EP0000561B1 - Water-soluble, reticulated nitrogenous condensation products and their use - Google Patents

Description

The invention relates to water-soluble, crosslinked nitrogen-containing condensation products, the viscosity of which increases in aqueous solution when the temperature rises and drops again when the temperature drops.

From US Pat. No. 3,347,803, incompletely condensed resins which are curable in an alkaline environment are known, which are prepared by reacting polyether chlorohydrins whose polyether chain has 3 to 70 alkylene oxide units with polyamines or ammonia in certain molar ratios. The products are used as curable coatings for metal and glass as well as textile finishing agents. The viscosity of aqueous solutions of the condensation products decreases with increasing temperature.

From FR-PS 2 280 670 it is known to produce water-soluble nitrogen-containing condensation products, in which one contains a nitrogen equivalent of 15 to 500 alkyleneimine units containing with polyalkylene polyamine with 0.08 to 0.001 mol parts of a polyether crosslinker at temperatures from 20 to 100 ° C to Formation of just water-soluble condensation products can react, which have a viscosity of more than 300 mPas at a temperature of 20 ° C in 20 to 25% aqueous solution. The polyether crosslinking agent is prepared by reacting polyalkylene oxides containing at least 8 alkylene oxide units with epichlorohydrin, the terminal OH groups of the polyalkylene oxide being replaced by glycidyl groups. Also suitable as alkylene oxides are block copolymers which are composed of ethylene oxide-propylene oxide and ethylene oxide blocks.

From DE-OS 1 546 290 it is known to use reaction products of amines with water-soluble polyfunctional derivatives of polyethylene glycols which contain chlorohydrin and / or glycidyl groups as flotation agents for fiber and filler recovery from paper machine waste water.

From BE-PS 554 506 a process for the production of condensation products by reacting α, w-diester of polyalkylene glycols with di- or polyamines is known.

GB-PS 961 891 describes a process for the preparation of condensation products, in which diglycidyl ethers of polyalkylene glycols or block copolymers are reacted with more than the equimolar amount of a polyamine.

From FR-PS 2 257 623 polyalkylene glycol polyamines are known which are obtained by first reacting a polyalkylene glycol having 5 to 50 alkylene oxide units with hydrogen chloride to give the corresponding α, w-dichloro compounds and then reacting these with a polyamine.

According to U.S. Patent 3,129,133, glycidyl polyethers of polyhydric alcohols, including also of polyethylene glycols, with polyfunctional epoxy curing agents, such as polyamines, in the presence of water.

In none of the references cited above is there any indication that the condensation gives products whose viscosity increases in aqueous solution when the temperature of the aqueous solution increases.

DE-OS 26 38 955 describes water-soluble crosslinked nitrogen-containing condensation products whose viscosity increases in aqueous solution when the temperature rises and which are obtained by reacting chlorohydrin ethers of block copolymers of ethylene oxide and propylene oxide with ethylene imine in a weight ratio of 1: 0.1 to 0.8 .

The object of the invention is to provide water-soluble resins, the viscosity of which increases in aqueous solution when the temperature rises and drops again when the temperature drops.

in der

mit n = 0,75 bis 3,

und x = 50 bis 250, y = 20 bis 100 und das Verhältnis x:y = 6,5:1 bis 1:15 ist, mit mindestens 4 basische NH-Gruppen enthaltenden Verbindungen aus den Gruppen

• 1. Polyaminen der Formel
  
  • R = H,
  • C₁- bis C₄―Alkyl,
  • C₁- bis C₆―Alkylsulfonate
  • und ―CH₂―COOH, wobei mindestens 2R = H n = 2-4,
• 2. Kondensationsprodukten von Ammoniak und Aminen mit Äthylenchlorid, Epichlorhydrin oder kurzkettigen Dichlorhydrinäthern,
• 3. Umsetzungsprodukten aus kurzkettigen Diepoxiden mit Diäthylentriamin oder Methylamin,
• 4. Kondensationsprodukten aus Harnstoff und Di- oder Polyaminen oder
• 5. Kondensationsprodukten aus Polyaminen mit Dicarbonsäuren, die 4 bis 10 Kohlenstoffatome enthalten,

im Gewichtsverhältnis 0,8:1 bis 30:1 in einem polaren Lösungsmittel bei Temperaturen von 20 bis 180°C.The invention relates to water-soluble, crosslinked nitrogen-containing condensation products, the viscosity of which increases in aqueous solution when the temperature rises and decreases again when the temperature drops, produced by reacting a block copolymer of the formula

in the

with n = 0.75 to 3,

and x = 50 to 250, y = 20 to 100 and the ratio x: y = 6.5: 1 to 1:15, with at least 4 basic NH groups-containing compounds from the groups

