stabilization, and washing and
rinse
effects.
Embodiments of the present invention in which the cationic polymers present in
the
thickener are prepared using little or no crosslinker are likewise associated
with
advantages. Due to the relatively high (water-)soluble components of the
polymer,
resoiling during a washing operation is reduced. Consequently, the article to
be
washed, even after repeated washing operations, has clean fibers which have
been
free effectively of soil particles, such that no graying is detected. Only
very slight, if any,
adhesion or redistribution of soil particles/polymers on the washed articles
is observed.
A further advantage of the inventive thickeners, in which the cationic polymer
is
obtained by inverse emulsion polymerization at constant temperature, is
manifested in
surfactant-containing formulations, especially in surfactant-containing acidic
EK10-1030PC ,,as originally filed"
PF0000071030/Wei CA 02851208 2014-04-04
formulations, because a high thickening performance and/or marked shear
dilution are
achieved in these formulations even at low thickener concentrations (< 1% by
weight).
In the context of the present invention, the definitions such as C1-C30-alkyl,
as defined,
5 for example, below for the R4 radical in formula (II), mean that this
substituent (radical)
is an alkyl radical having a carbon atom number from 1 to 30. The alkyl
radical may be
either linear or branched and optionally cyclic. Alkyl radicals which have
both a cyclic
and a linear component are likewise covered by this definition. The same also
applies
to other alkyl radicals, for example a C1-C4-alkyl radical or a C16-C22-alkyl
radical. The
alkyl radicals may optionally also be mono- or polysubstituted by functional
groups
such as amino, quaternary ammonium, hydroxyl, halogen, aryl or heteroaryl.
Unless
stated otherwise, the alkyl radicals preferably do not have any functional
groups as
substituents. Examples of alkyl radicals are methyl, ethyl, n-propyl,
isopropyl, n-butyl,
isobutyl, 2-ethylhexyl, tert-butyl (tert-Bu/t-Bu), cyclohexyl, octyl, stearyl
or behenyl.
The present invention is specified further hereinafter.
The inventive thickener comprises, as component i), at least one cationic
polymer. The
cationic polymer is preparable by polymerization of the following components
a) and b),
and optionally c) and d).
The component a) used is at least one water-soluble, ethylenically unsaturated
monomer comprising at least one cationic monomer, optionally at least one
anionic
monomer and/or optionally at least one nonionic monomer. Cationic monomers as
such, any anionic monomers present as such, and any nonionic monomers present
as
such are known to those skilled in the art.
The cationic monomer according to component a) is preferably selected from a
compound of the formula (II)
Rõ 0
16 I 4 1/
R¨C=C¨C¨X¨R R
H 3 5
R6 35
(II)
where
R1 is H or Ci ¨ 04 ¨ alkyl,
R2 is H or methyl,
R3 is C ¨ 04 ¨ alkylene,
EK10-1030PC as originally filed"
PF0000071030/Wei CA 02851208 2014-04-04
6
R4, R5 and R6 are each independently H or C1¨ C30 ¨ alkyl,
X is -0- or -NH- and
Y is Cl; Br; I; hydrogensulfate or methosulfate.
(TMAEC) or 2-trimethylammonioethyl methacrylate chloride (TMAEMC). TMAEC is
also referred to as quaternized dimethylaminoethyl acrylate (DMAEA, MeClq) and
TMAEMC as quaternized dimethylaminoethyl methacrylate (DMAEMA, MeClq).
monomer of the formula (II),
i) R1 and R2 are each H or
ii) R1 is H and R2 is CH3.
Any anionic monomer present in component a) is preferably selected from
acrylic acid,
methacrylic acid, itaconic acid, maleic acid or a salt thereof; the anionic
monomer is
especially sodium acrylate. When component a) comprises at least one anionic
monomer, it is present (based on component a)) preferably to an extent of 0.5
to 20%
Component a) may optionally comprise at least one nonionic monomer. Apart from
the
nitrogen-containing monomers described below, for example the compounds of the
formula (III), esters of the above-described anionic monomers are also
suitable as
selected from N-vinylpyrrolidone, N-vinylimidazole or a compound of the
formula (III)
R 0
1 8 11 /139
7
R10 (III)
where
R7 is H or C1 ¨ C4 ¨ alkyl,
R8 is H or methyl, and
PF0000071030/Wei CA 02851208 2014-04-04
7
The nonionic monomer is more preferably acrylamide, methacrylamide or
dialkylaminoacrylamide. When component a) comprises at least one nonionic
monomer, it is preferably present to an extent of 0.5 to 70% by weight.
In a preferred embodiment of the present invention, component a) in the
cationic
polymer comprises 30 to 99.5% by weight of at least one cationic monomer and
0.5 to
70% by weight of at least one nonionic monomer. In a further preferred
embodiment of
the present invention, component a) comprises 100% by weight of at least one
cationic
monomer.
Component b) used in the polymerization to prepare the cationic polymer is at
least
one ethylenically unsaturated associative monomer. Associative monomers as
such
are known to those skilled in the art. Suitable associative monomers are
described, for
example, in WO 2009/019225. Associative monomers are also described as
surfactant
monomers.
Preferably, the ethylenically unsaturated associative monomer according to
component
b) in the cationic polymer is selected from a compound of the formula (I)
R-0-(CH2-CHR'-0)n-CO-CR"=CH2 (I)
where
R is C6 ¨ Ca) ¨ alkyl, preferably C8 ¨ C30 ¨ alkyl, especially C16 ¨ C22¨
alkyl,
R' is H or C1 ¨ C4 ¨ alkyl, preferably H,
R" is H or methyl,
n is an integer from 0 to 100, preferably 3 to 50, especially 25.
More preferably, component b) used is a compound of the formula (I) in which
R is C16-C22-alkyl,
R is H,
R" is H or methyl and
n is 25.
Compounds of the formula (I) are commercially available in solution, for
example under
the Plex 6954 0 name from Evonik Reihm GmbH. These are methacrylates of fatty
alcohol ethoxylates. A suitable fatty alcohol ethoxylate is, for example, the
commercially available Lutensol AT 25 (BASF SE, Ludwigshafen, Germany).
EK10-1030PC ,,as originally filed"
PF000007103ONVei CA 02851208 2014-04-04
8
The R radical in the compounds of the formula (I) may also be present as a
mixture of
radicals with different chain lengths, such as 016 and C18. One example
thereof is C16-
C15-fatty alcohol-(ethylene glycol)25-ether methacrylate, where both 016 and
018 fatty
alcohol radicals (in non-negligible amounts) are present as a mixture. In
contrast, for
example, in the compounds (of the formula (I)) beheny1-25 methacrylate and
cety1-25
methacrylate, the particular R radical is not present as a mixture but as a
C22 or C16
chain. Other chain lengths occur only in the form of impurities. The number
"25" in
these compounds of the formula (I) represents the size of the variables n.
In the preparation of the cationic polymer by polymerization, at least one
crosslinker
may optionally be present as component c). Suitable crosslinkers are known to
those
skilled in the art. Preferably, the crosslinker according to component c) in
the cationic
polymer is selected from divinylbenzene; tetraallylammonium chloride; allyl
acrylates;
allyl methacrylates; diacrylates and dimethacrylates of glycols or
polyglycols;
butadiene; 1,7-octadiene, allylacrylamides or allylmethacrylamides;
bisacrylamido
aceticacid; N,N'-methylenebisacrylamide, or polyol polyallyl ethers such as
polyallyl
sucrose or pentaerythritol Many! ether. Additionally suitable as a preferred
crosslinker is
dialkyldimethylammonium chloride.
