EP4103633A1 - Polymère contenant des groupes silane - Google Patents

Polymère contenant des groupes silane

Info

Publication number
EP4103633A1
EP4103633A1 EP21703265.5A EP21703265A EP4103633A1 EP 4103633 A1 EP4103633 A1 EP 4103633A1 EP 21703265 A EP21703265 A EP 21703265A EP 4103633 A1 EP4103633 A1 EP 4103633A1
Authority
EP
European Patent Office
Prior art keywords
groups
polymer
diisocyanate
silane
group
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.)
Pending
Application number
EP21703265.5A
Other languages
German (de)
English (en)
Inventor
Andreas Kramer
Marcel Oertli
Ursula Stadelmann
Sven Reimann
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
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sika Technology AG filed Critical Sika Technology AG
Publication of EP4103633A1 publication Critical patent/EP4103633A1/fr
Pending legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C08L75/08—Polyurethanes from polyethers
    • 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
    • C08G18/4825—Polyethers containing two hydroxy groups
    • 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
    • C08G18/4833—Polyethers containing oxyethylene units
    • C08G18/4837—Polyethers containing oxyethylene units and other oxyalkylene units
    • C08G18/4841—Polyethers containing oxyethylene units and other oxyalkylene units containing oxyethylene end groups
    • 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
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J175/08—Polyurethanes from polyethers

Definitions

  • the invention relates to polymers containing silane groups and their use in curable compositions, in particular moisture-curing adhesives, sealants or coatings.
  • silane-functional or silane-terminated polymers are known as a component of moisture-curing adhesives, sealants or coatings.
  • the isocyanate group-containing polymers used as starting materials for their production are produced by reacting monomeric diisocyanates and polyether diols in an NCO / OH ratio of approximately 2/1, described for example in US Pat. No. 6,545,087 or US Pat. No. 9,790,315. They contain considerable amounts of monomeric diisocyanate and chain-extended polymers in which two or more polyether diols are linked via the monomeric diisocyanate.
  • the silane-containing polymers obtained therefrom have a high viscosity, as a result of which they typically have to be diluted with considerable amounts of plasticizers in order to be sufficiently fluid at room temperature and thus easy to handle.
  • the freedom when formulating moisture-curing adhesives, sealants or coatings is limited in terms of their plasticizer content.
  • sealants or adhesives with a very low plasticizer content are required in order not to risk damaging the substrates from migrating plasticizers.
  • these known polymers containing silane groups can still be improved with regard to curing speed, strength and thermal stability.
  • the object of the present invention is to provide silane-containing polymers which are easy to handle even without dilution with plasticizers or solvents at room temperature and have faster curing and / or higher strength with good ductility and elasticity and / or improved thermal properties Enable stability.
  • Polymer which was previously obtained by reacting a monomeric diisocyanate with a polyether polyol in an NCO / OH ratio of at least 3/1 and then removing a large part of the unreacted monomeric diisocyanate, with an amino, mercapto- or hydroxysilane in a stoichiometric ratio of at least 1/1 with respect to the isocyanate groups.
  • the polymer according to the invention containing silane groups is free from isocyanate groups and contains hardly any silane adducts of monomeric diisocyanate and only slightly chain-extended polymer components. As a result, it has a particularly low viscosity at room temperature and enables moisture-curing compositions with very good processability.
  • the polymers according to the invention show particularly rapid curing and in some cases also particularly high strength (tensile strength and / or modulus of elasticity and / or Shore hardness).
  • the polymers according to the invention can be used to produce sealants, adhesives or coatings with little or no plasticizers or solvents that are particularly stable in storage and are very easy to process, such as are not accessible from conventional polymers containing silane groups based on polymers containing isocyanate groups.
  • the products obtained with the polymers according to the invention surprisingly have advantageous properties even after curing, such as, in particular, improved thermal stability and / or particularly high strength with particularly high extensibility.
  • the invention relates to a polymer containing silane groups from the implementation of
  • the “NCO content” is the isocyanate group content in% by weight.
  • Organicsilane or “silane” for short is an organic compound with at least one silane group.
  • alkoxysilane group” or “silane group” for short is a silyl group bonded to an organic radical with one to three, in particular two or three, hydrolyzable alkoxy radicals on the silicon atom.
  • Aminosilane “Mercaptosilane” or “Hydroxysilane” are organosilanes that have an amino, mercapto or hydroxyl group on the organic residue in addition to the silane group.
  • Molecular weight is the molar mass (in grams per mole) of a molecule or a molecule residue.
  • Average molecular weight is the number average molecular weight (M n ) of a polydisperse mixture of oligomeric or polymeric molecules or molecular residues. It is determined by means of gel permeation chromatography (GPC) against polystyrene as the standard.
  • GPC gel permeation chromatography
  • a dashed line in the formulas represents the bond between a substituent and the associated remainder of the molecule.
  • Plasticizers are low-volatility substances that are not chemically incorporated into the polymer during curing and have a softening effect on the cured polymer.
  • a substance or a composition is referred to as “storage-stable” or “storable” if it can be stored at room temperature in a suitable container for a longer period of time, typically for at least 3 months to 6 months and more, without it being in their Application or usage properties changed by storage to an extent relevant to their use.
  • room temperature A temperature of 23 ° C is referred to as “room temperature”.
  • the polymer containing silane groups is preferably essentially free from plasticizers and solvents. In particular, it contains less than 1% by weight of plasticizer. When used in a curable composition, such a polymer leaves complete freedom as to whether, how much and which plasticizer the composition should contain.
  • the polymer containing silane groups preferably has silane groups of the formula (I), where b stands for 0, 1 or 2, in particular for 0 or 1
  • R 1 represents an alkyl radical with 1 to 10 carbon atoms, optionally containing ether groups
  • R 2 represents a divalent hydrocarbon radical with 1 to 12 carbon atoms, which optionally contains cyclic and / or aromatic components and optionally one or more heteroatoms, in particular an amido , Carbamate or morpholino group, has, and
  • X stands for O, S or NR 3 , where R 3 stands for H or a monovalent hydrocarbon radical with 1 to 20 carbon atoms with optionally heteroatoms in the form of alkoxysilyl, ether or carboxylic acid ester groups.
  • R 1 is preferably methyl or ethyl or isopropyl.
  • R 1 particularly preferably represents methyl. Such polymers containing silane groups are particularly reactive. R 1 also particularly preferably represents ethyl. Such polymers containing silane groups are particularly storage-stable and toxicologically advantageous.