• 1. Polyamines of the formula
  
  • R = H,
  • C ₁ - to C ₄ -alkyl,
  • C ₁ to C ₆ alkyl sulfonates
  • and ―CH ₂ ―COOH, where at least 2R = H n = 2-4,
• 2. condensation products of ammonia and amines with ethylene chloride, epichlorohydrin or short-chain dichlorohydrin ethers,
• 3. reaction products from short-chain diepoxides with diethylenetriamine or methylamine,
• 4. condensation products of urea and di- or polyamines or
• 5. condensation products from polyamines with dicarboxylic acids containing 4 to 10 carbon atoms,

in a weight ratio of 0.8: 1 to 30: 1 in a polar solvent at temperatures from 20 to 180 ° C.

wobei x = 50 bis 250, y = 20 bis 100 und das Verhältnis x:y = 6,5:1 bis 1:15 bedeutet, hergestellt.The compounds of the formula I are obtained by introducing reactive groups into block copolymers of the formula

where x = 50 to 250, y = 20 to 100 and the ratio x: y = 6.5: 1 to 1:15.

The compounds of formula 11 are obtained, for example, by adding ethylene oxide to polypropylene glycol which contains 20 to 100 propylene oxide units. The molar ratio of ethylene oxide to propylene oxide units in the block copolymer is chosen so that it is in the range from 6.5: 1 to 1:15 and the degree of ethoxylation per hydroxyl group in the polypropylene glycol is 50 to 250, preferably 75 to 150. In order to introduce reactive groups into this block copolymer, it can be reacted, for example, with epichlorohydrin in a molar ratio of 1: 1.5 to 6. This reaction is carried out in bulk or in a solvent using Lewis acids. In particular, boron trifluoride etherates, complexes of boron trifluoride with acetic acid, phosphoric acid and AlCl ₃ , ZnCl ₂ , FeCl ₃ , SnCl ₄ , H ₂ SO ₄ and HClO ₄ are used as Lewis acid. The reaction of compounds of the formula II with epichlorohydrin gives compounds of the formula 1 in which the substituent R =

If the products thus produced are treated with bases such as potassium hydroxide or sodium hydroxide, the corresponding diepoxides are obtained. In this case, the substituent R in formula I is the same

hat.If, however, the reactive radical R in formula I represents 2 or 3 epichlorohydrin units, reaction products of the formula I are obtained in the reaction of these compounds with bases, in which the substituent R then has the meaning

Has.

In addition, reactive groups can be introduced into compounds of the formula II by reacting them with phosgene. In this case, the substituent R in Formula 1 has the meaning

When compounds of the formula 11 are reacted with phosphorus trichloride, the corresponding dichlorides are obtained in which the substituent R of the formula I is BedeutungCH ₂ ―CH ₂ ―Cl. The reactions of compounds of formula II with the classes of compounds mentioned can be carried out in a wide temperature range, for example in the range from 10 to 120 ° C. It is usually advantageous to use a polar solvent, but the reaction can also be carried out in the absence of solvents.

• R = H,
• C₁- bis C_4-Alkyl,
• C₁- bis C₆―Alkylsulfonate
• und --CH₂-COOH, wobei mindestens 2R = H n = 2-4,

In order to produce the water-soluble, crosslinked nitrogen-containing condensation products according to the invention, the compounds of the formula I are reacted with compounds which contain at least four basic NH groups, for example polyamines. Of the polyamines, only those compounds are suitable which have at least four basic NH groups in the molecule. These compounds can be characterized, for example, using the following formula.