It is additionally possible, in the preparation of the cationic polymer by
polymerization,
to use at least one chain transfer agent as component d). Suitable chain
transfer
agents are known to those skilled in the art. Preferred chain transfer agents
according
to component d) are selected from mercaptan, lactic acid, formic acid,
isopropanol or
hypophosphites.
Suitable polymerization processes for preparation of the cationic polymer or
the
inventive thickener comprising at least one cationic polymer, and any
additives or
assistants used in the polymerization or the thickener preparation process,
are defined
in detail in the text below.
Preferably, the inventive thickener comprises at least one cationic polymer
preparable
by polymerization of
a) 20 to 99.99% by weight, preferably 95 to 99.95% by weight (based on
the
polymer), of at least one water-soluble ethylenically unsaturated monomer
comprising at least one cationic monomer, and optionally at least one anionic
monomer and/or at least one nonionic monomer,
EK10-1030PC as originally filed"
PF0000071030/Wei CA 02851208 2014-04-04
9
b) 0.01 to 80% by weight, preferably 0.05 to 5% by weight, more
preferably 0.1 to
1% by weight (based on the polymer), of at least one ethylenically unsaturated
associative monomer,
c) 0 to 0.3% by weight, preferably 0.01 to 0.1% by weight (based on the
polymer),
of optionally at least one crosslinker,
d) 0 to 0.3% by weight, preferably 0.01 to 0.1% by weight (based on the
polymer),
of optionally at least one chain transfer agent.
In a further embodiment of the present invention, the water-soluble components
of the
cationic polymer are more than 25% by weight (based on the total weight of the
cationic polymer), especially when little or no crosslinker is used in
addition to the
associative monomer. Preferably more than 40% by weight, especially 70 to 100%
by
weight, of the cationic polymer is soluble in water. The solubility of the
cationic polymer
is determined by methods known to those skilled in the art, by admixing the
cationic
polymer present in the inventive thickener with a defined amount of water
(see, for
example, EP-A 343 840 or preferably the determination method of the
sedimentation
coefficient in the unit of svedberg (sved) according to P. Schuck, 'Size-
distribution
analysis of macromolecules by sedimentation velocity ultracentrifugation and
Lamm
equation modeling', Biophysical Journal 78,(3) (2000), 1606-1619).
Preferably, in this embodiment, the proportion of crosslinker (component c))
used in the
polymerization of the cationic polymer is < 1% by weight (based on the total
amount of
components a) to d)). More preferably, no crosslinker is used in the
polymerization of
the cationic polymer.
The inventive thickener further comprises, as components ii), at least one
activator.
Activators as such are known in principle to those skilled in the art.
Suitable activators are preferably surfactants, for example anionic, nonionic,
cationic
and/or amphoteric surfactants, which are disclosed, for example, in WO
2009/019225.
Preference is given to using anionic and/or nonionic surfactants.
The nonionic surfactants used are preferably fatty alcohol alkoxylates. Fatty
alcohol
alkoxylates are also referred to as polyalkylene glycol ethers. Preferred
fatty alcohol
alkoxylates are alkoxylated, advantageously ethoxylated, especially primary
alcohols
having preferably 8 to 18 carbon atoms and an average of 1 to 12 mol of
ethylene
oxide (EO) per mole of alcohol, in which the alcohol radical may be linear or
branched,
preferably 2-methyl-branched, or may comprise linear and methyl-branched
radicals in
EK10-1030PC as originally filed"
PF0000071030/Wei CA 02851208 2014-04-04
a mixture, as typically present in oxoalcohol radicals. Especially preferred
are,
however, alcohol ethoxylates with linear radicals formed from alcohols of
native or
technical origin with 12 to 18 carton atoms, for example formed from coconut
alcohol,
palm alcohol, tallow fat alcohol or ley' alcohol - or mixtures as derivable,
for example,
5 from castor oil - and an average of 2 to 8 EO per mole of alcohol. The
preferred
ethoxylated alcohols include, for example, C12-C14-alcohols with 3 E0, 4 EO or
7 E0,
C9-C11-alcohol with 7 E0, C13-C19-alcohols with 3 E0, 5 E0, 7 EO or 8 E0, C12-
C18-
alcohols with 3 E0, 5 EO or 7 EO and mixtures thereof such as mixtures of C12-
C14-
alcohol with 3 EO and C12-C18-alcohol with 7 E0. The degrees of ethoxylation
reported
10 are statistical averages which may be an integer or a fraction for a
specific product.
Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range
ethoxylates, NRE). In addition to these nonionic surfactants, it is also
possible to use
fatty alcohols with more than 12 EQ. Examples thereof are tallow fat alcohol
with 14
EO, 25 EO, 30 EO or 40 EQ. It is also possible to use nonionic surfactants
comprising
E0 and PO groups together in a molecule. In this context, it is possible to
use block
copolymers with EO-P0 block units or P0-E0 block units, but also EO-PO-E0
copolymers or P0-E0-P0 copolymers. It will be appreciated that it is also
possible to
use mixed-alkoxylation nonionic surfactants in which EO and PO units are not
present
in blocks but in random distribution. Such products are obtainable by
simultaneous
action of ethylene oxide and propylene oxide on fatty alcohols.
In addition, further nonionic surfactants used may also be alkyl glycosides or
alkyl
polyglycosides. Alkyl glycosides or alkyl polyglycosides are generally
understood by
the person skilled in the art to mean compounds composed of at least one alkyl
fragment and at least one sugar or polysugar fragment. The alkyl fragments
preferably
derive from fatty alcohols having a carbon atom number of 12 to 22, and the
sugar
fractions preferably from glucose, sucrose or sorbitan.
For example, it is possible to use alkyl glycosides of the general formula (1)
R10(G), (1)
in which R1 is a primary straight-chain or methyl-branched, especially 2-
methyl-
branched, aliphatic radical having 8 to 22 and preferably 12 to 18 carbon
atoms, and G
is a glycoside unit having 5 or 6 carbon atoms, preferably glucose. The degree
of
oligomerization x, which specifies the distribution of monoglycosides and
oligoglycosides, is any number between 1 and 10; x is preferably 1.2 to 1.4.
A further class of nonionic surfactants used with preference, which are used
either as
the sole nonionic surfactant or in combination with other nonionic
surfactants, is that of
EK10-1030PC ,,as originally filed"
PF0000071030/Wei CA 02851208 2014-04-04
11
alkoxylated, preferably ethoxylated or ethoxylated and propoxylated, fatty
acid alkyl
esters, preferably having 1 to 4 carbon atoms in the alkyl chain, especially
fatty acid
methyl esters, as described, for example, in Japanese patent application
JP 58/217598, or which are preferably prepared by the process described in
international patent application WO-A-90/13533.
Nonionic surfactants of the amine oxide type may also be suitable, for example
N-
cocoalkyl-N,N-dimethylamine oxide and N-tallowalkyl-N,N-dihydroxyethylamine
oxide,
and of the fatty acid alkanolamide type. The amount of these nonionic
surfactants is
preferably not more than that of the ethoxylated fatty alcohols, especially
not more than
half thereof.
Further suitable surfactants are polyhydroxy fatty acid amides of the formula
(2),
0
R2 N (2)
I 3
in which R2C(=0) is an aliphatic acyl radical having 6 to 22 carbon atoms, R3
is
hydrogen, an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms, and [Z]
is a
linear or branched polyhydroxyalkyl radical having 3 to 10 carbon atoms and 3
to 10
hydroxyl groups. The polyhydroxy fatty acid amides are known substances, which
can
be obtained typically by reductive amination of a reducing sugar with ammonia,
an
alkylamine or an alkanolamine, and subsequent acylation with a fatty acid, a
fatty acid
alkyl ester or a fatty acid chloride.
