EP3755735A1 - POLYURETHANBASIERTES POLYMERMATERIAL MIT HERVORRAGENDER WÄRMEFORMBESTÄNDIGKEIT UND REIßDEHNUNG - Google Patents
POLYURETHANBASIERTES POLYMERMATERIAL MIT HERVORRAGENDER WÄRMEFORMBESTÄNDIGKEIT UND REIßDEHNUNGInfo
- Publication number
- EP3755735A1 EP3755735A1 EP19703730.2A EP19703730A EP3755735A1 EP 3755735 A1 EP3755735 A1 EP 3755735A1 EP 19703730 A EP19703730 A EP 19703730A EP 3755735 A1 EP3755735 A1 EP 3755735A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- compounds
- carbon
- isocyanate
- polyurethane
- carbon double
- 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
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—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
- C08G18/6696—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/36 or hydroxylated esters of higher fatty acids of C08G18/38
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/088—Removal of water or carbon dioxide from the reaction mixture or reaction components
- C08G18/0885—Removal of water or carbon dioxide from the reaction mixture or reaction components using additives, e.g. absorbing agents
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/16—Catalysts
- C08G18/22—Catalysts containing metal compounds
- C08G18/225—Catalysts containing metal compounds of alkali or alkaline earth metals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/36—Hydroxylated esters of higher fatty acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4804—Two or more polyethers of different physical or chemical nature
- C08G18/4816—Two or more polyethers of different physical or chemical nature mixtures of two or more polyetherpolyols having at least three hydroxy groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—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
- C08G18/4829—Polyethers containing at least three hydroxy groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/721—Two or more polyisocyanates not provided for in one single group C08G18/73 - C08G18/80
- C08G18/725—Combination of polyisocyanates of C08G18/78 with other polyisocyanates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
- C08G18/797—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing carbodiimide and/or uretone-imine groups
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- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
Definitions
- the present invention relates to processes for the preparation of a polyurethane material in which (a) di- and / or polyisocyanates, (b) compounds containing isocyanate-reactive hydrogen atoms which do not contain compounds having carbon-carbon double bonds, (c) compounds containing at least one carbon-carbon double bond (d) optionally the urethane reaction accelerating catalyst and (e) optionally further auxiliaries and additives, mixed into a reaction mixture and cured at temperatures of greater than 120 ° C, wherein the B) have on average at least 1.5 isocyanate-reactive hydrogen groups per molecule and the compounds with carbon-carbon double bond (c) contain those compounds (c1) which contain at least one carbon atom -Carbon double bond and at least one group selected from Iso cyanate-reactive groups or isocyanate groups and / or (c2) which have at least two carbon-carbon double bonds and wherein the reaction mixture is stabilized to such an extent that the polyurethane material obtained when the components (a) to ( c) and,
- the present invention relates to a polyurethane material obtainable by such a process, and to the use of the polyurethane material, in particular of a polyurethane fiber composite material as structural components.
- Polyurethane materials can be used many times, but are often characterized by their improved performance characteristics at high temperatures.
- Polyurethane fiber composite materials are known and are usually obtained by pultrusion, fiber-winding processes or impregnation processes, such as vacuum infusion or RTM.
- the resulting fiber composite materials are characterized by a relatively low weight of material with high hardness and rigidity, high corrosion resistance and good processability.
- Polyurethane fiber composite materials are used, for example, as exterior body parts in vehicle construction, as boat hulls, masts, for example as electricity pylons or telegraph poles, or rotor blades for wind power plants.
- Prepregs are prepreg-impregnated textile fiber-matrix semifinished products which are cured to produce components under temperature and pressure.
- the matrix is in the partially cross-linked, so-called B-state and is pasty to solid and can be cured.
- prepregs based on polyurethanes are known. These are based on blocked polyisocyanates and are described, for example, in WO 01/1147688, WO 10/108701 and US Pat
- Task was therefore to provide a polyurethane material with increased temperature resistance. It was another object of the present invention to provide a simple method for improving the mechanical properties of polyurethane at high temperatures and thus to make available polyurethanes which can be used as a replacement for metal structures, for example in the cathodic dip-coating or as supporting structures , Finally, it was an object of the present invention to provide polyurethane materials which have a high mechanical stability at high temperatures and at the same time at room temperature a high impact strength. Furthermore, it was an object, in particular for the use of these polyurethane materials in the context of fiber composite materials, to ensure the lowest possible viscosity of the reaction mixture at room temperature, so that rapid impregnation of the fibers can take place.
- this object is achieved by a process in which (a) di- and / or polyisocyanates, (b) compounds containing isocyanate-reactive hydrogen atoms which do not contain compounds having carbon-carbon double bonds, (c) compounds containing at least one carbon-carbon double bond, (d) optionally the urethane reaction accelerating catalyst and (e) optionally further auxiliaries and additives, mixed to a reaction mixture and cured at temperatures of greater 120 ° C.
