Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
1
CA 02760734 2011-11-01
1
HYDROPHOBICALLY ASSOCIATING COPOLYMERS
The present invention relates to water-soluble, hydrophobically associating
copolymers
which comprise new types of hydrophobically associating monomers. The monomers
comprise an ethylenically unsaturated group and a polyether group with block
structure
comprising a hydrophilic polyalkylene oxide block, which consists essentially
of ethylene
oxide groups, and a terminal, hydrophobic polyalkylene oxide block, which
consists of
alkylene oxides having at least 4 carbon atoms, preferably at least 5 carbon
atoms.
Water-soluble, thickening polymers are used in many areas of technology, for
example
in the area of cosmetics, in foods, for the production of cleaners, printing
inks, emulsion
paints and in the recovery of mineral oil.
Many chemically different classes of polymers are known which can be used as
thickeners. An important class of thickening polymers is the so-called
hydrophobically
associating polymers. This is understood by the person skilled in the art as
meaning
water-soluble polymers which have lateral or terminal hydrophobic groups, such
as, for
example, relatively long alkyl chains. In aqueous solution, such hydrophobic
groups can
associate with themselves or with other substances having hydrophobic groups.
As a
result of this, an associative network is formed, through which the medium is
thickened.
EP 705 854 Al, DE 100 37 629 Al and DE 10 2004 032 304 Al disclose water-
soluble,
hydrophobically associating copolymers and their use, for example in the
construction
chemistry sector. The described copolymers comprise acidic monomers, such as,
for
example, acrylic acid, vinylsulfonic acid, acrylamidomethylpropanesulfonic
acid, basic
monomers, such as acrylamide, dimethylacrylamide, or monomers comprising
cationic
groups, such as, for example, monomers having ammonium groups. Monomers of
this
type impart water solubility to the polymers. As hydrophobically associating
monomers,
the disclosed copolymers in each case comprise monomers of the following type:
H2C=C(Rx)-000-(-CH2-CH2-0-)q-RY or else H2C=C(Rx)-0-(-CH2-CH2-0-)q-RY), where
Rx
is typically H or CH3 and RY is a relatively large hydrocarbon radical,
typically
hydrocarbon radicals having 8 to 40 carbon atoms. Relatively long alkyl groups
or else a
tristyrylphenyl group are mentioned, for example, in the specifications.
CA 02760734 2011-11-01
2
A further important class of hydrophobically associating copolymers are alkali-
soluble
dispersions, as are disclosed, for example, by EP 13 836 Al or WO 2009/019225.
Dispersions of this type comprise on the one hand acidic monomers, in
particular acrylic
acid, the already mentioned hydrophobically associating monomers and also
nonhydrophilic monomers, such as, for example, alkyl acrylates. Copolymers of
this type
are present in the acidic pH range as dispersion, but form a solution in the
alkaline pH
range and thus develop their thickening effect.
Polymers which have polyethylene oxide blocks, blocks of higher alkylene
oxides and
additionally ethylenically unsaturated groups are also known from other areas
of
technology.
WO 2004/044035 Al discloses polyoxyalkylene block copolymers with a block
comprising polystyrene oxide which can be used as emulsifiers for the
preparation of
dispersions. The examples disclose compounds in which allyl alcohol or
hydroxybutyl
vinyl ether is firstly provided with a polystyrene oxide group and then with a
polyethylene
oxide group as terminal group. The terminal group can optionally also be
further
functionalized, for example with acid groups. The described block copolymer is
used for
the preparation of styrene-acrylate dispersions.
WO 2004/026468 Al discloses block copolymers comprising an alkylene oxide
block, a
block of glycidyl ethers and also an alkylene oxide block, where the block
copolymers
have an ethylenically unsaturated head group. The terminal group can
additionally be
functionalized with acid groups. The block copolymers are used as
polymerizable
emulsifiers. The use for the preparation of water-soluble, hydrophobically
associating
copolymers is not mentioned.
EP 1 069 139 A2 discloses aqueous dispersions which are obtained by
polymerization
of ethylenically unsaturated water-insoluble compounds in the presence of a
water-
soluble allyl or vinyl ether. The allyl or vinyl ethers have a polyalkylene
oxide group
which is formed from C2-C4-alkylene oxides, where ethylene oxide units must
obligatorily
be present. The alkylene oxide units can be arranged randomly or blockwise,
and the
polyalkylene oxide group can have H or a Ci to 04 group as terminal group. The
CA 02760734 2011-11-01
3
examples specifically mention polyethylene oxide-b-polypropylene oxide-
monobutyl vinyl
ether.
JP 2001-199751 A discloses the preparation of a dispersant for cement. Here,
nnaleic
anhydride is copolymerized with a macromonomer. The macromonomer is a
polyoxyalkylene block copolymer comprising a polyethylene oxide block and a
block of
an alkylene oxide selected from the group of propylene oxide, butylene oxide
or styrene
oxide, the terminal OH groups being etherified with a 02- to C5-alkenyl group
or with a
C1-05-alkyl group.
JP 2000-119699 A discloses a deinking auxiliary in the reprocessing of
wastepaper. For
this, a polyoxyalkylene block copolymer is used which has a terminal 08- to
C24-alkyl or
alkenyl group which is joined to an ethylene oxide-propylene oxide block, a
polyethylene
oxide block and also a block comprising propylene oxide or higher alkylene
oxides. The
preparation of polymers starting from this block copolymer is not described.
It is known to use hydrophobically associating copolymers in the field of
mineral oil
recovery, in particular for enhanced oil recovery (EOR). Details on using
hydrophobically
associating copolymers for enhanced oil recovery are described, for example,
in the
overview article by Taylor, K.C. and Nasr-El-Din, H.A. in J. Petr. Sci. Eng.
1998, 19,
265-280.
The techniques of enhanced oil recovery include "polymer flooding". A mineral
oil
deposit is not a subterranean "sea of mineral oil", but the mineral oil is
held in the tiny
pores of the mineral oil-conveying rock. The diameter of the cavities in the
formation is
usually only a few micrometers. For the polymer flooding, an aqueous solution
of a
thickening polymer is injected into a mineral oil deposit through injection
bores. By
injecting in the polymer solution, the mineral oil is forced through said
cavities in the
formation starting from the injection bore in the direction of the production
bore, and the
mineral oil is recovered via the production bore. It is important for this
application that
the aqueous polymer solution contains no gel particles at all. Even small gel
particles
with dimensions in the micrometer range can block the fine pores in the
formation and
thus bring the mineral oil recovery to a standstill. Hydrophobically
associating
CA 02760734 2011-11-01
4
copolymers for enhanced oil recovery should therefore have the lowest possible
fraction
of gel particles.
The aforementioned monomers H2C=C(Rx)-000-(-CH2-CH2-0-)q-RY and
H2C=C(Rx)-0-(-CH2-CH2-0-)q-RY are usually prepared by means of a two-stage
process.
In a first stage, an alcohol R-OH is ethoxylated, giving an ethoxylated
alcohol of the
general formula HO+CH2-CH2-0-)q-RY. This can be reacted in a second stage with
(meth)acrylic anhydride or acetylene to give the specified monomers. As a by-
product of
the first stage (i.e. of the ethoxylation of the alcohol), polyethylene oxide
HO-(-CH2-CH2-0)q-H is formed in small amounts. In the second stage, the
difunctional
molecules H2C=C(Rx)-000-(-CH2-CH2-0-)q-0C-C(Rx)=CH2 or
H2C=C(Rx)-0-(-CH2-CH2-0-)q-C(Rx)=CH2 can be formed therefrom. Since
purification is
extremely complex, these by-products are usually not separated off.
Difunctional
molecules of this type have a crosslinking effect and consequently lead in the
course of
a polymerization to the formation of crosslinked products. As a result of
this, the formed
polymers automatically have certain gel fractions which are extremely
troublesome
when using the polymers for EOR. Furthermore, for reasons of cost, it is in
any case
desirable to provide the simplest possible method for the preparation of the
monomers.
It was therefore an object of the invention to provide hydrophobically
associating
copolymers with low gel fractions. Furthermore, the copolymers should be able
to be
prepared more economically than hitherto.
Correspondingly, water-soluble, hydrophobically associating copolymers have
been
found which comprise at least the following monomers:
(a) 0.1 to 20% by weight of at least one monoethylenically unsaturated,
hydrophobically associating monomer (a), and
(b) 25% by weight to 99.9% by weight of at least one monoethylenically
unsaturated hydrophilic monomer (b) different therefrom,
õ .
CA 2760734 2017-03-03
where the quantitative data are based in each case on the total amount of all
of the
monomers in the copolymer, and where at least one of the monomers (a) is a
monomer of the general formula (I)
5 H2C.c(R1)-R4-0-(-CH2-CH(R2)-0-)k-(-CH2-CH(R3)-04-R5 (I)
where the units -(-CH2-CH(R2)-0-)k and -(-CH2-CH(R3)-0-)1are arranged in block
structure in the order shown in formula (I) and the radicals and indices have
the
following meaning:
k: a number from 10 to 150,
a number from 5 to 25,
R1: H or methyl,
R2: independently of one another, H, methyl or ethyl, with the proviso that
at least
50 mol% of the radicals R2 are H,
R3: independently of one another, a hydrocarbon radical having at least 2
carbon
atoms or an ether group of the general formula ¨CH2-0-R3', where R3' is a
hydrocarbon radical having at least 2 carbon atoms,
R4: a single bond or a divalent linking group selected from the group of
¨(CnH2n)-
[R4a], _
0-(CrvF120-Fil and ¨C(0)-0-(Cn-H2n-)[R49, where n, n' and n÷ is in
each case a natural number from 1 to 6,
R5: H or a hydrocarbon radical having 1 to 30 carbon atoms.
More particularly, according to one aspect there is provided a water-soluble,
hydrophobically associating copolymer comprising at least
a) 0.1 to 20% by weight of at least one monoethylenically unsaturated,
hydrophobically associating monomer (a), and
b) 25% by weight to 99.9% by weight of at least one monoethylenically
unsaturated
hydrophilic monomer (b) different therefrom,
CA 2760734 2017-03-03
5a
where the quantitative data are based in each case on the total amount of all
of the
monomers in the copolymer, wherein at least one of the monomers (a) is a
monomer
of the general formula (I)
H2C=C(R1)-R4-u ¨_
(-CH2-CH(R2)-0-)k+CH2-CH(R3)-0-)I-R5 (I)
where the units -(-CH2-CH(R2)-0-)k and -(-CH2-CH(R3)-0-)1 are arranged in
block
structure in the order shown in formula (I) and the radicals and indices have
the
following meaning:
k: a number from 10 to 150,
a number from 5 to 25,
R1: H or methyl,
R2: independently of one another, H, methyl or ethyl, with the proviso that
at least
50 mol% of the radicals R2 are H,
R3: independently of one another, a hydrocarbon radical having at least 2
carbon
atoms or an ether group of the general formula ¨CH2-0-R2', where R2' is a
hydrocarbon radical having at least 2 carbon atoms,
R4: a divalent linking group, -0-(Cry1120-, where n' is a natural number
from 1 to
6,
R5: H or a hydrocarbon radical having 1 to 30 carbon atoms.
Furthermore, the use of such copolymers for the development, exploitation and
completion
of subterranean mineral oil deposits and natural gas deposits, as additive for
aqueous
construction systems which comprise hydraulic binder systems and for the
production of
liquid detergents and cleaners has been found, as well as compositions of the
copolymers
preferred for the respective use.
Thus, according to another aspect there is provided the use of a copolymer as
defined
herein in the development, exploitation and completion of subterranean mineral
oil deposits
and natural gas deposits.
CA 2760734 2017-03-03
5b
According to another aspect there is provided the use of a copolymer as
defined herein for
enhanced oil recovery by injecting an aqueous formulation of said copolymer in
a
concentration of 0.01 to 5% by weight through at least one injection bore into
a mineral oil
deposit and removing crude oil from the deposit through at least one
production bore.
According to another aspect there is provided the use of water-soluble,
hydrophobically
associating copolymers in the development, exploitation and completion of
subterranean
mineral oil deposits and natural gas deposits, wherein the copolymers comprise
at least
(a) 0.1 to 12% by weight of at least one monoethylenically unsaturated,
hydrophobically associating monomer (a), and
(b) 70% by weight to 99.9% by weight of at least two
monoethylenically
unsaturated hydrophilic monomers (b) different therefrom, and the
monomers (b) are
= at least one neutral hydrophilic monomer (b1), and
= at least one hydrophilic anionic monomer (b2) which comprises at least
one acid group selected from the group of -COOH, -S03H, -P03H2 and
salts thereof,
where the quantitative data are based in each case on the total amount of all
of
the monomers in the copolymer, and at least one of the monomers (a) is a
monomer of the general formula (I)
H2C=C(R1)-R4-0-(-CH2-CH(R2)-0-)k+CH2-CH(R3)-0-)I-R5 (I)
where the units -(-CH2-CH(R2)-0-)k and -(-CH2-CH(R3)-0-), are arranged in
block
structure in the order shown in formula (I) and the radicals and indices have
the
following meaning:
k CA 2760734 2017-03-03
5c
k: a number from 10 to 150,
a number from 5 to 25,
R1: H or methyl,
R2: independently of one another, H, methyl or ethyl, with the proviso that
at least 50 mol% of the radicals R2 are H,
R3: independently of one another, a hydrocarbon radical having at least
2 carbon atoms or an ether group of the general formula -CH2-0-R2',
where R2' is a hydrocarbon radical having at least 2 carbon atoms,
R4: a single bond or a divalent linking group, selected from the group of
-(CnH2n)-, -0-(Cn'H2n')- and -C(0)-0-(Cn¨H2n+, where n, n' and n" is in
each case a natural number from 1 to 6,
R5: H or a hydrocarbon radical having 1 to 30 carbon atoms.
According to another aspect there is provided a process for the development,
exploitation, and completion of subterranean mineral oil deposits and natural
gas
deposits comprising utilizing a water-soluble, hydrophobically associating
copolymer comprising at least
(a) 0.1 to 12% by weight of at least one monoethylenically unsaturated,
hydrophobically associating monomer (a), and
(b) 70% to 99.5% by weight of at least one monoethylenically
unsaturated hydrophilic monomer (b) different therefrom,
wherein the quantitative data are based in each case on the total amount of
all of
the monomers in the copolymer, wherein at least one of the monomers (a) is a
monomer of the general formula (I)
H2C=C(R1)-R4-0-(-CH2-CH(R2)-0-)k-(-CH2-CH(R3)-0-)I-R5 (I)
wherein the units -(-CH2-CH(R2)-0-)k and +CH2-CH(R3)-0-)1 are arranged in
block structure in the order shown in formula (I) and the radicals and indices
have
the following meaning:
CA 2760734 2017-03-03
5d
k: a number from 10 to 150,
a number from 5 to 25,
R1: H or methyl,
R2: independently of one another, H, methyl, or ethyl, with the
proviso that at least 50 mol% of the radicals R2 are H,
R3: independently of one another, a hydrocarbon radical having
at least 2
carbon atoms or an ether group of the general formula -CH2-0-R2',
wherein R2' is a hydrocarbon radical having at least 2 carbon atoms,
R4: a single bond or a divalent linking group selected from the
group consisting of: -(CnH2n)-, -0-(Cry1-12), and
-C(0)-0-(Cn-H2n,,), wherein n, n', and n" is in each case a
natural number from 1 to 6, and
R5: H or a hydrocarbon radical having 1 to 30 carbon atoms,
wherein said water-soluble, hydrophobically associating copolymer is a
copolymer (Al) which comprises at least two different hydrophilic monomers
(b),
and these are at least
= one neutral hydrophilic monomer (b1), and
= at least one hydrophilic anionic monomer (b2) which comprises at least
one acid group selected from the group consisting of -COON, -603H,
-P03H2, and salts thereof.