The group of the polyhydroxy fatty acid amides also includes compounds of the
formula
(3)
5
R-0¨R6
R'4N \ 1
[Z] (3)
0
in which R4 is a linear or branched alkyl or alkenyl radical having 7 to 12
carbon atoms,
R6 is a linear, branched or cyclic alkylene radical having 2 to 8 carbon atoms
or an
arylene radical having 6 to 8 carbon atoms, and R6 is a linear, branched or
cyclic alkyl
radical or an aryl radical, or an oxyalkyl radical having 1 to 8 carbon atoms,
preference
EK10-1030PC ,,as originally filed"
PF000007103ONVei CA 02851208 2014-04-04
12
being given to C1-C4-alkyl or phenyl radicals, and [Z]l is a linear
polyhydroxyalkyl
radical whose alkyl chain is substituted by at least two hydroxyl groups, or
alkoxylated,
preferably ethoxylated or propoxylated, derivatives of this radical. [Z]l is
preferably
obtained by reductive amination of a sugar, for example glucose, fructose,
maltose,
lactose, galactose, mannose or xylose. The N-alkoxy- or N-aryloxy-substituted
compounds can then be converted to the desired polyhydroxy fatty acid amides,
for
example, according to WO-A-95/07331 by reaction with fatty acid methyl esters
in the
presence of an alkoxide as a catalyst.
The anionic surfactants used are, for example, those of the sulfonate and
sulfate type.
Useful surfactants of the sulfonate type include alkylbenzenesulfonates,
preferably C9-
C13-alkylbenzenesulfonates, olefinsulfonates, i.e. mixtures of alkene- and
hydroxyalkanesulfonates, and disulfonates as obtained, for example, from C12-
C18-
monoolefins with terminal or internal double bonds by sulfonation with gaseous
sulfur
trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation
products. Also
suitable are alkanesulfonates, preferably secondary alkanesulfonates, which
are
obtained, for example, from C12-C18-alkanes by sulfochlorination or
sulfoxidation with
subsequent hydrolysis or neutralization. Equally suitable are also the esters
of a-
sulfone fatty acids (ester sulfonates), for example the a-sulfonated methyl
esters of
hydrogenated coconut fatty acids, palm kernel fatty acids or tallow fatty
acids.
Further suitable anionic surfactants are sulfonated fatty acid glyceryl
esters. Fatty acid
glyceryl esters are understood to mean the mono-, di- and triesters, and
mixtures
thereof as obtained in the preparation by esterification of a monoglycerol
with 1 to
3 mol of fatty acid or in the transesterification of triglycerides with 0.3 to
2 mol of
glycerol. Preferred sulfonated fatty acid glyceryl esters are the sulfonation
products of
saturated fatty acids having 6 to 22 carbon atoms, for example of caproic
acid, caprylic
acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or
behenic acid.
Further suitable anionic surfactants are fatty alcohol sulfates, for example
alk(en)yl
sulfates. Preferred alk(en)yl sulfates are the alkali metal and especially the
sodium
salts of the sulfuric monoesters of the C12-C18 fatty alcohols, for example of
coconut
fatty alcohol, tallow fatty alcohol, lauryl alcohol, myristyl alcohol, cetyl
alcohol or stearyl
alcohol, or of the C10-C20 oxo alcohols and those monoesters of secondary
alcohols of
these chain lengths. Additionally preferred are alk(en)yl sulfates of the
chain length
mentioned which comprise a synthetic straight-chain alkyl radical produced on
a
petrochemical basis, which have analogous degradation behavior to the
equivalent
compounds based on fatty-chemical raw materials. In the interests of washing
technology, preference is given to the C12-C16-alkyl sulfates and C12-C15-
alkyl sulfates,
EK 10-1030PC as originally filed"
PF0000071030fVVei CA 02851208 2014-04-04
13
and also C14-C15-alkyl sulfates. Suitable anionic surfactants are also 2,3-
alkyl sulfates,
which are prepared, for example, according to US patents 3,234,258 or
5,075,041 and
can be obtained as commercial products from Shell Oil Company under the DAN
name.
Also suitable are the sulfuric monoesters of the straight-chain or branched C7-
C21-
alcohols ethoxylated with 1 to 6 mol of ethylene oxide, such as 2-methyl-
branched C9-
C11 alcohols with an average of 3.5 mol of ethylene oxide (EO) or C12-C18-
fatty alcohols
with 1 to 4 EO.
Further suitable anionic surfactants are also the salts of alkylsulfosuccinic
acid, which
are also referred to as sulfosuccinates or as sulfosuccinic esters, and which
are
monoesters and/or diesters of sulfosuccinic acid with alcohols, preferably
fatty alcohols
and especially ethoxylated fatty alcohols. Preferred sulfosuccinates comprise
C8-C18-
fatty alcohol radicals or mixtures thereof. Especially preferred
sulfosuccinates comprise
a fatty alcohol radical which derives from ethoxylated fatty alcohols.
Particular
preference is given in turn to sulfosuccinates whose fatty alcohol radicals
derive from
ethoxylated fatty alcohols with narrow homolog distribution. It is likewise
also possible
to use alk(en)ylsuccinic acid with preferably 8 to 18 carbon atoms in the
alk(en)yl chain
or salts thereof.
Further suitable anionic surfactants are alkyl carboxylates, for example the
sodium
salts of saturated or unsaturated fatty acids, where the alkyl radical of the
alkyl
carboxylate is preferably linear.
In the context of the present invention, the activator is preferably selected
from fatty
alcohol alkoxylates, alkyl glycosides, alkyl carboxylates,
alkylbenzenesulfonates,
secondary alkanesulfonates and fatty alcohol sulfates, more preferably
selected from
fatty alcohol alkoxylates. One example of a preferred fatty alcohol alkoxylate
is C6-
C17(secondary)-poly(3-6)ethoxylate.
It is additionally preferred in the context of the present invention to use an
activator
which has a (relatively) high HLB (hydrophilic-lipophilic balance) value. The
activator
preferably has an HLB value of 7 to 18, more preferably of 8 to 15 and
especially
preferably of 9 to 13.
Activators with a high HLB value are preferably i) fatty alcohol alkoxylates
formed from
secondary alcohols or mixtures of alcohols having 12 to 18 carbon atoms and
ethylene
oxide or propylene oxide, and ii) alkyl glycosides formed from sucrose and C8
to C22
fatty alcohols. Examples of such activators are the commercially available
Synperonic
EK10-1030PC as originally filed"
PF0000071030/Wei CA 02851208 2014-04-04
14
87K from Croda GmbH, Herrenpfad-Sud 33, 41334 Nettetal, Germany; Croduret 40
or
other ethoxylated hydrogenated castor oils (ricinus oils) such as Etocas 40 or
Crodesta
F110, all from Croda.
In a further embodiment of the present invention, it is preferred to use a
mixture of at
least two activators, at least one activator having a high HLB value and at
least one
activator a low HLB value. The activator with a high HLB value preferably has
a HLB
value of > 12 to 20, and the activator with a low HLB value preferably has an
HLB
value of 1 to 12. In this embodiment, the activator with a high HLB value and
the
activator with a low HLB value may be present in any desired ratios known to
those
skilled in the art. Preferably, in the mixture, 20 to 50% by weight of
activator with high
HLB value and 50 to 80% by weight of activator with low HLB value are used.
Additionally preferably, this ratio of activator with high HLB value to
activator with low
HLB value is adjusted such that the overall HLB value is 7 to 18, more
preferably 8 to
15 and especially preferably 9 to 13.