• R = H,
• C ₁ to C ₄ alkyl,
• C ₁ to C ₆ alkyl sulfonates
• and --CH ₂ -COOH, where at least 2R = H n = 2-4,

Also suitable as compounds containing four basic NH groups are condensation products of ammonia and amines with ethylene chloride, epichlorohydrin, short-chain dichlorohydrin ethers, e.g. Condensation products from ammonia and the dichlorohydrin ether of ethylene glycol, from ethylenediamines and ethylene chloride or from ethylenediamine and epichlorohydrin as well as reaction products from short-chain diepoxides e.g. Butadiol-1,4-bisglycidyl ether or ethylene glycol bisglycidyl ether with diethylenetriamine or methylamine and condensation products from urea and di- or polyamines, e.g. Ethylene diamine, diethylene triamine and tris-3-aminopropylamine. Short-chain bisglycidylamines are also suitable as diepoxides. The amines in question contain at least one NH-NH group. Suitable amines include mono- and polyamines containing at least one NH group, e.g. Methylamine, ethylamine, dimethylamine, ethylenediamine, diethylenetriamine and polyethyleneimine. The viscosity of the condensation products of ammonia and the amines in question is at most 2500 mPas (measured in 50% strength aqueous solution at 20 ° C.) and is generally in the range from 30 to 1700 mPas.

Also suitable as compounds containing at least four basic NH groups are condensation products of polyamines with dicarboxylic acids which contain 4 to 10 carbon atoms, for example succinic acid, maleic acid, adipic acid, glutaric acid, sebacic acid and terephthalic acid. The suitable polyamines have 2 to 6 alkylene bridges between the primary amino groups. Polyamines having 3 to 10 basic nitrogen atoms in the molecule are preferably used for the condensation with the dicarboxylic acids mentioned. Examples include diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dipropylenetriamine, tripropylenetetramine and dihexamethylenetriamine. The viscosity of the condensation products from amines and dicarboxylic acids is 40 to 1,800 mPas and should not exceed 2,500 mPas (measured in 50% strength aqueous solution at 20 ° C.).

To produce the products according to the invention, the reactive end groups-containing polyether of formula 1 with the compounds containing at least 4 basic NH groups in Weight ratio 0.8: 1 30: 1 implemented. This gives crosslinked nitrogen-containing condensation products which are soluble in water and whose viscosity increases in aqueous solution when the temperature rises and decreases again when cooling. The changes in viscosity in aqueous solution are therefore reversible. The condensation of the two components is carried out so that water-soluble substances are obtained. The reaction is carried out in a polar solvent. However, the procedure can also be such that the polyamines are placed in a reaction vessel and the other component is added until the viscosity of the reaction mixture increases. The reaction mixture is then diluted with a solvent and further amounts of compounds of the formula are added. Suitable solvents are, for example, water, alcohols, such as methanol, ethanol, propanols, ethylene glycol, propylene glycol and monoalkyl ethers derived from the polyhydric alcohols, for example monomethyl glycol ether and di- and triglycol ethers. Also suitable as solvents are dioxane and tetrahydrofuran and mixtures of polar solvents with water, for example mixtures of water and tetrahydrofuran in a ratio of 1: 1.

The water-soluble, crosslinked nitrogen-containing condensation products can also be obtained by reacting solutions of the compounds of the formula I with the compounds containing NH groups. The component that is used in the excess is usually placed in the reaction vessel. The condensation reaction can be carried out batchwise or continuously. Particularly uniform products are obtained if first about 5 to 15% of the substances to be reacted are condensed in a reaction vessel and the remaining feedstocks are added batchwise or continuously. The addition of the starting materials is adapted to the rate of conversion. If the viscosity increases too much in the course of the progressing reaction, it is advisable to lower the solids concentration in the reaction mixture by adding solvent, so that thorough mixing of the reactants is ensured. The reaction temperature can vary within a wide range, it is generally between room temperature and 160 ° C. If water is used as the sole solvent, it is preferably carried out at a temperature in the range from 40 to 80.degree.

The condensation products according to the invention can be prepared by the reverse suspension polymerization process. In this case, an aqueous solution of compounds of formula I and the compounds containing at least 4 NH groups is dispersed in a water-immiscible solvent, e.g. aliphatic or aromatic hydrocarbons or chlorinated hydrocarbons. Dispersions of the water-soluble, crosslinked nitrogen-containing condensation products according to the invention are then obtained.

The products produced according to the invention can be used in a number of applications. For example, they prevent dye migration and build-up on the rollers when pigment dyeing and finishing fabrics. For this purpose, the substances according to the invention are used in an amount of 0.05 to 7%, based on the printing paste. In the electroplating industry, an addition of 0.01 to 20% to electrolytic pretreatment baths results in increased gloss formation during the electrolytic deposition of metals. The products can also be used to improve the viscosity behavior of aqueous systems, such as polymer solutions and polymer dispersions. For example, an addition of 1 to 20% of a product according to the invention to a polymer solution or dispersion has the effect that the viscosity of the solutions or dispersions does not decrease when heated.

