WO2017162811A1 - Compositions durcissables à base de prépolymères contenant des groupes alcoxysilane - Google Patents

Compositions durcissables à base de prépolymères contenant des groupes alcoxysilane Download PDF

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WO2017162811A1
WO2017162811A1 PCT/EP2017/056963 EP2017056963W WO2017162811A1 WO 2017162811 A1 WO2017162811 A1 WO 2017162811A1 EP 2017056963 W EP2017056963 W EP 2017056963W WO 2017162811 A1 WO2017162811 A1 WO 2017162811A1
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alkoxysilane
silane
group
composition according
groups
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PCT/EP2017/056963
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German (de)
English (en)
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Jürgen Köcher
Thomas Klimmasch
Thomas FULSCHE
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Covestro Deutschland Ag
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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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—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
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/166—Catalysts not provided for in the groups C08G18/18 - C08G18/26
    • 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
    • C08G18/16—Catalysts
    • C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
    • C08G18/1875—Catalysts containing secondary or tertiary amines or salts thereof containing ammonium salts or mixtures of secondary of tertiary amines and acids
    • 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
    • C08G18/288—Compounds containing at least one heteroatom other than oxygen or nitrogen
    • C08G18/289—Compounds containing at least one heteroatom other than oxygen or nitrogen containing silicon
    • 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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
    • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes

Definitions

  • the present invention relates to curable compositions based on alkoxysilane group-containing prepolymers, a new class of catalysts for the crosslinking of alkoxy silane-containing prepolymers, and coatings, sealants and adhesives containing silane-functional prepolymers with alkoxysilane, preferably ethoxysilane, and said catalysts for curing.
  • compositions based on silane-functional polymers in particular silane-terminated prepolymers or STPs
  • STPs silane-terminated prepolymers
  • the crosslinking mechanism of these silanes occurs through a two-step process: First, an ambient alkoxysilane hydrolyzing an alkoxysilane group into a hydroxysilane group. This hydroxysilane group may condense in a second step with an alkoxysilane group or a second hydroxysilane group. After complete hydrolysis, a network of siloxane groups is formed.
  • silane-functional polymers thereby polymers are used, which are provided with different moisture-reactive silane groups. See, for example, F.D. Osterholtz and E.R. Pohl, J. Adhesion Sci. Technol. Vol 6, No 1, pages 127-149 (1992) and the publications WO 2013/174940, DE 10 2005 045 228 and EP 2 813 528.
  • silane group is understood as meaning a chemical group which comprises a silicon atom which on the one hand has at least one covalent silicon-carbon bond and which, on the other hand, is not linked via an oxygen atom to another silicon atom.
  • Groups containing at least two silicon atoms which are linked together via an oxygen atom, i. contain a (Si-O-Si) structural fragment are siloxane groups.
  • An essential criterion for the selection of the alkoxysilane groups is the reactivity of these groups, because due to the reactivity of these silane groups, the curing rate of the
  • Composition is significantly influenced.
  • methoxy and ethoxysilanes are used for the preparation and use of silane-functional polymers, in particular silane-terminated prepolymers, as a coating or adhesive.
  • an isocyanate-functional alkoxysilane can be bound to a polymer which has an iso cyanate-reactive group such as hydroxy, amino or m capto carries.
  • Another possibility for the preparation of silane-terminated (pre) polymers is the hydrosilylation of double bonds.
  • alkoxysilane-containing prepolymers there are other possibilities for the production of alkoxysilane-containing prepolymers.
  • polymeric polyisocyanates which are prepared by oligomerization of monomeric diisocyanates, with an alkoxysilane containing an isocyanate-reactive group.
  • Alkoxysilane-containing prepolymers can also be obtained by polymerization of epoxides, characterized in that the reaction mixture contains epoxides which comprise alkoxysilane groups.
  • EP 2 093 244 describes a process by means of which epoxides (such as, for example, propylene oxide and alkoxysilane-containing epoxides) alkoxysilane-containing polyethers are prepared.
  • the alkoxysilane groups can be lined up in any desired block-like manner in said polyether or can be randomly incorporated into the modified polymer chain. See especially Examples 1-4 of this document.
  • the alkoxysilanes are not only attached to the termini of the chains.
  • the publications DE 10 2010 038 768, DE 10 2010 038 774 and DE 10 2011 006 313 disclose further developments of the alkoxysilane-containing polyethers according to the process of EP 2 093 244.
  • DE 10 2010 038 768 and DE 10 2010 038 774 describe possibilities to stabilize or block the terminal OH groups of these alkoxysilane polyethers so that no undesired condensation of these OH groups with the alkoxysilanes can take place.
  • the alkoxysilane polyethers on which these patent applications are based are prepared in accordance with the process underlying EP 2 093 244 and modified at the terminal OH group.
  • longer-chain polyethers are used as starting molecules in the three aforementioned publications, otherwise the synthesis of the described polymers is likewise based on the teaching of EP 2 093 244.
  • alkoxysilane-containing polymers Another possibility for producing alkoxysilane-containing polymers is based on the reaction of unsaturated compounds. Once, one can react a polymeric compound with unsaturated groups with a hydrosilane as part of a hydrosilylation of the double bond.
  • many other groups are also conceivable. as mentioned in EP 2 01 1 834 in column [016].
  • Prepolymers known from the prior art contain at least one alkoxysilyl radical as silane functionality. Depending on the alkoxy radical contained and depending on the attachment, alkoxysilyl radicals can be differently reactive as the silane functionality. If a methylene group is located between the functional group and the alkoxysilyl radical and binds this methylene group to the silicon atom of the alkoxysilyl radical, this is referred to as alpha-alkoxysilanes. If there are three methylene groups (i.e., 1,3-propanediyl) between the functional group and the silicon atom of the alkoxysilyl group and bind to the silicon atom, this is called a gamma-alkoxysilane.
  • the alpha-silanes are particularly reactive, but often so reactive that these materials are difficult to process. In addition, they are expensive to produce, expensive and not very widely available commercially.
