EP1141483A1

EP1141483A1 - Modified cationic polymers, a method for the production thereof and their use during paper production

Info

Publication number: EP1141483A1
Application number: EP99955916A
Authority: EP
Inventors: Jürgen DECKER; Norbert Mahr; Anton Esser; Hubert Meixner; Rainer Dyllick-Brenzinger; Martin Aus Dem Kahmen; Martin Gercke
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 1998-11-04
Filing date: 1999-10-29
Publication date: 2001-10-10
Also published as: CA2347788A1; WO2000026468A1; DE19850817A1; US6716311B1; JP2002529612A

Abstract

The invention relates to modified cationic polymers which can be obtained by reacting (a) water-soluble, polymeric compounds containing NH groups with (b) compounds which are at least bifunctional with regard to NH groups, which contain at least one alkyl radical or alkenyl radical having at least 8 C atoms, and which contain, as a functional group, a halohydrin, epoxide, carboxyl, chloroformate or isocyanate group or a halogen atom. The invention also relates to a method for producing the polymers by reacting the compounds of groups (a) and (b), and to the use of the modified cationic polymers during the production of paper as fixing agents for papermaking stock containing interfering substances.

Description

Modified cationic polymers, processes for their manufacture and their use in papermaking

description

The invention relates to modified cationic polymers which can be obtained by reacting polymer compounds containing water-soluble NH groups with crosslinking agents, processes for their preparation and their use in paper production.

EP-A-0438707 discloses a process for the production of paper, cardboard and cardboard by dewatering a paper material containing impurities in the presence of hydrolyzed homo- and / or copolymers of N-vinylformamide with a degree of hydrolysis of at least 60% and cationic retention agents.

In order to inhibit the deposition of pitch in the manufacture of paper, a water-soluble polymer is added to the paper stock according to the process of EP-A-0649941, which at least

Contains 5 mol% of an N-alkyl-N-vinylcarboxamide, N-vinylformamide, N-vinylacetamide or partially hydrolyzed N-alkyl-N-vinylcarboxamide.

From US-A-5536370 condensation products of polyalkylene polyamines are known which are converted to crosslinked polyalkylene polyamines by partial amidation of polyalkylene polyamines and subsequent condensation of the partially amidated polyalkylene polyamines with at least bifunctional crosslinking agents. These products are used in paper production as fixatives for soluble contaminants.

From the unpublished DE-A-19719059.6, reaction products of polymers containing amino groups with reactive sizing agents, in particular alkyldiketenes, are known. The reaction products are used as fixatives for water-soluble and water-insoluble contaminants in the manufacture of paper, cardboard and cardboard from paper materials containing contaminants.

From US-A-5324787 modified polymers containing vinylamine units are known which can be obtained by reacting polymers containing vinylamine units with saturated aliphatic or aromatic glycidyl ethers. The reaction products are used as flocculants and to increase the retention of fines in papermaking. The aliphatic used for the modification Glycidyl ethers contain 1 to 18, preferably 4 to 12 carbon atoms in the alkyl group. The use of butyl glycidyl ether as a modifier is preferred.

The object of the invention is to provide new polymers which are effective as fixing agents in paper production.

The object is achieved according to the invention with modified cationic polymers which can be obtained by reacting

(a) water-soluble, NH groups-containing polymeric compounds

(b) Compared to NH groups, at least bifunctional compounds which contain at least one alkyl or alkenyl radical having at least 8 carbon atoms and as a functional group a halogenohydrin, epoxy, carboxyl, chloroformate or isocyanate group or a halogen atom .

The invention also relates to a method for producing the modified cationic polymers by reacting

(a) water-soluble, NH groups-containing polymeric compounds

(b) Compared to NH groups, at least bifunctional compounds which have at least one alkyl or alkenyl radical having at least 8 carbon atoms and as a functional group a halogenohydrin, epoxy, carboxyl, chloroformate or isocyanate group or a halogen atom .

