DD202298A5 - WATERPROOF NETWORKY POLYMERIC COMPOSITION - Google Patents

Abstract

The invention relates to a water-soluble crosslinkable polymer composition for use as thickeners of aqueous acids used in processes of pressure control in the recovery of petroleum. The aim of the invention is to increase the Foerderrate and Foerdermenge from Erdoellagerstaetten. According to the invention, the novel composition contains a polymeric compound which has at least two amidocarbonyl groups in the molecule and a compound having at least two formylamido groups in the molecule, the amidocarbonyl groups and the formylamido groups reacting in the presence of acid to form crosslinking bridging members of the formula -NR high x-CH-N-CO- where R is high x is hydrogen, alkyl having 1 to 4 carbon atoms or -CH 2 OH. For example, the composition A) contains a water-soluble homo- or copolymer with 10% amidocarbonyl groups and B) a compound of the formula I in which R is 1 and R is high 2 hydrogen, alkyl having 1 to 4 C atoms or -CH 2 OH, n a number from 1 to 3 and m is one of the numbers 0 or 1.

Description

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7 / Aqueous soluble crosslinkable polymer composition Field of application of the invention

The invention relates to a water-soluble crosslinkable polymer composition, its preparation and its use. The novel, crosslinked polymer compositions according to the invention have above all considerable significance in the stimulation of boreholes in crude oil deposits by the process of pressure acidification. However, they can also be used to advantage whenever it is expedient to increase the viscosity of acids, such as in various processes of metal cleaning «

Characteristic of the known technical solutions

In the stimulation of wells with the aim of increasing the yield of crude oil or natural gas from subterranean carbonate formations, the technique of so-called pressure acidification can be used * Carbonate formations are for example limestone, dolomite or other storage rocks, which contain limestone-like materials Usually, the pressure acidification is carried out in such a way that one injects aqueous acids, which may additionally contain so-called proppants, at such a speed and under such high pressure in the bore that the existing formation pressure is exceeded, the rock gives way and so new fractures fractures are naturally or artificially created cracks or channels in the rock matrix. In this technique of pressurized acidification, the surfaces of the rock fractures are etched by the acid. However, since these surfaces have a heterogeneous structure, the etching does not make the surface uniform, but local

-lOfi / iHNno ο ο η ο λ c \ a

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various degrees of erosion · As soon as the external pressure generated by the injection of the acid is reduced, the fractures of the rock collapse · However, because of the uneven etching of the surfaces, there is no longer a complete closure of the fractures a so-called proppant, for example, edge-rounded quartz sand injected so are prevented by the incorporation of the proppant between the surfaces of the fractures after the removal of external pressure and such surface areas of the fractures to the complete closure, which is little or no etched by the acid have been. In either case, a channel is created which has a higher permeability and allows the oil or gas to flow to the wellbore when the external pressure is withdrawn. In the case of pressure acidification, it is often desirable to add a thickener or gelling agent to the acid (see U.S. Patent Nos. 3,415,319, 3,434,971, 3,749,169, 3,236,305, and 3,252,904). Higher viscosity fluids (auxiliary fluids used in secondary and tertiary production of petroleum are commonly referred to as fluids) have various properties that are beneficial to the process of pressure acidification. Thus, for example ^, the volume and the inside width of a fracture are proportional to the viscosity of the fluid used to produce them. By increasing the viscosity of the acid, larger fracture volumes and larger clear widths of the fracture can thus also be produced in the process of pressurized acidification viscous acids reduces the etch rate of the surfaces and allows the acid to penetrate deep into the fractures formed. In addition, higher-viscosity acids show better transport behavior for optionally used proppants, resulting in an improvement of the deposition

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of the support medium in the open fractures.

Typically, higher viscosity fluids contain homo- or copolymers as viscosity increasing agents. In particular, in fluids for pressure acidification, viscosity-increasing agents are used as copolymers containing amido-carbonyl groups, such as polyacrylamide. The polymer concentration in the fluids is generally below 1.0% by weight. In order to increase the effectiveness of the thickening of fluids, it is known from DE-OS 2,657,443 to copolymers of acrylamide by addition of aldehydes, such as formaldehyde, acetaldehyde or crosslinking of glyoxal · The crosslinking reaction occurs in the alkaline range at ITormal temperature, in the acidic range, however, only at temperatures of 40 to 80 ⁰ C. The reaction time of the crosslinking can be up to 45 minutes, so that this thickening system is not suitable for practical use, at least in the process of pressurized acidification.

Object of the invention

The aim of the invention is the provision of new polymer compositions for the stimulation of boreholes by the process of pressurized acidification for the purpose of increasing the production rate from oil reservoirs.

Explanation of the essence of the invention

The invention has for its object to provide new aids for reducing the internal friction of the acidic fluids used in the so-called tertiary promotion.

According to the invention macromolecular compositions

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provided by new bridge members of the formula -NR ³ ^ -CH = N-CO- crosslinked. The new bridge member is obtained by the reaction of a macromolecule, preferably a polymer containing at least two aminocarbonyl groups, with a compound containing at least two formylamido groups in a strongly acidic aqueous medium. The formation of the new bridge member is carried out according to the following reaction equation:

R-IJR-C +

H ©> R-NR ^X CH = II-CO-R ¹ + H ₀ O

Compositions according to the present invention containing macromolecular compounds having at least two amido carbonyl groups and further a compound containing at least two formylamino groups may be used as a thickening or gelling agent for aqueous acids, wherein the aqueous acid between the constituents of the composition comprises the above The crosslinking reaction which takes place with formation of the new bridge member takes place. "Acids thickened or gelled in this way find an important application in the extraction of crude oil and natural gas from subterranean formations

The present invention relates to novel crosslinked polymer compositions in which crosslinking is effected by bridge members of the formula -NR 1 -CH = N-CO- wherein R ^{z is} hydrogen, alkyl of 1 to 4 carbon atoms or -CHpOH. The invention also relates to the uncrosslinked compositions containing a macromolecular compound having at least two amidocarbonyl groups and

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another compound containing at least two formylamido groups. The uncrosslinked compositions of the invention crosslink in an acidic aqueous medium to form the -NR 1 -C 4 N-CO bridges. The invention further relates to processes for crosslinking the crosslinkable compositions according to the invention. The invention furthermore relates to the use of the crosslinked polymer compositions according to the invention as thickeners for acids, the disadvantages of the hitherto known polymers used in the pressurized acidification being avoided.

