EP0158247B1 - Paper-making auxiliary agent - Google Patents

Description

The present invention relates to new agents for increasing the retention of fibers, fillers and pigments and for accelerating dewatering in papermaking and as flocculants in the processing of wastewater from papermaking by filtration, sedimentation and flotation.

German Offenlegungsschrift 2,736,651 (EP-A-0 000 714) describes condensation products which are obtained by reacting chloropolyethylene glycol ether amines with polyamide amines and then crosslinking with polyfunctional compounds. The chlorpolyethylene glycol ether amines are produced by addition of 2 moles of epichlorohydrin to 1 mole of polyethylene glycol ether catalyzed by boron trifluoride etherate and subsequent condensation of one side of the chain with special amines.

The use of an ambivalent polyether building block, i.e. a compound that can react with both amines and crosslinkers, but also with itself, leads to inconsistent products.

US Pat. No. 3,251,882 discloses polycondensates of a) epichlorohydrin and b) a precondensate of a polyalkylene polyamine and a polyoxyalkylene glycol chloride with a molecular weight of 100-800. The condensates are used to break petroleum / water-based emulsions.

From German published patent application 1932 394, water-soluble, self-crosslinking polyamine resins are known which are produced from aminoethers and epichlorohydrin and are used as wet strength agents for paper.

German Offenlegungsschrift 2,434,816 describes condensates composed of polyamide amines and polyalkylene oxide derivatives which are reacted with at least equivalent amounts of epichlorohydrin at the terminal OH groups. The condensation is carried out at 20 to 100 ° C. in aqueous solution, satisfactorily effective products being obtained in particular when the polyamide amines are grafted with ethylene imine.

European patent applications 0 033 104 and 0 074 558 disclose water-soluble condensation products of compounds containing amino groups and water-soluble crosslinking agents, which in turn were prepared in multi-stage reactions from epichlorohydrin or dichlorohydrin and compounds containing amino groups, and their use in papermaking.

The closure of the water cycles in paper production leads to an accumulation of contaminants in the system, which adversely affect the effect of the paper auxiliaries, in particular also the polyamide amines mentioned.

In particular, the contaminants form deposits and impair retention.

The object of the invention was therefore effective aids sensitive to impurities for the production of paper without having to graft monomeric ethyleneimine onto any component.

• A) aliphatischen, halogengruppenfreien Polyoletheraminen, die zusammenhängende Polyethersegmente enthalten, innerhalb dieser Segmente keine Aminogruppen tragen und erhalten werden aus m-Chlorpolyolethern und Polyalkylenpolyaminen im Molverhältnis von Chiorimω-Chlorpolyotether zu Polyalkylenpolyamin von 1 zu 0,95 bis 1,30 mit
• B) gegenüber Aminogruppen polyfunktionellen Verbindungen aus den Gruppen
  • a,co-Alkyldihalogenide,
  • Halogenhydrine,
  • Epihalogenhydrine,
  • Bisepoxyverbindungen,
  • Chlorameisensäureester und
  • Glycidylether von Polyalkylenoxiden sowie Verbindungen der Formel
  
  gegebenenfalls in Gegenwart von
• C) Polyaminopolyamiden und/oder
• D) Polyalkylenpolyaminen
  • erhältlich sind,
  • wobei soviel der Komponente B) eingesetzt wird, dass alle funktionellen Gruppen der Verbindungen B abreagiert haben und dass wasserlösliche Polykondensate entstehen, die bei 25°C in 25prozentiger wässriger Lösung eine Viskosität von 100 bis 1000 mPa_'s aufweisen.

It has now been found that extremely effective agents for increasing the retention of fibers, fillers and pigments and for accelerating dewatering in papermaking and as flocculants in the treatment of wastewater from papermaking by filtration, sedimentation and flotation can be obtained if one acts as an effective component uses one or more nitrogen-containing condensation products, which by reacting

• A) aliphatic, halogen group-free polyol ether amines, which contain contiguous polyether segments, do not carry any amino groups within these segments and are obtained from m-chloropolyol ethers and polyalkylene polyamines in a molar ratio of chloromω-chloropolyotether to polyalkylene polyamine from 1 to 0.95 to 1.30
• B) polyfunctional compounds from the groups with respect to amino groups
  • a, co-alkyl dihalides,
  • Halohydrins,
  • Epihalohydrins,
  • Bisepoxy compounds,
  • Chloroformate and
  • Glycidyl ethers of polyalkylene oxides and compounds of the formula
  
  optionally in the presence of
• C) polyaminopolyamides and / or
• D) polyalkylene polyamines
  • are available
  • so much of component B) is used that all functional groups of compounds B have reacted and that water-soluble polycondensates are formed which have a viscosity of 100 to 1000 mPa _' s in 25 percent aqueous solution at 25 ° C.

• a) ro-Polychlorpolyolethern mit einer Funktionalität von 1.90 - 3.10 Mol-CI/Mol und
• b) Polyalkylenpolyaminen der allgemeinen Formel
  
  • in der
  • R H oder CH₃,
  • y gleich oder verschieden die Zahl 0 oder 1 und
  • x eine Zahl von 1 bis 50 bedeuten,
  
  und oder

• c) Polyalkylenpolyaminen der allgemeinen Formel
  
  • in der
  • R^I = H oder CH₃,
  • x,y gleich oder verschieden die Zahl 0 oder 1,
  • m eine Zahl von 1 bis 50 und
  • n eine Zahl von 0 bis 50 bedeuten,

und/oder

• d) Polyalkylenpolyaminen der allgemeinen Formel
  
  • in der
  • Y = Sauerstoff, Schwefel oder den mindestens zweiwertigen Rest einer aliphatischen, cycloaliphatischen, araliphatischen oder aromatischen Hydroxyl- und/oder Sulfhydrylgruppen aufweisenden Verbindung,
  • R3= Wasserstoff oder CH₃,
  • p = eine ganze Zahl ≥ 1, vorzugsweise 1 - 3,
  • q = eine ganze Zahl ≥ 2, vorzugsweise 2 - 4,

und/oder

• e) Aminen der Formel
  
  • in der
  • R⁴ für einen gegebenenfalls durch eine Amino- oder Hydroxygruppe substituierten C₁-C₁₈-Alkylrest und
  • R⁵ und R⁶ unabhängig voneinander für Wasserstoff oder eine Methylgruppe stehen, und
  • r und s eine Zahl von 1 bis 20, vorzugsweise 1 bis 5, ist,

mit

• B) den vorstehend genannten, gegenüber Aminogruppen polyfuntionellen Verbindungen gegebenenfalls in Gegenwart von
• C) Polyaminopolyamiden, die aus 1 Molteil einer Dicarbonsäure mit 4 bis 10 Kohlenstoffatomen und 0,8 bis 1,4 Molteilen eines Polyalkylenpolyamins mit 3 bis 10 Alkylenimineinheiten erhalten worden sind, und/oder
• D) Polyalkylenpolyaminen der allgemeinen Formel
  
