WO2011069971A1 - Polyurethan-prepolymere - Google Patents

Polyurethan-prepolymere Download PDF

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Publication number
WO2011069971A1
WO2011069971A1 PCT/EP2010/068981 EP2010068981W WO2011069971A1 WO 2011069971 A1 WO2011069971 A1 WO 2011069971A1 EP 2010068981 W EP2010068981 W EP 2010068981W WO 2011069971 A1 WO2011069971 A1 WO 2011069971A1
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Prior art keywords
isocyanate
mixture
compounds
reactive
molecular weight
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PCT/EP2010/068981
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German (de)
English (en)
French (fr)
Inventor
Evelyn Peiffer
Mathias Matner
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Bayer Materialscience Ag
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Application filed by Bayer Materialscience Ag filed Critical Bayer Materialscience Ag
Priority to DK10785444.0T priority Critical patent/DK2510030T3/da
Priority to CN201080055474.6A priority patent/CN102639584B/zh
Priority to EP10785444.0A priority patent/EP2510030B1/de
Priority to US13/514,754 priority patent/US20120245241A1/en
Priority to JP2012542495A priority patent/JP5856976B2/ja
Priority to ES10785444T priority patent/ES2432433T3/es
Priority to PL10785444T priority patent/PL2510030T3/pl
Publication of WO2011069971A1 publication Critical patent/WO2011069971A1/de
Priority to HK13101392.7A priority patent/HK1174651A1/xx

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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
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—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
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
    • C—CHEMISTRY; METALLURGY
    • 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

Definitions

  • the present invention relates to polyurethane prepolymers, a process for their preparation and their use as binders for adhesives, coatings or foams.
  • Alkoxysilane-functional polyurethanes which crosslink via a silane polycondensation have long been known. A review on this topic can be found e.g. in "Adhesives Age” 4/1995, page 30 et seq. (authors: Ta-Min Feng, B.A. Waldmann). Such alkoxysilane-terminated, moisture-curing, one-component polyurethanes are increasingly being used as soft-elastic coating, sealing and adhesive compounds in construction and in the automotive industry.
  • Such alkoxysilane-functional polyurethanes can be prepared according to US-A 3,627,722 or DE-A 1 745 526 by e.g. Polyether polyols are reacted with an excess of polyisocyanate to form an NCO-containing prepolymer, which in turn is then further reacted with an amino-functional alkoxysilane.
  • EP-A 0 397 036, DE-A 19 908 562 (corresponding to EP-A 1 093 482) and US-A 2002/0100550 describe further different ways of producing alkoxysilane-terminated polymers. According to these documents, high molecular weight polyethers having an average molecular weight of 4000 g / mol or greater are used in each case.
  • the application EP-A 0 070 475 describes the preparation and use of alkoxysilane-terminated polymers starting from hydrogen-acid prepolymers by termination with NCO-functional alkoxysilanes.
  • polyols having a molecular weight of 500-6000 g / mol are used.
  • the polymers described therein are used as binders in sealant formulations, ie soft-elastic systems.
  • alkoxysilane-terminated polyurethanes which are liquid at room temperature and, when cured, achieve a high cohesive strength, so that they can formulate adhesives which enable structural bonding. It has now been found that such alkoxysilane-terminated polyurethanes can be prepared by first preparing a prepolymer containing isocyanate-reactive hydrogen from a polyisocyanate and a mixture of compounds with isocyanate-reactive groups.
  • low molecular weight, multifunctional isocyanate-reactive compounds having a molecular weight ⁇ 500 g / mol of from 1 to 40% by weight are present in the mixture of compounds with isocyanate-reactive groups.
  • the resulting isocyanate-reactive hydrogen-containing prepolymer is finally modified with an isocyanate-functional alkoxysilane.
