EP0000723A1 - Composés polyhydroxylés contenant des groupes uréthane-aryle-hydroxyalcoylester d'acide sulfonique, leur procédé de préparation et leur application comme produits de réaction dans la préparation de polyuréthanes - Google Patents

Composés polyhydroxylés contenant des groupes uréthane-aryle-hydroxyalcoylester d'acide sulfonique, leur procédé de préparation et leur application comme produits de réaction dans la préparation de polyuréthanes Download PDF

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Publication number
EP0000723A1
EP0000723A1 EP7878100486A EP78100486A EP0000723A1 EP 0000723 A1 EP0000723 A1 EP 0000723A1 EP 7878100486 A EP7878100486 A EP 7878100486A EP 78100486 A EP78100486 A EP 78100486A EP 0000723 A1 EP0000723 A1 EP 0000723A1
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Prior art keywords
groups
sulfonic acid
compounds
oxetane
acid
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German (de)
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EP0000723B1 (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
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
    • C07C309/63—Esters of sulfonic acids
    • C07C309/72—Esters of sulfonic acids having sulfur atoms of esterified sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
    • C07C309/76—Esters of sulfonic acids having sulfur atoms of esterified 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
    • 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
    • C08G18/28—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
    • 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 various OH functions are generally equivalent in terms of reactivity and distance from any branching center that may be present. Exceptions are low molecular alcohols which have primary and secondary hydroxyl groups, such as glycerin. With higher molecular weight polyether and Although polyesters are often also present both primary and secondary OH groups, their distribution is statistical, so that it is not possible to build up polymers with a defined structure due to this difference in reactivity.
  • the chain length distributions in branched polyethers and polyesters also obey the laws of statistics.
  • a separate production of OH prepolymers for the subsequent production of polyurethanes is usually not sensible, since the same polyurethane structures are produced by production using the one-shot process or using NCO prepolymers.
  • polyhydroxy compounds are now desired which, in a defined manner, have OH groups of different reactivity and chain branches of different lengths. It would be advantageous, for example, to have trifunctional polyhydroxy compounds which would have 2 OH groups of high reactivity at the ends of the main chain and an OH function of reduced reactivity on the shortest possible side chain, because of such a structure a polymer with particularly favorable mechanical properties is to be expected. It is also desirable to be able to use polyhydroxy compounds which provide polyurethanes with improved fire behavior. Finally, OH prepolymers are desired which do not produce toxicologically questionable aromatic diamines during hydrolytic degradation.
  • the present invention provides a solution to these problems. Surprisingly, it was found that by reacting polyhydroxy compounds with molar amounts of aromatic isocyanato sulfonic acids, optionally in a mixture with conventional polyisocyanates, and then reacting the reaction products with oxiranes or oxetanes, novel polyhydroxy compounds of higher functionality are obtained.
  • the OH group resulting from the reaction of the sulfonic acid group with the cyclic ether is located on a short side chain.
  • the present invention thus relates to compounds having an average molecular weight of 300 to 12,000 and having at least one hydroxyl group and at least one sulfonic acid ester group, in which at least one hydroxyl group is in the form of a urethane-aryl-sulfonic acid hydroxyalkyl ester.
  • compounds of the following general formulas are preferred: in particular and HO-R 1 -OCONH-Ar-NHCOO-R 1 -OCONH-Ar-NH-COO-R 1 -OH in particular HO-R 1 -O-CO-NH-Ar-NH-CO-OR 1 -O-CO-NH-Ar-NH-COO-R 1 -OH in which R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and Ar have the meaning already mentioned.
  • the present invention also relates to a process for the preparation of at least two hydroxyl groups and compounds having at least one sulfonic acid ester group, of average molecular weight 300 to 12,000, in which at least one hydroxyl group is in the form of a urethane-arylsulfonic acid hydroxyalkyl ester, characterized in that at least two compounds having molecular groups from molecular weight 62 to 10,000 at O-190 ° C.
  • the present invention finally 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.
  • the products obtained according to the invention or the chain segments obtained from these products in the construction of polyurethanes are not readily obtainable in any other way, since the direct reaction of isocyanatoarylsulfonic acids or NCO prepolymers prepared therefrom with oxiranes or oxetanes yields other products or chain segments of different construction .
