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    • 专利摘要:
    combination foam containing a matrix from polyurethane foam, use thereof and process for producing combination foams the present invention relates to a combination foam containing a matrix from polyurethane foam with particles foamed from polyurethane contained therein, in which matrix and particles, respectively, are constructed from polyol components and polyisocyanate components, in which at least 50% by weight of the modules that form the polyol components of the matrix and particles are identical and at least 50% by weight of the modules that form the polyisocyanate components of the matrix and particles are identical
    公开号:BR112015002711B1
    申请号:R112015002711-3
    申请日:2013-08-08
    公开日:2020-09-29
    发明作者:Frank Prissok；Michael Harms；Martin Vallo
    申请人:Basf Se；
    IPC主号:
    专利说明:

    [0001] The invention relates to a combination foam, which contains a matrix from polyurethane foam and foamed particles contained therein from thermoplastic polyurethane, its use and the method for its production.
    [0002] Polyurethanes are currently used, based on their wide profile of properties, in a plurality of applications. In this sense, polyurethanes can be used in compact as well as foamed form, in which a very wide density range, from compact bodies, with a density greater than 1.00 g / cm3, to foamed bodies with about 0, 01 g / cm3. Polyurethanes can, in this case, be present in the form of duromers, elastomers, thermoplastic elastomers (TPU), microcellular elastomers, integral foams, flexible foams, rigid foams or semi-rigid foams, for example.
    [0003] Through combinations of polyurethane with other materials, bonding materials can also be produced, through which the area of use of “polyurethane” material is further expanded. With this, it is possible to obtain hybrid materials with reduced density and special properties and / or reduce material costs by applying foamed particles in a polyurethane matrix.
    [0004] WO 2006/015440 discloses hybrid materials from a matrix of polyurethane and foamed polyurethane particles contained therein, for example, recycling material. The disadvantage of such joining materials from polyurethane and recycled polyurethane foam is poor adhesion between the foamed recycling particles and the matrix material. In addition, the mechanical properties of such a material are also worthy of improvement. Depending on the opening capacity of the recycling foam cells, these foams accept a greater amount of binders.
    [0005] WO 2008/087078 discloses hybrid materials containing a polyurethane matrix and foamed particles contained therein from thermoplastic polyurethane. The particles foamed from thermoplastic polyurethane are based on polyester polyol based on adipinic acid and butane-1,4-diol and 4,4'-diphenylmethanediisocyanate (4,4'MDI). Other foamed particles of thermoplastic polyurethane are based on polytetrafuran, butane-1,4-diol and 4,4'-MDI. The polyurethane matrix is based on polyetherols based on propylene oxide / ethylene oxide in combination with isocyanate prepolymers based on MDI and polyetherol mixtures with an NCO content of 13.9%.
    [0006] The adhesion between polyurethane matrix and particles foamed from thermoplastic polyurethane (TPU) is not good enough for all applications, so that the mechanical properties of the matrix foam are not sufficient for all applications.
    [0007] The task of the present invention is to provide a combination foam that presents an improved adhesion between matrix material and foamed particles.
    [0008] The mechanical properties should preferably be improved over known hybrid materials, for example, with respect to elasticity and resistance to breaking.
    [0009] The task is solved, according to the invention, by means of a combination foam containing a matrix of polyurethane foam and foamed particles contained therein from thermoplastic polyurethane, in which matrix and particles, respectively, are constructed from. from polyol components and polyisocyanate components, the combination foam characterized by the fact that at least 50% by weight of the modules that form the polyol components of the matrix and particles are identical and at least 50% by weight of the modules that form the components polyisocyanate of the matrix and the particles are identical.
    [0010] In addition, the task is solved through the use of this combination foam as shoe soles, saddles, upholstery, in construction parts in the internal and external areas of automobiles, in balls and sports articles or as a floor covering, especially for sports surfaces, athletics tracks, sports courts, playgrounds and sidewalks.
    [0011] In addition, the task is solved by means of a process for producing such combination foams by reacting the polyol components that form the matrix from polyurethane foam and the polyisocyanate components, as well as eventually chain extenders, agents crosslinking agents, catalysts, blowing agents, other additives or mixtures thereof in the presence of the thermoplastic polyurethane particles to be foamed or preferably foamed.
    [0012] Materials in which a foam is surrounded by a / a matrix / foam material are characterized in the context of this invention as combination foams.
    [0013] Polyurethane foams, in the context of the invention, comprise all polyisocyanate polyaddition products in foamed form known, such as flexible foams, rigid foams or integral foams, such as rigid foams. Further details regarding polyurethanes are found in “Kunststoffhandbuch, Volume 7, Polyurethane, Carl Hanser Verlag, 3rd edition, 1993, chapters 5 - 8 and 10 - 12”.
    [0014] In the context of the invention, polyurethane foams are preferably foams according to DIN 7726. In this sense, flexible polyurethane foams according to the invention have a compressive tension at 10% compression or pressure resistance according to DIN 53 421 / DIN EN ISO 604, from 15 kPa and even less, preferably from 1 to 14 kPa and especially from 4 to 14 kPa. Semi-rigid polyurethane foams according to the invention preferably have a compression stress at 10% compression according to DIN 53 421 / DIN EN ISO 604, from more than 15 to less than 80 kPa. Semi-rigid polyurethane foams and flexible polyurethane foams according to the invention preferably have a cell opening capacity according to DIN ISO 4590 of more than 85%, especially preferably more than 90%. Further details regarding flexible polyurethane foams and semi-rigid polyurethane foams according to the invention can be found in the “Kunststoffhandbuch, Volume 7, Polyurethane, Carl Hanser Verlag, 3rd edition, 1993, chapter 5.
    [0015] Polyurethane elastomeric foams, in the context of the present invention, are preferably polyurethane foams according to DIN 7726, which do not have any deformation, after a short deformation of 50% of the thickness according to DIN 53 577 after 10 minutes. remain above 2% of the initial thickness. In this sense, it can be a semi-rigid polyurethane foam or a flexible polyurethane foam.
    [0016] In the case of integral polyurethane foams, these are preferably polyurethane foams according to DIN 7726 with a margin, which, depending on the forming process, have a higher density than that of the core. The total apparent density estimated for the core and the margin is, in this case, preferably above 0.1 g / cm3. Also in the case of integral polyurethane foams in the context of the invention, semi-rigid polyurethane foams or flexible polyurethane foams can be used. Further details regarding the integral polyurethane foams according to the invention are found in "Kunststoffhandbuch, Volume 7, Polyurethane, Carl Hanser Verlag, 3rd edition, 1993, chapter 7".
    [0017] An elastic foam or integral foam with a density of 0.8 to 0.1 g / cm3, especially from 0.6 to 0.3 g / cm3, is especially preferred as a matrix material.