The compounds of group (a) are essentially polymers containing water-soluble amino and / or ammonium groups. An example of such polymers are polyalkylene polyamines such as diethylene triamine, triethylene tetramine, tetraethylene pentamine, pentaethylene hexamine, 3- (2-aminoethyl) aminopropylamine, 2 - (diethylamino) ethylamine, 3- (dimethylamino) propylamine, dimethyldipropylenetriamine, 4-aminoethyloctane -l.8-diamine, 3- (diethylamino)) propylamine, N, N-diethyl-1, -pentanediamine, dipropylenetriamine, bis (hexamethylene) triamine, N, N-bis (amino-propyDmethylamine, N, N-bis ( aminopropyl) ethylamine, N, N-bis (amino-propyDhexylamine, N, N-bis (aminopropyl) octylamine, N, N-dimethyldipropylenetriamine, N, N-bis (3-dimethylaminopropyl) amine, N- (amino-ethyl ) butylenediamine, N- (aminopropyl) butylenediamine, bis (aminopropyl) butylenediamine and polyethyleneimines. Polyalkylene polyamines which are preferably used are polyethyleneimines which, for example can be prepared by polymerizing ethyleneimine in aqueous solution in the presence of acid-releasing compounds, acids or Lewis acids. For example, the polyethyleneimines have molar masses of 1,000 to 5,000,000 g / mol. Polyethyleneimines with average molecular weights of 5,000 to 800,000 g / mol are particularly preferred.

Other suitable water-soluble polymeric compounds containing NH groups are polyamidoamines, which can be obtained, for example, by condensing dicarboxylic acids with polyamines. Suitable polyamidoamines are obtained, for example, by reacting dicarboxylic acids with 4 to 10 carbon atoms with polyethyleneimines (average molar masses from 300 to 1000 g / mol) or with polyalkylene polyamines which contain 3 to 10 basic nitrogen atoms in the molecule. Suitable dicarboxylic acids are, for example, succinic acid, maleic acid, adipic acid, glutaric acid, suberic acid, sebacic acid or terephthalic acid. Mixtures of dicarboxylic acids can also be used in the preparation of the polyamidoamines, as can mixtures of several polyalkylene polyamines. Suitable polyalkylene polyamines are, for example, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dipropylenetriamine, tripropylenetetramine, dihexamethylenetriamine, aminopropylethylenediamine and bis-aminopropylethylenediamine. The dicarboxylic acids and polyalkylene polyamines are heated to higher temperatures to produce the polyamidoamines, e.g. to temperatures in the range of 120 to 220, preferably 130 to 180 ° C. The water generated during the condensation is removed from the system. Lactones or lactams 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. The weight average molecular weights of the polyamidoamines are preferably at least 1000 g / mol.

Other polymers containing amino groups are polyamidoamines grafted with ethyleneimine. They are obtained from the polyamidoamines described above by reaction with ethyleneimine in the presence of acids such as sulfuric acid or Lewis acids, for example boron trifluoride etherates, at temperatures of, for example, 80 to 100 ° C. For example, 1 to 100 parts by weight of ethyleneimine are grafted on per 100 parts by weight of a polyamidoamine. It is preferred to use uncrosslinked polyamidoamines, optionally grafted with ethyleneimine. Compounds of this type are described for example in DE-B-24 34 816. Polyallylamines are also suitable as cationic polymers of group (a). Polymers of this type are obtained by homopolymerizing allylamine, preferably in acid-neutralized or quaternized form, or by copolymerizing allylamine with other monoethylenically unsaturated monomers, as described below as comonomers for N-vinylcarboxamides.

Other water-soluble polymeric compounds of group (a) containing NH groups are polymers containing vinylamine units. For example, open-chain N-vinylcarboxamides of the formula are used to prepare them

CH ₂ = CH N (I)

C - R ²

0

from in which R ¹ and R ^{2 may be the} same or different and stand for hydrogen and Ci- to Cβ-alkyl. Suitable monomers are, for example, N-vinylformamide (R ^{1 =} R ² = H in formula I), N-vinyl-N-methylformamide, N-vinylacetamide, N-vinyl -N-methylacetamide, N-vinyl-N-ethylacetamide, N- Vinyl -N-methylpropionamide and N-vinyl - propionamide. To prepare the polymers, the monomers mentioned can be polymerized either alone, as a mixture with one another or together with other monoethylenically unsaturated monomers. Homopolymers or copolymers of N-vinylformamide are preferably used. Polymers containing vinylamine units are known, for example, from US Pat. Nos. 4,421,602, EP-A-0 216 387 and EP-A-0 251 182. They are obtained by hydrolysis of polymers which contain the monomers of the formula I polymerized in with acids, bases or enzymes.

Examples of monoethylenically unsaturated monomers which are copolymerized with the N-vinylcarboxamides are vinyl esters of saturated carboxylic acids of 1 to 6 carbon atoms such as vinyl formate, vinyl acetate, vinyl propionate and vinyl butyrate and vinyl ethers such as Ci to Cβ alkyl vinyl ether, e.g.

