EP2931766A1

EP2931766A1 - Water-soluble, hydrophobically associating copolymers having novel hydrophobically associating monomers

Info

Publication number: EP2931766A1
Application number: EP13805363.2A
Authority: EP
Inventors: Christian Bittner; Björn LANGLOTZ; Benjamin Wenzke; Christian Spindler; Roland Reichenbach-Klinke
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2012-12-17
Filing date: 2013-12-13
Publication date: 2015-10-21
Also published as: AU2013363888A1; ECSP15030861A; US9777094B2; ZA201505109B; JP2016500384A; KR20150095906A; KR102161957B1; CN104995222B; CN104995222A; RU2015128885A; AU2013363888B2; BR112015014069A2; CA2893025C; JP6567423B2; BR112015014069B1; WO2014095621A1; AR094021A1; US20150329660A1; MY171132A; CA2893025A1

Abstract

The present invention relates to water-soluble, hydrophobically associating copolymers, which are obtained in the presence of a non-polymerisable, surface-active compound and which contain novel hydrophobically associating monomers. The monomers comprise an ethylenically unsaturated group and a polyether block, the polyether block containing a hydrophilic polyethyleneoxy block and a hydrophobic polyalkyleneoxy block, which consists of alkyleneoxy units having at least 4 carbon atoms. The monomers can optionally have a terminal polyethyleneoxy block. The invention further relates to a method for producing the copolymers and to the use thereof.

Description

Water-soluble, hydrophobically associating copolymers with novel hydrophobically associating monomers

description

The present invention relates to water-soluble hydrophobically associating copolymers obtained in the presence of a non-polymerizable surface-active compound and containing novel hydrophobically-associating monomers. The monomers include an ethylenically unsaturated group and a polyether block, wherein the polyether block contains a hydrophilic polyethyleneoxy block and a hydrophobic polyalkyleneoxy block consisting of alkyleneoxy units having at least 4 carbon atoms. Optionally, the monomers may have a terminal polyethyleneoxy block. The invention further relates to processes for the preparation of the copolymers and their use.

Water-soluble, thickening polymers are used in many fields of technology, for example in the field of cosmetics, in food, for the production of cleaning agents, printing inks, emulsion paints or in the production of oil.

There are many chemically different classes of polymers known which can be used as thickeners. An important class of thickening polymers are the so-called hydrophobically associating polymers. By this the skilled person means water-soluble polymers which have side or terminal hydrophobic groups, such as longer alkyl chains. In aqueous solution, such hydrophobic groups may associate with themselves or with other substances having hydrophobic groups. As a result, an associative network is formed, through which the medium is thickened. EP 705 854 A1, DE 100 37 629 A1 and DE 10 2004 032 304 A1 describe water-soluble, hydrophobically associating copolymers and their use, for example in the field of construction chemistry.

It is known to use hydrophobic associating copolymers in the field of crude oil production, in particular for tertiary oil recovery (Enhanced Oil Recovery, EOR). For details see, for example, the review by Taylor, KC and Nasr-El-Din, HA in J. Petr. Be. Closely. 1998, 19, 265-280. One of the techniques of tertiary oil production is the so-called "polymer flooding." An oil reservoir is not an underground "oil lake," but the oil is held in tiny pores of the oil-bearing rock. The diameter of the cavities in the formation is usually only a few microns. For polymer fl ow, an aqueous solution of a thickening polymer is injected through injection bores into a crude oil deposit. By injecting the polymer solution, the petroleum is forced through said cavities in the formation from the injection well towards the production well, and the petroleum is pumped through the production well. Important for this application is that the aqueous polymer solution does not contain any gel particles. Even small gel particles with dimensions in the micrometer range can clog the fine pores in the formation and thus bring the oil production to a standstill. Hydrophobic associating copolymers for tertiary mineral oil production should therefore have the lowest possible proportion of gel particles.

Another technique in oil production is the so-called "hydraulic fracturing". In "hydraulic fracturing" typically a high-viscosity, aqueous solution is pressed under high pressure into the oil or gas-carrying formation layer. The high pressure causes cracks in the rock, which facilitate the extraction of oil or gas. Guar and its more temperature-stable derivatives such as, for example, hydroxypropyl guar or carboxymethylhydroxypropyl guar are used here as thickeners (J.K. Fink, Oil Field Chemicals, Elsevier 2003, p. 240 ff). However, like most polymers, these biopolymers show a significant decrease in viscosity with increasing temperature. However, since elevated temperatures prevail in the subterranean formations, it would be advantageous to use thickeners for use in "hydraulic fracturing" whose viscosity does not decrease or even increase with increasing temperature.

Further fields of application of hydrophobically associating copolymers in the field of mineral oil production is the thickening of drilling fluids and completion fluids. For example, in the review article, Taylor, Ann. Transactions of the Nordic Rheology Society, Vol. 11, 2003.

WO 2010/133527 describes the preparation of hydrophobically associating monomers of the type H ₂ C =C (R ¹ ) -R ⁴ -O- (-CH ² -CH (R ² ) -O-) k - (- CH ₂ -CH (R ³ ) -O-) iR ⁵ and the subsequent reaction with further hydrophilic monomers to give copolymers. The macromonomers described have an ethylenically unsaturated group and a polyether group having a block structure which consists of a hydrophilic polyalkyleneoxy block consisting essentially of ethyleneoxy units and consists of a terminal, hydrophobic polyalkyleneoxy block consisting of alkyleneoxy units having at least 4 carbon atoms.

The document WO 201 1/015520 describes the copolymerization of hydrophobic-associating monomers and monoethylenically unsaturated hydrophilic monomers in the presence of nonionic surfactants and the use of the resulting copolymers for polymer flooding.

CN 102146159 A also describes a process for preparing a polyvinyl ether monomer, wherein the polyether monomer has the general formula H2C = C (R ² ) -O-R ¹ -O- (CaH ₂ aO) n - (CbH ₂ bO) m H wherein a and b are integers from 2 to 4, a is not equal to b and R ^{1 is} a Ci-Cs-alkylene group. The monomers described in the document have a polyalkyleneoxy block which is composed of ethylene oxide, propylene oxide and / or butylene oxide. The alkoxylation is preferably carried out at a temperature in the range from 120 to 160 ° C and with the addition of an alkylic catalyst, for example potassium methoxide.

To prepare the monomers, in the process according to WO 2010/133527, suitable monoethylenically unsaturated alcohols are used, which are then alkoxylated in a two-stage process, so that the abovementioned block structure is obtained. First, an alkoxylation with ethylene oxide, optionally in admixture with propylene oxide and / or butylene oxide and in a second step with alkylene oxides having at least 4 carbon atoms. The examples in WO 2010/133527 describe the performance of the alkoxylation using KOMe (potassium methoxide) as the catalyst at a reaction temperature of 140 ° C., the concentration of potassium ions being above 3 mol%.

The alkoxylation reaction is often carried out base catalysis. For this purpose, the alcohol used as starting material is usually mixed in a pressure reactor with alkali metal hydroxides or alkali metal and converted into the corresponding alkoxide. Subsequently, usually under inert gas atmosphere, for example, in several steps, the alkylene oxides are added. In order to control the reaction and avoid oversaturation of the reaction mixture with alkylene oxide, it is usually necessary to observe certain pressure and temperature ranges during the alkoxylation.

The process according to WO 2010/133527 is intended to avoid the formation of crosslinking by-products, so that the preparation of copolymers with a low gel content should be possible. However, it has been found that the prior art preparation methods are not a reliable method for preparing hydrophobically associating low gel copolymers. Fluctuating qualities of the copolymer were found, for example, with variation of pressure and reaction time during the alkoxylation steps, so that partially highly crosslinked copolymer products were obtained.

It has been found that prior art processes presumably form monomers having two ethylenically unsaturated groups as a by-product. These bifunctional by-products have a crosslinking effect and lead to increased gel formation in the copolymerization. It has been found that the higher the temperature, and the longer the reaction lasts, the more frequently these undesirable side reactions occur. Usually, copolymers with gel content are no longer filterable and no longer usable for injection into porous matrixes in oil reservoirs.

Typically, KOMe (potassium methoxide) is preferred as the basic catalyst over NaOMe (sodium methoxide) because KOMe is more basic than NaOMe and therefore the alkoxylation reaction proceeds faster. However, it has been found that the more basic KOM favors the formation of the above-described crosslinking monomers. Butylene and pentylene oxide react much slower than ethylene or propylene oxide, therefore, the side reactions in the alkoxylation with butylene or pentylene oxide have a clearer effect. It was therefore an object of the invention to provide hydrophobically associating copolymers with lower or undetectable gel fractions in comparison to the already known copolymers starting from novel, crosslinker-free monomers. In addition, the copolymers should be able to be produced more economically than hitherto and their effect as thickeners should be at least equal to the previous compounds.

It has now surprisingly been found that the formation of crosslinking bifunctional compounds and thus the gel content in the resulting copolymers can be reduced or almost completely prevented if a critical amount of potassium ions of less than or equal to 0.9 mol% is used attention is paid to the alcohol to be alkoxylated and a temperature of less than or equal to 135 ° C. in the second alkoxylation step (reaction with butylene oxide or pentylene oxide). It has also been found that the production process of the invention under the given safety requirements of the chemical and the operation (in particular a pressure of less than 2.1 bar in the alkoxylation with pentylene oxide and in particular a pressure of less than 3.1 bar in the alkoxylation with butylene oxide) ensures good reproducibility with adequate reaction time. Accordingly, water-soluble, hydrophobically associating copolymers have been found comprising the following monomers:

(A) 0.1 to 20 wt .-% of at least one hydrophobically associating monomer (a), and

(B) 25 to 99.9 wt .-% of at least one of monomer (a) different hydrophilic monomer (b), wherein in its synthesis prior to the initiation of the polymerization at least one further, but not polymerizable surface-active component (c) is used in which the quantities are in each case based on the total amount of all monomers in the copolymer, and wherein at least one of the monomers (a) is a monomer of the general formula (I)

H ₂ C = C (R ¹ ) -R ² -O - (- CH ₂ -CH ₂ -O-) k - (- CH ₂ -CH (R ³ ) -O-) i - (- CH ₂ -CH ₂ -O- ) _{m is} -R ⁴ (I); where the units - (- CH ₂ -CH ₂ -O-) k, - (- CH ₂ -CH (R ³ ) -O-) i and optionally

- (- CH 2 -CH 2 -O-) m are arranged in block structure in the order shown in formula (I), and the radicals and indices have the following meanings: k: is a number from 15 to 35, preferably from 20 to 28 , more preferably from 23 to 26;

I: is a number from 5 to 30, preferably from 5 to 28, preferably from 5 to

25;

m: is a number from 0 to 15, preferably from 0 to 10;

R ¹ : is H or methyl;

R ² : is independently a single bond or a divalent linking group selected from the group of - (C n F n) - and - O- (Cn'H n ') -, where n is a natural number from 1 to 6 and n' is a natural number from 2 to 6,

is independently a hydrocarbon radical with at least 2

Carbon atoms or an ether group of the general formula --CH 2 -OR ^{3 '} , wherein R ^{3' is} a hydrocarbon radical having at least 2 carbon atoms, with the proviso that the sum of the carbon atoms of all hydrocarbon radicals R ³ or R ³ 'in the range of 15 to 60 is preferably from 15 to 56, preferably from 15 to 50;

R ⁴ : is independently H or a hydrocarbon radical of 1 to 4 carbon atoms; and wherein the hydrophobically associating monomer (a) of the general formula (I) is obtainable by a process comprising the steps of: reacting a monoethylenically unsaturated alcohol A1 of the general one

Formula (II)

H ₂ C = C (R ¹ ) -R ² -OH (II), with ethylene oxide,

wherein the radicals R ¹ and R ^{2 have} the meanings defined above;

with the addition of an alkaline catalyst K1 containing KOMe and / or

NaOMe;

wherein an alkoxylated alcohol A2 is obtained;

Reacting the alkoxylated alcohol A2 with at least one alkylene oxide Z of the formula (Z) wherein R ^{3 has} the meaning defined above;

with the addition of an alkaline catalyst K2; wherein the concentration of potassium ions in the reaction in step b) less than or equal to 0.9 mol%, preferably from 0.01 to 0.9 mol%, particularly preferably 0.01 to 0.5 mol%, based on the alcohol used is A2; and wherein the reaction in step b) is carried out at a temperature of less than or equal to 135 ° C; where an alkoxylated alcohol A3 according to the formula (III)

H ₂ C = C (R ¹ ) -R ² -O - (- CH ₂ -CH ₂ -O-) k - (- CH ₂ -CH (R ³ ) -O-) i R ⁴ (III), where R ⁴ = H, wherein the radicals R ¹ , R ² and R ³ and the indices k and I have the meanings defined above; c) optionally reacting at least a portion of the alkoxylated alcohol A3 with ethylene oxide; wherein the alkoxylated alcohol A4 is obtained, which corresponds to the monomer (a) according to formula (I) with R ⁴ = H and m>0; d) optionally etherifying the alkoxylated alcohol A3 and / or A4 with a compound

R ₄ -X where R ^{4 has} the meanings defined above and X is a leaving group, preferably selected from the group of Cl, Br, I, -O-SO 2 -CH 3 (mesylate), -O-SO 2 -CF 3 (triflate) and O-SO 2 -OR ⁴ is; wherein a monomer (a) according to formula (I) and / or (III) is obtained with R ⁴ = hydrocarbon radical having 1 to 4 carbon atoms.

In a preferred embodiment, the invention relates to water-soluble, hydrophobically associating copolymers, wherein the radicals and indices in the monomers (a) according to formula (I) have the following meanings: k: is a number from 23 to 26;

I: is a number from 5 to 30, preferably from 5 to 28, preferably from 5 to

25;

m: is a number from 0 to 15, preferably from 0 to 10;

R ¹ : is H or methyl;

R ² : is independently a single bond or a divalent linking group selected from the group of - (CnF n) - and - O- (Cn'F n ') -, where n is a natural number from 1 to 6 and n 'is a natural number from 2 to 6, R ³ : is independently of one another a hydrocarbon radical having at least 2 carbon atoms or an ether group of the general formula --CH 2 -OR ^{3 '} , where R ^{3' is} a hydrocarbon radical having at least 2 carbon atoms, with the proviso that the sum of the carbon atoms of all Hydrocarbon radicals R ³ or R ³ 'in the range of

15 to 60, preferably from 15 to 56, preferably from 15 to 50;

R ⁴ : is independently H or a hydrocarbon radical having 1 to 4 carbon atoms. In a preferred embodiment, the total sum of all monomers in the copolymer is 100% by weight.

The monomer (a) is preferably exclusively a monomer of the general formula (I) as described above.

In a preferred embodiment, the invention relates to water-soluble, hydrophobically associating copolymers comprising the following monomers:

(C) 0.1 to 20 wt .-% of at least one hydrophobically associating monomer (a), and

(d) from 25 to 99.9% by weight of at least one hydrophilic monomer (b) other than monomer (a), wherein in its synthesis prior to the initiation of the polymerization reaction at least one further, but not polymerizable surface-active component (c) is used, wherein the quantities are in each case based on the total amount of all monomers in the copolymer, and wherein it is at least one of the monomers

(a) a monomer of the general formula (I)

H ₂ C = C (R ¹ ) -R ² -O - (- CH ₂ -CH ₂ -O-) k - (- CH ₂ -CH (R ³ ) -O-) i - (- CH ₂ -CH ₂ -O- ) _{m is} -R ⁴ (I); where the units are - (- CH ₂ -CH ₂ -O-) k, - (- CH ₂ -CH (R ³ ) -O-) i and optionally - (- CH ₂ -CH ₂ -O-) _m in block structure are arranged in the order shown in formula (I), and the radicals and indices have the following meanings: k: is a number from 23 to 26;

I: is a number from 8.5 to 17.25

m: is a number from 0 to 15, preferably from 0 to 10;

R ¹ : is H or methyl;

R ² : is independently a single bond or a divalent linking group selected from the group of - (CnF n) - and - O- (Cn H2n ') -, where n is a natural number from 1 to 6 and n 'stands for a natural number from 2 to 6,

R ³ : is independently of one another a hydrocarbon radical having at least 2 carbon atoms or an ether group of the general formula --CH 2 -OR ^{3 '} , where R ^{3' is} a hydrocarbon radical having at least 2 carbon atoms, with the proviso that the sum of the carbon atoms of all hydrocarbon radicals R ³ or R ³ 'is in the range of 25.5 to 34.5;

R ⁴ : is independently H or a hydrocarbon radical of 1 to 4 carbon atoms; and wherein the hydrophobically associating monomer (a) of general formula (I) is obtainable by a process comprising the following steps:

Reacting a monoethylenically unsaturated alcohol A1 of the general formula (II)

H ₂ C = C (R ¹ ) -R ² -OH (II), with ethylene oxide,

wherein the radicals R ¹ and R ^{2 have} the meanings defined above;

with the addition of an alkaline catalyst K1 containing KOMe and / or

NaOMe;

wherein an alkoxylated alcohol A2 is obtained;

H ₂ C = C (R ¹ ) -R ² -O - (- CH ₂ -CH ₂ -O-) k - (- CH ₂ -CH (R ³ ) -O-) i R ⁴ (III), where R ⁴ = H, wherein the radicals R ¹ , R ² and R ³ and the indices k and I have the meanings defined above; optionally reacting at least a portion of the alkoxylated alcohol A3 with ethylene oxide; wherein the alkoxylated alcohol A4 is obtained, which corresponds to the monomer (a) according to formula (I) with R ⁴ = H and m>0; optionally etherifying the alkoxylated alcohol A3 and / or A4 with a compound

In a preferred embodiment, the sum total of all monomers copolymer is 100% by weight.