  • the methoxysilanes are much more reactive than the ethoxysilanes.
  • the disadvantage of using methoxysilane-functionalized polymers is that they release methanol when crosslinked with water. Methanol and its metabolites are toxic to humans and may cause undesirable effects.
  • the gamma-ethoxysilanes are preferred over the methoxysilanes, but are very slow in their reactivity. As a result, these materials can very often not be used technically, especially when crosslinking to the degree of dry air is required within a few hours. is taken.
  • Catalysts for the accelerated hydrolysis and condensation of alkoxysilane groups are well known.
  • the reaction can be catalyzed by acids, bases, organic tin compounds, amines, titanium, zirconium, aluminum, zinc, phosphorus or bismuth compounds. See, for example, F.D. Osterholtz and E.R. Pohl, J. Adhesion Sci. Technol. Vol 6, No 1, pages 127-149 (1992) and the published patent applications WO 2013/174940, DE 10 2005 045 228 and EP 2 813 528. These catalysts have been used in the past predominantly for the crosslinking of gamma-methoxysilanes.
  • Anions such as alkoxide or hydroxide are known catalysts for the crosslinking of alkoxy silanes.
  • the object of the present invention is therefore to provide compositions based on silane-functionalized (in particular silane-terminated) polymers or corresponding prepolymers which overcome the disadvantages of the prior art and rapid curing, preferably without the release of methanol, allows.
  • compositions comprising at least one silane-functional prepolymer having at least one alkoxysilane group (preferably at least two alkoxysilane groups) and at least one compound containing at least one hydrogen polyfluoride anion accomplish this task.
  • alkoxysilane group containing prepolymers especially of alkoxysilane-terminated prepolymers
  • a hydrogen polyfluoride anion as a catalyst leads to coating and adhesive and sealing systems that cure very quickly.
  • Particularly surprising is the fact that hereby also ethoxysilane-containing prepolymers can cure very quickly.
  • aliphatic is intended to mean optionally substituted, linear or branched, alkyl, alkenyl and alkynyl groups in which non-adjacent methylene groups (-CH 2 -) are substituted by heteroatoms, such as in particular oxygen and sulfur, or may be replaced by secondary amino groups.
  • alicyclic or “cycloaliphatic” is intended to mean optionally substituted, carbocyclic or heterocyclic compounds which do not belong to the aromatic compounds, such as, for example, cycloalkanes, cycloalkenes or oxa-, thia-, aza- or Thiazazykloalkane.
  • Specific examples thereof include cyclohexyl groups, cyclopentyl groups, and their derivatives interrupted by one or two or O atoms, e.g. Pyrimidine, pyrazine, tetrahydropyran or tetrahydro-dro.
  • Further examples of alicyclic groups are polyisocyanates having ring structures such as e.g.
  • it represents a substitution by halogen (especially -F, -Cl), Ci - «- alkoxy (especially methoxy and ethoxy), hydroxy, trifluoromethyl and trifluoromethoxy.
  • halogen especially -F, -Cl
  • Ci - «- alkoxy especially methoxy and ethoxy
  • hydroxy trifluoromethyl and trifluoromethoxy.
  • the term "low molecular weight" is intended to mean compounds whose molecular weight is up to 800 g / mol.
  • high molecular weight is intended to mean compounds whose molecular weight exceeds 800 g / mol.
  • polyisocyanate for aliphatic, aromatic or cycloaliphatic polyisocyanates having an NCO functionality of> 1, preferably> 2, in particular di- and triisocyanates.
  • monomer is intended to be a low molecular weight compound having functional groups involved in the construction of polymers and having a defined molecular weight.
  • polymer is intended to mean compounds in which monomers of the same or different type are repeatedly linked to one another and which may differ with regard to the degree of polymerization, molecular size distribution or chain length.
  • a polymer according to the present invention is thus a compound which has in its molecular structure at least one at least one repeating structural unit which has been covalently inserted into the molecular structure during polymer synthesis by participation of a monomer.
  • the term "prepolymer” is intended to mean a polymer having functional groups. Analogously to the polymer definition, at least two monomers of the same or different type are repeatedly linked to form the molecular structure of the prepolymer. The prepolymer is involved in the final construction of polymers that have a larger molecular weight than the prepolymer.
  • the prepolymer term thus encompasses polymeric compounds which are each reactive via at least one functional group contained in the molecule and can react to form a (preferably crosslinked) polymer to form a repeating unit.
  • the prepolymer term likewise includes preferred polyurethane compounds which contain at least one diisocyanate and at least one diol unit, or at least two diisocyanate or at least two hydroxyl or amino groups and via the functional groups of these "Alkoxysilane-functionalized prepolymers" contain at least one alkoxysilane group as functional group (optionally in addition to other functional groups).
  • "Alkoxysilane-functionalized prepolymers include both" alkoxysilane-functionalized polyurethane prepolymers "and" alkoxysilane ".
  • a blocked isocyanate is understood as meaning an addition compound of a highly reactive isocyanate with an alcohol (to a urethane) or an amine (to a urea) which reverts to alcohol or amine and isocyanate at higher temperatures.
  • Known blocking agents are, for example, acetoacetic acid, malonic esters, 3, 5-dimethylpyrazole, butanone oxime, secondary amines, caprolactam or various alcohols.
  • isocyanate group always includes both free isocyanate groups (-NCO) and blocked isocyanate groups.
  • Preferred silane-functional prepolymers having at least one alkoxysilane group have a number-average molecular weight Mn of at most 20,000 g / mol, preferably at most 15,000 g / mol, particularly preferably at most 10,000 g / mol.
  • Preferred silane-functional prepolymers having at least one alkoxysilane group have a number-average molecular weight Mn of at least 500 g / mol, preferably at least 800 g / mol.
