WO2011069968A1 - Prépolymères de polyuréthane - Google Patents

Prépolymères de polyuréthane Download PDF

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Publication number
WO2011069968A1
WO2011069968A1 PCT/EP2010/068977 EP2010068977W WO2011069968A1 WO 2011069968 A1 WO2011069968 A1 WO 2011069968A1 EP 2010068977 W EP2010068977 W EP 2010068977W WO 2011069968 A1 WO2011069968 A1 WO 2011069968A1
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Prior art keywords
isocyanate
mixture
reactive
alkoxysilane
molecular weight
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PCT/EP2010/068977
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German (de)
English (en)
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Evelyn Peiffer
Mathias Matner
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Bayer Materialscience Ag
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Publication of WO2011069968A1 publication Critical patent/WO2011069968A1/fr

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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
    • 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
    • C08G18/65—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

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 automobile industry.
  • 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 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 claimed polymers are used as binders in sealant formulations, ie soft-elastic systems.
  • DE-AI 745 526 describes tensile strengths for polyoxypropylene glycol-based polymers in the range of 3.36 kg / cm 2 to 28.7 kg / cm 2 . Only with crystallizing polycaprolactones high strengths are achieved, which are sufficient for structural bonds.
  • alkoxysilane-terminated polyurethanes can be prepared by first preparing an NCO prepolymer or a prepolymer with isocyanate-reactive hydrogen from a polyisocyanate and a mixture of compounds containing isocyanate-reactive groups.
  • the mixture of compounds with isocyanate-reactive groups low molecular weight, multifunctional isocyanate-reactive compounds having a molecular weight ⁇ 500 g / mol to 1 to 40 wt.% Before.
  • the NCO prepolymer obtained is then modified in a second step with an isocyanate-reactive alkoxysilane.
  • the invention therefore relates to polymers modified with alkoxysilane groups which are obtained by reacting a) an isocyanate-functional 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,
  • Y 1 and Y 2 independently of one another represent nitrogen, oxygen or sulfur, linked together low molecular weight, multifunctional isocyanate-reactive Compounds (AI) and polyether polyols, polyester polyols, polycarbonate polyols or polytetrahydrofuran polyols (A2) is constructed, wherein the terminal groups of these substructures, wholly or partly, can also be the corresponding thio compounds or amine derivatives, wherein it is to 1 to 40% by weight of substructures Al 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 has an average functionality of 2-6,
  • X 2 and X 3 are identical or different alkoxy or alkyl radicals, which may also be bridged, but at least one alkoxy radical must be present on each Si atom,
  • Q is a difunctional linear or branched aliphatic
  • R is either a lone electron pair or hydrogen or any organic radical
  • 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 of 1-40% of a low molecular weight, multifunctional isocyanate-reactive compound (AI) with 2- 6 isocyanate-reactive groups and a number average molecular weight of less than 500 g / mol and 60- 99% of an isocyanate-reactive compound (A2) with 2-6 isocyanate-reactive groups and a number-average molecular weight of more than 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 above-described limits in terms of molecular weight fall.
  • AI multifunctional isocyanate-reactive compound
  • A2 an isocyanate-reactive compound with 2-6 isocyanate-reactive groups and a number-average molecular weight of more than 500 g / mol
  • component AI Preference is given in component AI to polyhydric, preferably dihydric or trihydric alcohols, for example ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,2-propanediol, 1,3- / 4-butanediol, 1.3 / 1.6 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-1,3-propanediol, 2,2,4-trimethylpentane-1,3-diol, 2-ethyl-1,3-hexanediol, dipropylene glycol, polypropylene glycols, dibutylene glycol, polybutylene glycols, 1,4-phenoldimethanol, bis