  • X preferably stands for 0 or NR 3 .
  • R 3 is preferably H, ethyl, butyl, phenyl or an aliphatic hydrocarbon radical with 6 to 20 carbon atoms, which optionally has ether or carboxylic acid ester groups.
  • X is NR 3 and R 3 is _ where R 4 in each case stands for methyl or ethyl, in particular for ethyl.
  • R 2 preferably stands for 1,3-propylene, 1, 3-butylene or 1,4-butylene, it being possible for butylene to be substituted by one or two methyl groups, particularly preferably 1, 3 -Propylene.
  • R 2 preferably represents a divalent hydrocarbon radical having 6 to 12 carbon atoms which has an amido, carbamate or morpholino group, in particular a radical of the formula
  • the preferred silane groups of the formula (I) enable high strengths with high extensibility.
  • the polymer containing silane groups preferably has an average of 1.3 to 4, particularly preferably 1.5 to 3.5, in particular 1.7 to 3.5, silane groups per molecule.
  • a particularly preferred polymer containing silane groups is linear and has an average of 1.7 to 2, preferably 1.8 to 2, in particular 1.9 to 2, silane groups per molecule. Such a polymer enables particularly high extensibility.
  • Another particularly preferred polymer containing silane groups is branched and has an average of 2.1 to 3, preferably 2.2 to 3, silane groups per molecule.
  • the polymer containing silane groups preferably has an average molecular weight M n in the range from 3-00 to 30-00 g / mol, preferably 5-00 to 20-00 g / mol.
  • the polymer containing isocyanate groups, from which the polymer containing silane groups is derived preferably has an NCO content in the range from 0.3 to 3.5% by weight, in particular 0.4 to 2.5% by weight.
  • the polymer containing isocyanate groups preferably has an average molecular weight M n in the range from 2,500 to 30-00 g / mol, preferably 4-00 to 20-00 g / mol.
  • the polymer containing isocyanate groups preferably has a monomeric diisocyanate content of at most 0.25% by weight, preferably at most 0.2% by weight, in particular at most 0.15% by weight.
  • aromatic or aliphatic diisocyanates in particular 4,4'-diphenylmethane diisocyanate, optionally with proportions of 2,4'- and / or 2,2'-diphenylmethane diisocyanate (MDI), are suitable as monomeric diisocyanate,
  • 1,4-phenylene diisocyanate PDI
  • NDI naphthalene-1,5-diisocyanate
  • HDI 1,6-hexane-diisocyanate
  • TMDI 4-trimethyl-1,6-hexamethylene diisocyanate
  • cyclo - hexane-1,3- or 1,4-diisocyanate 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (isophorone diisocyanate or IPDI), perhydro-2,4'- or -4,4 - Diphenylmethane diisocyanate (HMDI), 1,3- or 1,4-bis (isocyanatomethyl) cyclohexane, m- or p-xylylene diisocyanate (XDI), m-tetramethylxylylene diisocyanate (TMXDI), or mixtures thereof.
  • the monomeric diis is
  • IPDI is particularly preferred.
  • the polymers containing silane groups obtained in this way have a particularly low viscosity and enable compositions with particularly good processability, high extensibility and particularly good light stability.
  • MDI is very particularly preferred, in particular 4,4'-diphenylmethane diisocyanate (4,4'-MDI).
  • the polymers containing silane groups obtained in this way have a surprisingly low viscosity and enable compositions with good processability, particularly high strength and particularly good thermal stability.
  • silane group-containing polymers produced from conventional isocyanate group-containing polymers based on MDI have very high viscosities and must be diluted with a large amount of plasticizer or solvent in order to prevent gelling during production.
  • polyether polyols which are preferably liquid at room temperature, are suitable as the polyether polyol.
  • the polyether polyol preferably has 1,2-ethyleneoxy, 1,2-propyleneoxy, 1,3-propyleneoxy, 1,2-butyleneoxy or 1,4-butyleneoxy groups as repeating units.
  • polyoxyalkylene diols and / or polyoxyalkylene triols in particular polymerization products of ethylene oxide or 1,2-propylene oxide or 1,2 or 2,3-butylene oxide or oxetane or tetrahydrofuran or mixtures thereof, these using a starter molecule with two or more active Hydrogen atoms can be polymerized, in particular a starter molecule such as water, ammonia or a compound with several OH or NH groups such as 1,2-ethanediol, 1,2- or 1,3-propanediol, neopentyl glycol, diethylene glycol, triethylene glycol, the isomeric dipropylene glycols or tripropylene glycols, the isomeric butanediols, pentanediols, hexanediols, heptanediols, octanediols, nonanediol
  • Polyoxypropylene diols, polyoxypropylene triols, or ethylene oxide-terminated polyoxypropylene diols or triols are particularly preferred. These are polyoxyethylene polyoxypropylene mixed polyols which are obtained in particular in that polyoxypropylene diols or triols are further alkoxylated with ethylene oxide after the polypropoxylation reaction has ended and thus ultimately have primary hydroxyl groups.
  • the polyether polyol preferably has an OH number in the range from 5 to 58 mg KOH / g, in particular 6 to 40 mg KOH / g.
  • the polyether polyol preferably has an average molecular weight M n in the range from 2-00 to 20-00 g / mol.
  • the polyether polyol preferably has an average OH functionality in the range from 1.7 to 3.
  • the polyether polyol is preferably a polyether diol.
  • Such a polymer containing silane groups enables compositions with particularly high extensibility.
  • the polyether diol preferably has an average OH functionality in the range from 1.7 to 2, preferably 1.8 to 2, in particular 1.9 to 2.
  • Commercial polyether diols contain a certain amount of monols due to their production, which is typically slightly below 2 due to their average OH functionality.
  • the polyether diol preferably has an OH number in the range from 5 to 58 mg KOH / g, in particular 6 to 33 mg KOH / g.
  • Such a polymer enables compositions with particularly high extensibility and elasticity.
  • a polymer containing isocyanate groups which is produced with a polyetherdiol preferably has an NCO content in the range from 0.3 to 3.5% by weight, in particular 0.4 to 2.2% by weight.
  • the polyether polyol is a polyether triol with an average OH functionality in the range from 2.2 to 3.
  • Comhausal polyether triols contain a certain amount of monols as a result of their production, so that their average OH functionality is typically slightly below 3.
  • Such a polymer containing silane groups enables compositions with particularly good thermal stability after curing.