Methyl or ethyl vinyl ether. Further suitable comonomers are ethylenically unsaturated C ₃ to C ₆ carboxylic acids, for example acrylic acid, methacrylic acid, maleic acid, crotonic acid, itaconic acid and vinyl acetic acid, and also their alkali metal and alkaline earth metal salts, esters, amides and nitriles of the carboxylic acids mentioned, for example methyl acrylate, methyl methacrylate, Ethyl acrylate and ethyl methacrylate. Other suitable carboxylic acid esters are derived from glycols or polyalkylene glycols, only one at a time

OH group is esterified, e.g. Hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate and acrylic acid monoesters of polyalkylene glycols with a molecular weight of 500 to 10,000.

Other suitable comonomers are esters of ethylenically unsaturated carboxylic acids with amino alcohols, for example

Dirnethylaminoethyl acrylate, dimethylaminoethyl methacrylate,

Diethylaminoethyl acrylate, Diethylaminoethylmethacrylat, Dirnethyl - aminopropylacrylat, Dirnethylaminopropylmethacrylat, Diethylaminoopropylacrylat, Dimethylaminobutylacrylat and Diethylaminobutylacrylat. 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 radicals of 1 to 6 carbon atoms, e.g. N-methyl acrylamide, N, N-dimethylacrylamide, N-methyl methacrylamide, N-ethyl acrylamide, N-propylacrylamide and tert. Butylacrylamide and basic (meth) acrylic amides, e.g. Dimethylaminoethyl acrylamide, dimethylaminoethyl methacrylamide, diethylaminoethyl acrylamide, diethylaminoethyl methacrylamide, dimethylaminopropylacrylamide, diethylaminopropylacrylamide, dimethylaminopropyl methacrylamide and diethylaminopropyl methacrylamide.

Also suitable as comonomers are N-vinylpyrrolidone, N-vinylcaprolactam, acrylonitrile, methacrylonitrile, N-vinylimidazole and substituted N-vinylimidazoles such as, for example, 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-vinylimidazoles 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 dimethyl sulfate, diethyl sulfate, methyl chloride or benzyl chloride. Diallyldialkylammonium halides, such as diallyldimethylammonium chlorides, are also suitable. Also suitable as comonomers for the compounds of the formula I are monomers containing sulfo groups, such as, for example, vinylsulfonic acid, allylsulfonic acid, methallylsulfonic acid, styrene sulfonic acid, the alkali metal or ammonium salts of these acids or 3-sulfopropyl acrylate. A further modification of the polymers containing vinylamine units can be achieved by polymerizing up to 5 mol% of monomers with at least two ethylenically unsaturated double bonds. Comonomers of this type are usually used as crosslinkers in copolymerizations. The use of these comonomers during the copolymerization increases the molecular weights of the copolymers. Suitable compounds of this type are, for example, methylenebisacrylamide, esters of acrylic acid and methacrylic acid with polyhydric alcohols, for example glycol diacrylate, glycerol triacrylate, glycol dimethacrylate, glycerol tri methacrylate and at least two other polyols esterified with acrylic acid or methacrylic acid, such as pentaerythritol and glucose. Suitable crosslinkers are also divinylbenzene, divinyldioxane, pentaerythritol triallyl ether, pentaallylsucrose, divinylurea and divinylethyleneurea.

The copolymers contain, for example

99 to 1 mol%, preferably 95 to 5 mol% of N-vinylcarboxamides of the formula I and

1 to 99 mol%, preferably 5 to 95 mol% of other monoethylenically unsaturated monomers copolymerizable therewith

in polymerized form.

In order to prepare polymers containing vinylamine units, it is preferable to start from homopolymers of N-vinylformamide or from copolymers, preferably by copolymerizing

N-vinylformamide with

Vinyl formate, vinyl acetate, vinyl propionate, acrylonitrile, N-vinyl caprolactam, N-vinyl urea, acrylic acid, N-vinyl pyrrolidone or Ci to β-alkyl vinyl ethers

and subsequent hydrolysis of the homo- or of the copolymers to form vinylamine units from the copolymerized N-vinylformamide units, the degree of hydrolysis being, for. B. is 0.1 to 100 mol. The polymers described above are hydrolysed by known processes by the action of acids, bases or enzymes. In this case, the monomers of the formula I given above are polymerized in by splitting off the grouping

- C - R ² n ⁽ II ⁾ ,

where R ^{2 has} the meaning given for it in formula I, polymers, the vinylamine units of the formula

CH ₂ - CH -

N ^(III)

/ \

H Rl

contain in which R ^{1 has} the meaning given in formula I.

