WO2010102718A1 - Compositions de polyuréthane réactives - Google Patents

Compositions de polyuréthane réactives Download PDF

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Publication number
WO2010102718A1
WO2010102718A1 PCT/EP2010/001125 EP2010001125W WO2010102718A1 WO 2010102718 A1 WO2010102718 A1 WO 2010102718A1 EP 2010001125 W EP2010001125 W EP 2010001125W WO 2010102718 A1 WO2010102718 A1 WO 2010102718A1
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Prior art keywords
diisocyanate
mdi
compositions
component
molecular weight
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PCT/EP2010/001125
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German (de)
English (en)
Inventor
Marc Leimenstoll
Sebastian Dörr
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Bayer Materialscience Ag
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Publication of WO2010102718A1 publication Critical patent/WO2010102718A1/fr

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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
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/2805—Compounds having only one group containing active hydrogen
    • C08G18/2815—Monohydroxy compounds
    • C08G18/283—Compounds containing ether groups, e.g. oxyalkylated monohydroxy compounds
    • 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
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/2805—Compounds having only one group containing active hydrogen
    • C08G18/2815—Monohydroxy compounds

Definitions

  • the present invention relates to reactive polyurethane compositions and their preparation and their use in reactive one- and two-component adhesives / sealants, mounting foams, casting compounds and in soft, hard and integral foams.
  • Reactive polyurethanes have NCO end groups that can react with water or other compounds that have an acidic hydrogen atom. This form of reactivity makes it possible to bring the reactive polyurethanes in a workable state, for example liquid to highly viscous, to the desired location and to cure them by adding water or other compounds which have an acidic hydrogen atom.
  • Reactive polyurethanes can be used in many technical fields.
  • An important application of polyurethanes is e.g.
  • the polyisocyanates are usually mixtures of diphenylmethane diisocyanate (MDI) and / or polyphenylenepolymethylene polyisocyanates, often referred to as crude MDI or polymer MDI, and / or reaction products of polyisocyanates with a deficit of compounds having at least two isocyanate-reactive hydrogen atoms , so-called NCO prepolymers used.
  • MDI diphenylmethane diisocyanate
  • polyphenylenepolymethylene polyisocyanates often referred to as crude MDI or polymer MDI
  • reaction products of polyisocyanates with a deficit of compounds having at least two isocyanate-reactive hydrogen atoms so-called NCO prepolymers used.
  • polyisocyanate is usually polymer MDI.
  • polymer MDI polymer MDI
  • This usually contains a high proportion of 2-core MDI.
  • Aerosol foams are commonly used in the field of construction mounting means for the installation of windows and doors in buildings as well as filler for structural cavities or wall openings for pipe installations.
  • Such an aerosol container contains a prepolymer and blowing agents and additives. By discharging its contents by means of blowing agent, its foaming by evaporation of the blowing agent (so-called Froth effect) and its curing with atmospheric moisture, the desired foam is formed.
  • One-component foams based on NCO-containing prepolymers are the best-known foams of this type. There are different products which, depending on the composition, lead to hard to soft-elastic foams.
  • Reactive polyurethane compositions generally contain low molecular weight monomeric isocyanates as a result of the preparation. These have the disadvantage that they can cause health hazards. Thus, when the compositions are transferred to the vapor phase or aerosol, it must be ensured that persons can not come into contact with such vapors, containing low molecular weight, monomeric isocyanates. Furthermore, skin contacts with such reactive polyurethane compositions should be avoided as much as possible.
  • isocyanates may be harmful to health, but also the resulting reaction products with water, such as aromatic diamines or polyamines, may be of concern to health.
  • isocyanate groups are continuously converted to amino groups and further secondary products.
  • Such compounds can not only arise directly upon curing of the polyurethane systems. Due to the slowing reaction rate, it is also possible that these may arise from the polyurethane compositions in the long term under conditions of use, such as, for example, at higher temperatures and high atmospheric humidity.
  • These amino compounds can also migrate to the substrate surface or into surrounding layers.
  • Such migratory components based on low molecular weight, aromatic di- or polyamines are referred to below as Migrate.
  • compositions can be prepared with a low content of monomeric diisocyanates in a two-stage process. From a first reaction product, the unreacted monomeric diisocyanate is removed and the reacted product further to a prepolymer of higher molecular weight. This prepolymer is suitable for use as a binder for reactive one- or two-component adhesives / sealants or reactive hot melt adhesives.
  • EP-A 0 316 738 describes a process for the preparation of urethane-containing polyisocyanates having a starting diisocyanate content of not more than 0.4% by weight by reacting aromatic diisocyanates with polyhydric alcohols and subsequent distillative removal of the unreacted, excess starting diisocyanate ,
  • EP-A 1 518 874 it is known that a low-monomer isocyanate is used for the production of one-component foams which is obtained from a defined polyphenylene polymethylene polyisocyanate by distillative removal of the monomeric isocyanate.
  • this product optionally in admixture with diluents and other compounds containing isocyanate groups, low-monomer one-component foams are thus obtained.
  • the disadvantage here is that one-component aerosol foams manufactured in this way are less stable in storage, as a result of which the contents of the aerosol pressure containers become firm within a few weeks and thus become unusable.
  • WO2005 / 007 721 also describes the use of mixtures of low-monomer NCO-terminated prepolymers, ie reaction products of polyols and diphenylmethane diisocyanate in stoichiometric excess freed from monomers, demonomerized polyphenylene polymethylene polyisocyanate, trimerized hexamethylene diisocyanate and diluents.
  • Disadvantages here are the extremely low viscosities of the starting materials for realizing the required reduced monomer content of isocyanate, which make the use of technologically difficult and the fact that the storage stability as in the solution according to EP-A 1 518 874 is not guaranteed.
  • EP-A 1 451 239 describes a process for the preparation of monomer-poor prepolymers based on monomeric 2,4'-MDI. These prepolymers are distinguished from monomer-poor prepolymers based on monomeric 4,4'-MDI by significantly lower viscosities. However, the teaching does not describe the viscosities of low-monomer prepolymers based on aromatic polymeric isocyanates having an average functionality greater than 2.
  • EP-A 1 964 868 describes crosslinking 1-K or 2-K PU compositions which contain reaction products of polyols and aromatic diisocyanates, the composition containing less than 0.1% by weight of unreacted monomeric aromatic isocyanates.
  • a disadvantage of these compositions is their extremely high viscosity, especially when polyols with functionalities greater than 2 are used.
  • WO 2002/079291 and WO 2002/079292 mounting foams are described with low content of monomeric isocyanates. These foams are prepared by relaxing a low-monomer prepolymer present in a pressure vessel. This prepolymer in turn is prepared by reacting an optionally oligomerized diisocyanate with at least one hard foam polyol and subsequent removal by distillation of the monomeric isocyanate.
  • the disadvantage here is that already the prepolymer has a high viscosity, which increases further by the subsequent distillation. Therefore, an inert diluent must necessarily be added to this prepolymer. However, such compounds often have a negative effect on the properties of the foams.
  • demonomerized prepolymers which are obtainable, for example, by reacting a polyisocyanate with a polyol mixture consisting of at least one polyether alcohol a) having a functionality greater than or equal to 3 and a molecular weight below 1000 g / mol, which ensures the crosslinking of the foam, a predominantly composed of ethylene oxide polyether alcohol b) having a functionality of 2 to 3, which serves as a cell regulator, and a monofunctional alcohol c), in particular having a molecular weight between 32 and 500 g / mol , which acts as a molecular weight regulator.
  • the polyol a) is preferably in an amount between 65 and 80 wt.% And the polyols b) and c) in an amount between 2 and 35 wt .-%, based on the sum of the weights of a), b) and c ).
  • monofunctional Have alcohols having a molecular weight> 500 g / mol on the viscosity of the demonomerized prepolymer.
  • the reactive compositions should be suitable both for use as one- and two-component adhesives / sealants, in particular as hot-melt adhesives or laminating adhesives, as well as for the production of casting compounds, assembly foams as well as soft, hard and integral foams.
  • the object of the present invention was to provide these.
  • At least one polyisocyanate or one isocyanate prepolymer component At least one polyisocyanate or one isocyanate prepolymer component
  • C) optionally other components which do not correspond to A) and B), wherein A) and B) are linked together with urethane formation.
  • Another object of the invention is the use of such compositions as or in adhesives or sealants. Another object of the invention is the use of these compositions as a reactive potting compound or as a hardening plastic mass. Another object of the invention is the use of these compositions as an intumescent composition. Another object of the present invention are molded articles prepared from compositions of the invention by shaping and subsequent crosslinking.
  • Suitable polyisocyanate components of component A) are the di- or polyfunctional isocyanates known to the person skilled in the art or aliphatic, aromatic or cycloaliphatic isocyanate-functional prepolymers with the abovementioned NCO functionalities.
  • the isocyanate-functional prepolymers which can be used in A) are obtainable by reacting polyisocyanates with NCO-reactive compounds, preferably hydroxy-functional polyols, if appropriate with addition of catalysts and auxiliaries and additives.
  • NCO-reactive compounds preferably hydroxy-functional polyols
  • the process and preparation of isocyanate-functional prepolymers are Specialist known.
  • the low molecular weight polyisocyanates are reacted with the polyols at an NCO / OH ratio of preferably 1.1: 1 to 20: 1. puts.
  • the reaction temperature is usually 20 to 160 0 C, preferably 60 to 100 0 C.
  • the proportion of unreacted polyisocyanates is then separated by means of suitable methods. Typically, this thin-film distillation is used, with low-residue monomers having residual monomer contents of less than 5 wt .-%, preferably less than 1, 0 wt .-%, most preferably less than 0.5 wt .-% are obtained
  • Examples of such suitable isocyanate-functional building blocks A) are prepolymers based on polyols and low molecular weight isocyanate building blocks.
  • Low-molecular isocyanate building blocks are compounds such as diphenylmethane diisocyanate (MDI) with all its isomers [4,4'-diphenylmethane diisocyanate (4,4'-MDI), 2,4'-diphenylmethane diisocyanate (2,4'-MDI), 2, 2'-diphenylmethane diisocyanate (2,2'-MDI)], hydrogenated or partially hydrogenated MDI (H12MDI, H6MDI), xylylene diisocyanate (XDI), tetramethylxylylene diisocyanate (TMXDI), di- and tetraalkylenediphenylmethane diisocyanate, 4,4'- Dibenzyl diisocyanate, 1, 3-phenylene diisocyanate
  • Hexane-1,6-diisocyanate dicyclohexylmethane diisocyanate, tetramethylene, hexamethylene, undecane, dodecamethylene, 2,2,4-trimethyl-hexane-2,3,3-trimethyl-hexamethylene diisocyanate, cyclohexane-1 , 4-diisocyanate, ethylene diisocyanate, triphenylmethane-4,4 ', 4 "-triisocyanate (MIT), phthalic acid bis-isocyanatoethyl ester, diisocyanates with reactive halogen atoms, such as 1-chloromethylphenyl 2,4-diisocyanate, Bromomethyl-phenyl-2,6-diisocyanate, 3,3-bis-chloro-methyl-ether-4,4'-diphenyl-diisocyanate Further usable diisocyanates are trimethylhexamethylene diisocyanate,
  • aromatic diisocyanates having differently reactive NCO groups are the isomers of TDI, NDI, 1,3-phenylene diisocyanate or 2,4 'MDI and also alkyl 2,6-diisocyanatohexanoates (lysine diisocyanates) with C 1 -C 8 -alkyl groups.
  • the isocyanate-functional building blocks A) may contain, for example, uretdione, isocyanurate, urethane, urea, allophanate, biuret, iminooxadiazinedione or oxadiazinetrione structures and also mixtures of these. It is also possible to use all polymeric polyisocyanates known to the person skilled in the art. These are preferably aromatic isocyanate compounds which may have two or more NCO groups, such as Polyphenylenpolydimethylenpolyisocyanate. Proportionally, it is also possible for aliphatic or cycloaliphatic isocyanates to be present.
  • Suitable hydroxy-functional polyols for the preparation of isocyanate-functional prepolymers A) are the customary polyol compounds known to the person skilled in the art.
  • a variety of polyfunctional alcohols can be used. These should have from 2 to 10, in particular from 2 to 4, OH groups per molecule. These may be low molecular weight compounds or OH-functional polymers. However, it is necessary that these compounds have no further NCO-reactive functional groups.
  • the compounds with several OH groups may be those which carry only terminal OH groups, or they may be compounds which have (also) distributed via the chain side OH groups. In any case, the OH groups to be considered are those which can react with isocyanates.
  • Suitable compounds of this type are polyols based on polyethers, polyesters or polyalkylenes, which may be liquid, amorphous or crystalline.
  • aliphatic or araliphatic alcohols having 2 to 10 OH groups per molecule are suitable. It may be preferred to use primary and secondary alcohols. Trifunctional alcohols, such as glycerol, trimethylolethane and / or trimethylolpropane or higher functional alcohols, such as, for example, pentaerythritol or sugar alcohols, can be used. It is also possible to use hydroxyalkyl-substituted phenols or cycloaliphatic diols or polyols.
  • Suitable aliphatic alcohols include, for example, ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, heptanediol-1,7, octanediol-1,8,10-decanediol, 1,12-
  • Dodecanediol, dimer fatty alcohol and their higher homologs or isomers are also suitable.
  • higher-functional alcohols such as glycerol, trimethylolpropane, pentaerythritol or their homologs.
  • Suitable aliphatic alcohols have a molecular weight of 60 to
  • polystyrene resin also suitable as the polyol component are reaction products of low molecular weight polyfunctional alcohols with alkylene oxides, so-called polyethers.
  • 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'-dihydroxydiphenylpropane with Ethylene oxide, propylene oxide, butylene oxide or mixtures of two or more thereof.
  • polyether polyols are also suitable.
  • polyfunctional alcohols such as glycerol, trimethylolethane or trimethylolpropane, pentaerythritol or sugar alcohols with the said alkylene oxides to give polyether polyols.
  • polyether polyols which are suitable for the purposes of the invention are formed by polymerization of tetrahydrofuran (polyTHF).
  • polyTHF tetrahydrofuran
  • the polyether polyols are known and commercially available.
  • polyether polyols having a molecular weight of 100- 10,000 g / mol, preferably 400-6000 g / mol (number average molecular weight M n as measured by GPC vs. polystyrene standards in THF at 23 0 C), and especially polypropylene glycol or polyethylene glycol with 2 to 4 OH groups. It is possible to use random and / or block copolymers.
  • polyester polyols are suitable. Polyester polyols are either liquid at room temperature (glass transition temperature T g ⁇ 20 0 C) or solid. At room temperature solid polyester polyols are either amorphous (glass transition temperature T g > 20 0 C) or crystallizing.
  • Suitable crystallizing polyesters are, for example, those based on linear aliphatic dicarboxylic acids having at least 2 carbon atoms, preferably at least 6 carbon atoms, more preferably 6 to 14 carbon atoms in the molecule such as adipic acid, azelaic acid, sebacic acid and dodecanedioic acid, preferably adipic acid and dodecanedioic acid and linear diols having at least 2 carbon atoms , preferably at least 4 carbon atoms, more preferably 4-6 carbon atoms in the molecule, preferably with an even number of carbon atoms such as 1,4-butanediol and 1,6-hexanediol.
  • the polycaprolactone derivatives based on bifunctional starter molecules for example 1,6-hexanediol, are to be named as being particularly suitable.
  • Suitable amorphous polyester polyols are those based on adipic acid, isophthalic acid, terephthalic acid, ethylene glycol, neopentyl glycol and 3-hydroxy-2,2-dimethylpropyl-3-hydroxy-2,2-dimethylpropanoate.
  • Suitable polyester polyols which are liquid at room temperature are, for example, those based on adipic acid, ethylene glycol, 1,6-hexanediol and neopentyl glycol.
  • polyester polyols of oleochemical origin can be prepared, for example, by complete ring opening of epoxidized triglycerides of an at least partially olefinically unsaturated fatty acid-containing fat mixture with one or more alcohols having 1 to 12 carbon atoms and subsequent partial transesterification of the triglyceride derivatives to alkyl ester polyols having 1 to 12C atoms in the Alkyl residue can be produced.
  • OH-functional polyesters are generally known to the person skilled in the art and they are commercially available. available. Particularly suitable are two or three terminal OH-containing polyester polyols. Polyester polyols preferably have a molecular weight of about 100 to 6000 g / mol, in particular less than 5000 g / mol.
  • polyurethane polyols are reaction products of polyisocyanates, preferably diisocyanates, with polyols, especially diols.
  • the polyols can be selected from the above-mentioned group of polyols. The amounts are chosen so that terminally OH-terminated products are obtained.
  • the functionality of the PU polyols should preferably be between 2 and 4.
  • the molecular weight should be between 100 and 6000 g / mol.
  • Such OH-terminated PU polyols are known to the person skilled in the art.
  • polystyrene resin examples include polystyrene resin, polystyrene resin, polystyrene resin, polystyrene resin, polystyrene resin, polystyrene resin, polystyrene resin, polystyrene resin, polystyrene resin, polystyrene resin, polystyrene resin, polystyrene resin, polystyrene resin, polystyrene resin, polystyrene resin, polystyrene resin, polystyrene resin, polystyrene resin, polystyrene resin, polystyrene resin, polystyrene resin, polystyrene resin, polystyrene resin, polystyrene resin, polystyrene resin, polystyrene resin, polystyrene resin, polystyrene resin, polystyrene resin, polystyrene resin, polystyren
  • Suitable components B) are monohydroxy-functional polymers having a number average molecular weight of at least 500 g / mol.
  • M n 500 to 25,000 g / mol, particularly preferably 1000 to 10,000 g / mol and most preferably 2000 to 5000 g / mol. Most preferred is a number average molecular weight around 2500 g / mol.
  • Primary, secondary or tertiary hydroxyl groups can be used. Preference is given to primary or secondary hydroxyl groups.
  • PD Mw / Mn
  • B) consists essentially of mono-hydroxy-functional polyether polyols.
  • Such polyether alcohols B) are prepared in a manner known per se by alkoxylation of suitable starter molecules, for example by bases such as KOH or using double molecules.
  • cyanide catalysts DMC catalysis
  • DMC catalysis can be produced. This is described, for example, in US Pat. No. 5,158,922 (eg Example 30) and EP-A 0 654 302 (P. 5, Z. 26 to P. 6, Z. 32).
  • Suitable starter molecules for the preparation of the polyether alcohols B) are, for example, simple, low molecular weight monofunctional alcohols, organic monoamines having an N-H bond or any mixtures of such starter molecules.
  • Alkylene oxides which are suitable for the alkoxylation are, in particular, ethylene oxide and / or propylene oxide, which can be used in any order or also in a mixture in the alkoxylation.
  • Examples are the monohydroxy-functional polyalkylene oxide polyether alcohols having a statistical average of from 9 to 150, preferably from 20 to 70, alkylene oxide units per molecule, as are obtainable in a manner known per se by alkoxylation of suitable starter molecules (for example in Ulimanns Encyclopadie der ischen Chemie, 4th edition, Volume 19, Verlag Chemie, Weinheim pp. 31-38).
  • nonionic compounds are monofunctional polyalkylene oxide polyethers which have 50 to 100 mol% of propylene oxide units based on the total amount of oxyalkylene units.
  • Suitable starter molecules for such building blocks are saturated monoalcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, the isomeric pentanols, hexanols, octanols and nonanols, n-decanol, n-dodecanol, n Tetradecanol, n-hexadecanol, n-octadecanol, cyclohexanol, the isomeric methylcyclohexanols or hydroxymethylcyclohexane, 3-ethyl-3-hydroxymethyloxetane or tetrahydrofurfuryl alcohol, diethylene glyco
  • Alkylene oxides which are suitable for the alkoxylation reaction are, in particular, ethylene oxide and propylene oxide, which can be used in any desired order or else as a mixture in the alkoxylation reaction. Particular preference is given to components B) which are prepared only from propylene oxide as a chain-lengthening building block.
  • B) are, for example, monoalcohol-functional polytetramethylene glycol polyethers obtained by polymerization of tetrahydrofuran by means of cationic ring opening. Lich, as well as polycarbonate monoalcohols or mixtures thereof. Mono-alcohol-functional polyesters are also suitable, for example prepared by ring-opening polymerization of a lactone such as caprolactone based on a monofunctional starter. Also monohydric-functional siloxanes are suitable. A mixture of the polymers mentioned is also suitable. Very particular preference is B) but monofunctional polypropylene glycol.
  • An example of a very particularly preferred component B) is poly (propylene glycol) monobutyl ether (CAS No. [9003-13-8]) having a number average molecular weight (M n ) of 2500 g / mol.
  • Plasticizers flame retardants, thickeners or thixotropic agents, stabilizers, free-radical scavengers, binders, foam auxiliaries, antioxidants, light stabilizers, emulsifiers, plasticizers may be used as optional component (C) which is reactive neither with component (A) nor component (B) , Pigments, fillers and / or leveling agents are used.
  • the isocyanate-functional prepolymer A) is first prepared by reacting a diisocyanate preferably selected from the group consisting of diphenylmethane diisocyanate (MDI), particularly preferably from an MDI isomer mixture comprising 4,4'-MDI and 2,4 '.
  • a diisocyanate preferably selected from the group consisting of diphenylmethane diisocyanate (MDI), particularly preferably from an MDI isomer mixture comprising 4,4'-MDI and 2,4 '.
  • -MDI optionally containing small amounts of 2,2'-MDI
  • a polyether diol having a number average molecular weight between 100 g / mol and 2000 g / mol, preferably between 500 g / mol and 1000 g / mol according to those skilled in the known Process is prepared and then freed of known methods of the art of excess diisocyanate and this reaction product in excess with a component B) and optionally a component C) is reacted further.
  • component C) only after complete reaction of A) and B).
  • the isocyanate-functional prepolymer A) is first prepared by a diisocyanate preferably selected from the group diphenylmethane diisocyanate (MDI), more preferably from an MDI isomer mixture of 4,4'-MDI and 2,4 '-MDI, optionally containing small amounts of 2,2'-MDI, with a polyether diol having a number average molecular weight between 100 g / mol and 2000 g / mol, preferably between 500 g / mol and 1000 g / mol according to those skilled is prepared, is then reacted with a component B) in a further step, optionally C) is added and then freed from excess diisocyanate by methods known in the art.
  • the component B) are reacted simultaneously with the polyols which are used to prepare an isocyanate prepolymer with the diisocyanates.
  • a polyisocyanate preferably selected from the group diphenylmethane diisocyanate (MDI), reacted with a component B) according to the methods known in the art and then freed from excess isocyanate and this product in a further step, the temporally and spatially separated may be further reacted with the polyols listed above.
  • MDI diphenylmethane diisocyanate
  • the components A) to C) are preferably used in the following amounts ranges from 50 to 97 parts by weight, more preferably from 60 to 90 parts by weight of component A), from 3 to 50 parts by weight, more preferably 7 to 30 parts by weight of component B), 0 to 50 parts by weight, particularly preferably 0 to 20 wt .-% of component C).
  • reaction of A) and B) can be carried out in any order.
  • a polyurethane prepolymer is prepared from diisocyanate components with at least one polyol and the monohanol-functional component B) is mixed with the polyol.
  • B) the monohanol-functional component
  • Component C) can be added at any position and in any order.
  • Component C) may contain isocyanate-reactive as well as non-isocyanate-reactive components.
  • the suitable isocyanate-functional prepolymers according to the invention are prepared by known processes. This can for example be done at room temperature, it can also be applied to elevated temperatures.
  • the starting compounds generally react spontaneously with each other, but it may also be necessary to add catalysts such as organometallic compounds or organic amino compounds.
  • the known methods are used to remove the unreacted portions of monomeric diisocyanates. This can be done for example by distillation, by precipitating or intercepting the monomeric diisocyanates by low molecular weight reactive components. Preferred is the process of distillation using a short path evaporator.
  • the isocyanate-functional prepolymers according to the invention are intended to have a content of monomeric, unreacted diisocyanates of below 5% by weight, preferably below 3% by weight, in particular ders preferably below 1 wt .-%, most preferably below 0.2 wt .-% have.
  • the prepolymers according to the invention are isocyanate-functional because the polyisocyanate and / or isocyanate prepolymer component (A) is reacted with respect to their free NCO groups with a molar deficit of the monofunctional, NCO-reactive compound (B), so that after the reaction of (A) with (B) in the resulting prepolymer NCO groups remain, preferably between 1 to 5, more preferably between 1.8 to 4 NCO groups per prepolymer molecule.
  • Examples of use are the use in PU foams, coating compositions, lacquers, paints, adhesives, laminating materials, sealants, printing inks, inks, colorants, dyes, stains, corrosion and rust inhibitors, impregnating agents and graphic materials, for the production of wound dressing materials and incontinence products, for the preparation of pharmaceutical formulations, as lubricants, lubricants, release agents or coolants, in fuels, as an oil, in or as a diluent, cleaning or pretreatment agent, in foods of all kinds.
  • these isocyanate-setting products are liquid or solid. It is also possible that the isocyanate-functional prepolymers are dissolved in inert organic solvents.
  • isocyanate-functional prepolymers can be used as crosslinking constituents directly in reactive PU compositions, for example in 1K or 2K PU compositions, or they are reacted in further reaction steps with suitable compounds, for example the above-enumerated OH polyols, which can react with the NCO groups.
  • suitable compounds for example the above-enumerated OH polyols, which can react with the NCO groups.
  • Such PU prepolymers can then be used, for example, in the abovementioned PU compositions.
  • the isocyanate-functional prepolymers according to the invention can be used in reactive one- and two-component adhesives / sealants, assembly foams, casting compounds and in soft, hard and integral foams.
  • a significant advantage over the known reactive polyurethane compositions is the significantly lower proportion of occupationally hazardous, migratory, aromatic monomeric diisocyanates.
  • An advantage over plasticizer-containing systems is that the proportion of migratory plasticizers can be reduced or eliminated.
  • the PU compositions comprising the isocyanate-functional prepolymers of the invention may contain further additives. These may be, for example, catalysts, resins, solvents, pigments, stabilizers, adhesion promoters, dyes, leveling agents and act similar excipients. This can be selected by the person skilled in the art according to the purpose of use.
  • a preferred application of the PU compositions are reactive, one-component, moisture-curing hot melt adhesives.
  • These hotmelt adhesives may additionally comprise tackifying resins, adhesion-promoting additives, fillers, pigments, plasticizers, stabilizers and / or catalysts, waxes or mixtures thereof and other customary auxiliaries and additives.
  • tackifying resins e.g. Abietic acid, abietic acid esters, terpene resins, terpenphenol resins, phenol-modified styrenic polymers, phenol-modified ⁇ -methylstyrene polymers or hydrocarbon resins.
  • Suitable catalysts are the known organometallic and / or amine catalysts in amounts up to 2%, e.g. the organometallic compounds of tin, iron, titanium or bismuth, such as tin (II) salts of carboxylic acids or the dialkyl-tin (IV) carboxylates.
  • antioxidants it is possible to use, for example, the commercially available sterically hindered phenols and / or thioethers and / or substituted benzotriazoles or the sterically hindered amines of the HALS type.
  • Plasticizers may also be added in particular compositions. These are preferably plasticizers of the phthalic acid ester or naphthenic oils type.
  • a further embodiment of the invention uses the PU compositions of the invention as a laminating adhesive.
  • the reactive PU compositions can also be provided in solution, preferably in polar, aprotic solvents.
  • the preferred solvents have a boiling range (at atmospheric pressure) of about 50 0 C to 140 0 C. Particularly favored is dispensed solvent.
  • the second binder component can be selected according to the purpose and properties. These may be compounds which have at least two NCO-reactive functional groups. Examples of these are OH, SH, COOH, NH, NH 2 groups, preferably polyols.
  • the choice of polyols depends on the type of use of this adhesive / sealant composition, for example, hydroxy-functional polyols based on polyester, polyurethane polyether or polyolefin.
  • the NCO-terminated polyurethane prepolymer is preferred for higher molecular weight PU prepolymers implemented or is included in addition. Moisture crosslinking systems are then obtained.
  • the 1K or 2K polyurethane compositions suitable according to the invention are also to be used in particular as polyurethane foam.
  • polyurethane foam are mixtures of reactive polyurethanes which either form a foam when applied under the conditions of curing, for example by reaction with atmospheric moisture, or are mixtures containing foam-forming substances. These may be compressed gases which foam under reduced pressure, such as, for example, CO 2 , N 2 O, etc.
  • self-foaming PU compositions it is particularly expedient if high molecular weight, polymeric polyisocyanates are additionally present. They should contain no monomeric isocyanates, or less than 1 wt .-%.
  • Polyurethane foams according to the invention may contain further additives known to the person skilled in the art, for example adhesion promoters, plasticizers, wetting agents, fillers, flame retardants, foaming agents, fibers, masterbatches or pigments.
  • they contain catalysts which are suitable for a rapid curing reaction and foaming reaction. These are generally aliphatic tertiary amines, for example those which additionally carry reactive groups relative to the isocyanates.
  • very particularly preferred catalysts are the derivatives of morpholine, such as bis (morpholinopropyl) propylamine, morpholinopropylpyrrolidone or dimorpholinodiethyl ether (DMDEE) or di-2,6-dimethylmorpholinoethyl ether.
  • morpholine such as bis (morpholinopropyl) propylamine, morpholinopropylpyrrolidone or dimorpholinodiethyl ether (DMDEE) or di-2,6-dimethylmorpholinoethyl ether.
  • Assembly foams are produced at the place of their use, which is why one speaks of a local foam, in particular, it is here to moisture-curing one-component systems.
  • the composition to be foamed is usually in disposable pressure vessels.
  • These foams of polyurethane are mainly used in construction for sealing, dams and mounting, e.g. of joints, roof surfaces, windows and doors.
  • the NCO-terminated polyurethane prepolymers according to the invention can also be used in PU foam materials, for example as PU rigid foam for articles.
  • polyurethane compositions according to the invention as a constituent of kneadable molding compounds or casting compounds.
  • kneadable molding compounds or casting compounds are, for example, curable liquid or pasty materials which can also be used in the foodstuffs sector or in the medical field. Care must be taken to ensure that any necessary additional auxiliaries and additives have no health-endangering properties, in particular they should have the appropriate approval for use in medical products.
  • examples of such compositions are casting compounds for gluing of dialysis filters, potting compounds for bonding filters for liquid food, kneadable molding compositions for use as a plaster substitute in medical technology, or similar uses.
  • the principal compositions of such compositions are known, but the reactive PU compositions which can be used according to the invention give products which contain essentially no migration-capable, harmful polyamines and / or monomeric aromatic diisocyanates.
  • compositions according to the invention are particularly suitable in uses which can cause a danger to humans.
  • Examples include glued objects, such as films, labels, packaging that can come into contact with food.
  • Other examples include items in the medical field, such as patches, filters, medical support material, such as plaster substitute, and similar products.
  • articles made of PU materials are also concerned, which are in frequent contact with people, such as clothing, shoes, furniture surfaces or surfaces of attachments in motor vehicles.
  • the articles and products produced from the IK or 2K PU compositions according to the invention contain, after crosslinking, no migration-capable constituents derived from the isocyanates or their precursors. Even in later processing steps, such as sterilization, heating by the contents, storage in a humid atmosphere, no or only very small, from today's point of view uncritical proportions of migratory aromatic polyamine arise even in the longer term.
  • inventively suitable reactive isocyanate reaction products or PU prepolymers and the polyurethane compositions prepared therefrom are used in particular in reactive adhesives / sealants, potting compounds and in soft, hard and integral foams. The use happens, for example, in one or two-component form.
  • Products having a good crosslinking reaction and good mechanical properties are obtained without having to use additional oligomeric or monomeric isocyanates containing NCO groups.
  • An advantage over the known reactive one- and two-component adhesives / sealants, mounting foams, casting compounds as well as soft, hard and integral foams is the significantly lower proportion of occupationally hazardous and migratory monomeric diisocyanates and / or their hydrolysis products.
  • Another advantage over known monomer-poor reactive polyurethanes lies in the significantly reduced viscosity of the compositions according to the invention.
  • the viscosity is determined using the MCR 301 Rheometer from Anton Paar. The spindle / measuring cup system Z4 and CC27 was used. The viscosity was recorded as a function of shear rate and evaluated by the Carreau-Yasuda algorithm. The indicated viscosities at 50 ° C. are determined at shear rates of 50 s -1 . The indicated viscosities at 25 ° C. are determined at shear rates of 5 s -1 .
  • the solids contents were determined according to DIN-EN ISO 3251.
  • NCO contents were determined volumetrically in accordance with DIN-EN ISO 11909, unless expressly stated otherwise.
  • the stated molar masses are weight-average molar masses. They were determined by GPC analysis in tetrahydrofuran at a flow rate of 0.6 ml / min. The calibration was carried out by polystyrene standards.
  • Desmophen ® 1262 BD difunctional PPO polyether based on propylene glycol with an OH number of 260
  • Desmophen ® 1111 BD difunctional PPO polyether based on propylene glycol with an OH number of 111.4
  • Desmophen ® VPPU 28HS98 trifunctional PPO polyether based on glycerol with an OH number of 235
  • PPG Mono-Ol 2500 monofunctional propylene oxide based polyether started by n-butanol; number average molecular weight 2500 g / mol, (Aldrich, Taufkirchen, Germany)
  • Example 1 comparative experiment:
  • the number average molecular weight (determined by GPC) is 2200 g / mol.
  • Example 3 (comparative experiment): There are introduced 654.94 g of Desmodur 2460M ® at 80 0 C and a dewatered polyol mixture consisting of 66.39 g Desmophen ® 1262 BD, 192.40 g Desmophen ® 111 1 BD, and 86.26 g of the - Mophen ® VP PU 28HS98 added and while stirring at 80 0 C until a constant NCO content is achieved. Subsequently, the product is distilled at 180 0 C and 0.03 mbar via a short path evaporator.
  • the result is a product having an NCO content of 6.15 wt .-%, a content of free diisocyanate of 0.12 wt .-%, a viscosity of 28 490 mPas at 50 0 C and 817 700 mPas at RT and a calculated functionality of 2.33.
  • Desmodur 2460M ® at 80 0 C and submitted to a dewatered Polyolmi- research consisting of 92.47 g Desmophen ® 1262 BD, 268.04 g Desmophen ® 11 11 BD, 219,41 g
  • Example 4 it was possible to demonstrate that an isocyanate-containing prepolymer with identical functionality could be prepared in comparison to Example 3, but that this has a considerably reduced viscosity due to the use of the teaching according to the invention.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

La présente invention concerne des compositions de polyuréthane réactives, ainsi que leur fabrication et leur utilisation dans des masses coulées, des mousses de montage et des matériaux d'étanchéité/de collage réactifs à un ou à deux composants, ainsi que dans des mousses souples, rigides et intégrales.
PCT/EP2010/001125 2009-03-09 2010-02-24 Compositions de polyuréthane réactives WO2010102718A1 (fr)

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DE102018124332A1 (de) * 2018-10-02 2020-04-02 Ceracon Gmbh Zusammensetzung zur Herstellung wärmeaushärtender Polyurethanmassen
EP3988596A1 (fr) 2020-10-26 2022-04-27 Covestro Deutschland AG Composition de polyisocyanate modifié par polyéther
WO2022002808A1 (fr) 2020-06-29 2022-01-06 Covestro Deutschland Ag Composition de polyisocyanate modifiée par polyéther

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