The invention is illustrated by the following examples. The parts given in the examples are parts by weight, the percentages relate to the weight of the substances.

example 1

versetzt man bei Raumtemperatur mit 480 Teilen einer 33%igen wäßrigen Lösung eines Polyäther Vernetzers der Formel

und verdünnt die Mischung anschließend mit 280 Teilen Wasser. Die Mischung wird auf eine Temperatur von 60 bis 70°C aufgeheizt und 4 Stunden bei dieser Temperatur gehalten. Während der Kondensationsreaktion steigt die Viskosität der wäßrigen Lösung stark an. Im Verlauf der Kondensation gibt man daher weitere 733 Teile Wasser zu, so daß man eine 10%ige wäßrige Lösung eines vernetzten stickstoffhaltigen Kondensationsproduktes erhält. Eine 2,5%ige wäßrige Lösung des Kondensationsprodukts hat bei einer Temperatur von 20°C eine Viskosität von 5 mPas, bei 50°C eine Viskosität von 150 mPas und bei einer Temperatur von 80°C eine Viskosität von 380 mPas.100 parts of a 25% aqueous solution of a polyethylenimine of the formula

480 parts of a 33% aqueous solution of a polyether crosslinking agent of the formula are added at room temperature

and then dilute the mixture with 280 parts of water. The mixture is heated to a temperature of 60 to 70 ° C and held at this temperature for 4 hours. The viscosity of the aqueous solution rises sharply during the condensation reaction. A further 733 parts of water are therefore added in the course of the condensation, so that a 10% strength aqueous solution of a crosslinked nitrogen-containing condensation product is obtained. A 2.5% aqueous solution of the condensation product has a viscosity of 5 mPas at a temperature of 20 ° C, a viscosity of 150 mPas at 50 ° C and a viscosity of 380 mPas at a temperature of 80 ° C.

The condensation product is suitable as an aid in pigment dyeing and finishing fabrics. For example, if 1% of the condensation product produced according to the invention is added to the dyebath, the formation of deposits on the rollers is prevented when the printing paste is applied to the fabric, and dye migration is prevented when the fabric dries.

In Glavanotechnik, an addition of 0.01 to 20% to pretreatment baths in electrolytic metal deposition results in increased gloss formation.

Example 2

in der x = 75, y = 30 und das Verhältnis X:y = 2,5:1 ist, werden bei 35°C mit 4,6 Teilen konz. NaOH versetzt. Nach dreistündiger Reaktionszeit beträgt der Epoxid-Wert des Reaktionsprodukts (Diepoxid) 0,19 mVal/g.400 parts of a 50% aqueous solution of a dichlorohydrin ether of the general formula

in which x = 75, y = 30 and the ratio X: y = 2.5: 1, are concentrated at 35 ° C with 4.6 parts. NaOH added. After a reaction time of three hours, the epoxide value of the reaction product (diepoxide) is 0.19 meq / g.

520 parts of the diepoxide solution are added to 200 parts of a 20% strength aqueous solution of the polyamine given in Example 1 and the mixture is left to react at 55 °. 1,040 parts of water are added in three portions during the reaction.

The solution is stirred and heated to a temperature of 55 ° C. The viscosity of the aqueous solution rises sharply during the reaction. To ensure thorough mixing of the components, it is necessary to add water. A total of 1,040 parts of water were added in three portions. A 17% aqueous solution of the nitrogen-containing condensation product had a viscosity of 280 mPas at a temperature of 20 ° C and a viscosity of 36,000 mPas at 80 ° C.

The reaction product is used as an anti-migration agent in pigment printing pastes.

Example 3

x=113; y=44; n=1,25
umgesetzt. Der Epoxidwert der 40%igen wäßrigen Lösung beträgt 0,055 mVal/g.400 parts of a 50% aqueous solution of the crosslinking agent of the formula 111 described in Example 1 are combined with 3 parts of sodium hydroxide solution at a temperature of 30 ° C. within 4 hours to give a diepoxide of the formula

x = 113; y = 44; n = 1.25
implemented. The epoxy value of the 40% aqueous solution is 0.055 meq / g.

300 parts of a 33% aqueous solution of the diepoxide are mixed with 50 parts of a 20% aqueous solution of the polyamine described in Example 1. The two reactants are heated to a temperature of 50 ° C. The reaction is complete after 4 hours. 200 parts of water are added and a 20% strength aqueous solution of a nitrogen-containing crosslinked condensation product is obtained. Viscosity behavior of a 5% aqueous solution:

If a glass fiber fleece is impregnated with a dye dispersion which contains 0.4% of the crosslinked nitrogen-containing condensation product, the dye absorbs evenly. After drying, a non-woven fabric of any color is obtained. The binder and dye are evenly distributed in the fleece.