According to another aspect, there is provided a process for enhanced oil
recovery comprising
utilizing a water-soluble, hydrophobically associating copolymer comprising at
least
(a) 0.1 to 12% by weight of at least one monoethylenically unsaturated,
hydrophobically associating monomer (a), and
(b) 70% to 99.5% by weight of at least one monoethylenically unsaturated
hydrophilic monomer (b) different therefrom,
CA 2760734 2017-03-03
5e
wherein the quantitative data are based in each case on the total amount of
all of
the monomers in the copolymer, wherein at least one of the monomers (a) is a
monomer of the general formula (I)
H2C=C(R1)-R4-0-(-CH2-CH(R2)-0-)k+CH2-CH(R3)-0-)I-R5 (I)
wherein the units -(-CH2-CH(R2)-0-)k and -(-CH2-CH(R3)-0-)i are arranged in
block
structure in the order shown in formula (I) and the radicals and indices have
the
following meaning:
k: a number from 10 to 150,
a number from 5 to 25,
R1: H or methyl,
R2: independently of one another, H, methyl, or ethyl, with the proviso
that at
least 50 mol% of the radicals R2 are H,
R3: independently of one another, a hydrocarbon radical having
at least 2
carbon atoms or an ether group of the general formula -CH2-0-R2',
wherein R2' is a hydrocarbon radical having at least 2 carbon atoms,
R4: a single bond or a divalent linking group selected from the group
consisting of: -(CnFl2n)-, -0-(Cnf1211'), and -C(0)-0-(Cn-H2n,,), wherein n,
n',
and n" is in each case a natural number from 1 to 6, and
R5: H or a hydrocarbon radical having 1 to 30 carbon atoms.
and further comprising injecting an aqueous formulation of said water-soluble,
hydrophobically associating copolymer in a concentration of 0.01 to 5% by
weight
through at least one injection bore into a mineral oil deposit and removing
crude
oil from the deposit through at least one production bore,
wherein said water-soluble, hydrophobically associating copolymer is a
copolymer (Al) which comprises at least two different hydrophilic monomers
(b),
and these are at least
CA 2760734 2017-03-03
5f
= one neutral hydrophilic monomer (b1), and
= at least one hydrophilic anionic monomer (b2) which comprises at least
one acid group selected from the group consisting of -COOH, -S03H, -
P03H2, and salts thereof.
Regarding the invention, the details are as follows:
The hydrophobically associating copolymers according to the invention are
water-soluble
_______________________________________________________________________
copolymers which have hydrophobic groups. In aqueous solution, the
CA 02760734 2011-11-01
6
hydrophobic groups are able to associate with themselves or with substances
having
other hydrophobic groups and, through this interaction, thicken the aqueous
medium.
It is known to the person skilled in the art that the solubility of
hydrophobically
associating (co)polymers in water can be more or less dependent on the pH
depending
on the type of monomers used. A reference point for assessing the solubility
in water
should in each case therefore be the pH desired for the respective intended
use of the
copolymer. A copolymer which, at a certain pH, has an inadequate solubility
for the
intended use may have an adequate solubility at a different pH. The term
"water-soluble"
encompasses in particular also alkali-soluble dispersions of polymers, i.e.
polymers
which are present in the acidic pH range as dispersions and dissolve in water
and
develop their thickening effect only in the alkaline pH range.
In an ideal case, the copolymers according to the invention should be miscible
with
water in any desired ratio. According to the invention, however, it is
sufficient if the
copolymers are water-soluble at least at the desired use concentration and at
the
desired pH. As a rule, the solubility in water at room temperature should be
at least
g/I, preferably at least 50 g/I and particularly preferably at least 100 WI.
20 Besides the hydrophobic groups already mentioned, the hydrophobically
associating
copolymers according to the invention therefore comprise hydrophilic groups in
an
amount such that the described water solubility is ensured at least in the pH
range
intended for the respective application.
Monomer (a)
The hydrophobically associating copolymer according to the invention comprises
at least
one monoethylenically unsaturated monomer (a) which imparts hydrophobically
associating properties to the copolymer according to the invention and is
therefore
referred to below as hydrophobically associating monomer.
CA 02760734 2011-11-01
7
Monomer (a) of the formula (I)
According to the invention, at least one of the monoethylenically unsaturated
monomers
(a) is a monomer of the general formula
H2C=C(RTR4_0_(-CH2-CH(R2)-0-)k-(-CH2-CH(R3)-0-)I-R5 (I) .
In the monomers (a) of the formula (I), an ethylenic group H2C=C(R1)- is
bonded via a
divalent, linking group -R4-0- to a polyoxyalkylene radical with block
structure -(-CH2-CH(R2)-0-)k+CH2-CH(R3)-0-)I-R5 where the two
blocks -(-0H2-CH(R2)-0-)k and -(-CH2-CH(R3)-0-)1 are arranged in the order
shown in
formula (0. The polyoxyalkylene radical has either a terminal OH group or a
terminal
ether group -0R5.
In the aforementioned formula, R1 is H or a methyl group.
R4 is a single bond or a divalent, linking group, selected from the group of --
(CnH2n)-
[group R41, -0-(Cn.H2n,)-[group R49- and ¨C(0)-0-(Cn-H2n-[group R49. In the
specified
formulae, n, n' and n" are in each case a natural number from 1 to 6. In other
words, the
linking group is straight-chain or branched aliphatic hydrocarbon groups
having 1 to 6
hydrocarbon atoms which are linked to the ethylenic group H2C=C(R1)- either
directly,
via an ether group ¨0- or via an ester group -C(0)-0-. The groups -(CnH2n)-, -
(Cnfl2n)-
and -(Cn"H2n+ are preferably linear aliphatic hydrocarbon groups.
Preferably, the group R4a is a group selected from ¨CH2-, -CH2-CH2-
and -0H2-CH2-CH2-, and is particularly preferably a methylene group ¨CH2-.
Preferably, the group R4b is a group selected from -0-CH2-CH2-, -0-CH2-CH2-0H2-
and -0-CH2-CH2-CH2-0H2-, and is particularly preferably ¨0-CH2-CH2-CH2-CH2-.
Preferably, the group R4c is a group selected from ¨C(0)-0-CH2-CH2-
, -C(0)0-CH(CH3)-CH2-, -C(0)0-CH2-CH(CH3)-, -C(0)0-
CH2-CH2-CH2-CH2-
and -C(0)0-CH2-0H2-CH2-CH2-CH2-CH2-, particular preference being given
CA 02760734 2011-11-01
=
8
to -C(0)-0-CH2-CH2- and -C(0)0-CH2-CH2-CH2-CH2- and very particular preference
being given to ¨C(0)-0-CH2-CH2-.
The group R4 is particularly preferably a group R" or R4b, particularly
preferably a group
Ro.
Furthermore, R4 is particularly preferably a group selected from ¨CH2-
or -0-CH2-CH2-CH2-CH2-, and is very particularly preferably -0-CH2-CH2-CH2-CH2-
.
Furthermore, the monomers (I) have a polyoxyalkylene radical which consists of
the
units -(-CH2-CH(R2)-0-)k and -(-CH2-CH(R3)-0-)1, where the units are arranged
in block
structure in the order shown in formula (I). The transition between the two
blocks may be
abrupt or continuous.
In the block -(-CH2-CH(R2)-0-)k , the radicals R2, independently of one
another, are H,
methyl or ethyl, preferably H or methyl, with the proviso that at least 50
mol% of the
radicals R2 are H. Preferably, at least 75 mol% of the radicals R2 are H,
particularly
preferably at least 90 mol% and very particularly preferably exclusively H. In
the
specified block, a polyoxyethylene block which can optionally still have
certain fractions
of propylene oxide and/or butylene oxide units is thus preferably a pure
polyoxyethylene
block.
The number of alkylene oxide units k is a number from 10 to 150, preferably 12
to 100,
particularly preferably 15 to 80, very particularly preferably 20 to 30 and
for example ca.
22 to 25. For the person skilled in the art in the field of polyalkylene
oxides, it is clear
that the specified numbers are average values of distributions.
In the second, terminal block -(-CH2-CH(R3)-04-, the radicals R3,
independently of one
another, are hydrocarbon radicals of at least 2 carbon atoms, preferably at
least 3 and
particularly preferably 3 to 10 carbon atoms. These may be an aliphatic and/or
aromatic,
linear or branched carbon radical. These are preferably aliphatic radicals.
I
,
CA 02760734 2011-11-01
9
Examples of suitable radicals R3 comprise ethyl, n-propyl, n-butyl, n-pentyl,
n-hexyl, n-
heptyl, n-octyl, n-nonyl or n-decyl and also phenyl. Examples of preferred
radicals
comprise n-propyl, n-butyl, n-pentyl and particular preference is given to an
n-propyl
radical.
The radicals R3 may also be ether groups of the general formula ¨CH2-0-R3',
where R3'
is an aliphatic and/or aromatic, linear or branched hydrocarbon radical having
at least 2
carbon atoms, preferably at least 3 and particularly preferably 3 to 10 carbon
atoms.
Examples of radicals R3 comprise n-propyl, n-butyl, n-pentyl, n-hexyl, 2-
ethylhexyl, n-
heptyl, n-octyl, n-nonyl, n-decyl or phenyl.
The block -(-CH2-CH(R3)-0-)1- is thus a block which consists of alkylene oxide
units
having at least 4 carbon atoms, preferably at least 5 carbon atoms, and/or
glycidyl
ethers with an ether group of at least 2, preferably at least 3 carbon atoms.
Preferably,
the radicals R3 are the specified hydrocarbon radicals; the building blocks of
the second
terminal block are particularly preferably alkylene oxide units comprising at
least 5
carbon atoms, such as pentene oxide units or units of higher alkylene oxides.
The number of alkylene oxide units I is a number from 5 to 25, preferably 6 to
20,
particularly preferably 8 to 18, very particularly preferably 10 to 15 and for
example ca.
12.
The radical R5 is H or a preferably aliphatic hydrocarbon radical having 1 to
30 carbon
atoms, preferably 1 to 10 and particularly preferably 1 to 5 carbon atoms.
Preferably, R5
is H, methyl or ethyl, particularly preferably H or methyl and very
particularly preferably
H.
In the monomers of the formula (I), a terminal, monoethylenic group is thus
linked to a
polyoxyalkylene group with block structure, and specifically firstly to a
hydrophilic block
having polyethylene oxide units and this in turn to a second terminal,
hydrophobic block
which is composed at least of butene oxide units, preferably at least pentene
oxide units
or units of higher alkylene oxides, such as, for example, dodecene oxide. The
second
block has a terminal -0R5 group, in particular an OH group. In contrast to the
I
,
CA 02760734 2011-11-01
hydrophobically associating copolymers known from the prior art, the end group
does
not have to be etherified with a hydrocarbon radical for the hydrophobic
association, but
the terminal block -(-CH2-CH(R3)-0-)1 itself with the radicals R3 is
responsible for the
hydrophobic association of the copolymers prepared using the monomers (a). The
5 etherification is only one option which can be selected by the person
skilled in the art
depending on the desired properties of the copolymer.
For the person skilled in the art in the field of polyallvlene oxide block
copolymers, it is
clear that the transition between the two blocks can be abrupt or continuous
depending
10 on the type of preparation. In the case of a continuous transition,
between the two
blocks, there is also a transition zone which comprises monomers of the two
blocks. If
the block limit is fixed in the middle of the transition zone, correspondingly
the first block
-(-CH2-CH(R2)-0-)k can still have small amounts of units -CH2-CH(R3)-0- and
the second
block -(-CH2-CH(R3)-0-)1 can have small amounts of units -CH2-CH(R2)-0-,
although
these units are not distributed randomly over the block, but are arranged in
said
transition zone.
Preparation of the monomers (a) of the formula (I)
The preparation of the hydrophobically associating monomers (a) of the formula
(I) can
take place in accordance with methods known in principle to the person skilled
in the art.
In one preferred preparation process the preparation of the monomers (a)
starts from
suitable monoethylenically unsaturated alcohols (111) which are then
alkoxylated in a two-
stage process, so that the block structure mentioned is obtained. Monomers (a)
of the
formula (1) where R5 = H are obtained. The latter may optionally be etherified
in a further
process step.
The type of ethylenically unsaturated alcohols (III) to be used is governed
here in
particular by the group R4.
If R4 is a single bond, the starting materials are alcohols (111) of the
general formula
H2C=C(R1)-0-(-CH2-CH(R2)-0-)d-H (111a), where R1 has the meaning defined
above, R2'
CA 02760734 2011-11-01
11
is H and/or CH3, preferably H and d is a number from 1 to 5, preferably 1 or
2. Examples
of such alcohols comprise diethylene glycol vinyl ether H2C=CH-O-CH2-CH2-0-CH2-
CH2-0H
or dipropylene glycol vinyl ether H2C=CH-O-CH2-CH(CH3)-0-CH2-CH(CH3)-0H,
preference being given to diethylene glycol vinyl ether.
For the preparation of monomers (a) in which R4 is not a single bond, it is
possible to
use alcohols of the general formula H2C=C(R1)-R4-0H (111a) or even alcohols
having
alkoxy groups of the formula H2C=C(R1)-R4-0-(-CH2-CH(R2)-0-)d-H (111b), where
R2' and
d have the meaning defined above, and R4 is in each case selected from the
group R4a,
R4b and R4c.
For the preparation of the monomers with linking group R4a, preference is
given to
starting from alcohols of the formula H2C=C(R1)¨(CnH2n)-0H, in particular
H2C=CH-(CnH2n)-OH or alcohols of the formula H2C=C(R1)-0+CH2-CH(R2)-0-)d-H, in
particular those where R1 = H and R2 = H and/or CH3. Examples of preferred
alcohols
comprise allyl alcohol H2C=CH-CH2-0H or isoprenol H2C=C(CH3)-CH2-CH2-0H.
For the preparation of the monomers with linking group R4b, the starting
materials are
vinyl ethers of the formula
H2C=C(R1)-0-(Cn,H20-0H, preferably
H2C=CH-0-(Cn4-12)-0H. Particularly preferably, (o-hydroxybutyl vinyl ether
H2C=CH-O-CH2-CH2-CH2-CH2-0H can be used.
For the preparation of the monomers with linking group R4c, the starting
materials are
hydroxyalkyl (meth)acrylates of the general formula H2C=C(R1)-C(0)-0-(Cn-H2n-)-
OH,
preferably H2C=C(R1)-C(0)-0-(Cn-H2n)-OH. Examples of preferred hydroxyalkyl
(meth)acrylates comprise hydroxyethyl (meth)acrylate H2C=C(R1)-C(0)-0-CH2-CH2-
0H
and also hydroxybutyl (meth)acrylate H2C=C(R1)-C(0)-0-CH2-CH2-CH2-CH2-0H.
