DD207208A5 - NETWORKABLE, WATER-SOLUBLE POLYMER COMPOSITION - Google Patents

Abstract

The invention relates to a crosslinkable, water-soluble polymer composition for use as thickeners of aqueous acids, which are used in processes of Drucksaeuerung in the extraction of petroleum. According to the invention, the novel composition comprises a polymeric compound having 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. Above x-CH = N-CO-wherein R above x is hydrogen, alkyl having 1 to 4 carbon atoms or -CH 2 OH below. For example, the composition contains A) a water-soluble homo- or copolymer with 10% amidocarbonyl groups and B) a compound of formula I, wherein R above 1 and R above 2 hydrogen, alkyl having 1 to 4 carbon atoms or -CH down 2 OH, n is a number from 1 to 3 and m is one of the numbers 0 or 1.

Description

248959 5

..... ν · ςΠ: χτ-. ') _& 23-2 /

Crosslinkable, water-soluble polymer composition "Field of application of the invention

The invention relates to a crosslinkable, water-soluble polymer composition and its preparation. Above all, the crosslinked polymer compositions are of considerable importance in the stimulation of boreholes in oil reservoirs by the process of pressurized acidification. However, they can also be used with advantage whenever it is expedient to increase the viscosity of acids, for example in various methods of metal cleaning,

Characteristic of the known technical solutions

In the stimulation of holes with the aim to increase the yield of oil or natural gas from subterranean carbonate formations, the technique of so-called pressurized acidification can be used. Carbonate formations are, for example, limestone, dolomite or other storage rocks containing limestone-like materials. In the Hegel, the pressure acidification is carried out by adding aqueous acids, which may optionally contain so-called proppants, at such a rate and pressure injected into the hole that the existing formation pressure is exceeded, the rock gives way and so new fractures are blown into the formation. Fractures are naturally or artificially created cracks or channels in the rock matrix «,

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In this technique, the Drucksäuerung the surfaces of the rock fractures are etched by the acid * However, since these surfaces have a heterogeneous structure, the surface is by etching not uniform but locally different degrees removed "Once the external _pressure} by the injection of the acid is generated, is withdrawn, the rock fractures fall back together _e However, it occurs because of the uneven surfaces of Anatzung no complete Yerschluß of fractures more a ,, If the. Acid in combination with a so-called proppant, eg. B ₉ edge-rounded quartz sand, injected, the inclusion of the proppant between the surfaces of the fractures after removal of the external pressure also prevents such surface areas of the fractures from closing completely, which have been little or no etched by the acid * In each 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 Drucksäuerung it is often expedient, the acid a thickening or gelling agent be added (see, U.S. Patent No. 3,415,319; 3 4-34971 i ^{3 74-9 1 6 9 $ 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. Thus, by increasing the viscosity of the acid, it is likewise possible to use the method of pressurized acidification

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cause larger fracture volumes and larger clear widths of the fracture. In addition, in higher viscosity acids, the etch rate of the surfaces is reduced and the acid is allowed to penetrate deep into the fractures formed. In addition, higher-viscosity acids show a better transport behavior for optionally used proppants, which leads to an improvement in the deposition of the support medium in the open fractures »

Typically, higher viscosity fluids contain homo- or copolymers as viscosity-increasing agents. More particularly, in fluids for pressure acidification, viscosity-increasing agents are used which contain amido-carbonyl groups, e.g. B. polyacrylamide. The polymer concentration in the fluids is below 1.0% by weight in the rule. In order to increase the effectiveness of the thickening of fluids, it is known from DE-OS 2,657,443 to crosslink copolymers of acrylamide by addition of aldehydes, such as formaldehyde, acetaldehyde or glyoxal »The crosslinking reaction occurs in the alkaline range at normal temperature, acidic Range, however, only at temperatures of 40 to 80 ⁰ C on. 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 to provide novel, crosslinkable, water-soluble polymer compositions which are according to the

4 - 62 112 11

Networking -for. the stimulation of boreholes can be used in accordance with the process of pressurized acidification for the purpose of increasing the production rate from oil reservoirs »

Explanation of the essence of the invention

The object of the invention is to provide new aids for reducing the internal friction of the acidic fluids used in aerated so-called sertiärförderung »

According to the invention macromolecular compositions are provided which are crosslinked by new bridge members of the formula -M ^ -CH = N-OO-. The new bridge member is dush the reaction of a macromolecule, preferably a polymer _? containing at least two Aicinocarbonylgruppen, 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 equation5

_H Θ -> r-.kr ^x - OH = N-GO-R '+ H ₂ O

Brfindungsgemäße ^ compositions which macromolecular compounds include _s at least two have amidocarbonyl and further, a compound containing at least

24 8959 5

contains two formylamino groups can be used as a thickening or gelling agent for aqueous acids, wherein the above-mentioned crosslinking reaction takes place by forming the new bridge member by the aqueous acid between the components of the composition. Acids thickened or gelled in this way find significant application in the extraction of petroleum and natural gas from subterranean formations.

The present invention relates to novel crosslinkable, water-soluble polymer compositions in which crosslinking is effected by bridge members of the formula -KR ^x -OHsN-O-, where R ^{x is} hydrogen, alkyl of 1 to 4 carbon atoms or -OHpOH. These uncrosslinked compositions contain a macromolecular compound having at least two amido carbonyl groups and another compound containing at least two formylamido groups. The uncrosslinked compositions according to the invention crosslink in acidic bridges,

in an acidic aqueous medium to give -NR 1 -GH = N-CO-

The crosslinked polymer compositions have the further advantage for the process of pressure acidification that they do not tend to precipitate insoluble precipitates in acidic medium, even with prolonged exposure, as is the case with conventional thickeners, precipitates and precipitates, as in use known thickeners have a tendency to clog and seal the subterranean formations, and thus seriously jeopardize the success of drilling stimulation,

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yes, they can lead to complete drying up of the production. "The chemical degradation of the polymer compositions according to the invention gives rise to polymer chains which contain amino groups and therefore become completely soluble in the acidic medium without residue

The crosslinkable polymer compositions according to the invention contain

Δ. a water-soluble homo- or oligomer having amidocarbonyl groups and

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

0 0

HCNC _n H _2n -C OC _n H _2n VN-CH (I),

b I ²

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

in 0 or 1 and / or '

B, b) a water-soluble homo- or Copolymerj which formylamido groups of the formula

N _E 9

having,

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wherein E ^ is hydrogen, alkyl having 1 to 4 carbon atoms or -OHpOH * The crosslinkable polymer composition according to the invention may comprise 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 from 1: 0.2 to 1:20, preferably from 1: 0.2 to 1: 1.