    [0018] In the combination foam according to the invention, the polyurethane foam matrix is preferably and essentially open cell or very open cell. The foamed thermoplastic polyurethane particles contained in the matrix are preferably at least partially closed cells, especially preferably completely closed cells. The production of this combination foam is achieved by the fact that the open cell fraction of the foam is previously produced as foam of expandable particles and closed cells and, in a second step, is mixed with a very similar or chemically identical receptor to the modules, is delivered and put into reaction. The second fraction of foam forms, based on the additive employed, preferably an opening and free contraction cell matrix and connects to the previously applied closed cell particles. The matrix and the particles are preferably very predominantly identical or approximately chemically identical, with the result that better mechanical properties and greater elasticities, with lower densities on average, compared to foam systems or clean particles or also in comparison to the hybrid materials known from of WO 2008/087078, arise as a result. Due to the fact that the basic formulas of the open cell and closed cell fractions are continuously the same, a surprising adhesion of the phases to each other results, which contributes decisively to the high mechanical level.
    [0019] According to the invention, at least 50% by weight of the module forming the polyol component of the matrix and the particles are identical and at least 50% by weight of the module forming the polyisocyanate component of the matrix and the particles are identical .
    [0020] To calculate the corresponding weight fractions, proceed as follows:
    [0021] All the polyol components of the matrix and the particles are calculated and listed, in which the weight percentage of the individual polyols in the totality of the matrix or particle polyols, respectively, which results in 10% by weight, is determined. Then comparing the individual polyols and their parts by weight for the matrix and for the particles, then at least 50% by weight of the matrix polyols must also be contained in the particles and must be inverted. This can be explained based on the examples of the present invention:
    [0022] As shown in Table 1, different polyols (polyol 1, polyol 3, polyol 4 and the EC chain extender) are present in the combination foams according to the invention, whereas in the TPU particles (ETPU) are present polyol 1 and EC chain extender. Regarding the sum of polyols (polyol 1 to 6 plus chain extender), the fraction of polyol 1 according to example 1 is 68.8% and the fraction of chain extender is 7.5%. The polyol 1 fraction for ETPU is 91.8% and the chain extender fraction is 8.2%. Thus, polyol 1 (68.8%) and chain extender (7.5%) are, according to example 1, identical to the respective components of the ETPU, in total, therefore, 76.3% by weight.
    [0023] In this case, each polyol here must be individually related to each other: if the fraction of EC chain extender in the ETPU is evidently smaller than in example 1, then only the smallest value among both could be taken to be in both formulations. In the chosen example, the quantities according to example 1 are completely contained in the respective quantities according to the ETPU, in such a way that no differentiation of this type is necessary.
    [0024] Corresponding calculations apply to the quantities of polyisocyanate components.
    [0025] As a result, numerical values in weight percent indicate the degree of affinity between the matrix modules and the TPU particles. This affinity is, according to the invention, especially great, in such a way that they result in chemically very similar matrices and particles, which correspondingly show good adhesion to each other. In comparison to that, according to WO 2008/087078, different polyols are used in the matrix and in the TPU particles. On the other hand, adhesion can be further improved according to the invention.
    [0026] At least 60% by weight of the modules that form the polyol component of the matrix and the particles are preferably identical and at least 60% by weight of the modules that form the polyisocyanate component of the matrix and the particle.
    [0027] At least 65% by weight of the modules that form the polyol component of the matrix and particles are especially and preferably identical and at least 85% by weight of the modules that form the polyisocyanate component of the matrix and particles.
    [0028] In this case, they are present in the matrix and particle combination foam, preferably in a weight ratio in the range of 0.1 to 10: 1.
    [0029] According to the invention, by combining a closed cell particle foam with a chemically identical component, which is processed as a system foam and has surprising adhesion on the particle foam, a product is obtained which is also free of shrinkage when of lower density and which has better mechanical properties compared to a clean system foam on the same base. The good adhesion of the open cell phase to the closed cell phase is caused by the continuous and chemically identical construction.
    [0030] Another reason for the high mechanical level when of relatively less thickness can be explained by the fact that the combination foam has a type of three-dimensional sandwich component.
    [0031] Ideally, the TPU particle foam forms a filling from spheres with closed cells, highly elastic and low density. The interstices of this filling are filled with a non-shrinking system foam, preferably of greater density, which shows, due to its chemical construction, a very good adhesion to the TPU particles.
    [0032] The combined components of this three-dimensional sandwich structure show comparable tensile strength and extension values, so that when the two phases adhere well to each other, in the case of open cell tensile strength, the density phase higher tensile strength leads to forces and on the increase of elongation the embedded closed cell particles are compressed and can thus oppose the tension with a high force. In the case of compression of the combination foam and also in determining the rebound elasticity, the open cell foam system passes over pressure to the closed cell TPU particles. The compression of the gas bubbles that are completely surrounded by an elastic matrix allows the closed cell foam to build up with a significantly greater counter-force than an open cell foam and to pass it again.
    [0033] In the case of an open cell elastomer foam, the matrix therefore has essentially the tensile and compressive forces, whereas in the case of a closed cell system, the matrix is supported both in compression and in tension by the gas bubbles (air balloon effect). The closed cell foam particles thus reinforce the open cell foam, in terms of its mechanical behavior, although preferably they have a lower density than the last one. However, without open cell foam the tensile strength of closed cell foam alone would not be sufficient, since its density is very low for high tensile forces. The compression and rapid expansion of the gas allows the energy stored in the particles to be released again quickly, which leads to an improvement in the rebound elasticity. The density of the foam is determined by the combination of the individual layers and the proportions of the two phases used, viz. the preference for low density closed cell foam and the preference for higher density open cell foam.
    [0034] If, in comparison, an open cell foam is used, which, due to chemical incompatibility, has low adhesion to the particle foam, the reinforcement effect does not occur. If a connection system is used, in which the break length is very small, an early component failure also occurs.
    [0035] Preferred characteristics of a combination foam based on three-dimensional open cell and closed cell bands are:
    [0036] closed cell particles are wrapped with an essentially open cell system;
    [0037] combination foam, after production, contains macroscopic three-dimensional bands with open and closed cell structure;
    [0038] the closed cell bands have a diameter greater than 1 mm, preferably greater than 2 mm;
    [0039] foam with closed cell and with open cell is built essentially from the same raw materials;
    [0040] in the case of foam with open cells and closed cells, it is polyurethane;
    [0041] in the case of identical raw materials, these are diols and diisocyanate;
    [0042] the diols are preferably polyether or polyester diols;
    [0043] it is preferably polytetrahydrofuran and MDI;
    [0044] preferably expanded particulate foam is used as closed cell foam;
    [0045] the particle foam has a lower density than the system foam.
    [0046] The organic and / or modified polyisocyanates used for the production of the polyurethane composites according to the present invention comprise the aliphatic, bifunctional or polyfunctional, cycloaliphatic and aromatic isocyanates known in the prior art and any mixtures thereof. Examples are diphenylmethane-4,4'-diisocyanate, diphenylmethane-2,4'-diisocyanate, mixtures of diphenylmethane diisocyanates and monomeric diphenylmethane diisocyanate having more than two rings (polymeric MDI), tetramethylene diisocyanate, diisocyanate hexamethylene (HDI), isophorone diisocyanate (IPDI), methylenedi (cyclohexylisocyanate) (H12MDI), 2,4- or 2,6-diisocyanate (TDI) or mixtures of the mentioned isocyanates.
    [0047] Preference is given to the use of 4,4'-MDI. The 4,4'-MDI, which is preferably used can comprise from 0 to 20% by weight of 2,4'-MDI and small amounts of up to 10% by weight of modified polyisocyanates or allophanate-uretonimine. Small amounts of polyphenylenepolymethylene polyisocyanate (polymeric MDI) can also be used. The total quantity of these highly functional polyisocyanates must not exceed 5% by weight of the isocyanate used.