In these mixtures of at least two activators, the activators with a high HLB
value used
are preferably alkyl glycosides or polyalkyl glycosides or polyalkyl
oligoethylene oxide
glycoside based on sucrose or sorbitan and C8 to C22 fatty alcohols such as
polyethylene glycol sorbitan monostearate or polyoxyethylene sorbitan
monostearate.
Examples of such activators are the commercially available Crillet 1, Crillet
3 or
Crodesta F160, all obtainable from Croda. The activators used with a low HLB
value
are preferably alkyl glycosides formed from sucrose or sorbitan and C8 to C22
fatty
alcohols or fatty acids, such as sorbitan laurate or sorbitan stearate.
Examples of such
activators are the commercially available Crill 1, Crill 3 or Crodesta F10
from Croda.
According to the invention, the ratio of activator to the cationic polymer is
> 10 : 100 Pk
by weight/% by weight], preferably 10.5 to 50: 100 [io by weight/% by weight],
more
preferably 11.5 to 20: 100 [% by weight/% by weight].
In the inventive thickeners, further components may be present in addition to
the
cationic polymer and the activator. Suitable further components are defined in
detail in
the text which follows in the context of the preparation of the thickener and
of the
cationic polymer. Suitable further components may, for example, be oils and
solvents.
In the inventive thickener, the cationic polymer may be present dispersed in
the oil
phase, preferably as an inverse dispersion, water-in-oil dispersion, or as a
dispersed
anhydrous cationic polymer in oil.
EK10-1030PC as originally filed"
PF0000071030/Wei CA 02851208 2014-04-04
The present invention further provides a process for preparing the inventive
thickeners.
Thickener preparation processes as such and processes for preparing a polymer
are
known to those skilled in the art. The polymer is preferably obtained by an
emulsion
polymerization, especially by an inverse emulsion polymerization. The polymer
is
5 preferably first prepared and, after the polymerization, preferably by
inverse emulsion
polymerization, the activator is added to obtain the thickener.
The cationic polymer is preparable in various ways, preferably by emulsion
polymerization, especially by inverse emulsion polymerization. Inverse
emulsion
10 polymerization is understood by the person skilled in the art generally
to mean
polymerization processes according to the following definition; the
hydrophilic
monomers are dispersed in a hydrophobic oil phase. The polymerization is
effected
directly in this hydrophilic monomer particle by addition of initiator.
15 In addition, it is preferred that, after the inverse emulsion
polymerization and before the
addition of activator, at least a portion of water and at least a portion of
the low-boiling
constituents of the oil phase are distilled off, especially by means of LDP
technology
(Liquid Dispersion Polymer Technology). LDP technology as such is known to
those
skilled in the art; it is described, for example, in WO 2005/097834.
The information which follows, unless stated otherwise, applies to all kinds
of emulsion
polymerization, for example to emulsion polymerization in water, which then
constitutes
the continuous phase, and especially also to inverse emulsion polymerization
in which
the hydrophobic oil phase constitutes the continuous phase. A suitable
polymerization
initiator is used for the polymerization. Redox initiators and/or thermally
activatable
free-radical polymerization initiators are preferred.
Suitable thermally activatable free-radical initiators or the oxidative
component of the
redox initiator pair are in particular those of the peroxy and azo type. These
include
hydrogen peroxide, peracetic acid, t-butyl hydroperoxide, di-t-butyl peroxide,
dibenzoyl
peroxide, benzoyl hydroperoxide, 2,4-dichlorobenzoyl peroxide, 2,5-dimethy1-
2,5-
bis(hydroperoxy)hexane, perbenzoic acid, t-butyl peroxypivalate, t-butyl
peracetate,
dilauroyl peroxide, dicapryloyl peroxide, distearoyl peroxide, dibenzoyl
peroxide,
diisopropyl peroxydicarbonate, didecyl peroxydicarbonate, dieicosyl
peroxydicarbonate,
di-t-butyl perbenzoate, azobisisobutyronitrile, 2,2'-azobis-2,4-
dimethylvaleronitrile,
ammonium persulfate, potassium persulfate, sodium persulfate and sodium
perphosphate.
The persulfates (peroxodisulfates), especially sodium persulfate, are most
preferred.
EK10-1030PC ,,as originally filed"
= PF0000071030/Wei CA 02851208 2014-04-04
16
In the performance of the emulsion polymerization, the initiator is used in a
sufficient
amount to initiate the polymerization reaction. The initiator is typically
used in an
amount of about 0.01 to 3% by weight, based on the total weight of the
monomers
used. The amount of initiator is preferably about 0.05 to 2% by weight and
especially
0.1 to 1% by weight, based on the total weight of the monomers used.
The emulsion polymerization is effected typically at 0 C to 100 C. It can be
performed
either as a batch process or in the form of a feed process. In the feed
method, at least
a portion of the polymerization initiator and optionally a portion of the
monomers are
initially charged and heated to polymerization temperature, and then the rest
of the
polymerization mixture is supplied, typically over several separate feeds, one
or more
of which comprise the monomers in pure or emulsified form, continuously or
stepwise
while maintaining the polymerization. Preference is given to supplying the
monomer in
the form of a monomer emulsion. In parallel to the monomer supply, further
polymerization initiator can be metered in.
In preferred embodiments, the entire amount of initiator is initially charged,
i.e. there is
no further metering of initiator parallel to the monomer feed.
In a preferred embodiment, the thermally activatable free-radical
polymerization initiator
is therefore initially charged completely and the monomer mixture, preferably
in the
form of a monomer emulsion, is fed in. Before the feeding of the monomer
mixture is
started, the initial charge is brought to the activation temperature of the
thermally
activatable free-radical polymerization initiator or a higher temperature. The
activation
temperature is considered to be the temperature at which at least half of the
initiator
has decomposed after one hour.
In another preferred preparation method, the cationic polymer is obtained by
polymerization of a monomer mixture in the presence of a redox initiator
system. A
redox initiator system comprises at least one oxidizing agent component and at
least
one reducing agent component, in which case heavy metal ions are preferably
additionally present as a catalyst in the reaction medium, for example salts
of cerium,
manganese or iron(II).
Suitable oxidizing agent components are, for example, peroxides and/or
hydroperoxides such as hydrogen peroxide, tert-butyl hydroperoxide, cumene
hydroperoxide, pinane hydroperoxide, diisopropylphenyl hydroperoxide,
dicyclohexyl
percarbonate, dibenzoyl peroxide, dilauroyl peroxide and diacetyl peroxide.
Hydrogen
peroxide and tert-butyl hydroperoxide are preferred.
EK10-1030PC as originally filed"
PF0000071030/Wei CA 02851208 2014-04-04
17
Suitable reducing agent components are alkali metal sulfites, alkali metal
dithionites,
alkali metal hyposulfites, sodium hydrogensulfite, Rongalit C (sodium
formaldehydesulfoxylate), mono- and dihydroxyacetone, sugars (e.g. glucose or
dextrose), ascorbic acid and salts thereof, acetone bisulfite adduct and/or an
alkali
metal salt of hydroxymethanesulfinic acid. Sodium hydrogensulfite or sodium
metabisulfite is preferred.
Suitable reducing agent components or catalysts are also iron(II) salts, for
example
iron(II) sulfate, tin(II) salts, for example tin(II) chloride, titanium(III)
salts such as
titanium(III) sulfate.
The amounts of oxidizing agent used are 0.001 to 5.0% by weight, preferably
from
0.005 to 1.0% by weight and more preferably from 0.01 to 0.5% by weight, based
on
the total weight of the monomers used. Reducing agents are used in amounts of
0.001
to 2.0% by weight, preferably of 0.005 to 1.0% by weight and more preferably
of 0.01 to
0.5% by weight, based on the total weight of the monomers used.
