EP0000724B1 - Compounds containing hydroxylic groups and urethane-aryl-sulfonic acid groups, process for their preparation and their use as reaction components for polyisocyanates - Google Patents

Compounds containing hydroxylic groups and urethane-aryl-sulfonic acid groups, process for their preparation and their use as reaction components for polyisocyanates Download PDF

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Publication number
EP0000724B1
EP0000724B1 EP78100487A EP78100487A EP0000724B1 EP 0000724 B1 EP0000724 B1 EP 0000724B1 EP 78100487 A EP78100487 A EP 78100487A EP 78100487 A EP78100487 A EP 78100487A EP 0000724 B1 EP0000724 B1 EP 0000724B1
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EP
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Prior art keywords
groups
compounds
molecular weight
polyisocyanates
sulfonic acid
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EP78100487A
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German (de)
French (fr)
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EP0000724A1 (en
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Dieter Dr. Dieterich
Gerhard Dr. Ballé
Hans Georg Dr. Schmelzer
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Bayer AG
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Bayer AG
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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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/50—Polyethers having heteroatoms other than oxygen
    • C08G18/5072—Polyethers having heteroatoms other than oxygen containing sulfur
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
    • C07C309/01—Sulfonic acids
    • C07C309/28—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
    • C07C309/45—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing nitrogen atoms, not being part of nitro or nitroso groups, bound to the carbon skeleton
    • C07C309/52—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing nitrogen atoms, not being part of nitro or nitroso groups, bound to the carbon skeleton the carbon skeleton being further substituted by doubly-bound oxygen atoms
    • C07C309/53—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing nitrogen atoms, not being part of nitro or nitroso groups, bound to the carbon skeleton the carbon skeleton being further substituted by doubly-bound oxygen atoms the carbon skeleton containing carbon atoms of quinone rings
    • C07C309/54—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing nitrogen atoms, not being part of nitro or nitroso groups, bound to the carbon skeleton the carbon skeleton being further substituted by doubly-bound oxygen atoms the carbon skeleton containing carbon atoms of quinone rings at least one of the nitrogen atoms being part of any of the groups, X being a hetero atom, Y being any atom
    • C07C309/56—Y being a hetero atom
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
    • C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
    • C08G18/0828—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing sulfonate groups or groups forming them
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/46—Polycondensates having carboxylic or carbonic ester groups in the main chain having heteroatoms other than oxygen
    • C08G18/4676—Polycondensates having carboxylic or carbonic ester groups in the main chain having heteroatoms other than oxygen containing sulfur
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/71—Monoisocyanates or monoisothiocyanates
    • C08G18/715—Monoisocyanates or monoisothiocyanates containing sulfur in addition to isothiocyanate sulfur
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/775—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur sulfur

Definitions

  • the present invention provides a solution to these problems. Surprisingly, it has been found that by reacting polyhydroxy compounds with molar amounts of aromatic isocyanato sulfonic acids, optionally in a mixture with conventional polyisocyanates, novel hydroxy compounds are obtained which have increased polarity and surface-active properties and, for. B. foams made from it give improved fire behavior and high frequency weldability.
  • the present invention thus relates to at least one OH-functional chain and at least one urethano-arylsulfonic acid-containing compound having an average molecular weight of 300 to 12,000.
  • Chain links are e.g. B. CH (CH 3 ) - or CH 2 groups, ether oxygen atoms, CO groups, sulfur atoms and / or nitrogen atoms.
  • the present invention also relates to a process for the preparation of at least one OH-functional chain and at least one urethano-aryl-sulfonic acid group-containing compound having an average molecular weight of 300 to 12,000, characterized in that compounds having a molecular weight of 62 to 10,000, the at least two Have hydroxyl groups, are reacted at 0-190 ° C with aromatic isocyanatosulfonic acids, the equivalent ratio of the total amount of isocyanate groups (including those optionally in dimerized Form isocyanate groups) to sulfonic acid groups 0.5 to 50 and the equivalent ratio of the sum of the hydroxyl groups of the compounds having at least two hydroxyl groups to NCO groups is 1.5 to 30.
  • the present invention also relates to the use of the compounds according to the invention as a reaction component for polyisocyanates for the production of polyaddition products or polycondensation products.
  • OH groups of the polyhydroxy compounds used as starting material are added to the NCO groups and any uretdione groups of isocyanatoarylsulfonic acid which may be present, with the formation of higher molecular weight new polyhydroxy compounds which contain at least some urethane groups and one or more free sulfonic acid Groups included.
  • the sulfonic acid groups can then be completely or partially neutralized with conventional inorganic or organic bases.
  • the hydroxyl-containing polyesters are z. B. those as they are mentioned in DE-A 2 647 482, pages 8-9.
  • two hydroxyl-containing polyethers, polyethers modified by vinyl polymers, polythioethers, polyacetals, hydroxyl-containing polycarbonates and polyesteramides and polyamides are, for. B. those as described in DE-A 2 647 482, pages 9, 10 and 11.
  • polyhydroxyl compounds can also be used in which high molecular weight polyadducts or polycondensates are contained in finely dispersed or dissolved form.
  • modified polyhydroxyl compounds are obtained if polyaddition reactions (e.g. reactions between polyisocyanates and amino-functional compounds) or polycondensation reactions (e.g. between formaldehyde and phenols and / or amines) take place directly in situ in the above-mentioned compounds containing hydroxyl groups leaves.
  • Amino alcohols such as ethanolamine, propanolamine, diethanolamine can also be used provided that all the amino groups present are reacted with isocyanate groups.
  • Mono-, di- or polyamines and water can also be used in minor amounts.
  • the products obtained after the reaction should contain, apart from OH groups, at most in minor amounts of carboxyl groups or mercapto groups.
  • the sulfonation products of all known aromatic polyisocyanates can be used as isocyanatoarylsulfonic acids.
  • aromatic polyisocyanates which can be used in the form of their sulfonation products in the process according to the invention are those as described in DE-A 2 647 482, pages 5 and 6.
  • Phosgenation products of condensates of aniline and aldehydes or ketones such as, for. B. acetaldehyde, propionaldehyde, butyraldehyde, acetone, methyl ethyl ketone.
  • phosgenation products of condensates of alkyl-substituted anilines, especially toluidines, with aldehydes or ketones such as. B. formaldehyde, acetaldehyde, butyraldehyde, acetone, methyl ethyl ketone.
  • reaction products of the aromatic polyisocyanate mixtures mentioned with 0.2-50 mol% of polyols are also suitable, provided that the viscosity of the reaction products thus obtained does not exceed 50,000 cP at 25 ° C. and the NCO content of the reaction products is at least 6% by weight. % is.
  • Suitable polyols for modifying the starting materials are, in particular, the polyether and / or polyester polyols of the molecular weight range 200 to 6000, preferably 300 to 4000, which are known in polyurethane chemistry, and also low molecular weight polyols of the molecular weight range 62 to 200. Examples of such low molecular weight polyols are ethylene glycol, propylene glycol, Glycerin, trimethylolpropane, 1,4,6-hexanetriol.
  • Particularly preferred isocyanatoaryl sulfonic acids are the sulfonation products of 2,4-tolylene diisocyanate and mixtures of 2,4- and 2,5-tolylene diisocyanate, furthermore sulfonation products of the di- and polyisocyanates which are obtained by phosgenation of aniline / formaldehyde condensates, partial sulfonation of aromatic Get polyisocyanates.
  • partial sulfonation of chemically uniform diisocyanates or binary isomer mixtures gives suspensions, while partial sulfonation of multicomponent mixtures produces homogeneous solutions.
  • it is basically irrelevant whether solutions or suspensions are used.
  • Partially sulfonated polyisocyanate mixtures such as those obtained by phosgenation of aniline-formaldehyde condensates and described in German Offenlegungsschriften 2,227,111, 2,359,614 and 2,359,615, are very particularly preferred.
  • Suspensions of diisocyanatotoluene-sulfonic acid dimers and diisocyanatodiphenylmethane-sulfonic acid dimers in diisocyanatotoluene or diisocyanatodiphenylmethane are also particularly preferred.
  • the isocyanatoarylsulfonic acids to be used in the process according to the invention or their mixtures with unsulfonated aromatic polyisocyanates are prepared by the known processes of the prior art or in analogy to the known processes of the prior art, as can be seen, for example, from the publications already mentioned, or from US-A 3 826 769.
  • the processes of DE-A 2 524 476 or 2 615 876 are also suitable for the preparation of isocyanatoarylsulfonic acids which can be used in the process according to the invention.
  • solutions or suspensions of the isocyanato-arylsulfonic acids in aromatic, aliphatic or cycloaliphatic monoisocyanates can also be used.
  • aromatic, aliphatic or cycloaliphatic monoisocyanates examples of the latter compounds are phenyl isocyanate, tosyl isocyanate, n-hexyl isocyanate, 6-chloro-hexyl isocyanate, cyclohexyl isocyanate or methoxymethyl isocyanate.
  • sulfonated aromatic monoisocyanates such as. . B.
  • phenylisocyanate as isocyanatoaryl in combination with non-sulfonated polyisocyanates of the type exemplified above
  • the nature and proportions of the employed in the present process isocyanates, and the degree of sulfonation are often selected so that the equivalent ratio of optionally partly present in the dimerized form - isocyanate groups to sulfonic acid groups> 1: 1 d.
  • h is in particular between 1.05: 1 and 50: 1, preferably between 2: 1 and 30: 1.
  • a ratio between 2: 1 and 12: 1 is very particularly preferred.
  • isocyanato sulfonic acids are those aromatic mono-, di- or polyisocyanates which contain more than one sulfonic acid group and in particular two or three sulfonic acid groups.
  • isocyanatopolysulfonic acids are described in DE-A 2 615 876. 1 are as follows: Unless Monoisocyanatodisulfonklaren be used (with), the equivalent ratio of NCO groups to SO s H group can also be between 1: 1 and 0.5.
  • Monoisocyanato sulfonic acids are preferably used for the preparation of hydroxy compounds with terminal sulfonic acid or sulfonate groups, e.g. B. the sulfonation products of phenyl isocyanate, m-tolyl isocyanate, p-tolyl isocyanate, p-chlorophenyl isocyanate, p-nitrophenyl isocyanate, p-methoxyphenyl isocyanate, p-chloromethyl-phenyl isocyanate, m-chlorophenyl isocyanate, m-chloromethyl-phenyl isocyanate.
  • B the sulfonation products of phenyl isocyanate, m-tolyl isocyanate, p-tolyl isocyanate, p-chlorophenyl isocyanate, p-nitrophenyl isocyanate, p-methoxyphenyl isocyan
  • the quantitative ratio between polyhydroxy compounds and isocyanatosulfonic acid is usually chosen so that OH-functional products with a molecular weight below 12,000 and preferably below 6,000 are formed. A molar excess of hydroxy-functional components is therefore used, with at least 1.5 OH groups per NCO group.
  • NCO groups are not only to be understood as NCO groups present in free form, but also in the form of uretdione groups dimerized NCp groups. It is particularly preferred to only partially modify the hydroxy-functional compounds used as starting material with sulfonic acid groups, it being possible to use up to 30 OH groups on one NCO group. An equivalent ratio of OH groups to NCO groups between 2 and 20 is preferred.
  • monoisocyanates which contain 1 to 3 sulfonic acid groups can also be used in the context of the present invention. These monoisocyanates are reacted with the starting hydroxy compounds in molar amounts.
  • the reaction of the starting hydroxy compounds with the isocyanates containing sulfonic acid groups takes place in principle in a known manner.
  • the hydroxy compounds are introduced and the isocyanate component is added with mixing.
  • the isocyanate is liquid, as is the case, for example, with partially sulfonated MDI types, the mixing of the components and the subsequent reaction can readily take place at room temperature or even at a slightly elevated temperature.
  • the choice of temperature in this case depends exclusively on the viscosity of the reaction mixture and on the desired duration of the reaction.
  • solid isocyanatoaryl, mono- or polysulfonic acids a suspension is primarily formed during the mixing and it is advisable to carry out the reaction at a temperature at which the solid isocyanate dissolves rapidly.
  • Solid isocyanatosulfonic acids are particularly preferably used in the form of suspensions, pastes or wet powders, using inert solvents, as described in DE-A 2 640 103.
  • Solid isocyanatosulfonic acids can also be used in the form of solutions in organic solvents, liquid esters of an inorganic or organic acid of phosphorus being preferred as solvents (DE-A 2 650 172).
  • any inert solvents such as hydrocarbons, halogenated hydrocarbons, ethers, esters and ketones can of course be added to the reaction mixture.
  • the reaction in the absence of solvents or with the small amounts of solvents which are used for pasting or dissolving solid isocyanatosulfonic acids is preferred.
  • a preferred procedure consists in the production of asymmetrical hydroxy compounds using the different reactivity of the isocyanate groups.
  • a diisocyanatoarylsulfonic acid can first be primed with a monofunctional alcohol, a fatty acid, an amino alcohol. or sec. Amine reactions, e.g. B. 20-70% and then bring the remaining NCO groups to reaction with a di- or polyhydroxy compound.
  • the surface-active properties can be varied in many ways.
  • the monofunctional compounds which can be used in addition to the polyhydroxy compounds already listed include, for. B. methanol, ethanol, isopropanol, n-butanol, glycol monomethyl ether, glycol monoethyl ether, diglycol monomethyl ether, n-octanol, n-dodecanol, oleyl alcohol, stearyl alcohol, hydroxy-functional fatty acid esters of glycerol, trimethylol propane, and trimethylol ethanol, stearic acid, linoleic acid, linoleic acid, coconut oil Aminopropanol (amino alcohols of this type can be regarded approximately as monofunctional in the course of the procedure described above due to the greatly different reactivity of the amino and hydroxy functions), butylamine, sec. Butylamine, coconut fatty amine.
  • the stepwise preparation of such asymmetrical hydroxy compounds is particularly preferably carried out in a solvent, for. B. in acetone or an organic phosphoric acid ester.
  • Short-chain hydrophilic monofunctional compounds are preferably combined with predominantly hydrophobic polyhydroxy compounds and long-chain hydrophobic monofunctional compounds are preferably combined with hydrophilic polyhydroxy compounds.
  • the hydroxy compounds containing sulfonic acid groups can be completely or partially neutralized with inorganic or organic bases.
  • Suitable neutralizing agents are e.g. B. organic bases such as monofunctional primary, secondary and tertiary amines such as methylamine, diethylamine, triethylamine, trimethylamine, dimethylamine, ethylamine, tributylamine, pyridine, aniline, toluidine, alkoxylated amines such as ethanolamine, diethanolamine, triethanolamine, methyldiethanolamine, dimethylaminoethanolamine polyfunctional polyamines in which the individual amino groups may have different basicity, such as. B.
  • organic bases such as monofunctional primary, secondary and tertiary amines such as methylamine, diethylamine, triethylamine, trimethylamine, dimethylamine, ethylamine, tributylamine, pyridine, aniline, toluidine, alkoxylated amines such
  • neutralizing agents are guanidines, guanidine carbonate, urea, methylurea, dimethylurea, caprolactam, dimethylformamide, dimethylacetamide, pyrrolidone, and solid inorganic bases such as calcium oxide, calcium hydroxide, calcium carbonate, magnesium oxide, magnesium carbonate, dolomite, lithium hydroxide, lithium carbonate, zinc oxide, zinc carbonate and basic inorganic Fillers.
  • Weakly basic neutralizing agents such as urea or caprolactam, as well as basic fillers can also be used in excess in relation to the sulfonic acid groups present.
  • the products according to the invention are valuable starting materials for the production of polyurethane plastics by the isocyanate polyaddition process. They are suitable for. B. for the production of compact or cellular elastomers, soft foams and rigid foams, especially when high demands are placed on the crosslinking density, fire behavior or degradability.
  • the polyhydroxy compounds according to the invention are suitable, for example, for the production of upholstery materials, mattresses, elastic underlays, car seats, damping materials, shock absorbers, construction materials, soundproofing insulation, moisture-absorbing materials, eg. B. in the hygiene sector, for the production of substrates for growing plants, and for heat and cold protection.
  • polyhydroxy compounds according to the invention are very particularly suitable for the preparation of inorganic-organic plastics, for example in analogy to the procedures described in DE-C 2310559, DE-A 2 227 147, 2 359 608, and for surface coatings, impregnations and adhesives.
  • the products according to the present invention are suitable as versatile surface-active compounds, e.g. B. as emulsifiers.
  • a particular advantage of the hydroxy compounds according to the invention is their increased polarity.
  • these products are well tolerated with low-molecular glycols such as ethylene glycol, diethylene glycol, 1,4-butanediol, glycerin. Mixtures are homogeneous and therefore stable in storage.
  • reaction of the polyhydroxy compounds according to the present invention with polyisocyanates containing sulfonic acid ester groups is particularly favorable.
  • the use of the compounds according to the invention is particularly recommended when polyisocyanate components and polyhydroxy components initially form emulsions due to incompatibility, which only become homogeneous after a certain induction time. Even very small amounts of the products according to the invention favor the formation of particularly fine-particle emulsions which react much more quickly. Furthermore, the new products influence the pore structure of foams made from them and in many cases bring about a desirable increase in the compression hardness. Finally, the products are also suitable for hydrophobicizing surface-modified inorganic fillers.
  • Example 5 The procedure is as in Example 5, but starting from a corresponding polyether with OH number 28. A yellowish-brown, viscous, modified polyether is obtained.
  • uretdione of diisocyanate-toluenesulfonic acid (cf. Example 1) are triturated with 373 g toluene and mixed with 10 kg of a polypropylene glycol ether started on trimethylolpropane with 17% terminal ethylene glycol ether groups of OH number 35 at 50 ° C. with stirring. The temperature is then raised to 60 ° C. and the toluene is stripped off by applying a water jet vacuum. The uretdione dissolved practically quantitatively within 9 hours. The modified polyether is finally filtered through a fine metal sieve at 60 ° C.
  • the product goes into solution after a short time at 60 ° C.
  • toluene-moist uretdione of diisocyanatotoluenesulphonic acid (cf. Example 1), corresponding to 300 g of dry substance, are thoroughly triturated with 550 g of toluene and 15 kg of a polypropylene glycol ether started on trimethylolpropane with 13% terminal ethylene glycol ether groups of OH number 28 at 50 ° C. with stirring added. The mixture is then heated to 65 ° and stirred for 5 hours, during which most of the uretdione goes into solution. While stirring for a further 3 hours at 65 ° C., the toluene is distilled off in a water jet vacuum, the product is filtered off at 50 ° C. through a metal sieve of approx. 4 g of undissolved material.
  • the foams obtained correspond in mechanical properties and fire behavior to the foam from Example 14.
  • the comparison foam takes considerably longer periods of time to rise and harden than the foams described in the examples.
  • the surface also remains sticky for much longer.