- the compounds having isocyanate-reactive hydrogen atoms b) have on average at least 1.5 isocyanate-reactive hydrogen groups per molecule and the compounds having carbon-carbon double bond (c) contain those compounds (c1) which contain at least one Carbon-carbon double bond and at least one group selected from isocyanate-reactive groups or isocyanate groups and / or (c2) which have at least two carbon-carbon double bonds and wherein the reaction mixture is stabilized to such an extent that the polyurethane mate- rial, the is obtained by mixing the components (a) to (c) and, if before (d) and (e) at room temperature, injection into a tempered to 80 ° C metal mold measuring 20 cm x 30 cm x 0.4 cm, after 60 minutes demolding and cooling to room temperature, a heat deflection temperature (three-point bend at 0 , 45 MPa marginal fiber stress according to DIN EN ISO 75), which is at least 15 ° C lower than the heat distortion temperature of the identically produced polyurethane material, which is tempered
- Polyurethane in the context of the invention comprises all known polyisocyanate polyaddition products. These include isocyanate and alcohol addition products, as well as modified polyurethanes, which may contain isocyanurate, allophanate, urea, carbodiimide, uretonimine, biuret, and other isocyanate addition products. These polyurethanes of the invention comprise, in particular, massive polyisocyanate polyaddition products, such as duromers, and foams based on polyisocyanate polyaddition products, in particular rigid polyurethane foams, and also polyurethane coatings.
- the polyurethane is a solid polyurethane having a density of preferably more than 850 g / L, preferably 900 to 1400 g / L and particularly preferably 1000 to 1300 g / L.
- a solid polyurethane is obtained without the addition of a blowing agent.
- blowing agent for example water, which is contained in the polyols as a result of the preparation, are not to be understood as blowing agent addition in the context of the present invention.
- the reaction mixture for producing the compact polyurethane contains less than 0.2 wt .-%, more preferably less than 0.1 wt .-% and in particular less than 0.05 wt .-% water.
- the massive polyurethane contains fillers, in particular fibrous fillers. Suitable fillers are described under (e).
- di- or polyisocyanates it is possible to use all aliphatic, cycloaliphatic or aromatic isocyanates known for the preparation of polyurethanes and also any mixtures thereof.
- examples are 2,2 '-, 2,4' - and 4,4 'diphenylmethane diisocyanate, the Mixtures of monomeric diphenylmethane diisocyanates and polynuclear homologues of diphenylmethane diisocyanate (polymer MDI), isophorone diisocyanate (IPDI) or its oligomers, 2,4- or 2,6-toluene diisocyanate (TDI) or mixtures thereof, tetramethylene diisocyanate or its oligomers, hexamethylene diisocyanate (HDI) or its oligomers, naphthylene diisocyanate (NDI) or mixtures thereof.
- poly MDI the Mixtures of monomeric diphenylmethane diiso
- Diisocyanates or polyisocyanates (a) used are preferably isocyanates based on diphenylmethane diisocyanate, for example 2,4'-MDi, 4,4'-MDI or mixtures of these components, if appropriate also with higher-nuclear homologs of MDI.
- the di- and polyisocyanates (a) have a functionality of 2.0 to 2.9, more preferably 2.0 to 2.8.
- the viscosity of the di- or polyisocyanates (a) at 25 ° C. according to DIN 53019-1 to 3 is preferably between 5 and 600 mPas and particularly preferably between 10 and 300 mPas.
- the di- and / or polyisocyanates (a) particularly preferably have at least 50, more preferably 60 to 100 and in particular 70 to 90, mol% of isocyanates having a functionality of 2.
- Diisocyanates and polyisocyanates (a) can also be used in the form of polyisocyanate prepolymers.
- These polyisocyanate prepolymers are obtainable by the polyisocyanates (component (a-1)) described above in excess, for example at temperatures of 30 to 100 ° C., preferably at about 80 ° C., with compounds having at least two isocyanate-reactive groups (Component (a-2)), are reacted to the prepolymer.
- the NCO content of polyisocyanate prepolymers of the invention is preferably from 20 to 33% by weight of NCO, particularly preferably from 25 to 30% by weight of NCO.
- polyether or polyester oils such as those described below under (b) can be used as compounds having at least two isocyanate-reactive groups.
- polyether or polyester oils containing secondary OH groups such as, for example, polypropylene oxide, are preferably used as compounds having at least two isocyanate-reactive groups (a-2).
- the polyether or polyester oils preferably have a functionality of from 2 to 4, particularly preferably from 2 to 3, and a content of secondary OH groups of at least 50%, preferably at least 75% and in particular at least 85%.
- Suitable compounds having on average at least 1.5 hydrogen atoms which are reactive toward isocyanate groups per molecule are all compounds known in polyurethane chemistry with isocyanate-reactive hydrogen atoms, compounds having carbon-carbon double bonds and a molecular weight of less than 800 g / mol are not considered compounds (b), but fall under the definition of compounds (c).
