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EP4284851A1 - Polymères à terminaison silane - Google Patents

Polymères à terminaison silane

Info

Publication number
EP4284851A1
EP4284851A1 EP22703327.1A EP22703327A EP4284851A1 EP 4284851 A1 EP4284851 A1 EP 4284851A1 EP 22703327 A EP22703327 A EP 22703327A EP 4284851 A1 EP4284851 A1 EP 4284851A1
Authority
EP
European Patent Office
Prior art keywords
group
polymer
formula
polyester
branched
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
EP22703327.1A
Other languages
German (de)
English (en)
Inventor
Stefan Huber
Thomas ZUBER
Fritz Burkhardt
Claude Lerf
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.)
Merz and Benteli Ag
Merz and Bentili AG
Original Assignee
Merz and Benteli Ag
Merz and Bentili 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 Merz and Benteli Ag, Merz and Bentili AG filed Critical Merz and Benteli Ag
Publication of EP4284851A1 publication Critical patent/EP4284851A1/fr
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/91—Polymers modified by chemical after-treatment
    • C08G63/914—Polymers modified by chemical after-treatment derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/916—Dicarboxylic acids and dihydroxy compounds
    • 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
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
    • C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/22—Catalysts containing metal compounds
    • C08G18/222—Catalysts containing metal compounds metal compounds not provided for in groups C08G18/225 - C08G18/26
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/71—Monoisocyanates or monoisothiocyanates
    • C08G18/718—Monoisocyanates or monoisothiocyanates containing silicon
    • 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
    • C09D175/06—Polyurethanes from polyesters
    • 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
    • C09J167/00—Adhesives based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Adhesives based on derivatives of such polymers
    • C09J167/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • 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
    • C09J175/06—Polyurethanes from polyesters

Definitions

  • the present invention relates to a process for the production of silane-terminated polymers which can be used in sealants, adhesives and coating materials and are storage-stable for a long period of time.
  • the silane-terminated polymers are prepared using known methods.
  • a known method includes, for example, the reaction of polyols, in particular hydroxyl-terminated polyethers, polyurethanes or polyesters, and also hydroxyl-functional polyacrylates, with isocyanatoalkylalkoxysilanes.
  • Another method provides for a reaction of the above polyols with di- or polyisocyanates, the latter being used in excess, so that isocyanate-functional polymers are produced in this first reaction step, which are then reacted in a second reaction step with alkoxysilanes, which have an alkyl-bonded have isocyanate-reactive group.
  • EP 1 995 261 A1 discloses prepolymers containing alkoxysilane groups based on special, low-viscosity polyester polyols which have particularly high strength have, a process for their production and their use as binders for adhesives, primers or coatings.
  • organotin compounds are used to produce an OH-functional prepolymer and to cap this prepolymer or the polyester polyol in order to accelerate the reaction.
  • Organotin compounds have the disadvantage that they adversely affect the storage stability of the adhesive through transesterification of the polyester backbone. Another problem with tin catalysts is that they are difficult to remove completely after the reaction and are both toxicologically and ecologically unsafe.
  • WO 2010/136511 discloses silane-functional polyesters which are used as a component in moisture-curing compositions such as adhesives, sealants or coatings based on silane-terminated polymers.
  • EP 3 744 748 A1 discloses a process for preparing silane-terminated polymers, the urethanization reaction being carried out in the presence of at least one catalyst which is free from organically bound tin.
  • US2019/0031812 discloses a process for preparing silane-terminated polymers. The reaction is carried out in the presence of bismuth neodecanoate.
  • US9321878B2 discloses processes for preparing silane-terminated polymers in the presence of a tin-free catalyst.
  • EP 2 930 197 discloses a silane terminated adhesive for sealing seams in the navy.
  • US2020/0339729 discloses a process for preparing silane-terminated polymers by reacting polypropylene glycol with IPDI, 3-isocyanatopropyltrimethoxysilane and N-(2-triethoxysilylpropyl)aminosuccinic acid diethyl ester.
  • bismuth catalysts as described, for example, in EP 1535 940, leads to high catalytic activity and thus to acceleration of the reaction of isocyanatosilanes with the hydroxy-terminated polyol.