  • the number average molecular weight Mn is determined by gel permeation chromatography (GPC) in tetrahydrofuran at 23 ° C. The procedure is as described in DI 55672-1: "Gel Permeation Chromatography, Part 1 - Tetrahydrofuran as Eluent" (SECurity GPC system from PSS Polymer Service, flow rate 1.0 ml / min, columns: 2xPSS SDV linear M, 8x300 mm, 5 ⁇ ; RI D detector). This polystyrene samples of known molecular weight are used for calibration. The calculation of the number average molecular weight is software-based. Baseline points and evaluation limits are defined in accordance with DIN 55672 Part 1 valid on the filing date of this patent application.
  • composition according to the invention preferably contains at least one silane-functional prepolymer containing at least one alkoxysilane group (preferably at least two alkoxysilane groups) of the general formula (I)
  • R 1 is an alkyl group having 1-8 C atoms
  • R 2 is an alkyl group having 2 to 12 C atoms
  • R 3 is a linear or branched, optionally cyclic, alkylene group having 2 to 12 C atoms, optionally with aromatic moieties, and optionally with one or more heteroatoms
  • a is a value of 1 or 2 or 3.
  • * in formula (I) stands for a free valency of the residue / structural fragment marked thereby, to which the prepolymer binds.
  • R 1 of the formula (I) is a methyl group or an ethyl group, particularly preferably a methyl group.
  • R 2 of the formula (I) for each radical O - of the formula (I) is independently a methyl group or an ethyl group, particularly preferably an ethyl group.
  • the alkoxy radicals of the alkoxy group of the silane-functional prepolymer are selected from ethoxy and / or methoxy groups, in particular ethoxy groups.
  • R 3 of the formula (I) is an alkylene group having 2 to 6 carbon atoms, in particular having 2 to 3 carbon atoms, particularly preferably propane-1,3-diyl.
  • At least at the terminus of the silane-functional prepolymer each binds an alkoxysilane group.
  • further alkoxysilane groups can be distributed over the polymer backbone and bound to the prepolymer.
  • silane-functional polyurethane prepolymers in which an alkoxysilane group (in particular of the formula (I)) in each case binds at the terminus.
  • Suitable silane-functionalized prepolymers are polyurethanes having at least one alkoxysilane group, polymeric polyisocyanates having at least one alkoxysilane group, polyether polyols having at least one alkoxysilane group, polyester polyols having at least one alkoxysilane group, polycarbonate polyols having at least one alkoxysilane group, polyacrylate polyols having at least one alkoxysilane group , Polymethacrylate polyols having at least one alkoxysilane group and polyurethane polyols having at least one Alkoxysi langrupp e.
  • composition according to the invention contains a compound having at least one hydrogen polyfluoride anion. This compound acts as a catalyst for crosslinking or
  • the silane-functional polymer is a silane-functional polyurethane prepolymer which is obtainable by reacting a silane which has at least one isocyanate-reactive group with a polyurethane polymer which has isocyanate groups (the latter also below: isocyanate-functional prepolymer).
  • This polyurethane prepolymer is prepared by the reaction of a compound having such cyanate-reactive groups or mixtures of such materials and polyisocyanates, the isocyanate groups being used in excess of the cyanate-reactive groups.
  • Useful polymeric polyols for the preparation of the prepolymers have a number average molecular weight M n of from 400 to 8000 g / mol, preferably from 400 to 6000 g / mol and more preferably from 400 to 3000 g / mol.
  • Their hydroxyl number is 22 to 400 mg KOH / g, preferably 30 to 300 mg KOH / g and particularly preferably 40 to 250 mg KOH / g and have an OH functionality of 1.5 to 6, preferably 1.7 to 5 and more preferably from 2.0 to 5 on.
  • Polyols for the preparation of the prepolymers are the organic polyhydroxyl compounds known in polyurethane coating technology, such as, for example, the conventional polyester polyols, polyacrylate polyols, polyurethane polyols, polycarbonate polyols, polyether polyols, polyester polyacrylate polyols and polyurethane polyacrylate polyol, polyurethane polyester polyols, polyurethane polyether polyols, polyurethane polycarbonate polyols, polyester polycarbonate polyols, phenol / formaldehyde resins , alone or in mixtures.
  • the conventional polyester polyols such as, for example, the conventional polyester polyols, polyacrylate polyols, polyurethane polyols, polycarbonate polyols, polyether polyols, polyester polyacrylate polyols and polyurethane polyacrylate polyol, polyurethane polyester polyols, polyurethane polyether polyols, polyure
  • polyesterpolyols Preference is given to polyesterpolyols, polyetherpolyols, polyacrylatepolyols or polycarbonatepolyols; polyetherpolyols, polyetherpolyols and polycarbonatepolyols are particularly preferred.
  • suitable polyether polyols are the polyaddition products of styrene oxides, ethylene oxide, propylene oxide, tetrahydrofuran, butylene oxide, epichlorohydrins, and their Mischadditions- and graft products, and the polyether polyols obtained by condensation of polyhydric alcohols or mixtures thereof and by alkoxylation of polyhydric alcohols, amines and amino alcohols called.
  • Suitable hydroxy-functional polyethers have OH functionalities of 1.5 to 6.0, preferably 1.8 to 3.0, OH numbers of 50 to 700, preferably 100 to 600 mg KOH / g solids and molecular weights M n of 106 to 4000 g / mol, preferably from 200 to 3500, such as alkoxylation of hydroxy-functional starter molecules such as ethylene glycol, propylene glycol, butanediol, hexanediol, trimethylolpropane, glycerol, pentaerythritol, sorbitol or mixtures these and other hydroxy-functional compounds with propylene oxide or butylene oxide.
  • Preferred polyether components are polypropylene oxide polyols, polyethylene oxide polyols and polytetramethylene oxide polyols.
  • polyester polyols are the on are the known polycondensates of di- and optionally tri- and tetraols and di- and optionally tri- and tetracarboxylic acids or hydroxycarboxylic acids or lactones.
  • free polycarboxylic acids it is also possible to use the corresponding polycarboxylic acid anhydrides or corresponding polycarboxylic acid esters of lower alcohols for the preparation of the polyesters.