The polymer compositions according to the invention have the further advantage for the process of pressurized acidification that they do not tend to precipitate insoluble precipitates in the acidic medium, even with prolonged action, as is the case with conventional thickening agents. Precipitation and precipitation, which can occur when using known thickeners, tends to clog and seal the subterranean formations, and thus seriously jeopardizes the success of drilling stimulation, and may result in the complete drying up of production Degradation of the polymer compositions according to the invention gives rise to polymer chains which contain amino groups and are therefore completely soluble in the acidic medium without residue »

The crosslinkable polymer compositions according to the invention contain

A * a water-soluble homo- or copolymer which has amidocarbonyl groups and

B.a) a bis-Acylamidoverbindung of formula I.

O O

tt ti

AP C 08 G / 235 738/3 60 182/11

(D

I!

Ά Ά

R ¹ and R ^{2 are} hydrogen, alkyl having 1 to 4 carbon atoms or -CH ₂ OH,

η is a number from 1 to 3 and

m is 0 or 1 and / or

3.b) a water-soluble homo- or copolymer which formylamido groups of the formula

-N-C, has,

' H

wherein R ^ is hydrogen, alkyl having 1 to 4 carbon atoms

or -CH ₂ OH. The crosslinkable polymer composition of the present invention may have one or more of the components A) and / or B).

Ingredients A) and B) are present in the crosslinkable compositions of the invention in a weight ratio of 1: Ο, 2 to 1: 20, preferably from 1: 0.2 to 1: 1.

In principle, the homo- or copolymer of component A) before crosslinking can be any macromolecule, preferably any polymer which has sufficient solubility in water and has in its macromolecule so many amidocarbonyl groups (at least 2) that crosslinking via the new one Bridge member of the formula -NH -CH = N-CQ- can occur. Depending on which crosslinking agent (component B) is present in the composition according to the invention, the symbol R of the bridge member has the

'12 9 meanings of R, R or R. The water solubility of the component A) should not be lower than 10 g / l, and the content of amidocarbonyl groups should be at least 10 %, preferably at least 15 %, based on the weight of the macromolecule.

Particularly suitable as component A) of the compositions according to the invention are homopolymers or copolymers which, before crosslinking, contain 50 to 100% by weight of units of the formula II

R ⁴ -CH ₂ -C- (II)

CONH ₀

4 wherein R is hydrogen or methyl, and 0 to 50 wt. % Of units of formula III

.Ζ 'R ⁵

-CH ₉ -C- (III)

contain, in which

R is hydrogen or alkyl of 1 to 3 carbon atoms, preferably hydrogen and methyl, and Y is formamido; N-substituted formylamido, where the N-

Substituent is methyl or hydroxymethyl; cyano; Carboxyl or its alkali or ammonium salt; Alkoxycarbonyl of 1 to 6, preferably 1 to 3, carbon atoms; Hydroxyalkoxycarbonyl of 1 to 3 carbon atoms; N-methylolamidocarbonyl of the formula HOCH ₂ NH ^ CO-, whose methylol group is optionally etherified with alkanols of 1 to 4 carbon atoms; Alkanoylamino having 1 to 4 carbon atoms, which may be optionally N-substituted by methylol or alkyl having 1 to 4 carbon atoms'; Pyrrolidonyl (l); phenyl; pyridinium; the sulfonic acid group; Sulfoalkylamidocarbonyl having 1 to 4 carbon atoms; the phosphonic acid group, wherein the sulfonic acid and phosphonic acid groups may also be present in the form of their alkali metal or ammonium salts; a Best of Formula IV

-COO-C H ₉ -N j, (IY)

ρ 2p Λ ^ -Η ⁸

a radical of formula V

^ R ⁷

₈ (V)

where the radicals of the formulas IV and V can also be quaternized, for example by reaction with CH - Cl or dimethyl sulfate,

7 and wherein R and R are the same or different and are alkyl having 1 to 4, preferably 1 or 2, carbon atoms and wherein ρ is a number from 1 to 4.

% Of units of the formula are preferred as component A), such homopolymers or copolymers, the weight before its crosslinking 60 to 85. II and 15 to 40 GeV /. % Units of formula III.

In addition, it is preferable for component A) to use those homopolymers or copolymers in which R is hydrogen or methyl and / or

in which

Y carbonyl; the sulfonic acid group; 3-sulfo-2-methyl-propyl- (Ä ^ amidocarbonyl of the formula 13

CH ι °

-CONH-C-CH ₀ -SOoH

CH ₃

Alkanoylamino having 1 to 4 carbon atoms, which may be optionally N-substituted by methylol or alkyl I to 4 carbon atoms; Pyrrolidonyl <1) or a radical of the above-defined and defined formulas IV or V, wherein all acid groups may also be present in the form of sodium, potassium or ammonium salts.

Of the compositions according to the invention which comprise a bis-acylamido compound of the formula I as component B), preference is given to those in which

1 2 H ^! and R is hydrogen or methylol and η is 1.

As the homo- or copolymer for component B) of the compositions of the invention, any polymer which has sufficient solubility in water, i. its solubility should not be less than 10 g / l.

In addition to the obligatory formylamido groups, the copolymer used as component B) may also contain a proportion of amidocarbonyl groups which may be sufficient to provide stable crosslinked polymers of the novel chemical structure. In other words, it is possible that both the component A) and the component B) of the compositions according to the invention each of the required for crosslinking amounts of; Having amidocarbonyl and formylamido groups. It follows from this that in this case the component A) and the component B) can be the same and should be regarded as self-crosslinkable copolymers. Self-crosslinkable copolymers of this particular class are the subject of our concurrently filed patent application for "Water Soluble Self-Crosslinkable Copolymers".

The subject matter of this co-pending application is to be regarded as a special case of the present invention and to that extent also part of the subject matter of the present patent application.

Component B) of the compositions according to the invention must contain a sufficient proportion of formylamido groups in order to form the crosslinking bridge members according to the invention. A sufficient proportion of formylamido groups should not be less than 1 gm of formylamido groups, e.g. 71 g of N-vinylformamide per 500 g of the polymer.

