EP0000722B1 - Procédé pour la préparation de polyuréthanes contenant des groupes ester alcoyle d'acide arylsulfonique - Google Patents

Procédé pour la préparation de polyuréthanes contenant des groupes ester alcoyle d'acide arylsulfonique Download PDF

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Publication number
EP0000722B1
EP0000722B1 EP78100484A EP78100484A EP0000722B1 EP 0000722 B1 EP0000722 B1 EP 0000722B1 EP 78100484 A EP78100484 A EP 78100484A EP 78100484 A EP78100484 A EP 78100484A EP 0000722 B1 EP0000722 B1 EP 0000722B1
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Prior art keywords
groups
oxetane
acid
isocyanate
reaction
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EP0000722A1 (fr
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Dieter Dr. Dieterich
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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
    • C08G18/70—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
    • 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

Definitions

  • Linear polyurethane polysulfonic acid esters are known. For example, they can be prepared by using a sulfonic acid ester diol in the construction of a polyurethane.
  • DE-PS 1 156 977 and 1 184 946 propose, for example, reacting polyether diols with diisocyanates and glycerol monotosylate in order to subsequently carry out a quaternization reaction with mono- or difunctional tertiary amines from the polyurethane polysulfonic acid esters thus obtained, to produce ionomers.
  • pendant aromatic sulfonic acid ester units are bound to an aliphatic chain segment. During the quaternization, the aromatic sulfonic acid residue is split off as an anion.
  • reaction products containing sulfonic acid groups are then neutralized with a base and mixed with water, resulting in aqueous polyurethane ionomer dispersions.
  • Polyurethanes modified in this way by sulfonic acid groups or sulfonate groups often have considerable hydrophilicity, which is why the content of sulfonic acid groups is generally to be kept as low as possible.
  • dispersions e.g. Introduce only as much sulfonate groups as is absolutely necessary to achieve sufficient dispersion and to achieve stable dispersion. A higher content of sulfonic acid groups would impair the water resistance of the coatings obtained from the dispersions. For this reason, only 0.1-2%, based on the polyurethane, of sulfonating agents is recommended for the production of dispersions.
  • polyisocyanates in the form of their sulfonic acids would be of very special interest from a technical, toxicological and industrial hygiene point of view.
  • the sulfonic acids of aromatic isocyanates are solid, powdery substances that have no vapor pressure and are therefore particularly safe to process.
  • water-soluble diaminosulphonic acid is formed, which must not be too toxic. If isocyanate sulfonic acids are used exclusively for the construction of polyaddition products, however, highly hydrophilic, often even water-soluble, products are obtained.
  • polyurethanes containing sulfonic acid ester groups and having chain sulfonic acid alkyl ester groups bonded to aromatic nuclei.
  • These polyurethanes preferably contain repeating units of the general formula
  • Ar radical of an aromatic isocyanate, and in particular recurring units of the general formula
  • These polyurethanes preferably have a molecular weight of more than 12,000.
  • the present invention relates to a process for the preparation of polyurethanes containing arylsulfonic acid alkyl groups, characterized in that aromatic isocyanate sulfonic acids, which optionally contain polyethers and / or polyester units, are reacted at 0 to 190 ° C.
  • the sulfonation products of all known aromatic di- and polyisocyanates or technical mixtures of aromatic polyisocyanates can be used as isocyanates.
  • Polyisocyanates of this type are described, for example, on pages 6 and 7 of European patent application 0 000 722 and the literature cited therein.
  • 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 mPa.s at 25 ° C. and the NCO content of the reaction products is at least 6 percent 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, and low molecular weight polyols of the molecular weight range 62 to 200 known in polyurethane chemistry. Examples of such low molecular weight polyols are ethylene glycol, propylene glycol, glycerin , Trimethylolpropane, 1, 4, 6-hexanetriol etc.
  • Completely sulfonated isocyanates are preferably used which carry one to two sulfonic acid groups in the molecule.
  • the mono- and disulfonic acids of 4,4'-diisocyanato-diphenylmethane, 2,4'-diisocyanatodiphenylmethane, 2,4-diisocyanatotoluene, 2,4-diisocyanatotoluene and their isomer mixtures are very particularly preferred .
  • partially sulfonated polyisocyanates in particular partially sulfonated liquid mixtures of polyisocyanates, such as are used, for. B. are described in DE-OS-2 227 111, 2359614 and 2359615. Whole or partially sulfonated phosgenation products of aniline-formaldehyde condensates are particularly preferred.