  • diols examples include ethylene glycol, butylene glycol, diethylene glycol, triethylene glycol, polyalkylene glycols such as polyethylene glycol, furthermore 1,2-propanediol, 1,3-propanediol, butanediol (1,3), butanediol (1,4), hexanediol (l , 6) and isomers, neopentyl glycol or hydroxypivalic acid neo-pentylglycol ester, the latter three compounds being preferred.
  • polyalkylene glycols such as polyethylene glycol, furthermore 1,2-propanediol, 1,3-propanediol, butanediol (1,3), butanediol (1,4), hexanediol (l , 6) and isomers, neopentyl glycol or hydroxypivalic acid neo-pentylglycol este
  • polyols having a functionality of 3 may be used proportionally, for example trimethylolpropane, glycerol, erythritol, pentaerythritol, trimethylolbenzene or trishydroxyethyl isocyanurate.
  • Suitable dicarboxylic acids are, for example, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, cyclohexanedicarboxylic acid, adipic acid, azelaic acid, sebacic acid, glutaric acid, tetrachlorophthalic acid, maleic acid, fumaric acid, itaconic acid, malonic acid, suberic acid, 2-methylsuccinic acid, 3, 3-diethylglutaric acid, 2, 2-dimethyl-succinic acid.
  • Anhydrides of these acids are also useful, as far as they exist.
  • anhydrides are encompassed by the term "acid”.
  • Monocarboxylic acids such as benzoic acid and hexanecarboxylic acid may also be used, provided that the average functionality of the polyol is> 2.
  • Saturated aliphatic or aromatic acids are preferred, such as adipic acid or isophthalic acid.
  • trimellitic acid may be mentioned here.
  • Hydroxycarboxylic acids which may be used as reactants in the preparation of a hydroxyl-terminated polyester polyol include hydroxycaproic acid, hydroxybutyric acid, hydroxydecanoic acid, hydroxystearic acid and the like.
  • Useful lactones include caprolactone, butyrolactone and homologs.
  • polyester polyols based on butanediol and / or neopentyl glycol and / or hexanediol with adipic acid and / or phthalic acid.
  • the candidate polycarbonate polyols are prepared by reaction of carbonic acid derivatives, e.g. Diphenyl carbonate, dimethyl carbonate or phosgene with diols available.
  • diols come e.g. Ethylene glycol, 1,2- and 1,3-propanediol, 1,3- and 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, neopentyl glycol, 1,4-bishydroxymethylcyclohexane, 2-methyl-1,3- propanediol, 2,2,4- Trimethylpentandiol- 1, 3, dipropylene glycol, polypropylene glycols, dibutylene glycol, polybutylene glycols, bisphenol A, tetrabromobisphenol A, but also lactone-modified diols in question.
  • the diol component contains from 40 to 100% by weight of 1,6-hexanediol and / or hexanediol derivatives, preferably those having, in addition to terminal OH groups, ether or ester groups, e.g. Products obtained by reacting 1 mole of hexanediol with at least 1 mole, preferably 1 to 2 moles of ⁇ -caprolactone or by etherification of hexanediol with itself to di- or Trihexylenglykol. Polyether-polycarbonate polyols can also be used.
  • polycarbonate polyols based on dimethyl carbonate and hexanediol and / or butanediol and / or ⁇ -caprolactone.
  • polycarbonate polyols based on dimethyl carbonate and hexanediol and / or ⁇ -caprolactone.
  • low molecular weight polyols in the molecular weight range from 62 to 400 g / mol for the preparation of the isocyanate-containing prepolymers.
  • Suitable low molecular weight polyols are short chain, i. 2 to 20 carbon atoms, aliphatic, araliphatic or cycloaliphatic diols or triols.
  • diols examples are ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, neopentyl glycol, 2-ethyl-2-butylpropanediol, trimethylpentanediol, 2,2,4-trimethyl-1,3-pentanediol, positionally isomeric diethyloctanediol, 1,3-butylene glycol, cyclohexanediol, 1,4-cyclohexanedimethanol, 1,6-hexanediol, 1,2- and 1,4-cyclohexanediol, hydrogenated bisphenol A (2,2-bis (4-hydroxycyclohexyl) propane), 2,2-dimethyl-3-hydroxypropionic acid (2,2-dimethyl-3-
  • 1,4-butanediol 1,4-cyclohexanedimethanol and 1,6-hexanediol.
  • suitable triols are trimethylolethane, trimethylolpropane or glycerol, preference is given to trimethylolpropane.
  • the stated polyols can be used alone or in a mixture.
  • the above-mentioned isocyanate-reactive compounds can be reacted with all diisocyanates, aromatic as well as aliphatic before the actual prepolymerization to urethane-modified hydroxyl compounds.
  • Suitable isocyanate-containing components are aromatic, aliphatic and cycloaliphatic diisocyanates and mixtures thereof.
  • Suitable diisocyanates are compounds of the formula PIC (NCO) 2 having an average molecular weight below 400 g / mol, wherein PIC is a C6-C15 aromatic hydrocarbon radical, a C4-C12 aliphatic hydrocarbon radical or a cyclo-aliphatic Ce-Cn-carbon radical first, for example Diisocyanates from the series butane diisocyanate, 1,5-pentanediisocyanate (PDI), 1,6-hexanediisocyanate (hexamethylene diisocyanate, HDI), 4-isocyanatomethyl-1,8-octane diisocyanate (triisocyanatononane, TIN) 4,4'-methylenebis (cyclohexyl isocyanate) , 3,5,5-trimethyl-1-isocyanato-3-is
  • polymeric polyisocyanates mentioned below, as well as, for example, in the form of their derivatives such as urethanes, biurets, allophanates, uretdiones, isocyanurates and trimers and mixed forms of these derivatizations.
  • This urethanization can be accelerated by catalysis.
  • the person skilled in the known urethanization catalysts such as organotin compounds, Bismuthtagen, zinc compounds, titanium compounds, zirconium compounds or amine catalysts in question.