  • the polyether triol preferably has an OH number in the range from 15 to 58 mg KOH / g, in particular 20 to 40 mg KOH / g.
  • a polymer containing isocyanate groups which is produced with a polyether triol preferably has an NCO content in the range from 0.8 to 3.5% by weight, in particular 1.2 to 2.5% by weight.
  • a polymer containing silane groups derived from a polyether triol and 4,4'-MDI as a monomeric diisocyanate is very particularly preferred. Such a polymer cannot be obtained conventionally without the addition of large amounts of plasticizer or solvent, since it gels during production. When used proportionately in a moisture-curing composition based on polymers containing silane groups, it enables a massive increased strength with increased elasticity and improved thermal stability.
  • the molar NCO / OH ratio in the preparation of the isocyanate group-containing polymer is preferably in the range from 3/1 to 20/1, particularly preferably in the range from 4/1 to 15/1, in particular in the range from 5/1 until 13/1.
  • the reaction is preferably carried out with exclusion of moisture at a temperature in the range from 20 to 160 ° C., in particular from 40 to 140 ° C., if appropriate in the presence of suitable catalysts.
  • the monomeric diisocyanate remaining in the reaction mixture is removed by means of a suitable separation process, except for the residual content described.
  • a preferred separation process is a distillation process, in particular thin-film distillation or short-path distillation, preferably with application of a vacuum.
  • a multi-stage process in which the monomeric diisocyanate is removed in a short-path evaporator at a jacket temperature in the range from 120 to 200 ° C. and a pressure of 0.001 to 0.5 mbar is particularly preferred.
  • the preferred monomeric diisocyanate removal by distillation is particularly difficult. For example, it must be ensured that the condensate does not solidify and clog the system. It is preferred to run at 0.001 to 0.5 mbar at a jacket temperature in the range from 160 to 200.degree. C. and the removed monomeric diisocyanate is condensed at a temperature in the range from 40 to 60.degree.
  • reaction of the monomeric diisocyanate with the polyether polyol and the subsequent removal of the majority of the monomeric diisocyanate remaining in the reaction mixture are preferably carried out without the use of solvents or entrainers.
  • the monomeric diisocyanate removed after the reaction is then preferably reused, ie reused for the production of isocyanate group-containing polymer.
  • the OH groups of the polyether polyol react with the isocyanate groups of the monomeric diisocyanate.
  • chain extension reactions in which OH groups and / or isocyanate groups of reaction products between polyol and monomeric diisocyanate react.
  • a measure of the chain lengthening reaction is the average molecular weight of the polymer or the width and distribution of the peaks in the GPC analysis. Another measure is the effective NCO content of the monomer-free polymer in relation to the theoretical NCO content, calculated from the reaction of each OH group with a monomeric diisocyanate.
  • the polymer containing isocyanate groups preferably contains only a small amount of chain-extended fractions.
  • the NCO content of the polymer is preferably at least 90%, in particular at least 95%, of the theoretical NCO content, which is calculated from the addition of one mole of monomeric diisocyanate per mole of OH groups in the polyether polyol.
  • the polymer containing isocyanate groups is liquid at room temperature and has a low viscosity, contains a low content of monomeric diisocyanates and is very storage-stable in the absence of moisture.
  • the amino, mercapto- or hydroxysilane for the reaction with the polymer containing isocyanate groups is preferably a silane of the formula (II),
  • silanes of the formula (II) are selected from the group consisting of 3-aminopropyltrimethoxysilane, 3-aminopropyldimethoxymethylsilane, 4-aminobutyl-trimethoxysilane, 4-amino-3-methylbutyltrimethoxysilane, 4-amino-3,3-dimethylbutyl-trimethoxysilane, N- Ethyl 3-amino- (2-methylpropyl) trimethoxysilane, N-butyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N- (3-trimethoxysilylpropyl) aminosuccinic acid diethyl ester, N- (3-dimethoxymethylsyls
  • silane of the formula (II) is N- (3-trimethoxysilylpropyl) aminosuccinic acid diethyl ester, N- (3-triethoxysilylpropyl) aminosuccinic acid diethyl ester, N- (3-dimethoxymethylsilylpropyl) aminosuccinic acid diethyl ester, N- (3-dimethoxymethylsilylpropyl) aminosuccinic acid diethyl ester, diethylpropyl-aminosuccinic acid diethyl ester.
  • the amino, mercapto or flydroxysilane is reacted with the polymer containing isocyanate groups in a stoichiometric ratio of at least 1 mol of amino, mercapto or flydroxysilane per mol equivalent of isocyanate groups.
  • a catalyst is set, in particular a tertiary amine or a metal compound, in particular a bismuth (III), zinc (II), zirconium (IV) or tin (II) compound or an organotin (IV) compound.
  • a particularly preferred polymer containing silane groups is derived from a polyether triol, as already described. Such a polymer containing silane groups has on average more than 2, preferably 2.1 to 4, in particular 2.2 to 3.5, silane groups per molecule. It enables compositions with particularly good thermal stability after curing.
  • a particularly preferred polymer containing silane groups is derived from IPDI as a monomeric diisocyanate. It thus has in particular silane groups of the formula (la) or (Ib), where R 1 , R 2 , X and b have the meanings already mentioned.
  • Such a polymer enables high extensibility and particularly high light stability with particularly good thermal stability.
  • a polymer containing silane groups which is derived from a polyether triol and 4,4'-MDI as a monomeric diisocyanate is very particularly preferred. It thus has, in particular, silane groups of the formula (Ic), where R 1 , R 2 , X and b have the meanings already mentioned.
  • Such a polymer cannot be obtained conventionally without the addition of large amounts of plasticizer or solvent, since it gels during production. It enables compositions with particularly high strength and particularly good thermal stability. It is particularly preferably used in combination with a further, preferably linear, polymer containing silane groups, whereby it enables improved strength with very high extensibility and improved thermal stability.
  • the polymer containing silane groups is storage-stable in the absence of moisture.
  • the silane groups hydrolyze on contact with moisture.
  • Silanol groups (Si-OH groups) and subsequent condensation reactions form siloxane groups (Si-O-Si groups).
  • Si-OH groups Silanol groups
  • Si-O-Si groups siloxane groups
  • the moisture for curing can either come from the air (air humidity), or the polymer can be brought into contact with a water-containing component, for example by brushing, spraying or mixing in.