  • the invention therefore relates to polymers modified with alkoxysilane groups and containing by reaction a) an isocyanate-reactive hydrogen-containing prepolymer which contains structural units of the general formula (I),
  • PIC is a radical of a polyisocyanate (B) reduced by the isocyanate groups
  • ⁇ is nitrogen, oxygen or sulfur
  • R is either a free electron pair or hydrogen or any organic radical
  • A is the isocyanate-reactive groups reduced radical of an isocyanate-reactive polymer and low molecular weight, multifunctional isocyanate-reactive compounds, which in any order, so blockwise, alternately or statistically, via the derived from the polyisocyanates B structural element of the formula
  • ⁇ 1 and ⁇ 2 independently of one another represent nitrogen, oxygen or sulfur, low molecular weight, multifunctional isocyanate-reactive compounds (AI) and polyether polyols, polyester polyols, polycarbonate polyols or polytetrahydrofuran polyols (A2) which are linked together, the terminal groups of these substructures also being the corresponding thio compounds or amine derivatives, in whole or in part which may be 1 to 40% by weight of substructures AI having an average molecular weight (Mn) of less than 500 g / mol and 60 to 99% by weight of substructures A2 of an average molecular weight (Mn) of more than 500 g / mol, and where A has an overall average functionality of 2-6,
  • Z 1 , Z 2 and Z 3 are the same or different Ci-Cg-alkoxy or Ci-Cg-alkyl radicals, which may also be bridged, but at least one Ci-Cg-alkoxy must be present on each Si atom,
  • Q is a difunctional linear or branched organic radical, preferably an alkylene radical of 1 to 8 carbon atoms.
  • the compounds according to the invention are non-crystallizing substances which are liquid at room temperature and have a number-average molecular weight of less than 5000 g / mol, preferably less than 4000 g / mol and a viscosity of less than 700 Pas at 23 ° C., preferably less than 500 Pas at 23 ° C.
  • the mixture of isocyanate-reactive compounds (component A) consists to 1 - 40% of a low molecular weight, multifunctional isocyanate-reactive compound (AI) with 2-6 isocyanate natreepten groups and a number average molecular weight of less than 500 g / mol and to 60-99% of an isocyanate-reactive compound (A2) having 2-6 isocyanate-reactive groups and a number average molecular weight of over 500 g / mol, wherein both AI and A2 may each consist of combinations of compounds with isocyanate-reactive groups, as long as these compounds in the fall above the molecular weight limits described above.
  • AI multifunctional isocyanate-reactive compound
  • A2 an isocyanate-reactive compound having 2-6 isocyanate-reactive groups and a number average molecular weight of over 500 g / mol
  • component A all compounds known to those skilled in the art with isocyanate-reactive groups can be used which have a functionality of at least 2 on average.
  • these may be, for example, low molecular weight, multifunctional isocyanate-reactive compounds such as aliphatic polyols or polyamines, aromatic polyols or polyamines and A2 may be, for example, relatively high molecular weight isocyanate-reactive compounds such as polyether polyols, polycarbonate polyols, polyester polyols and polythioether polyols.
  • Such isocyanate-reactive compounds preferably have an average functionality of from 2 to 6, preferably from 2 to 3.5, and particularly preferably from 2 to 3.
  • Preferably used in component AI are polyhydric, preferably dihydric or trihydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,2-propanediol, l, 3- / l, 4-butanediol, l, 3- / l, 6-hexanediol , 1,8-octanediol, neopentyl glycol, 1,4-bis (hydroxymethyl) cyclohexane, bis (hydroxymethyl) tricyclo [5.2.1.02.6] decane or 1, 4-bis (2-hydroxyethoxy) benzene, 2-methyl -l, 3-propanediol, 2,2,4-trimethylpentane-l, 3-diol, 2-ethyl-l, 3-hexanediol, dipropylene glycol, polypropylene glycols, dibutylene glycol, polybutylene glycols, 1, 4-phenol dim
  • Suitable di- or triamines may be aliphatic amines, for example. Ethylenediamine, 1, 2- propylenediamine, 1, 3-propylenediamine, 1, 4-butanediamine, neopentanediamine, l, 5-diamino-2-methylpentane (Dytek ® A, DuPont), 2-butyl-2-ethyl-l, 5 pentanediamine, 1,6-hexamethylenediamine, 2,5-diamino-2,5-dimethylhexane, 2,2,4- and / or 2,4,4-trimethyl-1,6-diaminohexane, 1,8-diaminooctane, 1, 1 1 -Diaminoundecan, 1,12-diaminododecane, 4-aminomethyl-l, 8-octanediamine (triaminononane), diethylenetriamine, triethylenetetramine, cycloaliphatic
  • B C-monomethyl-diaminodicyclohexylmethane), 3 (4) -aminomethyl-1-methylcyclohexylamine (AMCA) and araliphatic di- or triamines, such as 1,3-diaminobenzene, 1,4- Diaminobenzene, 2,4- and / or 2,6-diaminotoluene (TDA), l, 3-bis (aminomethyl) benzene, 3,5-diethyltoluene-2,4-diamine, m-xylylenediamine.