Example 4

x = 113; y = 44; x:y=2,56:1
werden in 300 Teilen Dioxan gelöst und auf eine Temperatur von 40°C erhitzt. Man leitet dann 4 Stunden lang Phosgen in die Lösung ein. Danach treibt man das überschüssige Phosgen mit Stickstoff aus und destilliert das Dioxan unter vermindertem Druck ab. Zu 300 Teilen einer 33%igen wäßrigen Lösung des so hergestellten Chlorkohlensäurediesters werden 50 Teile einer 20%igen wäßrigen Lösung des im Beispiel 1 beschriebenen Polyamins gegeben. Die Mischung wird dann auf eine Temperatur von 70°C erhitzt. Innerhalb von 4 Stunden ist die Reaktion beendet. Man gibt 200 Teile Wasser zu und erhält eine 20%ige Lösung eines vernetzten stickstoffhaltigen Kondensationsproduktes. Eine 10%ige wäßrige Lösung zeigt folgendes Viskositätsverhalten:

300 parts of a block copolymer of the formula

x = 113; y = 44; x: y = 2.56: 1
are dissolved in 300 parts of dioxane and heated to a temperature of 40 ° C. Phosgene is then bubbled into the solution for 4 hours. The excess phosgene is then driven off with nitrogen and the dioxane is distilled off under reduced pressure. 50 parts of a 20% aqueous solution of the polyamine described in Example 1 are added to 300 parts of a 33% aqueous solution of the chlorocarbonic acid diester thus prepared. The mixture is then heated to a temperature of 70 ° C. The reaction is complete within 4 hours. 200 parts of water are added and a 20% solution of a crosslinked nitrogen-containing condensation product is obtained. A 10% aqueous solution shows the following viscosity behavior:

The product is used as an additive to paper coating inks in amounts of 2 to 10% by weight, based on the paper coating ink.

Example 5

400 parts of the block copolymer of the formula (V) (cf. Example 4) are dissolved in 300 parts of dioxane which contains three parts of pyridine. Then 6 parts of phosphorus trichloride are added and the reaction mixture is hydrolyzed after 4 hours by adding water and 3 parts of 48% sodium hydroxide solution. At a temperature of 80 ° C., 80 parts of the dihalogen compound obtained are dissolved in 237 parts of water and reacted with 50 parts of a 20% strength aqueous solution of the polyamine described in Example 1. After a reaction time of 140 minutes, 3 parts of concentrated sodium hydroxide solution are added and the reaction mixture is heated to a temperature of 85 ° C. for 3 hours. Then 15 parts of formic acid are added and the mixture is diluted with 145 parts of water to a solids content of 20%. A 20% aqueous solution of the crosslinked nitrogen-containing condensation product shows the following viscosity behavior:

Example 6

in der x = 75; y = 30; n = 2,25, x:y = 2,5:1 bedeutet, werden 30 Teile einer 50%igen Lösung von N,N'-Bis-(3-aminopropyl)-äthylendiamin gelöst. Bei pH 9 bis 10 und 80° reagieren die Substanzen. Nach fünf Stunden gibt man nochmals 220 Teile des Chlorhydrinäthers zu und verdünnt das Reaktionsgemisch anschließend mit 940 Teilen Wasser auf einen Gehalt von 20% an Kondensationsprodukt. Viskositätsverhalten einer 20%igen wäßrigen Lösung:

In 500 parts of a 50% aqueous solution of a chlorohydrin ether of the general formula

in which x = 75; y = 30; n = 2.25, x: y = 2.5: 1 means, 30 parts of a 50% solution of N, N'- Bis- (3-aminopropyl) ethylenediamine dissolved. The substances react at pH 9 to 10 and 80 °. After five hours, another 220 parts of the chlorohydrin ether are added and the reaction mixture is then diluted with 940 parts of water to a content of 20% of the condensation product. Viscosity behavior of a 20% aqueous solution:

Example 7

innerhalb von 6 Stunden vernetzt. Der pH wird während der Reaktion durch Zugabe von 117 Teilen ² 48%iger Natronlauge bei 10 gehalten. Die Viskosität einer 50%igen Harzlösung beträgt 320 mPas (20°C). Durch Verdünnen mit Wasser wird der Wirkstoffgehalt auf 20% eingestellt. 50 Teile einer so erhaltenen 20%igen Harzlösung werden bei einer Temperatur von 75°C innerhalb von 8 Stunden mit 246 Teilen einer 50%igen wäßrigen Lösung des Vernetzers der Formel III (vgl. Beispiel 1) umgesetzt. Der Vernetzer wird innerhalb der Reaktionszeit kontinuierlich zugesetzt. Außerdem wird die Reaktionsmischung mit 1 1 030 Teilen Wasser verdünnt, das in vier Portionen während der Kondensation zugefügt wurde. Eine 10%ige wäßrige Lösung zeigt folgendes Viskositätsverhalten:

230 parts of an amine mixture of parts of ethylenediamine, 45 parts of 3-aminopropyl-ethylenediamine and 35 parts of N, N'-bis (3-aminopropyl) -ethylenediamine are dissolved in 384 parts of water and at 95 ° C. with 382 parts of a chlorohydrin ether of the formula

Networked within 6 hours. The pH is kept at 10 during the reaction by adding 117 parts of ² 48% sodium hydroxide solution. The viscosity of a 50% resin solution is 320 mPas (20 ° C). The active substance content is adjusted to 20% by dilution with water. 50 parts of a 20% resin solution thus obtained are reacted at a temperature of 75 ° C. within 8 hours with 246 parts of a 50% aqueous solution of the crosslinking agent of the formula III (cf. Example 1). The crosslinker is added continuously within the reaction time. In addition, the reaction mixture is diluted with 1 1030 parts of water, which was added in four portions during the condensation. A 10% aqueous solution shows the following viscosity behavior:

If a flat nonwoven is impregnated with a conventional binder and a customary dye dispersion which contains 0.3% of the water-soluble, nitrogen-containing condensation product described above, then after squeezing and drying the nonwoven, an article of any color and uniformly solidified is obtained.

Example 8

1 287 parts of the amine mixture described in Example 7 are reacted with 300 parts of water and with stirring and ice cooling with 533 parts of epichlorohydrin. The reaction temperature is kept at 90 ° C. After 5 hours, 1,547 parts of water are added.

50 parts of a 20% aqueous solution of this resin are reacted at a pH of 9 to 10 with 344 parts of a 50% crosslinker solution, which is described in Example 1. The pH is kept constant by adding 6 parts of concentrated sodium hydroxide solution. As the viscosity of the mixture rises continuously, 1,420 parts of water are continuously added during the reaction. The reaction temperature is in the range of 60 to 85 ° C. A 10% aqueous solution of a crosslinked, nitrogen-containing condensation product is obtained. The 10% aqueous solution shows the following viscosity behavior:

Example 9

438 parts of adipic acid are added at 340 ° C. to 340 parts of diethylenetriamine with thorough mixing. The reaction temperature is then increased to 160 to 180 ° C. and water is distilled off from the reaction mixture until the acid number of the reaction product is less than 10. The mixture is then cooled and diluted to a solids content of 50% by adding 676 parts of water.

60 parts of the 50% solution of the polyamidoamine are mixed at room temperature with a solution consisting of 626 parts of water, 4 parts of concentrated sodium hydroxide solution and 270 parts of a dichlorohydrin ether according to Example 1. After a reaction time of 4 hours at a temperature of 60 to 70 ° C., the mixture is diluted by adding 530 parts of water and the reaction mixture is adjusted to a pH of 5 by adding 10 parts of formic acid. A 10% aqueous solution shows the following viscosity behavior:

Example 10

werden in 296 Teilen Isopropanol gelöst und unter einem Druck von 20 bis 40 bar bei 120°C mit 118 Teilen Ammoniak umgesetzt. Nach 6 Stunden wird das Reaktionsgemisch abgekühlt und entspannt. Das überschüssige Ammoniak zieht man bei vermindertem Druck ab. 7 Teile dieses Poly- ätheramins werden bei 70 bis 85°C mit einer Lösung aus 100 Teilen des Dichlorhydrinäthers aus Beispiel 1, 200 Teilen Wasser und 5 Teilen konzentrierter Natronlauge um gesetzt. Innerhalb von 4 Stunden bei 70 bis 85°C ist die Vernetzungsreaktion beendet. Das Reaktionsgemisch wird dann mit 213 Teilen Wasser verdünnt und mit 10 Teilen Ameisensäure auf pH 4 eingestellt.690 parts of the dichlorohydrin ether of the formula