As component B) of the compositions according to the invention, those homopolymers or copolymers are particularly suitable which, prior to crosslinking, comprise from 50 to 100% by weight of units of the formula VI -CH ₉ -CH- _n

. N-C ^ (VI)

- R ⁹ Λ ^Η

wherein R is hydrogen, methyl or hydroxymethyl, preferably hydrogen and methyl, and 0 to 50 wt. % of the units of the formula

-CH ₂ C- (VII), where

R is hydrogen or methyl and X is cyano} carbonyl or its alkali metal or ammonium salts; Alkoxycarbonyl of 1 to 6, preferably 1 to 3, carbon atoms; Hydroxyalkoxycarbonyl of 1 to 3 carbon atoms; amidocarbonyl; N-methylolamidocarbonyl of the formula HOCH ₂ NH-CO-, whose methylol group may optionally be etherified with alkanols having 1 to 4 carbon atoms; Alkanoylamino of 1 to 4 carbon atoms, which may be N-substituted by methylol or alkyl of 1 to 4 carbon atoms; Pyrrolidonyl (1); phenyl; pyridinium; the sulfonic acid group; Sulfoalkylamidocarbonyl having 1 to 4 carbon atoms; the phosphonic acid group, wherein sulfone and phosphonic acid groups may also be present in the form of their alkali metal or ammonium salts; a radical of the formula VIII 0

-, COOCH ₀ CH ₀ -OPR ¹² (VIII)

Wherein R or R are the same or different and are alkyl

.9- L yy ι www

with 1 to 4, preferably 1 or 2, carbon atoms, a radical of the formula IX

R ¹² -COQ-C EL · -N "" _1T . (IX)

Wherein R and R have the meanings given above and ρ is a number from 1 to 4, or a radical of the formula

CpH ₂ PX ^ ^ ₁₅ (X)

wherein R and R are the same or different and are each alkyl having 1 to 4, preferably 1 or 2, carbon atoms or the quaternized by CH ₃ Cl or dimethyl sulfate, for example, best of the formulas IX and X and ρ has the abovementioned meaning.

Preferred components B) are those homo- or copolymers, the weight before crosslinking from 60 to 95.% Of units of the formula VI and 5 to 40 wt.% Of units of the formula VII are included.

Furthermore, such homopolymers or copolymers are preferably used as component B) in compositions according to the invention in which X is carboxyl; the sulfonic acid group; 3-sulfo-2-methylpropyl (2) -amidocarbonyl of the formula

^CH 3

Alkanoylamino having 1 to 4 carbon atoms, which may be optionally Kf-substituted by methylol or alkyl having 1 to 4 carbon atoms; Pyrrolidonyl- (l) or a radical of the above-defined and defined formulas IX and X ,. wherein each acid group may also be present as sodium, potassium or ammonium salts.

Preferably used as component A) and B) are copolymers which, prior to crosslinking, have K values of from 15 to 300 (compare Fikentscher "Cellulose Chemistry" Bd 13, If "58 (1932)).

It goes without saying that the copolymers used according to the invention may contain several different radicals which are possible within the definitions of X and Y. In the R-egel, the symbols X and Y, when contained in one and the same hacromolecule, have no more than 3, preferably 2, different meanings. Copolymers of this type are prepared by using several, usually not more than 3, preferably 2, different comonomers containing different radicals X and Y in the polymerization.

The homo- or copolymer compositions of this invention are readily soluble in water prior to crosslinking and provide medium viscosity solutions. These solutions are easy to handle, and they retain this property as long as they are not acidified by the addition of acids, especially to a pH of 3 or below. In contrast to known combinations of polymers and aldehydes, the compositions according to the invention are storable for an unlimited time in the absence of acids. If acids are added to the aqueous solutions of compositions according to the invention, then the crosslinking reaction between the amidocarbonyl groups of component A) and the formylamido groups of component B) forms the characteristic bridge members of the formula -NR ^X -CH = N-CO-. The polymeric chains thereby crosslink to the new three-dimensional polymer network, and there is an abrupt increase in the viscosity of the aqueous solutions. For this reason, the compositions according to the invention can be used to increase the viscosity of acids. Depending on the amount of the composition according to the invention, which is added to a certain amount of acid, the viscosity can be varied within a wide range. The lower limit of this range is the viscosity of the pure acid which is free of copolymers. On the other hand, gels of the crosslinked polymer according to the invention can be obtained by a sufficient addition of composition according to the invention, which no longer flow freely, but are completely dimensionally stable. Any viscosity can be between these extremes

be adjusted by simple variation of the proportion of inventive polymer composition in the acid.

In the case of pressure acidification, the concentration of the acrylamido homopolymer or copolymer (component A) is normally 0.24 to 0.72% by weight, based on the total weight of the product, depending on polymer properties, treatment conditions of the well and the nature of the deposit Cleavage or treatment fluids. The crosslinker substance (component B) usually has a concentration of 0.05 to 1 wt.%, Preferably Q _? 25 to 0.6 wt,%, of the spin or Behandlungsf lu ^ ds ,, - The acrylamido-homo- or copolymer, the aqueous phase either as a fine powder, as a dispersion in hydrocarbons, preferably having a content of 20 to 50 wt.% of component a) or as an oil-in-water or water-inr-oil emulsion containing normally 20 to 50 wt% *% of component a) is added. The preferred system is an emulsion with the highest possible content of component A), which is normally 25 to 75 percent at.% Is. Suitable oils for the preparation of such water-in-oil emulsions are, for example, branched or unbranched paraffinic hydrocarbons having a boiling point of 150 to 25O ⁰ C.

The crosslinker (component B) is usually present in form of an aqueous solution with up to 50th% of the cross-linking substance, as a fine powder, as weight is a hydrocarbon dispersion of 20 to the 50th% of crosslinker, or as a water-in-oil or Oil-in-water emulsion with 20 to 50 wt.% Of crosslinking agent used. Preferably, the use takes place as an aqueous solution with about 50 wt.% Crosslinker substance.

Dissolving the acrylamido homopolymer or copolymer in the preferred concentration of 0.24 to 0.72 wt.% And the. Crosslinker substance in the preferred concentration of 0.25 to 0.5% by weight, together in water, to obtain a solution having only a mean viscosity of 20 to 60 cp, as measured in a Fann-35 viscometer at a shear rate of 511 see ".