  • this catalyst component if used, in amounts of 0.001 wt .-% to 5.0 wt .-%, preferably 0.001 wt .-% to 0.1 wt .-% and particularly preferably 0.005 wt .-% to 0 , 05 wt .-% based on the solids content of the process product used.
  • the urethanization reaction is carried out at temperatures of 20 ° C to 200 ° C, preferably 40 ° C to 140 ° C and more preferably from 60 ° C to 120 ° C.
  • the reaction is continued until a (preferably complete) conversion of the isocyanate-reactive groups is achieved.
  • the course of the reaction is usefully monitored by checking the NCO content and is complete when the corresponding theoretical NCO content is reached and constant. This can be monitored by suitable measuring devices installed in the reaction vessel and / or by analyzes on samples taken. Suitable methods are known to the person skilled in the art. These are, for example, viscosity measurements, measurements of the NCO content, the refractive index, the OH content, gas chromatography (GC), nuclear magnetic resonance spectroscopy (NMR), infrared spectroscopy (IR) and near near-infrared spectroscopy (NIR).
  • the NCO content of the mixture is determined titrimetrically.
  • the process is preferably carried out in a stirred reactor. If the conversion of polyisocyanate was not complete, unreacted polyisocyanate can be removed from the prepolymer by continuous distillation.
  • a continuous distillation process is understood here to mean a process in which only a respective subset of the prepolymer from the previously described process step is briefly exposed to an elevated temperature, while the amount not yet in the distillation process remains at a significantly lower temperature.
  • elevated temperature is to be understood as meaning the temperature required for the evaporation of the volatile constituents at a correspondingly selected pressure.
  • the distillation at a temperature of less than 170 ° C, more preferably 110 to 170 ° C, most preferably 125 to 145 ° C and at pressures of less than 20 mbar, more preferably less than 10 mbar, most preferably at 0.05 to 5 mbar.
  • the temperature of the prepolymer-containing reaction mixture not yet in the distillation process is preferably from 0 ° to 60 ° C., particularly preferably from 15 ° to 40 ° C. and very particularly preferably from 20 ° to 40 ° C.
  • the temperature increase between the distillation temperature and the temperature of the prepolymer-containing reaction mixture not yet in the distillation process is preferably at least 5 ° C., particularly preferably at least 15 ° C., very particularly preferably from 15 ° to 40 ° C.
  • the distillation is preferably conducted at such a rate that a volume increment of the polymer-containing reaction mixture to be distilled is subjected to the distillation temperature for less than 10 minutes, more preferably less than 5 minutes and then re-heated to the starting temperature of the pre-treatment by active cooling.
  • polymer-containing reaction mixture is brought before the distillation.
  • the T emp eraturb el treatment is carried out such that the temperature of the reaction mixture before distillation or the prepolymer after distillation relative to the distillation temperature used at least 5 ° C, more preferably at least 15 ° C, most preferably 15 ° to 40 ° C is higher.
  • Preferred continuous distillation techniques are short-path, falling-film and / or thin-film distillation (see, for example, Chemischetechnik, Wiley-VCH, Volume 1, 5th Edition, pages 333-334).
  • the continuous distillation technique used is preferably thin film distillation with the abovementioned parameters.
  • Another possibility is the provision of a silane-functionalized, polymeric polyisocyanate having at least one alkoxysilane group as a silane-functional prepolymer which is preferred according to the invention in the context of the second embodiment.
  • Said silane-functionalized polymeric polyisocyanates can be synthesized by the direct reaction of polymeric polyisocyanates with alkoxysilanes bearing an isocyanate-reactive group such as amino, mercapto or hydroxy.
  • Aromatic, aliphatic, aliphatic or cycloaliphatic polymeric polyisocyanates with an NCO functionality> 2 are used as suitable polymeric polyisocyanates.
  • These may also have iminooxadiazinedione, isocyanurate, uretdione, urethane, allophanate, biuret, urea, oxadiazinetrione, oxazolidinone, acylurea and / or carbodiimide structures.
  • Suitable diisocyanates for preparing the polymeric polyisocyanates are any diisocyanates which are obtainable by phosgenation or by phosgene-free processes, for example by thermal urethane cleavage, whose isocyanate groups are bonded via optionally branched aliphatic radicals to an optionally further substituted aromatic, such as preferably 1, 4-butane diisocyanate, 1 , 5-pentane diisocyanate (PDI), 1,6-hexane diisocyanate (hexamethylene diisocyanate, HDI), 4-isocyanatomethyl-1,8-octane diisocyanate (triisocyanatononane, TIN) 4,4'-methylenebis (cyclohexyl isocyanate), 3.5 , 5-trimethyl-1-so-cyano-3-cyanoatomethyl eye-lohexane (isophorone diisocyanate, IPDI), 2,4- and / or 2,
  • polymeric polyisocyanate components from the aforementioned diisocyanates by means of known per se modification reactions by reacting a portion of the original isocyanate present in the starting isocyanate groups to form polymeric Polyi so cyanatmol molecules, which consist of at least two Diso cyanatmolekülen.
  • Suitable such modification reactions are, for example, the customary processes for the catalytic oligomerization of isocyanates to form uretdione, isocyanurate, iminooxadiazinedione and / or oxadiazinetrione structures or for the biuretization of diisocyanates, as described, for example, in US Pat.
  • Laas et al. J. Prakt. Cham. 336, 1994, 185-200 in DE-A 1 670 666 and EP-A 0 798 299 are described by way of example.
  • silane-functionalized prepolymers for the preparation of inventive silane-functionalized prepolymers (in particular silane-functionalized prepolymers of the first and second embodiments) are well known to those skilled.
  • Formula I II means X identical or different alkoxy or alkyl radicals, which may also be bridged, but at least one alkoxy radical must be present on each Si atom, Q is a di functional linear or branched aliphatic radical and Z is an alkoxy radical 1 to 10 carbon atoms.