Description

Es ist bekannt, zur Herstellung von Polyurethanen Verbindungen zu verwenden, welche zwei bis sechs OH-Gruppen enthalten und ein Molekulargewicht zwischen 62 und etwa 10000 aufweisen. Zu diesen Polyhydroxyverbindungen zählen beispielsweise:

  • einfache, höherfunktionelle Alkohole, wie z. B. Äthylenglykol, Diäthylenglykol, Hexandiol, Glycerin, Trimethylolpropan sowie höhermolekulare Polyäther, Polythioäther, Polyester, Polyacetale. Diese höhermolekularen Polyhydroxyverbindungen werden in bekannter Weise aus niedermolekularen Bausteinen hergestellt. Im allgemeinen sind diese Hydroxyverbindungen wenig polar und tragen keine weiteren funktionellen Gruppen.
It is known to use compounds for the preparation of polyurethanes which contain two to six OH groups and have a molecular weight between 62 and about 10,000. These polyhydroxy compounds include, for example:
  • simple, higher functional alcohols, such as. B. ethylene glycol, diethylene glycol, hexanediol, glycerol, trimethylolpropane and higher molecular weight polyether, polythioether, polyester, polyacetals. These higher molecular weight polyhydroxy compounds are produced in a known manner from low molecular weight building blocks. In general, these hydroxy compounds are not very polar and do not carry any further functional groups.

Bei der Herstellung von Schaumstoffen aus Polyisocyanaten und Polyhydroxyverbindungen sind im allgemeinen oberflächenaktive Verbindungen, insbesondere aus der Gruppe der Organo-Polysiloxane, erforderlich. Diese Produkte bewirken eine Emulgierung der Reaktionskomponenten und vor allem eine Stabilisierung des zunächst noch flüssigen Schaumgerüsts. Auch bei der Herstellung nicht-zelliger Polyurethane werden zuweilen Emulgatoren mitverwendet, wenn mangelnde Verträglichkeit der Reaktionskomponenten oder die Mitverwendung von Füllstoffen dies erforderlich machen. In vielen Fällen muß der Emulgator bzw. Stabilisator als separate Komponente dem Reaktionsgemisch zugesetzt werden, was wegen der im allgemeinen geringen Mengen dieser Komponenten Dosierprobleme mit sich bringen kann.In the production of foams from polyisocyanates and polyhydroxy compounds, surface-active compounds, in particular from the group of organopolysiloxanes, are generally required. These products emulsify the reaction components and above all stabilize the initially still liquid foam structure. Sometimes emulsifiers are also used in the production of non-cellular polyurethanes, if the compatibility of the reaction components or the use of fillers make this necessary. In many cases, the emulsifier or stabilizer must be added to the reaction mixture as a separate component, which can cause metering problems because of the generally small amounts of these components.

Es wäre ein Vorteil, wenn beispielsweise bei Unverträglichkeit der Reaktanten auf spezielle oberflächenaktive Verbindungen verzichtet werden könnte, indem schon die verwendeten Polyole selbst die gewünschten oberflächenaktiven Eigenschaften aufwiesen. Es besteht also ein Bedarf für Polyole mit oberflächenaktiven Eigenschaften. Ferner besteht der Wunsch nach Polyolen höherer Polarität und Hydrophilie, um auf diese Weise die Wasserverträglichkeit von Polyolen zu verbessern und den aus den Polyolen hergestellten Schaumstoffen ein gewisses Wasseraufnahmevermögen sowie eine verbesserte Lösungsmittelresistenz zu verleihen. Ferner besteht ein Bedarf nach Polyhydroxylverbindungen, welche Polyurethane mit verbessertem Brandverhalten liefern. Schließlich wären OH-Präpolymere wünschenswert, welche beim hydrolytischen Abbau keine toxikologisch bedenklichen aromatischen Diamine liefern.It would be an advantage if, for example, if the reactants were incompatible, special surface-active compounds could be dispensed with, since the polyols used themselves already had the desired surface-active properties. There is therefore a need for polyols with surface-active properties. There is also a desire for polyols of higher polarity and hydrophilicity, in order in this way to improve the water compatibility of polyols and to impart a certain water absorption capacity and improved solvent resistance to the foams produced from the polyols. There is also a need for polyhydroxyl compounds which provide polyurethanes with improved fire behavior. Finally, it would be desirable to have OH prepolymers which, when hydrolytically degraded, do not produce aromatic diamines which are of toxicological concern.