The solution maintains this viscosity until it is mixed with a Bronsted-Lowery acid. The addition of acid causes the crosslinking reaction between AeryLamido homo or copolymer and the crosslinker containing formylamido to form the novel copolymer crosslinked via bridge members of the formula -NE ³ ^ CH-N-CO-. Here, the viscosity of the aqueous solution usually increases to over 300 cp, measured under the above conditions (Fann-35 viscometer at a shear rate of 511 see ").

According to the invention thickened acid gels of the invention contain acids or weight, generally 70 to 99.8.% Of one or more of the above acids, and 0.2 to 30 wt.% Of the over · characteristic bridge members of the formula -NR ^X is -CH-N-CO crosslinked polymer compositions of the invention.

Preferably, substantially all bridge members - at least 50 % and preferably at least 70 % of the bridge members - have the abovementioned formula. However, other known crosslinking bridges may be present in minor proportion in the crosslinked polymer. Such known bridge members may under certain circumstances be formed by reaction of other reactive groups in components A) or B) of the polymer composition according to the invention and / or due to the addition of other known crosslinkers.

As already mentioned above, the amidocarbonyl groups of component A) are bound to macromolecules. It has been shown that the macromolecules stabilize the bridge members of the above formula which form during the crosslinking reaction. On the other hand, if the amidocarbonyl groups are bound to molecules of too small a size, no or only a small number of said bridge members are stabilized. In this case, it appears that the bridges are degraded as a result of hydrolysis to formic acid, ammonium, carboxylic acid groups and possibly other fission products.

The usual method of preparing acid gels according to the invention,

consists of adding the desired, in particular the preferred concentration of acrylamido homopolymer or copolymer to an aqueous solution of the acid and awaiting the hydration of the polymer, which usually takes 3 to 45 minutes. In principle, any acid or aqueous solution An acid is thickened in the manner according to the invention. Acid concentrations of from 1/4 to 28% by weight are normally used for the acidification. Hydrochloric acid, acetic acid or formic acid are preferred. Depending on the conditions of the well treatment and the nature of the deposit, acid concentrations of from 3 to 15% by weight are preferred. If the with the acrylamido homo? or copolymerized acid has reached 90% of the viscosity resulting from the hydrated polymer, the desired, in particular the preferred, amount of crosslinker substance, namely from 0.25 to 0.5% by weight, is added. After this addition, a drastic increase in viscosity takes place as a result of the formation of the novel three-dimensionally crosslinked polymer according to the invention. Of course, the combination of the components of the inventive composition and the acid can be carried out in any other way and leads in each case to acid gels or to highly viscous acid preparations.

The high viscosity of the acids thickened according to the invention remains at room temperature over long Z eiträume, for example, longer than three months, received. At elevated temperatures, for example above 50, preferably above 80 C, the viscosity decreases and the highly viscous or gelled acids pass into liquids of low viscosity.

This transition is due to a hydrolytic degradation of the three-dimensionally crosslinked polymers of the invention to linear polymer chains. The time required to pass from a gel to the low viscosity liquid state depends to some extent on the structure of the polymer molecule and therefore can be varied within certain limits by selection of particular monomer building blocks and monomer ratios become.

However, the time required for dismantling is usually not more than 12 hours.

In principle, all acidic or aqueous solutions can be thickened in the manner according to the invention. Acids which are solid at normal temperature, e.g. aromatic sulfonic acids must be used in the form of aqueous solution. Preferred are those acids which are normally liquid and which are strong and inexpensive in view of their economic use in the oil recovery field. There are therefore primarily strong inorganic and strong lower organic acid into consideration.

Examples of acids which can be thickened according to the invention are hydrochloric acid, sulfuric acid, nitric acid, perchloric acid, phosphoric acid, hydrofluoric acid, formic acid, acetic acid, monochloroacetic acid, dichloroacetic acid and trichloroacetic acid.

Preferred acids for petroleum recovery are hydrochloric acid, hydrofluoric acid, formic acid and acetic acid.

The homo- or copolymers used as component A) compositions according to the invention by polymerization or copolymerization of 50 to 100 wt.%, Preferably 60 to 85 wt .-% acrylamide and / or methacrylamide and 0 to 50 wt.%, Preferably 15 to 40 % By weight of a comonomer of the formula UIa

B ⁵ CH ₂ - CY (HIa)

wherein R and Y have the meanings given above, prepared.

Monomers of the formula IIIa which are suitable for copolymerization with acrylamide and / or methacrylamide to give components A) of compositions according to the invention are, for example;

tu ϋ ι υ

R ⁵ TJ -CH ₃ -H -CH ₃ r ^H -H Y -CK. CN -COO H® -Cool I-C COCH -NH-CHO

.CH

-H

-H

COOCH

-COOC ₉ If,

-COOCoHc -COOC, H

₄ H ₉

-COOC ₄ H

₄ H ₉

CH.

CH.

-COOC ₆ H

₆ H ₁₃ -COOC ₂ H ₄ OH

-COOC ₂ H ₄ OH

-COOC ₃ H ₆ OH

-COOC ₃ E ₆ OH

CH.

-H

CH.

-CQKBCH ^ OH -CONHCH ₂ OH -CONHCH ₂ OCH ₃ -CONHCH ₂ OCH ₃

-H . -CH ₃ -E Y- -COKHCH ₂ OC ₂ H ₅ -CONHCH ₂ OC ₂ H ₅ -COKHCH ₂ OC ₄ H ₉

R ⁵ -NHCOCR ₃ : -B -H -CH ₃ Y -NHCOC ₂ H ₅ -NHCOC ₃ H ₇ -N-CHO

CH ₂ OH

-E

-K-COCH

CH ₂ OH

-H

N-COC ₂ H ₅

CH ₂ OH

-H

N-COC ₃ H ₇ CH ₂ OQ

-CH3

-N-CHO

CH ₃ -

-H

-N-CHO CH ₂ -OH

-H

-K-COCH. t ·?

GH _n

-K-COCoH, ι ^{ύ χ}

CH ₃ ^C 2 ^H 5

-Ξ

CH,

-H

-N-CQCB.

CH.

-so.

Ö

-H -CH.

-SO.

-COKH-CH ₂ SO ₃₁

-H

-CPNHC ₂ H ₄ -SO ₃ . -COKHCH-CH ₀ -SO

-H

-CO-NH-CH-CH ₀ Ch ₀ -SO-H

I Λ " ** * J

-H

CH ₃ '·

-CO-N ¹ HC-CH ₂ -SO ₃

y y

CH.