The specified starting compounds are alkoxylated, and specifically in a two-
stage
process firstly with ethylene oxide, optionally in a mixture with propylene
oxide and/or
butylene oxide and in a second step with alkylene oxides of the general
formulae (Xa) or
(Xb)
CA 02760734 2011-11-01
12
0 0
(Xa) /OR-3
(Xb)
3 CH2
where R3 in (Xa) or R3' in (Xb) has the meaning defined at the outset.
The procedure for an alkoxylation including the preparation of block
copolymers from
various alkylene oxides is known in principle to the person skilled in the
art. It is likewise
known to the person skilled in the art that it is possible to influence via
the reaction
conditions, in particular the choice of catalyst, the molecular weight
distribution of the
alkoxylates and the orientation of alkylene oxide units in a polyether chain.
The alkoxylates can be prepared, for example, by base catalyzed alkoxylation.
For this,
the alcohol used as starting material can be admixed in a pressurized reactor
with alkali
metal hydroxides, preferably potassium hydroxide, or with alcohol metal
alcoholates,
such as, for example, sodium methylate. Through a reduced pressure (for
example <100
mbar) and/or elevation of the temperature (30 to 150 C), water still present
in the
mixture can be stripped off. The alcohol is then in the form of the
corresponding
alcoholate. The system is then rendered inert with inert gas (e.g. nitrogen)
and in a first
step, ethylene oxide, optionally in the mixture with propylene oxide and/or
butylene
oxide, is added stepwise at temperatures of from 60 to 180 C, preferably 130
to 150 .
The addition takes place typically over the course of 2 to 5 hours without the
invention
being limited thereto. When the addition is complete, the reaction mixture is
expediently
left to after-react, for example for 1/2 h to 1 h. In a second step, the
alkylene oxides
having at least 5 carbon atoms are then metered in stepwise. The reaction
temperature
in the second stage can be maintained or else altered. A ca. 10 to 25 C lower
reaction
temperature than in the first stage has proven useful.
The alkoxylation can also be carried out using techniques which lead to
narrower
molecular weight distributions than in the case of the base-catalyzed
synthesis. For this,
double hydroxide clays as described in DE 43 25 237 Al, for example, can be
used as
catalyst. The alkoxylation can particularly preferably take place using double
metal
cyanide catalysts (DMC catalysts). Suitable DMC catalysts are disclosed, for
example,
in DE 102 43 361 Al, in particular sections [0029] to [0041] and the
literature cited
CA 02760734 2011-11-01
13
therein. For example, catalysts of the Zn-Co type can be used. To carry out
the reaction,
the alcohol used as starting material can be admixed with the catalyst, the
mixture
dewatered as described above and reacted with the alkylene oxides as
described.
Usually, not more than 250 ppm of catalyst with regard to the mixture are
used, and, on
account of this small amount, the catalyst can remain in the product.
The alkoxylation can furthermore also be carried out with acid catalysis. The
acids may
be Bronstedt acids or Lewis acids. To carry out the reaction, the alcohol used
as starting
material can be admixed with the catalyst, the mixture can be dewatered as
described
above and reacted with the alkylene oxides as described. At the end of the
reaction, the
acidic catalyst can be neutralized by adding a base, for example KOH or NaOH,
and, if
required, filtered off.
For the person skilled in the art in the field of polyalkylene oxides, it is
clear that the
orientation of the hydrocarbon radicals R3 and, if appropriate, R2 can depend
on the
conditions during the alkoxylation, for example on the catalyst selected for
the
alkoxylation. The alkylene oxide groups can thus be incorporated into the
monomer
either in the orientation -(-CH2-CH(R3)-0-) or
else in inverse
orientation -(-CH(R3)-CH2-0-)-. The depiction in formula (I) should therefore
not be
regarded as limited to a certain orientation of the groups R2 and/or R3.
If the monomers (a) of the formula (I) with a terminal OH group (i.e. R5 = H)
obtained as
described are to be optionally etherified, this can take place with customary
alkylating
agents known in principle to the person skilled in the art, for example alkyl
sulfates. For
the etherification, in particular dimethyl sulfate or diethyl sulfate can be
used.
The described preferred preparation process for the monomers (I) also differs,
including
in cases when R5 is not H, fundamentally from the synthesis of known
hydrophobically
associating monomers by the series of synthesis steps: whereas in the case of
the
synthesis processes for the synthesis of the known hydrophobically associating
monomers mentioned at the outset, the starting material used is an alcohol,
which is
alkoxylated and only at the end is a compound with an ethylenically
unsaturated group
reacted with the alkoxylated alcohol, in the case of the synthesis variant
described
CA 02760734 2011-11-01
14
according to the invention, the procedure is reversed: starting material is an
ethylenically
unsaturated compound which is alkoxylated and can then be optionally
etherified. This
prevents the formation of crosslinking by-products, meaning that the
preparation of
copolymers with a particularly low gel fraction is possible.
Further monomers (a)
Besides the monomers (1), it is also possible optionally to use monoethylenic,
hydrophobically associating monomers (a) different from the monomers (1).
Further
monomers (a) have the general formula H2C=C(R1)-Y-Z, where R1 is H or methyl,
Z is a
terminal hydrophobic group and Y is a linking hydrophilic group. The person
skilled in
the art is aware of such monomers and makes a suitable selection as
appropriate.
Examples of such monomers comprise in particular monomers of the general
formula
H2C=C(R1)-000-(-CH2-CH(R6)-0-)q-R7 (11a) or H2C=C(R1)-0-(-CH2-CH(R6)-0-)q-R7
(11b),
where q is a number from 10 to 150, preferably 12 to 100, particularly
preferably 15 to
80, very particularly preferably 20 to 30 and for example ca. 25, R1 is as
defined above
and the radicals R6, independently of one another, are H, methyl or ethyl,
preferably H or
methyl, with the proviso that at least 50 mol% of the radicals R6 are H.
Preferably, at
least 75 mol% of the radicals R6 are H, particularly preferably at least 90
mol% and very
particularly preferably exclusively H. The radical R7 is an aliphatic and/or
aromatic,
straight-chain or branched hydrocarbon radical having at least 6 carbon atoms,
in
particular 6 to 40 carbon atoms, preferably 8 to 30 carbon atoms. Examples
comprise
n-alkyl groups, such as n-octyl, n-decyl or n-dodecyl groups, phenyl groups,
and in
particular substituted phenyl groups. The substituents on the phenyl groups
may be alkyl
groups, for example Cl- to C6-alkyl groups, preferably styryl groups.
Particular
preference is given to a tristyrylphenyl group. The specified hydrophobically
associating
monomers of the formulae (11a) and (11b) are known in principle to the person
skilled in
the art.
Amounts of the monomers (a)
The amount of monoethylenically unsaturated, hydrophobically associating
monomers
(a) is governed by the respective intended use of the copolymer according to
the
CA 02760734 2011-11-01
invention and is generally 0.1 to 20% by weight, based on the total amount of
all of the
monomers in the copolymer, preferably 0.1 to 12% by weight. In a further
preferred
embodiment the amount is 0.5 to 20% by weight, particularly preferably 0.5 to
12% by
weight.
5
If further monomers (a) are also used besides the monomers (a) of the formula
(I), the
monomers of the formula (I) should generally be used in an amount of at least
0.1% by
weight with regard to the sum of all of the monomers in the copolymer,
preferably at
least 0.5% by weight. Furthermore, the fraction of monomers of the formula (I)
should
10 generally be at least 25% by weight with regard to the amount of all of
the monomers
(a), preferably at least 50% by weight, particularly preferably at least 75%
by weight and
particularly preferably only monomers of the formula (I) should be used as
monomers
(a).
15 Hydrophilic monomers (b)
Besides the monomers (a), the hydrophobically associating copolymer according
to the
invention comprises at least one monoethylenically unsaturated, hydrophilic
monomer
(b) different therefrom. It is of course also possible to use mixtures of two
or more
different hydrophilic monomers (b).
Besides an ethylenic group, the hydrophilic monomers (b) comprise one or more
hydrophilic groups. On account of their hydrophilicity, these impart adequate
solubility in
water to the copolymer according to the invention. The hydrophilic groups are
in
particular functional groups which comprise 0 and/or N atoms. They can,
moreover,
comprise in particular S and/or P atoms as heteroatoms.
The monomers (b) are particularly preferably miscible with water in any
desired ratio,
although it suffices for carrying out the invention that the hydrophobically
associating
copolymer according to the invention has the solubility in water mentioned at
the start.
Generally, the solubility of the monomers (b) in water at room temperature
should be at
least 100 g/I, preferably at least 200 g/I and particularly preferably at
least 500 g/I.
I
,
CA 02760734 2011-11-01
16
Examples of suitable functional groups comprise carbonyl groups >0=0, ether
groups -0-, in particular polyethylene oxide groups ¨(CH2-CH2-0-)n-, where n
is
preferably a number from 1 to 200, hydroxy groups ¨OH, ester groups ¨C(0)0-,
primary,
secondary or tertiary amino groups, ammonium groups, amide groups ¨C(0)-NH-,
carboxamide groups ¨0(0)-NH2 or acid groups such as carboxyl groups ¨COOH,
sulfonic acid groups ¨S03H, phosphonic acid groups -P03H2 or phosphoric acid
groups
¨0P(OH)3.
=
Examples of preferred functional groups comprise hydroxy groups ¨OH, carboxyl
groups -COOH, sulfonic acid groups ¨S03H, carboxamide groups ¨0(0)-NH2, amide
groups¨C(0)-NH-, and polyethylene oxide groups ¨(CH2-CH2-0-)n-H, where n is
preferably a number from 1 to 200.
The functional groups can be attached directly to the ethylenic group, or else
be bonded
to the ethylenic group via one or more linking hydrocarbon groups.
The hydrophilic monomers (b) are preferably monomers of the general formula
H20=C(R8)R9 (Ill) , where R8 is H or methyl and R9 is a hydrophilic group or a
group
comprising one or more hydrophilic groups.
The groups R9 are groups which comprise heteroatoms in an amount such that the
solubility in water defined at the start is achieved.
Examples of suitable monomers (b) comprise monomers comprising acid groups,
for
example monomers comprising ¨COOH groups, such as acrylic acid or methacrylic
acid,
crotonic acid, itatonic acid, maleic acid or fumaric acid, monomers comprising
sulfonic
acid groups, such as vinylsulfonic acid, allylsulfonic acid, 2-acrylamido-2-
methylpropanesulfonic acid (AMPS), 2-methacrylamido-2-methylpropanesulfonic
acid,
2-acrylamidobutanesulfonic acid, 3-acrylamido-3-methylbutanesulfonic acid or 2-
acrylamido-2,4,4-trimethylpentanesulfonic acid, or monomers comprising
phosphonic
acid groups, such as vinylphosphonic acid, allylphosphonic acid, N-
(meth)acrylamidoalkylphosphonic acids or (meth)acryloyloxyalkylphosphonic
acids.
CA 02760734 2011-11-01
17
Also to be mentioned are acrylamide and methacrylamide and also derivatives
thereof,
such as, for example, N-methyl(meth)acrylamide, N, N'-dimethyl(meth)acrylamide
, and
N-methylolacrylamide, N-vinyl derivatives such as N-vinylformamide, N-
vinylacetamide,
N-vinylpyrrolidone or N-vinylcaprolactam, and vinyl esters, such as vinyl
formate or vinyl
acetate. N-vinyl derivatives can be hydrolyzed after polymerization to
vinylamine units,
vinyl esters to vinyl alcohol units.
Further examples comprise monomers comprising hydroxy and/or ether groups,
such
as, for example, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate,
ally! alcohol,
hydroxyvinyl ethyl ether, hydroxyl vinyl propyl ether, hydroxyvinyl butyl
ether or
compounds of the formula H2C=C(R1)-000-(-CH2-CH(R18)-0-)b-R11 (IVa) or
H2C=C(R1)-0-(-CH2-CH(R10)-0-)b-R11 (IVb), where R1 is as defined above and b
is a
number from 2 to 200, preferably 2 to 100. The radicals R8 are, independently
of one
another, H, methyl or ethyl, preferably H or methyl, with the proviso that at
least 50
mol% of the radicals R8 are H. Preferably, at least 75 mol% of the radicals R8
are H,
particularly preferably at least 90 mol% and very particularly preferably
exclusively H.
The radical R11 is H, methyl or ethyl, preferably H or methyl. The individual
alkylene
oxide units can be arranged randomly or blockwise. In the case of a block
copolymer,
the transition between the blocks may be abrupt or gradual.
Suitable hydrophilic monomers (b) are also monomers having ammonium groups, in
particular ammonium derivatives of N-(co-aminoalkyl) (meth)acrylamides or (0-
aminoalkyl
(meth)acrylic esters.
In particular, the monomers (b) having ammonium groups may be compounds of the
general formulae H2C=C(R8)-CO_NR14-R12_NR133+ X- (Va) and/or
H2C=C(R8)-COO-R12-N R133+ X- (Vb), where R8 has the meaning given above, thus
is H or methyl, R12 is a preferably linear C1-C4-alkylene group and R14 is H
or a Ci-C4-
alkyl group, preferably H or methyl. The radicals R13, independently of one
another, are
C1-C4-alkyl, preferably methyl, or a group of the general formula ¨R18-S03H,
where R18
is a preferably linear to C4-alkylene group or a phenylene group, with the
proviso
that generally not more than one of the substituents R13 is a substituent
having sulfonic
acid groups. The three substituents R13 are particularly preferably methyl
groups, i.e. the
CA 02760734 2011-11-01
18
monomer has a group ¨N(CH3)3+. X- in the above formula is a monovalent anion,
for
example Cl-. X- can of course also be a corresponding fraction of a polyvalent
anion,
although this is not preferred. Examples of suitable monomers (b) of the
general formula
(Va) or (Vb) comprise salts of 3-trimethylammonium propylacrylamides or
2-trimethylammonium ethyl (meth)acrylates, for example the corresponding
chlorides,
such as 3-trimethylammonium propylacrylamide chloride (DIMAPAQUAT) and 2-
trimethylammonium ethyl methacrylate chloride (MADAME-QUAT).
The aforementioned hydrophilic monomers can of course be used not only in the
depicted acid or base form, but also in the form of corresponding salts. It is
also possible
to convert acidic or basic groups into corresponding salts after the formation
of the
polymer.
In one preferred embodiment of the invention, the copolymer according to the
invention
comprises at least one monomer (b) comprising acid groups. These are
preferably
monomers which comprise at least one group selected from the group of -COOH, -
S03H
or -P03H2, particular preference being given to monomers comprising COOH
groups
and/or -S03H groups, where the acid groups may also be present completely or
partially
in the form of the corresponding salts.
Preferably, at least one of the monomers (b) is a monomer selected from the
group of
(meth)acrylic acid, vinylsulfonic acid, allylsulfonic acid or 2-acrylamido-2-
methylpropanesulfonic acid (AMPS), particularly preferably acrylic acid and/or
APMS or
the salts thereof.
The amount of the monomers (b) in the copolymer according to the invention is
25 to
99.9% by weight, based on the total amount of all of the monomers in the
copolymer,
preferably 25 to 99.5% by weight. The exact amount is governed by the type and
the
desired intended use of the hydrophobically associating copolymers and is
established
accordingly by the person skilled in the art.
CA 02760734 2011-11-01
19
Monomers (c)
Apart from the hydrophilic monomers, the copolymers according to the invention
can
optionally comprise monoethylenically unsaturated monomers (c) different from
the
monomers (a) and (b). It is of course also possible to use mixtures of two or
more
different monomers (c).
