WO2010009993A1 - Dispersion polyuréthanne contenant une alcanolamine - Google Patents

Dispersion polyuréthanne contenant une alcanolamine Download PDF

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Publication number
WO2010009993A1
WO2010009993A1 PCT/EP2009/058885 EP2009058885W WO2010009993A1 WO 2010009993 A1 WO2010009993 A1 WO 2010009993A1 EP 2009058885 W EP2009058885 W EP 2009058885W WO 2010009993 A1 WO2010009993 A1 WO 2010009993A1
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groups
mol
monomers
alkanolamine
polyurethane dispersion
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PCT/EP2009/058885
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German (de)
English (en)
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Gerd BÜLOW
Manfred Dargatz
Karl Häberle
Maria Teresa Hechavarria Fonseca
Michael Jahn
Darijo Mijolovic
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Basf Se
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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
    • C08G18/08—Processes
    • C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
    • C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
    • C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
    • 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
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6633—Compounds of group C08G18/42
    • C08G18/6659—Compounds of group C08G18/42 with compounds of group C08G18/34
    • 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
    • C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
    • 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
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
    • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate

Definitions

  • the invention relates to an aqueous polyurethane dispersion containing an alkanolamine of the formula I.
  • R 1 and R 2 are a C 1 to C 4 alkyl group
  • R 3 is a hydrogen atom or a C 1 to C 4 alkyl group
  • R 4 and R 5 are each independently a C 1 to C 4 alkyl group.
  • Amines especially tertiary amines, are used in aqueous polyurethane dispersions especially as neutralizing agents and dispersants.
  • Polyurethane dispersions are used in particular as binders for coating compositions, sealants or adhesives.
  • alkanolamines are also described in G. N. Robinson, Proc. 3rd Intern. Congress on Paints, Vol. 1, 212 - 223, Sao Paulo 1993 and, moreover, have special significance as commercial products.
  • Suitable alkanolamines are also described in EP-A-1 362 897.
  • WO 2006/016991 and WO 2005/055720 disclose the use of alkanolamines as a biocide for aqueous systems.
  • the coatings, seals, impregnating compositions or bonds produced should have the best possible performance properties, in particular very good mechanical properties such as elasticity and hardness, but also the resistance to solvents and in particular water are desired in general.
  • the resistance to water is often problematic especially for aqueous coating compositions, sealants and impregnating compounds or adhesives, since the binders and / or pigments used are generally water-soluble or water-dispersible prior to their use. Insufficient water resistance often leads to turbidity of the resulting coating, bonding or sealing, also called whitening.
  • the object of the present invention therefore, were coating compositions, sealing and impregnating compositions or adhesives based on polyurethane dispersions which contain alkanolamines having a good neutralizing and / or dispersing action; the performance properties, the solvent and in particular the water resistance of the resulting coatings, seals or bonds should be as good as possible.
  • polyurethane dispersions according to the invention comprise an alkanolamine of the above formula I.
  • R 1 and R 2 are a C 1 to C 4 alkyl group.
  • the alkyl group is a methyl group, i. R1 and R2 represent a methyl group.
  • a most preferred compound is therefore N, N-dimethyl-1-amino-2-methyl-2-propanol (R1 and R2 methyl).
  • alkanolamines are obtainable in a known manner by reacting amines with epoxides of the formula
  • the polyurethane dispersions contain the alkanolamine preferably in an amount of 0.05 to 10 wt .-%, based on the dispersed polyurethane.
  • the minimum amount of alkanolamine is at least 0.1 wt .-%, most preferably at least 0.2 wt .-%.
  • the maximum amount is preferably 7% by weight, in particular 5% by weight. All percentages are based on the polyurethane.
  • the aqueous polyurethane dispersion preferably contains a polyurethane composed of
  • bi 10 to 100 mol%, based on the total amount of diols (b), have a molecular weight of 500 to 5000, and
  • diisocyanates X NCO 2
  • X is an aliphatic hydrocarbon radical having 4 to 12 carbon atoms, a cycloaliphatic or aromatic hydrocarbon radical having 6 to 15 carbon atoms or an araliphatic hydrocarbon radical having 7 to 15 carbon atoms