  • the compounds according to the invention preferably contain at least one segment which is a 2- to 6-valent radical of a polyether, polythioether, polyester or polyester amide.
  • a first reaction step is normally carried out first Addition of a portion of the OH groups of the polyhydroxy compounds used as starting material with the NCO groups and any uretdione groups of isocyanatoarylsulfonic acid that may be present, with the formation of higher molecular weight new polyhydroxy compounds which initially contain some urethane groups and one or more free sulfonic acid groups.
  • the sulfonic acid group is then esterified by the added oxirane or oxetane, whereby hydroxyalkyl sulfonic acid ester groups are formed.
  • the polyesters containing hydroxyl groups are, for example, reaction products of polyhydric, preferably dihydric and optionally additionally trihydric alcohols with polyhydric, preferably dihydric, carboxylic acids.
  • polyhydric preferably dihydric and optionally additionally trihydric alcohols
  • polyhydric preferably dihydric, carboxylic acids.
  • the corresponding polycarboxylic acid anhydrides or corresponding polyesrbonic acid esters of lower alcohols or mixtures thereof can also be used to produce the polyesters.
  • the polycarboxylic acids can be aliphatic, cycloaliphatic, aromatic and / or heterocyclic in nature and optionally substituted, for example by halogen atoms, and / or unsaturated.
  • Examples include: Bern succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, trimellitic acid, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, Tetrechlorphthelklareanhydrid, endo - methylenetetrahydrophthalic anhydride, glutaric anhydride, maleic acid, maleic anhydride, fumaric acid, dimeric and trimeric fatty acids such as oleic acid, optionally mixed with monomeric fatty acids, Dimethyl terephthalate, bis-glycol terephthalate.
  • Polyhydric alcohols include, for example, ethylene glycol, propylene glycol (1,2) and - (1,3), butylene glycol (1,4) and - (2,3), hexanediol (1,6), octanediol (1, 8), neopentylglycol-cyclohexanedimethanol (1,4-bis-hydroxymethylcyclohexane), 2-methyl-1,3-propanediol, glycerol, trimethylolpropane, hexanetriol- (1,2,6), butanetriol- (1,2,4), Trimethylolethane, pentaerythritol, quinite, mannitol and sorbitol, methylglycoside, also diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycols, dipropylene glycol, polypropylene glycols, dibutylene glycol and polybutylene glycols in question.
  • the polyethers which are preferred according to the invention and preferably have two hydroxyl groups are those of the type known per se and are obtained, for example, by polymerizing epoxides such as ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, styrene oxide, epichlorohydrin or 1,1,1-trichloroacetene-3 , 4-oxide with itself, for example in the presence of BF 3 , or by addition of these epoxides, optionally in a mixture or in succession, to starting components with reactive hydrogens such as alcohols or amines, for example water, xthylene glycol. Propylene glycol (1,3) or - (1,2), 4,4'-dihydroxydiphenyl, propane, aniline.
  • epoxides such as ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, styrene oxide, epichlorohydrin or 1,1,1-trichloro
  • polyethers such as those obtained by polymerizing styrene or acrylonitrile in the presence of foleyethers (American patents 3,383,351, 3,304,273, 3,523,093, 3,110,695, German patent 1,152,536) suitable.
  • the portion mizuverschreibden optionally higher-functional polyether produced in an analogous manner by known per se alkoxy --regulation of higher-functional starter molecules such as ammonia, ethanolamine, ethylene diamine or sucrose.
  • the condensation products of thiodiglycol with themselves and / or with other glycols, dicarboxylic acids, formaldehyde, aminocarboxylic acids or amino alcohols should be mentioned in particular.
  • the products are rplythiomise ether, polythioate ester, polythioether ether amide.
  • polyacetals e.g. the compounds which can be prepared from glycols, such as diethylene glycol, triethylene glycol, 4,4'-dioxethoxy-diphenyldimethylmethane, hexanediol and formaldehyde.
  • glycols such as diethylene glycol, triethylene glycol, 4,4'-dioxethoxy-diphenyldimethylmethane, hexanediol and formaldehyde.
  • Polyacetals suitable according to the invention can also be prepared by polymerizing cyclic acetals.