The monomers (c) are in particular monomers which essentially have hydrophobic
character and are water-soluble only to a small extent. Generally, the
solubility of the
monomers (c) in water at room temperature is less than 100 g/I, preferably
less than 50
g/I and particularly preferably less than 20 g/I.
Examples of such monomers (c) comprise hydrocarbons, in particular styrene and
hydrophobic derivatives, such as, for example, a-methylstyrene or
alkylstyrenes, such
as 4-methylstyrene or 4-ethylstyrene.
Preferably, the further monomers are those of the general formula H2C=C(R9R17
(V1),
where R16 is H or methyl and R17 is a further group which essentially has
hydrophobic
character.
R17 is preferably carboxylic acid ester groups ¨000R18, where R18 is a
straight-chain or
branched, aliphatic, cycloaliphatic and/or aromatic hydrocarbon radical having
1 to 30
carbon atoms, preferably 2 to 12 carbon atoms. They are particularly
preferably an
aliphatic, straight-chain or branched hydrocarbon radical having 2 to 10
carbon atoms.
Examples of such monomers (c) comprise esters of (meth)acrylic acid, for
example alkyl
(meth)acrylates, such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl
(meth)acrylate, n-butyl (meth)acrylate, 2-ethylhexyl acrylate or 2-
propylheptyl acrylate.
R16 may also be carboxamide groups -CONHR17 or -CON(R17)2, with the proviso
that the
number of carbon atoms in the radical R18 or both radicals R18 together is at
least 3,
preferably at least 4, where the two radicals R18 together may also form a
ring.
CA 02760734 2011-11-01
Examples of such monomers comprise N-butyl (meth)acrylamide, N-
cyclohexyl(meth)acrylamide or N-benzyl(meth)acrylamide.
The monomers (c) also include those monomers which do have hydrophilic groups
5 besides hydrophobic groups, but in which the hydrophobic molecular
moieties dominate,
meaning that the monomers no longer have the required solubility in water and
thus are
not alone able to impart the required solubility to the polymer.
The type and amount of further monomers (c) is governed by the desired
properties and
10 the intended use of the copolymer and is 0 to 74.9% by weight, based on
the total mount
of all of the monomers in the copolymer, preferably 0 to 74.5% by weight.
Monomers (d)
15 In special cases, besides the monomers (a) and (b) and, if appropriate,
(c), the
copolymers according to the invention can optionally also comprise monomers
(d) which
have two or more, preferably two, ethylenically unsaturated groups. As a
result of this, a
certain crosslinking of the copolymer can be achieved provided that this has
no
undesired negative effects in the intended use of the copolymer. An
excessively high
20 degree of crosslinking, however, should in any case be avoided; in
particular, the
required solubility in water of the copolymer must not be impaired. Although
slight
crosslinking may be useful in individual cases, it is governed by the
particular application
of the copolymer and the person skilled in the art makes an appropriate
choice.
Examples of suitable monomers (d) comprise 1,4-butanediol di(meth)acrylate,
1,6-
hexanediol di(meth)acrylate, 1,3-butylene glycol di(meth)acrylate, neopentyl
glycol
di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol
di(meth)acrylate,
triethylene glycol di(meth)acrylate or oligoethylene glycol di(meth)acrylates,
such as, for
example, polyethylene glycol bis(meth)acrylate, N,N'-
methylenebis(meth)acrylamide,
ethylene glycol divinyl ether, triethylene glycol divinyl ether,
triallylamine, triallylamine
methammonium chloride, tetraallylammonium chloride or tris(2-
hydroxy)isocyanurate
tri(meth)acrylate.
CA 02760734 2011-11-01
21
If present at all, crosslinking monomers (d) are only used in small amounts.
Generally,
the amount of the monomers (d) should not exceed 1% by weight with regard to
the
amount of all of the monomers used. Preferably, not more than 0.5% by weight
and
particularly preferably not more than 0.1% by weight should be used. Type and
amount
of the crosslinker are established by the person skilled in the art depending
on the
desired application of the copolymer.
Preparation of the hydrophobically associating copolymers
The copolymers according to the invention can be prepared by methods known in
principle to the person skilled in the art by free-radical polymerization of
the monomers
(a) and (b) and optionally (c) and/or (d), for example by bulk polymerization,
solution
polymerization, gel polymerization, emulsion polymerization, dispersion
polymerization
or suspension polymerization, preferably in aqueous phase.
The synthesis of the monomers (a) of the formula (I) used according to the
invention are
particularly preferably prepared by the preparation process described above by
alkoxylation of alcohols (III), optionally followed by an etherification.
In one preferred embodiment, the preparation is carried out by means of gel
polymerization in aqueous phase, provided all of the monomers used have
adequate
solubility in water. For the gel polymerization, firstly a mixture of the
monomers, initiators
and other auxiliaries is prepared with water for an aqueous solvent mixture.
Suitable
aqueous solvent mixtures comprise water and water-miscible organic solvents,
where
the fraction of water is generally at least 50% by weight, preferably at least
80% by
weight and particularly preferably at least 90% by weight. Organic solvents to
be
mentioned here are in particular water-miscible alcohols such as methanol,
ethanol or
propanol. Acidic monomers can be completely or partially neutralized before
the
polymerization. Preference is given to a pH of ca. 4 to ca. 9. The
concentration of all of
the components with the exception of the solvents is usually ca. 25 to 60% by
weight,
preferably ca. 30 to 50% by weight.
CA 02760734 2011-11-01
22
The mixture is then polymerized photochemically and/or thermally, preferably
at -5 C to
50 C. If thermal polymerization is carried out, preference is given to using
polymerization initiators which start even at a comparatively low temperature,
such as,
for example, redox initiators. The thermal polymerization can be carried out
even at
room temperature or by heating the mixture, preferably to temperatures of not
more than
50 C. The photochemical polymerization is usually carried out at temperatures
of
from -5 to 10 C. Photochemical and thermal polymerization can particularly
advantageously be combined with one another by adding to the mixture both
initiators
for the thermal and also for the photochemical polymerization. The
polymerization is
started in this case initially photochemically at low temperatures, preferably
-5 to +10 C.
As a result of the heat of reaction which is liberated, the mixture warms up
and as a
result of this the thermal polymerization is additionally started. By means of
this
combination it is possible to achieve a conversion of more than 99%.
The gel polymerization generally takes place without stirring. It can take
place batchwise
by irradiating and/or heating the mixture in a suitable vessel at a layer
thickness of from
2 to 20 cm. The polymerization produces a solid gel. The polymerization can
also be
carried out continuously. For this, a polymerization apparatus is used which
has a
conveyor belt for receiving the mixture to be polymerized. The conveyor belt
is equipped
with devices for heating or for irradiation with UV radiation. Here, the
mixture is poured
using a suitable device at one end of the belt, the mixture is polymerized in
the course of
transportation in the belt direction and the solid gel can be removed at the
other end of
the belt.
After the polymerization, the gel is comminuted and dried. The drying should
preferably
take place at temperatures below 100 C. To avoid sticking together, a suitable
separating agent can be used for this step. The hydrophobically associating
copolymer
is obtained as powder.
Further details for carrying out a gel polymerization are disclosed, for
example, in
DE 10 2004 032 304 Al, sections [0037] to [0041].
CA 02760734 2011-11-01
23
Copolymers according to the invention in the form of alkaline-soluble, aqueous
dispersions can preferably be prepared by means of emulsion polymerization.
The
procedure for an emulsion polymerization using hydrophobically associating
monomers
is disclosed, for example, by WO 2009/019225 page 5, line 16 to page 8, line
13.
The copolymers according to the invention preferably have a number-average
molecular
weight Mn of from 50 000 to 20 000 000 g/mol.
Use of the hydrophobically associating copolymers
The hydrophobically associating copolymers according to the invention can be
used for
thickening aqueous phases.
By selecting the type and amount of the monomers (a) and (b) and optionally
(c) and/or
(d) it is possible to adapt the properties of the copolymers to the particular
technical
requirements.
The use concentration is established by the person skilled in the art
depending on the
type of aqueous phase to be thickened and also on the type of copolymer. As a
rule, the
concentration of the copolymer is 0.1 to 5% by weight, with regard to the
aqueous
phase, preferably 0.5 to 3% by weight and particularly preferably 1 to 2% by
weight.
The copolymers can be used here on their own or in combination with other
thickening
components, for example other thickening polymers. Furthermore, they can be
formulated for example together with surfactants to give a thickening system.
In
aqueous solution, the surfactants can form micelles and, together with the
micelles, the
hydrophobically associating copolymers can form a three-dimensional,
thickening
network.
For use, the copolymer can be dissolved directly in the aqueous phase to be
thickened.
It is also conceivable to predissolve the copolymer and then to add the formed
solution
to the system to be thickened.
CA 02760734 2011-11-01
24
The aqueous phases to be thickened may be, for example, liquid detergent and
cleaner
formulations, such as, for example, detergents, washing auxiliaries such as,
for
example, pre-spotters, fabric softeners, cosmetic formulations, pharmaceutical
formulations, foods, coating slips, formulations for the manufacture of
textiles, textile
printing pastes, printing inks, printing pastes for textile printing, paints,
pigment slurries,
aqueous formulations for foam generation, deicing mixtures, for example for
aircraft,
formulations for the construction industry, such as, for example, as additive
for aqueous
construction systems based on hydraulic binders such as cement, lime, gypsum
and
anhydrite and also in water-based paint and coating systems, formulations for
the
recovery of mineral oil, such as, for example, drilling fluids, formulations
for the acidizing
or fracturing or formulations for enhanced oil recovery.
Preferred use and copolymer (Al) preferred for this
In one preferred embodiment of the invention, the hydrophobically associating
copolymers according to the invention can be used for the development,
exploitation
and completion of subterranean mineral oil deposits and natural gas deposits.
The copolymers according to the invention can be used, for example, as
additive to
drilling fluids or during well cementing and also in particular for
fracturing.
The copolymers are particularly preferably used for enhanced oil recovery, and
specifically for so-called "polymer flooding". For this, an aqueous
formulation is used
which, besides water, comprises at least one hydrophobically associating
copolymer. It
is of course also possible to use mixtures of different copolymers. Moreover,
further
components can of course also be used. Examples of further components comprise
biocides, stabilizers or inhibitors. The formulation can preferably be
prepared by initially
introducing the water and sprinkling in the copolymer as powder. The aqueous
formulation should be subjected to the smallest possible shear forces.
The concentration of the copolymer should generally not exceed 5% by weight
with
regard to the sum of all of the constituents of the formulation and is usually
0.01 to 5%
1
=
CA 02760734 2011-11-01
by weight, in particular 0.1 to 5% by weight, preferably 0.5 to 3% by weight
and
particularly preferably 1 to 2% by weight.
The formulation is injected through at least one injection bore into the
mineral oil
5 deposit, and crude oil is removed from the deposit through at least one
production bore.
In this connection, the term "crude oil" is of course intended to mean not
only phase-
pure oil, but the term also comprises the customary crude oil/water emulsions.
A deposit
is generally provided with a plurality of injection bores and with a plurality
of production
bores. As a result of the pressure generated by the injected formulation, the
so-called
10 "polymer flood", the mineral oil flows in the direction of the
production bore and is
recovered via the production bore. The viscosity of the flood medium should be
adapted
as far as possible to the viscosity of the mineral oil in the mineral oil
deposit. The
viscosity can be adjusted in particular via the concentration of the
copolymer.
15 To increase the mineral oil yield, the polymer flooding can
advantageously be combined
with other techniques for enhanced oil recovery.
In one preferred embodiment of the invention, the "polymer flooding" using the
hydrophobically associating copolymers according to the invention can be
combined
20 with a preceding, so-called "surfactant flooding". Here, before the
polymer flooding, an
aqueous surfactant formulation is initially injected into the mineral oil
formation. As a
result of this, the interfacial tension between the water of formation and the
actual
mineral oil is reduced, thereby increasing the mobility of the mineral oil in
the formation.
By combining the two techniques it is possible to increase the mineral oil
yield.
Examples of suitable surfactants for the surfactant flooding comprise
surfactants having
sulfate groups, sulfonate groups, polyoxyalkylene groups, anionically modified
polyoxyalkylene groups, betaine groups, glucoside groups or amine oxide
groups, such
as, for example, alkylbenzenesulfonates, olefinsulfonates or
amidopropylbetaines.
Preferably, anionic and/or betainic surfactants can be used.
CA 02760734 2011-11-01
26
The person skilled in the art is aware of the details for the technical
procedure for the
"polymer flooding" and of the "surfactant flooding", and will use an
appropriate technique
depending on the type of deposit.
It is of course also possible to use surfactants and the copolymers according
to the
invention in a mixture.
For the just mentioned preferred use for the development, exploitation and
completion of
subterranean mineral oil deposits and natural gas deposits, the copolymers
described at
the outset may be used. The copolymer described below can preferably be used.
Accordingly, in one preferred embodiment, the invention relates to a
preferred,
hydrophobically associating copolymer (Al).
Preferably, the copolymers (Al) comprises only monomers (a), (b) and (c) and
particularly preferably only monomers (a) and (b). The monomers (a) are
preferably only
one or more monomers of the formula (I). Preferred monomers (a) of the formula
(I)
have already been mentioned at the start.
In the hydrophobically associating copolymer (Al), the monomers (a) are used
in an
amount of from 0.1 to 12% by weight, preferably 0.1 to 5% by weight,
particularly
preferably 0.2 to 3% by weight and very particularly preferably 0.3 to 2% by
weight.
The amount of all of the monomers (b) together in the case of the copolymer
(Al) is 70
to 99.9% by weight, preferably 80 to 99.8% by weight, with regard to the
amount of all of
the monomers used. The amount of all of the monomers (c) together is ¨ if
present ¨ not
more than 29.9% by weight, preferably not more than 19.9% by weight.
The copolymers (Al) usually comprise at least one neutral hydrophilic monomer
(b1).
Examples of suitable monomers (b1) comprise acrylamide and methacrylamide,
preferably acrylamide and derivatives thereof, such as, for example, N-
methyl(meth)acrylamide, N,N'-dimethyl(meth)acrylamide and N-
methylolacrylamide.
Also to be mentioned are N-vinyl derivatives, such as N-vinylformamide, N-
vinylacetamide, N-vinylpyrrolidone or N-vinylcaprolactam. Also to be mentioned
are
CA 02760734 2011-11-01
27
monomers having OH groups, such as hydroxyethyl (meth)acrylate, hydroxypropyl
(meth)acrylate, allyl alcohol, hydroxyvinyl ethyl ether, hydroxyvinyl propyl
ether or
hydroxyvinyl butyl ether. The monomer (b1) in copolymer (Al) is preferably
acrylamide
or derivatives thereof, particularly preferably acrylamide.
In a further embodiment of the invention, the monomer used in copolymer (Al)
is at
least one anionic monomer (b2) and/or at least one cationic monomer (b2).
The anionic monomers (b2) are monomers comprising acid groups, preferably
monomers which comprise at least one group selected from the group of -COOH, -
S03H
or -P03H2. The monomers (b2) are preferably monomers comprising carboxyl
groups ¨
COON and/or sulfonic acid groups ¨S03H, particularly preferably monomers
comprising
sulfonic acid groups ¨S03H. They may of course also be the salts of the acidic
monomers. Suitable counterions comprise in particular alkali metal ions such
as Li, Na+
or K+, and also ammonium ions such as NH4 + or ammonium ions with organic
radicals.