  • diisocyanates are tetramethylene diisocyanate, hexamethylene diiso- cyanate, dodecamethylene diisocyanate, 1,4-diisocyanatocyclohexane, 1-isocyanato-3,5,5-trimethyl-5-isocyanatomethylcyclohexane (IPDI), 2,2-bis (4-isocyanatocyclohexyl) propane, trimethylhexane diisocyanate, 1,4-diisocyanatobenzene , 2,4-diisocyanatotoluene, 2,6-diisocyanatotoluen
  • Such diisocyanates are available commercially.
  • mixtures of these isocyanates are the mixtures of the respective structural isomers of diisocyanatotoluene and diisocyanato-diphenylmethane; in particular, the mixture of 80 mol% of 2,4-diisocyanatotoluene and 20 mol% of 2,6-diisocyanatotoluene is suitable.
  • mixtures of aromatic isocyanates such as 2,4-diisocyanatotoluene and / or 2,6-diisocyanatotoluene with aliphatic or cycloaliphatic isocyanates, such as hexamethylene diisocyanate or IPDI, are particularly advantageous, the preferred mixing ratio of the aliphatic to aromatic isocyanates being 4: 1 to 1: 4 is.
  • polyurethanes can be used as compounds in addition to the aforementioned also isocyanates, in addition to the free isocyanate groups further blocked isocyanate groups, e.g. Wear uretdione groups.
  • suitable diols (b) are primarily higher molecular weight diols (b1) which have a molecular weight of about 500 to 5,000, preferably about 1,000 to 3,000, g / mol.
  • the diols (b1) are, in particular, polyesterpolyols which are known, for example, from Ullmanns Encyklopadie der ischen Chemie, 4th Edition, Volume 19, pages 62 to 65. Preference is given to using polyesterpolyols which are obtained by reacting dihydric alcohols with dibasic carboxylic acids. Instead of the free polycarboxylic acids, it is also possible to use the corresponding polycarboxylic acid anhydrides or corresponding polycarboxylic acid esters of lower alcohols or mixtures thereof to prepare the polyesterpolyols.
  • the polycarboxylic acids may be aliphatic, cycloaliphatic, araliphatic, aromatic or heterocyclic and may optionally be substituted, for example by halogen atoms, and / or unsaturated. Examples which may be mentioned are: suberic acid, azelaic acid, phthalic acid, isophthalic acid, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, tetrachlorophthalic anhydride, endomethylenetetrahydrophthalic anhydride, glutaric anhydride, maleic acid, maleic anhydride, fumaric acid, dimer fatty acids.
  • dicarboxylic acids of the general formula HOOC- (CH 2) y - COOH, where y is a number from 1 to 20, preferably an even number from 2 to 20, for example succinic acid, adipic acid, sebacic acid and dodecanedicarboxylic acid.
  • polyhydric alcohols e.g. Ethylene glycol, propane-1, 2-diol, propane-1, 3-diol, butane-1, 3-diol, butene-1, 4-diol, butyne-1, 4-diol, pentane-1, 5-diol, Neopentylglycol, bis (hydroxymethyl) cyclohexanes such as 1,4-bis (hydroxymethyl) cyclohexane, 2-methylpropane-1,3-diol, methylpentanediols, furthermore diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, dipropylene glycol, polypropylene glycol, Dibutylene glycol and polybutylene glycols into consideration.
  • Ethylene glycol propane-1, 2-diol, propane-1, 3-diol, butane-1, 3-diol, butene-1, 4-diol, butyne
  • Alcohols of the general formula HO- (CH 2) x -OH are preferred, where x is a number from 1 to 20, preferably an even number from 2 to 20.
  • examples of these are ethylene glycol, butane-1, 4-diol, hexane-1, 6-diol, octane-1, 8-diol and dodecane-1, 12-diol. Further preferred is neopentyl glycol.
  • polycarbonate diols e.g. by reaction of phosgene with an excess of the mentioned as synthesis components for the polyester polyols low molecular weight alcohols, into consideration.
  • lactone-based polyesterdiols which are homopolymers or copolymers of lactones, preferably hydroxyl-terminated addition products of lactones to suitable difunctional starter molecules.
  • Suitable lactones are preferably those which are derived from compounds of the general formula HO- (CH 2) ⁇ -COOH, where z is a number from 1 to 20 and an H atom of a methylene unit by a C 1 to C 4 alkyl radical may be substituted. Examples are e-caprolactone, ß-propiolactone, gamma-butyrolactone and / or methyl epsilon-caprolactone and mixtures thereof.
  • Suitable starter components are e.g.
  • polyesterpolyols the low molecular weight dihydric alcohols mentioned above as the synthesis component for the polyesterpolyols.
  • the corresponding polymers of epsilon-caprolactone are particularly preferred.
  • Lower polyester diols or polyether diols can also be used as starters for the preparation of the lactone polymers.
  • the polymers of lactones it is also possible to use the corresponding, chemically equivalent polycondensates of the hydroxycarboxylic acids corresponding to the lactones.
  • suitable monomers (b1) are polyether diols. They are in particular by polymerization of ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, styrene oxide or epichlorohydrin with itself, for example in the presence of BF 3 or by addition of these compounds, optionally in admixture or in succession, to starting components having reactive hydrogen atoms, such as alcohols or amines.
