EP0000723B1 - 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

Info

Publication number
EP0000723B1
EP0000723B1 EP78100486A EP78100486A EP0000723B1 EP 0000723 B1 EP0000723 B1 EP 0000723B1 EP 78100486 A EP78100486 A EP 78100486A EP 78100486 A EP78100486 A EP 78100486A EP 0000723 B1 EP0000723 B1 EP 0000723B1
Authority
EP
European Patent Office
Prior art keywords
groups
sulfonic acid
sulphonic acid
molecular weight
compounds
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP78100486A
Other languages
German (de)
English (en)
Other versions
EP0000723A1 (fr
Inventor
Dieter Dr. Dieterich
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bayer AG
Original Assignee
Bayer AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Bayer AG filed Critical Bayer AG
Publication of EP0000723A1 publication Critical patent/EP0000723A1/fr
Application granted granted Critical
Publication of EP0000723B1 publication Critical patent/EP0000723B1/fr
Expired legal-status Critical Current

Links

Classifications

    • 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 weight alcohols which have primary and secondary hydroxyl groups, such as glycerin. In the case of higher molecular weight polyethers and polyesters, both primary and secondary OH groups are also frequently present, but their distribution is statistical, so that it is not possible to build up polymers with a defined structure on account of 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 useful, since the same polyurethane structures are produced by production using the one-shot process or using NCO prepolymers.
  • the present invention thus relates to at least two hydroxyl groups and compounds having at least one sulfonic acid ester group and having an average molecular weight of 300 to 12,000, in which at least one hydroxyl group is present in the form of a urethane-aryl-sulfonic acid hydroxyalkyl ester.
  • the present invention also relates to a process for the preparation of compounds having at least two hydroxyl groups and 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 aryl sulfonic acid hydroxyalkyl ester, characterized in that at least two hydroxyl-containing compounds with a molecular weight of 62 to 10,000 at 0 ⁇ 190 ° C with isocyanatosulfonic acid and then with oxiranes and / or oxetanes, the equivalent ratio of the total amount of isocyanate groups (including any dimerized isocyanate groups) to sulfonic acid groups 0 , 5 to 50, the equivalent ratio of the sum of the hydroxyl groups of the at least two hydroxyl group-containing compounds and the sulfonic acid groups to NCO groups 1.5 to 30 and the equivalent ratio of the oxirane or oxetane groups to sulf
  • 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 available in any other way, since the direct reaction of isocyanatoarylsulfonic acids or NCO prepolymers prepared therefrom with oxiranes or oxetanes provides 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 part of the OH groups of the polyhydroxy compounds used as starting material and the NCO groups and any uretdione groups of isocyanatoarylsulfonic acid which may be present are normally added in a first reaction step, with the formation of higher molecular weight new polyhydroxy compounds which initially contain urethane -Groups and contain 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.
  • all compounds usually used in polyurethane chemistry with at least two hydroxyl groups and a molecular weight of 62 to 10,000 can be used as the starting material.
  • these are low molecular weight glycols, polyesters, polyethers, polyesteramides, OH groups-containing oligomers and polymers, for example based on butadiene, and polyethers grafted with vinyl monomers or polyhydroxyl compounds which contain other polymers, such as e.g. Contain dispersed polyureas, urea resins, polyhydrazodicarbonamides or vinyl polymers.
  • Suitable compounds of this type containing hydroxyl groups are described, for example, in German Patent Specifications 1 152 536, 1 168 075 and 1 260 142, German Offenlegungsschriften 2,324,134, 2,423,984, 2,512,385, 2,513,815, 2,550,796, 2,550,797 , 2,550,833, 2,550,662 and 2,550,860, and U.S. Patents 3,383,351, 3,304,273, 3,523,093, 3,110,695, and 3,869,413.
  • 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 anilines substituted on the core alkyl in particular toluidines with aldehydes or ketones, such as, for example, formaldehyde, acetaldehyde, butyraldehyde, acetone, methyl ethyl ketone.
  • reaction products of the aromatic polyisocyanate mixtures mentioned with 0.2-50 mol% of polyols are also suitable, provided that the viscosity of the reaction products thus obtained does not exceed 50,000 cP at 25 ° C. and the NCO content of the reaction products is at least 6% by weight. % is.
  • Suitable polyols for modifying the starting materials are, in particular, the polyether and / or polyester polyols of the molecular weight range 200 to 6000, preferably 300 to 4000, which are known in polyurethane chemistry, and low molecular weight polyols of the molecular weight range 62 to 200. Examples of such low molecular weight polyols are ethylene glycol, propylene glycol, Glycerin, trimethylolpropane, 1,4,6-hexane trioi.