Die vorliegende Erfindung liefert eine Lösung dieser Probleme. Überraschenderweise wurde nämlich gefunden, daß durch Umsetzung von Polyhydroxyverbindungen mit molar unterschüssigen Mengen aromatischer Isocyanatosulfonsäuren, gegebenenfalls im Gemisch mit üblichen Polyisocyansten, neuartige Hydroxyverbindungen erhalten werden, welche erhöhte Polarität sowie oberflächenaktive Eigenschaften aufweisen und z. B. daraus hergestellten Schaumstoffen verbessertes Brandverhalten sowie Hochfrequenzverschweißbarkeit verleihen.The present invention provides a solution to these problems. Surprisingly, it has been found that by reacting polyhydroxy compounds with molar amounts of aromatic isocyanato sulfonic acids, optionally in a mixture with conventional polyisocyanates, novel hydroxy compounds are obtained which have increased polarity and surface-active properties and, for. B. foams made from it give improved fire behavior and high frequency weldability.

Gegenstand der vorliegenden Erfindung sind somit mindestens eine OH-funktionelle Kette und mindestens eine Urethano-arylsulfonsäuregruppe aufweisende Verbindungen vom durchschnittlichen Molekulargewicht 300 bis 12 000.The present invention thus relates to at least one OH-functional chain and at least one urethano-arylsulfonic acid-containing compound having an average molecular weight of 300 to 12,000.

Erfindungsgemäß bevorzugt sind dabei Verbindungen, welche ein durchschnittliches Molekulargewicht von 400 bis 12 000 aufweisen, gekennzeichnet durch mindestens eine OH-funktionelle Langkette, welche 15 bis 400 Kettenglieder, vorzugsweise 30 bis 300 Kettenglieder, enthält. Kettenglieder sind z. B. CH(CH3)- oder CH2-Gruppen, Äthersauerstoffatome, CO-Gruppen, Schwefelatome und/oder Stickstoffatome.According to the invention, preference is given to compounds which have an average molecular weight of 400 to 12,000, characterized by at least one OH-functional long chain which contains 15 to 400 chain links, preferably 30 to 300 chain links. Chain links are e.g. B. CH (CH 3 ) - or CH 2 groups, ether oxygen atoms, CO groups, sulfur atoms and / or nitrogen atoms.

Die erfindungsgemäßen Verbindungen enthalten bevorzugt mindestens eine Struktureinheit der allgemeinen Formel:

Figure imgb0001
in der

  • R1 einen 2- bis 6wertigen Rest eines Polyols, z. B. eines Polyesters, Polyäthers, Polythioäthers oder Polyesteramids und
  • Ar einen mehrwertigen Rest eines aromatischen Isocyanats darstellt.
The compounds according to the invention preferably contain at least one structural unit of the general formula:
Figure imgb0001
 in the
  • R 1 is a 2- to 6-valent radical of a polyol, e.g. B. a polyester, polyether, polythioether or polyester amide and
  • Ar represents a polyvalent radical of an aromatic isocyanate.

Erfindungsgemäß sind Verbindungen folgender allgemeiner Formeln bevorzugt:

Figure imgb0002
According to the invention, compounds of the following general formulas are preferred:
Figure imgb0002

Gegenstand der vorliegenden Erfindung ist auch ein Verfahren zur Herstellung von mindestens eine OH-funktionelle Kette und mindestens eine Urethano-aryl-sulfonsäuregruppe aufweisenden Verbindungen vom durchschnittlichen Molekulargewicht 300 bis 12 000, dadurch gekennzeichnet, daß Verbindungen vom Molekulargewicht 62 bis 10 000, die mindestens zwei Hydroxylgruppen aufweisen, bei 0-190°C mit aromatischen Isocyanatosulfonsäuren umgesetzt werden, wobei das Äquivalent- Verhältnis der Gesamtmenge an Isocyanatgruppen (einschließlich der gegebenenfalls in dimerisierter Form vorhandenen Isocyanatgruppen) zu Sulfonsäuregruppen 0,5 bis 50 und das Äquivalent-Verhältnis aus der Summe der Hydroxylgruppen der mindestens zwei Hydroxylgruppen aufweisenden Verbindungen zu NCO-Gruppen 1,5 bis 30 beträgt.The present invention also relates to a process for the preparation of at least one OH-functional chain and at least one urethano-aryl-sulfonic acid group-containing compound having an average molecular weight of 300 to 12,000, characterized in that compounds having a molecular weight of 62 to 10,000, the at least two Have hydroxyl groups, are reacted at 0-190 ° C with aromatic isocyanatosulfonic acids, the equivalent ratio of the total amount of isocyanate groups (including those optionally in dimerized Form isocyanate groups) to sulfonic acid groups 0.5 to 50 and the equivalent ratio of the sum of the hydroxyl groups of the compounds having at least two hydroxyl groups to NCO groups is 1.5 to 30.

Gegenstand der vorliegenden Erfindung ist schließlich auch die Verwendung der erfindungsgemäßen Verbindungen als Reaktionskomponente für Polyisocyanate zur Herstellung von Polyadditionsprodukten oder Polykondensationsprodukten.Finally, the present invention also relates to the use of the compounds according to the invention as a reaction component for polyisocyanates for the production of polyaddition products or polycondensation products.

Die neuen erfindungsgemäßen Verbindungen besitzen gegenüber den bisher bekannten Polyhydroxyverbindungen eine Reihe von vorteilhaften Eigenschaften:

  • 1. Sie besitzen stark polaren bzw. oberflächenaktiven Charakter, außerordentlich niedrigen Dampfdruck und sind hervorragend verträglich mit einer Vielzahl polarer und apolarer Medien und Reaktionspartnern.
  • 2. In Abhängigkeit von Art und Menge der eingesetzten Isocyanatoarylsulfonsäure sowie Art und Menge der zur Neutralisation der Sulfonsäure-Gruppen verwendeten Basen lassen sich die oberflächenaktiven Eigenschaften sowie die Hydrophilie in weiten Grenzen wunschgemäß steuern.
  • 3. Der hydrolytische Abbau der Produkte führt zu toxikologisch unbedenklichen Aminosulfonsäuren.
  • 4. Die Verwendung der erfindungsgemäßen Verbindungen beispielsweise bei der Herstellung von Polyurethanen führt zu Polymeren mit verbessertem Brandverhalten.
The new compounds according to the invention have a number of advantageous properties compared to the polyhydroxy compounds known hitherto:
  • 1. They have a strongly polar or surface-active character, extremely low vapor pressure and are excellently compatible with a large number of polar and apolar media and reaction partners.
  • 2. Depending on the type and amount of the isocyanatoarylsulfonic acid used and the type and amount of the bases used for neutralizing the sulfonic acid groups, the surface-active properties and the hydrophilicity can be controlled within wide limits as desired.
  • 3. The hydrolytic degradation of the products leads to toxicologically harmless aminosulfonic acids.
  • 4. The use of the compounds according to the invention, for example in the production of polyurethanes, leads to polymers with improved fire behavior.

Bei der Durchführung des erfindungsgemäßen Verfahrens erfolgt eine Addition eines Teils der OH-Gruppen der als Ausgangsmaterial verwendeten Polyhydroxyverbindungen mit den NCO-Gruppen sowie gegebenenfalls vorhandenen Uretdion-Gruppen der Isocyanatoarylsulfonsäure unter Ausbildung von höhermolekularen neuen Polyhydroxyverbindungen, welche zumindest anteilig UrethanGruppen und eine oder mehrere freie Sulfonsäure-Gruppen enthalten. Die Sulfonsäure-Gruppen können anschließend mit üblichen anorganischen oder organischen Basen ganz oder teilweise neutralisiert werden.When carrying out the process according to the invention, some of the OH groups of the polyhydroxy compounds used as starting material are added to the NCO groups and any uretdione groups of isocyanatoarylsulfonic acid which may be present, with the formation of higher molecular weight new polyhydroxy compounds which contain at least some urethane groups and one or more free sulfonic acid Groups included. The sulfonic acid groups can then be completely or partially neutralized with conventional inorganic or organic bases.

Beim erfindungsgemäßen Verfahren können als Ausgangsmaterial alle in der Polyurethanchemie üblicherweise verwendeten, mindestens zwei Hydroxylgruppen aufweisenden Verbindungen vom Molekulargewicht 62-10 000 eingesetzt werden. So eignen sich beispielsweise:

  • niedermolekulare Glykole, Polyester, Polyäther, Polyesteramide, OH-funktionelle Oligomere, Polymerisate, beispielsweise auf Basis Butadien sowie durch Vinylmonomere gepfropfte Polyäther oder auch solche Polyäther, welche andere Polymere, wie z. B. Polyharnstoffe, Harnstoffharze, Polyhydrazodicarbonamide oder Vinylpolymerisate dispergiert enthalten. Beispiele für geeignete hydroxyfunktionelle Verbindungen sind im folgenden aufgeführt.
In the process according to the invention, it is possible to use as starting material all of the compounds of molecular weight 62-10,000 which are usually used in polyurethane chemistry and have at least two hydroxyl groups. For example:
  • low molecular weight glycols, polyesters, polyethers, polyester amides, OH-functional oligomers, polymers, for example based on butadiene and polyethers grafted with vinyl monomers, or also polyethers which contain other polymers, such as, for. B. dispersed polyureas, urea resins, polyhydrazodicarbonamides or vinyl polymers. Examples of suitable hydroxy-functional compounds are listed below.

Die in Frage kommenden Hydroxylgruppen aufweisenden Polyester sind z. B. solche, wie sie in der DE-A 2 647 482, Seiten 8-9, genannt werden.The hydroxyl-containing polyesters are z. B. those as they are mentioned in DE-A 2 647 482, pages 8-9.

Auch die erfindungsgemäß in Frage kommenden, zwei Hydroxylgruppen aufweisenden Polyäther, durch Vinylpolymerisate modifizierten Polyäther, Polythioäther, Polyacetale, Hydroxylgruppen aufweisende Polycarbonate und Polyesteramide und Polyamide sind z. B. solche, wie sie in der DE-A 2 647 482, Seiten 9,10 und 11, beschrieben werden.Also suitable according to the invention, two hydroxyl-containing polyethers, polyethers modified by vinyl polymers, polythioethers, polyacetals, hydroxyl-containing polycarbonates and polyesteramides and polyamides are, for. B. those as described in DE-A 2 647 482, pages 9, 10 and 11.