  • Suitable polycarbonates containing hydroxyl groups are those of the type known per se, which e.g. by reacting diols such as propanediol (1,3), butanediol (1,4) and / or kexanediol (1,6), diethylene glycol, triethylene glycol tetraethylene glycol with diaryl carbonates, e.g. Diphenyl carbonate or phosgene can be produced.
  • diols such as propanediol (1,3), butanediol (1,4) and / or kexanediol (1,6)
  • diethylene glycol triethylene glycol tetraethylene glycol
  • diaryl carbonates e.g. Diphenyl carbonate or phosgene
  • polyester amides and polyamides include, for example, those of polyvalent saturated and unsaturated carboxylic acids or their anhydrides and polyvalent saturated and unsaturated saturated amino alcohols, diamines, polyamines and their mixtures obtained, predominantly linear condensates. Polyhydroxyl compounds already containing urethane or urea groups can also be used.
  • 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) are carried out directly in situ in the above-mentioned compounds containing hydroxyl groups.
  • Low molecular weight glycols which can be reacted in a mixture with the higher molecular weight polyhydroxy compounds mentioned or also alone with isocyanatosulfonic acids are, for example: ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, oligopropylene glycols, propylene glycol (1,3), 2-butanediol, hexanediol, hexanediol , Octanediol, glycerin, trimethylolpropane, 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.
  • Phosgenation products of condensates of aniline and aldehydes or ketones such as e.g. Acetaldehyde, propionaldehyde, butyraldehyde, acetone, methyl ethyl ketone.
  • phosgenation products of condensates of alkyl-substituted anilines in particular toluidines with aldehydes or ketones, such as e.g. Formaldehyde, acetaldehyde, butyraldehyde, acetone, methyl ethyl ketone.
  • reaction products of the aromatic polyisocyanate mixtures mentioned with 0.2-50 mol% of polyols are, 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 known from polyurethane chemistry in the molecular weight range 200 to 6000, preferably 300 to 4000, and low molecular weight polyols in 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 2,6-tolylene diisocyanate, and also sulfonation products of the di- and polyisocyanates, which are obtained by phosgenation of aniline / formaldehyde condensates become.
  • These mixtures contain, in particular, 4,4'-diisocyanatodiphenylmethane and 2,4'-diisocyanatodiphenylmethane as well as higher core homologs of these products. It is basically not a long process with which sulfonating agents the isocyanato-arylsulfonic acids have been produced.
  • Suitable sulfonating agents are, for example
  • Sulfur trioxide, oleum, sulfuric acid complexes of sulfur trioxide with Lewis bases, which contain oxygen, nitrogen or phosphorus atoms.
  • sulfonating agents such as chlorosulfonic acid and acyl sulfates, for example acetyl sulfate or reaction products of acid anhydrides with sulfuric acid or oleum can also be used.
  • Side reactions e.g., for the production of only partially sulfonated isocyanates, e.g.
  • Urea or biuret formation or the partial conversion of isocyanate groups into carbamic acid chloride groups or acylamide groups generally does not matter, so that in these cases, for example, sulfuric acid, chlorosulfonic acid or acetyl sulfate can be used without further ado.
  • sulfur trioxide or its complexes for example according to DT-OS 2 510 693, is preferably used for the production of highly sulfonated polyisocyanates. It follows that, in particular, aromatic polyisocyanatarylsulfonic acids based on tolylene diisocyanate or diphenylmethane diisocyanate are preferred which contain urea or biuret groups.
  • Solutions and dispersions of isocyanato-arylsulfonic acids in non-sulfonated liquid polyisocyanates are particularly preferred. Such products are used, for example, at partial sulfonation of aromatic polyisocyanates obtained.
  • partial sulfonation of chemically uniform diisocyanates or binary isomer mixtures gives suspensions, while partial sulfonation of multicomponent mixtures produces homogeneous solutions. In principle, it is irrelevant for the method according to the invention 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.
  • isocyanatoaryl or their mixtures with non-sulfonated aromatic polyisocyanates is carried out by the known methods of the prior art or in analogy to the known methods of the prior art, as for example from the already - called Publications , or from U.S. Patent No. 3,826,769.
  • the processes of German laid-open documents 25 24 476 or 26 15 Q76 are also suitable for producing isocyanatoarylsulfonic acids which can be used in the process according to the invention.
