AU2010251271B2 - Hydrophobically associating copolymers - Google Patents

Abstract

The invention relates to water-soluble, hydrophobically associating copolymers containing novel hydrophobically associating monomers. The monomers comprise an ethylenically unsaturated group and a polyether group with a block structure consisting of a hydrophilic polyalkylene oxide block, which essentially consists of ethylene oxide groups, and of a terminal, hydrophobic polyalkylene oxide block, which consists of alkylene oxides with at least 4 and preferably at least 5 carbon atoms.

Description

PF 62163 Hydrophobically associating copolymers The present invention relates to water-soluble, hydrophobically associating copolymers which comprise new types of hydrophobically associating monomers. The monomers 5 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. 10 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. 15 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 20 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 25 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: H 2 C=C(Rx) 30 COO-(-CH 2

-CH

2 -O-)-RY or else H 2 C=C(Rx)-O-CH2-CH2-O-)q-RY), where Rx is typically H or

CH

3 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.

PF 62163 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 5 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 10 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 15 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. 20 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. 25 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-C 4 -alkylene oxides, where ethylene oxide units must obligatorily be present. The alkylene 30 oxide units can be arranged randomly or blockwise, and the polyalkylene oxide group can have H or a C 1 to C 4 group as terminal group. The examples specifically mention polyethylene oxide-b-polypropylene oxide-monobutyl vinyl ether. JP 2001-199751 A discloses the preparation of a dispersant for cement. Here, maleic 35 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 PF 62163 3 selected from the group of propylene oxide, butylene oxide or styrene oxide, the terminal OH groups being etherified with a C2- to C 5 -alkenyl group or with a Ci-C 5 -alkyl group. JP 2000-119699 A discloses a deinking auxiliary in the reprocessing of wastepaper. For this, 5 a polyoxyalkylene block copolymer is used which has a terminal C 8 - to C2 4 -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. 10 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-EI-Din, H.A. in J. Petr. Sci. Eng. 1998, 19, 265-280. 15 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, 20 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. ?5 Hydrophobically associating copolymers for enhanced oil recovery should therefore have the lowest possible fraction of gel particles. The aforementioned monomers H2C=C(Rx)-COO-CH2-CH2-0-)q-RY and H 2 C=C(Rx)-O-(

CH

2

-CH

2 -O-)-Ry are usually prepared by means of a two-stage process. In a first stage, an 0 alcohol R-OH is ethoxylated, giving an ethoxylated alcohol of the general formula HO-(-CH 2 CH2-O-)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-O)q-H is formed in small amounts. In the second stage, the difunctional molecules H2C=C(Rx)-COO-(-CH2-CH2-0-)g-OC-C(Rx)=CH 2 or 5 H2C=C(Rx)-O-(-CH 2

-CH

2 -O-)q-C(Rx)=CH 2 can be formed therefrom. Since purification is extremely complex, these by-products are usually not separated off. Difunctional molecules PF 62163 4 of this type have a crosslinking effect and consequently lead in the course of a polymerization of 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 5 provide the simplest possible method for the preparation of the monomers. The invention may therefore provide hydrophobically associating copolymers with low gel fractions. Furthermore, the copolymers should be able to be prepared more economically than hitherto. 0 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, 5 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, 0 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 (1) H2

C

=C(R

1

)-R

4

-O-(-CH

2

-CH(R

2 )-O-)k-(-CH2-CH(R 3

)-O-)I-R

5 (1) 25 where the units -(-CH2-CH(R 2 )-O-)k and -(-CH 2

-CH(R

3 )-O-), are arranged in block structure in the order shown in formula (1) and the radicals and indices have the following meaning: 30 k: a number from 10 to 150, 1: 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 R 2 are H, 5865413 1 (GHMatters) P88688.AU FELISAS PF 62163 5 R3: independently of one another, a hydrocarbon radical having at least 2 carbon atoms or an ether group of the general formula -CH 2 -0-R 3 ', where R 3 ' is a hydrocarbon radical having at least 2 carbon atoms, R4: a single bond or a divalent linking group selected from the group of -(CnH 2 n) 5 [R 4 a], -O-(CoH 2 n.)-[R4b] and -C(O)-O-(Co-H2n")-[R4C], where n, n' and n" is in each case a natural number from 1 to 6,

R

5 : H or a hydrocarbon radical having 1 to 30 carbon atoms. The invention provides a water-soluble, hydrophobically associating copolymer comprising at 0 least (a) 0.1 to 20% by weight of at least one monoethylenically unsaturated, hydrophobically associating monomer (a), and 5 (b) 25% by weight to 99.9% by weight of at least one monoethylenically unsaturated hydrophilic monomer (b) different therefrom, 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 0 the general formula (1)

H

2

C=C(R

1

)-R

4

-O-(-CH

2

-CH(R

2 )-O-)k-(-CH2-CH(R 3

)-O-)I-R

5 (1) where the units -(-CH2-CH(R 2 )-O-)k and -(-CH 2

-CH(R

3 )-O-), are arranged in block 5 structure in the order shown in formula (1) and the radicals and indices have the following meaning: k: a number from 10 to 150, 1: a number from 5 to 25, 30 R 1 : H or methyl, R2: independently of one another, H, methyl or ethyl, with the proviso that at least 50 mol% of the radicals R 2 are H, R3: independently of one another, a hydrocarbon radical having at least 2 carbon atoms or an ether group of the general formula -CH 2 -0-R 2 ', where R 2 ' is a 35 hydrocarbon radical having at least 2 carbon atoms, R4: a divalent linking group -O-(Co'H 2 n.)-, where n, n' and n" is in each case a natural number from 1 to 6, amended sheets 6055682 1 (GHMatters) P88688.AU RDAULTON PF 62163 5A 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 5 preferred for the respective use. Regarding the invention, the details are as follows: The hydrophobically associating copolymers according to the invention are water-soluble 0 copolymers which have hydrophobic groups. In aqueous solution, the 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 5 (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 0 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 25 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 20 g/l, preferably at least 50 g/I and particularly preferably at least 100 g/l. 5865413 1 (GHMatters) P88688.AU FELISAS PF 62163 6 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 5 respective application. Monomer (a) 10 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. 15 Monomer (a) of the formula (1) According to the invention, at least one of the monoethylenically unsaturated monomers (a) is a monomer of the general formula 20 H2C=C(R 1

)-R

4 -0-(-CH 2

-CH(R

2 )-O-)k-(-CH 2 -CH(R3)-O-)-R5 (1). In the monomers (a) of the formula (1), an ethylenic group H 2 C=C(R1)- is bonded via a divalent, linking group -R 4 -0- to a polyoxyalkylene radical with block structure -(-CH 2

-CH(R

2

)

O-)k-(-CH 2

-CH(R

3 )-O-),-R5 where the two blocks -(-CH2-CH(R 2 )-O-)k and -(-CH 2

-CH(R

3 )-O-), ?5 are arranged in the order shown in formula (1). The polyoxyalkylene radical has either a terminal OH group or a terminal ether group -OR 5 . In the aforementioned formula, R 1 is H or a methyl group. 0 R 4 is a single bond or a divalent, linking group, selected from the group of -(CnH 2 n)-[group

R

4 a], -O-(Cn-H 2 n-)-[group R4b]- and -C(O)-O-(C'-H 2 n')-[group R4c]. 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 H 2 C=C(R1)- either directly, via an ether group -0- or 5 via an ester group -C(O)-O-. The groups -(CnH 2 n)-, -(Co-H 2 n-)- and -(C.-H 2 n.)- are preferably linear aliphatic hydrocarbon groups.