  • starting components having reactive hydrogen atoms such as alcohols or amines.
  • BF 3 BF 3
  • tetrahydrofuran such as styrene oxide
  • styrene oxide or epichlorohydrin such as alcohols or amines.
  • starting components having reactive hydrogen atoms such as alcohols or amines.
  • BF 3 BF 3
  • polyhydroxyolefins preferably those having 2 terminal hydroxyl groups, for example a, -w-dihydroxypolybutadiene, a, -w-Dihydroxypolymethacrylester or a, -w-Dihydroxypolyacrylester as monomers (c1).
  • Such compounds are known, for example, from EP-A 0622378.
  • Further suitable polyols are polyacetals, polysiloxanes and alkyd resins.
  • the polyols can also be used as mixtures in the ratio of 0.1: 1 to 1: 9.
  • the hardness and modulus of elasticity of the polyurethanes can be increased if, as diols (b), low molecular weight diols (b2) having a molecular weight of from about 60 to 500, preferably from 62 to 200, g / mol are used in addition to the diols (b1).
  • the monomers (b2) used are in particular the synthesis components of the short-chain alkanediols mentioned for the preparation of polyester polyols, the unbranched diols having 2 to 12 carbon atoms and an even number of carbon atoms and pentane-1, 5-diol and neopentyl glycol to be favoured.
  • the proportion of the diols (b1), based on the total amount of the diols (b) is 10 to 100 mol% and the proportion of the monomers (b2), based on the total amount of the diols (b) 0 to 90 mol%.
  • the ratio of the diols (b1) to the monomers (b2) is particularly preferably 0.1: 1 to 5: 1, particularly preferably 0.2: 1 to 2: 1.
  • the polyurethanes in addition to the components (a), (b) and, if appropriate, (d) are monomers (c) which are different from components (a), (b) and (d) and which are at least one Isocyanate group or at least one isocyanate-reactive group and, moreover, at least one hydrophilic group or a group which can be converted into a hydrophilic Ie carry constructed.
  • the term "hydrophilic groups or potentially hydrophilic groups” is abbreviated to "(potentially) hydrophilic groups”. The (potentially) hydrophilic groups react much more slowly with isocyanates than the functional groups of the monomers which serve to build up the polymer main chain.
  • the proportion of components having (potentially) hydrophilic groups in the total amount of components (a), (b), (c), (d) and (e) is generally such that the molar amount of (potentially) hydrophilic groups, based on the amount by weight of all monomers (a) to (e), 30 to 1000, preferably 50 to 500 and particularly preferably 80 to 300 mmol / kg.
  • the (potentially) hydrophilic groups may be nonionic or, preferably, (potentially) ionic hydrophilic groups.
  • Suitable nonionic hydrophilic groups are, in particular, polyethylene glycol ethers of preferably 5 to 100, preferably 10 to 80, ethylene oxide repeat units.
  • the content of polyethylene oxide units is generally 0 to 10, preferably 0 to 6 wt .-%, based on the amount by weight of all monomers (a) to (e).
  • Preferred monomers with nonionic hydrophilic groups are polyethylene oxide diols, polyethylene oxide monools and the reaction products of a polyethylene glycol and a diisocyanate which carry a terminally etherified polyethylene glycol radical.
  • diisocyanates and processes for their preparation are given in the patents US-A 3,905,929 and US-A 3,920,598.
  • Ionic hydrophilic groups are especially anionic groups such as the sulfonate, the carboxylate and the phosphate group in the form of their alkali metal or ammonium salts and cationic groups such as ammonium groups, in particular protonated tertiary amino groups or quaternary ammonium groups.
  • ionic hydrophilic groups are, above all, those which can be converted by simple neutralization, hydrolysis or quaternization reactions into the above-mentioned ionic hydrophilic groups, e.g. Carboxylic acid groups or tertiary amino groups.
  • cationic monomers (c) especially monomers having tertiary amino groups are of particular practical importance, for example: tris (hydroxyalkyl) amines, N, N'-bis (hydroxyalkyl) alkylamines, N-hydroxyalkyl-dialkylamines , Tris- (aminoalkyl) -amines, N, N'-bis (aminoalkyl) -alkylamines, N-aminoalkyl-dialkylamines, wherein the alkyl radicals and alkanediyl moieties of these tertiary amines independently of one another consist of 1 to 6 carbon atoms.
  • polyethers having tertiary nitrogen atoms and having preferably two terminal hydroxyl groups are used. by the alkoxylation of two amine-containing hydrogen atoms, e.g. Methylamine, aniline or N, N'-dimethylhydrazine, in a conventional manner are accessible, into consideration.
  • Such polyethers generally have a molecular weight between 500 and 6000 g / mol.
