NO842737L - PHOSPHONIC ACID GROUPS CONTAINING POLYMERISATES, THEIR PROCEDURES AND PREPARATION - Google Patents

Description

The invention relates to new homo- and copolymers, which can also be cross-linked and which have substituents in the basic chains

These substituents give the polymers according to the invention a combination of valuable technical application properties, which open up numerous application possibilities for them.

A special group of polymers according to the invention are homo- and copolymers with formula I

wherein R means hydrogen or methyl,

M 1 and M 2 are the same or different and mean hydrogen or

an equivalent of a cation, and r is an average number greater than or equal to 100.

Another special group of polymers according to the invention

are copolymers that are made up of various known polymer building blocks and are characterized by the fact that their chain molecules contain, among other things, building blocks of formula II

11 2

in which R , M and M have the meaning given above.

The various known polymer building blocks present in the copolymers according to the invention derive in principle from all known copolymerizable compounds with one or two olefinic C-C double bonds.

Such known copolymerizable compounds are in particular the groups of acrylic acid derivatives, methacrylic acid derivatives, vinyl chloride, styrene derivatives, vinyl heterocycles, vinyl sulfonic acids, vinyl phosphonic acid, and allyl compounds as well as dienes such as butadienes and isoprene.

Copolymers according to the invention with different structural groups are especially those which are made up of structural groups with formula II, III and possibly IV and V

in which

11 2

R , M and M have the above meaning and X means the carbonamide group -CONH 2 , a group of formula VI

in which R means hydrogen, methyl, ethyl or hydroxymethyl and R means hydrogen or alkyl of 1 to 4 C atoms, or R 2 and R 3 together mean a polymethylene chain of 3 to 6 C-1 2 atoms, carboxyl or its salt with a cation M or M , alkylcarbonyl (alkyl-CO-) with a total of 2 to 20 C atoms, alkoxycarbonyl with 2 to 19,-preferably 2 to 5 C atoms, hydroxyalkylcarbonyl with 3 to 5 C atoms, N-methylolcarbonamide with formula HOCI^NH-CO-, whose methylol group can optionally be etherified with alkanols with 1 to 18 C atoms, alkoxy with 1 to 20 C atoms, alkanoyloxy with 1 to 20 C atoms, fluorine, cyan, optionally substituted phenyl or benzyl, pyridyl, imidazolyl-(1), sulfonic acid group, sulfoalkylamidocarbonyl with 1 to 4 C atoms in the alkyl residue, the phosphonic acid group, since the sulfonic acid and phosphonic acid group can also exist in the form of their salts with a cation M<1> or M 2, the phosphonic acid ester group of the formulas VII and VIII

wherein R 4 means alkyl with 1 to 4, preferably 1 or 2 C atoms, a residue of formula IX

wherein R and R are the same or different and mean alkyl of 1 to 7, preferably 1 or 2 C atoms, a residue of formula X

in which R<5> and R<6> have the above meaning and p means a number from 1 to 4, a residue of formula XI 1 2 in which M and M have the above meaning, or a residue of formula XII 7 8 in which R r and R are the same or different and. means alkyl with 1 to 4, preferably 1 or 2 C atoms and p means a number from 1 to 4, as well as those to the formulas X and XII corresponding for example to quaternized groups with dimethyl sulfate or methyl chloride, Y means hydrogen or if X means carboxyl, resp. . its salt, Y means hydrogen or carboxyl or its salt, or X and Y together form a divalent substituent of formula XIII

Z means hydrogen or halogen, preferably chlorine, and b can be any time

have the values.0 or 1, and the sum a + b is likewise 0 or 1> and A means a cross-linking bridge link of a known cross-linker or a cross-linking bridge link of formula XIV, XV or XVI

where R g means hydrogen or alkyl with 1 to 24 C atoms, and R<10> means alkyl with 1 to 24 C atoms,

11 12

R and R independently mean hydrogen or alkyl with 1 to 4 C atoms, m means a number from 0 to 6, preferably 0 to 2, and t means a number from 1 to 3, preferably 1. Alkyl residues contained in residues X with more than 3 to 4 C atoms, may be primary, secondary or tertiary straight or branched. Also the hydrocarbon bridges -C P H2„ p- contained in the residues of formula X and XII can be straight or branched.

Of the copolymers according to the invention which, among other things, contain structural groups with formula III, those are preferred where in this structural group a means 0, b means 1 and Z means hydrogen, where this structural group thus corresponds to formula

XVII

wherein R"<*>", X and Y have the above meanings.

In particular, such copolymers are preferred where in a structural group of formula XVII R and Y have the above meaning and X means the carbonamide group -CONI^, a group of formula

WE

in which R 2 means hydrogen, methyl, ethyl and

R 3 means hydrogen or alkyl with 1 to 4 carbon atoms, or

R 2 and R 3 together mean a polymethylene chain with 3 to 6 C atoms,

1 2

carboxyl or its salt with a cation, M or M , alkoxycarbonyl with 2 to 5 C atoms, hydroxyalkylcarbonyl with

3 to 5 C atoms, N-methylolcarbonamide with the formula HOCH2NH-CO-, alkoxy with 1 to 4 C atoms, alkanoyloxy with 1 to 4 C atoms cyan, phenyl, sulfonic acid groups, sulfoalkylamidocarbonyl with 1 to 4 C atoms in the alkyl residue , the phosphonic acid group, the sulphonic acid and phosphonic acid groups can also exist in the form of its salts with a cation M 1 or M 2 , the phosphonic acid ester group of formula VII

wherein R 4 means alkyl of 1 to 4, preferably 1 or 2 C atoms, a residue of formula X in which R and R are the same or different and means alkyl of 1 to 7, preferably 1 or 2 C atoms, and p means a number from 3 to 4, or, a residue of formula XII 7 8 in which R and R are the same or different and means alkyl with 1 to 4, preferably 1 or 2, C atoms, and p means a number from 1 to 4 , as well as those with formulas X and XII corresponding, for example, to groups quaternized with dimethyl sulfate or methyl chloride. Of the cross-linked copolymers according to the invention, those which contain a cross-linking bridge link as a known cross-linker, or a cross-linking bridge link of formula XV or XVI where R g means hydrogen or alkyl with 1 to 4 C atoms, and R<10> means alkyl with 1 to 4 C atoms, R<11> and R<12> independently mean hydrogen or alkyl with 1 to 4 C atoms, and m means a number from 0 to 6, preferably 0 or 2. In those according to invention cross-linking copolymers, the bridge links with formula XVI can all have the same structure. This is the case when a single pure cross-linking substance of formula XVIa is used in the manufacture of the products

However, according to the invention, cross-linked copolymers can also contain several types of structurally different bridge links. Thus, the bridge links with respect to the significance of the residues R 11 and R 12 and/or the building group index m ad can differ from each other, in particular the building group index m in statistical distribution can assume values from 0 to 6.

The frequency of the individual values for m can then each time lie between 0 and 1, as the frequency for the part of a value m is defined with reference to all present values for m.

In practice, according to the invention, cross-linked copolymers containing different cross-linking bridge links with different m-values are particularly advantageous for those with good application technical properties that can be produced significantly more easily and thus more cost-effectively. The cross-linking substances of formula XVIa used for introducing the bridge link into the macromolecules can only be produced in a relatively cumbersome manner as uniform substances. However, it is easy to get mixtures of these substances, e.g. according to one in the European application publication no. 32,663 describing method. Such mixtures are defined in the above-mentioned European application with formula

where R<1> means hydrogen or alkyl with 1 to 4 C atoms and n in practice can have: values from 1 to 8. Such mixtures can be used tel quel without disadvantages for the production of the products according to the invention. Preferably, according to the invention, cross-linked copolymers are then obtained where, within the framework of the statistical distribution of the structural group index m, the frequency of the individual m values is correlated with the frequency of the values for n in a raw product when producing a compound with formula

according to European published application no. 32 663, namely such that the frequency of a value m is equal to the frequency of this value n which in context satisfies n=m+2.

The non-cross-linked and cross-linked copolymers according to the invention made up of different structural groups contain the structural groups that characterize them with formula II usually in a proportion of from 1 to 99% by weight, preferably 2 to 50% by weight, referred to the total polymeric weight .

