WO2004013207A1

WO2004013207A1 - Polymethylene amine, method for the production and use thereof

Info

Publication number: WO2004013207A1
Application number: PCT/EP2003/007682
Authority: WO
Inventors: Rainer Dyllick-Brenzinger; Ulrich Steuerle; Volker Braig
Original assignee: Basf Aktiengesellschaft
Priority date: 2002-07-25
Filing date: 2003-07-16
Publication date: 2004-02-12
Also published as: DE10233930A1; AU2003250069A1

Abstract

The invention relates to polymethylene amine, containing recurrent units of general formula (I). Polymethylene amine is produced from imidazole or the derivatives thereof, e.g. by hydrolyis of poly(1,3-diacyl-4-imidazoline-2-thione), containing recurrent units of general formula (III) wherein R is selected from a group containing hydrogen, linear and branched C1-C8-alkyl groups, linear and branched C1-C40-alkoxy groups, and phenyl, preferably hydrogen and linear and branched C1-C3-alkyl groups, R is particularly a methyl group; X is O or S, preferably O. Polymethylene amine can also be produced by hydrolisis of poly(1,2-diaminoethene) derivatives in suitable conditions. Polymethylene amine has a very high charge density and is expecially suitable for use as a retention agent / fixing agent in the production of paper.

Description

Polymethylene amine, process for its preparation and its use

The present invention relates to polymethylene amine, a process for its production and its use.

Cationic polymers with high charge densities are mainly used in the paper industry. They often serve as fixatives, drainage agents, flocculants and / or retention agents and are added to the paper pulp before or during its manufacture. As a retention agent, they reduce the entrainment of the fibers and fillers that form the paper pulp (retention) when the solids are separated from the water. The yield of the solid / liquid separation is thus improved by these retention agents. Wood pulp, thermo-mechanical material, chemo-thermo-mechanical material, pressure sanding as well as sulphite and sulphate pulp in short and long-fiber form, if necessary also, are basically used as raw material components for the production of paper

Pulp and wood pulp and, increasingly, waste paper are used. Suitable fillers are, for example, clay, kaolin, precipitated and natural, ground chalk, talc, titanium dioxide, calcium sulfate, barium sulfate, aluminum oxide and satin white, as well as mixtures of the fillers mentioned.

Typical cationic polymers that are used as retention or fixing agents are, for example, cationic polyacrylamide (cPAM) polyethyleneimine (PEI), poly-diallyldimethylammonium chloride (poly-DADMAC) and polyvinylamine (PVAm). The theoretical charge density of PEI and PVAm (complete protonation) is 23.2 meq / g.

Polymers containing vinylamine units are known, cf. US-A-4,421,602, US-A-5, 334, 287, EP-A-0 216 387, US-A-5, 981, 689, WO-A-00/63295 and US-A-6, 121, 409. They are prepared by hydrolysis of open-chain polymers containing N-vinylcarboxamide units. These polymers are e.g. B. available by polymerizing N-vinylformamide, N-vinyl-N-methylformamide, N-vinyl acetamide, N-vinyl-N-methylacetamide, N-vinyl-N-ethyl acetamide and N-vinyl propionamide. The monomers mentioned can be polymerized either alone or together with other monomers.

The monoethylenically unsaturated monomers which are copolymerized with the N-vinylcarboxamides are vinyl esters of saturated carboxylic acids of 1 to 6 carbon atoms, vinyl ethers such as C ~ to C ₆ -alkyl vinyl ether and esters, amides and nitriles of ethylenically unsaturated C ₃ - to C _ß- carboxylic acids.

Other suitable carboxylic acid esters of unsaturated carboxylic acids are derived from glycols or polyalkylene glycols, in each of which only one OH group is esterified, and acrylic acid monoesters of polyalkylene glycols with a molecular weight of 500 to 10,000 are also suitable. Other suitable comonomers are esters of ethylenically unsaturated carboxylic acids with amino alcohols. The basic acrylates can be used in the form of the free bases, the salts with mineral acids such as hydrochloric acid, sulfuric acid or nitric acid, the salts with organic acids such as formic acid, acetic acid, propionic acid or the sulfonic acids or in quaternized form. Other suitable comonomers are amides of ethylenically unsaturated carboxylic acids, such as acrylamide, methacrylamide and N-alkylmono- and diamides of monoethylenically unsaturated carboxylic acids with alkyl radicals of 1 to 6 carbon atoms, and basic (meth) acrylamides.

Also suitable as comonomers are dimethylaminoalkyl (meth) acrylate CH ₃ Cl, N-vinylpyrrolidone, N-vinylcaprolactam, acrylonitrile, methacrylonitrile, N-vinylimidazole and substituted N-vinylimidazoles.

Also suitable are polyethyleneimines which can be prepared, for example, by polymerizing ethyleneimine in aqueous solution in the presence of acid-releasing compounds, acids or Lewis acids as a catalyst. Polyethyleneimines have molar masses of up to 50,000; after further crosslinking measures, molasses of up to 2 million, preferably from 200 to 1,000,000, can be achieved. Polyethyleneimines with molecular weights of> 1,000,000, which are obtainable by ultrafiltration, are particularly preferably used. The polyethyleneimines can optionally be modified, e.g. B. alkoxylated, alkylated or amidated. They can also be subjected to Michael addition or stretcher synthesis.

Polyamidoamines grafted with ethyleneimine are also suitable, which can be obtained, for example, by condensing dicarboxylic acids with polyamines and then grafting ethyleneimine. Higher molecular weights can be achieved through further crosslinking. Suitable polyamidoamines are obtained, for example, by reacting dicarboxylic acids having 4 to 10 carbon atoms with polyalkylene polyamines which contain 3 to 10 basic nitrogen atoms in the molecule. Mixtures of dicarboxylic acids can also be used in the preparation of the polyamidoamines, as can mixtures of several polyalkylene polyamines. Lactones or lactae of carboxylic acids having 4 to 8 carbon atoms can optionally also be used in the condensation. For example, 0.8 to 1.4 moles of a polyalkylene polyamine are used per mole of a dicarboxylic acid. These polyamidoamines are grafted with ethyleneimine.

In addition, water-soluble crosslinked polyethyleneimines are suitable, which can be obtained by reacting polyethyleneimines with crosslinking agents such as

Epichlorohydrin or bischlorohydrin ethers of polyalkylene glycols with 2 to 100 ethylene oxide and / or propylene oxide units are available and still have free primary and / or secondary amino groups. Amidic polyethyleneimines are also suitable, which are obtainable, for example, by amidating polyethyleneimines with C ₁ -C ₂ -monocarboxylic acids. Other suitable cationic polymers are alkylated polyethyleneimines and alkoxylated polyethyleneimines. In the alkoxylation z. B. per NH unit in polyethyleneimine 1 to 5 ethylene oxide or propylene oxide units.

With the polymers mentioned, high retention of the solids can be achieved in paper production. However, it is clear that in principle it is desirable to improve retention behavior to such an extent that only minimal amounts of the paper pulp or - ideally - nothing more are carried away by the running water. For this reason, efforts are constantly being made to improve the known cationic polymers used as retention aids.

It is known that the charge density of a particular polymer affects its retention properties. In general, the retention behavior of a polymer can be optimized for certain paper materials. Fixing agents with the highest charge density are particularly preferred. For this reason, the development aims to develop cationic polymers with high charge density.