The monomer (a) is preferably exclusively a monomer of the general formula (I) as described above. Furthermore, the preparation of such copolymers has been found, as well as their use for the development, exploitation and completion of underground oil and gas deposits. In detail, the following is to be accomplished for the invention:

The hydrophobically associating copolymers according to the invention are water-soluble copolymers which have hydrophobic groups. In aqueous solution, the hydrophobic groups can associate with themselves or with the hydrophobic groups of other substances and thicken the aqueous medium through these interactions.

It is known to the person skilled in the art that the solubility of hydrophobically associating (co) polymers in water can be more or less dependent on the pH, depending on the type of monomers used. The reference point for the assessment of the water solubility should therefore be in each case the desired pH value for the respective intended use of the copolymer.

Monomer (a)

The hydrophobically associating copolymer according to the invention comprises at least one monoethylenically unsaturated monomer (a) which imparts hydrophobically associating properties to the copolymer according to the invention and is therefore referred to below as a hydrophobically associating monomer.

According to the invention, at least one of the hydrophobically associating monomers (a) is a monomer of the general formula (I)

H ₂ C = C (R ¹ ) -R ² -O - (- CH ₂ -CH ₂ -O-) k - (- CH ₂ -CH (R ³ ) -O-) i - (- CH ₂ -CH ₂ -O- _m -R ⁴ (I).

In the monomers (a) of the general formula (I), an ethylenic group H2C = C (R ¹ ) - via a divalent, linking group -R ² -O- with a polyalkyleneoxy radical having a block structure - (- CH ₂ -CH ₂ -O -) k - (- CH ₂ -CH (R ³ ) -O-) iR ⁴ wherein the blocks - (- CH ₂ -CH ₂ -O-) _k and - (- CH ₂ -CH (R ³ ) -0-) i are arranged in the order shown in formula (I). Optionally, the monomer (a) of formula (I) may have another polyethyleneoxy block - (- CH 2 -CH 2 -O-) _m . The polyalkyleneoxy group has either a terminal OH group or a terminal ether group OR ⁴ . In the above formula, R ^{1 is} H or a methyl group. Preferably, R ¹ is H.

R ² is a single bond or a divalent linking group selected from the group - (CnF n) - and -O- (Ο _η Ή2η) -. In said formulas, n is a natural number from 1 to 6 and n 'is a natural number from 2 to 6. In other words, the linking group is straight-chain or branched aliphatic hydrocarbon groups having 1 to 6 carbon atoms or 2 to 6 carbon atoms, which are linked either directly or via an ether group -O- with the ethylenic group H2C = C (R ¹ ) -. The groups - (CnF n) - and - {C _n H _2n - are preferably linear aliphatic hydrocarbon groups.

Preferably, the group R ² = - (CnF n) - is a group selected from -CH ² -, -CH ² -CH ² - and -CH ² -CH ² -CH ² -, more preferably a methylene group is -CH 2 -.

Preferably, the group R ² = -O- (Ο _η Ή2η) - is a group selected from -O-CH ² -CH ² -, -O-CH ² -CH ² -CH ² - and -O-CH 2 -CH 2 -CH 2 -CH 2 -, more preferably -O-CH 2 -CH 2 -CH 2 -CH 2 -.

Particularly preferably, the group R ² is a group -O- (Ο _η Ή2η) -.

With particular preference, R ² is a group selected from -CH ₂ - or -O-CH ₂ -CH ₂ -CH ₂ -CH ₂ -, very particularly preferably -O-CH ₂ -CH ₂ -CH ₂ -CH ₂ -.

The monomers (a) furthermore have a polyalkyleneoxy radical which consists of the units - (- CH ₂ -CH ₂ -O-) _k , - (- CH ₂ -CH (R ³ ) -O-) i and optionally - (- CH ₂ -CH ₂ -O-) _m , wherein the units are arranged in block structure in the order shown in formula (I). The transition between the blocks can be abrupt or continuous.

The number of ethyleneoxy units k is a number from 15 to 35, preferably from 20 to 28, particularly preferably from 23 to 26.

The number of ethyleneoxy units k is preferably from 23 to 26. It is clear to those skilled in the art of polyalkylene oxides that the numbers mentioned are average values of distributions. In the second block - (- CH 2 -CH (R ³ ) -O-) i-, the radicals R ^{3 are} independently hydrocarbon radicals having at least 2 carbon atoms, preferably having 2 to 14 carbon atoms, preferably 2 to 4, and particularly preferred with 2 or 3 carbon atoms. This may be an aliphatic and / or aromatic, linear or branched carbon radical. Preference is given to aliphatic radicals. Particularly preferred is an aliphatic, unbranched hydrocarbon radical having 2 or 3 carbon atoms. The said block is preferably a polybutyleneoxy block or a polypentyleneoxy block.

Examples of suitable radicals R ³ include ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl or n-decyl, n-dodecyl, n-tetradecyl and phenyl.

Examples of suitable radicals R ³ include ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl or n-decyl and also phenyl. Examples of preferred radicals include n-propyl, n-butyl, n-pentyl, particularly preferably an ethyl radical or an n-propyl radical.

The radicals R ³ may furthermore be ether groups of the general formula --CH 2 -OR ^{3 '} , where R ^3' is an aliphatic and / or aromatic, linear or branched hydrocarbon radical having at least 2 carbon atoms, preferably 2 to 10 Carbon atoms and more preferably at least 3 carbon atoms. Examples of radicals R ^{3 '} include n-propyl, n-butyl, n-pentyl, n-hexyl, 2-ethylhexyl, n-heptyl, n-octyl, n-nonyl, n-decyl or phenyl.

Examples of radicals R ^{3 '} include n-propyl, n-butyl, n-pentyl, n-hexyl, 2-ethylhexyl, n-heptyl, n-octyl, n-nonyl n-decyl, n-dodecyl, n-tetradecyl or phenyl.

The block - (- CH 2 -CH (R ³ ) -O-) i- is thus a block consisting of alkyleneoxy units having at least 4 carbon atoms, preferably having 4 or 5 carbon atoms and / or glycidyl ethers having an ether group of at least 2, preferably at least 3 carbon atoms. Preferred radicals R ³ are the hydrocarbon radicals mentioned; the building blocks of the second block are particularly preferably alkyleneoxy units comprising at least 4 carbon atoms, such as butyleneoxy and pentyleneoxy units or units of higher alkylene oxides, very particular preference being given to butylene oxide or pentyleneoxy units.

It will be clear to one skilled in the art of polyalkylene oxides that the orientation of the hydrocarbon radicals R ³ will depend on the conditions of the alkoxylation can, for example, from the catalyst selected for the alkoxylation. Thus, the alkyleneoxy groups can be incorporated into the monomer either in the orientation - (- CH 2 -CH (R ³ ) -O-) or in the inverse orientation - (- CH (R ³ ) -CH 2 O -) - , The representation in formula (I) should therefore not be regarded as being restricted to a specific orientation of the group R ³ .

The number of alkyleneoxy units I is a number from 5 to 30, preferably from 5 to 28, preferably from 5 to 25, preferably from 7 to 23, preferably from 7 to 18, particularly preferably from 8.5 to 17, 25 with the proviso that the sum of the carbon atoms in all hydrocarbon radicals R ³ or R ³ 'is in the range from 15 to 60, preferably from 15 to 56, preferably from 15 to 50, preferably from 25.5 to 34.5. If the radicals R ³ are an ether group -CH 2 -OR ^{3 '} , the proviso is that the sum of the hydrocarbon radicals of ste R ^3' in the range from 15 to 60, preferably from 15 to 56, preferably 15 to 50, especially preferably from 25.5 to 34.5, wherein the carbon atom of the linking -Ch -O group in -CH 2 OR ^{3 'is} not taken into account.

A preferred embodiment relates to a copolymer described above comprising a monomer (a), wherein R ^{3 is} ethyl and I is a number from 7.5 to 28, preferably from 7.5 to 25, particularly preferably from 12.75 to 25, particularly preferred from 13 to 23, particularly preferably from 12.75 to 17.25, for example 14, 16 or 22.

The number of alkyleneoxy units I in a preferred embodiment is a number from 8.5 to 17.25, with the proviso that the sum of the carbon atoms in all hydrocarbon radicals R ³ or R ³ 'in the range from 25.5 to 34.5 lies. If the radicals R ³ are an ether group -CH 2 -OR ^{3 '} , the proviso that the sum of the hydrocarbon radicals R ^{3' is} in the range from 25.5 to 34.5, wherein the carbon atom of the linking -CH 2 - 0 group in -CH2-OR ^{3 'is} not taken into account. A preferred embodiment relates to a copolymer described above comprising a monomer (a), wherein R ^{3 is} ethyl and I is a number from 12.75 to 17.25, in particular from 13 to 17, for example 14 or 16, is. A further preferred embodiment relates to a copolymer described above comprising a monomer (a), wherein R ^{3 is} n-propyl and I is a number from 8.5 to 1, 5, preferably from 9 to 1 1, for example 10 or 1 1, is. It will be apparent to those skilled in the art of polyalkylene oxides that the numbers given are means of distribution.

The optional block - (- CH2-CH2-0-) _m is a polyethyleneoxy block. The number of ethyleneoxy units m is a number of 0 to 15, preferably from 0 to 10, particularly preferably from 0.1 to 10, particularly preferably from 0.1 to 5, particularly preferably from 0.5 to 5 and very particularly preferably from 0.5 to 2.5. It will be apparent to those skilled in the art of polyalkylene oxides that the numbers given are means of distribution.

In a preferred embodiment of the invention, m is greater than 0 (i.e., the optional step c) is performed). In particular, in this embodiment, m is a number from 0.1 to 15, preferably from 0.1 to 10, particularly preferably from 0.5 to 10, particularly preferably from 1 to 7, more preferably from 2 to 5. For the expert In the field of polyalkylene oxides, it is clear that the numbers mentioned are mean values of distributions.

The radical R ⁴ is H or a preferably aliphatic hydrocarbon radical having 1 to 4 carbon atoms. R ⁴ is preferably H, methyl or ethyl, particularly preferably H or methyl and very particularly preferably H.

In the case of the monomers of the formula (I), therefore, a terminal, monoethylenic group is linked to a block-structured polyalkyleneoxy group, first with a hydrophilic block having polyethyleneoxy units and this in turn with a second hydrophobic block which consists of alkyleneoxy units, preferably at least butyleneoxy units or units of higher alkylene oxides and more preferably composed of butyleneoxy or Pentylenoxyeinheiten. The second block may have a terminal -OR ⁴ group, in particular an OH group. The end group need not be etherified with a hydrocarbon radical for hydrophobic association, but the second block - (- CH 2 -CH (R ³ ) -O-) even with the radicals R ³ or R ^{3 '} is for the hydrophobic association of the responsible for the use of monomers (a). The etherification is only an option that can be selected by the skilled person depending on the desired properties of the copolymer.

It will be clear to one skilled in the art of polyalkyleneoxy block copolymers that the transition between the two blocks can be abrupt or continuous, depending on the nature of the preparation. In a continuous transition, there is still a transition zone between the blocks, which comprises monomers of both blocks. Accordingly, if the block boundary is set to the middle of the transition zone, the first block can still contain - (-Ch-CH-O- small amounts of units - (- CH ₂ -CH (R ³ ) -0 -) and the second Block - (- CH ₂ -CH (R ³ ) -O-) i have small amounts of units - (- CH ₂ -CH ₂ -O -) - but these units are not statistically distributed over the block, but are arranged in said transition zone. In particular, the optional third block (-CH 2 -CH 2 -O-) _m may contain small amounts of units - (- CH 2 -CH (R ³ ) -O -) -. The present invention relates to a process for the preparation of a monomer M according to formula (I), wherein the units (-CH ₂ -CH ₂ -O-) _k and (-CH ₂ -CH (R ³ ) -O-) i and optionally - (- CH 2 -CH 2 -O-) _{m arranged} in block structure in the order shown in formula (I). Block structure in the sense of the present invention means that the blocks are composed of at least 85 mol%, preferably at least 90 mol%, more preferably at least 95 mol%, based on the total amount of substance of the respective block, of the corresponding units are. This means that the blocks in addition to the corresponding units can have small amounts of other units (in particular other polyalkyleneoxy units). In particular, the optional polyethyleneoxy block - (- CH 2 -CH 2 -O-) _{m contains} at least 85 mole%, preferably at least 90 mole%, based on the total amount of the block, of the unit (-CH 2 -CH 2 -O-). In particular, the optional polyethyleneoxy block - (- CH ₂ -CH ₂ -O-) _m consists of from 85 to 95 mol% of the unit (-CH ₂ -CH ₂ -O-) and from 5 to 15 mol% of the unit - (-CH ₂ - CH (R ³ ) -O-).

The invention preferably relates to a copolymer in which the radicals and indices have the following meanings: k: is a number from 15 to 35, preferably from 20 to 28, preferably from 23 to 26; I: is a number from 5 to 30, preferably from 5 to 28, preferably from 5 to 25;

m: is a number from 0 to 15, preferably 0 or preferably from 0.5 to 10;

R is H;

R ² is a divalent linking group -O- (C _n H 2n) -, where n ^'is 4; R ³ is, independently of one another, a hydrocarbon radical having 2 carbon atoms; in particular ethyl;

R ⁴ : is H.

m: is a number from 0.1 to 10, preferably from 0.5 to 10, particularly preferably from 2 to 5;

R: is H; R ² : is a divalent linking group -O- (Cn'H 2n) -, where n ^'is 4; R ³ : is independently a hydrocarbon radical having 2 carbon atoms; in particular ethyl;

R ⁴ : is H.

The invention preferably relates to a copolymer in which the radicals and indices have the following meanings: k: is a number from 15 to 35, preferably from 20 to 28, particularly preferably from 23 to 26;

I: is a number from 7.5 to 28, preferably from 7.5 to 25, particularly preferably from 12.75 to 25; more preferably from 13 to 23, for example 14, 16 or 22;

m: is a number from 0 to 15, preferably 0 or preferably from 0.5 to 10;

R ¹ : is H;

R ² : is a divalent linking group -O- (Cn'H 2n) -, where n ^'is 4; R ³ : is independently a hydrocarbon radical having 2 carbon atoms; in particular ethyl;

R ⁴ : is H.

The invention preferably relates to a copolymer in which the radicals and indices have the following meanings: k: is a number from 15 to 35, preferably from 20 to 28, preferably from 23 to 26; I: is a number from 7.5 to 28, preferably from 7.5 to 25, particularly preferably from 12.75 to 25; more preferably from 13 to 23, for example 14, 16 or 22;

R ¹ : is H;

R ² : is a divalent linking group -O- (C _n 1 -l 2n ') -, where n ^{' is} 4; R ³ : is independently a hydrocarbon radical having 2 carbon atoms; in particular ethyl;

R ⁴ : is H.

The invention preferably relates to a copolymer in which the radicals and indices have the following meanings: k: is a number from 23 to 26; I: is a number from 12.75 to 17.25;

m: is a number from 0 to 15; preferably 0 or preferably from 0.5 to 10;

R: is H;

R ⁴ : is H.

Furthermore, the invention preferably relates to a copolymer in which the radicals and indices have the following meanings: k: is a number from 23 to 26;

I: is a number from 8.5 to 1, 5;

m: is a number from 0 to 15, preferably from 0 to 10; preferably 0 or preferably from 0.5 to 10;

R: is H;

R ² : is a divalent linking group -O- (Cn'H 2n) -, where n 'is 4; R ³ : is a hydrocarbon radical having 3 carbon atoms, in particular n-propyl; R ⁴ : is H.

The invention furthermore preferably relates to a copolymer in which the monomer (a) of the formula (I) is a mixture of a monomer (a) of the formula (I) with m = 0 and a monomer (a) of the formula (I) m = 1 to 15, preferably 1 to 10. Further preferred, the invention relates to a copolymer in which the weight ratio of the monomer (a) of the formula (I) with m = 0 and the monomer (a) of the formula (I) with m = 1 to 15, preferably 1 to 10, in the range from 19: 1 to 1:19, preferably in the range from 9: 1 to 1: 9. Particularly preferably, this mixture of monomer (a) of formula (I) with m = 0 and monomer (a) of formula (I) with m = 1 to 15 gives an average value (averaged over all monomers (a) in the Mixture) in the range from m = 0.1 to 10, preferably from 0.1 to 5, particularly preferably from 0.5 to 5, particularly preferably from 0.5 to 2.5.