  • the use of such aspartic acid esters is preferred. Examples of particularly preferred aspartic acid esters are diethyl N- (3-triethoxysilylpropyl) aspartate, diethyl N- (3-triethoxysilylpropyl) aspartate and diethyl N- (3-dimethoxymethylsilylpropyl) aspartate. Very particular preference is given to the use of ⁇ ⁇ - (3-triethoxysilylpropyl) aspartic acid diethyl ester.
  • the ethoxysilane derivatives are preferred over the methoxy derivatives.
  • the alkoxysilyl group-containing prepolymers used according to the invention are prepared using isocyanate-reactive alkoxysilane compound by reacting isocyanate-functional prepolymer (preferably those of the first embodiment (isocyanate-functional polyurethane) or the second embodiment (polymeric polyisocyanates)) to the silane-terminated prepolymer by reaction with an isocyanate-reactive alkoxysilane compound.
  • isocyanate-functional prepolymer preferably those of the first embodiment (isocyanate-functional polyurethane) or the second embodiment (polymeric polyisocyanates)
  • Said reaction with isocyanate-reactive alkoxysilanes is carried out within a temperature range of 0 ° C to 150 ° C, preferably from 20 ° C to 120 ° C, the proportions are generally selected so that per mole of NCO groups used 0.8 to 1 , 3 moles of the isocyanate-reactive alkoxysilane compound are used, preferably 1.0 mole of isocyanate-reactive alkoxysilane compound per mole of NCO groups used.
  • the silane-functional prepolymer is a silane-functional prepolymer obtainable by the reaction of an isocyanatosilane with a polymer which has isocyanate-reactive functional end groups, in particular hydroxyl groups, mercapto groups and / or amino groups.
  • Preferred polymers which contain functional groups which are reactive toward isocyanate groups are the abovementioned polymeric polyols, very particularly polyether, polyester, polycarbonate and polyacrylate polyols, and also polyurethane polyols prepared from polyisocyanates and the stated polyols. It is also possible to use mixtures of all the stated polyols.
  • Isocyanate-functional alkoxysilane compounds are in principle suitable for all alkoxysilane-containing monoisocyanates having a molecular weight of from 140 g / mol to 500 g mol.
  • examples of such compounds are isocyanatomethyltrimethoxysilane, isocyanatomethyltriethoxysilane, (isocyanatomethyl) methyldimethoxysilane, (isocyanatomethyl) methyldiethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropylmethyldimethoxysilane, 3-isocyanatopropyltriethoxysilane and 3-isocyanatopropylmethyldiethoxysilane.
  • Preferred here is the use of 3 -I so cyanatopropyltrimethoxy silane or 3-isocyanatopropyltriethoxysilane, very particularly preferably the use of 3-iso cyanatopropyltri ethoxy silane.
  • isocyanate-functional silanes which have been prepared by reacting a diisocyanate with an amino or thiosilane, as described in US Pat. No. 4,146,585 or EP-A 1 136 495.
  • the reaction of the isocyanatosilanes with the polyols preferably used is carried out in the same manner as described above for the preparation of the isocyanate-containing prepolymer from the polyisocyanate component with the polyol component.
  • the ratio of the NCO groups of the isocyanatosilane to the isocyanate-reactive groups, preferably the hydroxyl groups of the polyols, is between 0.5: 1 and 1: 1, preferably between 0.75: 1 and 1: 1, very particularly preferably between 0 , 9: 1 and 1: 1.
  • the silane functional polymer is a silane functional polymer obtainable by a hydrosilylation reaction of double bond polymers, for example, poly (meth) acrylate polymers and polyether polymers, especially allyl terminated polyoxyalkylene polymers described, for example, in US 3,071,751 and US 6,207,766.
  • composition according to the invention comprises at least one compound having at least one hydrogen polyfluoride anion for the crosslinking of silane-functional prepolymers.
  • the compound having at least one hydrogen polyfluoride anion acts as a catalyst for crosslinking the alkoxysilane groups of the prepolymer.
  • the compound having at least one hydrogen polyfluoride anion is preferably selected from at least one compound of the group formed from adducts of at least one fluoride anion and hydrogen fluoride (hydrogen polyfluorides), more preferably selected from at least one adduct of at least one fluoride anion and hydrogen fluoride.
  • Hydrogen polyfluorides are sometimes commercially available or can be prepared in a simple manner and in any stoichiometry by mixing appropriate fluorides with the desired amount of HF.
  • Hydrogenpolyfluoride are unproblematic.
  • composition according to the invention contains as compound with at least one fluoride anion at least one compound of the general formula II.
  • M represents an equivalent of one or more cations optionally bearing a charge number equal to n as cationic charge and causes the electroneutrality of the compound of formula (II)
  • n stands for the number 1
  • m stands for a number from 1 to 5. It is inventively preferred if m according to formula (II) is a number from 1 to 5.
  • n is 1 and m is 1.
  • M is an equivalent of one or more cations that preserve the electroneutrality of the compound.
  • cations which may be used are alkali metal or alkaline earth metal cations and tetraalkylammonium and tetraalkylphosphonium compounds, the alkyl groups of the tetraalkylammonium or tetraalkylphosphonium groups preferably being linear or branched, optionally cyclic, alkylene groups composed of 2 to 12 C atoms , consist.
  • the composition according to the invention comprises at least one compound of the formula (II) in which M is a tetraalkylammonium or tetraalkylphosphonium or piperidinium-1-spiro-1'-pyrrolidinium ion, in particular a tetrabutylammonium or a tetrabutylphosphonium ion.
  • catalyst at least one compound of the formula (II-1): in which E is N or P, R is the same or different, optionally branched, optionally cyclic, optionally substituted (O, N, halogen) aliphatic, araliphatic and aromatic radicals each having 1 to 25 C atoms and m is: m is a number between 0 and 5, more preferably m is 0 or 1, most preferably m is 1.
  • catalysts compounds of formula (II-1) are used, wherein E is N and P, R is the same or different, optionally branched, optionally substituted (O, N, halogen) (cyclo) aliphatic and araliphatic radicals each having 1 to 20 C atoms and m is a number between 1 and 5, most preferably m is 1.