A particularly preferred redox initiator system is the sodium
peroxodisulfate/sodium
hydrogensulfite system, for example 0.001 to 5.0% by weight of sodium
peroxodisulfate
and 0.001 to 2.0% by weight of sodium hydrogensulfite, especially 0.005 to
1.0% by
weight of sodium peroxodisulfate and 0.005 to 1.0% by weight of sodium
hydrogensulfite, more preferably 0.01 to 0.5% by weight of sodium
peroxodisulfate and
0.01 to 0.5% by weight of sodium hydrogensulfite.
A further particularly preferred redox initiator system is the t-butyl
hydroperoxide/hydrogen peroxide/ascorbic acid system, for example 0.001 to
5.0% by
weight of t-butyl hydroperoxide, 0.001 to 5.0% by weight of hydrogen peroxide
and
0.001 to 2.0% by weight of ascorbic acid, especially 0.005 to 1.0% by weight
of t-butyl
hydroperoxide, 0.005 to 1.0% by weight of hydrogen peroxide and 0.005 to 1.0%
by
weight of ascorbic acid, more preferably 0.01 to 0.5% by weight of t-butyl
hydroperoxide, 0.01 to 0.5% by weight of hydrogen peroxide and 0.01 to 0.5% by
weight of ascorbic acid.
The cationic polymer is preferably prepared by inverse emulsion
polymerization, by first
separately preparing an aqueous phase of the water-soluble components and an
oil
phase. Thereafter, the two phases are mixed with one another to obtain a water-
in-oil
dispersion. The mixture is polymerized by adding a redox initiator system;
optionally,
another, thermal initiator can subsequently be added or, if already present,
thermally
activated.
EK10-1030PC ,,as originally filed"
= PF0000071030/Wei CA
02851208 2014-04-04
18
The aqueous phase comprises, for example, a chain transfer agent, a
crosslinker, a
cationic monomer and optionally an uncharged monomer, and also the associative
monomer, and optionally further components. Suitable further components are,
for
example, complexing agents for salts such
as pentasodium
diethylenetriaminepentaacetic acid, or compounds which can be used to adjust
the pH,
such as citric acid. In addition, an anionic monomer may optionally be present
in the
aqueous phase.
The oil phase preferably comprises an emulsifier, a stabilizer, a high-boiling
oil, a low-
boiling oil and/or optionally the associative monomer. In addition, the oil
phase may
optionally comprise a nonionic monomer.
Emulsifiers, stabilizers, low-boiling oils and high-boiling oils as such are
known to those
skilled in the art. These compounds can be used individually or in the form of
mixtures.
Typical emulsifiers are anionic emulsifiers, for example sodium laurylsulfate,
sodium
tridecyl ether sulfates, dioctylsulfosuccinate sodium salt and sodium salts of
alkylaryl
polyether sulfonates; and nonionic emulsifiers, for example alkylaryl
polyether alcohols
and ethylene oxide-propylene oxide copolymers. Sorbitan trioleate is likewise
suitable
as an emulsifier.
Preferred emulsifiers have the following general formula:
R-0-(CH2-CHR'-0),-X
in which R is C6-C30-alkyl,
R' is hydrogen or methyl,
X is hydrogen or SO3M,
M is hydrogen or one alkali metal, and
n is an integer from 2 to 100.
Suitable stabilizers are described, for example, in EP-A 172 025 or EP-A 172
724.
Preferred stabilizers are copolymers of stearyl methacrylate and methacrylic
acid.
Suitable high-boiling oils are, for example, 2-ethylhexyl stearate and
hydroheated
heavy naphtha, and suitable low-boiling oils are, for example, dearomatized
aliphatic
hydrocarbons or mineral oils of low viscosity.
EK10-1030PC ,,as originally filed"
PF0000071030/VVei CA 02851208 2014-04-04
19
In a preferred embodiment of the present invention, component b) (at least one
ethylenically unsaturated associative monomer) is added to the oil phase in
the inverse
emulsion polymerization.
In the inverse emulsion polymerization, the temperature can be kept constant
or else it
can rise. The rise in the temperature can be performed continuously or in
stages. For
example, the temperature can rise by 0.2 to 10 C per minute during the
polymerization,
preferably from 1 to 3 C per minute. The temperature rise is controlled by the
rate of
initiator addition. The starting temperature value may be 0 to 30 C,
preferably 10 to
20 C.
In another embodiment of the present invention, the temperature in the inverse
emulsion polymerization is kept constant (cold method); the temperature is 0
to 30 C,
preferably 10 to 20 C. In a further embodiment of the present invention, the
temperature is kept constant within a higher temperature range (hot method).
The
temperature in the polymerization is 40 to 150 C, preferably 70 to 120 C.
In a particularly preferred embodiment of the present invention, the
temperature is kept
constant during the inverse emulsion polymerization, the temperature being at
least
40 C, preferably 50 to 90 C.
If, in the context of the present invention, the temperature is kept constant
in a
polymerization, especially in an inverse emulsion polymerization, this means
that the
temperature is kept at a constant value from the start of the polymerization.
Variations
of +1- 5 C, preferably +1- 2 C and especially +1- 1 C during the
polymerization process
are considered to be a constant temperature (based on the desired constant
temperature value). The temperature is kept constant until the polymerization
has
ended, which is preferably the case after a conversion of more than 90% of the
monomers used, more preferably more than 95% by weight and especially
preferably
at full conversion (100% by weight). The temperature can be kept constant by
removing the heat of reaction which arises by cooling. The start of the
polymerization is
normally the addition of the polymerization initiator, preferably the addition
of a redox
initiator system. Normally, the system is first heated to the desired
temperature and a
constant temperature is awaited while stirring. Subsequently, the
polymerization
initiator is added, as a result of which the polymerization process commences.
In one
embodiment of the present invention, the temperature is kept constant at a
value above
the melting point of the associative monomer used.
EK10-1030PC ,,as originally filed"
' PF0000071030ANe1 CA 02851208 2014-04-04
The present invention further provides surfactant-containing acidic
formulations
comprising at least one inventive thickener according to the above
definitions. The pH
of the formulation is 1 to < 7.
5 The present invention further provides surfactant-containing alkaline
formulations
comprising at least one inventive thickener according to the above
definitions. The pH
of the formulation is 7 to 13.
The inventive surfactant-containing acidic or alkaline formulations may
comprise further
10 ingredients known to those skilled in the art. Suitable ingredients
comprise one or more
substances from the group of the builders, bleaches, bleach activators,
enzymes,
electrolytes, nonaqueous solvents, pH modifiers, fragrances, perfume carriers,
fluorescers, dyes, hydrotropes, foam inhibitors, silicone oils,
antiredeposition agents,
optical brighteners, graying inhibitors, antishrink agents, anticrease agents,
dye
15 transfer inhibitors, active antimicrobial ingredients, germicides,
fungicides, antioxidants,
corrosion inhibitors, antistats, ironing aids, hydrophobizing and impregnating
agents,
swelling and antislip agents, and UV absorbers.
In one embodiment of the present invention, the surfactant-containing
formulations,
20 especially surfactant-containing acidic formulations, comprise less than
1% by weight
of thickener (based on the overall formulation), the cationic polymer of the
thickener
being obtained by inverse emulsion polymerization at constant temperature.
Preferably,
the formulations comprise 0.1 to < 1% by weight of thickener.
The present invention further provides for the use of an inventive surfactant-
containing
acidic formulation in hair cosmetics, in hair styling, as a shampoo, as a
softener, as a
conditioner, as a skin cream, as a shower gel, as a fabric softener for
laundry, or as an
acidic detergent, preferably for toilets or baths.
