EP1456265A1 - Verfahren zur herstellung von monomerarmen polyurethan prepolymeren - Google Patents

Verfahren zur herstellung von monomerarmen polyurethan prepolymeren

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Publication number
EP1456265A1
EP1456265A1 EP02793051A EP02793051A EP1456265A1 EP 1456265 A1 EP1456265 A1 EP 1456265A1 EP 02793051 A EP02793051 A EP 02793051A EP 02793051 A EP02793051 A EP 02793051A EP 1456265 A1 EP1456265 A1 EP 1456265A1
Authority
EP
European Patent Office
Prior art keywords
polyol
diisocyanate
molecular weight
mol
acid
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.)
Withdrawn
Application number
EP02793051A
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German (de)
English (en)
French (fr)
Inventor
Guido Kollbach
Gerd Bolte
Nina Hassel
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.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
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 Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP1456265A1 publication Critical patent/EP1456265A1/de
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • 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
    • 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
    • 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
    • C08G2101/00—Manufacture of cellular products
    • 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
    • C08G2190/00—Compositions for sealing or packing joints

Definitions

  • the present invention relates to a process for the preparation of polyurethane prepolymers with terminal isocyanate groups by stepwise reaction of polyisocyanates with polyols, and the use thereof.
  • laminating and coating adhesives based on polyurethane (PU) prepolymers that have reactive end groups are often used to produce composite materials, in particular composite films. They are in particular end groups which can react with water or other compounds which have an acidic hydrogen atom.
  • This form of reactivity makes it possible to bring the reactive PU prepolymers in the processable state (usually liquid to highly viscous) in the desired manner to the desired location and by adding water or other compounds that have an acidic hydrogen atom ( in this case called hardener) harden.
  • the hardener is usually added immediately before application, with the processor only having a limited processing time after adding the hardener.
  • the polyurethanes with reactive end groups usually used in 1K or 2K systems include, for example, the polyurethanes with preferably terminal isocyanate (NCO) groups.
  • NCO terminal isocyanate
  • polyfunctional alcohols with an excess of monomeric polyisocyanates, generally at least predominantly diisocyanates.
  • a content of monomeric polyisocyanate has a disruptive effect, for example, when it comes to volatile diisocyanates: adhesives / sealants and, in particular, PU-based hotmelt adhesives are processed at elevated temperature.
  • the processing temperatures of hot melt adhesives are between 100 ° C and 200 ° C, those of laminating adhesives between room temperature and 150 ° C.
  • volatile diisocyanates such as IPDI or TDI, have a vapor pressure that should not be neglected. This noticeable vapor pressure is particularly serious when spraying, since significant quantities of isocyanate vapors or aerosols can occur above the application device, which are toxic because of their irritating and sensitizing effects.
  • volatile means substances which have a vapor pressure of more than about at about 30 ° C Have 0.0007 mm Hg or a boiling point less than about 190 ° C (70 mPa).
  • low volatile diisocyanates are used, in particular the widespread bicyclic diisocyanates, for example diphenylmethane diisocyanates, PU prepolymers or adhesives based thereon are generally obtained with a viscosity which is usually outside the range which can be used for simple processing methods. This also happens / or additionally if you want to reduce the monomer content by reducing the NCO / OH ratio. In these cases, the viscosity of the polyurethane prepolymers can be reduced by adding suitable solvents.
  • Another possibility for lowering the viscosity is to add an excess of monofunctional or polyfunctional monomers, for example monomeric polyisocyanates, as so-called reactive diluents.
  • monofunctional or polyfunctional monomers for example monomeric polyisocyanates
  • reactive diluents for example monomeric polyisocyanates
  • the content of the resulting amines, especially the primary aromatic amines, must be below the detection limit of 0.2 micrograms of aniline hydrochloride / 100 ml sample based on aniline hydrochloride (Federal Institute for Consumer Health Protection and Veterinary Medicine, BGVV, according to official collection from Examination procedure according to ⁇ 35 LMBG - Examination of foods / Determination of primary aromatic amines in aqueous test foods).
  • Migrates are undesirable in the packaging sector, especially in food packaging.
  • the migration of the migrates through the packaging material can lead to contamination of the packaged goods; on the other hand, depending on the amount of free monomeric polyisocyanate capable of migration, long waiting times are necessary before the packaging material is "migrat-free" and may be used.
  • the laminated plastic films often contain a lubricant based on fatty acid amides.
  • a lubricant based on fatty acid amides.
  • urea compounds are formed on the surface of the film which have a melting point which can be above the sealing temperature of the plastic films. This creates an alien anti-seal layer between the film parts to be sealed, which counteracts a uniform seal seam formation.
  • Polyurethanes containing NCO groups which are suitable for the production of composite materials, should therefore have a suitable processing viscosity, but should preferably not release or contain any volatile or migrable substances into the environment. Furthermore, there is a requirement for such polyurethanes that they are used immediately after application have at least one of the materials to be bonded after they have been joined together with a sufficiently good initial adhesion, which prevents the composite material from separating into its original components or, as far as possible, prevents the bonded materials from shifting relative to one another.