    [0048] The polyisocyanate component is preferably used in the form of polyisocyanate prepolymers to produce the open cell system. These polyisocyanate prepolymers can be obtained by reacting the polyisocyanates described above with polyols, for example at temperatures of 30 to 100 ° C, preferably about 80 ° C, to form the prepolymer. In order to produce the prepolymers according to the invention, preference is given to the use of 4,4'-MDI with MDI and commercial polyols modified with uretonimine, in particular polytetrahydrofuran or polyester polyalcohol. The uretonimine modification liquefies the prepolymer at room temperature, which helps the production of the matrix system. Small proportions of polyester based polyols, for example derivatives of adipic acid, or polyethers, for example, derivatives of ethylene oxide and / or propylene oxide, as described in WO 2008/087078, can be used concomitantly.
    [0049] Polyols are known to those skilled in the art and are described, for example, “Kunststoffhandbuch, volume 7, Polyurethane”, Carl Hanser Verlag, 3rd edition, 1993, chapter 3.1.
    [0050] The usual chain extenders or crosslinking agents are optionally added to the aforementioned polyols for the preparation of the isocyanate prepolymers. Particular preference is given to the use of dipropylene glycol or tripropylene glycol as chain extenders or crosslinking agents.
    [0051] Compounds of relatively high molecular weight having at least two H atoms, which are reactive with isocyanate groups, are preferably polyester polyols or polytetrahydrofuran.
    [0052] Polytetrahydrofuran is prepared by known processes, for example, from one or more alkylene oxides, such as tetrahydrofuran, by anionic polymerization using alkali metal hydroxides or alkali metal alkoxides as catalysts, with the addition of at least one initiation molecule comprising 2 or 3 reactive hydrogen atoms in bonded form or by cationic polymerization with Lewis acids, such as antimony pentachloride or boride fluoride etherate. In addition, multimetalcyanide cyanide compounds, known as DMC catalysts, can also be used as catalysts.
    [0053] Possible starting molecules are water or trihydric and dihydric alcohols, such as ethylene glycol, 1,2- and 1,3-propanediol, diethylene glycol, dipropylene glycol, 1,4-butanediol, glycerol or trimethylolpropane.
    [0054] The polytetrahydrofuran preferably has a functionality of 2 to 3, preferably 2, and the molecular weights are between 250 to 8000 g / mol, preferably between 500 to 4,000 g / mol, where the thermoplastic polyurethane has from 600 to 2500 g / mol.
    [0055] Polyester polyols can, for example, be prepared from organic dicarboxylic acids with 2 to 12 carbon atoms, preferably aliphatic dicarboxylic acids with 4 to 10 carbon atoms and polyfunctional alcohols, preferably from 2 to 12 carbon atoms, preferably between 2 to 6 carbon atoms. Dicarboxylic acids are possible, for example: succinic acid, glutaric acid, adipic acid, submeric acid, azelaic acid, sebacic acid, decanedicarboxylic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid and terephthalic acid. Dicarboxylic acids can be used individually or in a mixture with each other. Instead of the free dicarboxylic acids, it is also possible to use the corresponding dicarboxylic acid derivatives, such as dicarboxylic esters of alcohols with 1 to 4 carbon atoms or dicarboxylic anhydrides. Preference is given to the use of mixtures of dicarboxylic acids of succinic, glutaric and adipic acids in proportions by weight of, for example, 20 to 35: 35 to 50: 20 to 32, and in particular adipic acid. Examples of dihydric and polyhydric alcohols, especially diols, are: ethanediol, diethylene glycol, 1,2 or 1,3-propanediol, dipropylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol , 1,10-decanediol, glycerin and trimethylolpropane. Preference is given to the use of ethanediol, diethylene glycol, 1,4-butanediol, 1,5-pentanediol and 1,6-hexanediol. It is also possible to use polyester polyols derived from lactones, for example, ε-caprolactone, or hydroxycarboxylic acids, for example, ω-hydroxycaproic acid.
    [0056] To prepare organic polyester polyols, for example, aromatic and preferably aliphatic polycarboxylic acids, and / or their derivatives, polyhydric alcohols can be polycondensed in the absence of catalysts or preferably in the presence of esterification catalysts, advantageously in an atmosphere of inert gas, eg nitrogen, carbon monoxide, helium, argon, etc. in the melt at temperatures of 150 to 250 ° C, preferably from 180 to 220 ° C, optionally under reduced pressure, so that the desired acid number is preferably below 10, particularly preferably below 2. In a preferred embodiment, the mixture of esterification is polycondensed at the above temperatures to an acid number of 80 to 30, preferably 40 to 30, under atmospheric pressure and then under a pressure of less than 500 mbar, preferably 50 to 150 mbar. Possible esterification catalysts are, for example, iron, cadmium, cobalt, lead, zinc, antimony, magnesium, titanium and tin catalysts in the form of metals, metal oxides or metal salts. However, polycondensation can also be carried out in a liquid phase in the presence of diluents and / or entraining agents, such as benzene, toluene, xylene or chlorobenzene to distill off azeotropically condensed water. To prepare polyol polyesters, organic polycarboxylic acids and / or their derivatives and polyfunctional alcohols are advantageously polycondensed in a molar ratio of 1: 1 to 1.8, preferably 1: 1.05 to 1.2.
    [0057] The polyester polyesters obtained preferably have a functionality of 2 to 4, in particular 2 to 3 and a molecular weight of 480 to 3000 g / mol, preferably 1000 to 3000 g / mol, in which the thermoplastic polyurethane of 500 to 2500 g / mol.
    [0058] The polyurethane foam of the matrix can be produced with or without the concomitant use of diluents and / or chain crosslinking agents. However, the addition of chain extenders, crosslinking agents or mixtures thereof can optionally be found to be advantageous for modifying mechanical properties, for example, hardness. Diluents and / or chain crosslinking agents are substances with a molecular weight of preferably less than 400 g / mol, particularly preferably from 60 to 400 g / mol, with chain extenders with two hydrogen atoms that are reactive with isocyanates and crosslinkers having 3 hydrogen atoms that are reactive with isocyanate. These can be used either individually or in the form of mixtures. Preference is given to the use of diols and / or triols with molecular weights less than 400, particularly preferably from 60 to 300 and in particular from 60 to 150. The possibilities are, for example, aliphatic, cycloaliphatic and / or aliphatic diols having 2 to 14, preferably with 2 to 10 carbon atoms, for example, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,10-decanediol, o-, m, p-dihydroxycyclo- hexane, diethylene glycol, dipropylene glycol and preferably butanediol-1,4, 1,6-hexanediol and bis (2-hydroxyethyl) hydroquinone, triols, such as 1,2,4, 1,3,5-trihydroxycyclohexane, glycerol and trimethylolpropane and low molecular weight comprising hydroxyl ethylene-based polyalkylene oxides and / or 1,2-propylene oxide and the diols and / or triols referred to above starting molecules.
    [0059] If chain extenders, cross-linking agents or mixtures thereof are employed, they are advantageously used in amounts of 1 to 60% by weight, for example, preferably from 1.5 to 50% by weight, and in particular of 2 to 40% by weight, based on the weight of the chain extender polyols and / cross-linking agents.
