BRPI0719575A2 - THICKNESS SYSTEM, USE OF A THICKNESS SYSTEM, PROCESS TO PREPARE THICKNESS COMPOSITION, THICKNESS COMPOSITION, AND PROCESS TO TREAT UNDERGROUND GEOLOGICAL FORMATIONS - Google Patents

Description

"THICKNESS SYSTEM, USE OF A THICKNESS SYSTEM, PROCESS TO PREPARE THICKNESS COMPOSITION, THICKNESS COMPOSITION, AND PROCESS TO TREAT UNDERGROUND GEOLOGICAL FORMATIONS" Description

The present invention relates to thickening compositions which are useful for use in aqueous compositions, especially in the field of development and extraction of natural gas and mineral oil deposits.

The viscosity of the aqueous system plays a crucial role for a multitude of applications. Thickener compositions in water-based systems, for example for well drilling treatment fluids, detergent compositions, wash compositions, leather and textile treatment formulations, hydraulic fluids, etc. They are often used in such a way as to provide the rheological properties required for their specific applications.

WO 2005/040554 describes the use of organic compounds, especially alcohols and amines, in order to increase the viscosity of viscoelastic surfactant gels and to reduce the amount of salt used to ensure a particular viscosity.

WO 2005/071038 describes viscoelastic surfactant compositions, especially quaternized betaines and amines, comprising small amounts of amphiphilic triblock oligomer, which shortens the relaxation time after shear and, in addition, increases the viscosity of the composition.

US 2005/0107503 describes aqueous compositions comprising a viscoelastic surfactant and a hydrophobically modified polymer at a concentration above their overlapping concentration c * and below their entanglement concentration c and c.

EP 061251.6, unpublished as of the priority date of this document, describes pH dependent viscosity aqueous thickening compositions which are especially suitable for the development and extraction of natural gas and mineral oil deposits.

It is an object of the present application to provide thickening compositions, which are notable for a thickening action, suitable for their end use and are additionally notable for a provisioning method which overcomes the problems that occur in providing known thickening compositions, in particular. those problems connected to the viscosity of the thickeners and surfactants used. The thickening compositions should preferably further reform the gel within a short time after shear. Moreover, it is advantageous when the thickening systems or thickening compositions are and remain homogeneous over a wide temperature range, that is, where there is no separation of the present components. Homogenization is manifested, for example, by the fact that the thickening systems or thickening composition are present as a clear fluid. Depending on the intended use, another advantage may arise from the fact that the thickening composition is viscous and non-viscoelastic at low shear rates. It has been surprisingly found that the viscosity

of the thickening compositions and the temperature at which the viscosity of such thickening compositions decreases are significantly increased simply by the addition of amounts of polymers below their overlapping concentration c *. The present invention therefore provides a thickening system,

which is suitable for preparing a thickening composition, and consisting of:

(A) at least one anionic surfactant A, and

(B) at least one polymer B having at least one hydrophobic group, the concentration of polymer B in the thickening composition being below the overlapping concentration c * of the polymer.

The overlapping concentration c * of polymer B is determined by logarithmic graphing of the viscosity of an aqueous solution of the polymer (without the addition of surfactant A) at a given shear rate against the concentration Iog. The overlap concentration c * corresponds to the concentration of polymer B, which corresponds to the intersection point of the best fit lines of the two linear slopes of the resulting function. In overlapping networks of the inventive thickening compositions, the concentration of polymers B is below their overlapping concentration c *.

Inventive thickener systems, which consist of component AeB, are used in a manner to adjust the rheological properties of inventive thickening compositions. As with the inventive thickener system, thickening folk compositions comprise water, inorganic salts and, if appropriate, other components specified below.

The amount of use of components other than water and salt which include AeB components in the thickening compositions is typically within a range of from 0.1 to 10% by weight of a preferably from 0.5 to 6 wt%, more preferably from 2 to 4 wt%, based on the total weight of the thickening compositions. In this connection, the term "salt" does not include salts of components A and B and, if appropriate, other organic components, which are present in the form of their salts.

The term "viscosity" refers, in the context of the present invention, generally to dynamic viscosity. Methods for determining viscosity are explained below.

The term "rheological properties" is used in a broad sense in the context of the present invention and means both viscosity and elasticity, but preferably viscosity.

The inventive thickener systems preferably comprise the anionic surfactants A which are present in the thickener compositions which can be prepared at a concentration at which, without the addition of polymer B, at a shear rate of 100 rad / s, a viscosity of 20 mPa.s is not exceeded. More preferably, the viscosity of anionic surfactants A under these conditions is less than 10 mPa.s.

The inventive thickener systems comprise in a

Preferably, polymers B, which are present in the thickening composition which can be prepared at a concentration at which, without the addition of anionic surfactant A, at a shear rate of 100 rad / s, a viscosity of 5 mPa.s. is exceeded.

The present invention further relates to the use of a system

inventive thickener for the preparation of a thickener composition.

The present invention relates to a process for the preparation of a thickening composition comprising:

(a) the provision of at least one surfactant A and at least

a polymer B,

(b) preparation of a solution of anionic surfactant A, provided in an aqueous medium,

(c) preparing a solution of polymer B provided in an aqueous medium, and

(d) mixing surfactant A and polymer B solutions

prepared,

the concentration of polymer B in the prepared thickening composition being below the overlapping concentration c * of the polymer.

The concentration of polymer B in the prepared thickening composition is preferably at least 0.1 ° C. More preferably, the concentration of polymer B in the prepared thickener composition is within a range of 0.3 to 0.7 ° C.

In a preferred embodiment of the process according to the invention, the solution of the anionic surfactant A prepared at stage b) at a shear rate of 100 rad / s does not exceed a viscosity of 20 mPa.s.

In another preferred embodiment of the process according to the invention, the solution of polymer B prepared at stage c) at a shear rate of 100 rad / s does not exceed a viscosity of 5 mPa.s.

In a particularly preferred embodiment of the process according to the invention, the solution of the anionic surfactant A prepared at stage b) at a shear rate of 100 rad / s does not exceed a viscosity of 20 mPa.and the solution of polymer B prepared at stage c) does not exceed a viscosity of 5 mPa.s ..