It is known from theoretical considerations that polymethylene amine (PMAm) should have a charge density which is higher than that of the cationic polymers available hitherto. PMAm, which consists of recurring units of the formula I

* 2

exists, has not yet been described in the literature.

The object of the present invention is to provide polymethylene amine or a process for its synthesis.

This object is achieved by recurring units of the general formula I.

NH,

containing polymethylene amine.

The present invention further relates to methods for producing PMAm. In all of these processes, the starting material for the synthesis of PMAm is a compound of the general formula (II).

In the general formula (II), the dashed line denotes a double bond which may optionally be present, R ¹ and R ² are substituents which may optionally be present and are selected independently of one another from the group consisting of: hydrogen, saturated and unsaturated, linear and branched, unsubstituted and optionally aryl-substituted C 1 -C ₄ o -alkyl groups; Formyl groups and saturated and unsaturated, linear and branched, unsubstituted and optionally aryl-substituted aliphatic C _x -C ₄₀ acyl groups; Groups of the type R0C (0) -, in which R5 is a saturated or unsaturated, linear or branched, unsubstituted or optionally aryl-substituted C 1 -C ₄ -alkyl group; Groups of Types -C (0) NR ⁶ R ⁷ , in which R ⁶ and R ^{7 are} independently selected from hydrogen, saturated and unsaturated, linear and branched, unsubstituted and optionally aryl-substituted C 1 -C ₄ -alkyl groups; and optionally substituted aromatic C ₆ acyl groups;

R ³ and R ⁴ are substituents which are optionally present and are selected independently of one another from the group consisting of hydrogen, saturated and unsaturated, linear and branched, substituted and unsubstituted C 1 -C ₄ -alkyl groups and hydroxyl groups; or

R ³ , R ^{4 taken} together = 0 or = S.

In a preferred embodiment of the present invention, R ¹ and R ^{2 are} independently selected from the group consisting of: hydrogen, saturated linear and branched, unsubstituted and optionally aryl-substituted C 1 -C ₂ -alkyl groups; Formyl groups and saturated linear and branched, unsubstituted and optionally aryl-substituted aliphatic C 1 -C 8 acyl groups; Groups of the type R ⁵ 0C (0) -, in which R ^{5 is} a saturated linear or branched, unsubstituted or optionally aryl-substituted C 1 -C ₃₀ -alkyl group; Groups of the type -C (0) NR ⁶ R ⁷ , in which R ⁶ and R ^{7 are} independently selected from hydrogen, saturated linear and branched, unsubstituted and optionally aryl-substituted C 1 -C 4 -alkyl groups; and optionally substituted aromatic C _δ acyl groups;

R ³ and R ⁴ are substituents which are optionally present and are selected independently of one another from the group consisting of hydrogen, saturated and unsaturated, linear and branched, substituted and unsubstituted C 1 -C ₂ -alkyl groups and hydroxyl groups; or

R ³ , R ^{4 taken} together = 0.

In a further preferred embodiment of the present invention, R ¹ and R ^{2 are} independently selected from the group consisting of: hydrogen, saturated linear and branched, unsubstituted and optionally aryl-substituted Ci-Cs-alkyl groups; Formyl groups and saturated linear and branched, unsubstituted "and optionally aryl-substituted aliphatic C-Cs-acyl groups; groups of the type R ⁵ OC (0) -, in which R ^{5 is} a saturated linear or branched, unsubstituted or optionally aryl-substituted C 1 -C ₂ alkyl group; and optionally substituted aromatic Cξ acyl groups;

R ³ , R ^{4 taken} together = 0.

In the simplest embodiment of the present invention, the molecule of formula (II) is imidazole.

In one embodiment of the present invention, a 1,3-diacyl-4-imidazolin-2-one or a 1,3-diacyl-4-imidazol-2-thione is used as the starting monomer. Polymerization gives poly (1, 3-diacyl-4-imidazolin-2- (thi) on) (II), the repeating units of the general formula III

contains.

In formula III:

R is hydrogen, a linear or branched C 1 -C ₄ -alkyl group, a linear or branched C 1 -C ₄ o -alkoxy group, or phenyl, preferably hydrogen or a linear or branched C 1 -C ₄ -alkyl group, in particular a methyl group;

X is 0 or S, preferably 0.

Then, to prepare PMAm, poly (1, 3-diacyl-4-imidazolin-2- (thi) on) is saponified to give PMAm with elimination of the acyl groups and opening of the N-heterocycle. The reaction is shown in equation (1) below.

+ n RC (0) 0-B ⁺ + n / 2 C (0) Cr ₂ 2B ⁺ equation 1

In equation (1), the degree of polymerization n of PMAm Ia is> 2, preferably> 10. It is more preferred if the degree of polymerization n is from 1000 to 1,000,000, in particular from 10,000 to 100,000. The molecular weight of the PMAm is> 100,000 D, preferably> 300,000 D, more preferably 300,000 D to 10,000,000 D, in particular 300,000 D to approx. 2,000,000 D.

The PMAm according to the present invention may contain only units of the formula (I), that is to say be present as a homopolymer. However, one or more further monomer units different from (I) can also be incorporated. There are then copolymers, for example bi- or terpolymers. These can be in the form of block or statistical polymers.

In a corresponding copolymer according to the present invention, all monomer units compatible therewith can be present as further units in addition to the methylene amine units. Comonomers which can be copolymerized with the monomers of the formula (II) or (IV) are preferably used in the copolymerization. Examples of these are vinyl esters of saturated carboxylic acids with 1 to 6 carbon atoms such as vinyl formate, vinyl acetate, vinyl propionate and vinyl butyrate and vinyl ethers such as Ci to C ₆ alkyl vinyl ether, for example methyl or ethyl inyl ether. Other suitable comonomers are esters, amides and nitriles of ethylenically unsaturated C ₃ -C ₆ -carboxylic acids, for example methyl acrylate, methyl methacrylate, ethyl acrylate and ethyl methacrylate, acrylamide and methacrylamide, and acrylonitrile and methacrylonitrile. Finally, there are also ethylenically unsaturated ones

C ₃ -C ₆ carboxylic acids are suitable, for example acrylic acid and methacrylic acid.

Other suitable carboxylic acid esters are derived from glycols or polyalkylene glycols, only one OH group being esterified in each case, for example hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxypropyl methacrylate acrylate, hydroxybutyl methacrylate and acrylic acid monoesters of polyalkylene glycols with a molecular weight of 500 to 10,000. Further suitable comonomers are esters of ethylenically unsaturated carboxylic acids with amino alcohols, such as, for example, dimethylaminoethyl acrylate, dimethylamino methyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, dimethylaminopropylacrylate, dimethylaminopropyl methacrylate, diethylaminopropylacrylate acrylate, dimethyl aminobutyl acrylate, dimethyl amine acrylate. The basic acrylates can be used in the form of the free bases, the salts with mineral acids such as hydrochloric acid, sulfuric acid or nitric acid, the salts with organic acids such as formic acid, acetic acid, propionic acid or the sulfonic acids or in quaternized form. Suitable quaternizing agents are, for example, dimethyl sulfate, diethyl sulfate, methyl chloride, ethyl chloride or benzyl chloride.