  • such an adhesive bond should also have a sufficient degree of flexibility to withstand the various tensile and tensile loads to which the composite material which is still in the processing stage is usually exposed, without damage to the adhesive bond and without damage to the bonded material, to survive.
  • 98/29466 They are produced by reacting the diisocyanate with NCO groups of different reactivity (unsymmetrical diisocyanate) with polyfunctional alcohols in the ratio OH: NGO between 4 and 0.55 in a first reaction step and after the reaction of virtually all fast NCO groups with one part of the OH groups present in a second reaction step, compared to the less reactive NCO group of the isocyanate from reaction step 1, a more reactive diisocyanate (symmetrical diisocyanate) in deficit, based on free OH groups, is added, if desired using customary catalysts and / or elevated temperatures are used.
  • WO 01/40342 describes reactive polyurethane adhesive / sealant compositions based on reaction products made from polyols and high molecular weight diisocyanates, a diol component with a stoichiometric excess of monomeric diisocyanate being converted into a high molecular weight diisocyanate in a first stage, and that high molecular weight diisocyanate is precipitated from the reaction mixture, for example by adding a non-solvent for the high molecular weight diisocyanate, from the monomeric diisocyanate.
  • DE 130908 A1 relates to pressure-sensitive PU compositions produced by reacting an NGO-bearing PU prepolymer (A) with a corresponding OH group-curing agent (B).
  • Component (A) is produced by a two-stage reaction, an at least difunctional isocyanate being reacted with at least one first polyol component in an NCO: OH ratio of ⁇ 2 in the first stage. There are still free OH groups.
  • a second stage another at least difunctional isocyanate is added and reacted with the prepolymer from the first stage, the further at least difunctional isocyanate having a higher reactivity than the predominant proportion of the NCO groups of the prepolymer from stage 1.
  • DE 4136490 relates to solvent-free coating systems and adhesive systems made from prepolymers containing polyols and isocyanate groups, which provide low migration values shortly after production.
  • the prepolymers containing NCO groups are made from polyol mixtures with an average functionality of 2.05 to 2.5 with at least 90 mol% of secondary hydroxyl groups and diisocyanates with differently reactive isocyanate groups in a ratio of the NCO groups to OH groups of 1.6: 1 built up to 1.8: 1.
  • Residual monomer contents of, for example, 0.03% TDI (example C) and 0.4% 2.4 ' MDI (example B) are found in the prepolymer.
  • US Pat. No. 5,925,781 describes a prepolymer with an NCO content of 2 to 16%, with a viscosity of approx. 10,000 mPas at room temperature and a TDI monomer content of preferably less than 0.3%. It is made from 2,4-TDI and at least one polyether polyol with an average molecular weight of 3000 to 8000 in an NCO: OH ratio of 1.3: 1 to 2.3: 1 and further reaction with a liquid diisocyanate of the diphenylmethane series and subsequent reaction with an alcohol or polyol.
  • DE 2438948 describes polyurethane prepolymers which are obtainable by reacting arylene diisocyanate with a polyoxypropylene triol in a first reaction stage at an NCO / OH equivalent weight ratio of 1.6: 0.1 to 2.25: 0.6 and reacting with a polyoxypropylene diol and the rest Arylene diisocyanate in a second stage, by means of which an NCO / OH ratio of 2.0: 1.0 is set and subsequent addition of aliphatic diisocyanate.
  • WO 98/02303 describes a process for the accelerated curing of laminates, in which an ink together with a catalyst is applied almost completely to a first film and then this first film is laminated against a second film with the aid of an adhesive, the Hardening of the adhesive is accelerated by the catalyst.
  • the object of the present invention was therefore to provide solvent-free or solvent-containing polyurethane prepolymers with terminal NCO groups with low viscosity, which can be prepared with shortened reaction times and which have a low content of monomeric polyisocyanates without complex workup steps.
  • the solution to the problem according to the invention can be found in the patent claims.
  • (I) in a first synthesis step a) uses at least one asymmetrical diisocyanate as the polyisocyanate, b) uses at least one polyol with an average molecular weight (M n ) of 60 to 3000 g / mol as the polyol, c) the ratio of isocyanate groups to hydroxyl groups in the range between
  • the molecular weight data relating to polymeric compounds in the further text relate to the number average molecular weight (M n ). Unless otherwise stated, all molecular weight data relate to values as can be obtained by gel permeation chromatography (GPC).
  • isocyanates examples include 1,5-naphthylene diisocyanate, 2,4- or 4,4'-diphenylmethane diisocyanate (MDI), hydrogenated MDI (H ⁇ 2 MDI), xylylene diisocyanate (XDI), tetramethylxylylene diisocyanate (TMXDI), 4,4-diphenyldimethyl methane diisocyanate, di- and tetraalkylene diphenyl methane diisocyanate, 4,4'-dibenzyl diisocyanate, 1, 3-phenylene diisocyanate, 1, 4-phenylene diisocyanate, the isomers of tolylene diisocyanate (TDI), 1-methyl-2,4-diisocyanato-cyclohexane, 1, 6-diisocyanato-2,2,4-trimethylhexane, 1,6-diisocyanato-2,4,4-trimethylhexane, 1-iso
  • aromatic polyisocyanates From the group of aromatic polyisocyanates, methylene triphenyl triisocyanate (MIT) is used, for example.