Erfindungsgemäß können jedoch auch Polyhydroxylverbindungen eingesetzt werden, in welchen hochmolekulare Polyaddukte bzw. Polykondensate in feindisperser oder gelöster Form enthalten sind. Derartige modifizierte Polyhydroxylverbindungen werden erhalten, wenn man Polyadditionsreaktionen (z. B. Umsetzungen zwischen Polyisocyanaten und aminofunktionellen Verbindungen) bzw. Polykondensationsreaktionen (z. B. zwischen Formaldehyd und Phenolen und/oder Aminen) direkt in situ in den oben genannten, Hydroxylgruppen aufweisenden Verbindungen ablaufen läßt. Derartige Verfahren sind beispielsweise in den Deutschen Auslegeschriften 1 168 075 und 1 260 142 sowie den Deutschen Offenlegungsschriften 2324134, 2423984, 2512385, 2513815, 2550796, 2 550 797, 2550833 und 2 550 662 beschrieben. Es ist aber auch möglich, gemäß US-Patent 3869413 bzw. Deutscher Offenlegungsschrift 2 550 860 eine fertige wäßrige Polymerdispersion mit einer Polyhydroxylverbindung zu vermischen und anschließend aus dem Gemisch das Wasser zu entfernen. Niedermolekulare Glykole, welche im Gemisch mit den genannten höhermolekularen Polyhydroxylverbindungen oder auch allein mit Isocyanatosulfonsäuren umgesetzt werden können, sind z. B.: Äthylenglykol, Diäthylenglykol, Triäthylenglykol, Tetraäthylenglykol, Propylenglykol, Oligopropylenglykol, Butandiol, Hexandiol, 2-Äthylhexandiol, Octandiol, Glycerin, Trimethylpropan, Dodecandiol. Auch Aminoalkohole wie Äthanolamin, Propanolamin, Diäthanolamin können eingesetzt werden unter der Voraussetzung, daß alle vorhandenen Aminogruppen mit Isocyanatgruppen zur Reaktion gebracht werden. In untergeordneten Mengen können auch Mono-, Di- oder Polyamine sowie 'Wasser Verwendung finden. Die nach der Umsetzung erhaltenen Produkte sollen außer OH-Gruppen höchstens in untergeordneten Mengen Carboxylgruppen oder Mercaptogruppen enthalten.According to the invention, however, polyhydroxyl compounds can also be used in which high molecular weight polyadducts or polycondensates are contained in finely dispersed or dissolved form. Such modified polyhydroxyl compounds are obtained if polyaddition reactions (e.g. reactions between polyisocyanates and amino-functional compounds) or polycondensation reactions (e.g. between formaldehyde and phenols and / or amines) take place directly in situ in the above-mentioned compounds containing hydroxyl groups leaves. Such methods are described, for example, in German Auslegeschrift 1 168 075 and 1 260 142 and German Offenlegungsschriften 2324134, 2423984, 2512385, 2513815, 2550796, 2 550 797, 2550833 and 2 550 662. However, it is also possible to mix a finished aqueous polymer dispersion with a polyhydroxyl compound in accordance with US Pat. No. 3,869,413 or German Offenlegungsschrift 2,550,860 and then to remove the water from the mixture. Low molecular weight glycols, which can be reacted in a mixture with the above-mentioned higher molecular weight polyhydroxyl compounds or alone with isocyanato sulfonic acids, are, for. E.g .: ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, oligopropylene glycol, butanediol, hexanediol, 2-ethylhexanediol, octanediol, glycerin, trimethylpropane, dodecanediol. Amino alcohols such as ethanolamine, propanolamine, diethanolamine can also be used provided that all the amino groups present are reacted with isocyanate groups. Mono-, di- or polyamines and water can also be used in minor amounts. The products obtained after the reaction should contain, apart from OH groups, at most in minor amounts of carboxyl groups or mercapto groups.

Beim erfindungsgemäßen Verfahren können als Isocyanatoarylsulfonsäuren die Sulfonierungsprodukte aller bekannten aromatischen Polyisocyanate eingesetzt werden. Beispiele für derartige in Form ihrer Sulfonierungsprodukte beim erfindungsgemäßen Verfahren einsetzbare aromatische Polyisocyanate sind solche, wie sie in der DE-A 2 647 482, Seiten 5 und 6, beschrieben werden.In the process according to the invention, the sulfonation products of all known aromatic polyisocyanates can be used as isocyanatoarylsulfonic acids. Examples of such aromatic polyisocyanates which can be used in the form of their sulfonation products in the process according to the invention are those as described in DE-A 2 647 482, pages 5 and 6.

Geeignet sind auch Phosgenierungsprodukte von Kondensaten von Anilin und Aldehyden oder Ketonen, wie z. B. Acetaldehyd, Propionaldehyd, Butyraldehyd, Aceton, Methyläthylketon. Ferner geeignet sind die Phosgenierungsprodukte von Kondensaten von am Kern Alkyl-substituierten Anilinen, insbesondere Toluidinen, mit Aldehyden oder Ketonen, wie z. B. Formaldehyd, Acetaldehyd, Butyraldehyd, Aceton, Methyläthylketon.Phosgenation products of condensates of aniline and aldehydes or ketones, such as, for. B. acetaldehyde, propionaldehyde, butyraldehyde, acetone, methyl ethyl ketone. Also suitable are the phosgenation products of condensates of alkyl-substituted anilines, especially toluidines, with aldehydes or ketones, such as. B. formaldehyde, acetaldehyde, butyraldehyde, acetone, methyl ethyl ketone.

Weiterhin geeignet sind Umsetzungsprodukte der genannten aromatischen Polyisocyanatgemische mit 0,2-50 Mol-% an Polyolen, vorausgesetzt, daß die Viskosität der so erhaltenen Umsetzungsprodukte 50 000 cP bei 25°C nicht überschreitet und der NCO-Gehalt der Umsetzungsprodukte mindestens 6 Gew.-% beträgt. Geeignete Polyole zur Modifizierung der Ausgangsmaterialien sind insbesondere die in der Polyurethan-Chemie bekannten Polyäther- und/oder Polyesterpolyole des Molekulargewichtsbereichs 200 bis 6000, vorzugsweise 300 bis 4000, sowie niedermolekulare Polyole des Molekulargewichtsbereichs 62 bis 200. Beispiele derartiger niedermolekularer Polyole sind Äthylenglykol, Propylenglykol, Glyzerin, Trimethylolpropan, 1,4,6-Hexantriol.Also suitable are reaction products of the aromatic polyisocyanate mixtures mentioned with 0.2-50 mol% of polyols, provided that the viscosity of the reaction products thus obtained does not exceed 50,000 cP at 25 ° C. and the NCO content of the reaction products is at least 6% by weight. % is. Suitable polyols for modifying the starting materials are, in particular, the polyether and / or polyester polyols of the molecular weight range 200 to 6000, preferably 300 to 4000, which are known in polyurethane chemistry, and also low molecular weight polyols of the molecular weight range 62 to 200. Examples of such low molecular weight polyols are ethylene glycol, propylene glycol, Glycerin, trimethylolpropane, 1,4,6-hexanetriol.

Besonders bevorzugte Isocyanatoaryl-sulfonsäuren sind die Sulfonierungsprodukte von 2,4-Toluylendiisocyanat sowie Gemischen aus 2,4- und 2,5-Toluylendiisocyanat, ferner Sulfonierungsprodukte der Di- bzw. Polyisocyanate, welche durch Phosgenierung von Anilin/Formaldehyd-Kondensaten erhalten teilweiser Sulfonierung aromatischer Polyisocyanate erhalten. Im allgemeinen erhält man bei der Teilsulfonierung von chemisch einheitlichen Diisocyanaten oder von binären Isomerengemischen Suspensionen, während bei der Teilsulfonierung von Mehrkomponenten-Gemischen homogene Lösungen entstehen. Für das erfindungsgemäße Verfahren ist es grundsätzlich ohne Belang, ob Lösungen oder Suspensionen eingesetzt werden. Ganz besonders bevorzugt sind teilsulfonierte Polyisocyanatgemische, wie sie durch Phosgenierung von Anilin-Formaldehyd-Kondensaten erhalten werden und in den deutschen Offenlegungsschriften 2 227 111, 2 359 614 und 2 359 615 beschrieben sind. Ebenfalls besonders bevorzugt sind Suspensionen von Diisocyanato-toluol-sulfonsäure-Dimeren sowie Diisocyanatodiphenylmethan-sulfonsäure-Dimeren in Diisocyanatotoluol bzw. Diisocyanatodiphenylmethan.Particularly preferred isocyanatoaryl sulfonic acids are the sulfonation products of 2,4-tolylene diisocyanate and mixtures of 2,4- and 2,5-tolylene diisocyanate, furthermore sulfonation products of the di- and polyisocyanates which are obtained by phosgenation of aniline / formaldehyde condensates, partial sulfonation of aromatic Get polyisocyanates. In general, partial sulfonation of chemically uniform diisocyanates or binary isomer mixtures gives suspensions, while partial sulfonation of multicomponent mixtures produces homogeneous solutions. For the process according to the invention it is basically irrelevant whether solutions or suspensions are used. Partially sulfonated polyisocyanate mixtures, such as those obtained by phosgenation of aniline-formaldehyde condensates and described in German Offenlegungsschriften 2,227,111, 2,359,614 and 2,359,615, are very particularly preferred. Suspensions of diisocyanatotoluene-sulfonic acid dimers and diisocyanatodiphenylmethane-sulfonic acid dimers in diisocyanatotoluene or diisocyanatodiphenylmethane are also particularly preferred.

Die Herstellung der beim erfindungsgemäßen Verfahren einzusetzenden Isocyanatoarylsulfonsäuren bzw. ihrer Gemische mit nicht sulfonierten aromatischen Polyisocyanaten erfolgt nach den bekannten Verfahren des Standes der Technik bzw. in Analogie zu den bekannten Verfahren des Standes der Technik, wie er sich beispielsweise aus den bereits genannten Veröffentlichungen, oder aus US-A 3 826 769 ergibt. Die Verfahren der DE-A 2 524 476 oder 2 615 876 sind zur Herstellung von beim erfindungsgemäßen Verfahren einsetzbaren Isocyanatoarylsulfonsäuren ebenfalls geeignet.The isocyanatoarylsulfonic acids to be used in the process according to the invention or their mixtures with unsulfonated aromatic polyisocyanates are prepared by the known processes of the prior art or in analogy to the known processes of the prior art, as can be seen, for example, from the publications already mentioned, or from US-A 3 826 769. The processes of DE-A 2 524 476 or 2 615 876 are also suitable for the preparation of isocyanatoarylsulfonic acids which can be used in the process according to the invention.