Other suitable comonomers are amides of ethylenically unsaturated carboxylic acids such as acrylamide, methacrylamide and N-alkyl mono- and diamides of monoethylenically unsaturated carboxylic acids with alkyl residues of 1 to 6 carbon atoms, e.g. N-methyl acrylamide, N, N-dimethyl acrylamide, N-methyl methacrylamide, N-ethyl acrylamide, N-propylacrylamide and tert. Butylacrylamide and basic (meth) acrylic amides, e.g. Dimethylaminoethyl acrylamide, dimethylaminoethyl ethacrylamide, diethylaminoethyl acrylamide, diethylaminoethyl methacrylamide, dimethylaminopropylacrylamide, diethylaminopropyl methacrylamide, dimethylaminopropyl methacrylamide and diethylaminopropyl methacrylamide.

Also suitable as comonomers are N-vinylpyrrolidone, N-vinylcaprolactam, acrylonitrile, methacrylonitrile, N-vinylimidazole and substituted N-vinylimidazoles such as e.g. N-vinyl-2-methylimidazole, N-vinyl-4-methylimidazole, N-vinyl-5-methylimidazole, N-vinyl-2-ethylimidazole and N-vinylimidazolines such as N-vinylimidazoline, N-vinyl- 2-methylimidazoline and N-vinyl-2-ethylimidazoline. In addition to the free bases, N-vinyllimidazoles and N-vinylimidazolines are also used in neutralized or in quaternized form with mineral acids or organic acids, the quaternization preferably being carried out with methyl sulfate, diethyl sulfate, methyl chloride or benzyl chloride. Diallyldialkylammonium halides such as e.g. Diallyldimethylammonium chloride.

Finally, vinyl formamide, styrene, butadiene, maleic anhydride (MA), fumaric acid and maleic acid are also suitable. The hydrolysis can be carried out in solution or in bulk, using conditions and reagents known to the person skilled in the art. This hydrolysis is preferably carried out with strong bases. Suitable are the alcoholates of the known lower and higher alcohols, for example methanolates or ethanolates. Particularly suitable bases include NaOH, KOH, LiOH, CaOH and mixtures thereof. Particularly suitable as a base is a eutectic mixture or a mixture of NaOH and KOH lying close to the eutectic.

The copolymers contain, for example

99 to 1 mol%, preferably 90 to 10 mol% methylene amine units - 1 to 99 mol%, preferably 10 to 90 mol% other, polymerized-in units

in polymerized form.

Poly (1, 3-diacyl-4-imidazolin-2- (thi) on) is prepared by radical or ionic, preferably radical polymerization from 1, 3-diacyl-4-imidazolin-2-one or -thione. The polymerization can be carried out in bulk, in solution, suspension, emulsion or dispersion. It is preferably carried out in bulk. The usual radical initiators known to those skilled in the art are used.

Basically all initiators which can be used as initiators are those by which free-radical polymerization of ethylenically unsaturated monomers can be achieved. Examples include azo compounds, organic or inorganic peroxides, salts of peroxodisulfuric acid and redox initiator systems. As a rule, the initiator is used in the process according to the invention in an amount of 0.1 to 5% by weight, based on the amount of the monomers to be polymerized. The amount of initiator used depends in a known manner on the effectiveness with which the radical polymerization of the monomers is triggered. Small amounts of initiator will often be used in the polymerization in a water-in-oil emulsion, especially if hydrophobic initiators are used. Of course, the polymerization can also be triggered by actinic radiation, microwave radiation or α, β or γ radiation.

Examples of azo initiators include 2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2-amidinopropane) dihydrochloride (V50) and 2.2 '-Azo- bis (2- (2-rmidazolin-2-yl) propane) dihydrochloride. Examples of other organic peroxides are hydrogen peroxide and percarbonates, examples of organic peroxides include alkyl hydroperoxides such as tert-butyl hydroperoxide, cumene hydroperoxide, and furthermore peroxycarboxylic acid esters such as tert. -Butyl peroctoate and diacyl peroxides such as dibenzoyl peroxide. Suitable salts of peroxodisulfuric acid are in particular the sodium, potassium and ammonium salts. Examples of redox initiator systems include systems which use one of the abovementioned organic or inorganic peroxides, in particular hydrogen peroxide, as the oxidation component and at least one further reduction component such as ascorbic acid, hydroxylamine or adducts of the sulfurous acid with aldehydes, for example the bisulfite adduct with acetone or hydroxymethanesulfinic acid sodium salt contain. Both the aforementioned peroxides and the redox initiator systems can be used in the presence of redox-active transition metals such as iron, vanadium or copper, preferably in the form of water-soluble salts.

Examples of further initiator systems include hydrogen peroxide, tert. -Butyl peroxide and salt-like azo compounds, e.g. B. the aforementioned hydrochlorides. Examples are bisazo (alkylnitriles) such as 2,2 'azobis (valeronitrile), 2,2-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (4-methoxy-2-4-dimethylvaleronitrile) ), 2, 2 'azobis (isobutyronitrile); Alkyl and cycloalkyl percarbonates such as dicyclohexyl peroxodicarbonate, di-2-ethylhexyl peroxide carbonate, tert. -Butylperoxoisopropylcarbonat; Diacyl peroxides such as acetyl peroxide, dioctanoyl peroxide, dilauroyl peroxide, dibenzoyl peroxide; Peroxy esters, especially tert-butyl peroxy carboxylic acid esters such as tert. Butyl perpivalate, per-2-ethylhexanoate, perneodecanoate; Hydroperoxides such as cumene hydroperoxide, p-menthane hydroperoxide, pinane hydroperoxide and tert. -Butyl hydroperoxide and peroxides such as dicumol peroxide, di-tert-butyl peroxide and di-tert. -amylperoxid.

In radical polymerization, chain transfer agents (regulators) are generally used. The amount of chain transfer agent used naturally depends on the effectiveness of the chain transfer agent and is generally in the range from 0.0001 to 5% by weight, based on the total amount of monomers. Examples of chain transfer agents are: aliphatic mercaptans such as C ₆ -C-alkyl mercaptans such as n-hexyl mercaptan; n-octyl mercaptan, tert-octyl mercaptan, 2-ethylhexyl mercaptan, n-decyl mercaptan, 2-propylheptyl mercaptan, n-dodecyl mercaptan and tert-dodecyl mercaptan; water-soluble mercaptans such as 2-mercaptoethanol, mercaptopropanol, mercaptobutanol, mercaptopropionic acid and mercaptoeetic acid, furthermore formic acid, isopropanol, allyl alcohols, aldehydes such as butyraldehyde, halohydrocarbons εtoffe such as chloroform, bromoform, carbon tetrachloride and the like.

The polymerization temperature generally depends on the initiator system used and is frequently in the range from 20 to 160 ° C. and in particular in the range from 130 to 150 ° C.

The polymerization time is usually in the range from 1 min to 24 h.

The pH of the reaction medium is preferably in the range from 3 to 10.

The implementation can be carried out as a batch process. The monomers to be polymerized are initially introduced into the aqueous reaction medium and the polymerization initiator is fed in under polymerization conditions, preferably depending on its consumption, or is introduced together with the monomers in the polymerization vessel and then heated to the polymerization temperature.

Tert-butyl hydroperoxide is preferably used as the radical initiator.

Poly (1, 3-diacyl-4-imidazolin-2- (thi) on) polymers are a further subject of the present invention.

Poly (1, 3-diacetyl-4-imidazolin-2-one) with a degree of polymerization n of 3 to 4 is described by G. 0. Schenck in Chem. Ber. 100, pages 369 to 3978 (1967).

1,3-diacyl-4-imidazolin-2-ones and -thiones can be obtained by conventional acylation of 4-imidazolin-2-one or -2-thione known to the person skilled in the art.