With particular preference, this mixture of monomer (a) of the formula (I) with m = 0 and monomer (a) of the formula (I) with m = 1 to 15 results in a mean value (averaged over all monomers (a) in the mixture) in the range of m = 0, 1 to 10, preferably from 0.1 to 5, particularly preferably from 0.5 to 5, particularly preferably from 0.5 to 3.5, particularly preferably from 0.5 to 2 ; 5. In general, an ethoxylation of the alkoxylated alcohol A3 in step c) is preferably carried out on already ethoxylated chains, since the primary alkoxide group is more active in comparison to the secondary alcoholate group of the alcohol A3. Thus, in particular after step c), there may be a mixture of chains which have a terminal ethyleneoxy block comprising at least one unit - (- CH 2 -CH 2 -O-) _m (monomers of the formula (I)), and chains which do not have a terminal ethyleneoxy block - have (- CH 2 -CH 2 -O-) m (monomers of the formula (III)).

Preparation of the monomers (a) of the formula (I)

The preparation of the monomers (a) of the general formula (I)

H ₂ C = C (R ¹ ) -R ² -O - (- CH ₂ -CH ₂ -O-) k - (- CH ₂ -CH (R ³ ) -O-) i - (- CH ₂ -CH ₂ -O- ) _m -R ⁴ (I), takes place in the steps described above. The preferred embodiments of the monomer (a) correspond to those already mentioned above.

Step a) of the process according to the invention comprises the reaction of a monoethylenically unsaturated alcohol A1 with ethylene oxide with the addition of an alkaline catalyst K1 comprising KOMe (potassium methoxide) and / or NaOMe (sodium methanolate) to give an alkoxylated alcohol A2.

The preferred conditions mentioned below (for example pressure and / or temperature ranges) in the reactions according to step a), b), c) and / or d) mean that the respective step is carried out wholly or partly under the stated conditions.

Preferably, step a) first comprises the reaction of the monoethylenically unsaturated alcohol A1 with the alkaline catalyst K1. Typically, to this end, the alcohol A1 used as the starting material is mixed with an alkaline catalyst K1 in a pressure reactor. By reduced pressure of typically less than 100 mbar, preferably in the range of 50 to 100 mbar and / or increasing the temperature typically to 30 to 150 ° C, water and / or low boilers still present in the mixture can be withdrawn. The alcohol is then essentially present as a corresponding alcoholate. Subsequently, the reaction mixture is typically treated with inert gas (e.g., nitrogen).

Further preferably, step a) comprises first the reaction of the monoethylenically unsaturated alcohol A1 with the alkaline catalyst K1. Typically will to the alcohol used as starting material A1 in a pressure reactor with an alkaline catalyst K1. By reduced pressure of typically less than 100 mbar, preferably in the range of 30 to 100 mbar and / or increasing the temperature typically to 30 to 150 ° C, water and / or low boilers still present in the mixture can be withdrawn. The alcohol is then present essentially as a corresponding alkoxide. Subsequently, the reaction mixture is typically treated with inert gas (eg nitrogen).

Preferably, step a) comprises the addition of ethylene oxide to the above-described mixture of alcohol A1 with the alkaline catalyst K1 (as described above). After completion of the addition of ethylene oxide, the reaction mixture is typically allowed to react. The addition and / or after-reaction typically takes place over a period of from 2 to 36 h, preferably from 5 to 24 h, particularly preferably from 5 to 15 h, particularly preferably from 5 to 10 h.

Further preferably, step a) comprises the addition of ethylene oxide to the above-described mixture of alcohol A1 with the alkaline catalyst K1 (as described above). After completion of the addition of ethylene oxide, the reaction mixture is typically allowed to react. The post-reaction typically occurs over a period of 0.1 to 1 h. The addition including optional relaxation (intermediate reduction of the pressure from, for example, 6 to 3 bar absolute) and including post-reaction takes place, for example, over a period of 2 to 36 hours, preferably from 5 to 24 hours, particularly preferably from 5 to 15 hours, more preferably from 5 to 10 h.

Step a) is typically carried out at temperatures of 60 to 180 ° C, preferably from 130 to 150 ° C, more preferably from 140 to 150 ° C. In particular, step a) comprises the addition of the ethylene oxide to the mixture of alcohol A1 with the alkaline catalyst K1 at a temperature of 60 to 180 ° C, preferably from 130 to 150 ° C, particularly preferably from 140 to 150 ° C.

The addition of the ethylene oxide to the mixture of alcohol A1 and alkaline catalyst K1 preferably takes place at a pressure in the range from 1 to 7 bar, preferably in the range from 1 to 5 bar. In order to meet the safety requirements, the addition in step a) is typically carried out at a pressure in the range of 1 to 3.1 bar. In particular, the addition of ethylene oxide and / or the post-reaction are carried out under the conditions mentioned above. Further preferably, the ethylene oxide is added to the mixture of alcohol A1 and alkaline catalyst K1 at a pressure in the range of 1 to 7 bar, preferably in the range of 1 to 6 bar. To meet the safety requirements, the addition in step a) typically at a pressure in the range of 1 to 4 bar, preferably 1 to 3.9 bar, more preferably from 1 to 3.1 bar or in another embodiment of the invention from 3 to 6 bar. In particular, the addition of ethylene oxide and / or the post-reaction are carried out under the conditions mentioned above. Preferably, step a) comprises the addition of the ethylene oxide to a mixture of alcohol A1 and alkaline catalyst K1 over a period of less than or equal to 36 h, preferably less than or equal to 32 h, more preferably over a period of 2 to 32 h, and a Pressure of less than or equal to 5 bar, preferably at 1 to 3.1 bar. In particular, the above period comprises the addition of ethylene oxide and / or the post-reaction.

Further preferably, step a) comprises the addition of the ethylene oxide to a mixture of alcohol A1 and alkaline catalyst K1 over a period of less than or equal to 36 h, preferably less than or equal to 32 h, particularly preferably over a time period of from 2 to 32 h, and at a pressure of less than or equal to 5 bar, preferably at 1 to 4 bar, more preferably at 1 to 3.9 bar and most preferably at 1 to 3.1 bar. In particular, the above period comprises the addition of ethylene oxide and / or the post-reaction. In particular, the reaction of a monoethylenically unsaturated alcohol A1 with ethylene oxide with addition of an alkaline catalyst K1 comprising KOMe (potassium methoxide) and / or NaOMe (sodium methoxide) according to step a) of the process according to the invention can be carried out in one or more ethoxylation steps. Preferred is a method as described above, wherein step a) comprises the following steps:

Reaction of the monoethylenically unsaturated alcohol A1 with the alkaline catalyst K1, reaction of the mixture of alcohol A1 and catalyst K1 with a portion of the ethylene oxide, in particular 10 to 50 wt .-%, in particular 10 to 30 wt .-%, of the total amount of ethylene oxide, an intermediate step comprising a quiescent phase and / or a pressure release and the reaction with the remaining part of the ethylene oxide. Further preferred is a method as described above, wherein step a) comprises the following steps:

Reaction of the monoethylenically unsaturated alcohol A1 with the alkaline catalyst K1, reaction of the mixture of alcohol A1 and catalyst K1 with a portion of the ethylene oxide, in particular 50 to 98 wt .-%, in particular 80 to 98 wt .-%, of the total amount of ethylene oxide, a step for removing low boilers under pressure release to a pressure of less than 100 mbar, preferably 50 to 100 mbar and / or increasing the

Temperature typically in the range of 30 to 150 ° C,

Reaction of the obtained ethoxylation product with the alkaline catalyst K1 and reaction of the remaining part of the ethylene oxide with the mixture of ethoxylation product and alkaline catalyst K1.

Further preferred is a process as described above, wherein step a) comprises the following steps: reaction of the monoethylenically unsaturated alcohol A1 with the alkaline one

Catalyst K1, reaction of the mixture of alcohol A1 and catalyst K1 with a portion of the ethylene oxide, in particular 50 to 98 wt .-%, in particular 80 to 98 wt .-%, of the total amount of ethylene oxide, a step to remove low boilers under pressure release a pressure of less than 100 mbar, preferably 30 to 100 mbar and / or an increase in the temperature typically in the range of 30 to 150 ° C,

The alkaline catalyst K1 contains in particular 10 to 100 wt .-% KOMe and / or NaOMe, preferably 20 to 90 wt .-%. The catalyst K1 may contain, in addition to KOMe and / or NaOMe, further alkaline compounds and / or a solvent (especially a C1 to C6 alcohol). For example, a compound selected from alkali metal hydroxides, alkaline earth metal hydroxides, alkali metal alkoxides (C2 to C6 potassium alkoxides, C2 to C6 sodium alkoxides, preferably ethanolate), alkaline earth alkoxides (in particular C1 to C6 alkoxides, are preferred Methanolate and / or ethanolate). In addition to KOMe and / or NaOMe, the catalyst K1 preferably contains at least one further alkaline compound selected from sodium hydroxide and potassium hydroxide. In another preferred embodiment, the alkaline catalyst K1 is KOMe or a mixture of KOMe and methanol (MeOH). Typically, a solution of 20 to 50% by weight KOMe in methanol (MeOH) can be used.

In a further preferred embodiment, the alkaline catalyst K1 consists of NaOMe or of a mixture of NaOMe and methanol (MeOH). Typically, a solution of 20 to 50 wt .-% NaOMe in methanol (MeOH) can be used.

In a further preferred embodiment, the alkaline catalyst K1 consists of a mixture of KOMe and NaOMe or a solution of KOMe and NaOME in methanol.

If KOM is used as basic catalyst K1 in the reaction in step a), it is advantageous to use K1 in such an amount that an upper limit of 2,500 ppm (about 0.4 mol%) KOMe with respect to the alcohol A1 used is maintained in order to avoid the decomposition of the monoethylenically unsaturated alcohol A1. The concentration of potassium ions in step a) is preferably less than or equal to 0.4 mol%, based on the total amount of the alcohol A1 used, particularly preferably 0.1 to 0.4 mol%. If KOMe is added in such an amount that the concentration is above 0.9 mol% based on the ethoxylated alcohol A2 (product of process step a)), KOMe must be completely or partially separated before step b) in order to obtain a potassium To obtain ion concentration of less than 0.9 mol% in process step b). This can be done, for example, by isolating the ethoxylated alcohol A2 after step a) and optionally purifying it.

In a further preferred embodiment, KOMe is used in such an amount that the concentration of potassium ions after the reaction in step a) is already less than or equal to 0.9 mol% based on A2.

Step b) of the process according to the invention comprises reacting the ethoxylated alcohol A2 with at least one alkylene oxide Z with the addition of an alkaline catalyst K2 to give an alkoxylated alcohol A3 which corresponds to the monomer (a) of the formula (III) H ₂ C = C (R ¹ ) -R ² -O- (- CH ² -CH ² -O-) k - (- CH 2 -CH (R ³ ) -O-) iR ⁴ (III) where R ⁴ = H ,

Preferably, step b) first comprises the reaction of the ethoxylated alcohol A2 with the alkaline catalyst K2. Typically, the alcohol A2 is added to the alkaline catalyst K2 in a pressure reactor. By reduced pressure of typically less than 100 mbar, preferably in the range of 50 to 100 mbar, and / or increasing the temperature, typically in the range of 30 to 150 ° C, water and / or low boilers still present in the mixture can be withdrawn. The alcohol is then present essentially as a corresponding alkoxide. Subsequently, the reaction mixture is typically treated with inert gas (e.g., nitrogen).

Further preferably, step b) first comprises the reaction of the ethoxylated alcohol A2 with the alkaline catalyst K2. Typically, the alcohol A2 is added to the alkaline catalyst K2 in a pressure reactor. By reduced pressure of typically less than 100 mbar, preferably in the range of 30 to 100 mbar, and / or increasing the temperature, typically in the range of 30 to 150 ° C, water still present in the mixture and / or low boilers can be withdrawn. The alcohol is then present essentially as a corresponding alkoxide. Subsequently, the reaction mixture is typically treated with inert gas (e.g., nitrogen).

Preferably, step b) comprises the addition of the at least one alkylene oxide Z to the above-described mixture of alcohol A2 with alkaline catalyst K2. After completion of the addition of the alkylene oxide Z, the reaction mixture is typically allowed to react. The addition and / or after-reaction typically takes place over a period of from 2 to 36 hours, preferably from 5 to 24 hours, particularly preferably from 5 to 20 hours, particularly preferably from 5 to 15 hours.

Preferably, step b) comprises the addition of the at least one alkylene oxide Z to the above-described mixture of alcohol A2 with alkaline catalyst K2. After completion of the addition of the alkylene oxide Z, the reaction mixture is typically allowed to react. The addition including optional relaxation and including post-reaction typically takes place over a period of 2 to 36 hours, preferably from 5 to 30 hours, particularly preferably from 10 to 28 hours, particularly preferably from 1 to According to the invention, the concentration of potassium ions in the reaction in step b) is less than or equal to 0.9 mol%, preferably less than 0.9 mol%, preferably from 0.01 to 0.9 mol%, particularly preferably from 0.1 to 0.6 mol%, based on the alcohol used A2. In the preparation of monomer (a), the concentration of potassium ions in the reaction in step b) is preferably 0.01 to 0.5 mol%, based on the alcohol A2 used.

In a particularly preferred embodiment, the concentration of potassium ions in the reaction in step b) 0.1 to 0.5 mol% and the reaction in step b) is carried out at temperatures of 120 to 130 ° C.

The alkaline catalyst K2 preferably contains at least one alkaline compound selected from alkali metal hydroxides, alkaline earth metal hydroxides, alkali metal alkoxides (in particular C 1 - to C 6 -alkanolates, preferably methanolate and / or ethanolate), alkaline earth alkoxides (in particular C 1 - to C 6 -alkanolates, preferably methanolate and / or ethanolate). The catalyst preferably contains at least one basic sodium compound, in particular selected from NaOH, NaOMe, and NaOEt, particularly preferably NaOMe or NaOH. As catalyst K2, a mixture of said alkaline compounds can be used, preferably the catalyst K2 consists of one of said basic compounds or mixtures of said alkaline compounds. Frequently, an aqueous solution of the alkaline compounds is used. In another preferred embodiment, the alkaline catalyst K1 is NaOMe or a mixture of NaOMe and methanol. Typically, a solution of 20 to 50 wt .-% NaOMe can be used in methanol. Preferably, the catalyst K2 contains no KOMe.

In the preparation in step b), preference is given to using a catalyst K2 comprising at least one basic sodium compound, in particular selected from NaOH, NaOMe, and NaOEt, the concentration of sodium ions in the reaction in step b) from 3.5 to 12 mol%, preferably 3.5 to 7 mol%, particularly preferably 4 to 5.5 mol%, based on the alcohol A2 used.

According to the invention, the reaction in step b) is carried out at a temperature of less than or equal to 135 ° C. The reaction in step b) is preferably carried out at temperatures of 60 to 135 ° C., preferably at 100 to 135 ° C., particularly preferably at 120 to 130 ° C. In particular, step b) comprises the addition of the at least one alkylene oxide Z to a mixture of alcohol A2 with alkaline catalyst K2 at a temperature of less than or equal to 135 ° C., preferably at temperatures of 60 to 135 ° C, more preferably at 100 to 135 ° C, particularly preferably at 120 to 135 ° C.

Preferably, step b) is carried out at a pressure in the range from 1 to 3.1 bar, preferably from 1 to 2.1 bar. In order to meet the safety conditions, the reaction in step b) is preferably carried out at a pressure in the range of less than or equal to 3.1 bar (preferably 1 to 3.1 bar), if R ^{3 is} a hydrocarbon radical having 2 carbon atoms, or at a pressure of less than or equal to 2.1 bar (preferably 1 to 2.1 bar), if R ^{3 is} a hydrocarbon radical having more than 2 carbon atoms.

Further preferably, step b) is carried out at a pressure in the range from 1 to 6 bar, preferably from 1 to 3.1 bar, preferably from 1 to 2.1 bar. The reaction in step b) is preferably carried out at a pressure in the range from 1 to 6 bar, preferably from 1 to 3.1 bar, preferably from 4 to 6 bar, if R ^{3 is} a hydrocarbon radical having 2 carbon atoms. In particular, the addition of alkylene oxide Z and / or the after-reaction are carried out at the abovementioned pressures.

In particular, the present invention relates to a copolymer wherein R ^{3 is} a hydrocarbon radical having 2 carbon atoms and in the preparation of monomer (a) step b) is carried out at a pressure in the range of 1 to 3.1 bar; or wherein R ^{3 is} a hydrocarbon radical having at least 3 carbon atoms (preferably having 3 carbon atoms) and in the preparation of monomer (a) step b) is carried out at a pressure of 1 to 2.1 bar.