-CONH-C ₂ H ₄ SO ₃ ,

- ^CH 3

CH _n -CO-NH-J-CH ₂ SO ₃ H ¹

CH _n

-H -CH.

'CH. -COO-CH CH _n -K _n

-H -CH.

-COO-CH ₂ CH ₂ -N

^C 2 ^H 5 ^C 2 ^H 5 ' ^C 3 ^H 7 COO-CH _n CH _n -N ^J

2 "2

CH,

-H- -H

Y is -COO-CH ₂ CH ₂ -N ₁ -COO-CH ₀ CH ₀ -N 2

 CH.

-H -CH.

γ-COO-CH ₂ CH ₂ CH ₂ -N.

• CH. -COO-CH ₀ CH ₀ CH ₀ -N

Δ 4 Δ ·

-H-CH,

Y 'is -COO-CH-CH ₂ -N-COO-CH-CH ₀ -N

-H -CH.

-CONH-CH ₀ CH ₀ -N

, CH.

CH. -CONH-CH _n CH _n -N '

-H

^C 2 ^H 5

-H

CH.

-CONH-CH ₂ CH ₂ -N:

P TT

^C 2 ^H 5

-COKH-Cn _n CH ₀ -H

CH ₇

-COKH-CH ₀ CH ₀ -K

' ^C 4 ^H 9 C ₄ H ₉

-H

Y is -COKH-CH ₂ CH ₂ -K

^ Ptl

-COKH-CH ₀ CH ₀ CH ₀ N 'Δ 2 2

-COKU-CH ₂ CH ₂ CH ₂ -K

^CH 3

- ^C 2 ^H 5

-COKH-CH-CH ₀ -K ^ -

'^ CoK =, ⁴ 3 - ^ °

CH.

-H

-CONH-CH-CH ₀ -N

-COKH-C-CH ₀ -N

CH.

CH.

-H

-f)

-COO-CH ₀ CH ₀ -K

^2H 5

C H

-COO-CH ₀ CH ₀ -N ^ ^{3 7;}

^{2 N} PB

CH ₃

Since N-vinyl amides are not stable under acidic conditions, mixtures containing acidic substances must be neutralized prior to polymerization, for example with the inorganic or organic bases indicated above * or basic comonomers.

V?

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The homopolymers or copolymers which are to be incorporated as component B) of the compositions according to the invention are prepared by polymerization or »copolymerization of from 50 to 100% by weight, preferably from 60 to 95% by weight, of a monomer of the formula VIa

(Via)

in which R has the meaning indicated above and 0 to 50% by weight, preferably 5 to 40% by weight, of a comonomer of the formula VIIa ·

R ¹¹ t

CH ₂ = CX (VIIa)

11 wherein R and X have the meanings given above.

Common monomers of the formula VIa which are suitable for preparing component B) by homopolymerization or copolymerization with monomers of the formula VIIa are, for example, N-vinyl! -Formamide, N-vinyl-N-methyl-formamide and N-vinyl N-hydroxymethylformamide "Common monomers of the formula VIIa are, for example, acrylamide and monomers which have been defined above under formula IIIa.

The crosslinking of the component A) of compositions according to the invention can also be brought about by compounds of the formula I.

Examples of compounds of the formula I are shown in the following table:

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R ¹ R ² η m

H H

Ή H

C -iH

9 C ₄ H ₉ CH ₃

C, Hy CpHj-

H H

wH -j OH ο

H H

CH ₃ CH ₃

C ₂ H ₅ C ₂ H ₅

C nHry C oHry

H H

CH ₃ 'CH ₃

H H

C ₂ H ₅ C ₂ H ₅

C oiiry C-jHry

Preferred compounds of the formula I are:

0 0

HC-IIH-CH ₂ -NH-CH (methylene-bis-formamide) and

0 0

HC-ITH-CH ₂ -O-CH ₂ -M-CH (bis (IT-formyl-aminoethyl) ether).

The compounds of the formula I can be prepared in a simple manner according to the specifications of British Pat. No. 1,410,722.

1 0 1 1 1 0 1 1 1 0 1 1 1 0 1 0 1 0 1 0 2 0 2 0 2 1 2 1 IV) 0 2 0 3 0 3 0 3 1 3 0 3 0

12 * 5 * 1982

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If copolymers are to be prepared which have a plurality of different radicals Y 'and X' in components A) and B), then a plurality of different, generally 3) or preferably 2, different comonomers of the formulas IIIa or VIIa are used for the copolymerization

The polymerization or copolymerization for the preparation of components A) or B can be carried out by all known polymerization processes. "If one of the comonomers used is a vinyl formamide derivative, it is expedient, at a pH of from S to 12, preferably 7 to 9 years to work

For adjusting the pH, alkali-reacting salts of alkali metals, eg. Bo alkali carbonates, alkali metal bicarbonates, alkali metal borates, di- or tri-alkali phosphates, alkali hydroxides, ammonia or organic amines of the formula NR used, wherein R is hydrogen,.

Alkyl having 1 to 4 carbon atoms or hydroxyethyl

16 and wherein at least one of the radicals R is different from hydrogen. Preferred bases for adjusting the pH are the abovementioned alkali compounds, especially sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate and potassium bicarbonate, and sodium or potassium borates. Another preferred base is NH.

The polymerization reaction can be initiated by high-energy electromagnetic or corpuscular radiation or by substances that form radicals. Accordingly, suitable as polymerization initiators are organic per compounds, such as. Benzoyl peroxide, alkyl hydroperoxide, such as ZoB butyric hydroperoxide, cumene hydroperoxide _; p-Me N-

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thahydroperoxide, diacyl peroxides, such as ζ. For example, di-, tert-butyl peroxide or inorganic per-compounds, such as ζ. Β * potassium or ammonium persulfate and hydrogen peroxide, and azo compounds, such as ζ "as azo-bis-isobutyronitrile, 2,2-azobis ^f (2-amidinopropane) hydrochloride or azobis-isobutyramide" It is preferable that the organic or inorganic Examples of suitable reducing substances are sodium pyrosulphite, sodium bisulphite or condensation products of formaldehyde with sulfoxide. "The polymerization can be carried out particularly advantageously by using Mannich adducts of sulfinic acids, aldehydes and amino compounds. as described for example in DE-PS 1,301 »566.

