EP0000561B1 - Produits de condensation azotés, réticulés, solubles dans l'eau et leur application - Google Patents

Produits de condensation azotés, réticulés, solubles dans l'eau et leur application Download PDF

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Publication number
EP0000561B1
EP0000561B1 EP78100466A EP78100466A EP0000561B1 EP 0000561 B1 EP0000561 B1 EP 0000561B1 EP 78100466 A EP78100466 A EP 78100466A EP 78100466 A EP78100466 A EP 78100466A EP 0000561 B1 EP0000561 B1 EP 0000561B1
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Prior art keywords
parts
water
aqueous solution
soluble
formula
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EP78100466A
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German (de)
English (en)
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EP0000561A1 (fr
Inventor
Werner Dr. Streit
Rolf Dr. Fikentscher
Karl Gans
Gerhard Dr. Welzel
Klaus Glaser
Emil Schaefer
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BASF SE
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BASF SE
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/338—Polymers modified by chemical after-treatment with inorganic and organic compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • C08G59/5006—Amines aliphatic
    • C08G59/502—Polyalkylene polyamines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/333—Polymers modified by chemical after-treatment with organic compounds containing nitrogen
    • C08G65/33303—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing amino group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/02—Polyalkylene oxides

Definitions

  • 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.
  • FR-PS 2 280 670 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.
  • alkylene oxides Also suitable as alkylene oxides are block copolymers which are composed of ethylene oxide-propylene oxide and ethylene oxide blocks.
  • 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.
  • polyalkylene glycol polyamines which are obtained by first reacting a polyalkylene glycol having 5 to 50 alkylene oxide units with hydrogen chloride to give the corresponding ⁇ , w-dichloro compounds and then reacting these with a polyamine.
  • glycidyl polyethers of polyhydric alcohols including also of polyethylene glycols, with polyfunctional epoxy curing agents, such as polyamines, in the presence of water.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.).
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the substances according to the invention are used in an amount of 0.05 to 7%, based on the printing paste.
  • 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.
  • 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.
  • 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.
  • 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.
  • the solution is stirred and heated to a temperature of 55 ° C.
  • the viscosity of the aqueous solution rises sharply during the reaction.
  • water 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.
  • 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.
  • 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.
  • adipic acid 438 parts 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.
  • the condensation product can be used as a cold lubricant when cutting metals.
  • 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.
  • 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.
  • the solution is 5% suitable as a thickener for paper coating colors.
  • the product is used in the form of a 0.3% aqueous solution as a quenching bath for the hardening of steels.
  • a hardness curve is obtained which is similar to that when hardening with quenching oil.
  • the product is also suitable as a quenching agent for inductive hardening.
  • 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. Produits de condensation azotés réticulés, solubles dans l'eau, dont la viscosité en solution aqueuse augmente, lorsque la température croît, et diminue à nouveau, lorsque la température diminue, préparés par réaction d'un copolymère à blocs de la formule
Figure imgb0046
dans laquelle
Figure imgb0047
Figure imgb0048
x = 50 à 250, y = 20 à 100 et le rapport x:y = 6,5:1 à 1:15,
avec des composés contenant au moins 4 groupes -NH basiques choisis parmi:
1. les polyamines de la formule
Figure imgb0049
dans laquelle R = H, alkyle en C1 à C4, alkyl (en C1 à C6) - sulfonate ou -CH2-COOH, au moins deux R étant H, et n = 2 à 4;
2. les produits de condensation de l'ammoniac et d'amines sur le chlorure d'éthylène, l'épichlor- hydrine ou des éthers de dichlorhydrine à courte chaîne;
3. les produits de la réaction de diépoxydes à courte chaîne avec la diéthylène-triamine ou la méthyl-amine;
4. les produits de la condensation de l'urée et de diou de poly-amines;
5. les produits de la condensation de poly-amines et d'acides dicarboxyliques en C4 à C10;

