EP0000722A1 - 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
EP0000722A1
EP0000722A1 EP7878100484A EP78100484A EP0000722A1 EP 0000722 A1 EP0000722 A1 EP 0000722A1 EP 7878100484 A EP7878100484 A EP 7878100484A EP 78100484 A EP78100484 A EP 78100484A EP 0000722 A1 EP0000722 A1 EP 0000722A1
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Prior art keywords
groups
acid
oxetane
epoxy
reaction
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German (de)
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EP0000722B1 (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.
  • DT-PS 1 156 977 and 1 184 946 it is proposed to implement, for example, polyether diols with diisocyanates and glycerol monotosylate in order to carry out a duating reaction from the polytethane polysulfonic acid esters obtained in this way, finally with mono- or difunctional tertiary amines, and so on To produce polyurethane 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, and the content of sulfonic acid groups should generally be kept as low as possible.
  • dispersions e.g. B. Only introduce as much sulfonate groups as are absolutely necessary to achieve sufficient dispersion and to achieve a stable dispersion. A higher content of sulfonic acid groups would impair the water resistance of the coatings obtained from the dispersions. For this reason, the use of only 0.1-2%, based on the polyurethane, of sulfonating agents is recommended for the production of dispersions.
  • DT-OS 2 359 611 The production of highly filled polyurethanes or polyureas using polyisocyanate sulfonic acids is also known from DT-OS 2 359 611.
  • the sulfonic acid groups achieve special interactions between the organic binder and the fillers used, which results in high adhesive forces, even when very small amounts of binder are used.
  • the sulfonic acid groups are generally neutralized directly on the particle surface. In this process too, in general I only use partially sulfonated polyisocyanates in order not to endanger the water and moisture resistance of the composites obtained.
  • polyisocyanates in the form of their sulfonic acids would be of particular 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 acids are formed which should not be toxic.
  • isocyanate sulfonic acids for the construction of polyaddition products, however, highly hydrophilic, often even water-soluble products are obtained.
  • the present invention thus relates to polyurethanes containing sulfonic acid ester groups, characterized by alkyl arylsulfonic acid groups bonded to aromatic nuclei as chain links. These products preferably contain recurring units of the general formula
  • Ar radical of an aromatic isocyanate, and in particular recurring units of the general formula
  • the new polyurethanes preferably have a molecular weight of over 12,000.
  • the present invention furthermore relates to a process for the preparation of arylsulfonic acid alkyl ester groups, characterized in that aromatic isocyanatosulfonic acids are reacted at 0-190 ° C. with oxiranes and / or oxetanes, the equivalent ratio of NCO groups to SO 3 H groups. 0.1 to 1.99 (preferably 0.2-1) and the equivalent ratio of epoxy or oxetane groups to SO 3 H groups is 0.2-5 (preferably 0.5-2). It is particularly preferred to use polyether and / or polyester polyols (customary in polyurethane chemistry) or to use aromatic isocyanate sulfonic acids which already contain polyethers and / or polyester units.
  • the sulfonation products of all known aromatic di- or polyisocyanates can be used as isocyanates.
  • Ketones such as acetaldehyde, propionaldehyde, butyraldehyde, acetone, methyl ethyl ketone, etc.
  • phosgenation products of condensates of anilines which are alkyl-substituted at the core, in particular toluidines with aldehydes or ketones, such as, for example, formaldehyde, acetaldehyde, butyraldehyde, acetone, methyl ethyl ketone, etc.
  • Reaction products of the aromatic polyisocyanate mixtures mentioned with 0.2-50 mol percent 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 Weight percent 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, glycerol, 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'-diisocyanatodiphenylmethane, 2,4'-diisocyanatodiphenylmethane, 2,4-diisocyanatotoluene, 2,4-diisocyanatotoluene and their mixtures of isomers are very particularly preferred.
  • partially sulfonated polyisocyanates in particular partially sulfonated liquid mixtures of polyisocyanates, as described, for example, in DT-OS 2 227 111, 2 359 614 and 2 . 359,615.