    [0060] If the catalysts are used for the production of the hybrid materials according to the invention, preference is given to the use of compounds that strongly accelerate the reaction of the polyols with the possibly modified organic polyisocyanates. Examples of amidines such as 2,3-dimethyl-3,4,5,6-tetrahydropyrimidine, tertiary amines, such as triethylamine, tributylamine, dimethylbenzylamine, N-methylmorpholine, N-ethylmorpholine, N-cyclo- hexyl-morpholine, N, N, N ', N'-tetramethylethylenediamine, N, N, N', N'-tetramethylbutanediamine, N, N, N ', N'- tetramethylhexanediamine, pentamethyldiethylenetriamine, bis (dimethylaminoethyl) ether, bis dimethylaminopropyl) urea, dimethylpiperazine, 1,2-dimethylimidazole, 1-azabicyclo [3.3.0] octane and preferably 1,4-diazabicyclo [2.2.2] octane and alkanolamine compounds, such as triethanolamine, triisopropanolamine, N-methyldiethanolamine and N- ethyl diethanolamine and dimethylethanolamine. Other possibilities are metallic organic compounds, organic tin compounds, such as, preferably tin (II) salts of organic carboxylic acids, for example, tin (II) tin (II) acetate (II) and ethylhexanoate tin (II), dialkyl tin (IV) laurate, salts of organic carboxylic acids, for example, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin maleate and dioctyltin diacetate, and also carboxylates of bismuth, such as bismuth (III) neodecanoate, bismuth 2-ethylhexanoate and bismuth octanoate or mixtures thereof. Organic metal compounds can be used alone or preferably in combination with strongly basic amines. If component (b) is an ester, preference is given to the use of amine catalysts exclusively.
    [0061] Preference is given to using 0.001 to 5% by weight, in particular 0.05 to 2% by weight of catalyst or combination of catalysts, based on the weight of the polyols.
    [0062] In addition, blowing agents can be present in the production of polyurethane foams as a matrix material. These blowing agents optionally comprise water. Compounds that are chemically and / or physically act beyond water, generally known, can be used instead of or in addition to water as a blowing agent. For the purposes of the present invention, chemical blowing agents are compounds that react with the isocyanate to form gaseous products, for example, formic acid. Physical blowing agents are compounds that are dissolved or emulsified in the starting materials for the production of polyurethane and are volatile under the conditions of polyurethane formation. These are, for example, hydrocarbons, halogenated hydrocarbons and other compounds, such as perfluorinated alkanes, for example, perfluorohexane, chlorofluorocarbons, and ethers, esters, ketones and / or acetals, for example, aliphatic (cyclo) hydrocarbons between 4 to 8 carbon atoms or fluorinated hydrocarbons, such as Solkane® 365 mfc. In a preferred embodiment, a mixture of these blowing agents, which comprise water, is used as a blowing agent; Particular preference is given to the use of water as the sole blowing agent. If water is not used as the blowing agent, preference is given to using physical blowing agents exclusively. The water content is, in one embodiment, from 0.1 to 2% by weight, preferably from 0.2 to 1.5% by weight, particularly preferably from 0.3 to 1.2% by weight, in particular 0 , 4 to 1% by weight, based on the total weight of the matrix.
    [0063] In another embodiment, hollow microspheres containing physical blowing agents are added as an additional blowing agent. The hollow microspheres can also be used in mixture with water, with the chemical mentioned above and / or with physical blowing agents.
    [0064] The hollow microspheres generally comprise a thermoplastic polymer shell and have a core filled with a liquid substance, low boiling point based on alkanes. The production of such hollow microspheres is described, for example, in US 3,615,972. The hollow microspheres generally have a diameter of about 5 to 50 µm. Examples of suitable hollow microspheres can be obtained under the trade name Expancell® from Firma Akzo Nobel.
    [0065] The foam particles are added, in general, in an amount of 0.5 to 5% in relation to the total weight of the matrix.
    [0066] The particles from thermoplastic polyurethane (TPU) are produced from expandable particles, expanded particles or in a continuous process in an extruder.
    [0067] These foam particles preferably have a diameter of 0.1 mm to 10 cm and, preferably, 0.5 mm to 5 cm and particularly preferably 1 mm to 2 cm, and are preferably spherical or ellipsoidal. In the case of non-spherical particles, for example, ellipsoidal particles, the diameter is the longest axis. Foam particles having a density preferably from 0.005 to 0.50 g / cm3, in particular preferably from 0.01 to 0.3 g / cm3 and in particular 0.02 to 0.2 g / cm3. The foam particles which preferably have a compact outer film. Here, a compact skin means that the foam cells on the outside of the foam particles are smaller than on the inside. Particular preference is given to the outer region of the foam particles which do not comprise any pores and the particle cells to be closed.
    [0068] Polytetrahydrofuran was used for the production of foam particles that are preferably based on a thermoplastic polyurethane. The molecular weight of the polytetrahydrofuran used is preferably 600 to 2500 g / mol. In another preferred embodiment, a polyester polyalcohol having a molecular weight of 500 to 2,500 g / mol, preferably 600 to 900 g / mol, is used to produce the foam particles.
    [0069] As expandable particles of thermoplastic polyurethane, which comprise blowing agents in dispersed or dissolved form, it is possible to use, for example, thermoplastic polyurethane particles impregnated with blowing agent. Such particles and their production are described, for example, in WO 94/20568 and WO 2007/082838.
    [0070] The expanded and / or expandable particles are particularly and preferably produced using thermoplastic polyurethanes whose melting range of a DSC measurement is at a heating rate of 20 K / min, starting below 130 ° C, especially preferably below 120 ° C, and in the case of thermoplastic polyurethane (also referred to as TPU), it has a melting flow rate (MFR) at 190 ° C under a load of 21.6 kg, in accordance with DIN EN ISO 1 133, of not more than 250 g / 10 min, particularly preferably a melt flow rate of less than 200 g / 10 min. Thermoplastic polyurethane comprising blowing agent preferably has an average diameter of 0.1 to 10 mm.
    [0071] Such a thermoplastic polyurethane is preferably based on a polyalcohol, particularly preferably a polyether diol. In this sense, polytetrahydrofuran is particularly preferred. TPU is particularly preferably based on polytetrahydrofuran with a molecular weight in the range of 600 g / mol to 2500 g / mol. Polyalcohols can be employed individually or in admixture with each other.
    [0072] Alternatively, good results can be achieved using TPU based on polyester alcohol, preferably polyester diol, preferably based on adipic acid and 1,4-butanediol, having a molecular weight in the range of 500 to 2500 g / mol, particularly preferably from 600 g / mol to 900 g / mol.
    [0073] Thermoplastic polyurethane used according to the invention is produced, for example, by reaction of isocyanates (d) with compounds that are reactive with isocyanates and that have a molecular weight from 500 to 10,000 (c2) and, optionally, extenders chain having a molecular weight comprised between 50-499 (c3), optionally in the presence of catalysts (c4) and / or usual auxiliary agents and / or additives (c5).