  • R is identical or different, optionally branched, aliphatic radicals each having 1 to 15 C-atoms, R 'is optionally branched, aliphatic radicals having 1 to 4 C-atoms and m is a number from 1 to 5, very particularly preferably m is 1.
  • Preferred compounds having at least one hydrogen polyfluoride anion are selected from at least one compound of the group which is formed from tetrabutylammonium hydro- gendifluoride, tetrabutylphosphonium hydrogendifluoride, piperidinium-1-spiro-1'-pyrrolidinium hydrogendifluorid.
  • the total amount of compound having at least one hydrogen polyfluoride anion on the composition according to the invention is from 0.1 to 10% by weight, preferably from 0.2 to 5% by weight and more preferably from 0.2 to 3% by weight.
  • the compound having at least one hydrogen polyfluoride anion may also be diluted with a solvent.
  • a solvent it is possible or in some cases even preferred to use mixtures of different compounds with at least one fluoride anion.
  • composition according to the invention when it is carried out as a coating agent, may additionally contain auxiliaries and / or additives known in coating technology, such as stabilizers, light stabilizers, fillers, pigments, matting agents, flame retardants, water scavengers, adhesion promoters, leveling agents or rheological aids. If necessary, conventional inorganic or organic colorants and / or effect pigments can also be present in the coating system in coating technology.
  • these aids are admixed with the inventive mixture of silane component and compound having at least one hydrogen polyfluoride anion (catalyst).
  • the amounts of these excipients may also be significantly lower and are determined by the intended application.
  • the amount of auxiliaries may be> 50%, based on the mixture of silane component and catalyst used, very low when used for example Topcoats.
  • the composition according to the invention may additionally contain solvents.
  • solvents examples include 2-ethylhexanol, acetone, 2-butanone, methyl isobutyl ketone, butyl acetate, ethyl acetate, 1-methoxy-2-propyl acetate (MPA), 3-methoxy-1-butyl acetate, propylene-n-butyl ether, toluene, methyl ethyl ketone, xylene , 1,4-dioxane, diacetone alcohol, N-methylpyrrolidone, dimethylacetamide, dimethylformamide, dimethyl sulfoxide, methyl ethyl ketone, solvent naphtha (hydrocarbon mixture) or any mixtures of such solvents.
  • Preferred solvents here are the solvents customary in polyurethane chemistry, such as butyl acetate, ethyl acetate, 1-methoxy-2-propyl acetate (MPA), 3-methoxy-1-butyl acetate, propylene-n-butyl ether, toluene, 2-butanone, xylene, 1,4-dioxane, ethyl ethyl ketone, N-methyl pyrrolidone, dimethylacetamide, dimethylformamide, methyl ethyl ketone, solvent naphtha (hydrocarbon mixture) or any mixtures of such solvents.
  • solvents customary in polyurethane chemistry such as butyl acetate, ethyl acetate, 1-methoxy-2-propyl acetate (MPA), 3-methoxy-1-butyl acetate, propylene-n-butyl ether, toluene, 2-butanone,
  • solvents such as butyl acetate, 1-methoxy-2-propyl acetate (MPA), 3-methoxy-1-butyl acetate, ethyl acetate, propylene-n-butyl ether, methyl ethyl ketone, toluene, xylene, solvent naphtha (hydrocarbon mixture). as well as their mixtures.
  • MPA 1-methoxy-2-propyl acetate
  • 3-methoxy-1-butyl acetate 3-methoxy-1-butyl acetate
  • ethyl acetate propylene-n-butyl ether
  • methyl ethyl ketone propylene-n-butyl ether
  • toluene xylene
  • solvent naphtha hydrocarbon mixture
  • compositions of the invention can be used as coating agents, adhesives and sealants.
  • the formulations for coating can be used as a pigment-free system, i. be formulated as a clearcoat, as well as a pigmented system.
  • Pigment-free systems can be used as clearcoats, for example for the coating of metal surfaces in automotive finishing (automotive OEM and automotive refinishing).
  • Coating formulations with fillers and / or pigments can be used in the field of corrosion protection.
  • formulations of the systems according to the invention in pigmented form can also be used as adhesives or sealants.
  • the invention additionally relates to the use of a compound having at least one hydrogen polyfluoride anion, for crosslinking alkoxysilane-group-containing, in particular alkoxysilane-terminated polymers with moisture, more particularly for crosslinking ethoxy silane groups.
  • Preferred polymers and preferred compounds having at least one hydrogen polyfluoride anion are those defined in the first subject of the invention (vide supra).
  • a further subject of the invention is a method for bonding, sealing or coating a substrate, comprising a step in which a composition of the first subject of the invention is applied to a substrate and containing a further step in which the composition applied to the substrate in the presence of Moisture is cured by crosslinking of the silane-functional prepolymer.
  • composition of the first subject of the invention prior to application to the substrate by mixing i) at least one catalyst composition containing at least one compound having at least one Hydrogenpolyfluoridanion and ii) at least one prepolymer containing at least one silane-functional prepolymer having at least one Alkoxysilan interven will be produced.
  • Said catalyst composition and prepolymer composition preferably contain said fluoride compound or said prepolymer, each in its own carrier.
  • the carrier comprises at least one solvent or dispersant.
  • the application of the composition according to the invention of the first subject of the invention can by all the usual application methods, such as. As spraying, knife coating, brushing, pouring, dipping, watering, trickling or rolling done.
  • the substrate to be coated can rest as such, wherein the application device or -anläge is moved.
  • the substrate to be coated can also be moved, with the application system resting relative to the substrate or being moved in a suitable manner.
  • the curing of the applied composition according to the invention can take place after a certain rest period. This rest period is used for example for the course and degassing of the paint layers or for the evaporation of volatile components such as solvents.
  • the rest period can be supported and / or shortened by the application of elevated temperatures and / or reduced air humidity.
  • the thermal curing of the formulation is carried out by methods such as heating in a convection oven or irradiation with IR lamps. Here, the thermal curing can also be done gradually.