  • the sulfonation products of aromatic monoisocyanates for. B. of phenyl isocyanate, p-tolyl isocyanate, p-chlorophenyl isocyanate, p-nitrophenyl isocyanate, p-methoxyphenyl isocyanate, m-chlorophenyl isocyanate, m-chloromethylphenyl isocyanate, p-chloromethylphenyl isocyanate.
  • Sulfonation in situ is particularly preferred when sulfonic acids of isocyanate prepolymers are used.
  • the sulfonation can be carried out in a known manner with sulfuric acid, oleum or sulfur trioxide and with organic compounds in which sulfur oxide is additively bound, with the exclusion of water.
  • the sulfur trioxide can be in liquid, dissolved or in gaseous, e.g. B. be used by nitrogen diluted form.
  • Suitable solvents are e.g. Tetrahydrofuran, aliphatic ether, dioxane, dimethylformamide, dichloroethane, chlorobenzene, tetrachloroethane, dichloroethane, methylene chloride, chloroform, sulfur dioxide.
  • Very particularly suitable solvents for the sulfonation component are products that can remain as plasticizers or as blowing agents in the reaction mixture or in the finished product, such as.
  • Powdered isocyanate sulfonic acids are often used in the form of wet powders, pastes or suspensions prepared with inert suspending agents (DE-OS-2 642 114). For in situ sulfonation, care must be taken to ensure that the sulfonation reaction is complete when the epoxy is mixed in.
  • polyisocyanates customary in polyurethane chemistry can optionally be used, e.g. the polyisocyanates already mentioned above as starting material for the sulfonation, furthermore aliphatic polyisocyanates, such as ethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,12-dodecane diisocyanate, cyclobutane-1,3-diisocyanate, cyclohexane-1, 3- and -1,4-diisocyanate and any mixtures of these isomers, 1-isocyanato-3,3,5-trimethyl -5-isocyanatomethyl-cyclohexane (DE-AS-1 202 785, US Pat.
  • DE-AS-1 202 785 1-isocyanato-3,3,5-trimethyl -5-isocyanatomethyl-cyclohexane
  • Component optionally to be used according to the invention are furthermore compounds having at least two isocyanate-reactive hydrogen atoms with a molecular weight of generally 400-10,000.
  • These include compounds containing amino groups, thiol groups or carboxyl groups, preferably polyhydroxyl compounds, in particular compounds containing two to eight hydroxyl groups, especially those from molecular weight 800 to 10,000, preferably 1000 to 6000, e.g. at least two, usually 2 to 8, but preferably 2 to 4, hydroxyl-containing polyesters, polyethers, polythiol ethers, polyacetals, polycarbonates, polyester amines, as are known per se for the production of homogeneous and cellular polyurethanes.
  • compounds according to the invention can also be used with at least 2 isocyanate-reactive hydrogen atoms and a molecular weight between 32 and 400 or mixtures of such compounds.
  • the products are suitable for the epoxidation of natural fats and oils, such as soybean oil, olive oil, linseed oil, oil, and of synthetic di- or polyesters, which contain unsaturated fatty acids, such as oleic acid, linoleic acid, linolenic acid, ricinoleic acid, erucic acid.
  • natural fats and oils such as soybean oil, olive oil, linseed oil, oil, and of synthetic di- or polyesters, which contain unsaturated fatty acids, such as oleic acid, linoleic acid, linolenic acid, ricinoleic acid, erucic acid.
  • Esters of glycid with monocarboxylic acids e.g. Glycidyl acetate, glycidyl chloroacetate, glycidyl dichloroacetate, glycidyl trichloroacetate, glycidyl bromoacetate, glycidyl acrylate, glycidyl methacrylate, glycidyl caproate, glycidyl octoate, glycidyl dodecanoate, glycidyl oleate, glycidyl oleate.
  • reaction products of hydroxy-oxiranes in particular of glycid with aliphatic, cycloaliphatic and aromatic mono- and polyisocyanates, are also very suitable.
  • Such di- and polyfunctional epoxides are, for example, the epoxidation products of aliphatic and cycloaliphatic diolefins, such as diepoxibutane, diepoxihexane, vinyl-cyclohexene dioxide, dicyclopentadiene dioxide, limonene dioxide, dicyclopentadiene dioxide, ethylene glycol bis (3,4-epoxytetrahydro-dicyc) opentadien-8-yrodehyde-ethylacetate (ether), ethylacetate - 8 - yl) - glycidyl ether, epoxidized polybutadienes or copolymers of butadiene with ethylenically unsaturated compounds, such as styrene or vinyl acetate, compounds with two epoxy cyclohexyl radicals, such as diethylene glycol bis (3,3-epoxycyclohexane carboxylate), bis-3, 4-
  • polyesters such as those obtained by reacting a dicarboxylic acid or by reacting cyanuric acid with epichlorohydrin or dichlorohydrin in the presence of an alkali.
  • Such polyesters can be derived from aliphatic dicarboxylic acids, such as succinic acid or adipic acid, and in particular from aromatic dicarboxylic acids, such as phthalic acid or terephthalic acid.
  • Diglycidyl adipate, diglycidyl phthalate and triglycidyl isocyanurate can be mentioned in this connection.