In principle, the homopolymer or copolymer of component A) prior to crosslinking may 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 -HH ³ ^ -OH = N-CO- can occur. Depending on which crosslinking agent (component b) is present in the composition according to the invention, the symbol E ^{x of} the bridge member

Ί 2 Q are the meanings of R, R or R ^. The water solubility of ingredient 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

t is -CH ₂ -O- (II),

959

62 112 11 15.3.83

IL

wherein R is hydrogen or methyl, and 0 to 50 G-ew * ~% units of the formula III

> -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, wherein the N-substituent is methyl or hydroxymethyl; cyano; Carboxyl or its alkali or ammonium salt; Alkoxycarbonyl having 1 to 6, preferably 1 to 3, carbon atoms; Hydroxyalkoxycarbonyl of 1 to 3 carbon atoms; N-methylolamidocarbonyl of the formula HOCH ₂ M-CO-, the methylol group of which is optionally etherified with alkanols of 1 to 4 carbon atoms; alkanoylamino of 1 to 4 carbon atoms which may optionally be N-substituted by methylol or alkyl of 1 to 4 carbon atoms; Pyrrolidonyl (1); phenyl; pyridinium; the sulfonic acid group; Sulfoalkylamidocarbonyl of 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 radical of the formula IY

^ R "is a radical of the formula V

248959 5 -9-

62 112 11 15-3.83

where the radicals of the formulas IV and V can also be quaternized, z _e B * by reaction with CH ₀ -Cl or dimethylsulfonyl

n o J

fat, and wherein S 'and E 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.

Preference is given as component A) to those homo- or copolymers which before crosslinking contain 60 to 85% by weight of units of the formula II and 15 to 40% by weight of units of the formula III.

In addition, preference is given to using for the component A) those homopolymers or copolymers in which Ir is hydrogen or methyl and / or in which Y is carbonyl; the sulfonic acid group; 3-sulfo-2-methyl-propyl- (2) -amidocarbonyl of formula 13

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

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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 E 1 and H 4 signify hydrogen or methylol and η is the number 1

As a homo- or copolymer for component B) of the compositions according to the invention, it is possible to use any polymer which has sufficient solubility in water, that is to say whose solubility should not be less than 10 g / l.

In addition to the obligatory formylamido groups, the oligomer 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 component A) and component B) of the compositions according to the invention each have the amounts of amidocarbonyl and formylamido groups required for crosslinking. It follows that in this case the component A) and the component B) may be the same and as self-crosslinkable copolymers of this special class are the subject of our co-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 *

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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 formyl azido groups should not be less than 1 g mole formylamido groups, corresponding to z, B, 71 g of N-vinylformamide per 500 g of the polymer.

As component B) of the compositions according to the invention are those homopolymers or copolymers are particularly suitable, prior to crosslinking from 50 to 100 wt .-% units of the formula VI

-GH ₀ -CH-

I of °

wherein r "is hydrogen, methyl or hydrosymethyl, preferably hydrogen and methyl, and 0 to 50 wt .-% units of the formula

-CH ₂ -C- (VII)

exist, where

R is hydrogen or methyl and X is cyano; Carbonyl or its alkali or ammonium salts; Alkoxycarbonyl having 1 to 6, preferably 1 to 3, carbon atoms

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Atomsatomic Hydro: xyalkoxycarbonyl having 1 to 3 carbon atoms! amidocarbonyl; N-Methylolamidocarbonyl of the formula HOCHpM-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 (I); phenyl; pyridinium; the sulfonic acid group; Sulfoalkylamidocarbonyl having 1 to 4 carbon atoms; the phosphonic acid group ₉ wherein sulfonic and phosphonic acid groups may also be present in the form of their alkali metal or ammonium salts; a radical of formula VIII

-COOOH ₂ CH ₂ -OPR ^id (VIII),

R ^

In which R or R- * are identical or different and are alkyl having 1 to 4, preferably 1 or 2, carbon atoms, a radical of the formula IX

12 1 ^ wherein R and R ^{J have} the meanings given above and ρ is a number from 1 to 4, or a radical of formula x ₁₄

8 9 5 9 5 -13 - S ₂

15.3 * 83

in which ^^ ΐΐ ^ '·; Β ^ _; : .beta.-βϊΛ; 'οoΓΓ are different and are alkyl of 1 Ms 4-, preferably 1 or 2, carbon atoms or the quaternized example of OHoGl or dimethyl sulfate radicals of the formulas IX and X and ρ has the meaning given above.

Preferred as component B) are those homopolymers or copolymers which before crosslinking contain 60 to 95% by weight of units of the formula VI and 5 to 40% by weight of units of the formula VII "

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

-COKH-C-CH ₂ -SO ₃ H CH ₃

Alkanoylamino having 1 to 4 carbon atoms, which may optionally be N-substituted by methylol or alkyl of 1 to 4 carbon atoms; Pyrrolidonyl- (1) or a radical of the formulas IX and X given above and defined, where each acid group can 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 (see Fikentscher "Cellulose Chemistry" Bd, 13, page 58 (1932)).

