WO2021160493A1 - Verzweigtes silangruppen-haltiges polymer - Google Patents
Verzweigtes silangruppen-haltiges polymer Download PDFInfo
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- WO2021160493A1 WO2021160493A1 PCT/EP2021/052560 EP2021052560W WO2021160493A1 WO 2021160493 A1 WO2021160493 A1 WO 2021160493A1 EP 2021052560 W EP2021052560 W EP 2021052560W WO 2021160493 A1 WO2021160493 A1 WO 2021160493A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/2805—Compounds having only one group containing active hydrogen
- C08G18/288—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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—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
- C08G18/40—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
- C08G18/28—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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/08—Polyurethanes from polyethers
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- 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
- C09K3/1006—Materials in mouldable or extrudable form for sealing or packing joints or covers characterised by the chemical nature of one of its constituents
- C09K3/1021—Polyurethanes or derivatives thereof
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. Because of these secondary components, the silane-containing polymers obtained therefrom have a high viscosity, as a result of which they are typically diluted with a little plasticizer in order to be easier to handle at room temperature.
- compositions containing these silane-containing polymers show weaknesses in terms of thermal stability after curing, in particular at temperatures of 80 or 90 ° C. or higher.
- polymers containing silane groups from the reaction of polyether triols with isocyanatosilanes for example from US 2014/187705. These polymers are significantly less viscous, but show a significantly lower strength and elasticity and are likewise unsatisfactory in terms of thermal stability after curing.
- the object of the present invention is therefore to provide polymers containing silane groups which, with high strength and good ductility, allow improved thermal stability after curing.
- This object is achieved according to claim 1 with a branched polymer containing silane groups. It is obtained from the reaction of a polymer containing isocyanate groups, which is herge based on a polyether triol, with an amino, mercapto or flydroxysilane 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.
- It is branched and has an average of more than two silane groups per molecule. It is preferably used in a curable composition which additionally contains at least one further, in particular linear, polymer containing silane groups. Surprisingly, it significantly improves the thermal stability of the composition without causing any significant loss in the strength and extensibility of the composition.
- the monomeric diisocyanate is IPDI.
- IPDI is particularly low-viscosity polymers which can be easily handled at room temperature even without a high NCO excess and subsequent monomer removal. They enable particularly good processability and improved thermal stability after curing.
- the monomeric diisocyanate is 4,4'-MDI and the polymer containing isocyanate groups is produced with an NCO / OFI ratio of at least 3/1 and subsequent removal of unreacted monomeric diisocyanate.
- NCO / OFI ratio of at least 3/1 and subsequent removal of unreacted monomeric diisocyanate.
- the inventive polymer containing silane groups is storage-stable, liquid at room temperature and easy to handle and enables curable compositions with excellent processability, rapid curing, high strength with good ductility and surprisingly good thermal stability. It is particularly suitable as a component of moisture-curable sealants, adhesives or coatings which, in particular, additionally contain a further, in particular linear, polymer containing silane groups.
- the invention relates to a branched polymer containing silane groups from the reaction 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 branched polymer containing silane groups preferably contains only a small amount of plasticizers. In particular, it contains less than 15% by weight, preferably less than 12% by weight, plasticizers. Most preferably it is completely free from plasticizers. When used in a curable composition, such a polymer allows a high degree of freedom as to whether, how much and which plasticizer the composition should contain.
- the branched 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 is a divalent hydrocarbon radical having 1 to 12 carbon atoms, which optionally has cyclic and / or aromatic components and optionally one or more fletero atoms, in particular an amido, carbamate or morpholino group, and
- X stands for 0, S or NR 3 , where R 3 stands for Fl or a monovalent hydrocarbon radical with 1 to 20 carbon atoms with optionally fleteroatoms 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 branched polymer containing silane groups preferably has no further silane groups which do not correspond to the formula (I). In particular, it does not have any isocyanatosilane directly to the poly- isocyanate groups attached to ethertriol. Such silane groups attached via isocyanatosilane weaken the strength and thermal stability after curing.
- the branched polymer containing silane groups preferably has an average of 2.1 to 4, particularly preferably 2.2 to 3.5, silane groups per molecule.
- the branched polymer containing silane groups preferably has an average molecular weight M n in the range from 500 to 30000 g / mol, preferably from 600 to 2000 g / mol, in particular from 700 to 1500 g / mol.