The homopolymers of the N-vinylcarboxamides of the formula I and their copolymers can be hydrolyzed to 0.1 to 100, preferably 1 to 99 mol%. In most cases, the degree of hydrolysis of the homo- and copolymers is 5 to 95 mol%. The degree of hydrolysis of the homopolymers is synonymous with the vinylamine units in the polymers. In the case of copolymers which contain vinyl esters in copolymerized form, in addition to the hydrolysis of the N-vinylformamide units, hydrolysis of the ester groups can occur with formation of vinyl alcohol units. This is particularly the case when the copolymers are hydrolysed in the presence of sodium hydroxide solution. Polymerized acrylonitrile is also chemically changed during hydrolysis. This creates, for example, amide groups or carboxyl groups. The homo- and copolymers containing vinylamine units can optionally contain up to 20 mol% of amidine units which are formed, for example, by reaction of formic acid with two adjacent amino groups or by intramolecular reaction of an amino group with an adjacent amide group, for example of polymerized N-vinylformamide. The molar masses of the polymers containing vinylamine units are, for example, 1000 to 10 million, preferably 10,000 to 5 million (determined by light scattering). This molar mass range corresponds, for example, to K values of 5 to 300, preferably 10 to 250 (determined according to H. Fikentscher in 5% aqueous sodium chloride solution at 25 ° C. and a polymer concentration of 0.5% by weight). The polymers containing vinylamine units are preferably used in salt-free form. Salt-free aqueous solutions of polymers containing vinylamine units can be prepared, for example, from the salt-containing polymer solutions described above by means of dialysis or ultrafiltration on suitable membranes at separation limits of, for example, 1000 to 500,000 dalons, preferably 10,000 to 300,000 daltons. The aqueous solutions of other polymers containing amino and / or ammonium groups described below can also be obtained in a salt-free form with the aid of dialysis or ultrafiltration. In ultrafiltration on membranes with the abovementioned separation limits, apart from the separation of salts which arise, for example, from the hydrolysis of polymers containing N-vinylformamide units with acids or bases, fractionation of the polymers is also achieved, so that polymers with a narrower molar mass distribution M _w / M _n receives. The fractions of more narrowly distributed polymers obtained as the retentate in the ultrafiltration give reaction products when reacting with the compounds of group (b), which usually have a higher activity than reaction products which result from the reaction of non-fractionated polymers of the same composition with such compounds arise.

The compounds (a) containing NH groups, which are preferably used for the production of the modified cationic polymers, are polyalkylene polyamines, polyamidoamines, polyamidoamines grafted with ethyleneimine and polymers containing vinylamine units. The molar masses of the compounds (a) containing NH groups are preferably at least 1000 g / mol.

The compounds of group (a) are reacted with compounds (b) which are at least bifunctional with respect to NH groups, at least one alkyl or alkenyl radical having at least 8 carbon atoms and as a functional group a halohydrin, epoxide or carboxyl group - Contain chloroformate or isocyanate group or a halogen atom. Preferred compounds of group (b) can be characterized, for example, using the following formulas: (0A) _n - X 0

^^ ₍₀ A) _n - χ ^θdβr - ^(A0) r_- ^χ ,

R ^ ^" ^ ^

(AO) _n - X

(IV) (V)

where each R = C ₈ - to C ₃₀ alkyl or alkenyl radical, A = C ₂ - bis

C -alkylene group, n = 0-50 and X = halohydrin, epoxy,

Carboxyl, chloroformate or isocyanate group or a halogen atom.

The compounds of the formula IV can be obtained starting from α-olefin diols, which are optionally alkoxylated and then provided with a functional group. For example, long-chain α-olefin diols are reacted with preferably 5 to 20 mol of ethylene oxide and a halogenohydrin group is introduced into the reaction product by reaction with epichlorohydrin. For example, 0.5 to 2.5, preferably 0.9 to 1.2, mol of epichlorohydrin are used per OH group. The halohydrin groups of the formula IV can be converted into epoxy groups by treatment with, for example, aqueous bases.

The compounds of the formula V are obtained, for example, by reacting fatty acids with at least 8 carbon atoms in the molecule with, for example, diethanolamine with amide formation and alkoxylating the resulting fatty acid amides, if appropriate, and then introducing a functional group. This can be done most simply, for example, by reacting the fatty acid amide or the alkoxylated fatty acid amides with epichlorohydrin. This gives compounds of the type of the formula V in which X is a halohydrin group. Treatment with aqueous bases results in epoxide groups from the halohydrin groups.

Further compounds of group (b) can be used, for example, using the formula

are characterized in which R = Cs to C ₃₀ alkyl or alkenyl, A = C ₂ to C alkylene, n = 0 to 50 and X = halohydrin, preferably chlorohydrin, epoxy, carboxyl, chloroformate or isocyanate group or a halogen atom, preferably a chlorine atom.