  • Aromatic diisocyanates are defined in that the isocyanate group is arranged directly on the benzene ring.
  • aromatic diisocyanates are used, such as 2,4- or 4,4'-diphenylmethane diisocyanate (MDI), the isomers of tolylene diisocyanate (TDI), naphthalene-1,5-diisocyanate (NDI).
  • Sulfur-containing polyisocyanates are obtained, for example, by reacting 2 mol of hexamethylene diisocyanate with 1 mol of thiodiglycol or dihydroxydihexyl sulfide.
  • Other usable diisocyanates are, for example, trimethylhexamethylene diisocyanate, 1,4-diisocyanatobutane, 1,12-diisocyanatododecane and dimer fatty acid diisocyanate.
  • tetramethylene hexamethylene, undecane, dodecamethylene
  • 2,2,4-trimethylhexane-2,3,3-trimethyl-hexamethylene- 1,3-cyclohexane
  • 1,4-cyclohexane 1, 3- or 1
  • 4-tetramethylxylene isophorone, 4,4-dicyclohexyl methane, tetramethylxylylene (TMXDI) and lysine ester diisocyanate.
  • Suitable at least trifunctional isocyanates are polyisocyanates which are formed by trimerization or oligomerization of diisocyanates or by reaction of diisocyanates with polyfunctional compounds containing hydroxyl or amino groups.
  • Isocyanates suitable for the preparation of trimers are the diisocyanates already mentioned, the trimerization products of the isocyanates HDI, MDI or IPDI being particularly preferred. Blocked, reversibly capped polykisisocyanates such as 1,3,5-tris [6- (1-methyl-propylidene-aminoxycarbonylamino) -hexyl] -2,4,6-trixo-hexahydro-1,3,5- triazine.
  • polymeric isocyanates such as those obtained as a residue in the distillation bottoms from the distillation of diisocyanates.
  • polymeric MDI as is available in the distillation of MDI from the distillation residue, is particularly suitable.
  • Desmodur N 3300 Desmodur N 100 or the IPDI trimeric isocyanurate T 1890 (manufacturer: Bayer AG) is used.
  • the NCO groups of the polyisocyanates can have different reactivities to compounds bearing functional groups reactive with isocyanates. This applies in particular to diisocyanates with NCO groups in different chemical environments, that is to say to asymmetrical diisocyanates. It is known that the reaction rate of dicyclic diisocyanates or generally symmetrical diisocyanates is higher than that of the second isocyanate group of unsymmetrical or monocyclic diisocyanates.
  • polyol encompasses a single polyol or a mixture of two or more polyols which can be used for the production of polyurethanes.
  • a polyol is understood to be a polyfunctional alcohol, ie a compound with more than one OH Group in the molecule.
  • Usable polyols are, for example, aliphatic alcohols with 2 to 4 OH groups per molecule.
  • the OH groups can be either primary or secondary.
  • Suitable aliphatic alcohols include, for example, ethylene glycol, propylene glycol, 1,4-butanediol, 1-pentanediol, 5, 1-hexanediol, 6, 1-heptanediol, 7, 1-octanediol, 8 and their higher homologs or isomers, as described for the expert from a gradual extension of the hydrocarbon chain each result in a CH 2 group or by introducing branches into the carbon chain.
  • Highly functional alcohols such as, for example, glycerol, trimethylolpropane, pentaerythritol and oligomeric ethers of the substances mentioned with themselves or in a mixture of two or more of the ethers mentioned are also suitable.
  • reaction products of low molecular weight polyfunctional alcohols with alkylene oxides can be used as the polyol component.
  • the alkylene oxides preferably have 2 to 4 carbon atoms.
  • Suitable examples are the reaction products of ethylene glycol, propylene glycol, the isomeric butanediols, hexanediols or 4,4'-dihydroxy-diphenylpropane with ethylene oxide, propylene oxide or butylene oxide, or mixtures of two or more thereof.
  • reaction products of polyfunctional alcohols such as glycerol, trimethylolethane or trimethylolpropane, pentaerythritol or sugar alcohols, or mixtures of two or more thereof, with the alkylene oxides mentioned to form polyether polyols are also suitable.
  • polyether polyols can be obtained by condensation of e.g. Glycerin or pentaerythritol can be produced with elimination of water.
  • Polyols commonly used in polyurethane chemistry continue to be formed by the polymerization of tetrahydrofuran.
  • the reaction products of polyfunctional low-molecular alcohols with propylene oxide under conditions in which at least some secondary hydroxyl groups are formed are particularly suitable for the first synthesis stage.