  • Polyglycidyl ethers such as those obtained by etherifying a dihydric or polyhydric alcohol, a diphenol or a polyphenol with epichlorohydrin or dichlorohydrin in the presence of an alkali, are preferably used.
  • glycols such as ethylene glycol, diethylene glycol, triethylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2,4,6-hexanetriol, glycerol and in particular from Diphenols or polyphenols, such as resercine, pyrocatechol, hydroquinone, phenolphthalein, phenolformaldehyde condensation products of the novolak type, 1,4-di-hydroxynaphthalene, dihydroxy-1,5-naphthalene, bis (hydroxy-4-phenyl) methane, Tetrahydroxyphenyl-1,1,2,2-ethane, bis (hydroxy-4-phenyl) methylphenylmethane, the bis- (hydroxy-4-phenyl) tolylmethanes, dihydroxy-4,4'-diphenyl, bis (hydroxy-4- phenyl) sulfone and
  • epoxy resins with two or more epoxy groups and possibly with free hydroxyl groups.
  • Particularly suitable among them are the epoxy resins which have been produced from polyphenols and are marketed under the trade name NOVOLAK resins which are polycondensation products of a phenol with formol.
  • the epoxy resins obtained are represented by the following formula:
  • polyglycidyl ethers of diphenols which have been obtained by esterifying 2 moles of the sodium salt of an aromatic oxycarboxylic acid with one mole of a dihaloalkane or dihalodialkyl ether (cf. GB-PS-1 017 612), of polyphenols which are obtained by condensation of phenols and long-chain, halogen paraffins containing at least 2 halogen atoms were obtained (cf. GB-PS-1 024 288).
  • N-Di (2,3-epoxypropyl) aniline N, N'-dimethyl-N, N'-diepoxypropyl-4,4'-diamino-diphenylmethane, N, N'-tetra-epoxypropyl-4 , 4'-diaminodiphenylmethane, N-diepoxypropyl-4-aminophenylglycidether (see GB-PS-772 830 and 816 923).
  • glycidyl esters of polyvalent aromatic and cycloaliphatic carboxylic acids for example phthalic acid diglycidyl with more than 5.5 epoxide equivalents per kg
  • glycidyl esters of reaction products from 1 mol of an aromatic or cycloaliphatic dicarboxylic acid anhydride and 1/2 mol of a diol or 1 / n mol of a poly n-hydroxyl groups or hexahydrophthalic acid diglycidyl esters, which may optionally be substituted by methyl groups.
  • Glycidyl compounds based on inorganic acids such as. B. triglycidyl phosphate, glycidyl ether of hydroxyphenyl phosphoric acid ester, diglycidyl carbonate, tetraglycidyl titanate, and also epoxy alkyl phosphine oxides (DE-AS-1 943 712).
  • heterocyclic epoxy compounds are the triglycidyl isocyanurate of the following formula as well as the N, N'-diglycidyl-dimethylhydantoin of the following formula
  • bis-phenol A bis (p-hydroxyphenyl) dimethyl methane
  • diepoxides are, for example: glycerol diglycidyl ether, diglycidyl-N, N'-ethylene urea, diglycidyl-N, N'-propylene urea, N, N'-diglycidyl urea, N, N'-diglycidyl dimethyl urea, and Oligomers of these compounds. Di-, tri- or tetraglycidyl-acetylene diurea, as well as oligomers of these compounds. Further epoxides which are used according to the invention can be found, for example, in Houben-Weyl, edited by Eugen Müller, 1963, volume XIV / 2, pages 462-538.
  • Suitable monooxetanes are: trimethylene oxide, 3,3-dimethyloxetane, 3,3-diethyloxetane, 3,3-dipropyloxetane, 3,3-dibutyl-oxetane, 3-methyl-3-dodecyl-oxetane, 3-ethyl-3-stearyl -oxetane, 3,3-tetramethyten-oxetane, 3,3-pentamethyleneoxetane, 2,6-dioxaspiro (3,3) -heptane, 3-methyl-3-phenoxymethyl-oxetane, 3-ethyl-3-phenoxymethyl-oxetane, 3-methyl-3-chloromethyl-oxetane, 3-ethyl-3-chloromethyl-oxetane, 3-butyl-3-chloromethyl-oxetane, 3-dodecyl-3-
  • oxetane analogs of the glycid derivatives listed above can also be used, e.g. B. 3-ethyl-3-acryl-oxy-oxetane, 3-ethyl-3-methacryloxy-oxetane, 3-methyl-3-trichloroacetoxy-oxetane, 3-methyl-3-ß-cy-anäthoxymethyl-oxetane, 3- Ethyl-ß-cyanoethoxymethyl-oxetane, 3-ethyl-3-phenoxymethyl-oxetane.
  • di- and polyoxetanes which can be used according to the invention, the reaction products of 3-alkyl-3-hydroxymethyl-oxetanes with di- and polycarboxylic acids, and with di- and polyisocyanates are of particular importance.
  • the di- and polyethers of the hydroxy-oxetanes derived from aliphatic, cycloaliphatic and aromatic diols and polyols are also very suitable, furthermore bis-oxetanyl esters (DE-AS-1 907 117), as well as phosphoric acid esters and phosphorous acid esters, such as tris (3 -methyloxetanylmethyl) -phosphite, tris (3-ethyl-oxetanyl-methyl) -phosphite, tris (3-ethyl-oxetanylmethyl) -phosphate.
  • bis-oxetanyl esters DE-AS-1 907 117
  • phosphoric acid esters and phosphorous acid esters such as tris (3 -methyloxetanylmethyl) -phosphite, tris (3-ethyl-oxetanyl-methyl) -phosphite, tris (3-ethyl-o
  • Hydrophobic, water-insoluble and liquid mono- and poly-epoxides such as, for example, polyglycidyl ethers of polyhydric phenols, in particular from bisphenol A, are very particularly preferred;
  • Polyepoxide compounds based on aromatic amines in particular bis (N-epoxypropyl) aniline, N, N'-dimethyl-N, N'-diepoxypropyl-4,4'-diamino-di-phenylmethane and N-diepoxypropyl-4-amino - phenylglycidyl ether;