    [0074] As organic isocyanates (d), it is possible to use generally known aliphatic, cycloaliphatic, araliphatic and / or aromatic isocyanates, preferably diisocyanates, for example, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene and / or octamethylene diisocyanate, 2-methylpentamethylene 1,5-diisocyanate, 2-ethylbutylene 1,4-diisocyanate, pentamethylene-diisocyanate 1,5, 1,4-butylene, 1-isocyanate-3,3,5 diisocyanate -trimethyl-5-isocyanatomethylcyclohexane (isophorone diisocyanate, IPDI), 1,4 and / or 1,3-bis (isocyanate-methyl) cyclohexane (HXDI), cyclohexane-1,4-diisociaπate, 1-methyl -cyclohexane 2,4 and / or 2,6-diisocyanate and / or dicyclohexylmethane 4,4 ', 2,4' and 2,2'-diisocyanate, diphenylmethane-2,2 ', 2,4' and / or 4,4'-diisocyanate (MDI), 1,5-naphthylene diisocyanate (NDI), 2,4 tolylene and / or 2,6-diisocyanate (TDI), diphenylmethane diisocyanate, 3,3'-dimethylbiphenyl, diisocyanate 1,2-diphenylethane and / or phenylene diisocyanate.
    [0075] As compounds (c2) that are reactive with isocyanates, it is possible to use the generally known compounds that are reactive with isocyanates, for example polyester polyesterols and / or polycarbonate diols, which are usually combined under the term "polyols ", which have an average number of molecular weights of 500 to 8000 g / mol, preferably 600 to 6000 g / mol, especially 800 to 4000 g / mol, and preferably, an average functionality of 1.8 to 2.3, preferably 1.9-2.2, in particular 2, and also their mixtures.
    [0076] In a particularly preferred embodiment, the compound (c2) which is reactive with isocyanates comprises a polytetrahydrofuran with an average molecular weight of 600 to 2,500 g / mol.
    [0077] In another particularly preferred embodiment, the compound (c2) which is reactive with isocyanates comprises a polyester alcohol, preferably polyester diol, preferably based on adipic acid and 1,4-butanediol, having a molecular weight average in number in the range 500 to 2500 g / mol, particularly preferably from 600 g / mol to 2400 g / mol.
    [0078] As well as chain extenders (c3), it is possible to use generally known aliphatic, araliphatic, aromatic and / or cycloaliphatic compounds with a molecular weight of from 50 to 499, preferably 2-functional compounds, for example, diamines and / or alkanodiols having 2 to 10 carbon atoms in the alkylene radical, in particular 1,4-butanediol, 1,6-hexanediol and / or dialkylene, trialkylene, tetraalkylene, pentaalkylene, hexaalkylene, heptaalkylene, octaalkylene, nonaalkylene and / or decalalkylene glycols from 3 to 8 carbon atoms, preferably corresponding to oligopropylene and / or polypropylene glycols, with mixtures of chain extenders also being able to be used.
    [0079] Suitable catalysts (c4) which, in particular, accelerate the reaction between the NCO groups of the diisocyanates (d) and the hydroxyl groups of the structural components (c2) and (c3) are the tertiary amines, which are known and customary in the prior art, for example, triethylamine, dimethylcyclohexylamine, N-methylmorpholine, N, N'-dimethylpiperazine, 2 (dimethylamino-ethoxy) ethanol, diazabicyclo [2.2.2] octane and the like, and also, in particular, organic metallic compounds , such as titanic esters, iron compounds such as iron (III) acetylacetonate, tin compounds, for example, tin diacetate, tin dioctoate, tin dilaurate or the dialkyl tin salts of aliphatic carboxylic acids, for example diacetate dibutyltin, dibutyltin dilaurate, or the like. Catalysts are generally used in amounts of 0.0001-0.1 part by weight per 100 parts by weight of the polyhydroxy compound (c2).
    [0080] In addition to catalysts (c4), usual auxiliary agents and / or additives (c5) can also be added to the forming components (d) to (c3). Examples include blowing agents, surface active substances, fillers, flame retardants, nucleating agents, oxidation stabilizers, lubricants and mold release agents, dyes, pigments and, optionally, others stabilizers, for example, against hydrolysis, light, heat or discoloration, in addition to the stabilizer mixtures according to the invention, inorganic and / or organic fillers, and reinforcing plasticizers.
    [0081] In addition to the components mentioned above (d) and (c2) and, optionally, (c3), (c4) and (c5), it is also possible to use chain regulators, usually those that have a molecular weight of 31- 499 g / mol. Such chain regulators are compounds that have only one functional group that is reactive with isocyanates, for example, monofunctional alcohols, monofunctional amines and / or monofunctional polyols. Such chain regulators allow flow behavior to be fixed in a targeted manner, particularly in the case of TPUs. Chain regulators can generally be used in an amount of 0 to 5 parts by weight, preferably 0.1 to 1 part by weight, based on 100 parts by weight of the component (c2) and, by definition are under the component (c3 ).
    [0082] The reaction can be carried out at usual rates, preferably with an index of 60 to 120, especially preferably with an index of 80 to 110. The index is defined as the ratio between the total isocyanate groups of component (d) used in the reaction with groups that are reactive with isocyanates, that is, the active hydrogens, of the components (c2) and (c3). At an index of 100, an active hydrogen atom, that is, a group that is reactive with isocyanates, components (c2) and (c3) is present per component isocyanate group (d). At rates above 100, more isocyanate groups than OH groups are present.
    [0083] The production of TPUs can also occur according to known methods on a continuous basis, for example, with reaction extruders or with the mat method according to one-shot or prepolymer method, or discontinuously according to known prepolymerization processes. In these processes, the components (d), (c2) and eventually (c3), (c4) and / or (C5) entering the reaction can be mixed successively or simultaneously with each other, in which the reaction is used immediately.
    [0084] In the case of extrusion processes, the structural components (d), (c2) and, optionally, (c3), (c4) and / or (C5) are introduced individually or as a mixture in the extruder, reacted to , for example, temperatures from 100 to 280 ° C, preferably 140-250 ° C, the TPU obtained is extruded, cooled and pelleted. It can be advantageous for the heat treatment of the TPU obtained at 80 to 120 ° C, preferably from 100 to 110 ° C, for a period of time from 1 to 24 hours before further processing.
    [0085] To produce the expandable particles of thermoplastic polyurethane, the TPU according to the invention is preferably loaded with blowing agent in the suspension or extrusion process.
    [0086] In the case of the suspension process, the thermoplastic polyurethane is used in the form of pellets and heated with water, a suspension aid and the blowing agent, in a closed reactor above the softening temperature. This results in the polymer particles to be impregnated with the blowing agent. The impregnation temperature is preferably greater than 100 ° C, particularly preferably in the range of 100 to 150 ° C and in particular 110 to 145 ° C. Under the conditions of impregnation, blowing agent diffuses into the polymer granules. The impregnation time is generally from 0.5 to 10 hours. The hot suspension is subsequently cooled, resulting in solidification with the blowing agent inclusion particles, and the reactor is depressurized. This gives expandable TPU particles that are subsequently separated out of the suspension in a conventional manner. Adhering water is usually removed by drying, for example, in a flow dryer. If necessary, adhering suspension aids can be removed before or after drying by treating the particles with a suitable reagent. For example, treatment with an acid, such as nitric acid, hydrochloric acid, or sulfuric acid can be carried out to remove acid-soluble suspension auxiliaries, for example, metal carbonates or tricalcium phosphate.