  • Suitable di- or triamines can be aliphatic amines such as ethylenediamine, 1,2-propylenediamine, 1,3-propylenediamine, 1, 4-butanediamine, neopentanediamine, 1,5-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- l, 6-diaminohexane, 1, 8-diaminooctane, 1,1-diaminoundecane, 1,12-diaminododecane, 4-aminomethyl-1,8-octanediamine (triaminononane), diethylenetriamine, triethylenetetramine, cycloaliphatic amines, such as
  • 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 having an unsaturated end group content of less than or equal to 0.02 milliequivalents per gram of polyol (meq / g), preferably less than or equal to 0.015 meq / g, particularly 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, 1,2-propanediol, 2,2-bis (4-hydroxyphenyl) propane, 1,3-propylene glycol and 1,4-butanediol , 1,6-hexanediol, 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 /
  • polyether polyol mixtures which comprise at least one polyol having at least one tertiary amino group.
  • Such polyether polyols having tertiary amino groups can be prepared by alkoxylation of starter molecules or mixtures of starter molecules, at least containing a starter molecule having at least 2 epoxide-reactive hydrogen bonds, at least one of which is NH bond, or low molecular weight polyol compounds bearing the tertiary amino groups.
  • starter molecules are ammonia, methylamine, ethylamine, n-propylamine, isopropylamine, ethanolamine, diethanolamine, triethanolamine, ethylenediamine, ethylenetriamine, triethanolamine, N-methylamine ethyldiethanolamine, ethylenediamine, ⁇ , ⁇ '-dimethylethylenediamine, tetramethylenediamine, hexamethylenediamine, 2,4-tolylenediamine, 2,6-toluenediamine, aniline, diphenylmethane-2,2'-diamine, diphenylmethane-2, 4'-diamine, diphenylmethane-4,4'-diamine, 1-aminomethyl-3-amino-1, 5,5-trimethylcyclohexane (isophoronediamine), dicyclohexylmethane-4,4'-diamine, xylylenediamine and polyoxyalkyleneamines.
  • Polyether polyols with organic fillers dispersed therein such as, for example, addition products of tolylene diisocyanate with hydrazine hydrate or copolymers of styrene and acrylonitrile, can also be used.
  • polyethylene tetramethylene glycols obtainable by polymerization of tetrahydrofuran with molecular weights of from 400 g / mol to 4000 g / mol, but also hydroxyl-containing polybutadienes.
  • hydroxylpolycarbonates are reaction products of glycols of the type ethylene glycol, 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 or dimethyl carbonate.
  • the reaction is a condensation reaction in which phenol and / or methanol are split off.
  • hydroxyl polyesters are reaction products of aliphatic, cycloaliphatic, aromatic and / or heterocyclic polybasic, but preferably dibasic, carboxylic acids, for example adipic acid, azelaic acid, sebazine and / or dodecanedioic acid, phthalic acid, isophthalic acid, succinic acid, suberic acid, tri-mellitic acid, phthalic anhydride, Tetrahydrophthalic anhydride, glutaric anhydride, tetrachlorophthalic anhydride, Endomethylentetrahydrophthalklareanhydrid, maleic anhydride, maleic acid, fumaric acid, dimeric and trimeric fatty acids such as oleic acid, optionally in admixture with monomeric fatty acids, terephthalate or terephthalic acid bis-glycolate, ortho-, iso or terephthalic acid with polyvalent, preferably dihydric or trihydric alcohols, such
  • the corresponding polycarboxylic acid anhydrides or corresponding polycarboxylic acid esters of lower alcohols or mixtures thereof can also be used to prepare the polyester.
  • 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.
  • polyethe-ramines in addition to the polyhydroxy compounds, it is also possible to use polyethe- ramines in component A. With regard to the preferred molecular weights and composition of the mixture, the same limits apply as already enumerated for the polyether polyols.
  • the above-mentioned isocyanate-reactive compounds can be reacted with all polyisocyanates, aromatic as well as aliphatic hydroxyl compounds which have been modified to urethane before the actual prepolymerization.
  • Suitable diisocyanates are compounds of the formula PIC (NCO) 2 with an average molecular weight below 400 g / mol, wherein PIC an aromatic C6-Ci5-hydrocarbon radical, an aliphatic C4-Ci 2 denote hydrocarbon radical or a cycloaliphatic Coe-Cis hydrocarbon radical, for example diisopropyl socyanates from the series butanediisocyanate, pentanediisocyanate, hexanediisocyanate (hexamethylene diisocyanate, HDI), 4-isocyanatomethyl-l, 8-octanediisocyanate (triisocyanatonanine, TIN) 4,4'-methylenebis (cyclohexyl isocyanate), 3,5,5-trimethyl -l-isocyanato-3-isocyanatomethylcycl
