EP2651956A1 - Aminosilanes secondaires - Google Patents

Aminosilanes secondaires

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Publication number
EP2651956A1
EP2651956A1 EP11793844.9A EP11793844A EP2651956A1 EP 2651956 A1 EP2651956 A1 EP 2651956A1 EP 11793844 A EP11793844 A EP 11793844A EP 2651956 A1 EP2651956 A1 EP 2651956A1
Authority
EP
European Patent Office
Prior art keywords
formula
dimethyl
groups
propanal
aminosilane
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.)
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Application number
EP11793844.9A
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German (de)
English (en)
Inventor
Urs Burckhardt
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.)
Sika Technology AG
Original Assignee
Sika Technology AG
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Filing date
Publication date
Application filed by Sika Technology AG filed Critical Sika Technology AG
Priority to EP11793844.9A priority Critical patent/EP2651956A1/fr
Publication of EP2651956A1 publication Critical patent/EP2651956A1/fr
Withdrawn legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • C07F7/1804—Compounds having Si-O-C linkages
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/2805—Compounds having only one group containing active hydrogen
    • C08G18/288—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
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4866—Polyethers having a low unsaturation value
    • 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
    • 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
    • C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
    • C08G18/7628—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring containing at least one isocyanate or isothiocyanate group linked to the aromatic ring by means of an aliphatic group
    • C08G18/765—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring containing at least one isocyanate or isothiocyanate group linked to the aromatic ring by means of an aliphatic group alpha, alpha, alpha', alpha', -tetraalkylxylylene diisocyanate or homologues substituted on the aromatic ring
    • 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
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/02—Polyamines
    • C08G73/0246—Polyamines containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain
    • 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

Definitions

  • the invention relates to secondary aminosilanes and their use, in particular as adhesion promoters and crosslinkers, and as a structural component of silane-functional polymers; and curable compositions, in particular silane-crosslinking curable compositions, and their use, in particular as casting compounds, sealants, adhesives, coatings, coatings and paints.
  • curable compositions in particular silane-crosslinking curable compositions, and their use, in particular as casting compounds, sealants, adhesives, coatings, coatings and paints.
  • Amino-containing organoalkoxysilanes are used inter alia as adhesion promoters, as crosslinkers for curable compositions and as synthesis components of silane-functional polymers.
  • Aminosilanes with primary amino groups (“primary aminosilanes") are the most widely used because of their ease of preparation, but they have some drawbacks in their use, and due to the relatively hydrophilic primary amino group, they tend to be unwanted for moisture absorption, which adversely affects the adhesion of moisture
  • primary aminosilanes lead to high viscosities, complicate the processability of the silane-functional polymers and worsen the application properties and extensibility of the silane-functional polymers It may therefore be advantageous to use, instead of the primary aminosilanes, those having secondary amino groups (“secondary aminosilanes"
  • Secondary aminosilanes are classically obtained by hydrosilylation of allylsilanes, described, for example, in US Pat. No. 6,197,912, or by nucleophilic substitution of chloro or bromoalkylsilanes with primary amines, or of alkyl or aryl halides with primary aminosilanes, described, for example, in US Pat. No. 3,676,478 or US Pat. US 6,197,912.
  • the Michael adducts of primary aminosilanes have additional functional groups, such as cyano groups and especially ester groups.
  • ester groups leads to silane-functional polyurethane polymers of relatively low viscosity.
  • this has the disadvantage that the ester groups are reactive with primary or secondary amino groups and thereby form amides.
  • Silane-curing curable compositions which are usually formulated with primary amines and aminosilanes as catalysts and adhesion promoters, this is undesirable because it can lead to the deactivation of the amines and increased crosslinking density and thus to higher brittleness of the cured polymer. Incompletely alkylated aminosilanes with ester groups are often also poorly storable because of creeping self-condensation to give polyamides. Presentation of the invention
  • the object of the invention is therefore to provide new secondary aminosilanes which have advantageous properties in use as adhesion promoters and crosslinkers and as structural components of silane-functional polymers. So they should be produced in a simple process, be liquid at room temperature and have a low viscosity. In particular, they are to enable silane-functional polymers which have a low viscosity, a rapid curing and a good thermal resistance.
  • secondary aminosilanes according to claim 1 solve this problem. They are usually liquid at room temperature and relatively low viscosity and still have a low volatility and little odor. They can be prepared from commercial primary amino silanes and special aldehydes containing a secondary or tertiary amino group in a simple process which does not require any elaborate work-up steps. Advantageous properties such as the rapid hydrolysis rate of the silane groups, the good compatibility in many curable compositions and the particularly good adhesion-promoting properties can presumably be attributed to the presence of the additional amino group derived from the aldehyde.
  • Silane-crosslinkable curable compositions containing such silane-functional polymers are of comparatively low viscosity, cure quickly and completely upon contact with moisture, and surprisingly have excellent thermal stability which is substantially better than that of comparable prior art secondary aminosilanes manufactured systems.
  • the invention relates to an aminosilane of the formula (I)
  • bivalent hydrocarbon radical having 4 to 12 carbon atoms, which is part of an optionally substituted, carbocyclic ring having 5 to 8, preferably 6, carbon atoms;
  • R 3 represents a hydrogen atom or an alkyl group or arylalkyl group or
  • Alkoxycarbonyl group each having 1 to 12 C atoms
  • R 4 is a monovalent aliphatic, cycloaliphatic or arylaliphatic radical having 1 to 20 C atoms which optionally contains heteroatoms, and
  • R 5 represents a hydrogen atom or a monovalent aliphatic, cycloaliphatic or arylaliphatic radical having 1 to 20 C atoms, which optionally contains heteroatoms,
  • R 4 and R 5 together represent a divalent aliphatic radical having 3 to 30 carbon atoms which is part of an optionally substituted heterocyclic ring having 5 to 8, preferably 6, ring atoms, this ring optionally containing, in addition to the nitrogen atom, further heteroatoms, stand;
  • R 6 is a linear or branched alkylene or cycloalkylene radical having 1 to 20 C atoms, optionally with aromatic moieties, and optionally with one or more heteroatoms, in particular nitrogen atoms;
  • R 7 is an alkyl group having 1 to 10 C atoms, which optionally has ether-oxygen;
  • R 8 is an alkyl group having 1 to 8 C atoms; and x stands for 0, 1 or 2.
  • Two OR 7 groups may together represent a divalent glycolate group which rings with the silicon atom.
  • secondary aminosilane refers to an organoalkoxysilane whose radical bound directly to the silicon atom has at least one secondary amino group.
  • Primary aminosilane refers to an organoalkoxysilane whose radical bonded directly to the silicon atom has at least one primary amino group.
  • An “iminosilane” is an organoalkoxysilane whose radical bound directly to the silicon atom has at least one imino group.
  • Organicalkoxysilane or “silane” for short is a silicon-containing compound in which the silicon atom carries at least one, in particular two or three, alkoxy groups, as well as a directly bonded organic radical and thus at least one silane. Having C bond.
  • silane group refers to the silicon-containing group bonded to the organic radical of an organoalkoxysilane.
  • primary amino group refers to an NH 2 group which is bonded to an organic radical
  • secondary amino group refers to an NH group which is bonded to two organic radicals, which may also be part of a ring together , and as "tertiary
  • Amino group is an amino group called its nitrogen atom
  • Tertiary Armin nitrogen is bonded to three organic radicals, wherein two of these radicals can also be part of a ring together.
  • silane-crosslinking is meant a curable composition in which a silane-containing (“silane-functional”) polymer can be cured primarily via the reaction of the silane groups with moisture.
  • aliphatic or an isocyanate is referred to as "aliphatic” if its amino or isocyanate groups are each bonded to aliphatic, cycloaliphatic or arylaliphatic radicals, correspondingly their functional groups being referred to as aliphatic amino or aliphatic isocyanate groups.