Poly (4-imidazolin-2-one), which is obtained by partial hydrolysis of

Poly (1, 3-diacyl-4-imidazolin-2-one) is available, is also an object of the present invention.

Another object of the present invention is the preparation of PMAm by polymerizing 1,2-diaminoethene derivatives of the following formula IV, which are obtainable from imidazole.

In the formula IV, R ¹ and R ^{2 are} independently a radical of the formula R ⁵ , OR ⁶ or NR ⁷ R ⁸ , where R ⁵ , R ⁶ , R ⁷ and R ⁸ are selected independently of one another from the group consisting of hydrogen, linear and branched Cχ-C ₄ o-alkyl groups, which optionally have one or more substituents from the group of optionally alkyl-substituted Cε-aromatics, and Cg-aromatics, which optionally have one or more substituents from the group consisting of -C-C ₄ o- Have alkyl groups; R ³ and R ⁴ are independently selected from the group consisting of hydrogen, -CC ₄ o-alkyl groups and aromatics.

The diaminoethene derivatives of the formula (IV) can be in the ice or trans form or can be used in the polymerization reaction.

Polymerization can be used to obtain substituted polymethylene amines from the monomers of the formula IV in which a hydrogen of the amino group has been replaced by a —C (0) R group, as shown in formula IV. The polymerization is carried out cationically or radically. The polymerization is preferably carried out cationically, it being possible to use the customary Lewis acids.

Of course, the polymerization can also be triggered by actinic radiation, microwave radiation or α, β or γ radiation.

The polymerization temperature generally depends on the initiator system used and is frequently in the range from -10 to 110 ° C. and in particular in the range from 0 to 40 ° C.

The polymerization time is generally in the range from 1 to 10 h, but in individual cases can also be above or below these values.

The pH of the reaction medium is preferably in the range from 3 to 10. The implementation can be carried out as a batch process. The monomers to be polymerized are initially introduced into the reaction medium and the polymerization initiator is fed in under polymerization conditions, preferably depending on its consumption, or is introduced together with the monomers in the polymerization vessel and then heated to the polymerization temperature.

Lewis acids, for example BF ₃ diethyl ether, SnCl ₄ , TiCl ₃ , or C0, are preferably used for the polymerization. The polymerization is preferably carried out cationically, in which case advantageous results have been achieved with BF ₃ / diethyl ether as Lewis acid.

The best results were obtained when using monomers in which R ¹ and R ² are OR ⁶ and R ⁶ are Ci-Cε-alkyl, benzyl or phenyl. R ³ and R ⁴ are preferably hydrogen.

The cationic polymerization of the compounds of the formula (IV) is preferably carried out in homogeneous solution in an organic solvent. Solvents which dissolve the compounds of the formula (IV) and are known to the person skilled in the art are preferred, preferably dimethyl sulfoxide (DMSO), N-methylpyrrolidone (NMP), dimethylformamide (DMF), formamide or hexamethylphosphorus triamide (HMPTA) ). DMSO is particularly suitable. In this way, oligomers and polymers are accessible.

The resulting polymers, which are composed of the molecular units with the formula IV, are hydrolyzed to produce PMAm in a manner known to the person skilled in the art.

A part of the substituted 1, 2-diaminoethenes of the general formula IV can be obtained by a so-called Bamberger cleavage (E. Bamberger, Ann. 273, 267 (1893)) from imidazole. The reaction is shown in equation (2) below, where X is Cl, Br or I, preferably Cl or Br.

(V) (VI) Equation 2 The compounds obtained can be reacted in a reaction known to those skilled in the art and N-alkylated or arylated in order to obtain the compounds of the formula (IV). The radical R ^* in the carbonyl compound (VI) corresponds to the radicals R ¹ and R ² in the formula (IV). The reaction proceeds via the mono- and diacylated imidazole, which reacts with hydrolysis and ring opening to give the di-inoethene derivatives of the formula (IVa). The usual conditions known to those skilled in the art are observed during the implementation. The reaction is preferably carried out in a neutral reaction medium, since the best results have been obtained here.

Of course, 1,2-diaminoethenes which are not obtained from imidazole can also be used.

The polymers according to the invention are particularly suitable as dewatering, flocculating and retention agents and as fixing agents in the manufacture of paper. For this purpose they are added to the respective pulp in an amount of 0.01 to 2 and preferably in an amount of 0.01 to 0.5% by weight, e.g.

0.01 to 0.1 wt .-% added, each based on the solids contained in the paper stock.

The polymers according to the invention in particular lead to improved retention of fine substances compared to the polymers of the prior art. They have particularly advantageous effects for the retention of fillers such as calcium carbonate. The polymers are particularly characterized by good fixing properties. The polymers according to the invention are particularly suitable for fixing impurities, coated rejects and stickies.

The polymers according to the invention can be used for the production of all paper, cardboard and cardboard qualities, for example for the production of papers for newspaper printing (high-pressure / offset printing), so-called medium-fine writing and printing papers, natural gravure papers and also lightweight coating base papers. For the production of the papers mentioned, wood pulp, thermomechanical material (TMP), chemo-thermomechanical material (CTMP), pressure grinding (PGW), and sulphite and sulphate pulp are used as the raw material component. The substances mentioned can be both short and long-fiber. Waste paper, pulp and wood pulp are also considered as raw materials for the production of the paper stock, which are further processed into paper in the so-called integrated factories in more or less moist form without prior thickening or drying. Some of these substances still contain residues of impurities. Inclusions that arise during the digestion and that strongly disrupt the normal paper manufacturing process. These impurities are fixed in a particularly good manner on the paper by the polymers according to the invention.

With the aid of the polymers according to the invention, both filler-free and filler-containing papers can be produced. The filler content of filler-containing papers can be up to a maximum of 40% by weight and is preferably in the range from 5 to 30% by weight. Suitable fillers are, for example, clay, kaolin, chalk, talc, titanium dioxide, calcium sulfate, barium sulfate, aluminum oxide, satin white or mixtures of the aforementioned fillers.

In particular, the good fixing effect in the production of cardboard, cardboard, newsprint from waste paper and such material systems that contain contaminants and that accumulate in the at least partially closed water cycles of paper machines come into consideration.

Examples of the use of the polymethylene amines or copolymers according to the invention are their use as retention agents in the manufacture of paper, cardboard and cardboard, as fixatives for rendering harmful substances in the paper manufacture, as fixatives for anionic stabilized sizing agents, as fixatives for the fixation of anionic dyes, as a primary for adhesion to anionic surfaces, as an aid in oil production, as a textile and leather aid, as a component in detergents, as an emulsifier for emulsions / dispersions, as a crosslinker in the manufacture of PUR, as Catcher of formaldehyde and higher aldehydes, as a binder for fiberboard, as an aid for sludge dewatering, and as a vector in cancer therapy.

The preparation of the polymers according to the invention is now explained in the examples below.

Examples

A Synthesis of polymethylene amine starting from poly (1, 3-diacetyl-4-imidazolin-2-one)

1. Synthesis of 4-imidazolin-2-one

In a 2 1 four-necked round-bottomed flask with distillation attachment, dropping funnel and thermometer, 285 g (1.63 ol) of alpha-ureidoacetaldehyde diethylacetal are filled in 1245 ml at room temperature (RT). desalinated water. With 14 g of 98-100% formic acid, the pH is adjusted to 2.45. The reaction mixture is heated to 55 ° C. A water jet vacuum of 350 to 400 mbar is applied in order to distill off the ethanol formed. After 1 hour at 55 ° C, the vacuum is switched off and the reaction mixture is cooled to 0 to 5 ° C. The precipitated crystals are filtered off with suction and dried in a vacuum drying cabinet at 40 to 50 ° C. and 200 mbar (62.2 g of clean product). 42.4 g of product were isolated from the mother liquor.