- the isocyanate group-containing polymer from which the branched silane group-containing polymer is derived preferably has an NCO content in the range from 0.8 to 3.5% by weight, particularly preferably 1 to 3% by weight, in particular 1.2 to 2.5% by weight %, on.
- 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 diisocyanate is particularly preferably selected from the group consisting of MDI, TDI, HDI and IPDI.
- the polymers containing silane groups obtained in this way have a particularly low viscosity and enable compositions with particularly good processability, high elasticity and particularly good light stability.
- MDI is also particularly preferred, in particular 4,4'-diphenylmethane diisocyanate (4,4'-MDI).
- 4,4'-diphenylmethane diisocyanate (4,4'-MDI) 4,4'-diphenylmethane diisocyanate
- triols which are preferably liquid at room temperature, are suitable as the polyether triol.
- the polyether triol has an average OH functionality in the range from 2.2 to 3.
- Commercial polyether triols contain a certain amount of monols as a result of their manufacture, which means that their average OH functionality is typically slightly below 3. So they typically contain trifunctional and monofunctional components.
- the polyether triol preferably has 1,2-ethyleneoxy, 1,2-propyleneoxy, 1,3-propyleneoxy, 1,2-butyleneoxy or 1,4-butyleneoxy groups as repeating units, in particular 1,2-ethyleneoxy and / or 1,2-propyleneoxy groups.
- the polyether triol particularly preferably has a majority or exclusively 1,2-propyleneoxy groups as repeating units.
- the polyether triol based on all repeating units, has 80 to 100% by weight of 1,2-propylenoxy groups and 0 to 20% by weight of 1,2-ethyleneoxy groups.
- the polyether triol is preferably started by means of trimethylolpropane or glycerol.
- the polyether triol has an OH number in the range from 15 to 58 mg KOH / g. It preferably has an OH number in the range from 20 to 40 mg KOH / g.
- Such a polyether triol has, in particular, an average molecular weight M n in the range from 3 ⁇ 00 to 10 ⁇ 00 g / mol, preferably from 400 to 9 ⁇ 00 g / mol.
- the reaction between the monomeric diisocyanate and the polyether triol is preferably carried out with exclusion of moisture at a temperature in the range from 20 to 160 ° C., in particular 40 to 140 ° C., if appropriate in the presence of suitable catalysts.
- 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 extension 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 molar NCO / OH ratio during the reaction is in the range from 1.6 / 1 to 2.5 / 1, particularly preferably in the range from 1.8 / 1 to 2.3 / 1, in particular in the range from 1.9 / 1 to 2.2 /1.
- Such a polymer containing isocyanate groups is particularly easy to manufacture. It contains a certain proportion of unreacted monomeric diisocyanates, typically in the range from about 0.5 to 3.5% by weight, and a certain amount of chain-extended fractions. As a result, its viscosity is somewhat higher.
- the monomeric diisocyanate is preferably TDI or IPDI, in particular IPDI.
- a polymer produced with it has a particularly low viscosity and is easy to handle at room temperature.
- the molar NCO / OH ratio in the reaction is at least 3/1, 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 to 13/1, and after the reaction, a large part of the unreacted monomeric diisocyanate is removed by means of a suitable separation process.
- Such a polymer containing isocyanate groups has a particularly low content of monomeric diisocyanates and a particularly low content of chain-extended fractions.
- It preferably has a monomeric diisocyanate content of at most 0.3% by weight, preferably at most 0.25% by weight.
- Such a polymer containing isocyanate groups has a particularly low viscosity.
- monomeric diisocyanates can also be used with this production process, which are otherwise less suitable for the reaction with polyether triols, such as MDI in particular, since an undesirably high viscosity up to gelling can occur during production.
- 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.
- 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 monomeric diisocyanate is preferably IPDI or MDI.
- MDI in particular 4,4′-MDI
- 4′-MDI is very particularly preferred for this.
- a silane-containing polymer from the reaction of a polyether triol and 4,4'-MDI enables particularly high strength with high thermal stability. But it is also particularly demanding in the lowering position.
- isocyanate group-containing polymers are typically so highly viscous that they are difficult to handle without dilution with large amounts of plasticizers or solvents. Such a polymer often gels during manufacture.