    Suitable TPU pellets are, for example, mini pellets having a preferred average diameter of 0.2 to 10 mm, in particular 0.5 to 5 mm. These mini pellets, usually cylindrical or round, are produced by extruding the TPU and optionally other additives, the expression from the extruder, cooling and optionally pelletizing. In the case of cylindrical mini pellets, the length is preferably 0.2 to 10 mm, in particular 0.5 to 5 mm.
    [0088] As an expansion agent for the suspension process, preference is given to the use of inorganic organic liquids or gases or their mixtures. Organic liquids are possible halogenated but preferably saturated hydrocarbons, aliphatic hydrocarbons, in particular those having 3 to 8 carbon atoms, for example, butane and pentane. Suitable inorganic gases are nitrogen, air, ammonia and carbon dioxide. In addition, the mentioned blowing agent mixtures can be used. The amount of blowing agent is preferably from 0.1 to 40 parts by weight, in particular from 0.5 to 35 parts by weight and especially preferably from 1 to 30 parts by weight, based on 100 parts by weight of TPU used. Suitable suspension aids are water-insoluble inorganic stabilizers such as tricalcium phosphate, magnesium pyrophosphate, metal carbonates; also polyvinyl alcohol and surfactants, such as sodium dodecylarylsulfonate. They are generally used in amounts of 0.05 to 10% by weight, based on thermoplastic polyurethane.
    [0089] In the extrusion process, the thermoplastic polyurethane is, in an extruder, melted and mixed with a blowing agent that is fed into the extruder. The blowing agent mixture comprising is expressed and pelletized under such conditions of pressure and temperature that it does not expand. An industrially advantageous method is pelletizing submerged in a water bath, which has a temperature below 100 ° C and under a pressure of at least 2 bar (absolute). The temperature must not be too low since the melt material otherwise solidifies on the molding plate and must not be too high because otherwise the melt expands. The higher the boiling point of the blowing agent and the smaller the amount of blowing agent, the higher the water temperature can be the lower and the water pressure can be. In the case of particularly preferred blowing agents pentane and butane, the ideal temperature of the water bath is 30 to 60 ° C and the ideal water pressure is 8 to 12 bar (absolute). It is also possible to use other suitable cooling means instead of water. Water pellet ring can also be used. Here, the cutting space is encapsulated in such a way that the pelletizing apparatus can be operated under superatmospheric pressure. This gives expandable particles of thermoplastic polyurethane, which are subsequently separated by water and optionally dried.
    [0090] Possible extruders are all conventional screw machines, in particular single-screw and double-screw extruders (for example, Werner & Pfleiderer ZSK model), Ko-Kneters, Kombiplast machines, MPC mixers, FCM mixers, KEX extruders and cutting roller extruders, as described, for example, in Saechtling (editor), Kunststoff-Taschenbuch, 27th edition, Hanser-Verlag, Munich 1998, chapters 3.2.1 and 3.2.4. The extruder is usually operated at a temperature at which the TPU is present as a melt, for example, from 150 to 250, in particular from 180 to 210 ° C. Rotation speed, length, diameter and configuration of the screw (s) of the extruder, in quantities fed to the extruder and yield are selected in a known manner so that the additives are evenly distributed in the extruded TPU.
    [0091] In the case of an extrusion process, volatile organic compounds having a boiling temperature at atmospheric pressure of 1013 mbar from -25 to 150 ° C, in particular from 10 to 125 ° C, are preferably used as expansion. Well-suited blowing agents are hydrocarbons which are preferably halogen-free, in particular C4-w-alkanes, for example, the isomers of butane, pentane, hexane, heptane and octane, particularly preferably s-pentane. Other suitable blowing agents are relatively bulky compounds, such as alcohols, ketones, esters, ethers and organic carbonates. It is also possible to use mixtures of the blowing agents mentioned. These blowing agents are preferably used in an amount of 0.1 to 40 parts by weight, particularly preferably from 0.5 to 35 parts by weight and in particular from 1 to 30 parts by weight, based on 100 parts by weight of polyurethane. thermoplastic.
    [0092] If the preferably previously expanded thermoplastic polyurethane particles are used instead of expandable thermoplastic polyurethane particles in the process of the invention to produce the hybrid material of the invention, these are preferably obtained by expanding the expandable particles, for example, when the granules they are impregnated depressurized at temperatures above the softening temperature of the thermoplastic polyurethane in the suspension process or when, in the extrusion process, the extruder outlet is not cooled and kept under pressure not exceeding atmospheric.
    [0093] The auxiliaries and / or additives can also be optionally added to the reaction mixture for the production of the matrix or particles. Examples of surfactants, foam stabilizers, cell regulators, release agents, fillers, dyes, pigments, hydrolysis inhibitors, odor-absorbing substances and fungistatic and bacteriostatic substances can be mentioned.
    [0094] Possible surfactant substances are, for example, compounds that serve to assist the homogenization of starting materials and may also be suitable for the regulation of cell structure. Examples of emulsifying agents, such as sodium salts of castor oil sulphates or fatty acids, as well as fatty acid salts with amines, for example, diethylamine oleate, diethanolamine stearate, diethanolamine ricinoleate, can be mentioned. , salts of sulfonic acids, for example, alkali metal or ammonium salts of dodecylbenzenesulfonic acid or dinaftilmethanedisulfonic acid and ricinoleic acid; foam stabilizers, such as siloxane-oxyalkylene copolymers and other organopolysiloxanes, ethoxylated alkylphenols, ethoxylated fatty alcohols, paraffin oils, castor or ricinoleic oil esters, red Turkey oil and peanut oil and cell regulators, such as paraffins, alcohols fatty and dimethylpolysiloxanes. In addition, oligomeric acrylates with polyoxyalkylene and fluoroalkane radicals as side groups are also suitable for improving the emulsifying action, cell structure and / or foam stabilization. Surfactants are usually employed in amounts of 0.01 to 5 parts by weight, based on 100 parts by weight of the polyol component.
    Suitable mold release agents are, for example: reaction products of fatty acid esters with polyisocyanates, polysiloxane salts containing amino groups with fatty acids, salts of saturated or unsaturated fatty acids (cyclo) aliphatic carboxylic acids with at least 8 carbon atoms, with tertiary amines and also, in particular, internal release agents from the mold, such as carboxylic esters and / or carboxamides prepared by esterification or amidation of a mixture of montanic acid and at least one aliphatic carboxylic acid with at least 10 carbon atoms with at least bifunctional alkanolamines, polyols and / or polyamines with molecular weights of 60 to 400 (EPA 153 639), mixtures of organic amines, metallic salts of stearic acid and organic monocarboxylic and / or acids dicarboxylics or their anhydrides (DE A 3 607 447) or mixtures of an imino compound, the metal salt of a carboxylic acid and, optionally, a carbohydrate xylic (US 4,764,537).