  • “Aromatic” refers to an amine or an isocyanate if their amino or isocyanate groups are each bonded to an aromatic radical, correspondingly their functional groups are referred to as aromatic amino or aromatic isocyanate groups.
  • curable composition encompasses liquid or meltable reactive organic compositions and compositions thereof which are at least partially synthetically produced and which can cure on their own and / or by air contact with plastics and plastic compositions.
  • polymer comprises on the one hand a collective of chemically uniform, but different in terms of degree of polymerization, molecular weight and chain length macromolecules, which was produced by a polyreaction (polymerization, polyaddition, polycondensation) on the other hand also includes derivatives of such a collective of Macro-molecules of polyreactions, ie compounds which have been obtained by reactions, such as additions or substitutions, of functional groups on predetermined macromolecules and which may be chemically uniform or chemically non-uniform Precursors whose functional groups are involved in the construction of macromolecules.
  • polyurethane encompasses all polymers which are prepared by the so-called diisocyanate-polyaddition process
  • polyurethanes usually have urethane or thiourethane groups and, in particular, urea groups, but the term polyurethane also includes polymers which are almost or completely free
  • polyureas polyether-polyureas and polyester-polyureas
  • polyether-polyurethanes polyisocyanurates and polycarbodiimides.
  • poly such as polyamine, polyol or polyepoxide
  • polyisocyanate encompasses compounds having two or more isocyanate groups, irrespective of whether they are monomeric di- or triisocyanates, oligomeric diisocyanates or isocyanate-containing adducts and polymers.
  • RG, SP, PUP, S1, S2 or the like are merely for better reading comprehension and identification.
  • room temperature refers to a temperature of 23 ° C.
  • R 1 and R 2 each represent a methyl radical.
  • R 3 is a hydrogen atom.
  • R 1 and R 2 are each a methyl radical and / or R 3 is a hydrogen atom.
  • R 4 is preferably methyl, ethyl, propyl, isopropyl, butyl, 2
  • R 4 and R 5 form together - including the
  • R 6 is a linear or branched alkylene radical
  • R 6 preferably represents a linear alkylene radical having 5 to 7 C atoms which has one or 2 secondary amino groups in the chain, in particular for a - (CH 2 ) 2 -NH- (CH 2 ) 3 - or for a - (CH 2 ) 2 - NH- (CH 2 ) 2 -NH- (CH 2 ) 3 - radical.
  • R 7 preferably represents a methyl or an ethyl or isopropyl group, in particular a methyl or an ethyl group.
  • R 8 is a methyl or an ethyl group, in particular a methyl group.
  • x is 0 or 1, in particular 0.
  • Another object of the present invention is an iminosilane of the formula (II).
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 and x have the meanings already mentioned.
  • an iminosilane of the formula (II) can be hydrogenated. This hydrogenation can be done directly with molecular hydrogen or indirectly by hydrogen transfer from other reagents.
  • reagents are formic acid, with CO 2 being released (in the style of a Leuckart-Wallach reaction); Cyclohexene, which is thereby dehydrogenated to benzene, and other alkenes such as limonene; organosilanes; Alkali metals in protic solvents; or hydrazine in the presence of an oxidizing agent.
  • hydrolysis is meant to be (2-methoxyethoxy) aluminum hydride (Vitride ®, Red-Al ®), incorporated herein also the reduction by hydrides, such as lithium aluminum hydride, sodium borohydride and sodium. The hydrogenation with molecular hydrogen is preferred.
  • the hydrogen required for the hydrogenation is preferably used at elevated pressure, in particular 5 to 250 bar, and elevated temperature, in particular 20 to 160 ° C, in the presence of a suitable catalyst.
  • the conditions are advantageously chosen so that on the one hand the imino groups are hydrogenated as completely as possible and on the other hand hydrogenated or decomposed other possible components of the imine of the formula (IV).
  • Suitable catalysts for the hydrogenation are homogeneous catalysts such as rhodium, ruthenium or iridium, and in particular heterogeneous catalysts such as platinum, palladium, rhodium, ruthenium, osmium, rhenium, nickel, cobalt or iron, and their compounds or preparations on support materials, wherein as Support materials in particular pumice, diatomaceous earth, aluminum, silica gel or activated carbon are suitable. Particularly suitable are palladium on carbon (Pd / C), platinum on carbon (Pt / C), Adams catalyst and Raney nickel.
  • homogeneous catalysts such as rhodium, ruthenium or iridium
  • heterogeneous catalysts such as platinum, palladium, rhodium, ruthenium, osmium, rhenium, nickel, cobalt or iron, and their compounds or preparations on support materials, wherein as Support materials in particular pumice, diatomaceous earth, aluminum, si
  • the reductive alkylation is preferably carried out in the liquid phase. It can optionally be carried out without solvent or in the presence of a solvent, with suitable solvents being inert under the reaction conditions.
  • suitable solvents are C 1 - to C 10 -alkanes, such as, for example, hexane, heptane or cyclohexane, and alcohols, in particular primary C 1 - to C 6 -alcohols, such as methanol or ethanol, but also secondary alcohols, such as isopropanol and tertiary alcohols, such as tert-butanol.
  • an alcohol as solvent it is preferred to use that alcohol which is liberated in the hydrolysis of the silane groups, that is, for example, methanol when using a methoxysilane, or ethanol when using an ethoxysilane.
  • the hydrogenation can be carried out batchwise or in a continuous process, for example in a continuously operating hydrogenation apparatus.
  • at least one iminosilane of the formula (II), if appropriate in solution is continuously mixed under pressure with hydrogen and passed through a suitable catalyst.
  • the hydrogen can be generated continuously by means of water electrolysis.
  • the aminosilane of the formula (I) can be purified subsequently to the preparation, for example by means of distillation.
  • An iminosilane of the formula (II) is obtained in particular by a process for the preparation in which at least one aminosilane AS of the formula (III) is condensed with at least one aldehyde ALD of the formula (IV).
  • the reactants can be present in free or in derivatized form.
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 and x have the meanings already mentioned.
  • the aldehyde ALD can be used stoichiometrically or in stoichiometric excess with respect to the aminosilane AS.
  • condensation reactions between primary amines and aldehydes are well known.
  • an aminosilane is used in the present case as the primary amine.
  • condensation products in the form of organosiloxanes are formed, in the present case molecules which consist of two or more iminosilanes linked via siloxane groups.
  • an iminosilane of the formula (II) by condensation of an aminosilane AS of the formula (III) with an aldehyde ALD of the formula (IV)
  • the reaction can be carried out at temperatures of 5 to 250 ° C. Preferred is a Reaction temperature in the range of 20 to 100 ° C.
  • iminosilanes of the formula (II) of good quality by completely dispensing with the use of solvents in their production.
  • the aminosilane AS is initially charged and the aldehyde ALD is added dropwise in vacuo.
  • an iminosilane of the formula (II) can be obtained in particular also indirectly as the product of a Umimin istsretician.
  • an intermediate in the form of an imine of the formula (V a) is first prepared by reacting at least one aldehyde ALD of the formula (IV) with a small, relatively volatile primary monoamine, wherein the water formed in the condensation in a suitable manner as completely as possible Will get removed. Subsequently, the largely anhydrous
  • R 9 represents the alkyl radical of the small, relatively volatile primary monoamine, preferably an alkyl group having 1 to 6 C atoms, in particular a propyl, isopropyl or butyl group,
  • R 1 , R 2 , R 3 , R 4 and R 5 have the meanings already mentioned.
  • an iminosilane of the formula (II) can be obtained in particular also indirectly via an intermediate in the form of an acetal of the formula (Vb).
  • R 10 represents the alkyl radical of the small, relatively volatile alcohol, preferably an alkyl group having 1 to 6 C atoms, in particular a methyl, ethyl or isopropyl group,
  • R 1 , R 2 , R 3 , R 4 and R 5 have the meanings already mentioned.