Examples of anionic monomers (b2) comprise acrylic acid or methacrylic acid,
crotonic
acid, itaconic acid, maleic acid or fumaric acid, monomers comprising sulfonic
acid
groups, such as vinylsulfonic acid, allylsulfonic acid, 2-acrylamido-2-
methylpropanesulfonic acid (AMPS), 2-methacrylamido-2-methylpropanesulfonic
acid,
2-acrylamidobutanesulfonic acid, 3-acrylamido-3-methylbutanesulfonic acid or 2-
acrylamido-2,4,4-trimethylpentanesulfonic acid or monomers comprising
phosphonic
acid groups, such as vinylphosphonic acid, allylphosphonic acid, N-
(meth)acrylamidoalkylphosphonic acids or (meth)acryloyloxyalkylphosphonic
acids.
Examples of preferred anionic monomers (b2) comprise acrylic acid,
vinylsulfonic acid,
allylsulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid (AMPS), 2-
acrylamidobutanesulfonic acid, 3-acrylamido-3-methylbutanesulfonic acid and 2-
acrylamido-2,4,4-trimethylpentanesulfonic acid, very particular preference
being given to
2-acrylamido-2-methylpropanesulfonic acid (AMPS).
Cationic monomers (b3) are generally monomers comprising ammonium groups,
preferably the aforementioned monomers of the
formulae
CA 02760734 2011-11-01
28
H2C=C(R8)-CO-NR14-R12_NR133+ X- (Va) and/or H2C=C(R7)-COO-R12-NR133+ X- (Vb),
where the radicals and the ranges and/or species preferred in each case are in
each
case as defined above. Examples of preferred monomers (b3) comprise 3-
trimethylammonium propylacrylamide chloride (DIMAPAQUAT).
Examples of such preferred copolymers (Al) comprise those which comprise at
least
one monomer (a) and acrylamide or one of the aforementioned acrylamide
derivatives,
in each case in the aforementioned amounts, and also copolymers which, besides
the
monomers (a), comprise as monomer (b), monomers comprising sulfonic acid
groups, in
particular the aforementioned monomers comprising sulfonic acid groups and
particularly preferably AMPS.
In a further preferred embodiment of the invention, the copolymer (Al)
comprises at
least one neutral monomer (b1) and at least one anionic monomer (b2) or at
least one
cationic monomer (b3), particularly preferably at least one neutral monomer
(b1) and at
least one anionic monomer (b2).
In this embodiment, it has proven useful to use the neutral monomer (b1) in an
amount
of from 20 to 95% by weight, preferably 30 to 90% by weight, and the anionic
monomer
(b2) and/or the cationic monomer (b3) in an amount of from 4.9 to 79.9% by
weight,
preferably 20 to 69.9% by weight, with the proviso that the total amount of
the
monomers (b) together is 70 to 99.9% by weight. The monomers (a) are used in
the
amounts given above.
Examples of such preferred copolymers (Al) comprise copolymers which comprise
at
least one monomer (a) and acrylamide or one of the aforementioned acrylamide
derivatives and also, as monomer (b2), monomers comprising sulfonic acid
groups, in
particular the aforementioned monomers comprising sulfonic acid groups and
particularly preferably AMPS.
In a further preferred embodiment of the invention, the copolymer (Al)
comprises at
least one neutral monomer (b1), at least one anionic monomer (b2) and at least
one
cationic monomer (b3).
CA 02760734 2011-11-01
29
In the case of this embodiment, it has proven useful to use the neutral
monomer (b1) in
an amount of from 20 to 95% by weight, preferably 30 to 90% by weight, and the
ionic
monomers (b2) and (b3) together in an amount of from 4.9 to 79.9% by weight,
preferably 20 to 69.9% by weight, with the proviso that the total amount of
the
monomers (b) together is 70 to 99.9% by weight. In one preferred embodiment,
the
molar ratio of the anionic monomers (b2) used and of the cationic monomers
(b3)
(b2)/(b3) is 0.5 to 1.5, preferably 0.7 to 1.3, particularly preferably 0.8 to
1.2 and for
example 0.9 to 1.1. This measure makes it possible for copolymers to be
obtained which
react particularly insensitively to salt content.
Examples of such preferred copolymers (Al) comprise copolymers which comprise
at
least one monomer (a) and acrylamide or one of the aforementioned acrylamide
derivatives and also, as monomer (b2) monomers comprising sulfonic acid
groups, in
particular the aforementioned monomers comprising sulfonic acid groups and
particularly preferably AMPS, and also, as monomer (b3), a salt of 3-
trimethylammonium
propylacrylamide.
The preparation of the copolymer (Al) preferably takes place photochemically
by means
of the gel polymerization already described.
The copolymers (Al) preferably have a weight-average molecular weight Mw of
from
1 000 000 g/mol to 20 000 000 g/mol, preferably 5 000 000 g/mol to 20 000 000
g/mol
and particularly preferably 10 000 000 g/mol to 20 000 000 g/mol.
The copolymers (Al) are notable for the described use for the development,
exploitation
and completion, in particular the enhanced oil recovery by particularly high
thermal
stability and salt stability. Furthermore, the inventive use of the monomers
(a) of the
formula (I) leads to copolymers with a particularly low gel fraction. This
effectively avoids
blockage of the mineral oil deposits.
CA 02760734 2011-11-01
Second preferred use and copolymers (A2) and (A3) preferred for this
In a second preferred embodiment of the invention, the copolymers according to
the
invention can be used as additive for aqueous construction systems which
comprise
5 hydraulic binder systems. Examples of such hydraulic binder systems
comprise cement,
lime, gypsum or anhydrite.
Examples of such construction systems comprise nonflowable construction
systems
such as tile adhesives, plasters or gap fillers, and flowable construction
systems such as
10 self-leveling floor screeds, sealing and repair mortars, flow screeds,
flow concrete, self-
compacting concrete, underwater concrete or underwater mortar.
The preferred use amounts of the copolymers according to the invention are
between
0.001 and 5% by weight, based on the dry weight of the construction system,
depending
15 on the type of use.
The hydrophobically associating copolymers according to the invention can also
be used
in combination with nonionic polysaccharide derivatives such as
methylcellulose (MC),
hydroxyethylcellulose (HEC), hydroxypropylcellulose (HPC), methylhydroxyethyl-
20 cellulose (MHEC), methylhydroxypropylcellulose (MHPC) and also WeIan gum
or Diutan
gum.
For dry mortar applications (e.g. tile adhesive, sealing mortar, plasters,
flow screeds),
the hydrophobically associating copolymers according to the invention are used
in
25 powder form. In this connection, it is advisable to select the size
distribution of the
particles by adapting the grinding parameters such that the average particle
diameter is
less than 100 pm and the fraction of particles with a particle diameter
greater than 200
pm is less than 2% by weight. Preference is given to those powders whose
average
particle diameter is less than 60 pm and the fraction of particles with a
particle diameter
30 greater than 120 pm is less than 2% by weight. Particular preference is
given to those
powders whose average particle diameter is less than 50 pm and the fraction of
particles
with a particle diameter greater than 100 pm is less than 2% by weight.
CA 02760734 2011-11-01
31
In the concrete, the copolymers according to the invention are preferably used
in the
form of aqueous solutions. Of suitability for preparing these solutions are
particularly the
relatively coarse granules of the copolymers according to the invention with
an average
particle diameter between 300 pm and 800 pm, where the fraction of particles
with a
particle diameter of less than 100 pm is less than 2% by weight. The same is
true if the
copolymers according to the invention are dissolved in other concrete
additives or
formulations of concrete additives (e.g. in a flow agent).
For the just mentioned preferred use, as additive for hydraulic binder-
comprising
aqueous construction systems, it is possible to use, besides the
hydrophobically
associating copolymers Al according to the invention, preferably the
hydrophobically
associating copolymer (A2) described below.
Accordingly, in a preferred embodiment, the invention relates to a preferred,
hydrophobically associating copolymer (A2). The preferred copolymer (A2) is
suitable in
particular as additive for nonflowable construction systems such as tile
adhesives,
plasters or gap fillers.
In the hydrophobically associating copolymer (A2), the monomers (a) are used
in an
amount of from 0.1 to 12% by weight, preferably 1 to 10% by weight and
particularly
preferably 1.5 to 8% by weight. Preferably, the copolymer (A2) comprises only
monomers (a), (b) and (d) and particularly preferably only monomers (a) and
(b).
The monomers (a) may be exclusively monomers (a) of the formula (1), in one
preferred
embodiment, however, in the case of copolymer (A2), the monomers (a) of the
formula
(1) can also be used in a mixture with other hydrophobically associating
monomers,
preferably those of the general formulae H2C=C(R1)-000-(-CH2-CH(R6)-0-)q-R7
(11a)
and/or H2C=C(R1)-0-(-CH2-CH(R6)-0-)q-R7 (11b). The meaning of the radicals and
indices and preferred ranges have already been described at the start. In such
a
mixture, the fraction of the monomers of the formula (I) should usually be at
least 25%
by weight with regard to the amount of all of the monomers (a), preferably 40
to 90% by
weight and for example 40 to 60% by weight. Preferred monomers (a) of the
formula (I)
have already been mentioned above.
CA 02760734 2011-11-01
32
The copolymer (A2) comprises as monomers (b) at least one neutral monomer (b1)
and
at least one anionic monomer (b2) and/or at least one cationic monomer (b3),
preferably
at least one neutral monomer (b1) and at least one cationic monomer (b3).
Examples of suitable monomers (b1), (b2) and (b3) have already been
specified..
The neutral monomers (b1) in copolymer (A2) are preferably acrylamide or
methacrylamide and derivatives thereof, such as, for example, N-
methyl(meth)acrylamide, N,N'-dimethyl(meth)acrylamide, N-methylolacrylamide
and N-
vinyl derivatives such as N-vinylformamide, N-vinylacetamide, N-
vinylpyrrolidone or N-
vinylcaprolactam. Preferred monomers (b1) in the case of copolymer (A2) are
acrylamide, methacrylamide and N-vinylpyrrolidone.
The anionic monomers (b2) in copolymer (A2) are monomers comprising acid
groups,
preferably monomers which comprise at least one group selected from the group
of
carboxyl groups ¨COOH, sulfonic acid groups ¨S03H or phosphonic acid
groups -P03H2.
The anionic monomers (b2) in the copolymer (A2) are preferably monomers
comprising
sulfonic acid groups ¨S03H. Examples of preferred monomers comprise
vinylsulfonic
acid, allylsulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid (AMPS), 2-
acrylamidobutanesulfonic acid, 3-acrylamido-3-methylbutanesulfonic acid and 2-
acrylamido-2,4,4-trimethylpentanesulfonic acid, preference being given to 2-
acrylamido-
2-methylpropanesulfonic acid (AMPS).
The cationic monomers (b3) in copolymer (A2) are preferably the aforementioned
monomers of the formulae H2C=C(R8)-CO-NR14-R12-NR133+ X- (Va) and/or
H2C=C(R8)-COO-R12-NR133+ X- (Vb), where the radicals and the ranges and/or
species
preferred in each case are in each case as defined above. Particular
preference is given
to 3-trimethylammonium propylacrylamide chloride (DIMAPAQUAT).
CA 02760734 2011-11-01
33
In the copolymers (A2), the amount of the anionic monomers (b2) and of the
cationic
monomers (b3) is generally 25 to 80% by weight, with regard to the sum of all
of the
monomers, preferably 40 to 75% by weight, particularly preferably 45 to 70% by
weight
and that of the neutral monomers (b1) is 15 to 60% by weight, preferably 20 to
50% by
weight, with the proviso that the sum of the monomers (b1) and (b2) and (b3)
together is
70 to 99.9% by weight. The monomers (a) are used in the amounts mentioned at
the
start.
Preferred copolymers (A2) comprise either an anionic monomer (b2) or a
cationic
monomer (b3) in the amounts already given. If a mixture of (b2) and (b3) is
used, the
weight ratio (b2)/(b3) can in principle be chosen freely.
For the just mentioned preferred use as additive for hydraulic binder-
comprising
aqueous construction systems, the hydrophobically associating copolymer (A3)
described below can also be used.
Accordingly, in a third preferred embodiment, the invention relates to a
hydrophobically
associating copolymer (A3). The preferred copolymer (A3) is suitable in
particular as
additive for flowable construction systems, in particular for concrete, flow
screeds, self-
leveling troweling compositions and sealing mortars.
In the case of the hydrophobically associating copolymer (A3), the monomers
(a) are
used in an amount of from 0.1 to 12% by weight, preferably 1 to 10% by weight
and
particularly preferably 1.5 to 8% by weight. Preferably, the copolymer (A3)
comprises
only monomers (a), (b) and (d) and particularly preferably only monomers (a)
and (b).
The monomers (a) may be exclusively monomers (a) of the formula (I), in a
preferred
embodiment in the case of copolymer (A3), however, the monomers (a) of the
formula
(I) can also be used in a mixture with other hydrophobically associating
monomers,
preferably those of the general formula H2C=C(R1)-000-(-CH2-CH(R6)-0-)q-R7
(11a)
and/or H2C=C(R1)-0-(-CH2-CH(R6)-0-)q-R7 (11b). The meaning of the radicals and
indices and also preferred ranges have already been described at the start. In
the case
of such a mixture, the fraction of the monomers of the formula (1) should
generally be at
CA 02760734 2011-11-01
34
least 25% by weight with regard to the amount of all of the monomers (a),
preferably 40
to 90% by weight and for example 40 to 60% by weight. Preferred monomers (a)
of the
formula (I) have already been mentioned above.
The copolymer (A3) comprises as monomers (b) at least one neutral monomer (b1)
and
at least one anionic monomer (b2). Examples of suitable monomers (b1) and (b2)
have
already been given.
The neutral monomers (b1) in copolymer (A3) are acrylamide or methacrylamide
and
derivatives thereof, such as, for example, N-methyl(meth)acrylamide,
N,N'-dimethyl(meth)acrylamide, N-methylolacrylamide and N-vinyl derivatives
such as
N-vinylformamide, N-vinylacetamide, N-vinylpyrrolidone or N-vinylcaprolactam.
Preferred monomers (b1) in copolymer (A3) are acrylamide, methacrylamide and N-
vinylpyrrolidone.
The anionic monomers (b2) in copolymer (A3) are monomers comprising acid
groups,
preferably monomers which comprise at least one group selected from the group
of
carboxyl groups ¨COOH, sulfonic acid groups ¨S03H or phosphonic acid
groups -P03H2.
Preferably, in copolymer (A3) the monomers (b2) are monomers comprising
sulfonic
acid groups ¨S03H. Examples of preferred monomers comprise vinylsulfonic acid,
allylsulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid (AMPS), 2-
acrylamidobutanesulfonic acid, 3-acrylamido-3-methylbutanesulfonic acid and 2-
acrylamido-2,4,4-trimethylpentanesulfonic acid, preference being given to 2-
acrylamido-
2-methylpropanesulfonic acid (AMPS).
In the preferred copolymers (A3), the amount of anionic monomers (b2) is
generally 25
to 94.9% by weight, with regard to the sum of all of the monomers, preferably
50 to 90%
by weight, particularly preferably 60 to 90% by weight and that of the neutral
monomers
(b1) is 5 to 50% by weight, preferably 5 to 30% by weight, with the proviso
that the sum
of the monomers (b1) and (b2) together is 70 to 99.9% by weight. The monomers
(a) are
used in the amounts mentioned at the start.