A further group of preferred copolymers according to the invention are those which contain 1 to 99, especially 2 to 50 parts by weight of structural groups of formula II, 1 to 90, especially 15 to 60 parts by weight of structural groups of formula III, 0 to 80, especially 10 to 40 structural groups with formula IV and 0 to 80, especially 10 to 40 building groups with formula V.

If the copolymer according to the invention is to be predominantly water-soluble or water-swellable, then it must be ensured that at least 70% of the basic chain building blocks have residues X that have a hydrophilic character, and at least have approx. 2% preferably at least 7% of the residues X acidic groups or their salts with the cation M<1> and/or M<2>.

Typical groups which have a hydrophilic character are sulfonic acid residues with carboxyl and the group X which has these acidic residues, carbonamide (-C0-Nr^) and its methylol derivative and the group with formula VI.

Typical groups without a hydrophilic character are e.g. cyan, phenyl or benzyl.

Preferred copolymers according to the invention are also

such where in 10 to 90% by weight, especially in 30 to 70

% by weight of the bridge members of formula III, X is a sulfo- or sulfoalkylamidiocarbonyl group with 1 to 4 Cratoms in the alkyl residue, 10 to 90% by weight, especially in 20 to 60% by weight, X is a group of formula VI and in 5 to 90, especially 10 to 80% by weight, X has one of the other meanings mentioned above.

The nature of cation M 1 and M 2 is based on the desired property of homo- or copolymers according to the invention.

If water solubility of the products is desired or should the

chelatable products are reached, then M and M can in principle be derived from a water-soluble known base whose strength is sufficient to neutralize the sulfone groups or the carboxyl groups of the copolymers according to the invention and which do not affect their hydrophilicity. The selection can thus take place in a simple known manner.

Appropriately, however, M<1> and/or M<2> means an alkaline earth or preferably an alkaline cation, especially a sodium or potassium cation, ammonium or a cation derived from lower aliphatic amines. Lower aliphatic amines from which the cations M 1 and/or M 2 can be derived are primary, secondary or tertiary and optionally have -OH groups substituted alkyl groups with 1 to 4 C atoms. Preferred are those which contain at least one B-hydroxyethyl residue, such as e.g. 3-amino-ethanol, 2-aminor2-methylpropanol-1, B-dimethylamino-ethanol, bis-(3-hydroxy-ethyl)-methylamine, tris-(B-hydroxyethyl±)-amine, diethyl-B-hydroxyethylamine, bis -(O-hydroxyethyl)ethylamine.

However, M 1 and/or M 2 can also be polyvalent metal cations and metal cations with a coordination number greater than 1. Such products according to the invention exist in extremely high viscosity to gel-forming metal chelates of the products according to the invention. Multivalent or high-coordinating metal cations mainly correspond to the metals of the periodic system's 3rd to 8th group, as well as 2 subgroup.

The copolymers according to the invention can contain in the molecule from any of those of the general formulas I to V

and VI defined building groups naturally also contain several different individuals that differ in the meaning of the symbols M<1>, M<2>, X, Y, Z or R<1> to R<12>.

Thus, they can e.g. in the same polymeric molecule contain both 2-acrylamido-2-methylpropanesulfonic acid (3) and also vinylsulfonic acid building blocks, or ring-open planar ring-closed vinylamide groups with formula VI, or also phosphonic acid ester groups with different alkyl residues R 4 of different chain length . Generally, the copolymers according to the invention contain from certain groups with the general formulas I to V, resp. XVII no more than each time 3, preferably no more than each time 2 different building stones.

In the copolymers according to the invention, the individual types of chain building blocks and possibly the bridge links are usually distributed statistically in the macromolecules of the copolymers according to the invention.

Deviations from the purely statistical distribution of the bridge links and also of the monomeric base chains change nothing in terms of the application technical usability of the cross-linked co-polymers. according to the invention. Small modifications from: the purely statistical distribution can already be achieved by the different reactivity of the monomers and crosslinkers.

Should special properties such as e.g. in particular, interfacial activity of the copolymers according to the invention is particularly emphasized, so it can also be appropriate when the distribution of the structural groups in the polymer chain is not statistical,

e.g. larger chain segments of different hydrophilicity are present. The copolymers according to the invention then have a structural core of blocks and graft polymers.

Preferred are copolymers according to the invention with an approximately statistical building group distribution.

When producing the copolymers according to the invention,

to observe the same principles that apply to the production of other known copolymers with acidic groups. Admittedly, as far as is known, copolymers are . with groups of formula

0

-CO-NH-C(CH-) .:.-CH0-p,-OM1

ABOUT^

has not yet been produced, however, the preparation of polymers is analogous. which contains built-in sulfonic acid groups in the macromolecule already described in detail in numerous patents and in the technical literature. Thus, e.g. the synthesis of copolymers of vinyl sulfonic acid with acrylamide and vinyl pyrrolidone published in J. Polymer Sei. 30, 147 (1959).

British patent 11 01 760 describes a method for producing water-soluble copolymer of vinyl sulphonic acid and acrylonitrile, resp. methacrylonitrile, optionally in mixtures with further ethylenic unsaturated compounds. Copolymers of vinyl or alkylsulfonates with acrylic amides and vinyl amides are e.g. discussed in DE-AS 24 44 108. Water-soluble copolymers containing 2-acryl-amido-2-methyl-propanesulfonic acid-(3) are hereinafter abbreviated with AIBS as comonomers are numbers in US patents no. 3,953,342, 3,768 .565, 3,907,927, 3,926,718, as well as in DE-OS 25 02 012 and 25 47 773.

The copolymers according to the invention only contain residues

3 4

with formula VI where R , R together means trimethylene or pentamethylene, can be prepared in the manner known from the state of the art, e.g. according to the information in US patent 3,929,741, when reacting monomers at temperatures from approx. 10 to 120°C, preferably at 40 to 80°C in the presence of suitable polymerization catalysts.

If one wants to prepare copolymers according to the invention that contain groups of formula VI in which R 4 and R 5 do not., together mean tri- or pentamethylene, under analogous conditions, the copolymerization AIBS, styrene or vinylsulfonic acid is carried out with non-ring-closed N-vinylamides of formula Via

then it is necessary to transfer the acidic components before the polymer is ionized by adding bases to salts. The bases used for this purpose are the hydroxides or salts of cations, M 1 and/or M 2 which lead to water-soluble polymers with weak acids, such as e.g. carbonic acid or phosphoric acid, or in the case of amine bases NH^ or the free amines, which were already mentioned in detail above.

The neutralization of the acidic components before polymerization is, however, also possible in the copolymerization of ring-closed compounds Via and usually even advantageous.

Homopolymers or copolymers according to the invention which contain substituents with the formula at the polymer chain

is consequently obtained by analogously to the previously known polymerization methods, compounds of formula Ila are homopolymerized in pure form, or copolymerized in a mixture with each other and/or with other known copolymerizable compounds, whereas if homopolymers or copolymers are produced, they are only obtained using different compounds of formula Ila or copolymerized, is prepared using other known copolymerizable compounds, however, in the absence of ring-opening vinyl amides of formula Via in acidic groups of the monomers used can be neutralized during the polymerization but must not, if, however, the copolymer is prepared in the presence of ring-opening compounds of formula Via , the acidic groups are neutralized before the polymerisation. Appropriately, for the production of each time 100 parts by weight of the copolymers of according to the invention are polymerised in a desired amount, preferably 1 to 99 parts by weight of an acrylic acid resp. Methacrylic acid derivative of formula Ila in which R and R have the above meaning in pure form or a mixture of several compounds of the general formulas with the complementary amount to 100 parts by weight, preferably 9 9 to 1 parts by weight of other known copolymerizable monomers, preferably of comonomers of formula Ila and in particular are those of formula XVIIa in which r\ X, Y, Z, a and b have the above-mentioned meaning, and between a and b the above-mentioned conditions exist, as well as optionally a diene of formula IVa and optionally a known cross-linking substance and/or multiple unsaturated compound of formula Va

in which R1 and A have the above meaning, in that for the case that a comonomer of formula Illa is used in which X means a group of formula VI, in which R 2 and R<3> do not together form a tri- or pentamethylene group, mandatory for that case that no such comonomer is used, is optionally neutralized by adding a base of acidic groups and the copolymerization is initiated in a known manner and carried out at 10 to 120°C.