  • 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.
  • These mixtures contain, in particular, 4,4'-diisocyanatodiphenylmethane and 2,4'-diisocyanatodiphenyimethane as well as higher core homologues of these products. It is basically irrelevant 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.
  • Solutions and dispersions of isocyanato-arylsulfonic acids in non-sulfonated liquid polyisocyanates are particularly preferred. Such products are obtained, for example, with partial sulfonation of aromatic polyisocyanates.
  • partial sulfonation of chemically uniform diisocyanates or binary isomer mixtures gives suspensions, while partial sulfonation of multicomponent mixtures produces homogeneous solutions.
  • it is basically irrelevant whether solutions or suspensions are used.
  • Tellsulfonated polyisocyanate mixtures such as those obtained by phosgenation of aniline-formaldehyde condensates and described in German Offenlegungsschriften 2,227,111, 2,359,614 and 2,359,615 are very particularly preferred.
  • Suspensions of diisocyanatotoluene-sulfonic acid dimers and diisocyanatodiphenylmethane sulfonic acid dimers in diisocyanatotoluene or diisocyanatodiphenylmethane are also particularly preferred.
  • the isocyanatoarylsulfonic acids to be used in the process according to the invention or their mixtures with unsulfonated aromatic polyisocyanates are prepared by the known processes of the prior art or in analogy to the known Ver drive the state of the art, as it is for example from the publications already mentioned. or from U.S. Patent No. 3,826,769
  • solutions or suspensions of the above-mentioned isocyanatoaryisulfonic acids in aliphatic or cycloaliphatic polyisocyanates or also aromatic can also be used.
  • aliphatic or cycloaliphatic monoisocyanates are used. Examples of such isocyanates can be found in US Pat. No. 3,963,679.
  • the type and quantity ratios of the isocyanates to be used in the process according to the invention and their degree of sulfonation are expediently chosen so that the equivalence ratio of (if present in part in dimerized form) isocyanate groups to sulfonic acid groups is greater than 1.1, and in particular between 1.05 and 50.1, preferably between 2-1 and 30: 1, particularly preferably between 2: 1 and 12: 1.
  • isocyanato sulfonic acids preferred according to the invention are the aromatic mono-, di- or polyisocyanates described in DE-A 2 615 876, which contain more than one sulfonic acid group (in particular 2 or 3 sulfonic acid groups).
  • the preferred ratio of isocyanate to sulfonic acid groups is between 0.5: 1 and 1.2: 1.
  • any organic compounds which have at least one epoxy group and are optionally also substituted with isocyanate or hydroxyl groups, but are otherwise largely inert under the reaction conditions under which the oxirane / sulfonic acid addition takes place can be used.
  • Monoepoxides of the molecular weight range 44-400 corresponding to this definition are preferably used in the method according to the invention.
  • 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-oxide, epichlorohydrin, epibromohydrin, glycid, glycerin mono-glycidyl ether, isobutene oxide, p-glycidyl styrene, N-glycidyl carbazole, cyanoethyl glycated ether , Tri-ethyl glycidyl ether, chloroethyl glycidyl ether, bromoethyl glycidyl ether, vinyl oxirane, 3,4-dichlor
  • 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 dodecanoyl, glycidyl ether, glycidyl ether, glycidyl ether, glycidyl glycidyl ether, glycidyl ether, glycidyl ether, glycidyl ether, glycidyl glycidyl ether, e.g. with phenol and substituted, especially halogenated phenols.
  • di- and polyepoxides can also be used, if appropriate in part, for example epoxidation products of aliphatic and cycloaliphatic diolefins, epoxidized polybutadienes or butadiene copolymers or polyglycidyl esters, such as, for example, by reacting a dicarboxylic acid or by Reaction of cyanuric acid with epichlorohydrides or dichlorohydrin can be obtained in the presence of alkali.
  • Polyglycidyl ethers such as those obtained by etherifying a dihydric or polyhydric alcohol, a diphenol or a polyphenol with epichlorohydrin or di-chlorohydrin in the presence of an alkali, are preferably used.
  • glycols such as ethylene glycol, diethylene glycol, triethylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2,4,6-hexanetriol, glycerol and in particular from Diphenols or polyphenols such as resorcinol, pyrocatechol, hydroquinone, phenolphthalein, phenol-formaldehyde condensation products of the novolak type, 1,4-di-hydroxynaphthalene, dihydroxy-1,5-naphthalene, bis- (hydroxy-4-phenyl) methane .
  • Epoxy resins which are produced from polyphenols and are marketed under the trade name Novolak resins are also particularly suitable.
  • 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 oxetanes can be found, for example, in German Auslegeschrift 1,668,900, columns 3 and 4.
  • oxetane analogs of the glycid derivatives listed above can also be used, e.g. 3-ethyl-3-acryloxy-oxetane, 3-ethyl-3-methacryloxyoxetane, 3-methyl-3-trichloroacetoxy-oxetane, 3-methyl-3-ß-cyanoethoxymethyl-oxetane, 3-ethyl-ß-cyanoethoxymethyloxetane, 3- Ethyl 3-phenoxymethyl oxetane.