959 5 -κ.- ⁶

· 15 · 3 * 83

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 general, the symbols X and Y, if they are contained in one and the same macromolecule, have not more than 3 "preferably 2, different meanings" copolymers of this type are • prepared by adding several, usually not more than 3. preferably 2, various comonomers containing different X or Y radicals used 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 addition of acids, in particular 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, the crosslinking reaction between the amidocarbonyl groups of component A) and the i-amylamido groups of component B) begins with the formation of the characteristic bridge members of the formula -M ² ^ -CH = N-OO-. 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

59 5

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The composition of 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 rigid in temperature. Any viscosity can be adjusted between these extremes by simply varying the proportion of the polymer composition according to the invention in the acid.

In the case of pressure acidification, the concentration of the acrylamido homo- or copolymers (component A) is normally from 0.24 to 0.72% by weight, based on the polymer properties, hole treatment conditions and deposit nature Total weight of the cleavage or treatment fluid. The crosslinker substance (component B) generally has a concentration of 0.05 to 1% by weight, preferably 0.25 to 0.6% by weight, of the cleavage or treatment fluid. The acrylamido homo- or Oopolymerisat is weight of the aqueous phase, either as a fine powder, as a dispersion in hydrocarbons, preferably having a content of 20 to 50 -.% Of component Δ) or as an oil-in-water or water-in- oil emulsion, which normally contains from 20 to 50% by weight of component A). The preferred system is an emulsion having the highest possible content of component A), which is normally from 25 to 75% by weight. Suitable oils for the preparation of such water-in-oil emulsions are, for example

248 9 59 5

e ₂ n ₂

branched or unbranched paraffin hydrocarbons having a boiling point of 150 to 250 ⁰ G ₆

The crosslinking substance (component B) is normally used in the form of an aqueous solution containing up to 50% by weight of the crosslinking substance, as a fine powder, as a hydrocarbon dispersion containing from 20 to 50% by weight of the crosslinking substance or as water-in-solution. Oil or ül-in-water-Stnulsion with 20 to 50% by weight of the crosslinking agent used *, Preferably used as an aqueous solution with ca, 50 wt _e -% crosslinking substance ·

Solving the Acryiamido homo- or copolymer in the preferred concentration of 0 | 24 to 0.72 percent by _e -% and the crosslinking substance in the preferred concentration of 0.25 to 0.5 wt .-% together in water so obtained a solution having only a mean viscosity of 20 to 60 cp, 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 acid addition causes the crosslinking reaction to occur between acrylamido homo or (y) polymer and the formylamido group-containing crosslinker to form the new via bridging linkages -KR formula ³ ^ -CH = N-OO-crosslinked copolymer of the invention. Here, the viscosity of the aqueous solution usually rises to about 300 cp at _s measured under the conditions indicated above (Fann 35 viscometer at a shear rate of 511 see) ·

2 4 8 9 5 9 5 - ¹⁷ - ⁶²¹¹²

Ί 5 * 3 · 83

Thickened acids or acid gels generally contain 70 to 99% by weight of one or more of the abovementioned acids and 0.2 to 30% by weight of the characteristic bridge members of the formula -NR ² OH 0 N-OO crosslinked polymer compositions according to the invention

Preferably, substantially all bridging members - at least 50 % and preferably at least 70 % of the bridging members - have the abovementioned formula, but in the crosslinked polymer, other known crosslinking bridges may also be present to a lesser extent. Such known bridge members may under certain circumstances be formed by reaction of other reactive groups in components A) and 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. Namely, it has been found that the macromolecules to stabilize the bridging members of the above formula which form during the crosslinking reaction. By contrast, 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 thickened acid gels is to achieve the desired, especially the preferred

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Concentration of acrylamido homopolymer or copolymer to add to an aqueous solution of the acid and wait for the hydration of the polymer, which usually takes 3 to 45 min * to complete "Basically, any acid or aqueous solution of an acid can be thickened in accordance with the invention the use for pressure acidification usually employ acid concentrations of from 1/4 to 28% by weight. Preference is given here to hydrochloric acid, acetic acid or formic acid. Acid concentrations of from 3 to 15% by weight are preferred, depending on wellbore conditions and reservoir conditions. "When the acid mixed with the acrylamido homo- or copolymer has reached 90% of the viscosity resulting from the hydrating polymer the desired, in particular the preferred, amount of crosslinking agent, namely 0.25 to 0.5 wt .-%, added. Of course, the combination of the components of the composition according to the invention 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 thickened acids remains at hemium

three months receive "At elevated temperatures, above, for example, 50% ^u ^ ⁿ ^ u ^ BeFore sweise ψ above -80% y - ⁰ ^ decreases the viscosity abv ^'? These acids pass into liquids of low viscosity.

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This transition is due to hydrolytic degradation of the three-dimensionally crosslinked polymers 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 usually does not exceed 12 hours ·

Basically, all acid or aqueous solutions can be thickened "acids, which are solid at normal temperature _s such _s, aromatic sulfonic acids have to be used in the form of aqueous solution · Preferred are those acids that are normally liquid and in view of their economic use In the field of oil extraction are strong and inexpensive ", Bs are therefore primarily strong inorganic and strong lower organic acids into consideration»

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

Preferred acids for the production of crude oil are hydrochloric acid, hydrofluoric acid, formic acid and acetic acid,

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The invention as component A) compositions used homo- or copolymers are obtained by polymerizing or "copolymerization of 50 to 100 wt, -% _f preferably 60 to 85 wt .-%, acrylamide and / or methacrylamide and from 0 to 50 wt # - #, preferably 15 "to 40% by weight, one

Comonomers of the formula IHa _ς

CH ₂

= C-Y

(IIIa)

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?