  • in der
  • R H oder CH₃,
  • y gleich oder verschieden die Zahl 0 oder 1 und
  • x eine Zahl von 4 bis 2500 bedeuten,

oder Mischungen dieser Polyalkylenpolyamine mit Aminen der gleichen allgemeinen Formel, in der aber

• x eine Zahl von 1 bis 3 bedeutet, enthalten,
• wobei soviel der Komponente B eingesetzt wird, dass alle funktionellen Gruppen der Verbindungen B abreagiert haben und dass wasserlösliche Polykondensate entstehen, die bei 25°C in 25prozentiger wässriger Lösung eine Viskosität von 100 bis 1000 mPa · s aufweisen.

Agents are preferably used which, as an effective component, are reaction products of aliphatic, halogen-free polyetheramines obtained by reacting

• a) ro-polychloropolyol ethers with a functionality of 1.90 - 3.10 mol-CI / mol and
• b) polyalkylene polyamines of the general formula
  
  • in the
  • RH or CH ₃ ,
  • y the same or different the number 0 or 1 and
  • x is a number from 1 to 50,
  
  and or

• c) polyalkylene polyamines of the general formula
  
  • in the
  • R ^I = H or CH ₃ ,
  • x, y the same or different the number 0 or 1,
  • m is a number from 1 to 50 and
  • n is a number from 0 to 50,

and or

• d) polyalkylene polyamines of the general formula
  
  • in the
  • Y = oxygen, sulfur or the at least divalent radical of an aliphatic, cycloaliphatic, araliphatic or aromatic hydroxyl and / or sulfhydryl group,
  • R3 = hydrogen or CH ₃ ,
  • p = an integer ≥ 1, preferably 1-3,
  • q = an integer ≥ 2, preferably 2-4,

and or

• e) amines of the formula
  
  • in the
  • R ^{4 is} a C ₁ -C ₁₈ -alkyl radical which is optionally substituted by an amino or hydroxyl group and
  • R ⁵ and R ⁶ independently represent hydrogen or a methyl group, and
  • r and s is a number from 1 to 20, preferably 1 to 5,

With

• B) the above-mentioned compounds which are polyfunctional with respect to amino groups, if appropriate in the presence of
• C) polyaminopolyamides obtained from 1 mole part of a dicarboxylic acid having 4 to 10 carbon atoms and 0.8 to 1.4 mole parts of a polyalkylene polyamine having 3 to 10 alkyleneimine units, and / or
• D) Polyalkylene polyamines of the general formula
  
  • in the
  • RH or CH ₃ ,
  • y the same or different the number 0 or 1 and
  • x is a number from 4 to 2500,

or mixtures of these polyalkylene polyamines with amines of the same general formula, but in which

• x represents a number from 1 to 3,
• so much of component B is used that all the functional groups of compounds B have reacted and that water-soluble polycondensates are formed which have a viscosity of 100 to 1000 mPa · s in 25 percent aqueous solution at 25 ° C.

Addition compounds of polyol ethers and epichlorohydrin, which have a functionality of 1.90-3.10 mol-CI / mol, are used as preferred ω-polychloropolyol ethers a).

The invention further relates to a process for the preparation of these water-soluble polycondensates and their use as an agent for increasing the retention of fibers, fillers and pigments and for accelerating the dewatering in paper manufacture and for processing paper machine waste water by filtration, sedimentation and flotation.

The aliphatic polyol ether amines are obtained by reacting ω-chloropolyethers with polyalkylene polyamines in the absence of solvents, preferably in the presence of small amounts of water (e.g. residual water of the technical polyalkylene polyamines), at a temperature of 80 to 200 ° C, preferably 100 to 180 ° C. 30 to 50% of the (o-chloropolyol ether) are advantageously brought to the reaction temperature together with the total amount of amine, and only then is the remaining amount of ω-chloropolyol ether added and the reaction is completed. Of course, it is also possible to add the total amount of ω-chloropolyol ether first Another way of carrying out the reaction is to mix the total amounts of ω-chloropolyol ether and amine at a temperature at which the reaction time is long in relation to the mixing time (ie temperatures preferably below 90 ° C.), and then When the reaction has ended, sufficient water is added to the reaction product to form a homogeneous solution, giving 20-80% aqueous solutions of the polyol ether amines.

The ratio of co-chloropolyol ether to polyalkylene polyamines should be chosen so that uniform products are obtained. This requires at least almost equimolar amounts of polyalkylene polyamine. The amine excess in moles is based on the content of reactive chlorine groups in the ω-chloropolyol ether.

The polyetheramines are obtained when 0.95 to 1.30 mol per 1 mol of chlorine in the ω-chloropolyol ether Polyalkylene polyamine can be used. Preferably 1.05 to 1.20 moles of polyalkylene polyamine are used per mole of chlorine in the w-chloropolyol ether. But it can also be condensed in the presence of a large excess of polyalkylene polyamine. The removal of the unreacted polyalkylene polyamine is generally not necessary since this is incorporated into the polycondensate in the subsequent reaction with the crosslinking agents.

The production of co-chloropolyol ethers is known. They can be obtained by reacting polyethylene glycols with phosgene or thionyl chloride according to DE-OS 2 934 854. Another way describes e.g. DE-OS 2 434 816. Polyethylene glycols are added with the addition of Lewis acids as catalysts, such as e.g. Tin (IV) chloride, zinc chloride, iron (III) chloride, aluminum chloride or boron trifluoride or their addition compounds on electron donors, such as e.g. Water, ether, carboxylic acids, with addition compounds of 100 parts of polyethylene glycol and 0.05 to 10 parts of boron trifluoride being preferred, reacted with epichlorohydrin at 40 to 100 ° C. The molar ratio of OH groups to epichlorohydrin is chosen so that polyglycol addition compounds having 1.90 to 3.10 moles of reactive chlorine atoms per mole of addition compound are obtained. A functionality of 2.10-2.80 mol-CI / mol is preferred. The functionality Moi-CI / Moi is determined by quantitative analysis.

The polyalkylene polyols that can be used are essentially composed of ethylene oxide units. However, propylene oxide up to a content of 25 mol%, but preferably only up to 10 mol%, can also be copolymerized randomly or in blocks. The average molecular weights of the polyglycols mentioned are 200 to 1200, in particular 400 to 1000.