The process described above for the preparation of a thickener composition according to the invention is particularly noteworthy in that, even at comparatively high concentrations, neither the surfactant A solution nor the polymer B solution has a high viscosity. This ensures that there is no poor solubility caused by premature gel formation, as in the formulation of conventionally used thickeners in the form of concentrates or powders.

More preferably, anionic surfactants A in inventive thickener systems and compositions are selected from

compounds of the general formula (Ia) to (I.f) and salts thereof,

0 oo

Il! 11 λ 11,

HO-P-O-Y-R R-Y-O-P-O-Y-R HO-P-Z-O-Y-R

1 I I

OH OH OH

(Ia) (Ib) (l.c) Oo O 11 1 11 1 Il

HO-S-O-Y-R1 HO-S-Z-O-Y-R A 1

N Il HO Ζ — Ο — Υ — R

ο ο

(Id) (ie) (I.f)

in which:

R1 is selected from C1-22 alkyl, C16-22 alkenyl, C1-22 alkynyl, (C1-21 alkyl) carbonyl, ((C1-21 alkenyl) carbonyl and (C15-21 alkynyl) carbonyl,

Y is a group consisting of 1 to 20 alkylenoxy units, and

Z is C 1.4 alkylene.

When salts of compounds (I.a) to (I.f) are used, they comprise, as well as the anion of particular compounds, a corresponding positively charged counterion, for example Na + or K +. In the context of the present invention, the term "alkyl

"comprises straight and branched chain alkyl groups. Suitable lower alkyl groups are, for example, straight or branched C 1-7 alkyl, preferably C 6 alkyl, and more preferably C 1-6 alkyl groups. These particularly include methyl, ethyl, propyl, isopropyl, n-butyl, 2-butyl sec-butyl, tert-butyl, etc.

In the context of the present invention, the term "C1-22 alkyl" includes straight chain and branched chain alkyl groups. They are preferably straight chain and branched chain C1-220 alkyl radicals, more preferably straight chain and branched chain C16-18 alkyl radicals and more preferably straight chain branched C16-18 alkyl radicals. . They are especially predominantly linear alkyl radicals, as they also occur in fatty acids and natural or synthetic fatty alcohols, and also in oxo alcohols. They include, for example, n-undecyl, n-dodecyl, n-tridecyl, myristyl, pentadecyl, palmityl (= cetyl), heptadecyl, octadecyl, nonadecyl, arachinyl, beenila, etc.

In the context of the present invention, C8.32 alkenyl, especially C12-22 alkenyl, represents straight and branched chain alkenyl groups which may be mono-, di- or polyunsaturated. They are preferably straight and branched C 1-12 alkenyl, more preferably straight and branched C 1-18 alkenyl and more preferably straight C 1-18 alkenyl. They are especially predominantly linear alkenyl radicals, as they also occur in fatty acids and natural or synthetic fatty alcohols, as well as oxo alcohols. They include, in particular, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nonolecyl, linolylyl, linostenyl, and especially oleecyl.

In the context of the present invention, C 1-22 alkynyl represents straight and branched chain alkynyl groups which may be mono-, di- or polyunsaturated. They are preferably C1-5 alkynyl. They are especially predominantly linear alkynyl radicals.

In the context of the present invention, the term "C1-21 alkoxycarbonyl" comprises straight and branched chain alkyl groups as defined above which are attached via a carbonyl (-C (= O) -) group. The same applies to the terms "Cn21 alkenylcarbonyl" and "Cn21i alkynylcarbonyl".

The radicals R1 of the compounds of the general formulas (I.a) to (I.f) have, on average, preferably at most one, more preferably at most 0.5 and in particular at most 0.2 branches. . In particular, the R1 radicals are each independently selected from palmityl, stearyl, oleyl, linoleyl, arachidyl, gadoleyl, beenyl, erucyl, isostearyl, 2-hexyldecyl, 2-heptyldecyl, 2-heptyldecyl and 2- octyldodecyl.

Y groups in the compounds of formula (Ia) to (I.f) are preferably selected from groups of formula (II),

- [(0- (CH2) 2) xi (O-CH (CH3) (CH2) x2] - (II) wherein the sequence of the alkylenoxy units is as desired and x1 and x2 are each independently an integer of 0 to 20, where the sum of x1 and x2 is 1 to 20.

The ratio of x1 to x2, on average, with respect to surfactants of the general formulas I (I.a) to (I.f) present is preferably at least 2: 1. In a specific embodiment of the inventive composition, the poly (alkylenoxy) groups of general formula (II) consist exclusively of ethylenoxy units. X2 is thus especially 0.

In the compounds of formulas (La) to (I.f), the ratio of anionogenic groups to the alkylenoxy units of the groups R1 is preferably in a range from 1: 2 to 1:10. In connection with this, anionogenic groups refer to those groups, which have an acidic proton and form an anionic group under basic conditions. Where instead of the compounds of the formulas (Ia) and (I.f) their salts are used, the above mentioned ratio refers accordingly to the anionic groups.

Surfactants A are preferably selected from the compounds of the general formulas (II) or (I.b). Surfactants A are more preferably selected from the compounds of formula (La).

The surfactants of the general formulas (La) and (Ib) used according to the invention may, for example, be provided by the reaction of phosphoric acid or a suitable phosphoric acid derivative, for example P2O5, P4P10, polyphosphoric acid (H3PO4 χ (HPO3) n, where η> 1) or metaphosphoric acid ((HPO3) n, where η> 3), with a suitable alkoxylated alcohol of the formula,

R1 - [(0- (CH2) 2) xi (0-CH (CH3CH2) x2] -OH or mixtures of these alkoxylated alcohols, as especially provided by the reaction of natural or synthetic mixtures of fatty alcohols and oxo alcohols with ethylene oxide and / or propylene oxide Like inorganic phosphoric acids, it typically provides mixtures of phosphoric monoesters and phosphoric diesters of the general formulas (I. a) and (I. b) .

The inventive thickening systems and compositions preferably comprise as anionic surfactants A at least one phosphoric monoester of the general formula (I.a). Preferably at least 50%, more preferably at least 80% and especially at least 90% of the present surfactants A are selected from compounds of the general formula (I.a).

The inventive thickener systems advantageously comprise an amount in the range of from 50 to 99.9 wt.%, Preferably from 70 to 99.5 wt.%, More preferably from 80 to 99.9 wt.%. 99% by weight of anionic surfactant A.