  • silanol groups can condense with, for example, hydroxyl groups on a substrate to which the polymer is applied, which can result in an additional improvement in the adhesion to the substrate during crosslinking.
  • the invention also relates to a process for producing the polymer containing silane groups, characterized in that (a) at least one monomeric diisocyanate with at least one polyether polyol with an OH number in the range from 5 to 58 mg KOH / g, in particular 6 to 40 mg KOH / g is converted in a molar NCO / OH ratio of at least 3/1, (b) a large part of the unreacted monomeric diisocyanate is then removed by means of a suitable separation process,
  • the invention also provides a curable composition
  • a curable composition comprising the inventive silane-containing polymer and at least one other component selected from the group consisting of catalysts, crosslinkers, adhesion promoters, drying agents, plasticizers and fillers.
  • Metal catalysts and / or nitrogen-containing compounds which accelerate the crosslinking of polymers containing silane groups are suitable as catalysts.
  • Suitable metal catalysts are in particular compounds of titanium, zirconium, aluminum or tin, in particular organotin compounds, organotitanates, organozirconates or organoaluminates, these compounds in particular alkoxy groups, aminoalkoxy groups, sulfonate groups, carboxyl groups, 1,3-diketonate groups, 1, 3-ketoesterate groups, dialkyl phosphate groups or dialkyl pyrophosphate groups.
  • organotin compounds are dialkyltin oxides, dialkyl zinndichloride, dialkyltin dicarboxylates and Dialkylzinndiketonate, particularly dibutyltin oxide, dibutyltin dichloride, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin oxide, dioctyltin oxide, dioctyltin dichloride, Dioctylzinndi- acetate, dioctyltin dilaurate or Dioctylzinndiacetylacetonat or Alkylzinnthio ester.
  • organotitanates are bis (ethylacetoacetato) diisobutoxy titanium (IV), bis (ethylacetoacetato) diisopropoxy titanium (IV), bis (acetylacetonato) diisopropoxy titanium (IV), bis (acetylacetonato) diisobutoxytitanium (IV), tris (oxyopropethyl) amine xytitanium (IV), bis [tris (oxyethyl) amine] diisopropoxytitanium (IV), bis (2-ethylhexane-1, 3- dioxy) titanium (IV), tris [2 - ((2-aminoethyl) amino) ethoxy] ethoxytitanium (IV), bis (neopentyl- (diallyl) oxydiethoxytitanium (IV), titanium (IV) tetrabutanolate, tetra (2-ethylhexyloxy)
  • Tyzor ® AA GBA, GBO, AA-75, AA-65, AA-105, DC, BEAT, BTP, TE, TnBT, KTM, TOT , TPT or IBAY (all from Dorf Ketal); Tytan PBT, TET, X85, TAA, ET, S2, S4 or S6 (all from Borica Company Ltd.) and Ken- React ® KR ® TTS, 7, 9QS, 12, 26S, 33DS, 38S, 39DS, 44, 134S, 138S, 133DS, 158FS or LICA 44 ® (all from Kenrich Petrochemicals).
  • organozirconates are the types commercially available Ken-React ® NZ ® 38J, KZ ® TPPJ, KZ ® TPP, NZ ® 01, 09, 12, 38, 44, or 97 (all available from Kenrich Petro Chemicals) or Snapcure ® 3020, 3030, 1020 (all by Johnson Matthey & Brandenberger).
  • a particularly suitable organoaluminate is the commercially available type K-Kat 5218 (from King Industries).
  • Nitrogen-containing compounds suitable as catalysts are, in particular, amines such as, in particular, N-ethyl-diisopropylamine, N, N, N ', N'-tetramethyl-alkylenediamines, polyoxyalkyleneamines, 1,4-diazabicyclo [2.2.2] octane; Aminosilanes such as, in particular, 3-aminopropyltrimethoxysilane, 3-aminopropyldimethoxymethylsilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -N'- [3- (trimethoxysilyl) propyl] ethylenediamine or analogs thereof with ethoxy instead of methoxy groups on silicon; cyclic amidines
  • catalysts in particular combinations of at least one metal catalyst and at least one nitrogen-containing compound, are also suitable.
  • Organotin compounds, organotitanates, amines, in particular aminosilanes, amidines, guanidines or imidazoles are preferred as catalysts.
  • adhesion promoters and / or crosslinkers are aminosilanes, mercaptosilanes, epoxysilanes, (meth) acrylosilanes, anhydridosilanes, carbamatosilanes, alkylsilanes or iminosilanes, or oligomeric forms of these silanes, or adducts of primary aminosilanes with epoxysilanes or (meth) acrylosilanes or anhydridosilanes .
  • drying agents are tetraethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, organosilanes which have a functional group in the ⁇ -position to the silane group, in particular N- (methyldimethoxysilylmethyl) -0-methylcarbamate or (methacryloxymethyl) silanes, methoxymethyl esters, and ortho-silanes, ortho-silanes Calcium oxide or molecular sieves.
  • Vinyl trimethoxysilane or vinyl triethoxysilane is preferred.
  • Vinyltrimethoxysilane is preferred when the polymer containing silane groups has methoxysilane groups, while vinyltriethoxysilane is preferred when the polymer containing silane groups has ethoxysilane groups.
  • Particularly suitable plasticizers are carboxylic acid esters such as phthalates, especially diisononyl phthalate (DINP), diisodecyl phthalate (DIDP) or di (2-propylheptyl) phthalate (DPHP), hydrogenated phthalates or 1,2-cyclohexanedicarboxylic acid esters, especially hydrogenated diisononyl phthalate or diisononyl 1,2-cyclohexanedicarboxylate (DINCH), terephthalates, especially bis (2-ethylhexyl) terephthalate (DOTP) or diisononyl terephthalate (DINT), hydrogenated terephthalates or 1,4-cyclohexanedicarboxylic acid esters, especially hydrogenated bis (2-ethylhexyl) terephthalate or bis (2-ethylhexyl) -1, 4-cyclohexanedicarboxylate or hydrogenated diisonony
  • Particularly suitable fillers are ground or precipitated calcium carbonates, which are optionally coated with fatty acids, especially stearates, barytes (heavy spar), quartz flours, quartz sands, dolomites, wollastonites, calcined kaolins, sheet silicates such as mica or talc, zeolites, aluminum hydroxides, magnesium hydroxides , Silicas including highly dispersed silicas from pyrolysis processes, cements, plasters, fly ash, industrially produced carbon black, graphite, metal powder, for example aluminum, copper, iron, silver or steel, PVC powder or hollow spheres. Precipitated calcium carbonate and / or carbon black coated with fatty acid is preferred.