  • organic aliphatic, cycloaliphatic or heterocyclic polyisocyanates may also be wholly or partly in the form of their derivatives, for example urethanes, biurets, allophanates, uretdiones, isocyanurates and trimers and mixed forms of these derivatives.
  • Isocyanate-reactive alkoxysilane compound of the general formula (II) (component C) are well known to the person skilled in the art.
  • zz represents the same or different alkoxy or alkyl radicals, which may also be bridged, but at least one alkoxy radical must be present on each Si atom, Q is a difunctional linear or branched aliphatic radical and Z is an alkoxy radical having 1 to 10 carbon atoms.
  • aspartic acid esters is preferred. Examples of particularly preferred aspartic acid esters are diethyl N- (3-triethoxysilylpropyl) aspartate, diethyl N- (3-tri-methoxysilylpropyl) aspartate and diethyl N- (3-dimethoxymethylsilylpropyl) aspartate. Very particular preference is given to the use of N- (3-trimethoxysilyl-propyl) aspartic acid diethyl ester.
  • the invention further provides a process for the preparation of polymers modified with alkoxysilane groups as described above, in which a mixture of isocyanate-reactive compounds (component A) is first reacted with a polyisocyanate (component B) to give an isocyanate-functional prepolymer which is subsequently reacted by reaction with an isocyanate-reactive alkoxysilane (component C) is capped.
  • an excess of component B is used, preferably an NCO: ⁇ ! Ratio of 1.3: 1.0 to 3.0: 1.0, more preferably from 1.5: 1.0 to 2.0: 1.0 and most preferably from 0.8: 1, 0 to 1.3: 1.0 selected.
  • organotin compounds such as organotin 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 abovementioned tin catalysts may be used in combination nation with aminic catalysts such as aminosilanes or 1, 4-diazabicyclo [2.2.2] - octane can be used.
  • 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 further reaction of the isocyanate-functional prepolymers with isocyanate-reactive alkoxysilanes (component C) is carried out within a temperature range of 0 ° C to 150 ° C, preferably from 20 ° C to 120 ° C, the proportions are usually chosen so that per mole of used NCO groups 0.8 to 1.3 moles of the isocyanate-reactive alkoxysilane compound are used.
  • a cyclocondensation can occur which can lower the viscosity of the alkoxysilane-containing prepolymers according to the invention even further. Accordingly, in a preferred embodiment of the present invention, this hydantoin formation can also be intentionally brought about.
  • This cyclocondensation can be brought about by simple stirring of the polyurethane prepolymers capped with an isocyanate-reactive alkoxysilane of the formula (III) at from 70.degree. C. to 180.degree. C., preferably from 80.degree. C. to 150.degree.
  • the reaction can be carried out without further catalysis, or, preferably, accelerated by catalysis.
  • Suitable catalysts are both basic and acidic organic compounds, for example ⁇ , ⁇ , ⁇ , ⁇ -benzyltrimethylammonium hydroxide, other hydroxides soluble in organic media, DBN, DBU, other amines, tin octoate, dibutyltin dilaurate, other organic tin compounds , Zinc octoate, acetic acid, other alkanoic acids, benzoic acid, benzoyl chloride, other acid chlorides or dibutyl phosphate, or other derivatives of phosphoric acid.
  • the catalyst is added in amounts of 0.005 wt% to 5 wt%, preferably 0.05 wt% to 1 wt%.
  • 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 comprise, 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 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 of a mixture of two or more solvents, up to 5% by weight of such alkoxysilane-modified polymers.
  • a moisture stabilizer or a mixture of two or more moisture stabilizers up to 5 wt .-% of a UV stabilizer or a mixture of two or more UV stabilizers, up to 5 wt .-% of a catalyst or a mixture of two or more catalysts and up to 80% by weight of a filler or a mixture of two or more fillers.
  • Suitable fillers are, by way of example, carbon black, precipitated silicas, fumed silica, 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 which may be mentioned are pyrogenic silicic acids, polyamides, hydrogenated castor oil derived products or else polyvinyl chloride.