PF 62163 7 Preferably, the group R 4 a is a group selected from -CH 2 -, -CH 2

-CH

2 - and -CH 2

-CH

2

-CH

2 -, and is particularly preferably a methylene group -CH 2 -. 5 Preferably, the group R4b is a group selected from -O-CH 2

-CH

2 -, -O-CH 2

-CH

2

-CH

2 - and -0

CH

2

-CH

2

-CH

2

-CH

2 -, and is particularly preferably -0-CH 2

-CH

2

-CH

2

-CH

2 -. Preferably, the group Re is a group selected from -C(O)-O-CH 2

-CH

2 -, -C(O)O-CH(CH 3

)-CH

2 , -C(O)O-CH 2

-CH(CH

3 )-, -C(O)O-CH 2

-CH

2

-CH

2

-CH

2 - and -C(O)O-CH 2

-CH

2

-CH

2

-CH

2

-CH

2 10 CH 2 -, particular preference being given to -C(O)-O-CH 2

-CH

2 - and -C(O)O-CH 2

-CH

2

-CH

2 CH 2 - and very particular preference being given to -C(O)-O-CH 2

-CH

2 -. The group R 4 is particularly preferably a group R 4 a or R4b, particularly preferably a group R4b. 15 Furthermore, R 4 is particularly preferably a group selected from -CH 2 - or -O-CH 2

-CH

2

-CH

2 CH 2 -, and is very particularly preferably -O-CH 2

-CH

2

-CH

2

-CH

2 -. Furthermore, the monomers (1) have a polyoxyalkylene radical which consists of the units -(-CH2-CH(R 2 )-O-)k and -(-CH 2

-CH(R

3 )-0-)I, where the units are arranged in block 20 structure in the order shown in formula (1). The transition between the two blocks may be abrupt or continuous. In the block -(-CH2-CH(R 2 )-O-)k ,the radicals R 2 , independently of one another, are H, methyl or ethyl, preferably H or methyl, with the proviso that at least 50 mol% of the radicals R 2 are 25 H. Preferably, at least 75 mol% of the radicals R 2 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. 10 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. 5 In the second, terminal block -(-CH 2

-CH(R

3 )-O-)-, the radicals R 3 , independently of one another, are hydrocarbon radicals of at least 2 carbon atoms, preferably at least 3 and PF 62163 8 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. Examples of suitable radicals R 3 comprise ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, 5 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 R 3 may also be ether groups of the general formula -CH 2

-O-R

3 ', where R 3 ' is an aliphatic and/or aromatic, linear or branched hydrocarbon radical having at least 2 carbon 10 atoms, preferably at least 3 and particularly preferably 3 to 10 carbon atoms. Examples of radicals R 3 ' comprise n-propyl, n-butyl, n-pentyl, n-hexyl, 2-ethylhexyl, n-heptyl, n-octyl, n-nonyl, n-decyl or phenyl. The block -(-CH 2 -CH(R3)-O-)i- is thus a block which consists of alkylene oxide units having at 15 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 R 3 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. 20 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 R 5 is H or a preferably aliphatic hydrocarbon radical having 1 to 30 carbon atoms, 25 preferably 1 to 10 and particularly preferably 1 to 5 carbon atoms. Preferably, R 5 is H, methyl or ethyl, particularly preferably H or methyl and very particularly preferably H. In the monomers of the formula (1), a terminal, monoethylenic group is thus linked to a polyoxyalkylene group with block structure, and specifically firstly to a hydrophilic block 30 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 -OR 5 group, in particular an OH group. In contrast to the hydrophobically associating copolymers known from the prior art, the end group does not have to be 35 etherified with a hydrocarbon radical for the hydrophobic association, but the terminal block (-CH 2 -CH(R3)-O-) itself with the radicals R 3 is responsible for the hydrophobic association of PF 62163 9 the copolymers prepared using the monomers (a). The etherification is only one option which can be selected by the person skilled in the art depending on the desired properties of the copolymer. 5 For the person skilled in the art in the field of polyalkylene oxide block copolymers, it is clear that the transition between the two blocks can be abrupt or continuous depending 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(R 2 )-O-)k can still have 10 small amounts of units -CH 2 -CH(R3)-O- and the second block -(-CH 2 -CH(R3)-O-) can have small amounts of units -CH 2 -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 (1) 15 The preparation of the hydrophobically associating monomers (a) of the formula (1) 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 20 suitable monoethylenically unsaturated alcohols (Ill) which are then alkoxylated in a two stage process, so that the block structure mentioned is obtained. Monomers (a) of the formula (1) where R 5 = H are obtained. The latter may optionally be etherified in a further process step. 25 The type of ethylenically unsaturated alcohols (111) to be used is governed here in particular by the group R 4 . If R 4 is a single bond, the starting materials are alcohols (Ill) of the general formula H2C=C(R 1

)-O-(-CH

2

-CH(R

2 ')-O-)d-H (Illa), where R 1 has the meaning defined above, R 2 ' is H 30 and/or CH 3 , 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-CH 2

-CH

2 -0-CH 2

-CH

2 -OH or dipropylene glycol vinyl ether H2C=CH-O-CH 2

-CH(CH

3

)-O-CH

2

-CH(CH

3 )-OH, preference being given to diethylene glycol vinyl ether. 15 For the preparation of monomers (a) in which R 4 is not a single bond, it is possible to use alcohols of the general formula H 2

C=C(R

1

)-R

4 -OH (Illa) or even alcohols having alkoxy PF 62163 10 groups of the formula H2C=C(R 1

)-R

4 -0-(-CH 2

-CH(R

2 ')-O-)d-H (Illb), where R 2 ' and d have the meaning defined above, and R 4 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 5 from alcohols of the formula H 2

C=C(R

1 )-(CnH 2 n)-OH, in particular H 2 C=CH-(CnH 2 n)-OH or alcohols of the formula H2C=C(R 1

)-O-(-CH

2

-CH(R

2 )-O-)d-H, in particular those where R 1 = H and R 2 = H and/or CH 3 . Examples of preferred alcohols comprise allyl alcohol H 2

