WO2011069969A1 - Prépolymères de polyuréthane - Google Patents

Prépolymères de polyuréthane Download PDF

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Publication number
WO2011069969A1
WO2011069969A1 PCT/EP2010/068978 EP2010068978W WO2011069969A1 WO 2011069969 A1 WO2011069969 A1 WO 2011069969A1 EP 2010068978 W EP2010068978 W EP 2010068978W WO 2011069969 A1 WO2011069969 A1 WO 2011069969A1
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WO
WIPO (PCT)
Prior art keywords
isocyanate
reactive
mixture
alkoxysilane
mol
Prior art date
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PCT/EP2010/068978
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German (de)
English (en)
Inventor
Evelyn Peiffer
Mathias Matner
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Bayer Materialscience Ag
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Filing date
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Application filed by Bayer Materialscience Ag filed Critical Bayer Materialscience Ag
Priority to EP10784325.2A priority Critical patent/EP2510027B1/fr
Priority to US13/514,782 priority patent/US20120245242A1/en
Priority to CN201080056202.8A priority patent/CN102686627B/zh
Priority to JP2012542494A priority patent/JP6144491B2/ja
Publication of WO2011069969A1 publication Critical patent/WO2011069969A1/fr
Priority to HK13103198.9A priority patent/HK1175797A1/zh

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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
    • 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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08G2170/00—Compositions for adhesives
    • C08G2170/40—Compositions for pressure-sensitive adhesives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds

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.
  • DE-A 1 745 526 describes, for polyoxypropylene glycol-based polymers, tensile strengths in the range from 3.36 kg / cm 2 to 28.7 kg / cm 2 . Strengths that are sufficiently high for structural bonds are achieved only with crystallizing polycaprolactones.
  • the invention therefore provides polymers modified with alkoxysilane groups which are prepared by reacting: a) an isocyanate-functional prepolymer which contains structural units of the general formula (I),
  • A is a isocyanate-reactive group reduced to the radical of an isocyanate-reactive polymer, which in any order, so blockwise, alternately or statistically, on the derived from the polyisocyanates
  • Y 1 and Y 2 independently represent nitrogen, oxygen or sulfur, linked together polyether polyols, polyester polyols , Polycarbonate polyols or polytetrahydrofuran polyols, wherein the terminal groups of these substructures, wholly or partly, can also be the corresponding thio compounds or amine derivatives, with 50-100% by weight being substructures A1 of a average molecular weight (Mn) between 200 g / mol and 2000 g / mol and 0-50 wt .-% to substructures A2 of an average molecular weight (Mn) of more than 2000 g / mol, and wherein A is an average functionality of 2-4, with b) an isocyanate-reactive alkoxysilane compound (component C) of the general formula (II):
  • X, X and X 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
  • Y is nitrogen or sulfur
  • R is either a lone electron pair or hydrogen or any organic radical
  • the compounds of the invention are non-crystallizing, liquid at room temperature substances having a number average molecular weight of less than 7000 g / mol, preferably less than 5000 g / mol and a viscosity less than 1000 Pas at 23 ° C, preferably with a viscosity less than 500 Pas at 23 ° C. , particularly preferably with a viscosity less than 100 Pas at 23 ° C.
  • the mixture of isocyanate-reactive compounds (component A) consists of 50-100% of an isocyanate-reactive compound (AI) having 2-4 isocyanate-reactive groups and a number average molecular weight of 200 g / mol to 2000 g / mol and 0-50% of an isocyanate-reactive Compound (A2) having 2-4 isocyanate-reactive groups and a number average molecular weight of over 2000 g / mol, wherein both AI and A2 may each consist of combinations of compounds with isocyanate-reactive groups, as long as these compounds fall within the limits described above in terms of molecular weight ,
  • isocyanate-reactive groups which have a functionality of at least two on average.
  • These may be, for example, relatively high molecular weight isocyanate-reactive compounds such as polyether polyols, polycarbonate polyols, polyester polyols and polythioether polyols.
  • isocyanate-reactive compounds preferably have an average functionality of from 2 to 4, preferably from 2 to 3.5 and particularly preferably from 2 to 3.
  • polyether polyols 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 with at least at least two 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.
  • Alkylene oxides which are suitable for the alkoxylation are, in particular, ethylene
  • 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-methyldiethanolamine, ethylenediamine, N, N'-dimethylethylenediamine , Tetramethylenediamine, hexamethylenediamine, 2,4-toluenediamine, 2,6-toluenediamine, aniline, diphenylmethane-2,2'-diamine, diphenylmethane-2,4'-diamine, diphenylmethane-4,4'-diamine, 1- Amino methyl-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. It is also possible to use the 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 ethylene glycol, diethylene glycol, 1,2-propylene glycol, 1,4-butanediol, neopentyl glycol or 1,6-hexanediol type 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.
  • liquid to wax-like, amorphous types with Tg values of> -40 ° C.
  • melt ranges of 40-90 ° C. whose molecular weight range is from 200 g / mol to 10,000 g / mol, result .
  • 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 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.
  • 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.
  • 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.
  • component B for the synthesis of an isocyanate-functional prepolymer an excess of 2,4'-MDI or a 2,4'-MDI-containing mixture of several polyisocyanates with at least 50 wt .-% 2,4'-MDI is used.
  • Suitable polyisocyanates which can be used in addition to 2,4'-MDI are aromatic, aliphatic and cycloaliphatic diisocyanates and mixtures thereof.
  • 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 hydrocarbon radical, C4-Ci 2 or a cycloaliphatic C 1 -C 6 -hydrocarbon radical, for example diisocyanates from the series of butane diisocyanate, pentane diisocyanate, hexane diisocyanate (hexamethylene diisocyanate, HDI), 4-isocyanatomethyl-1,8-octane diisocyanate (triisocyanatonanone, TIN) 4,4 ' -Methylenbis (cyclohexylisocyanate), 3,5,5-trimethyl-l-isocyanato-3-isocyanatomethylcyclohexane (isophorone diisocyanate, IPDI), 2,4- and / or 2,6
  • organic aliphatic, cycloaliphatic or heterocyclic polyisocyanates in the form of their derivatives, such as, for example, urethanes, biurets, allophanates, uretdiones, isocyanurates and trimers and mixed forms of these derivatizations, is also included.
  • 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, characterized in that first isocyanate-reactive polymers AI or optionally mixtures of such isocyanate-reactive polymers AI with isocyanate-reactive polymers A2 (according to definition A with isocyanate-reactive groups present) with a Excess polyisocyanate (component B) are reacted to form an isocyanate-functional prepolymer, which is then capped by reaction with an isocyanate-reactive alkoxysilane (component C).
  • 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.
  • urethanization can be accelerated by catalysis.
  • organotin compounds such as organotin compounds or amine catalysts in question.
  • suitable organotin compounds are: dibutyltin diacetate, dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin bisacetoacetonate and tin carboxylates, such as, for example, wise tin octoate.
  • the abovementioned tin catalysts may optionally be used in combination with amine catalysts, such as aminosilanes or 1,4-diazabicyclo [2.2.2] octane.
  • 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 process according to the invention is preferably carried out in a stirred reactor.
  • the further reaction with isocyanate-reactive alkoxysilanes (component C) takes place within a temperature range from 0 ° C to 150 ° C, preferably from 20 ° C to 120 ° C, the proportions are generally selected so that per mole of NCO groups used 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 polyether-based polyurethane prepolymers capped with an isocyanate-reactive alkoxysilane of the formula (III) at from 70 ° C. to 180 ° C., preferably from 80 ° C. to 150 ° C.
  • 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 amidines, 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 according to the invention in adhesives, particularly preferably in adhesives which, according to DIN EN 14293, have a tensile shear strength of at least 5 N / mm 2 , preferably more than 6 N / mm 2 , particularly preferably more than 8 N / mm 2 .
  • 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 .-% 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 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 pyrogenic silicic acids, polyamides, hydrogenated castor oil derived products or else polyvinyl chloride.
  • 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.
  • 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, 1,6-diazabicyclo [5.4.0] undec-7-ene or 1,5-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-aminopropyltrimethoxy and / or N-aminoethyl-3-aminopropylmethyldimethoxysilane, 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 under ISO / DIS 3219: 1990 at a constant temperature of 23 ° C and a constant shear rate of 250 / sec with a plate-cone rotary viscometer of the type Physica MCR (Anton Paar Germany GmbH, Ostfildern, DE) under Use 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):
  • alkoxysilane endblocked polyurethane prepolymer had a viscosity of 81400 mPas (23 ° C.) and a number average molecular weight of 5900 g / mol.
  • the Drying Recorder is located in a climate room at 23 ° C and 50% rel. Air 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 be 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)
  • Polyurethanes Or Polyureas (AREA)
  • Paints Or Removers (AREA)
  • Adhesives Or Adhesive Processes (AREA)