They are obtained in a known manner by reacting polyols with the alkylene oxides mentioned. Polyols suitable for the purposes of the invention contain at least two OH groups and are derived from trimethylolpropane or glycerol.

• in der
• R = H oder CH₃,
• y gleich oder verschieden die Zahl 0 oder 1 und
• x = 1 bis 3 bzw. 4 bis 50 bedeuten,

seien vor allem die Polyethylenpolyamine genannt, bei denen y für null steht, z.B. Ethylendiamin, Propylendiamin-1,2, Diethylentriamin, Dipropylentriamin, Triethylentetramin, Tripropylentetramin, Tetraethylenpentamin, Tetrapropylenpentamin, Pentaethylenhexamin, Pentapropylenhexamin, Hexaethylenheptamin, Heptaethylenoktamin, Heptapropylenoktamin und ihre Gemische sowie Polyethylenpolyamine, die zudem noch einen oder mehrere Piperazinringe enthalten, wie Aminoethylpiperazin, Pentaethylenpentamin, Oktaethylenheptamin und deren Gemische, insbesondere aber

• a) das bei der diskontinuierlichen, (z.B. Houben-Weyl, 4. Auflage, XI/1, Seite 44), oder bei der kontinuierlichen (z.B. im GB-PS 1 832 534 und 2 049 467) Umsetzung von 1 Mol 1,2-Dichlorethan mit wässrigem Ammoniak (6 - 30 Mol), gegebenenfalls in Gegenwart von zugesetztem Ethylendiamin oder Diethylentriamin (US-PS 2 769 841 und US-PS 3 484 488) erhaltene Polyethylenpolyamingemisch, das erhebliche Anteile an Tetraethylenpentamin, Pentaethylenhexamin, Hexaethylenhexamin, Hexaethylenheptamin, Heptaethylenheptamin und höhere Amine enthält, und vor allem
• b) das nach Abdestillieren von Ethylendiamin, evtl. auch noch Diethylentriamin und Triethylentetramin aus dem gemäss a) hergestellten Basengemisch verbleibende Polyethylenpolyamingemisch, insbesondere Basengemische,
• c) die durch Kondensation von 1,2-Dichlorethan mit den obengenannten Polyethylenpolyaminen, einzeln oder im Gemisch, herstellbaren mehrwertigen oligomeren Amine mit einem mittleren Molekulargewicht von 200 bis 2000, insbesondere 500 bis 1500,
• d) die durch Polymerisation von 1,2-Alkyleniminen erhältlichen mehrwertigen Amine mit einem mittleren Molekulargewicht von 200 bis 2000, insbesondere 500 bis 1500.

As polyalkylene polyamines of the formula

• in the
• R = H or CH ₃ ,
• y the same or different the number 0 or 1 and
• x = 1 to 3 or 4 to 50,

Mention should be made above all of the polyethylene polyamines in which y is zero, for example ethylenediamine, 1,2-propylenediamine, diethylenetriamine, dipropylenetriamine, triethylenetetramine, tripropylenetetramine, tetraethylenepentamine, tetrapropylenpentamine, pentaethylenehexamine, pentapropylenhexamine, hexaethylenepheptamine, heptaethylenephenamine, heptaethylenephenamine, heptaethylenephenamine, heptaethylenephenamine, heptaethylenephenamine, heptaethylenephenamine, heptaethylenephenamine, heptaethylenepeptamine, heptaethylenephenamine, heptaethylenephenamine, heptaethylenepeptamine, which also contain one or more piperazine rings, such as aminoethylpiperazine, pentaethylene pentamine, octaethylene heptamine and mixtures thereof, but in particular

• a) that in the discontinuous (eg Houben-Weyl, 4th edition, XI / 1, page 44), or in the continuous (eg in GB-PS 1 832 534 and 2 049 467) reaction of 1 mole of 1,2 -Dichloroethane with aqueous ammonia (6-30 mol), optionally in the presence of added ethylenediamine or diethylenetriamine (US Pat. No. 2,769,841 and US Pat. No. 3,484,488), polyethylene polyamine mixture obtained, which contains considerable amounts of tetraethylenepentamine, pentaethylenehexamine, hexaethylenehexamine, hexaethyleneheptamine, Contains heptaethylene heptamine and higher amines, and most importantly
• b) the polyethylene polyamine mixture remaining after the distilling off of ethylenediamine, possibly also diethylenetriamine and triethylenetetramine from the base mixture prepared according to a), in particular base mixtures,
• c) the polyvalent oligomeric amines with an average molecular weight of 200 to 2000, in particular 500 to 1500, which can be prepared by condensation of 1,2-dichloroethane with the above-mentioned polyethylene polyamines, individually or in a mixture,
• d) the polyvalent amines with an average molecular weight of 200 to 2000, in particular 500 to 1500, obtainable by polymerizing 1,2-alkyleneimines.

• e) reine Polypropylenpolyamine und deren Gemische und
• f) gemischte Polyethylenpolypropylenpolyamine und deren Gemische, vor allem die durch ein- bzw. mehrmalige Umsetzung von Ethylendiamin bzw. Propylen-diamin-1,3 mit Acrylnitril und jeweils nachfolgender Hydrierung erhalten sind, z.B. mehrwertige Amine der Formel
  
  • wobei
  • x eine ganze Zahl von 1 bis 10 bedeutet,
  sowie diejenigen der Formel
  
  wobei
  • m eine ganze Zahl von 1 bis 5 und
  • n eine ganze Zahl von 0 bis 5 bedeutet, ausserdem
• g) die durch Kondensation von 1,2-Dichlorethan mit den unter e) und f) genannten Polyalkylenpolyaminen herstellbaren mehrwertigen Amine mit einem mittleren Molekulargewicht von 200 bis 2000 insbesondere 500 bis 1500.

The following may also be mentioned as further polyalkylene polyamines:

• e) pure polypropylene polyamines and their mixtures and
• f) mixed polyethylene polypropylene polyamines and mixtures thereof, especially those obtained by reacting ethylenediamine or 1,3-propylene-diamine-1,3 with acrylonitrile once or several times and in each case subsequent hydrogenation, for example polyhydric amines of the formula
  
  • in which
  • x represents an integer from 1 to 10,
  as well as those of the formula
  
  in which
  • m is an integer from 1 to 5 and
  • n also means an integer from 0 to 5
• g) the polyvalent amines which can be prepared by condensation of 1,2-dichloroethane with the polyalkylene polyamines mentioned under e) and f) and have an average molecular weight of 200 to 2000, in particular 500 to 1500.

bestehen, worin

• R' = H oder CH₃,
• x,y gleich oder verschieden die Zahl 0 oder 1,
• m eine Zahl von 1 bis 50 und
• n eine Zahl von 0 bis 50 bedeuten.