- Compounds (b) have an average functionality of at least 1, 5, preferably 1, 7 to 8, particularly preferably 1, 9 to 6 and in particular 2 to 4.
- chain extenders and crosslinking agents having an OH functionality of 2 to 6, and a molecular weight of less than 300 g / mol, preferably a functionality of 2 to 4 and more preferably of 2 to 3, as well as relatively high molecular weight compounds Isocyanate-reactive hydrogen atoms and a molecular weight of 300 g / mol and greater.
- Chain extenders are molecules having two isocyanate-reactive hydrogen atoms, and molecules having more than two isocyanate-reactive hydrogens are referred to as crosslinkers. These can be used individually or preferably in the form of mixtures. Preference is given to using diamines, diols and / or triols having molecular weights of less than 300 g / mol, particularly preferably from 62 g / mol to less than 300 g / mol and in particular from 62 g / mol to 250 g / mol.
- Suitable examples include aliphatic, cycloaliphatic and / or araliphatic or aromatic diamines and diols having 2 to 14, preferably 2 to 10 carbon atoms, such as diethyltoluenediamine (DEDTA), m-phenylenediamines, ethylene glycol, 1, 2-propanediol, 2-methyl -1, 3-propanediol, 1, 3-propanediol, 1, 4-butanediol, 1, 6-hexanediol, 1, 10-decanediol and bis (2-hydroxyethyl) hydroquinone (HQEE), 1, 2 , 1, 3, 1, 4-dihydroxycyclohexane, bisphenol A bis (hydroxyethyl ether), diethylene glycol, dipropylene glycol, tripropylene glycol, triols such as 1, 2,4-, 1, 3,5-trihydroxycyclohexane, glycerol and trimethylolp - Ropan, diethanolamine
- crosslinkers particular preference is given to using low molecular weight hydroxyl-containing polyalkylene oxides based on ethylene and / or 1,2-propylene oxide, particularly preferably 1,2-propylene, and trifunctional starters, in particular glycerol and trimethylolpropane.
- Particularly preferred chain extenders are ethylene glycol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, 1,4-butadiol, diethylene glycol, bis (2-hydroxyethyl) hydroquinone and dipropylene glycol.
- the proportion of chain extenders and / or crosslinkers (e) is usually 1 to 50, preferably 2 to 20 wt .-%, based on the total weight of components (a) to (e).
- chain extender or crosslinking agent it is also possible to dispense with the chain extender or crosslinking agent.
- the addition of chain extenders, crosslinking agents or possibly also mixtures thereof may prove advantageous.
- Higher molecular weight compounds having isocyanate-reactive hydrogen atoms preferably have a number-average molecular weight of 400 to 15,000 g / mol.
- compounds selected from the group of polyether polyols, polyester polyols or mixtures thereof can be used.
- Polyetheroics are prepared, for example, from epoxides such as propylene oxide and / or ethylene oxide or from tetrahydrofuran with hydrogen-starter compounds such as aliphatic alcohols, phenols, amines, carboxylic acids, water or natural-based compounds such as sucrose, sorbitol or mannitol using a catalyst ,
- hydrogen-starter compounds such as aliphatic alcohols, phenols, amines, carboxylic acids, water or natural-based compounds such as sucrose, sorbitol or mannitol using a catalyst
- basic catalysts or Doppelmetallcyanidkatalysatoren such as in
- Polyester oils are e.g. prepared from aliphatic or aromatic dicarboxylic acids and polyhydric alcohols, polythioether polyols, polyester amides, hydroxyl-containing polyacetals and / or hydroxyl-containing aliphatic polycarbonates, preferably in the presence of an esterification catalyst. Further possible polyols are given, for example, in “Kunststoffhandbuch, Volume 7, Polyurethanes", Carl Hanser Verlag, 3rd edition 1993, Chapter 3.1.
- the higher molecular weight compounds containing isocyanate-reactive hydrogen atoms contain compounds having hydrophobic groups.
- Particularly preferred are hydroxyl-functionalized compounds having hydrophobic groups.
- Such hydrophobic groups have hydrocarbon groups of preferably more than 6, more preferably more than 8 and less than 100 and especially more than 10 and less than 50 carbon atoms.
- the hydroxyl-functionalized hydrophobic compound used is preferably a hydroxyl-functionalized oleochemical compound, a fat-chemical polyol.
- hydroxyl functional oleochemical compounds are known that can be used. Examples are castor oil, hydroxyl group-modified oils such as grapeseed oil, black caraway oil, pumpkin seed oil, borage seed oil, soybean oil, wheat germ oil, rapeseed oil, sunflower oil, peanut oil, apricot kernel oil, pistachio kernel oil, almond oil, olive oil, macadamia nut oil, avocado oil, sea buckthorn oil, sesame oil, hazelnut oil, evening primrose oil, wild rose oil , Hemp oil, thistle oil, walnut oil, hydroxyl-modified fatty acid esters based on myristoleic acid, palmitoleic acid, oleic acid, vaccenic acid, petroselinic acid, gadoleic acid, erucic acid, nervonic acid, linole
- Another group of oleochemical polyols which is preferably used can be obtained by ring opening of epoxidized fatty acid esters with simultaneous reaction with alcohols and, if appropriate, following further transesterification reactions.