CA 02760734 2011-11-01
For the use as additive for aqueous construction systems, it may be
advantageous to
use additionally crosslinking monomers (d). These give the hydrophobically
associating
copolymers (Al), (A2) and (A3) according to the invention a slightly branched
or
5 crosslinked structure.
Examples of preferred monomers (d) comprise triallylamine,
triallylmethylammonium
chloride, tetraallylammonium chloride, N,N'-methylenebisacrylamide,
triethylene glycol
bismethacrylate, triethylene glycol bisacrylate, polyethylene glycol(400)
bismethacrylate
10 and polyethylene glycol(400) bisacrylate.
The amount of monomers (d) is determined by the person skilled in the art
depending on
the desired properties of the copolymers. However, the monomers (d) must only
be
used in amounts such that the solubility in water of the hydrophobically
associating
15 copolymers according to the invention is not impaired. As a rule, the
amount of the
monomers (d) should not exceed 1% by weight with regard to the amount of all
of the
monomers used. Preferably, not more than 0.5% by weight and particularly
preferably
not more than 0.1% by weight should be used; however, a person skilled in the
art can
easily determine the maximum amount of monomers (d) that can be used.
Third preferred use and copolymers (A4) preferred for this
A fourth preferred embodiment of the invention deals with a hydrophobically
associating
copolymer (A4). The copolymer (A4) is usually an alkali-soluble dispersion.
Copolymers
of this type are suitable in particular for use as thickeners in the field of
detergents and
cleaners, cosmetic formulations and technochemical applications.
Besides the monomers (a), the copolymer (A4) comprises at least one monomer
(b)
having acid groups, and at least one monomer (c). It is of course also
possible for
several different monomers (c) to be used.
Preferred monomers (a) have already been mentioned at the start.
CA 02760734 2011-11-01
36
The monomers (b) having acid groups in copolymer (A4) are preferably the
monomers
(b2) already cited above. These are preferably monomers having carboxylic acid
groups, such as, for example, acrylic acid, methacrylic acid, crotonic acid,
itaconic acid,
maleic acid or fumaric acid, particularly preferably (meth)acrylic acid.
The monomers (c) are preferably at least one (meth)acrylic acid ester of the
general
formula H2C=C(R16)-000R18, where R16 and R18 are as defined above. Examples of
such monomers (c) comprise esters of (meth)acrylic acid, for example alkyl
(meth)acrylates, such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl
(meth)acrylate, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate or 2-
propylheptyl
(meth)acrylate.
The copolymer (A4) preferably comprises at least one (meth)acrylic acid ester
in which
R9 is an aliphatic, straight-chain or branched hydrocarbon radical having 2 to
10 carbon
atoms, preferably 4 to 8 carbon atoms. Examples comprise ethyl (meth)acrylate,
n-propyl (meth)acrylate, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate
or
2-propylheptyl (meth)acrylate.
In the hydrophobically associating copolymer (A4), the monomers (a) are used
in an
amount of from 0.1 to 20% by weight, preferably 0.5 to 15% by weight and
particularly
preferably 2 to 12% by weight, in each case based on the total amount of all
monomers
in the copolymer.
The amount of monomers (b) in the copolymers (A4) is 25 to 94.9% by weight,
preferably 25 to 50% by weight and particularly preferably 25 to 40% by
weight.
The amount of the monomers (c) in the copolymers (A4) is 5 to 74.9% by weight,
preferably 25 to 74.5% by weight and particularly preferably 50 to 70% by
weight.
The copolymers (A4) according to the invention are particularly suitable as
thickeners or
rheology modifiers in coating slips, for example for detergents, washing
auxiliaries such
as, for example, pre-spotters, fabric softeners, cosmetic formulations,
pharmaceutical
formulations, foods, coating slips, formulations for textile production,
textile printing
CA 02760734 2011-11-01
37
pastes, printing inks, printing pastes for textile printing, paints, pigment
slurries, aqueous
formulations for generating foam, deicing mixtures, for example for aircraft,
formulations
for the construction industry, such as, for example, as additive for aqueous
construction
systems based on hydraulic binders such as cement, lime, gypsum and anhydrite,
and
also in water-based paint and coating systems.
Particular preference is given to the use in liquid detergents and cleaners.
Besides a
copolymer (A4), liquid detergents and cleaners comprise one or more anionic,
nonionic,
cationic and/or amphoteric surfactants as well as other typical detergent
additives.
Preference is given to mixtures of anionic and nonionic surfactants. The total
surfactant
content of the liquid detergents or cleaners is preferably 0.5 to 80% by
weight and
particularly preferably 0.5 to 50% by weight, based on the total liquid
detergent or
cleaner. Suitable surfactants are known to the person skilled in the art and
disclosed, for
example, in WO 2009/019225, page 8, line 34 to page 12, line 37.
The further components are one or more substances selected from the group of
builders, bleaches, bleach activators, enzymes, electrolytes, nonaqueous
solvents, pH
extenders, fragrances, perfume carriers, fluorescent agents, dyes, hydrotopes,
foam
inhibitors, silicone oils, antiredeposition agents, optical brighteners,
graying inhibitors,
antishrink agents, crease protection agents, color transfer inhibitors,
antimicrobial active
ingredients, germicides, fungicides, antioxidants, corrosion inhibitors,
antistats, ironing
aids, phobicizing and impregnation agents, antiswell and antislip agents and
also UV
absorbers. Such detergent additives are known to the person skilled in the art
and
disclosed, for example, in WO 2009/019225, page 12, line 39 to page 24, line
4.
The following examples are intended to illustrate the invention in more
detail:
Part A) Preparation of the monomers (I)
Preparation of a hydroxybutyl vinyl ether alkoxylate having 22 EO units and 8
Pe units
(monomer M1):
I
CA 02760734 2011-11-01
38
52.3 g of hydroxybutyl vinyl ether were initially introduced into a 1 I
stirred autoclave
made of stainless steel. 2.99 g of KOMe (32% strength in Me0H) were then
metered in
and the methanol was drawn off at 80 C and ca. 30 mbar. The mixture was then
heated
to 140 C, the reactor was flushed with nitrogen and a nitrogen pressure of 1.0
bar was
established. 436 g of EO were then metered in over the course of ca. 3.5 h.
After a
postreaction for half an hour at 140 C, the reactor was cooled to 125 C and a
total of
310 g of pentene oxide were metered in over the course of 3.0 h. The
postreaction ran
overnight.
The product had an OH number of 34.2 mg KOH/g (theory: 31.6 mg KOH/g). The OH
number was determined by means of the ESA method.
Preparation of a hydroxybutyl vinyl ether alkoxylate with 22 EO units and 12
Pe0 units
(monomer M2):
44.1 g of hydroxybutyl vinyl ether were initially introduced into a 1 I
stirred autoclave
made of stainless steel. 3.12 g of KOMe (32% strength in Me0H) were then
metered in
and the methanol was drawn off at 80 C and ca. 30 mbar. The mixture was then
heated
to 140 C, the reactor was flushed with nitrogen and a nitrogen pressure of 1.0
bar was
established. 368 g of EO were then metered in over the course of ca. 3 h.
After a
postreaction for half an hour at 140 C, the reactor was cooled to 125 C and a
total of
392 g of pentene oxide were metered in over the course of 3.5 h. The
postreaction ran
overnight.
The product had an OH number of 31.9 mg KOH/g (theory: 26.5 mg KOH/g). The OH
number was determined by means of the ESA method.
Preparation of a hydroxybutyl vinyl ether alkoxylate with 22 EO units and 16
Pe0 units
(monomer M3):
37.8 g of hydroxybutyl vinyl ether were initially introduced into a 1 I
stirred autoclave
made of stainless steel. 3.01 g of KOMe (32% strength in Me0H) were then
metered in
and the methanol was drawn off at 80 C and ca. 30 mbar. The mixture was then
heated
CA 02760734 2011-11-01
39
to 140 C, the reactor was flushed with nitrogen and a nitrogen pressure of 1.0
bar was
established. 315 g of EO were then metered in over the course of ca. 3 h.
After a
postreaction for half an hour at 140 C, the reactor was cooled to 125 C and a
total of
448 g of pentene oxide were metered in over the course of 4.5 h. The
postreaction ran
overnight.
The product had an OH number of 25.2 mg KOH/g (theory: 22.7 mg KOH/g). The OH
number was determined by means of the ESA method.
Preparation of a hydroxybutyl vinyl ether alkoxylate with 22 EO units and 20
Pe units
(monomer M4):
33.2 g of hydroxybutyl vinyl ether were initially introduced into a 1 I
stirred autoclave
made of stainless steel. 3.01 g of KOMe (32% strength in Me0H) were then
metered in
and the methanol was drawn off at 80 C and ca. 30 mbar. The mixture was then
heated
to 140 C, the reactor was flushed with nitrogen and a nitrogen pressure of 1.0
bar was
established. 277 g of EO were then metered in over the course of ca. 2.5 h.
After a
postreaction for half an hour at 140 C, the reactor was cooled to 125 C and a
total of
492 g of pentene oxide were metered in over the course of 5 h. The
postreaction ran
overnight.
The product had an OH number of 23.2 mg KOH/g (theory: 20.0 mg KOH/g). The OH
number was determined by means of the ESA method.
Preparation of a hydroxybutyl vinyl ether alkoxylate with 68 EO units and 8
Pe0 units
(monomer M5):
24.3 g of hydroxybutyl vinyl ether were initially introduced into a 1 I
stirred autoclave
made of stainless steel. 2.98 g of KOMe (32% strength in Me0H) were then
metered in
and the methanol was drawn off at 80 C and ca. 30 mbar. The mixture was then
heated
to 140 C, the reactor was flushed with nitrogen and a nitrogen pressure of 1.0
bar was
established. 627 g of EO were then metered in over the course of ca. 5.5 h.
After a
postreaction for half an hour at 140 C, the reactor was cooled to 125 C and a
total of
CA 02760734 2011-11-01
144 g of pentene oxide were metered in over the course of 2.5 h. The
postreaction ran
overnight.
The product had an OH number of 17.6 mg KOH/g (theory: 14.7 mg KOH/g). The OH
5 number was determined by means of the ESA method.
Preparation of a hydroxybutyl vinyl ether alkoxylate with 22 EO units and 12
Pe0 units
(monomer M6):
10 22.5 g of hydroxybutyl vinyl ether were initially introduced into a 1 I
stirred autoclave
made of stainless steel. 3.01 g of KOMe (32% strength in Me0H) were then
metered in
and the methanol was drawn off at 80 C and ca. 30 mbar. The mixture was then
heated
to 140 C, the reactor was flushed with nitrogen and a nitrogen pressure of 1.0
bar was
established. 580 g of EO were then metered in over the course of ca. 5 h.
After a
15 postreaction for half an hour at 140 C, the reactor was cooled to 125 C
and a total of
200 g of pentene oxide were metered in over the course of 3.0 h. The
postreaction ran
overnight.
The product had an OH number of 16.8 mg KOH/g (theory: 13.5 mg KOH/g). The OH
20 number was determined by means of the ESA method.
Preparation of a hydroxybutyl vinyl ether alkoxylate with 132 EO units and 8
Pe0 units
(monomer M7):
25 14.1 g of hydroxybutyl vinyl ether were initially introduced into a 1 I
stirred autoclave
made of stainless steel. 3.02 g of KOMe (32% strength in Me0H) were then
metered in
and the methanol was drawn off at 80 C and ca. 30 mbar. The mixture was then
heated
to 140 C, the reactor was flushed with nitrogen and a nitrogen pressure of 1.0
bar was
established. 706 g of EO were then metered in over the course of ca. 8 h.
After a
30 postreaction for half an hour at 140 C, the reactor was cooled. On the
next day, at
125 C, a total of 83.6 g of pentene oxide were metered in over the course of
2.0 h. A
postreaction of 5 hours at 125 C followed.
CA 02760734 2011-11-01
41
The product had an OH number of 10.2 mg KOH/g (theory: 8.5 mg KOH/g). The OH
number was determined by means of the ESA method.
The data for the synthesized monomers M1 to M7 are summarized in table 1
below. All
monomers have a terminal OH group.
Monomer Alcohol Block 1 Block 2 OH number
No. [mg KOH/g]
Number of Alkylene oxide Number of
EO units units
M1 4-hydroxybutyl vinyl ether 22 pentene oxide 8 34.2
M2 4-hydroxybutyl vinyl ether 22 pentene oxide 12 31.9
M3 4-hydroxybutyl vinyl ether 22 pentene oxide 16 25.2
M4 4-hydroxybutyl vinyl ether 22 pentene oxide 20 23.2
M5 4-hydroxybutyl vinyl ether 68 pentene oxide 8 17.6
M6 4-hydroxybutyl vinyl ether 68 pentene oxide 12 16.8
M7 4-hydroxybutyl vinyl ether 132 pentene oxide 8 10.2
Table 1: Synthesized monomers (I)
For the comparative experiments, commercially available, hydrophobically
associating
monomers of the following general formula were used: H2C=C(CH3)-000-(E0),-R.
R and x here in the monomers M8 and M9 have the following meaning:
M8: x = 25, R=tristyrylphenyl
M9: x = 7, R= n-dodecyl
Part B) Preparation of the hydrophobically associating copolymers
Part B-1) Preparation of hydrophobically associating copolymers of the type
(Al)
Example 1:
CA 02760734 2011-11-01
42
Hydrophobically associating amphoteric copolymer of the type (Al) of
acrylamide
(35.9% by weight), an anionic monomer (acrylamido-2-methylpropanesulfonic
acid, Na
salt, 32.1% by weight), a cationic monomer (3-trimethylammonium
propylacrylamide
chloride, 31.0% by weight) and the monomer M1 according to the invention (1%
by
weight)
The following components were mixed together in a 2 I three-necked flask
fitted with
stirrer and thermometer:
139.1 g acrylamido-2-methylpropanesulfonic acid, Na salt (58% strength by
weight solution in water; 17.6 mol%),
1.2 g silicone defoamer,
2.4 g pentasodium diethylenetriaminepentaacetate (complexing agent),
111.6 g 3-trimethylammonium propylacrylamide chloride (60% strength by
weight
solution in water; 18.8 mole/0),
160.1 g acrylamide (50% strength by weight solution in water; 63.5
mole/0),
2.1 g monomer Ml,
12g urea
1.5 g of sodium hypophosphite (0.1% strength by weight solution in water) were
added
as molecular weight regulator. The solution was adjusted to pH 6 using 20%
strength
sodium hydroxide solution, rendered inert by flushing for 10 minutes with
nitrogen and
cooled to ca. 5 C. The solution was transferred to a plastic container and
then, in
succession, 150 ppm of 2,2'-azobis(2-amidinopropane) dihydrochloride (as 1%
strength
by weight solution), 10 ppm of tert-butyl hydroperoxide (as 0.1% strength by
weight
solution) and 20 ppm of sodium hydroxymethanesulfinate (as 1% strength by
weight
solution) were added. The polymerization was started by irradiating with UV
light (two
Philips tubes; Cleo Performance 40 W). After ca. 2 h, the hard gel was removed
from
the plastic container and cut using scissors into gel cubes measuring ca. 5 cm
x 5 cm x
5 cm. Before the gel cubes were comminuted using a conventional meat grinder,
they
were coated with a standard commercial release agent. The release agent is a
polydimethylsiloxane emulsion which was diluted 1:20 with water. The resulting
gel
CA 02760734 2011-11-01
43
granules were slump uniformly on drying meshes and dried to constant weight in
a
convection drying oven at ca. 90 to 120 C in vacuo.