  • the polyol to be reacted with an isocyanate-functional compound must be dried prior to using a bismuth catalyst to avoid side-reaction of the isocyanate function with the water otherwise present, which impairs the activity of bismuth catalysts. This additional effort is a significant disadvantage of the proposed reaction.
  • bismuth catalysts cannot be used for the production of hydroxy-terminated polyols, particularly hydroxy-terminated polyesters and hydroxy-terminated polycarbonates.
  • WO 2020/035154 discloses that a reaction with a bismuth catalyst with a water content of less than 250 ppm is possible without massively restricting the activity. This can limit the drying effort, but it cannot be avoided.
  • adhesives, sealants and coating materials, which use bismuth catalysts polymers produced contain a significant increase in viscosity during storage and thus poor storage stability.
  • the object of the present invention is to provide an efficient process for producing a silane-terminated polymer which has excellent storage stability.
  • Coating materials have an extremely high storage stability having.
  • the degradation of the polymer backbone which is selected from the group consisting of a polycarbonate, a polyester, a copolymer containing a polyester and/or a polycarbonate and a polymer containing at least one ester group and/or carbonate group, can be avoided .
  • These polymer backbones can be degraded by the presence of a tin catalyst, which can be avoided by the process according to the invention.
  • the degradation of the polymer chain - or even a break in the polymer chain of the silane-terminated polymer - leads to a significant reduction in the mechanical properties after storage of the composition. In the present invention, it was found that even traces of a tin catalyst used in the production of the starting material can lead to such a degradation. It is therefore very important that the starting materials used are also free of a
  • the silane-terminated polymer of the formula (I) is obtained by reacting a hydroxy-terminated organic polymer of the formula (III) with an isocyanate of formula (IV)
  • Hydrocarbon atoms which can optionally be interrupted with heteroatoms selected from the group consisting of oxygen, nitrogen and sulphur,
  • A stands for a polymer backbone which is selected from the group consisting of a polycarbonate, a polyester, a copolymer containing a polyester and/or a polycarbonate and a polymer containing at least one ester group and/or carbonate group,
  • R 1 , R 1 ', R 2 and R 2 ' independently represent a linear, branched or cyclic
  • Hydrocarbon radical with 1 to 10 carbon atoms which optionally has one or more heteroatoms selected from the group consisting of oxygen, may include sulfur and nitrogen,
  • - F is a linear, branched or cyclic organic radical which contains no isocyanate-reactive groups, i.e. in particular contains neither primary nor secondary amine groups,
  • - G is a linear or branched hydrocarbon group having 1 to 20 carbon atoms, which can optionally be interrupted with heteroatoms selected from the group consisting of oxygen, nitrogen and sulfur,
  • - E is an isocyanate-reactive reactive group selected from the group consisting of NH 2 , NHR 4 and SH, where R 4 is a linear, branched or cyclic hydrocarbon radical having 1 to 10 carbon atoms, optionally containing one or more heteroatoms from the group consisting of oxygen, sulfur and nitrogen.
  • tin catalyst is understood to mean any compound containing tin ions and/or organometallic tin compounds which can accelerate the preparation of the starting materials used or the reaction.
  • Typical tin catalysts are, for example, tributyltin, dibutyltin oxide, dioctyltin oxide, dibutyltin dilaurate, dioctyltin dilaurate, and fatty acid salts of tin such as tin(II) stearates or tin(II) laurates.
  • Tin catalysts are widely used in the preparation of hydroxy-terminated polyesters and polycarbonates, ie, a hydroxy-terminated organic polymer of formula (III) having a polyester or a polycarbonate backbone. At least traces of these remain as active catalysts in the prepolymer, which is then used as starting material for the production of silane-terminated polymers.
  • the tin catalysts lead to degradation of the polymer chain of the silane-terminated polymer and thus to a significant reduction in the mechanical properties after storage of the mass, in particular in a significant reduction in the Shore A hardness and /or the tensile strength.
  • the adhesive, sealing and coating compositions in which the silane-terminated polymers according to the invention are used are stable on storage for several months. No impairment of the mechanical properties is observed, especially with Storage of the adhesive, sealing or coating masses at higher temperatures such as 50°C.
  • the present process relates to the preparation of a silane-terminated polymer of formula (I) by reacting a hydroxy-terminated organic polymer of formula (III) with an isocyanate of formula (IV)
  • the silane-terminated polymer relates to a linear polymer of general formula IA where R 1 , R 2 , D and n have the same definition as above.