  • suitable catalysts for curing it is possible to use all organometallic compounds and amine catalysts which, as is known, promote the silane polycondensation.
  • organometallic compounds are in particular compounds of tin and titanium.
  • Preferred tin compounds are, for example: dibutyltin diacetate, dibutyltin dilaurate, dioctyltin maleate and tin carboxylates such as tin (II) octoate or dibutyltin-bis-acetoacetonate.
  • the said 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-bis-acetoacetic acid ethyl ester titanate.
  • Particularly suitable for the sole use of amine catalysts are 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, for example aminosilanes of the abovementioned type but also N-aminoethyl-3-amino propyl-trimethoxy and / or N-aminoethyl-3-aminopropyl-methyl-dimethoxysilane, epoxysilanes and / or mercaptosilanes.
  • the determination of the NCO content in% was carried out by back titration with 0.1 mol / 1 hydrochloric acid after reaction with butylamine, based on DIN EN ISO 11909.
  • 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 using a Physica MCR plate-cone rotational viscometer (Anton Paar Germany GmbH, Ostfildern, DE) of the measuring cone CP 25-1 (25mm diameter, 1 ° cone angle).
  • RT The ambient temperature of 23 ° C prevailing at the time of the experiment.
  • Example 1 (according to the invention): A mixture of 1104.7 g of polypropylene glycol having a hydroxyl number of 28 mg KOH / g and 153.5 g of tripolypropylene glycol having a hydroxyl number of 585 mg of KOH was placed in a 5 L sulfonation beaker with cover, stirrer, thermometer and nitrogen flow / g heated to 120 ° C. Subsequently, 289.0 g of hexamethylene diisocyanate (Desmodur ® H, Bayer MaterialScience AG) was added, and until reaching the theoretical NCO content of 3.5%.
  • Desmodur ® H Bayer MaterialScience AG
  • the resulting alkoxysilane endblocked polyurethane prepolymer had a viscosity of 31,000 mPas (23 ° C.) and a number-average molecular weight of 3000 g / mol.
  • Example 4 (According to the Invention) A mixture of 1048.1 g of polypropylene glycol having a hydroxyl number of 28 mg KOH / g, 96.7 g of tripolypropylene glycol having a hydroxyl number of 585 mg of KOH was placed in a 5 L sulfonation beaker with cover, stirrer, thermometer and nitrogen flow / g and 48.9 g of 1, 4-butanediol heated to 120 ° C. Then, 353.4 g of hexamethylene diisocyanate (Desmodur ® H, Bayer MaterialScience AG) were added and until reaching the theoretical NCO content of 4.28%.
  • Desmodur ® H Bayer MaterialScience AG
  • N- (3-trimethoxysilylpropyl) aspartic acid diethyl ester prepared according to EP-A 0 596 360, Ex. 5
  • the resulting alkoxysilane endblocked polyurethane prepolymer had a viscosity of 26,800 mPas (23 ° C) and a number average molecular weight of 5300 g / mol.
  • N- (3-trimethoxysilylpropyl) aspartic acid diethyl ester prepared according to EP-A 0 596 360, Ex. 5
  • the resulting alkoxysilane endblocked polyurethane prepolymer had a viscosity of 1268,000 mPas (23 ° C) and a number average molecular weight of 5700 g / mol.
  • 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.
  • Catalyst (Lupragen ® N700) 0.05
  • the polymer is as a binder with the filler (Socal ® U1S2;. Solvay GmbH, Germany) and drying means (Dynasylan ® VTMO; Fa. Evonik AG, Germany) was added and mixed in a vacuum with wall scraper at 3000U / min .
  • the adhesion promoter (. Dyna Sylan ® 1146; Fa Evonik) is added and stirred in within 5 min at 1000 U / min.
  • the catalyst is (Lupragen ® N700, BASF SE.) Were stirred at 1000 U / min and, finally, the finished mixture deaerated under vacuum.
  • 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 be stored.

Abstract

La présente invention concerne des prépolymères de polyuréthane, un procédé de préparation de ces prépolymères de polyuréthane et leur utilisation comme liants pour adhésifs, revêtements ou mousses.
PCT/EP2010/068977 2009-12-09 2010-12-06 Prépolymères de polyuréthane WO2011069968A1 (fr)

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DE200910057600 DE102009057600A1 (de) 2009-12-09 2009-12-09 Polyurethan-Prepolymere
DE102009057600.2 2009-12-09

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DE102011087603A1 (de) * 2011-12-01 2013-06-06 Wacker Chemie Ag Vernetzbare Massen auf Basis von organyloxysilanterminierten Polyurethanen

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