  • Another preferred curing method is near infrared
  • the thermal curing is carried out at a temperature of 25 ° C to 200 ° C, preferably at a temperature of 25 ° C to 100 ° C, more preferably at a temperature of 25 ° C to 80 ° C.
  • the time of this curing can vary between 1 min and 24 h, depending on the application and temperature, especially at temperatures ⁇ 40 ° C, even longer curing times come into question.
  • Substrates that can be coated or glued or sealed are metal, concrete, ceramic, Hol /. Paper, textile or plastic.
  • the application temperature is preferably ⁇ 100 ° C due to the active catalyst.
  • a further subject of the invention is therefore a kit-of-parts comprising in a first container at least one compound having at least one fluoride anion (in particular a catalyst composition comprising at least one compound having at least one hydrogen polyfluoride anion and separately in a second container at least one silane-functional prepolymer having at least an alkoxysilane group (in particular a prepolymer composition comprising at least one silane-functional prepolymer having at least one alkoxysilane group).
  • the features characterized as preferred for the first subject of the invention, in particular the said prepolymer and the said compound having at least one fluorine anion, are also preferred for the other subjects of the invention.
  • the flow times were determined in accordance with DIN EN ISO 2431 ("Determination of the flow time with flow cups”).
  • the drying times (Tl, T3 and T4) were determined in accordance with DIN EN ISO 9117-5 (Drying test Part 5: Modified Bandow-Wolff process).
  • the silane-terminated prepolymer of Example 1 was admixed with a proportion of catalyst (wt .-% with respect to the amount of STP) and geräkelt with a 120 ⁇ doctor blade on a dry glass plate.
  • the silane-terminated prepolymer was further diluted with solvent 1-methoxypropyl-2-acetate.
  • the glass plate was stored in a climatic chamber at 23 ° C and 50% relative humidity. After the times listed in Table 1 below, the coating is tested for curing. For this purpose, the hardness was examined with a pendulum damping device (according to König). A slow pendulum damping in seconds, d. H. a high value in seconds means progressive hardening of the silane.
  • Catalyst 1 Tetrabutylammonium hydrogen difluoride 70% in isopropanol
  • Catalyst 2 Tetrabutlyammonium hydrogen difluoride 70% in 2-ethylhexanol
  • Catalyst 3 Tetrabutylammonium hydrogen difluoride (50% in methylene chloride, Sigma Aldrich)
  • Example 3 Preparation of STP 2 In a flask with thermometer, KPC i stirrer. Reflux cooler and dropping funnel were under
  • the silane-terminated prepolymer of Example 2 was admixed with a proportion of catalyst (wt .-% with respect to the amount of STP) and with a 120 ⁇ doctor on a dry glass plate geräkelt.
  • the silane-terminated prepolymer was further diluted with solvent 1-methoxypropyl-2-acetate.
  • the glass plate was stored in a climatic chamber at 23 ° C and 50% relative humidity. After the times given in Table 1 below, the coating was tested for cure. For this purpose, the hardness was examined with a pendulum damping device (according to König). A slow pendulum damping in seconds, d. H. a high value in seconds means progressive hardening of the silane.
  • Catalyst 1 Tetrabutylphosphonium hydrogen difluoride 70% in isopropanol (inventive)
  • Catalyst 2 piperidinium 1-spiro-1'-pyrrolidinium hydrogen difluoride in 2-ethylhexanol (inventive)
  • Catalyst 3 Tetrabutylphosphonium hydrogen difluoride 70% in 2-ethylhexanol (inventive)
  • Catalyst 4 Tetrabutylammonium hydrogen difluoride (50% in methylene chloride, Sigma Aldrich)
  • Catalyst 5 30 2.0 10 32 89
  • the inventive catalysts 1 -4 based on the Hydrogengendifluoridanions show a much higher catalytic activity than the Fluoridanion 5.
  • the achieved pendulum hardness of the coatings are with the inventive Hydrogengendifluoriden significantly higher than those of the fluoride anion.
  • EXAMPLE 8 Preparation of STP 6 222.3 g of isophorone diisocyanate (1.0 mol) were initially introduced into a flask with thermometer, KPG stirrer, reflux condenser and dropping funnel under nitrogen atmosphere at 83.degree. At this temperature 75.3 g of 2,2,4-trimethyl-l, 3-pentanediol (97%, 0.5 mol) were added within 1 hour. After a reaction time of 3.25 hours at 84 ° C and 6 hours at 104 ° C, the NCO content had dropped to 14.1 wt .-%. The reaction was then cooled to 50 ° C and diluted with 309.0 g of 1-methoxypropyl 2-acetate (MPA).
  • MPA 1-methoxypropyl 2-acetate
  • Example 12 Testing of Catalyst 1 of Example 4 with Various STPs
  • the silane-terminated prepolymers of Example 3-8 were diluted, if necessary, with MPA to a polymer content of 70% by weight, then with a proportion of catalyst 1 (% by weight in%) Reference to the amount of ST) and laced with a 120 ⁇ squeegee on a dry glass plate.
  • the silane-terminated prepolymer was further diluted with solvent 1 -methoxypropyl-2-acetate.
  • the glass plate was stored in a climatic chamber at 23 ° C and 50% relative humidity. After the times given in Table 1 below, the coating was tested for cure. The hardness was examined with a pendulum damping device (König). A slow pendulum damping in seconds, ie a high value in seconds, means a progressive hardening of the silane.
  • Table 3 Testing STPs 3-8 with Catalyst 1

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Abstract

La présente invention concerne des compositions durcissables contenant au moins un prépolymère à fonction silane comprenant au moins un groupe alcoxysilane et au moins un composé comprenant au moins un anion polyfluorure d'hydrogène. Ces compositions trouvent application comme revêtements, produits d'étanchéité et adhésifs.
PCT/EP2017/056963 2016-03-23 2017-03-23 Compositions durcissables à base de prépolymères contenant des groupes alcoxysilane WO2017162811A1 (fr)

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