  • di- and polyoxetanes that can be used according to the invention, the reaction products of 3-alkyl-3-hydroxymethyl-oxetanes with di- and polycarboxylic acids, as well as with di- and polyisocyanates, are of particular importance.
  • the di- and polyethers of the hydroxyoxetanes which are divided 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 l of trichlorobutene-3,4-oxide and epichlorohydrin.
  • the preferred oxetane is 3-hydroxymethyl-3-ethyloxetane.
  • 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 only partially modify the hydroxy-functional compounds used as starting material with sulfonic acid groups, it being possible to use up to 30 OH groups and SO 3 H groups on 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, however, also be used in equivalence with the starting hydroxyl compounds in molar amounts, with 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 at a slightly elevated temperature.
  • the choice of temperature in this case depends exclusively on the viscosity of the reaction mixture and on the desired duration of the reaction.
  • solid isocyanatoaryl, mono- or polysulfonic acids a suspension is primarily formed during the mixing and it is advisable to carry out the reaction at a temperature at which the solid isocyanate dissolves rapidly.
  • Solid isocyanatosulfonic acids can also be used in the form of solutions in organic solvents, liquid esters of an inorganic or organic acid of phosphorus being preferred as solvents (DE-A-2 650 172).
  • any inert solvents such as hydrocarbons, halogenated hydrocarbons, ethers, esters and ketones can of course be added to the reaction mixture.
  • the reaction in the absence of solvents or with the small amounts of solvents which are used for pasting or dissolving solid isocyanatosulfonic acids is preferred.
  • 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 prepared 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 isocyanatosulfonic acids, since the presence of oxygen Heterocycles increase the dissolution rate.
  • the epoxy or oxetane component can also be used in excess, for example to ensure quantitative esterification of the sulfonic acid groups when using mono-epoxides or mono-oxetanes, or to use more than one epoxy or oxetane group having compounds to incorporate free epoxy or oxetane groups into the process products according to the invention.
  • epoxy groups incorporated in this way can be used for subsequent reactions, such as trimerization of the isocanate groups, oxazolidone formation or amine crosslinking.
  • 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 of 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 is generally carried out in the temperature range from 0-190 ° 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 about 10%, it may be appropriate to carry out the reaction at lower temperatures, e.g. perform between 0 and 20 ° C and, if necessary, 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.
  • 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-methyl-3-hydroxymethyl-oxetane, 3-ethyl-3-hydroxymethyl-oxetane.
  • oxiranes or oxetanes will be preferred. While oxetanes generally supply 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, in particular when high demands are placed on the crosslinking 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 insulations, moisture-absorbing materials, for example in the hygiene sector, for the production of substrates for growing plants, and for heating and Cold protection.
  • Polyhydroxy compounds according to the invention for the production of inorganic-organic plastic, for example in analogy to the procedures described in DBP 2 310 559, DE-A-2 227 147, 2359608, and for surface coatings, impregnations and adhesives.
  • a particular advantage of the hydroxy compounds according to the invention is their increased polarity.
  • these products are well tolerated with low molecular weight glycols such as ethylene glycol, diethylene glycol, 1,4-butanediol, glycerin. Mixtures are homogeneous and therefore stable in storage.
  • the reaction of the polyhydroxy compounds according to the present invention with polyisocyanates containing sulfonic acid ester groups is particularly favorable.
  • polyisocyanates containing sulfonic acid or sulfonic acid ester groups are often not very compatible due to their high polarity with hydrophobic, long-chain polyethers, so that segregation effects occur which may make a polyaddition reaction impossible. 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. A clear light brown liquid is obtained which no longer contains any NCO groups. Viscosity at 25 ° C: 4500 mPas. Light brown, clear liquid.
  • Example 5 The procedure is as in Example 5, but using 5.8 g of 3-ethyl-3 hydroxymethvloxetane instead of the epichlorohydrin. The mixture was stirred at 60 ° C. for 8 hours, at 80 ° C. for 6 hours, 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.
  • 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.