C=CH-CH

2 OH or isoprenol H 2

C=C(CH

3

)-CH

2

-CH

2 -OH. 10 For the preparation of the monomers with linking group R4b, the starting materials are vinyl ethers of the formula H2C=C(R 1 )-O-(Cn-H 2 n-)-OH, preferably H 2 C=CH-O-(Cn.H 2 n')-OH. Particularly preferably, o>-hydroxybutyl vinyl ether H2C=CH-0-CH 2

-CH

2

-CH

2

-CH

2 -OH can be used. 15 For the preparation of the monomers with linking group R4c, the starting materials are hydroxyalkyl (meth)acrylates of the general formula H 2

C=C(R

1 )-C(O)-O-(Cn..H 2 n..)-OH, preferably H 2

C=C(R

1 )-C(O)-O-(Cn.H 2 n-)-OH. Examples of preferred hydroxyalkyl (meth)acrylates comprise hydroxyethyl (meth)acrylate H 2 C=C(R1)-C(O)-O-CH 2

-CH

2 -OH and also hydroxybutyl (meth)acrylate H2C=C(R 1

)-C(O)-O-CH

2

-CH

2

-CH

2

-CH

2 -OH. 20 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) O O0 Z R\ (Xa) CH 7 0-R' (Xb) 25

OH

2 where R 3 in (Xa) or R 3 'in (Xb) has the meaning defined at the outset. The procedure for an alkoxylation including the preparation of block copolymers from various 30 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.

PF 62163 11 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 5 elevation of the temperature (30 to 150 0 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 0 C, preferably 130 to 1500. The addition takes place typically over the course 10 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 % 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 0 C lower reaction temperature than in the first stage has proven useful. 15 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 20 (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 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 25 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 Br6nstedt acids or Lewis acids. To carry out the reaction, the alcohol used as starting 30 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. 5 For the person skilled in the art in the field of polyalkylene oxides, it is clear that the orientation of the hydrocarbon radicals R 3 and, if appropriate, R 2 can depend on the PF 62163 12 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 -(-CH 2

-CH(R

3 )-0-) or else in inverse orientation -(-CH(R 3

)-CH

2 -O-)-. The depiction in formula (1) should therefore not be regarded as limited to a certain orientation of 5 the groups R 2 and/or R 3 . If the monomers (a) of the formula (1) with a terminal OH group (i.e. RS = 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 10 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 R 5 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 15 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 according to the invention, the procedure is reversed: starting material is an ethylenically unsaturated compound which is 20 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.

PF 62163 13 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 5 monomers (a) have the general formula H 2 C=C(R1)-Y-Z, where R 1 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 H 2

C=C(R

1

)-COO-(

CH2-CH(R 6 )-O-)q-R 7 (Ila) or H2C=C(R 1

)-O-(-CH

2

-CH(R

6 )-O-)q-R 7 (Ilb), where q is a number 10 from 10 to 150, preferably 12 to 100, particularly preferably 15 to 80, very particularly preferably 20 to 30 and for example ca. 25, R 1 is as defined above and the radicals R 6 , independently of one another, are H, methyl or ethyl, preferably H or methyl, with the proviso that at least 50 mol% of the radicals R 6 are H. Preferably, at least 75 mol% of the radicals R 6 are H, particularly preferably at least 90 mol% and very particularly preferably exclusively H. 15 The radical R 7 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 C 1 - to C6-alkyl groups, preferably styryl groups. 20 Particular preference is given to a tristyrylphenyl group. The specified hydrophobically associating monomers of the formulae (Ila) and (1Ib) are known in principle to the person skilled in the art. 25 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 invention and is generally 0.1 to 20% by weight, based on the total amount of all of the monomers in the 30 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. If further monomers (a) are also used besides the monomers (a) of the formula (1), the monomers of the formula (1) should generally be used in an amount of at least 0.1% by 15 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 generally be PF 62163 14 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 (1) should be used as monomers (a). 5 Hydrophilic monomers (b) Besides the monomers (a), the hydrophobically associating copolymer according to the invention comprises at least one monoethylenically unsaturated, hydrophilic monomer (b) 10 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 15 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, 20 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/l, preferably at least 200 g/I and particularly preferably at least 500 g/l. 25 Examples of suitable functional groups comprise carbonyl groups >C=O, ether groups -0-, in particular polyethylene oxide groups -(CH 2

-CH

2 -O-)n-, where n is preferably a number from I to 200, hydroxy groups -OH, ester groups -C(0)0-, primary, secondary or tertiary amino groups, ammonium groups, amide groups -C(O)-NH-, carboxamide groups -C(O)-NH 2 or acid groups such as carboxyl groups -COOH, sulfonic acid groups -SO 3 H, phosphonic acid 30 groups -P0 3

H

2 or phosphoric acid groups -OP(OH) 3 . Examples of preferred functional groups comprise hydroxy groups -OH, carboxyl groups -COOH, sulfonic acid groups -SO 3 H, carboxamide groups -C(O)-NH 2 , amide groups-C(O)-NH-, and polyethylene oxide groups -(CH 2

-CH

2 -O-)n-H, where n is preferably a 35 number from 1 to 200.

PF 62163 15 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 H 2 C=C(R8)R 9 5 (111), where R 8 is H or methyl and R 9 is a hydrophilic group or a group comprising one or more hydrophilic groups. The groups R 9 are groups which comprise heteroatoms in an amount such that the solubility in water defined at the start is achieved. 10 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 15 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. 20 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 ?5 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, allyl alcohol, 0 hydroxyvinyl ethyl ether, hydroxyl vinyl propyl ether, hydroxyvinyl butyl ether or compounds of the formula H2C=C(R1)-COO-(-CH2-CH(R10)-O-)b-R1 (IVa) or H 2

C=C(R

1

)-O-(-CH

2 CH(R 10 )-O-)b-R 11 (lVb), where R 1 is as defined above and b is a number from 2 to 200, preferably 2 to 100. The radicals R 9 are, independently of one another, H, methyl or ethyl, preferably H or methyl, with the proviso that at least 50 mol% of the radicals R 9 are H. .5 Preferably, at least 75 mol% of the radicals R 9 are H, particularly preferably at least 90 mol% and very particularly preferably exclusively H. The radical R 1 1 is H, methyl or ethyl, preferably PF 62163 16 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 5 particular ammonium derivatives of N-(o-aminoalkyl) (meth)acrylamides or L-aminoalkyl (meth)acrylic esters. In particular, the monomers (b) having ammonium groups may be compounds of the general formulae H2C=C(Ra)-CO-NR14-R12-NR13 3 + X- (Va) and/or H 2 C=C(Ra)-COO-R 1 2

-NR

1 3 3 + X 10 (Vb), where R 8 has the meaning given above, thus is H or methyl, R1 2 is a preferably linear C1-C 4 -alkylene group and R 1 4 is H or a C 1

-C

4 -alkyl group, preferably H or methyl. The radicals R1 3 , independently of one another, are C 1