Compounds of the formula VI are obtained, for example, by reacting diethanolamine with an alkyldiketene such as stearyldiketene or oleyldiketene, optionally alkoxylation with ethylene oxide, propylene oxide and / or butylene oxide and then introducing chlorohydrin groups by reaction with epichlorohydrin.

If X represents a halohydrin group, the corresponding epoxides can be prepared from the compounds of the formula VI by treatment with bases.

Compounds of the formula also come as compounds of group (b)

into consideration, in which R = Cs to C ₃₀ alkyl or alkenyl, A = C ₂ to C alkylene, n = 0-50 and X = halohydrin, epoxy, carboxyl,

Chloroformate or isocyanate group or a halogen atom.

Compounds of formula VII are obtained e.g. from a long-chain α-olefin epoxide (epoxide with 10 to 32 carbon atoms) by reaction with diethanolamine in a molar ratio of 1: 3, optionally alkoxylation with ethylene oxide, propylene oxide and / or butylene oxide and reaction with epichlorohydrin.

Other compounds (b) can be prepared, for example, by alkoxylating Ca to C ₃ o -alkylamines and reacting the products thus obtainable with epichlorohydrin. Such compounds have the formula

(AO) _n -X

in the R = Cβ "to C ₀ alkyl or alkenyl, A = C ₂ - to C ₄ alkylene, n = 0-50 and X = halohydrin, epoxy, carboxyl, chloroformate or isocyanate group or a halogen atom.

The alkoxylation can be carried out using ethylene oxide, propylene oxide or butylene oxide. Ethylene oxide is preferably used. The ethoxylation of the long-chain (-C ₀ - to C ₃₂ ) α-olefin diols, the fatty amines or the long-chain carboxylic acid amides is carried out in a manner known per se in the presence of the customary catalysts such as bases, for example alkali metal, alkaline earth metal or ammonium hydroxides, and carbonates or alcohols of alkali metals or alkaline earth metals. The alkoxylation takes place, for example, in a pressure autoclave at temperatures of 60 to 230 ° C. and pressures of, for example, 1 to 10 bar. After the reaction, the reaction product is neutralized with acid, if appropriate separated from the neutralized catalyst by filtration through a pressure filter, a plate filter or a glass frit.

The addition of epichlorohydrin to the OH groups of the starting compounds is preferably carried out in the presence of Lewis acids at temperatures from 50 to 150 ° C. Methods of this type are known, cf. DE-B 2434816. Compounds (b) which are particularly preferred are compounds of the formula derived from α-olefin diols

in which n = 5 - 27; x, y = 0 - 40 mean.

The compounds of the invention are obtained by reacting at least one

(a) Water-soluble NH-containing polymeric compound with (b) Compared to NH groups, at least bifunctional compounds which have at least one alkyl or alkylene radical having at least 8 carbon atoms and as a functional group have a halohydrin, epoxy, carboxyl, chloroformate or isocyanate group or a halogen atom.

The reaction of the compounds (a) and (b) is preferably carried out in aqueous solution at temperatures from 20 to 100 ° C. to form aqueous solutions or dispersions. The weight ratio of the compounds (a) to the compounds (b) can be varied within a wide range and is, for example, in the range from 15,000: 1 to 1: 1, preferably 500: 1 to 10: 1. The quantitative ratios of the components (a) and (b) are chosen so that water-soluble or self-emulsifying polymers are formed. According to the preferred embodiment of the method according to the invention, one sets

a) NH-containing compounds selected from the group of polyalkylene polyamines, polyamidoamines, polyamidoamines grafted with ethyleneimine and polymers containing vinylamine units with

(b) at least one compound of the formula

(A0) _n - _X

(IV) (V)

um, in which R = Cβ to C ₃₀ alkyl or alkenyl, A = C ₂ to C alkylene group, n = 0 - 50 and X = halohydrin, epoxy, carboxyl, chloroformate or isocyanate group or a halogen atom mean. The substituent X in the formulas IV and V preferably denotes an epichlorohydrin group or the epoxide group obtainable therefrom by treatment with bases.

The modified cationic polymers, which can be obtained by reacting the compounds of groups (a) and (b), are used as fixatives for paper materials containing interfering substances in papermaking. The term paper manufacture encompasses the manufacture of paper, cardboard and cardboard by dewatering a paper stock. In paper production, so-called stickies are often the cause of production disruptions. Both Stickies are sticky contaminants that get into the paper manufacturing process, for example, when recycling waste paper with the recycled fibers. Such contaminants lead to deposits on screens, felts, rollers and other moving parts of paper machines. As the water cycles in the paper mills are increasingly restricted, anionic compounds accumulate in the returned water, which severely impair the effectiveness of cationic polymeric process chemicals in the dewatering of paper stock and the retention of fillers and fibers. Fixing agents are used in practice to process paper materials containing such contaminants. In the absence of fixing agents, for example, imperfections form in the paper web, usually in the form of thin spots or holes, which on the one hand negatively influences the quality of the paper produced and on the other hand can cause tears in the paper web in the paper machine.