It is often advantageous if the polyalkylene polyamines consist predominantly of polyamines of the general formula

consist in what

• R '= H or CH ₃ ,
• x, y the same or different the number 0 or 1,
• m is a number from 1 to 50 and
• n is a number from 0 to 50.

• in der
• Y für Sauerstoff, Schwefel oder den mindestens zweiwertigen Rest einer aliphatischen, cycloaliphatischen, araliphatischen oder aromatischen Hydroxyl- und/oder Sulfhydrylgruppen aufweisenden Verbindung steht,
• R³ Wasserstoff oder die Methylgruppe bedeutet,
• p eine ganze Zahl von mindestens 1, vorzugsweise 1 - 3, ist und
• q für eine ganze Zahl von mindestens 2, vorzugsweise 2 - 4 steht.

In some cases it is advantageous to use di-, tri-, tetra-, penta- or hexaamines of the following formula:

• in the
• Y represents oxygen, sulfur or the at least divalent radical of an aliphatic, cycloaliphatic, araliphatic or aromatic hydroxyl and / or sulfhydryl group,
• R ^{3 represents} hydrogen or the methyl group,
• p is an integer of at least 1, preferably 1-3, and
• q represents an integer of at least 2, preferably 2-4.

• in der
• R⁴ für einen gegebenenfalls durch eine Amino- oder Hydroxygruppe substituierten C,-C_'8-Alkylrest und
• R⁵ und R⁶ unabhängig voneinander für Wasserstoff oder eine Methylgruppe stehen und
• r und s eine Zahl von 1 bis 20, vorzugsweise 1 bis 5, sind.

Representatives of these polyamines are, for example, bis (3-aminopropyl) ether, bis (3-aminopropyl) sulfide, ethylene glycol bis (3-aminopropyl) ether, diethylene glycol bis-13-aminopropyl ) ether, neopentylene glycol bis (3-aminopropyl) ether, hexa- hydro-p-xylylene glycol bis (3-aminopropyl) ether and hydroquinone bis (3-amino -propyl) ether, and amines of the formula

• in the
• R ^{4 is} a C, -C _'8 -alkyl radical optionally substituted by an amino or hydroxyl group and
• R ⁵ and R ⁶ independently of one another represent hydrogen or a methyl group and
• r and s are a number from 1 to 20, preferably 1 to 5.

Representatives of these polyamines are, for example, ethyl bis (3-aminopropyl) amine, 2-hydroxyethyl bis (3-aminopropyl) amine, n-butyl bis (3-aminopropyl) amine , Tris (3-aminopropyl) amine and especially methyl bis (3-aminopropyl) amine.

A base mixture which consists of at least 60 mol% of aminoethylpiperazine, a maximum of 20 mol% of diethylenetriamine and, moreover, of other amines mentioned above is very particularly preferred.

Aliphatic, halogen group-free polyetheramines according to the invention can also be produced in other ways. DAS 1 215 373 describes e.g. the reductive amination of polyglycol ethers. The reaction of polyalkylene polyols with acrylonitrile and subsequent hydrogenation is also one way, for example, of polyetheramines according to the invention.

Suitable polyfunctional compounds compared to amino groups for the preparation of the polycondensates according to the invention are, in particular, those polyfunctional compounds which are able to react completely in aqueous solution at pH values above 6, preferably above 8, with the amino groups contained in the basic polyamides.

• bifunktionelle Verbindungen, wie α,ω-Alkyldihalo- genide, z.B. insbesondere 1,2-Dichlorethan, 1,2-Dibromethan, 1,2-Dichlorpropan, 1,3-Dichlorpropan, 1,6-Dichlorhexan;

Examples of polyfunctional compounds compared to amino groups are:

• bifunctional compounds, such as α, ω-alkyl dihalides, for example in particular 1,2-dichloroethane, 1,2-dibromoethane, 1,2-dichloropropane, 1,3-dichloropropane, 1,6-dichlorohexane;

Halohydrins or epihalohydrins, e.g. Epichlorohydrin, 1,3-dichloropropanol (2), bis (3-chloro-2-hydroxypropyl) ether, 1,4-dichloro-2,3-epoxy-butane;

Bis-epoxy compounds, e.g. 1,2,3,4-diepoxybutane, diglycidyl ether, ethane-1,2-bis-glycidyl ether;

• trifunktionelle Verbindungen, wie 1,3,5-Triacryloylhexahydro-s-triazin, sowie das bifunktionelle Alkylierungsmittel hergestellt nach US-PS 3 632 559, Beispiel 2, 1.

Chloroformate, 3-chloro-2-hydroxypropyl ether and glycidyl ether of polyalkylene oxides, for example polyethylene oxides, and of reaction products of 1-50 moles of alkylene oxides, such as ethylene oxide and / or propylene oxide, with 1 mole of di- or polyhydric polyols or other compound containing at least two active hydrogen atoms ;

• trifunctional compounds, such as 1,3,5-triacryloylhexahydro-s-triazine, and the bifunctional alkylating agent prepared according to US Pat. No. 3,632,559, Example 2, 1.

Particularly preferred compounds B are dichloroethane and epichlorohydrin.

The structure of the polyaminopolyamides C according to the invention is already known from the publications DE-PS 1 771 814 and DE-PS 1 771 043.

in der R = H oder CH₃, y gleich oder verschieden die Zahl 0 oder 1 und x = 1 bis 3 bzw. 4 bis 2500 bedeuten, seien vor allem die Polyethylenpolyamine genannt, bei denen y für null steht z.B. Ethylendiamin, Propylendiamin, Diethylentriamin, Dipropylentriamin, Triethylentetramin, Tripropylentetramin, Tetraethylenpentamin, Tetrapropylenpentamin, Pentaethylenhexamin, Pentapropylenhexamin, Hexaethylenheptamin, Heptaethylenoktamin, Heptapropylenoktamin und ihre Gemische sowie Polyethylenpolyamine, die zudem noch einen oder mehrere Piperazinringe enthalten, wie Aminoethylpiperazin, Pentaethylenpentamin, Oktaethylenheptamin und deren Gemische, insbesondere aber