  • Tetramethylene diisocyanate or hexamethylene diisocyanate and / or in cycloaliphatic or mixed aliphatic-cycloaliphatic polyisocyanates such as 4,4'-diisocyanatodicyclohexylneethane, 2,4- or 2,6-diisocyanato-hexahydrotoluene or 1-isecyanato-3,3,5-trimethyl- Use 5-isocyanatomethylcyclohexane.
  • solutions or suspensions of the isocyanato-arylsulfonic acids in aromatic, aliphatic or cycloaliphatic monoisccyanates can also be used.
  • phenyl isocyanate examples include phenyl isocyanate, tosyl isocyanate, n-hexyl isocyanate, 6-chloro-hexyl isocyanate, cyclohexyl isocyanate or methoxymethyl isocyanate.
  • Conceivable in principle is also the use of sulfonated aromatic monoisocyanates such as phenyl isocyanate as Isocyanatoaryl - sulfonic acid in combination with non-sulfonated Polyisotyanaten the type exemplified the nature and proportions of the employed in the present process isocyanates, and the degree of sulfonation are often selected such that the equivalent ratio.
  • isocyanate groups which are sometimes present in dimerized form, to sulfonic acid groups> 1: ie 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. Such isocyanatopolysulfonic acids are described in DT-OS 2,615,876.
  • the preferred ratio of isocyanate to sulfonic acid groups is 0.5: 1 to 1.2: 1.
  • any oxiranes which have at least one epoxy group and which are optionally also substituted with isocyanate or hydroxyl groups, but are otherwise largely inert, are inert under the reaction conditions under which the oxirane / sulfonic acid addition takes place organic compounds are used.
  • Suitable monoepoxides are ethylene oxide, propylene oxide, butene-1,2-oxide, butene-2,3-oxide, 1,4-dichlorobutene-2,3-oxide, styrene oxide, 1,1,1-trichloropropene-2,3- oxide, 1,1,1-trichlorobutene-3,4-oxide, 1,4-dibromobutene-2,3-xoxide, epichlorohydrin, epibromohydrin, glycid, glycerin mono-glycidyl ether, isobutene oxide, p-plycidylstyrene, N-glycidylcarbazole, Cyanäthylglydicyläther-, Trichloräthylglycidyläther, Chloräthylglycidyläther, Brom- äthylglycidyläther, vinyloxi
  • 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, glycidyldodecanoate, glycidyl oleate, glycidyl oleate, glycidyl oleate, glycidyl oleate, e.g. with phenol and substituted, especially halogenated phenols.
  • the reaction products of hydroxy-oxiranes in particular of glycid with aliphatic, cycloaliphatic and aromatic mono- and polyisocyanates, are also very suitable.
  • di- and polyepoxides can also be used, either alone or in combination with the monoepoxides listed above.
  • Such di- and polyfunctional epoxides are for example the E poxidations consist of aliphatic and cycloaliphatic diolefins, such as diepoxybutane, Diepoxihexan, vinyl cyclohexendioxid, dicyclopentadiene dioxide, limonene dioxide, dicyclopentadiene dioxide, ethylene glycol-bis (3,4-pentadiene epoxitetrahydrodieyclo--8-yl) - ether, (3,4-epoxitetrahydrodicyclopentadien- 8 -yl) glycidyl ether, epoxidized polybutadienes or copolymers of butadiene with ethylenically unsaturated ver Bonds, such as styrene or vinyl acetate, compounds with two epoxy cyclohexyl radicals, such as diethylene glycol bis (3,3-epoxy cyclohexane carboxylate),
  • 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 epichlorohydri 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, glycerin and in particular from Diphenols or polyphenols such as resorcinol, pyrocatechol, hydroquinone, phenolphthalein, phenol-formaldehyde condensation products of the novolak type, 1,4- D i-hydroxynaphthalene, dihydroxy-1,5-naphthalene, bis- (hydroxy-4-phenyl) methane, Tetrahydroxyphenyl-1,1,2,2-ethane, bis (hydroxy-4-phenyl) methyl phenylmethane, the bis (hydroxy-4-phenyl) tolylmethane, dihydroxy-4,4'-diphenyl, bis (hydroxy-4-phenyl) sulf
  • epoxy resins which are produced from polyphenols and are marketed under the trade name NOVOLAK resins, which are polycondensation products of a phenol with formol.