In particular, the addition of alkylene oxide Z and / or the post-reaction are carried out at the abovementioned pressure. Preferably, step b) comprises the addition of the at least one alkylene oxide Z to a mixture of alcohol A2 and alkaline catalyst K2 at a pressure in the range of less than or equal to 3.1 bar (preferably 1 to 3.1 bar), if R ^{3 is} a hydrocarbon radical with 2 carbon atoms, or at a pressure of less than or equal to 2.1 bar (preferably 1 to 2.1 bar) if R ^{3 is} a hydrocarbon radical having at least 3 carbon atoms.

Preferably, step b) comprises the addition of the at least one alkylene oxide Z to a mixture of alcohol A2 with alkaline catalyst K2 over a period of less than or equal to 36 h, preferably less than or equal to 32 h, particularly preferably over a period of from 2 to 32 h, most preferably over a period of 5 to 24 h, and at a pressure of less than or equal to 3.1 bar, preferably at 1 to 2, 1 bar (further preferably at the above pressures). Further preferably, step b) comprises the addition of the at least one alkylene oxide Z to a mixture of alcohol A2 with alkaline catalyst K2 over a period of less than or equal to 36 h, preferably less than or equal to 32 h, more preferably over a period of from 2 to 32 h, most preferably over a period of 1 1 to 24 h, and at a pressure of less than or equal to 3, 1 bar (further preferred at the above pressures).

Particularly preferably, step b) is carried out at a pressure in the range from 1 to 3.1 bar (preferably at the abovementioned pressures) and at a temperature of 120 to 130 ° C.

The process of the invention may optionally comprise step c) wherein at least a portion of the alkoxylated alcohol A3 is reacted with ethylene oxide; wherein an alkoxylated alcohol A4 is obtained, which is the monomer (a) according to the formula (I) with R ⁴ = H and m> 0, preferably 0 to 15, preferably 0 to 10, particularly preferably 0.1 to 10, particularly preferably 0.1 to 5, more preferably 0.5 to 5, and most preferably 0.5 to 2.5. In a preferred embodiment, step c) comprises the reaction of the entire alkoxylated alcohol A3 with ethylene oxide.

In a preferred embodiment of the invention, the process comprises step c), wherein at least a portion of the alkoxylated alcohol A3 (preferably the entire alkoxylated alcohol A3) is reacted with ethylene oxide; wherein an alkoxylated alcohol A4 is obtained which is the macromonomer M according to formula (I) with R ⁴ = H and m is a number from 0.1 to 15, preferably from 0.1 to 10, particularly preferably from 0.5 to 10 , particularly preferably from 1 to 7, more preferably from 2 to 5, corresponds. The optional step c) is carried out in particular without further addition of an alkaline catalyst. The optional step c) is especially at a pressure in the range of 1 to 7 bar, preferably from 1 to 5 bar, and a temperature in the range of 60 to 140 ° C, preferably from 120 to 140 ° C, particularly preferably from 125 to 135 ° C, performed. The ethoxylation in optional step c) takes place in particular over a period of from 0.5 to 7 h, in particular from 0.5 to 5 h, preferably from 0.5 to 4 h.

The optional step c) is furthermore preferably carried out without further addition of an alkaline catalyst. The optional step c) is especially at a pressure in the range of 1 to 7 bar, preferably from 1 to 6 bar, and a temperature in the range of 60 to 140 ° C, preferably from 120 to 140 ° C, more preferably from 120 to 135 ° C carried out. The ethoxylation in optional step c) takes place in particular over a period of 0.5 to 7 h, in particular 1 to 5 h, preferably from 1 to 4 h. The optional step c) preferably comprises the addition of ethylene oxide to the reaction mixture according to step b) containing the alkoxylated alcohol A3 of the formula (III) without further workup and / or depressurization. After completion of the addition of the ethylene oxide, the reaction mixture is typically allowed to react. The addition and / or after-reaction typically takes place over a period of 0.5 to 10 h, in particular 0.5 to 7 h, in particular 0.5 to 5 h, preferably from 0.5 to 4 h.

Further preferably, the optional step c) comprises the addition of ethylene oxide to the reaction mixture after step b) containing the alkoxylated alcohol A3 according to formula (III) without further workup and / or pressure release. After completion of the addition of the ethylene oxide, the reaction mixture is typically allowed to react. The addition including optional relaxation and including post-reaction typically takes place over a period of 0.5 to 10 hours, in particular 2 to 10 hours, in particular 4 to 8 hours.

The performance of optional step c), i. a final ethoxylation, should in particular cause possibly after step b) still in the reaction mixture present alkylene oxide Z is reacted and removed. It is also possible to remove alkylene oxide Z, which is not reacted after step b), by a pressure release and / or temperature increase after step b).

The process according to the invention may optionally comprise step d), wherein the alkoxylated alcohol A3 and / or A4 is etherified with a compound R ⁴ -X, where X is a leaving group, preferably selected from Cl, Br, I, -O-SO 2 -CH 3 (Mesylate), -O-SO 2-CF 3 (triflate) or -O-SO 2 -CR ⁴ .

If the alkoxylated alcohol A3 of the formula (III) and / or A4 of the formula (I) is to be etherified with a terminal OH group (ie R ⁴ = H), this can also be carried out with conventional alkylating agents known in principle to those skilled in the art, for example, alkyl sulfates and / or alkyl halides. Typically, the compound R ⁴ -X may be alkyl halides. For etherification it is also possible in particular to use dimethyl sulfate or diethyl sulfate. The etherification is just an option which can be selected by the skilled person depending on the desired properties of the copolymer.

Hydrophilic monomers (b)

In addition to the monomers (a), the hydrophobically associating copolymer according to the invention comprises at least one different, monoethylenically unsaturated, hydrophilic monomer (b). Of course, mixtures of several different hydrophilic monomers (b) can be used.

The hydrophilic monomers (b) comprise, in addition to an ethylenic group, one or more hydrophilic groups. These impart sufficient water solubility to the copolymer of the invention because of their hydrophilicity. The hydrophilic groups are, in particular, functional groups which comprise O and / or N atoms. In addition, they may comprise as heteroatoms in particular S and / or P atoms.

With particular preference, the monomers (b) are miscible with water in any desired ratio, but it is sufficient for carrying out the invention that the hydrophobically associating copolymer according to the invention has the aforementioned water solubility. As a rule, the solubility of the monomers (b) in water at room temperature should be at least 100 g / l, preferably at least 200 g / l and particularly preferably at least 500 g / l. Examples of suitable functional groups include carbonyl groups> C = 0, ether groups -O-, in particular polyethyleneoxy groups - (CH 2 -CH 2 -O-) _n -, where n preferably represents a number from 1 to 200, hydroxyl groups -OH, ester groups C (0) 0, primary, secondary or tertiary amino groups, ammonium groups, amide groups - C (0) -NH-, carboxamide groups -C (0) -NH2 or acidic groups such as carboxyl groups -COOH, sulfonic acid groups -SO3H, phosphonic acid groups -PO3H2 or Phosphoric acid groups -OP (OH) 3.

Examples of preferred functional groups include hydroxy groups -OH, carboxyl groups -COOH, sulfonic acid groups -SO 3 H, carboxamide groups -C (O) -NH 2, amide groups -C (O) -NH- and polyethyleneoxy groups - (CH 2 -CH 2 -O-) _n -H, where n is preferably from 1 to 200. The functional groups may be attached directly to the ethylenic group, or linked to the ethylenic group via one or more linking hydrocarbon groups. The hydrophilic monomers (b) are preferably monomers of the general formula (IV) wherein R ^{5 is} H or methyl and R ^{6 is} a hydrophilic group or a group comprising one or more hydrophilic groups. The groups R ⁶ are groups which comprise heteroatoms in such an amount that the water solubility defined above is achieved.

Examples of suitable monomers (b) include monomers comprising acidic groups, for example monomers containing COOH groups, such as acrylic acid or methacrylic acid, crotonic acid, itaconic acid, maleic acid or fumaric acid, monomers comprising sulfonic acid groups, such as vinylsulfonic acid, allylsulfonic acid, 2-acrylamido-2- methylpropanesulfonic acid (AMPS), 2-methacrylamido-2-methylpropanesulfonic acid, 2-acrylamidobutanesulfonic acid, 3-acrylamido-3-methyl-butanesulfonic acid or 2-acrylamido-2,4,4-trimethylpentanesulfonic acid or phosphonic acid group-containing monomers such as vinylphosphonic acid, allylphosphonic acid, N - (meth) acrylamidoalkylphosphonic acids or (meth) acryloyloxyalkylphosphonic acids.

Also to be mentioned are acrylamide and methacrylamide and derivatives thereof, such as N-methyl (meth) acrylamide, N, N'-dimethyl (meth) acrylamide and N-methylolacrylamide, N-vinyl derivatives such as N-vinylformamide, N-vinylacetamide, N- Vinylpyrrolidone or N-vinylcaprolactam and vinyl esters, such as vinyl formate or vinyl acetate. N-vinyl derivatives can be hydrolyzed after polymerization to vinylamine units, vinyl esters to vinyl alcohol units. Further examples include monomers comprising hydroxyl and / or ether groups, for example hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, allyl alcohol, hydroxyvinyl ethyl ether, hydroxyvinyl propyl ether, hydroxyvinyl butyl ether or compounds of the formula H ₂ C =C (R ¹ ) -O - (- CH ₂ -CH (R ⁷ ) -O-) b R ⁸ (V) wherein R ^{1 is} as defined above and b is a number from 2 to 200, preferably 2 to 100. The radicals R ⁷ 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 ⁸ are H. Preferably, at least 75 mol% of the radicals R ⁷ are H, more preferably at least 90 mol% and most preferably exclusively H. The radical R ⁸ is H, methyl or ethyl, preferably H or methyl. The individual alkyleneoxy units can be arranged randomly or in blocks. For a block copolymer, the transition between blocks may be abrupt or gradual. Further suitable hydrophilic monomers (b) are described in WO 201 1/133527 (page 15, lines 1 to 23).

Of course, the abovementioned hydrophilic monomers can be used not only in the acid or base form shown, 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. The corresponding salts are preferably alkali metal salts or ammonium salts, more preferably organic ammonium salts, particularly preferably water-soluble organic ammonium salts.

Preference is given to a copolymer in which at least one of the monomers (b) is a monomer comprising acidic groups, the acidic groups being at least one group selected from the group of -COOH, -SO 3 H and -PO 3 H , and their salts.

At least one of the monomers (b) is preferably a monomer selected from the group of (meth) acrylic acid, vinylsulfonic acid, allylsulfonic acid and 2-acrylamido-2-methylpropanesulfonic acid (AMPS), particularly preferably acrylic acid and / or APMS or their salts.

Preferably, the invention relates to a copolymer which comprises at least two different hydrophilic monomers (b), and at least one neutral hydrophilic monomer (b1), and

- At least one hydrophilic anionic monomer (b2), which comprises at least one acidic group selected from the group of -COOH, -SO3H and -POsH and their salts, is.

Examples of suitable monomers (b1) include acrylamide and methacrylamide, preferably acrylamide and derivatives thereof, such as 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 OH-containing monomers such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, allyl alcohol, Hydroxyvi- nylethyl ether, hydroxyvinyl propyl ether or hydroxyvinyl butyl ether. The monomer (b1) in the copolymer according to the invention is preferably acrylamide or derivatives thereof, more preferably acrylamide. Examples of anionic monomers (b2) include acrylic acid or methacrylic acid, crotonic acid, itaconic acid, maleic acid or fumaric acid, monomers comprising sulfonic acid groups, such as vinylsulfonic acid, allylsulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid (AMPS), 2-methacrylamido-2-methylpropanesulfonic acid, 2-acrylamidobutanesulfonic acid , 3-acrylamido-3-methyl-butanesulfonic acid or 2-acrylamido-2,4,4-trimethylpentanesulfonic acid or phosphonic acid-containing monomers such as vinylphosphonic acid, allylphosphonic acid, N- (meth) acrylamidoalkylphosphonsäuren or (meth) acryloyloxyalkylphosphonsäuren.

Examples of preferred anionic monomers (b2) include acrylic acid, vinylsulfonic acid, allylsulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid (AMPS), 2-acrylamidobutanesulfonic acid, 3-acrylamido-3-methyl-butanesulfonic acid and 2-acrylamido-2,4,4 -trimethylpentanesulfonic acid, most preferred is 2-acrylamido-2-methylpropanesulfonic acid (AMPS). It is preferably a copolymer which comprises acrylamide as monomer (b1) and monomer comprising acidic groups as monomer (b2).

It is preferably a copolymer which comprises acrylamide as monomer (b1) and monomer comprising acidic groups as monomer (b2), the acidic group being -SO3H. In particular, it is preferably a copolymer which comprises acrylamide as monomer (b1) and 2-acrylamido-2-methylpropanesulfonic acid (AMPS) as monomer (b2).

It is preferably a copolymer which comprises acrylamide as monomer (b1) and acrylic acid as monomer (b2).

Further preferably, it is a copolymer comprising as monomer (b1) acrylamide and at least two further different acidic groups comprising monomers (b2). In particular, it is preferably a copolymer which comprises, as monomer (b1), acrylamide and monomer (b2) comprising acidic groups, a monomer comprising the group -SO3H and a monomer comprising the group -COOH. Further preferably, it is a copolymer comprising as monomer (b1) acrylamide, as monomer (b2) 2-acrylamido-2-methylpropanesulfonic acid (AMPS) and a monomer comprising the group -COOH. Further preferably, it is a copolymer comprising as monomer (b1) acrylamide, as monomer (b2) 2-acrylamido-2-methylpropanesulfonic acid (AMPS) and acrylic acid.

The amount of monomers (b) in the copolymer according to the invention is from 25 to 99.9% by weight, based on the total amount of all monomers in the copolymer, preferably from 25 to 99.5% by weight. The exact amount will depend on the nature and intended use of the hydrophobically associating copolymers and will be determined by one skilled in the art.

Preferably, the invention relates to a copolymer comprising (a) 2 wt .-% of at least one hydrophobically associating monomer (a), and

(b) 50% by weight of acrylamide as a neutral hydrophilic monomer (b1), and (c) 48% by weight of acrylamido-2-methylpropanesulfonic acid (AMPS) as anionic hydrophilic monomer (b2), the amounts given are based on the total amount of all Monomers are based in the copolymer.

Non-polymerizable surface-active components (c)

The copolymers of the invention are prepared in the presence of at least one non-polymerizable, surface-active compound, which is preferably at least one nonionic surfactant. However, anionic and cationic surfactants are also suitable if they do not participate in the polymerization reaction.

Component (c) is preferably at least one nonionic surfactant.

They may in particular be surfactants, preferably nonionic surfactants of the general formula R ¹⁰ -Y ', where R ^{10 is} a hydrocarbon radical having 8 to 32, preferably 10 to 20 and particularly preferably 12 to 18 carbon atoms and Y 'for a hydrophilic group, preferably a nonionic hydrophilic group, in particular a polyalkoxy group.

The nonionic surfactant is preferably an ethoxylated long-chain aliphatic alcohol having 10 to 20 carbon atoms, which may optionally contain aromatic moieties.

Examples of its called: Ci2Ci4-fatty alcohol ethoxylates, C16C18 fatty alcohol ethoxylates, Ci3-oxo alcohol ethoxylates, Cio-Oxoalkoholethoxylate, C13C15- Oxoalkoholethoxylate, Cio Guerbetalkoholethoxylate and Alkylphenolethoxylate. Compounds having 5 to 20 ethyleneoxy units, preferably 8 to 18 ethyleneoxy units, have proven particularly suitable. Optionally, small amounts of higher alkyleneoxy units, in particular propyleneoxy and / or butyleneoxyoxy units, may also be present, but the amount as ethyleneoxy units should generally be at least 80 mol% with respect to all alkyleneoxy units.

Particularly suitable are surfactants selected from the group of ethoxylated alkylphenols, ethoxylated, saturated iso-C13 alcohols and / or ethoxylated C10 Guerbet alcohols, wherein in each case 5 to 20 ethyleneoxy units, preferably 8 to 18 ethyleneoxy units are present in the alkoxy radicals.

Preparation of hydrophobically associating copolymers

The copolymers according to the invention can be prepared by methods known in principle to the person skilled in the art by free-radical polymerization of the monomers (a) and (b), for example by bulk, solution, gel, emulsion, dispersion or suspension polymerization, preferably in an aqueous phase however, each of the possible polymerization variants must be carried out in the presence of at least one component (c).

The present invention relates to a process for preparing a copolymer according to the invention described above, wherein at least one hydrophobically associating monomer (a) and at least one hydrophilic monomer (b) is subjected to aqueous solution polymerization in the presence of at least one surface-active component (c), and wherein the monomer (a) of general formula (I) is prepared by the method described above. With regard to the process for the preparation of the copolymer according to the invention, the preferred embodiments which have been described above in connection with the copolymers according to the invention apply. Preferably, the present invention relates to a process for producing the copolymer of the present invention, wherein the solution polymerization is carried out at a pH of 5.0 to 7.5.