• a) das bei der diskontinuierlichen, (z.B. Houben-Weyl, 4. Auflage, XI/1, Seite 44), oder bei der kontinuierlichen (z.B. im GB-PS 1 832 534 und 2 049 467) Umsetzung von 1 Mol 1,2-Dichlorethan mit wässrigem Ammoniak (6 - 30 Mol), gegebenenfalls in Gegenwart von zugesetzten Ethylendiamin oder Diethylentriamin (US-PS 2 769 841 und US-PS 3 484 488) erhaltene Polyethylenpolyamingemisch, das erhebliche Anteile an Tetraethylenpentamin, Pentaethylenhexamin, Hexaethylenhexamin, Hexaethylenheptamin, Heptaethylenheptamin und höhere Amine enthält, und vor allem
• b) das nach Abdestillieren von Ethylendiamin, evtl. auch noch Diethylentriamin und Triethylentetramin aus dem gemäss a) hergestellten Basengemisch verbleibende Polyethylenpolyamingemisch,
• c) die durch Kondensation von 1,2-Dichlorethan mit den obengenannten Polyethylenpolyaminen, einzeln oder im Gemisch, herstellbaren mehrwertigen oligomeren Amine mit einem mittleren Molekulargewicht von 1000 bis 10 000, insbesondere 2000 bis 5000,
• d) die durch Polymerisation von 1,2-Alkyleniminen erhältlichen mehrwertigen Amine mit einem mittleren Molekulargewicht von 1000 bis 10 000, insbesondere 2000 bis 5000.

As polyalkylene polyamines D of the formula

in which R = H or CH ₃ , y are the same or different and represent the number 0 or 1 and x = 1 to 3 or 4 to 2500, especially the polyethylene polyamines in which y is zero, for example ethylenediamine, propylenediamine, diethylenetriamine , Dipropylenetriamine, triethylene tetramine, tripropylene tetramine, tetraethylene pentamine, tetrapropylene pentamine, pentaethylene hexamine, pentapropylene hexamine, hexaethylene heptamine, heptaethylene octamine, heptapropylene octamine and their mixtures and polyethylene polyamines which also contain one or more piperazine rings, such as aminoethylpiperazine, pentaethylene pentamine, octaethylene heptamine and mixtures thereof, but in particular

• a) that in the discontinuous (eg Houben-Weyl, 4th edition, XI / 1, page 44), or in the continuous (eg in GB-PS 1 832 534 and 2 049 467) reaction of 1 mole of 1,2 -Dichloroethane with aqueous ammonia (6-30 mol), optionally in the presence of added ethylenediamine or diethylenetriamine (US Pat. No. 2,769,841 and US Pat. No. 3,484,488), polyethylene polyamine mixture obtained which contains considerable amounts of tetraethylenepentamine, pentaethylenehexamine, hexaethylenehexamine, hexaethyleneheptamine, Contains heptaethylene heptamine and higher amines, and most importantly
• b) the polyethylene polyamine mixture remaining after distilling off ethylenediamine, possibly also diethylenetriamine and triethylenetetramine from the base mixture prepared according to a),
• c) the polyvalent oligomeric amines with an average molecular weight of 1,000 to 10,000, in particular 2,000 to 5,000, which can be prepared by condensation of 1,2-dichloroethane with the above-mentioned polyethylene polyamines, individually or in a mixture,
• d) the polyvalent amines with an average molecular weight of 1000 to 10,000, in particular 2000 to 5000, obtainable by polymerizing 1,2-alkyleneimines.

• e) reine Polypropylenpolyamine und deren Gemische und
• f) gemischte Polyethylenpolypropylenpolyamine und deren Gemische, vor allem die durch ein- bzw. mehrmalige Umsetzung von Ethylendiamin bzw. Propylendiamin-1,3 mit Acrylnitril und jeweils nachfolgender Hydrierung erhalten sind, z.B. mehrwertige Amine der Formel
  
  wobei
  • x eine ganze Zahl von 1 bis 10 bedeutet
  • sowie diejenigen Reste der Formel
    
  wobei
  • m eine ganze Zahl von 1 bis 5 und
  • n eine ganze Zahl von 0 bis 5 bedeutet, ausserdem
• g) die durch Kondensation von 1,2-Dichlorethan mit den unter e) und f) genannten Polyalkylenpolyaminen herstellbaren mehrwertigen Amine mit einem mittleren Molekulargewicht von 1000 bis 10 000 insbesondere 2000 bis 5000.

The following may also be mentioned as further polyalkylene polyamines:

• e) pure polypropylene polyamines and their mixtures and
• f) mixed polyethylene polypropylene polyamines and their mixtures, especially those obtained by reacting ethylenediamine or 1,3-propylenediamine with acrylonitrile one or more times and subsequent hydrogenation, for example polyhydric amines of the formula
  
  in which
  • x represents an integer from 1 to 10
  • as well as those residues of the formula
    
  in which
  • m is an integer from 1 to 5 and
  • n also means an integer from 0 to 5
• g) the polyvalent amines which can be prepared by condensation of 1,2-dichloroethane with the polyalkylene polyamines mentioned under e) and f) and have an average molecular weight of 1000 to 10,000, in particular 2000 to 5000.

in der

• Y für Sauerstoff, Schwefel oder den mindestens zweiwertigen Rest einer aliphatischen, cycloaliphatischen, araliphatischen oder aromatischen Hydroxyl- und/oder Sulfhydrylgruppen aufweisenden Verbindung steht,
• R³ Wasserstoff oder die Methylgruppe bedeutet,
• p eine ganze Zahl von mindestens 1, vorzugsweise 1 - 3, ist und
• q für eine ganze Zahl von mindestens 2, vorzugsweise 2 - 4 steht.

In some cases it is advantageous if some of the polyalkylene polyamines D used are replaced by other di-, tri-, tetra-, penta- or hexamines, for example by amines of the formula

in the

• Y represents oxygen, sulfur or the at least divalent radical of an aliphatic, cycloaliphatic, araliphatic or aromatic hydroxyl and / or sulfhydryl group,
• R ^{3 represents} hydrogen or the methyl group,
• p is an integer of at least 1, preferably 1-3, and
• q represents an integer of at least 2, preferably 2-4.

in der

• R⁴ für einen gegebenenfalls durch eine Amino- oder Hydroxygruppe substituierten C_i-C_i8-A)ky!rest und
• R⁵ und R⁶ unabhängig voneinander für Wasserstoff oder eine Methylgruppe stehen und
• r und s eine Zahl von 1 bis 20, vorzugsweise 1 bis 5, sind.

Representatives of these polyamines are, for example, bis- (3-aminopropyl) ether, bis- (3-aminopropyl) sulfide, ethylene glycol bis- (3-aminopropyl) ether, diethylene glycol bis- (3- aminopropyl) ether, neopentylene glycol bis (3-aminopropyl) ether, hexa- hydro-p-xylene-glycot-bis (3-aminopropyl) ether and hydroquinone bis (3 -amino-propyl) ether, and amines of the formula

in the

• R ⁴ for a C _i -C _i8 -A) ky! Rest optionally substituted by an amino or hydroxyl group and
• R ⁵ and R ⁶ independently of one another represent hydrogen or a methyl group and
• r and s are a number from 1 to 20, preferably 1 to 5.