  • 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 obtained by esterifying 2 moles of the sodium salt of an aromatic oxicarboxylic acid with one mole of a dihaloalkane or dihalodialkyl ether (cf. British Patent 1,017,612), from polyphenols which are obtained by condensation of phenols and long-chain, at least 2 Halogen paraffins containing halogenatanes were obtained (cf. British Patent 1,024,288).
  • polyepoxide compounds based on aromatic amines and epichlorohydrin for example N-di (2,3-epoxypropyl) aniline, N, N'-dimethyl-N, N'-diepoxipropyl-4,4'-diamino- diphenylmethane, N, N'-tetra epoxipropyl-4,4'-diaminodiphenylmethane, N-diepoxipropyl-4-aminophenyl-glycidyl ether (see British Patents 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 and 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 polyol n-hydroxyl groups or hexahydrophthalic acid diglycidyl esters, which may optionally be substituted by methyl groups.
  • glycidyl y joints on the basis of inorganic acids such as Triglycidylphosphat, glycidyl ethers of Hydroxyphenylphosphorklareester, Diglycidylcarbonat, T etraglycidyltitanat.
  • inorganic acids such as Triglycidylphosphat, glycidyl ethers of Hydroxyphenylphosphorklareester, Diglycidylcarbonat, T etraglycidyltitanat.
  • Cycloaliphatic epoxy compounds are also suitable.
  • Suitable heterocyclic epoxy compounds are both the triglycidyl isocyanurate of the following formula as well as the N, N'-diglycidyl-dimethylhydantoin of the following formula
  • Suitable compounds are the polyglycidyl ethers of 3is (p-hydroxyphenyl) dimethyl methane (bisphenol A), which correspond to the following average formula: where z is an integer or fractional small number in the range of 0 to 2.
  • 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-di-Earnstcff, and 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 Steiten 462-538.
  • the products are also suitable for the epoxidation of natural fats and oils, such as soybean oil, olive oil, linseed oil, trans-oil and synthetic di- or polyesters, which contain unsaturated fatty acids, such as oleic acid, linoleic acid, linolenic acid, cinolic acid, erucic acid.
  • natural fats and oils such as soybean oil, olive oil, linseed oil, trans-oil and synthetic di- or polyesters, which contain unsaturated fatty acids, such as oleic acid, linoleic acid, linolenic acid, cinolic acid, erucic acid.
  • Hydrophobic, water-insoluble, and liquid mono- and polyepoxides such as e.g. Polyglycidyl ether polyhydric phenols, especially from bisphenol A; Polycpoxide compounds based on aromatic amines, in particular bis (N-epoxipropyl) aniline, N, N'-dimethyl-N, N'-diepoxipropyl-4,4'-diamino-diphenylmethane and N, N'-dicpoxiuropyl-4- amino-phcnylglycidyl ether; Polyglycidyl esters of aromatic or cycloaliphatic dicarboxylic acids, in particular hexahydrophthalic acid diglycidyl esters or phthalic acid diglycidyl esters with more than 5.5 epoxide equivalents / kg and phosphoric acid triglycidyl ester.
  • Suitable oxetanes in the process according to the invention are any organic compounds which have at least one oxetane ring and are optionally substituted by isocyanate or hydroxyl groups, but are otherwise largely inert under the reaction conditions under which the oxetane / sulfonic acid addition takes place.
  • Preferred oxetanes are monooxetanes of the molecular weight range 58-400 corresponding to this definition.
  • 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 -oxetah, 3,3-tetramethylene-oxetane, 3,3-pentamethyleneoxetane, 2,6-dioxaspiro (3,3) -heptane, 3-methyl-3-phenoxymethyl-oxetane, 3-ethyl-3-phenoxymethyl-oxetane, 3-methyl-3-chloro-methyl-oxetane, 3-ethyl-3-chloromethyl-oxetane, 3-butyl-3-chloro-mathyl-oxetane, 3-dodecy
  • oxetane analogs of the glycid derivatives listed above can also be used, e.g. 3-ethyl-3-acryloxy-oxetane, 3-ethyl-3-methacryloxy-oxetane, 3-methyl-3-trichloroacetoxy-oxetane, 3-methyl-3-ß-cyanoethoxymethyl-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 also with di- and polyisocyanates are of particular importance.