  • AMCA -aminomethyl-1-methylcyclohexylamine
  • TDA 2,6-diaminotoluene
  • l 3-bis (aminomethyl) benzene, 3,5-diethyltoluene-2,4-diamine, m-xylylenediamine.
  • Polyether polyols are preferably used in component A2. These are accessible in a manner known per se by alkoxylation of suitable starter molecules with base catalysis or use of double metal cyanide compounds (DMC compounds).
  • Suitable starter molecules for the preparation of polyether polyols are molecules having at least 2 epoxide-reactive element hydrogen bonds or any mixtures of such starter molecules.
  • Particularly suitable polyether polyols are those of the abovementioned type with an unsaturated end group content of less than or equal to 0.02 meq / gram of polyol (meq / g), preferably less than or equal to 0.015 meq / g, more preferably less than or equal to 0.01 meq / g (method of determination ASTM D2849-69).
  • Suitable starter molecules for the preparation of polyether polyols are, for example, simple, low molecular weight polyols, water, ethylene glycol, propanediol 1, 2, 2-bis (4-hydroxyphenyl) propane, propylene glycol-1,3- and 1-butanediol , Hexanediol-1, 6, neopentyl glycol, 2-ethylhexanediol-l, 3, trimethylolpropane, glycerol, pentaerythritol, sorbitol, organic polyamines having at least two NH bonds such as Triethanolamine, ammonia, methylamine or ethylenediamine or any mixtures of such starter molecules.
  • suitable alkylene oxides are in particular ethylene oxide and / or propylene oxide, which can be used in any order or in a mixture in the Alkoxylierang.
  • polyether polyol mixtures which contain at least one polyol having at least one tertiary aminograft.
  • Such polyether polyols containing tertiary aminopolyols can be obtained by alkoxylation of starter molecules or mixtures of starter molecules, at least containing a starter molecule having at least 2 epoxide-reactive hydrogen bonds, of which at least one is an NH bond, or low molecular weight polyol compounds carrying the tertiary aminographers, produce.
  • starter molecules are ammonia, methylamine, ethylamine, n-propylamine, isopropylamine, ethanolamine, diethanolamine, triethanolamine, ethylenediamine, ethylenetriamine, triethanolamine, N-methyl-diethanolamine, ethylenediamine, ⁇ , ⁇ '-dimethyl-ethylenediamine, tetra-n-propylamine.
  • methylenediamine hexamethylenediamine, 2,4-toluenediamine, 2,6-toluenediamine, aniline, diphenyl- 1-amino-methyl-3-amino-1, 5,5-trimethylcyclohexane (isophoronediamine), 4,4'-diamine, xylylenediamine and polyoxyalkyleneamines.
  • Polyether polyols with organic fillers dispersed therein such as, for example, adducts of tolylene diisocyanate with hydrazine hydrate or copolymers of styrene and acrylonitrile, can also be used.
  • polytetramethylene glycol ethers obtainable by polymerization of tetrahydrofuran with molecular weights of from 400 g / mol to 4000 g / mol, but also hydroxyl-containing polybutadienes.
  • hydroxyl polycarbonates are reaction products of glycols of the ethylene glycol type, diethylene glycol, 1,2-propylene glycol, 1,4-butanediol, neopentyl glycol or 1,6-hexanediol and / or triols such as glycerol, trimethylolpropane, pentaerythritol or sorbitol with diphenyl and / or dimethyl carbonate.
  • the reaction is a condensation reaction in which phenol and / or methanol are split off.