Es ist auch möglich, beim erfindungsgemäßen Verfahren Lösungen bzw. Suspensionen der beispielhaft genannten Isocyanatoarylsulfonsäuren in aliphatischen Polyisocyanaten wie z. B. Tetramethylendiisocyanat oder Hexamethylendiisocyanat und/oder in cycloaliphatischen bzw. gemischt aliphatisch-cyclo-aliphatischen Polyisocyanaten wie z. B. 4,4'-Diisocyanato-dicydohexylmethan, 2,4- bzw. 2,6-Diisocyanato-hexahydrotoluol oder 1-Isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexan einzusetzen. Falls eine Erniedrigung der NCO-Funktionalität der erfindungsgemäßen Verfahrensprodukte erwünscht ist können auch Lösungen bzw. Suspensionen der Isocyanato-arylsulfonsäuren in aromatischen, aliphatischen oder cycloaliphatischen Monoisocyanaten zum Einsatz gelangen. Beispiele für die letztgenannten Verbindungen sind Phenylisocyanat, Tosylisocyanat, n-Hexylisocyanat, 6-Chlor-hexylisocyanat, Cyclohexylisocyanat oder Methoxymethylisocyanat. Grundsätzlich denkbar ist auch der Einsatz von sulfonierten aromatischen Monoisocyanaten, wie z. B. Phenylisocyanat als Isocyanatoarylsulfonsäure in Kombination mit nicht sulfonierten Polyisocyanaten der beispielhaft genannten Art. Die Art und Mengenverhältnisse der beim erfindungsgemäßen Verfahren einzusetzenden Isocyanate, sowie der Sulfonierungsgrad werden häufig so gewählt, daß das Äquivalentverhältnis von gegebenenfalls teilweise in dimerisierter Form vorliegenden- Isocyanatgruppen zu Sulfonsäuregruppen > 1 : 1 d. h insbesondere zwischen 1,05 : 1 und 50 : 1, vorzugsweise zwischen 2 : 1 und 30 : 1, liegt. Ganz besonders bevorzugt ist ein Verhältnis zwischen 2:1 und 12: 1.It is also possible in the inventive method solutions or suspensions of the exemplified isocyanatoarylsulfonic acids in aliphatic polyisocyanates such as. B. tetramethylene diisocyanate or hexamethylene diisocyanate and / or in cycloaliphatic or mixed aliphatic-cyclo-aliphatic polyisocyanates such as. B. 4,4'-diisocyanato-dicydohexylmethane, 2,4- or 2,6-diisocyanato-hexahydrotoluene or 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane. If a reduction in the NCO functionality of the process products according to the invention is desired, solutions or suspensions of the isocyanato-arylsulfonic acids in aromatic, aliphatic or cycloaliphatic monoisocyanates can also be used. Examples of the latter compounds are phenyl isocyanate, tosyl isocyanate, n-hexyl isocyanate, 6-chloro-hexyl isocyanate, cyclohexyl isocyanate or methoxymethyl isocyanate. In principle, the use of sulfonated aromatic monoisocyanates, such as. . B. phenylisocyanate as isocyanatoaryl in combination with non-sulfonated polyisocyanates of the type exemplified above, the nature and proportions of the employed in the present process isocyanates, and the degree of sulfonation are often selected so that the equivalent ratio of optionally partly present in the dimerized form - isocyanate groups to sulfonic acid groups> 1: 1 d. h is in particular between 1.05: 1 and 50: 1, preferably between 2: 1 and 30: 1. A ratio between 2: 1 and 12: 1 is very particularly preferred.

Eine weitere Gruppe von bevorzugten Isocyanatosulfonsäuren sind solche aromatischen Mono-, Di-oder Polyisocyanate, welche mehr als eine Sulfonsäuregruppe und insbesondere zwei oder drei Sulfonsäuregruppen enthalten. Solche Isocyanatopolysulfonsäuren sind in der DE-A 2 615 876 beschrieben. Sofern Monoisocyanatodisulfonsäuren (mit) eingesetzt werden, kann das Äquivalentverhältnis von NCO-Gruppen zu SOsH-Gruppen auch zwischen 1 : 1 und 0,5 : 1 betragen.Another group of preferred isocyanato sulfonic acids are those aromatic mono-, di- or polyisocyanates which contain more than one sulfonic acid group and in particular two or three sulfonic acid groups. Such isocyanatopolysulfonic acids are described in DE-A 2 615 876. 1 are as follows: Unless Monoisocyanatodisulfonsäuren be used (with), the equivalent ratio of NCO groups to SO s H group can also be between 1: 1 and 0.5.

Zur Herstellung von Hydroxyverbindungen mit endständigen Sulfonsäure- bzw. Sulfonatgruppen werden vorzugsweise Monoisocyanatosulfonsäuren eingesetzt, z. B. die Sulfonierungsprodukte von Phenylisocyanat, m-Tolylisocyanat, p-Tolylisocyanat, p-Chlorphenylisocyanat, p-Nitrophenylisocyanat, p-Methoxyphenylisocyanat, p-Chlormethyl-phenylisocyanat, m-Chlorphenylisocyanat, m-Chlormethyl-phenylisocyanat.Monoisocyanato sulfonic acids are preferably used for the preparation of hydroxy compounds with terminal sulfonic acid or sulfonate groups, e.g. B. the sulfonation products of phenyl isocyanate, m-tolyl isocyanate, p-tolyl isocyanate, p-chlorophenyl isocyanate, p-nitrophenyl isocyanate, p-methoxyphenyl isocyanate, p-chloromethyl-phenyl isocyanate, m-chlorophenyl isocyanate, m-chloromethyl-phenyl isocyanate.

Das Mengenverhältnis zwischen Polyhydroxyverbindungen und Isocyanatosulfonsäure wird meist so gewählt, daß OH-funktionelle Produkte eines Molekulargewichts unter 12000 und vorzugsweise unter 6000 entstehen. Es wird also ein molarer Überschuß an hydroxyfunktionellen Komponenten eingesetzt, wobei auf eine NCO-Gruppe mindestens 1,5 OH-Gruppen entfallen sollen. Unter NCO-Gruppen sollen dabei nicht nur in freier Form vorliegende NCO-Gruppen verstanden werden, sondern auch in Form von Uretdion-Gruppen vorliegende dimerisierte NCp-Gruppen. Es ist besonders bevorzugt, die als Ausgangsmaterial verwendeten hydroxyfunktionellen Verbindungen nur anteilig mit Sulfonsäure-Gruppen zu modifizieren, wobei auf eine NCO-Gruppe bis zu 30 OH-Gruppen eingesetzt werden können. Bevorzugt ist ein Äquivalent-Verhältnis von OH-Gruppen zu NCO-Gruppen zwischen 2 und 20.The quantitative ratio between polyhydroxy compounds and isocyanatosulfonic acid is usually chosen so that OH-functional products with a molecular weight below 12,000 and preferably below 6,000 are formed. A molar excess of hydroxy-functional components is therefore used, with at least 1.5 OH groups per NCO group. NCO groups are not only to be understood as NCO groups present in free form, but also in the form of uretdione groups dimerized NCp groups. It is particularly preferred to only partially modify the hydroxy-functional compounds used as starting material with sulfonic acid groups, it being possible to use up to 30 OH groups on one NCO group. An equivalent ratio of OH groups to NCO groups between 2 and 20 is preferred.

Die genannten Mengenverhältnisse gelten im wesentlichen für Umsetzungen, die unter Verwendung von Di- bzw. Polyisocyanaten durchgeführt werden und die unmittelbar zu durch Sulfonsäuregruppen modifizierten Polyhydroxyverbindungen führen.The quantitative ratios mentioned essentially apply to reactions which are carried out using di- or polyisocyanates and which lead directly to polyhydroxy compounds modified by sulfonic acid groups.

Im Rahmen der vorliegenden Erfindung können jedoch auch Monoisocyanate, welche 1 bis 3 Sulfonsäuregruppen enthalten, Verwendung finden. Diese Monoisocyanate werden mit den Ausgangs-Hydroxyverbindungen in molar unterschüssigen Mengen umgesetzt.However, monoisocyanates which contain 1 to 3 sulfonic acid groups can also be used in the context of the present invention. These monoisocyanates are reacted with the starting hydroxy compounds in molar amounts.

Bevorzugt ist ein Äquivalentverhältnis von OH-Gruppen zu NCO-Gruppen zwischen 2 und 6.An equivalent ratio of OH groups to NCO groups between 2 and 6 is preferred.

Die Umsetzung der Ausgangs-Hydroxyverbindungen mit den Sulfonsäuregruppen enthaltenden Isocyanaten erfolgt im Prinzip in bekannter Weise. Im allgemeinen werden die Hydroxyverbindungen vorgelegt und Isocyanatkomponente unter Vermischen zugegeben. Ist das Isocyanat flüssig, wie es beispielsweise bei teilsulfonierten MDI-Typen der Fall ist, so kann die Vermischung der Komponenten und die anschließende Reaktion ohne weiteres bei Raumtemperatur oder auch bei geringfügig erhöhter Temperatur stattfinden. Die Wahl der Temperatur hängt in diesem Fall ausschließlich von der Viskosität des Reaktionsgemisches und von der gewünschten Zeitdauer der Umsetzung ab. Bei Verwendung von festen Isocyanatoaryl-, Mono- oder Polysulfonsäuren entsteht bei der Vermischung primär eine Suspension und es ist zweckmäßig, die Umsetzung bei einer Temperatur vorzunehmen, bei der das feste Isocyanat rasch in Lösung geht.The reaction of the starting hydroxy compounds with the isocyanates containing sulfonic acid groups takes place in principle in a known manner. In general, the hydroxy compounds are introduced and the isocyanate component is added with mixing. If the isocyanate is liquid, as is the case, for example, with partially sulfonated MDI types, the mixing of the components and the subsequent reaction can readily take place at room temperature or even at a slightly elevated temperature. The choice of temperature in this case depends exclusively on the viscosity of the reaction mixture and on the desired duration of the reaction. When using solid isocyanatoaryl, mono- or polysulfonic acids, a suspension is primarily formed during the mixing and it is advisable to carry out the reaction at a temperature at which the solid isocyanate dissolves rapidly.

Hierfür sind Temperaturen zwischen 40 und 180°C, insbesondere 60 und 120°C zweckmäßig. Insbesondere bei ausschließlichem Einsatz verhältnismäßig niedermolekularer Polyhydroxyverbindungen werden Temperaturen über 120°C bis etwa 200°C bevorzugt, um ein Festwerden des Reaktionsansatzes während der Umsetzung zu vermeiden. Feste Isocyanatosulfonsäuren werden besonders bevorzugt in Form von Suspensionen, Pasten oder Feuchtpulvern, unter Verwendung inerter Lösungsmittel eingesetzt, wie dies in der DE-A 2 640 103 beschrieben ist.Temperatures between 40 and 180 ° C., in particular 60 and 120 ° C., are expedient for this. In particular when relatively low molecular weight polyhydroxy compounds are used, temperatures above 120 ° C. to approximately 200 ° C. are preferred in order to avoid the reaction mixture becoming solid during the reaction. Solid isocyanatosulfonic acids are particularly preferably used in the form of suspensions, pastes or wet powders, using inert solvents, as described in DE-A 2 640 103.

Weiterhin können feste Isocyanatosulfonsäuren in der Form von Lösungen in organischen Lösungsmitteln eingesetzt werden, wobei als Lösungsmittel flüssige Ester einer anorganischen oder organischen Säure des Phosphors bevorzugt werden (DE-A 2 650 172).Solid isocyanatosulfonic acids can also be used in the form of solutions in organic solvents, liquid esters of an inorganic or organic acid of phosphorus being preferred as solvents (DE-A 2 650 172).