- the incorporation of hydroxyl groups into oils and fats is mainly due to epoxidation of the olefinic double bond contained in these products, followed by reaction of the epoxide groups formed with a monohydric or polyhydric alcohol.
- the epoxide ring becomes a hydroxyl group or, in the case of polyfunctional alcohols, a structure with a higher number of OH groups. Groups.
- oils and fats are usually glycerol esters
- parallel transesterification reactions take place in the abovementioned reactions.
- the compounds thus obtained preferably have a molecular weight in the range between 500 and 1500 g / mol.
- Such products are offered for example by the company BASF (as Sovermol®) or the company Altropol Kunststoff GmbH as Neukapol®.
- oleochemical polyols which contain carbon-carbon double bonds and have a molecular weight of less than 1000 g / mol are assigned to the compounds (c).
- the compounds (c) contain at least one carbon-carbon double bond. Furthermore, the compounds (c) contain compounds (c1) which have at least one carbon-carbon double bond and at least one group selected from isocyanate-reactive groups or isocyanate groups and / or (c2) which has at least two carbon atoms. Have carbon double bonds. If compounds (c1) are present which have at least one isocyanate-reactive group and at least one carbon-carbon double bond, these are taken into account in determining the average functionality of the compounds with isocyanate-reactive hydrogen atoms.
- the compounds (c1) and (c2) can be used in any ratio to one another. In a particularly preferred embodiment, no compound (c1) is used.
- Typical compounds (c) are, for example, butadiene, isoprene, 1, 3-pentadiene, 1, 5-hexadiene, 1, 7-octadiene, styrene, alpha-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2,4 Dimethylstyrene, ethylstyrene, isopropylstyrene, butylstyrene, phenylstyrene, cyclohexylstyrene, benzylstyrene and like derivatives; substituted styrenes such as cyanostyrene, nitrostyrene, N, N-dimethylaminostyrene, acetoxystyrene, methyl-4-vinylbenzoate, phenoxystyrene, p-vinylphenoxide and similar derivatives and mixtures thereof;
- the double bond functionality of compound (c) is greater than 1.
- Preferred ethylenically unsaturated monomers are methyl acrylate, trimethylolpropane triacrylate, and hydroxyl terminated polybutadiene, available under the tradename Krasol, mixtures thereof.
- polyfunctional olefins and monofunctional olefins together and thus to optimize the crosslinking density of the product on the one hand and the viscosity of the starting materials on the other hand, where the monofunctional olefin may or may not be isocyanate-reactive.
- the proportion of compounds (c) is preferably from 10 to 70% by weight, particularly preferably from 25 to 60% by weight and in particular from 30 to 50% by weight, in each case based on the total weight of components (a) to (e).
- the double bond density based on the starting materials and the total weight of the components (a) to (e), preferably more than 0.1 wt .-%, preferably 1, 0 to 30 wt .-% and in particular 4.0 to 16% by weight.
- those components c) which contain no isocyanate-reactive hydrogen atoms can also be added to the isocyanate component.
- the ratio of isocyanate groups of the di- and polyisocyanates (a) to the number of carbon-carbon double bonds of the compound (c) is from 0.1: 1 to 4: 1, more preferably from 0.4: 1 to 3 to 1 and especially 0.5 to 1 to 2 to 1
- customary polyurethane catalysts can be used as catalysts (d). These strongly accelerate the reaction of the compounds with isocyanate-reactive hydrogen atoms (b) with the di- and polyisocyanates (a).
- customary catalysts which can be used for the preparation of the polyurethanes are amidines, such as 2,3-dimethyl-3,4,5,6-tetrahydropyrimidine, tertiary amines, such as triethylamine, tributylamine, dimethylbenzylamine, Dimethylcyclohexylamine, N-methyl, N-ethyl, N-cyclohexylmorpholine, N, N, N ', N'-tetramethylethylenediamine, N, N, N', N'-tetramethylbutanediamine, N, N, N ', N '-Tetramethylhexanediamine, pentamethyl-diethylenetriamine, tetramethyl-diaminoethyl ether
- organic metal compounds preferably organic tin compounds, such as tin (II) salts of organic carboxylic acids, for example tin (II) acetate, tin (II) octoate, tin (II) ethylhexoate and Tin (II) laurate and the dialkyltin (IV) salts of organic carboxylic acids, for example dibutyltin diacetate, dibutyltin dilaurate, dibutyltin maleate and dioctyltin diacetate, and also bismuth carboxylates such as bismuth (III) neodecanoate, bismuth 2-ethylhexa- noate and bismuth octanoate or mixtures thereof.