  • Polyglycidyl esters of aromatic or cycloaliphatic dicarboxylic acids especially hexahydrophthalic acid or phthalic acid with more than 5.5 epoxide equivalents / kg and Phosphor Acidtriglycidylester, 3-ethyl-3-hydroxymethyl-oxetane and its esters, ethers and urethanes,
  • the catalysts are generally used in an amount between about 0.001 and 10% by weight, based on component a).
  • epoxy hardeners for example amines which contain at least 2 hydrogen atoms which are bonded directly to the nitrogen, for example aliphatic and aromatic, primary and secondary amines such as mono- and dibutylamine, p -Phenylenediamine, bis- (p-aminophenyl) methane, ethylenediamine, N, N-diethyl-ethylenediamine, diethylenetriamine, tetra- (hydroxyethyl) -diethylenetriamine, triethylenetetramine, tetraethylenepentamine, piperidine, guanidine and guaniduanidine derivative, such as phenylghenididine derivatives, such as phenylghenididine derivatives, , Polymers of aminostyrenes and polyaminoamides, for example those made from aliphatic polyamines and dimerized or trimerized unsatur
  • surface-active additives emulsifiers and foam stabilizers
  • emulsifiers such.
  • Alkali or ammonium salts of sulfonic acids such as dodecylbenzenesulfonic acid or dinaphthylmethane disulfonic acid or also of fatty acids such as ricinoleic acid or of polymeric fatty acids can also be used as surface-active additives.
  • Water-soluble polyether siloxanes are particularly suitable as foam stabilizers. These compounds are generally constructed in such a way that a copolymer of ethylene oxide and propylene oxide is linked to a polydimethylsiloxane radical. Such foam stabilizers are such. B. described in US-PS-2764565. These additives are preferably used at 0.02% by weight, based on the reaction mixture.
  • oxetane can be regarded as a polyol component, as it reacts bifunctionally as a monoepoxide with an isocyanate sulfonic acid.
  • the isocyanate sulfonic acid is mixed with the epoxide or oxetane, whereupon the polyaddition takes place at room temperature and a polymer is formed.
  • This procedure is particularly suitable when sulfonated liquid polyisocyanates or liquid NCO prepolymers are used.
  • additional catalysts and blowing agents are added to the reaction mixture, and water can also be used to initiate the foaming reaction.
  • the isocyanate sulfonic acid is first reacted with a polyol, in particular one of the polyether or polyester components customary in PU chemistry, with stirring and, if appropriate, external heat, to give a prepolymer having completely or largely homogeneous NCO groups, and only then the epoxy or oxetane added.
  • the solid polyisocyanate sulfonic acid which can be dispersed in conventional polyisocyanates, is mixed with the mixture of polyhydroxy compounds and epoxide or oxetane to form a dispersion. As soon as the reaction starts, the sulfonic acid goes into solution.
  • the proportions between the reaction components can be varied within wide limits, but it must always be taken into account that the reaction product should be a high molecular weight polyurethane which is essentially free of NCO groups.
  • the equivalents of all zerewitinoff-active corctants, including the OH groups, which may be introduced into the reaction by hydroxyoxiranes or hydroxyoxetanes, must first be subtracted from the NCO group equivalents used in the form of the isocyanates .
  • NCO groups of the prepolymer formally formed from the sum of all isocyanates and the sum of all Zerewitinoff-active co-reactants (mostly polyols), regardless of whether such a prepolymer is actually formed in whole or in part in a first reaction step , or whether the reaction with the epoxy component is carried out in the oneshot process.
  • the equivalent ratio of the NCO groups calculated in this way to the S0 3 H groups should be between 0.1 and 1.99. However, this ratio is preferably 0.2-1.
  • the lower range (below 0.8) is realized when practically exclusively isocyanate sulfonic acids are used and polyhydroxy compounds are also used.
  • the upper range (above 0.8) is realized either when working in the absence of additional polyols or other Zerewitinoff-active compounds, or when conventional unsulfonated isocyanates are used to a greater extent and an approximately equivalent amount of polyols is used. If the NCO / S0 3 H ratio is above 1, the use of zerewitinoff-active compounds in the formulation is mandatory, to the extent that the ratio exceeds 1.
  • a ratio of 1.8 thus requires at least 0.8 equivalents of polyol or the like.
  • the equivalents of any epoxy hardener that may be used must first be subtracted in an analogous manner.
  • Primary and secondary amines generally react faster with the isocyanate group than with the epoxy group, so they can only be counted as epoxy hardeners if they are either added separately to the epoxy component for modification from the start, or if they are added after the NCO groups have reacted Reaction approach are added at the end.