Im übrigen können selbstverständlich beliebige inerte Lösungsmittel, wie Kohlenwasserstoffe, Halogenkohlenwasserstoffe, Äther, Ester und Ketone dem Reaktionsgemisch zugegeben werden. Bevorzugt ist indessen die Umsetzung in Abwesenheit von Lösungsmitteln bzw. mit den geringen Lösungsmittelmengen welche zum Anpasten oder Lösen fester Isocyanatosulfonsäuren Verwendung finden.In addition, any inert solvents such as hydrocarbons, halogenated hydrocarbons, ethers, esters and ketones can of course be added to the reaction mixture. However, the reaction in the absence of solvents or with the small amounts of solvents which are used for pasting or dissolving solid isocyanatosulfonic acids is preferred.

Eine bevorzugte Arbeitsweise besteht in der Herstellung unsymmetrischer Hydroxyverbindungen unter Ausnutzung der unterschiedlichen Reaktionsfähigkeit der Isocyanatgruppen. So kann man beispielsweise eine Diisocyanatoarylsulfonsäure zunächst mit einem monofunktionellen Alkohol, einer Fettsäure, einem Aminoalkohol, prim. oder sek. Aminumsetzen, z. B. zu 20-70% und anschließend die verbleibenden NCO-Gruppen mit einer Di- bzw. Polyhydroxyverbindung zur Reaktion bringen, In Abhängigkeit von Art und Menge der monofunktionellen wie auch der polyfunktionellen Komponente können die oberflächenaktiven Eigenschaften vielfältig variiert werden.A preferred procedure consists in the production of asymmetrical hydroxy compounds using the different reactivity of the isocyanate groups. For example, a diisocyanatoarylsulfonic acid can first be primed with a monofunctional alcohol, a fatty acid, an amino alcohol. or sec. Amine reactions, e.g. B. 20-70% and then bring the remaining NCO groups to reaction with a di- or polyhydroxy compound. Depending on the type and amount of the monofunctional and also the polyfunctional component, the surface-active properties can be varied in many ways.

Die zusätzlich zu den bereits aufgeführten Polyhydroxyverbindungen einsetzbaren monofunktionellen Verbindungen umfassen z. B. Methanol, Äthanol, Isopropanol, n-Butanol, Glykolmonomethyläther, Glykolmonoäthyläther, Diglykolmonomethyläther, n-Octanol, n-Dodecanol, Oleylalkohol, Stearylalkohol, hydroxyfunktionelle Fettsäureester des Glycerins, Trimethylolpropans, und Trimethyloläthans, Stearinsäure, Kokosfettsäure, Leinölfettsäure, Sojafettsäure, Aminoäthanol, Aminopropanol (derartige Aminoalkohole können im Rahmen der oben beschriebenen Arbeitsweise infolge der stark unterschiedlichen Reaktivität von Amino- und Hydroxy-Funktion näherungsweise als monofunktionell angesehen werden), Butylamin, sec. Butylamin, Kokosfettamin.The monofunctional compounds which can be used in addition to the polyhydroxy compounds already listed include, for. B. methanol, ethanol, isopropanol, n-butanol, glycol monomethyl ether, glycol monoethyl ether, diglycol monomethyl ether, n-octanol, n-dodecanol, oleyl alcohol, stearyl alcohol, hydroxy-functional fatty acid esters of glycerol, trimethylol propane, and trimethylol ethanol, stearic acid, linoleic acid, linoleic acid, coconut oil Aminopropanol (amino alcohols of this type can be regarded approximately as monofunctional in the course of the procedure described above due to the greatly different reactivity of the amino and hydroxy functions), butylamine, sec. Butylamine, coconut fatty amine.

Die stufenweise Herstellung derartiger unsymmetrischer Hydroxyverbindungen wird besonders bevorzugt in einem Lösungsmittel durchgeführt, z. B. in Aceton oder einem organischen Phosphorsäureester. Dabei werden kurzkettige hydrophile monofunktionelle Verbindungen vorzugsweise mit überwiegend hydrophoben Polyhydroxyverbindungen und langkettige hydrophobe monofunktionelle Verbindungen vorzugsweise mit hydrophilen Polyhydroxyverbindungen kombiniert.The stepwise preparation of such asymmetrical hydroxy compounds is particularly preferably carried out in a solvent, for. B. in acetone or an organic phosphoric acid ester. Short-chain hydrophilic monofunctional compounds are preferably combined with predominantly hydrophobic polyhydroxy compounds and long-chain hydrophobic monofunctional compounds are preferably combined with hydrophilic polyhydroxy compounds.

Die Sulfonsäuregruppen enthaltenden Hydroxyverbindungen können mit anorganischen oder organischen Basen ganz oder teilweise neutralisiert werden. Geeignete Neutralisationsmittel sind z. B. organische Basen wie monofunktionelle primäre, sekundäre und tertiäre Amine wie beispielsweise Methylamin, Diäthylamin, Triäthylamin, Trimethylamin, Dimethylamin, Äthylamin, Tributylamin, Pyridin, Anilin, Toluidin, alkoxylierte Amine wie Äthanolamin, Diäthanolamin, Triäthanolamin, Methyldiäthanolamin, Dimethylaminoäthanol, Oleyldiäthanolamin, sowie polyfunktionelle Polyamine, bei denen die einzelnen Aminogruppen gegebenenfalls unterschiedliche Basizität aufweisen können, wie z. B. die durch Hydrierung von Additionsprodukten von Acrylnitril an primäre und sekundäre Amine erhaltenen Polyamine, per- oder partiell alkylierte Polyamine wie N,N-Dimethyläthylendiamin, ferner Verbindungen wie α-Aminopyridin, N,N-Dimethylhydrazin; anorganische Basen, basisch reagierende oder basenabspaltende Verbindungen wie Ammoniak, einwertige Metallhydroxide, -carbonate und -oxide wie Natriumhydroxid, Kaliumhydroxid.The hydroxy compounds containing sulfonic acid groups can be completely or partially neutralized with inorganic or organic bases. Suitable neutralizing agents are e.g. B. organic bases such as monofunctional primary, secondary and tertiary amines such as methylamine, diethylamine, triethylamine, trimethylamine, dimethylamine, ethylamine, tributylamine, pyridine, aniline, toluidine, alkoxylated amines such as ethanolamine, diethanolamine, triethanolamine, methyldiethanolamine, dimethylaminoethanolamine polyfunctional polyamines in which the individual amino groups may have different basicity, such as. B. the polyamines obtained by hydrogenation of addition products of acrylonitrile to primary and secondary amines, per- or partially alkylated polyamines such as N, N-dimethylethylenediamine, furthermore Compounds such as α-aminopyridine, N, N-dimethylhydrazine; inorganic bases, basic reacting or base releasing compounds such as ammonia, monovalent metal hydroxides, carbonates and oxides such as sodium hydroxide, potassium hydroxide.

Ferner eignen sich als Neutralisationsmittel Guanidine, Guanidincarbonat, Harnstoff, Methylharnstoff, Dimethylharnstoff, Caprolactam, Dimethylformamid, Dimethylacetamid, Pyrrolidon, sowie feste anorganische Basen wie Calciumoxid, Calciumhydroxid, Calciumcarbonat, Magnesiumoxid, Magnesiumcarbonat, Dolomit, Lithiumhydroxid, Lithiumcarbonat, Zinkoxid, Zinkcarbonat sowie basische anorganische Füllstoffe.Also suitable as neutralizing agents are guanidines, guanidine carbonate, urea, methylurea, dimethylurea, caprolactam, dimethylformamide, dimethylacetamide, pyrrolidone, and solid inorganic bases such as calcium oxide, calcium hydroxide, calcium carbonate, magnesium oxide, magnesium carbonate, dolomite, lithium hydroxide, lithium carbonate, zinc oxide, zinc carbonate and basic inorganic Fillers.

Schwach basische Neutralisationsmittel wie Harnstoff oder Caprolactam, sowie basische Füllstoffe können ohne weiteres auch in Überschuß gegenüber den vorhandenen Sulfonsäuregruppen angewandt werden.Weakly basic neutralizing agents such as urea or caprolactam, as well as basic fillers can also be used in excess in relation to the sulfonic acid groups present.

Die erfindungsgemäßen Produkte sind wertvolle Ausgangsmaterialien zur Herstellung von Polyurethankunststoffen nach dem Isocyanat-Polyadditionsverfahren. Sie eignen sich z. B. zur Herstellung von kompakten oder zelligen Elastomeren, Weichschäumen und Hartschäumen, insbesondere dann, wenn hohe Anforderungen an die Vernetzungsdichte, das Brandverhalten oder die Abbaubarkeit gestellt werden. So eignen sich die erfindungsgemäßen Polyhydroxyverbindungen beispielsweise zur Herstellung von Polstermaterialien, Matratzen, elastischen Unterlagen, Autositzen, Dampfungsmaterialien, Stoßabsorbern, Konstruktionswerkstoffen, schalldämmenden Isolierungen, feuchtigkeitsaufnehmenden Materialien, z. B. im Hygienesektor, zur Herstellung von Substraten zur Pflanzenaufzucht, sowie für den Wärme- und Kälteschutz. Ganz besonders geeignet sind die erfindungsgemäßen Polyhydroxyverbindungen zur Herstellung anorganisch-organischer Kunststoffe beispielsweise in Analogie zu den in DE-C 2310559, DE-A 2 227 147, 2 359 608 beschriebenen Verfahrensweisen, sowie für Oberflächenbeschichtungen, Imprägnierungen und Verklebungen geeignet.The products according to the invention are valuable starting materials for the production of polyurethane plastics by the isocyanate polyaddition process. They are suitable for. B. for the production of compact or cellular elastomers, soft foams and rigid foams, especially when high demands are placed on the crosslinking density, fire behavior or degradability. The polyhydroxy compounds according to the invention are suitable, for example, for the production of upholstery materials, mattresses, elastic underlays, car seats, damping materials, shock absorbers, construction materials, soundproofing insulation, moisture-absorbing materials, eg. B. in the hygiene sector, for the production of substrates for growing plants, and for heat and cold protection. The polyhydroxy compounds according to the invention are very particularly suitable for the preparation of inorganic-organic plastics, for example in analogy to the procedures described in DE-C 2310559, DE-A 2 227 147, 2 359 608, and for surface coatings, impregnations and adhesives.

Ferner eignen sich die Produkte gemäß vorliegender Erfindung als vielseitig zu verwendende oberflächenaktive Verbindungen, z. B. als Emulgatoren. Schaumstabilisatoren, als Färbereihilfsmittel, als Flotationsmittel und zur Herstellung von Polyurethandispersionen.Furthermore, the products according to the present invention are suitable as versatile surface-active compounds, e.g. B. as emulsifiers. Foam stabilizers, as dyeing aids, as flotation agents and for the production of polyurethane dispersions.

Ein besonderer Vorteil der erfindungsgemäßen Hydroxy-Verbindungen ist ihre erhöhte Polarität. Dadurch sind diese Produkte im Gegensatz beispielsweise zu reinen Polypropylenglykoläthern mit niedermolekularen Glykolen wie Athylenglykol, Diäthylenglykol, 1,4-Butandiol, Glycerin, gut verträglich. Mischungen sind homogen und damit lagerstabil.A particular advantage of the hydroxy compounds according to the invention is their increased polarity. In contrast to pure polypropylene glycol ethers, for example, these products are well tolerated with low-molecular glycols such as ethylene glycol, diethylene glycol, 1,4-butanediol, glycerin. Mixtures are homogeneous and therefore stable in storage.