  • the di- and polyethers of the hydroxyoxetanes derived from aliphatic, cycloaliphatic and aromatic diols and polyols are also very suitable.
  • the oxiranes are preferred as starting materials in the process according to the invention over the oxetanes.
  • Particularly preferred oxiranes are ethylene oxide, propylene oxide, styrene oxide, 1,1,1-trichlorobutene-3,4-oxide and epichlorohydrin.
  • Preferred oxetane is 3-hydroxymethyl-3-ethyl-oxetane.
  • 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 and SO 3 H groups being to be accounted for by one NCO group.
  • NCO groups are not only to be understood as NCO groups present in free form but also as dimerized NCO groups present in the form of uretdione groups. It is particularly preferred to modify only part of the hydroxy-functional compounds used as starting material with sulfonic acid groups, it being possible to use up to 30 OH groups and SQ 3 H groups for one NCO group. An equivalent ratio of OH group to NCO group between 2 and 20 is preferred.
  • monoisocyanates which contain 1 to 3 sulfonic acid groups can also be used. These monoisocyanates can be used with the starting hydroxy compounds in molar amounts, but also in equivalence, all OH functions being reacted with isocyanate groups in the latter case. Polysulfonic acids are obtained, which are then reacted with oxiranes or oxetanes to give new polyhydroxy compounds . According to this procedure, products can be obtained whose OH functionality is the same as that of the starting compounds used, but whose reactivity changes, for example, is reduced.
  • 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. In this case, the choice of temperature depends exclusively on the viscosity of the reaction mixture and on the desired duration of the reaction.
  • solid isocyanatoaryl mono- or polysulfonic acids are used, a suspension is primarily formed during the mixing and it is advisable to add the reaction to make a temperature at which the solid isocyanate quickly dissolves.
  • relatively low molecular weight polyhydroxy compounds are temperatures above 120 ° C preferably up to about 200 Q C, a solidification of the reaction approach to avoid during the reaction.
  • Solid isocyanatosulfonic acids are particularly preferably used in the form of suspensions, pastes or wet powders, using an inert solution, as described in DT-OS 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 (DT-OS 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.
  • the reaction of the introduced sulfonic acid groups with oxiranes or oxetanes can be carried out either after the reaction of all the isocyanate groups in a second reaction stage or else simultaneously or overlapping with the urethanization reaction.
  • a simultaneous reaction is particularly suitable when the OH groups of the starting components are primary, whereas the OH groups resulting from the epoxy reaction are secondary. Under these conditions, a reaction of secondary OH groups with isocyanate groups can only be expected to a minor extent.
  • reaction products according to the invention can therefore in principle also be produced in a one-pot process, with hydroxy compounds, isocyanate component and oxirane or oxetane being mixed and reacted simultaneously.
  • This method is also particularly suitable for poorly soluble isocyanato sulfonic acids, since the presence of oxygen heterocycles increases the dissolution rate.
  • the oxiranes or oxetanes or their amounts used in the process according to the invention are selected so that the equivalent ratio of the epoxy or oxetane groups to sulfonic acid groups is between 0.2: 1 and 5: 1, preferably between 0.6: 1 and 2: 1.
  • the SO 3 H groups present are only partially esterified, so that the process products according to the invention still have free sulfonic acid groups, so that the hydrophilicity of the process products according to the invention caused by these sulfonic acid groups is within the range by the said equivalent ratio can be varied from 0.2: 1 to 1: 1.
  • the epoxy or oxetane component can also be used in excess, for example when using mono-epoxides or mono-oxetanes
  • Epoxy groups incorporated in this way in particular can be used for subsequent reactions, e.g. Trimerization of the isocyanate groups, oxazolidone formation or amine crosslinking can be used.
  • Free sulfonic acid groups can also be completely or partially neutralized, for example with tert. Amines or inorganic bases.
  • An excess of monoepoxide or monooxetane which may be used can, if desired, be removed from the process product according to the invention by distillation after the process according to the invention has ended.
  • the process according to the invention is very simple to carry out and generally takes place in the temperature range from 190 ° C., preferably 20-140 ° C.