  • Linear silane-terminated polymers are used with particular preference for sealants and coating materials for which greater elasticity is required, such as for joint compounds, elastic adhesives, surface seals or in the marine sector, for example for pointing teak.
  • silane-terminated polymer of the formula IB is preferably essentially free of free OH groups, ie y and x are essentially identical and the difference between yx is therefore approximately 0.
  • Branched silane-terminated polymers of the formula IB are particularly preferred for adhesive, sealant and coating compounds that require a higher Shore A hardness and a higher crosslinking density, such as high-modulus adhesives, surface seals or floor coatings.
  • no bismuth and/or zinc catalysts are used in the reaction either, since these catalysts have poor hydrolytic stability, can lead to side reactions and/or are complicated to handle.
  • bismuth and/or zinc catalysts cannot be used for the production of the hydroxy-terminated polymer, especially for polyesters and polycarbonates.
  • the same catalyst is preferably used in the reaction as in the preparation of the hydroxy-terminated polymer, which is advantageous for ecological and economic reasons.
  • adhesives, sealants and coating materials which contain polymers produced using bismuth catalysts exhibit a significant increase in viscosity during storage and therefore poor storage stability.
  • At least one catalyst is preferably used for the process according to the invention, which can be used both for the production of the hydroxy-terminated prepolymer and for the reaction of the isocyanatosilane with the hydroxy-terminated polymer and which does not adversely affect the storage stability of the adhesives, sealants and coating materials produced therefrom.
  • the at least one catalyst is particularly preferably a titanium-containing organometallic compound, which can optionally also be combined with other catalysts such as lithium compounds. This further catalyst can optionally also only be added during the reaction of the hydroxy-terminated prepolymer and the isocyanatosilane. These catalysts do not adversely affect the storage stability of the adhesives, sealants and coating materials produced from them and do not have to be removed from the polymer in a complicated manner.
  • the titanium-containing organometallic compounds which are preferably used as catalysts in the process according to the invention preferably contain ligands which are selected from
  • alkoxy group such as isobutoxy, n-butoxy, isopropoxy, ethoxy and 2-ethylhexoxy;
  • a sulfonate group such as aromatic sulfonates, the aromatics of which are substituted with an alkyl group and
  • ketoester group such as
  • the titanium-containing organometallic compounds particularly preferably have at least one polydentate ligand as ligand, which makes chelation possible.
  • the multidentate ligand is preferably a bidentate ligand.
  • the titanium-containing organometallic compounds are particularly preferably selected from the group consisting of bis(ethylacetoacetato)diisobutoxytitanium (IV), bis(ethylacetoacetato)diisopropoxytitanium (IV), bis(acetylacetonato)diisopropoxytitanium (IV) , bis(acetylacetonato)diisobutoxytitanium (IV), tris(oxyethyl)amineisopropoxytitanium (IV), bis[tris(oxyethyl)amine]diisopropoxytitanium (IV), bis(2-ethylhexane-1,3 -dioxy)-titanium (IV), tris[2-((2-aminoethyl)amino)ethoxy]-ethoxy-titanium (IV), bis(neopentyl(diallyl)oxy-diethoxytitanium (IV
  • the hydroxy-terminated organic polymer of formula (III) preferably has a polymer backbone A selected from the group consisting of polyesters, polycarbonates and copolymers containing a polyester and/or a polycarbonate.
  • the term “copolymers containing a polyester and/or a polycarbonate” is understood to mean polymers composed of two or more monomer units.
  • the term also includes, in particular, block polymers which consist of longer sequences or blocks of each monomer and can be linked to one another via linker connections. Preferred combinations of blocks are
  • copolymer containing a polyester and/or a polycarbonate stands for a copolymer which contains at least one block made from a polyester and/or a polycarbonate and contains further blocks.
  • the polyester moiety or the polycarbonate moiety is at least 10% by weight, preferably at least 25% by weight and most preferably at least 50% by weight. Basically, the higher the polyester and/or polycarbonate content, the greater the risk of degradation of the polymer backbone.
  • Preferred linker compounds are urethane, ester and amide compounds, most preferably urethane compounds.
  • the polymer backbone A contains one or more ester and/or carbonate groups. They preferably contain more than 2, more preferably more than 10 ester and/or carbonate groups.