-H

-H

-CH

-H

CF

CN

COOH

COOH

COOCH

KH-CHO

COOCH

-H

-H

-COOC ₂ H ₅

-CH ₃

-COOC ₂ H ₅

-H

--COOC

-H

₄ H ₉

-H

-COOC ₄ H ₉

CH ₃

-COOC ₆ H ₁₃

-COOC ₂ H ₄ OH

-COOC ₂ H ₄ OH

--COOC

₃ H ₆ OH

COOC

₃ Hg0H

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62 112 15.3.83 ·

-H

-CH

-OOMCHgOH

-OOMCHgOH -COMOHgOCHo

-COMCHgOOHo

-H -H

-C

OMOHgOCgH ₅

-COMOH ₂ OC ₂ H ₅ -COMOH ₂ OO ₄₁ Hq

-H

-H

-H

-MCOOH

-MOOOgH ₅

-MCOC oHr ₇

-N-OHO

HgOH

-H

-H -ho

-H

N-OOCHo CHgOH

-H

-N-COCH CH ₃

N-OOC ₂ H ₅ OHgOH

-H

-N-OOCoHr, OHgOH

-H N-OHO CH ₃

N-COO ₃ H ₆

N-COC ₂ H ₅

-H

-OH

N-OHO OHgOH

-H

-NO

-H -OH,

-PO

'3 * 2

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62 112 15.3.83

-H

-GOMCHgCH ₂ CHgSO ₃ H '

-H

-COMCgH ₄ -SO ₃ H ¹

-GOKEiCH-CH ₂ -SO ₃ H ¹ CH ₃

-H

-H

-GO-M-CH ₂ CHgCHgCH ₂ -SO ₃ H '

-GO-MC-CHg-SO ₃ H

CH.

CH.

-CONH-CgH ₄ SO ₃ H

-GH. -GO-MG-GHgSO ₃ H OH «·»

COO-GHgCHg-

 ν:

GH.

COO-CHgCHg-W

CH.

-COO-CH ^ CKU-N

₂ CHg-l

GH.

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62 112 15.3.83

-H -H

COO-CHgGHg-I

COO-CHgCHg-

CH.

r5 -H -GH ₃ υ OH ₃ -GOO-CHgCHgCHg-N ^ -GOO-CHgGHgGH ₂ -N GH ₃

-H -CH.

R-

-GOO-CH-GH ₂ -N GIL ·

-H-COO-CH-GHg-N ^

CH.

CH.

-CONH-GH ^ CH ^ -N,

CH.

CH. -GONH-CHgCHg-

CH.

CH.

R-

-H -σ

-CONH- CHgCHg-N

-CONH- CHgCHg-N:

-H-

-CONH-CH ₀ GH ₀ -

° 3 ^Η 7

-CONH-GH ₀ GH ₀ -N

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62 112 11 15.3.83

-CONH-GH ₀ CH ₀ -N

C.C.

CH.

^σ 4 ^Η 9

-OH.

-COM-CH-CH ₂ -N

CH.

GH.

-CONH-CH ₂ CH ₂ GH ₂ -N '

-H

GH ₃

CH.

-GONH-GH-CH ₂ -N.

CH.

CH,

-H

-CONH-C-CH ₂ -N

-GH.

-GH.

-H

-GOO-CH ₂ GH ₂ -:

 N

-GOO-GH ₂ CH ₂ -.

 N

CH.

1 Since N-yinyl amides are not stable under acidic conditions, batches containing acidic substances must be neutralized prior to polymerization, for example with the inorganic or organic bases or basic gomonomers indicated above,

The homopolymers or copolymers which can be used as component B) of compositions according to the invention are prepared by

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Polymerization or copolymerization of 50 to 100% by weight, preferably 60 to 95% by weight, of a monomer of the formula VIa

(Via),

wherein R ° has the abovementioned meaning and 0 to 50 % by weight, preferably 5 to 40% by weight, of a comonomer of the formula VIIa 11

= C-X (VIIa),

11

where 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-vinylformamide, N-vinyl-N-methylformamide and N-vinyl-N -hydroxymethylformamid. Common monomers of the formula VIIa are, for example, acrylamide and monomers which have been defined above under formula IIIa.

The crosslinking of 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

48959

R ¹ B ² η. m

H H

H H

H H

H H

CH ₃ OH ₃

Ott Γ "IT

2 5 2

H H

CH

1 3 3 0 A 1 A 0 A 1 A 0 A 1 A 0 1 0 A '0 A 0 2 0 2 0 2 A 2 A 2. ; 0 2 0 3 0 3 0 3 A 0 O

H H

J ₃ H ₇

Preferred compounds of formula I are;

-H (methylene-bis-formamide) and

0

(Βther bis (N ~ fοrmy1-aminomethy1)) »

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

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

The polymerization b ^ zw. 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 to work at a pH of 6 to 12, preferably 7 to 91.

To adjust the pH, alkaline salts of alkali metals, eg. B, alkali metal carbonates, alkali metal bicarbonates, alkali metal borates, di- or tri-alkali metal phosphates, alkali metal hydroxides, ammonia or organic amines of the formula HR used, wherein R is hydrogen, alkyl having 1 to 4 carbon atoms or hydroxyethyl and wherein at least one of the radicals R is different from Hydrogen, Preferred bases for adjusting the pH are the abovementioned alkali compounds, in particular sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate and potassium bicarbonate and sodium or potassium borates. Another preferred base is NHo,