Zur Herstellung von Polyadditionsprodukten mit günstigem Brandverhalten ist die Umsetzung der Polyhydroxyverbindungen gemäß vorliegender Erfindung mit Sulfonsäureester-Gruppen aufweisenden Polyisocyanaten besonders günstig.For the production of polyaddition products with favorable fire behavior, the reaction of the polyhydroxy compounds according to the present invention with polyisocyanates containing sulfonic acid ester groups is particularly favorable.

Der Einsatz der erfindungsgemäßen Verbindungen empfiehlt sich insbesondere dann, wenn Polyisocyanat-Komponenten und Polyhydroxi-Komponenten infolge Unverträglichkeit zunächst Emulsionen bilden, die erst nach einer gewissen Induktionszeit homogen werden. Bereits sehr geringe Mengen der erfindungsgemäßen Produkte begünstigen die Bildung besonders feinteiliger Emulsionen, die wesentlich rascher reagieren. Weiterhin beeinflussen die neuen Produkte die Porenstruktur von daraus hergestellten Schaumstoffen und bewirken in vielen Fällen eine wünschenswerte Erhöhung der Stauchhärte. Schließlich eignen sich die Produkte auch zur Hydrophobierung oberflächenmodifizierter anorganischer Füllstoffe.The use of the compounds according to the invention is particularly recommended when polyisocyanate components and polyhydroxy components initially form emulsions due to incompatibility, which only become homogeneous after a certain induction time. Even very small amounts of the products according to the invention favor the formation of particularly fine-particle emulsions which react much more quickly. Furthermore, the new products influence the pore structure of foams made from them and in many cases bring about a desirable increase in the compression hardness. Finally, the products are also suitable for hydrophobicizing surface-modified inorganic fillers.

Beispiel 1example 1

2000 g eines auf ein Gemisch aus 84% Trimethylolpropan und 16% 1,2-Propylenglykol gestarteten Polypropylenglykoläthers der OH-Zahl 42 werden mit 62 g toluolfeuchtem Uretdion der Dilsocyanatotoluolsulfonsäure (hergestellt aus Toluylendiisocyanat, Isomerengemisch 2,4 : 2,8=80 : 20), entsprechend 40 g Trockensubstanz bei Raumtemperatur innig vermischt. Innerhalb von 45 Minuten wird die Suspension auf 100°C geheizt und 3 Stunden bei 100-125°C gehalten. Toluol wird bei 100°C und 1866 Pa (14 Torr) abgezogen und die Lösung filtriert.

Figure imgb0003
2000 g of a polypropylene glycol ether of OH number 42 started on a mixture of 84% trimethylolpropane and 16% 1,2-propylene glycol are mixed with 62 g toluene-moist uretdione of dilsocyanatotoluenesulfonic acid (made from tolylene diisocyanate, isomer mixture 2.4: 2.8 = 80: 20 ), correspondingly mixed intimately 40 g of dry matter at room temperature. The suspension is heated to 100 ° C. within 45 minutes and kept at 100-125 ° C. for 3 hours. Toluene is drawn off at 100 ° C. and 1866 Pa (14 torr) and the solution is filtered.
Figure imgb0003

Beispiel 2Example 2

1021 g des Produkts gemäß Beispiel 1 werden mit 38 g 15prozentiger methanolischer Kalilauge versetzt und bei 35° C das Methanol im Vakuum abgezogen.

Figure imgb0004
1021 g of the product according to Example 1 are mixed with 38 g of 15 percent methanolic potassium hydroxide solution and the methanol is removed at 35 ° C. in vacuo.
Figure imgb0004

Beispiel 3Example 3

Es wird wie in Beispiel 1 verfahren, jedoch unter Verwendung von 154 g (100 g Trockensubstanz) an Uretdion.

Figure imgb0005
The procedure is as in Example 1, but using 154 g (100 g dry substance) of uretdione.
Figure imgb0005

Beispiel 4Example 4

1064 g des Produkts gemäß Beispiel 3 werden mit 83 g 15prozentiger methanolischer Kalilauge versetzt und bei 35° C das Methanol im Vakuum abgezogen.

Figure imgb0006
1064 g of the product according to Example 3 are mixed with 83 g of 15 percent methanolic potassium hydroxide solution and the methanol is removed at 35 ° C. in vacuo.
Figure imgb0006

Beispiel 5Example 5

4000 g eines auf Trimethylolpropan gestarteten Polypropylenglykoläthers mit 13% endständigen Äthylenglykoläthergruppen der OH-Zahl 35 werden mit 123 g (80 g Trockensubstanz) des im Beispiel 1 beschriebenen Uretdions bei Raumtemperatur innig vermischt. Es wird unter Stickstoff 1 Stunde bei 25-27°C gerührt, dann auf 50°C erwärmt und 4 Stunden bei dieser Temperatur gehalten, währenddessen durch Anlegen von Wasserstrahlvakuum das Toluol abgezogen wurde. Dabei ging der größte Teil des Uretdions in Lösung. Anschließend wird noch 8 Stunden bei 60―65° C untergerührt und die Lösung filtriert. Auf dem Filter verbleiben ca. 0,3 g Rückstand.

Figure imgb0007
4000 g of a polypropylene glycol ether started on trimethylolpropane with 13% terminal ethylene glycol ether groups of OH number 35 are intimately mixed with 123 g (80 g dry substance) of the uretdione described in Example 1 at room temperature. The mixture is stirred under nitrogen at 25-27 ° C. for 1 hour, then warmed to 50 ° C. and kept at this temperature for 4 hours, during which the toluene was removed by applying a water jet vacuum. Most of the uretdione went into solution. The mixture is then stirred in at 60-65 ° C for 8 hours and the solution is filtered. About 0.3 g of residue remains on the filter.
Figure imgb0007

Beispiel 6Example 6

2060 g des Produkts gemäß Beispiel 5 werden mit 77 g 15prozentiger methanolischer Kalilauge versetzt und bei 35° C das Methanol im Vakuum abgezogen.

Figure imgb0008
2060 g of the product according to Example 5 are mixed with 77 g of 15 percent methanolic potassium hydroxide solution and the methanol is removed at 35 ° C. in vacuo.
Figure imgb0008

Beispiel 7Example 7

Es wird wie in Beispiel 5 verfahren, jedoch ausgehend von einem entsprechenden Polyäther der OH-Zahl 28. Es wird ein gelblich-brauner viskoser modifizierter Polyäther erhalten.

Figure imgb0009
The procedure is as in Example 5, but starting from a corresponding polyether with OH number 28. A yellowish-brown, viscous, modified polyether is obtained.
Figure imgb0009

Beispiel 8Example 8

2060 g des Produkts gemäß Beispiel 7 werden mit'69 g 15%iger methanolischer Kalilauge versetzt und bei 35° C das Methanol im Vakuum abgezogen.

Figure imgb0010
2060 g of the product according to Example 7 are mixed with 69 g of 15% methanolic potassium hydroxide solution and the methanol is removed at 35 ° C. in vacuo.
Figure imgb0010

Beispiel 9Example 9

200 g Uretdion der Düsocyanätotoluolsulfonsäure (vgl. Beispiel 1) werden mit 373 g Toluol verrieben und mit 10 kg eines auf Trimethylolpropan gestarteten Polypropylenglykoläthers mit 17% endständigen Äthylenglykoläthergruppen der OH-Zahl 35 bei 50°C unter Rühren vermischt. Anschließend wird die Temperatur auf 60° C erhöht und durch Anlegen von Wasserstrahlvakuum das Toluol abgezogen. Innerhalb von 9 Stunden ging das Uretdion praktisch quantitativ in Lösung. Der modifizierte Polyäther wird zum Schluß bei 60° C über ein feines Metallsieb filtriert.

Figure imgb0011
200 g uretdione of diisocyanate-toluenesulfonic acid (cf. Example 1) are triturated with 373 g toluene and mixed with 10 kg of a polypropylene glycol ether started on trimethylolpropane with 17% terminal ethylene glycol ether groups of OH number 35 at 50 ° C. with stirring. The temperature is then raised to 60 ° C. and the toluene is stripped off by applying a water jet vacuum. The uretdione dissolved practically quantitatively within 9 hours. The modified polyether is finally filtered through a fine metal sieve at 60 ° C.
Figure imgb0011

Wird das Uretdion vor der Zugabe zum Polyäther mit 200 g Tris-chlor-äthylphosphat anstelle des Toluols verrieben, so geht das Produkt schon nach kurzer Zeit bei 60° C in Lösung.If the uretdione is triturated with 200 g of tris-chloroethylphosphate instead of the toluene before it is added to the polyether, the product goes into solution after a short time at 60 ° C.

Beispiel 10Example 10

380 g toluolfeuchtes Uretdion der Diisocyanatotoluolsulfonsäure (vgl. Beispiel 1), entsprechend 300 g Trockensubstanz, werden mit 550 g Toluol gründlich verrieben und zu 15 kg eines auf Trimethylolpropan gestarteten Polypropylenglykoläthers mit 13% endständigen Äthylenglykoläthergruppen der OH-Zahl 28 bei 50°C unter Rühren zugefügt. Anschließend wird auf 65° erwärmt und 5 Stunden gerührt, währenddessen der größte Teil des Uretdions in Lösung geht. Während weiteren 3 Stunden Rührens bei 65°C wird das Toluol im Wasserstrahlvakuum abdestilliert, das Produkt wird bei 50°C über ein Metallsieb von ca. 4 g Ungelöstem abfiltriert.

Figure imgb0012
380 g of toluene-moist uretdione of diisocyanatotoluenesulphonic acid (cf. Example 1), corresponding to 300 g of dry substance, are thoroughly triturated with 550 g of toluene and 15 kg of a polypropylene glycol ether started on trimethylolpropane with 13% terminal ethylene glycol ether groups of OH number 28 at 50 ° C. with stirring added. The mixture is then heated to 65 ° and stirred for 5 hours, during which most of the uretdione goes into solution. While stirring for a further 3 hours at 65 ° C., the toluene is distilled off in a water jet vacuum, the product is filtered off at 50 ° C. through a metal sieve of approx. 4 g of undissolved material.
Figure imgb0012

Beispiel 11Example 11

Zu 5000 g des nach Beispiel 10 erhaltenen Produktes werden bei Raumtemperatur innerhalb 1 Stunde 156 g 15%ige methanolische Kalilauge unter Rühren zugetropft. Anschließend wird im Wasserstrahlvakuum bei bis zu 55°C das Methanol abdestilliert. Der erhaltene Sulfonatgruppen aufweisende Polyäther hat eine Viskosität von 3400 mPa · s.

Figure imgb0013
156 g of 15% strength methanolic potassium hydroxide solution are added dropwise to 5000 g of the product obtained according to Example 10 at room temperature with stirring. The methanol is then distilled off in a water jet vacuum at up to 55 ° C. The polyether obtained has sulfonate groups and has a viscosity of 3400 mPa · s.
Figure imgb0013

Beispiel 12Example 12

Zu 5000 g des nach Beispiel 10 erhaltenen Polyäthers werden bei Raumtemperatur innerhalb von 2 Stunden 42 g Triäthylamin zugetropft. Anschließend wird noch 5 Stunden bei Raumtemperatur nachgerührt.