• A: 20 bis 100 Gewichtsteile, vorzugsweise 40 bis 80 Gewichtsteile,
• C: 0 bis 80 Gewichtsteile, vorzugsweise 20 bis 60 Gewichtsteile,
• D: 0 bis 80 Gewichtsteile, vorzugsweise 20 bis 60 Gewichtsteile.

The quantitative ratios of components A: C: D in the production of the nitrogen-containing condensation products contained in the agents according to the invention are:

• A: 20 to 100 parts by weight, preferably 40 to 80 parts by weight,
• C: 0 to 80 parts by weight, preferably 20 to 60 parts by weight,
• D: 0 to 80 parts by weight, preferably 20 to 60 parts by weight.

The weight ratios of essential component B vary greatly depending on the type and amount of A, C and D. As described above, component B is used to such an extent that water-soluble polycondensates are formed which have a viscosity of 100 to 1000 mPa · s at 25 ° C. in 25 percent aqueous solution.

The quantitative ratios of the polyfunctional compounds B to the other components A, C and D are expediently such that the amounts necessary to form the desired degree of condensation of the water-soluble polycondensate are not substantially exceeded. The minimum amount of compounds B which are polyfunctional with respect to amino groups and which are to be used to convert reaction products with the desired high molecular weight or solutions thereof to the desired viscosity at 25 ° C. (ie 100-1000 mPa.s, preferably 200 to 400 mPa.s a 25 % aqueous solution) depend mainly on the molecular weight of the components and can be easily determined by preliminary tests from case to case.

It is important that all functional groups of the compounds B have reacted so that the reaction product is practically free of self-crosslinked groups.

The polycondensates can be prepared from the polyether amines A and, if appropriate, the polyamide amines C and / or the polyalkylene polyamines D, by processes known per se, e.g. by stirring mixtures of A, if appropriate C and / or D, and the compounds B which are polyfunctional with amino groups in aqueous media at pH values above 6 and at temperatures between 0 and 150 ° C. until a sample of the reaction mixture in the form of a 10% aqueous solution at 25 ° C has a viscosity of at least 10 mPa-s. It is often advantageous if the polyfunctional compounds are added gradually to the mixture of A and / or C and / or D in an aqueous medium under otherwise identical reaction conditions until the desired viscosity is reached. The content of reaction products in the reaction solution, which is preferably between 10 and 30% by weight, if the reaction has been carried out at a higher concentration, is then adjusted to the desired final value by dilution with water. In some cases it is necessary to stop the action after reaching the desired viscosity by adjusting the pH of the reaction solution by adding acids, e.g. Hydrochloric acid, sulfuric acid, phosphoric acid or acetic acid to adjust to pH 6, preferably to 4 to 5. This is especially true in the event that the minimum amount of functional compounds required to form the desired degree of condensation of the water-soluble polycondensate has been significantly exceeded.

The condensation can also be carried out in a closed vessel at temperatures above the boiling point of the compound B which is polyfunctional with respect to amino groups, in particular when using dihaloalkanes, preferably between 90 to 150 ° C. and pressures between 3-8 bar. It is normally not necessary to stop the reaction by adding acid.

The total concentration of the components in the aqueous reaction mixture should be 10 to 50 percent by weight.

In the preparation of the reaction products according to the invention, the reaction of the polyfunctional compound B need not necessarily take place with a mixture of A and / or C and / or D. It is also possible to first allow one of the three components A or C or D or combinations of two of these compounds to react with the polyfunctional compound B to form a precondensate and then to implement this in a second stage with the other component.

The polycondensates are characterized by a minimum molecular weight of 2500, preferably 5000. The upper limit of their molecular weight is given by their property of being water-soluble. A numerical description of the upper limit of their molecular weight is not possible, since this strongly depends on the underlying polyamines and the number of water-solubilizing groups they contain.

When using the polycondensates as auxiliaries for increasing the retention of fibers, fillers and pigments and as dewatering accelerators, the procedure is known in such a way that the polycondensates according to the invention are added to the paper stock suspension in the form of dilute aqueous solutions before the headbox, the Dosing point is chosen so that a good distribution of the aid in the raw material suspension is ensured, but a too long contact time is avoided. The amounts of polycondensate that are required to achieve the desired retentive effect and / or drainage-accelerating effect can be determined without difficulty by preliminary tests; in general, it is advisable to use 0.005 to 0.5 percent by weight of polycondensate, based on the dry weight of the paper. The addition of polyamines according to the invention before the headbox of a paper machine also has an advantageous effect on the processing of the paper machine waste water by filtration, flotation or sedimentation; The coagulating effect of the polycondensates according to the invention makes it much easier to separate paper constituents from the paper machine waste water.

When the polycondensates according to the invention are used as auxiliaries in the processing of paper machine waste water by filtration, flotation or sedimentation, it is also possible to proceed in a manner known per se, preferably in such a way that the reaction products in question are expediently added to the paper machine waste water in the form of dilute aqueous solutions before entering the fabric scoop.

The amounts of polyamines which cause sufficient coagulation of the pulp constituents contained in paper machine wastewater are to be measured according to the composition of the wastewater and can easily be determined from case to case by preliminary tests; In general, amounts of 0.005 to 2 g of polyamine per m ^{3 of} waste water are sufficient for this.

The condensates according to the invention show a rise in comparison with similar known compounds in the application range of pH 4.0-8.0 retention effectiveness, but in particular drainage acceleration.

The polycondensates according to the invention show a particularly low sensitivity to enriched contaminants in closed water circulation systems.

Some of the polycondensates according to the invention and their use for increasing the retention of fibers, fillers and pigments and for accelerating dewatering in papermaking are described below.

Examples Preparation of the polyglycol ether amines A

a part of polyglycol ether with the composition b and the average molecular weight c were mixed with d parts of boron trifluoride etherate, heated to 70 ° C. and e parts of epichlorohydrin (f moles of epichlorohydrin per mole of polyglycol ether) were added in g hours at 70-80 ° C., h hours at Stirred 80 ° C and then cooled.

i parts of this reaction product were stirred into 1 part of amine or amine mixture m at k ° C. and the mixture was stirred at 0 ° C. for a further hour. The mixture was then cooled to 90-95 ° C. and diluted to a solids content of 50% with water.