  • tertiary amines are either with acids, preferably strong mineral acids such as phosphoric acid, sulfuric acid, hydrohalic acids or strong organic see acids or converted by reaction with suitable quaternizing agents such as d- to C ⁇ -alkyl halides or benzyl halides, eg bromides or chlorides, in the ammonium salts.
  • acids preferably strong mineral acids such as phosphoric acid, sulfuric acid, hydrohalic acids or strong organic see acids
  • suitable quaternizing agents such as d- to C ⁇ -alkyl halides or benzyl halides, eg bromides or chlorides, in the ammonium salts.
  • Suitable monomers with (potentially) anionic groups are usually aliphatic, cycloaliphatic, araliphatic or aromatic carboxylic acids and sulfonic acids which carry at least one alcoholic hydroxyl group or at least one primary or secondary amino group. Preference is given to dihydroxyalkyls, especially those having 3 to 10 carbon atoms, as are also described in US Pat. No. 3,412,054. In particular, compounds of the general formula (ci)
  • R 1 and R 2 are a C to C4 alkanediyl unit and R 3 is a C to C 4 - represents alkyl moiety and especially of dimethylolpropionic acid (DMPA) are preferred.
  • DMPA dimethylolpropionic acid
  • dihydroxysulfonic acids and dihydroxyphosphonic acids such as 2,3-dihydroxypropanephosphonic acid.
  • Suitable monomers (c) with isocyanate-reactive amino groups are amino carboxylic acids such as lysine, ⁇ -alanine or the adducts of aliphatic diprimary diamines mentioned in DE-A 20 34 479 to ⁇ , ⁇ -unsaturated carboxylic or sulfonic acids into consideration.
  • R 4 and R 5 independently represent a C to C ⁇ alkanediyl unit, preferably ethylene, and X represents COOH or SO 3 H.
  • Particularly preferred compounds of the formula (C2) are N- (2-aminoethyl) -2-aminoethanecarboxylic acid and also N- (2-aminoethyl) -2-aminoethanesulfonic acid or the corresponding alkali metal salts, Na being particularly preferred as the counterion.
  • the sulfonate or carboxylate groups are particularly preferably present in the form of their salts with an alkali metal ion or an ammonium ion as the counterion.
  • particularly preferred polyurethane dispersions are those in which the polyurethane has a content of carboxylic acid groups, in particular by selecting appropriate compounds (d) according to the above formula, most preferably by the concomitant use of DMPA.
  • Alcohols of a higher valence than 2 which can serve to set a certain degree of branching or crosslinking, are known, for example. Trimethylolpropane, glycerine or sugar.
  • monoalcohols which, in addition to the hydroxyl group, carry a further isocyanate-reactive group, such as monoalcohols having one or more primary and / or secondary amino groups, e.g. Monoethanolamine.
  • Polyamines having 2 or more primary and / or secondary amino groups are used especially when the chain extension or crosslinking is to take place in the presence of water, since amines usually react faster than alcohols or water with isocyanates. This is often necessary when aqueous dispersions of crosslinked polyurethanes or high molecular weight polyurethanes are used. wishes to be. In such cases, the procedure is to prepare prepolymers with isocyanate groups, to rapidly disperse them in water and then to chain extend or crosslink them by adding compounds containing several isocyanate-reactive amino groups.
  • Amines suitable for this purpose are generally polyfunctional amines of the molecular weight range from 32 to 500 g / mol, preferably from 60 to 300 g / mol, which contain at least two amino groups selected from the group of primary and secondary amino groups.
  • diamines such as diaminoethane, diamino propanes, diaminobutanes, diaminohexanes, piperazine, 2,5-dimethylpiperazine, amino-3-aminomethyl-3,5,5-trimethylcyclohexane (isophoronediamine, IPDA), 4,4'-diaminodicyclo - hexylmethane, 1, 4-diaminocyclohexane, aminoethylethanolamine, hydrazine, hydrazine hydrate or triamines such as diethylenetriamine or 1, 8-diamino-4-aminomethyloctan.
  • the amines may also be in blocked form, e.g. in the form of the corresponding ketimines (see, for example, CA-A 1 129 128), ketazines (see, for example, US-A 4,269,748) or amine salts (see US-A 4,292,226).
  • oxazolidines as used for example in US Pat. No. 4,192,937, are blocked polyamines which can be used for the preparation of the polyurethanes according to the invention for chain extension of the prepolymers. When using such capped polyamines they are generally mixed with the prepolymers in the absence of water and this mixture is then mixed with the dispersion water or a part of the dispersion water, so that the corresponding polyamines are hydrolytically released.
  • mixtures of di- and triamines particularly preferably mixtures of isophoronediamine (IPDA) and diethylenetriamine (DETA).
  • IPDA isophoronediamine
  • DETA diethylenetriamine
  • the polyurethanes preferably contain from 1 to 30, particularly preferably from 4 to 25, mol%, based on the total amount of components (b) and (d), of a polyamine having at least 2 isocyanate-reactive amino groups as monomers (d).