The modified cationic polymers described above are effective fixatives for contaminants. The fixatives can be used in the processing of all fiber qualities. In practice, water is used for the production of the paper stock, which is at least partially or completely returned from the paper machine. These are either clarified or untreated white water and mixtures of such water qualities. The returned water contains - just like recycled waste paper - more or less large amounts of contaminants. In addition to resins and lignin components, which are produced in the fiber production from cooking and mechanical processing of wood, the main sources of contaminants and sticky are mainly dispersions, natural colloidal systems such as starch, caseins and dextrins as well as hot melt adhesives. For example, these can be residual components of chemicals and printing inks from the deinking process as well as binders made from paper coating colors.

Specifically, these are resins, lignin residues, adhesives made from spine gluing, from adhesive labels and envelopes, and binders made from coating and printing inks. Depending on the recycled goods brought in, sticky particles or white pitch appear as different sized particles or as coarsely to finely dispersed and in different quantities and are often only insufficiently removed from the mixture of materials by flotation systems or machine-based stock preparation and sorting systems. The content of such interfering substances in the paper stock can be characterized, for example, with the sum parameter chemical oxygen demand (COD value). The COD values of such paper stock are 300 to 40,000, preferably 1000 to 30,000 mg oxygen / kg of the aqueous phase of the paper stock. These amounts of contaminants severely impair the effectiveness of conventional cationic drainage and retention agents as long as they are used in the absence of fixatives in papermaking.

All the qualities customary for this purpose can be considered as pulps for the production of the pulps, for example wood pulp, bleached and unbleached cellulose and pulps from all annual plants. For example, wood pulp includes wood pulp, thermomechanical substance (TMP), chemo-thermomechanical substance (CTMP), pressure sanding, semi-pulp, high-yield pulp and refiner mechanical pulp (RMP). Examples of suitable pulps are sulfate, sulfite and sodium pulps. The unbleached pulps, which are also referred to as unbleached kraft pulp, are preferably used. Suitable annual plants for the production of paper materials are, for example, rice, wheat, sugar cane and kenaf. Waste paper and what is known as coated scrap, which contains more or less large amounts of binder for coating and printing inks and starch, adhesive from adhesive labels and envelopes, remnants of dispersion from paper finishing and adhesives from spine gluing and so-called hot melts, are also used to produce the pulps. either alone or in a mixture with other fibers. Pulps of the type described above contain more or less large amounts of interfering substances which, as already explained, can be determined using the COD value or also using the so-called cationic requirement. Cationic requirement is the amount of a cationic polymer that is necessary to bring a defined amount of white water to the isoelectric point. Since the cationic requirement is very strongly dependent on the composition of the cationic retention agent used for the determination, a polyamidoamine obtained according to Example 3 of DE-C 2434816 from adipic acid and diethylenetriamine was used, which was grafted with ethyleneimine and mixed with polyimide. ethylene glycol dichlorohydrin ether was crosslinked. The pulps containing impurities have COD values in the range given above and, for example, have a cationic requirement of more than 50 mg of polymer 1/1 white water. The modified cationic polymers to be used according to the invention lead to a significant reduction in the contaminant loads consisting of resins, stickies, white pitch and other anionic contaminants such as humic acids, wood extracts, lignin and lignin sulfate residues when paper materials containing impurities are used. This manifests itself depending on the type of contaminant, for example in a lower turbidity of the filtrate water, a reduced COD value as well as fewer defects in the paper, a lower frequency of tearing of the paper web, shorter downtimes and cleaning times and less deposits on moving machine parts. The fixing agents thus contribute to an increase in the productivity of paper and board machines. In many cases, the modified cationic polymers to be used according to the invention additionally support the retention and dewatering and thus significantly improve the runnability of the machines in the paper manufacturing process. The modified cationic polymers are used, for example, in amounts of 0.01 to 2, preferably 0.02 to 1.0,% by weight, based on dry paper stock, in papermaking.