Figure imgb0014
42 g of triethylamine are added dropwise at room temperature to 5000 g of the polyether obtained according to Example 10 within 2 hours. The mixture is then stirred for a further 5 hours at room temperature.
Figure imgb0014

Beispiel 13Example 13

Zu 4800 g des gemäß Beispiel 10 erhaltenen Polyäthers werden 143 g bis Bis-(2-Hydroxiäthyl)-oleyl- amin zugetropft. Anschließend wird 4 Stunden'bei Raumtemperatur nachgerührt.

Figure imgb0015
143 g of bis- (2-hydroxyethyl) oleylamine are added dropwise to 4800 g of the polyether obtained according to Example 10. The mixture is then stirred for 4 hours at room temperature.
Figure imgb0015

Für die Verschäumungsversuche wurden folgende Materialien eingesetzt:

  • Polyol A: Polyoxyalkylenäthertriol vom Äquivalentgewicht 2000 mit endständigen Polyoxyäthylenblöcken und einem Anteil an primären Hydroxylgruppen von über 80%.
  • Polyol B: Das Sulfonsäuregruppen enthaltende Polyätherpolyol aus Beispiel 8, neutralisiert mit KOH.
  • Polyol C: Das Sulfonsäuregruppen enthaltende Polyätherpolyol aus Beispiel 11, neutralisiert mit KOH.
  • Polyol D: Entspricht Polyol C, jedoch neutralisiert mit Triäthylamin (Beispiel 12).
  • Polyol E: Entspricht Polyol C, jedoch neutralisiert mit N,N-Dihydroxyäthyloleylamin (Beispiel 13).
    Figure imgb0016
The following materials were used for the foaming tests:
  • Polyol A: polyoxyalkylene ether triol of equivalent weight 2000 with terminal polyoxyethylene blocks and a proportion of primary hydroxyl groups of over 80%.
  • Polyol B: The polyether polyol from Example 8 containing sulfonic acid groups, neutralized with KOH.
  • Polyol C: The polyether polyol from Example 11 containing sulfonic acid groups, neutralized with KOH.
  • Polyol D: Corresponds to polyol C, but neutralized with triethylamine (example 12).
  • Polyol E: Corresponds to polyol C, but neutralized with N, N-dihydroxyethyloleylamine (example 13).
    Figure imgb0016

Beispiel 14Example 14

In einem Pappbecher wurden folgende Komponenten eingewogen und 60 Sekunden lang mit einem hochtourigen Rührwerk intensiv verrührt:

Figure imgb0017
The following components were weighed into a paper cup and mixed intensively with a high-speed stirrer for 60 seconds:
Figure imgb0017

In die homogene Mischung wurden 55,4 Gew.-Teile (entsprechend einem NCO/OH-Index=100) eines modifizierten Toluylendiisocyanats (Desmodur MT 58 Allophanat-TDI) gegeben und schnell untergemischt. Nach 5 Sekunden begann das Gemisch aufzuschäumen. Es wurde sofort in eine aus Papier gefaltete quadratische Form gegossen und schäumte innerhalb von 60 Sekunden auf und war 10 Sekunden nach beendetem Aufschäumen abgebunden. Es entstand ein hochelastischer Schaumstoff mit feiner Zellstruktur, einem Raumgewicht von 36 g/I und guter Stauchhärte und Zugfestigkeit. Ein 2 cm starker und 10 cm breiter Streifen des Schaums wurde an einem Ende mit der entleuchteten Flamme eines Bunsenbrenners beflammt. Der Schaum brannte unter schwacher Rauchentwicklung und Abschmelzen, verlosch jedoch kurze Zeit nach Entfernen der Bunsenflamme.55.4 parts by weight (corresponding to an NCO / OH index = 100) of a modified tolylene diisocyanate (Desmodur MT 58 allophanate-TDI) were added to the homogeneous mixture and mixed in rapidly. After 5 seconds the mixture started to foam. It was immediately poured into a square form folded from paper and foamed within 60 seconds and was set 10 seconds after the foaming was complete. The result was a highly elastic foam with a fine cell structure, a density of 36 g / I and good compression hardness and tensile strength. A 2 cm thick and 10 cm wide strip of the foam was flamed at one end with the lit flame of a Bunsen burner. The foam burned with weak smoke and melting, but went out shortly after the Bunsen flame was removed.

Beispiele 15-17Examples 15-17

In der in Beispiel 14 beschriebenen Weise wurden nach folgenden Rezepturen Schaumstoffe hergestellt (Mengen in Gew.-Teilen):

Figure imgb0018
In the manner described in Example 14, foams were produced according to the following recipes (amounts in parts by weight):
Figure imgb0018

Bei der Verschäumung wurden folgende Reaktionszeiten beobachtet:

Figure imgb0019
The following reaction times were observed during foaming:
Figure imgb0019

Die erhaltenen Schaumstoffe entsprechen in mechanischen Eigenschaften und Brandverhalten dem Schaum aus Beispiel 14.The foams obtained correspond in mechanical properties and fire behavior to the foam from Example 14.

Zum Vergleich wurde nach der gleichen Rezeptur ein Schaumstoff unter alleiniger Verwendung von Polyol A hergestellt.

Figure imgb0020
For comparison, a foam was produced using only polyol A using the same recipe.
Figure imgb0020

Folgende Reaktionszeiten wurden beobachtet:

Figure imgb0021
The following response times were observed:
Figure imgb0021

Der Vergleichsschaum benötigt zum Aufsteigen und Aushärten erheblich längere Zeitspannen als die in den Beispielen beschriebenen Schaumstoffe. Auch bleibt die Oberfläche deutlich länger klebrig.The comparison foam takes considerably longer periods of time to rise and harden than the foams described in the examples. The surface also remains sticky for much longer.

Claims (5)

1. Compounds having an average molecular weight of from 300 to 12,000 having at least one OH-functional chain and at least one urethano-aryl-sulphonic acid group.
2. Compounds according to Claim 1, characterised by at least one OH-functional chain containing from 15 to 400 chain members and by a molecular weight of from 400 to 12,000.
3. Compounds according to Claim 2, characterized by at least one OH-functional chain which contains from 30 to 300 chain members.
4. Process for the preparation of compounds having an average molecular weight of from 300 to 12,000 having at least one OH-functional chain and at least one urethano-aryl-sulphonic acid group, characterised in that compounds having a molecular weight of from 62 to 10,000 having at least two hydroxyl groups are reacted at from 0 to 190°C with aromatic isocyanato sulphonic acids, the equivalent ratio of the total quantity of isocyanate groups (including any isocyanate groups present in dimerised form) to sulphonic acid groups being from 0.5 to 50 and the equivalent ratio of the sum of hydroxyl groups in the compounds having at least two hydroxyl groups to NCO groups being from 1.5 to 30.
5. Use of compounds according to Claim 1 as reactants for polyisocyanates for the production of polyaddition products and/or polycondensation products.
EP78100487A 1977-08-03 1978-07-24 Compounds containing hydroxylic groups and urethane-aryl-sulfonic acid groups, process for their preparation and their use as reaction components for polyisocyanates Expired EP0000724B1 (en)

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DE2735013 1977-08-03
DE19772735013 DE2735013A1 (en) 1977-08-03 1977-08-03 HYDROXYL GROUPS AND COMPOUNDS CONTAINING URETHANO-ARYL-SULPHONIC ACID

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EP0000724A1 EP0000724A1 (en) 1979-02-21
EP0000724B1 true EP0000724B1 (en) 1981-04-08

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DE2735047A1 (en) * 1977-08-03 1979-02-15 Bayer Ag POLYURETHANES CONTAINING ARYLSULPHONIC ACID ALKYLESTER GROUPS
DE2936039A1 (en) * 1979-09-06 1981-04-02 Bayer Ag, 5090 Leverkusen WATER-DISPERSIBLE, JET-CROSS-LINKABLE BINDERS FROM URETHANACRYLATE, A METHOD FOR THE PRODUCTION THEREOF AND THE USE OF THESE BINDERS IN AQUEOUS DISPERSION ON THE PAINTING, PRINTING COLOR AND TEXTILE COLOR
US4452924A (en) * 1983-05-05 1984-06-05 Mobay Chemical Corporation Flexible polyurethane foams having improved load bearing characteristics
US4482691A (en) * 1983-09-22 1984-11-13 Ppg Industries, Inc. Air-drying fatty acid-modified acrylic resins
US4738992A (en) * 1985-12-09 1988-04-19 Minnesota Mining And Manufacturing Company Hydrophilic polyurethane/polyurea sponge
DE3622609A1 (en) * 1986-07-05 1988-01-07 Bayer Ag METHOD FOR THE PRODUCTION OF LIQUID CRYSTALLINE NCO-POLYURETHANE PRE-POLYMERS AND THE USE THEREOF
US5185423A (en) * 1989-01-06 1993-02-09 Minnesota Mining And Manufacturing Company Method of making sulfonated hydroxy-functional polyurethane binder for magnetic recording media
US4939184A (en) * 1989-03-07 1990-07-03 University Of Akron Polyurethane foam
GB2235927B (en) * 1989-09-14 1992-10-21 Asahi Chemical Ind A sulfonic acid group-containing polyurethane and a photosensitive resin composition containing the same
FR2690918B1 (en) * 1992-05-06 2001-12-28 Poudres & Explosifs Ste Nale Use of an arylsulfonylurethane as a filling resin in nitrocellulose nail varnishes. New arylsulfonylurethanes and new nitrocellulose nail polishes.
US6165239A (en) * 1997-07-28 2000-12-26 3M Innovative Properties Company Aqueous sulfopolyurea colloidal dispersions, films and abrasive articles
US6649727B1 (en) 2000-07-27 2003-11-18 3M Innovative Properties Company Aqueous colloidal dispersions of sulfonated polyurethane ureas and products
US6517821B1 (en) 2000-07-27 2003-02-11 L'oreal Reshapable hair styling composition comprising aqueous colloidal dispersions of sulfonated polyurethane urea
BR112012007898A2 (en) * 2009-08-27 2016-03-22 Polinvent Kft amine-epoxy adduct, its preparation process and its use
US8263713B2 (en) * 2009-10-13 2012-09-11 Kraton Polymers U.S. Llc Amine neutralized sulfonated block copolymers and method for making same

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FR1546668A (en) * 1966-10-05 1968-11-22 Gen Aniline & Film Corp Sulfoalkylcarbamate esters of alkyl ethers of ethylene glycols, primary aliphatic alcohols and adducts of these alcohols with alkylene oxides
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DE2412217A1 (en) * 1974-03-14 1975-10-09 Bayer Ag URETHANE POLYOLS CONTAINING POLYALKYLENE OXIDE WITH SULPHONIC ACID GROUP (N)
DE2615876C2 (en) * 1976-04-10 1986-05-15 Bayer Ag, 5090 Leverkusen Aromatic isocyanato-polysulphonic acids and process for their preparation

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EP0000724A1 (en) 1979-02-21
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US4174434A (en) 1979-11-13
DE2860598D1 (en) 1981-04-30
IT7850566A0 (en) 1978-08-01
DE2735013A1 (en) 1979-02-15
US4224418A (en) 1980-09-23

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