  • Alcohols of a higher valence than 2 which can serve to set a certain degree of branching or crosslinking, are known, for example. Trimethylolpropane, glycerine or sugar.
  • divalent isocyanates can also be used as monomers (d).
  • Commercially available compounds are, for example, the isocyanurate or the biuret of hexamethylene diisocyanate.
  • Monomers (e), which are optionally used, are monoisocyanates, monohydric alcohols and monoprimary and secondary amines. In general, their share at most 10 mol%, based on the total molar amount of the monomers.
  • These monofunctional compounds usually carry further functional groups, such as olefinic groups or carbonyl groups, and serve to introduce functional groups into the polyurethane, which make possible the dispersion or crosslinking or further polymer-analogous reaction of the polyurethane.
  • Suitable for this purpose are monomers such as isopropenyl- ⁇ , ⁇ -dimethylbenzyl isocyanate (TMI) and esters of acrylic or methacrylic acid such as hydroxyethyl acrylate or hydroxyethyl methacrylate.
  • TMI isopropenyl- ⁇ , ⁇ -dimethylbenzyl isocyanate
  • esters of acrylic or methacrylic acid such as hydroxyethyl acrylate or hydroxyethyl methacrylate.
  • the ratio A: B is as close as possible to 1: 1.
  • the monomers (a) to (e) used carry on average usually 1.5 to 2.5, preferably 1.9 to 2.1, particularly preferably 2.0 isocyanate groups or functional groups which can react with isocyanates in an addition reaction ,
  • the polyaddition of components (a) to (e) for the preparation of the polyurethane present in the aqueous dispersions of the invention is carried out at reaction temperatures of 20 to 18O 0 C, preferably 50 to 15O 0 C under atmospheric pressure or under autogenous pressure.
  • the required reaction times are in the range of 1 to 20 hours, in particular in the range of 1, 5 to 10 hours. It is known in the field of polyurethane chemistry how the reaction time is affected by a variety of parameters such as temperature, concentration of monomers, reactivity of the monomers.
  • Rlickkessel come into consideration as polymerization, especially when provided by the concomitant use of solvents for a low viscosity and good heat dissipation.
  • Preferred solvents are immiscible with water indefinitely, have a boiling point at atmospheric pressure of 40 to 100 0 C and do not react or only slowly with the monomers.
  • the dispersions are prepared by one of the following methods:
  • C 0-boiling solvent is removed from the components (a) to (c) an ionic ULTRASONIC polyurethane in a solvent miscible with water and at normal pressure under 100th Add enough water to form a dispersion in which water is the coherent phase.
  • the "prepolymer mixing process” differs from the acetone process in that it does not produce a fully reacted (potentially) ionic polyurethane, but first a prepolymer bearing isocyanate groups.
  • the components are chosen so that the ratio A: B is greater than 1, 0 to 3, preferably 1, 05 to 1, 5.
  • the prepolymer is first dispersed in water and then optionally crosslinked by reaction of the isocyanate groups with amines carrying more than 2 isocyanate-reactive amino groups, or chain-extended with amines bearing 2 isocyanate-reactive amino groups. Chain extension also occurs when no amine is added. In this case, isocyanate groups are hydrolyzed to amino groups, which react with remaining isocyanate groups of the prepolymers with chain extension.
  • the dispersions preferably have a solvent content of less than 10% by weight and are particularly preferably free from solvents.
  • the polyurethane dispersions generally have a solids content of 10 to 75, preferably from 20 to 65 wt .-% and a viscosity of 10 to 500 m Pas (measured at a temperature of 2O 0 C and a shear rate of 250 S " 1 ).
  • the polyurethane in a preferred embodiment contains hydrophilic groups, in particular those selected from carboxyl groups, hydroxyl groups, amino groups and carboxamide groups.
  • the content of these hydrophilic groups is in particular 0.001 to 0.5 mol per 100 g of polymer.
  • the content is preferably at least 0.005 mol, particularly preferably at least 0.008 mol and not more than 0.2 mol, in particular not more than 0.1 mol, very particularly preferably not more than 0.05 or 0.03 mol per 100 g / polymer.
  • Particularly preferably, at least 20 mol%, particularly preferably at least 50 mol% of the total molar amount of these groups are carboxyl groups.
  • Carboxyl groups are understood as meaning both carboxylic acid groups and their salts.
  • polyurethane dispersions according to the invention can be used in particular as a coating composition, sealant, impregnating composition or adhesive.
  • the coating compositions, sealants, impregnating compounds or adhesives may contain, in addition to the alkanolamine and the polyurethane dispersion, further constituents. However, they can also consist solely of the alkanolamine and the aqueous polyurethane dispersion.