Examples of compounds of formula IIa which are used in the preparation of copolymers according to the invention: 2-acrylamido-2-methyl-propane-1-phosphonic acid, 2-methacrylamido-2-methyl-propane-1-phosphonic acid and their alkali or ammonium salts . Examples of compounds of formula IIIa are acrylamide, methacrylamide, N-vinylformamide, N-vinyl-N-methyl-formamide, N-vinylacetamide, N-vinyl-methyl-acetamide, N-vinyl-N-ethyl-acetamide, N-vinyl -N-propyl-acetamide, N-vinyl-propionamide, N-vinyl-N-methyl-propionamide, N-vinyl-N-ethyl-propionamide, N-vinyl-butyramide, N-vinyl-N-methyl-butyramide, N -vinylcapronamide, N-vinyl-N-methyl-capronamide, N-vinyl-N-hydroxymethyl-formamide, N-vinyl-N-hydroxymethyl-acetamide, N-vinyl-N-hydroxymethyl-propionamide, N-allylformamide, N-allyl -N-methyl-formamide, N-allyl-acetamide, N-allyl-N-methyl-acet- : amide, N-allyl-N-ethyl-acetamide, N-allyl-N-methyl-propionamide, N-allyl- butyramide, N-allyl-N-hydroxymethyl-acetamide, N-vinylpyrrolactin, N-vinyl-caprolactam, acrylic acid and methacrylic acid slowly their alkali and ammonium alters, vinyl ethyl ketone, vinyl butyl ketone, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, butyl acrylate, isobutyl acrylate, tert-butyl acrylate lat, butyl methacrylate, isobutyl methacrylate, amyl acrylate, amyl methacrylate, hexyl acrylate, hexyl methacrylate, 2- ethyl hexyl acrylate, 2-ethyl hexyl methacrylate, n-octyl acrylate, n-octyl methacrylate, dodecyl acrylate, dodecyl methacrylate, hexadecyl acrylate, hexadecyl methacrylate, 3- hydroxyethyl acrylate, 3-hydroxyethyl methacrylate, 3- or α-hydroxypropyl acrylate, or -methacrylate, hydroxyisopropyl acrylate, N-methylolacrylamide, N-methylol methacrylamide, N-methoxymethylacrylamide, N-methoxymethyl methacrylate, N-butoxymethylacrylamide, N-butoxymethylmethacrylamide, isooctyloxymethylacrylamide , vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, vinyl isopropyl ether, vinyl butyl ether, vinyl isobutyl ether, vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl capronate, vinyl chloride, vinylidene chloride, allyl chloride, acrylonitrile,

methacrylonitrile, styrene, 2-, 3- or 4-methylstyrene, 2-, 3- or 4-ethylstyrene, 2,4-, 2,6-, 3,4- or 3,5-dimethylstyrene, 2-, 3- or 4-chloro- or -fluorostyrene, 4-bromostyrene, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5-dichlorostyrene, 4-ethylhexyl- styrene, 3- -bromomethylstyrene, 1-phenylpropene-1, 2-phenylpropene-1, 2-(2-, 3- or 4-methylphenyl)-propene-1, vinylpyrudin-1, vinylimidazole, vinylsulfonic acid, 2-acrylamido -2-methylpropane-1-sulfone-

acid, vinyl phosphonic acid, vinyl phosphonic acid monomethyl ester, vinyl phosphonic acid monoethyl ester, vinyl tosphonic acid monopropyl ester, vinyl phosphonic acid monoisopropyl ester, vinyl phosphonic acid monobutyl ester, vinyl phosphonic acid monoisobutyl ester, and their alkali or ammonium salts, vinyl phosphonic acid dimethyl ester, vinyl phosphonic acid diethyl ester, vinyl phosphonic acid dipropyl ester, vinyl phosphonic acid dibutyl ester, 2-methacrylamide-2-methylpropane-l-sulfonic acid , dimethylphosphinic acid ester res. diethylphosphinic acid ester of 3-hydroxyethyl acrylate or 3-hydroxyethyl methacrylate, 2-dimethylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate, 2-diethylaminoethyl acrylate, resp. -methacrylate, 4-dimethylaminobutyl acrylate resp. -methacrylate, 4-diethylaminobutyl acrylate or -methacrylate, acrylamidomethylphosphonic acid, methacrylamidomethylphosphonic acid, N-(2-methylaminoethyl)-acrylamide and -methacrylamine, N-(2-diethyl-aminoethyl)-acrylamide and -methacrylamide, N-(3-dimethylaminopropyl)- acrylamide and -methacrylamide, N-(4-dimethylaminobutyl)-acrylamide and -methacrylamide, N-(2-dimethylamiriobutyl)-acrylamide and -methacrylamide, 2-trimethylammoniummethyl acrylate and -methacrylate hydrochloride, 2-triethylammoniummethyl acrylate and -methacrylate -hydrochloride, N-(2-trimethylammoniummethyl)-acrylamide- and -methacrylamide -methodulf at , N-(2-triethylammoniummethyl)-acrylamide- and -methacrylamide hydrobromide, maleic acid resp. maleic anhydride.

Examples for compounds of formula IVa are: Butadiene and isuprene.

In the group of compounds of formula Va there are known crosslinkers, such as divinylbenzene, methylene bisacrylamide, butanediol diacrylate and butanediol dimethacrylate, tetraallyloxetane, trisacryloylperhydrotriazine, triallyl isocyanurate. Compounds from group Va which can introduce a bridge link of formula XIII are, for example, methyldiallylamine or ethyldiallylamine, isooctyldiallylamine.

Compounds of formula Va which can introduce a residue of formula XIV are, for example, dimethyldiallylammonium chloride, diethyldiallylammonium chloride.

Compounds of formula Va which can introduce a bridge link of formula XV are vinylphosphonic acid anhydrides, in particular mixtures of these with each other, and with vinylphosphonic acid esters, such as can be obtained, for example, according to publication of the published European patent application no. 32,663.

In the preparation of cross-linked copolymers according to the invention, it is particularly appropriate not to use pure compounds of formula Ia as cross-linkers, but a raw product of the preparation of the compound of formula XVIII

according to published European application No. 32,663.

In this case, cross-linked copolymers according to the invention are obtained which contain several different bridge links with formula XVI, in that within the framework of the statistical distribution of the structural group index m, the frequency of the individual m values is correlated with the frequency of the value for m in the raw product used so that the frequency of a value m = the frequency of this value m which fulfills the relation n=m+2.

Of the copolymers according to the invention that are not exclusively formed by the copolymerization of compounds of formula IIa, those obtained by the copolymerization of 1 to 99, especially of 2 to 50 parts by weight of compounds of formula IIa, and 99 to 1, especially 98 to 50 parts by weight of comonomers of formula Illa, IVa, and Va.

A further group of preferred copolymers according to the invention is obtained when 1 to 99, especially 2 to 50 parts by weight of monomers of formula IIa, 1 to 90, especially 15 to 60 parts by weight of monomers of formula Illa, 0 to 80, especially 10 to 40 parts by weight of monomers of formula IVa and 0 to 80, especially 0 to 40 parts by weight of monomers of formula Va, are subjected to copolymerization.

Should copolymers according to the invention be produced

with particularly pronounced hydrophilicity, i.e. should they be water-soluble or water-swellable, it must be ensured that at least 70%

of the starting monomers have such residues X that have a hydrophilic character, and at least approx. 2%, preferably at least 7% of the residues X have acidic groups or their salts. Typical groups that have a hydrophilic character are the sulfonic acid residue or carboxyl as well as groups X, which have the acidic residues, carbonamide (-CO-NI^), as well as its methylol derivative, the group with formula VI with lower alkyl residues R 2 and R 3, as well as residues with amino or lower alkylamino or lower alkylammonium groups.

Preferred copolymers according to the invention are also obtained

when in 10 to 90% by weight, especially in 30 to 70% by weight of the comonomers of formula Illa, X is a sulfo- or sulfoalkyl-amidocarbonyl group with up to 4 C atoms in the alkyl residue, in 10 to 90% by weight , especially in 20 to 60% by weight of comonomers of formula Illa, X is a group of formula VI and 5 to 90, especially 10 to 80% by weight of the comonomers of formula Illa, X is one of the other above-mentioned meanings.