  • the definition of the polymer backbone A also includes polymers that are extended with a linker compound, such as polymers that are terminally extended with a diol, polymers that have been dimerized or oligomerized by means of a diisocyanate or dicarboxylic acid dichloride and copolymers, which have been copolymerized using diisocyanates or dicarboxylic acid dichlorides.
  • Such polymers can have 1, 2 or preferably 3 and more ester and/or carbonate groups within the polymer backbone. The higher the number of ester and/or carbonate groups, the higher the risk of polymer backbone degradation with the corresponding stability consequences for the final end product.
  • hydroxy-terminated stands for polymers which carry free hydroxy groups at the end of the molecule
  • y is a natural number from 1 to 10.
  • y 1 and then corresponds to an ⁇ , ⁇ -dihydroxy-terminated organic polymer, ie a polymer with two terminals OH groups.
  • y is greater than 1, the hydroxy-terminated polyol has more than two terminal OH groups, ie it is a polyol whose OH groups are designed to react with the isocyanate of formula IV.
  • the OH groups are preferably not attached directly to the polymer backbone, but rather to the end of side chains of the polymer backbone.
  • Polystyrene resins can be obtained, for example, by reactions with polyols or polycarboxylic acids. Both linear and branched hydroxy-terminated organic polymers are known to those skilled in the art and are also commercially available.
  • Polycarbonates can be obtained, for example, by reacting diols such as propylene glycol, 1,4-butanediol or 1,6-hexanediol, diethylene glycol, triethylene glycol or tetraethylene glycol or mixtures of two or more thereof with diaryl carbonates, for example diphenyl carbonate or phosgene.
  • polyester also includes polyester polyols which are formed by reacting low molecular weight alcohols or mixtures thereof, in particular ethylene glycol, diethylene glycol, propanediol, dipropylene glycol, neopentyl glycol, hexanediol, butanediol, pentanediol, hexanediol, propylene glycol, glycerol or trimethylolpropane with caprolactone and their terminal Hydroxy groups then represent the hydroxy groups of the organic polymer of formula III.
  • the polymer backbone contains a branched diol component.
  • Such a branched diol component of the low molecular weight alcohol used to prepare the polyester or polycarbonate is particularly preferably a branched diol selected from the group consisting of 3-methyl-1,5-pentanediol, 2-methyl- 1,3-propanediol, 3-ethylpentane-1,5-diol, 1,2-propanediol and 2,4-diethyl-1,5-pentanediol, since the polymers produced from them have particularly good processability and stability.
  • A is particularly preferably a polycarbonate selected from the group consisting of polypropylene carbonate, polycyclohexene carbonate, poly(4,4'-isopropylidene diphenyl carbonate), poly(4,4'-diphenyl-1,1'-cyclohexane carbonate) and poly(propylene).
  • PET poly(ethylene terephthalate)
  • PBT poly(ethylene naphthalate), poly(propylene terephthalate), polybutylene terephthalate (PBT), Polycyclohexylenedimethylene-2,5-furandicarboxylate (PCF), polybutylene adipate-co-terephthalate (PBAT), polybutylene sebacate-co-terephthalate (PBSeT), polybutylene succinate-co-terephthalate (PBST), poly-butylene-2,5-furandicarboxylate-cosuccinate (PBSF), poly-butylene -2,5-furandicarboxylate-coadipate (PBAF), poly-butylene-2,5-furandicarboxylate-coazelate (PBAzF), poly-butylene-2,5-furandicarboxylate-cosebacate (PBSeF),
  • PAT polybutylene adipate-co-terephthalate
  • adipic acid, Azelaic acid, sebacic acid, terephthalic acid, isophthalic acid and naphthalenedicarboxylic acid are preferably used.
  • cyclic carboxylic anhydrides such as phthalic anhydride, maleic anhydride, succinic anhydride or with a side group such as 3-methylglutaric anhydride.
  • Aliphatic dicarboxylic acids or their esters with side groups can also be used, such as 2,4-diethylglutaric acid, 2,4-methylglutaric acid, 3-methylglutaric acid, methylmalonic acid.