The inventive thickening compositions advantageously comprise an amount in the range of from 0.5 to 9.9 wt.%, Preferably from 0.7 to 5.0 wt.%, And more preferably. 1-3% by weight of surfactants A based on the total weight of components in the inventive composition other than water and salt is preferred.

The inventive thickener systems advantageously comprise an amount in the range of from 0.1 to 50% by weight, preferably from 0.5 to 30% by weight, and more preferably from 1 to 50%. 20% of polymer B.

The inventive thickening compositions advantageously comprise an amount in the range of from 0.001 to 5% by weight, preferably from 0.005 to 3% by weight, and more preferably from 0.01 to 2%. by weight of polymer B based on the total weight of the components in the inventive composition other than water and salt.

The concentration of polymer B in the inventive thickening compositions is preferably at least 0.1 ° C. More preferably, the concentration of polymer B is within a range of from 0.2 to 0.7 c *.

Polymer B in the inventive thickening systems and compositions is preferably selected from compounds comprising at least one hydrophobic group and at least one hydrophilic group.

Polymer B in the thickening systems and compositions according to the invention is preferably selected from compounds comprising at least two hydrophobic radicals R2, which are linked together by a bridging hydrophilic group (a). ).

Polymers B are preferably water soluble. These polymers B comprise hydrophilic groups (a) to which the hydrophobic groups R2 are attached. For this reason, B polymers are both hydrophobic and hydrophilic. Hydrophobic R 2 groups preferably have a structure that corresponds to the R 1 hydrophobic groups of surfactants A.

The rheological properties of inventive thickener compositions are determined by interactions of polymers (B), specifically their hydrophobic R2 groups, in surfactant micelles. These interactions are hydrophobic-hydrophobic physical interactions. This forms overlapping networks.

Surfactants form micelles in water, even at very low concentrations. The concentration at which the first micelles are formed is referred to as a critical micelle concentration (cmc). This is typically determined by surface tension, solubilization, conductivity (in anionic surfactants) or NMR. Anionic surfactants A, preferably used according to the invention, are notable for a highly critical micelle concentration. The micelle concentration of such anionic surfactants A is preferably within a range of 1 to 50 mg / l, more preferably within a range of 15 to 30 mg / l. at concentrations determined at 25 ° C for a salt concentration and a pH corresponding to the conditions of use. In such a way that overlapping networks are formed, the concentration of surfactant A in the thickening compositions is preferably above its critical micelle concentration.

The hydrophobic R2 groups of polymers B preferably preferably comprise at least 14 and especially at least 16 carbon atoms. The upper limit of the number of carbon atoms is generally not critical, and is, for example, up to 100, preferably up to 50, and especially up to 35. More specifically. Preferably, less than 10% of the hydrophobic R2 groups present in polymers B comprise less than 15 and more than 23 carbon atoms.

Preferably, on average, less than 20% and especially less than 5% of the present R2 groups have a carbon-carbon double bond.

The hydrophobic groups R2 are preferably selected from straight or branched C12-22 alkyl, C12-22 alkenyl or 2-hydroxy (C1-22-22-1-yl). The R2 radicals of the B polymers present in the systems

Inventive thickeners preferably have on average at most one, more preferably at most 0.5, and especially at most 0.2 branches. In particular, the R2 radicals are each independently selected from palmityl, stearyl, oleyl, linoleyl, arachidyl, gadoleyl, beenyl, erucyl, isostearyl, 2-hexyldecyl, 2-heptyldecyl, 2-heptyldecyl, 2- octyldecyl and 2-hydroxyipalmityl, 2-hydroxystearyl, 2-hydroxyoleyl, 2-hydroxyyloleyl, 2-hydroxyraidyl, 2-hydroxydadoleyl, 2-hydroxybeenyl, 2-hydroxyierucyl and 2-hydroxyisoestearyl.

Preferably at least 70% of the R2 groups present in polymers B are unbranched.

In a specific embodiment, hydrophilic groups (a) comprising at least two hydrophilic units (β) are used. Hydrophilic units (β) may have identical or different definitions. Identical hydrophilic units (β) are always linked together through a bridging group (γ). Different hydrophilic management units are always linked together through a bridging group (γ).

In a preferred embodiment of the present invention, the hydrophilic bridging group (a) comprises, as hydrophilic units (β), polyether units and / or polyvinyl alcohol units. More preferably, the bridging hydrophilic group (a) consists of at least 90% polyether units.

In a specific embodiment of the present invention, the hydrophilic units (β) of the polymers present in the thickener systems according to the present invention are at least partially selected from polyester units of the general formula (III):

- [(- (CH2) 2) yl (0-CH (CH3) CH2) y2] - (III)

wherein the sequence of the alkylenoxy units, as desired, and y1 and y2 are each independently an integer from 0 to 300, wherein the sum of y1 and y2 is from 10 to 300.

The sum of y1 and y2 denotes the number of alkylenoxy units of this polyether chain and is, on average, relative to all the polyether units of formula (III) present, preferably a value in the range of from 20 to 200, of a most preferably from 30 to 150 ° C.

The ratio of y1 to y2 expresses the ratio of ethylenoxy units to propylenoxy units. On average, relative to the polyester chain of the general formula (III) present, the ratio of y1 to y2 is preferably at least 2: 1, more preferably at least 5: 1. Several hydrophilic polyester units are preferably bonded together without bridging groups (γ). These include, for example, EO / PO block copolymer units.

In a specific embodiment of the present invention, the polyester chain of formula (III) consists exclusively of ethylenoxy units. In this embodiment, y2 is 0.

In another specific embodiment of the present invention, hydrophilic groups (a) are composed of hydrophilic units (β), which are linked together by bridging groups (γ), bridging groups (γ). γ) being structurally different from repeating units, of which hydrophilic units (β) are composed.