Landscapes

  • 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)

Claims (5)

1. Composés comportant au moins deux groupes hydroxy et au moins un groupe d'ester d'acide sulfonique, ces composés ayant un poids moléculaire moyen de 300 à 12.000, tandis qu'ils comportent au moins un groupe hydroxy sous forme d'un ester hydroxyalkylique d'acide uréthane-aryl-sulfonique.
2. Composés suivant la revendication 1, caractérisés par au moins une longue chaîne à fonctionnalité OH contenant 6 à 400 chaînons, et par au moins une courte chaîne à fonctionnalité OH reliée à un point de ramification par un radical d'ester d'acide sulfonique et contenant 2 ou 3 chaînons, ainsi que par au moins un groupe aryle au moins trifonctionnel comme point de ramification.
3. Composés suivant la revendication 2, caractérisés en ce qu'ils comportent au moins une longe chaîne à fonctionnalité OH contenant 20 à 300 chaînons.
4. Procédé de préparation de composés comportant au moins deux groupes hydroxy et au moins un groupe d'ester d'acide sulfonique, ces composés ayant un poids moléculaire moyen de 300 à 12.000, tandis qu'ils comportent au moins un groupe hydroxy sous forme d'un ester hydroxyalkylique d'acide uréthane-aryl-sulfonique, caractérisé en ce qu'on fait réagir des composés comportant au moins deux groupes hydroxy et ayant un poids moléculaire de 62 à 10.000, à une température de 0 à 190°C, avec des acides isocyanato-sulfoniques aromatiques, puis avec des oxirannes et/ou oxétannes, le rapport équivalent entre la quantité totale de groupes isocyanates (y compris les groupes isocyanates éventuellement présents sous forme dimérisée) et les groupes d'acides sulfoniques étant de 0,5 à 50, le rapport équivalent entre la somme des groupes hydroxy des composés comportant au moins deux groupes hydroxy, ainsi que des groupes d'acides sulfoniques, et les groupes NCO étant de 1,5 à 30, tandis que le rapport équivalent entre les groupes oxirannes ou oxétannes et les groupes d'acides sulfoniques est de 0,2 à 5.
5. Utilisation des composés suivant la revendication 1 comme composants réactionnels pour des polyisocyanates en vue de préparer des produits de polyaddition et/ou des produits de polycondensation.
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)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE2735032 1977-08-03
DE19772735032 DE2735032A1 (de) 1977-08-03 1977-08-03 Urethan-aryl-sulfonsaeure-hydroxyalkylester-gruppen aufweisende polyhydroxyverbindungen

Publications (2)

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

Family

ID=6015548

Family Applications (1)

Application Number Title Priority Date Filing Date
EP78100486A Expired EP0000723B1 (fr) 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

Country Status (5)

Country Link
US (1) US4189562A (fr)
EP (1) EP0000723B1 (fr)
JP (1) JPS5427537A (fr)
DE (2) DE2735032A1 (fr)
IT (1) IT1106613B (fr)

Families Citing this family (4)

* 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

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3959333A (en) * 1973-06-29 1976-05-25 The Lubrizol Corporation Polymerizable hydroxy-containing esters of amido-substituted sulfonic acids
US3892720A (en) * 1973-06-29 1975-07-01 Lubrizol Corp Polymerizable hydroxy-containing esters of amido-substituted sulfonic acids
DE2412217A1 (de) * 1974-03-14 1975-10-09 Bayer Ag Polyalkylenoxidhaltige urethanpolyole mit sulfonsaeuregruppe(n)
DE2651065A1 (de) * 1976-11-09 1978-05-18 Bayer Ag Modifizierte, sulfonsaeureestergruppen aufweisende polyisocyanate

Also Published As

Publication number Publication date
US4189562A (en) 1980-02-19
EP0000723A1 (fr) 1979-02-21
JPS5427537A (en) 1979-03-01
DE2860414D1 (en) 1981-02-26
IT7850516A0 (it) 1978-07-28
DE2735032A1 (de) 1979-02-15
IT1106613B (it) 1985-11-11