- the organic metal compounds can be used alone or preferably in combination with strongly basic amines. When component (b) is an ester, it is preferred to use only amine catalysts.
- Catalysts (d) can be used, for example, in a concentration of 0.001 to 5% by weight, in particular 0.05 to 2% by weight, as catalyst or catalyst combination, based on the weight of component (b) ,
- auxiliaries and / or additives can be used.
- auxiliaries and additives can be used.
- all known for the production of polyurethanes auxiliaries and additives can be used.
- surface-active substances blowing agents, foam stabilizers, cell regulators, release agents, fillers, dyes, pigments, flame retardants, hydrolysis protectants, fungistatic and bacteriostatic substances.
- foam stabilizers blowing agents, foam stabilizers, cell regulators, release agents, fillers, dyes, pigments, flame retardants, hydrolysis protectants, fungistatic and bacteriostatic substances.
- auxiliary agents and additives (e) may comprise basic catalysts which are not conventional polyurethane-forming catalysts. These include, for example, catalysts which catalyze polyisocyanurate formation.
- Polyisocyanuric acid catalysts include alkali metal carboxylates. These preferably include formates and acetates, in particular acetates, such as sodium acetate and potassium acetate.
- the polyurethane material according to the invention preferably contains substantially no compounds containing epoxide groups. This means that the proportion of compounds containing epoxide groups, based on the total weight of components (a) to (e), is preferably less than 1% by weight, particularly preferably less than 0.1% by weight.
- the di and / or polyisocyanates (a), the compounds with isocyanate-reactive hydrogen atoms (b) and, if used, further compounds with isocyanate-reactive hydrogen atoms, such as blowing agents, in such amounts brought that the equivalence ratio of NCO groups of the polyisocyanates (a) to the sum of the isocyanate-reactive hydrogen atoms of the other components 0.7 to 1.4, preferably 0.8 to 1, 2, particularly preferred 0.9 to 1, 1 and in particular 1, 0.
- a ratio of 1: 1 corresponds to an isocyanate index of 100.
- the curing then takes place at temperatures of greater than 120 ° C, preferably at 140 to 225 ° C, more preferably at 150 to 210 ° C and especially at 160 to 200 ° C.
- the specific starting substances (a) to (e) for the preparation of polyurethanes according to the invention differ only quantitatively and qualitatively only slightly if an elastomer, a rigid foam or a duromer is to be produced as the polyurethane according to the invention.
- no propellants are used for the production of solid polyurethanes.
- the elasticity and hardness of the polyurethane according to the invention can be varied, for example, via the functionality and the chain length of the relatively high molecular weight compound having at least two reactive hydrogen atoms.
- reaction mixture is stabilized.
- a Stabilisie tion of the reaction mixture in the context of the invention is given when the polyurethane material, the mixed with a mixing of the components at room temperature and injection into a tempered at 80 ° C metal mold with the dimensions 20 cm X 30 cm x 0.4 cm and 60 after And a heat distortion temperature in three-point bending at 0.45 MPa Randmaschinetress according to DIN EN ISO 75 which at least 15 ° C, preferably at least 25 ° C, more preferably at least 40 ° C and esp - Specifically, at least 60 ° C is lower than the heat deflection temperature of the identically prepared polyurethane material, which is tempered after production for 120 minutes at 150 ° C in the oven and then cooled to room temperature.
- radical inhibitors substances can be used, which lead to a termination of the radical polymerization of the carbon-carbon double bonds.
- Radical inhibitors also referred to as radical scavengers, include bis (trifluoromethyl) nitroxide, aminoxyl radicals, 2,2-diphenyl-1-picrylhydrazyl and 2,2,6,6-tetramethylpiperidin-1-yloxy.
- Preferred free radical inhibitors are phenothiazine, nitrobenzene, hydroquinone monomethyl ether, p-benzoquinone and diphenylpicrylhydrazole.
- the reaction mixture contains from 0.0001 to 2.0% by weight, preferably from 0.0005 to 1.0% by weight and in particular from 0.001 to 0.5% by weight of free radical inhibitor, based on Total weight of components (a) to (e).
- Stabilization does not always require the addition of radical inhibitor. It may also be that the reactivity, in particular the reactivity of the compounds having at least one carbon-carbon double bond (c) is so low that an addition of the radical inhibitor is not required in order to stabilize at 80 ° C. to effect.
- the reaction mixture according to the invention contains no compounds which initiate a free-radical reaction.
- This includes conventional free-radical initiators, such as peroxides, for example dibenzoyl peroxide, disulfides, onium compounds or AIBN and photoinitiators, such as ⁇ -hydroxy-, ⁇ -alkoxy or ⁇ -amino aryl ketones or acylphosphine and photolabile aliphatic azo compounds or mixtures of those mentioned Verbinnditch. That concludes also the absence of compounds that could form only during storage of the reaction components and could initiate radical reactions. Therefore, the reaction mixture according to the invention may contain compounds which cause a decomposition of peroxides, for example organic sulfides, phosphites and phosphonites.