Total yield: 104.6 g = 76.5% of theory. theory

FP: 242 to 244 ° C (decomp. Reddish brown color)

C, H, N analysis: theory found

C 42, 8 42, 3

H 4, 76 4, 9

N 33, 33 33, 0

iH NMR (DMSO-D6, TMS, 400 MHz): 6.25 (s, 2H; HC = CH); 9,

(s, 2H; HN-CO-NH).

IR spectrum: 1652 cm " ¹ (s); 1399 (m); 1073 (m); 697 (s)

2. Synthesis of 1, 3-diacetyl-4-imidazolin-2-one

31.7 g (127 mol) of 4-imidazolin-2-one, 307.3 g (four times the molar excess) of acetic anhydride and 1.5 g of 4-dimethylaminopyridine are added as a catalyst in a 1000 ml four-necked flask with a condenser and thermometer. The solution is carefully brought to reflux at first 106, then 116 and finally 124 ° C. The reaction is complete after 5 hours. When cooling to RT, colorless crystals precipitate out. Mp 102 ° C (from ethyl acetate or cyclohexane). Total yield 51 g corresponds to approx. 80% of theory. Theory.

H-NMR (CDC1 ₃ , TMS, 400 MHz): 2.63 (s, 6H, CO-CH ₃ ); 7.05 (s, 2H, - HC = CH -).

"C-NMR (CDCI ₃ , TMS, 100 MHz): 24.1 (-CH ₃ ); 109.5 (= CH-); 149.5 (-HN-CO-NH-); 167.7 (- CO-CH ₃ )

3. Substance polymerization of 1,3-diacetyl-4-imidazolin-2-one

In a 50 ml round bottom flask, 10 g of 1.3 are flushed with N ₂

Diacetyl-4-imidazolin-2-one presented and then brought the internal temperature to 140 ° C. This creates a clear melt of the 1, 3-diacetyl-4-imidazolin-2-one. 10 drops of a 70% aqueous solution of tert are first added. -Butyl hydroperoxide and then every 5 minutes 10 additional drops to a total of 40 drops. Three minutes after the addition of the first 10 drops, the monomer reacts to form a solid polymer block. The temperature is kept at 140 ° C. for 1 hour. After cooling to room temperature, 9.5 g of a colorless, brittle polymer, which can be easily pulverized, is isolated. The polymer dissolves in THF and chloroform, it is insoluble in water.

The C, H, N analysis showed:

ⁱ H-MR (CDC1 ₃ , TMS, 400 MHz): 2.43 (br. S, 6H, (-CO-CH ₃ )); 3.85 ^• 4.65 (br., 2H, -CH-CH-)

¹³ C NMR (CDCI ₃ , TMS, 100 MHz): 23.6 (br. Q, CH ₃ ); 54.8 (br. D, -CH-); 149.9 (br. S, N-CO-N); 171.2 (br. S, -CO-CH ₃ )

According to the Maldi analysis, the polymer has repeat units made from 1,3-diacetyl-4-imidazolin-2-one.

4. Hydrolysis of the polymer in a NaOH / KOH melt

In 13 g of a eutectic mixture of 5.4 g of NaOH and 7.6 g of KOH, 1 g of the polymer is introduced at 200 ° C. and kept at this temperature for 1 1/2 hours. The melt turns brown and becomes thinner after a short time. The melt is then added to 110 g of water, a pH of> 14 being established. With 3.22 g HCl conc. a pH of 7.6 is set. The sample is filtered. The acetic acid content of the solution was determined to be 16.5 mmol / lOOg using an enzymatic determination method, which corresponds to a yield of 48%.

The softening point of the polymer was> 260 ° C, the charge density of the polymer was determined to be 1.94 mmol / g. A molecular mass of 300,000 D was determined using static light scattering.

B Synthesis of polymethylene amine from 1,2-diamino ethenes B.1 Syntheses of diaminoethenes

1) N, N'-dibenzoyl-1,2-diaminoethene

216 g of water are placed in a 0.25 1 four-shake flask with intensive cooler, thermometer, dropping funnel, stirrer, multiple attachment and pH electrode and 6.8 g of imidazole (0.1 mol) are dissolved therein. At a temperature of 20-25 ° C a pH of 9.6 is reached. 28.1 g (0.2 mol) of benzoyl chloride are then added dropwise at 20-25 ° C. with gentle cooling (slightly exothermic reaction). The reaction solution turns yellow and a white solid precipitates. The pH slowly drops below 8. A further 7.0 g of benzoyl chloride (0.05 mol) were added dropwise within 60 minutes while maintaining a pH of 7-8. For this purpose 25.2 g NaOH 50% were needed. After a further 4 hours of reaction time at 20-25 ° C, the pH remaining constant at 7.5 for 1 hour, the temperature was raised to 40-45 ° C, which was raised from 7 to 7.25 and then remained there for 1 hour ,

A further 7.2 g of 50% strength NaOH were required to adjust the pH.

The reaction mixture was then suctioned off through a G 3 glass filter. The residue was dried at 50-60 ° C./13 mbar on a rotary evaporator for 3 hours. Yield: 10 g.

The filtrate, which according to HPLC did not yet contain a fully reacted monoadduct, was slowly reacted with a further 7.0 g of benzoyl chloride (0.05 mol) at 20-25 ° C. while maintaining a pH of 7-8 in 2.75 hours. Post-reaction time 1 hour at 20-25 ° C. 3.4 g of NaOH 50% were required to adjust the pH. Then the reaction mixture ^'was a glass suction filter G 3 sucked. The residue dried at 50-60 ° C / 17 mbar on a rotary evaporator for 3 hours. Yield: 3.4 g (according to HPLC the solid still contained 35% product of value) = 1.2 g. The filtrate was reacted again slowly at 20-25 ° C. while maintaining the pH 7-8 in 2 hours with 3.5 g of benzoyl chloride (0.025 mol). Post-reaction time 1 hour at 20-25 ° C. 3.7 g of 50% strength NaOH were required to adjust the pH. The residue was suctioned off through a glass suction filter G 3 and dried at 40-50 ° C./15 mbar on a rotary evaporator for 3 hours. Yield: lg 66.4% ig = 0.7 g.

Yield from three fractions: 11.5 g correspond to 43.2% of theory The C, H, N analysis of a recrystallized twice from ethanol

Sample (mp. 206-208 ° C) provided:

Found in theory

5

C 72. 18% 72. 2% H 5. 26% 5. 2% N 10. 52% 10. 5%

10 ¹³ C-NMR (100 MHz, DMS0-d6): 106.7 / d; 127.9 / d; 128.45 / d; 131, 7 / d; 133.8 / s; 163.87 / s; probably only small amounts of trans isomer.