  • the equivalent ratio of epoxy groups to SO 3 H groups should be 0.2-5, preferably 0.5-2. This means that in extreme cases only 20% of the total sulfonic acid groups present are esterified, for example if an ionic product carrying sulfonate groups is desired and the reaction with the epoxide is only intended to provide partial hydrophobization or to increase the degree of branching.
  • the epoxy component can of course be used in excess, for example to ensure quantitative esterification, to introduce free epoxy groups into the polymer (e.g. to achieve optimum adhesion in coating materials or to have free epoxies as plasticizers or adhesion promoters in the polymer) .
  • the reaction can be carried out in the presence or absence of solvents. If the presence of solvents does not interfere, it is expedient to first convert the isocyanate and the polyol components to a higher molecular weight prepolymer which, for. B. has an average molecular weight of 5000 to 20,000 and can be dissolved in one or more solvents. To produce a coating, the epoxy component, which can also be dissolved in a solvent, is then combined with the solution of the prepolymer, the solution is applied and the solvent is removed by evaporation. At the same time or subsequently, the implementation according to the invention takes place on the substrate. Suitable solvents are e.g.
  • the reaction is preferably carried out in the absence of customary solvents or in the presence of very small amounts of apolar solvents with which the isocyanate sulfonic acid is stabilized or in the presence of liquid plasticizers.
  • the process is particularly suitable for the technologies of casting, reaction injection molding (RIM technology) and for the production of foams.
  • liquid polyisocyanates are used, such as sulfonated phosgenation products of aniline-formaldehyde condensation.
  • the polyisocyanate is then homogeneously liquid and can be processed as usual.
  • Dispersions of solid sulfonated polyisocyanates in non-sulfonated liquid polyisocyanates can also be used, such as are obtained, for example, in the partial sulfonation of tolylene diisocyanate.
  • Dispersions that are not stable to sedimentation can e.g. B. immediately before foaming by adding an epoxide or oxetane under reaction and then foamed with the polyhydroxy component.
  • the dispersion can also be reacted directly with polyol and epoxy or oxetane and the customary additional components with foaming in the one-shot process.
  • polyisocyanate sulfonic acids are used as the polyisocyanate component, these can be added to the reaction mixture in dry form, for example like fillers. It is cheaper to paste the solid polyisocyanate with the liquid polyol component and then to react it with blowing agent and epoxy. You can also dissolve the polyisocyanate in the epoxy component under reaction and then mix with the other components.
  • reaction according to the invention takes place already at 0-30 ° C., in particular at room temperature. Heating the reaction mixture greatly accelerates the reaction and is therefore only necessary if a correspondingly rapid reaction is desired. Of course it is possible, but not necessary, to work at temperatures above 80 ° C up to about 190 ° C. The preferred temperature range is 20-60 ° C with the temperature increasing by about 10-80 ° C during the reaction.
  • Polar hydroxy compounds such as polyethers and polyesters, which contain oxyethylene units, are particularly suitable as reactants for solid sulfonated polyisocyanates.
  • Particularly suitable oxiranes or oxetanes are those which additionally contain free hydroxyl groups, such as glycid and 3-alkyl-3-hydroxymethyl-oxetane.
  • a very particularly preferred embodiment of the process according to the invention consists in reacting a monosulfonated diisocyanate, such as sulfonated tolylene diisocyanate or sulfonated diisocyanato-diphenylmethane, with approximately the equivalent amount of glycid or 3-ethyl-3-hydroxymethyl-oxetane and an approximately equivalent amount for additionally used polyhydroxy compounds to add conventional polyisocyanates.
  • a monosulfonated diisocyanate such as sulfonated tolylene diisocyanate or sulfonated diisocyanato-diphenylmethane
  • inorganic fillers are chalk, talc, dolomite, gypsum, clay, anhydrite, quartz powder, aluminum oxide hydrate, calcium aluminum silicates, cement, glass in the form of fiber, powder or beads.
  • Other fillers of inorganic and organic types can, for. B. DE-OS-2 359 609.
  • blowing agents such as hydrocarbons, halogenated hydrocarbons are also used to produce foams. But it can also be done using carbon dioxide (e.g. by using water in the recipe) or by means of dissolved gases, e.g. B. compressed air can be foamed.
  • the process products are used in the usual fields of application known for compact or cellular elastomers, flexible foams, semi-rigid foams and rigid foams, in particular when high demands are placed on the crosslinking density, the fire behavior or the degradability.
  • the products obtainable by the process of 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, e.g. in the hygiene sector, as substrates for plant breeding and for heat and cold protection.