  • the aldehyde ALD of the formula (IV) is condensed with a small, relatively volatile alcohol, the water liberated being removed as completely as possible in a suitable manner. Subsequently, the largely anhydrous intermediate with at least one amino silane AS of the formula (III) at elevated temperature and reduced pressure to the aminosilane of the formula (I), optionally in the presence of a catalyst, reacted, wherein the small, relatively volatile alcohol by means of vacuum running is removed from the reaction mixture.
  • an aminosilane of the formula (I) is also possible by reacting at least one aminosilane AS of the formula (III) with at least one aldehyde ALD of the formula (IV) in a one-pot reaction with hydrogenation, without the corresponding iminosilane of the formula (II) to isolate.
  • the aminosilane AS can be initially charged in a suitable solvent in the presence of a molecular sieve, then the aldehyde ALD is added dropwise and finally the reaction solution - optionally after removal of the molecular sieve - hydrogenated with a suitable method.
  • Particularly suitable aminosilane AS of the formula (III) are the following primary aminosilanes:
  • diaminosilanes which, in addition to a primary amino group, carry a secondary amino group (NH group) which is in particular in the ⁇ -position to the silicon atom, in particular N- (2-aminoethyl) -3-amino-propyltrimethoxysilane, N (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltriethoxysilane and N- (2-aminoethyl) -3-aminopropyltriisopropoxysilane; - So-called triaminosilanes, which in addition to a primary amino group two secondary amino groups (NH groups) carry, in particular N- (2-aminoethyl) -N '- [3- (trimethoxysilyl) propyl] ethylenediamine.
  • the aminosilane AS of the formula (III) is preferably selected
  • aldehyde ALD of the formula (IV) are the products of a Mannich reaction analogous ⁇ -Aiminoalkyl mich, as is known from the literature.
  • R 1 , R 2 , R 3 , R 4 and R 5 have the meanings already mentioned.
  • This reaction can be carried out either with the free reagents Y1, Y2 and C according to the formulas (VI), (VII) and (VIII), or the reagents can be used partially or completely in derivatized form. In a preferred embodiment, the reaction is with all
  • Reagents in free form performed as a one-pot reaction and the aldehyde ALD purified by distillation after the reaction. Preference is given to using no organic solvents.
  • aldehyde Y1 of the formula (VI) isobutyraldehyde, 2-methylbutyraldehyde, 2-ethylbutyraldehyde, 2-methylvaleraldehyde, 2- Ethyl caproaldehyde, cyclopentanecarboxaldehyde, cyclohexanecarboxaldehyde, 1,2,3,6-tetrahydrobenzaldehyde, 2-methyl-3-phenylpropionaldehyde, 2-phenylpropionaldehyde and diphenylacetaldehyde.
  • Isobutyraldehyde is preferred.
  • aldehyde Y 2 of the formula (VII) are formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, isobutyraldehyde, phenylacetaldehyde and glyoxylic acid esters, in particular ethyl glyoxylate.
  • Preferred is formaldehyde.
  • amine C of the formula (VIII) are methylamine, dimethylamine, ethylamine, diethylamine, propylamine, dipropylamine, isopropylamine, diisopropylamine, butylamine, dibutylamine, isobutylamine, diisobutylamine, sec-butylamine, di-sec-butylamine, hexylamine , Dihexylamine, 2-ethylhexylamine, di- (2-ethylhexyl) amine, octylamine, decylamine, dodecylamine, ethanolamine, diethanolamine, isopropanolamine, diisopropanolamine, cyclohexylamine, dicyclohexylamine, N-methylbutylamine, N-ethylbutylamine, N-methylcyclohexylamine, N-ethylcyclohexylamine, bis
  • Particularly preferred are methylamine, dimethylamine and in particular
  • aldehydes ALD are formed in the form of dialdehydes, which can be used in the reaction with aminosilanes AS in a molar ratio of 1: 2 for the preparation of aminosilanes of the formula (I) having two silane groups and at least two secondary amino groups.
  • the aldehyde ALD of the formula (IV) is preferably selected from the group consisting of 2,2-dimethyl-3-methylaminopropanal, 2,2-dimethyl-3-dimethylaminopropanal, 2,2-dimethyl-3-ethylamino propanal, 2,2-dimethyl-3-diethylamino-propanal, 2,2-dimethyl-3-bis (2-methoxyethyl) amino-propanal, 2,2-dimethyl-3-butylamino-propanal, 2,2-dimethyl 3-dibutylamino-propanal, 2,2-dimethyl-3-hexylamino-propanal, 2,2-dimethyl-3- (2-ethylhexyl) -amino-propanal, 2,2-dimethyl-3-dodecylamino-propanal, 2,2 Dimethyl-3- (N-pyrrolidino) -propanal, 2,2-dimethyl-3- (N -piperidino)
  • silane groups of the aminosilanes of the formula (I) and the silane groups of the iminosilanes of the formula (II) have the property of hydrolyzing on contact with moisture.
  • organosilanols silicon-organic compounds containing one or more silanol groups, Si-OH groups
  • organosiloxanes organosilicon compounds containing one or more siloxane groups, Si-O-Si groups
  • the corresponding alcohol for example methanol in the case of methoxysilane or ethanol in the case of ethoxysilane is liberated.
  • n 1 or 2 or 3, with the proviso that n has at most the value (3-x).
  • R 7 and R 8 and x have the meanings already mentioned.
  • Such hydrolyzed or partially hydrolyzed compounds having silanol groups of the formula (IX) are very reactive and can continue to react very rapidly, either by condensation with other silanol groups to form siloxane groups (Si-O-Si groups) or for example by condensation with hydroxyl groups of a substrate.
  • Both the aminosilanes of the formula (I) and the iminosilanes of the formula (II) have the ability to build up strong adhesion to various substrates, or to improve the adhesion of compositions containing these silanes to a substrate.
  • the buildup of adhesion may involve mainly the silanol groups, which, rather than exclusively condense with one another to form organosiloxanes, partially form a compound with the respective substrate.
  • the aminosilanes of the formula (I) have, in addition to the secondary amino group, at least one further, either secondary or tertiary amino group. This can exert a catalytic effect on the hydrolysis of the silane groups.
  • the iminosilanes of the formula (II) in addition to the imino group to a secondary or tertiary amino group which can exert a catalytic effect on the hydrolysis of the silane groups.
  • Organotin compounds such as dibutyltin dilaurate or di- butyltin diacetylacetonate, titanates and zirconates and amines, amidines and guanidines such as, for example, 1, 4-diazabicyclo [2.2.2] octane (DABCO), diazabicyclo [5.4.0] undec-7-ene (DBU) or 1, 1, 3 , 3-tetramethylguanidine.
  • DABCO diazabicyclo [2.2.2] octane
  • DBU diazabicyclo [5.4.0] undec-7-ene
  • 1, 1, 3 3-tetramethylguanidine.
  • aminosilanes of the formula (I) and / or the iminosilanes of the formula (II) are advantageously usable as adhesion promoters between plastics and various substrates, for coating surfaces, for example in order to improve their properties with regard to tendency to fouling, ease of cleaning, etc., as accelerators and / or or as a drying agent. They may be used as such or as part of solutions and compositions, for example as pretreatment or activator, primer or primer.
  • Suitable substrates for the application of the aminosilanes of the formula (I) or the iminosilanes of the formula (II) as adhesion promoters or for coating their surfaces are, in particular, the substrates S1 and S2 mentioned below.
  • aminosilanes of the formula (I) and the iminosilanes of the formula (II) as constituents of curable compositions, where they can act as crosslinkers and / or as adhesion promoters and / or as accelerators and / or as drying agents in the curable compositions, as well as
  • the aminosilanes of the formula (I) are novel compounds with surprising properties. They are usually liquid at room temperature and relatively low viscosity, which is a great advantage for many applications. Nevertheless, they have a low volatility and little odor, which is often not the case for low-viscosity amino compounds. Furthermore, they can be prepared from commercial primary aminosilanes and the described aldehydes ALD of the formula (IV) in a simple process which does not require any elaborate work-up steps.