  • Whole or partially sulfonated phosgenation products of aniline-formaldehyde condensates are particularly preferred.
  • aromatic monoisocyanates e.g. of phenyl isocyanate, p-tolyl isocyanate, p-chlorophenyl isocyanate, p-nitrophenyl isocyanate, p-methoxyphenyl isocyanate, m-chlorophenyl isocyanate, m-chloromethylphenyl isocyanate, p-chloromethylphenyl isocyanate.
  • both the isocyanate group and the sulfonic respond are those Monoisocyanatsulfon acids to be regarded as difunctional or polyfunctional compounds.
  • the sulfonation of the isocyanates is carried out in a known manner, preferably using sulfur trioxide, oleum or sulfuric acid.
  • the sulfonation can be carried out in a separate reaction step and the sulfonic acid isocyanates isolated from the sulfonation mixture and, if appropriate, dried and fed to the process according to the invention in this form.
  • it is possible just as well sulfonic fonierun g in situ perform which has the advantage that the moisture-sensitive Isocyanatsulfonklad.
  • 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 trioxide is additively bound, with the exclusion of water.
  • the sulfur trioxide can be in liquid, dissolved or gaseous, e.g. form diluted by nitrogen.
  • 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 which can remain in the reaction mixture or in the finished product as plasticizers or as blowing agents, such as Chlorofluorocarbons, chloroethane, methylene chloride, triethyl phosphate, tris chloroethyl phosphate, tris dibromopropyl phosphate. (DT-OS 2 650 172) '
  • Powdered isocyanate sulfonic acids are often used in the form of wet powders, pastes or suspensions prepared with inert suspending agents (DT-OS 2 642 114). When in situ sulfonation is used, care must be taken to ensure that the sulfonation reaction is complete when the epoxy is mixed in.
  • polyisocyanates customary in polyurethane chemistry (up to 50% by weight, based on the isocyanate component), such as the polyisocyanates already mentioned above as the 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 (DT-AS 1 202 785, US Pat.
  • DT-AS 1 202 785 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl-cyclohexane
  • Components which may also 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 are preferably polyhydroxyl compounds, in particular two to eight hydroxyl group-containing compounds, especially selche from molecular weight 800 to 10,000, preferably 1000 to 6000, for example at least two, usually 2 to 8, but preferably 2 to 4, hydroxyl-containing polyesters, polyethers.
  • 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 anhydrides or corresponding polycarboxylic 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: succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, trimellitic acid, phthalic anhydride, tetrahydrophthalic acid anhydride, hexahydrophthalic anhydride, tetrachlorophthalic anhydride, malefic acid, malefic acid, malefic acid, anhydride, maleic acid, malefic acid anhydride, maleic acid, malefic acid, fatty acid, malefic acid, fatty acid, malefic acid, anhydrous acid 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), neopentyl glycol, cyclohexanedimethanol (1,4-bis-hydroxymethylcyclohexane), 2-methyl-1,3-propanediol, glycerin, trimethylolpropane, hexanetriol- (1,2,6), butanetriol- (1,2,4), Trimethylolethane, pentaerythritol, quinite, mannitol and sorbitol, methylglycoside, also diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol Dipropylene glycol, polypropylene glycols, dibutylene glycol and polybutylene glycols in question.
  • the at least two, generally two to eight, preferably two to three, hydroxyl-containing polyethers which are suitable according to the invention are also 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 or Epichlorohydrin with itself, e.g. in the presence of BF 3 , or by attaching these epoxides, optionally in a mixture or in succession, to starting components with reactive hydrogen atoms such as alcohols or amines, e.g.
  • epoxides such as ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, styrene oxide or Epichlorohydrin
  • Sucrose polyethers such as are described, for example, in German publications 1 176 358 and 1 064 938, are also suitable according to the invention. In many cases, those polyethers are preferred which predominantly (up to 90% by weight, based on all the OH groups present in the polyether) have primary OH groups.