  • the result depending on the composition, liquid to waxy, amorphous types with Tg values of> -40 ° C or crystalline polycarbonate polyols with melting ranges of 40-90 ° C.
  • the molecular weight range is from 200 g / mol to 10,000 g / mol.
  • the molecular weight range of 400 g / mol to 5000 g / mol is preferred.
  • the molecular weight range of 500 g / mol to 3000 g / mol is particularly preferred.
  • hydroxyl polyesters are reaction products of aliphatic, cycloaliphatic, aromatic and / or heterocyclic polybasic, but preferably dibasic carboxylic acids, such as adipic acid, azelaic acid, sebazine and / or dodecanedioic acid, phthalic acid, isophthalic acid, succinic acid, suberic acid, trimellitic acid, phthalic anhydride, tetrahydrophthalic anhydride, glutaric anhydride , Tetrachlorophthalic anhydride, endomethylenetetrahydrophthalic anhydride, maleic anhydride, maleic acid, fumaric acid, dimeric and trimeric fatty acids such as oleic acid, optionally in admixture with monomeric fatty acids, dimethyl terephthalate or terephthalic acid bis-glycolester, ortho, iso or terephthalic acid with polyvalent, preferably dihydric or trihydric alcohols such as
  • the reaction is a normal melt condensation, as described in Ullmann's Encyclopedia of Industrial Chemistry, "Polyester”, 4th edition, Verlag Chemie, Weinheim, 1980. Depending on the composition, this results in liquid, amorphous types with Tg values of> 20 ° C. or crystalline polyester polyols with melting ranges of 40-90 ° C.
  • the polyester polyols which can be used according to the invention have number-average molecular weights of from 500 g / mol to 2500 g / mol, preferably from 800 g / mol to 2000 g / mol.
  • Particularly noteworthy here are the products which are derived from reaction products of glycerol and hydroxyl fatty acids, in particular castor oil and its derivatives, such as, for example, simply dehydrated castor oil.
  • polyetheramines can also be used in component A in addition to the polyhydroxy compounds.
  • the preferred molecular weights and composition of the mixture the same limits apply, as already enumerated for the polyether polyols.
  • isocyanate-reactive compounds can be reacted with all polyisocyanates, aromatic and aliphatic before the actual prepolymerization to urethane-modified hydroxyl compounds.
  • component B are aromatic, aliphatic and cycloaliphatic diisocyanates and mixtures thereof into consideration.
  • Suitable diisocyanates are compounds of the formula PIC (NCO) 2 with an average molecular weight below 400 g / mol, wherein PIC an aromatic C ⁇ -cis-hydrocarbon radical, an aliphatic C4-Ci2 hydrocarbon radical or a cycloaliphatic C6-Ci 5 -hydrocarbon for example, diisocyanates from the series butanediisocyanate, pentane diisocyanate, hexane diisocyanate (hexamethylene diisocyanate, HDI), 4-isocyanatomethyl-l, 8-octane diisocyanate (triisocyanatononane, TIN) 4,4'-methylenebis (cyclohexyl isocyanate), 3 , 5, 5-trimethyl-1-isocyanato-3-isocyanatomethylcycloh ex an (I s ophorondiisocyanat, IPDI), 2,4- and / or 2,6-
  • organic aliphatic, cycloaliphatic or heterocyclic polyisocyanates may also be present, in whole or in part, in the form of their derivatives, for example urethanes, biurets, allophanates, uretdiones, isocyanurates and trimers and mixed forms of these derivatives.
  • Isocyanate-functional alkoxysilane compound of the general formula (II) (component C) are in principle suitable all alkoxysilane-containing monoisocyanates having a molecular weight of 140 g / mol to 500 g / mol.
  • Examples of such compounds are isocyanatomethyltrimethoxysilane, isocyanatomethyltriethoxysilane, (isocyanatomethyl) methyldimethoxysilane, (isocyanatomethyl) methyldiethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropylmethyldimethoxysilane, 3-isocyanatopropyltriethoxysilane and 3-isocyanatopropylmethyldiethoxysilane.
  • Preferred here is the use of 3-isocyanatopropyltrimethoxysilane.