The bridging groups (γ) between hydrophilic units (β) of polymer B present in the inventive composition are preferably selected from m-valent groups, preferably from 2 to 4. -valents, with from 1 to 10 bridging atoms between the flank bonds, where the m-valiant groups have structures, which are selected from -0C (= 0) -, -C (= 0) 0C (= 0) -, -0C (= 0) 0-, - 0C (= 0) NH-, -NC (= 0) NH-, alkylene, alkenylene, arylene, heterocyclylene, cycloalkylene, where alkylene and alkenylene may be interrupted. time or more than once, by oxygen, sulfur, -NH-, and -N (C1-10 alkyl) -, arylene, heterocyclylene and cycloalkylene may be mono- or polysubstituted by C1-6 alkyl, and is an integer in the range of 2 to 4. The bridging groups (γ) preferably have -0C (= 0) NH- as terminal structural units. In this context, the term "m-brave group" means that the

bridging group (γ) is capable of forming m chemical bonds, where m is an integer and is preferably 2, 3, or 4.

When alkylene or alkenylene is interrupted by one or more, for example 1, 2, 3, 4, 5, 6, 7 or 8 non-adjacent groups, which are independently selected from oxygen, sulfur, -NH- and N ( alkyl) - the alkylene or alkenylene group is formed by carbon atoms. Examples thereof are: - (CH2) 3N (CH3) CH2 -, - (CH2) 3N (C2H5) (CH2) -, - (CH2) 3-OCH2 -, - (CH2) 3-O-CH (CH3 ) CH 2 -, - (CH 2) 2 O (CH 2) 2-OCH 2 -, -CH 2 - (CH 2) 2-CH 2 -N (CH 3) (CH 2) 3 -, - (CH 2) 2 -N [CH (CH 3) 2] CH 2 -, - (CH 2) 2 -N (C 2 H 5) CH 2 -, - (CH 2) 2 N (CH 3) CH 2 -, - (CH 2) 2 OCH 2 -, - (CH 2) 2 OCH 2 CH 2 -, - (CH 2) 3-SCH 2 -, - (CH2) 3-S-CH (CH3) CH2 -, - (CH2) 2S (CH2) 2-SCH2-, - (CH2) 2SCH2-e - (CH2) 2SCH2CH2-.

When the m-valent group (γ) has a valence greater than 2, this enables branching of polymer B. In this case, polymer (B) may also comprise more than two hydrophobic R2 groups.

Polymer B preferably comprises from two to six, more preferably from two to four hydrophobic R 2 groups.

The preferred range for the molecular weight of polymer B present is obtained by multiplying the number of hydrophobic R2 groups present with a value of from 1500 to 8000 g / mol.

The B polymers present in the inventive thickening systems preferably have on average a molecular weight in the range of 3000 to 50,000 g / ml, more preferably in a range of 5,000 to 30,000 g / mol.

The B polymers used according to the invention may, for example, be provided by reacting polyisocyanates, polyols, polyamines, polycarboxylic acids with a suitable alkoxylated alcohol, for example an alkoxylated alcohol of the formula, R2 - [(0- ( CH 2) 2) yi (0-CH (CH 3) CH 2) y 2] -OH, or mixtures of these alkoxylated alcohols. These alcohols are especially provided by the reaction of synthetic or natural mixtures of fatty alcohols and oxo alcohols with ethylene oxide and / or propylene oxide. This typically provides mixtures of alcohols with a different number of alkylenoxy units which may be used as such. The B polymers used according to the invention may also be provided by reacting compounds comprising at least two different functional groups with the abovementioned alcohols.

Polymers B are preferably provided from polyisocyanates or polyols.

Suitable polyisocyanates, in particular diisocyanates and triisocyanates, to provide polymers B, are aliphatic, cycloaliphatic, araliphatic and aromatic diisocyanates mentioned below, by way of example. These preferably include 4,4'-diphenylmethane diisocyanate, mixtures of monomeric diphenyl methane diisocyanates and oligomeric diphenyl methane diisocyanates (polymer-MDI), tetramethylene diisocyanate, tetramethylene diisocyanate hexamers, , hexamethylene diisocyanate trimers, isophorone diisocyanate trimer, 4,4'-methylenobis (cyclohexyl) diisocyanate, xylene diisocyanate, tetramethylxylene diisocyanate, dodecyl diisocyanate, alkyl ester diisocyanate, alkyl ester diisocyanate C 1-10 alkyl, 1,4-diisocyanate cyclohexane or 4-isocyanatomethyl-1,8-octamethylene diisocyanate, and more preferably hexamethylene diisocyanate and 4,4'-diphenylmethane diisocyanate. Suitable diols for the provision of B polymers are the

straight and branched chain aliphatic and cycloaliphatic alcohols generally having about 1 to 30, preferably about 2 to 20 carbon atoms. These include 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol, 1,5-pentanediol, 2,3-pentanediol, 2,4-pentanediol, 1,2-hexanediol, 1,3-hexanediol, 1,4-hexanediol, 1, 5-hexanediol, 1,6-hexanediol, 2,5-hexanediol, 1,2-heptanediol, 1,7-heptanediol, 1,2-octanediol, 1,8-octanediol, 1,2-nonanediol, 1,9- nonanediol, 1,2-decanediol, 1,10-decanediol, 1,12-dodecanediol, 2-methyl-1,3-propanediol, 2-methyl-2-butyl-1,3-propanediol, 2,2-dimethyl 1,3-propanediol, 2,2-dimethyl-1,4-butanediol pinacol, 2-ethyl-2-butyl-1,3-propanediol, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, polyalkylene glycols, cyclopentanediols, cyclohexanediols, etc.

Triols suitable for providing B polymers are, for example,

glycerol, butane-1,2,4-triol, n-pentane-1,2,5-triol, n-pentane-1,3,5-triol, n-hexane-1,2,6-triol, n-hexane-1,2,5-triol, trimethylolpropane, trimethylolbutane. Suitable triols are also esters of hydroxycarboxylic acids with trihydric alcohols. They are preferably triglycerides of hydroxycarboxylic acids, for example lactic acid, hydroxostearic acid and ricinoleic acid. Naturally occurring mixtures comprising triglycerides of hydroxycarboxylic acid, in particular castor oil, are also suitable. Preferred triols are glycerol and trimethylolpropane,