  • Polyethers modified by vinyl polymers such as those obtained by polymerizing styrene or acrylonitrile in the presence of polyethers (American patents 3,383,351, 3,304,273, 3,523,093, 3,110,695, German patent 1,152,536) are also suitable. likewise polybutadienes containing OH groups.
  • 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 polythio ether, polythio ether ester, polythlo ether amide.
  • polyacetals e.g. the compounds which can be prepared from glycols, such as diethylene glycol, triethylene glycol, 4,4'-dioxethoxy-diphenyldiaethylmethane, hexanediol and formaldehyde.
  • glycols such as diethylene glycol, triethylene glycol, 4,4'-dioxethoxy-diphenyldiaethylmethane, 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 hexanediol (1,6), diethylene glycol, triethylene glycol, tetreethylene glycol with diaryl carbonates, e.g. Diphenyl carbonate or phosgene can be produced.
  • diols such as propanediol (1,3), butanediol (1,4) and / or hexanediol (1,6)
  • diethylene glycol triethylene glycol
  • tetreethylene glycol e.g. Diphenyl carbonate or phosgene
  • polyester amides and polyamides include e.g. the predominantly linear condensates obtained from polyvalent saturated and unsaturated carboxylic acids or their anhydrides and polyvalent saturated and unsaturated amino alcohols, diamines, polyamines and their mixtures.
  • urethane or urea group-containing poly-h y droxylENSen and optionally modified natural polyols such as castor oil, carbohydrates, starch.
  • Addition products of alkylene oxides on phenol-formaldehyde resins or also on urea-formaldehyde resins can also be used according to the invention.
  • 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 of this type are obtained if polyaddition reactions (for example reactions between polyisocyanates and amino-functional compounds) or polycondensation reactions (for example between formaldehyde and phenols and / or amines) are carried out directly in situ in the abovementioned hydroxyl groups Connections expire.
  • Compounds with at least two hydrogen atoms which are reactive towards isocyanates and have a molecular weight of 32-400 are also suitable as components to be used according to the invention.
  • bonds have 2 to 8 isocyanate-reactive hydrogen atoms, preferably 2 or 3 reactive hydrogen atoms.
  • Examples of such compounds are: ethylene glycol, (1,2) and - (1,3) propylene glycol, (1,4) and - (2,3) butylene glycol, (1,5) pentanediol, hexanediol (1,6), octanediol- (1,8), neopentyl glycol, 1,4-bis-hydroxymethyl-cyclohexane, 2-methyl-1,3-propanediol, glycerin, trimethylolpropane, hexanetriol- (1,2,6), Trimethylolethane, pentaerythritol, quinite, mannitol and sorbitol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycols with a molecular weight of up to 400, dipropylene glycol, polypropylene glycols with a molecular weight of up to 400, dibutylene glycol, polybutylene glycols,
  • mixtures of different compounds with at least two isocyanate-reactive hydrogen atoms with a molecular weight of 32-400 can be used.
  • the products are also suitable for the epoxidation of natural fats and oils, such as soybean oil, olive oil, linseed oil, trans-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, trans-oil
  • 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 ether, e.g. glycidyl oleate, glycidyl oleate, e.g. with phenol and substituted, especially halogenated phenols.
  • monocarboxylic acids e.g. Glycidyl acetate, glycidyl chloroacetate, glycidyl dichloroacetate, glycidyl trichloroacetate, glycidyl
  • 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-dicyclopentadien-8-yl) ether, (3,4-epoxytetrahydrodadyl -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- (epoxycyclohexy
  • polyesters can be derived from aliphatic dicarboxylic acids, such as succinic acid or adipic acid, and in particular from nromatic dicarboxylic acid, such as phthalic acid or terephthalic acid.
  • Diglycidyl adipate, diglycidyl phthalot and triglycidyl isocyanur 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 didhlorohydrin in the presence of an alkali, are carefully used.