- the preparation of the reaction mixture is carried out in a two-component process.
- the compounds (b) to (d) and optionally (e) are combined to form a polyol component.
- the isocyanate component contains isocyanates (a) and optionally (constituents of component (e)), the composition of the polyol component preferably being adjusted so that the viscosity thereof is preferably less than 1000 mPas at 25 ° C.
- the viscosity is measured on the basis of DIN 53019. 1 to 3.
- it is possible to adjust the viscosity adjustment in particular by selecting the compound of component (c) and its amount of use,
- the use of acrylates makes it possible to reduce the viscosity of the polyol component.
- the reaction is carried out as a one-pot reaction after mixing all components a) to e) via a two-stage curing.
- the reaction mixture after mixing components (a) to (e) for a period of at least 10 minutes, preferably 10 to 30 minutes at temperatures of less than 120 ° C, preferably in the temperature range 30 to 110 ° C. , more preferably 50 to 80 ° C held.
- the reaction is continued to the polyurethane material according to the invention at a temperature of greater than 120 ° C, preferably a temperature of greater than 150 ° C and in particular a temperature in the range of 160 to 225 ° C.
- the temperature in the second step is usually maintained for at least 2 minutes, preferably 3 to 120 minutes and more preferably 10 to 60 minutes.
- the reaction mixture can also be cooled after the first step, for example to temperatures of -20 to 30 ° C. At this temperature, the reaction mixture is storable after completion of the first step and can be stored for several weeks.
- a polyurethane obtainable by a process according to the invention is also the subject of the invention.
- the polyurethane material of the invention is a polyurethane fiber composite material.
- fibers are wetted with the reaction mixture and then cured to form the polyurethane fiber composite material.
- the fibers there are preferably used glass fibers, carbon fibers, polyester fibers, natural fibers such as cellulose fibers, aramid fibers, nylon fibers, basalt fibers, boron fibers, cylon fibers (poly (p-phenylene-2,6-benzobisoxazole), silicon carbide fibers, asbestos fibers, metal fibers, and combinations thereof
- they may be in the form of short or long glass fibers, continuous fibers, scrims, knits, knits, random fiber mats, and layers of the same or different fiber orientation.
- Techniques for wetting the fibers are not limited and generally known. These include, for example, the fiber winding method, the pultrusion method, the hand lamination method and the infusion method such as the vacuum infusion method.
- the polyurethane materials according to the invention exhibit improved heat resistance, an increased glass transition temperature, very good resistance to water and hydrophobic liquids and very good duration load properties.
- the polyurethane materials according to the invention particularly preferably have heat distortion resistance in three-point bending at 0.45 MPa marginal fiber stress to DIN EN ISO 75 of greater than 120 ° C., more preferably greater than 130 ° C. and in particular greater than 140 ° C. and simultaneously an impact strength (Charpy) DIN En ISO 179-1 / 1 fU of over 25 KJ / m 2 .
- polyurethane fiber composite materials according to the invention for example, as adhesives, especially for thermally stressed areas, structural components, for example body exterior parts in vehicle construction, such as fenders, boat hulls, hot water tank, for example in the home, as parts of electric motors, masts, for example as Electricity pylons or telegraph poles, insulators and other components in the field of high-voltage engineering, rotor blades for wind power plants or as pipes, for example fiber-reinforced pipelines for the oil and gas industry, or equipment and aids for drilling, extraction and transport of oil and gas.
- the polyurethane materials according to the invention are suitable for use in cathodic dip coating, which is used in particular in the automotive industry.
- component (c) in the production of pipes can by the use of 25 to 60 parts by weight, particularly preferably 30 to 50 parts by weight of component (c), each based on the total weight of components (a) to (e), in Combination with the use of polyol, containing hydrophobic groups, as compound (b) even under tropical climates with temperatures in the range of 25 to 40 ° C and a relative humidity of greater than 50% up to greater than 90% polyurethane materials , which are essentially free of gas bubbles, have a high resistance to media, even with respect to hydrophobic liquids and have a high glass transition temperature and thus a high temperature application of the medium to be passed through.
- reaction mixture according to the invention can be used in vacuum infusion.
- preferably 2 to 15 wt .-%, preferably 3 to 10 wt .-% compounds of component (c), based on the total weight of components (a) to (e), together with higher molecular weight compounds (b), the one average functionality of preferably 1, 5 to 2.2, more preferably 1, 8 to 2.1 and in particular 1, 9 to 2.05 have used.
- component (b) may further contain chain extenders, for example 2 to 30 Wt .-%, based on the total weight of components (a) to (e).
- Such reaction mixtures are characterized in particular by low shrinkage during curing, good flowability and a long open time.