It is also known to add to the polymerization batches small amounts of so-called moderators, which harmonize the course of the reaction by flattening the reaction rate-time diagram. They lead to an improvement of the reproducibility of the reaction and thus make it possible to produce uniform products with extremely low quality deviations. Examples of suitable moderators of this type are Uitrilotris propionyl

amide or hydrohalides of monoalkylamines, dialkylamines or trialkylamines, e.g. Dibutylamine. It is also possible with advantage to use such moderators in the preparation of the copolymers which can be used as component A) or B) according to the invention.

Furthermore, so-called regulators can be added to the polymerization batches; These are those compounds which influence the molecular weight of the polymers produced. Useful known regulators are e.g. Alcohols, such as, methanol, ethanol, propanol, iso-propanol, n-butanol, sec-butanol and amyl alcohols, alkyl mercaptans, e.g. Dodecylmercaptan and tert-dodecylmercaptan, isooctylthioglycolate and some halogen compounds, e.g. Carbon tetrachloride, chloroform and methylene chloride,

Usually, the polymerization is carried out in a protective gas atmosphere, preferably under nitrogen.

The reaction can be carried out in solution, in emulsion, or under the conditions of precipitation polymerization at temperatures of up to 120 ⁰ C, preferably from 40 to 100 ° C.

When water is used as a solvent for the polymerization reaction, it runs in solution, and an aqueous viscous solution of the polymer or copolymers is obtained. The reaction product can be isolated, either by distilling off the water from the solution, or by mixing the aqueous solution with orgnaoischen solvents which are completely miscible with water, but in which the copolymer is insoluble. Upon addition of such organic solvents to the aqueous polymer solution, the resulting polymerizate or copolymer precipitates and may be separated from the liquid phase, e.g. be separated by filtration. Preferably, however, the resulting aqueous solution of the polymer or copolymers, used directly for further use, optionally after adjustment to a certain desired concentration.

When the copolymerization in an organic solvent

ie

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like ζ Eo in a lower alkanol, eg. Bo in terto-butanol, so it runs under the conditions of precipitation polymerization »In this case, the resulting polymer or copolymer precipitates in the course of the reaction in solid form and can easily in the usual manner, such as. Of course, it is also possible and in some cases preferable to distill the 'solvent from the reaction mixture.'

embodiment

The invention is explained in more detail below with reference to some examples

The following embodiments show the use of polymer compositions according to the invention for the production of thickened acids according to the invention, of acid gels, and the preparation of the polymer compositions according to the invention used. Further illustrative embodiments for the preparation of the as component B) -and as far as Y formylamido means, also as component A) used polymers or copolymers can be taken from our already mentioned above parallel application entitled "Water-soluble self-crosslinkable copolymers"

The abbreviations contained in the following embodiments and tables have the following meanings

AM: acrylamide VMA: N-vinyl-N-methylacetamide AMPS: 2-acrylamido-2-methylpropane-sulphonic acid wherein the exponent

V W

AP C 08 G / 235 738/3 60 182/11

the ammonium salt,

the salt with dimethyl-β-hydroxylethylamine

means AS: acrylic acid MAS: methacrylic acid HMA: N-methylolacrylamide YSSNa: Na salt of yinyl sulfonic acid NMYA: N-methylol viny! Acetamide YA: Vinyl acetate! D YP: Yiny1fοrmamid NMYP: N-methylol-vinylformamide d

VPA: vinylphosphonic acid A: Ämmoniumperoxidisulfat

B; Sine combination of ammonium peroxidisulfate + dibutylammonium hydrochloride +

SO ₀ -Ch-NH-COOCH ₀

COOH

C: azo-isobutyronitrile VIP: vinylpyrrolidone.

example 1

a) 5 g of N-methylene-bis-formamide are added to 100 g of a 1% strength aqueous solution of a copolymer of 80% by weight of acrylamide, 15% by weight of AMPS and 5% by weight of vinylpyrrolidone (K * 201) , '' "''

The clear, slightly viscous solution thus obtained can be stored unchanged for an unlimited time. Put this solution with IQO ml conc. Hydrochloric acid, the viscosity increases rapidly ^, and within 30 min. Forms a dimensionally stable gel. At normal temperatures of 20 to 25 ° C, this acid gel is virtually unchanged over a period of at least 15 days. At 80 to 90 ° C, however, the gel turns into a slightly yellowish-brown liquid of low viscosity within 20 min.

That in this beispjä. used copolymer can be prepared as follows:

b) In a 2 1 polymerization vessel equipped with stirrer, thermometer, gas inlet, dropping funnel and heating bath 600 ml of deionized water are introduced and then with stirring and passing a slight stream of nitrogen, the following monomers added: 80 g of acrylamide 15 g AMPS and 5 g of vinylpyrrolidone

Then, 0.5 g of azo-di-isobutyronitrile are added and the reaction mixture is heated to a temperature of 50 C by means of the heating bath. At this temperature, 1 ml

a 10% solution of benzoyl peroxide in acetone added to start the polymerization reaction. In the course of the onset of polymerization, a significant increase in viscosity is observed and the temperature rises to 58 ° C.

After the reaction has subsided, the mixture is stirred for a further hour at 8O ⁰ C. The highly viscous polymer composition is finally diluted to a content of 1% by weight with stirring with water.

c) Gels of similar properties are obtained when the copolymer used above is replaced by a copolymer of 55% by weight of acrylamide, 40% by weight of AMPS and 5% by weight of vinylmethylacetamide (K-165) or by a copolymer of 60% by weight of % Acrylamide, 35% by weight AMPS and 5% by weight vinyl methacrylate (K 179).

Example 2

. A 3.5 wt% aqueous solution of a copolymer of 70 percent,% acrylamide, 10% by weight AMPS, 15 wt% formamide and 5% w G _e vinyl pyrrolidone (K-value - 152)... Is 1% by weight. N-methylenebisformamide added. The resulting clear solution can be stored unchanged for an unlimited period of time. Substituting this solution, the same volume conc. Hydrochloric acid, so you get within 20 min. An acid gel whose properties remain virtually unchanged at 20 to 25 ° C over a period of at least 10 days.

At 80-90 ° C, on the other hand, this gel "melts" within 20 minutes to form a clear, low-viscosity liquid.

Acid gels of similar behavior can be obtained when the copolymer used in this example is replaced by the copolymers of the following table.