  • Polyester polyols and polycarbonates are particularly preferred which contain >10 mol % of a branched diol as the hydroxyl group-containing component, such as 3-methyl-1,5-pentanediol, 2-methyl-1,3-propanediol, 3-ethyl-pentane-1, 5-diol, 1,2-propanediol, 2,4-diethyl-1,5-pentanediol, as these have proven to be particularly stable.
  • the fraction of the branched diol is particularly preferably >50 mol % of the diol used.
  • Aliphatic dicarboxylic acids are used as the preferred dicarboxylic acid.
  • the diols as well as the dicarboxylic acids can be based on petroleum or have been produced from renewable raw materials.
  • the hydroxy-terminated organic polymer is liquid at room temperature.
  • This viscosity is optimal for handling the composition according to the invention, in particular in the production of sealant preparations.
  • the polyesters according to the invention have a relatively low viscosity and are inexpensive. Hence they are for some uses more suitable than the polycarbonates according to the invention.
  • the hydroxy-terminated organic polymer preferably has an average molecular weight of 1000-20000 g/mol, in particular 2000-12000 g/mol, since the handling of these polymers is optimal.
  • molecular weight means the molar mass (in grams per mole) of a molecule.
  • the “average molecular weight” is the number-average molecular weight Mn of a polydisperse mixture of oligomeric or polymeric molecules, which is usually determined by titrating the acid number and OH number.
  • the OH number (hydroxyl number) is a measure of the hydroxyl group content in polymers and is a value known to those skilled in the art.
  • the acid number is a measure of the content of acid groups in polymers and is a value known to those skilled in the art.
  • the hydroxy-terminated organic polymers of the formula (III) used according to the invention can be commercially available compounds which, for better handling, can optionally be diluted with a plasticizer or solvent. However, it is important that they are produced tin-free, since even traces of a tin catalyst in the hydroxy-terminated organic polymer of the formula (III) adversely affect the storage stability of the silane-terminated polymer and in particular of the adhesive, sealing and coating compositions produced therefrom.
  • the same catalyst is preferably used in the production of the hydroxy-terminated organic polymer and the silane-terminated polymer, so that it does not have to be removed from the hydroxy-terminated organic polymer, which makes process engineering sense and is more ecological.
  • the catalyst is preferably used in amounts of 0.5 to 500 ppm of the hydroxy-terminated organic polymer of the formula (III).
  • R 2 3-n (R 1 O) n Si-D-NCO (IV) are commercially available products or can be prepared by processes customary in silicon chemistry.
  • Ri and R2 are independently a linear, branched or cyclic hydrocarbon radical having 1 to 10 carbon atoms, which can optionally include one or more heteroatoms selected from the group consisting of oxygen, sulfur and nitrogen, n can have the value 1, 2 or 3, the values 2 or 3 being preferred, since the silane-terminated polymers produced therefrom have a particularly balanced reactivity.
  • R 1 and R 2 are independently alkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, n-hexyl, n-heptyl, octyl, n-octyl, isooctyl, 2,2,4-trimethylpentyl, n-nonyl, decyl, n-decyl , dodecyl radicals or an n-dodecyl radical.
  • alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert-butyl, n-pentyl, isopentyl, neopenty
  • alkenyl radicals such as a vinyl or an allyl radical
  • cycloalkyl groups such as cyclopentyl, cyclohexyl, cycloheptyl and methylcyclohexyl
  • aryl radicals such as phenyl and naphthyl
  • alkaryl groups such as o-, m-, p-tolyl groups, xylyl groups and ethylphenyl groups
  • Aralkyl radicals such as the benzyl radical, the ⁇ - and the ⁇ -phenylethyl radical.
  • substituted radicals R 1 are alkoxyalkyl radicals such as ethoxy and methoxyethyl radicals.
  • the radicals R 1 and R 2 are preferably each independently a hydrocarbon radical having 1 to 6 carbon atoms, particularly preferably an alkyl radical having 1 to 4 carbon atoms, in particular the methyl or ethyl radical.
  • D represents a linear or branched hydrocarbon group having 1 to 20 carbon atoms, which can optionally be interrupted with heteroatoms selected from the group consisting of oxygen, nitrogen and sulfur.
  • D is selected from the group consisting of methylene, ethylene, propylene, butylene, methylene oxide, ethylene oxide and propylene oxide and more preferably propylene or methylene as this results in polymers with a particularly balanced reactivity.