  • the mixture or reaction product of the hydroxy component and polyisocyanate containing sulfonic acid groups is preferably introduced into a stirred vessel at room temperature and the epoxide or oxetane is stirred in.
  • the reaction generally begins immediately with self-heating. If the proportion of sulfonic acid groups is more than approx. 10%, it may be expedient to carry out the reaction at lower temperatures, for example between 0 and 20.degree. C. and, if appropriate, to work with cooling. However, such a measure is generally not necessary, since heating the reaction mixture to, for example, 140 ° C. or above is not a disadvantage.
  • the reaction may be expedient to carry out the reaction at elevated temperature, for example between 40-140 o C, in In special cases, the temperature can be up to approximately 190 ° C.
  • Gaseous epoxides are expediently introduced with stirring.
  • the reaction is preferably carried out without solvent, but it is of course also possible in the presence of inert solvents, e.g. Dichloroethane, chloroform, tetrachloroethane, trichlorofluoromethane, acetone, toluene, chlorobenzene.
  • inert solvents e.g. Dichloroethane, chloroform, tetrachloroethane, trichlorofluoromethane, acetone, toluene, chlorobenzene.
  • a particularly strong increase in functionality can be achieved by using di- or polyoxiranes or the corresponding oxetanes, in particular if work is carried out approximately in equivalence to the sulfonic acid groups present. It is easily possible to achieve OH functionalities of 4 to 8 with this type of operation. However, it is also possible to set a functionality below 4 if monoisocyanatoarylmonosulfonic acids and / or monofunctional alcohols are used at least in part.
  • oxiranes and oxetanes with OH groups e.g. Glycid, 3-ethyl-3-hydroxymethyl-oxetane, 3-ethyl-3-hydroxymethyl-oxetane.
  • oxiranes or oxetanes may be preferred. While oxetanes generally provide primary OH groups, the use of oxiranes usually leads to secondary or even tertiary OH groups. Only ethylene oxide gives a primary OH group, glycid simultaneously introduces a primary and a secondary OH group within a short chain.
  • the process products according to the invention are valuable starting materials for the production of polyurethane plastics by the isocyanate polyaddition process. They are suitable, for example, for the production of compact or cellular elastomers, flexible foams, semi-rigid foams and rigid foams, particularly when high demands are made the networking density, the fire behavior or the 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, for example 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 producing inorganic-organic compounds
  • Plastics for example, in analogy to the procedures described in DBP 2 310 559, DT-OS 2 227 147, 2 359 608, and suitable for surface coatings, impregnations and adhesives.
  • a particular advantage of the hydroxy compounds according to the invention is their increased polarity.
  • pure polypropylene glycol column with low molecular weight glycols such as ethylene glycol, diethylanglycol, 1,4-butanediol, glycerin, these products are therefore well contracted. Mixtures are homogeneous and therefore stable in storage.
  • the implementation of the polyhydroxy compounds according to the present invention with polyisocyanates containing sulfonewureeater groups is particularly favorable.
  • Such poly- or sulfonic acid or sulfonic acid ester groups Due to their high polarity, isocyanates are often not very compatible with hydrophobic, long-chain polyethers, so that segregation effects occur, which may make a polyaddition reaction possible. If such polyethers according to the present invention are modified with sulfonic acid ester groups, there is usually good compatibility with polyisocyanates containing sulfonic acid or sulfonic acid ester groups.
  • the suspension obtained is diluted with 500 ml of toluene, suction filtered, and the solid residue is suspended twice with 500 ml of toluene and suction filtered.
  • the toluene-moist product is filled. Yield 1285 g, toluene content 23%, dry matter 990 g, corresponding to 93% of theory.
  • the product is a slightly moist powder that can be handled very well without dusting. It is easy to fill and refill, does not cake and does not stick to the spatula.
  • Example 4 the epichlorohydrin is stirred in immediately after the isocyanate. The mixture is stirred for 90 minutes at room temperature, the isocyanate partially dissolving. The mixture is then heated to 60 ° C. and stirred at this temperature for 7 hours. You get a clear light brown liquid which no longer contains any NCO groups. Viscosity at 25 ° C: 4500 cP. Light brown, clear liquid. Medium functionality: 5
  • Example 5 The procedure is as in Example 5, but using 5.8 g of 3-ethyl-3-hydroxymethyloxetane instead of the epichlorohydrin. It was 8 hours at 60 ° C, 6 hours at 80 ° C. Stirred at 95 ° C for 6 hours and at 120 ° C for 2 hours. 4 g of undissolved isocyanate were filtered off. Brown, green fluorescent liquid. Viscosity at 25 ° C: 4000 cP Medium functionality: 6
  • the mass is crosslinked as early as 2 hours after mixing.