Comparative example 1:
Polymer analogous to example 1, but without hydrophobically associating
monomer
The following components were mixed together in a 2 I three-necked flask
fitted with
stirrer and thermometer:
139.1 g acrylamido-2-methylpropanesulfonic acid, Na salt (58% strength
by
weight solution in water; 17.4 mol%),
1.2 g silicone defoamer,
2.4 g pentasodium diethylenetriaminepentaacetate (complexing agent),
111.6 g 3-trimethylammonium propylacrylamide chloride (60% strength by
weight
solution in water; 18.5 mol%),
164.5 g acrylamide (50% strength by weight solution in water; 64.2
mol%),
12g urea
The solution was adjusted to pH 6 using 20% strength sodium hydroxide
solution,
rendered inert by flushing for 10 minutes with nitrogen and cooled to ca. 5 C.
The
solution was transferred to a plastic container and then, in succession, 150
ppm of 2,2'-
azobis(2-amidinopropane) dihydrochloride (as 1% strength by weight solution),
10 ppm
of tert-butyl hydroperoxide (as 0.1% strength by weight solution) and 20 ppm
of sodium
hydroxymethanesulfinate (as 1% strength by weight solution) were added. The
polymerization was started by irradiating with UV light (two Philips tubes;
Cleo
Performance 40 W). After ca. 2 h, the hard gel was removed from the plastic
container
and cut using scissors into gel cubes measuring ca. 5 cm x 5 cm x 5 cm. Before
the gel
cubes were comminuted using a conventional meat grinder, they were coated with
a
standard commercial release agent. The release agent is a polydimethylsiloxane
emulsion which was diluted 1:20 with water. The resulting gel granules were
distributed
uniformly on drying meshes and dried to constant weight in a convection drying
oven at
ca. 90 to 120 C in vacuo.
I
CA 02760734 2011-11-01
44
Comparative example 2:
Polymer analogous to example 1, but instead of the hydrophobically associating
monomer according to the invention, monomer M8 was used
The following components were mixed together in a 2 I three-necked flask
fitted with
stirrer and thermometer:
139.1 g acrylamido-2-methylpropanesulfonic acid, Na salt (58% strength
by
weight solution in water; 17.6 mol%),
1.2 g silicone defoamer,
2.4 g pentasodium diethylenetriaminepentaacetate (complexing agent),
111.6 g 3-trimethylammonium propylacrylamide chloride (60% strength by
weight
solution in water; 18.8 mol%),
155.2 g acrylamide (50% strength by weight solution in water; 63.5 mol%),
3.5 g monomer M8,
12g urea
1.5 g of sodium hypophosphite (0.1% strength by weight solution in water) were
added
as molecular weight regulator. The solution was transferred to a plastic
container and
then, in succession, 150 ppm of 2,2'-azobis(2-amidinopropane) dihydrochloride
(as 1%
strength by weight solution), 10 ppm of tert-butyl hydroperoxide (as 0.1%
strength by
weight solution) and 20 ppm of sodium hydroxymethanesulfinate (as 1% strength
by
weight solution) were added. The polymerization was started by irradiating
with UV light
(two Philips tubes; Cleo Performance 40 W). After ca. 2 h, the hard gel was
removed
from the plastic container and cut using scissors into gel cubes measuring ca.
5 cm x 5
cm x 5 cm. Before the gel cubes were comminuted using a conventional meat
grinder,
they were coated with a standard commercial release agent. The release agent
is a
polydimethylsiloxane emulsion which was diluted 1:20 with water. The resulting
gel
granules were distributed uniformly on drying meshes and dried to constant
weight in a
convection drying oven at ca. 90 to 120 C in vacuo.
I
CA 02760734 2011-11-01
Comparative example 3:
Polymer analogous to example 1, but instead of the hydrophobically associating
monomer according to the invention, the monomer M9 was used
5
The following components were mixed together in a 2 I three-necked flask
fitted with
stirrer and thermometer:
139.0 g acrylamido-2-methylpropanesulfonic acid, Na salt (58% strength
by
10 weight solution in water; 17.6 mol%),
1.2 g silicone defoamer,
2.4 g pentasodium diethylenetriaminepentaacetate (complexing agent),
111.6 g 3-trimethylammonium propylacrylamide chloride (60% strength by
weight
solution in water; 18.8 mol%),
15 155.2 g acrylamide (50% strength by weight solution in water; 63.4
mol%),
2.2 g monomer M9,
12g urea
1.5 g of sodium hypophosphite (0.1% strength by weight solution in water) were
added
20 as molecular weight regulator. The solution was transferred to a plastic
container and
then, in succession, 150 ppm of 2,2'-azobis(2-amidinopropane) dihydrochloride
(as 1%
strength by weight solution), 10 ppm of tett-butyl hydroperoxide (as 0.1%
strength by
weight solution) and 20 ppm of sodium hydroxymethanesulfinate (as 1% strength
by
weight solution) were added. The polymerization was started by irradiating
with UV light
25 (two Philips tubes; Cleo Performance 40 W). After ca. 2 h, the hard gel
was removed
from the plastic container and cut using scissors into gel cubes measuring ca.
5 cm x 5
cm x 5 cm. Before the gel cubes were comminuted using a conventional meat
grinder,
they were coated with a standard commercial release agent. The release agent
is a
polydimethylsiloxane emulsion which was diluted 1:20 with water. The resulting
gel
30 granules were distributed uniformly on drying meshes and dried to
constant weight in a
convection drying oven at ca. 90 to 120 C in vacuo.
CA 02760734 2011-11-01
=
46
Examples 2 to 8:
Hydrophobically associating copolymers of the type (Al) of acrylamide (48% by
weight)
and acrylamido-2-methylpropanesulfonic acid, Na salt (50% by weight) and a
hydrophobically associating monomer according to the invention (2% by weight)
The following components were mixed together in a 2 I three-necked flask
fitted with
stirrer and thermometer:
290 g distilled water,
242.5 g acrylamido-2-methylpropanesulfonic acid, Na salt (58%
strength by
weight solution in water; 24.7 mol%),
1.2 g silicone defoamer,
2.4 g pentasodium diethylenetriaminepentaacetate (complexing
agent),
228.8 g acrylamide (50% strength by weight solution in water; 75.2 mol%),
4.6 g monomers of one of the monomers M1 to M7 (as in table)
The solution was adjusted to pH 6 using 20% strength sodium hydroxide
solution,
rendered inert by flushing for 10 minutes with nitrogen and cooled to ca. 5 C.
The
solution was transferred to a plastic container and then, in succession, 200
ppm of 2,2'-
azobis(2-amidinopropane) dihydrochloride (as 1% strength by weight solution),
10 ppm
of tert-butyl hydroperoxide (as 0.1% strength by weight solution), 5 ppm of
FeSO4*7H20
(as 1% strength by weight solution) and 6 ppm of sodium bisulfite (as 1%
strength by
weight solution) were added. The polymerization was started by irradiating
with UV light
(two Philips tubes; Cleo Performance 40 W). After ca. 2 h, the hard gel was
removed
from the plastic container and cut using scissors into gel cubes measuring ca.
5 cm x 5
cm x 5 cm. Before the gel cubes were comminuted using a conventional meat
grinder,
they were coated with a standard commercial release agent. The release agent
is a
polydimethylsiloxane emulsion which was diluted 1:20 with water. The resulting
gel
granules were distributed uniformly on drying meshes and dried to constant
weight in a
convection drying oven at ca. 90 to 120 C in vacuo.
CA 02760734 2011-11-01
47
Part B-2) Preparation of hydrophobically associating copolymers of the types
(A2) and
(A3)
Example 9
Hydrophobically associating copolymer of the type (A2) of acrylamide (33% by
weight),
3-(acrylamino)propyltrimethylammonium chloride (57% by weight), acrylic acid
(2% by
weight) and a mixture of the hydrophobically associating monomer M8 (3% by
weight)
and the monomer M5 according to the invention (5% by weight)
The following components were mixed together in a 2 I three-necked flask
fitted with
stirrer and thermometer:
170 g distilled water,
1.6g silicone defoamer,
2.4 g pentasodium diethylenetriaminepentaacetate (complexing agent),
5.8 g acrylic acid (99.5% strength by weight; 3.6 mol%),
273.6 g 3-(acrylamino)propyltrimethylammonium chloride (60% strength by
weight
solution in water; 35.7 mol%),
190.5 g acrylamide (50% strength by weight solution in water; 60.3 mol%),
14.4 g monomer M8 (60% strength by weight solution in water),
14.4 g monomer M5 (0.2 mol%),
0.5 g of formic acid (10% strength by weight solution in water) was added as
molecular
weight regulator. The solution was adjusted to pH 7 using 20% strength sodium
hydroxide solution, rendered inert by flushing for 5 minutes with nitrogen and
cooled to
ca. 5 C. The solution was transferred to a plastic container and then, in
succession, 250
ppm of 2,2'-azobis(2-amidinopropane) dihydrochloride (as 1% strength by weight
solution), 20 ppm of tett-butyl hydroperoxide (as 0.1% strength by weight
solution) and
30 ppm of sodium bisulfite (as 1% strength by weight solution) were added. The
polymerization was started by irradiating with UV light (two Philips tubes;
Cleo
Performance 40 W). After ca. 2 h, the hard gel was removed from the plastic
container
and cut using scissors into gel cubes measuring ca. 5 cm x 5 cm x 5 cm. Before
the gel
1
CA 02760734 2011-11-01
48
cubes were comminuted using a standard commercial meat grinder, they were
coated
with a standard commercial release agent. The release agent is a
polydimethylsiloxane
emulsion which was diluted 1:20 with water. The resulting gel granules were
distributed
uniformly on drying meshes and dried to constant weight in a convection drying
oven at
ca. 90 to 120 C in vacuo.
Example 10:
Hydrophobically associating copolymer of the type (A2) of dimethylacrylamide
(32% by
weight), 3-(acrylamino)propyltrimethylammonium chloride (59% by weight),
acrylic acid
(2% by weight) and a mixture of the hydrophobically associating monomer M8 (2%
by
weight) and a monomer M5 according to the invention (5% by weight)
The procedure was as in example 9, except that the following components were
used:
170 g distilled water,
1.6 g silicone defoamer,
6.9 g acrylic acid (99.5% strength by weight; 4.3 mol%),
338.2 g 3-(acrylamino)propyltrimethylammonium chloride (60% strength by
weight
solution in water; 44.6 mol%),
111.2 g dimethylacrylamide (50.6 mol%),
14.4 g monomer M8 (60% strength by weight solution in water),
17.2 g monomer M5
Example 11:
Hydrophobically associating copolymer of type (A2) of acrylamide (10% by
weight),
N-vinylpyrrolidone (28% by weight), acrylamido-2-methylpropanesulfonic acid,
Na salt
(50% by weight), acrylic acid (2% by weight) and the monomer M6 according to
the
invention (10% by weight)
The procedure was as in example 9, except that the following components were
used:
CA 02760734 2011-11-01
49
170 g distilled water,
1.6 g silicone defoamer,
2.4 g pentasodium diethylenetriaminepentaacetate,
6.1 g acrylic acid (99.5% strength by weight; 4.2 mol%),
336.1 g acrylamido-2-methylpropanesulfonic acid, Na salt (58% strength by
weight solution in water; 36.2 mol%),
60.9 g acrylamide (50% strength by weight solution in water; 21.2
mol%),
85.9 g N-vinylpyrrolidone (38.1 mol%)
30.4 g monomer M6
Example 12:
Hydrophobically associating copolymer of the type (A2) of acrylamide (10% by
weight),
N-vinylpyrrolidone (38.1% by weight), 3-(acrylamino)propyltrimethylammonium
chloride
(50% by weight), acrylic acid (2% by weight) and the monomer M6 according to
the
invention (10% by weight)
The procedure was as in example 9, except that the following components were
used:
170 g distilled water,
1.6 g silicone defoamer,
2.4 g pentasodium diethylenetriaminepentaacetate,
7.7 g acrylic acid (99.5% strength by weight; 4.1 mol%),
320.0 g 3-(acrylamino)propyltrimethylammonium chloride (60% strength by
weight
solution in water; 36.2 mol%),
79.4 g acrylamide (50% strength by weight solution in water; 21.2
mol%),
108.6 N-vinylpyrrolidone (38.1 mol%),
38.4 g monomer M6
Example 13:
Hydrophobically associating copolymer of the type (A3) of dimethylacrylamide
(19.2% by
weight), acrylamido-2-methylpropanesulfonic acid, Na salt (77% by weight) and
a
1
CA 02760734 2011-11-01
-
mixture of the hydrophobically associating monomer M8 (0.8% by weight) and a
monomer M1 according to the invention (3% by weight)
The following components were mixed together in a 2 I three-necked flask
fitted with
5 stirrer and thermometer:
1377 g distilled water,
3 g silicone defoamer,
315 g acrylamido-2-methylpropanesulfonic acid, Na salt (58%
strength by
10 weight solution in water; 65.5 mol%),
35.8 g dimethylacrylamide (34.1 mol%),
2.6 g monomer M8 (60% strength by weight solution in water),
5.6 g monomer M1
15 The solution was adjusted to pH 7 using 20% strength sodium hydroxide
solution,
rendered inert by flushing for 10 min with nitrogen, heated to ca. 50 C and,
in
succession, 1500 ppm of sodium peroxodisulfate (as 20% strength by weight
solution)
and 240 ppm of tetraethylenepentamine (as 20% strength by weight solution)
were
added. After ca. 2 hours, the polymer solution was dried to constant weight in
a
20 convection drying oven at ca. 90 to 120 C in vacuo and finally ground.
Example 14:
Hydrophobically associating copolymer of the type (A3) of dimethylacrylamide
(35% by
25 weight), acrylamido-2-methylpropanesulfonic acid, Na salt (60% by
weight) and the
monomer M1 according to the invention (5% by weight)
The following components were mixed together in a 2 I three-necked flask
fitted with
stirrer and thermometer:
539.2 g acrylamido-2-methylpropanesulfonic acid, Na salt (58%
strength by
weight solution in water; 44.9 mol%),
1.6 g silicone defoamer,
CA 02760734 2011-11-01
51
143.51 g dimethylacrylamide (54.7 mol%),
20.4 g monomer M1
4 g of formic acid (10% strength by weight solution in water) were added as
molecular
weight regulator. The solution was adjusted to pH 7 using 20% strength sodium
hydroxide solution, rendered inert by flushing for 10 min with nitrogen and
cooled to ca.
5 C. The solution was transferred to a plastic container and then, in
succession, 150
ppm of 2,2'-azobis(2-amidinopropane)dihydrochloride (as 1% strength by weight
solution), 6 ppm of ten-butyl hydroperoxide (as 0.1% strength by weight
solution), 6 ppm
of sodium hydroxymethanesulfinate (as 1% strength by weight solution) and 3
ppm of
FeSO4*7H20 (as 1% strength by weight solution) were added. The work-up was
carried
out as described above.