The fixing agents to be used according to the invention can optionally be used with other customary process chemicals for papermaking. Such process chemicals are retention aids, for example. These are, for example, polyethyleneimines, polyamines with molecular weights of more than 50,000, polyamides grafted with ethyleneimine if appropriate, polyetheramines, polyvinylimidazoles, polyvinylpyrrolidines, polyvinylimidazolines, polydialkyldiaminoalkylvinylethers, polydialkylaminoalkyl (meth) acrylates in protonated or quaternized form. Other suitable retention agents are, for example, polydiallyldialkylammonium halides, in particular polydiallyldimethylammonium chloride. Particularly preferred retention agents are the crosslinked polyamidoamines described in DE-C-2434816, which are obtained by condensation of dicarboxylic acids such as adipic acid with polyalkylene polyamines such as diethylenetriamine,

Grafting the polyamidoamines with ethyleneimine and reaction of the products grafted with ethyleneimine with dichlorohydrin ethers of polyalkylene glycols are available. Other commercially available retention agents are, for example, copolymers of acrylamide or methacrylamide and dialkylaminoalkyl acrylates or dialkylaminoalkyl methacrylates, e.g. Copolymers of acrylamide and N, N-dimethylaminoethyl acrylate or copolymers of acrylamide and N, N-diethylaminoethyl acrylate. The basic acrylates are preferably used in acid neutralized or in quaternized form. The quaternization can, for example, with

Methyl chloride, dimethyl sulfate or benzyl chloride can be made. The cationic retention agents have, for example Fikentscher K values (determined in 5% aqueous saline solution at a polymer concentration of 0.5% by weight and at a temperature of 25 ° C.) of at least 140. The retention aids are usually used in amounts of 0.02 to 1.0 % By weight, based on 5 dry fibers, used in papermaking.

The K values were determined according to H. Fikentscher, Cellulose-Chemie, Vol. 13, 58-64 and 71-74, (1932) in 5% aqueous saline solution at a polymer concentration of 0.5% and a temperature of 25 ° C certainly.

example 1

860 g of a 25% strength aqueous polyethyleneimine solution were placed in a two-liter four-necked flask equipped with a stirrer, 15 reflux condenser and internal thermometer. The polyethyleneimine had an average molecular weight M _w of 750,000 g / mol. The aqueous polymer solution was heated to a temperature of 60 ° C. with vigorous stirring and at this temperature with 7.03 g of the compound of the formula

30 in which n = 17-21, x = 9 and y = 10. The reaction mixture was stirred at this temperature for 2 hours. A slightly yellow, cloudy solution with a viscosity of 460 mPas was obtained (measured in a Brookfield viscometer, spindle 2, 35 23 ° C.).

Example 2

In a 1 1 four-necked flask equipped with a stirrer, reflux condenser and a thermometer, 190 g of a 13.5% strength aqueous polyvinylformamide solution were introduced. The polyvinylformamide had a K value of 89 (M _w = 250,000 g / mol). The polymer solution was stirred and heated to a temperature of 80 ° C. 10 g of a 50% strength 45 aqueous sodium hydroxide solution (125 mmol) were added within 10 minutes and the reaction mixture was then stirred at 80 ° C. for a further 2 hours. 200 g of an aqueous polymer solution with a polymer content of 11.8% were obtained. The Polymer contained 67 mol% vinylformamide and 33 mol% vinylamine units. The polymer solution was cooled to a temperature of 60 ° C. and 0.054 g of the compound of the formula X described in Example 1 was added at this temperature. The reaction mixture was stirred at a temperature of 60 ° C. for 2 hours and then cooled to room temperature. A slightly cloudy solution was obtained.

Example 3

In a 1 liter four-necked flask equipped with a stirrer, reflux condenser and internal thermometer, 500 g of a 9.6% strength aqueous solution of a modified polyethyleneimine were prepared, which according to Example 3 of DE-C-2434816 were grafted with a polyamidoamine prepared from adipic acid and polyalkylene polyamine with ethyleneimine and then crosslinked with polyethylene glycol dichlorohydrin ether and subjected to ultrafiltration, the high molecular weight fraction (more than 500 kD) being isolated. The modified polyethyleneimine was heated to a temperature of 60 ° C. with stirring and 0.530 g of the compound of the formula X described in Example 1 was added at this temperature. The reaction mixture was stirred at 60 ° C for 2 hours and then cooled to room temperature. A slightly yellow, slightly cloudy solution with a viscosity of 112 mPas (Brookfield viscometer, spindle No. 1, 23 ° C.) was obtained.