υ υ

AT THE AMPS 20 VIPs Jj_ / rel. K value < 215 60 20 25 VIPs 206 55 20 20 VIPs 208 60 20 20 VIPs 39.46 60 20 20 VIPs 30.3 70 10 32.6

All quantities in this table are parts by weight.

Example 3

100% of a 1% strength by weight aqueous solution of a copolymer of 65% by weight of acrylamide and 35% by weight of sodium acrylate (K-203), 11 ml of conc. Hydrochloric acid mixed. The strongly acidic mixture thus obtained is a slightly viscous liquid which can be stored unchanged for a long time. By adding 0.5% by weight of methylene-bis-formamide to the strongly acidic solution, it transforms over 10 minutes into a dimensionally stable gel. At 20 to 25 ° C, this acid gel keeps unchanged for at least 12 days, while it passes at 80 to 90 ⁰ C within yon 30 minutes in a clear low-viscosity liquid, "."

A similar acid gel can be obtained when the methylene bis-formamide is replaced by the same amount of a compound of the formula

C-NH-CH ₀ -O-CH ₀ -NH-C

is replaced.

The aqueous polymer solution used in this example can be prepared by dripping with vigorous stirring into 97.5 ml of water 2.6 ml of a copolymer emulsion which can be obtained as described below.

The copolymer emulsion is prepared as follows:

1.85 g of sorbitan monostearate are dissolved in 30 g of a technical grade

ws ¥ W

Mixture of isomeric hydrocarbons having a boiling range of 200 to 24O ° C dissolved. This solution is charged into a 2 liter reaction vessel equipped with stirrer, thermometer and nitrogen gas inlet.

Now, a monomer solution is prepared by dissolving 33.9 g of acrylamide and 18.2 g of acrylic acid in 50 ml of deionized water and adjusting the pH to 8.5 by addition of a 20 wt.% Aqueous solution of sodium hydroxide. The aqueous monomer solution thus obtained is _o solution slowly dripped under strong stirring in the presented sorbitan monostearate solution, and then the air displaced in the reaction vessel by nitrogen. 0.07 g of 2,2'-azo-bis-isobutyronitrile, dissolved in acetone, are added to the monomer emulsion then present and the reaction mixture is slowly warmed to 60 ° C. with stirring. After 2.5 hours, the polymerization reaction is complete ^ and we obtain a stable 39 wt.% Emulsion of the copolymer with a K value of 203,

Example 4

A 1% strength by weight aqueous solution of a copolymer of 90% by weight of acrylamide and 10% by weight of dimethylaminoethyl methacrylate containing 5% by weight of N-methylene-bis-formamide is concentrated in a volume ratio of 1: 1 Hydrochloric acid mixed.

Within 10 min _._ results in a dimensionally stable acid gel, which is unchanged at 20 to 30 C for at least eight days unchanged, but at 80 to 90 ° C in a short time in a clear low-viscosity liquid. Substitution of the above-used N-methylene-bis-formamide by the same amount of a compound of the formula

^ C -N-CH-N-C ^

H '' ^ CH ₃ CH ₃ CH ₃

leads to the same result.

The aqueous polymer solution used above can be obtained _; by mixing 95.2 ml of water and 4.8 g of a copolymer emulsion, the preparation of which is described below, with vigorous stirring, and then 5 g

N-methylene-bis-formamide added.

The copolymer emulsion is prepared as follows:

185, Og of a mixture of 84% saturated aliphatic hydrocarbons and 16 % naphthenic hydrocarbons (boiling range of the mixture 192 to 254 °), 188.3 g of a technical grade chloroalkane having a chlorine content of 66.5% by weight

and a density of 1.575 g / cm and 32 g of sorbitan monooleate are mixed together in a reaction vessel equipped with stirrer, thermometer and nitrogen inlet and outlet. After thorough mixing of the ingredients, a solution of 180 g acrylamide and 20 g DimethylaminoethylmethacrylatacetätV in 387.5 g of water under Kräfigem stirring is added, wherein the aqueous phase is emulsified in the organic phase. Through the mixture is then nitrogen was passed for 30 minutes and then the temperature / increased within 15 minutes at 60 _(C. At this temperature the mixture is added a solution of 0.212 g of 2,2'-azo-bis-isobutyronitrile in a small amount The polymerization reaction is complete after stirring the mixture for 3 hours at 60 ° C. This gives an emulsion which does not clot and does not tend to settle and which has a viscosity of 710 mPa see at a shear rate of 29.2 contains 20.8% by weight of a polymer having a K value of 201.

Example 5

a) 1.85 g of sorbitan monostearate are dissolved in 28 g of a technical grade mixture of isomeric hydrocarbons having a boiling range of 200 to 24 ° C. (Isopar M, sales product of _: Exxon Corporation). The solution is placed in a 2 liter reaction vessel equipped with stirrer, thermometer and nitrogen gas inlet. Then, a monomer solution is prepared by dissolving 33.9 g of acrylamide and 2.4 g of acrylic acid in 40 ml of deionized water and adjusting the pH to 8.5 by adding 20 % aqueous sodium hydroxide solution. The aqueous Monomerenr solution is then added dropwise slowly with vigorous stirring in the organic sorbitan monostearate solution and the

Air in the reaction vessel replaced by nitrogen. The obtained emulsion is added 2,2'-azobis-iso-butyronitrile in acetone and then the reaction mixture heated gradually with stirring to 6O ⁰ C, a solution of 0.07 g. At this temperature, the polymerization reaction is completed within 2.5 hours, and gives a stable emulsion of the copolymers.

b) In a 1 1 polymerization 67 g of Isopar M are initially introduced and heated up to a temperature of 6O ⁰ C. Then, with stirring, 0.27 sorbitan monolaurate, 1.3 g sorbitan monostearate, 0.17 sorbitan monolaurate, and 4.3 g polyoxiethylene sorbitan monostearate are added and dissolved successively. With further gentle stirring, a nitrogen flow is now introduced into the solution and set its temperature to 60 C. In the meantime, an aqueous monomer solution is prepared in the following way:

2.4 g of AiMPS, IQ g-VJMA, 10.0 g of vinylpyrrolidone and 10.6 g of N-vinyl-formamide are dissolved with stirring in 94 ml of water in a separate vessel. This solution is adjusted by dropwise addition of 10 wt.% Aqueous sodium hydroxide solution to a pH of 8 to 10. Subsequently, 0.1 g of ammonium persulfate are added. This aqueous monomer solution is added dropwise with rapid stirring into the organic phase introduced in the polymerization vessel, whereby the aqueous solution is emulsified in the organic phase. The polymerization reaction begins after about 30 minutes and manifests itself by an increase in the temperature over the course of 15 Min., The temperature rises to 80 to 90 C. After the polymerization reaction has subsided, the mixture is heated to 8O ⁰ C for a further two hours. This gives a stable emulsion having a polymer content of 30 wt.%. The molecular weight of the polymer is

The two emulsions prepared in paragraphs a) and b) of this example are mixed for 5 minutes

long touched. The copolymer composition thus obtained has a copolymer content of about 27% and is a highly active valuable thickener for aqueous acids.