  • Adhesives in particular pressure-sensitive adhesives, can e.g. Fillers, colorants, leveling agents, thickeners or tackifiers (tackifying resins)
  • Tackifiers are, for example, natural resins, such as rosin resins and their derivatives resulting from disproportionation or isomerization, polymerization, dimerization, hydrogenation, which can be used in their salt form (with, for example, mono- or polyhydric Alcohols used for esterification may be monohydric or polyhydric, for example, methanol, ethanediol, diethylene glycol, triethylene glycol, 1,2,3-propanethiol, pentaerythritol.
  • Sealants may in particular contain fillers. Furthermore, they contain aids to increase the stability, e.g. Thickener to increase the viscosity.
  • Particularly suitable coating compositions are coating materials which contain pigments and / or fillers. Examples of these are in particular plasters and paint compounds, both for the interior and for outdoor applications. Particularly preferred are coating compositions for outdoor applications. In particular, coating compositions or impregnating compositions for textiles and in particular leather are also considered.
  • pigments in particular inorganic, particulate pigments may be mentioned.
  • White pigments such as titanium dioxide, preferably in the rutile form, barium sulfate or zinc oxide, or color pigments such as iron oxides, carbon black, luminescent pigments, zinc yellow, zinc green or ultramarine.
  • Fillers which may be mentioned in particular inorganic, particulate fillers. Suitable examples are aluminosilicates, such as feldspars, silicates, such as kaolin, talc, Mica, wollastonite, magnesite, alkaline earth carbonates such as calcium carbonate, for example in the form of calcite or chalk, magnesium carbonate, dolomite, alkaline earth sulfates such as calcium sulfate, silica, Plastorit®, etc.
  • the fillers may be used singly or in admixture.
  • the coating compositions preferably contain 10 to 1000 parts by weight of pigments, fillers or mixtures of pigments and fillers per 100 parts by weight of binder.
  • they particularly preferably contain from 300 to 800 parts by weight and as gloss coating 10 to 100 parts by weight of pigments, fillers or mixtures of pigments and fillers per 100 parts by weight of binder.
  • compositions which may be contained in the coating compositions are e.g. Antifreeze, leveling agent and thickener.
  • polyurethane dispersions or coating compositions, sealants, impregnating compositions or adhesives of the invention can be processed by conventional methods, or be used in the usual way as an adhesive sealant, impregnating or coating material.
  • the composition is applied to the desired substrate or surface to be coated, and then the solvent is removed, e.g. by drying at ambient temperature or at elevated temperatures.
  • the above alkanolamines of the formula I are very suitable as neutralizing and / or dispersing agents in the polyurethane dispersions. They have a similar base strength as AMP (other amines have lower base strength and are therefore needed in larger amounts to adjust the pH).
  • the compositions according to the invention may be completely or partially neutralized with the alkanolamine;
  • the pH of the compositions may be in particular 5 to 9.
  • the performance properties, the solvents, chemicals and in particular the water resistance of the resulting coatings, seals, impregnations or bonds are very good, also in comparison to the AMP or DMAMP. A blushing is not or hardly observed in the compositions of the invention.
  • Example 2 In a stirred flask with thermometer and reflux condenser, 500 g (0.25 mol) of a polyester of OH number 56 from hexanediol-1,6-neopentyl glycol and adipic acid, 20.1 g (0.15 mol) DMPA and 120 g Heated acetone to 50 0 C. To this was added 87.4 g (0.52 mol) of HDI and heated to 67 ° C. After 240 minutes, it was diluted with 580 g of acetone and cooled to 32 ° C. The NCO content of the solution was determined to be 0.78% (calculated: 0.77%). To the solution was added 14.75 g (0.126 mol) of Al.
  • Example 4 In a stirred flask with thermometer and reflux condenser, 400 g (0.20 mol) of a polyester of OH number 56 from hexanediol-1,6-neopentylglycol and adipic acid, 20.1 g (0.15 mol) of DMPA and 150 g acetone heated to 50 0 C. To this was added 12.6 g (0.67 mol) of HDI and heated to 67 ° C. After 240 minutes, it was diluted with 550 g of acetone and cooled to 25 ° C. The NCO content of the solution was determined to be 2.20% (calculated: 2.18%).
  • Example 1 was repeated except that 10.1 g (0.10 mol) of TEA were used instead of A1.
  • Example 2 was repeated except that 12.7 g (0.126 mol) of TEA were used instead of A1. Comparative Example V4
  • Example 1 was repeated except that 14.7 g (0.10 mol) of DMEA were used in place of the A1.
  • films of about 1 mm thickness were cast and stored for 48 hours at room temperature.