The monomers (a) of the formula (I) used according to the invention are prepared by the above-described preparation process by multistage alkoxylation of alcohols (II) optionally followed by etherification. With regard to the process for the preparation of the monomer (a), the preferred embodiments which have been described above in connection with the copolymers according to the invention apply.

In a preferred embodiment, the preparation of the copolymer is carried out by means of gel polymerization in aqueous phase, provided that all the monomers used have sufficient water solubility. For gel polymerization, a mixture of the monomers, initiators and other auxiliaries is first provided with water or an aqueous solvent mixture. Suitable aqueous solvent mixtures include water and water-miscible organic solvents, wherein the proportion of water as a rule at least 50 wt .-%, preferably at least 80 wt .-% and particularly preferably at least 90 wt .-% is. To name as organic solvents here are in particular water-miscible alcohols such as methanol, ethanol or propanol. Acidic monomers can be completely or partially neutralized prior to polymerization.

The concentration of all components except the solvents is usually 25 to 60 wt .-%, preferably 30 to 50 wt .-%.

The mixture is then polymerized photochemically and / or thermally, preferably at -5 ° C to 50 ° C. If thermally polymerized, preference is given to using polymerization initiators which start even at a comparatively low temperature, for example redox initiators. The thermal polymerization can be carried out even at room temperature or by heating the mixture, preferably to temperatures of not more than 50 ° C. The photochemical polymerization is usually carried out at temperatures of -5 to 10 ° C. It is particularly advantageous to combine photochemical and thermal polymerization with one another by adding both thermal and thermal initiators to the mixture adds the photochemical polymerization. The polymerization is first started photochemically at low temperatures, preferably -5 to + 10 ° C. The liberated heat of reaction heats up the mixture, which additionally initiates thermal polymerization. By means of this combination, a turnover of more than 99% can be achieved.

The gel polymerization is usually carried out without stirring. It can be carried out batchwise by irradiating and / or heating the mixture in a suitable vessel at a layer thickness of 2 to 20 cm. The polymerization produces a solid gel. The polymerization can also be continuous. For this purpose, use is made of a polymerization apparatus which has a conveyor belt for receiving the mixture to be polymerized. The conveyor belt is equipped with means for heating or for irradiation with UV radiation. After this, the mixture is poured on by means of a suitable device at one end of the strip, in the course of transport in the direction of the strip, the mixture polymerizes and at the other end of the strip, the solid gel can be removed.

The gel is comminuted and dried after the polymerization. The drying should preferably be carried out at temperatures below 100 ° C. To avoid sticking together you can use a suitable release agent for this step. The hydrophobically associating copolymer is obtained as a powder.

Further details for carrying out a gel polymerization are disclosed, for example, in DE 10 2004 032 304 A1, Sections [0037] to [0041].

Copolymers of the invention in the form of alkali-soluble, aqueous dispersions can preferably be prepared by means of emulsion polymerization. The performance of an emulsion polymerization using hydrophobically associating monomers is disclosed, for example, in WO 2009/019225 page 5, line 16 to page 8, line 13.

The copolymers of the invention preferably have a number average molecular weight M _{n of} from 1,000,000 to 30,000,000 g / mol. Use of the hydrophobically associating copolymers

As already mentioned, the hydrophobically associating copolymers according to the invention can be used according to the invention for thickening aqueous phases. The present invention relates to the use of the copolymers of the invention in the development, exploitation and completion of underground oil and gas deposits. In particular, the use relates to the preferred embodiments described above in connection with the copolymers of the invention.

The copolymers can be used alone or in combination with other thickening components, for example with other thickening polymers together. They can also be formulated, for example together with surfactants to a thickening system. The surfactants can form micelles in aqueous solution, and the hydrophobically associating copolymers can form, together with the micelles, a three-dimensional, thickening network. For use, the copolymer can be dissolved directly in the aqueous phase to be thickened. It is also conceivable to pre-dissolve the copolymer and then add the solution formed to the system to be thickened.

By selecting the type and amount of the monomers (a) and (b), as well as the component (c), the properties of the copolymers can be adapted to the respective technical requirements.

The copolymers according to the invention can be used, for example, in the field of crude oil production as an additive for thickening drilling fluids and completion fluids.

Furthermore, the copolymers according to the invention are used as thickeners in hydraulic fracturing. In this case, a highly viscous, aqueous solution is typically injected under high pressure into the oil or gas-conducting formation layer.

The invention preferably relates to the use of the copolymers according to the invention for tertiary mineral oil production, wherein an aqueous formulation of said copolymers is pressed in a concentration of 0.01 to 5 wt .-% by at least one injection well in a Erdöllagerstätte and the deposit by at least one Production drilling crude oil is taken.

The concentration of the copolymer should generally not exceed 5% by weight with respect to the sum of all constituents of the formulation and is usually 0.01 to 5 wt .-%, in particular 0.1 to 5 wt .-%, preferably 0.5 to 3 wt .-% and particularly preferably 1 to 2 wt .-%.

The formulation is injected through at least one injection well into the oil reservoir and the deposit is extracted from at least one production well of crude oil. Of course, the term "crude oil" in this context does not only mean pure phase oil, but also includes the usual crude oil-water emulsions, as a rule, a deposit is provided with several injection wells and several production wells , the so-called "polymer flood", creates a pressure that causes the oil to flow towards the production well and be pumped through the production well. The viscosity of the flood medium should be adjusted as far as possible to the viscosity of the petroleum in the oil reservoir. The viscosity can be adjusted in particular via the concentration of the copolymer. In polymer fl uening, an aqueous formulation is used which, in addition to water, comprises at least one hydrophobically associating copolymer. Of course, mixtures of different copolymers can be used. In addition, of course, other components can be used. Examples of other components include biocides, stabilizers or inhibitors. The formulation can preferably be prepared by initially charging the water and scattering the copolymer as a powder. The aqueous formulation should be exposed to the lowest possible shear forces.

To increase the oil yield, the polymer flooding can be advantageously combined with other techniques of tertiary mineral oil production.

The invention preferably relates to the use of the copolymers according to the invention in the development, exploitation and completion of underground oil and natural gas deposits, in particular for tertiary mineral oil production, wherein the aqueous formulation of said copolymers contains at least one surfactant.

In a further 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, an aqueous surfactant formulation is first pressed into the petroleum formation prior to the polymer flooding. This reduces the interfacial tension between the formation water and the actual petroleum and thus increases the mobility of the petroleum in the formation. By combining both techniques, the oil yield can be increased. Examples of suitable surfactants for surfactant flooding include sulfate groups, sulfonate groups, polyoxyalkylene groups, anionically modified polyoxyalkylene groups, betaine groups, glucoside groups or amine oxide-containing surfactants, for example alkylbenzenesulfonates, olefinsulfonates or amidopropylbetaines. Preferably anionic and / or betainic surfactants can be used.

The person skilled in the art knows details of the technical implementation of the polymer flooding and the surfactant flooding, and applies a corresponding technique depending on the nature of the deposit.

It is of course also possible to use surfactants and the copolymers according to the invention in a mixture.

The following examples are intended to illustrate the invention in more detail:

Part I: Syntheses 1-a Preparation of Monomers (a) Unless explicitly stated, the reactions were carried out so that the target fill level at the end of the alkoxylation was about 65% of the reactor volume.

Example M1 HBVE - 22 EO (0.4 mol% potassium ion) In a 2 l pressure autoclave with anchor stirrer, 135.3 g (1.16 mol) of hydroxybutylvinyl ether (HBVE) (stabilized with 100 ppm potassium hydroxide (KOH) ) and the stirrer is started. 1, 06 g of potassium methoxide (KOMe) solution (32% KOMe in methanol (MeOH), equivalent to 0.0048 mol of potassium) were fed in and the stirred tank was evacuated to a pressure of less than 10 mbar, heated to 80 ° C and 70 min operated at 80 ° C and a pressure of less than 10 mbar. MeOH was distilled off.

In an alternative procedure, the potassium methoxide (KOMe) solution (32% KOMe in methanol (MeOH)) was fed and the stirred tank to a pressure of 10 - 20 mbar evacuated, heated to 65 ° C, 70 min at 65 ° C and a Pressure of 10 - 20 mbar operated. MeOH was distilled off.

It was rinsed three times with N 2 (nitrogen). Thereafter, the container was tested for pressure tightness, 0.5 bar overpressure (1, 5 bar absolute) set and heated to 120 ° C. It was completely depressurized to 1 bar and metered in 1 126 g (25.6 mol) of ethylene oxide (EO) until pmax was 3.9 bar absolute and T _ma x 150 ° C. After addition of 300 g of EO, the dosage was stopped (about 3 hours after the start), maintained for 30 minutes and relaxed to 1, 3 bar absolute. Thereafter, the remaining EO was added. The addition of EO lasted 10 hours including relaxation.

It was stirred to constant pressure at about 145-150 ° C (1 h), cooled to 100 ° C and freed at a pressure of less than 10 mbar for 1 h of low boilers. The product was filled at 80 ° C under N ₂ . The analysis (OH number, GPC, 1 H NMR in CDCl ₃ , 1 H NMR in MeOD) confirmed the structure.

Example M2 HBVE - 22 EO - 10.6 PeO (0.4 mol% potassium ion, 4.6 mol% sodium ion), addition of the PeO at 140 ° C to 3.2 bar

135.3 g (1.16 mol) HBVE (stabilized with 100 ppm KOH) were placed in a 2 l pressure autoclave with anchor stirrer and the stirrer was started. 1.06 g of KOMe solution (32% KOM in MeOH, corresponds to 0.0048 mol K) were fed in and the stirred tank was evacuated to <10 mbar, heated to 80 ° C. and operated at 80 ° C. and <10 mbar for 70 min. MeOH was distilled off.

It was rinsed three times with N2. Thereafter, the container was tested for pressure tightness, 0.5 bar overpressure (1, 5 bar absolute) set and heated to 120 ° C. It was relaxed to 1 bar absolute and metered 255 g (5.8 mol) of EO to p _ma x 3.9 bar absolute and Tmax 150 ° C. It was stirred to constant pressure at about 145-150 ° C (1 h), cooled to 100 ° C and freed at a pressure of less than 10 mbar for 1 h of low boilers. The product (HBVE-5 EO) was filled at 80 ° C under N ₂ .

180 g (0.54 mol) of the above HBVE-5 EO were initially introduced into a 2 l pressure autoclave with anchor stirrer and the stirrer was switched on. Thereafter, 4.32 g of 30% NaOMe (sodium methoxide) in MeOH solution (0.024 mol NaOMe, 1.30 g NaOMe) was added, vacuum of <10 mbar applied, heated to 100 ° C and held for 80 min To distill off MeOH. It was rinsed three times with N2. Thereafter, the container was tested for pressure tightness, 0.5 bar overpressure (1, 5 bar absolute) set and on Heated to 150 ° C. It was completely relaxed to 1, 0 bar. 398 g (9.04 mol) of EO were metered to a pressure of 2 bar absolute and left to react for 1 h. It was cooled to 140 ° C and metered at 1, 2 bar absolute and 140 ° C 502 g (5.83 mol) PeO (Pentylen oxide) until the pressure to 3.2 bar absolute rise. The PeO could be added within two hours. It was cooled to 80 ° C, withdrawn residual oxide until the pressure for at least 10 minutes below 10 mbar. The vacuum was released with N2 and 100 ppm BHT (butylhydroxytoluene) was added. The bottling was carried out at 80 ° C under N ₂ . The analysis (mass spectrum, GPC, 1 H NMR in CDCl ₃ , 1 H NMR in MeOD) confirmed the structure.

Example M3 HBVE - 22 EO - 10.5 PeO (0.4 mol% potassium ion, 3.3 mol% sodium ion), addition of the PeO at 140 ° C to 2.1 bar

135.3 g (1.16 mol) of hydroxybutyl vinyl ether (stabilized with 100 ppm KOH) were introduced into a 2 l pressure autoclave with anchor stirrer and the stirrer was started up. 1.06 g of KOMe solution (32% COM in MeOH, corresponds to 0.0048 mol K) were fed in and the stirred tank was evacuated to <10 mbar, heated to 80 ° C., operated at 80 ° C. and <10 mbar for 70 min. MeOH was distilled off.

It was rinsed three times with N2. Thereafter, the container was tested for pressure tightness, 0.5 bar overpressure (1, 5 bar absolute) set and heated to 120 ° C. It was depressurized to 1 bar absolute and metered 255 g (5.8 mol) of EO to p _ma x 3.9 bar abso lut and Tmax 150 ° C. It was freed from low boilers to 10 mbar for 1 h until the pressure remained constant. The product (HBVE-5 EO) was filled at 80 ° C under N ₂ .

180 g (0.54 mol) of HBVE-5 EO were introduced into a 2 l pressure autoclave with anchor stirrer and the stirrer was switched on. Thereafter, 3.18 g of 30% NaOMe in MeOH solution (0.018 mol NaOMe, 0.95 g NaOMe) was added, vacuum of <10 mbar applied, heated to 100 ° C and held for 80 min to the MeOH distill. It was rinsed three times with N2. Thereafter, the container was tested for pressure tightness, 0.5 bar overpressure (1, 5 bar absolute) set and heated to 150 ° C. It was completely relaxed to 1, 0 bar. 398 g (9.04 mol) of EO were metered in to a pressure of 2 absolute, allowed to react for 1 h, then was cooled to 100 ° C and freed at a pressure of less than 10 mbar for 1 h from low boilers. The product (HBVE-22 EO) was filled at 80 ° C under N ₂ . In a 1 l autoclave with anchor stirrer, 450 g (0.425 mol) of the above HBVE-22 EO were initially charged and the stirrer was switched on. It was rinsed three times with N2. Thereafter, the container was tested for pressure tightness, 0.5 bar overpressure (1, 5 bar absolute) set and heated to 140 ° C. It was completely relaxed to 1, 0 bar. 384 g (5.83 mol) of PeO at 48 g / h were metered in at 1.4 bar absolute and 140 ° C. until the pressure rose to 2.1 bar absolute. It had to be interrupted twice. It was allowed to react at 140 ° C until the pressure fell again. The PeO was added within two days. It was cooled to 80 ° C and withdrawn residual oxide until the pressure for at least 10 minutes below 10 mbar. The vacuum was released with N2 and 100 ppm BHT was added. The bottling was carried out at 80 ° C under N2.

The analysis (mass spectrum, GPC, 1 H NMR in CDCl ₃ , 1 H NMR in MeOD) confirmed the structure. Example M4 HBVE - 22 EO - 10 PeO (0.4 mol% potassium ion, 4.6 mol% sodium ion), addition of the PeO at 127 ° C to 2.1 bar

The starting material used was monomer M1 from example M1. 745 g (0.69 mol) of HBVE-22 EO were placed in a 2 l pressure autoclave with anchor stirrer and the stirrer was switched on. Thereafter, 5.36 g of 32% NaOMe in MeOH solution (0.0317 mol NaOMe, 1.71 g NaOMe) was added, vacuum of <10 mbar applied, heated to 80 ° C and held for 80 min. To the MeOH distill.

One rinsed three times with N2. Thereafter, the container was tested for pressure tightness, 0.5 bar overpressure (1, 5 bar absolute) set, heated to 127 ° C and then the pressure to 1 bar absolute.

There were added 591 g (6.9 mol) of PeO at 127 ° C, p _ma x was 2.1 bar absolute. An intermediate two-fold relaxation due to Füllgradzunahme became necessary. The PeO-Dosage was stopped, allowed to react for 2 h until the pressure was constant and relaxed to 1, 0 bar absolute. Thereafter, the addition of PeO was continued. Pmax remained at 2.1 bar. After the end of the PeO dosage, the reaction was allowed to continue until the pressure remained constant or for 4 h. It was cooled to 110 ° C. and residual oxide was drawn off until the pressure was below 10 mbar for at least 10 minutes. Then the accession be of 0.5% water at 1 10 ° C and then stripping until the pressure for at least 10 minutes below 10 mbar. The vacuum was released with N2 and 100 ppm BHT was added. The bottling was carried out at 80 ° C under N2. The analysis (mass spectrum, GPC, 1 H NMR in CDCl ₃ , 1 H NMR in MeOD) confirmed the structure.

Example M5 HBVE - 22 EO - 1 1 PeO (0.4 mol% potassium ion, 4.6 mol% sodium ion), addition of the PeO at 127 ° C to 2.1 bar

The preparation was carried out analogously to Example M4 with the difference that 1 1 instead of 10 eq (molar equivalents) PeO were added.

Example M6 HBVE - 24.5 EO - 1 1 PeO (0.4 mol% of potassium ions, 4.6 mol% of sodium ions), addition of the PeO at 127 ° C to 2.1 bar

The starting material used was monomer M1 from example M1. 650 g (0.60 mol) of HBVE-22 EO were introduced into a 2 l pressure autoclave with anchor stirrer and the stirrer was switched on. Thereafter, 5.96 g of 25% NaOMe in MeOH solution (0.0276 mol NaOMe, 1.49 g NaOMe) was added, vacuum of <10 mbar applied, heated to 100 ° C and held for 80 min to the MeOH distill.