  • the aminosilanes of the formula (I) have, in addition to the secondary amino group formed by hydrogenation from the imino group, at least one further amino group in the form of a tertiary or secondary amino group derived from the aldehyde ALD.
  • Particularly advantageous properties have the aminosilanes of the formula (I) in adducted form as a curable, silane-crosslinking polymer.
  • Such polymers are obtainable by the reaction of isocyanate-functional polyurethane polymers with aminosilanes. If aminosilanes of the formula (I) are used, silane-functional polymers having a relatively low viscosity are formed which rapidly and completely harden on contact with moisture.
  • curable compositions comprising silane-functional polymers which are derived from aminosilanes of the formula (I) in the cured state exhibit excellent thermal stability is particularly surprising. The thermal stability of these systems is significantly better than the thermal stability of comparable systems which are derived from aminosilanes containing secondary amino groups according to the prior art.
  • the iminosilanes of formula (II) are also novel compounds with surprising properties. They are usually liquid at room temperature and relatively low viscosity and have a low volatility and little smell on. In the absence of moisture, they are storage-stable. Upon contact with water, hydrolysis of both the imino groups and also the silane groups takes place. The imino groups react formally to primary amino groups during hydrolysis, releasing the corresponding aldehyde ALD. In the presence of amine-reactive groups, such as, for example, isocyanate groups, the primary amino groups continue to react, for example with the formation of urea groups. As a result, the hydrolysis of the imino groups proceeds rapidly and completely.
  • the released aldehyde ALD has no or only a slight, amine-like odor. So it causes no or at most a slight odor in a composition such as an adhesive, sealant or coating.
  • the reaction of components which are reactive toward primary amines with the hydrolyzing iminosilane of the formula (II) does not necessarily have to take place via the released aminosilane AS of the formula (III).
  • reactions with intermediates of the hydrolysis of the iminosilane to aminosilane are possible.
  • the hydrolyzing iminosilane of the formula (II) reacts in the form of a hemiaminal directly with amine-reactive components.
  • iminosilanes of the formula (II) are particularly interesting iminosilanes of the formula (II a).
  • R 6 represents a linear alkylene radical having 5 to 7 carbon atoms and having one or 2 secondary amino groups in the chain, in particular a - (CH 2 ) 2 -NH- (CH 2 ) 3 or - (CH 2 ) 2 -NH- (CH 2 ) 2 -NH- (CH 2 ) 3 -Ray, and R 1 , R 2 , R 3 , R 4 , R 5 , R 7 , R 8 and x have the meanings already mentioned.
  • the particular Aminosilane AS having both primary and secondary amino groups which are based on the iminosilanes of the formula (II a), are of particular interest as adhesion promoters, but their primary amino groups have problems when stored in compositions, in particular in ester groups Compositions can lead. This difficulty can be avoided in an elegant manner when using the iminosilanes of the formula (IIa) as adhesion promoters.
  • a further subject of the invention is an adduct AD from the reaction of at least one aminosilane of the formula (I) with at least one compound VB which carries at least one, preferably at least two, reactive groups RG, where the reactive groups RG are selected from the group consisting of isocyanate, isothiocyanate, cyclocarbonate, epoxide, episulfide, aziridine, acrylic, methacrylic, 1-ethynylcarbonyl, 1-propynylcarbonyl, maleimide, citraconimide, vinyl, isopropenyl and allyl Groups.
  • Particularly preferred reactive group RG is the isocyanate group and the epoxide group.
  • At least one secondary amino group of an aminosilane of the formula (I) reacts in an addition reaction with at least one reactive group RG of the compound VB to form an adduct AD.
  • the reaction can be carried out in such a way that the secondary amino groups of the aminosilane of the formula (I) are present stoichiometrically or in a stoichiometric excess over the reactive groups RG of compound VB, adducts AD with at least one, preferably at least two, silane groups being obtainable, which are largely free of reactive groups RG.
  • reaction can also be carried out in such a way that the reactive groups RG of the compound VB are present in a stoichiometric excess over the secondary amino groups of the aminosilane of the formula (I).
  • the compound VB contains at least two reactive Groups RG, adducts AD are thus obtainable with at least one reactive group RG and at least one silane group.
  • the reaction between the aminosilane of the formula (I) and the compound VB to form an adduct AD takes place under known conditions which are typically used for reactions between the reactive groups RG involved in the respective reaction.
  • the reaction is carried out using a solvent or preferably solvent-free.
  • auxiliaries such as catalysts, initiators or stabilizers may be included.
  • the reaction with isocyanate groups is preferably carried out at room temperature, the reaction with epoxide groups preferably at elevated temperature, for example at 40 to 100 ° C.
  • Polyepoxides such as bis (2,3-epoxycyclopentyl) ethers, polyglycidyl ethers of polyhydric aliphatic and cycloaliphatic alcohols such as 1, 4-butanediol, polypropylene glycols and 2,2-bis (4-hydroxycyclohexyl) propane; Polyglycidyl ethers of polyhydric phenols such as resorcinol, bis (4-hydroxyphenyl) methane (bisphenol-F), 2,2-bis (4-hydroxyphenyl) -propane (bisphenol-A), 2,2-bis - (4-hydroxy-3,5-dibromophenyl) -propane, 1,1,2,2-tetrakis (4-hydroxyphenyl) -ethane, condensation products of phenols with formaldehyde obtained under acidic conditions, such as phenol novolacs and cresol novolacs, as well as with these alcohols and phenols, or with polycarboxylic acids such
  • heterofunctional compounds ie at least two different compounds bearing the abovementioned reactive groups
  • RG monofunctional compounds in particular those which additionally carry a silane group, in particular isocyanatosilanes, epoxy silanes and (meth) acrylic silanes, in particular 3-isocyanatopropyltrimethoxysilane and 3-glycidoxypropyltrimethoxysilane.
  • Such hydrolyzed or partially hydrolyzed adducts AD with silanol groups of the formula (IX) are very reactive and can continue to react very rapidly, in the same way as previously described.
  • Particularly suitable compounds VB in one embodiment are monomeric and oligomeric polyisocyanates, isocyanatosilanes, polyepoxides, epoxysilanes and (meth) acrylic group-containing compounds.
  • Adducts AD with such compounds VB are particularly suitable as a constituent of curable compositions, where they can act as curatives in the curable compositions as crosslinkers and / or as adhesion promoters and / or as accelerators and / or as drying agents, and as constituents of activators or primers.
  • Particularly suitable as compound VB in a further embodiment are more than one isocyanate group-containing reaction products of polyisocyanates with polyols (also called isocyanate-containing polyurethane polymers).
  • Adducts AD with such compounds VB are particularly suitable as a constituent of curable compositions, wherein they can be used in the curable compositions as a curable, silane-functional polymer.
  • Both the aminosilanes of the formula (I) and the iminosilanes of the formula (II) and the adducts AD are advantageously usable as adhesion promoters and / or accelerators and / or drying agents, for coating surfaces or as components of curable compositions, activators or primers.
  • compositions containing at least one aminosilane of the formula (I) and / or at least one iminosilane of the formula (II) and / or at least one adduct AD are compositions containing at least one aminosilane of the formula (I) and / or at least one iminosilane of the formula (II) and / or at least one adduct AD.
  • such a composition is an activator which additionally contains at least one solvent, and optionally further constituents such as, in particular, catalysts, further silanes, titanates and zirconates.
  • An activator is typically used to clean substrate surfaces and, at the same time, prepare them for subsequent application of a curable composition to provide improved substrate-to-mass adhesion.
  • the ingredients in an activator are typically metered so that after evaporation of the solvents no closed film remains on the substrate surface.
  • such a composition is a primer which additionally contains at least one solvent and at least one film-forming component, and optionally further constituents, in particular catalysts, fillers, further silanes, titanates, zirconates, wetting agents and other additives.
  • Suitable film-forming components are, in particular, mono- and / or oligomeric aliphatic, cycloaliphatic, arylaliphatic or aromatic polyisocyanates, polyurethane polymers having isocyanate and / or silane groups, epoxy resins and the adducts AD described.