  • the suspension is stirred for 12 hours, the temperature rising from 25 ° C. to 41 ° C. and most of the isocyanate dissolving under reaction. After 4 hours of stirring at 70-76 ° C, a clear, viscous NCO prepolymer was formed. After adding 85 g of tris-chloroethylphosphate, the viscosity at room temperature is 65000 cP. 89g of the product contain O, 02Val NCO and 0.043Val S0 3 H.
  • 111: 132g (0.05Moi) of an adipic acid diethylene glycol polyester with terminal OH groups are moistened with 100g (0.3Mol) toluene Uretdione of diisocyanatotoluenesulfonic acid, corresponding to 76 g dry substance mixed at 60 ° C.
  • the mixture is slowly heated to 95 ° C. with stirring in the course of 12 hours, a viscous ester-modified diisocyanate being formed.
  • Example 4 The procedure is as in Example 4, but using 27.2 g of the 50 percent. Epoxy solution.
  • the elastomer is significantly harder and more cross-linked than that obtained in Example 4.
  • Example 3 is repeated, however, using 58 g II instead of I. A very soft, hardly tacky, crosslinked elastomer is obtained.
  • Example 4 The procedure is as in Example 4, but using 58 g II instead of I. After 1 hour, the mixture is still flowable. After 24 hours, a very soft, clear elastomer developed.
  • 30 g 111 are stirred at 90 ° C. with a mixture of 3 g of the bis-glycidyl ether of bisphenol A and 2 g of epichlorohydrin. A hard cross-linked elastomer is created within a minute.
  • Component A 100 g (0.05 Moi) of a linear polyether with a molecular weight of 2000 and which contains 80% propylene oxide and terminally 20% ethylene oxide, started with propylene glycol, are mixed with 11.6 g (0.1 mol) 3-hydroxymethyl-3-ethyl-oxetane mixed and added as a catalyst 2g Dabco 33 LV.
  • Component A heated to 60 °, is intimately mixed with component B.
  • the isocyanatosulfonic acid increasingly dissolves in the liquid mixture. After 15 minutes, the mixture stops flowing. After a few hours at room temperature, a slightly cloudy, completely tack-free elastomer is formed.
  • Hardening can be accelerated strongly if the mixture is reheated at 100 °.
  • Example 11 The procedure is as in Example 11, but using 7.2 g (0.1 mol) of glycide instead of the oxetane.
  • the elastomer obtained corresponds to that obtained in Example 11.
  • Component A as in Example 11, but with 0.2 g of tin dioctoate as catalyst instead of Dabco 33bV.
  • Component B as example 11.
  • the two components are mixed intimately at room temperature. The temperature rises to 380 ° C. After 60 minutes, the mixture stops flowing. The elastomer obtained is somewhat softer than that obtained in Example 11 and is slightly sticky.
  • Component B according to Example 11 is first mixed intimately with the polyether described in Example 11, component A, with a white paste being heated gently arises. This is mixed with 11.6 g of 3-hydroximethyl-3-ethyloxetane and 2 g of dimethylbenzylamine. The mixture is baked at 160 ° C. for 30 minutes. A transparent, tack-free elastomer is obtained.
  • Component A 184.5 g (0.3 mol) of a linear polyethylene glycol polyether with a molecular weight of 615 are mixed with 29 g (0.25 mol) of 3-hydroximethyl-3-ethyloxetane.
  • Component B 63.5 g (0.25 mol) uretdione of the diisocyanatotoluenesulfonic acid, 52.2 g (0.3 mol) tolylene diisocyanate and 20 g toluene are mixed to form a suspension.
  • Component A is heated to 40 ° C and mixed with component B. The temperature rises quickly to 85 ° C and a clear mixture is created. 8 minutes after the components have been combined, the polyaddition has progressed to such an extent that the mixture has become highly viscous. A cross-linked polyurethane has formed after 15 minutes. The thermoset formed is hard, tough and clearly transparent.
  • Component A as in Example 15.
  • Component B as in Example 15, but only 34.8 g (0.02 mol) of tolylene diisocyanate.
  • Component A is heated to 60 ° C and mixed quickly with component B.
  • the temperature rises rapidly to 100 ° C., the isocyanatosulfonic acid dissolving.
  • the mixture solidified 3 minutes after the components had been combined.
  • the thermoset formed is softer and somewhat more elastic than that obtained according to Example 15.
  • Component A 60.2 g (0.1 mol) of a linear polyether with a molecular weight of 602, which contains 50% propylene oxide and 50% ethylene oxide as structural components, are mixed with 23.2 g (0.2 mol) 3-hydroxymethyl-3 -thyl-oxetane mixed.
  • Component B 50.8 g (0.2 mol) uretdione of diisocyanatotoluenesulfonic acid, 17.4 g (0.1 mol) tolylene diisocyanate and 18 g toluene are mixed to a paste.
  • the two components are mixed at 50 ° C.
  • the solidification begins after 2 minutes. A very hard, but not brittle, colorless, only slightly cloudy Duromer is obtained.
  • Component A is heated to 50 ° C and quickly mixed with component B.
  • the reaction mixture is foamed while the temperature rises rapidly to 117 ° C.
  • An elastic, fine-pored foam is obtained.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)