  • Fibers in particular glass fibers, carbon fibers, metal fibers, ceramic fibers, plastic fibers such as polyamide fibers or polyethylene fibers, or natural fibers such as wool, cellulose, hemp or sisal;
  • Nanofillers such as graphene or carbon nanotubes
  • Inorganic or organic pigments in particular titanium dioxide, chromium oxides or iron oxides;
  • - Rheology modifiers especially thickeners, especially sheet silicates such as bentonites, derivatives of castor oil, hydrogenated castor oil, polyamides, polyamide waxes, polyurethanes, urea compounds, pyrogenic silicic acids, cellulose ethers or hydrophobically modified polyoxyethylenes; - Stabilizers against oxidation, heat, light or UV radiation;
  • Non-reactive polymers in particular homopolymers or copolymers of unsaturated monomers, in particular from the group comprising ethylene, propylene, butylene, isobutylene, isoprene, vinyl acetate or alkyl (meth) acrylates, in particular polyethylene (PE), polypropylene (PP) , Polyisobutylenes, ethylene vinyl acetate copolymers (EVA) or atactic poly- ⁇ -olefins (APAO);
  • PE polyethylene
  • PP polypropylene
  • EVA ethylene vinyl acetate copolymers
  • APAO atactic poly- ⁇ -olefins
  • Additives in particular wetting agents, leveling agents, defoamers, deaerators, stabilizers against oxidation, heat, light or UV radiation or biocides.
  • the curable composition preferably contains 5 to 80% by weight, particularly preferably 10 to 70% by weight, in particular 20 to 60% by weight, of polymers containing silane groups.
  • the curable composition comprises at least one inventive polymer containing silane groups derived from a polyether triol and at least one further, in particular linear, polymer containing silane groups.
  • the weight ratio between the inventive polymer containing silane groups derived from a polyether triol and the further polymer containing silane groups is preferably in the range from 10/90 to 70/30, in particular 15/85 to 60/40.
  • the further polymer containing silane groups is preferably selected from the group consisting of - Polymers according to the invention containing silane groups derived from a polyether diol;
  • Polyethers containing silane groups obtained from the reaction of polyether polyols, in particular diols, with isocyanatosilanes, optionally with chain extension with diisocyanates.
  • the inventive polymer containing silane groups derived from a polyether triol, improves, in particular, the thermal stability and, if appropriate, the strength and / or elasticity of the composition.
  • the curable composition is produced in particular with the exclusion of moisture and stored in moisture-tight containers at ambient temperature.
  • a suitable moisture-proof container consists in particular of an optionally coated metal and / or plastic and represents in particular a barrel, a container, a flobbock, a bucket, a canister, a can, a bag, a tubular bag, a cartridge or a tube.
  • the curable composition can be in the form of a one-component or in the form of a two-component composition.
  • One-component is a composition in which all components of the composition are stored mixed in the same container and which can be hardened with moisture.
  • a composition is referred to as “two-component” in which the constituents of the composition are present in two different components, which are stored in separate containers. The two components are only mixed with one another shortly before or during the application of the composition, whereupon the mixed composition cures, the curing only taking place or being completed by the action of moisture.
  • the curable composition is preferably one-component. With suitable packaging and storage, it is stable in storage, typically for several months to a year or longer.
  • the silane groups present come into contact with moisture, whereby the curing process begins. Curing takes place at different speeds depending on the temperature, the type of contact, the amount of moisture and the presence of any catalysts.
  • a skin is initially formed on the surface of the composition. The so-called skin formation time is a measure of the hardening speed. The hardened composition is the result.
  • an accelerator component which contains or releases water and / or a catalyst and / or a hardener, can be added to the composition during application, or the composition can be mixed with such an accelerator component after its application nents are brought into contact
  • the curable composition is preferably applied at ambient temperature, in particular in the range from about -10 to 50.degree. C., preferably in the range from -5 to 45.degree. C., in particular from 0 to 40.degree.
  • Curing is also preferably carried out at ambient temperature.
  • the composition has pronounced elastic properties, in particular high strength and high extensibility, good thermal stability and good adhesion properties on various substrates. This makes it suitable for a multitude of uses, in particular as a sealant, adhesive, covering, coating or paint for construction or industrial applications, for example as a joint sealant, parquet adhesive, assembly adhesive, window adhesive, for body sealing, seam sealing or cavity sealing, as flooring , Floor coating, balcony coating, roof coating or parking garage coating.
  • the curable composition is preferably used as an elastic adhesive or elastic sealant or elastic coating.
  • the curable composition can be formulated in such a way that it has a pasty consistency with structurally viscous properties.
  • a composition is applied by means of a suitable device, for example from commercially available cartridges or barrels or hobbocks, for example in the form of a caterpillar, which can have an essentially round or triangular cross-sectional area.
  • the curable composition can furthermore be formulated in such a way that it is liquid and so-called self-leveling or only slightly thixotropic and can be poured out for application.
  • As a coating for example, it can then be spread over a large area to the desired layer thickness, for example by means of a roller, a slider, a notched trowel or a spatula.
  • Suitable substrates for gluing or sealing or coating are in particular special - glass, glass ceramics, screen printing ceramics, concrete, mortar, cement screed, fiber cement, in particular fiber cement panels, brick, bricks, gypsum, in particular special gypsum panels or anhydride screed, or natural stones like granite or marble; - Metals or alloys such as aluminum, copper, iron, steel, non-ferrous metals, including surface-refined metals or alloys such as galvanized or chrome-plated metals;
  • Plastics especially hard or soft PVC, polycarbonate (PC), polyamide (PA), polyester, PMMA, ABS, SAN, epoxy resins, phenolic resins, PUR, POM, TPO, PE, PP, EPM or EPDM, whereby the plastics if necessary, surface-treated by means of plasma, corona or flame;
  • PCC polymer-modified cement mortar
  • ECC epoxy resin-modified cement mortar
  • - Insulating foams especially made of EPS, XPS, PUR, PIR, rock wool, glass wool or foamed glass (foam glass).
  • the substrates can be pretreated before application, in particular by physical and / or chemical cleaning processes or the application of an activator or a primer.
  • Two substrates of the same type or two different substrates can be glued or sealed.
  • the curable composition additionally comprises at least one epoxy resin.