The present invention further provides for the use of a surfactant-containing
alkaline
formulation as a liquid washing composition or as a machine or manual
dishwashing
detergent.
The present invention further provides for the use of the inventive thickener
as a
viscosity modifier, for optimization of shear dilution, as a thickening agent,
for
stabilization of suspended constituents having a size in the range from
nanometers to
millimeters and/or in surfactant-containing acidic or alkaline formulations.
In the description including the examples, the following abbreviations are
used:
EK10-1030PC ,,as originally filed"
PF0000071030/Wei CA 02851208 2014-04-04
21
Monomers
ACM acrylamide
AA acrylic acid
MAA methacrylic acid
NaAc sodium acrylate
TMAEC 2-trimethylammoniumethyl acrylate chloride
TMAEMC 2-trimethylammoniumethyl methacrylate
chloride
BEM beheny1-25 methacrylate
MBA methylene-bis-acrylamide (crosslinker)
TAAC tetraallyl-ammonium chloride (crosslinker)
NaHP sodium hypophosphite (chain transfer agent)
C16E025MAc C16-C15-fatty alcohol-(ethylene glycol)25 ether
methacrylate
Others
pphm parts per hundred parts of monomers (based
on components a) and b))
The invention is illustrated hereinafter by the examples.
Examples
Comparative example Cl
Synthesis of a thickener/polymer proceeding from cationic monomers without
associative monomer, but with crosslinker and chain transfer agent and rising
polymerization temperature.
An aqueous phase of water-soluble components is prepared by mixing the
following
components:
1.23 g (0.5 pphm) of citric acid 1-hydrate,
43.73 g (17.85 pphm) of water,
0.7 g (0.29 pphm) of pentasodium diethylenetriaminepentaacetic acid,
14.78 g (0.06 pphm) of methylenebisacrylamide (1% in water),
4.9 g (0.02 pphm) of tetraallylammonium chloride (1% in water),
8 g (0.16 pphm) of sodium hypophosphite (5% in water), and
326.66 g (100 pphm) of 2-trimethylammoniumethyl methacrylate chloride
(quaternized
dimethylaminoethyl methacrylate) (TMAEMC, 75% in water).
EK10-1030PC ,,as originally filed"
= PF000007103ONVe1 CA 02851208 2014-04-04
22
An oil phase is prepared by mixing the following components:
8 g (2.45 pphm) of sorbitan trioleate (75% in dearomatized aliphatic
hydrocarbon
[Exxsol D40]),
67.83 g (5.23 pphm) of a polymeric stabilizer: stearyl methacrylate-
methacrylic acid
copolymer (19% in dearomatized aliphatic hydrocarbon [Exxsol D40]),
151.29 g (61.75 pphm) of 2-ethylhexyl stearate (Crodamol OS) and
60.17 g (24.56 pphm) of dearomatized aliphatic hydrocarbon [Exxsol D40].
The two phases are mixed in a ratio of 58.2 parts of aqueous phase to 41.8
parts of oil
phase with high shear, and a water-in-oil emulsion is thus prepared. The water-
in-oil
emulsion which forms is introduced into a reactor equipped with nitrogen spray
line,
stirrer and thermometer. The emulsion is purged with nitrogen, which removes
the
oxygen, and is then cooled to 20 C.
The polymerization is achieved by adding a redox pair composed of
10 g (0.04 pphm) of sodium metabisulfite (1% in dearomatized aliphatic
hydrocarbon
[Exxsol D40]) and
10 g (0.04 pphm) of tert-butyl hydroperoxide (1% in dearomatized aliphatic
hydrocarbon [Exxsol D40]).
The redox pair is added stepwise such that there is a temperature increase of
2 C/min.
Once the isotherm has been attained, a free radical initiator (2,2'-azobis(2-
methylbutyronitrile), CAS: 13472-08-7) is added in two steps (the 2nd step
after
45 min) and the emulsion is kept at 85 C for 75 minutes.
By means of vacuum distillation, water and low-boiling constituents of the oil
phase
(Exxsol D40) are removed.
2-ethylhexyl stearate (Crodamol OS) is added to the vacuum-distilled product,
which
achieves a solids content of 53.5%. Thereafter, 7% (based on the total
proportion by
mass of this product) of a fatty alcohol alkoxylate [alcohol C6-C17(secondary)
poly(3-
6)ethoxylate: 97% secondary alcohol ethoxylate + 3% poly(ethylene oxide)],
known as
Tergitol TM 15-S-7 (CAS No. 84133-50-6), are added to produce a thickener
(dispersion)
with 50% polymer solids content. The ratio of activator to cationic polymer is
thus 14.0:
100 [% by weight / ')/0 by weight].
Comparative example C2
EK10-1030PC as originally filed"
= PF0000071030/Wei CA 02851208 2014-04-04
23
Synthesis of a thickener/polymer proceeding from cationic monomers without
associative monomer and chain transfer agent, but with crosslinker and rising
polymerization temperature.
The synthesis is performed as in Cl, but with the difference that no sodium
hypophosphite (5% in water) and no tetraallylammonium chloride (1% in water)
are
added, and the amount of water is increased by 12.9 g of water. The ratio of
activator
to cationic polymer is 14.0: 100 FA by weight / % by weight].
Comparative example C3
Synthesis of a thickener/polymer proceeding from cationic monomers without
associative monomer, chain transfer agent and crosslinker at constant
polymerization
temperature.
An aqueous phase of water-soluble components is prepared by mixing the
following
components:
1.88 g (0.5 pphm) of citric acid 1-hydrate,
109.85 g (29.32 pphm) of water,
1.07 g (0.29 pphm) of pentasodium diethylenetriaminepentaacetic acid,
500.00 g (100 pphm) of 2-trimethylammoniumethyl methacrylate chloride
(quaternized
dimethylaminoethyl methacrylate) (TMAEMC 75% in water).
An oil phase is prepared by mixing the following components:
12.24 g (2.45 pphm) of sorbitan trioleate (75% in dearomatized aliphatic
hydrocarbon
[Exxsol 040]),
103.83 g (5.22 pphm) of a polymeric stabilizer: stearyl methacrylate-
methacrylic acid
copolymer (19% in dearomatized aliphatic hydrocarbon [Exxsol D40]),
231.57 g (61.75 pphm) of 2-ethylhexyl stearate (Crodamol OS), and
92.10 g (24.56 pphm) of dearomatized aliphatic hydrocarbon [Exxsol 040].
The two phases are mixed in a ratio of 58.2 parts of aqueous phase to 41.8
parts of oil
phase with high shear to produce a water-in-oil emulsion. The water-in-oil
emulsion
which forms is introduced into a reactor equipped with nitrogen spray line,
stirrer and
thermometer. The emulsion is purged with nitrogen, which removes the oxygen.
The polymerization is achieved by adding a redox pair consisting of
13 g (0.05 pphm) of sodium metabisulfite (1% in demineralized water) and
13 g (0.05 pphm) of tert-butyl hydroperoxide (1% in demineralized water).
EK10-1030PC ,,as originally filed"
PF000007103ONVei CA 02851208 2014-04-04
24
The rate for the addition of the redox pair is 13 g in 2 hours, the
temperature being kept
constant at 50 C. Thereafter, a free radical initiator (2,2'-azobis(2-
methylbutyronitrile),
CAS: 13472-08-7) is added in two steps (the 2nd step after 45 min) and the
emulsion is
kept at 85 C for 75 minutes.
By means of vacuum distillation, water and low-boiling constituents of the oil
phase
(Exxsol D40) are removed.