-C

4 -alkyl, preferably methyl, or a group of the general formula -R 1 5

-SO

3 H, where R 1 5 is a preferably linear C1- to C4-alkylene group or a phenylene group, with the proviso that generally not more than one of the substituents R 13 is 15 a substituent having sulfonic acid groups. The three substituents R 1 3 are particularly preferably methyl groups, i.e. the monomer has a group -N(CH 3

)

3 +. X- in the above formula is a monovalent anion, for example CI-. 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 20 2-trimethylammonium ethyl (meth)acrylates, for example the corresponding chlorides, such as 3-trimethylammonium propylacrylamide chloride (DIMAPAQUAT) and 2-trimethy lammonium ethyl methacrylate chloride (MADAME-QUAT). The aforementioned hydrophilic monomers can of course be used not only in the depicted 25 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 30 monomers which comprise at least one group selected from the group of -COOH, -SO 3 H or -P0 3

H

2 , particular preference being given to monomers comprising COOH groups and/or -SO 3 H groups, where the acid groups may also be present completely or partially in the form of the corresponding salts. 35 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- PF 62163 17 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% 5 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. 10 Monomers (c) Apart from the hydrophilic monomers, the copolymers according to the invention can optionally comprise monoethylenically unsaturated monomers (c) different from the 15 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 20 water at room temperature is less than 100 g/l, preferably less than 50 g/l and particularly preferably less than 20 g/l. Examples of such monomers (c) comprise hydrocarbons, in particular styrene and hydrophobic derivatives, such as, for example, a-methylstyrene or alkylstyrenes, such as 25 4-methylstyrene or 4-ethylstyrene. Preferably, the further monomers are those of the general formula H 2 C=C(Rl6)Rl7 (VI), where

R

1 6 is H or methyl and R 1 7 is a further group which essentially has hydrophobic character. 30 R1 7 is preferably carboxylic acid ester groups -COOR 1 8 , where R 1 8 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.

PF 62163 18 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. 5 R 16 may also be carboxamide groups -CONHR 1 7 or -CON(R 17

)

2 , with the proviso that the number of carbon atoms in the radical R 1 8 or both radicals R 1 8 together is at least 3, preferably at least 4, where the two radicals R 18 together may also form a ring. Examples of such monomers comprise N-butyl (meth)acrylamide, N-cyclohexyl(meth)acrylamide or N-benzyl(meth)acrylamide. 10 The monomers (c) also include those monomers which do have hydrophilic groups 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. 15 The type and amount of further monomers (c) is governed by the desired properties and 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. 20 Monomers (d) 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 25 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 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 30 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 35 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 PF 62163 19 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. 5 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 10 are established by the person skilled in the art depending on the desired application of the copolymer. Preparation of the hydrophobically associating copolymers 15 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 20 polymerization, preferably in aqueous phase. The synthesis of the monomers (a) of the formula (1) used according to the invention are particularly preferably prepared by the preparation process described above by alkoxylation of alcohols (1ll), optionally followed by an etherification. ?5 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 0 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. 5 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.

PF 62163 20 The mixture is then polymerized photochemically and/or thermally, preferably at -5*C to 500C. 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 5 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 0 C. The photochemical polymerization is usually carried out at temperatures of from -5 to 100C. 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 10 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%. 15 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 20 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. 25 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 30 DE 10 2004 032 304 Al, sections [0037] to [0041]. 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 5 example, by WO 2009/019225 page 5, line 16 to page 8, line 13.

PF 62163 21 The copolymers according to the invention preferably have a number-average molecular weight Mn of from 50 000 to 20 000 000 g/mol. 5 Use of the hydrophobically associating copolymers The hydrophobically associating copolymers according to the invention can be used for thickening aqueous phases. 10 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 15 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 20 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 25 also conceivable to predissolve the copolymer and then to add the formed solution to the system to be thickened. 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, 30 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 15 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, PF 62163 22 drilling fluids, formulations for the acidizing or fracturing or formulations for enhanced oil recovery. 5 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. 10 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 15 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 20 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% by weight, in 25 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 deposit, and crude oil is removed from the deposit through at least one production bore. In this 30 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 "polymer flood", the mineral oil flows in the direction of the production bore and is recovered via the production 35 bore. The viscosity of the flood medium should be adapted as far as possible to the viscosity PF 62163 23 of the mineral oil in the mineral oil deposit. The viscosity can be adjusted in particular via the concentration of the copolymer. To increase the mineral oil yield, the polymer flooding can advantageously be combined with 5 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 with a preceding, so-called "surfactant flooding". Here, before the polymer flooding, an aqueous 10 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. 15 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. 20 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. 25 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 0 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 5 preferably only monomers (a) and (b). The monomers (a) are preferably only one or more PF 62163 24 monomers of the formula (1). Preferred monomers (a) of the formula (1) have already been mentioned at the start. In the hydrophobically associating copolymer (Al), the monomers (a) are used in an amount 5 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 10 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 15 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 monomers having OH groups, such as hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, allyl alcohol, hydroxyvinyl ethyl 20 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). 25 The anionic monomers (b2) are monomers comprising acid groups, preferably monomers which comprise at least one group selected from the group of -COOH, -SO 3 H or -P0 3

H

2 . The monomers (b2) are preferably monomers comprising carboxyl groups -COOH and/or sulfonic acid groups -SO 3 H, particularly preferably monomers comprising sulfonic acid 30 groups -S0 3 H. 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 NH 4 + or ammonium ions with organic radicals. Examples of anionic monomers (b2) comprise acrylic acid or methacrylic acid, crotonic acid, 15 itaconic acid, maleic acid or fumaric acid, monomers comprising sulfonic acid groups, such as vinylsulfonic acid, allylsulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid (AMPS), PF 62163 25 2-methacrylamido-2-methylpropanesulfonic acid, 2-acrylamidobutanesulfonic acid, 3-acrylamido-3-methylbutanesulfonic acid or 2-acrylamido-2,4,4-trimethylpentanesulfonic acid or monomers comprising phosphonid acid groups, such as vinylphosphonic acid, allylphosphonic acid, N-(meth)acrylamidoalkylphosphonic acids or 5 (meth)acryloyloxyalkylphosphonic acids. Examples of preferred anionic monomers (b2) comprise acrylic acid, vinylsulfonic acid, allylsulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid (AMPS), 2-acrylamidobutane sulfonic acid, 3-acrylamido-3-methylbutanesulfonic acid and 2-acrylamido-2,4,4-trimethyl 10 pentanesulfonic 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 H2C=C(R 8 )-CO-NR1 4 -R1 2 -NR13 3 + X- (Va) 15 and/or H 2

C=C(R

7 )-COO-R2-NR13 3 + 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 20 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. 25 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). 30 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 35 to 99.9% by weight. The monomers (a) are used in the amounts given above.