Claims (2)

1. Procédé de préparation de polyuréthanes comportant des groupes d'esters alkyliques d'acides arylsulfoniques, caractérisé en ce que, à une température de 0 à 190° C, on fait réagir des acides isocyanato-sulfoniques aromatiques contenant éventuellement des motifs polyéther et/ou polyester, éventuellement en mélange avec des po- lyisocyanates habituels en une quantité allant jusqu'à 50% en poids, calculé sur tout le composant isocyanate, avec des oxirannes et/ou des oxétannes ou encore des polyoxirannes et/ou des polyoxétannes, le rapport d'équivalence entre les groups NCO et les groupes S03H étant de 0,1:1 à à 1,99:1, tandis que le rapport d'équivalence entre les groupes époxy (ou oxétanne) et les groupes S03H est de 0,2:1 à 5:1, avec cette réserve qu'en présence d'un rapport d'équivalence supérieur à 1:1 entre les groupes NCO et les groupes S03H, on utilise conjointement des composés actifs de Zerewitinoff, de préférence, des polyéther-polyols et/ou des polyester-polyols, en une quantité équivalant au moins à l'excès d'isocyanate.
2. Procédé suivant la revendication 1, caractérisé en ce que le rapport d'équivalence entre les groupes NCO et les groupes S03H est de 0,2:1 à 1:1, tandis que le rapport d'équivalence entre les groupes époxy et les groupes S03H est de 0,5:1 à 2:1.
EP78100484A 1977-08-03 1978-07-24 Procédé pour la préparation de polyuréthanes contenant des groupes ester alcoyle d'acide arylsulfonique Expired EP0000722B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19772735047 DE2735047A1 (de) 1977-08-03 1977-08-03 Arylsulfonsaeurealkylestergruppen aufweisende polyurethane
DE2735047 1977-08-03