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/EP2010/068978 2009-12-09 2010-12-06 Prépolymères de polyuréthane WO2011069969A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
EP10784325.2A EP2510027B1 (fr) 2009-12-09 2010-12-06 Prepolymeres polyurethane
US13/514,782 US20120245242A1 (en) 2009-12-09 2010-12-06 Polyurethane prepolymers
CN201080056202.8A CN102686627B (zh) 2009-12-09 2010-12-06 聚氨酯预聚物
JP2012542494A JP6144491B2 (ja) 2009-12-09 2010-12-06 ポリウレタンプレポリマー
HK13103198.9A HK1175797A1 (zh) 2009-12-09 2013-03-14 聚氨酯預聚物

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102009057584A DE102009057584A1 (de) 2009-12-09 2009-12-09 Polyurethane-Prepolymere
DE102009057584.7 2009-12-09

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WO2011069969A1 true WO2011069969A1 (fr) 2011-06-16

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US (1) US20120245242A1 (fr)
EP (1) EP2510027B1 (fr)
JP (1) JP6144491B2 (fr)
CN (1) CN102686627B (fr)
DE (1) DE102009057584A1 (fr)
HK (1) HK1175797A1 (fr)
WO (1) WO2011069969A1 (fr)

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WO2014009557A1 (fr) 2012-07-13 2014-01-16 Sika Technology Ag Composition fortement chargées à base de polymères à terminaisons silane

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JP2013513677A (ja) 2013-04-22
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CN102686627A (zh) 2012-09-19
EP2510027A1 (fr) 2012-10-17
CN102686627B (zh) 2016-04-20
EP2510027B1 (fr) 2018-10-03
US20120245242A1 (en) 2012-09-27
HK1175797A1 (zh) 2013-07-12

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