- the polymer containing isocyanate groups 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),
- Preferred 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-trim- diethyl thoxysilylpropyl) aminosuccinate, N- (3-dimethoxymethylsilylpro- pyl) diethyl aminosuccinate, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyld
- 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.
- silane of the formula (II) is N- (3-trimethoxysilylpropyl) aminosuccinic acid diethyl ester, N- (3-triethoxysilylpropyl) aminosuccinic acid diethyl ester, N- (3-dimethoxymethylsilylpropyl) aminosuccinate (3-triethoxysilylpropyl) aminosuccinic acid diethyl ester, N- (3-dimethoxymethylsilylpropyl) aminosuccinic acid ethyl diethylsilylpropyl ester (3-dimethoxymethylsilylpropyl) aminosuccinate (3-diethyl diethyl ester) or N- (3-dimethoxymethylsilylpropyl) aminosuccinate.
- 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 branched polymer containing silane groups is derived from IPDI as a monomeric diisocyanate. It thus has, in particular, silane groups of the formula (Ia) 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 good thermal stability.
- a molar NCO / OH ratio in the range from 1.5 / 1 to 2.5 / 1 without subsequent removal of monomeric diisocyanate, or with an NCO / OH ratio of at least 3/1 and subsequent removal of a large part of the monomeric diisocyanate by means of a suitable separation process. It is particularly preferably produced with a molar NCO / OH ratio in the range from 1.5 / 1 to 2.5 / 1 without subsequent removal of monomeric diisocyanate.
- Another particularly preferred branched polymer containing silane groups is derived from 4,4'-MDI as a monomeric diisocyanate. It thus has, in particular, silane groups of the formula (Ic), where R 1 , R 2 , X and b have the meanings already mentioned. It enables light compositions with particularly high strength and good thermal stability.
- It is preferably produced with a molar NCO / OH ratio of at least 3/1 and subsequent removal of a large part of the monomeric diisocyanate by means of a suitable separation process.
- the branched polymer containing silane groups has a long shelf life in the absence of moisture.
- the silane groups hydrolyze on contact with moisture.
- Silanol groups (Si-OFI groups) and subsequent condensation reactions form siloxane groups (Si-O-Si 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.
- Another object of the invention is a process for producing the branched polymer containing silane groups, characterized in that
- At least one polyether diol is present in step a) in addition to the polyether triol.
- a mixture of a branched silane-group-containing polymer according to the invention and a linear silane-group-containing polymer not according to the invention is formed in situ.
- the weight ratio between the polyether triol and the polyether diol is preferably in the range from 10/90 to 70/30, in particular 15/85 to 60/40.
- a polyether diol suitable for this has in particular an OH number in the range from 5 to 40 mg KOH / g, preferably 6 to 20 mg KOH / g, in particular 7 to 15 mg KOH / g.
- Such a linear polymer containing silane groups enables compositions with particularly high extensibility and elasticity.
- the invention also relates to the reaction product from the process according to the invention.
- the invention also provides a curable composition
- a curable composition comprising the branched silane group-containing polymer according to the invention and at least one further component selected from the group consisting of catalysts, crosslinkers, adhesion promoters, drying agents, plasticizers and fillers.
- catalysts branched silane group-containing polymer according to the invention
- at least one further 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] diisopropoxy titanium (IV), bis (2-ethylhexane-1,3-dioxy) titanium (IV), tris [2 - ((2-aminoethyl) amino) ethoxy] ethoxy titanium (IV), suitable bis (neopentyl (diallyl) oxydiethoxytitan (IV), titanium (IV) tetrabutanolat, tetra (2-ethylhexyloxy) titanate,
- Particularly suitable organozirconates are the commercially available types Ken-React ® NZ ® 38J, KZ ® TPPJ, KZ ® TPP, NZ ® 01, 09, 1238, 44 or 97 (all from Kenrich Petrochemicals) 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]
- Combinations of different 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 branched polymer containing silane groups has methoxysilane groups, while vinyltriethoxysilane is preferred when the branched 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 (DPFIP), 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 diisonon
- 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 acids from pyrolysis processes, cements, plaster, 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;
- 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. It can be useful to chemically or physically dry certain ingredients before mixing them into the composition.
- 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 further polymer not according to the invention containing silane groups.