    [0096] For the purposes of the present invention, fillers, in particular fillers, are the usual organic and inorganic fillers, reinforcing materials, weighting agents, agents for improving the abrasion behavior of paints, compositions coating, etc., known by itself. Specific examples are: inorganic fillers, such as siliceous minerals, for example leaf silicates such as antigorite, bentonite, serpentine, hornblends (hornblendes), amphiboles, chrysotile, talc; metal oxides, such as kaolin, aluminum oxides, titanium oxides, zinc oxide and iron oxides, metallic salts such as chalk, barite and inorganic pigments, such as cadmium sulfide, zinc sulfide and also glass, etc. Preference is given to the use of kaolin (China clay), aluminum silicate and co-precipitates of barium sulphate and aluminum silicate and natural and synthetic fibrous minerals, also, such as volastonite, metal and in particular fiber glass of various lengths, which can optionally be coated in one size. Possible organic fillers are, for example: carbon black, melamine, rosin, cyclopentadienyl resins and graft polymers and also cellulose fibers, polyamide fibers, polyacrylonitrile fibers, polyurethane fibers, polyester fibers based on esters aromatic and / or araliphatic dicarboxylics and in particular carbon fibers.
    [0097] Inorganic and organic fillers can be used individually or as mixtures and are advantageously added to the matrix, in amounts of 0.5 to 50% by weight, preferably 1 to 40% by weight, based on the weight of the matrix, but the content of mats, nonwovens and fabrics made of natural and synthetic fibers can reach values of up to 80% by weight.
    [0098] In a combination foam according to the invention, the volume ratio of the thermoplastic polyurethane foam particles is preferably 20% by volume and more, particularly preferably 40% by volume and more, more preferably 60% by volume and more, and in particular 70% by volume, and more, in each case based on the volume of the foam the combination of the invention. An appropriate upper limit is 99% by volume.
    [0099] In a preferred embodiment, the equivalence ratio of NCO groups of the polyisocyanates to some of the reactive hydrogen atoms of the polyols is 1: 0.8 to 1: 1.25, preferably between 1: 0.9 to 1: 1.15. The integral foams are preferably produced by the process of a single use of low pressure or the high-pressure technique of closed molds, in an advantageously heated way. Molds are usually made of metal, for example, aluminum or steel. These processes are described, for example, by Piechota and Rõhr in "Integralschaumstoff", Carl-Hanser-Verlag, Munich, Vienna, 1975, or in Kunststoff-Handbuch, Volume 7, Polyurethane, 3rd edition, 1993, chapter 7.
    [00100] The starting components are mixed for that purpose at a temperature of 15 to 90 ° C, preferably from 20 to 35 ° C, and optionally introduced under superatmospheric pressure, inside the closed mold. The mixing can be carried out mechanically by means of a stirrer or a stirring screw or under high pressure in the opposite jet injection process. The mold temperature is advantageously from 20 to 90 ° C, preferably from 30 to 60 ° C.
    [00101] The amount of the reaction mixture introduced into the mold is calculated so that the integral molded foam bodies obtained have a density of 0.08 to 0.70 g / cm3, in particular 0.12 to 0.60 g / cm3. The degrees of compaction for the production of molds with a compact outer zone and a cell core are in the range of 1.1 to 8.5, preferably 2.1 to 7.0.
    [00102] The processes of the invention make it possible to produce foams in combination, which have a matrix composed of polyurethane and thermoplastic polyurethane of particles contained in the same foam and in which there is a homogeneous distribution of the foam particles. Particularly when using expandable particles in the process for the production of hybrid materials of the invention, specific auxiliary devices are not necessary to ensure homogeneous distribution after the introduction of the starting substances in the mold. In addition, the expandable particles can also be easily used in a process according to the invention, since, due to their small size, they are free flowing and without placing particular demands on the processing.
    [00103] Preferably, if the previously expanded thermoplastic polyurethane particles are used for the production of integral polyurethane foams or compact frames, a closed mold is filled with the expanded particles and the reaction mixture comprising the remaining constituents is subsequently injected, due to the large differences in density between the reaction mixture of the fully expanded matrix material not yet reacted and the thermoplastic polyurethane particles. Particularly, at low degrees of filling with the expanded particles, optional techniques are used to homogeneously distribute the expanded particles, for example, slow mold rotation.
    [00104] The combination foams according to the invention, in particular with a matrix from cellular polyurethane, are characterized by a very good adhesion of the matrix material to the expanded thermoplastic polyurethane particles. In this sense, a combination foam according to the invention does not break at the interface of the matrix material and the expanded thermoplastic polyurethane particles. This makes it possible to produce combination foams that improve mechanical properties, for example, tensile strength and elasticity, compared to conventional polyurethane materials with the same density. Thus, the tensile strength, based on DIN EN ISO 527-1 of a combination foam according to the invention with a cell matrix is, in the case of an average density of 0.25 to less than 0.4 g / cm3, preferably greater than 2,500 kPa and, in the case of an average density of 0.1 to less than 0.4 g / cm3, is preferably greater than 1,500. In this sense, a combination foam with a cellular polyurethane matrix preferably has an average density of 0.05 to 0.60 g / cm3, particularly preferably 0.10 to 0.50 g / cm3 and in particular 0.20 up to 0.30 g / cm3.
    [00105] The elasticity of the combination foam according to the invention in the form of integral foams is preferably greater than 40% and particularly preferably greater than 50%, in accordance with DIN 53512.
    [00106] In addition, the combination foams of the invention based on integral foams exhibit high rebound resilience at a low density and are therefore highly suitable as materials for shoe soles. Light and comfortable soles with good durability properties can be obtained in this way. Such materials are particularly suitable as midsoles for sports shoes.
    [00107] Another advantage of a process according to the invention is that the combination foam having a low average density, in particular integral foams, can be produced without the usual disadvantages occurring in the production of conventional foams with the same density, for example example, sink points or places of skin detachment. As a result, less rejections are obtained, as a result of which the costs can be saved.
    [00108] Other possibilities for using the combination foams according to the invention are upholstery, for example, furniture and mattresses
    [00109] For the production of layered materials, reference can be made to WO 2008/087078.
    [00110] The invention will be explained in more detail by means of the following examples. EXAMPLES
    [00111] In order to determine the mechanical properties of cured foam sheets, four 25 mm pull rods are stamped from each sheet. In these tensile rods, the tensile strength and the rupture extension are calculated, based on DIN EN ISO 527-1, in which a rod width of 25 mm and a tensile speed of 100 mm were used, starting from this standard. / min Finally, from the results, the average value for a respective plate was formed.
    [00112] According to Table 1, the following polyurethane systems were examined. Examples 1 - 3 according to the invention were combined with expanded thermoplastic polyurethane particles (hereinafter referred to as ETPU) with a mass density of 86 g / l. Test plates were produced in a 0.6 I test shoe shape heated to 50 ° C, which were then mechanically tested. The formula compositions, including the fractions of ETPU's in the test body, are shown in Table 1. The index, the proportion of the amount of matter of the isocyanate component in relation to the polyol component occurs, in all systems 1, with a smaller deviation than 0.1.