  • isocyanates of the formula (IV) are isocyanatomethyldimethylmethoxysilane, isocyanatopropyldimethylmethoxysilane, isocyanatomethylmethyldimethoxysilane, isocyanatopropylmethyldimethoxysilane, isocyanatomethyltrimethoxysilane, isocyanatomethyltriethoxysilane and isocyanatopropyltrimethoxysilane , wherein isocyanato-methyl-methyldimethoxysilane, isocyanato-propyl-methyldimethoxysilane, isocyanato-propyl-trimethoxysilane, isocyanato-propyl-triethoxysilane and isocyanato-methyl-triethoxysilane are preferred.
  • the process according to the invention for preparing the silane-terminated polymer of the formula (II) is carried out by reacting a hydroxy-terminated organic polymer of formula (III) with a multifunctional isocyanate of formula (V)
  • Particularly suitable polyfunctional isocyanates of the formula (V) are isocyanates having two or more, preferably 2 to 10, isocyanate groups in the molecule.
  • Suitable for this purpose are the known aliphatic, cycloaliphatic, aromatic, oligomeric and polymeric multifunctional isocyanates, which contain no isocyanate-reactive groups, ie in particular have no free primary and/or secondary amino groups.
  • a representative of the aliphatic multifunctional isocyanates is, for example, hexamethylene diisocyanate (HDI); a representative of the cycloaliphatic multifunctional isocyanates is z.
  • TDI technical isomer mixture
  • MDI technical isomer mixture
  • NDI naphthalene-1,5-diisocyanate
  • MDI naphthalene-1,5-diisocyanate
  • NDI 4,4',4"-triisocyanatotriphenylmethane
  • Alkoxysilanes of the formula (VI) are preferably selected from the group consisting of 3-aminopropyltrimethoxysilane, 3-aminopropyldimethoxymethylsilane, 3-amino-2-methylpropyltrimethoxysilane, 4-aminobutyltrimethoxysilane, 4-aminobutyldimethoxymethylsilane, 4-amino-3- methylbutyltrimethoxysilane, 4-amino-3,3-dimethylbutyltrimethoxysilane, 4-amino-3,3-dimethylbutyldimethoxymethylsilane, 2-aminoethyltrimethoxysilane, 2-aminoethyldimethoxymethylsilane, aminomethyltrimethoxysilane, aminomethyldimethoxymethylsilane, aminomethylmethoxydimethylsilane and 7-amino-4- oxaheptyldimethoxymethyls
  • a further catalyst which does not adversely affect the storage stability of the products and the adhesives, sealants or coating materials produced from them can optionally be used.
  • This catalyst preferably consists of
  • manganese stearates manganese laurates, iron stearates,
  • Inorganic acids such as phosphoric acid and its half esters, such as butyl phosphate, dibutyl phosphate and propyl phosphate.
  • the other catalysts are very particularly preferably selected from the group consisting of lithium neodecanoate, lithium ethyl hexanoate, lithium laurate, lithium stearate, manganese ethyl hexanoate, manganese neodecanoate, manganese laurate, manganese stearate, cobalt ethyl hexanoate, cobalt laurate, cobalt stearate and cobalt neodecanoate.
  • the further catalyst is particularly preferably combined with a titanium-containing organometallic compound.
  • the catalyst is preferably added in an amount of 1 to 1000 ppm, particularly preferably 5 to 500 ppm and very particularly preferably 5 to 200 ppm.
  • the linear silane-terminated polymers are particularly preferably selected from the group consisting of whereby
  • A represents a polymer backbone as defined above.
  • the reaction is preferably carried out at temperatures between 50° C. and 150° C., particularly preferably at 60° C. to 120° C. and preferably at normal pressure.
  • the crosslinkable compositions produced according to the invention are excellently suited as Sealing compounds for joints, including vertical joints, and similar empty spaces, e.g. in buildings, land, water and air vehicles, or as adhesives or cementing compounds, e.g. in window construction or in the manufacture of showcases, and for the production of protective coatings or rubber-elastic moldings as well as for the insulation of electrical or electronic devices.
  • the compositions according to the invention are particularly suitable as sealing compounds for joints with possible high absorption of movement.