- this further polymer containing silane groups is linear. It preferably has an average of 1.7 to 2, particularly preferably 1.8 to 2, in particular 1.9 to 2, silane groups per molecule.
- the weight ratio between the branched polymer containing silane groups according to the invention 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
- Preferred as further polymers containing silane groups are those derived from polymers containing isocyanate groups from the reaction of monomeric diisocyanates and polyether diols in a molar NCO / OH ratio of at least 1.5 / 1.
- a polyether diol suitable for this has in particular an OH number in the range from 5 to 40 mg KOH / g, preferably 6 to 20 mg KOH / g, in particular 7 to 15 mg KOH / g.
- it has an average molecular weight M n in the range from 3,500 to 20,000 g / mol, preferably 5,500 to 18,000 g / mol, in particular 7,500 to 16,000 g / mol.
- Such a polymer enables compositions with particularly high extensibility and elasticity.
- Such a mixture of branched polymer according to the invention and polymer not according to the invention can in particular also be produced in such a way that the monomeric diisocyanate is mixed with a mixture of at least one polyether triol as described and at least one polyether diol in a molar
- 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 hobbock, 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. Only shortly before or during the application of the composition are the two components mixed with one another, whereupon the mixed composition hardens, the hardening only proceeding or being completed by the action of moisture.
- the curable composition is preferably one-component. With suitable packaging and storage, it is stable on 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 curing speed.
- the cured composition is formed.
- a one-component composition In the case of a one-component composition, this is applied as such and then begins to harden under the influence of moisture or water.
- an accelerator component which contains or releases water and / or a catalyst and / or a hardener can be admixed, or the composition can be mixed with such an accelerator component after its application be 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 0 to 40.degree.
- Curing is also preferably carried out at ambient temperature.
- the composition In the cured state, 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.
- a layer thickness in the range from 0.5 to 3 mm, in particular 1 to 2.5 mm, is typically applied in one operation.
- Suitable substrates for gluing or sealing or coating are in particular special
- 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.
- This article can be a building or a part thereof, in particular a building construction or civil engineering, a bridge, a roof, a staircase or a facade, or it can be an industrial good or a Be a consumer good, in particular a window, a pipe, a household machine or a means of transport such as in particular an automobile, a bus, a truck, a rail vehicle, a ship, an airplane or a helicopter, or a component thereof.
- Another object of the invention is the cured composition obtained from the curable composition after it has come into contact with moisture.
- the composition according to the invention is storage-stable and easy to process in the absence of moisture. It hardens quickly and, after hardening, has high strength with good ductility, good adhesion properties and surprisingly good thermal stability.
- NK standard climate
- 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 ).
- the content of monomeric diisocyanate was determined by means of HPLC (detection via photodiode array; 0.04 M sodium acetate / acetonitrile as mobile phase) after prior derivatization using N-propyl-4-nitrobenzylamine.
- 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, from Evonik) were in the presence of 0.01 g of dibutyltin dilaurate by a known method at 80 ° C to 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 implemented.
- the volatile constituents in particular the majority 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.
- Polymer T-3 725.0 g ethylene oxide-terminated polyoxypropylene triol (OH number 28 mg KOH / g,
- Desmophen ® 5031 BT, from Covestro) and 275 g of 4,4'-diphenylmethane diisocyanate (Desmodur ® 44 MC L, from Covestro) were by a known method at 80 ° C to a polymer with an NCO content of 7.6% by weight, a Viscosity of 6.5 Pa s at 20 ° C and a content of monomeric 4,4'-diphenylmethane diisocyanate of approx. 20% by weight converted.
- the volatile constituents in particular a large part of the monomeric 4,4'-diphenylmethane diisocyanate, were then des- Tillatively removed (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.
- 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 ST-1 (according to the invention, branched)
- polymer T-1 240.0 g of polymer T-1, prepared as described above, were placed under a nitrogen atmosphere and with exclusion of moisture, mixed with 36.2 g of silane A-1 and stirred at 60 ° C. until isocyanate groups were no longer detected by FT-IR spectroscopy became.
- the polymer obtained was cooled to temperature and stored in the absence of moisture. It contained 10% by weight of plasticizer (diisodecyl phthalate), was clear and had a viscosity of 97 Pa s at 20.degree. C. on the day after it was opened.