  • isocyanate-functional silanes which have been prepared by reacting a diisocyanate with an amino or thiosilane, as described in US Pat. No. 4,146,585 or EP-A 1 136 495.
  • a process for the preparation of alkoxysilane-modified polymers as described above is the subject of the invention, in which a mixture of isocyanate-reactive compounds (component A) is first reacted with a polyisocyanate (component B) to give a prepolymer with isocyanate-reactive hydrogen, which is then capped by reaction with an isocyanate-functional alkoxysilane (component C).
  • component A For the synthesis of a prepolymer with isocyanate-reactive hydrogen, an excess is used of component A, and preferably an NCO: Y 1 - !! - ratio of 1.0: 1.3 to 1.0: 3.0, particularly preferably 1, 0: 1.5 to 1.0: 2.0 selected.
  • This urethanization can be accelerated by catalysis.
  • organo-tin compounds such as organo-tin compounds or amine catalysts in question.
  • organotin compounds are dibutyltin diacetate, dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin-bis-acetoacetonate and tin carboxylates such as, for example, tin octoate.
  • the said tin catalysts may optionally be used in combination with amine catalysts such as aminosilanes or 1,4-diazabicyclo [2.2.2] octane.
  • Dibutyltin dilaurate is particularly preferably used as the urethanization catalyst.
  • this catalyst component if used, in amounts of 0.001 wt .-% to 5.0 wt .-%, preferably 0.001 wt .-% to 0.1 wt .-% and particularly preferably 0.005 wt .-% to 0.05 wt .-% based on the solids content of the process product used.
  • the urethanization of components A and B is carried out at temperatures of 20 ° C to 200 ° C, preferably 40 ° C to 140 ° C and more preferably from 60 ° C to 120 ° C.
  • the reaction is continued until complete conversion of the isocyanate-reactive groups is achieved.
  • the course of the reaction is usefully monitored by checking the NCO content and is complete when the corresponding theoretical NCO content is reached and constant. This can be monitored by suitable measuring devices installed in the reaction vessel and / or by analyzes on samples taken. Suitable methods are known to the person skilled in the art. These are, for example, viscosity measurements, measurements of the NCO content, the refractive index, the OH content, gas chromatography (GC), nuclear magnetic resonance spectroscopy (NMR), infrared spectroscopy (IR) and near near infrared spectroscopy (NIR).
  • the NCO content of the mixture is determined titrimetrically.
  • the method according to the invention is continuous, e.g. in a static mixer, extruder or kneader or discontinuously e.g. is carried out in a stirred reactor.
  • the process according to the invention is preferably carried out in a stirred reactor.
  • the further reaction of the prepolymers with isocyanate-reactive hydrogen with isocyanate-functional alkoxysilanes (component C) is carried out as described in EP-B 1 924 621 within a temperature range from 20 ° C to 200 ° C, preferably from 40 ° C to 120 ° C and especially preferably from 60 ° C to 100 ° C, wherein the proportions are generally selected so that an excess NCO groups is used, which is trapped at the end with isocyanate-reactive compounds or by allophanatization.
  • Another object of the invention are adhesives, coatings or foams based on the polyurethane prepolymers of the invention. These adhesives, coatings or foams cross-link via the action of atmospheric moisture via a silanol polycondensation. Preference is given to the use of the prepolymers of the invention in adhesives, particularly preferably in adhesives which have a tensile shear strength of at least 5 N / mm 2 according to DIN EN 14293.
  • the polyurethane prepolymers of the invention having alkoxysilane end groups can be formulated by known processes together with customary plasticizers, fillers, pigments, drying agents, additives, light stabilizers, antioxidants, thixotropic agents, catalysts, adhesion promoters and optionally further auxiliaries and additives ,
  • Typical adhesive and coating formulations according to the invention contain, for example, 10% by weight to 100% by weight of an alkoxysilane-modified polymer according to any one of claims 1 to 4 or a mixture of two or more such alkoxysilane-modified polymers, up to 30% by weight.