Higher polyhydric polyols suitable for providing the

B polymers are, for example, sugar alcohols and derivatives thereof, such as erythritol, pentaerythritol, dipenta erythritol, treitol, inositol and sorbitol. Also suitable are reaction products of the polyols with alkylene oxides, such as ethylene oxide and / or propylene oxide. It is also possible to use higher molecular weight polyols with an average molecular weight number in the range of from about 400 to 6000 g / ml, preferably from 500 to 4000 g / mol. These include, for example, di-, tri- and aliphatic, cycloaliphatic and / or aromatic di-, tri- and / or polyol-based polyesterols, and also lactone-based polyesterols. These further include polyetherols, which are obtainable, for example, by polymerization of cyclic ethers or by reaction of alkylene oxides with a starter molecule. These also include the usual terminal hydroxyl group polycarbonates, which are known to those skilled in the art and are obtainable by the reaction of the above described diols or bisphenols, such as bisphenol A, phosgene or carbonic esters. In addition, α, ω-polyamidols, α, ω-polymethyl (meth) acrylate diols and / or α, β-polybutyl (meth) acrylate diols, for example Goldschmidt's A1D-1000 and BD-1000 are also suitable.

r

Suitable dicarboxylic acids to provide the B polymers are, for example, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, undecane-a, co-dicarboxylic acid, dodecane-a acid. , co-dicarboxylic acid, cis-and trans-cyclohexane-1,2-dicarboxylic acid, eis- and trans-cyclohexane-1,3-dicarboxylic acid, cis-and trans-cyclohexan-1,4 -dicarboxylic acid, eis- and trans-cyclopentane-1,2-dicarboxylic acid, cis-and trans-cyclopentane-1,3-dicarboxylic acid, italic acid, isophthalic acid, terephthalic acid, and mixtures thereof.

The aforementioned dicarboxylic acids may also be substituted. Suitable substituted dicarboxylic acids may have one or more radicals, which are preferably selected from alkyl, cycloalkyl and aryl as defined above. Suitable substituted dicarboxylic acids are, for example, 1-methylmalonic acid, 2-ethylmalonic acid, 2-phenylmalonic acid, 2-methylsuccinic acid, 2-ethylsuccinic acid, 2-phenylsuccinic acid, itaconic acid, 3,3-dimethylglutaric acid, etc. .

Dicarboxylic acids may be used as such or as derivatives. Suitable derivatives are anhydrides and their oligomers, mono and diesters, preferably mono and dialkyl esters, and acid halides, preferably chlorides. Suitable esters are mono- and dimethyl esters, mono or diethyl esters, and also mono and diesters of higher alcohols, for example n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol, n-pentanol, n-hexanol etc., and also the mono and divinyl esters and mixed esters, preferably methyl ethyl esters. Preferred polycarboxylic acids to provide the B polymers are succinic acid, glutaric acid, adipic acid, italic acid, isophthalic acid, terephthalic acid or their mono or dimethyl esters. In particular, adipic acid is preferred.

Suitable polyamides are, for example, ethylenediamine,

propylenediamine, diethylenetriamine, triethylenetetraamine,

tetraethylenepentamine, polyethyleneimine, 1,3-propanediamine, N5N-bis (aminopropyl) amine, N, N, N-tris (aminoethyl) amine, Ν, Ν, Ν ', Ν'-tetracis (aminoethyl) ethylenediamine, Ν, Ν, Ν ', N ", N" -pentacis (aminotyl)

diethylenetriamine, neopentanediamine, hexamethylenediamine,

octamethylenediamine, or isophoronadiamine.

Other compounds suitable for providing polymers (B) are compounds comprising at least two different functional groups, for example ethanolamine, N-methylethanolamine, propanolamine, hydroxyacetic acid, lactic acid, glutamic acid, aspartic acid.

In a particularly preferred embodiment, polymer B is provided from (a) C14.22 fatty alcohol ethoxylates and mixtures thereof, (b) polyethylene glycol, EO-PO copolymers, trimethylolpropane ethoxylates, trimethylolpropane ethoxylates, ethoxylates / propoxylates glyceryl compounds, and mixtures thereof, and (c) hexamethylene diisocyanates.

In another particularly preferred embodiment, polymer B is preceded by (a) polyethylene glycol, EO-PO copolymers, trimethylolpropane ethoxylates / trimethylolpropane propoxylates, and mixtures thereof, and (b) 1,2 -poxy alkanes C 14.22 and mixtures thereof.

The inventive thickener compositions may, as well as surfactants A and polymer B, comprise other components.

In a preferred embodiment of the present invention, the thickening composition further comprises at least one linear or branched (C) C6-18 monoalcohol. The monoalcohols preferably have at least one branch. When a plurality of C6-18 monoalcohols are present in the inventive thickener composition, they preferably have on average at most 0.5 and more preferably at most 0.2 branches. Preferred C 6-18 (C) monoalcohols are, for example, h-hexanol, n-heptanol, n-octanol, n-nonanol, n-decanol, n-undecanol and n-dodecanol.

In this preferred embodiment, the inventive thickening compositions advantageously comprise an amount in the range of from 0.1 to 20% by weight, preferably from 0.5 to 15% by weight, and more preferably. from 1 to 8% by weight of C6-Is (C) monoalcohols based on the total weight of the components other than water in the inventive composition.

In this preferred embodiment, the thickening compositions according to the invention advantageously comprise an amount in the range of from 0.1 to 20% by weight, preferably from 0.5 to 15% by weight, and more preferably from 1 to 8% by weight of C6-18 (C) monoalcohols based on the total weight of the components other than water in the inventive composition.

In a specific embodiment, the inventive thickener composition comprises, in addition, at least one surfactant (D) of the general formula (IV):

R3 - [(0 (CH2) 2) Z1 (0CH (CH3) CH2) z2] - OH (IV)

in which,

the sequence of alkylenoxy units is as desired, R3 is selected from C12-22 alkyl, C12-22 alkenyl, C12.22 alkynyl, carbonyl (Cn21i) alkenylcarbonyl and (C11.21 alkynyl) carbonyl. ) carbonyl, and

ζ1 and z2 are each independently an integer from 0 to 20, wherein the sum of z1 and z2 is from 1 to 20. The radicals R3 of the nonionic surfactants of formula (IV) present in the thickener composition have preferably on average at most one, more preferably at most 0.5 and particularly at most 02 branches. In particular, the R 3 radicals are each independently selected from palmityl, stearyl, oleyl, linoleyl, arachidyl, gadoleyl, beenyl, erucyl, isostearyl, 2-hexyldecyl, 2-heptyldecyl, 2-heptyldecyl and 2-octyldodecyl.