The polymers according to the invention can be prepared according to

the usual polymerization methods, such as solution polymerization, substance polymerization, emulsion polymerization, inverse emulsion polymerization, precipitation polymerization, gel polymerization.

Preferably, the polymerization is carried out as gel polymerization, precipitation polymerization or in reverse emulsion.

When the copolymerization is carried out in a water-miscible organic solvent, one works under the conditions for the precipitation polymerization. In this way, the polymer phase appears directly in solid form, and can be isolated by the solvent

distillation, or extraction and drying.

As water-miscible organic solvents are suitable

for carrying out the method according to the invention, water-soluble alkanols, namely those with 1 to 4 C atoms, such as methanol, ethanol, propanol, isopropanol, n-, sec- and iso-butanol, are particularly taken into account, preferably

however, show tert,-butanol. The water content of the hereby

lower alkanols used as solvent should not exceed 6% by weight, otherwise clumping may occur during the polymerization. Preferably, work is carried out at a water content of 0-3% by weight.

The amount of the solvent to be used depends to a certain extent on the type of comonomer used. Usually used per 100 g of total monomer 200 to 1000 g of the solvent.

When carrying out the polymerization in reverse emulsion, the usual monomer solution is emulsified in a known manner in a water-immiscible organic solvent, such as cyclohexane, toluene, xylene, heptane or boiling petrol fractions with the addition of 0.5 to 8% by weight, preferably 1 to 4% by weight known emulsifiers of the water-in-oil type and are polymerized using common radical-forming initiators. The principle of the inverse emulsion polymerization is known from US patent 3,284,393. In this method, water-soluble monomers are polymerized with a mixture thereof hot, into high molecular weight copolymers, by first emulsifying the monomer or aqueous solutions thereof while adding water in - oil emulsifiers in a water-immiscible organic solvent which forms the cohesive phase, and heats this emulsion in the presence of radical initiators. The comonomers used can be emulsified in it as such

water immiscible organic solvent, or they can be used in the form of an aqueous solution containing between 100 and 5% by weight of comonomers, and 0 to 95% by weight of water, the composition of the aqueous solution being a matter of

The solubility of the comonomer in water, and the prescribed polymerization temperature. The ratio between water and monomer phase is variable within wide limits, they are usually around 70:30 to 30:70.

In order to emulsify monomeric phases as water-immiscible organic solvents into a water-in-oil emulsion, 0.1 to 10% by weight, referred to the oil phase, of a water-in-oil emulsifier is added to the mixtures. such emulsifiers are preferably used which have a relatively low HLB value. In principle, any water-insoluble liquid can be used as the oil phase, i.e. in principle any hydrophobic organic solvent. Generally, within the framework of the present invention, hydrocarbons whose boiling point lies in a range from 120 to 350°C are used. These hydrocarbons can be saturated, linear or branched paraffin hydrocarbons, as they predominantly exist in petroleum fractions, as these can also contain the usual amounts of naphthenic hydrocarbons. However, aromatic hydrocarbons can also be used, such as toluene or xylene, as well as mixtures of the above-mentioned hydrocarbons as oil phases. Preferably, a mixture of saturated normal and isoparaffin hydrocarbons is used, which contains up to 20% by weight of naphthenes.

A detailed description of the method can be found, for example, in German patent no. 10 89 173 and in US patents 3 284 393 and 3 624 019.

Cross-linked copolymers with a particularly high degree of polymerization in the basic chains are obtained when the polymerization is carried out in aqueous solutions by the method of so-called gel polymerization. Thereby, 15 to 60% aqueous solutions of the comonomer are polymerized with known suitable catalysts, without mechanical thorough mixing - to utilize the Tromms-dorff-Norrisch effect (Bios Final Rep. 363,22, Makromol. Chem. 1, 169, ( 1947)).

By post-heating the polymerizate gels formed by the gel polymerization in the temperature range from 50 to 130°C, preferably 70 to 100°C, the quality characteristics of the polymerizates can also be improved.

The copolymers according to the invention produced in this way, in the form of aqueous gels, can be dissolved directly in water and used after mechanical crushing with egrated devices. However, they can also be obtained after removal of water by known drying processes in solid form, and only after their use again dissolved in water.

The polymerization reaction is carried out in temperature ranges between -60° and 200°C, preferably -10 and 120°C, as it can be carried out under normal pressure as well as under elevated pressure. Usually, the polymerization is carried out in a protective gas atmosphere, preferably under nitrogen.

To trigger the polymerization, energy-rich electromagnetic rays or the usual chemical polymerization initiators can be used, e.g. organic peroxides such as benzoyl peroxide, butyl hydroperoxide, methyl ethyl ketone peroxide, cumene hydroperoxide, azo compounds such as azo-di-iso-butyronitrile or 2'-azo-bis-(2-amidinopropane)-dihydrochloride

as well as inorganic peroxy compounds such as (NH.J-S^Oor

4Z2 O

K2S2°8e^^er H2°2'possibly 1 combination with reducing agents such as sodium hydrogen sulphite and iron-II-sulphate, or redox systems whose reducing component contains an aliphatic and aromatic sulphonic acid, such as benzenesulphonic acid or toluenesulphonic acid or derivatives of these acids, such as Mannich adducts, of sulfinic acid, aldehydes and amino compounds, as described in German patent 13 01 566. Pr.

100 g of total monomer is usually used 0.03 to 2 g of poly-

the merization initiator.

It is also known to add smaller amounts of so-called moderators to the polymerization mixture, which harmonize the course of the reaction by flattening the reaction rate-time diagram. They thus lead to an improvement in reaction reproducibility, and thus make it possible to produce uniform products with very small quality deviations.

Examples of suitable moderators of this type are nitrilo-tris-propylamide or monoalkylamines, dialkylamines or trialkylamines, such as e.g. dibutylamine. Such moderators can also be used with advantage in the production of copolymers according to the invention. Furthermore, so-called regulators can be added to the polymerisation mixtures, these are compounds which affect the molecular weight of the polymerisations produced. Usable known regulators are e.g. alcohols, methanol, ethanol, propanol, isopropanol, n-butanol, sec.-butanol and alkyl alcohols, alkyl mercaptans such as e.g. dodecyl mercaptan, and tert.-dodecyl mercaptan, isooctylthioglycolate and some halogen compounds such as e.g. carbon tetrachloride, chloroform and methylene chloride.

The copolymers according to the invention can be converted to chelates by multivalent methane cations, especially those from the third to eighth groups of the periodic table and other secondary groups. Even the metals from other main groups still show a clear chelating effect. To this end, the aforementioned copolymers are combined with salts of these metals, as it is usually per g equivalent of the metal cation brings together 1 to 100 g equivalent of the copolymer seed. The reaction is usually carried out in water, or in a water-miscible organic solvent, or in mixtures thereof, preferably, however, in water, the metal cation being used in the form of an aqueous solution of a water-soluble salt of the metal in question. Depending on the type of cation, the chelation reaction takes place in a neutral or alkaline pH range, or in the case of highly active cations (such as titanium or zircon) already in a strongly acidic range. It already proceeds at room temperature at high speed, and in most cases is e.g. at Ten,

Zr, Fe or Al completely terminated after a few seconds

to minutes, in rarer cases after a few hours (such as, for example, with cadmium).

During the chelation reaction, the added amount of multivalent metal ions releases an equivalent amount of the cation standing for X<+>, over multivalent metal ions a cross-linking of the polymer strands occurs.

This chelating ability of the polymers defined above can be used, on the one hand, to firmly bind and mask the relevant cations in order to eliminate them or render them inactive. On the other hand, the polymers' metal chelates themselves have very valuable technical properties. Particularly striking is the extremely high viscosity of already very dilute aqueous solutions of the chelated copolymers.

The substituents with formula

gives the polymers according to the invention a high degree of hydrophilicity. The cross-linked copolymers according to the invention are therefore water-soluble, cross-linked polymers swell-

only with high water absorption. In addition, the polymers according to the invention have a high dispersing effect and anti-corrosive properties.