  • a composition is preferably two-component. In particular, it contains at least one further component selected from aminosilanes, epoxysilanes, vinylsilanes, polyamines with two or three primary or secondary aliphatic amino groups and accelerators for the reaction of epoxy groups. It may also contain water.
  • the weight ratio between polymers containing silane groups and the epoxy resin is preferably in the range from 20/80 to 70/30.
  • Such a composition has a particularly high strength, with a high content of epoxy resin enabling particularly high strength and a high content of polymer containing silane groups enables high extensibility and elasticity with high strength.
  • a liquid epoxy resin which is flowable at room temperature and has a glass transition temperature below 25 ° C. is particularly suitable as the epoxy resin.
  • a liquid epoxy resin based on a bisphenol A, bisphenol F or bisphenol A / F diglycidyl ether is preferred, in particular a technical grade such as is commercially available, for example, from Dow, Fluntsman or Momentive, optionally with proportions of Solid bisphenol A resin or phenol novolak.
  • silanes for such a composition are 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyl-trimethoxysilane, N- (2-aminoethyl) -3-aminopropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, vinyltrimethoxysilane or vinyltriethoxysilane.
  • Suitable polyamines are in particular 2,2-dimethyl-1,3-propanediamine, 1,3-pentanediamine (DAMP), 1,5-pentanediamine, 1,5-diamino-2-methylpentane (MPMD), 2-butyl-2- ethyl-1,5-pentanediamine (C11 -neodiamine), 1,6-hexanediamine, 2,5-dimethyl-1,6-hexanediamine, 2.2 (4), 4-trimethylhexamethylenediamine (TMD), 1.7 - Heptanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine, 1,11-undecanediamine, 1, 12-dodecanediamine, 1,2-, 1,3- or 1,4-diaminocyclohexane, 1 , 3- bis (aminomethyl) cyclohexane, 1, 4-bis (aminomethyl) cyclohexane, 1-amino-3-a
  • 1,3-diaminocyclohexane bis (4-aminocyclohexyl) methane, bis (4-amino-3-methylcyclohexyl) methane, bis (4-amino-3-ethylcyclohexyl) methane, bis (4-amino-3,5-dimethylcyclohexyl) methane, bis (4-amino-3-ethyl-5-methylcyclohexyl) methane, 2,5 (2,6) -bis (aminomethyl) bicyclo [2.2.1] heptane (NBDA), 3 (4), 8 (9 ) -Bis (aminomethyl) tricyclo [5.2.1.0 2 ' 6 ] decane, 1,4-diamino-2,2,6-trimethylcyclohexane (TMCDA),
  • 1,8-menthediamine 1,3-bis (aminomethyl) benzene (MXDA) or 1,4-bis (aminomethyl) benzene, 3- (2-aminoethyl) aminopropylamine, bis (hexamethylene) triamine (BHMT), diethylenetriamine (DETA), triethylenetetramine (TETA), tetraethylene pentamine (TEPA), pentaethylene hexamine (PEHA) or higher homologues of linear polyethylene amines, dipropylenetriamine (DPTA), N- (2-aminoethyl) -1, 3-propanediamine (N3-amine), N , N'-bis (3-aminopropyl) ethylenediamine (N4-amine), N, N'-bis (3-aminopropyl) -
  • Epoxy resins or monoepoxides such as, in particular, cresyl glycidyl ethers, as well as the polyamidoamines mentioned or so-called Mannich bases, especially phenalkamines.
  • 1,4-diaminocyclohexane 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) -cyclohexane, IPDA, 2 (4) -methyl-1,3-diaminocyclohexane, bis (4-aminocyclohexyl) -methane , NB DA, MXDA, BHMT, TETA, TEPA, N4-amine, DMAPAPA, N-benzyl-1,2-ethanediamine, polyoxypropylenediamines or triamines with an average molecular weight M n in the range from 200 to 500 g / mol, or adducts of MPMD or 1,2-propanediamine with cresyl glycidyl ether.
  • Suitable accelerators for the reaction of epoxy groups are, in particular, acids or compounds which can be hydrolyzed to acids, in particular organic carboxylic acids such as salicylic acid, organic sulfonic acids such as p-toluenesulfonic acid, sulfonic acid esters, phosphoric acid, or nitrates such as, in particular, calcium nitrate, or tertiary amines such as, in particular, 1,4-diazabicyclo [ 2.2.2] octane, triethanolamine, imidazoles such as in particular N-methylimidazole, N-vinylimidazole or 1,2-dimethylimidazole, amidines or guanidines, phenols, Mannich bases such as in particular 2,4,6-tris (dimethylaminomethyl) phenol, or mercapto groups having compounds.
  • organic carboxylic acids such as salicylic acid
  • organic sulfonic acids such as p-toluenesulf
  • a curable composition comprising epoxy resin particularly preferably contains at least one aminosilane and optionally a vinylsilane, optionally 2,4,6-tris (dimethylaminomethyl) phenol, optionally a polyamine and optionally a tin catalyst.
  • a curable composition comprising such an epoxy resin cures in that the two components of the composition are mixed with one another and the composition comes into contact with moisture.
  • Silane groups present react with moisture, as described above, and epoxy groups present react with primary or secondary amino groups and / or with one another, the aminosilane being able to connect the polyether polymer phase and the epoxy resin phase to one another via the silane group and via the amino group.
  • the result is a high-quality material of high strength, impact resistance, stability and, depending on the ratio between silane-containing polymer and epoxy resin, more or less high ductility and elasticity.
  • Another object of the invention is the cured composition obtained from the curable composition after it has come into contact with moisture.
  • NK standard climate
  • Diisodecyl phthalate was used as Palatinol 10-P ® (from BASF).
  • the viscosity was measured with a thermostated cone-plate viscometer Rheotec RC30 (cone diameter 25 mm, cone angle 1 °, cone tip-plate distance 0.05 mm, shear rate 10 s -1 ).
  • IPDI 1-isocyanato-3,3,5-trimethyl-5 -isocyanatomethylcyclohexane, Vestanat ® IPDI, from Evonik
  • the volatile constituents in particular a large part of the monomeric IPDI, were then removed by distillation in a short-path evaporator (jacket temperature 160 ° C., pressure 0.1 to 0.005 mbar).
  • the linear polymer thus obtained had an NCO content of 0.85% by weight, a viscosity of 19.1 Pa s at 20 ° C. and a monomeric IPDI content of 0.06% by weight.