2) N, N ^% -ethoxycarbonyl-l, 2-diaminoethene

15

1306.8 g of water were placed in a 21 four-necked flask with intensive cooler, thermometer, dropping funnel, stirrer, multiple attachment and pH electrode and 41.14 g (0.605 mol) of imidazole were dissolved therein. At a temperature of 20-25 ° C there is a pH value

20 out of 9.8. 131.3 g (1.21 mol) of ethyl chloroformate are then added dropwise at 20-25 ° C. with gentle cooling (slightly exothermic reaction). The pH falls slowly and is kept at 8-9 by dropwise addition of 147.2 g of NaOH 50%. The reaction solution becomes cloudy and a white solid precipitates. After 1 hour and

The ethyl chloroformate was added dropwise for 10 minutes. The experiment was stopped after a further 30 minutes. The product was suctioned off through a glass suction filter G 3 and washed three times with cold water, sucked dry, and then dried on a rotary evaporator at 40-45 ° C./15 mbar for 2 hours. The solid became out

30 recrystallized ethanol and dried again at 40-45 ° C / <15 mbar for 2 hours.

Yield: 74.2 g correspond to 60.6% of theory.

35 The C, H, N analysis of a sample recrystallized from ethanol (mp: 136-138 ° C) provided:

.eo. retic finds sn

40 C 47. 50% 47. 7%

H 6. 93% 7. 0% N 13. 86% 13. 8% 0 31. 68% 31. 9%

45 ¹³ C NMR (100 MHz, DMSO-d6): 14.38 / t; 60.46 / d (major component);

60.85 / d (minor component); 104.68 / d (minor component); 105.31 / d

(Main component); 152.54 (minor component);

5 Only traces of the trans isomer can be detected.

3) N, N * -methoxycarbonyl-1, 2-diaminoethene

1306.8 g of water were placed in a 21 four-necked flask with intensive cooler, thermometer, 10 dropping funnel, stirrer, multiple attachment and pH electrode and 41.14 g (0.605 mol) of imidazole were dissolved therein. At a temperature of 20-25 ° C, a pH of 10.3 is set. 114.4 g (1.21 mol) of methyl chloroformate are then added dropwise at 20-25 ° C. while cooling with ice (slightly exothermic reaction). The pH falls slowly and is kept at 8-9 by dropwise addition of 147.2 g of NaOH 50%. The reaction solution becomes cloudy and a white solid precipitates. The methyl chloroformate was added dropwise after 1 hour. After a further 3 hours the temperature was raised to 65 ° C and held for 4 hours. The 20 product was suction filtered through a G 3 glass filter and washed three times with 1 liter of cold water each time. The crude yield was 55.1 g moist. The crystalline mass was then dried at 40-45 ° C / 15 mbar for 2 hours. Yield: 30.1g correspond to 28.6% of theory.

25

C, H, N analysis of a sample recrystallized from ethanol (mp: 158-160 ° C) provided:

Found in theory

30 c 47. 3% 47. 1 %

H 5, 8% 6. 0% N 16, 1% 16. 1 %

35

¹³ C-NMR (100 MHz, DMS0-d6): 51.97 / t (main); 52.29 / t (minor); 104.87 / d; 105.41 / d (main); 152.95 / s (minor); 153.72 / s (main)

The sample is a mixture of the eis and trans isomers.

40

4) N, N-benzyloxycarbonyl-l, 2-diaminoethene

₄₅ 240 g of 5% NaOH were placed in a 0.5 1 four-necked flask with intensive cooler, thermometer, dropping funnel, stirrer, multiple attachment and pH electrode, and 6.8 g (0.1 mol)

Imidazole dissolved. At a temperature of 20-25 ° C a pH of 13.8 is reached. Then with slight cooling at 20-25 ° C 34.1 g (0.2 mol) of benzyloxychloroformate were added dropwise (slightly exothermic reaction). At a pH of 13.2, the reaction solution becomes cloudy and a solid flocculates. After about 1.5 hours at 25-30 ° C, the chloroformate is added dropwise. The pH has dropped to 10.5. The temperature is raised to 30-35 ° C. After 45 minutes at this temperature, the temperature is increased again to 60-65 ° C. After another hour at 60-65 ° C the pH drops to 9.5. The experiment was stopped after a further 20 minutes.

10

The mixture was suctioned off through a G 3 glass filter, the aqueous phase was discarded.

The solid, kneaded mass is washed with cold water and then dissolved in ethanol, anhydrously dried with Na S0 ₄ and filtered off.

The solution is rotated in at 50-55 ° C / 15 mbar on a rotary evaporator.

20

Yield: 25.8 g correspond to 79.1% of theory.

The C, H, N analysis of a sample 25 recrystallized from cyclohexane (mp: 89-90 ° C.) gave:

Found in theory

C 66.20% 66.2% 30 H 5.52% 5.4%

N 8.58% 8.7%

¹³ C NMR (100 MHz, DMS0-d6): 66.01 / t; 105, 5 / d; 127, 8 / d; 128, 0 / d; 128, 3 / d; 136.3 / s; 153, 02 / s smallest amounts of trans isomer

35

5) N, N ^λ -2-ethylhexyloxycarbonyl-l, 2-diaminoethene

In a 0.25 1 four-necked flask with intensive cooler, thermometer, dropping funnel, stirrer, multiple attachment and pH electrode

40 158 ml of m-xylene, 3.4 g (0.05 mol) of imidazole and 1.1 g of tetrabutylammonium hydroxide 40% pure. At a temperature of 20-25 ° C, a pH of> 13 is established. 19.2 g ^' (0.1 mol) of 2-ethylhexyl chloroformate are then added dropwise at 20-25 ° C. with gentle cooling (slightly exothermic reaction). The pH drops

45 slowly, the reaction solution becomes cloudy. When the pH has reached 7-8, it is kept with 50% sodium hydroxide solution. The chloroformate is added dropwise after about 3.5 hours at 20-25 ° C. The Temperature is raised to 30-35 ° C. After 3 hours at this temperature, this is increased again to 60-65 ° C. After a further 6.5 hours at 60-65 ° C, the pH is constant at 7.55. 10.8 g (0.14 mol) of 50% sodium hydroxide solution were required to adjust the pH. The mixture was sucked off through a G 4 glass filter. The white precipitate was washed with a little m-xylene. Residue 3.1 g water-soluble. The aqueous phase was separated off in a separating funnel. The organic phase is diluted with 100 ml of THF and dried anhydrous with sodium sulfate, then filtered off. M-xylene and THF were rotated off on a rotary evaporator at 50-55 ° C./11 mbar. 21.9 g of a yellowish oil containing about 90% of product were obtained.

13C-NMR (100 MHz, DMSO-d6): 66.01 / t; 105, 5 / d; 127, 8 / d; 128.0 / d; 15 128, 3 / d; 136.3 / s; 153.02 / s; smallest amounts of trans isomer

Yield: 18.17 g corresponds to approximately 98% of theory

6) N, N ^x -MyriΞtyloxycarbonyl-l, 2-diaminoethene

20

108 ml of m-xylene, 3.4 g (0.05 mol) of imidazole and 1.1 g of 40% strength tetrabutylammonium hydroxide were placed in a 0.25 l four-necked flask with intensive cooler, thermometer, dropping funnel, stirrer, multiple attachment and pH electrode , At a temperature of

25 20-25 ° C a pH of> 13 is reached. With gentle cooling, 27.6 g (0.1 mol) of myristyl chloroformate is then added dropwise at 20-25 ° C. (slightly exothermic reaction). The pH drops slowly, the reaction solution becomes cloudy. When the pH has reached 7-8, it is kept with 50% sodium hydroxide solution. After about

The chloroformate is added dropwise at 30-25 ° C. for 3 hours. The temperature is kept at 20-25 ° C for 3 hours. Then the temperature is increased again to 40-45 ° C. After another hour at 40-45 ° C, the pH is constant at 8.2. 11 g (0.14 mol) 50% sodium hydroxide solution were required to adjust the pH. to

35 Removal of the sodium chloride, the mixture was suctioned off through a G 4 glass filter. This gave an aqueous, clear and an organic, cloudy phase. The aqueous phase was taken up in THF, anhydrously dried with sodium sulfate, filtered off and evaporated at 30-35 ° C. on a rotary evaporator. It

40 resulted in a residue of 10 g. This was recrystallized from ethanol and cyclohexane. Yield 6.8 g.