2-ethylhexyl stearate (Crodamol OS) is added to the vacuum-distilled product
to
achieve a solids content of 53.5%.
Thereafter, 7% (based on the total proportion by mass of this product) of a
fatty alcohol
alkoxylate [alcohol C6-C17(secondary) poly(3-6)ethoxylate: 97% secondary
alcohol
ethoxylate + 3% poly(ethylene oxide)], known as TergitolTm 15-S-7 (CAS No.
84133-
50-6), is added to prepare a thickener (dispersion) with polymer solids
content 50%.
The ratio of activator to cationic polymer is thus 14.0: 100 Pk by weight 1%
by weight].
Comparative examples C4 ¨ C5
As Cl, but with changes according to Table 1:
Table 1
Exam- TMAE MBA TAAC NaHP Comment
pies MC
(pphm)
C4 50 0.00 0.0025 0.001 50 pphm of
acrylamide
C5 100 0.18 0.06 0.02
The ratio of activator to cationic polymer in comparative examples C4 and C5
is in each
25 case 14.0: 100 [(Y0 by weight / % by weight].
Example 1
Thickeners / polymers proceeding from cationic monomers with associative
monomer:
The examples which follow according to Table 2 are produced like comparative
example C3 with incorporation of the specified changes in the monomer
composition
and in the temperature regime. The associative monomer C16E025MAc is
introduced
EK10-1030PC as originally filed"
PF0000071030/Wei CA 02851208 2014-04-04
into the oil phase. The commercial product Plex 6954 0 is used, which
comprises 60%
by weight of associative monomer and, as solvents, water and MAA in a ratio of
approx. 1 : 1. The weight data in Table 2 are based on the amount of
associative
monomer without solvent. The ratio of activator to cationic polymer in all
examples
5 according to Table 1 is in each case 14.0 : 100 [c/0 by weight / % by
weight]; unless
stated otherwise, the particular thickeners (dispersion) have polymer solids
content
50%.
Table 2
Exam- C16E025 TMAEMC MBA TAAC NaHP Comment
pies MAc (pphm)
(pphm)
1.1 0.19 99.75
-
1.2 0.19 99.75 Temperature regime as Cl;
polymer solids content 30%;
amount of activator adjusted
correspondingly
1.3 0.19 99.75 Temperature regime as Cl, but
+1 C /min
1.4 0.19 99.75 0.16 Temperature regime as Cl
1.5 0.19 99.75 0.06 0.02 0.05
1.6 0.19 99.75 Temperature regime as C1
1.7 0.38 74.50 25 pphm of acrylamide
1.9 0.76 99.00
1.10 0.38 49.5 50 pphm of acrylamide
General test methods
Unless stated otherwise, the following general test methods are used in the
examples
which follow:
Determination of viscosity
With reference to the methods according to DIN 51550, DIN 53018, DIN 53019,
the
Brookfield model DV II viscometer is used, unless stated otherwise within the
following
tables, at the speed of 10 revolutions per minute with the specified spindle
no. 2 to
measure the viscosities reported in mPas.
Determination of shear dilution
EK10-1030PC õas originally filed"
PF0000071030/Wei CA 02851208 2014-04-04
26
Measurement is effected in an ASC (automatic sample changer) rotary rheometer
from
Antonpaar, with the CC27 cylinder geometry, a radius of the measurement body
of
13.33 mm and a radius of the measurement cup of 14.46 mm. The measurement
temperature is 23 C. The samples are measured at steady-state shear beginning
at
small shear, increasing (0.01 s-1 ¨ 1000 s-1) and decreasing again (1000 s-1¨
0.01 s-1).
Example 2
Thickeners/polymers proceeding from cationic monomers with associative
monomer,
and influence of the amount of activator on the thickening rate in aqueous
formulations:
Examples 2.1 to 2.5 listed in Table 3 are prepared in accordance with example
1.5
from Table 2, except that the amount of activator added after the distillation
is varied
according to the activator concentration (A %) in the thickener specified in
Table 3 (all
figures in % by weight based on the amount of cationic polymer in the
thickener). All
thickeners thus prepared (dispersion) have polymer solids content 50%. The
thickeners
are subsequently added to the water while stirring. These resulting aqueous
formulations comprise 1% by weight of thickener to 99% by weight of water,
i.e. 0.5%
by weight of polymer to 99.5% by weight of water. C means comparative example.
Table 3
Thickening rate (Brookfield visc. mPes)
of the aqueous formulations
Exam- A % 1 min. 2 min. 3 min. 5 min. 10 min. 20 40 1H
pies min. min.
2.1 2.0 20 20 24 28 36 248 4800 7370
(C)
2.2 6.0 20 24 28 128 3640 8300 9630 10600
(C)
2.3 14.0 72 740 2600 6200 9100 11120 12220 12440
2.4 20.0 9100 10000 11060 11880 12540 12540 12780 12780
2.5 34.0 13280 13200 13140 13060 12920 12900 12800 12800
Aqueous formulations based on thickeners with 6% activator (ex. 2.2) have only
attained a viscosity in the lower three-digit mPas range after 5 minutes. In
contrast, the
EK10-1030PC as originally filed"
PF000007103ONVei CA 02851208 2014-04-04
27
corresponding value for example 2.3 (14.0% activator) is already in the middle
four-
digit mPas range after 5 minutes.
Example 3
Use of the thickeners/polymers in standard formulations of fabric softeners
W1: Preparation of a di(hydrogenated tallow)dimethylammonium chloride
(DHTDMAC)
fabric softener (active content 4%)
To 1890g of deionized preheated water are slowly added, while stirring, 111 g
of
DHTDMAC (Arguad 2HT-75) melted at 50 C. The dispersion is stirred and heated
to
50 C while stirring constantly for 15 minutes. The mixture is cooled to 30 C
while
stirring. The pH is adjusted to 4.0 by adding citric acid solution. The fabric
softener is
homogenized by stirring.
LV Brookfield Viscosity (22 C, 30 rpm) = 90 mPa-s.
W3: Preparation of a methyltris(hydroxyethvI)ammonium ditallow fatty acid
ester
methosulfate, partly hydrogenated, fabric softener (active content 5.5%)
The fabric softener has a pH of 2.7 and comprises 5.5% by weight of
methyltris(hydroxyethyl)ammonium ditallow fatty acid ester methosulfate
(partly
hydrogenated) and 94.5% by weight of demineralized water.
Addition of the thickener to fabric softener formulations W1 to W3:
The thickeners according to example 1 (Table 2) and comparative examples are
added
gradually at room temperature to the particular fabric softener formulation
and stirred
until the formulation has homogenized.
The Brookfield viscosity is measured one day after the preparation. The
results are
compiled in Table 4.
Table 4: Thickener performance and shear dilution in fabric softeners
Rheology of fabric softeners comprising thickeners/polymers proceeding from
cationic
monomers:
EK10-1030PC ,,as originally filed"
= PF0000071030/Wei CA 02851208 2014-04-04
28
Exam- Form- Thick- Thick- Vis- Vis- Vis- Vis-
pie ulation ener ener cosity at cosity at cosity at
cosity at
No. No. concen- 0.1 s-1 10 100 s'l 1000
s-1
tration (mPa*s) (mPa*s) (mPa*s) (mPa*s)
(yo)
3.1 W3 V1 0.5 27992 833 221 63
(C)
3.2 W3 1.5 0.5 65986 1599 377 67
3.3 W3 V1 1.0 47051 1441 352 106
(C)
3.4 W3 V3 1.0 11062 901 213 56
(C)
3.5 W3 1.7 1.0 58440 2579 470 104
In addition to the high thickening performance, the relative percentage shear
dilution in
the inventive thickeners is also much greater than in the comparative examples
without
associative monomer (like 3.1, 3.3 and 3.4).