  • the volatile constituents in particular a large part of the monomeric 4,4'-diphenylmethane diisocyanate, were then distilled off in a short-path evaporator (jacket temperature 180 ° C., pressure 0.1 to 0.005 mbar, condensation temperature 47 ° C.).
  • the polymer thus obtained had an NCO content of 1.7% by weight, a viscosity of 19 Pa s at 20 ° C. and a monomeric 4,4'-diphenylmethane diisocyanate content of 0.04% by weight.
  • Polymer D-3 780.0 g ethylene oxide-terminated polyoxypropylene triol (OH number 28 mg KOH / g,
  • Desmophen ® 5031 BT, of Covestro) and 220 g IPDI (1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl thyl, Vestanat ® IPDI, Evonik) were dissolved in Ge genwart of 0.01 g dibutyltin dilaurate to a known method at 80 ° C a polymer with an NCO content of 6.4% by weight, a viscosity of 4.1 Pa s at 20 ° C. and a content of monomeric IPDI of approx. 12% by weight.
  • the volatile constituents in particular most of the monomeric IPDI, were then removed by distillation in a short-path evaporator (jacket temperature 160 ° C., pressure 0.1 to 0.005 mbar).
  • the polymer thus obtained had an NCO content of 1.9% by weight, a viscosity of 8.2 Pa s at 20 ° C. and a monomeric IPDI content of 0.02% by weight.
  • the volatile constituents in particular a large part of the monomeric 4,4'-diphenylmethane diisocyanate, were then distilled off in a short-path evaporator (jacket temperature 180 ° C., pressure 0.1 to 0.005 mbar, condensation temperature 47 ° C.).
  • the linear polymer thus obtained had an NCO content of 1.8% by weight, a viscosity of 13.3 Pa s at 20 ° C. and a content of monomeric 4,4'-diphenylmethane diisocyanate of 0.08% by weight.
  • Silane A-1 N- (3-trimethoxysilylpropyl) aminosuccinic acid diethyl ester (351.5 g / mol), obtained from the reaction of 3-aminopropyltrimethoxysilane and maleic acid diethyl ester in a molar ratio of about 1/1
  • Polymer S-1 (according to the invention)
  • Polymer S-2 (Invention) 300 g of the polymer D-1, prepared as described previously, were hydrogen atmosphere under stick and exclusion of moisture introduced with 16.8 g of silane A-3 and 0.06g Bi catalyst (Coscat ® 83, Vertellus) was added and at 80 ° C for as long stirred until no more isocyanate groups were detected by means of FT-IR spectroscopy. The polymer obtained was cooled to room temperature and stored in the absence of moisture. It was clear and had a viscosity of 90 Pa s at 20 ° C. on the day after the Fier position.
  • Bi catalyst Coscat ® 83, Vertellus
  • Polymer S-3 (according to the invention)
  • Polymer S-4 (according to the invention)
  • Polymer S-5 (according to the invention)
  • polymer C-1 333.3 g of polymer C-1, prepared as described above, were placed under nitrogen atmosphere and exclusion of moisture, mixed with 18.1 g of silane A-1 sets and stirred at 60 ° C until no more isocyanate groups were detected by means of FT-IR spectroscopy.
  • the polymer obtained was cooled to room temperature and stored with exclusion of moisture. It contained 10% by weight of plasticizer (diisodecyl phthalate), was clear and had a viscosity of 99 Pa s at 20.degree. C. on the day after it was opened.
  • plasticizer diisodecyl phthalate
  • polymer C-1 333.3 g of polymer C-1, prepared as described above, were placed under a nitrogen atmosphere and with exclusion of moisture, mixed with 20.2 g of silane A-2 and stirred at 60 ° C. until isocyanate groups were no longer detected by FT-IR spectroscopy became.
  • the polymer obtained was cooled to room temperature and stored with exclusion of moisture. It contained approx. 10% by weight of plasticizer (diisodecyl phthalate), was clear and had a viscosity of 79 Pa s at 20 ° C. on the day after it was opened.
  • plasticizer diisodecyl phthalate
  • polymer C-1 333.3 g of polymer C-1, prepared as described above, were initially charged under a nitrogen atmosphere and with exclusion of moisture, 13.6 g of silane A-3 and 0.06 g of bi-catalyst (Coscat ® 83, from Vertellus) were added and the mixture was stirred at 80 ° C until until no more isocyanate groups were detected by means of FT-IR spectroscopy.
  • the polymer obtained was cooled to room temperature and stored in the absence of moisture. It contained 10% by weight of plasticizer (diisodecyl phthalate), was clear and had a viscosity of 113 Pa s at 20 ° C. on the day after it was opened.
  • compositions Z1 to Z12 are Moisture-curing compositions: compositions Z1 to Z12:
  • compositions were tested as follows:
  • the viscosity after storage with exclusion of moisture in a closed aluminum tube after one day at room temperature (1d RT) and after 7 days in a convection oven at 60 ° C (7d 60 ° C) was determined as a measure of the open time.
  • a few grams of the composition were applied to cardboard in a layer thickness of approx. 2 mm and the time was determined in a standard climate until, for the first time, no residues remained on the pipette when the surface of the composition was lightly touched with a pipette made of LDPE.
  • the Shore A hardness was determined according to DIN 53505, on test specimens cured for 7 days in a standard climate (7d NK), or on for 7 days in a standard climate and then for the specified time at the specified temperature in one Convection oven at 80 ° C, 90 ° C or 100 ° C test specimen.
  • the composition was applied to a silicone-coated release paper to form a film 2 mm thick, this was stored for 14 days in a standard climate, some dumbbells with a length of 75 mm with a web length of 30 mm and a web width of 4 mm punched out of the film and this according to DIN EN 53504 at a tensile speed of 200 mm / min for tensile strength (breaking force), elongation at break and modulus of elasticity 5% (at 0.5-5% elongation) and modulus of elasticity 50% (at 0.5- 50% elongation).
  • the tensile shear strength (ZSF) on glass was determined as a measure of the strength of an adhesive bond.
  • ZSF tensile shear strength
  • Table 2 Composition (in parts by weight) and properties from Z1 to Z6. "n.b.” stands for “not determined”
  • compositions according to the invention Z8 to Z10 and Z12 have good thermal stability, while the comparative compositions Z7 and Z11 have inadequate thermal stability. After 14 days of storage at 90 ° C and 7 days of storage at 100 ° C, their Shore A test specimens are decomposed to such an extent that measurement was no longer possible.