The organic phase is not completely soluble in THF. The insoluble part was sucked off through a glass suction filter G 3 and 45 was 4.4 g (NaCl). The THF phase was dried anhydrous with sodium sulfate and on a rotary evaporator at 35-40 ° C / ll Rotated in mbar and dried at 65-70 ° C / 9 mbar on a rotary evaporator. The yield was 15 g.

Yield: 21.8 g correspond to 81% of theory (MW 538) 5

The C, H, N analysis of a sample recrystallized from cyclohexane (mp: 88-89 ° C.) gave:

Found in theory

10 c 71, 30% 71, 5%

H 11, 50% 11, 3% N 5, 20% 5, 1%

15 ¹³ C NMR (100 MHz, CDC1 ₃ ): 14.11 / q; 22.7; 25.8; 28.9; 29.36; 29.39; 29.6; 29.65; 29.67; 31.96 (all ts); 65.6 and 66.78 (both ts); 104.9 and 107.2 (both ds); 154.18 and 155.35 (both singlets); the substance is a mixture of ice and trans isomers.

20

7) N, N-Cetyloxycarbonyl-l, 2-diaminoethene

25 108 ml of m-xylene, 3.4 g (0.05 mol) of imidazole and 1.1 g of tetrabutylammonium hydroxide 40% pure. At a temperature of 20-25 ° C, a pH of> 13 is established. With gentle cooling, 30.4 g (0.1 mol) of cetyl chloroformate is then added dropwise at 20-25 ° C. (slightly exothermic reaction). The pH drops slowly

30 and the reaction solution becomes cloudy. When the pH has reached 7-8, it is kept with 50% sodium hydroxide solution. After about 3.5 hours at 20-25 ° C the chloroformate is added dropwise. Another 50 ml of m-xylene were added dropwise. The temperature was raised to 40-45 ° C. After stirring for a further 3 hours, the

35 Temperature again at 60-65 ° C. After 4 hours at 60-65 ° C the pH is constant at 7.45. 10.85 g (0.14 mol) of sodium hydroxide solution were required to adjust the pH.

To remove the sodium chloride, the entire batch was taken up in 40 about 600 ml of THF, dried anhydrous with sodium sulfate and then suctioned off through a G 4 glass filter. The solution is rotated in at 60-65 ° C / 13 mbar on a rotary evaporator. The crude yield was 31.5 g.

45 It was recrystallized from n-hexane and on a rotary evaporator at 50-55

° C / <10 mbar dried.

5 Yield: 24.8 g correspond to 83.5% of theory

C, H, N analysis of a sample recrystallized from n-hexane (mp: 66-67 ° C) gave:

10 Found in theory

C 72.7% 71.5%

H 11.8% 11.4%

N 4.7% 4.5%

15 ¹³ C NMR (100 MHz, DMS0-d6): 66.01 / t; 100, 5 / d; 153, 2 / s; the substance was slightly contaminated with cetyl chloroformate according to ¹³ C-NMR; smallest amounts of trans isomer.

B.2 Radical polymerization with diaminoethenes 20

1. Radical copolymerization of N, N ^v -ethoxycarbonyl-1, 2-diaminoethene with MSA

0.828 g of N, N ^x -ethoxycarbonyl-l, 2-diaminoethene and 0.172 g of maleic acid anhydride are weighed into 2.5 g of NMP, gassed with N and then the temperature is raised to 140 ° C. and 0.2 g of tertiary Butyl hydroperoxide added. The reaction mixture is then kept at 140 ° C. for 30 minutes and then cooled to RT.

30 The reaction mixture was analyzed using GPC (eluent THF) and MALDI-TOF up to approx. 800 D.

2. Radical polymerization of N, N ^λ- ethoxicarbonyl-l, 2-diaminoethene in bulk

35

1 g of N, N ^x -ethoxycarbonyl-l, 2-diaminoethene is melted at 140 ° C. and the melt is gassed with N, and 0.2 g of tertiary butyloxyacetate is then added. The reaction mixture is kept at this temperature for 1 h and then reduced to RT

40 cools. The reaction mixture was analyzed by means of GPC (eluent THF).

The molar mass is around 1,000 D.

45 B.3. Cationic polymerization with 1,2-diaminoethenes 1. Cationic oligomerization of N, N'-ethoxicarbonyl-l, 2-diaminoethene

1 g of a 10% DMSO solution of N, N -ethoxycarbonyl-1,2-diaminoethene is treated with 0.3 ml of BF ₃ / EtOEt while cooling with ice. This mixture is then warmed to RT and kept at this temperature, up to a maximum of 50 ° C. The reaction takes several days. The reaction is analyzed using GPC (eluent = THF) and MALDI-TOF spectroscopy. The maximum molar mass of the oligomers obtained is approximately 1000 D.

Claims

claims

1. Polymethylene amine containing recurring units of the general formula I

2. Polymethylene amine according to claim 1 with a degree of polymerization n> 2, preferably> 10, more preferably 1000 to 1,000,000, in particular 10,000 to 100,000.

3. Polymethylene amine according to claim 1 or 2 with a molecular weight of> 100,000 D, preferably ≥ 300,000 D, more preferably 300,000 D to 10,000,000 D, in particular 300,000 D to 2,000,000 D.

4. A process for the preparation of polymethylene amine according to one of claims 1 to 3, characterized in that a compound of the general formula (II) is used as starting material

in which mean:

the dashed line is a double bond that may optionally be present, R ¹ and R ² are substituents that may optionally be present and are independently selected from the group consisting of: hydrogen, saturated and unsaturated, linear and branched, unsubstituted and optionally aryl-substituted Cχ-Co-alkyl groups; Formyl groups and saturated and unsaturated, linear and branched, unsubstituted and optionally aryl-substituted aliphatic C 1 -C 8 acyl groups; Groups of the type R ⁵ OC (0) -, in which R5 is a saturated or unsaturated, linear or branched, unsubstituted or optionally aryl-substituted C ₁ -C ₆ -alkyl group; Groups of the type -C (0) NR ⁶ R ⁷ , in which R ⁶ and R ^{7 are} independently selected from hydrogen, saturated and unsaturated, linear and branched, unsubstituted and optionally aryl-substituted Cχ-Co-alkyl groups; and optionally substituted aromatic Cβ acyl groups;

R ³ and R ⁴ are substituents which are optionally present and are selected independently of one another from the group consisting of hydrogen, saturated and unsaturated, linear and branched, substituted and unsubstituted C 1 -C 8 -alkyl groups and hydroxyl groups; or

R ³ , R ⁴ are taken together = 0 or = S, and the starting material is polymerized in a manner known per se.