  • % of a plasticizer or a mixture of two or more plasticizers up to 30% by weight of a solvent or a mixture of two or more solvents, up to 5% by weight of a moisture stabilizer or a mixture of two or more Moisture stabilizers, up to 5 wt .-% e ine s UV stabilizer or a mixture of two or more UV stabilizers, up to 5% by weight of a catalyst or a mixture of two or more catalysts and up to 80 wt. -% of a filler or a mixture of two or more fillers.
  • suitable fillers are carbon black, precipitated silicas, pyrogenic silicic acids, mineral chalks and precipitation precipitates.
  • suitable plasticizers include phthalic acid esters, adipic acid esters, alkylsulfonic acid esters of phenol, phosphoric esters or else relatively high molecular weight polypropylene glycols.
  • thixotropic agents examples include fumed silicas, polyamides, hydrogenated castor oil derivatives or else polyvinyl chloride.
  • organometallic compounds and amine catalysts which, as is known, promote silane polycondensation.
  • organometallic compounds are in particular compounds of tin and titanium.
  • Preferred tin compounds are, for example: dibutyltin diacectate, dibutyltin dilaurate, dioctyltin maleate and tin carboxylates such as tin (II) octoate or dibutyltin-bis-acetoacetonate.
  • tin catalysts may optionally be used in combination with amine catalysts, such as aminosilanes or 1,4-diazabicyclo [2.2.2] octane.
  • amine catalysts such as aminosilanes or 1,4-diazabicyclo [2.2.2] octane.
  • Preferred titanium compounds are, for example, alkyl titanates, such as diisobutyl-bisacetoacetic acid ethyl ester titanate.
  • amine catalysts are particularly suitable those which have a particularly high base strength, such as amines with amidine structure.
  • Preferred amine catalysts are therefore, for example, l, 8-diazabicyclo [5.4.0] undec-7-ene or l, 5-diazabicyclo [4.3.0] non-5-ene.
  • drying agents are alkoxysilyl compounds such as vinyltrimethoxysilane, methyltrimethoxysilane, i-butyltrimethoxysilane, hexadecyltrimethoxysilane.
  • Adhesion promoters used are the known functional silanes, such as, for example, aminosilanes of the abovementioned type but also N-aminoethyl-3-aminopropyltrimethoxy and / or N-aminoethyl-3-aminopropylmethyldimethoxysilane, epoxysilanes and / or mercaptosilanes ,
  • the viscosity measurements were carried out in accordance with ISO / DIS 3219: 1990 at a constant temperature of 23 ° C. and a constant shear rate of 250 / sec with a plate cone type Physica MCR rotational viscometer (Anton Paar Germany GmbH, Ostfildern, DE). using the measuring cone CP 25-1 (25mm diameter, 1 ° cone angle).
  • the ambient temperature of 23 ° C prevailing at the time of the test is referred to as RT.
  • Example 1 (according to the invention):
  • the resulting alkoxysilane endblocked polyurethane prepolymer had a viscosity of 98100 mPas (23 ° C) and a number average molecular weight of 3500 g / mol.
  • Comparative Example 1 A mixture of 1758.8 g of polypropylene glycol having a hydroxyl number of 56 mg KOH / g was heated to 120 ° C. in a 1 L sulfonation beaker with cover, stirrer, thermometer and nitrogen flow. Then, 87.0 g of hexamethylene diisocyanate (Desmodur ® H, Bayer MaterialScience AG) were added and prepolymerized until titrimetric no NCO content was no longer detected. Subsequently, 154.2 g of 3-isocyanatopropyltrimethoxysilane were added at 120 ° C. and the mixture was stirred until the theoretical NCO content reached 0.05%.
  • hexamethylene diisocyanate (Desmodur ® H, Bayer MaterialScience AG) were added and prepolymerized until titrimetric no NCO content was no longer detected.
  • 154.2 g of 3-isocyanatopropyltrimethoxysilane were added
  • the excess NCO was trapped by the addition of methanol.
  • the resulting alkoxysilane endblocked polyurethane prepolymer had a viscosity of 56,500 mPas (23 ° C) and a number average molecular weight of 3100 g / mol. Determination of skin formation time
  • a film is applied to a previously cleaned with ethyl acetate glass plate and immediately loaded into the Drying Recorder.