  • the primer is usually applied in such a way that after evaporation of the solvents, a closed film in a layer thickness in the range of a few micrometers to a few hundred micrometers remains on the substrate.
  • a primer is typically used to improve adhesion between substrate and mass by allowing adhesion of the primer film to both the substrate and a curable composition applied to the primer film.
  • Particularly suitable solvents for such activators or primers are alcohols, such as methanol, ethanol, isopropanol; Ketones like
  • Acetates such as ethyl acetate, propyl acetate, butyl acetate; Formates, propionates and malonates such as diethyl malonate;
  • Ethers such as dialkyl ethers, ketone ethers and ester ethers, for example diisopropyl ether, diethyl ether, dibutyl ether, diethylene glycol diethyl ether and ethylene glycol diethyl ether;
  • aliphatic and aromatic hydrocarbons such as toluene, xylene, heptene, octane and petroleum fractions, such as naphtha, white spirit, petroleum ether and gasoline, for example Solvesso TM grades (from Exxon); halogenated
  • such a composition is a curable composition in the form of an isocyanate-containing polyurethane composition, or in the form of an epoxy resin composition, or in the form of a silane-functional hardenable mass which cures mainly via the hydrolysis and condensation of silane groups.
  • curable compositions can be used in particular as potting compounds, sealants, adhesives, coverings, coatings and paints for construction and industrial applications, for example as electrical insulation materials, fillers, joint sealants, assembly adhesives, car body adhesives, window adhesives, sandwich element adhesives, laminating adhesives, laminate adhesives, anchoring adhesives , Floor coverings and coatings, balcony and roof coatings, concrete protective coatings,
  • silanes in curable compositions, activators and primers are widely used in the art, where the silanes can act as crosslinkers and / or as adhesion promoters and / or as accelerators and / or as drying agents and / or as curable polymer.
  • the aminosilanes of the formula (I) have an additional amino group makes them particularly interesting for such applications.
  • Silane-functional polymers SP which are obtainable from the reaction of at least one polyurethane polymer PUP having isocyanate groups with at least one aminosilane of the formula (I) are particularly interesting among the adducts AD described.
  • aminosilanes of the formula (I) having only one secondary amino group ie aminosilanes of the formula (I) in which R 5 is not a hydrogen atom and in which R 6 has no secondary amino groups.
  • the secondary amino groups of the aminosilanes of the formula (I) are preferably used stoichiometrically or in slight stoichiometric excess over the isocyanate groups of the polyurethane polymers PUP.
  • silane-functional polymers SP which are free of isocyanate groups.
  • An isocyanate-functional polyurethane polymer PUP suitable for producing a silane-functional polymer SP is, in particular obtainable from the reaction of at least one polyol with at least one polyisocyanate, in particular a diisocyanate. This reaction can take place in that the polyol and the polyisocyanate with conventional
  • Process for example, at temperatures of 50 ° C to 100 ° C, optionally with the concomitant use of suitable catalysts, are reacted, wherein the polyisocyanate is metered so that its isocyanate groups in proportion to the hydroxyl groups of the polyol in stoichiometric excess are present.
  • the polyisocyanate is metered so that an NCO / OH ratio of 1 .3 to 5, in particular one of 1 .5 to 3, is maintained.
  • the "NCO / OH ratio" is understood to mean the ratio of the number of isocyanate groups used to the number of hydroxyl groups used.
  • the content of free isocyanate groups is preferably from 0.25 to 5% by weight. particularly preferably from 0.3 to 2.5% by weight.
  • the polyurethane polymer PUP may be made using plasticizers, with the plasticizers used containing no isocyanate-reactive groups.
  • polyurethane polymers PUP having the stated content of free isocyanate groups which are obtained from the reaction of diisocyanates with high molecular weight diols in an NCO / OH ratio of from 1.5 to 2.
  • polyols for the preparation of a polyurethane polymer PUP in particular the following commercial polyols or mixtures thereof can be used:
  • Polyoxyalkylenpolyole also called polyether polyols or oligoetherols, which are polymerization of ethylene oxide, 1, 2-propylene oxide, 1, 2- or 2,3-butylene oxide, oxetane, tetrahydrofuran or mixtures thereof, possibly polymerized with the aid of a starter molecule having two or more active Hydrogen atoms, such as water,
  • Ammonia or compounds having a plurality of OH or NH groups such as, for example, 1,2-ethanediol, 1,2- and 1,3-propanediol, neopentyl glycol, diethylene glycol, triethylene glycol, the isomeric dipropylene glycols and triphosphoric acid.
  • ethylene glycols the isomeric butanediols, pentanediols, hexanediols, heptanediols, octanediols, nonanediols, decanediols, undecanediols, 1,3- and 1,4-cyclohexanedimethanol, bisphenol A, hydrogenated bisphenol A, 1,1,1-trimethylolethane, 1, 1, 1-trimethylolpropane, glycerol, aniline, and mixtures of the aforementioned compounds.
  • Both polyoxyalkylene polyols having a low degree of unsaturation (measured according to ASTM D-2849-69 and expressed in milliequivalents of unsaturation per gram of polyol (mEq / g)) prepared, for example, by means of so-called double metal cyanide complex catalysts (US Pat. DMC catalysts), as well as polyoxyalkylene polyols having a higher degree of unsaturation, prepared for example with the aid of anionic catalysts such as NaOH, KOH, CsOH or alkali metal alkoxides.
  • anionic catalysts such as NaOH, KOH, CsOH or alkali metal alkoxides.
  • polyoxyalkylenediols or polyoxyalkylenetriols are particularly suitable, in particular polyoxyethylene and polyoxypropylene di- and triols.
  • polyoxyalkylenediols and -triols having a degree of unsaturation lower than 0.02 meq / g and having a molecular weight in the range of 1 ⁇ 00 - 30 ⁇ 00 g / mol
  • polyoxypropylene diols and triols having a molecular weight of 400 - 8 ⁇ 00 g / mol.
  • ethylene oxide-terminated EO-endcapped
  • ethylene oxide-endcapped ethylene oxide-endcapped
  • the latter are special Polyoxypropylenpolyoxyethylenpolyole, which are obtained, for example, that pure polyoxypropylene, in particular polyoxypropylenediols and triols, after completion of the
  • Polypropoxylation reaction with ethylene oxide are further alkoxylated and thereby have primary hydroxyl groups.
  • Polyesterpolyols also called oligoesterols, prepared by known processes, in particular the polycondensation of hydroxycarboxylic acids or the polycondensation of aliphatic and / or aromatic
  • Polycarboxylic acids with dihydric or polyhydric alcohols are Polycarboxylic acids with dihydric or polyhydric alcohols.
  • polyester polyols are those which are prepared from dihydric to trivalent, in particular dihydric, alcohols, such as For example, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, neopentyl glycol, 1, 4-butanediol, 1, 5-pentanediol, 3-methyl-1, 5-hexanediol, 1, 6-hexanediol, 1, 8-octanediol, 1 , 10-decanediol, 1, 12-dodecanediol, 1, 12-hydroxystearyl alcohol, 1, 4-cyclohexanedimethanol, dimer fatty acid diol (dimerdiol), hydroxypivalate neopentyl glycol ester, glycerol, 1,1,1-trimethylolpropane or mixtures of the abovementioned alcohols, with organic di or tricarboxylic acids, in particular dicarboxylic acids, in
  • polyester polyols are polyester diols.
  • Polycarbonate polyols as obtainable by reacting, for example, the abovementioned alcohols used to form the polyesterpolyols with dialkyl carbonates, diaryl carbonates or phosgene.
  • polyether polyester polyols have at least two different blocks with polyether, polyester and / or polycarbonate structure of the type described above, in particular polyether polyester polyols.