  • the polyethers are reacted in a manner known to those skilled in the art by reacting the starting compound with a reactive hydrogen atom with alkylene oxides, for example ethylene oxide, propylene oxide, butylene oxide, styrene oxide, tetrahydrofuran or epichlorohydrin or mixtures of two or more thereof.
  • Suitable starting compounds are, for example, water, ethylene glycol, propylene glycol-1, 2 or -1.3, butylene glycol-1, 4 or -1, 3, hexanediol-1, 6, octanediol-1, 8, Neopentylglycol, 1, 4-hydroxymethylcyclohexane, 2-methyl-1, 3-propanediol, glycerin, trimethylolpropane, hexanetriol-1, 2,6, butanetriol-1, 2,4 trimethylolethane, pentaerythritol, mannitol, sorbitol, methylglycoside, sugar, phenol , Isononylphenol, resorcinol, hydroquinone, 1,2,2- or 1,1,2-tris- (hydroxyphenyl) -ethane, ammonia, methylamine, ethylenediamine, tetra- or hexamethyleneamine, triethanolamine, aniline, phenylened
  • polyethers which have been modified by vinyl polymers.
  • Such products are available, for example, in which styrene or acrylonitrile, or a mixture thereof, is polymerized in the presence of polyethers.
  • Polyester polyols are also suitable for producing the polyurethane prepolymer with terminal isocyanate groups.
  • polyester polyols can be used which are formed by reacting low molecular weight alcohols, in particular ethylene glycol, diethylene glycol, neopentyl glycol, hexanediol, butanediol, propylene glycol, glycerol or trimethylolpropane with caprolactone.
  • low molecular weight alcohols in particular ethylene glycol, diethylene glycol, neopentyl glycol, hexanediol, butanediol, propylene glycol, glycerol or trimethylolpropane with caprolactone.
  • polyfunctional alcohols for the production of polyester polyols are 1,4-hydroxymethylcyclohexane, 2-methyl-1, 3-propanediol, butanetriol-1, 2.4,
  • Triethylene glycol Triethylene glycol, tetraethylene glycol, polyethylene glycol, dipropylene glycol, polypropylene glycol, dibutylene glycol and polybutylene glycol.
  • polyester polyols can be produced by polycondensation.
  • difunctional and / or trifunctional alcohols with a deficit of dicarboxylic acids and / or tricarboxylic acids or their reactive derivatives can be condensed to polyester polyols.
  • Suitable dicarboxylic acids are, for example, adipic acid or succinic acid and their higher homologues with up to 16 carbon atoms, furthermore unsaturated dicarboxylic acids such as maleic acid or fumaric acid and aromatic dicarboxylic acids, in particular the isomeric phthalic acids such as phthalic acid, isophthalic acid or terephthalic acid.
  • tricarboxylic acids for example, citric acid or trimellitic acid.
  • polyester polyols from at least one of the dicarboxylic acids and glycerol mentioned, which have a residual content of OH groups are particularly suitable.
  • Particularly suitable alcohols are hexanediol, ethylene glycol, diethylene glycol or neopentyl glycol or mixtures of two or more thereof.
  • Particularly suitable acids are isophthalic acid or adipic acid or a mixture thereof.
  • High molecular weight polyester polyols can be used in the second synthesis step and include, for example, the reaction products of polyfunctional, preferably difunctional alcohols (optionally together with small amounts of trifunctional alcohols) and polyfunctional, preferably difunctional carboxylic acids.
  • polyfunctional, preferably difunctional alcohols instead of free polycarboxylic acids, the corresponding polycarboxylic acid anhydrides or corresponding polycarboxylic acid esters with alcohols with preferably 1 to 3 C atoms can also be used (if possible).
  • the polycarboxylic acids can be aliphatic, cycloaliphatic, aromatic or heterocyclic or both. They can optionally be substituted, for example by alkyl groups, alkenyl groups, ether groups or halogens.
  • Suitable polycarboxylic acids succinic acid, adipic acid, suberic acid, azelaic acid, sebacic for example, acid, phthalic acid, isophthalic anhydride, terephthalic acid, trimellitic acid, phthalic anhydride, Tetrahydrophthal Text-, hexahydrophthalic anhydride, tetrachlorophthalic anhydride, endo methylenetetrahydrophthalic anhydride, glutaric anhydride, maleic acid, maleic anhydride, fumaric acid, dimer fatty acid or trimer fatty acid or mixtures suitable from two or more of them. If necessary, minor amounts of monofunctional fatty acids can be present in the reaction mixture.
  • polyesters can optionally have a small proportion of carboxyl end groups.
  • Polyesters obtainable from lactones, for example based on ⁇ -caprolactone, also called “polycaprolactones”, or hydroxycarboxylic acids, for example co-hydroxycaproic acid, can also be used.
  • polyester polyols of oleochemical origin can also be used.
  • polyester polyols can be obtained, for example, from complete ring opening of epoxidized triglycerides of an at least partially olefinically unsaturated fatty acid-containing fat mixture with one or more alcohols with 1 to 12 carbon atoms and subsequent partial transesterification of the triglycerol rid derivatives to alkyl ester polyols having 1 to 12 carbon atoms in the alkyl radical are prepared.