5. The method according to claim 4, characterized in that the substituents R ¹ , R ² , R ³ and R ^{4 have} the following meaning:

R ¹ and R ² are independently selected from the group consisting of: hydrogen, saturated linear and branched, unsubstituted and optionally aryl-substituted Cχ-Ci ₂ alkyl groups; Formyl groups and saturated linear and branched, unsubstituted and optionally aryl-substituted aliphatic C 1 -C ₂ -acyl groups; Groups of the type R ⁵ 0C (0) -, in which R ^{5 is} a saturated linear or branched, unsubstituted or optionally aryl-substituted C ₁ -C ₃ -alkyl group; Groups of the type -C (0) NR ⁶ R ⁷ , in which R ⁶ and R ^{7 are} independently selected from hydrogen, saturated linear and branched, unsubstituted and optionally aryl-substituted C 1 -C ₂ -alkyl groups; and optionally substituted aromatic C ₆ acyl groups;

R ³ and R ⁴ are substituents which are optionally present and are selected independently of one another from the group consisting of hydrogen, saturated and unsaturated, linear and branched, substituted and unsubstituted C 1 -C 4 -alkyl groups and hydroxyl groups; or

R ³ , R ^{4 taken} together = 0.

6. The method according to claim 5, characterized in that the substituents R ¹ , R ² , R ³ and R ^{4 have} the following meaning: R ¹ and R ² are independently selected from the group consisting of: hydrogen, saturated linear and branched , Unsubstituted and optionally aryl-substituted -CC ₅ alkyl groups; Formyl groups and saturated li middle and branched, unsubstituted and optionally aryl-substituted aliphatic Ci-Cs-acyl groups; Groups of the type R ⁵ OC (0) -, in which R ^{5 is} a saturated linear or branched, unsubstituted or optionally aryl-substituted. C 1 -C ₂ alkyl group; and optionally substituted aromatic C _β -acyl groups;

R ³ and R ⁴ are substituents which are optionally present and are selected independently of one another from the group consisting of hydrogen, saturated and unsaturated, linear and branched, substituted and unsubstituted Cχ-Cι ₂ alkyl groups and hydroxyl groups; or

R ³ , R ^{4 taken} together = 0.

Method according to one of claims 4 to 6, characterized in that PMAm is produced by hydrolysis of poly (1, 3-diacyl-4-imidazolin-2- (thi) on) containing recurring units of the general formula III

in which R is selected from the group consisting of hydrogen, linear and branched C 1 -C 8 -alkyl groups, linear and branched C 1 -C 8 -alkoxy groups, and phenyl, preferably hydrogen and linear and branched C 1 -C 4 -alkyl groups, in particular R is a methyl group;

X is 0 or S, preferably 0.

8. The method according to claim 7, characterized in that the hydrolysis is carried out by strong bases, preferably alcoholates, NaOH, KOH, LiOH, CaOH and mixtures thereof, in particular a eutectic mixture or a mixture of NaOH and KOH lying close to the eutectic ,

9. Polymethylene amine copolymer containing, in addition to units of the formula (I), one or more further monomer units different from (I) derived from those with methylene amine units copolymerizable monomers, preferably monoethylenically unsaturated monomers.

10. Polymethyleneamine copolymer according to claim 9, characterized in that the monomers are selected from the group

Vinyl esters of saturated carboxylic acids with 1 to 6 carbon atoms and vinyl ethers such as C ₁ -C ₆ -alkyl vinyl ethers, esters, amides and nitriles of ethylenically unsaturated C ₃ - to C ₆ -carboxylic acids, carboxylic acid esters derived from glycols and polyalkylene glycols, where in each case just one oh

Group is esterified, acrylic acid monoesters of polyalkylene glycols with a molecular weight of 500 to 10,000, esters of ethylenically unsaturated carboxylic acids with amino alcohols, amides of ethylenically unsaturated carboxylic acids, N-alkyl mono- and diamides of monoethylenically unsaturated carboxylic acids with alkyl radicals of 1 to 6 carbon atoms, basic (meth ) acrylic amides, N-vinylpyrrolidone, N-vinylcaprolactam, acrylonitrile, methacrylonitrile, N-vinylimidazole, substituted N-vinylimidazoles and N-vinylimidazolines, acrylic acid, methacrylic acid, vinylformamide, styrene, butadiene, maleic anhydride, fumaric acid and maleic acid.

11. Poly (1, 3-diacyl-4-imidazolin-2- (thi) on) containing repeating units of the general formula III

R is selected from the group consisting of hydrogen, linear and branched Cx-Cs-alkyl groups, linear and branched Cχ-C o-alkoxy groups, and phenyl, preferably hydrogen and linear and branched C ₁ -C ₃ -alkyl groups, in particular R is a methyl group;

X is 0 or S, preferably 0,

with the proviso that poly (1, 3-diacetyl-4-imidazolin-2-one) with a degree of polymerization n of 3 to 4 is excluded.

12. Process for the preparation of

Poly (1, 3-diacyl-4-imidazolin-2- (thi) on) according to claim 11 by polymerization of 1, 3-diacyl-4-imidazolin-2- (thi) on, preferably by radical polymerization. 5

13. A process for the preparation of polymethylene amine according to one of claims 1 to 3 by hydrolysis of poly (1, 2-diaminoethen) derivatives under conditions known per se.

14. The method according to claim 13, characterized in that the poly (1, 2-diaminoethene) derivatives by radical or cationic polymerization, preferably cationic polymerization, of 1,2-diaminoethene derivatives of the general formula IV

15

are obtained in which R ¹ and R ^{2 are} independently a radical of the formula R ⁵ , OR ⁶ or NR ⁷ R ⁸ , where R ⁵ , R ⁶ , R ⁷ and R ⁸ are selected independently of one another from the group consisting of Hydrogen, linear and branched C ₁ -C ₆ -alkyl groups, which optionally have one or more substituents from the group of optionally alkyl-substituted C ₆ aromatics, and C ₆ aromatics, which optionally have one or more substituents from the group consisting of Cι ~ Have co-alkyl groups, R ³ and R ⁴ are independently selected from hydrogen, -C ~ co-alkyl groups and aromatics. 35

15. The method according to claim 14, characterized in that R ¹ and R ² are OR ⁶ with R ⁶ are -CC ₆ alkyl, phenyl or benzyl.

16. The method according to claim 14 or 15, characterized in that the 1, 2-diaminoethene derivative of the formula IV is obtained by reacting imidazole with an acyl halide derivative.

45 17. Poly (1,3-diacyl-4-imidazolin-2- (thi) on).

18th Poly (4-imidazolin-2-one).

19. Poly (1,2-diaminoethene) derivatives.

20. Use of polymethyleneamine according to one of claims 1 to 3 as a retention agent in the production of paper, cardboard and cardboard, as a fixing agent for rendering harmless in the manufacture of paper, as a fixing agent for anionically stabilized sizing agents, as a fixing agent for fixing anionic dyes, as a primer for adhesion to anionic surfaces, as an aid in oil production, as a textile and leather aid, as a component in detergents, as an emulsifier for emulsions / dispersions, as a crosslinker in the manufacture of PUR, as a scavenger of formaldehyde and higher aldehydes, as Binder for fiberboard, as an aid for sludge dewatering and as a vector in cancer therapy.

21. Use according to claim 20, characterized in that the paper is selected from papers for newspaper printing, so-called medium-fine writing and printing papers, gravure papers and lightweight coating base papers.

22. Use according to claim 20, characterized in that the cardboard, the cardboard box or the newspaper paper is selected

Waste paper and such material systems which contain contaminants and which accumulate in the at least partially closed water cycles of paper machines.