8 9 5 9 5 - ²⁸ - ⁶²

15/3/83

The polymerization reaction can be initiated by high-energy electromagnetic or corpuscular radiation or substances that "form radicals." Accordingly, suitable as polymerization initiators are organic per compounds such as benzoyl peroxide, alkyl hydroperoxide such as z, B, butyl hydroperoxide, cumene hydroperoxide , p-Menthahydroperoxid, dialkyl peroxides such as Ze B _e di-, SDert.-butyl peroxide or inorganic per-compounds, such as. B, potassium or ammonium persulfate and hydrogen peroxide, further azo compounds, such as. B, azo-bis-isobutyronitrile, 2,2-azobis ^f (2-amidinopropane) hydrochloride or azobis-isobutyramide "Bs is advantageous to use the organic or inorganic per-compounds in combination with reducing substances. Examples of suitable reducing substances are sodium pyrosulfite, sodium hydrogen sulfite or condensation products of formaldehyde with sulfoxylates. "The polymerization can be carried out particularly advantageously by using Mannich adducts of sulfinic acids, aldehydes and amino compounds, as described, for example, in German Pat. No. 1,301,566 have been·

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 in 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 nitrilotris propionyl amide or Hydrohalogenide.von monoalkylamines, dialkylamines or trialkylamines, such as. B. Dibutylamine hydrochloride * Also in the preparation of the as component A)

248 95 9 5 -29-

62112

or B) copolymers of the invention can be used with advantage such moderators.

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 z. Alcohols, such as methanol, ethanol, propanol, isopropanol, n-butanol, sec-butanol and amyl alcohols, alkyl mercaptans such as dodecyl mercaptan and tert-dodecyl mercaptan, isooctyl thioglycolate and some halogen compounds such. As carbon tetrachloride, chloroform and methylene chloride.

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

The reaction may take place in solution, in emulsion or under the conditions of precipitation polymerization at temperatures of 20 to 30 minutes.

become.

From 20 to 120 ^° C., preferably from 40 to 100 ^° C., is carried out

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 organic solvents which are completely miscible with water, but in which the oligomer is insoluble. When adding such organic

24 8 959 5 -30. 6 ₂

15/3/83

see solvent to the aqueous polymer solution precipitates the resulting polymer or copolymer and can der.flüssigen from the liquid phase, for. B, be separated by filtration. Preferably, however, the resulting aqueous solution of the polymer or "copolymers is used directly for further use, optionally after adjustment to a certain desired concentration."

When the copolymerization in an organic solvent such as _e in a lower Alkonol, z. B * is carried out in tert-butanol _e, it runs under the conditions of precipitation polymerisation. In this case, the resulting polymer or copolymer precipitates in solid form during the course of the reaction and can easily be converted in a customary manner, such as ζ. Β _β by suction and subsequent drying, isolated. Of course, it is also possible, and in some cases preferred, to distill the solvent from the reaction mixture.

embodiment

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

The following exemplary embodiments show the use of polymer compositions according to the invention for the preparation of thickened acids or of acid gels as well as the preparation of the inventive polymer compositions used, further illustrative embodiments for the preparation of the component B), and where Y is formylamido.

248959 5

Polymers or copolymers also used as component A) can be taken from our parallel application, already mentioned above, entitled "Water-soluble self-crosslinkable copolymers".

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

AM: acrylamide

VMA: N-vinyl-N-methylacetamide AMPS: 2-acrylamido-2-methylpropane-sulphonic acid, wherein the

exponent

1, the ammonium salt, 2 · the salt with Dimethy1-ß-hydroxylethylamine

means

AS: acrylic acid MAS: methacrylic acid NMA: N-methylol-acrylamide VSSNa: Na-salt of vinylsulfonic acid MiVA: N-methylol-vinylacetamide VA: vinylacetamide VF: vinylformamide KMVF: N-methylol-vinylformamide VPA: vinylphosphonic acid A: ammonium peroxydisulfate B: A combination of ammonium peroxydisulfate + dibutylammonium hydrochloride +

So ₂ -OH-NH-COOCH ₃

COOH

C: azo-isobutyronitrile VIP: vinylpyrrolidone »

5 -

32 - 62 112 11

Example 1 :

a) To 100 g of a 1% / aqueous solution of a copolymer / of 80% by weight of acrylamide, 15% by weight of AMPS and 5% by weight of Tiaylpyrrolidpn (K = 201), 5 S N-methylene-bis- formamide s ^ esetat "The clear, slightly viscous solution thus obtained can be stored indefinitely without change." If this solution is mixed with 100 ml of concentrated hydrochloric acid, the viscosity rises rapidly and a dimensionally stable gel forms within 30 minutes. " at normal temperatures, 20 to 25 ⁰ G of this acid gel is preserved virtually unchanged over a period of at least 15 days, at 80 to 90 ⁰ C, however, the gel is within 20 minutes in a slightly yellowish-brown liquid of low viscosity over ·

The copolymer used in this example can be prepared as follows:

b) 600 ml of deionized water are introduced into a 2 l polymerization vessel equipped with a stirrer, thermometer, gas inlet, dropping funnel and heating bath and the following monomers are subsequently added with stirring and passage of a slight stream of nitrogen:

80 g acrylamide 15 g AMPS and

5 g of vinylpyrrolidone.

Then, 0.5 g of azo-di-isobutyronitrile was added, and * the reaction mixture heated by the heating bath at a temperature of 50 ⁰ G · At this temperature, 1 m. a 10% solution of benzoyl peroxide in acetone added ₉ to start the polymerization reaction. in the

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As the polymerization begins, a marked 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 80 ⁰ C. The high-viscosity polymer composition is finally diluted with stirring to a content of 1 wt .-% with stirring.

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 an oligomer 60% by weight of acrylamide, 35% by weight of MiPS and 5% by weight of vinylmethylacetamide (K = 179).

Example 2

A 3 »5gew .-% aqueous solution of a copolymer of 70 wt .-% acrylamide, 10 wt .-% MCPS, 15 wt .-% vinyl formamide and 5 wt .-% vinyl pyrrolidone (K value = 152) is 1 wt % N-methylene-bis-formamide added. The resulting clear solution can be stored unchanged for an indefinite 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 ⁰ C over a period of at least 10 days.

At 80 to 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.