PF 62163 26 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 5 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). 10 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 15 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. 20 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. 25 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 M, of from 30 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 35 salt stability. Furthermore, the inventive use of the monomers (a) of the formula (1) leads to PF 62163 27 copolymers with a particularly low gel fraction. This effectively avoids blockage of the mineral oil deposits. 5 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 hydraulic binder systems. Examples of such hydraulic binder systems comprise cement, 10 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 self-leveling floor screeds, sealing and repair mortars, flow screeds, flow concrete, self-compacting 15 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 on the type of use. 20 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), methylhydroxyethylcellulose (MHEC), methylhydroxypropylcellulose (MHPC) and also Welan gum or Diutan gum. ?5 For dry mortar applications (e.g. tile adhesive, sealing mortar, plasters, flow screeds), the hydrophobically associating copolymers according to the invention are used in 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 0 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 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 .5 less than 2% by weight.

PF 62163 28 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 5 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 10 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 15 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 20 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) 25 can also be used in a mixture with other hydrophobically associating monomers, preferably those of the general formulae H2C=C(R 1

)-COO-(-CH

2

-CH(R

6 )-O-)q-R7 (Ila) and/or H 2 C=C(R1) O-(-CH2-CH(R 6 )-O-)q-R 7 (lib). 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 (1) should usually be at least 25% by weight with regard to the amount of all of 30 the monomers (a), preferably 40 to 90% by weight and for example 40 to 60% by weight. Preferred monomers (a) of the formula (1) have already been mentioned above. 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 35 least one neutral monomer (b1) and at least one cationic monomer (b3).

PF 62163 29 Examples of suitable monomers (bl), (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, 5 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. 10 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 -SO 3 H or phosphonic acid groups -P0 3

H

2 . The anionic monomers (b2) in the copolymer (A2) are preferably monomers comprising 15 sulfonic acid groups -SO 3 H. Examples of preferred monomers comprise vinylsulfonic acid, allylsulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid (AMPS), 2-acrylamidobutane sulfonic acid, 3-acrylamido-3-methylbutanesulfonic acid and 2-acrylamido-2,4,4-trimethyl pentanesulfonic acid, preference being given to 2-acrylamido-2-methylpropanesulfonic acid (AMPS). 20 The cationic monomers (b3) in copolymer (A2) are preferably the aforementioned monomers of the formulae H 2

C=C(R)-CO-NR

4 -R12-NR13 3 + X- (Va) and/or H 2 C=C(R)-COO-R1 2 -NR13 3 + 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 25 propylacrylamide chloride (DIMAPAQUAT). 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 30 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 15 (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.

PF 62163 30 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. 5 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. 10 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). 15 The monomers (a) may be exclusively monomers (a) of the formula (1), in a preferred embodiment in the case of copolymer (A3), however, the monomers (a) of the formula (1) can also be used in a mixture with other hydrophobically associating monomers, preferably those of the general formula H2C=C(R 1

)-COO-(-CH

2

-CH(R

6 )-O-)q-R 7 (Ila) and/or H 2

C=C(R')-O-(

20 CH2-CH(R 6 )-O-)q-R 7 (lIb). 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 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 (1) have already been mentioned 25 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. 30 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 15 monomers (b1) in copolymer (A3) are acrylamide, methacrylamide and N-vinylpyrrolidone.

PF 62163 31 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 -SO 3 H or phosphonic acid groups -P0 3

H

2 . 5 Preferably, in copolymer (A3) the monomers (b2) are monomers comprising sulfonic acid groups -SO 3 H. 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). 10 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 (bl) is 5 to 50% by weight, preferably 5 to 30% by weight, with the proviso that the sum of the 15 monomers (b1) and (b2) together is 70 to 99.9% by weight. The monomers (a) are used in the amounts mentioned at the start. For the use as additive for aqueous construction systems, it may be advantageous to use additionally crosslinking monomers (d). These give the hydrophobically associating 20 copolymers (Al), (A2) and (A3) according to the invention a slightly branched or crosslinked structure. Examples of preferred monomers (d) comprise triallylamine, triallylmethylammonium chloride, tetraallylammonium chloride, N,N'-methylenebisacrylamide, triethylene glycol 25 bismethacrylate, triethylene glycol bisacrylate, polyethylene glycol(400) bismethacrylate 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 50 amounts such that the solubility in water of the hydrophobically associating 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 5 amount of monomers (d) that can be used.

PF 62163 32 Third preferred use and copolymers (A4) preferred for this A fourth preferred embodiment of the invention deals with a hydrophobically associating 5 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 10 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. 15 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. 20 The monomers (c) are preferably at least one (meth)acrylic acid ester of the general formula

H

2

C=C(R

1 6

)-COOR

1 8 , where R 16 and R 1 8 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. 25 The copolymer (A4) preferably comprises at least one (meth)acrylic acid ester in which R 9 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 30 (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. 35 PF 62163 33 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 5 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 10 formulations, foods, coating slips, formulations for textile production, textile printing 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 15 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. 20 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. 25 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 30 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. 5 The following examples are intended to illustrate the invention in more detail: PF 62163 34 Part A) Preparation of the monomers (1) Preparation of a hydroxybutyl vinyl ether alkoxylate having 22 EO units and 8 PeO units 5 (monomer M1): 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 MeOH) were then metered in and the methanol was drawn off at 80 0 C and ca. 30 mbar. The mixture was then heated to 140 0 C, 10 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 0 C, the reactor was cooled to 125 0 C and a total of 310 g of pentene oxide were metered in over the course of 3.0 h. The postreaction ran overnight. 15 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 PeO units 20 (monomer M2): 44.1 g of hydroxybutyl vinyl ether were initially introduced into a 1 1 stirred autoclave made of stainless steel. 3.12 g of KOMe (32% strength in MeOH) were then metered in and the methanol was drawn off at 80*C and ca. 30 mbar. The mixture was then heated to 140 0 C, 25 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 1400C, 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. 30 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 PeO units 35 (monomer M3): PF 62163 35 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 MeOH) were then metered in and the methanol was drawn off at 800C and ca. 30 mbar. The mixture was then heated to 140 0 C, the reactor was flushed with nitrogen and a nitrogen pressure of 1.0 bar was established. 5 315 g of EO were then metered in over the course of ca. 3 h. After a postreaction for half an hour at 1400C, the reactor was cooled to 125 0 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 10 number was determined by means of the ESA method. Preparation of a hydroxybutyl vinyl ether alkoxylate with 22 EO units and 20 PeO units (monomer M4): 15 33.2 g of hydroxybutyl vinyl ether were initially introduced into a I I stirred autoclave made of stainless steel. 3.01 g of KOMe (32% strength in MeOH) were then metered in and the methanol was drawn off at 80*C and ca. 30 mbar. The mixture was then heated to 1400C, the reactor was flushed with nitrogen and a nitrogen pressure of 1.0 bar was established. 20 277 g of EO were then metered in over the course of ca. 2.5 h. After a postreaction for half an hour at 1400C, the reactor was cooled to 1250C 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 ?5 number was determined by means of the ESA method. Preparation of a hydroxybutyl vinyl ether alkoxylate with 68 EO units and 8 PeO 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 MeOH) were then metered in and the methanol was drawn off at 800C and ca. 30 mbar. The mixture was then heated to 1400C, the reactor was flushed with nitrogen and a nitrogen pressure of 1.0 bar was established. 5 627 g of EO were then metered in over the course of ca. 5.5 h. After a postreaction for half PF 62163 36 an hour at 1400C, the reactor was cooled to 1250C and a total of 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 PeO units (monomer M6): 10 22.5 g of hydroxybutyl vinyl ether were initially introduced into a 1 1 stirred autoclave made of stainless steel. 3.01 g of KOMe (32% strength in MeOH) were then metered in and the methanol was drawn off at 800C and ca. 30 mbar. The mixture was then heated to 1400C, the reactor was flushed with nitrogen and a nitrogen pressure of 1.0 bar was established. 15 580 g of EO were then metered in over the course of ca. 5 h. After a 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 PeO units (monomer M7): 25 14.1 g of hydroxybutyl vinyl ether were initially introduced into a 1 1 stirred autoclave made of stainless steel. 3.02 g of KOMe (32% strength in MeOH) were then metered in and the methanol was drawn off at 800C and ca. 30 mbar. The mixture was then heated to 1400C, the reactor was flushed with nitrogen and a nitrogen pressure of 1.0 bar was established. 30 706 g of EO were then metered in over the course of ca. 8 h. After a postreaction for half an hour at 1400C, the reactor was cooled. On the next day, at 1250C, 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 1250C followed. 35 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.