Comparative example 4:
Hydrophobically associating copolymer with acrylamide
and 3-
(acrylamino)propyltrimethylammonium chloride without monomers according to the
invention
The procedure was as in example 9, except that the following components were
used:
170 g distilled water,
1.6 g silicone defoamer,
2.4 g pentasodium diethylenetriaminepentaacetate,
5.4 g acrylic acid (99.5% strength by weight; 2.9 mol%),
148 g 3-(acrylamino)propyltrimethylammonium chloride (60% strength by
weight
solution in water; 18.3 mol%),
259.7 g acrylamide (50% strength by weight solution in water; 78.6
mol%),
20.0 g polyethylene glycol (3000) vinyl oxybutyl ether (VOB, 60%
strength by
weight solution in water; 0.2 mol%),
8.0 g monomer M8 (60% strength by weight solution in water).
CA 02760734 2011-11-01
52
Comparative example 5:
Hydrophobically associating copolymer with dimethylacrylamide and acrylamido-2-
methylpropanesulfonic acid, Na salt without monomer according to the invention
The procedure was as in example 9, except that the following components were
used:
170 g distilled water,
1.6 g silicone defoamer,
2.4 g pentasodium diethylenetriaminepentaacetate,
528 g acrylamido-2-methylpropanesulfonic acid, Na salt (58% strength
by
weight solution in water; 48.1 mol%),
175 g acrylamide (50% strength by weight solution in water; 51.5
mol%),
29.2 g polyethylene glycol (3000) vinyl oxybutyl ether (VOB, 60%
strength by
weight solution in water; 0.2 mol%),
11.9 g monomer M8 (60% strength by weight solution in water)
Comparative example 6:
The following components were mixed together in a 2 I three-necked flask
fitted with
stirrer and thermometer:
1.6 g silicone defoamer,
578.0 g acrylamido-2-methylpropanesulfonic acid, Na salt (58% strength
by
weight solution in water; 62.2 mol%),
104.8 g acrylamide (50% strength by weight solution in water; 36.4
mol%),
43.5 g polyethylene glycol (1100) vinyloxy butyl ether (VOB, 60%
strength by
weight solution in water)
300 ppm of formic acid (10% strength by weight solution in water) were added
as
molecular weight regulator. The solution was adjusted to pH 7 using 20%
strength
sodium hydroxide solution, rendered inert by flushing for 10 min with nitrogen
and
cooled to ca. 5 C. The solution was transferred to a plastic container and
then, in
CA 02760734 2011-11-01
53
succession, 150 ppm of 2,2'-azobis(2-amidinopropane) dihydrochloride (as 1%
strength
by weight solution), 6 ppm of tert-butyl hydroperoxide (as 0.1% strength by
weight
solution), 6 ppm of sodium hydroxymethanesulfinate (as 1% strength by weight
solution)
and 3 ppm of FeSO4*7H20 (as 1% strength by weight solution) were added. The
work-
up was carried out as described above.
Part B-3) Preparation of hydrophobically associating copolymer dispersions of
the
type (A4)
Comparative example 7
The copolymer preparation was carried out in accordance with the method
described
below. The resulting aqueous polymer dispersion comprised the copolymers in
their acid
form.
In a stirred apparatus, consisting of a 4 liter HWS vessel with anchor stirrer
(150 rpm),
reflux condenser, internal thermosensor and metering station, 484.5 g of
demineralized
water (DM water) and 8.21 g of an emulsifier (sodium lauryl ether sulfate; 28%
strength
in water) were mixed as initial charge.
At 75 C, 12.49 g of a 7% strength aqueous sodium peroxodisulfate solution were
added
to this solution and the mixture was stirred at 75 C for 5 minutes. Then, at
75 C and with
further stirring, an emulsion consisting of 429.91 g of completely
demineralized water,
the monomers (140.82 g of methacrylic acid, 161 g of ethyl acrylate, and 161 g
of
n-butyl acrylate) and 16.43 g of sodium lauryl ether sulfate (27-28% strength
in water)
were uniformly metered in over the course of 2 hours. The reaction mixture was
then
stirred for a further 1 hour at 75 C and then brought to room temperature. At
room
temperature, 0.23 g of a 4% strength solution of [EDTA-Fe]K (CAS No. 54959-35-
2) and
9.2 g of a 5% strength hydrogen peroxide solution were added, and 69 g of a 1%
strength ascorbic acid solution was metered in uniformly over the course of 30
min. This
gave an aqueous polymer dispersion with 31% solids content.
To characterize the dispersion, the following values were measured:
I
CA 02760734 2011-11-01
54
Solids content:
The dispersion was dried at 140 C for 30 min and the solids content was
determined in
percent from the ratio of dry residue to initial weight.
Particle size:
The dispersion was diluted to 0.01% and the particle size was measured by
means of
light scattering in the High Performance Particle Sizer 5001 (HPPS) from
Malvern
Instruments.
LD value:
The dispersion was diluted to 0.01% and the light transmission (LT) of the
dispersion
compared to pure water was measured visually in the Hach DR/2010 as a measure
of
the particle size.
The results are summarized in table 2.
Example 15
In a stirred apparatus consisting of a 4 liter HWS vessel with anchor stirrer
(150 rpm),
reflux condenser, internal thermosensor and metering station, 484.5 g of
demineralized
water (DM water) and 4.11 g of an emulsifier 28% strength (sodium lauryl ether
sulfate;
28% strength in water) in water were mixed as initial charge.
At 75 C, 12.49 g of a 7% strength aqueous sodium peroxodisulfate solution were
added
to this solution and the mixture was stirred at 75 C for 5 minutes. Then, at
75 C and with
further stirring, the emulsion consisting of 429.91 g of completely
demineralized water
(DM water), the monomers 140.82 g of methacrylic acid, 149.94 g of ethyl
acrylate,
159.56 g of n-butyl acrylate and 12.5 g of the associative monomer M1
according to the
invention and 20.54 g of sodium lauryl ether sulfate (28% strength in water)
were
metered in uniformly over the course of 2 hours. The reaction mixture was then
stirred
for a further 1 hour at 75 C and then brought to room temperature. At room
temperature,
0.23 g of a 4% strength solution of [EDTA-Fe]< (CAS No. 54959-35-2) and 9.2 g
of a
CA 02760734 2011-11-01
5% strength hydrogen peroxide solution were added, and 69 g of a 1% strength
ascorbic
acid solution were metered in uniformly over the course of 30 min. This gave
an
aqueous polymer dispersion with 31% solids content.
5 The dispersion was characterized as described above. The results are
summarized in
table 2.
Examples 16 to 21
10 Further dispersions were prepared analogously to the procedure of
example 15, except
in each case the hydrophobically associating monomer M1 was replaced by
another
monomer M2 to M7. The dispersions were in each case characterized as described
above. The results are summarized in each case in table 2.
Copolymer Hydrophobically Number Number of Solids Particle LT ¨
0.1%
No. associating of EO pentene content (%) size (nm)
strength
monomer units oxide units (cY0)
C 7 without
15 M1 22 8 31.1 76 97
16 M7 132 8 31.0 65 98
17 M5 68 8 30.8 63 98
18 M6 68 12 30.3 63 98
19 M2 22 12 31.0 64 98
20 M3 22 16 30.8 66 98
21 M4 22 20 30.8 63 98
Table 2: Data of the resulting dispersions
Part C) Applications-related tests
Part C-1) Test of the copolymers of the type Al
Determination of the gel fraction:
CA 02760734 2011-11-01
56
1 g of the respective copolymer is stirred in 249 g of synthetic seawater in
accordance
with DIN 50900 for 24 h until completely dissolved. The solution is then
filtered over a
200 pm sieve and the volume of the residue remaining on the sieve is measured.
This
value is the gel fraction.
Determination of the viscosity:
The viscosity of the filtrate is measured using a rheometer with double-slit
geometry at 7
s-1 and 60 C.
The results are summarized in tables 3 and 4.
Copolymer Hydrophobically associating Gel fraction [ml] Viscosity
[mPas]
monomer
Example 1 M1 <5 25
Cl without <5 10
02 M8 8 16
03 M9 9 12
Table 3: Results of the applications-related experiments with amphoteric
copolymers of
the type (Al)
Copolymer Monomer used Number of EO Number of
Viscosity [mPas]
units pentene oxide
units
Example 2 M1 22 8 27
Example 3 M2 22 12 52
Example 4 M3 22 16 9
Example 5 M4 22 20 22
Example 6 M5 68 8 17
Example 7 M6 68 12 30
Example 8 M7 132 8 3
CA 02760734 2011-11-01
57
Table 4: Results of the applications-related experiments with copolymers of
the type
(Al) of acrylamide and AMPS
The data in table 3 show that the solution of the copolymer according to the
invention
according to example 1 in seawater has the highest viscosity of all of the
tested
copolymers for a simultaneously low gel fraction. The copolymer according to
comparative example 1, thus without monomers which can hydrophobically
associate,
likewise has a low gel fraction, but the viscosity is also naturally lower.
The monomers
according to prior art M8 and M9 do increase the viscosity, as expected, but
not as great
by far as the monomers used according to the invention and, moreover, the gel
fraction
is in each case significantly higher.
Table 4 shows that the viscosity of the copolymers according to the invention
depends
on the nature of the monomers used. Example 3 represents the best currently
known
embodiment of the invention.
Part C-2) Test of the copolymers of the type (A2) and (A3)
Test in a tile adhesive mortar:
The properties of the copolymers of the type (A2) were tested in a test
mixture of a tile
adhesive mortar. The composition of the test mixture is given in DE 10 2006
050 761
Al, page 11, table 1. This is a ready-to-use formulated dry mixture to which
in each
case 0.5% by weight of the hydrophobically associating copolymer to be tested
was
admixed in solid form. After the dry mixing, a certain amount of water was
added and
the mixture was intensively stirred using a suitable mixing device (drilling
machine with
G3 mixer). The required mixing time was measured. The tile adhesive was
initially left to
ripen for 5 min.
The following tests were carried out on the stirred tile adhesive mortar:
Slump The determination of the slump was carried out in
accordance with
DIN 18555, part 2 and was carried out directly after the ripening
CA 02760734 2011-11-01
58
time and, if appropriate, at later time points.
Water retention The water retention was ascertained 15 min after stirring
in
accordance with DIN 18555, part 7.
Wetting The tile adhesive formulation was applied to a concrete
slab in
accordance with EN 1323 and after 10 min, a tile (5 cm x 5 cm) was
laid onto it. The tile was then weighted with a weight of 2 kg for 30
s. After a further 60 min, the tile was removed and it was
ascertained to what percentage the back of the tile was still
adhered to by tile mortar.
Slip The slip was determined 3 min after stirring in accordance
with DIN
EN 1308. The slip distance in mm is stated.
Tack The determination of the tack and/or ease of handling of
the test
mixture was carried out by a qualified person skilled in the art.
Air pore stability The determination of the air pore stability was carried
out visually
by a qualified person skilled in the art.
The copolymers used in each case and the results obtained are summarized in
table 5.
Test in a self-compacting concrete
The properties of the copolymers of the type (A3) were tested in a test
mixture of a self-
compacting concrete. The composition of the test mixture is given in DE 10
2004 032
304 Al, page 23, table 11. The polymers to be tested are used in each case in
an
amount of 0.02% by weight.
The preparation of the mortar mixtures was carried out in accordance with
section
[0105] of DE 10 2004 032 304 Al, the determination of the flowability (slump
flow) was
carried out in accordance with the method described in section [0106], and the
bleeding
CA 02760734 2011-11-01
59
and the sedimentation were assessed visually by a person skilled in the art.
The values
were taken directly after stirring and after 20 minutes.
The copolymers used in each case and the results obtained are summarized in
table 6.
Copolymer Example 6 Example 9 Example 10 Example 11 Example
12 C4 , C5 C6
Cellulose
ether MHPC
30 000
_
Mixing time [s] 16 18 20 15 12
16 18 6
0
Slump 19.0 18.4 18.3 20.5 18.1
17.2 18.2 16.2
0
Water retention [%] 98.0 98.1 98.0 97.7 98.0
97.8 98.1 98.6 iv
--1
61
0
Wetting [%] 88.2 95 87 90 93
89 91 70 --1
LO
FP
Slip [mm] 3 2 1 5 2
2 3 8 iv
0
Tack good high high good high
high high very high H
H
I
Air pore stability good very good very good good very good
good very good CD H
H
0
I
0
good
H
Table 5: Results of the examples and comparative examples
Copolymer Example 8 Example 13 Example 14 C7
C8
Without polymer Polymer
according to
DE102004032304
Al
Example 8
_
Slump (immediate) [cm] 72.5 73 72 75
74
_
Bleeding (immediate) no no no severe
no
Sedimentation (immediate) no no no severe
no n
Slump (after 20 min) [cm] 72 73 72 74
72 0
I.)
-.3
Bleeding (after 20 min) no no no _ severe
no c7,
0
-.3
u.)
Sedimentation (after 20 min) no no no
severe no
I.)
0
H
Cr)
H
-w,
I
Table 6: Results of the examples and comparative examples
H
H
I
0
H
CA 02760734 2011-11-01
62
Part C-3) Test of the Copolymers of the type A4
Preparation of an exemplary liquid detergent
The following stock formulations are prepared (% by weight, based on the
finished
formulation):
Component Amount
Anionic surfactant (linear alkylbenzene sulfonic acid, 010-13) 13.44
Nonionic surfactant (013/15 oxo alcohol, alkoxylated with ca. 7 7.5
EO units)
Coconut oil fatty acid 8.5
KOH 4.38
Sodium citrate dihydrate 3
1,2-Propylene glycol 8
Ethanol 2
Water qs
The above constituents were mixed and topped up to 90% by weight with water,
i.e. a
formulation gap of 10% by weight remained. The stock formulations were
adjusted to
pH 8.6 with KOH.
For the (unthickened) reference formulations, the stock formulations were
topped up to
100% by weight with water. For the thickened test formulations, the stock
formulations
were topped up with thickener dispersion and water so that, taking into
consideration the
solids content of the dispersion, a thickener concentration of 1.4% by weight,
based on
the finished formulation, was established. Prior to the viscosity measurement,
the
formulations were left to stand for at least 5 hours.
The low-shear viscosity was measured taking into consideration the
instructions in
accordance with DIN 51550, DIN 53018, DIN 53019 using the Brookfield
viscometer
CA 02760734 2011-11-01
63
model RV-03 at a rotary speed of 20 revolutions per minute using spindle No.
62 at
20 C. The viscosity of the unthickened reference formulations was 112 mPas.
To quantify the transparency of the thickened formulations, the transmission
in % was
measured at 440 nm at 23 C using a LICO 200 from Dr. Lange. The values found
for the
thickened formulations are given as a percentage, relative to the transmission
of the
unthickened reference formulation.
The results are summarized in tables 7.
Polymer used according to Transmission (%) Low-shear viscosity
(mPas)
Without thickening polymer - 112
Comparative example 7 99 1023
(without monomer (a))
Example 15 99 1392
Example 16 100 1472
Example 17 100 1392
Example 18 100 1424
Example 19 100 1360
Example 20 100 1472
Example 21 100 1408
Table 7: Applications-related evaluation of the thickener dispersions:
Formulation with 1.4% by weight thickener
1
CA 02760734 2011-11-01
64
It can be seen that the use of the thickeners leads to a considerable
viscosity increase
compared to the reference formulation without thickener.
Examples 15 to 21 which comprise the hydrophobically associating monomers
according to the invention produce a significantly higher viscosity than
comparison
sample 7 which does not comprise any hydrophobically associating monomer. The
use
of the associative monomers according to the invention does not adversely
effect the
high transparency of the liquid detergent formulation, expressed by the
transmission
measurement.