  • the cross-linked elastomer is homogeneous, tack-free and has good tensile strength.
  • Example 11 is repeated with 20 g of the polypropylene glycol of MW 1000 used as the starting material in Example 8 and 8 g of the product described below as polyisocyanate A.
  • a two-phase mixture is obtained, the dark, heterogeneous isocyanate phase of which settles out muddy.
  • the mixture is mixed several times by stirring within 5 hours, but phase separation always occurs again after a few minutes. After 8 hours the mixture is still liquid.
  • a mixture of sulfur trioxide and nitrogen is passed onto the surface of 3800 g of this product until 102 g of welding trioxide have been absorbed by the isocyanate mixture.
  • the product obtained has a viscosity of 120 cP and a sulfur content of 1.05%.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Polyethers (AREA)
EP78100486A 1977-08-03 1978-07-24 Composés polyhydroxylés contenant des groupes uréthane-aryle-hydroxyalcoylester d'acide sulfonique, leur procédé de préparation et leur application comme produits de réaction dans la préparation de polyuréthanes Expired EP0000723B1 (fr)

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DE2735032 1977-08-03
DE19772735032 DE2735032A1 (de) 1977-08-03 1977-08-03 Urethan-aryl-sulfonsaeure-hydroxyalkylester-gruppen aufweisende polyhydroxyverbindungen

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EP0000723A1 true EP0000723A1 (fr) 1979-02-21
EP0000723B1 EP0000723B1 (fr) 1981-01-07

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EP (1) EP0000723B1 (fr)
JP (1) JPS5427537A (fr)
DE (2) DE2735032A1 (fr)
IT (1) IT1106613B (fr)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3534929A1 (de) * 1985-10-01 1987-04-09 Bayer Ag Verfahren zur herstellung von sulfonsaeureestergruppen aufweisenden polyhydroxylverbindungen, die nach diesem verfahren erhaltenen verbindungen und ihre verwendung als polyolkomponente in giessharzen
US4638017A (en) * 1985-12-09 1987-01-20 Minnesota Mining And Manufacturing Company Hydrophilic polyurethane/polyurea sponge
DE3807660A1 (de) * 1988-03-09 1989-09-21 Bayer Ag Lagerstabile reaktionsharzmischung, herstellung und verwendung
US5102961A (en) * 1989-01-05 1992-04-07 King Industries Isocyanate modified blocked sulfonic acid ester as a crosslinking catalyst

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2264010A1 (fr) * 1974-03-14 1975-10-10 Bayer Ag
FR2370064A1 (fr) * 1976-11-09 1978-06-02 Bayer Ag Polyisocyanates modifies contenant des groupes ester d'acide sulfonique, leur preparation et leur utilisation comme matieres premieres de la preparation de produits de polyaddition oligomeres ou polymeres

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Publication number Priority date Publication date Assignee Title
US3892720A (en) * 1973-06-29 1975-07-01 Lubrizol Corp Polymerizable hydroxy-containing esters of amido-substituted sulfonic acids
US3959333A (en) * 1973-06-29 1976-05-25 The Lubrizol Corporation Polymerizable hydroxy-containing esters of amido-substituted sulfonic acids

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2264010A1 (fr) * 1974-03-14 1975-10-10 Bayer Ag
FR2370064A1 (fr) * 1976-11-09 1978-06-02 Bayer Ag Polyisocyanates modifies contenant des groupes ester d'acide sulfonique, leur preparation et leur utilisation comme matieres premieres de la preparation de produits de polyaddition oligomeres ou polymeres

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DE2860414D1 (en) 1981-02-26
DE2735032A1 (de) 1979-02-15
EP0000723B1 (fr) 1981-01-07
IT1106613B (it) 1985-11-11
IT7850516A0 (it) 1978-07-28
US4189562A (en) 1980-02-19

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