  • Polyhydroxy-functional fats and oils for example natural fats and oils, in particular castor oil; or obtained by chemical modification of natural fats and oils - so-called oleochemical - polyols, for example, obtained by epoxidation of unsaturated oils and subsequent ring opening with carboxylic acids or alcohols epoxy polyesters or epoxypolyethers, or obtained by hydroformylation and hydrogenation of unsaturated oils polyols; or from natural fats and oils by degradation processes such as alcoholysis or ozonolysis and subsequent chemical linkage, for example by transesterification or Dimerization, the degradation products or derivatives thereof obtained polyols.
  • oleochemical - polyols for example, obtained by epoxidation of unsaturated oils and subsequent ring opening with carboxylic acids or alcohols epoxy polyesters or epoxypolyethers, or obtained by hydroformylation and hydrogenation of unsaturated oils polyols
  • degradation processes such as alcoholysis or ozonolysis and subsequent chemical linkage, for
  • Suitable degradation products of natural fats and oils are in particular fatty acids and fatty alcohols and fatty acid esters, in particular the methyl esters (FAME), which can be derivatized for example by hydroformylation and hydrogenation to hydroxy fatty acid esters.
  • FAME methyl esters
  • Polyhydrocarbyl polyols also called oligohydrocarbonols, such as in particular polyhydroxy-functional polyolefins, polyisobutylenes, polyisoprenes; polyhydroxy-functional ethylene-propylene, ethylene-butylene or ethylene-propylene-diene copolymers, such as those produced by Kraton Polymers; polyhydroxy-functional polymers of dienes, in particular of 1, 3-butadiene, which may in particular also be prepared from anionic polymerization; polyhydroxy-functional copolymers of dienes such as 1, 3-butadiene or diene mixtures and vinyl monomers such as styrene, acrylonitrile, vinyl chloride, vinyl acetate, vinyl alcohol, isobutylene and isoprene, for example polyhydroxy-functional acrylonitrile / butadiene copolymers, such as, for example, epoxides or aminoalcohols and carboxyl-terminated acrylonitrile / butadiene
  • These stated polyols preferably have an average molecular weight of 250-30 ⁇ 00 g / mol, in particular of 1-0000-30 ⁇ 00 g / mol, and preferably have an average OH functionality in the range of 1.6-3.
  • Preferred polyols are polyether, polyester, polycarbonate and polyacrylate polyols, preferably diols and triols. Particularly preferred are poly ether diols, in particular polyoxypropylene and Polyoxypropylenpolyoxy- ethylenediols. Most preferred are high molecular weight polyoxypropylene diols having a degree of unsaturation lower than 0.02 meq / g and having a molecular weight in the range of 4000-30 ⁇ 00 g / mol, especially 8 ⁇ 00-30 ⁇ 00 g / mol.
  • small amounts of low molecular weight di- or polyhydric alcohols such as 1, 2-ethanediol, 1, 2- and 1, 3-propanediol, neopentyl glycol, diethylene glycol, triethylene glycol, the isomeric dipropylene glycols and tripropylene glycols, the isomers Butanediols, pentanediols, hexanediols, heptanediols, octanediols, nonanediols, decanediols, undecanediols, 1, 3 and 1, 4-cyclohexanedimethanol, hydrogenated bisphenol A, dimeric fatty alcohols, 1, 1, 1-trimethylolethane, 1, 1, 1-trimethylol propane, glycerol, pentaerythritol, sugar alcohols such as xylitol, sorbitol
  • Aromatic or aliphatic polyisocyanates are used as the polyisocyanate for the preparation of a polyurethane polymer PUP containing isocyanate groups.
  • aromatic polyisocyanates are monomeric di- or triisocyanates such as 2,4- and 2,6-toluene diisocyanate and any desired compounds
  • TDI 4,4'-, 2,4'- and 2,2'-diphenylmethane diisocyanate and any mixtures of these isomers
  • MDI mixtures of MDI and MDI homologs (polymeric MDI or PMDI)
  • 1, 3 and 1 4-phenylene diisocyanate, 2,3,5,6-tetramethyl-1,4-diisocyanatobenzene, naphthalene-1,5-diisocyanate (NDI), 3,3'-dimethyl-4,4 'Diisocyanatodiphenyl (TODI), dianisidine diisocyanate (DADI), tris (4-isocyanatophenyl) methane, tris (4-isocyanatophenyl) thiophosphate, and any mixtures of the aforementioned isocyanates.
  • MDI and TDI are examples of MDI and TDI.
  • a silane-functional polymer SP has end groups of the formula (X).
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 and x have the meanings already mentioned.
  • a silane-functional polymer SP can be stored in the absence of moisture. Upon contact with moisture, the silane groups of polymer SP hydrolyze, whereupon it hardens to a crosslinked plastic.
  • the present invention also describes a crosslinked plastic obtained by the reaction of at least one silane-functional polymer SP with moisture.
  • a silane-functional polymer SP has various advantageous properties. It is easily understood from the described amino silanes of the formula (I) accessible and has little smell even with an excess of aminosilane. Its viscosity is relatively low, significantly lower than that of a corresponding silane-functional polymer made using a primary aminosilane. Upon contact with moisture, it rapidly and completely crosslinks to form a cured polymer having excellent properties, in particular good elasticity with high strength and high ductility and a surprisingly good thermal resistance, for example at a temperature load of 90.degree. Thermal stability is significantly superior to cured silane functional polymers made using secondary aminosilanes known in the art.
  • a silane-functional polymer SP is particularly suitable as a constituent of curable compositions, in particular for the formulation of silane-functional moisture-curing compositions.
  • Another object of the invention is a moisture-curing composition containing at least one silane-functional polymer SP, as described above, and at least one other
  • the silane-functional polymer SP is present in an amount of 10-80% by weight, preferably in an amount of 15-50% by weight, based on the moisture-curing composition.
  • the following auxiliary and Zuticianzstoff may be present:
  • Silanes which are used as adhesion promoters, crosslinkers, drying agents and / or
  • Catalysts in particular further aminosilanes, in particular the described aminosilanes of the formula (I), the aminosilanes AS mentioned for their preparation with primary amino groups and further aminosilanes with secondary or tertiary amino groups,
  • N-phenyl, N-cyclohexyl and N-alkylaminosilanes furthermore mercaptosilanes, epoxysilanes, vinylsilanes, (meth) acrylsilanes, isocyanato silanes, carbamatosilanes, alkylsilanes, S- (alkylcarbonyl) -mercaptosilanes and iminosilanes, and oligomeric forms of these silanes, in particular 3-glycidoxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- ( 2-aminoethyl) -N '- [3- (trimethoxysilyl) propyl] ethylenediamine, 3-mercaptopropyltrimethoxysilane, 3-isocyanatopropyltrimethoxys
  • Plasticizers in particular carboxylic acid esters such as phthalates, in particular dioctyl phthalate, diisononyl phthalate or diisodecyl phthalate, adipates, in particular dioctyl adipate, azelates, sebacates, polyols, in particular polyoxyalkylene polyols or polyester polyols, glycol ethers, glycol esters, organic phosphoric and sulfonic acid esters or polybutenes;
  • carboxylic acid esters such as phthalates, in particular dioctyl phthalate, diisononyl phthalate or diisodecyl phthalate, adipates, in particular dioctyl adipate, azelates, sebacates, polyols, in particular polyoxyalkylene polyols or polyester polyols, glycol ethers, glycol esters, organic phosphoric and sulfonic acid esters or poly
  • Reactive diluents and crosslinkers for example silane-functional oligomers and polymers, natural resins, fats or oils such as rosin, shellac, linseed oil, castor oil and soybean oil;
  • thermoplastic polymers for example homopolymers or copolymers of unsaturated monomers, in particular from the group comprising ethylene, propylene, butylene, isobutylene, isoprene, vinyl acetate and alkyl (meth) acrylates, in particular polyethylenes (PE), polypropylenes (PP) , Polyisobutylenes, ethylene-vinyl acetate copolymers (EVA) and atactic polyc-olefins (APAO);
  • PE polyethylenes
  • PP polypropylenes
  • EVA ethylene-vinyl acetate copolymers
  • APAO atactic polyc-olefins
  • inorganic and organic fillers in particular ground or precipitated calcium carbonates, which are optionally coated with fatty acids, in particular stearates, barytes, talcs, quartz flours, quartz sand, dolomites, wollastonites, kaolins, calcined kaolins, mica (potassium aluminum silicate ), Molecular sieves, aluminum oxides, aluminum hydroxides, magnesium hydroxide, silicic acids including highly dispersed silicas from pyrolysis processes, carbon black including industrially produced carbon black, graphite, metal powders such as aluminum, copper, iron, silver or steel, PVC powder or hollow spheres; Fibers, in particular glass fibers, carbon fibers, metal fibers, ceramic fibers or plastic fibers such as polyamide fibers or polyethylene fibers;
  • Pigments for example titanium dioxide or iron oxides
  • Catalysts in particular organotin compounds, in particular di-butyltin dichloride, dibutyltin oxide, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin diacetylacetonate, further dibutyltin dicarboxylates, dioctyltin dicarboxylates, in particular dioctyltin dilaurate, monobutyltin trichloride, tin (II) octoate, alkyltin thioester, furthermore compounds of zinc, manganese, iron, chromium, Cobalt, copper, nickel, molybdenum, lead, cadmium, mercury, antimony, vanadium, titanium, zirconium or potassium, and furthermore amines, amidines and guanidines, in particular N-ethyldiisopropylamine, ⁇ , ⁇ , ⁇ ',
  • DBU undec-7-ene
  • DBN non-5-ene
  • N N'-dimethylpiperazine
  • 1, 1, 3,3-tetramethylguanidine nitrogen aromatic compounds such as 4-dimethylaminopyridine, N-methylimidazole, N-vinylimidazole or 1, 2-Dim ethylimidazole; organic ammonium compounds or alkoxylated tertiary amines; and furthermore combinations of the compounds mentioned, in particular combinations of different metal compounds or combinations of metal compounds and nitrogen-containing compounds.