dans des proportions en poids dans un rapport de 0,8:1 à 30:1 à une température comprise entre 20 et 180°C dans un solvant polaire.
2. Produits de condensation azotés réticulés, solubles dans l'eau, suivant la revendication 1, caractérisés en ce que l'on fait réagir les composés de la formule avec des polyamines comprenant au moins quatre groupes -NH basiques dans leur molécule.
3. Produits de condensation azotés réticulés, solubles dans l'eau, suivant l'une des revendications 1 et 2, caractérisés en ce que l'on emploie en tant que composés comprenant au moins quatre groupes -NH basiques de la poly(éthylène-imine).
4. Utilisation des produits de condensation azotés réticulés hydrosolubles suivant l'une des revendications 1 à 3 pour améliorer le comportement rhéologique de systèmes aqueux tels que des solutions et dispersions de polymères.
5. Utilisation des produits de condensation azotés réticulés hydrosolubles suivant l'une des revendications 1 à 3 comme additifs pour bains d'èlectrolyse.
EP78100466A 1977-07-28 1978-07-21 Produits de condensation azotés, réticulés, solubles dans l'eau et leur application Expired EP0000561B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE2733973 1977-07-28
DE19772733973 DE2733973A1 (de) 1977-07-28 1977-07-28 Wasserloesliche, vernetzte stickstoffhaltige kondensationsprodukte

Publications (2)

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EP0000561A1 EP0000561A1 (fr) 1979-02-07
EP0000561B1 true EP0000561B1 (fr) 1981-10-14

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US (1) US4224421A (fr)
EP (1) EP0000561B1 (fr)
JP (1) JPS5425998A (fr)
AT (1) AT383369B (fr)
CA (1) CA1133190A (fr)
DE (2) DE2733973A1 (fr)
IT (1) IT1106107B (fr)

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US4451618A (en) * 1982-09-29 1984-05-29 The B. F. Goodrich Company Block copolymers and process for their preparation
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US4891111A (en) * 1988-04-25 1990-01-02 Ppg Industries, Inc. Cationic electrocoating compositions
DE3835040A1 (de) * 1988-10-14 1990-04-19 Basf Ag Neue polytetrahydrofuranderivate und ihre herstellung
USRE34272E (en) * 1989-05-04 1993-06-08 Rem Chemicals, Inc. Method and composition for refinement of metal surfaces
DE4007597A1 (de) * 1990-03-09 1991-09-12 Henkel Kgaa Wasserloesliche oder wasserdispergierbare, polyetherketten und quaternaere ammoniumgruppen enthaltende verbindungen
US6649733B1 (en) * 1993-05-27 2003-11-18 Cognis Corporation Polymeric thickeners for aqueous compositions
US20030005527A1 (en) * 2001-07-03 2003-01-09 Basf Corporation Thickeners for paper dye compositions
EP1400555A1 (fr) * 2002-09-17 2004-03-24 Kawamura Institute Of Chemical Research Copolymère à blocs hydrosoluble et son procédé de fabrication
CN101541857B (zh) * 2006-11-27 2012-12-12 阿克塔马克斯手术器材有限责任公司 多官能聚环氧烷、水凝胶和组织粘合剂
EP2504396B1 (fr) * 2009-11-27 2021-02-24 Basf Se Composition pour électroplaquage de cuivre comprenant un agent de nivellement
WO2020184414A1 (fr) * 2019-03-13 2020-09-17 日本製鉄株式会社 Procédé de surveillance du soudage d'un tuyau en acier soudé par résistance électrique, procédé de fabrication de tuyau en acier soudé par résistance électrique, dispositif de surveillance du soudage d'un tuyau en acier soudé par résistance électrique, et dispositif de fabrication de tuyau en acier soudé par résistance électrique

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Also Published As

Publication number Publication date
JPS5425998A (en) 1979-02-27
IT1106107B (it) 1985-11-11
AT383369B (de) 1987-06-25
JPS6221013B2 (fr) 1987-05-11
CA1133190A (fr) 1982-10-05
EP0000561A1 (fr) 1979-02-07
DE2733973A1 (de) 1979-02-15
US4224421A (en) 1980-09-23
ATA548378A (de) 1986-11-15
IT7850399A0 (it) 1978-07-20
DE2861157D1 (en) 1981-12-24

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