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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)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

L’invention concerne une dispersion aqueuse de polyuréthanne contenant une alcanolamine de formule (I) dans laquelle R1 et R2 représentent un groupe alkyle en C1 à C4, R3 représente un atome d’hydrogène ou un groupe alkyle en C1 à C4, et R4 et R5 représentent indépendamment un groupe alkyle en C1 à C4.
PCT/EP2009/058885 2008-07-22 2009-07-13 Dispersion polyuréthanne contenant une alcanolamine WO2010009993A1 (fr)

Applications Claiming Priority (2)

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EP08160894.5 2008-07-22
EP08160894 2008-07-22

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WO2010009993A1 true WO2010009993A1 (fr) 2010-01-28

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3608344A1 (fr) 2018-08-06 2020-02-12 Basf Se Copolymères solubles ou dispersibles dans l'eau dotés de groupes fonctionnels d'oxazoline et d'acide sulfonique

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0531820A1 (fr) * 1991-09-10 1993-03-17 Bayer Ag Mélanges de polyisocyanate, procédé de leur préparation et leur utilisation
DE10127208A1 (de) * 2001-06-05 2002-12-12 Basf Ag Polyurethanispersionen und deren Verwendung
DE102005029626A1 (de) * 2005-06-23 2007-01-04 Bayer Materialscience Ag Polymermischung auf Basis von Polycarbonatpolyolen

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0531820A1 (fr) * 1991-09-10 1993-03-17 Bayer Ag Mélanges de polyisocyanate, procédé de leur préparation et leur utilisation
DE10127208A1 (de) * 2001-06-05 2002-12-12 Basf Ag Polyurethanispersionen und deren Verwendung
DE102005029626A1 (de) * 2005-06-23 2007-01-04 Bayer Materialscience Ag Polymermischung auf Basis von Polycarbonatpolyolen

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3608344A1 (fr) 2018-08-06 2020-02-12 Basf Se Copolymères solubles ou dispersibles dans l'eau dotés de groupes fonctionnels d'oxazoline et d'acide sulfonique

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