• PEO/TMP: Polyethylenoxid auf Trimethylolpropan gestartet
• PPO/Glykol: Polypropylenoxid auf Glykol gestartet
• DTRA: Diethylentriamin
• AEP: Aminoethylpiperazin
• BAPMA: Bis-aminopropylmethylamin
• AEP-DTRA: Gemisch aus Aminoethylpiperazin und Diethylentriamin
• AEP-DTRA-BAPMA: Gemisch aus Aminoethylpiperazin, Diethylentriamin und Bis-aminopropylmethylamin.

In the following, the abbreviations mentioned have the following meaning:

• PEO / TMP: polyethylene oxide started on trimethylolpropane
• PPO / glycol: polypropylene oxide started on glycol
• DTRA: diethylene triamine
• AEP: aminoethylpiperazine
• BAPMA: bis-aminopropylmethylamine
• AEP-DTRA: mixture of aminoethylpiperazine and diethylenetriamine
• AEP-DTRA-BAPMA: Mixture of aminoethylpiperazine, diethylenetriamine and bis-aminopropylmethylamine.

A 11

673 parts by weight of PEO started on TMP with a molecular weight of 673 were mixed with 2.0 parts of boron trifluoride etherate, heated to 70 ° C. and at 70-80 ° C., 208 parts by weight of epichlorohydrin were added in 1 hour and the Mixture stirred at 80 ° C for 3 hours.

50 parts by weight of the reaction product were stirred at room temperature with a mixture of 42 parts by weight of AEP, 4 parts by weight of DETA and 8 parts by weight of BAPMA and heated to 100.degree. At this temperature, a further 100 parts by weight of the reaction product were then added in 1 hour and stirring was continued at 120 ° C. for 3 hours. After cooling to 90-95 ° C., 204 parts by weight of water were stirred in with further cooling.

A 12

As described in A 11, 150 parts by weight of reaction product from polyethylene glycol and epichlorohydrin were prepared and cooled from 80 to 60 ° C. At this temperature, the mixture of 42 parts by weight of AEP, 4 parts by weight of DTRA and 8 parts by weight of BAPMA was stirred in for 1 hour. The mixture was then heated to 120 ° C. for 3 hours, cooled to 90-95 ° C. and adjusted to a solids content of 50% by weight with water.

Polyamide polyamine C 1

In a reaction vessel with a gas inlet tube and a descending cooler, 108 g (1.05 mol) of diethylenetriamine are mixed with 146 g (1 mol) of adipic acid with the addition of 9 g (0.05 mol) of adipic acid dihydrazide, and the mixture is stirred and Transfer of oxygen-free nitrogen heated to 190 ° C within 3-4 hours, the reaction temperature being increased in the range of 150-190 ° C to such an extent that the water formed distilled off uniformly. After about 30 g of water and small amounts of diethylenetriamine have distilled over, the reaction mixture is stirred at 190-180 ° C. under reduced pressure (20-50 mm / Hg) until a total of 44 g of distillate has been obtained, then to 130 ° C. cooled and mixed with the same amount by weight (219 g) of water. The basic polyamide formed is thus obtained in the form of a 50% strength aqueous solution which has a viscosity of 300-400 mPas (= 300-400 cP) at 25 ° C. and an equivalent weight of 340.

Polyamide polyamine C 2

a) 108 g (1.05 mol) of diethylenetriamine, 146 g (1.0 mol) of adipic acid and 28 g (0.25 mol) of ε-caprolactam are added with the addition of 9 g (0.05 mol) of adipic acid dihydrazide, such as described in the preparation of the reaction product C 1, converted to the corresponding basic polyamide. The 50% polyamide solution obtained after adding the same weight of water has a viscosity of 400-500 mPas (= 400-500 cP) at 25 ° C and an equivalent weight of 400.

Condensation product 1

77.0 parts by weight of A 8 were stirred in 77.0 parts by weight of water, together with 2.8 parts by weight of epichlorohydrin, at 80 ° C. for 24 hours.

Solids content: 27.2% by weight.

Viscosity at 25 ° C: 208 mPa · s.

Condensation product 2

85.0 parts by weight of C 1, 40.0 parts by weight of A 8 were stirred in 129.0 parts by weight of water with 2.9 parts by weight of epichlorohydrin at 80 ° C. for 24 hours.

Solids content: 25.8% by weight.

Viscosity at 25 ° C: 361 mPas.

Condensation product 3

75.0 parts by weight of A 3 were stirred in 75 parts by weight of water with 5.2 parts by weight of epichlorohydrin at 80 ° C. for 24 hours.

Solids content: 29.2% by weight.

Viscosity at 25 ° C: 200 mPa · s.

Condensation product 4

54.0 parts by weight of A 4, 62 parts by weight of C 1 and 119 parts by weight of water were heated to 80 ° C. for 16 hours with 3.9 parts by weight of epichlorohydrin.

Solids content: 27.7% by weight.

Viscosity at 25 ° C: 459 mPa · s.

Condensation product 5

54.0 parts by weight of A4, 62.0 parts by weight of C 2 and 110 parts by weight of water were stirred with 4.1 parts by weight of epichlorohydrin at 80 ° C. for 16 hours.

Solids content: 26.9% by weight.

Viscosity at 25 ° C: 12.

Condensation product 6

200.0 parts by weight of A 8, 200 parts by weight of water and 12.0 parts by weight of dichloroethane were stirred at 80-90 ° C. for 24 hours.

Solids content: 24.5% by weight.

Viscosity at 25 ° C: 355 mPa · s.

Condensation product 7

200.0 parts by weight of A 8, 200 parts by weight of water and 14.0 parts by weight of dichloroethane were stirred in a pressure vessel at 125 ° C. for 6 hours.

Solids content: 25.8% by weight.

Viscosity at 25 ° C: 370 mPa · s.

Condensation product 8

100.0 parts by weight of A 8, 100.0 parts by weight of C 1 and 200 parts by weight of water were stirred together with 8.6 parts by weight of dichloroethane in a pressure vessel at 125 ° C. for 4 hours.

Solids content: 24.1% by weight.

Viscosity at 25 ° C: 337 mPa · s.

Application example 1

• a) saurer Bereich
  • Zusatz von 40% China Clay als Füllstoff,
  • 1 % Harzleim
  • 4% Aluminiumsulfat
  zur Papiermasse. Der pH-Wert wurde mit Schwefelsäure auf 5,5 eingestellt.
• b) neutraler Bereich
  • Zusatz von 40% Kreide als Füllstoff,
  • 1 % ®Aquapel 360 XZ (synthetischer Leim auf basis Stearyldiketen von Fa. Hercules Inc.)

zur Papiermasse. Der pH-Wert wurde mit Natronlauge auf 7,5 eingestellt.Papers with a basis weight of approx. 80 g / m ² were produced on a laboratory paper machine (type Kämmerer) from 40% bleached needle sulfite pulp, 60% bleached birch sulfate pulp. One worked in the acidic range, the other at neutral pH values.