  • glycols such as ethylene glycol, diethylene glycol, triethylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-fentanediol, 1,6-hexanediol, 2,4,6-eexanetrioc, glycerol and in particular from Diphenols or polyphenols, such as resorcinol, pyrocatechol, hydroquinone, phenolputhalein.
  • Pherol-formaldohyd condensation products of the type of Novolaks 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) tolylmethane, dihydroxy-4,4'-diphenyl, Bi 8 (hydroxy-4-phenyl) sulfone and in particular bis- (hydroxy-4-phenyl) 2,2-propane or the condensation products a phenolic with an aldehyde or a ketone.
  • epoxy resins with two or more epoxy groups and possibly with free hydroxyl groups.
  • the epoxy resins which are produced from polyphenols and are marketed under the trade name NOVOLAK resins and which are polycondensation products of a phenol with formol are particularly suitable.
  • 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), from polyphenols, at least by the condensation of phenols and long-chain 2 halogen paraffins containing halogen atoms were obtained (cf. GB-PS 1 024 288).
  • polyepoxide compounds based on aromatic amines and E p ichlor- hydrin for example, N-di- (2,3-epoxypropyl) -aniline, N, N'-dimethyl-N, N'-4,4-diepoxypropyl '-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 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 moles of a polyol with n-hydroxyl groups or hexahydrophthalic acid diglycidyl esters, which may optionally be substituted by methyl groups.
  • Glycidyl compounds based on inorganic acids such as e.g. Triglycidyl phosphate, glycidyl ether of hydroxyphenyl phosphoric acid ester, diglycidyl carbonate, tetraglycidyl titanate, furthermore epoxy alkyl phosphine oxides (DT-AS 1 943 712).
  • Cycloaliphatic epoxy compounds are also suitable.
  • heterocyclic epoxy compounds are the triglycidyl isocyanurate of the following formula as well as the N, N'-diglycidyl-dimethylhydantoin of the following formula
  • polyglicydyl ethers of bis (p-hydroxyoxyphenyl) dimethyl methane bis-phenol A
  • 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 diurea, 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, pages 462-538.
  • Suitable monooxetanes are; Trimethylene oxide, 3,3-dimethyloxetane, 3,3-diethyloxetane, 3,3-dipropyloxetane, 3,3-dibutyl-oxetane, 3-methyl-3-dodceyl-oxetane, 3-ethyl-3-stearyl-oxetane, 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 -chlorine methyl-exetane, 3-ethyl-e-chloromethyl-oxetane, 3-butyl-3-chloromethyl-oxetane, 3-dodecyl-3-chloro
  • 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- ⁇ -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 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 (DT-AS 1 907 117),
  • phosphoric acid esters and phosphoric acid esters such as tris (3-methyloxetanylmethyl) phosphite, tris (3-ethyloxetanylmethyl) phosphite, tris (3-ethyloxetanylmethyl) phosphate.
  • Hydrophobic, water-insoluble, and liquid mono- and polyepoxides such as, for. B. polyglycidyl ether of polyhydric phenols, especially from bisphenol A; Polyepoxide compounds based on aromatic amines, in particular bis (N-epoxypropyl) aniline, N.
  • Tertiary amines which have hydrogen atoms active against isocyanate groups are e.g. Triethanolamine, triisopropanolamine, N-methyl-diethanolamine, N-ethyl-diethanolamine, N, N-dimethyl-ethanolamine, and their reaction products with alkylene oxides, such as propylene oxide and / or ethylene oxide.
  • Silaamines with carbon-silicon bonds such as those e.g. described in DT-PS 1 229 290, in question, e.g. 2,2,4-trimethyl-2-silamorpholine, 1,3-diethylaminomethyl-tetramethyl-disiloxane.
  • Suitable catalysts are also nitrogen-containing bases such as tetraalkylammonium hydroxides, alkali metal hydroxides such as sodium hydroxide, alkali phenolates such as sodium phenolate or alkali metal alcoholates such as sodium methylate.