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AM MiPS ^ / rel. K value

60 20 20 VIPs 39.46 215 55 20 25 vrp 30.3 206 60 20 20VIP 32.6 208 60 20 20 VIPs 70 10 20 VIPs

All quantities in this table are parts by weight. Example 3

100 ml of a 1 wt .-% aqueous solution of a copolymer of 65 wt .-% acrylamide and 35 wt .-% of sodium acrylate (K = 203) 11 ml of conc. Hydrochloric acid mixed The strong acid 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, the latter changes into a ferm stable gel over the course of 10 minutes. At 20 to 25 ⁰ C, this acid gel keeps unchanged for at least 12 days _s while it passes at 80 to 90 ⁰ C within 30 viscous liquid.

80 to 90 ^° C within 30 minutes into a clear low

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

⁰ V

C-NH-OH ₀ -O-CH ²

is replaced «

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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 mixture of isomeric hydrocarbons having a boiling range of 200 to 240 ⁰ O. This solution is charged to a 2-1 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. Then, the aqueous monomer solution thus obtained is slowly added dropwise with vigorous stirring in the submitted sorbitan monostearate solution and then displaced the air in the reaction vessel by nitrogen. At the then present monomer emulsion 0.07 g of 2,2'-azo-bis-isobutyronitrile, dissolved in acetone, is added and the reaction mixture was slowly warmed with stirring to 60 ⁰ C. After 2.5 hours, the polymerization reaction is complete, and we obtain a stable 39 wt .-% emulsion of copolymers with a K value of 203.

Example 4

A 1% strength by weight aqueous solution of a copolymer of 90% by weight

- 36 - 62 112. 11

, ; -ν ':. V -..- ' ::. 15 · 3 «83

Acrylamide, and 10 wt .-% dimethylaminoethyl methacrylate containing 5 wt .-% N-methylene-bis-formamide is mixed in a volume ratio of 1: 1 with concentrated hydrochloric acid. Within 10 min results in a dimensionally stable acid gel at 80 to 90 ⁰ C, however, the remains stable at 20 to 30 ⁰ C for at least eight days, in a short time passes 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

⁰ X

^ O -N-CH-N-C

et CH

leads to the same result »

The aqueous polymer solution used above can be obtained by mixing together with vigorous stirring 95 _f 2 ml of water and 4.8 g of a copolymer emulsion, whose preparation is described below, and then 5 g of N-methylene-bis-formamide added.

The oopolymer emulsion is prepared as follows:

185.0 g of a mixture of 84 % saturated aliphatic hydrocarbons and 16 % naphthenic hydrocarbons (boiling range of the mixture 192 to 254 ⁰ C), 188.3 g of a technical grade chloroalkane having a chlorine content of 66.5% by weight and a density of 1.575 g / cirr and 32 g of sorbitan monooleate are placed in a reaction vessel equipped with stirrer,

248959 5 -

^3? -

Thermometer and nitrogen inlet and outlet, mixed together. After thorough mixing of the ingredients, a solution of 180 g of acrylamide and 20 g of dimethylaminoethyl methacrylate in 387 »5 g of water is added with vigorous stirring, wherein the aqueous phase is emulsified in the organic phase. The mixture is then passed nitrogen for 30 minutes and then the temperature within 15 minutes to 60 ⁰ C increased. At this temperature, a solution of 0.212 g of 2.2 ^{l of} azo-bis-isobutyronitrile in a small amount of acetone is added to the mixture. After stirring the mixture at 60 ^° C. for 3 hours, the polymerization reaction is complete. An emulsion is obtained which does not clot and does not tend to settle. It has a viscosity of 710 mPa see at a shear rate of 29.2. 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 commercial mixture of isomeric hydrocarbons with a boiling range of 200 to 240 ⁰ C (Isopar M, a product of Exxon Corporation). The solution is charged in a 2-1 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 monomer solution is then added dropwise slowly with vigorous stirring in the organic sorbitan monostearate solution and the

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15/3/83

Air in aera. Replaced reaction vessel with nitrogen. The obtained emulsion is added in acetone and then the reaction mixture was gradually heated with stirring to 60 ⁰ C a solution of 0.07 g of 2,2 '~ azobis-iso-butyronitrile. 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 60 ⁰ C. 0.27 sorbitan monolaurate, 1.3 g sorbitan monostearate, 0.17 sorbitan monolaurate and 4.3 g polyoxiethylene sorbitan monostearate are then added in succession with stirring and dissolved. With further gentle stirring, a stream of nitrogen is now introduced into the Solution introduced and their temperature adjusted to 60 ⁰ O »Meanwhile, preparing an aqueous monomer solution in the following manner

2.4 g of AMPS, g of VIMA, 10.0 g of vinylpyrrolidone and 10.6 g of N-vinyl-formamide are dissolved in 9 ml of water in a separate vessel with stirring. This solution is obtained by dropwise addition of 10 wt. % aqueous sodium hydroxide solution adjusted to a pH of 8-10. Then another 0.1 g of ammonium persulfate are added. This aqueous monomer solution is added dropwise with rapid stirring in the organic phase introduced in the poly merisationsgefäß, whereby the aqueous solution is emulsified in the organic phase. The polymerization reaction starts after about 30 minutes and manifests itself by an increase in the temperature. In the course of 15 min, the temperature rises to 80 to 90 ⁰ O. Nach

8 95 9 5-

Decay of the polymerization reaction, the mixture is still a further two hours is heated to 80 ⁰ O. 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 and stirred vigorously for 5 minutes. The copolymer composition thus obtained has an olefin 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 .-% saturated aliphatic hydrocarbons and 16 wt .-% naphthenic hydrocarbons (boiling range of the mixture 192 to 254 ⁰ C), 188.3 parts by weight of a technical Chloroalkanes having a chlorine content of 66.5 % and a density of 1.575 g / cnr ⁵ 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.