  • Other suitable polyols are polycarbonate polyols and dimer diols (from Henkel) and castor oil and its derivatives.
  • the hydroxy-functional polybutadienes as are available, for example, under the trade name "Poly-bd", can also be used as polyols for the compositions according to the invention.
  • Polyacetals are also suitable as the polyol component.
  • Polyacetals are understood to mean compounds such as are obtainable from glycols, for example diethylene glycol or hexanediol, or a mixture thereof with formaldehyde.
  • Polyacetals which can be used in the context of the invention can likewise be obtained by the polymerization of cyclic acetals.
  • Polycarbonates are also suitable as polyols.
  • Polycarbonates can be obtained, for example, by the reaction of diols such as propylene glycol, 1,4-butanediol or 1,6-hexanediol, diethylene glycol, triethylene glycol or tetraethylene glycol or mixtures of two or more thereof with diaryl carbonates, for example diphenyl carbonate, or phosgene.
  • Polyacrylates bearing OH groups are also suitable as polyol components. These polyacrylates can be obtained, for example, by polymerizing ethylenically unsaturated monomers which carry an OH group. Such monomers can be obtained, for example, by the esterification of ethylenically unsaturated carboxylic acids and difunctional alcohols, the alcohol usually being in a slight excess. Suitable ethylenically unsaturated carboxylic acids are, for example, acrylic acid, methacrylic acid, crotonic acid or maleic acid.
  • Corresponding esters carrying OH groups are, for example, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate or 3-hydroxypropyl methacrylate or mixtures of two or more thereof.
  • At least one asymmetrical diisocyanate is used as the polyisocyanate.
  • the asymmetrical diisocyanate is selected from the group of aromatic, aliphatic or cycloaliphatic diisocyanates.
  • suitable aromatic diisocyanates with differently reactive NCO groups are all isomers of tolylene diisocyanate (TDI) either in isomerically pure form or as a mixture of several isomers, naphthalene-1,5-diisocyanate (NDI) and 1,3-phenylene diisocyanate.
  • Examples of aliphatic diisocyanates with differently reactive NCO groups are 1,6-diisocyanato-2,2,4-trimethylhexane, 1,6-diisocyanato-2,4,4-trimethylhexane and lysine diisocyanate.
  • Suitable cycloaliphatic diisocyanates with differently reactive NCO groups are e.g. 1-isocyanatomethyl-3-isocyanato-1,5,5-trimethyl-cyclohexane (isophorone diisocyanate, IPDI) and 1-methyl-2,4-diisocyanatocyclohexane.
  • TDI tolylene diisocyanate
  • IPDI isophorone diisocyanate
  • M n average molecular weight
  • M n molecular weight
  • At least one polyol which has differently reactive hydroxyl groups is used in the first synthesis stage.
  • polyols to be used according to the invention are 1,2-propanediol, 1,2-butanediol, dipropylene glycol, tripropylene glycol,
  • Tetrapropylene glycol the higher homologues of polypropylene glycol with an average molecular weight (number average M n ) of up to 3,000, in particular up to 2,500 g / mol, and copolymers of polypropylene glycol, for example block or statistical copolymers of ethylene and propylene oxide.
  • the ratio of isocyanate groups to hydroxyl groups is set in the range between 1.2: 1 to 4: 1, preferably 1.5: 1 to 3: 1 and particularly preferably 1.8: 1 to 2 , 5: 1 a.
  • the reaction between the at least one asymmetrical diisocyanate and the at least one polyol with an average molecular weight (M n ) of 60 to 3000 g / mol takes place at a temperature between 20 ° C. to 80 ° C., preferably between 40 to 75 ° C. In a particular embodiment, the reaction in the first synthesis stage takes place at room temperature.
  • the reaction in the first synthesis stage takes place in aprotic solvents.
  • the proportion by weight of the reaction mixture in the mixture with the aprotic solvent is 20 to 80% by weight, preferably 30 to 60% by weight, particularly preferably 35 to 50% by weight.
  • the reaction in the aprotic solvents takes place at temperatures in the range from 20 ° C. to 100 ° C., preferably 25 ° C. to 80 ° C. and particularly preferably from 40 ° C. to 75 ° C.
  • Aprotic solvents are, for example, halogen-containing organic solvents, but acetone, methyl isobutyl ketone or ethyl acetate are preferred.
  • the reaction mixture of the first synthesis stage contains a catalyst.
  • Suitable catalysts according to the invention are organometallic compounds and / or tertiary amines in concentrations between 0.1 and 5% by weight, preferably between 0.3 and 2% by weight and particularly preferably between 0.5 to 1% by weight.
  • Organometallic compounds of tin, iron, titanium, bismuth or zirconium are preferred.
  • organometallic compounds such as tin (II) salts or titanium (IV) salts of carboxylic acids, strong bases such as alkali hydroxides, alcoholates and phenolates, e.g. B.