The combination of the aforementioned valuable properties opens up numerous technical application possibilities for the new products, as surprising technical advantages emerge. Thus, products according to the invention with considerable technical advantage, e.g. used as dye

and textile aid. It appears, e.g. considerable

^advantages when using the copolymers according to the invention with the dyeing of cellulose-containing fiber material according to the fullarding-cold holding method. By adding the copolymers according to the invention, the bath absorption of the cellulose-containing textile materials to be dyed is considerably increased, which leads to a better through-dyeing of even voluminous textile raft structures such as e.g. leotard. This results in colorings of high equality, outstanding product image. When using the new copolymers according to the invention in pigment dyeing, dyeings of high uniformity and color depth are obtained.

The copolymers according to the invention, when added to dispersion dye-containing fularding baths as they are used for dyeing polyester materials, cause an excellent evenness and brilliance of the thus finished dyeings.

The high viscosity of aqueous solutions of the polymers according to the invention and their metal chelates enables their use as thickeners in aqueous paints by printing ink, resp. binder dispersions for the impregnation and coating of textile raft structures as an aid in the petroleum industry such as e.g. as drilling or cementing additives, in polymers for secondary and tertiary transport.

The copolymers according to the invention are particularly valuable for thickening acid fluids which are used for the stimulation of petroleum and natural gas formations according to the per se known method of pressure acidification. In this stimulation method, an aqueous acid is injected at high pressure through the transport bore or through an auxiliary bore into the formation. A high pressure must thereby be built up in the formation that contains the oil, which is sufficient to explode new fractures in the rock. When penetrating into the formed cracks, the acid etches their surface irregularly, whereby upon pressure relief no complete closure of the fractures takes place, but etched channels remain open which enables an improved flow of the crude oil resp. the natural gas. A prerequisite for pressure acidizing to be successful is that the pumped-in acid cannot flow away too quickly through the formation's natural pores and fissures, because then the normal pumping performance is not sufficient to produce the necessary high blasting pressure in the formation.

It is therefore of great advantage to increase the viscosity of the aqueous acid because this prevents too rapid draining of the acid in the rock and, with a given pump performance in the formations, can produce a significantly higher pressure. The copolymers according to the invention and especially their metal chelates are now excellently suited as thickeners for aqueous acid fluids to be used for the pressure acidification process. For this purpose, they are added to aqueous acids in amounts of 0.1 to 5.0%, preferably from 0.2 to 1.5%.

A particularly advantageous design of the pressure acidification method is made possible by the high speed of the chelation reaction between the copolymers according to the invention and chelatable metal cations. The procedure is such that the metal cations in the form of a metal salt solution or a cation-splitting chelate solution are dosed to the solution of non-chelated copolymers in the acid only immediately before the entry of the acid fluid into the borehole.

The amount of metal salt dosed in this method depends on the concentration of the polymer in the acid. One works so that per phosphonic acid equivalent of the copolymer is dosed 1 to 1/100 g equivalent of the metal cation.

The phosphonic acid equivalent P is calculated from the weight % part a of the structural group with formula II in the copolymers according to the lianina

In the case of a copolymer such as contains 10% building groups of formula II, P thus amounts to 2,072, and when using e.g. zircon, whose equivalent weight amounts to<91>/4 = 22.75 is further added for chelating 2072 g of the polymer 22.75 to 0.23 g of zirconium cations corresponding to approx. 59 to 0.59

g zirconium tetrachloride.

Furthermore, the copolymers according to the invention can be used as a dispersing agent as scale inhibitors, as a scale inhibitor as well as a fluffing and filtering aid, further as an aid in paper production and as a corrosion protection agent.

One further area of application consists in the production of water-resistant coatings and polishes on wood, ~rubber, glass, flor, plastic and linoleum surfaces with a combination of suitable aqueous polymer dispersions with the cross-linked copolymers according to the invention by the addition of polyvalent metal ions.

Polymers according to the invention can also be used as cosmetic raw materials and as aids in leather production. Due to the suitability of the phosphonic acid grouping to

form metal chelates, the polymers according to the invention can also be used for binding polyvalent metal cations and crosslinkers, over such cations. The polymers according to the invention are also suitable for addition to cleaning agents, especially for metal surfaces, as well as modifiers for aminoplast resins.

The copolymers according to the invention with molecular weights of less than 50,000 are also suitable as so-called post-tanners, especially for chrome leather. The 2-acrylamido-resp. 2-methacrylamido-2-methylpropane-phosphonic acid with formula and their salts can be prepared by reacting acrylonitrile, resp. methacrylonitrile with 1 mol of water and 2-methylprop-1-en-1-phosphonic acid resp. an isomeric 2-methyl-prop-2-ene-1-phosphonic acid in the presence of strong acids, such as ^SO^, H3P04, HCIO^ or HF according to the known scheme, and under conditions known in and of themselves as the Ritter reaction.

2-methyl-propen-1-yl- or 2-methyl-propen-1-yl-phosphonic acids can be conveniently prepared by hydrolysis of the corresponding phosphonic acid chlorides. Isomeric 2-methyl-propenephosphonic acid dichlorides have already been extensively discussed in the literature (US Patent 2,471,472, L Maier, Phosphorus 5, 223, (1975)).

The salts of phosphonic acid IIa are prepared according to methods common to those skilled in the art, e.g. in reaction with an equivalent amount of a metal hydroxide or carbonate in aqueous or alcoholic solutions.

The following examples show the production of the polymers according to the invention. All percentages refer to quantities by weight.

The abbreviations used in the execution and table examples have the following meaning:

AMPP 2-Acrylatiido-2-methyl-propanephosphonic acid

MAMPP 2-methacrylamido-2-methyl-propanephosphonic acid

AM acrylamide

VIMA N-vinyl-N-methyl-acetamide

VIPY N-vinyl pyrrolidone

AIBS 2-acrylamido-2-methyl-propanesulfonic acid

VA vinyl acetamide

VIFA vinylformamide

VSS-Na sodium vinyl sulfonate

Styrene SS styrene sulfonic acid

VPS vinylphosphonic acid

VPE vinylphosphonic acid methyl ester

AS acrylic acid

MAS methacrylic acid

VAc vinyl acetate

ACN acrylonitrile

VPA viny<l>f osphonic anhydride

DADMAC diallyl-dimethyl-ammonium chloride

MASA maleic anhydride

The numerical values of the composition given in the tables are % by weight.

Example 1

(emulsion polymerization)

7.2 g "Arkopal" N 100 (non-ionic emulsifier based on an oxytylated phenol derivative) and 19.4 g "Span" (non-ionic emulsifier based on a sugar alcohol stearate) are dissolved in

"Isopar" M (technical mixture of isoparaffin with a boiling point of

about. 200 to 240°C) and the resulting solution is filled into a 1-liter reaction vessel equipped with a stirring

works, thermometer and a nitrogen inlet. Then forward-

a monomer solution is prepared by dissolving 97.2 g of acrylamide, 10.2 g of AMPP and 1.1 g of vinylphosphonic acid monomethyl ester (VPE) in 105 ml of water. The pH of the monomer solution

value is set to 8.5 with ammonia (25%). With rapid stirring, the aqueous monomer solution is added to the organic phase. The reaction vessel is evacuated and then filled with nitrogen. Now the solution of 0.0275 g of ammonium persulfate in 3 ml of water is added to the mixture, thus starting the polymerisation process. The reaction lasts for 1^ hours, the reaction temperature is kept between 30 and 40°C. A stable emulsion is produced which, using commercially available surface-active agents, is inverted in a manner known per se in water. The resulting polymer solution has a co value of 128.9.

Example 2

(emulsion polymerization)

7.2 g "Arkopal" N 100 (non-ionic emulsifiers based on an oxyethylated phenol derivative and 19.4 g "Span" (non-ionic emulsifier based on a sugar alcohol stearate) are dissolved in "Isopar" M (technical mixture of isoparaffin with a boiling point of about 200 to 240°C) and the resulting solution is filled into a 1-liter reaction vessel equipped with a pipework, thermometer, and a nitrogen inlet. A monomer solution is then prepared by dissolving 87.5 g of acrylamide and 21, 8 g of AMPP in 110 ml of water. The pH value of the monomer solution is adjusted to 8.5 with ammonia (25 %). With rapid stirring, the aqueous monomer solution is added to the organic phase. The reaction derivative is evacuated and then filled with nitrogen. A solution of 0 .0275 g of ammonium persulphate in 3 ml of water to the mixture, and thus the polymerization is started. The reaction lasts \\ hour, the reaction temperature is kept at 130°C. A stable emulsion appeared which under

application of commercially available surfactants in a manner known per se is inverted in water.