Publications (2)

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EP0000722A1 EP0000722A1 (fr) 1979-02-21
EP0000722B1 true EP0000722B1 (fr) 1982-09-29

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EP78100484A Expired EP0000722B1 (fr) 1977-08-03 1978-07-24 Procédé pour la préparation de polyuréthanes contenant des groupes ester alcoyle d'acide arylsulfonique

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US (1) US4237250A (fr)
EP (1) EP0000722B1 (fr)
JP (1) JPS5428400A (fr)
DE (2) DE2735047A1 (fr)
IT (1) IT1105388B (fr)

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2651065A1 (de) * 1976-11-09 1978-05-18 Bayer Ag Modifizierte, sulfonsaeureestergruppen aufweisende polyisocyanate
DE2851341A1 (de) 1978-11-28 1980-06-04 Bayer Ag Dispersionen aromatischer isocyanatosulfonsaeure-uretdione in organischen polyisocyanaten und ein verfahren zu ihrer herstellung
DE3240396A1 (de) * 1982-11-02 1984-05-03 Hoechst Ag, 6230 Frankfurt Kontaktklebstoffe und deren verwendung
US4638017A (en) * 1985-12-09 1987-01-20 Minnesota Mining And Manufacturing Company Hydrophilic polyurethane/polyurea sponge
US5017664A (en) * 1987-06-03 1991-05-21 Wisconsin Alumni Research Foundation Biocompatible polyurethane devices wherein polyurethane is modified with lower alkyl sulfonate and lower alkyl carboxylate
DE3807660A1 (de) * 1988-03-09 1989-09-21 Bayer Ag Lagerstabile reaktionsharzmischung, herstellung und verwendung
US6127490A (en) * 1997-08-26 2000-10-03 Ranbar Electrical Materials, Inc. Varnish compositions, methods of making and components made therefrom
US6136890A (en) * 1998-02-17 2000-10-24 3M Innovative Properties Company Ink jet ink containing polyurethane dispersant
CN110183609B (zh) * 2019-04-23 2021-12-24 合肥科天水性科技有限责任公司 一种无溶剂聚氨酯树脂及其应用

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3148167A (en) * 1958-11-14 1964-09-08 Gen Tire & Rubber Co Polyurethane composition containing an epoxy compound
NL280840A (fr) * 1961-07-12
BE758976A (fr) * 1969-11-17 1971-05-17 Dow Chemical Co Composition adhesive amelioree a base de resine epoxy
US4036906A (en) * 1969-12-30 1977-07-19 The Goodyear Tire & Rubber Company Cured polyurethane compositions containing epoxy resins
US4038232A (en) * 1972-12-19 1977-07-26 Ppg Industries, Inc. Electrodepositable compositions containing sulfonium resins and capped polyisocyanates
US3959329A (en) * 1973-05-24 1976-05-25 Bayer Aktiengesellschaft Polyisocyanates containing sulphonic acid or sulphonate groups
DE2640103C2 (de) 1976-09-07 1986-05-07 Bayer Ag, 5090 Leverkusen Lagerstabile Gemische aus aromatischen Isocyanatosulfonsäuren und organischen Flüssigkeiten sowie Verfahren zu deren Herstellung
DE2651065A1 (de) * 1976-11-09 1978-05-18 Bayer Ag Modifizierte, sulfonsaeureestergruppen aufweisende polyisocyanate
DE2735013A1 (de) * 1977-08-03 1979-02-15 Bayer Ag Hydroxylgruppen und urethano-aryl- sulfonsaeuregruppenenthaltende verbindungen

Also Published As

Publication number Publication date
DE2735047A1 (de) 1979-02-15
US4237250A (en) 1980-12-02
IT7850542A0 (it) 1978-07-31
IT1105388B (it) 1985-10-28
EP0000722A1 (fr) 1979-02-21
JPS5428400A (en) 1979-03-02
DE2862047D1 (en) 1982-11-11

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