Comparative Example 1 (Example 1 of US-A-5536370)

799 g of an anhydrous polyethyleneimine with an average molecular weight M _w of 25,000 g / mol were placed in a flask equipped with a stirrer, thermometer and a device for working under nitrogen, heated to 140 ° C. in a stream of nitrogen and inside 69 g of propionic acid were added over 30 minutes. The temperature was then raised to 180 ° C. and the water of reaction was distilled off continuously over a period of 5 hours. 200 g of the polymer thus obtained were then diluted with 700 ml of water and heated to 70 ° C. 36.5 ml of a 21% strength aqueous solution of an α, ω-bischlorohydrin of a polyethylene glycol with a molecular weight of 400 g / mol were added in portions over the course of 3 hours. The reaction mixture was then stirred for a further 1 hour at 70 ° C. and then adjusted to pH 8 with 85 g of an 85% strength formic acid. 1018 g of a 20.7% strength polymer solution with a viscosity of 884 mPas (Brookfield viscometer, spindle no. 2, 20 ° C.) were obtained. Example 4

To an aqueous fiber slurry of TMP (thermomechanical pulp) with a material concentration of 0.8%, 0.16 g / 1 of an aqueous dispersion of filmed and reopened latex particles was added as a sticky substance. The latex was an acrylate copolymer dispersion. The same amount (0.05%, based on TMP) of the polymer indicated in each case in Table 1 was added to samples of this paper stock and paper sheets were formed on a Rapid-Koethen sheet former after mixing. The filtrate was checked for the content of particles using a laser-optical method, cf. Nordic Pulp & Paper Research Journal, No. 1, 1994, 9 pages 26-30 and 36). The relative total volume of the unfixed stickies with an addition amount of fixative of 0.05% polymer is of crucial importance for the effectiveness of the fixative, because this amount corresponds approximately to the amounts used in the paper production process. The smaller this value, the more effective the fixative.

Table 1

Example 5

Example 4 was repeated with the exception that latex particles based on a styrene-butadiene copolymer were added as an impurity to TMP in an amount of 0.16 g / l. The polymers specified in Table 2 were used as fixing agents. After the addition of the polymers, the fibrous material was mixed and dewatered on a Rapid-Koethen sheet former. The filtrate was then examined for the content of sticky particles. Table 2 shows the relative volume of unfixed sticky particles. Table 2

Claims

claims

1. Modified cationic polymers, characterized in that they are obtainable by reacting

(a) water-soluble, NH groups-containing polymeric compounds

(b) Compared to NH groups, at least bifunctional compounds which contain at least one alkyl or alkenyl radical having at least 8 carbon atoms and as a functional group a halohydrin, epoxy, carboxyl, chloroformate or isocyanate group or a halogen atom .

2. Modified cationic polymers according to claim 1, characterized in that the compounds containing NH groups

(a) are selected from the group of polyalkylene polyamines, polyamidoamines, polyamidoamines grafted with ethyleneimine and polymers containing vinylamine units.

3. Modified cationic polymers according to claim 1 or 2, characterized in that the NH group-containing compounds (a) have molecular weights of at least 1000 g / mol.

4. Modified cationic polymers according to one of claims 1 to 3, characterized in that

(a) Polyethyleneimines, polyamidoamines, polyamidoamines grafted with ethyleneimine, polymers containing vinylamine units or mixtures thereof

(b) at least one compound of the formula

(OA) _n - xo

_R A _^ «»> »- * ^or _R A _N - ^< * °> ^» - *

(AO) _n - x

(IV) (V) implemented in the R = Ca to C ₃₀ alkyl or alkenyl radical, A = C to C allylene group, n = 0-50 and X = halohydrin, epoxy, carboxyl, chloroformate or isocyanate group or a halogen atom mean.

5. A process for the preparation of the modified cationic polymers according to one of claims 1 to 4, characterized in that

(a) water-soluble, NH groups-containing polymeric compounds

(b) Compared to NH groups, at least bifunctional compounds which have at least one alkyl or alkenyl radical having at least 8 carbon atoms and as functional

Group have a halohydrin, epoxy, carboxyl, chloroformate or isocyanate group or a halogen atom.

6. The method according to claim 5, characterized in that one carries out the reaction of the compounds (a) and (b) in aqueous solution at temperatures of 20 to 100 ° C to form aqueous solutions or dispersions.

7. The method according to claim 5 or 6, characterized in that

a) compounds containing NH groups selected from the group of polyalkylene polyamines, polyamidoamines, polyamidoamines grafted with ethyleneimine and polymers containing vinylamine units with

(b) at least one compound of the formula

(AO) _n - _X

(IV) (V)

implemented in the R = C ₈ - to C ₃₀ -alkyl or alkenyl radical, A = C - to C ₄ -alkylene group, n = 0 - 50 and X = halohydrin, epoxy, carboxyl, chloroformate or isocyanate group or a Halogen atom mean. Use of the cationically modified polymers according to claims 1 to 4 as fixing agents for paper materials containing interfering substances in papermaking.