The nonionic surfactants (D) present in the inventive composition have a (poly) alkylenoxy group consisting of z1 ethylenoxy and z2 propylenoxy groups joined together in any sequence.

The nonionic surfactants of formula (IV) used according to the invention are, for example, provided by reacting natural or synthetic mixtures of fatty alcohols and oxo alcohols with ethylene oxide and / or propylene oxide. This typically provides mixtures of compounds of formula (IV) with a different number of alkylenoxy units. These may be used as mixtures in the inventive compositions.

The sum of z1 and z2 on average with respect to the compounds of formula (IV) present is preferably in the range from 1 to 10 and more preferably in the range from 3 to 9. Specifically, each nonionic surfactant of the general formula (IV) present in the thickener composition has, for the sum of z1 and z2, a value in the range of 1 to 10 and more preferably a value in the range of 3 to 9

The ratio of z1 to z2 on average with respect to the nonionic surfactants of formula (IV) present is preferably at least 2: 1. In a specific embodiment of the inventive thickener composition, the (poly) alkylenoxy groups of the surfactants of general formula (IV) consist exclusively of ethylenoxy units. z2 is therefore, in a special way, 0.

In another specific embodiment, the inventive thickening composition comprises, in addition, at least one water-miscible solvent (E) other than C6.18 (C) monoalcohols.

The solvent (E) preferably has a molecular weight of less than 400 g / mol.

Suitable water miscible solvents (E) are, for example, ethylene oxide and / or propylene oxide homo and heterooligomers, for example ethylene glycol or propylene glycol, alcohols, for example methanol, ethanol, isopropanol, butyl monoglycol, butyl diglycol, butyl triglycol, phenoxyethanol, phenoxypropanol or sec-butylphenol, N-alkyl pyrrolidones, such as N-methyl pyrrolidone, and alkylene carbonates.

The inventive thickener compositions may optionally, depending on intended use, comprise other components, for example salts, metal oxide particles, complexing agents, bases, acids, biocides or antifreeze agents.

r

Particularly preferred is the use of inventive fluid thickening compositions which are used in the development and / or exploitation of underground natural gas and / or mineral oil deposits. They serve to adjust the rheological properties of these fluids. Fluids are, for example, treatment fluids for rock formation rupture, acid treatment of rock formations (acidification), use during drilling, processing, stream redirection, control of permeability and for water blockage. They are preferably gelling agents or drilling muds.

Depending on the concentration of the components herein, the inventive thickening compositions allow, by using a small amount, to maintain the viscosity of the treatment fluids during treatment within a required viscosity range over a wide temperature range. The required viscosity range in the aforementioned treatment fluids is typically between 50 and 100 mPa. s at a shear rate of 100 s "1. The inventive thickening compositions have, at temperatures of 50 ° C, preferably 60 ° C and higher, viscosities above 50 mPa. s.

The present invention further provides a process for treating underground rock formations using an inventive thickening composition, especially in acid gelling agents and / or drilling mud.

In the context of the present invention, the term "

Acid gelling "is used for relatively highly viscous treatment fluids, which are used for acidic treatments of underground rock formations.

In the context of the present invention, the term "drilling mud" is used for relatively high viscosity treatment fluids that are used to sweep the hole during the drilling operation.

The present invention provides the use of an inventive thickener composition in washing and cleaning compositions.

As with the inventive thickening compositions, the washing and cleaning compositions comprise at least one solid or liquid carrier and, if appropriate, the usual additives.

Examples of usual additives include: reinforcers and co-reinforcers, for example polyphosphates, zeolites, polycarboxylates, phosphonates, citrates, complexing agents, ionic surfactants, for example alkyl benzene sulfonates,

α-olefin sulfonates and other alcohol sulfates / ether sulfates, sulfosuccinates,

-other nonionic surfactants, for example alkyl amino and alkyl polyglycoside alkoxylates, amphoteric surfactants, for example alkyl amine oxides, betaines,

-optical brighteners,

dye transfer inhibitors, for example polyvinyl

pyrrolidone,

standardizers, for example sodium sulphate, sodium sulphate

magnesium,

dirt release agents, for example polyethers / polyesters, carboxymethyl cellulose,

-fouling inhibitors, for example polyacrylates, acrylic acid and maleic acid copolymers,

-bleaching systems, which consist of bleaches, for example perborate or percarbonate, in addition to bleach activators, for example tetraacetylene diamine, in addition to bleach stabilizers, -perfume,

-suppressants, for example silicone oils, alcohol propoxylates (in particular in liquid wash compositions),

enzymes, for example amylases, lipases, proteases or

carboxylases,

alkali donors, for example pentasodium metasilicate or sodium carbonate.

Other known constituents of those skilled in the art may also be present.

Gel wash compositions comprise thickeners, for example highly cross-linked polysaccharides and polycarboxylates (e.g., BF Goodrich's Carbopol® brands).

In hard surface detergents, for example acidic detergents, neutral detergents, dishwasher, metal degreasing, glass detergents, floor detergents, to name a few, the inventive thickening compositions are used in combination with the additives below. are present in amounts of from 0.01 to 40% by weight, preferably from 0.1 to 20% by weight:

- ionic surfactants, for example alkylbenzene sulfonates, α-olefin sulfonates, other alcohol sulfates / ether sulfates, sulfosuccinates,

other nonionic surfactants, for example alkyl amine and alkyl polyglycoside alkoxylates, including C1-3 alkyl polyglycosides. Inventive I5,

- amphoteric surfactants, for example alkylamine oxides,

betaines,

- reinforcers, for example polyphosphonates, polycarboxylates, phosphonates, complexing agents,

- reinforcers, eg naphthalene sulfonic acid condensates, polycarboxylates,

- enzymes, for example lipases, amylases, proteases,

carboxylases,

- perfume,

- dyes

- biocides, for example isothiazolinones, 2-bromo-2-nitro-1,3

propanediol,

- bleaching systems consisting of bleaches, for example perborate, percarbonate, bleach activators, for example tetraacetylene diamine, and bleach stabilizers,

- solubilizers, for example cumene sulfonates, toluene sulfonates, short chain fatty acids, alkyl / aryl phosphates,

solvents, for example lower alkyl oligoglycols, alcohols such as ethanol or propanol, organic solvents such as toluene or xylene, N-alkyl pyrrolidones, alkylene carbonates, thickeners, for example slightly cross-linked polysaccharides and polycarboxylates (for example , BF Goodrich's Carbopol® brands).