One rinsed three times with N2. Thereafter, the container was tested for pressure tightness, 0.5 bar overpressure (1, 5 bar absolute) set, heated to 120 ° C and then the pressure to 1 bar absolute. There were 66 g (1, 577 mol) of EO added at 127 ° C, pmax was 2.1 bar absolute. It was maintained for 30 min until the pressure remained stable, after which it was completely depressurized to 1, 0 bar.

There were 567 g (6.6 mol) of added PeO at 127 ° C, p _ma x was 2.1 bar absolute. An interim two-time relaxation due to Füllgradzunahme became necessary. The PeO-Dosage was stopped, allowed to react for 2 h until the pressure was constant and relaxed to 1, 0 bar absolute. Thereafter, the addition of PeO was continued. Pmax remained at 2.1 bar. After the end of the PeO dosage, the mixture was left to react for 4 hours or allowed to react. It was cooled to 110 ° C. and residual oxide was drawn off until the pressure was below 10 mbar for at least 10 minutes. Then, the addition of 0.5% water at 1 10 ° C and subsequent removal took place until the pressure for at least 10 minutes below 10 mbar. The vacuum was released with N2 and 100 ppm BHT was added. The bottling was carried out at 80 ° C under N2. The analysis (mass spectrum, GPC, 1 H NMR in CDCl ₃ , 1 H NMR in MeOD) confirmed the structure.

Example M7 HBVE - 24.5 EO - 10 PeO (0.4 mol% potassium ions, 4.6 mol% sodium ions), addition of the PeO at 127 ° C to 2.1 bar

Production was carried out analogously to Example M6 with the difference that 10 instead of 1 1 eq pentene oxide were added. Example M8 HBVE - 24.5 EO - 10 PeO (0.9 mol% potassium ion, 4.1 mol% sodium ion), addition of the PeO at 127 ° C to 2.1 bar

The preparation was carried out analogously to Example M6, with the difference that the catalyst concentration was 0.9 mol% potassium ions and 4.1 mol% sodium ions and that 10 instead of 1 1 eq PeO were added.

Example M9 HBVE - 24.5 EO - 10 PeO (1.5 mol% potassium ions, 4.6 mol% sodium ions), addition of the PeO at 127 ° C to 2.1 bar The preparation was carried out analogously to Example M6 with the difference that the catalyst concentration was 1, 5 mol% of potassium ions and 4.1 mol% of sodium ions and that 10 instead of 1 1 eq PeO were added.

Example M10 HBVE - 24.5 EO - 10 PeO (0.4 mol% potassium ion, 5.5 mol% sodium ion), addition of the PeO at 127 ° C to 2.1 bar

The starting material used was monomer M1 from example M1. 684.0 g (0.631 mol) of HBVE-22 EO were placed in a 2 l pressure autoclave with anchor stirrer and the stirrer was switched on. Thereafter, 2.78 g of 50% NaOH (sodium hydroxide) solution (0.0348 mol NaOH, 1.39 g NaOH) were added, a vacuum of <10 mbar applied, heated to 100 ° C and kept for 80 min, to distill off the water.

One rinsed three times with N2. Thereafter, the container was tested for pressure tightness, 0.5 bar overpressure (1, 5 bar absolute) set, heated to 120 ° C and then the pressure to 1, 6 bar absolute. 69.4 g (1.757 mol) of EO were metered in at 127 ° C., pmax was 2.1 bar absolute. It was maintained for 30 min until the pressure remained stable, after which it was completely depressurized to 1, 0 bar. There were added 542.5 g (6.03 mol) of PeO at 127 ° C, p _ma x was 2.1 bar absolute. An intermediate relaxation due to Füllgradzunahme became necessary. The PeO-Dosage was stopped, allowed to react for 1 h until the pressure was constant and relaxed to 1, 0 bar absolute. Thereafter, the addition of PeO was continued. P _ma x was still 2.1 bar (first relaxation after 399 g PeO, total dosing time PeO 7 h including relaxation break). After the end of the PeO dosage, the reaction was allowed to continue until the pressure remained constant or for 3 hours. It was cooled to 110 ° C. and residual oxide was removed in vacuo until the pressure was below 10 mbar for at least 10 minutes. Then, 0.5% of water was added at 110.degree. C., followed by removal until the pressure was below 10 mbar for at least 10 minutes. The vacuum was released with N2 and 100 ppm BHT was added. The bottling was carried out at 80 ° C under N2.

The analysis (mass spectrum, GPC, 1 H NMR in CDCl ₃ , 1 H NMR in MeOD) confirmed the structure.

Example M1 1 HBVE - 24.5 EO - 9 PeO (0.4 mol% potassium ion, 5.5 mol% sodium ion), addition of the PeO at 127 ° C to 2.1 bar

The preparation was carried out analogously to Example M10 with the difference that 9 instead of 10 eq PeO were added.

Example M12 HBVE - 24.5 EO - 9 PeO (5.8 mol% potassium ions), Addition of the

PeO at 127 ° C to 2.1 bar The starting material used was monomer M1 from example M1. 889.2 g (0.820 mol) of HBVE-22 EO were introduced into a 2 l pressure autoclave with anchor stirrer and the stirrer was switched on. Thereafter, 9.69 g of 32% KOMe in MeOH solution (0.0443 mol

KOMe, 3.1 1 g KOMe), vacuum of <10 mbar applied, heated to 80 ° C and held for 80 min to distill off MeOH.

One rinsed three times with N2. Thereafter, the container was tested for pressure tightness, 0.5 bar overpressure (1, 5 bar absolute) set, heated to 120 ° C and then the pressure to 1 bar absolute. There were 90.2 g (2.050 mol) of EO added to 140 ° C. It was maintained for 30 min until pressure constancy set, then it was relaxed to 1, 0 bar absolute at 120 ° C.

A larger sample was drawn so that 789 g (0.66 mol) of HBVE-24.5 EO remained in the reactor. It was again inertized with N2, set to 1, 0 bar absolute and warmed to 127 ° C for safety. There were 51 1 g (5.95 mol) of added PeO at 127 ° C, p _ma x was 2.1 bar absolute. An intermediate relaxation due to Füllgradzunahme became necessary. The PeO-Dosage was stopped, allowed to react for 2 h until pressure was constant and relaxed to 1, 0 bar absolute. Thereafter, the addition of PeO was continued. Pmax remained at 2.1 bar. After the end of the PeO dosage, the reaction was allowed to continue until the pressure remained constant or 3 h. It was cooled to 110 ° C. and residual oxide was removed in vacuo until the pressure was below 10 mbar for at least 10 minutes. Then, the addition of 0.5% water at 1 10 ° C and subsequent removal took place until the pressure for at least 10 minutes below 10 mbar. The vacuum was released with N2 and 100 ppm BHT was added. The bottling was carried out at 80 ° C under N2.

Example M13 HBVE - 24.5 EO - 8 PeO (0.4 mol% potassium ion, 4.6 mol% sodium ion), addition of the PeO at 127 ° C to 2.1 bar

The preparation was carried out analogously to Example M6 with the difference that 8 instead of 1 1 eq PeO were added. Example M14 HBVE - 26.5 EO - 10 PeO (0.4 mol% potassium ion, 5.5 mol% sodium ion), addition of the PeO at 127 ° C to 2.1 bar

The preparation was carried out analogously to Example M10 with the difference that, starting from HBVE -22 EO, 4.5 eq of EO were added instead of 2.5 eq of EO.

Example M15 HBVE - 24.5 EO - 10 PeO (0.4 mol% potassium ions, 5.5 mol% sodium ions), Addition of the PeO at 122 ° C to 2.1 bar The preparation was carried out analogously to Example M10 with the difference that PeO was added at 122 ° C instead of 127 ° C.

Example M16 HBVE - 24.5 EO - 10 PeO (0.4 mol% potassium ion, 5.5 mol% sodium ion), addition of the PeO at 132 ° C to 2.1 bar

The preparation was carried out analogously to Example M10 with the difference that PeO was added at 132 ° C instead of 127 ° C. Example M17 HBVE - 24.5 EO - 10 BuO (0.4 mol% potassium ion, 5.5 mol% sodium ion), addition of BuO at 127 ° C to 2.1 bar

The starting material used was monomer M1 from example M1. 730.8 g (0.674 mol) of HBVE-22 EO were placed in a 2 l pressure autoclave with anchor stirrer and the stirrer was switched on. Thereafter, 2.97 g of 50% NaOH solution (0.0371 mol NaOH, 0.85 g NaOH) was added, vacuum of <10 mbar applied, heated to 100 ° C and held for 80 min to distill off the water , One rinsed three times with N2. Thereafter, the container was tested for pressure tightness, 0.5 bar overpressure (1, 5 bar absolute) set, heated to 120 ° C and then the pressure to 1, 6 bar absolute. There were 74.1 g (1, 685 mol) of EO added to 127 ° C, pmax was 3.9 bar absolute. It was maintained for 30 min until the pressure remained stable, after which it was completely depressurized to 1, 0 bar.

485.3 g (6.74 mol) of BuO (butylene oxide) were metered in at 127 ° C., p _ma x was 2.1 bar absolute. An intermediate relaxation due to Füllgradzunahme became necessary. The BuO dosage was stopped, allowed to react for 1 h until pressure was constant and relaxed to 1, 0 bar absolute. Thereafter, the addition of BuO was continued. Pmax still amounted to 2.1 bar (first relaxation after 246 g BuO, total dosage time BuO 10 h including relaxation break). After the end of the BuO dosage, the reaction was allowed to continue until the pressure remained constant or for 3 hours. It was cooled to 1 10 ° C, residual oxide withdrawn until the pressure was at least 10 min unterl O mbar. Then, the addition of 0.5% water at 1 10 ° C and subsequent removal took place until the pressure for at least 10 minutes below 10 mbar. The vacuum was released with N2 and 100 ppm BHT was added. The bottling was carried out at 80 ° C under N2.

Example M18 HBVE - 24.5 EO - 12 BuO (0.4 mol% potassium ion, 5.5 mol% sodium ion), addition of BuO at 127 ° C to 2.1 bar

The preparation was carried out analogously to Example M17 with the difference that 12 instead of 10 eq BuO were added.

Example M19 HBVE - 24.5 EO - 14 BuO (0.4 mol% potassium ion, 5.5 mol% sodium ion), addition of BuO at 127 ° C to 2.1 bar The preparation was carried out analogously to Example M17 with the difference that 14 instead of 10 eq BuO were added.

Example M20 HBVE - 24.5 EO - 16 BuO (0.4 mol% potassium ion, 5.5 mol% sodium ion), addition of BuO at 127 ° C to 2.1 bar

The preparation was carried out analogously to Example M17 with the difference that 16 instead of 10 eq BuO were added.

Example M21 HBVE - 24.5 EO - 18 BuO (0.4 mol% potassium ions, 5.5 mol% sodium ions), addition of BuO at 127 ° C to 2.1 bar The preparation was carried out analogously to Example M17 with the difference that 18 instead of 10 eq BuO were added.

Example M22 HBVE - 24.5 EO - 16 BuO (5.8 mol% potassium ions), Addition of the

BuO at 127 ° C to 3.1 bar

The starting material used was monomer M1 from example M1. 622.8 g (0.575 mol) of HBVE-22 EO were introduced into a 2 l pressure autoclave with anchor stirrer and the stirrer was switched on. Thereafter, 6.92 g of 32% KOM in MeOH solution (0.0316 moles of KOM, 2.21 g of KOMe) was added, vacuum of <10 mbar applied, heated to 80 ° C and held for 80 min to the methanol distill.

One rinsed three times with N2. Thereafter, the container was tested for pressure tightness, 0.5 bar overpressure (1, 5 bar absolute) set, heated to 120 ° C and then the pressure to 1, 6 bar absolute. There were 50.3 g (1, 144 mol) of EO added to 127 ° C, pmax was 3.9 bar absolute. It was maintained for 30 min until the pressure remained stable, after which it was completely depressurized to 1, 0 bar.

There were 662 g (9.19 mol) of BuO added at 127 ° C, p _ma x was 3.1 bar absolute. After the end of the BuO dosage, the reaction was allowed to continue until the pressure remained constant or for 5 h. It was cooled to 1 10 ° C, withdrawn residual oxide until the pressure for at least 10 minutes below 10 mbar. Then, the addition of 0.5% water at 1 10 ° C and subsequent removal took place until the pressure for at least 10 minutes below 10 mbar. The vacuum was released with N2 and 100 ppm BHT was added. The bottling was carried out at 80 ° C under N ₂ . The analysis (mass spectrum, GPC, 1 H NMR in CDCl ₃ , 1 H NMR in MeOD) confirmed the structure.

Example M23 HBVE - 24.5 EO - 16 BuO (0.4 mol% potassium ions, 1 1 mol% sodium ion), addition of BuO at 127 ° C to 3.1 bar

The starting material used was monomer M1 from example M1. 595.1 g (0.549 mol) of HBVE-22 EO were introduced into a 2 l pressure autoclave with anchor stirrer and the stirrer was switched on. Thereafter, 4.83 g of 50% NaOH solution (0.060 mol NaOH, 2.41 g NaOH) was added, vacuum of <10 mbar applied, heated to 100 ° C and held for 80 min to distill off the water.

One rinsed three times with N2. Thereafter, the container was tested for pressure tightness, 0.5 bar overpressure (1, 5 bar absolute) set, heated to 120 ° C and then the pressure to 1, 6 bar absolute. There were added 60.4 g (1, 373 mol) of EO to 127 ° C, pmax was 3.9 bar absolute. It was maintained for 30 min until the pressure remained stable, after which it was completely depressurized to 1, 0 bar.

632.2 g (8.748 mol) of BuO were metered in at 127 ° C., p _max was 3.1 bar absolute. An intermediate relaxation due to Füllgradzunahme became necessary. The BuO dosage was stopped, allowed to react for 1 h until pressure was constant and relaxed to 1, 0 bar absolute. Thereafter, the addition of BuO was continued. P _ma x was still 3.1 bar (first relaxation after 334 g BuO, total dosage time BuO 5 h incl. Relaxation break). After the end of the BuO dosage, the mixture was heated to 135 ° C. and allowed to react for 3.5 h. It was cooled to 100 ° C, withdrawn residual oxide until the pressure for at least 10 minutes below 10 mbar. Then the addition of 0.5% water at 120 ° C and subsequent removal took place until the pressure for at least 10 minutes below 10 mbar. The vacuum was released with N2 and 100 ppm BHT was added. The bottling was carried out at 80 ° C under N ₂ .

Example M24 HBVE - 23 EO - 17 BuO - 2.5 EO (0.4 mol% potassium ion, 5.5 mol% sodium ion), addition of BuO at 127 ° C to 3.1 bar

The starting material used was monomer M1 from example M1. 576.7 g (0.532 mol) of HBVE-22 EO were introduced into a 2 l pressure autoclave with anchor stirrer and the stirrer was switched on. Thereafter, 2.33 g of 50% NaOH solution (0.029 mol NaOH, 1.17 g NaOH), vacuum of <10 mbar applied, heated to 100 ° C and held for 80 min to distill off the water.

One rinsed three times with N2. Thereafter, the container was tested for pressure tightness, 0.5 bar overpressure (1, 5 bar absolute) set, heated to 127 ° C and then the pressure to 1, 6 bar absolute. There were 23.4 g (0.532 mol) of EO added at 127 ° C, pmax was 3.9 bar absolute. It was maintained for 30 min until the pressure remained stable, after which it was completely depressurized to 1, 0 bar. There were 651, 2 g (9.044 mol) of BuO added at 127 ° C, p _ma x was 3.1 bar absolute. After the end of the BuO dosage, the mixture was heated to 135 ° C. and allowed to react for 2 h. Thereafter, 58.5 g (1, 331 mol) of EO were metered in at 135 ° C, p _ma x was 3.2 bar absolute. After the end of the EO dosage was allowed to react for 2 h. It was cooled to 100 ° C, withdrawn residual oxide until the pressure for at least 10 minutes below 10 mbar. Then the addition of 0.5% water at 120 ° C and subsequent removal took place until the pressure for at least 10 minutes below 10 mbar. The vacuum was released with N2 and 100 ppm BHT was added. The bottling was carried out at 80 ° C under N2. The analysis (mass spectrum, GPC, 1 H NMR in CDCl ₃ , 1 H NMR in MeOD) confirmed the structure.

Example M25 HBVE - 24.5 EO - 16 BuO - 3.5 EO (0.4 mol% potassium ion, 5.5 mol% sodium ion), addition of BuO at 127 ° C to 3.1 bar

The starting material used was monomer M1 from example M1. 588.6 g (0.543 mol) of HBVE-22 EO were introduced into a 2 l pressure autoclave with anchor stirrer and the stirrer was switched on. Thereafter, 2.39 g of 50% NaOH solution (0.030 mol NaOH, 1.19 g NaOH) was added, vacuum of <10 mbar applied, heated to 100 ° C and held for 80 min to distill off the water ,

One rinsed three times with N2. Thereafter, the container was tested for pressure tightness, 0.5 bar overpressure (1, 5 bar absolute) set, heated to 127 ° C and then the pressure to 1, 6 bar absolute. There were 59.7 g (1.358 mol) of EO added at 127 ° C, pmax was 3.9 bar absolute. It was maintained for 30 min until the pressure remained stable, after which it was completely depressurized to 1, 0 bar.