  • Rheology modifiers in particular thickeners, for example phyllosilicates such as bentonites, derivatives of castor oil, hydrogenated castor oil, polyamides, polyurethanes, urea compounds, fumed silicas, cellulose ethers and hydrophobically modified polyoxyethylenes;
  • thickeners for example phyllosilicates such as bentonites, derivatives of castor oil, hydrogenated castor oil, polyamides, polyurethanes, urea compounds, fumed silicas, cellulose ethers and hydrophobically modified polyoxyethylenes;
  • Desiccants in particular tetraethoxysilane, vinyltrimethoxysilane, and organoalkoxysilanes which have a functional group in the position to the silane group, in particular N- (methyldimethoxysilylmethyl) -O-methyl-carbamate, (methacryloxymethyl) silanes, methoxymethylsilanes, orthoformic acid esters, calcium oxide or molecular sieves;
  • Fillers aluminum hydroxide and magnesium hydroxide, as well as in particular organic phosphoric esters, in particular triethyl phosphate, tricresyl phosphate, triphenyl phosphate, diphenyl cresyl phosphate, isodecyl diphenyl phosphate, tris (1,3-dichloro-2-propyl) phosphate, tris (2-chloroethyl) phosphate, tris (2-ethylhexyl) phosphate, tris (chloroisopropyl) phosphate, tris (chloropropyl) phosphate, isopropylated triphenyl phosphate, mono-, bis- and tris (isopropylphenyl) phosphates of different degrees of isopropylation, resorcinol bis (diphenyl phosphate), bisphenol A bis (diphenyl phosphate) and ammonium polyphosphates;
  • Biocides such as algicides, fungicides or fungal growth
  • the moisture-curing composition preferably comprises plasticizers, fillers, silanes and / or catalysts.
  • the moisture-curing composition may be stored in the absence of moisture in a suitable packaging or assembly, such as a keg, bag or cartridge, over a period of time from several months to one year and longer without its application characteristics or in their properties after hardening in a manner relevant to their use changed mass.
  • a suitable packaging or assembly such as a keg, bag or cartridge
  • the storage stability is determined by measuring the viscosity, the Auspressmenge or the Auspresskraft.
  • composition preferably contains no free isocyanate groups.
  • isocyanate-free composition is advantageous from the toxicological point of view.
  • the moisture-curing composition may be in the form of a one-component or in the form of a two-component composition.
  • composition in which all components of the composition are stored mixed in the same container, and which is storage stable at room temperature over a period of several weeks to months, that is not or only slightly changed in their application or use properties by the storage, and which is curable with moisture.
  • compositions in which the components of the composition in two different components are present which are stored in separate containers and which in each case at
  • the silane groups of the polymer and optionally present further silanes come into contact with moisture.
  • the silane groups have the property of hydrolyzing on contact with moisture.
  • organosilanols silicon-organic compounds containing one or more silanol groups, Si-OH groups
  • organosiloxanes silicon-organic
  • niche compounds containing one or more siloxane groups, Si-O-Si groups As a result of these reactions, which can be accelerated by the use of catalysts, the composition finally hardens; This process is also referred to as networking.
  • silanol groups may condense with, for example, hydroxyl groups of the substrate to which the moisture-curing composition is applied, whereby upon curing, excellent adhesion of the composition to the substrate can be formed.
  • the water needed for the curing reaction can either come from the air (atmospheric moisture) or the composition can be contacted with a water-containing component, for example by brushing, for example with a smoothing agent, or by spraying, or it can be of the composition in the case of the application, a water-containing component is added, for example in the form of a water-containing paste, which is mixed in, for example via a static mixer.
  • the described moisture-curing composition cures on contact with moisture.
  • the present invention also describes a cured composition obtained by the reaction of at least one silane-functional polymer SP with moisture.
  • Curing takes place at different speeds depending on the temperature, type of contact, the amount of moisture and the presence of any catalysts.
  • a skin is first formed on the surface of the composition.
  • the so-called skinning time therefore represents a measure of the curing rate.
  • the composition has a good elasticity with high strength and high ductility in the cured state and a surprisingly good thermal stability, for example at a temperature load of 90 ° C.
  • Suitable applications are, for example, the bonding of
  • Composition used as an elastic adhesive or sealant used as an elastic adhesive or sealant.
  • composition for, for example, joints in civil engineering, or for an application as
  • Adhesive for elastic bonds for example in vehicle construction, the composition preferably has a pasty consistency with pseudoplastic properties.
  • a pasty sealant or adhesive is applied to the substrate by means of a suitable device.
  • suitable methods for application are, for example, the application of commercially available cartridges, which are operated manually or by means of compressed air, or from a barrel or hobbock by means of a feed pump or an extruder, optionally by means of an application robot.
  • a sealant or adhesive with good application properties has a high stability and a short string. That means he stays After application in the applied form, so does not flow apart, and pulls after discontinuation of the application device no or only a very short thread, so that the substrate is not contaminated.
  • An adhesive for elastic bonds for example in vehicle construction, is preferably applied in the form of a bead having a substantially round or triangular cross-sectional area.
  • the composition When used as an adhesive, the composition is applied to a substrate S1 and / or a substrate S2.
  • the adhesive can thus be applied to one or the other substrate or to both substrates. Thereafter, the parts to be bonded are joined, whereupon the adhesive cures by contact with moisture. It must be ensured that the parts are joined within the so-called open time to ensure that both parts are reliably bonded together.
  • the composition between the substrates S1 and S2 is applied and then the curing of the composition is effected by contact with moisture. Usually, the sealant is pressed into a joint.
  • the substrate S1 may be the same as or different from substrate S2.