PF 62163 37 The data for the synthesized monomers M1 to M7 are summarized in table 1 below. All monomers have a terminal OH group. 5 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 (1) For the comparative experiments, commercially available, hydrophobically associating 10 monomers of the following general formula were used: H2C=C(CH 3 )-COO-(EO)x-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 15 Part B) Preparation of the hydrophobically associating copolymers Part B-1) Preparation of hydrophobically associating copolymers of the type (Al) ?0 Example 1: 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 !5 weight), a cationic monomer (3-trimethylammonium propylacrylamide chloride, 31.0% by weight) and the monomer M1 according to the invention (1% by weight) PF 62163 38 The following components were mixed together in a 2 I three-necked flask fitted with stirrer and thermometer: 5 139.1 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 10 solution in water; 18.8 mol%), 160.1 g acrylamide (50% strength by weight solution in water; 63.5 mol%), 2.1 g monomer M1, 12 g urea 15 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 0 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), 20 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 25 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 slump uniformly on drying meshes and dried to constant weight in a convection drying oven at ca. 90 to 120 0 C in vacuo. 30 Comparative example 1: Polymer analogous to example 1, but without hydrophobically associating monomer 35 The following components were mixed together in a 2 1 three-necked flask fitted with stirrer and thermometer: PF 62163 39 139.1 g acrylamido-2-methylpropanesulfonic acid, Na salt (58% strength by weight solution in water; 17.4 mol%), 1.2 g silicone defoamer, 5 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 10 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. 50C. 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 ter-butyl 15 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 20 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. ?5 PF 62163 40 Comparative example 2: Polymer analogous to example 1, but instead of the hydrophobically associating monomer 5 according to the invention, monomer M8 was used The following components were mixed together in a 2 1 three-necked flask fitted with stirrer and thermometer: 10 139.1 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 15 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, 12 g urea 20 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 ted-butyl hydroperoxide (as 0.1% strength by weight solution) and 20 ppm of sodium hydroxymethanesulfinate (as 1% strength by weight solution) were 25 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 30 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 0 C in vacuo. Comparative example 3: 35 PF 62163 41 Polymer analogous to example 1, but instead of the hydrophobically associating monomer according to the invention, the monomer M9 was used The following components were mixed together in a 2 1 three-necked flask fitted with stirrer 5 and thermometer: 139.0 g acrylamido-2-methylpropanesulfonic acid, Na salt (58% strength by weight solution in water; 17.6 mol%), 1.2 g silicone defoamer, 10 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; 63.4 mol%), 2.2 g monomer M9, 15 12 g 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 I% strength by 20 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 ?5 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 1200C in vacuo. 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 5 associating monomer according to the invention (2% by weight) PF 62163 42 The following components were mixed together in a 2 1 three-necked flask fitted with stirrer and thermometer: 290 g distilled water, 5 242.5 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%), 10 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 0 C. The solution was transferred to a plastic container and then, in succession, 200 ppm of 2,2'-azobis(2 15 amidinopropane) dihydrochloride (as 1 % strength by weight solution), 10 ppm of tert-butyl hydroperoxide (as 0.1 % strength by weight solution), 5 ppm of FeSO 4 *7H 2 0 (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 20 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. 25 Part B-2) Preparation of hydrophobically associating copolymers of the types (A2) and (A3) Example 9 30 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) 35 PF 62163 43 The following components were mixed together in a 2 1 three-necked flask fitted with stirrer and thermometer: 170 g distilled water, 5 1.6 g 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%), 10 190.5 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 15 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 0 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 te/1-butyl hydroperoxide (as 0.1 % strength by weight solution) and 30 ppm of sodium bisulfite 20 (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 standard commercial meat grinder, they were coated with a standard commercial release agent. The release agent ?5 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 1200C in vacuo. 0 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 5 a monomer M5 according to the invention (5% by weight) PF 62163 44 The procedure was as in example 9, except that the following components were used: 170 g distilled water, 1.6 g silicone defoamer, 5 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), 10 17.2 g monomer M5 Example 11: 5 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) 20 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 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%) 0 30.4 g monomer M6 Example 12: 5 Hydrophobically associating copolymer of the type (A2) of acrylamide (10% by weight), N-vinylpyrrolidone (38.1% by weight), 3-(acrylamino)propyltrimethylammonium chloride (50% PF 62163 45 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: 5 170 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%), 10 320.0 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 15 Example 13: Hydrophobically associating copolymer of the type (A3) of dimethylacrylamide (19.2% by 20 weight), acrylamido-2-methylpropanesulfonic acid, Na salt (77% by weight) and a 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 1 three-necked flask fitted with stirrer 25 and thermometer: 1377 g distilled water, 3 g silicone defoamer, 315 g acrylamido-2-methylpropanesulfonic acid, Na salt (58% strength by weight 30 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 35 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 0 C and, in succession, 1500 ppm of PF 62163 46 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 convection drying oven at ca. 90 to 120 0 C in vacuo and finally ground. 5 Example 14: Hydrophobically associating copolymer of the type (A3) of dimethylacrylamide (35% by 10 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: 15 539.2 g acrylamido-2-methylpropanesulfonic acid, Na salt (58% strength by weight solution in water; 44.9 mol%), 1.6 g silicone defoamer, 143.51 g dimethylacrylamide (54.7 mol%), 20 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 0 C. The solution was 25 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 te/t-butyl hydroperoxide (as 0.1% strength by weight solution), 6 ppm of sodium hydroxymethanesulfinate (as 1 % strength by weight solution) and 3 ppm of FeSO 4 *7H 2 0 (as 1 % strength by weight solution) were added. The work-up was carried out as described )0 above.