  • the adhesives, sealants and coating materials according to the invention have significantly better weathering stability than standard products. As a result of the significantly better weathering stability, the coating materials of the invention are particularly suitable for roof waterproofing and surface waterproofing or for coating other surfaces which are exposed to severe weathering.
  • the usual water content of the air is sufficient for the crosslinking of the composition according to the invention.
  • the crosslinking can be carried out at room temperature or, if desired, also at higher or lower temperatures, for example at -5 to 10°C or at 30 to 50°C.
  • the crosslinking is preferably carried out under atmospheric pressure.
  • the silane-terminated polymers according to the invention can also be formulated as a 2-component system.
  • the second component also contains water, which greatly accelerates deep curing after mixing with the first component.
  • Corresponding 2-component systems are known to the person skilled in the art and are described, for example, in EP2009063 or EP2535376, the content of which is incorporated by reference becomes.
  • the preparations according to the invention can also contain other auxiliaries and additives, which likewise must not contain any tin catalysts.
  • auxiliaries and additives include, for example, other silane-terminated polymers, plasticizers, stabilizers, antioxidants, fillers, reactive diluents, drying agents, adhesion promoters and UV stabilizers, rheological auxiliaries, color pigments or color pastes and/or possibly also to a small extent solvents.
  • auxiliaries and additives are known to those skilled in the art.
  • polyester polyol P-4010 (Kuraray Co, Ltd) synthesized using an organotitanate catalyst (titanium (IV) isopropoxide) and having a hydroxyl value of 28.7 mg KOH/g was heated to 90°C with stirring heated. 22.4 g of (trimethoxysilyl)propyl isocyanate were added and stirred at 90°C. After 90 minutes, free isocyanate was no longer detected by FT-IR. The obtained trimethoxysilane-terminated polyester was used for the formulation of the adhesive.
  • organotitanate catalyst titanium (IV) isopropoxide
  • polyester polyol SS 4080 (Songstar), which was synthesized with an organotitanate catalyst and has a hydroxyl number of 29.4 mg KOH/g, was heated to 90° C. with stirring. 22.4 g (trimethoxysilyl)propyl isocyanate were added and stirred at 90°C. After 90 minutes, free isocyanate was no longer detected by FT-IR. The obtained trimethoxysilane-terminated polyester was used to formulate the adhesive.
  • polyester polyol SS 4080S (Songstar), which was synthesized with an organotin catalyst and has a hydroxyl number of 28.0 mg KOH/g, was heated to 90° C. with stirring. 22.4 g of (trimethoxysilyl)propyl isocyanate were added and stirred at 90°C. After 600 minutes, free isocyanate was no longer detected by means of FT-IR. The obtained trimethoxysilane-terminated polyester was used to formulate the adhesive.
  • polyester polyol SS 4080 (Songstar), which was synthesized with an organotitanate catalyst and has a hydroxyl number of 29.4 mg KOH/g, was heated to 90° C. with stirring. 63 mg of dibutyltin dilaurate as a tin catalyst and 22.4 g of (trimethoxysilyl)propyl isocyanate were added and the mixture was stirred at 90.degree. After 90 minutes, free isocyanate was no longer detected by FT-IR. The obtained trimethoxysilane-terminated polyester was used to formulate the adhesive.
  • polyester polyol SS 4080S (Songstar) synthesized with an organotin catalyst and having a hydroxyl number of 28.0 mg KOH/g was heated to 90°C with stirring.
  • the obtained trimethoxysilane-terminated polyester was used to formulate the adhesive. The results are shown in Figure 1 (Table 1).
  • the final adhesive is only stable if no tin catalysts are present during the production of the hydroxy-terminated polyester, the reaction with the isocyanate silane and the formulation as an adhesive, sealing or coating material. Otherwise, the Shore A hardness (measured according to DIN 53505) and the tensile strength (measured according to DIN 53504) decrease significantly after the sealant has been stored in a cartridge at room temperature for 4 to 8 weeks. At higher storage temperatures, the mechanical properties decrease even more quickly in the presence of a tin catalyst.