  • Suitable substrates S1 or S2 are in particular
  • Metals and alloys such as aluminum, iron, steel and non-ferrous metals, as well as surface-treated metals and alloys, such as galvanized or chromium-plated metals;
  • resins for example phenolic, melamine or epoxy resins, bonded wood-based materials, resin-textile composites and other so-called polymer composites;
  • Plastics such as polyvinyl chloride (hard and soft PVC), acrylonitrile-butadiene-styrene copolymers (ABS), polycarbonate (PC), polyamide (PA), polyester, poly (methyl methacrylate) (PMMA), polyester, epoxy resins , Polyurethanes (PUR), polyoxymethylene (POM), polyolefins (PO), polyethylene (PE) or polypropylene (PP), ethylene / propylene copolymers (EPM) and ethylene len / propylene / diene terpolymers (EPDM), wherein the plastics may preferably be surface treated by means of plasma, corona or flames;
  • PUR polyurethanes
  • POM polyoxymethylene
  • PO polyolefins
  • PE polyethylene
  • PP polypropylene
  • EPM ethylene / propylene copolymers
  • EPDM ethylene len / propylene / diene terpolymers
  • CFRP Carbon Fiber Reinforced Plastics
  • GRP Glass Fiber Reinforced Plastics
  • SMC Sheet Molding Compounds
  • coated substrates such as powder-coated metals or alloys
  • the substrates can be pretreated prior to application of the adhesive or sealant.
  • pretreatments include, in particular, physical and / or chemical cleaning processes, for example grinding, sandblasting, brushing or the like, or treatment with cleaners or solvents or the application of an adhesion promoter, a primer solution or a primer.
  • a glued or sealed article is obtained.
  • Such an article may be a building, in particular a building of civil engineering, or he may be a
  • Be means of transport, such as a vehicle on land or water, in particular an automobile, a bus, a truck, a train or a ship, or an attachment thereof.
  • the moisture-curing composition has a relatively low intrinsic viscosity, since the silane-functional polymer SP has a relatively low viscosity, which makes it possible to set good application properties.
  • the moisture-curing composition hardens quickly and has a good elasticity in the cured state with high strength and high ductility and a surprisingly good thermal stability, for example at a temperature load of 90 ° C.
  • the thermal stability in the cured state is significantly better. Examples
  • the amine content ie the total content of free amino groups and blocked amino groups (aldimino groups) in the compounds prepared, was determined by titrimetry (with 0.1 N HClO 4 in glacial acetic acid, against crystal violet) and is always given in mmol N / g.
  • Infrared spectra were measured as neat films on a Perkin-Elmer FT-IR instrument 1600 equipped with ZnSe crystal horizontal ATR measuring unit; the absorption bands are given in wavenumbers (cm -1 ) (measurement window: 4000-650 cm -1 ), and the suffix sh indicates a band appearing as a shoulder.
  • the viscosities were measured on a Rheotec RC30 cone-plate viscometer (cone diameter 50 mm, cone angle 1 °, cone tip-plate distance 0.05 mm, shear rate 10-100 s -1 ).
  • FT-IR 2940m, 2889m, 2837m, 2800m, 2677vw, 1465mh, 1455m, 1411vw, 1396vw, 1373w, 1358w, 1318w, 1305w, 1283w, 1264w, 1190s, 1114s,
  • FT-IR 2971m sh, 2939s, 2867m, 2837m, 2814m, 2763m, 1885vw br, 1463m sh, 1454m, 1410w, 1387w, 1373w, 1359w, 1303w, 1268m, 1189s, 1150m, 1084vs sh, 1080vs, 1043s, 868m, 815s, 778s, 761s sh, 679w.
  • FT-IR 2970m, 2937m sh, 2926m, 2881m, 2814m, 2764m, 2730w sh, 1880vw br, 1465m sh, 1454m, 1443m, 1410w, 1389m, 1362w, 1295w, 1263w, 1 166m, 1 101s, 1075vs, 1043s, 953s, 845m, 775s, 680w.
  • polyol Acclaim ® 12200 (Bayer; low monol polyoxypropylene diol, OH number 1 1 .0 mg KOH / g, water content approximately 0.02% by weight), 22.0 g of isophorone diisocyanate (IPDI Vestanat ®, Degussa) and 0.05g Di-n-butyl-tin dilaurate heated with constant stirring to 90 ° C and left at this temperature until the titrimetrically determined content of free isocyanate groups had reached a value of 0.75% by weight. The product was cooled to room temperature and stored with exclusion of moisture. The viscosity at 20 ° C was 40 Pa-s.
  • Table 1 Composition and viscosity of Examples 8 to 1 1 and the
  • the ingredients listed in Table 2 were mixed in the indicated amounts (in parts by weight) by means of a centrifugal mixer (SpeedMixer TM DAC 150, FlackTek Inc.).
  • the aspect (“aspect Zus.") was evaluated and the skin formation time ("HBZ") in the standard environment (23 ⁇ 1 ° C, 50 ⁇ 5% relative humidity) determined as a measure of the cure rate.
  • HBZ skin formation time
  • a few grams of the space temperature-warm composition in a layer thickness of about 2 mm were applied to cardboard and determined in standard climate, the time it took to lightly tapping the surface of the adhesive by means of a pipette of LDPE for the first time no residue on the The eyedropper remained behind.
  • the second film was then each stored after curing in standard atmosphere for 7 days at 70 ° C and 100% relative humidity and then determined in the same way, the tensile strength, elongation at break and modulus at 0.5-5% elongation (values in the table was labeled "(70/100)") Curing in standard atmosphere for 7 days stored at 90 ° C and then determined in the same way, the tensile strength, elongation at break and modulus at 0.5-5% elongation (values in the table with "(90 ° C)"). From this film was finally judged the aspect ("aspect film 90 ° C").
  • Comparative Examples 15, 17 and 18 all exhibited tack-free films, while Comparative Examples 20 and 21, each containing a silane-secondary polymer with the secondary aminosilane of the prior art, had a somewhat sticky surface. The differences in surface tack clearly showed after heat load at 90 ° C.
  • the films of Comparative Examples 20 and 21 were yellowed and tacky, while the films of Examples 15, 17 and 18 remained colorless and tack-free.
  • Comparative Example 19 which is derived from a primary aminosilane was only slightly tacky after heat stress, but it had a typical low elongation at break, which is not sufficient for many applications.
  • the triethoxysilane crosslinking Example 16 exhibited slow cure and was therefore still sticky after 14 days. However, under heat load, it hardened well, as evidenced by both the mechanical values and the decrease in tackiness.

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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)
  • Adhesives Or Adhesive Processes (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Silicon Polymers (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Paints Or Removers (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

La présente invention concerne de nouveaux aminosilanes et iminosilanes secondaires, ainsi que leur procédé de production et leur utilisation. Les aminosilanes secondaires peuvent aisément être obtenus à partir de produits de départ facilement disponibles. Ils sont caractérisés notamment par une faible viscosité et sont idéalement appropriés pour la formation de polymères à fonction silane, qui présentent une faible viscosité, un durcissement rapide et une bonne résistance thermique.
EP11793844.9A 2010-12-17 2011-12-13 Aminosilanes secondaires Withdrawn EP2651956A1 (fr)

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EP10195811A EP2468759A1 (fr) 2010-12-17 2010-12-17 Aminosilanes secondaires
PCT/EP2011/072631 WO2012080266A1 (fr) 2010-12-17 2011-12-13 Aminosilanes secondaires
EP11793844.9A EP2651956A1 (fr) 2010-12-17 2011-12-13 Aminosilanes secondaires

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CN109804010B (zh) * 2016-10-17 2021-11-12 科思创德国股份有限公司 用于粘合剂-、密封剂-和涂料组合物的稳定剂
JP6510098B1 (ja) * 2018-02-14 2019-05-08 Ａｇｃ株式会社 ポリウレタンフォーム製造用組成物、ポリオールシステム液及びポリウレタンフォームの製造方法
CN109535412B (zh) * 2018-11-16 2021-05-11 上海东大化学有限公司 一种仲氨基硅烷偶联剂及其制备方法
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JP2014501237A (ja) 2014-01-20
CN103313995A (zh) 2013-09-18
US20130281562A1 (en) 2013-10-24
CN103313995B (zh) 2016-08-10
JP6133783B2 (ja) 2017-05-24
EP2468759A1 (fr) 2012-06-27
WO2012080266A1 (fr) 2012-06-21

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