Example 6

a) 185.0 parts by weight of a mixture containing 84 wt.% Of saturated aliphatic hydrocarbons and 16 wt.% Naphthene hydrocarbons (boiling range of the mixture 192 to 254 ° C), 188.3 parts by weight of a technical chloroalkane with a chlorine content of 66.5 % and a density of

3 1.575 g / cm and 32 parts by weight of sorbitan monooleate are mixed together in a reaction vessel equipped with stirrer, thermometer and nitrogen inlet and outlet ports.

After thorough mixing of the constituents, a separately prepared solution of 212.5 parts by weight of acrylamide in 387.5 parts by weight of water is emulsified with vigorous stirring in the submitted organic phase. Nitrogen is allowed to pass through the mixture for 30 minutes and then heated to a temperature of 60 ° C. over 15 minutes. A solution of 0.212 parts by weight of 2,2'-azobisisobutyronitrile in a small amount of acetone is added The emulsion is heated to 60 C for three hours. After that, the polymerization reaction is completed. This gives a non-clumping polymer dispersion, which shows no tendency to settle and at a shear rate of 29.3 see. "" A viscosity of 710 m Pa see. having. The polymer has a K value of 201.

b) 150 parts by weight of a deodorized Kerosinfraktion boiling range 190 to 240 ° C (Exsol D Esso Chemie, Germany) are placed in a 1 1 polymerization flask and heated to 60 ° C. With gentle stirring, 1.3 parts by weight of sorbitan monolaurate, 6.5 parts by weight of sorbitan inonostearate, 0.8 parts by weight of sorbitan monooleate and 22 parts by weight of polyoxyethylene sorbitan monostearate are added in succession and solved. With continued gentle stirring, a stream of nitrogen is introduced into the solution

and the temperature is set to 6O ⁰ C. In a separate vessel, 30 parts by weight of AMPS, 45 parts by weight of vinylpyrrolidone and 55 parts by weight of N-vinylformamide are dissolved in 150 parts by weight of water. This solution is adjusted by dropwise addition of 10 wt.% Aqueous sodium hydroxide solution to a pH of 8 to 10. Thereafter, 0.3 g of ammonium persulfate are added. The aqueous monomer solution thus obtained is then added dropwise with vigorous stirring in the submitted organic phase and emulsified. After about 30 minutes dia polymerization begins, and the temperature rises spontaneously within 15 min. At 80 to 90 ° C. After the polymerization reaction has subsided, the mixture is heated to 8O ⁰ C for a further two hours. This gives a stable polymer emulsion having a polymer content of 30 wt.%; the molecular weight of the polymer is 95,000.

c) The two emulsions prepared in paragraphs a) and b) of this example are mixed with vigorous stirring for 5 min. The copolymer composition according to the invention thus obtained has a copolymer content of about 27% and is a highly active valuable thickener for aqueous acids.

Example 7

For the pressure acidification a natural gas drilling in West Texas is selected. The hole has a production interval between a depth of 2940 to 2970 meters. The sole temperature in this interval is 76 to 77 ° C. The pressure permeability of the formation averages 0.1 md (millidarcy). The spontaneous productivity of the well is before the treatment

3 qa. 112 m of gas and about 790 1 condensate per day.

The pressurizing fluid to be used is prepared by mixing 151,400 liters of 15% hydrochloric acid containing 302 l (0.2 wt%) of a commercial corrosion inhibitor with kg of a finely powdered (100-200 mesh) copolymer of wt% acrylamide, 40 % By weight of AMPS and 5% by weight of N-methyl-N-viny! Acetamide (K = 165). In addition, the mixture is admixed with 3002 l (0.2% by weight) of a nonionic fluorine-containing

he L υ y ι υ υ w

Wetting agent added. The mixture is stored for one hour in two tanks, and then represents a homogeneous liquid with a viscosity of about 35 cps, measured at a Seer slope of 511 See. "In a Fann-35 viscometer This treatment fluid is in the above-mentioned deep hole pumped in, wherein at the same time per 250 l of the treatment liquid 1 1 of an aqueous crosslinker solution are metered into the inflowing treatment fluid containing 50% by weight of an active polymer of 80% by weight of N-vinylformamide, 10% by weight of acrylic acid and 10% by weight. The rate of injection of the treatment fluid is about 1900 1 per minute with a surface treatment pressure of 414 bar, and after about 80 to 85 minutes all of the treatment fluid is forced into the well and sealed for 6 hours In order to give the acid opportunity to react with the rock, after this time the pressure at the head of the bore will be relieved t and the promotion restored. Measuring the delivery rate results in a substantial increase in the productivity of the well.

Claims (1)

AP C 08 G / 235 738/3 , A process for the preparation of a crosslinked polymer composition which has crosslinking bridge members of the formula -2TR ^ -CH = IT-CO-, characterized in that there is a component A which has at least two amidocarbonyl groups in the molecule and a component B which is at least has two Formylamidogruppen react in acidic aqueous medium with each other ο Process according to item 1, characterized in that the component A is a homopolymer or copolymer which contains amidocarbonyl groups and the component B is a bis-acyl-amido compound of the formula I. 0 0 1 ?
where R and R are hydrogen, alkyl having 1 to 4 C atoms or -CH ₂ OH. 3β The method according to item 1, characterized in that the component A is a homo- or copolymer! Sat containing amidocarbonyl groups and the component B is a homo- or copolymer, the formylamido groups of the formula -H - C ^ _R 9 H wherein R 1 is hydrogen, alkyl of 1 to 4 C atoms or -CHpOH.