Example 4
Use of the thickeners/polymers in standard formulations of acidic detergents
R1: Preparation of an acidic detergent of the following composition:
pH = 5.3;
12 g of C13-C15 oxo alcohol ethoxylate with 8 EO
4 g of C13-C15 oxo alcohol ethoxylate with 5 EO
2.5 g of ethylhexanol ethoxylate
81.5 g of demineralized
water
R2: Preparation of an acidic detergent of the following composition:
pH = 1.8;
10.3 g of C13-C15 oxo alcohol ethoxylate with 8 EO
3.4 g of C13-C15 oxo alcohol ethoxylate with 5 EO
2.2 g of ethylhexanol alkoxylate
8.6 g of citric acid
75.5 g of demineralized water
EK10-1030PC as originally filed"
PF0000071030fVVel CA 02851208 2014-04-04
29
The particular thickeners are added to these standard formulations as
described above
in example 3. The Brookfield viscosity is measured one day after the
preparation. The
results are compiled in Table 5.
Table 5: Thickener performance in acidic detergents
Rheology of acidic detergents comprising thickeners/polymers proceeding from
cationic
monomers:
Example Formulation Thickener Thickener Viscosity Viscosity
Viscosity
No. No. concentration at 0.1 s at 10
s at 100 s-
(%) (mPa*s) (mPa*s) (mPa*s)
4.1 R1 V1 1 16408 1850 618
(C)
4.2 R1 1.5 1 140080 6100 1425
4.3 R1 V3 1 4620 810 232
(C)
4.4 R1 1.7 1 13124 1163 301
4.5 R2 V1 1 7550 962 350
(C)
4.6 R2 V3 1 927 405 140
(C)
4.7 R2 1.5 1 20918 1775 593,
In addition to the high thickening performance, the relative percentage shear
dilution in
the inventive thickeners is also much greater than in the comparative examples
without
associative monomer (like 4.1).
Example 5
Use of the thickeners/polymers in aqueous formulations
The aqueous formulations are prepared as described above in example 2. The
Brookfield viscosity is measured one day after the preparation. The results
are
compiled in Table 6.
Table 6
Rheology of thickeners/polymers proceeding from cationic monomers in water
EK10-1030PC as originally filed"
,. PF0000071030/Wei CA 02851208 2014-04-04
Example Form- Thick- Thickener Brook- Brook- Brook- Brook-
No. ulation ener No. concen- field
field field field
tration spindle spindle spindle
3 spindle 3
(%) 3 3 (50 rpm) (100
rpm)
(1 rpm) (10 rpm) /mPas
/mPas
/mPas /mPas
5.1 Water V2 1 120 20 36
42
(C)
5.2 Water 1.2 1 480 300 182
145
Example 6
In Tables 7 and 8 below, the storage stability of the inventive thickeners
(according to
5 example 1) and corresponding fabric softener formulations
(according to example 3) is
examined. It is found that the inventive thickeners are much more stable.
Table 7:
Storage stability of thickeners/polymers proceeding from cationic monomers:
Example Thickener Imm- Precipitate Precipitate
Precipitate
No. ediate after 4 days after 3 weeks after
precip- at 40 C at 40 C
10 weeks
itate at 40 C
,
6.1 V1 none distinct, distinct,
distinct,
(C) redispersible
redispersible redispersible
6.2 1.1 none none none none
6.3 1.2 none none none none
6.4 1.3 none none none none
. .
6.5 1.4 none none none none
. _
6.6 1.5 none none none none
Table 8
Storage stability of fabric softeners W1 comprising thickeners/polymers
proceeding
from cationic monomers:
Exam- Cationic Imm- Precipitate Precipitate Precipitate
ple LDP ediate after 4 days after 3
weeks after
dispersion precip- at 40 C at 40 C 10 weeks
EK10-1030PC ,,as originally filed"
PF0000071030/Wei CA 02851208 2014-04-04
31
itate at 40 C
6.7 V1 none distinct, distinct, distinct,
(C) redispersible redispersible
redispersible
6.8 1.1 none none none none
6.9 1.2 none none none none
6.10 1.3 none none none none
6.11 1.4 none none none none
6.12 1.5 none none none none
Example 7
Thickeners/polymers proceeding from cationic monomers with associative
monomer,
and influence of the amount of activator on the thickening rate in fabric
softener
formulations:
Examples 2.1 to 2.5 in aqueous formulation described in Table 3 are performed
analogously according to example 3 in fabric softener formulations with fabric
softeners
(W3) according to Table 9 as examples 7.1-7.5: again, the activator
concentration (A
%) in the thickener is varied, and the amount of activator added after the
distillation is
varied in accordance with the activator concentration (A %) in the thickener
specified in
Table 9 (all figures in % by weight are based on the amount of cationic
polymer in the
thickener). All thickeners thus prepared (dispersion) have polymer solids
content 50%.
These thickeners are added to the fabric softener W3 while stirring. The
thickened
fabric softener formulations obtained comprise 1% by weight of thickener to
99% by
weight of fabric softener W3, i.e. 0.5% by weight of polymer to 99.5% by
weight of
fabric softener W3.
EK10-1030PC ,,as originally filed"
PF0000071030/Wei CA 02851208 2014-04-04
32
Table 9
Thickening rate (Brookfield visc. mPa*s at 10 rpm)
Example A% 1 2 3 5 10 20 40 1H 3H
min. min. min. min. min. min. min.
7.1 3.0 152 244 368 644 1316 2376 3616 4930 9180
(C)
7.2 6.0 248 492 784 1400 - 2468 3336 4520 5020 7560
(C)
7.3 14.0 1900 2900 3680 4650 5200 5420 5600 5750 6280
7.4 20.0 2700 3572 3996 4600 4690 4650 4880 4820 5400
7.5 34.0 5600 5560 5480 5340 5200 4810 4810 4810 5000
Fabric softeners based on thickeners with an activator content of more than
10% (ex.
7.3-7.5) have obtained about 75% of the final viscosity within 5 minutes.
Below this
limit, this value is attainable only after 40 minutes. The higher the
activator
concentration established, the more rapidly the final viscosity in the
formulation is
obtained.
Example 8
Influence of the amount of crosslinker on the solubility of the polymers
present in the
thickener (proceeding from cationic monomers):
The measurement of the soluble polymer components given in Table 10 is
effected
according to the method of P. Schuck ('Size-distribution analysis of
macromolecules by
sedimentation velocity ultracentrifugation and Lamm equation modeling',
Biophysical
Journal 78,(3) (2000), 1606-1619.).
Table 10: Determination of the solubility of the TMAEMC copolymers present in
the
thickener by means of an analytical ultracentrifuge (AUC)
EK10-1030PC as originally filed"
= PF0000071030/Wei CA
02851208 2014-04-04
33
Soluble TMAEMC copolymer in thickener (dispersion)
Examples Polymer (% based on overall polymer)
8.1
V1 24
(C)
8.2
V5 <1
(C)
8.3 1.6 100
8.4 1.9 100
8.5
(C) V4 22
8.6 1.10 83
The TMAEMC copolymers which have been prepared with 800 pphm or more of
crosslinker comprise less than 24% soluble components. The TMAEMC copolymers
which have been prepared without crosslinker and in some cases with less than
1 pphm of associative monomers comprise more than 99% soluble components.
Acrylamide as a comonomer in TMAEMC copolymers reduces the solubility of the
copolymer.
EK10-1030PC as originally filed"