625.5 g (8.688 mol) of BuO were metered in at 127 ° C., while p _ma x was 3.1 bar absolute. An intermediate relaxation due to Füllgradzunahme became necessary. The BuO dosage was stopped, allowed to react for 1 h until pressure was constant and relaxed to 1, 0 bar absolute. Thereafter, the addition of BuO was continued. P _ma x was still 3.1 bar (first relaxation after 610 g BuO, total dosage time BuO 8 h incl. Relaxation break). After the end of the BuO dosage was allowed to react for 8 h and then heated to 135 ° C. Thereafter, 83.6 g (1.901 mol) of EO were metered in at 135 ° C., pmax was 3.1 bar absolute. After the end of the EO dosage was allowed to react for 4 h. It was cooled to 100 ° C, withdrawn residual oxide until the pressure for at least 10 minutes below 10 mbar. Then the addition of 0.5% water at 120 ° C and subsequent removal took place until the pressure for at least 10 minutes below 10 mbar. The vacuum was released with N2 and 100 ppm BHT was added. The bottling was carried out at 80 ° C under N ₂ .

The analysis (mass spectrum, GPC, 1 H NMR in CDCl ₃ , 1 H NMR in MeOD) confirmed the structure. Example M26 HBVE - 24.5 EO - 16 BuO - 5 EO (0.4 mol% potassium ion, 5.5 mol.

% Sodium ions), addition of BuO at 127 ° C to 3.1 bar

The starting material used was monomer M1 from example M1. The preparation was carried out analogously to Example M25 with the difference that after the end of the BuO dosage and polymerization 5 instead of 3.5 eq EO were added, i. 1 19.5 g (2.715 mol) EO at 135 ° C were added.

Example M27 HBVE - 24.5 EO - 10 BuO - 3.5 EO (0.4 mol% potassium ion, 5.5 mol% sodium ion), addition of BuO at 127 ° C to 3.1 bar

The starting material used was monomer M1 from example M1. 685.2 g (0.632 mol) of HBVE-22 EO were introduced into a 2 l pressure autoclave with anchor stirrer and the stirrer was switched on. Thereafter, 2.78 g of 50% NaOH solution (0.035 mol NaOH, 1.39 g NaOH) was added, vacuum of <10 mbar applied, heated to 100 ° C and held for 80 min to distill off the water.

One rinsed three times with N2. Thereafter, the container was tested for pressure tightness, 0.5 bar overpressure (1, 5 bar absolute) set, heated to 127 ° C and then the pressure to 1, 6 bar absolute. There were 69.8 g (1.587 mol) of EO added at 127 ° C, pmax was 3.9 bar absolute. It was maintained for 30 min until the pressure remained stable, after which it was completely depressurized to 1, 0 bar. There were 455.2 g (6.322 mol) of BuO added at 127 ° C, p _ma x was 3.1 bar absolute. After the end of the BuO dosage was allowed to react for 7 h. Thereafter, 97.4 g (2.213 mol) of EO were added at 127 ° C, p _ma x was 3.1 bar absolute. After the end of the EO dosage was allowed to react for 2 h. It was cooled to 100 ° C., residual oxide was removed until the pressure was below 10 mbar for at least 10 minutes. Then the addition of 0.5% water at 120 ° C and subsequent removal took place until the pressure for at least 10 minutes below 10 mbar. The vacuum was released with N2 and 100 ppm BHT was added. The bottling was carried out at 80 ° C under N2. The analysis (mass spectrum, GPC, 1 H NMR in CDCl ₃ , 1 H NMR in MeOD) confirmed the structure.

Example M28 HBVE - 24.5 EO - 5 BuO - 3.5 EO (0.4 mol% potassium ion, 5.5 mol% sodium ion), addition of BuO at 127 ° C to 3.1 bar

The starting material used was monomer M1 from example M1. 822.0 g (0.758 mol) of HBVE-22 EO were placed in a 2 l pressure autoclave with anchor stirrer and the stirrer was switched on. Thereafter, 3.34 g of 50% NaOH solution (0.042 mol NaOH, 1.67 g NaOH) were added, vacuum of <10 mbar applied, heated to 100 ° C and held for 80 min to distill off the water ,

One rinsed three times with N2. Thereafter, the container was tested for pressure tightness, 0.5 bar overpressure (1, 5 bar absolute) set, heated to 127 ° C and then the pressure to 1, 6 bar absolute. There were 83.4 g (1.895 mol) of EO added at 127 ° C, pmax was 3.9 bar absolute. It was maintained for 30 min until the pressure remained stable, after which it was completely depressurized to 1, 0 bar.

There were added 273.0 g (3.792 mol) BuO at 127 ° C, p _ma x was 3.1 bar absolute. After the end of the BuO dosage was allowed to react for 15 h. Thereafter, 1.168 g (2.654 mol) EO were added at 127 ° C, p _ma x was 3.1 bar absolute. After the end of the EO dosage was allowed to react for 4 h. It was cooled to 100 ° C, withdrawn residual oxide until the pressure for at least 10 minutes below 10 mbar. Then the addition of 0.5% water at 120 ° C and subsequent removal took place until the pressure for at least 10 minutes below 10 mbar. The vacuum was released with N2 and 100 ppm BHT was added. The bottling was carried out at 80 ° C under N ₂ .

The analysis (mass spectrum, GPC, 1 H NMR in CDCl ₃ , 1 H NMR in MeOD) confirmed the structure. Example M29 HBVE - 24.5 EO - 22 BuO - 3.5 EO (0.4 mol% potassium ion, 5.5 mol% sodium ion), addition of BuO at 127 ° C to 3.1 bar

The starting material used was monomer M1 from example M1. In a 2 l pressure autoclave with anchor stirrer 493.3 g (0.455 mol) of HBVE-22 EO were submitted and turned on the stirrer. Thereafter, 2.00 g of 50% NaOH solution (0.025 mol NaOH, 1.00 g NaOH) was added, vacuum of <10 mbar applied, heated to 100 ° C and held for 80 min to distill off the water. One rinsed three times with N2. Thereafter, the container was tested for pressure tightness, 0.5 bar overpressure (1, 5 bar absolute) set, heated to 127 ° C and then the pressure to 1, 6 bar absolute. There were 50.0 g (1, 138 mol) of EO added at 127 ° C, pmax was 3.9 bar absolute. It was maintained for 30 min until the pressure remained stable, after which it was completely depressurized to 1, 0 bar.

There were 720.9 g (10.012 mol) of BuO added at 127 ° C, p _ma x was 3.1 bar absolute. After the end of the BuO dosage was allowed to react for 9 h. It was heated to 135 ° C. Thereafter, 70.1 g (1, 593 mol) of EO were added at 135 ° C, p _ma x was 3.1 bar absolute. After the end of the EO dosage was allowed to react for 2 h. It was cooled to 100 ° C, withdrawn residual oxide until the pressure for at least 10 minutes below 10 mbar. Then the addition of 0.5% water at 120 ° C and subsequent removal took place until the pressure for at least 10 minutes below 10 mbar. The vacuum was released with N2 and 100 ppm BHT was added. The bottling was carried out at 80 ° C under N ₂ .

Example M30 HBVE - 24.5 EO - 16 BuO - 3.5 EO (0.4 mol% potassium ions, 5.5 mol% sodium ions), addition of BuO at 127 ° C up to 4 to 6 bar

The starting material used was monomer M1 from Example M1 568.6 g (0.525 mol) of HBVE-22 EO were introduced into a 2 l pressure autoclave with anchor stirrer and the stirrer was switched on. Thereafter, 2.31 g of 50% NaOH solution (0.029 mol NaOH, 1.16 g NaOH) was added, vacuum of <10 mbar applied, heated to 100 ° C and held for 80 min to distill off the water.

One rinsed three times with N2. Thereafter, the container was tested for pressure tightness, 0.5 bar overpressure (1, 5 bar absolute) set, heated to 127 ° C and then the Pressure set to 3 bar absolute. There were added 57.7 g (1, 31 1 mol) of EO at 127 ° C, pmax was 6 bar absolute. It was maintained for 30 min until the pressure stabilized, then it was completely relaxed to 4.0 bar. There were added 604.2 g (8.392 mol) of BuO at 127 ° C, p _ma x was 6 bar absolute. An intermediate relaxation due to Füllgradzunahme became necessary. The BuO dosage was stopped, allowed to react for 1 h until pressure was constant and relaxed to 4.0 bar absolute. Thereafter, the addition of BuO was continued. P _ma x continued to be 6 bar (first release after 505 g BuO, total dosing time BuO 1 1 h incl. Relaxation break). After the end of the BuO dosage was allowed to react for 6 h at 127 ° C. One relaxed to 4 bar absolute.

Thereafter, 80.8 g (1, 836 mol) of EO were added at 127 ° C, p _ma x was 6 bar absolute. After the end of the EO dosage was allowed to react for 4 h. It was cooled to 100 ° C, withdrawn residual oxide until the pressure for at least 10 minutes below 10 mbar. About 1400 ppm of volatile components were separated. Then the addition of 0.5% water at 120 ° C and subsequent removal took place until the pressure for at least 10 minutes below 10 mbar. The vacuum was released with N2 and 100 ppm BHT was added. The bottling was carried out at 80 ° C under N2. The analysis (mass spectrum, GPC, 1 H NMR in CDCl ₃ , 1 H NMR in MeOD) confirmed the structure. lb Preparation of the Copolymers Based on Monomers (M2-M30) Example C1 General Preparation of a Copolymer of 2% by Weight of Monomer M,

50% by weight of acrylamide and 48% by weight of 2-acrylamido-2-methylpropanesulfonic acid

121.2 g of a 50% strength aqueous solution of NaATBS (2-acrylamido-2-methylpropanesulfonic acid, Na salt) were placed in a plastic bucket with magnetic stirrer, pH meter and thermometer and subsequently 155 g of distilled water, 0.6 g a defoamer (Surfynol ^® DF-58), 0.2 g of a silicone antifoam (Baysilon ^® EN), 2.3 g of monomer M, 1 14.4 g of a 50% aqueous solution of acrylamide, 1, 2 g Pentasodium diethylenetriaminepentaacetate (complexing - ner, as a 5% aqueous solution) and 2.4 g of a nonionic surfactant (isotridekanol, alkoxylated with 15 units of ethylene oxide) was added.

After adjusting the pH to 6 with a 20% or 2% sulfuric acid solution and adding the remaining water, the monomer solution became set to the starting temperature of 5 ° C. The total amount of water was such that, after polymerization, a solids concentration of about 30 to 36 wt .-% was achieved. The solution was transferred to a thermos flask, a thermocouple was mounted for temperature recording and rinsed with N2 for 30 minutes. The polymerization was then carried out by adding 1.6 ml of a 10% aqueous solution of a water-soluble, cationic azo initiator 2,2'-azo-bis (2-amidinopropane) dihydrochloride (Wako V-50), 0.12 ml of a 1% aqueous solution of ferric butyl hydroperoxide and 0.24 ml of a 1% sodium sulfite solution started. After addition of the initiators, the temperature rose within 15 to 30 minutes to about 80 ° C. After 30 minutes, the reaction vessel was placed in a drying oven of about 80 ° C for about 2 h to complete the polymerization. The total duration of the polymerization was about 2 hours to 2.5 hours.

There was obtained a gel block which was crushed after completion of the polymerization using a meat grinder. The resulting gel granules were dried in a fluidized bed dryer at 55 ° C for two hours. This gave a white, hard granules, which was converted by means of centrifugal mill into a powdery state. A copolymer having a weight-average molecular weight of about 1,000,000 g / mol to 30,000,000 g / mol was obtained.

Example C2 copolymer based on monomer M2

The copolymer was obtained according to the above general preparation procedure by using monomer 2 from Comparative Example M2.

Examples C3 to C30

The copolymers C3 to C30 were prepared according to the above general instructions by using the respective monomers M3 to M30.

Part II: Application Testing

With the obtained copolymers based on the above monomers, the following tests were conducted to evaluate their suitability for tertiary petroleum production.

Description of the measurement methods a) Determination of solubility The copolymers were dissolved in synthetic seawater according to DIN 50900 (35 g / l salinity) so that a polymer concentration of 2000 ppm resulted: 0.5 g of the respective copolymer were in 249 g of synthetic seawater (DIN 50900) 24 h to complete Loosened stirring (preferably a blade stirrer should be used as KPG stirrer, the polymer was slowly scattered into the forming vortex). b) Determination of Viscosity The abovementioned copolymer solutions were used to determine the viscosities on a Haake rheometer with a double-gap geometry at 7 Hz and 60 ° C. After about 5 minutes, a plateau value for the viscosity, which was read. Viscosities greater than or equal to 150 mPas were considered to be very good values (2000 ppm copolymer in synthetic seawater at 60 ° C. and 7 Hz). As good values, viscosities of 120 to 149 mPas were considered. Viscosity values of 80 to 1 19 mPas were considered moderate. Viscosities of less than 80 mPas were considered poor. c) Determination of filterability

Before the actual filtration test was filtered through a 200 μηη Retsch sieve and thereby determined the gel content of the polymer solution.

The filtration test for determining the MPFR value - the ratio of the flow rate of the first quarter to that of the fourth quarter represents the so-called "Millipore Filter Ratio" (MPFR) - was determined by means of a Satorius pressure filtration cell 16249 (filter diameter 47 mm) and an Isopore polycarbonate membrane filter (Diameter 47 mm, 3 μηη pore size) carried out at room temperature and 1 bar overpressure. 210-220 g of polymer solution was used. During the test, at least 180 g of filtrate should be released within 30 minutes. As good values, MPFRs of less than or equal to 1.3 were considered. If they are between 1, 3 and 1, 6, the filterability was considered moderate. If less than 30 g of filtrate passed through, the sample was considered non-filterable. d) Determination of Gel Content 1 g of the respective copolymer of Preparation Examples 2 to 30 was stirred in 249 g of synthetic seawater according to DIN 50900 (salt content 35 g / l) for 24 hours until complete dissolution. Subsequently, the solution was filtered through a sieve with a mesh size of 200 μm and the volume of the residue remaining on the sieve was measured. The value obtained corresponds to the gel content. Test results:

Viscosity-filterable gel

Copolymer soluble

playfulness share

C2 based on M2

HBVE - 22 EO - 10.6 PeO (0.4

2 mol% potassium ions, 4.6 mol% yes well good 0 ml

Sodium ions), addition of the

PeO at 140 ° C to 3.2 bar

C3 based on M3

HBVE - 22 EO - 10.5 PeO (0.4

not filtered

3 mol% potassium ion, 3.3 mol% yes well 2 ml bar

Sodium ions), addition of the

PeO at 140 ° C to 2.1 bar

C4 based on M4

HBVE - 22 EO - 10 PeO (0.4

4 mol% potassium ions, 4.6 mol% yes well good 0 ml

Sodium ions), addition of the

PeO at 127 ° C to 2.1 bar

C5 based on M5

HBVE - 22 EO - 1 1 PeO (0.4

not filtered

5 mol% potassium ions, 4.6 mol% yes well 12 ml bar

Sodium ions), addition of the

PeO at 127 ° C to 2.1 bar

C6 based on M6

HBVE - 24.5 EO - 1 1 PeO (0.4

6 mol% potassium ions, 4.6 mol% yes well good 0 ml

Sodium ions), addition of the

PeO at 127 ° C to 2.1 bar

C7 based on M7

HBVE - 24.5 EO - 10 PeO (0.4

7 mol% potassium ions, 4.6 mol% yes well good 0 ml

Sodium ions), addition of the

PeO at 127 ° C to 2.1 bar

C8 based on M8

HBVE - 24.5 EO - 10 PeO (0.9

8 mol% potassium ions, 4.1 mol% yes, moderately good 0-1 ml

Sodium ions), addition of the

PeO at 127 ° C to 2.1 bar C9 based on M9

HBVE - 24.5 EO - 10 PeO (1, 5

not filtered mol% potassium ions, 4.6 mol% yes well 3 ml bar

Sodium ions), addition of the

PeO at 127 ° C to 2.1 bar

C10 based on M10

HBVE - 24.5 EO - 10 PeO (0.4

mol% potassium ions, 5.5 mol% yes well good 0 ml sodium ions), Addition of the

PeO at 127 ° C to 2.1 bar

C1 1 based on M1 1

HBVE - 24.5 EO - 9 PeO (0.4

mol% potassium ions, 5.5 mol% yes well good 0 ml sodium ions), Addition of the

PeO at 127 ° C to 2.1 bar

C12 based on M12

HBVE - 24.5 EO - 9 PeO (5.8 not filtrierja good 48 ml mol% potassium ions), addition bar

of the PeO at 127 ° C to 2.1 bar

C13 based on M13

HBVE - 24.5 EO - 8 PeO (0.4

mol% of potassium ions, 4.6 mol% yes well moderately 0-1 ml sodium ions), Addition of the