The resulting polymer solution has a K value of 198.5.

Analogous to this method, it is also possible to prepare the copolymers in the following tables I and II.

Example 27

(gel polymerization))

In a polymerization flask of 1 liter capacity equipped with a flat-ground lid, pipework, thermometer and gas introduction tube, is prepared by dissolving 60 g of acrylamide, 30 g of AMPP and 10 g of VPE, 250 g of water and a monomer solution. The pH value is set to 8.5 with ammonia (25% strength). While stirring and introducing nitrogen, 1 g of an aqueous 10% dibutylamine-HCl solution and 0.1 g of ammonium persulfate are now added.

It is allowed to continue stirring for 3 minutes at an elevated speed while nitrogen is being introduced. The nitrogen introduction is terminated, introduction pipes and tubes are removed. After an induction time of 30 minutes, polymerization starts, and the temperature increases from 20°C to 48°C, and the solution turns into a form-stable gel. The K-value amounts to 203.9.

Example 28

(precipitation polymerization)

In a polymerization flask of 1 liter capacity equipped with piping, reflux cooler, thermometer, dropping funnel and gas introduction tube, dissolve 440 ml of tert.-butanol, 49.7 g of acrylamide, 7.1 g of AIBS, 10.7 g of AMPP and 3, 6 g of methacrylic acid (MAS). While stirring and introducing nitrogen, the monomer solution is heated to 50°C and 1 g of acoisobutyronitrile dissolved in 5 ml of DMF is added dropwise, after an induction time of 30 minutes the polymerization starts, the reaction temperature increases to 68°C and the polymer precipitates out. It is further reheated for 2 hours at 80°C. The copolymer can be isolated by suction and drying. However, the solvent can also be distilled off directly at reduced pressure. You get the polymeric form of a white light powder, dissolves well in water and has a K-value of 195.0.

Example 29

(solution polymerization)

In a polymerization flask of 1 liter capacity equipped with a flat-ground lid, piping, thermometer and gas introduction tube, dissolve 20 g of AIBS and 50 g of AMPP in 200 g of water and neutralize with ammonia (25%). 10 g of acrylamide and 10 g of VPE are then added. The pH value is set to 8.5 and 10 g of N-vinyl-N-methyl-acetamide are added. While stirring and introducing nitrogen, the reaction mixture is heated to 60°C. Now you also add 1 g of an aqueous 10% dibutylamine-HCl solution and 0.1 g of ammonium persulphate. The reaction lasts for approx. 30 minutes as the temperature increases to 70°C. The reaction mixture becomes viscous. It is reheated with stirring for a further 2 hours at 80°C. You get a clear, highly viscous solution. The K-value amounts to 136.1.

Analogously, it is also possible, for example, to prepare the copolymers in the following table III

Example 48

(precipitation polymerization)

In a polymerization flask of 1 liter capacity equipped with piping, reflux condenser, thermometer, dropping funnel, gas introduction tube dissolve in 44 0 ml tert.-butanol, 15 g deionized water, 46.2 g AM, 21.3 g AS, 3.6 g AMPP and 1 g of tetraallyloxetane. While stirring and introducing nitrogen, the monomer solution is heated to 50°C and 1 g of azoisobutyronitrile is added. After an induction time of approx. 30 minutes, the polymerization starts, the temperature increases to 77°C, and the polymerization precipitates out. It is still reheated for 2 hours,

at 80°C. The polymer can be isolated by suction and drying, however the solvent can also be distilled off directly under reduced pressure. You get the polymeric form of a white/light powder. Of the product prepared with destilled water of a 0.2% by weight solution, and adjusted with a base MOH at pH 8.0. The solution has a viscosity of 6140

mPa s (Brookfield LVT, Spindle, 3.60 rpm, 20°C).

Analogously, it is possible to prepare the polymers in table IV. The polymers in examples 50 and 51 were saponified with 30%

Moles of NaOH.

Example 58

a) A natural gas well in West Texas is selected for pressure acidizing. The well has a production interval between a depth of 2,940 to 2,970 metres. The sun temperature in this interval amounts to 76 to 77°C. The permeability of the formation averages 0.1 md (millidarcy). The borehole's spontaneous productivity before treatment amounts to approx. 89 m 3 gas and approx. 500 liters of condensate per day.

The pressurized acidizing fluid to be used is produced by mixing 150,000 liters of 15% hydrochloric acid containing 300 liters (0.2% by weight) of a commercial corrosion inhibitor with 1700 kg of a water-in-oil emulsion of a copolymer of 33, 5 wt% acrylamide, 47.8 wt% AIBS, 9.2 wt% AMPP and 9.6 wt% VIPY which has a polymer content of 30 wt%.

In addition, 300 liters (0.2% by weight) of a non-ionic fluorine-containing cross-linking agent are added to the mixture. The mixture is stored for 1 hour and is then a homogeneous liquid with a viscosity of approx.

32 mPa.s measured at a Scher drop of 511 sec in a Fann-35 viscometer. This treatment fluid is pumped into the above-mentioned deep bore, while at the same time 150 liters of treatment fluid are dosed with 300 ml of a 10% by weight zircon tetrachloride solution in 15% hydrochloric acid. The injection speed of the treatment fluid amounts to approx. 2,000 liters per minute at a surface treatment pressure of 420 bar. After approx. 75 to 80 minutes, the combined treatment fluid is pressed into the borehole, which is closed for 6 hours to give the acid the opportunity to react with the rock. After this time, the pressure is relieved at the top of the bore and the transport is established. Measuring the transport rate increases the productivity of the drilling

3

to 600 m gas per day.

b) The copolymer used in section a) was prepared as follows: 43.2 kg "Arkopal" N 100 (non-ionic emulsifier based on an oxytylated phenol derivative) and 116.4 kg "Span 80" (non-ionic emulsifier based on a sugar alcohol stearate) is dissolved in 600 kg of "Isopar" M (technical mixture of isoparaffin with a boiling point of approx. 200-240°C). and the resulting solution is filled into a one liter reaction vessel which is equipped with piping, a thermometer, and a nitrogen inlet. A monomer solution is then prepared by dissolving 227 kg of acrylamide, 324 kg of AIBS, 62.1 kg of AMPP and 65 kg of VIPY in 630 liters of water.

The monomer solution's pH value is adjusted to 8.5 with ammonia (25%). With rapid stirring, an aqueous monomer solution is added to the organic phase. The reaction vessel is evacuated and then filled with nitrogen. Now the solution of 165 g of ammonium persulphate in 18 liters of water is added to the mixture,

and thus the polymerization is started. The reaction lasts for 1% hour. The reaction temperature is kept between 30 and 40°C. A stable emulsion is produced, which can be inverted in water using commercially available surfactants in a manner known per se. The resulting polymer solution has . a K value of 14 0.1.

The following technical application examples show the viscosity ratio and the chelation of the solution of the copolymers according to the invention.

The experiments make it possible to determine the viscosity values relevant for practical application.

Example 59

150 ml of 15% hydrochloric acid are placed in a beaker and, with stirring, 1.7 g of a water-in-oil emulsion of a copolymer of 35% acrylamide, 50% AIBS, 5% AMPP is dissolved at 20°C and 10% VIPY which has a polymer content of 30%. It is stirred for a further 10 minutes at 20°C and a homogeneous 0.34% solution of the copolymer is obtained which has a viscosity of 32 iriPa.s measured in a rotational viscometer at a shear rate of 515 sec.<-1>.

0.3 ml of

a 10% zirconium tetrachloride solution in 15% hydrochloric acid, corresponding to an added amount of 7.7 -10% zirconium, referred to

to the overall acidic polymer solution or 2.3% zirconium, referred to the amount of copolymer used.