- reaction mixture according to the invention can be used for the production of storage-stable polyurethane prepregs by impregnating fibrous fabrics or fabrics at temperatures of preferably less than 100 ° C., more preferably less than 80 ° C. and in particular less than 50 ° C. and subsequent curing at temperatures of greater than 120 ° C, preferably 140 ° C to 225 ° C, more preferably 150 ° C to 210 ° C and especially 160 ° C to 200 ° C.
- prepregs according to the invention are stable in storage at room temperature and can be cured rapidly at temperatures of greater than 120.degree.
- the polyurethane reaction in the B state of the polyurethane prepreg according to the invention (that is to say in the uncured state) is already well advanced and is preferably substantially complete.
- the isocyanate content (NCO content) of the polyurethane prepreg is preferably 0 to 1% by weight NCO, particularly preferably 0 to 0.1% by weight NCO.
- An advantageous property of the prepreg resins is to undergo a B-state in which the resin is only pre-polymerized or partially polymerized, in a barely tacky state, and can be converted by temperature and possibly pressure before the resin in the final form Increased temperature completely hardens and strongly cross-linked.
- tackier intermediates will tend to be obtained which can be added and combined and are dimensionally stable in the final cured state. If a tack-free intermediate is desired, this can be achieved by reducing the proportions of the high equivalent weight polyols.
- the reaction mixtures according to the invention show a low viscosity and thus good impregnability. Due to the low viscosity of the reaction mixture according to the invention at temperatures below 80 ° C., for example at 10 to 30 ° C., it is possible to strip reaction mixture from the impregnated fiber material and thereby obtain a high fiber volume fraction. Therefore, an impregnation technique is preferable in which it is possible to efficiently remove and recycle excess resin from the fibers.
- the starting materials (details in all tables in percent by weight, customary batch size: 300 g of polyol component) are mixed at room temperature, then adding the isocyanate and mixing for 60 s in Speedmixer (FA Hauschild), then casting the reaction mixture into a metal mold 20X30X0.4 cm or 20X30X0.2 cm, stripping off the excess resin with a knife and curing at 80 ° C for 1 h, then for 2 h at 120 ° C and 2 h at 170 ° C. The material is then stored at room temperature after 1 week
- Comp. 2 It will be 99.5 TI. TMPTA and 0.5 TI. Free-radical initiator 1 mixed at room temperature and at 80 ° C for 10 min. hardened. This gives an inhomogeneous, brittle polymer with an irregular surface, from which no test specimens can be removed.
- the Tg (determined by DSC) is 122 ° C. The person skilled in the art is aware of the fact that, in the case of a polymer of the Tg, this is usually above the heat deflection temperature. The comparison 2 with radically produced homopolymer of the olefin thus has a significantly lower heat resistance than the inventive examples.
- Example 2 oruploadssbsp. 1 The starting materials of Example 2 oruploadssbsp. 1 are mixed at room temperature, adding the isocyanate and mixing for 60 s in the Speedmixer (FA Hauschild), then pouring the reaction mixture into a metal mold 20X30X0.4 cm or 20X30X0.2 cm, stripping off the excess resin with a squeegee , The reaction mixture is cured for 1 hour at 40 ° C. Subsequently, specimens of the size 4mm x 80mm x 10mm are punched out for the measurement of the heat resistance. Some of these test specimens are tempered according to the specifications in Table 2 and then the heat resistance measured. The results illustrate the course of the reaction. In the presence of a radical inhibitor, the reaction is only partial at temperatures below 80 ° C.
- the reaction product is storable in this state and sticky. Due to higher temperatures> 120 ° C, the heat resistance of the inventive Ex. Rises significantly above 100 ° C and only then reaches the final properties. The heat resistance of the inventive Ex. With complete curing is (160 ° C) significantly above theexceptsbsp. 1 with radical starter (120 ° C).
- Example 3 shows a better heat resistance and at the same time much better impact strength than Ex 4 (without catalysts).
- Table 4 shows a better heat resistance and at the same time much better impact strength than Ex 4 (without catalysts).
- the starting materials (Table 5) are mixed at room temperature.
- the reaction mixture is then filled continuously at room temperature by means of a metering system into an open bath.
- the impregnation takes place analogously to the wet winding process.
- a total of 42 rovings (external trigger, use of thread brakes for each roving) Tex 2400 are first passed through a perforated plate and then continuously through the impregnating bath.
- the wiper integrated in the impregnation device the excess resin is separated and can run back into the bath so that no resin drips from the impregnated rovings.
- the impregnated rovings are then passed through a 5.5 ⁇ 0.2 cm metallic bore, placed between release paper and cured at 80 ° C. The thus produced, 5.5 cm wide unidirectional prepreg can be wound on a spool after passing through the heating section.
- the prepreg is a tack-free, solid mass and can be manually deformed without the use of tools.
- the prepregs produced in this way are unwound and cut off several 30 cm long pieces.
- Two layers of prepreg are placed in the mold, fiber orientation 0 °, 90 °.
- the mold is then closed and heated first to 120 ° C and then for 1 h at 150 ° C for 1 h. Subsequently, a hard, no longer manually deformable three-dimensional component can be removed.