Hard surface detergents are usually, but not exclusively, aqueous, and are present in the form of microemulsions, emulsions or solutions.

In addition, the inventive thickening compositions are suitable, for example, for applications in leather and textile treatment formulations, in hydraulic fluids, surface treatment formulations in aqueous formulations, which are used in civil and structural engineering.

The present invention is illustrated in detail with reference to figures 1 to 7.

Figure 1 shows the dynamic viscosity of an inventive thickener composition at different component concentrations other than water and salt at a temperature of 25 ° C.

Figure 2 shows the dynamic viscosity of an inventive thickener composition at different component concentrations other than water and salt at a temperature of 60 ° C.

Figure 3 shows the oscillatory rheology of an inventive thickening composition at a concentration of components other than water and salt of 2%, a deformation of 10% and a temperature of 25 ° C. The elastic component (G ') values are shown as ■. The values of the viscous component (G ") are given as ·. The dynamic viscosity magnitudes | η * | in Pa.s are given as

25

Figure 4 shows the oscillatory rheology of an inventive thickening composition at a concentration of components other than water and salt of 2%, a deformation of 10% and a temperature of 60 ° C. The elastic component (G ') values are shown as ■. The values of the viscous component (G ") are given as ·. The dynamic viscosity magnitudes | η * | in Pa.s are given as

Figure 5 shows the rheological properties of an aqueous solution of a polymer B used according to the invention in different concentrations and the overlapping concentration of polymer B derived therefrom.

Figure 6 shows the rheological properties of an aqueous solution of a surfactant A used according to the invention in different concentrations at a temperature of 25 ° C.

Figure 7 shows the rheological properties of an aqueous solution of a surfactant A used according to the invention in different concentrations at a temperature of 60 ° C.

The present invention will be illustrated in detail with reference to non-restrictive examples. Examples: 1. Test Methods

Measurements of constant linear shear shear viscosity were performed on a RheoStress RS 150 thermostat cone-and-plate rheometer (cone d = 60 mm / 0.5o).

Oscillatory shear experiments were performed on a calibrated Physika MCR type cone-and-plate rheometer with thermostat (cone d = 50 mm, 2o). The linear viscoelastic range of the samples was determined at a temperature of 25 ° C to a shear amplitude of approximately 60% or a temperature of 60 ° C to a shear amplitude of approximately 20%. Subsequently, the samples were analyzed in a 10% shear, in a frequency dependent mode, that is, in a frequency range from 0.1 to 100 s "1. 2. Preparation Example

a) Surfactant A used according to the invention (Al)

Oleyl alcohol was reacted with about 4.5 equivalents of ethylene oxide in the presence of KOH. This resulted in an ethoxylate which had an OH number of 124 mg KOH / g. The resulting ethoxylate was reacted with tetraphophoric acid in a 3: 1 molar ratio. Dilute sodium hydroxide solution was added to the reaction mixture to give an aqueous solution of oleic alcohol -4.5 EO. PO3Na2, which comprised 25% by weight of oleic alcohol. 4.5 EO. PO3H2.

The critical micelle concentration (cmc) of surfactant Al in a 3% by weight aqueous KCl solution is 21 mg / l at neutral pH; under the conditions of use in the inventive thickening compositions (D1), that is, at a pH of 4.3, the cmc is 26 mg / l. b) Polymer B used according to the invention (B1)

25% solution of a reaction mixture comprising polymers obtained from the reaction of C 1-6 alkyl - [(O- (CH 2) 2) i 40]) - OH (78% by weight) of polyethylene glycol (PEG 12) 000, 20 wt%) and hexamethylene diisocyanate (2 wt%), in a mixture of 1,2-propanediol, isopropanol and water.

c) Inventive thickener compositions (D1)

A mixture consisting of 86 wt% Al surfactant, 10 wt% BI polymer and 4 wt% n-octanol was homogenized at different concentrations in an aqueous KCl solution. 3% by weight, and then adjusted with hydrochloric acid to a pH of 4,3.

The thickener composition (D1) in the inventive concentration range is present in clear liquid form within a temperature range of 15 to 90 ° C. 3. Examination of rheological properties

Example 3.1: Examination of the rheological properties of an inventive thickening composition (D1).

The rheological properties of four inventive thickening compositions (D1) comprising components other than water, salt and organic solvents used to provide component B1 in an amount of 1, 2, 3 and 5 wt% were analyzed. on a cone-and-plate rheometer using the test method described above.

a) Results at a temperature of 25 ° C are shown graphically in Figure 1). Depending on the quantities of water, salt and

components other than the organic solvents used to provide component BI, extrapolation provides zero shear viscosities of the inventive 4 mPa * s thickening composition for the 1% thickening composition, 1500 mPa * s for the 2% thickening composition, 3200 mPa * s for the 3% thickening composition and 10,000 mPa * s for the 5% thickening composition, based in each case on the total weight of the thickening composition.

b) the results at a temperature of 60 ° C are shown graphically in Figure 2. At this temperature, the extrapolated zero shear viscosities of the inventive 7 mPa * s thickening compositions for the

1% thickening composition, 400 mPa * s for 2% thickening composition, 1300 mPa * s for 3% thickening composition and 4800 mPa * s for 5% thickening composition are based on each case the total weight of the thickening composition.

The results of examination of the rheological properties of inventive thickening agent compositions at 25 ° C and 60 ° C show that even when using 2% by weight of components other than water, salt and Organic solvents, used to provide the BI component, based on the total weight of the thickening composition, a significant thickening action is obtained. This thickening action is also maintained at shear rates of some 100 rad / s.

Example 3.2: Examination of the viscoelastic properties of an inventive thickening composition (D1) by oscillatory rheology.