With the addition of zircon, a stopwatch is started, and the time that elapses until the formation of a viscoelastic gel structure is measured. In the present case, this is 5 seconds.

In an analogous way, the copolymers according to the invention listed in the following table can be examined, obtaining the indicated values.

Example 77

A copolymer of 50 parts by weight of 2-acrylamido-2-methylpropane-phosphonic acid and 50 parts by weight of acrylic acid was prepared by radical-initiated solution polymerization in a water/isopropanol mixture at 85°C.

The resulting copolymer with a K-value of 23 (according to Fikentscher) was tested according to NACE standard TM-03-74 (NACE - National Association of Corrosion Engineers 1440 South Creek, Houston Texas) as a scale inhibitor to inhibit calcium sulfate and calcium carbonate -precipitation in aqueous solutions.

By adding 10 ppm of polymer according to the test device, a good commercial scale inhibitor was examined on the basis of a polyacrylate against a copolymer according to the above-mentioned composition of the invention.

With the copolymers according to the invention of a different composition, the following Ca-sulphate and Ca-carbonate retention values were obtained.

Example 78

In a polymerization flask of 1 liter capacity equipped with a ground lid, pipework, thermometer and gas introduction tube, a monomer solution is prepared by dissolving 80 g of acrylic acid, 10 g of AMPP, 10 g of vinylphosphonic acid monomethyl ester and 0.1 g of methylene bisacrylamide in 250 g of water. The K-value is set with ammonia (25%) to 8.5. While stirring and introducing nitrogen, 1 g of an aqueous 10% dibutylamine-HCl solution of 0.1 g of ammonium persulfate must be added. It is allowed to stir while introducing nitrogen for a further 3 minutes at too high a speed. The nitrogen introduction ends. The introduction pipe and piping are taken up. After an induction time of 30 minutes, polymerization starts as the temperature increases from 20°C to 78°C and the solution turns into a form-stable gel.

After crushing the gel in an extruder, it is dried at 90°C and then ground. You get a powdered polymer that stands out for its extreme water-binding capacity during swelling. 1 g of the polymers is stirred into it for approx. 1 liter of water, and filter off the swollen gel material after 2 hours over a sieve and determine the amount of water taken up by weighing. In the case of the polymer produced according to the above-mentioned examples, the weight of the gel mass was 422 g.

When a mixture of 20 g of acrylic acid and 60 g of AIBS is used instead of acrylic acid, the weight of the gel mass amounts to 489 g.

Example 79

7.2 g "Arkopal N 100" (non-ionic emulsifier based on an oxyethylated phenol derivative) and 19.4 g "Span 80" (non-ionic emulsifier based on a sugar-alcohol stearate) are dissolved in "Isopar M" (technical mixture of isoparaffin with a boiling point of approximately 200-240°C) and the resulting solution is filled into a 1 liter reaction vessel which. is equipped with a stirrer, thermometer and a nitrogen inlet. A monomer solution is then prepared by dissolving 67.2 g of acrylamide, 30 g of acrylic acid, 10.2 g of AMPP and 1.1 g of vinylphosphonic acid monomethyl ester (VPE) and 0.15 g of methylenebisacrylamide in 105 ml of water. The monomer solution's pH value is adjusted to 8.5 with ammonia (25%). With rapid stirring, the aqueous monomer solution is added to the organic phase. The reaction vessel is evacuated and filled there-

after with nitrogen. Now the solution of 0.0275 g of ammonium persulphate and 3 ml of water is added to the mixture, and thus the polymerization starts. The reaction lasts for 1^ hours, the reaction temperature is kept between 30 and 40°C. A stable emulsion is produced which can be inverted using a commercially available surface-active agent in a manner known per se in water, resulting in highly viscous masses which are suitable for the production of printing pastes. Viscosity: 0.2% in water 25°C, 22 00 mPa.s.

On a cotton fabric, in flat film printing, a printing ink that follows the production process is applied in the usual way. 45 parts by weight of the 20% dispersion (produced by dispersing 60 parts by weight of the polymer dispersion formed according to the above-mentioned manufacturing regulations in 47 parts by weight of test gasoline with a boiling range of 140-200°C and 32.2 parts by weight of test gasoline with a boiling range of 13 0-175°C while adding 0.4 parts by weight of an addition product of 9 mol of ethylene oxide to 1 mol of nonylphenol and 0.4 parts by weight of a propylene oxide-ethylene oxide block polymer of PrP-EO molar ratio 90:10) is stirred on high speed stirrer in 785 parts by weight of water. Then, 120 parts by weight of a commercial approx. 40% copolymer dispersion on a polyacrylate basis, 15 parts by weight of a mixed resin on a melamine urea-formaldehyde basis, 25 parts by weight of a 37% aqueous dispersion of the pigment with CI. No. 12,485 and 10 parts by weight of a 33.3% aqueous solution of an inorganic acid-splitting compound.

After drying and fixing for 5 minutes at 150°C on a hot air machine, the red pigment print has good friction and scrub resistance, as well as solvent resistance - and is particularly distinguished by a soft grip.

Example 80

Dissolve 1,200 g of water, 20 g of AIBS and 10 g of AMPP in a polymerization flask of 1 liter capacity, equipped with a flat-ground lid, stirrer, thermometer and gas introduction tube and neutralize with ammonia (25%). 60 g of acrylamide are then added. The pH value is set to 8.5, and 10 g of N-vinyl-N-methyl-acetamide are added. While stirring and introducing nitrogen, the reaction mixture is heated to 60°C. 1 g of an aqueous 10% dibutylamide HCl solution and 0.1 g of ammonium persulphate are also added. The reaction lasts approx. 30 minutes as the temperature rises to 70°C. The reaction mixture became viscous. It is reheated with stirring for a further 2 hours at 80°C. You get a clear, highly viscous solution.

The K-value amounts to 196.1.

Untreated cotton tricot (Interlock) is fullarded on a special fullard for tricot knitting at a roller pressure of 1 bar/m 2 and at 22°C in an aqueous bath which per liter contains 21 g of reactive dyes Reactiv Orange 16 (CI. no. 17 757) , 40 g of the reactive dye with formula

8 g of a commercially available anionic wetting agent and 30 g of the mixed polymer (fullerating aid) which was formed according to the above-mentioned manufacturing regulations.

The necessary alkali is dosed with a dosing pump in a quantity of 130 m 3 of a (commercially available) soda ash solution with a specific gravity of 1.345 (=37°Be), in the ratio Na20:SiO2 which is 1:3.3, and 34 cm caustic soda 32.5% by weight per liter ful arding bath. The bathroom uptake achieved in this way amounts to 171%.

After the fularded product has been undocked, covered with foil, with low tension and smooth edges, "the product is allowed to rest at long-"

as rotation for 15 hours.

You get a completely even, full red colouring.

However, if the dyeing as discussed above is carried out excluding the mixed polymer, then after fullarding and squeezing, a bath uptake of only 104% is achieved at the same squeezing pressure. The coloring achieved in this way differs in color depth from that formed during the addition of the mixed polymer with one more, the different bath absorption proportional value, and is not equal (edge marking).

The AMPP used in the above-mentioned embodiments can be prepared according to the following regulation: 1041 g (5 mol) PCI,- are suspended in 2.5 1 anhydrous toluene and at 10-15°C 281 g (5 mol) isobutene are introduced. After-stirring for 30 minutes at 15°C, then introducing at 10-

15°C S02 until a clear solution is formed.

The toluene and SOC12 are distilled off. When splitting off hydrogen chloride, the residue is heated for 8 hours while adding 3 g of triphenylphosphine at 270 mbar at 180°C.

Distillation gives 550 g of an isomeric mixture of 2-methylpropene-phosphonic acid dichloride. KPi6mbar=90~93°c* Yield 64%.

173 g (1 mol) of 2-methylpropene-phosphonic acid dichloride are dropped at 20°C into 200 ml of water. Then evaporated in vacuum and de-

is watered azeotropically with toluene in water. The toluene is distilled off

1 vacuum and the free phosphonic acid is mixed with 53.5 g (1 mol) of acrylonitrile. Then, at 25 - 30°C, 104 g (1 mol) of 96% sulfuric acid are added dropwise. After 22 hours, the reaction mixture is mixed with 100 g of ice, the sulfuric acid is neutralized with 80 g of NaOH in 200 ml of water. Evaporate in vacuo to dryness, extract the salt residue with isobutanol, evaporate and precipitate the phosphonium

acid I with acetone.