  • nitrogen-containing bases such as tetraalkylammonium hydroxides, alkali metal hydroxides such as sodium hydroxide, alkali phenolates such as sodium phenolate or alkali metal alcoholates such as sodium methylate.
  • Hexahydrotriazines, 2,4,6-tris (dimethylaminomethyl) phenol, aluminum alcoholates and triphenylphosphine can also be used as catalysts.
  • organic metal compounds in particular organic tin compounds, can also be used as catalysts.
  • Preferred organic tin compounds are tin (II) salts of carboxylic acids such as tin (II) acetate.
  • the catalysts are generally used in an amount between about 0.001 and 10% by weight, based on component a).
  • undershot amounts of conventional epoxy hardeners can also be used, 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 guanidineamine, such as phenylgandididine derivatives, such as phenylgandididine derivatives, such as phenylgandididine derivatives, such as phenylgandididine derivatives, such as phenylgandididine derivatives, such as phenylgandididine derivatives, such as phenylgandididine derivatives, such as phen
  • surface-active additives emulators and foam stabilizers
  • emulsifiers come .t z.
  • B the sodium salts of castor oil sulfonates or of fatty acids or salts of fatty acids with amines v ie oleic acid diethylamine or stearic acid diethanolamine in question.
  • 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 used as foam stabilizers. These compounds are generally designed so that a copolymer of ethylene oxide and propylene oxide is linked to a polydimethylsiloxane residue. Such foam stabilizers are such. Described in U.S. Patent 2,764,565. These additives are preferably used at 0.20% by weight, based on the reaction mixture.
  • the practical implementation of the method based on the starting materials mentioned is very simple and different do not differ from the procedures customary in polyurethane chemistry and known to the person skilled in the art.
  • the epoxide or oxetane can be regarded as a polyol component, as it reacts bifunctionally as a monoepoxide with an isocyanate sulfonic acid.
  • the isocyanatosulfonic acid is mixed with the epoxy 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 isocyanatosulfonic 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 polyisocyanatosulfonic acid which can be dispersed in conventional polyisocyanates, is mixed with the mixture of polyhydroxy compounds and epoxide or oxetane to form a dispersion mixes. As soon as the reaction starts, the sulfonic acid goes into solution.
  • the quantity ratios between the reaction components can be varied within wide limits, but it must always be taken into account that a high molecular weight poly. urethane should arise, which is essentially free of NCO groups.
  • NCO group equivalents relevant to the invention first of all the equivalents of all zerewitinoff-active co-reactants, including the OH groups, which may be introduced into the reaction by hydroxyoxiranes or hydroxioxetanes, must be subtracted from the NCO group equivalents used in the form of the isocyanates be introduced.
  • NCO groups in 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 wholly or partially in a first reaction step or whether the reaction with the epoxy component is carried out in a one-shot process.
  • the equivalent ratio of the NCC groups calculated in this way to the SO 3 H groups should be between 0.1 and 1.99. However, this ratio is preferably 0.2-1.
  • the lower area is realized when practically only isocyanatosulfonic acids are used and polyhydroxy compounds are also used.
  • the upper area is realized either when working in the absence of additional polyols or other Zerewitinoffactive compounds, or when conventional non-sulfonated isocyanates are used to a greater extent and an approximately equivalent amount of polyols is used. If the NCO / SO 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 therefore 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 outset, 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, in order to introduce free epoxy groups into the polymer (for example to achieve optimal adhesion in coating materials or to have free epoxies as plasticizers or adhesion promoters in the polymer).
  • an epoxy / SO 3 H ratio above 1 is also preferably selected.
  • 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 example, has an average molecular weight of 5,000 to 20,000 and can be dissolved in one or more solvents. To make a coating then the epoxy component, which can also be dissolved in a solvent, is 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. B.