- the fiber volume content is 60%.
- Polyol 1 Propoxylated / ethoxylated mixture of sucrose and diethylene glycol, OHZ 400 and a functionality of 4.5, viscosity 3000 mPas [25 ° C.]
- Polyol 2 branched fatty acid ester, OHZ 173, viscosity 3400 mPas [25 ° C]
- Polyol 3 non-NCO reactive fatty acid ester, viscosity 7 mPas [25 ° C.]
- Polyol 4 Propoxylated mixture of sucrose and glycerol, OH 490 and a functionality of 4.4, viscosity 8450 mPas [25 ° C.]
- Polyol 5 Propoxylated Glycerine OHZ 805, Viscosity 1275 mPas [25 ° C]
- Polyol 6 Propoxylated Glycerol, OHZ 400, Viscosity 375 mPas [25 ° C]
- Polyol 7 Propoxylated Propylene Glycol, OHZ 248, Viscosity 75 mPas [25 ° C]
- Polyol 8 castor oil, OHZ 160, viscosity 1025 mPas [25 ° C]
- Polyol 9 Cationic propoxylated glycerine, OHZ 555, viscosity 690 mPas [25 ° C]
- TMPTA trimethylolpropane triacrylate
- Catalyst 1 40% solution of potassium acetate in DPG radical initiator 1: benzoyl peroxide radical inhibitor 1: phenothiazine defoamer 1: Efka Sl 2008, BASF SE defoamer 2: Efka Sl 2723, BASF SE
- Isocyanate 1 1 1 mixture of a prepolymer based on 4,4'-MDI, dipropylene glycol / polypropylene glycol and carbodiimide-modified 4,4'-MDI with an NCO content of 26%.
- Isocyanate 2 1: 1 Mixture of polymer-MDI and a 1: 1 mixture of 2,4'-MDi and 4,4'-MDI with an NCO content of 32.5% Exams:
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
Claims
Applications Claiming Priority (2)
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EP18158170 | 2018-02-22 | ||
PCT/EP2019/053234 WO2019162115A1 (de) | 2018-02-22 | 2019-02-11 | POLYURETHANBASIERTES POLYMERMATERIAL MIT HERVORRAGENDER WÄRMEFORMBESTÄNDIGKEIT UND REIßDEHNUNG |
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EP3755735A1 true EP3755735A1 (de) | 2020-12-30 |
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US (1) | US12037445B2 (de) |
EP (1) | EP3755735A1 (de) |
JP (1) | JP7359520B2 (de) |
KR (1) | KR20200125965A (de) |
CN (1) | CN111757899B (de) |
AU (1) | AU2019225884C1 (de) |
CA (1) | CA3091506A1 (de) |
EA (1) | EA202091902A1 (de) |
MX (1) | MX2020008799A (de) |
PH (1) | PH12020551287A1 (de) |
TW (1) | TW201936740A (de) |
WO (1) | WO2019162115A1 (de) |
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CN115181231B (zh) * | 2021-04-02 | 2024-01-23 | 上海高铁电气科技有限公司 | 一种液体组合物和由其制备的预浸料和复合材料 |
CN114437310B (zh) * | 2021-12-22 | 2024-02-23 | 四川东树新材料有限公司 | 改性聚氨酯组合物及其应用 |
CN115745799B (zh) * | 2022-11-25 | 2024-01-26 | 科顺民用建材有限公司 | 一种丙三醇三甲基丙烯酸酯、防水涂料组合物、防水涂料及其制备方法 |
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2019
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- 2019-02-11 JP JP2020544620A patent/JP7359520B2/ja active Active
- 2019-02-11 AU AU2019225884A patent/AU2019225884C1/en active Active
- 2019-02-11 US US16/971,987 patent/US12037445B2/en active Active
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- 2019-02-11 CA CA3091506A patent/CA3091506A1/en active Pending
- 2019-02-11 EP EP19703730.2A patent/EP3755735A1/de active Pending
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BR112020016339A2 (pt) | 2021-03-02 |
US20200399418A1 (en) | 2020-12-24 |
CA3091506A1 (en) | 2019-08-29 |
JP2021514419A (ja) | 2021-06-10 |
JP7359520B2 (ja) | 2023-10-11 |
AU2019225884B2 (en) | 2024-02-15 |
CN111757899A (zh) | 2020-10-09 |
TW201936740A (zh) | 2019-09-16 |
PH12020551287A1 (en) | 2021-07-12 |
AU2019225884C1 (en) | 2024-06-06 |
EA202091902A1 (ru) | 2020-12-10 |
KR20200125965A (ko) | 2020-11-05 |
WO2019162115A1 (de) | 2019-08-29 |
US12037445B2 (en) | 2024-07-16 |
MX2020008799A (es) | 2020-10-14 |
AU2019225884A1 (en) | 2020-09-03 |
CN111757899B (zh) | 2023-01-17 |
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