- plasticizer diisodecyl phthalate
- Polymer ST-2 (according to the invention, branched)
- Polymer ST-3 (according to the invention, branched)
- Polymer SL-1 (not according to the invention, linear)
- polymer L-1 333.3 g of polymer L-1, prepared as described above, were placed under a nitrogen atmosphere and with exclusion of moisture, mixed with 18.1 g of silane A-1 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 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
- compositions Z1 to Z9 are Compositions Z1 to Z9:
- compositions were tested as follows:
- the skin formation time was determined as a measure of the open time. For this purpose, 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 in accordance with 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 Switzerlandge speed of 200 mm / min for tensile strength (breaking force), elongation at break and modulus of elasticity 5% (at 0.5-5% elongation). The results are given in Tables 1-2. Comparative examples are marked with (Ref.).
- Tables 1 and 2 show that the compositions according to the invention Z2 to Z4 and Z6 to Z9 have good to very good thermal stability, while the comparative compositions Z1 and Z5 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 have decomposed to such an extent that measurements were no longer possible.
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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)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Polyurethanes Or Polyureas (AREA)
- Sealing Material Composition (AREA)
- Paints Or Removers (AREA)
Abstract
Description
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JP2022546641A JP2023513877A (ja) | 2020-02-10 | 2021-02-03 | シラン基含有分岐ポリマー |
KR1020227025535A KR20220139865A (ko) | 2020-02-10 | 2021-02-03 | 실란기-함유 분지형 중합체 |
BR112022014200A BR112022014200A2 (pt) | 2020-02-10 | 2021-02-03 | Polímero ramificado contendo grupo silano |
US17/792,794 US20230054396A1 (en) | 2020-02-10 | 2021-02-03 | Silane group-containing branched polymer |
CN202180013553.9A CN115066447A (zh) | 2020-02-10 | 2021-02-03 | 含有硅烷基的支化聚合物 |
EP21703266.3A EP4103634A1 (de) | 2020-02-10 | 2021-02-03 | Verzweigtes silangruppen-haltiges polymer |
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Citations (4)
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US6545087B1 (en) | 1998-10-29 | 2003-04-08 | Bayer Aktiengesellschaft | Polyurethane prepolymers having alkoxysilane end groups, method for the production thereof and their use for the production of sealants |
US20060205859A1 (en) * | 2003-11-17 | 2006-09-14 | Thomas Bachon | Polyurethane compositions with NCO and silyl reactivity |
US20140187705A1 (en) | 2011-06-08 | 2014-07-03 | Bayer Intellectual Property Gmbh | Adhesives |
US9790315B2 (en) | 2013-07-30 | 2017-10-17 | Sika Technology Ag | Polymer containing silane groups |
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WO2013174891A2 (de) * | 2012-05-23 | 2013-11-28 | Sika Technology Ag | Silangruppen-haltiges polymer |
EP2805985A1 (de) * | 2013-05-22 | 2014-11-26 | Sika Technology AG | Hydroxysilan und Silangruppen-haltiges Polymer |
CN106232668B (zh) * | 2014-03-11 | 2019-08-23 | Sika技术股份公司 | 具有低单体二异氰酸酯含量和良好交联速度的聚氨酯热熔粘合剂 |
JP6708645B2 (ja) * | 2014-11-24 | 2020-06-10 | シーカ テクノロジー アクチェンゲゼルシャフト | シラン基を含む急速硬化性組成物 |
EP3023428A1 (de) * | 2014-11-24 | 2016-05-25 | Sika Technology AG | Silangruppen-haltiges Polymer |
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Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6545087B1 (en) | 1998-10-29 | 2003-04-08 | Bayer Aktiengesellschaft | Polyurethane prepolymers having alkoxysilane end groups, method for the production thereof and their use for the production of sealants |
US20060205859A1 (en) * | 2003-11-17 | 2006-09-14 | Thomas Bachon | Polyurethane compositions with NCO and silyl reactivity |
US20140187705A1 (en) | 2011-06-08 | 2014-07-03 | Bayer Intellectual Property Gmbh | Adhesives |
US9790315B2 (en) | 2013-07-30 | 2017-10-17 | Sika Technology Ag | Polymer containing silane groups |
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EP4103634A1 (de) | 2022-12-21 |
KR20220139865A (ko) | 2022-10-17 |
BR112022014200A2 (pt) | 2022-10-04 |
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