  • di-n-octyl tin mercaptide dibutyltin maleate, diacetate, dilaurate, dichloride, bisdodecyl marcaptide, tin ll acetate, ethylhexoate and diethylhexoate, tetraisopropyl titanate or lead phenyl ethyl dithiocarbate
  • Another class of compounds are the dialkyltin (IV) carboxylates.
  • the carboxylic acids have 2, preferably at least 10, in particular 14 to 32, carbon atoms. Dicarboxylic acids can also be used.
  • acids adipic acid, maleic acid, fumaric acid, malonic acid, succinic acid, pimelic acid, terephthalic acid, phenylacetic acid, benzoic acid, acetic acid, propionic acid and 2-ethylhexanoic, caprylic, capric, lauric, myristic, palmitic and stearic acid.
  • Specific compounds are dibutyl and dioctyl tin diacetate, maleate, bis (2-ethylhexoate), dilaurate, tributyl tin acetate, bis ( ⁇ -methoxycarbonyl-ethyl) tin dilaurate and bis ( ⁇ -acetyl-ethyl) tin dilaurate.
  • Tin oxides and sulfides and thiolates can also be used.
  • Specific compounds are: bis (tributyltin) oxide, bis (trioctyltin) oxide, dibutyl and diocytyltin bis (2-ethylhexylthiolate) dibutyl and dioctyltin didodecylthiolate, bis ( ⁇ -methoxycarbonyl-ethyl) tin dididodecylthiolate, bis acetyl-ethyl) tin bis (2-ethyl hexyl thiolate), dibutyl and dioctyl tin didodecyl thiolate, butyl and octyl tin tris (thioglycolic acid 2-ethyl hexoate), dibutyl and dioctyl tin bis (thioglycolic acid, 2-ethyl he
  • Bismuth-organic compounds for example triaryl bismuth compounds, oxides of these compounds and alkyl- or arylhalogen bismuthines of the types R 2 BiX and R 3 BiX 2 as well as phenolates and carboxylates of bismuth can also be used.
  • Bismuth carboxylates are used in particular as bismuth-organic compounds, the carboxylic acids having 2 to 20 C atoms, preferably 4 to 14 atoms. The following are expressly mentioned as acids: butyric acid, caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, isobutyric acid and 2-ethylhexanoic acid.
  • Mixtures of bismuth carboxylates with other metal carboxylates, for example tin carboxylates can also be used.
  • tertiary amines are used as catalysts, alone or in combination with at least one of the above-mentioned catalysts: diazabicyclo-octane (Dabco), triethylamine, dimethylbenzylamine (Desmorapid DB, Bayer), bis-dimethylaminoethyl ether (Calalyst AI, UCC), Teramethylguanidine, bis-dimethylaminomethylphenol, 2,2'-dimorpholinodiethyl ether, 2- (2-
  • the catalysts can also be in oligomerized or polymerized form, e.g. B. as N-methylated polyethyleneimine.
  • 1-methylimidazole 2-methyl-1-vinyldimidazole, 1-allylimidazole, 1-phenylimidazole, 1, 2,4,5-tetramethylimidazole, 1 (3-aminopropyl) imidazole, pyrimidazole, 4-dimethylamino-pyridine, 4 -Pyrrolidinopyridine, 4-morpholino-pyridine, 4 methylpyridine and N-dodecyl-2-methyl-imidazole.
  • Combinations of organometallic compounds and amines are particularly preferred according to the invention, the ratio of amine to organometallic compound 0.5: 1 to 10: 1, preferably 1: 1 to 5: 1 and particularly preferably 1.5: 1 to 3: 1.
  • ⁇ -caprolactam is used as the catalyst. Based on the total amount of asymmetrical diisocyanate and polyol used in the first synthesis stage, the amount of ⁇ -caprolactam used is 0.05 to 6% by weight, preferably 0.1 to 3% by weight, particularly preferably 0.2 up to 0.8% by weight.
  • the ⁇ -caprolactam can be used as a powder, as granules or in liquid form.
  • the reaction product from the first synthesis stage preferably has an NCO value of 3 to 22% by weight and particularly preferably an NCO value of 3.5 to 11.5% by weight (according to Spiegelberger, EN ISO 11909) ,
  • At least one further polyol is added, such that an overall ratio of isocyanate groups to hydroxyl groups of 1.1: 1 to 2: 1, preferably 1.3: 1 to 1.8: 1 and particularly preferably from 1.45:
  • the temperature is between 20 ° C and
  • This is preferably a polyether or polyether mixture with a
  • M n Molecular weight (M n ) from about 100 to 10,000 g / mol, preferably from about 200 to about 5,000 g / mol and / or a polyester polyol or polyester polyol mixture with a molecular weight (M n ) from about 200 to 10,000 g / mol.
  • the second synthesis step is also carried out in at least one of the abovementioned aprotic solvents.
  • the proportion by weight of the total reaction mixture in the mixture with the aprotic solvent is 30 to 60% by weight, preferably 35 to 50% by weight. If solvent-free polyurethanes are desired, the solvent is distilled off after the reaction has ended and after stirring for 30 to 90 minutes.