are dissolved in 296 parts of isopropanol and reacted with 118 parts of ammonia under a pressure of 20 to 40 bar at 120 ° C. After 6 hours, the reaction mixture is cooled and let down. The excess ammonia is drawn off under reduced pressure. 7 parts of this polyetheramine are reacted at 70 to 85 ° C. with a solution of 100 parts of the dichlorohydrin ether from Example 1, 200 parts of water and 5 parts of concentrated sodium hydroxide solution. The crosslinking reaction is complete within 4 hours at 70 to 85 ° C. The reaction mixture is then diluted with 213 parts of water and adjusted to pH 4 with 10 parts of formic acid.

Viscosity behavior of the 20% solution:

The condensation product can be used as a cold lubricant when cutting metals.

Example 11 1

300 parts of a 20% solution of a polyethyleneimine, which has an average molecular weight of 21,000, were crosslinked at a temperature of 65 to 80 ° C with 270 parts of a 22% aqueous solution of the dichlorohydrin ether, which in Example 6 is specified. 597 parts of water were added during the reaction time. After cooling, the pH of the reaction mixture is adjusted to a value of 8 by adding 27 parts of formic acid. Viscosity behavior of a 10% aqueous solution:

Example 12

in der x = 75; y = 30; n = 1,5 und das Verhältnis x:y = 2,5:1 ist, und 38 Teilen konzentrierter Natronlauge. Während der vierstündigen Reaktionszeit verdünnt man die Mischung kontinuierlich mit 634 Teilen Wasser auf 20%. Viskositätsverhalten einer 10%igen Lösung:

Das Kondensationsprodukt wird in Abschreckbädern eingesetzt.370 parts of a 46.5% solution of a polyethyleneimine according to Example 1 were mixed with 126 parts of dimethyl sulfate at 50 ° C. while cooling. The mixture is left to react for two hours at 50 ° C. for another two hours at 80 ° C. 586 parts of a 50% strength aqueous solution of the dichlorohydrin ether of the general formula are added to 400 parts of a 20% strength aqueous solution of the methylated polyethyleneimine at a temperature of 70 to 85 ° C.

in which x = 75; y = 30; n = 1.5 and the ratio x: y = 2.5: 1, and 38 parts of concentrated sodium hydroxide solution. During the four-hour reaction time, the mixture is continuously diluted to 20% with 634 parts of water. Viscosity behavior of a 10% solution:

The condensation product is used in quench baths.

Example 13

127 parts of a polyethyleneimine with an average molecular weight of 800 are placed in the form of a 5096 solution in a reaction vessel and slowly mixed with 520 parts of a 25% aqueous solution of sodium vinyl sulfonate at a temperature of 25 ° C. After a reaction time of 5 hours at a temperature of 80 ° C, the entire vinyl sulfonate is added to polyethyleneimine. The proportion of tertiary amine has increased by 30% of the total amine content.

90 parts of a 30% aqueous solution of the above-mentioned reaction product are crosslinked with 495 parts of a 33% aqueous solution of the dichlorohydrin ether according to Example 1 within 4 hours at a temperature of 80 ° C. 280 parts of water, which contain 5 parts of sodium hydroxide solution, are continuously added during the crosslinking reaction. The mixture is then cooled and a 10% aqueous solution of a crosslinked, nitrogen-containing condensation product is obtained by adding 934 parts of water. A 5% aqueous solution of this condensation product shows the following viscosity behavior:

The nitrogen-containing, cross-linked condensation product, when added in quantities of 0.001 to 5% to galvanic baths, improves the gloss formation of the treated metals.

Example 14

212 parts of a polyethyleneimine with an average molecular weight of 800 are placed in a reaction vessel provided with a stirrer as a 50% strength aqueous solution. At 60 ° C., 145 parts of sodium chloroacetate are added in portions with cooling. The reaction is complete after about four hours. The amount of free chloride ions corresponding to the sodium chloroacetate is present (2.2 meq / g). Of the polyethyleneimine substituted with carboxymethyl groups, 20.1 parts as a 5096 aqueous solution are mixed with 495 parts of a 33% aqueous solution of the dichlorohydrin ether according to Example 1. To dilute to 20%, 330 parts of water are added at 80 ° C. during the reaction. After 4.5 hours, the mixture is cooled and a 1096 solution is prepared by adding more water.