PeO at 127 ° C to 2.1 bar

C14 based on M14

HBVE - 26.5 EO - 10 PeO (0.4

mol% potassium ions, 5.5 mol% yes well moderately 0-1 ml sodium ions), Addition of the

PeO at 127 ° C to 2.1 bar

C15 based on M15

HBVE - 24.5 EO - 10 PeO (0.4

mol% potassium ions, 5.5 mol% yes well good 0 ml sodium ions), Addition of the

PeO at 122 ° C to 2.1 bar

C16 based on M16

HBVE - 24.5 EO - 10 PeO (0.4

mol% potassium ions, 5.5 mol% yes well good 0 ml sodium ions), Addition of the

PeO at 132 ° C to 2.1 bar C17 based on M17

HBVE - 24.5 EO - 10 BuO (0.4

mol% potassium ions, 5.5 mol% yes bad good 0 ml sodium ions), Addition of the

BuO at 127 ° C to 2.1 bar

C18 based on M18

HBVE - 24.5 EO - 12 BuO (0.4

mol% potassium ions, 5.5 mol% yes bad good 0 ml sodium ions), Addition of the

BuO at 127 ° C to 2.1 bar

C19 based on M19

HBVE - 24.5 EO - 14 BuO (0.4

mol% potassium ions, 5.5 mol% yes well good 0 ml sodium ions), Addition of the

BuO at 127 ° C to 2.1 bar

C20 based on M20

HBVE - 24.5 EO - 16 BuO (0.4

mol% potassium ions, 5.5 mol% yes well good 0 ml sodium ions), Addition of the

BuO at 127 ° C to 2.1 bar

C21 based on M21

HBVE - 24.5 EO - 18 BuO (0.4

not filtered mol% potassium ion, 5.5 mol% yes well 2 ml bar

Sodium ions), addition of the

BuO at 127 ° C to 2.1 bar

C22 based on M22

HBVE - 24.5 EO - 16 BuO (5.8 not filtrierja good 5-10 ml mol% potassium ions), addition bar

of the BuO at 127 ° C to 3.1 bar

C23 based on M23

HBVE - 24.5 EO - 16 BuO (0.4

mol% potassium ions, 1 1 mol% yes, well good 0 ml sodium ions), addition of the

BuO at 127 ° C to 3.1 bar

C24 based on M24

HBVE - 23 EO - 17 BuO - 2.5

EO (0.4 mol% potassium ion, very good at all 0 ml 5.5 mol% sodium ion), addition of BuO at 127 ° C to 3.1 bar

C25 based on M25

HBVE - 24.5 EO - 16 BuO - 3.5

EO (0.4 mol% potassium ion,

yes very good good 0 ml 5.5 mol% sodium ions), addition of BuO at 127 ° C to 3.1

bar

C26 based on M26

HBVE - 24.5 EO - 16 BuO - 5

EO (0.4 mol% potassium ion,

bar

C27 based on M27

HBVE - 24.5 EO - 10 BuO - 3.5

EO (0.4 mol% potassium ion,

yes moderately good 0 ml 5.5 mol% sodium ions), addition of BuO at 127 ° C to 3.1

bar

C28 based on M28

HBVE - 24.5 EO - 5 BuO - 3.5

EO (0.4 mol% potassium ion,

bar

C29 based on M29

HBVE - 24.5 EO - 22 BuO - 3.5

EO (0.4 mol% potassium ion,

yes very good very good 0 ml 5.5 mol% sodium ions), addition of BuO at 127 ° C to 3.1

bar

C30 based on M30

HBVE - 24.5 EO - 16 BuO - 3.5

EO (0.4 mol% potassium ion,

yes very good good 0 ml 5.5 mol% sodium ions), addition of BuO at 127 ° C of 4

up to 6 bar Examples 2 and 3 show that the pressure window for the PeO dosage at 140 ° C has a great influence on the product quality. A larger pressure window allows fast dosage and short cycle time (2 h for PeO). However, if one sticks to the pressure windows due to safety specifications, as in example 3, the reaction will be protracted (2 days for PeO). As a result of the high temperature, side reactions and the formation of crosslinkers, which in the subsequent copolymerization cause a thickening no longer filterable copolymer, which is not for use in porous matrix (eg petroleum-bearing rock layers, thickeners in petroleum production) not more usable.

Example 4 shows that by lowering the reaction temperature while maintaining the small pressure window copolymers can be prepared which are free of crosslinking agents. As can be seen in the examples, the concentration of potassium ions is of central importance. As the examples 9 and 12 show, above 0.9 mol% potassium ions, the polymer is no longer filterable despite temperatures of 127 ° C in the PeO dosage. A potassium ion concentration of greater than 0.9 mol% obviously leads to the formation of crosslinking compounds, which lead to a no longer filterable copolymer. In addition, the exact content of sodium ion catalyst also seems to play an important role.

Surprisingly, it can also be seen that the hydrophilic-hydrophobic ratio of the monomer is also of great importance. Despite the crosslinker-free mode of operation, the copolymer according to Example 5 is slightly poorer in filtration than copolymers based on monomers with only 1 eq PeO less (Example 4). When monomers with 24.5 units EO are used, the variation of the PeO units has no influence on the filterability of the copolymers (comparison of Examples 6 and 7 and comparison of Examples 10 and 11). The particular selection of hydrophilic-hydrophobic ratio, i. Ratio of EO and PeO units; led to a surprising robustness of the process. In Examples 10 and 11 (24.5 EO units), a variation in the PeO content is not noticeable. This provides good stability for large-scale production where variations of less than 1 eq of alkylene oxide are not easily guaranteed. Deviations from process and structure are much better tolerated in the later copolymer synthesis or application.

A similar picture is seen for copolymers based on monomers having terminal BuO groups. A comparison of Examples 20 and 22 shows that even in the preparation of copolymers based on monomers having terminal BuO groups surprisingly, a concentration of potassium ions of less than 0.9 mol% to improved copolymers leads. Excessive levels of potassium ions in the copolymer lead to non-filterable structures.

Examples 19 and 20 show that optimum product properties (good viscosities and good filterability) can be achieved, in particular at a degree of butoxylation above 12 and below 18. A comparison of the results regarding monomers having terminal PeO groups and regarding monomers having terminal BuO groups has also shown that the total number of carbon atoms in the side chains of the monomers, in particular in the terminal alkylene oxide blocks, is of crucial importance for the property of the resulting Copolymers is. For example, the total number of carbon atoms in the side chains of the terminal alkylene oxide block of Examples 19 and 20 (total of 28 to 32 carbon atoms in side chains) falls within the range of the total number in Examples 6, 10 and 11 (total 27 to 33 carbon atoms in Side chains) related to monomers having terminal PeO groups. Other degrees of butoxylation, as in Examples 17, 18 and 21, no longer lead to optimal properties of the monomer in all areas.

It has also been shown that it may be advantageous to modify monomers with BuO blocks, in particular blocks with 16 to 22 BuO units, with a terminal EO block. Thus, in particular copolymers with very good viscosity properties and good filterability can be obtained (Examples 24 to 26 and 29). In contrast, the introduction of a terminal EO block with monomers having less than 12 BuO units in the BuO block does not appear to produce a particularly advantageous effect (Examples 27 and 28).

Example 23 shows that the concentration of sodium ions in the addition of the butylene oxide can be at least up to 1 mol%.

Example 30 shows that even at pressures of 4 to 6 bar, the addition of butylene oxide is advantageously possible.

Claims

claims

1 . A water-soluble, hydrophobically associating copolymer comprising

(a) 0.1 to 20% by weight of at least one hydrophobically associating monomer

(a),

such as

(B) 25 to 99.9 wt .-% of at least one of monomer (a) different hydrophilic monomer (b), wherein in its synthesis prior to the initiation of the polymerization at least one further, but not polymerizable surface-active component

(c) is used, wherein the quantities are in each case based on the total amount of all monomers in the copolymer, wherein at least one of the monomers (a) is a monomer of the general formula (I)

H ₂ C = C (R ¹ ) -R ² -O - (- CH ₂ -CH ₂ -O-) k - (- CH ₂ -CH (R ³ ) -O-) i - (- CH ₂ -CH ₂ -O- ) _{m is} -R ⁴ (I), where the units - (- CH ₂ -CH ₂ -O-) k, - (- CH ₂ -CH (R ³ ) -O-) i and optionally - (- CH ₂ -CH ₂ -O-) m in block structure in the are arranged in formula (I) and the radicals and indices have the following meanings: k: is a number from 15 to 35;

I: is a number from 5 to 25;

m: is a number from 0 to 15;

R ¹ : is H or methyl;

R ² : is independently a single bond or a divalent linking group selected from the group consisting of - (CnF n) - and -O- (Cn'H2n) -, wherein n is a natural number from 1 to 6 and n 'is a natural number from 2 to 6;

R ³ : is independently of one another a hydrocarbon radical having at least 2 carbon atoms or an ether group of the general formula --CH 2 -OR ^{3 '} , where R ^{3' is} a hydrocarbon radical having at least 2 carbon atoms; with the proviso that the sum of the carbon atoms of all hydrocarbon radicals R ³ or R ³ 'is in the range of 15 to 50; R ⁴ : is independently H or a hydrocarbon radical of 1 to 4 carbon atoms; and wherein the hydrophobically associating monomer (a) of the general formula (I) is obtainable by a process comprising the following steps: a) reacting a monoethylenically unsaturated alcohol A1 of the general formula (II)

H ₂ C = C (R ¹ ) -R ² -OH (II), with ethylene oxide, wherein the radicals R ¹ and R ^{2 have} the meanings defined above;

with the addition of an alkaline catalyst K1 comprising KOMe and / or NaOMe; wherein an alkoxylated alcohol A2 is obtained;

with the addition of an alkaline catalyst K2; wherein the concentration of potassium ions in the reaction in step b) is less than or equal to 0.9 mol% based on the alcohol A2 used; and wherein the reaction in step b) is carried out at a temperature of less than or equal to 135 ° C., where an alkoxylated alcohol A 3 according to the formula (III)

H ₂ C = C (R ¹ ) -R ² -O - (- CH ² -CH ² -O-) k - (- CH 2 -CH (R ³ ) -O-) iR ⁴ (III) with R ⁴ = H is, wherein the radicals R ¹ , R ² and R ³ and the indices k and I have the meanings defined above; c) optionally reacting at least a portion of the alkoxylated alcohol A3 with ethylene oxide; wherein an alkoxylated alcohol A4 is obtained which corresponds to the monomer (a) according to formula (I) with R ⁴ = H and m is greater than 0; d) optionally etherifying the alkoxylated alcohol A3 and / or A4 with a compound

R ₄ -X where R ^{4 has} the meanings defined above and X is a leaving group, preferably selected from the group of Cl, Br, I, -O-SO 2 -CH 3 (mesylate), -O-SO 2 -CF 3 (triflate) and -O-SO 2 -OR ⁴ ; wherein a monomer (a) according to formula (I) is obtained with R ⁴ = hydrocarbon radical having 1 to 4 carbon atoms.

Copolymer according to Claim 1, characterized in that the radicals and indices have the following meanings: k: is a number from 23 to 26;

I: is a number from 5 to 25;

m: is a number from 0 to 15;

R ¹ : is H or methyl;

R ³ : is independently of one another a hydrocarbon radical having at least 2 carbon atoms or an ether group of the general formula --CH 2 -OR ^{3 '} , where R ^{3' is} a hydrocarbon radical having at least 2 carbon atoms; with the proviso that the sum of the carbon atoms of all hydrocarbon radicals R ³ or R ³ 'is in the range of 15 to 50;

R ⁴ : is independently H or a hydrocarbon radical having 1 to 4 carbon atoms.

Copolymer according to claim 1 or 2, characterized in that the radicals and indices have the following meanings: k: is a number from 23 to 26; is a number from 8.5 to 17.25;

is a number from 0 to 15;

is H or methyl;

is independently a single bond or a divalent linking group selected from the group consisting of - (CnH n) - and -O- (Cn'H2n) -, where n is a natural number from 1 to 6 and n 'is a natural number from 2 to 6;

is independently of one another a hydrocarbon radical having at least 2 carbon atoms or an ether group of the general formula --CH 2 -OR ^{3 '} , where R ^{3' is} a hydrocarbon radical having at least 2 carbon atoms; with the proviso that the sum of the carbon atoms of all hydrocarbon radicals R ³ or R ³ 'is in the range of 25.5 to 34.5;

is independently H or a hydrocarbon radical having 1 to 4 carbon atoms.

Copolymer according to one of Claims 1 to 3, characterized in that the radicals and indices have the following meanings: k: is a number from 23 to 26;

I: is a number from 12.75 to 17.25;

m: is a number from 0 to 15;

R: is H;

R ² : is a divalent linking group -O- (Ο _η Ή2η) -, where n ^'is 4,

R ³ : is independently a hydrocarbon radical having 2 carbon atoms;

R ⁴ : is H.

Copolymer according to any one of Claims 1 to 3, characterized in that the radicals and indices have the following meaning: k: is a number from 23 to 26;

I: is a number from 8.5 to 1, 5;

m: is a number from 0 to 15;

R: is H;

R ² : is a divalent linking group -O- (Ο _η Ή2η) -, where n ^'is 4,

R ³ : is a hydrocarbon radical having 3 carbon atoms;

R ⁴ : is H.

6. A copolymer according to any one of claims 1 to 5, characterized in that the monomer (a) of the general formula (I) is a mixture of a monomer (a) of the formula (I) with m = 0 and a monomer (a) of the formula (I) with m = 1 to 15.

7. A copolymer according to claim 6, characterized in that the weight ratio of the monomer of the formula (I) with m = 0 and the monomer (a) of the formula 1 with m = 1 to 15 in the range of 19: 1 to 1: 19 ,

8. A copolymer according to any one of claims 1 to 7, characterized in that in the preparation of monomer (a) the concentration of potassium ions in the reaction in step b) 0.01 to 0.5 mol%, based on the used alcohol A2 is.

9. A copolymer according to any one of claims 1 to 8, characterized in that in the preparation of monomer (a) in step b) a catalyst K2 containing at least one basic sodium compound is used, wherein the concentration of sodium ions in the reaction in step b) in the range from 3.5 mol% to 12 mol%, based on the alcohol A2 used.

10. A copolymer according to any one of claims 1 to 9, characterized in that in the preparation of monomer (a) step b) is carried out at a pressure in the range of 1 to 3.1 bar and a temperature of 120 to 135 ° C.

1 1. Copolymer according to one of claims 1 to 10, characterized in that R ^{3 is} a hydrocarbon radical having 2 carbon atoms and in the preparation of monomer (a) step b) is carried out at a pressure in the range of 1 to 3.1 bar; or that R ^{3 is} a hydrocarbon radical having at least 3 carbon atoms and in the preparation of monomer (a) step b) is carried out at a pressure of 1 to 2.1 bar.

12. A copolymer according to any one of claims 1 to 1 1, characterized in that at least one of the monomers (b) is a monomer comprising acidic groups, wherein the acidic groups are at least one group selected from Group of -COOH, -SO3H and -PO3H2, and their salts.

13. A copolymer according to any one of claims 1 to 12, characterized in that it comprises at least two different hydrophilic monomers (b), and these are - at least one neutral hydrophilic monomer (b1), and

at least one hydrophilic anionic monomer (b2) comprising at least one acidic group selected from the group consisting of -COOH, -SO3H and -PO3H2 and their salts. 14. A copolymer according to claim 1 to 13, comprising

(a) 2% by weight of at least one hydrophobically associating monomer (a); and (b) 50% by weight of acrylamide as the neutral hydrophilic monomer (b1), and

(C) 48 wt .-% acrylamido-2-methylpropanesulfonic acid (AMPS) as anionic hydrophilic monomer (b2), wherein the amounts are in each case based on the total amount of all monomers in the copolymer.

15. A copolymer according to any one of claims 1 to 14, characterized in that component (c) is at least one nonionic surfactant.

16. A process for preparing a water-soluble, hydrophobically associating co-polymer according to any one of claims 1 to 15, characterized in that at least one hydrophobically associating monomer (a) and at least one hydrophilic monomer (b) an aqueous solution in the presence of at least one surface-active component (c), and wherein the monomer (a) of the general formula (I) is prepared by a process as described in claim 1.

17. A process for the preparation of a copolymer according to claim 16, characterized in that the solution polymerization is carried out at a pH in the range of 5.0 to 7.5.

18. Use of copolymers according to one of claims 1 to 15 in the development, exploitation and completion of underground oil and gas deposits. Use of copolymers according to claim 18 for tertiary mineral oil production, characterized in that an aqueous formulation of said copolymers in a concentration of 0.01 to 5 wt .-% is injected through at least one injection well in an oil reservoir and the deposit by at least one Production drilling crude oil is taken.

Use of copolymers according to claim 19, characterized in that the aqueous formulation of said copolymers contains at least one surfactant.