  • the polyurethane prepolymer with terminal isocyanate groups may additionally contain stabilizers, adhesion-promoting additives such as tackifying resins, fillers, pigments, plasticizers and / or solvents.
  • “Stabilizers” in the sense of this invention are, on the one hand, stabilizers which bring about a viscosity stability of the polyurethane according to the invention during manufacture, storage or application.
  • stabilizers e.g. monofunctional carboxylic acid chlorides, monofunctional highly reactive isocyanates, but also non-corrosive inorganic acids are suitable, examples being benzoyl chloride, toluenesulfonyl isocyanate, phosphoric acid or phosphorous acid.
  • antioxidants, UV stabilizers or hydrolysis stabilizers are to be understood as stabilizers in the sense of this invention.
  • these stabilizers depends on the one hand on the main components of the polyurethane according to the invention and on the other hand on the application conditions and the expected loads on the cured product. If the low-monomer polyurethane according to the invention is predominantly composed of polyether units, mainly antioxidants, possibly in combination with UV protection agents, are necessary. Examples of these are the commercially available sterically hindered phenols and / or thioethers and / or substituted benzotriazoles or the sterically hindered amines of the HALS type ("hindered amine light stabilizer").
  • hydrolysis stabilizers e.g. of the carbodiimide type can be used.
  • the polyurethane prepolymers with terminal NCO groups produced by the process according to the invention can also contain tackifying resins such as abietic acid, abietic acid esters, terpene resins, terpene phenol resins or hydrocarbon resins and fillers (for example silicates, talc, calcium carbonates, clays or carbon black) ) Contain plasticizers (e.g. phthalates) or thixotropic agents (e.g. bentones, pyrogenic silicas, urea derivatives, fibrillated or pulp short fibers) or color pastes or pigments.
  • tackifying resins such as abietic acid, abietic acid esters, terpene resins, terpene phenol resins or hydrocarbon resins and fillers (for example silicates, talc, calcium carbonates, clays or carbon black)
  • fillers for example silicates, talc, calcium carbonates, clays or carbon black
  • plasticizers e.g. phthalates
  • the polyurethane prepolymers produced by the process according to the invention can also be prepared in solution and used as 1K or 2K laminating adhesives, preferably in polar, aprotic solvents.
  • the preferred solvents have a boiling range of about 50 ° C to 140 ° C.
  • halogenated hydrocarbons are also suitable, ethyl acetate, methyl ethyl ketone (MEK) or acetone are particularly preferred.
  • diisocyanates but preferably triisocyanates
  • triisocyanates can be used in the second reaction stage. This can be done in combination with the polyol or simply by adding the diisocyanate / triisocyanate.
  • Adducts of diisocyanates and low molecular weight triols are preferred as the triisocyanate, in particular the adducts of aromatic
  • Diisocyanates and triols such as. B. trimethylolpropane or glycerin.
  • Aliphatic triisocyanates such as the biuretization product of
  • Hexamethylene diisocyanates (HDI) or the isocyanuration product of HDI or the same trimerization products of isophorone diisocyanate (IPDI) are suitable for the compositions according to the invention, provided that the proportion of diisocyanates is ⁇ 1% by weight and the proportion of tetra- or higher-functional isocyanates is not greater than 25% by weight.
  • Trimerization products of the HDI and the IPDI are particularly preferred.
  • the polyisocyanate can be added at a temperature of 25 ° C to 100 ° C.
  • the polyurethane prepolymer with terminal isocyanate groups produced by the process according to the invention is low in monomers.
  • “Low-monomer” means a low concentration of the starting polyisocyanates in the polyurethane prepolymer produced according to the invention.
  • the monomer concentration is below 1, preferably below 0.5, in particular below 0.3 and particularly preferably below 0.1% by weight, based on the total weight of the solvent-free polyurethane prepolymer.
  • the proportion by weight of the asymmetrical monomeric diisocyanate is determined by gas chromatography, by means of high pressure liquid chromatography (HPLC) or by means of gel permeation chromatography (GPC).
  • the viscosity of the polyurethane prepolymer produced by the process according to the invention is 100 mPas to 15,000 mPas at 100 ° C., preferably 150 mPas to 12,000 mPas and particularly preferably 200 to 10,000 mPas. measured according to Brookfield (ISO 2555).
  • the NCO content in the polyurethane prepolymer produced according to the invention is 1% by weight to 10% by weight, preferably 2% by weight to 8% by weight and particularly preferably 2.2% by weight to 6% by weight. % (according to Spiegelberger, EN ISO 11909).
  • the polyurethane prepolymers produced according to the invention are therefore distinguished by an extremely low proportion of monomeric, volatile diisocyanates, which are hazardous to occupational hygiene and have a molecular weight below 500 g / mol.
  • the process has the economic advantage that the low monomer content is achieved without complex and costly work steps.
  • the polyurethane prepolymers produced in this way are moreover free of the by-products usually obtained in thermal workup steps, such as crosslinking or depolymerization products. Shorter reaction times are achieved by the process according to the invention, nevertheless the selectivity between the different reactive NCO groups of the asymmetrical diisocyanate remains to the extent that polyurethane prepolymers with low viscosities are obtained.
  • the polyurethane prepolymers produced according to the invention are suitable in bulk or as a solution in organic solvents, preferably as an adhesive or adhesive component for the bonding of plastics, metals and Papers. Because of the extremely low proportion of monomeric diisocyanates capable of migration, the polyurethane prepolymers produced according to the invention are particularly suitable for laminating textiles, aluminum and plastic films, and metal or oxide-vapor-coated films and papers. Conventional hardeners, such as polyfunctional, higher molecular weight polyols, can be added (two-component systems) or surfaces with a defined moisture content can be directly bonded to the products produced according to the invention.
  • Film composites produced on the basis of the polyurethane prepolymers produced according to the invention show high processing reliability when heat-sealing. This is due to the greatly reduced proportion of low molecular weight products capable of migration in the polyurethane.
  • the low-monomer polyurethane prepolymers containing NCO groups prepared according to the invention can also be used in extrusion, printing and metallization primers and for heat sealing.
  • the polyurethanes produced according to the invention are suitable for producing hard, soft, integral foams and in sealants.
  • Apparatus three-neck flask agitator with contact thermometer, agitator with agitator motor, reflux condenser with drying tube and patio heater.
  • End point of the 1st stage 3.9% by weight of NGO in the polyurethane prepolymer.
  • the polyester polyol is then added.
  • the reaction mixture is stirred again under reflux conditions.
  • End point of the 2nd stage 1.4% by weight of NGO in the polyurethane prepolymer.
  • Polyurethane prepolymer is 6 hours.
  • NCO value 2.1% by weight
  • polyester polyol (OHZ: 60) 134.1 g IPDI (NGO: 37.8%) 122.7 g polyether polyol (OHZ: 275) 50.0 g isocyanurate based (NGO: 17.2%)
  • Apparatus three-neck flask agitator with contact thermometer, agitator with agitator motor, reflux condenser with drying tube and patio heater.
  • the polyester polyol is placed in ethyl acetate. After adding the IPDI and the catalyst (dibutyltin dilaurate), the mixture is heated and stirred under reflux conditions.
  • the catalyst dibutyltin dilaurate
  • End point of the 1st stage 4.6% by weight of NGO in the polyurethane prepolymer.
  • the polyether polyol is then added.
  • the reaction mixture is stirred again under reflux conditions.
  • End point of the 2nd stage 1.3% by weight of NGO in the polyurethane prepolymer.
  • Polyurethane prepolymer is 6 hours.
  • NCO value 2.1% by weight
  • Viscosity 281 mPa s
  • the polyether polyol 1 is initially introduced and the catalyst ( ⁇ -caprolactam) is added. Then TDI is added. After the exothermic reaction has subsided, the batch is stirred at about 70-80 ° C. until the end point of the 1st stage is reached.
  • End point of the 2nd stage 4.0% by weight in the polyurethane prepolymer.
  • Polyurethane prepolymer is 3 hours.
  • Viscosity 4000-6000 mPa s
  • Apparatus three-necked flask stirring apparatus with contact thermometer, stirrer with stirring motor, drying tube and heating element.
  • the polyether polyol 1 is initially introduced and catalyst (DABCO) is added. Then TDI is added. After the exothermic reaction has subsided, the batch is stirred at about 70-80 ° C. until the end point of the 1st stage is reached.
  • End point of the 1st stage 5.5% by weight of NCO in the polyurethane prepolymer.
  • End point of the 2nd stage 3.9% by weight of NCO in the polyurethane prepolymer.
  • Viscosity 28,000-32,000 mPa s
  • Apparatus three-necked flask stirring apparatus with contact thermometer, stirrer with stirring motor, drying tube and heating element.
  • the polyether polyol 1 is presented. Then TDI is added. After the exothermic reaction has subsided, the batch is stirred at about 70-80 ° C. until the end point of the 1st stage is reached.
  • End point of the 1st stage 7.1% by weight NCO in the polyurethane prepolymer.
  • Polyurethane prepolymer is 5 hours.
  • Viscosity 3250 mPa s
  • TDI monomer content 0.55% by weight

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  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Sealing Material Composition (AREA)
  • Adhesives Or Adhesive Processes (AREA)
EP02793051A 2001-12-18 2002-12-17 Verfahren zur herstellung von monomerarmen polyurethan prepolymeren Withdrawn EP1456265A1 (de)

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DE10259248A1 (de) 2003-07-10
HUP0402474A3 (en) 2005-10-28
US20050020706A1 (en) 2005-01-27
BR0215060A (pt) 2004-11-23
CA2471252A1 (en) 2003-06-26
KR20040068953A (ko) 2004-08-02
AU2002358740A1 (en) 2003-06-30
HUP0402474A2 (hu) 2005-03-29
JP2005511873A (ja) 2005-04-28
WO2003051951A1 (de) 2003-06-26
RU2004122092A (ru) 2006-01-20
MXPA04005750A (es) 2004-09-10
PL369173A1 (en) 2005-04-18

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