Viscosity behavior of the 10% solution:

The solution is 5% suitable as a thickener for paper coating colors.

Example 15

mit n = 1,3 und x = 34 reagieren. Dabei wird kontinuierlich mit 61,3 Teilen Wasser verdünnt. Nach der Reaktion stellt man die Lösung durch Zugabe von 0,4 Teilen Ameisensäure auf ein pH von 7.14.4 parts of a 20% aqueous solution of a polyethyleneimine with an average molecular weight of 800 are heated to 60 ° C. with 38.4 parts of a 25% solution of the crosslinking agent according to Example 6. Dilute with 36.3 parts of water over 2.5 hours. A 14% aqueous solution of a condensation product is obtained. 20 parts of this polyetheramine solution are mixed with 0.4 parts of concentrated sodium hydroxide solution at 60 to 70 ° C. The solution is then left for 5 hours with 6.6 parts of an 18% strength aqueous solution of a chlorohydrin ether of the general formula

react with n = 1.3 and x = 34. It is continuously diluted with 61.3 parts of water. After the reaction, the solution is adjusted to pH 7 by adding 0.4 parts of formic acid.

Viscosity behavior of the 4.5% aqueous solution:

The product is used in the form of a 0.3% aqueous solution as a quenching bath for the hardening of steels. When hardening a steel (K 8, 30 CrMo V 9), a hardness curve is obtained which is similar to that when hardening with quenching oil. In the same concentration, the product is also suitable as a quenching agent for inductive hardening.

Example 16

225.6 parts of tris (3-aminopropyl) amine are placed in a flask. 60 parts of urea are added at room temperature and the temperature of the mixture is raised to 140 ° C. in the course of 45 minutes. A strong ammonia development occurs. After a reaction time of 60 minutes, the mixture is diluted with 200 parts of water and the solids content is determined (52.3%). Dilute with 71.4 parts of water to an active substance content of 45% (acid number 0.47 mVal / g; amine number 11.9 mVal / g). 50 parts of the 45% solution are mixed with 750 parts of a 15% aqueous solution of the polyether crosslinker according to Example 1. The mixture is then heated. During the three-hour reaction time at 80 ° C, 66.5 parts of water containing 4 parts of concentrated NaOH are added. The mixture is then cooled, adjusted to pH 4 with 20 parts of formic acid and diluted to 12% of active substance with a further 238 parts of water.

Viscosity behavior of a 5% solution:

With a 3% addition, the product is suitable as a thickener for printing pastes in textile printing. This prevents the dye from streaking through, so that the prints appear significantly more brilliant. A 0.4% solution is suitable as a quenching agent for aluminum and aluminum alloys.

Claims (5)

1. A water-soluble, crosslinked nitrogen-containing condensation product, the viscosity of which, in aqueous solution, increases with increasing temperature, obtained by reacting a block copolymer of the formula:

n being from 0.75 to 3,

x is from 50 to 250, y is from 20 to 100, and the ratio of y to y is from 6.5 to 1:15, with a compound having at least four basic NH groups and selected from the groups:

1. Polyamines of the formula

where R is H, alkyl of 1 to 4 carbon atoms, C₁ to C_. alkyl sulfonate or ―CH₂―COOH, at least two of the R's being H and n is from 2 to 4;

2. Condensation products of ammonia or an amine with ethylene chloride, epichlorohydrin or a short-chain dichlorohydrin ether;

3. Reaction products of a short-chain diepoxide with diethylenetriamine or methylamine;

4. Condensation products of urea and a diamine or polyamine; or

5. Condensation products of a polyamine with a dicarboxylic acid of 4 to 10 carbon atoms,

in a polar solvent at a temperature of from 20 to 180°C in a weight ratio of from 0.8:1 to 30:1.

2. A water-soluble, crosslinked nitrogen-containing condensation product as claimed in claim 1, characterized in that a compound of the formula I is reacted with a polyamine having at least four basic NH groups in the molecule.

3. A water-soluble, crosslinked nitrogen-containing condensation product as claimed in claims 1 and 2, characterized in that polyethyleneimine is used as the compound having at least four basic NH groups.

4. Use of a water-soluble, crosslinked nitrogen-containing condensation product as claimed in claims 1 to 3 for improving the viscosity characteristics of aqueous systems, such as polymer solutions and polymer dispersions.

5. Use of a water-soluble, crosslinked nitrogen-containing condensation product as claimed in claims 1 to 3 as an electroplating bath additive.