• a) acidic area
  • Addition of 40% china clay as filler,
  • 1% resin glue
  • 4% aluminum sulfate
  to the paper pulp. The pH was adjusted to 5.5 with sulfuric acid.
• b) neutral area
  • Addition of 40% chalk as filler,
  • 1% ®Aquapel 360 XZ (synthetic glue based on stearyl diketene from Hercules Inc.)

to the paper pulp. The pH was adjusted to 7.5 with sodium hydroxide solution.

Before the headbox of the paper machines, the 1% aqueous solutions of the condensation products 1 to 8 were metered in by means of a metering pump. For comparison, 1% dilutions of the known retention agent 1 according to Example 1 of DE-PS 1 771 814 or of the known retention agent 11 according to Example 1 from DE-OS 2 736 651 (EP-A-0 000 714) or of the known retention agent III (US Pat. No. 3,972,939, Example 1) metered in.

The solids content in the wastewater of the paper machine was determined as a measure of the retention effect. The lower this solids content, the better the retention effect.

The following Table 2 illustrates that the polyamines according to the invention have a very good retention effect both in the acidic and in the neutral range and that this is better than that which is obtained when the known retention agents are used. The amounts added relate to the weight of the air-dry pulp and the 25% solution of the retention aid.

Example of use 2

The so-called drainage time was determined as a measure of the drainage acceleration to be expected on a paper machine. This is determined by measuring the time required in the Schopper-Riegler grinding degree tester to set a certain degree of grinding or water volume in the outlet cup. The shorter the time, the better the drainage acceleration that can be achieved.

• a) Saurer Bereich:
  • Zusatz von 0,5% Aluminiumsulfat, Einstellung von pH 4,5 mit Schwefelsäure.
• b) Neutraler Bereich:
  • Einstellung von pH 7,0 mit Natronlauge.

A mixture of waste paper and 10% clay was whipped up using the high-speed stirrer and the pH was adjusted:

• a) Acid area:
  • Add 0.5% aluminum sulfate, adjust pH 4.5 with sulfuric acid.
• b) Neutral area:
  • Adjustment of pH 7.0 with sodium hydroxide solution.

200 ml of the 1% paper pulp suspension prepared according to a) or b) were in each case in row A with fresh water, in row B with a circulating water (closed circuit, fresh water requirement 10 - 12 I / kg paper, 27 ° dH total hardness, 2480 mg evaporation residue / I, 1149 mg 0 _2/1 COD value) to 1000 ml and filled the Schopper-Riegler apparatus determined by means of the drainage time.

The additional quantities each relate to the weight of the air-dry paper stock and to the 25% solution of the condensation products 1 to 8.

The following Table 3 illustrates the good dewatering effect of the polyalkylene polyamines according to the invention both in the acidic and in the neutral range. For comparison, the known retention agents listed in Application Example 1 were also metered in.

Claims (6)

1. Agents for increasing the retention fibres, filters and pigments and for accelerating drainage in papermaking and as flocculating agents in the working up of effluents from papermaking by filtration, sedimentation and flotation, characterised in that they contain, as the active component, one or more nitrogen-containing condensation products which can be obtained by reacting

A) aliphatic, polyol-ether-amines which are free from halogen groups, contain cohesive polyether segments, carry no amino groups within these segments and are obtained from co-chloropolyol-ethers and polyalkylene polyamines in a molar ratio of chlorine in the ω-chloropolyol-ether to polyalkylene polyamine of 1 : 0.95 to 1.30

with

B) compounds which are polyfunctional towards amino groups, from the groups comprising

α,ω-alkyldihalides,

halogenohydrins,

epihalogenohydrins,

bis-epoxy compounds,

chloroformic acid esters and

glycidyl ethers of polyalkylene oxides and compounds of the formula

if appropriate in the presence of

C) polyaminopolyamides and/or

D) polyalkylene polyamines

such a quantity of component B) being employed that water-soluble polycondensates are formed which are free from self-crosslinking groups and have a viscosity of 100 to 1000 mPa·s. at 25°C in 25 per cent strength aqueous solution.

2. Agents according to claim 1, characterised in that the aliphatic, polyether-amines which are free from halogen groups are obtained by reaction of

a) ω-polychloropolyol-ethers with a functionality of 1.90 - 3.10 moles of CI/mole and

b) polyalkylenepolyamines of the general formula

in which

R denotes H or CH₃,

y is identical or different and denotes the number 0 or 1 and

x denotes a number from 1 to 50,

and/or

c) polyalkylenepolyamines of the general formula

in which

R^I = H or CH₃,

x and y are identical or different and denote the number 0 or 1,

m denotes a number from 1 to 50 and

n denotes a number from 0 to 50,

and/or

d) polyalkylenepolyamines of the general formula

in which

Y = oxygen, sulphur or the radical, which is at least divalent, of an aliphatic, cycloaliphatic, araliphatic or aromatic compound containing hydroxyl, and/or sulphhydryl groups,

R³= hydrogen or CH₃,

p = is an integer > 1, preferably 1 - 3, and

q = an integer ≥ 2, preferably 2 - 4,

and/or

e) amines of the formula

in which

R⁴ represents a C₁-C₁₈-alkyl radical which is optionally substituted by an amino or hydroxyl group,

R⁵ and R⁶ independently of one another represent hydrogen or a methyl group and

r and s are a number from 1 to 20, preferably 1 to 5,

without the addition of solvents at a temperature of 80 to 200°C.

3. Agents according to claim 1 and 2, characterised in that the ro-polychloropolyol-ethers are addition compounds of polyol-ethers and epichlorhydrin which have a funtionality of 1.9 to 3.10 moles of CI/mole.

4. Agents according to claims 1 to 3, characterised in that the aliphatic polyol-ether-amines are obtained by reacting addition compounds of polyethers with at least 2 OH groups and an average molecular weight of 200 to 1,200 and such an amount of epichlorhydrin that 1 mole of this adduct contains 1.0 to 3.1 moles of CI/mole, with polyalkylenepolyamines.

5. Agents according to claims 1 to 4, characterised in that the aliphatic polyol-ether-amines are obtained by reacting

ro-polychloropolyol-ethers with a functionality of 1.9-3.1 moles of CI/mole

and a polyalkylenepolyamine mixture which contains at least 60 mole % of N-aminoethylpiperazine, less than 20 mole % of diethylenetriamine and other polyalkylenepolyamines.

6. Agents according to claims 1 to 5, characterised in that dichloroethane and/or epichlorhydrin are employed as compounds which are polyfunctional towards amine groups.