By 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 initial organic phase. Nitrogen is allowed to pass through the mixture for 30 minutes and heated

62 112 11 15 * 3.83

these then within 15 _s * azo-bis-isobutyronitrile in a small amount of acetone, the emulsion is heated to 60 for three hours ⁰ O 2 min to a temperature of 60 ° C · After addition of a solution of 0.212 parts by weight _e 2 , Thereafter, the polymerization reaction is completed. This gives a non-clumping polymer dispersion showing no tendency to sedimentation and has ¹ at a shear rate of 29.3 · lake ""'has a viscosity of 710 m Pa lake. " The polymer has a K value of 201,

b) 150 parts by weight of a deodorized Kerosinfraktion boiling range 190 to 240 ⁰ O (Exsol D Esso Chemie, Germany) are placed in an II polymerization and heated to 60 ⁰ O. With gentle stirring, 1.3 parts by weight of sorbitan monolaurate, 6.5 parts by weight of sorbitan monostearate, 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 adjusted to 60 ° C. In a separate vessel in 30 parts by weight of water are dissolved 30 parts by weight of ARCPS, 45 parts by weight of vinylpyrrolidone and 55 parts by weight of N-vinylformamide. This solution is adjusted to a pH of 8 to 10 by the dropwise addition of 10% by weight aqueous sodium hydroxide solution. Thereafter, 0.3 g of ammonium persulfate are added to the resulting aqueous monomer solution is then added dropwise with vigorous stirring in the submitted organic phase and emulsified. After about 30 minutes, the polymerization begins, and the temperature rises spontaneously within 15 min to 80 to 90 ⁰ O, after

8 9 5 9 5 - 41 - ^

15.3 * 83

After the polymerization reaction has subsided, the mixture is heated to 80 ^° C. for a further two hours. This gives a stable polymer Knulsion with a polymer content of 30 wt .-% j 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 minutes. The resulting copolymer composition according to the invention has an olefin content of about 27 % and is a highly active valuable thickener for aqueous acids.

Claims (14)