Similar Documents

Publication Publication Date Title
DE2446440C3 (de) Verfahren zur Herstellung von wäßrigen Dispersionen von Sulfonatgruppen aufweisenden Polyurethanen
DE2009179C3 (de) Verfahren zur Herstellung von Allophanatpoly isocy anaten
DE2040644C3 (de) Verfahren zur herstellung von polyurethankunststoffen
DE2651065C2 (fr)
EP0097298B1 (fr) Polyamines, procédé pour la préparation de polyamines et leur utilisation pour la préparation de polyuréthanes
DE102012218081A1 (de) Neuartige hydrophile Polyisocyanate mit verbesserter Lagerstabilität
EP0097290B1 (fr) Procédé en une seule étape pour la préparation de polyamines à partir de prépolymères du type NCO, polyamines et l'utilisation de ces dernières pour la production de polyuréthannes
DE102014209183A1 (de) Reaktive Zusammensetzung aus einer Uretdiongruppen haltigen Dispersion und Polyaminen
EP0056153A2 (fr) Procédé de production de composés présentant des unités de s-triazine, et des groupes époxydes, et leur utilisation en tant que charges incorporables lors de la production de matières plastiques à base de polyuréthane
EP0273243A2 (fr) Polyols de polyester contenant des groupes amino et amide et les poly(urée)uréthanes dérivés de ceux-ci
EP0097299B1 (fr) Polyamines, procédé pour la préparation de polyamines et leur utilisation pour la préparation de polyuréthanes
DE2758614C2 (de) Polyetherpolyol-Gemische auf Basis von Toluylendiamin, deren Herstellung und Verfahren zur Herstellung von Polyurethanschaumstoffen
EP0000724A1 (fr) Composés contenant des groupes hydroxylés et des groupes uréthane-aryle-acide sulfonique, leur procédé de préparation et leur application comme composants de réaction avec des polyisocyanates
EP0000723B1 (fr) 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
DE4217525A1 (de) Verfahren zur Standardisierung und Stabilisierung von organischen Polyisocyanaten und ihre Verwendung
EP0013923B1 (fr) Suspensions d'isocyanates à groupes urée dans des prépolymères d'isocyanates, procédé pour leur préparation et leur utilisation dans la préparation de matières plastiques de polyuréthane à haut poids moléculaire
EP0000722B1 (fr) Procédé pour la préparation de polyuréthanes contenant des groupes ester alcoyle d'acide arylsulfonique
EP0148462B1 (fr) Procédé pour la préparation in situ de diisocyanates contenant des groupes urée dans des polyols, des dispersions ou des solutions selon ce procédé et leur utilisation
EP1240235B1 (fr) Procede de fabrication de polyether polyols
EP0045892B1 (fr) Procédé pour la préparation de précurseurs de matières plastiques contenant des noyaux oxazolin-2-one et leur utilisation dans la fabrication de matières plastiques de poids moléculaire élevé
EP0388781A2 (fr) Procédé de préparation de poudres de polyuréthane-polyurée réticulées et leur utilisation comme charges organiques dans des laques polyuréthane en deux composants
EP0000551A1 (fr) Résines de polyuréthanes contenant des groupes thio et leur procédé de préparation
WO2019229039A1 (fr) Procédé de fabrication d'un produit alcoxylé
EP0003102B1 (fr) Procédé de préparation de polyisocyanates contenant des groupes alcoylester d'acide sulfonique et leur application comme matière première pour la préparation de produits de polyaddition
EP0220485B1 (fr) Composés polyhydroxyliques comprenant des groupements esters d'acides sulfoniques, et leur emploi comme composante polyolique dans des résines à couler

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed
AK Designated contracting states

Designated state(s): BE DE FR GB NL

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Designated state(s): BE DE FR GB NL

REF Corresponds to:

Ref document number: 2860414

Country of ref document: DE

Date of ref document: 19810226

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 19840630

Year of fee payment: 7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 19840703

Year of fee payment: 7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 19840709

Year of fee payment: 7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 19870731

Year of fee payment: 10

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Effective date: 19880724

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Effective date: 19880731

BERE Be: lapsed

Owner name: BAYER A.G.

Effective date: 19880731

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Effective date: 19890201

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee
GBPC Gb: european patent ceased through non-payment of renewal fee
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19890331

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Effective date: 19890401

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT