EP2807206A2 - Isocyanates microencapsulés, leur procédé de production et leur utilisation dans des adhésifs - Google Patents

Isocyanates microencapsulés, leur procédé de production et leur utilisation dans des adhésifs

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Publication number
EP2807206A2
EP2807206A2 EP13702956.7A EP13702956A EP2807206A2 EP 2807206 A2 EP2807206 A2 EP 2807206A2 EP 13702956 A EP13702956 A EP 13702956A EP 2807206 A2 EP2807206 A2 EP 2807206A2
Authority
EP
European Patent Office
Prior art keywords
polyol
diisocyanate
polyamine
microcapsules
adhesive
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Withdrawn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
EP13702956.7A
Other languages
German (de)
English (en)
Inventor
Andreas ZILLESSEN
Andreas Ritter
Andreas Sengespeick
Lena KARSCH
Erich Jelen
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.)
Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
Original Assignee
Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
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 Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV filed Critical Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
Publication of EP2807206A2 publication Critical patent/EP2807206A2/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • C08G18/0838—Manufacture of polymers in the presence of non-reactive compounds
    • C08G18/0842—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents
    • C08G18/0861—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of a dispersing phase for the polymers or a phase dispersed in the polymers
    • C08G18/0871—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of a dispersing phase for the polymers or a phase dispersed in the polymers the dispersing or dispersed phase being organic
    • C08G18/0876—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of a dispersing phase for the polymers or a phase dispersed in the polymers the dispersing or dispersed phase being organic the dispersing or dispersed phase being a polyol
    • 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
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3206—Polyhydroxy compounds aliphatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4833—Polyethers containing oxyethylene units
    • 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
    • C08G18/703—Isocyanates or isothiocyanates transformed in a latent form by physical means
    • C08G18/705—Dispersions of isocyanates or isothiocyanates in a liquid medium
    • C08G18/707—Dispersions of isocyanates or isothiocyanates in a liquid medium the liquid medium being a compound containing active hydrogen not comprising water
    • 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
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • 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
    • C09J175/08—Polyurethanes from polyethers

Definitions

  • the present application is directed in a first aspect to a process for the preparation of liquid isocyanate-filled microcapsules.
  • this is a process for the microencapsulation of liquid isocyanate with polyol and / or polyamine.
  • the present invention is directed to correspondingly available microcapsules and adhesive systems with these microcapsules. These adhesive systems are used inter alia in methods for bonding two connecting sections, in particular for the cohesive bonding of wood.
  • the present application is directed to corresponding workpieces made of glued wood or wood with other materials, such as metal, glass or plastic. State of the art
  • Microencapsulation is a versatile and well-established process for the coating of liquids, but also solid or gaseous substances with polymeric or inorganic wall materials.
  • Capsules usually consist of a shell and a filling.
  • the shell is usually in solid form, while the filling may be gaseous, liquid and / or in solid form.
  • Microencapsulated materials are used in various fields, such as in chemistry, in pharmacy but also in environmental technology. In general, microencapsulation can encapsulate volatile substances as well as liquid or solid substances.
  • the properties of the materials can be changed by encapsulation, eg. B. to protect the materials from environmental influences, such as light, air or liquid, but also to improve the mechanical, chemical and physical properties of the encapsulated materials.
  • encapsulation offers the advantage of being able to use an easily handled material.
  • a microencapsulation in the adhesive for. B. to achieve a targeted activation of the adhesive.
  • Such activation of microencapsulated adhesives generally occurs either mechanically or thermally.
  • Typical mechanical activations include activation by pressure or shearing of the microcapsules.
  • thermal activation takes place in that the wall materials are melted, thus releasing the encapsulated materials.
  • auxiliary agents can be used by thermal activation to achieve bonding.
  • microencapsulations and their use for gluing and gluing are discussed in detail. Shown are also the possible activations of the microencapsulated adhesives.
  • Adhesive capsule systems used are adhesive adhesives based on solvent-based acrylate and rubber adhesives, which are microencapsulated using melamine-formaldehyde resins, polyamides, polyesters or complex coacervation.
  • microencapsulated reactive adhesives epoxy resin systems are used which are encapsulated by means of urea-formaldehyde or melamine-formaldehyde resins, in some cases also polyurea and polyurethanes.
  • EP 0 063 475 describes inter alia an adhesive system based on microencapsulated epoxy, which is suitable, inter alia, for fixing screws and nuts
  • polyurethane or polyurea components are microencapsulated and are known from WO 97/25360, which describes a one-component curable polyurethane adhesive in which the hardeners are encapsulated in a coating material
  • a polyurethane polyurethane adhesive is obtained by microencapsulating triols
  • Such microencapsulated systems are suitable, for example, for gluing car windows.
  • WO 02/1 8499 describes systems in which the catalysts, for.
  • tertiary amines such as those used for polyurethane production, encapsulated and mixed with magnetic nanoparticles.
  • the magnetic nanoparticles in the capsules allow breaking of the capsules upon application of a magnetic or electrical alternating field and thus a release of the catalysts. This allows the corresponding reaction, i. H. the polymerization of the polyurethanes can be accelerated.
  • WO 88/061 65 describes the encapsulation of isocyanate prepolymers from diisocyanants and polyols. In this case, blocked, encapsulated amines were used, which must be thermally activated for bonding. These heat sources may include microwave radiation or the like.
  • EP 0 671 423 likewise discloses hot-curing one-component polyurethane adhesives. These are also described by Kopp, R. et al, The Applied Macromolecular Chemistry, 223 (1 994), 61-67.
  • the microencapsulation is used to a spatial delimitation of the reactive components by the two-phase nature of the mixtures as well achieved an additional coating of the solid, finely divided polyisocyanate particles with a very thin diffusion barrier layer.
  • This diffusion barrier layer can be achieved by thermal activation of z. B. about 80 ° C activate.
  • solid oligomeric diisocyanates are present in the core of the capsules, while the barrier layer is achieved by reacting highly reactive polyamines with free isocyanate groups on the solid surface. From a melting point of 80-120 ° C., activation and thus conversion of the isocyanates into polyurethane begin.
  • microencapsulation of HDI for self-healing coatings has been described.
  • a problem with the use of reactive isocyanates is namely a reaction of the reactive group of the isocyanate with residual water, so that storage is not possible.
  • reactive groups of the isocyanate are necessary in order to carry out a mechanical activation without thermal activation, in particular to temperatures which lead to an undesired emission of substances.
  • the present application is directed to a process for the preparation of liquid isocyanate-filled microcapsules.
  • This process comprises the step of encapsulating liquid diisocyanates with polyol and / or polyamine.
  • the inventive method is characterized in that the encapsulation is carried out under exclusion of water with a wall formation of the microcapsule by reacting a polyol with the diisocyanate.
  • the process according to the invention is particularly preferably characterized in that the polyol and / or polyamine forms the continuous phase by emulsifying the diisocyanate.
  • diisocyanate means both monomeric and oligomeric diisocyanates, especially the diisocyanates are those of 2-ring isomers (monomers), 3-ring isomers, 4-ring isomers or 5-ring isomers.
  • the isocyanates are preferably those with at least partially reactive, unblocked groups.
  • the polyol and / or polyamine forms the continuous phase in which the microencapsulation takes place by then emulsifying the isocyanates.
  • This trained wall is an effective diffusion barrier to the polyol and / or polyamine and also to water. Accordingly, it is possible to provide microcapsules in which the diisocyanates are in liquid form. This microencapsulation makes it possible to use isocyanates in one-component adhesives in a targeted manner. PMDI as a liquid is z. B.
  • microcapsules according to the invention containing liquid isocyanates can be activated purely mechanically, a thermal activation alone is not necessary, in particular a thermal activation at high temperatures of about 80 ° C, such as over 1 00 ° C.
  • a thermal activation alone is not necessary, in particular a thermal activation at high temperatures of about 80 ° C, such as over 1 00 ° C.
  • the existing problems to overcome at the processing time.
  • moisture-curing systems such as the isocyanate system
  • the processing time is limited to approximately two times the cure time. Depending on the application, this leads to considerable problems and limitations and thus limits the scope of application of such adhesive systems.
  • an adhesive system based on the microcapsules according to the invention it is possible to perform a cold bonding of materials, in particular of wood. Furthermore, it is no longer necessary to use high-melting or blocked isocyanates. Rather, simple diisocyanates, such as. As technical diphenylmethane diisocyanate used. Ie. , the isocyanates present in the microcapsule have reactive groups. This has economic benefits. The encapsulation makes it possible to control the processing time, the curing and above all the penetration behavior of the adhesive system. Of course, the microcapsules are suitable for use in hot blending.
  • the diisocyanates are added dropwise to the initially introduced solution of polyol and / or polyamine and treated with appropriately suitable methods, for. B. emulsified by means of propeller stirrer or rotor-stator system to form corresponding microcapsules.
  • microcapsules such particles which are between 0, 1 ⁇ and 5 mm in size and consist of two phases.
  • the core phase also called filling, of the particle lies inside of this. It may consist of one or more substances including diisocyanate.
  • the particles furthermore have an outer wall phase, also referred to as a shell, which may consist of one or more substances, including reaction products of the polyol, polyamine with the diisocyanate, the core and wall phases consisting of different substances.
  • further adjuvants may be added to the diisocyanate and / or the polyol and / or polyamine.
  • these include, in particular, surfactants, cosurfactants, reaction accelerators, reaction restrainers, pH regulators, crosslinkers and / or viscosity reagents.
  • surfactants include, in particular, surfactants, cosurfactants, reaction accelerators, reaction restrainers, pH regulators, crosslinkers and / or viscosity reagents.
  • suitable compounds and compositions are known.
  • the polyol used for the encapsulation and / or polyamine is a polyol of the general formula I.
  • R 3 0 - [(CHR 1 ) x -O] nR 2 (I) wherein R 1 is independently selected from H, OH, OR 4 or C (O) - R 5, wherein
  • R 4 is independently selected from H or a Ci-C 6 alkyl group
  • R 5 is independently selected from H, OH, OR 4 or N (R 4 ) 2
  • R 2 and R 3 are independently selected from H or a hydrocarbon radical which may contain heteroatoms
  • x is independently an integer from 1 to 10;
  • n is an integer from 1 to 30.
  • the radicals R ; R 2 , R 3 , R 4 , R 5 are selected such that at least two hydroxy radicals are present in the polyol.
  • the polyol is a diol or triol having C to C 6 carbon atoms.
  • polyol is understood as meaning compounds which contain a plurality of hydroxyl groups (OH) .
  • Polyols may also be termed polyalcohols. Polyols may be present either linearly or cyclically. Polyols are, in particular, those alcohols which are an oligomer.
  • short-chain alcohols such as polyalkylene glycols or oligomeric glycerols but also particularly preferred are short-chain polyols, such as those having C 2 to C 6 carbon atoms, in particular C 2 , C 3 , C 4 , C 5 , C 6 carbon atoms having two to four OH groups per molecule.
  • a multiplicity of polyols can be used as the polyol component.
  • the OH groups can be both primary and secondary.
  • Suitable aliphatic alcohols include, for example, ethylene glycol, propylene glycol, butanediol-1, 4, pentanediol-1, 5, hexanediol-1, 6, heptanediol-1, 7, octanediol-1, 8 and their higher homologs or isomers, such as for the skilled person from a gradual extension of the hydrocarbon chain by one CH2 group or by introducing branches into the carbon chain.
  • higher-functional alcohols such as glycerol, trimethylolpropane, pentaerythritol and oligomeric ethers of said substances with themselves or in a mixture of two or more of said ethers with one another.
  • polyethers As a polyol component reaction products of low molecular weight polyfunctional alcohols with alkylene oxides, so-called polyethers can be used.
  • 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 or butylene oxide, or mixtures of two or more thereof.
  • polyether polyols having a molecular weight of from about 100 to about 1000, preferably from about 200 to about 5000.
  • polyether polyols such as those formed, for example, from the polymerization of tetrahydrofuran.
  • polyethers are reacted in a manner known to the person 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.
  • 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, 8, neopentyl glycol, 1, 4-hydroxymethylcyclohexane , 2-methyl-1,3-propanediol, glycerol, trimethylolpropane, hexanetriol-1, 2,6, butanetriol-1, 2,4-trimethylolethane, pentaerythritol, mannitol, sorbitol, methylglycosides, sugars, phenol, isononylphenol, resorcinol, hydroquinone, 1, 2,2- or 1, 1, 2-tris (hydroxyphenyl) ethane, ammonia, methylamine, ethylenediamine, tetra- or hexamethyleneamine, triethanolamine, aniline, phenylenediamine, 2,
  • polyester polyols having a molecular weight of from about 200 to about 1,000.
  • 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.
  • polyester polyols are 1,4-hydroxymethylcyclohexane, 2-methyl-1, 3-propanediol, butanetriol-1, 2,4, triethylene glycol, tetraethylene glycol, polyethylene glycol, dipropylene glycol, polypropylene glycol, dibutylene glycol and polybutylene glycol.
  • Other suitable polyester polyols can be prepared by polycondensation.
  • difunctional and / or trifunctional alcohols with a lower amount of dicarboxylic acids and / or tricarboxylic acids, or their reactive derivatives can be condensed to form polyester polyols.
  • Suitable dicarboxylic acids are, for example, adipic acid or succinic acid and their higher homologues having up to 16 C 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 are suitable.
  • the acids mentioned can be used individually or as mixtures of two or more thereof.
  • I in the context of the invention are particularly suitable polyester polyols of at least one of said dicarboxylic acids and glycerol, which have a residual content of OH groups.
  • 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 include, for example, the reaction products of polyfunctional, preferably difunctional, alcohols (optionally together with minor amounts of trifunctional alcohols) and polyfunctional, preferably difunctional, carboxylic acids.
  • polyfunctional, preferably difunctional, alcohols instead of free polycarboxylic acids (if possible), the corresponding polycarboxylic anhydrides or corresponding polycarboxylic acid esters can be used with alcohols having preferably 1 to 3 carbon atoms.
  • the polycarboxylic acids may be aliphatic, cycloaliphatic, aromatic or heterocyclic or both. They may optionally be substituted, for example by alkyl groups, alkenyl groups, ether groups or halogens.
  • polycarboxylic acids examples include succinic acid, adipic acid, suberic acid, Azelaic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, tetrachlorophthalic anhydride, endomethylenetetrahydrophthalic anhydride, glutaric anhydride, maleic acid, maleic anhydride, fumaric acid, dimer fatty acid or trimer fatty acid, or mixtures of two or more thereof.
  • minor amounts of monofunctional fatty acids may be present in the reaction mixture.
  • the polyesters may optionally have a low content of carboxyl end groups.
  • Lactones for example s-caprolactone or hydroxycarboxylic acids, for example co-hydroxycaproic acid, available polyesters, can also be used.
  • polyol component are polyacetals.
  • Polyacetals are understood as compounds obtainable from glycols, for example diethylene glycol or hexanediol, or their mixture 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, butanediol-1, 4 or hexanediol-1, 6, diethylene glycol, triethylene glycol or tetraethylene glycol or mixtures of two or more thereof with diaryl carbonates, for example diphenyl carbonate, or phosgene.
  • OH-bearing polyacrylates are also suitable as a polyol component.
  • These polyacrylates are obtainable, for example, by the polymerization of ethylenically unsaturated monomers which carry an OH group.
  • Such monomers are obtainable, for example, by the esterification of ethylenically unsaturated carboxylic acids and difunctional alcohols, the alcohol generally being present in a slight excess.
  • suitable ethylenically unsaturated carboxylic acids are, for example, acrylic acid, methacrylic acid, crotonic acid or maleic acid.
  • Corresponding OH-bearing esters 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.
  • Particularly preferred polyols are those selected from 1, 4-butanediol, 1, 3-propanediol, 1, 2-ethanediol, 1, 5-pentanediol, and 1, 3-butanediol and 1, 3-pentanediol.
  • polyamines can be used.
  • Polyamines are in particular those selected from a polyamine of the general formula (I I):
  • R 7 is independently selected H or a Ci-do alkyl group
  • n is an integer from 0 to 30;
  • the polyamine is a diamine or triamine having C to C 0 carbon atoms.
  • R 6 is preferably a C 1 -C 6 -alkyl group
  • R 7 is a C 1 -C 6 -alkyl group
  • / or R 8 is a C 1 -C 6 -alkyl group.
  • Particularly preferred polyamines are those selected from triethylenetetramine, diethylenetriamine, ethylenediamine, propanediamine, trimethylhexamethylenediamine, and spermidine.
  • diisocyanates are furthermore used, such as an isocyanate selected from the group comprising aliphatic and aromatic isocyanates, especially those selected from hexamethylene diisocyanate (HDI), isophorone diisocyanate (I PDI) and 1,4-cyclohexyl diisocyanate (CH DI).
  • Preferred aromatic polyisocyanates include polymeric diphenylmethane diisocyanate (PMDI), toluene diisocyanate (TDI) and diphenylmethane diisocyanate (MDI). Particularly preferred is the use of PMDI, also referred to as technical MDI.
  • PMDI is a heterologous mixture in which both 2-ring (monomer) and 3-ring, 4-ring or 5-ring isomers may be present.
  • suitable isocyanates are 1,5-naphthylene diisocyanate, 4,4'-diphenylmethane diisocyanate (MDI), hydrogenated MDI (H2MDI), xylylene diisocyanate (XDI), tetramethylxylylene diisocyanate (TMXDI), 4,4'-diphenyidimethylmethane diisocyanate, di- and tetraalkylenediphenylmethane diisocyanate,
  • MDI 4,4'-diphenylmethane diisocyanate
  • H2MDI hydrogenated MDI
  • XDI xylylene diisocyanate
  • TMXDI tetramethylxylylene diisocyanate
  • ethyl esters furthermore diisocyanates with reactive halogen atoms, such as 1-chloromethylphenyl-2, 4-diisocyanate, 1-bromomethylphenyl-2, 6- diisocyanate, called 3,3-bis-chloromethyl ether-4,4'-diphenyl diisocyanate.
  • reactive halogen atoms such as 1-chloromethylphenyl-2, 4-diisocyanate, 1-bromomethylphenyl-2, 6- diisocyanate, called 3,3-bis-chloromethyl ether-4,4'-diphenyl diisocyanate.
  • Sulfur-containing polyisocyanates are obtained, for example, by reacting 2 mol of hexamethylene diisocyanate with 1 mol of thiodiglycol or dihydroxydihexyl sulfide.
  • Further usable diisocyanates are, for example, trimethylhexamethylene diisocyanate, 1,4-diisocyanatobutane, 1,1,2-diisocyanatododecane and dimer fatty acid diisocyanate.
  • tetramethylene hexamethylene, undecane, dodecamethylene, 2,2,4-trimethylhexane, 1, 3-cyclohexane, 1,4-cyclohexane, 1, 3 or 1, 4 Tetramethylxylene, isophorone, 4,4-dicyclohexylmethane and lysine ester diisocyanate.
  • TMXDI tetramethylxylylene diisocyanate
  • m-TMXDI from Cyanamid.
  • Suitable at least trifunctional isocyanates are, for example, the tri- and oligomerization products of the polyisocyanates already mentioned above, as obtainable with formation of isocyanurate rings by suitable reaction of polyisocyanates, preferably of diisocyanates. If oligomerization products are used, in particular those oligomerization products having an average degree of oligomerization of about 3 to about 10 are suitable.
  • Isocyanates suitable for the preparation of trimers are the diisocyanates already mentioned above, with the trimerization products of the isocyanates HDI, MDI or I PDI being particularly preferred. Besides pure isocyanate, liquid prepolymers which have been prepared by reacting polyols and / or polyamines with a stoichiometric excess of isocyanates are also suitable.
  • the polyol and / or polyamine has a low solubility over the diisocyanate.
  • the process according to the invention allows the preparation of microcapsules having the following composition:
  • Nonionic surfactants of the type: polyalkylene glycol ethers, alkylpolyglycosides, octylphenol ethoxylates, nonylphenol ethoxylates, alkylglucosides, in particular polysorbates, polysorbitan monooleate, can be used as surfactants, and ionic surfactants are those of the type: alkylcarboxylates, alkylbenzenesulphonates, fatty alcohol sulphates.
  • crosslinkers known crosslinkers can be used.
  • the crosslinkers can also be used in combination, for. B. two different crosslinkers, each with up to 5 shares.
  • the abovementioned constituents of the microcapsules may vary.
  • the diisocyanate is introduced into the continuous phase, for example by a drop.
  • the continuous phase is stirred, for example by means of a propeller stirrer or rotor / stator system. Thereby, the diisocyanate can be emulsified in the continuous phase.
  • the particle size of the resulting capsules can be adjusted to the desired size, preferably those in the range from 20 to 5,000 ⁇ m, depending on the type of dispersion.
  • the present application is directed to microcapsules obtainable by the process of the present invention.
  • the present application is directed to microcapsules containing liquid isocyanate having a wall phase of isocyanate and polyol and / or polyamine.
  • microcapsules preferably have a composition as stated below: polyol and / or polyamine 1 0-30
  • the microcapsules according to the invention are preferably used in adhesive systems. These microcapsules are e.g. such that they are provided as adhesive microcapsule granules.
  • the adhesive system of the invention is one of adhesive microcapsule suspension or dispersion.
  • the microcapsules are in a continuous liquid phase, which consists of the second component of the adhesive before.
  • the second component may also consist of a solution or a dispersion of another adhesive system.
  • Another possibility of the adhesive system is an adhesive microcapsule suspension wherein the microcapsules are in a fusible, solid, continuous phase consisting of the second component of the adhesive.
  • the second component is a polyol or a polyamine as described herein.
  • the adhesive system of the invention may further contain other auxiliaries, in particular surfactants, cosurfactants, reaction accelerators, reaction retarders, pH regulators, fibers, fillers and / or viscosity regulators.
  • auxiliaries in particular surfactants, cosurfactants, reaction accelerators, reaction retarders, pH regulators, fibers, fillers and / or viscosity regulators.
  • the present invention is directed to a method for bonding two connecting sections, comprising applying a first adhesive system according to the invention comprising the microcapsules according to the invention.
  • This method is characterized in that a usually cohesive bonding occurs under the action of mechanical forces, such as pressure or shear or by ultrasound. That is, it has been found according to the invention that a pure mechanical activation is sufficient to allow the bonding of two connecting sections.
  • Thermal activation is not necessary with the present inventive adhesive system. In one embodiment, however, a thermal activation can additionally take place.
  • the method according to the invention for gluing is one in which activation takes place purely mechanically, in particular under the action of pressure, ultrasound and / or shear.
  • the activation of the adhesive system according to the invention by mechanical activation allows better processability, in particular with respect to the time of implementation, etc. Due to the fact that the isocyanate is present in liquid form in the microcapsules, is a thermal activation including melting of oligomeric isocyanate particles, as described in State of the art are known, not necessary. Rather, a simplified and improved activation and thus bonding can be achieved.
  • the inventive method allows a prolonged processing time of the adhesive system.
  • a cold bonding of two connecting sections is thus possible.
  • the connecting portions are those made of wood, metal or plastic for forming a workpiece made of wood / wood, wood / metal or wood / plastic.
  • the process according to the invention also overcomes the problems known from heat bonding in the use of isocyanate-containing adhesives, namely the emission of toxic isocyanates. Furthermore, cost reductions are possible in particular when using neither high-melting nor blocked isocyanates.
  • the present application is directed to a workpiece obtainable by a method according to the invention for bonding two connecting sections.
  • 1,4-butanediol 4,000 ml of 1,4-butanediol are introduced into a beaker and 5 ml of Tween 80 are added to a polysorbate and heated.
  • the diisocyanate used is an unmodified Desmodur Type 1 520 A2 from Bayer.
  • the PMDI is added to the 1,4-butanediol with stirring of an anchor and paddle stirrer at 700 rpm.
  • the exothermic reaction is controlled so that 60 ° C are reached after the end of the addition. This temperature is kept constant for a further 30 minutes.
  • 40 ml of triethylenetetramine are added to the postcapsule and cooled to 0 ° C over 30 min.
  • microcapsules produced are separated off by means of 25 ⁇ m filter paper and washed with 2-propanol until all the 1,4-butanediol has been removed.
  • the 2-propanol is removed by vacuum, e.g. withdrawn from the capsules in a rotary evaporator at 20 mbar and 40 ° C.
  • the capsules prepared in Example 1 are dispersed in polyethylene glycol (M w 1 .000 g / mol) at elevated temperature (50 ° C.) with a catalyst (for example dibutyltin dilaurate) and, if appropriate, admixed with further additives.
  • a catalyst for example dibutyltin dilaurate
  • the suspension can be used as a reactive one-component adhesive.
  • the capsules prepared in Example 1 are dispersed in a mixture of polyethylene glycol (Mw 1 .000 g / mol), polypropylene glycol (M n 425 g / mol) and polyethylene glycol (M n 400 g / mol) at elevated temperature (50 ° C.) a catalyst (eg., Dibutylzinndilaurat) and optionally mixed with other additives.
  • the suspension can be used as a reactive one-component adhesive.
  • capsules were prepared by dissolving diethylenetetraamine or 1,4-butanediol in water to encapsulate the liquid diisocyanate as set forth in Example 1.
  • the PMDI was encapsulated in a first batch with the addition of said amine in the presence of water. After working up and drying, it was already evident that the reactive cyanate had largely reacted with the residual water.
  • the preparation according to the invention of microcapsules in pure polyol / polyamine excludes water to capsules, which in a closed vessel after 1 8 months storage still 60 to 70% of the reactive NCO compared to the NCO Show content immediately after production.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Dispersion Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Dry Formation Of Fiberboard And The Like (AREA)

Abstract

Un premier aspect de l'invention concerne un procédé de production de microcapsules remplies d'isocyanate liquide. Il s'agit en particulier d'un procédé de microencapsulation d'isocyanate liquide avec un polyol et/ou une polyamine. L'invention concerne en outre des microcapsules pouvant être obtenues selon ce procédé ainsi que des systèmes d'adhésifs comprenant ces microcapsules. Ces systèmes d'adhésifs sont utilisés entre autres dans des procédés de collage de deux parties à assembler, notamment pour le collage de bois par liaison de matière. La présente invention concerne enfin des pièces correspondantes en bois collé ou en bois associé à d'autres matériaux, tels que du métal ou une matière plastique.
EP13702956.7A 2012-01-27 2013-01-28 Isocyanates microencapsulés, leur procédé de production et leur utilisation dans des adhésifs Withdrawn EP2807206A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE201210100672 DE102012100672A1 (de) 2012-01-27 2012-01-27 Mikroverkapselte Isocyanate und Verfahren zur Herstellung hierfür sowie deren Anwendung in Klebstoffen
PCT/EP2013/051545 WO2013110805A2 (fr) 2012-01-27 2013-01-28 Isocyanates microencapsulés, leur procédé de production et leur utilisation dans des adhésifs

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EP2807206A2 true EP2807206A2 (fr) 2014-12-03

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CN108057402A (zh) * 2018-02-02 2018-05-22 成都优创复材科技有限公司 一种制备含纯多元胺的微胶囊的方法及其微液滴化装置
CN112266758B (zh) * 2020-10-13 2022-07-01 深圳市安博瑞新材料科技有限公司 一种含微胶囊的聚氨酯单组份胶黏剂及其制备方法

Citations (1)

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WO2002048232A1 (fr) * 2000-12-14 2002-06-20 Bayer Aktiengesellschaft Adhesifs pour bois a base de prepolymeres a terminaison isocyanate

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DE3112054A1 (de) * 1981-03-27 1982-10-07 Basf Ag, 6700 Ludwigshafen Lagerstabile, hitzhaertbare stoffmischungen aus polyisocyanat und polyol, verfahren zu deren herstellung und verwendung
CA1217294A (fr) 1981-04-21 1987-01-27 Ronald L. Hart Colle a l'epoxy micro-encapsule
DE3343124A1 (de) * 1983-11-29 1985-06-05 Basf Ag, 6700 Ludwigshafen Bei raumtemperatur lagerstabile, durch hitzeeinwirkung haertbare stoffmischungen auf basis von verbindungen mit reaktiven wasserstoffatomen und polyisocyanaten, verfahren zu ihrer herstellung und ihre verwendung zur herstellung von formteilen
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DE3820705A1 (de) * 1988-06-18 1989-12-21 Basf Ag Lagerstabile, hitzehaertbare stoffmischungen, enthaltend oberflaechenmodifizierte polyisocyanate und verbindungen mit reaktiven wasserstoffatomen, und ihre verwendung zur herstellung von folien
DE3940271A1 (de) * 1989-12-06 1991-06-13 Bayer Ag Waermehaertbare reaktiv-pulver auf basis von polyurethanen
DE4407490A1 (de) 1994-03-07 1995-09-14 Bayer Ag Verfahren zur Herstellung heißhärtender Einkomponenten-Polyurethan-Reaktivmassen
ES2179224T3 (es) 1996-01-11 2003-01-16 Essex Specialty Prod Adhesivo de poliuretano curable en un componente.
DE10141674A1 (de) 2000-09-01 2002-03-14 Henkel Kgaa Reaktionsklebstoff mit mindestens einer mikroverkapselten Komponente

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WO2013110805A2 (fr) 2013-08-01
WO2013110805A3 (fr) 2013-10-31

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