  • the needle is loaded with 10 g and moves over a period of 24 hours over a distance of 35 cm.
  • the Drying Recorder is located in a climate room at 23 ° C and 50% rel. Humidity.
  • the skin-forming time is the time at which the permanent trace of the needle disappears from the film.
  • both membranes of 2 mm thickness and samples for determining the tensile shear strength are produced.
  • To measure the tensile shear strength specimens are used oak, which for 7 days at 23 ° C / 50% rel. Humidity, then 20 days at 40 ° C and then one day at 23 ° C / 50% rel. Humidity are stored.
  • the hardness of the films is measured according to DIN 53505 and the tensile shear strength according to DIN EN 14293.

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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)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Paints Or Removers (AREA)
  • Adhesives Or Adhesive Processes (AREA)
PCT/EP2010/068981 2009-12-09 2010-12-06 Polyurethan-prepolymere WO2011069971A1 (de)

Priority Applications (8)

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DK10785444.0T DK2510030T3 (da) 2009-12-09 2010-12-06 Polyurethan-præpolymerer
CN201080055474.6A CN102639584B (zh) 2009-12-09 2010-12-06 聚氨酯预聚物
EP10785444.0A EP2510030B1 (de) 2009-12-09 2010-12-06 Polyurethan-prepolymere
US13/514,754 US20120245241A1 (en) 2009-12-09 2010-12-06 Polyurethane prepolymers
JP2012542495A JP5856976B2 (ja) 2009-12-09 2010-12-06 ポリウレタンプレポリマー
ES10785444T ES2432433T3 (es) 2009-12-09 2010-12-06 Prepolímeros de poliuretano
PL10785444T PL2510030T3 (pl) 2009-12-09 2010-12-06 Prepolimery poliuretanowe
HK13101392.7A HK1174651A1 (en) 2009-12-09 2013-01-31 Polyurethan-prepolymere

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DE102009057598.7 2009-12-09
DE102009057598A DE102009057598A1 (de) 2009-12-09 2009-12-09 Polyurethan-Prepolymere

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EP2905296B1 (de) * 2014-02-10 2015-12-23 Evonik Degussa GmbH Copolymere aus Isocyanatoalkyltrialkoxysilanen und Urethandiolen
WO2018094611A1 (zh) * 2016-11-23 2018-05-31 广州艾科新材料股份有限公司 一种柔软聚氨酯发泡材料
EP3501641A1 (de) 2017-12-22 2019-06-26 Covestro Deutschland AG Feuchtigkeitshärtende zusammensetzungen
EP3502185A1 (de) 2017-12-22 2019-06-26 Covestro Deutschland AG Feuchtigkeitshärtende zusammensetzungen
JP2022502521A (ja) * 2018-08-21 2022-01-11 エボニック オペレーションズ ゲーエムベーハー アミジン塩により触媒されるシラン官能性ポリウレタン樹脂を含有する熱硬化性コーティング組成物
JP7380592B2 (ja) * 2018-12-21 2023-11-15 セメダイン株式会社 湿気硬化型ホットメルト接着剤
JP7232041B2 (ja) * 2018-12-27 2023-03-02 太陽ホールディングス株式会社 硬化性樹脂組成物、ドライフィルム、硬化物、配線基板及び電子部品
EP3715396A1 (de) * 2019-03-26 2020-09-30 PolyU GmbH Zusammensetzung und verfahren zur herstellung silylierter polymere und deren verwendung
CN112812680A (zh) * 2021-01-26 2021-05-18 广东爱上体育产业股份有限公司 一种强渗透型提升水泥混凝土强度的密封底漆及其制备方法

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EP2510030B1 (de) 2013-08-28
CN102639584B (zh) 2015-04-29
ES2432433T3 (es) 2013-12-03
HK1174651A1 (en) 2013-06-14
JP5856976B2 (ja) 2016-02-10
PL2510030T3 (pl) 2014-01-31
EP2510030A1 (de) 2012-10-17
DE102009057598A1 (de) 2011-06-16
DK2510030T3 (da) 2013-11-25
JP2013513678A (ja) 2013-04-22

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