PF 62163 47 Comparative example 4: Hydrophobically associating copolymer with acrylamide and 3-(acrylamino)propyltrimethyl ammonium chloride without monomers according to the invention 5 The procedure was as in example 9, except that the following components were used: 170 g distilled water, 1.6 g silicone defoamer, 10 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%), 15 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). 20 Comparative example 5: Hydrophobically associating copolymer with dimethylacrylamide and acrylamido-2-methyl propanesulfonic acid, Na salt without monomer according to the invention 25 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, 0 528 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%), .5 11.9 g monomer M8 (60% strength by weight solution in water) PF 62163 48 Comparative example 6: The following components were mixed together in a 2 1 three-necked flask fitted with stirrer 5 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%), 10 104.8 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 15 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 tert butyl hydroperoxide (as 0.1% strength by weight solution), 6 ppm of sodium 20 hydroxymethanesulfinate (as 1 % strength by weight solution) and 3 ppm of FeSO 4 *7H 2 0 (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) 25 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. 30 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. 35 PF 62163 49 At 75 0 C, 12.49 g of a 7% strength aqueous sodium peroxodisulfate solution were added to this solution and the mixture was stirred at 75 0 C for 5 minutes. Then, at 75 0 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 5 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 0 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 10 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: 15 Solids content: The dispersion was dried at 140 0 C for 30 min and the solids content was determined in percent from the ratio of dry residue to initial weight. Particle size: 20 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 ?5 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. 10 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 5 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.

PF 62163 50 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 0 C for 5 minutes. Then, at 75 0 C and with further stirring, the emulsion consisting of 429.91 g of completely demineralized water (DM water), 5 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 10 [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 were metered in uniformly over the course of 30 min. This gave an aqueous polymer dispersion with 31 % solids content. The dispersion was characterized as described above. The results are summarized in 15 table 2. Examples 16 to 21 Further dispersions were prepared analogously to the procedure of example 15, except in 20 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 (%) 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 ?5 Table 2: Data of the resulting dispersions PF 62163 51 Part C) Applications-related tests Part C-1) Test of the copolymers of the type Al 5 Determination of the gel fraction: 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 10 sieve and the volume of the residue remaining on the sieve is measured. This value is the gel fraction. Determination of the viscosity: 15 The viscosity of the filtrate is measured using a rheometer with double-slit geometry at 7 s and 60*C. The results are summarized in tables 3 and 4. 20 PF 62163 52 Copolymer Hydrophobically associating Gel fraction [ml] Viscosity [mPas] monomer Example 1 M1 < 5 25 C1 without < 5 10 C2 M8 8 16 C3 M9 9 12 Table 3: Results of the applications-related experiments with amphoteric copolymers of the type (Al) 5 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 Table 4: Results of the applications-related experiments with copolymers of the type (Al) of acrylamide and AMPS 0 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, 5 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 0 nature of the monomers used. Example 3 represents the best currently known embodiment of the invention.

PF 62163 53 Part C-2) Test of the copolymers of the type (A2) and (A3) Test in a tile adhesive mortar: 5 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 0 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: 5 Slump The determination of the slump was carried out in accordance with DIN 18555, part 2 and was carried out directly after the ripening 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.

PF 62163 54 The copolymers used in each case and the results obtained are summarized in table 5.

PF 62163 55 Test in a self-compacting concrete The properties of the copolymers of the type (A3) were tested in a test mixture of a self 5 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 mount of 0.02% by weight. The preparation of the mortar mixtures was carried out in accordance with section [0105] of 10 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 and the sedimentation were assessed visually by a person skilled in the art. The values were taken directly after stirring and after 20 minutes. 15 The copolymers used in each case and the results obtained are summarized in table 6.

56 (1 CL) U) C) )> 00 c6 c6 e .2) a) 0) C\( xmN = -D 0) C 0) 0 06 0- c - C M (D LO r 0) 0 0) 0 80 0) CY- ) ~ 0 0D 0) o CD 0a) 0) E 0) 0 E CO CD CCu co E 0 E 000 -c

(

00 -D -E( 0)) E E 0).t oE ca( V_ _ 3: CIu 57 0 C) 1' 0 0 0N 0 0 cu--2 r-Cc r- c C cc 0 w

C

E 2%)a) a)0) D. to 0)0 0 0 o -> > >' > 0)0) a)0() 0 1) (0 ) cl) a C~N 0 0 (N00 CV) E r'- c c r- c c a.C)00l)0 CL E a, cu a 0 0 CN 0 0 E a'~c r c E cu 0) E CUEE -F E 0 c U) E 2 c C MC c 0) - c 0D i5EaL1 E w :6E w-; 0 .22 02 T w cu oD co U)CD colI (0 PF 62163 58 Part C-3) Test of the Copolymers of the type A4 Preparation of an exemplary liquid detergent 5 The following stock formulations are prepared (% by weight, based on the finished formulation): Component Amount Anionic surfactant (linear alkylbenzene sulfonic acid, C 10

-

1 3 ) 13.44 Nonionic surfactant (C 13 1 5 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 0 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 5 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. 20 - The low-shear viscosity was measured taking into consideration the instructions in accordance with DIN 51550, DIN 53018, DIN 53019 using the Brookfield viscometer 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.

PF 62163 59 To quantify the transparency of the thickened formulations, the transmission in % was measured at 440 nm at 23 0 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. 5 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 10 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 15 the invention produce a significantly higher viscosity than comparison sample 7 which does PF 62163 60 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. 5 It is to be understood that, if any prior art publication is referred to herein, such reference does not constitute an admission that the publication forms a part of the common general knowledge in the art, in Australia or any other country. In the claims which follow and in the preceding description of the invention, except where the 0 context requires otherwise due to express language or necessary implication, the word "comprise" or variations such as "comprises" or "comprising" is used in an inclusive sense, i.e. to specify the presence of the stated features but not to preclude the presence or addition of further features in various embodiments of the invention. 5865413 1 (GHMatters) P88688.AU FELISAS

Claims (23)

1. A water-soluble, hydrophobically associating copolymer comprising at least 5 (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, 0 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 (1) 5 H 2 C=C(R 1 )-R 4 -O-(-CH 2 -CH(R 2 )-O-)k-(-CH2-CH(R 3 )-O-)I-R 5 (1) where the units -(-CH2-CH(R 2 )-O-)k and -(-CH 2 -CH(R 3 )-O-), are arranged in block structure in the order shown in formula (1) and the radicals and indices have the following meaning: 0 k: a number from 10 to 150, 1: 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 5 50 mol% of the radicals R 2 are H, R3: independently of one another, a hydrocarbon radical having at least 2 carbon atoms or an ether group of the general formula -CH 2 -0-R 2 ', where R 2 ' is a hydrocarbon radical having at least 2 carbon atoms, R4: a divalent linking group, -O-(Co'H 2 n.)-, where n' is a natural number from 1 to 6, 30 R 5 : H or a hydrocarbon radical having 1 to 30 carbon atoms.