24 89 59 5 -42 - 62 112 11 15 * 3.83 Invention claim, 1 »Crosslinkable, water-soluble polymer composition, characterized in that it contains A) a polymeric compound having at least two amidocarbonyl groups in the molecule, and B) a compound having in the molecule at least two Forraylamidogruppen and that the components A and B in a weight ratio of 1; 0.2 to 1 s 20 are included 2. Crosslinkable, water-soluble polymer composition according to item 1, characterized in that it contains: A) a water-soluble homo- or oligomer having amidocarbonyl groups in an amount of 10% based on the weight of the * polymer and B) a) a compound of the formula I. O O II Il HC-MH _2n - (OC _n H _2n ) ^ - CH (I), '1 ^l i a 'R ¹ wherein E ¹ and R ^{2 are} hydrogen, alkyl having 1 to 4 C atoms or -CHpOH, η is a number from 1 to 3 and m is one of the numbers O or 1, and / or b) a water-soluble homo- or copolymer, the formylamido groups of the formula : 0 24 89 59 5-43- 15/3/83 in an amount of at least 1 mole per 500 g of the polymer, wherein R ^ is hydrogen, alkyl having 1 to C atoms or -CH ₀ OH. 3. Crosslinkable, water-soluble polymer composition according to item 2, characterized in that its component A to 50 to 100 wt _e -% of units of formula III f
-CH ₂ -C- (II) V? is hydrogen or alkyl of 1 to 3 carbon atoms and Y is formylamido; N-substituted formylamido, wherein the N-substituent is methyl or hydroxymethyl; cyano; Carboxyl or its alkali or ammonium salt; Alkoxycarbonyl having 1 to 6, preferably 1 to 3, carbon atoms; Hydroxy-alko2-ycarbonyl having 1 to 3 carbon atoms; IT-methylolamidocarbonyl of the formula HOCH ₂ NH-CO-, whose methylol group is optionally etherified with alkanols of 1 to 4 carbon atoms; Alkanoylamino of 1 to 4 carbon atoms which may optionally be N-substituted by methylol or alkyl of 1 to 4 carbon atoms; Pyrrolidonyl ~ (1); phenyl; pyridinium; the sulfonic acid group; Sulfoalkylamidocarbonyl of 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 radical of the formula IY 8 9 5 3 b - 44 - 62 112 11 15/3/83 R ⁷ a best of formula V  wherein the radical of the formula IV and V can also be quaternized, z. B, by reaction with CHo-Cl or dimethyl ΓΙ O J sulfate, and wherein R 'and R are the same or different and are alkyl having 1 to 4, preferably 1 or 2 carbon atoms and in which ρ is a number from 1 to 4, there is * 4, crosslinkable, water-soluble polymer composition according to item 2, characterized in that its component B is a copolymer containing from 50 to 100% by weight of units of the formula VI Η? Η wherein R ° is hydrogen, methyl or hydroxymethyl and O to 50 wt .-% of units of formula VII   , ·. ι '· -CH ₂ -C- (VII), 24 8 9 59 5 - 45 - 62 112 11 15/3/83 wherein R ^ is hydrogen or methyl and X is cyano; Carboxyl or its alkali or ammonium salts; Alkoxycarbonyl having 1 to 6, preferably 1 to 3 carbon atoms; Hydroxyalkoxycarbonyl having 1 to 3 carbon atoms; Aiüidocarbonyl; N-Methylölamidocarbonyl the formula HOOH ₂ NH-CO-, the 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 (i); phenyl; pyridinium; the sulfonic acid group; Sulfoalkylamidocarbonyl having 1 to 4 carbon atoms; the phosphonic acid group _s 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 R ^ (VIII), wherein R and R ^{J are the} same or different and are alkyl having 1 to 4, preferably 1 or 2, Kohlenstoffato men, a radical of formula IX 12 R ^u 12 1 * 3 wherein R and R ^{J have} the meanings given above and ρ is a number from 1 to 4, or a radical of formula X. 8 9 59 5 - ⁴⁶ - ^6211211 . ' , 15/3/83 -COM-C JLy-rTS ' (X), wherein R and R ¹ * are the same or different and for alkyl of 1 to 4 x _$ preferably 1 or 2, carbon atoms, or the quaternized moiety of Formulas IX and X and ρ is as defined above. 5 »crosslinkable, water-soluble polymer composition according to item 2, characterized in that the components A and B are contained in a weight ratio of 1 % 0.2 to 1: 20, 6. Crosslinkable, water-soluble polymer composition according to items 1 and 2, characterized in that it contains a water-soluble homo- or copolymer which has amidocarbonyl groups and a Bisacylamidoverbindung of formula I '~ r O O NCVH-. (...) in which R and R 1 represent hydrogen or alkyl having 1 to A-C atoms or -CHpOH · 7 * A process for preparing a crosslinkable, water-soluble polymer composition, characterized in that 4 8 9 b 9 b - 47 - 62112 15/3/83 A) a water-soluble polymeric compound having at least two amidocarbonyl groups in the molecule and B) a water-soluble compound having at least two Forraylaminogruppen in the molecule, in the weight ratio of A: B = 1: 0.2 to 1: 20 mixed. 8. A process for the preparation of a crosslinkable, water-soluble polymer composition according to item 7 »gekennzeichr net characterized in that A) a water-soluble homo- or copolymer having amidocarbonyl groups in an amount of 10% based on the weight of the polymer and B) a) a compound of the formula I. 0 0 Seed (I), where h ' ¹ and K ^{2 are} hydrogen, alkyl having 1 to 4 C atoms or -OHpOH, η is a number from 1 to 3 and m is one of the numbers 0 or 1, and / or b) a water-soluble homo- or copolymer, the formylamido groups of the formula 8959 5 -M- « 15.3 * 83 in an amount of at least 1 mole per 500 g of the polymer, wherein R ° is hydrogen, alkyl having 1 to 4 carbon atoms or -OHpOH, in a weight ratio of A: B = 1: 0.2 to 1 s 20 mixed. A process for the preparation of a crosslinkable, water-soluble polymer composition according to items 7 and 8, characterized in that the component A) used is a polymer which contains from 50 to 100% by weight of units of the formula III r> 5 -CH ₂ -G- R ^ is hydrogen or alkyl of 1 to 3 carbon atoms and Y is formylamido % N-substituted formylamido, wherein the N-substituent is methyl or hydroxymethyl; Cyano} carboxyl or its alkali or ammonium salt; Alkoxycarbonyl having from 1 to 6, preferably from 1 to 3, carbon atoms $ hydroxyalkoxycarbonyl having from 1 to 3 carbon atoms} N-methylolamidocarbonyl of the formula HOCH ₂ NH-CO-, the methylthio group of which is optionally etherified with alkanols of 1 to 4 carbon atoms; Alkanoylamino having 1 to 4 carbon atoms, which may optionally be N-substituted by methylol or alkyl having 1 to 4 carbon atoms \ pyrrolidonyl (I); phenyl; pyridinium; the sulfonic acid group; Sulfoalkylamido-carbonyl of 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 radical of formula IV TIV), R ^{0 is} a radical of the formula V 8 959 5 - * »- ^ ™ ι 15/3/83 -COM-CH ₂ -N (V), \ _S 8 where the radicals of the formula IV and V can also be quaternized, for. B. by reaction with CH ₀ -Cl or dimethyl 7 * x sulfate, and where R 'and R are the same or different and are alkyl having 1 to 4, preferably 1 or 2, carbon atoms and' in which ρ is a number from 1 to 4, 10, A process for preparing a crosslinkable, water-soluble polymer composition according to the items 7 and 8, characterized in that the component A used is a bisacylamido compound of the formula I. (D, wherein R and R are hydrogen, alkyl having 1 to 4 C atoms or -CHoOH, is. 11. A process for preparing a crosslinkable, water-soluble polymer composition according to items 7 and 8, characterized in that the component B used is an oligomer containing from 50 to 100 wt .-% of units of the formula VI 59 5 - έί- 62 112 11 15/3/33 -CH ₂ -CH- wherein R ^ is hydrogen, methyl or hydroxymethyl and 0 to 50 wt - . % Of units of formula VII -CH ₂ -G- (VII), • x. , ' wherein R is hydrogen or methyl and X is cyano; Carboxyl or its alkali or ammonium salts; Alkoxycarbonyl having 1 to 6, preferably 1 to 3 carbon atoms; Hydroxyalkoxycarbonyl of 1 to 3 carbon atoms; amidocarbonyl; N-methylolamidocarbonyl of the formula HOCHpEH-CO-, whose methylol group may optionally be etherated with alkanols having 1 ibis Λ carbon atoms; Alkanoylamino of Λ to 4 carbon atoms, which may be N-substituted by methylol or alkyl of 1 to 4 carbon atoms; Pyrrolidonyl d); phenyl; pyridinium; the sulfonic acid group; Sulfoalkylamidocarbonyl having 1 to 4 carbon atoms; the phosphonic acid group, wherein sulfonic and phosphonic acid groups may also be present in the form of their alkali metal or ammonium salts; a radical of formula VIII -COOCH ₂ CH ₂ -OPR ¹² (VIII), 24 8 959 B-ZF- 62 15/3/83 wherein R and R ^ are the same or different and are alkyl having 1 to 4, preferably 1 or 2, carbon atoms, a radical of formula IX 'R ¹² -σοο-CH -ν (ix), ι? η wherein R and R- * have the meanings given above and ρ is a number from 1 to 4, or a radical of the formula X. .R η ^ _ 14- 1 ^
in which R and R 1 are identical or different and are alkyl having 1 to 4, preferably 1 or 2, ₉ carbon atoms or the quaternized radicals of the formulas IX and X and p has the meaning indicated above,