  • nc stands for normal climate, 23°C, 50% relative humidity, * means no crosslinking within the given range

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

La présente invention concerne un procédé de préparation d'un polymère à terminaison silane stable au stockage de formule (I) ou (II), D étant un groupe hydrocarboné linéaire ou ramifié ayant 1 à 20 atomes d'hydrocarbure et pouvant éventuellement être interrompu par des hétéroatomes sélectionnés dans le groupe constitué par l'oxygène, l'azote et le soufre, A est un squelette polymère sélectionné dans le groupe constitué par un polycarbonate, un polyester, un copolymère comprenant un polyester et/ou un polycarbonate et un copolymère comprenant au moins un groupe ester et/ou un groupe carbonate, R1, R1', R2 et R2' représentent indépendamment les uns des autres un groupe linéaire, ramifié ou cyclique ayant 1 à 10 atomes de carbone et peut éventuellement comprendre un ou plusieurs hétéroatomes sélectionnés dans le groupe constitué par l'oxygène, le soufre et l'azote, n est 1, 2 ou 3, x et y sont des nombres naturels compris entre 1 et 10, G est un groupe hydrocarboné linéaire ou ramifié ayant de 1 à 20 atomes d'hydrocarbure et peut éventuellement être interrompu par des hétéroatomes sélectionnés dans le groupe constitué par l'oxygène, l'azote et le soufre, F est un groupe linéaire, ramifié ou cyclique ne contenant pas de groupes réactifs vis-à-vis des isocyanates, m est un nombre naturel supérieur à 1, E est un groupe réactif réagissant avec le groupe isocyanate et sélectionné dans le groupe constitué par NH2, NHR4 et SH, R4 étant un radical hydrocarboné linéaire, ramifié ou cyclique ayant de 1 à 10 atomes de carbone et pouvant éventuellement comprendre un ou plusieurs hétéroatomes sélectionnés dans le groupe constitué par l'oxygène, le soufre et l'azote.
EP22703327.1A 2021-01-30 2022-01-28 Polymères à terminaison silane Pending EP4284851A1 (fr)

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PCT/EP2022/051972 WO2022162106A1 (fr) 2021-01-30 2022-01-28 Polymères à terminaison silane

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WO2024136687A1 (fr) * 2022-12-22 2024-06-27 Pcc Rokita Spółka Akcyjna Procédé de préparation d'un prépolymère de polyuréthane silanisé, son utilisation et procédé de production d'une mousse à un composant silanisée durcie à l'humidité

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DE10355318A1 (de) 2003-11-27 2005-06-23 Wacker-Chemie Gmbh Verfahren zur Herstellung von organyloxysilylterminierten Polymeren
DE102004028488A1 (de) 2004-02-20 2005-09-08 Degussa Ag Feuchtigkeitshärtende Schmelzklebstoffe, Verfahren zu deren Herstellung und deren Verwendung
DE102007023197A1 (de) 2007-05-22 2008-11-27 Bayer Materialscience Ag Polyester-Prepolymere
ATE524521T1 (de) 2007-06-29 2011-09-15 Merz & Benteli Ag Zwei- oder mehrkomponentige vergussmasse
EP2267051A1 (fr) 2009-05-27 2010-12-29 Sika Technology AG Polyester à silane fonctionnel dans des compositions durcissant à l'humidité à base de polymères à silane fonctionnel
EP2535376A1 (fr) 2011-06-14 2012-12-19 Merz+Benteli AG Composition à plusieurs composants comme colle pour matériaux difficiles à coller
US9321878B2 (en) 2013-12-16 2016-04-26 Momentive Performance Materials Inc. Process for the preparation of silylated polyurethane polymers using titanium-containing and zirconium-containing catalysts
EP2930197A1 (fr) 2014-04-10 2015-10-14 Sika Technology AG Colle terminée par du silane pour jointoyer des joints dans le domaine maritime
JP6708644B2 (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 シラン基を含有する急速硬化性組成物
ES2645863T3 (es) 2015-03-11 2017-12-11 Henkel Ag & Co. Kgaa Poliuretanos sililados, su preparación y su uso
EP3501642A1 (fr) 2017-12-22 2019-06-26 Covestro Deutschland AG Procédé de préparation de polymères à terminaison silane mélangés
EP3740524B1 (fr) * 2018-08-17 2021-05-26 Wacker Chemie AG Procédé de fabrication de polymères à terminaison silane
EP3744748A1 (fr) 2019-05-27 2020-12-02 Covestro Deutschland AG Procédé de production d'un polymère à terminaison silane mélangé

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WO2022162106A1 (fr) 2022-08-04

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