  • ketones, esters, halogenated hydrocarbons optionally in a mixture with hydrocarbons, dimethylformamide.
  • 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 foam materials.
  • Various embodiments of the method according to the invention are of particular importance for the production of foams or microcellular materials and molded parts:
  • partially sulfonated liquid polyisocyanates can be 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. If such dispersions are stable to sedimentation, for example after the dispersed phase has been comminuted in a milling device, they can be handled like liquid polyisocyanates. Dispersions that are not stable to sedimentation can, for example, be brought into solution by addition of an epoxide or oxetane under reaction immediately before foaming and then foamed with the polyhydroxy component the. However, 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.
  • the reaction according to the invention takes place at 0-30 ° C., in particular at room temperature. Heating the reaction mixture leads to a rapid acceleration of the reaction and is therefore only necessary if 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 of a monosulfonated diisocyanate, such as sulfonated tolylene to implement diisocyanate or sulfonated diisocyahatodiphenylmethane with approximately the equivalent amount of glycid or 3-ethyl-3-hydroxymethyl-oxetane and to add an approximately equivalent amount of conventional polyisocyanates for additionally used polyhydroxy compounds.
  • a monosulfonated diisocyanate such as sulfonated tolylene to implement diisocyanate or sulfonated diisocyahatodiphenylmethane with approximately the equivalent amount of glycid or 3-ethyl-3-hydroxymethyl-oxetane and to add an approximately equivalent amount of conventional polyisocyanates for additionally used polyhydroxy compounds.
  • 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 inorganic and organic fillers can e.g. can be found in DT-OS 2 359 609.
  • blowing agents such as hydrocarbons, halogenated hydrocarbons are also used to produce foams.
  • carbon dioxide e.g. by using water in the formulation
  • dissolved gases e.g. 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 crosslinking density, fire behavior or 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, soundproof insulation, moisture-absorbing materials, e.g. in the hygiene sector, as substrates for plant breeding and for heat and cold protection.
  • Example 4 The procedure is as in Example 4, but using 27.2 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 of II instead of I. After 1 hour, the mixture is still flowable. After 24 hours, a very soft, clear elastomer developed.
  • Component A heated to 606, is intimately mixed with component B.
  • the tsocyanatosulfonic acid increasingly dissolves in the liquid mixture. After 15 minutes the mixture stopped flowing. After a few hours at room temperature, a slightly cloudy, completely tack-free elastomer is formed.
  • the hardening rate can be greatly accelerated 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.
  • 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 according to Example 11 and slightly sticky.
  • Component B according to Example 11 is first mixed intimately with the polyether described in Example 11, component A, a white paste being formed with gentle heating. This is mixed with 11.6 g of 3-hydroxymethyl-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 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 had been combined, the polyaddition had progressed to such an extent that the mixture had become highly viscous. A cross-linked polyurethane is formed after 15 minutes. The thermoset formed is hard, tough and clearly transparent.
  • Component A is heated to 60 ° and mixed quickly with component B. The temperature rises rapidly to 100 °, the isowyanato sulfonic acid dissolving. 3 minutes after combining the components, the mixture has solidified.
  • the thermoset formed is softer and somewhat more elastic than that obtained in Example 15.
  • 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)
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

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

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

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN110183609A (zh) * 2019-04-23 2019-08-30 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

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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

Citations (1)

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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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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
DE2735013A1 (de) * 1977-08-03 1979-02-15 Bayer Ag Hydroxylgruppen und urethano-aryl- sulfonsaeuregruppenenthaltende verbindungen

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN110183609A (zh) * 2019-04-23 2019-08-30 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
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

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DE2735047A1 (de) 1979-02-15
US4237250A (en) 1980-12-02
IT7850542A0 (it) 1978-07-31
IT1105388B (it) 1985-10-28
JPS5428400A (en) 1979-03-02
EP0000722B1 (fr) 1982-09-29
DE2862047D1 (en) 1982-11-11

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