  • compositions Z13 and Z14 are Compositions Z13 and Z14:
  • a first component-1 was prepared by mixing 62.2 parts by weight (pbw) of the silane-containing polymer shown in Table 4, 1.4 GT diisodecyl phthalate, 2.4 GT vinyltrimethoxysilane, 27.4 GT 1,2-di aminocyclohexane (Dytek ® DCH-99 , silane from Invista), 2.3 GT-3 Aminopropyltrimethoxy-, 2.3 GT 2,4,6-tris (dimethylaminomethyl) phenol (Ancamine ® K54 from Evo nik), 0.4 GT stabilizer (Irganox 1010, BASF), 1.5 GT Carbon black and 0.1 pbw of dibutyltin dilaurate were mixed using a centrifugal mixer (SpeedMixer TM DAC 150, FlackTek Inc.) and stored with exclusion of moisture.
  • a centrifugal mixer SpeedMixer TM DAC 150, FlackTek Inc.
  • a second component-2 was also produced by adding 70.2 GT bisphenol A diglycidyl ether (Araldite ® GY 250, from Huntsman), 23.4 GT flexandioldiglycidyl ether (Araldite ® DY-FI, from Fluntsman), 0.5 GT emulsifier, 1.9 pbw of water, 2.4 pbw of fumed silica, 1.5 pbw of carbon black and 0.1 pbw of dibutyltin dilaurate were processed and stored using the centrifugal mixer.
  • the two components were then processed into a homogeneous liquid in a weight ratio of 0.6 / 1 first / second component using a centrifugal mixer and this was immediately tested as follows: To determine the mechanical properties, the mixed composition was put on a PTFE-coated film to form a 2 mm film Thickness poured out and stored in a standard climate. After 1 day, some dumbbell-shaped test specimens with a length of 75 mm with a web length of 30 mm and a web width of 4 mm were punched out of the film and stored for a further 6 days in a standard climate.
  • Table 4 Polymer containing silane groups and properties of the compositions Z-13 and Z-14.
  • compositions Z-13 and Z-14 show in the tensile test according to DIN EN 53504 a less elastic, but mostly plastic deformation. They are particularly suitable as structural adhesives for frictional connection of substrates or as potting compounds of high hardness and toughness.

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Abstract

La présente invention concerne un polymère contenant des groupes silane issu de la réaction (i) d'un polymère contenant des groupes isocyanate dont la teneur en NCO est comprise dans la plage de 0,3 à 4 % en poids et dont la teneur en diisocyanate monomère est d'au plus 0,3 % en poids issu de la réaction d'au moins un diisocyanate monomère avec au moins un polyol de polyéther dans un rapport molaire NCO/OH d'au moins 3/1 et de l'élimination ultérieure d'une majeure partie des diisocyanates monomères n'ayant pas réagi au moyen d'un procédé de séparation approprié (ii) avec au moins un amino-, mercapto- ou hydroxysilane dans un rapport stœchiométrique d'au moins 1 mole d'amino-, de mercapto- ou d'hydroxysilane par équivalent molaire de groupes isocyanate. Le polymère contenant des groupes silane est stable au stockage et facile à manipuler à température ambiante sans dilution à l'aide de plastifiants ou de solvants, et fournit des compositions durcissables présentant une excellente aptitude au traitement, un durcissement rapide, une résistance élevée avec un bon allongement, et, dans des modes de réalisation préférés, une stabilité thermique améliorée. Il convient particulièrement à une utilisation en tant que composant de produits de revêtement, d'adhésifs ou de produits d'étanchéité durcissables à l'humidité.
EP21703265.5A 2020-02-10 2021-02-03 Polymère contenant des groupes silane Pending EP4103633A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP20156460 2020-02-10
PCT/EP2021/052559 WO2021160492A1 (fr) 2020-02-10 2021-02-03 Polymère contenant des groupes silane

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EP4103633A1 true EP4103633A1 (fr) 2022-12-21

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EP21703265.5A Pending EP4103633A1 (fr) 2020-02-10 2021-02-03 Polymère contenant des groupes silane

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US (1) US20230072857A1 (fr)
EP (1) EP4103633A1 (fr)
JP (1) JP2023512697A (fr)
KR (1) KR20220139872A (fr)
CN (1) CN115551910A (fr)
BR (1) BR112022015012A2 (fr)
WO (1) WO2021160492A1 (fr)

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DE60032938T2 (de) 1999-11-30 2007-07-05 Chemtura Corporation, Middlebury Verfahren zur herstellung von mdi-präpolymeren mit reduziertem gehalt an freiem mdi-monomer
US6884904B2 (en) 2001-04-12 2005-04-26 Air Products And Chemicals, Inc. MDI-based polyurethane prepolymer with low monomeric MDI content
DE10353663A1 (de) * 2003-11-17 2005-06-16 Henkel Kgaa Polyurethanzusammensetzungen mit NCO- und Silylreaktivität
US20050154172A1 (en) 2004-01-08 2005-07-14 Conner Mark D. Low residual monomer IPDI-PPG prepolymer
EP1975187A1 (fr) * 2007-03-28 2008-10-01 Sika Technology AG Procédé de fabrication de composition de polyuréthane ayant une teneur en isocyanat monomère moindre
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WO2014037265A1 (fr) * 2012-09-04 2014-03-13 Bayer Materialscience Ag Liants silanofonctionnels à structure de thio-uréthanne
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EP2832757A1 (fr) * 2013-07-30 2015-02-04 Sika Technology AG Polymère contenant des groupes de silanes
US9982173B2 (en) * 2014-03-11 2018-05-29 Sika Technology Ag Polyurethane hot-melt adhesive having a low content of diisocyanate monomers and good cross-linking speed
EP3088435A1 (fr) * 2015-04-28 2016-11-02 Sika Technology AG Procédé en deux étapes destiné à la fabrication d'une colle polyuréthane à fondre à chaud à faible teneur en diisocyanates monomères et à durcissement rapide
EP3263619A1 (fr) * 2016-06-27 2018-01-03 Evonik Degussa GmbH Moyens de revêtement fonctionnalisés par un alkoxysilane et un allophanate
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CN115551910A (zh) 2022-12-30
JP2023512697A (ja) 2023-03-28
US20230072857A1 (en) 2023-03-09
WO2021160492A1 (fr) 2021-08-19
BR112022015012A2 (pt) 2022-09-20
KR20220139872A (ko) 2022-10-17

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