Yield 87 g (42% of theoretical),

sm.p. 148-150°C.

The MAMPPs used in the examples can be produced in an analogous way.

Claims (14)

1. Homo- and copolymers of formula I in which R means hydrogen or methyl, M 1 and M 2 are the same or different and mean hydrogen, or an equivalent of a cation, and r is an average number ) that is greater than or equal to 100. 2. The copolymer characterized in that it contains structural groups of formula II in the polymers 112 in which R , M and M have the meaning specified in claim 1. 3. Copolymers according to claim 2, characterized in that they consist of building groups with formula II, III and possibly IV and V in that 11 2 R, M and M have the meaning stated in claim 1, and X means the carbonamide group -CONI^, a group of formula VI in which R^ means hydrogen, methyl, ethyl or hydroxymethyl and R 3 means hydrogen or alkyl of 1 to 4 C atoms, or R 2 and R 3 together mean a polymethylene chain of 3 to 6 C atoms, carboxyl or its salt with a cation M"*" or M <2> , alkylcarbonyl (alkyl-CO-) with a total of 2 to 2 0 C atoms, alkoxycarbonyl with 2 to 19, preferably 2 to 5 C atoms, hydroxyalkylcarbonyl with 3 to 5 C- atoms, N-methylolcarbonamide with the formula HOCf^NH-CO-, whose methylol group can optionally be etherified with alkanols with 1 to 18 C atoms, alkoxy with 1 to 2 0 C atoms, alkanoyloxy with 1 to 2 0 C- atoms, chlorine, cyan, optionally substituted phenyl or benzyl, pyridyl, imidazolyl-(1), the sulfonic acid group, sulfoalkylamidocarbonyl with 1 to 4 C atoms in the alkyl residue, the phosphonic acid group, the sulfonic acid and phosphonic acid groups can also be present in the form of their salts with a cation 2 M or M , phosphonic acid ester groups of formulas VII and VIII wherein R 4 means alkyl with 1 to 4, preferably 1 or 2 C atoms, a residue of formula IX wherein R and R are the same or different and mean alkyl of 1 to 7, preferably 1 or 2 C atoms, a residue of formula X wherein R^ and R^ have the above meaning and p means a number from 1 to 4, a residue of formula XI wherein M 1 and M 2 have the above meaning, or a residue of formula XII 7 ' 8 in which R and R are the same or different, and means alkyl with 1 to 4, preferably 1 or 2 C atoms, and p means a number from 1 to 4, as well as those in the formulas X and XII corresponding, for example, to groups quaternized with dimethyl sulfate or methyl chloride , Y means hydrogen or if X means carboxyl, its number means, means hydrogen or carboxyl resp. its salt, or X and Y together form a 2-valent substituent of formula XIII Z means hydrogen or halogen, a and b can each have the values 0 or 1, and the sum a + b is likewise 0 or 1, and A is a cross-linking bridge link of a known cross-linker or a cross-linking bridge link of formula XIV, XV or XVI where R g means hydrogen or alkyl with 1 to 24 C atoms, and R <10> means alkyl with 1 to 24 C atoms, R<11> and R12 independently mean hydrogen or alkyl with 1 to 4 C atoms, m means a number from 0 to 6, preferably 0 to 2, and t means a number from 1 to 3, preferably 1. 4. Copolymers according to claim 3, characterized in that in building groups with formula III means a 0 and b 1, Z stands for hydrogen, and thus corresponds to formula XVII wherein R"<*>" and Y have the meaning stated in claim 3, and X means the carbonamide group -CONH2, a group of formula VI wherein R 2 means hydrogen, methyl, ethyl, and R 3 means hydrogen or alkyl with 1 to 4 carbon atoms, or 2 3 R and R together mean a polymethylene chain of 3 to 6 C atoms, carboxyl or its salt with a cation M^" or M 2 , alkyloxycarbonyl of 2 to 5 C atoms, hydroxyalkylcarbonyl of 3 to 5 C atoms, N-methylolcarbonamide with the formula HOCH2 NH-CO-, alkoxy with 1 to 4 C atoms, alkanoyloxy with 1 to 4 C atoms, cyan, phenyl, the sulfonic acid group, sulfaalkylamidocarbonyl with 1 to 4 C atoms in the alkyl residue, the phosphonic acid group, the sulfonic acid and phosphonic acid groups can also exist in the form of their salts with a cation M 1 or M 2, the phosphonic acid ester group of formula VII, wherein R 4 means alkyl with 1 to 4, preferably 1 or 2 C atoms, a residue of formula X wherein R and R are the same or different and mean alkyl of 1 to 7, preferably 1 or 2 C atoms, and p means a number of 1 to 4, or a residue of formula XII in which R 7 and R 8 are the same or different and mean alkyl with 1 to 4, preferably 1 or 2 C atoms, and p means a number from 1 to 4, as well as those in formulas X and XII corresponding, for example, with dimethyl sulfate or methyl chloride quaternized groups, Y means hydrogen or if X means carboxyl or its salt, means hydrogen or carboxyl resp. its salt, or X and Y together form a divalent substituent of formula XIII and A means a cross-linking bridge link of a cross-linker or a cross-linking agent of formula XV or XVI where R g means hydrogen or alkyl with 1 to 24 C atoms and R <10> means alkyl with 1 to 24 C atoms, R <11> and R<12> independently means hydrogen or alkyl with 1 to 4 carbon atoms and m means a number from 0 to 6, preferably 0 to 2. 5. Copolymers according to claims 2 to 4, characterized in that the polymerization chains contain building groups with formula II in a proportion of 1 to 99% by weight. 6. Method for producing homo- and copolymers with formula I according to claim 1, characterized in that a compound or a mixture of different compounds with the general formula Ila gay or is copolymerized in a manner known per se. 7. Process for the production of copolymers according to claim 2, which with the polymer chain has a substituent of the formula in which M ] and M 2 have the meaning stated in claim 1, characterized in that compounds of formula IIa are polymerized in a manner known per se in pure form or in admixture with each other with other known copolymerizable compounds, if the copolymer. are prepared in the absence of ring-opened vinyl amides of formula Via can in acidic groups of the monomers used be neutralized with the polymerization but must not, if, however, the copolymer is prepared in the presence of ring-opening compounds of formula Via, the acidic groups are neutralized before the polymerization. 8. Process according to claim 7 for the preparation of the copolymer which has substituents of the formula at the polymer chains in which M 1 and M 2 have the meaning mentioned in claim 1, characterized in that for the production of each time 100 parts by weight of the copolymers according to the invention are polymerized in pure form or in a mixture of several compounds with this general formula with the complementary to 100 parts by weight quantity of other known copolymerizable monomers of formula Illa in which R <1> , X, Y, Z, a and b have the above meaning, and between a and b is the above ratio, as well as possibly a diene of formula IVa and optionally a known cross-linking substance and/or polyunsaturated compounds of formula Va in which r! pg R has the above meaning, in that for the case that a comonomer of formula Illa is used * ~wherein~^X is a group with formula VI, in which R"1 and RJ do not together form a tri- or pentamethylene group mandatory for the case that such comonomers are not used, optionally neutralized by adding a base to acidic groups, and the copolymerization is initiated in a known manner and carried out at 10 to 120°C. 9. Method according to claim 8, characterized in that compounds of formula IIa are reacted with the other known copolymerizable monomers in a weight ratio of 1:99 to 99:1. 10. Method according to claim 8, characterized in that a compound of formula Illa is used in which a = 0 and b = 1, which thus corresponds to formula XVIIa in which R <1> , X and Y have the meaning specified in claim 3. 11. Use of copolymers according to claim 2, and their metal chelates as thickeners, for tertiary transport fluids. 12. Use of homo- and copolymers according to claim 1 or 2 as scale inhibitors. 13. Use of homo- and copolymers according to claim 1 or 2 as pressure thickeners and fularding aids in textile dyeing. 14. Use of cross-linked or chelated homo- and copolymers according to claim 1 or 2, as absorbent for aqueous liquids. -