An inventive thickener composition (D1) comprising components other than water, salt and organic solvents used to provide component B1 at a concentration of 2% by weight has been subjected to the oscillatory shear experiments described above, in a deformation of 10%. From the resulting measurements, the elastic component (G ') and the viscous component (G') were determined and

graphed as a function of frequency. From the intersection point of the two resulting curves, it is possible according to US 2005/01076503 to determine the gel point of the composition.

a) The results of these experiments at a temperature of 25 ° C are presented by Figure 3). The intersection point of the curves for

G5 and G ”obtained for the inventive thickener composition used is about

4 rad / s. Below this frequency, the thickener composition examined is therefore viscous, i.e. non-viscoelastic.

b) The results of these experiments at a temperature of 60 ° C are presented in Figure 4). The intersection point of curves G 'and G,

obtained for the inventive thickener composition used is about 14 rad / s. Below this frequency, the thickener composition examined is therefore viscous, i.e. non-viscoelastic.

Example 3.3: Examination of the rheological properties of a polymer B (BI) used according to the invention.

Different amounts of component Bl were

homogenized in a 3.00 wt% aqueous KCl solution and adjusted to pH 4.3 with concentrated hydrochloric acid or KOH. The resulting compositions were analyzed on a cone-and-plate rheometer. The resulting measurements were plotted against a concentration of polymer B1. The graphical evaluation of the measurement series is shown in Figure

5. The overlap concentration was estimated as described in US 2005/0107503. For the polymer B1 used according to the invention, the resulting curve profile gives an overlap concentration of 0.45% by weight based on the total weight of the aqueous composition.

Example 3.4: Examination of the rheological properties of an anionic surfactant A (Al) used according to the invention.

Different quantities (1, 2, 3 and 5% by weight based on the total weight of the composition) of a mixture consisting of 95,5% by weight of the anionic surfactant Al and 4,5% by weight, of n-octanol were homogenized in a 3 wt% aqueous KCl solution and adjusted to pH 4.3 with concentrated hydrochloric acid or KOH. The resulting compositions were analyzed on a cone-and-plate rheometer.

a) Measurement results at a temperature of 25 ° C are 15 shown in Figure 6). For the surfactant Al used according to the invention extrapolation yields a zero shear viscosity of 1 mPa * s for a 1% composition of 3 mPa * s for a 2% composition of 7 mPa * s for a 3% composition and 50 mPa * s for a 5% composition based, in each case, on the total weight of the composition.

(b) Measurement results at a temperature of 60 ° C shall be

shown in Figure 7). For the surfactant Al used according to the invention, extrapolation gives a zero shear viscosity of 1 mPa * s for a 1% composition of 7 mPa * s for a 2% composition of 40 mPa * s for a 3% composition and 1200 mPa * s for a 5% composition based, in each case, on the total weight of the composition.

These measurements show that the anionic surfactant Al in an inventive polymer B in an amount used according to the invention is not capable of forming significant viscosities, i.e. a viscosity of 10 mPa * s is not achieved.

Claims (21)

Thickening system, characterized in that it is suitable for preparing a thickening composition, consisting of: (A) at least one anionic surfactant A, and (B) at least one polymer B, comprising at least one hydrophobic group and at least one hydrophilic group, the concentration of polymer B in the thickening composition being below the overlapping concentration c * of the polymer. Thickening system according to Claim 1, characterized in that: (A) at least one anionic surfactant A, and (B) at least one polymer B, comprising at least two hydrophobic radicals R2, which are bonded, each other, via a hydrophilic bridging group (a), the concentration of polymer B in the thickening composition being below the overlapping concentration c * of the polymer. Thickener system according to any one of claims 1 to 2, characterized in that the concentration of polymer B in the thickener composition is at least 0.1 c *. Thickener system according to Claim 3, characterized in that the concentration of polymer B in the thickener composition is within a range of 0.3 to 0.7c *. Thickener system according to any one of the preceding claims, characterized in that the anionic surfactant A is present in the thickener composition at a concentration in which, without the addition of polymer B, at a shear rate of 100 rad / s, a viscosity of 20 mPa.s is not exceeded. Thickener system according to any one of the preceding claims, characterized in that polymer B is present in the thickener composition at a concentration in which, without the addition of anionic surfactant A, at a shear rate of 100 rad / s, a viscosity of 5 mPa.s is not exceeded. Use of a thickening system as defined in any one of claims 1 to 6, characterized in that it is for preparing a thickening composition. A process for preparing a thickener composition, comprising: (a) providing at least one surfactant A and at least one polymer B as defined in any one of claims 1 to 7, (b) preparing a solution of anionic surfactant A, provided in an aqueous medium, (c) preparing a solution of polymer B, provided in an aqueous medium, and (d) mixing the prepared solutions of surfactant A and polymer B, a concentration of polymer B in the prepared thickener composition being below the overlapping concentration c * of the polymer. Process according to Claim 8, characterized in that the concentration of polymer B in the prepared thickening composition is at least 0.1 c *. Process according to Claim 9, characterized in that the concentration of polymer B in the prepared thickener composition is within a range of 0.3 to 0.7 c *. Process according to any one of claims 8 to 10, characterized in that the solution of the anionic surfactant A prepared at stage b) at a shear rate of 100 rad / s does not exceed a viscosity of 20 mPa. s. Process according to any one of claims 8 to 10, characterized in that the solution of polymer B prepared at stage c) at a shear rate of 100 rad / s does not exceed a viscosity of 5 mPa. s. Process according to any one of claims 8 to 10, characterized in that the solution of the anionic surfactant A prepared at stage b) at a shear rate of 100 rad / s does not exceed a viscosity of 20 mPa. The polymer B solution prepared at stage c) at a shear rate of 100 rad / s does not exceed a viscosity of 5 mPa.s. Thickener composition, characterized in that it comprises a thickening system as defined in any one of claims 1 to 6, in an amount of from 0.1 to 10%. Use of a thickening composition as defined in claim 13, characterized in that it is in the development and / or exploitation of underground natural gas and / or mineral oil deposits. Use of a thickening composition as defined in claim 13, characterized in that it is in washing and cleaning compositions. Use of a thickening composition as defined in claim 13, characterized in that it is in formulations for the treatment of leather and textiles. Use of a thickening composition as defined in claim 13, characterized in that it is in hydraulic fluids. Use of a thickening composition as defined in claim 13, characterized in that it is in aqueous surface treatment compositions. Use of a thickener composition as defined in claim 13, characterized in that it is in formulations which are used in civil and structural engineering. Process for treating underground geological formations, characterized in that it uses a thickening system as defined in any one of claims 1 to 5, acid gelling agents and drilling mud.