2. The copolymer according to claim 1, wherein R 3 is a hydrocarbon radical having at least 3 carbon atoms. 35

3. The copolymer according to claim 1 or 2, wherein R 1 is H and R 4 is -O-CH 2 -CH 2 -CH 2 CH 2 -.

4. The copolymer according to any one of claims 1 to 3, wherein R 5 is H. amended sheets 6055682 1 (GHMatters) P88688.AU RDAULTON 62

5. The copolymer according to any one of claims 1 to 4, wherein at least one of the monomers (b) is a monomer comprising acid groups or salts thereof.

6. The copolymer according to claim 5, wherein the acidic groups are at least one group 5 selected from the group of -COOH, -SO 3 H and -P0 3 H 2 or salts thereof.

7. The copolymer according to any one of claims 1 to 4, which is a copolymer (Al) which comprises at least two different hydrophilic monomers (b), and these are at least 0 0 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, -SO 3 H or -P0 3 H 2 or salts thereof, 5 where the amount of the monomers (a) is 0.1 to 12% by weight and that of all the monomers (b) together is 70 to 99.9% by weight with regard to the amount of all of the monomers in the copolymer.

8. The copolymer according to claim 7, wherein the neutral monomer (b1) is a monomer 0 selected from the group of (meth)acrylamide, N-methyl(meth)acrylamide, N,N' dimethyl(meth)acrylamide, N-methylol(meth)acrylamide or N-vinyl-2-pyrrolidone, and the monomer (b2) is at least one selected from the group of (meth)acrylic acid, vinylsulfonic acid, allylsulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid (AMPS), 2-methacrylam ido-2-methylpropanesulfonic acid, 2-acrylam idobutanesulfonic 5 acid, 3-acrylamido-3-methylbutanesulfonic acid or 2-acrylamido-2,4,4 trimethylpentanesulfonic acid or vinylphosphonic acid.

9. The copolymer according to claim 7 or 8, wherein the copolymer moreover also comprises at least one cationic monomer (b3) having ammonium groups. 30

10. The copolymer according to claim 9, wherein the cationic monomer is salts of 3-trimethylammonium propyl(meth)acrylam ides and 2-trimethylammonium ethyl (meth)acrylates. 35

11. The copolymer according to any one of claims 7 to 10, wherein the amount of the monomers (a) is 0.1 to 5% by weight with regard to the amount of all of the monomers in the copolymer.

12. The copolymer according to any one of claims 1 to 4, which is a copolymer (A2) which 40 comprises at least two different hydrophilic monomers (b), and these are at least * one neutral hydrophilic monomer (b1), and amended sheets 5994121 1 (GHMatters) P88688.AU RDAULTON PF 62163 63 * at least one cationic monomer (b3), where the amount of the monomers (a) is 0.1 to 12% by weight and that of all of the 5 monomers (b) together is 70 to 99.9% by weight with regard to the amount of all of the monomers in the copolymer.

13. The copolymer according to any one of claims 1 to 4, which is a copolymer (A3) which comprises at least two different hydrophilic monomers (b), and these are at least 0 * 5 to 50% by weight of at least one neutral hydrophilic monomer (b1), and * 25 to 94.9% by weight of at least one anionic monomer (b2) comprising sulfonic acid groups, 5 where the amount of the monomers (a) is 0.1 to 12% by weight, and that of all of the monomers (b) together is 70 to 99.9% by weight with regard to the amount of all of the monomers in the copolymer. 0

14. The copolymer according to claim 12 or 13, wherein the copolymer comprises, as monomer (a), additionally at least one monomer of the general formulae H 2 C=C(R 1 ) COO-CH 2 -CH(R 5 )-O-)q-R 6 (Ila) and/or H 2 C=C(R)-O-(-CH 2 -CH(R 5 )-O-)q-R 6 (Ilb), where R 1 is H or methyl, 5 q is a number from 10 to 150, R 5 , independently of one another, are H, methyl or ethyl, where at least 50 mol% of the radicals R 5 are H, and R 6 is an aliphatic and/or aromatic, straight-chain or branched hydrocarbon radical having 6 to 40 carbon atoms, 30 with the proviso that at least 0.1% by weight of the monomers (a) of the formula (1) are used, and furthermore at least 25% by weight of the amount of all of the monomers (a) are monomers of the formula (1).

15. The copolymer according to any one of claims 12 to 14, wherein the copolymer also 35 comprises up to 1% by weight of a crosslinking monomer (d) comprising at least two ethylenically unsaturated groups, where monomer (d) is at least one selected from the group of 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 40 or oligoethylene glycol di(meth)acrylates such as, for example, polyethylene glycol bis(meth)acrylate, N,N'-methylenebis(meth)acrylamide, ethylene glycol divinyl ether, amended sheets 5994121 1 (GHMatters) P88688.AU RDAULTON PF 62163 64 triethylene glycol divinyl ether, triallylamine, triallylamine methammonium chloride, tetraallylammonium chloride and tris(2-hydroxy)isocyanurate tri(meth)acrylate.

16. The copolymer according to claim 1 or 2, which is a copolymer (A4) which comprises 5 * at least one monomer (b) comprising COOH groups, and * at least one monomer (c) of the general formula H 2 C=C(R 16 )-COOR 18 , where R 16 is H or methyl and R 18 is a straight-chain or branched, aliphatic, cycloaliphatic 0 and/or aromatic hydrocarbon radical having 1 to 30 carbon atoms, where the amount of all of the monomers (a) together is 0.1 to 20% by weight, that of all of the monomers (b) is 25 to 94.9% by weight and that of all of the monomers (c) is 5 to 74.9% by weight. 5

17. The copolymer according to claim 16, wherein the amount of all of the monomers (c) together is 25 to 74.5% by weight.

18. The copolymer according to claim 16 or 17, wherein at least one of the monomers (c) is 0 one selected from the group of ethyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate or 2-propylheptyl (meth)acrylate.

19. The use of copolymers according to any one of claims 1 to 11 in the development, exploitation and completion of subterranean mineral oil deposits and natural gas 5 deposits.

20. The use of copolymers according to any one of claims 1 to 11 for enhanced oil recovery by injecting an aqueous formulation of said copolymers in a concentration of 0.01 to 5% by weight through at least one injection bore into a mineral oil deposit and 30 removing crude oil from the deposit through at least one production bore.

21. The use according to claim 20, wherein the aqueous formulation additionally comprises at least one surfactant. 35

22. The use of copolymers according to any one of claims 1 to 15 as additive for aqueous construction systems which comprise hydraulic binder systems.

23. The use of copolymers according to any one of claims 1 to 6 and 16 to 18 for the production of liquid detergents and cleaners. amended sheets 5994121 1 (GHMatters) P88688.AU RDAULTON