    [00113] In this sense, we have: ETPU: expanded particles of TPU with a mass density of 86 g / l Polyol 1: polytetrahydrofuran with an average molecular weight (MW) of 1,500 g / mol Polyol 2: castor oil with weight average molecular weight (PM) of 900 g / mol Polyol 3: polypropylene glycol with average molecular weight (PM) of 2,000 g / mol Polyol 4: polypropylene glycol with average molecular weight (PM) of 200 g / mol Polyol 5: polypropylene glycol containing acrylonitrile / styrene with an average molecular weight (MW) of 4,400 g / mol Iso 1: 4,4-diphenylmethanediisocyanate partially modified with carbodiimide with a total NCO fraction of 33.6 parts by mass Iso 2: aliphatic polyisocyanate based on hexamethylenediisocyanate with an isocyanurate mass fraction of 22-part EC NCO: chain extender, diol with a hydroxy number greater than 580 mg / g Stabilizer: polyethersiloxane copolymer Cat. 1: 1-methylimidazo Cat. 2 dimethylzincocarboxylate Cat. 3 catalyst mix based in tertiary amines, tr iethylenediamine, triethanolamine and dimethylaminoeter Expansion agent 1: water Additive 1: sulfated sodium salt with castor oil based on fatty acids in 50% water Additive 2: antioxidant, steric derivative prevented by phenol Additive 3: K, Ca silicate , Na, Al in castor oil Additive 4: polydimethylsiloxane EXAMPLES
    [00114] The following examples describe the production and properties of polyurethane systems. In examples 1, 2 and 3 as well as in comparative examples 1 and 4, a prepolymer with a total isocyanate fraction of 18 parts by weight, consisting of 4,4-diphenylmethanediisocyanate conversion products with a diphenylmethane-4, was used, 4'-diisocyanate, with a polypropylene glycol with average molecular weight (MW) of 1970 g / mol, and tripropylene glycol as well as a UV stabilizer. These individual prepolymer parts are shown in fractions in Table 1. With respect to processing, this pre-conversion product is characterized as a prepolymer in the following examples.
    [00115] In addition, EPTU particles consisting of 61.2 parts by weight of polytetrahydrofuran with an average molecular weight (MW) of 1,000 g / mol, 31.8 parts by weight of 4,4-difeπilmetaπodiisocyanate with a total fraction of NCO of 33.6 parts by mass, 6 parts by mass of butane-1,4-diol with a hydroxy number of 1,245 mg / g as well as 0.1 part by mass of UV stabilizer corresponding to its total fraction were presented in the Table 1. The production of these occurred in a similar way to WO 2008/087078, pages 23/24. They were processed in the expanded form already reacted. The products according to the invention were produced in the laboratory with a vertical mixer. EXAMPLE 1 (ACCORDING TO THE INVENTION)
    [00116] According to Table 1, the parts, with the exception of the prepolymer and ETPU particles, were weighed together and homogenized. This component A was heated to 50 ° C in the thermal cabinet. Then there was the addition of prepolymer at room temperature and an intensive mixing of 10 seconds. These components were poured into a container in which the ETPU particles were weighed in advance. Directly after the particles were mixed in two containers with the PU system for 30 seconds. Subsequently, this particle union mixture was filled into a sheet metal mold tempered at 50 ° C and left to cure in the mold. From the test plates thus produced, the test bodies were removed, on which the mechanical tests were carried out. Example 2 (according to the invention)
    [00117] The test bodies were formed and tested according to example 1. According to the data in Table 1, the parts were varied according to the columns in example 2. EXAMPLE 3
    [00118] The test bodies were formed and tested according to example 1. According to the data in Table 1, the parts were varied according to the columns for example 3. COMPARATIVE EXAMPLE 1 (WITHOUT EPTU)
    [00119] According to Table 1, the parts, with the exception of the prepolymer, were weighed together and homogenized. This component A was heated to 50 ° C in the thermal cabinet. Subsequently, prepolymer was added at room temperature and intensive mixing for 10 seconds. Directly after the system was filled in a sheet metal tempered at 50 ° C and allowed to cure in the form. From the test plates thus produced, test bodies were removed, in which mechanical tests were carried out. Comparative example 1 corresponds to the matrix formula of example 3, in which the resulting density was adjusted to example 1. COMPARATIVE EXAMPLE 2
    [00120] The EPTU particles were filled in a metal form suitable for steam fusion. Subsequently, water vapor was introduced, with which the ETPU particles were sintered together. From the test plates thus produced, test bodies were removed, in which mechanical tests were carried out. COMPARATIVE EXAMPLE 3
    [00121] According to Table 1, the parts, with the exception of the isocyanate component 3 and the ETPU particles, were jointly weighed and homogenized. Subsequently, the addition of isocyanate and an intensive mixing lasting 10 seconds took place. All components were removed from the oven at an ambient temperature of 22 ° C and processed. The components were poured into a second container, in which the ETPU particles were weighed in advance. Directly after the particles were filled in a second container with the PU system for 30 seconds, evenly planned and left to cure in the mold. From the test plates thus produced, test bodies were removed, in which mechanical tests were carried out. COMPARATIVE EXAMPLE 4
    [00122] According to Table 1, the parts, with the exception of the prepolymer, were jointly weighed and homogenized. This component A was heated to 50 ° C in the thermal cabinet. Subsequently, prepolymer was added at room temperature and intensive mixing for 10 seconds. Directly after the system was filled in a sheet metal tempered at 50 ° C and allowed to cure in the form. From the test plates thus produced, test bodies were removed, in which mechanical tests were carried out. COMPARATIVE EXAMPLE 5
    [00123] According to Table 1, the parts, with the exception of the prepolymer, were jointly weighed and homogenized. This component A was heated to 50 ° C in the thermal cabinet. Subsequently, prepolymer was added at room temperature and intensive mixing for 10 seconds. Directly after the system was filled in a sheet metal tempered at 50 ° C and allowed to cure in the form. From the test plates thus produced, test bodies were removed, in which mechanical tests were carried out. PROPERTIES OF PRODUCTS OBTAINED TABLE 2
    Density: volumetric weight of the test plate [kg / m3] Tensile strength: tensile strength [kPa] according to DIN EN ISO 527-1
    [00124] Extension of rupture: extension of rupture at the time of rupture [%] according to DIN EN ISO 527-1 n.d .: not determined
    [00125] From Table 2, it can be recognized that the examples according to the invention, in the same low density range of 300 g / l +/- 10 g / l, have a greater tensile strength than systems comparable. The rupture extension values are also better in the examples according to the invention. TABLE 3
    Density: volumetric weight of the test plate [kg / m3] Tensile strength: tensile strength [kPa] according to DIN EN ISO 527-1 Impact: rebound elasticity [%] according to DIN EN ISO 8307 Table 3 shows that the examples of agreement with the invention they also have even better tensile strengths and rebound elasticities at lower densities. From comparative examples 1, 2 and 5, no model capable of being tested could be produced in this lower density range.
    权利要求:
    Claims (13)
    [0001]
    1. COMBINATION FOAM, characterized by comprising a matrix composed of polyurethane foam and foamed particles of thermoplastic polyurethane contained therein, in which matrix and particles, respectively, are constructed of polyol components and polyisocyanate components, in which at least 50% by weight the modules that form the polyol components of the matrix and the particles are identical and at least 50% by weight of the modules that form the polyisocyanate component of the matrix and the particles are identical, in which the matrix is completely open cell and the foamed particles that are comprised in the matrix are at least partially closed cells.
    [0002]
    2. FOAM according to claim 1, characterized in that at least 60% by weight of the modules that form the polyol component of the matrix and the particles are identical and at least 60% by weight of the modules that form the polyisocyanate component of the matrix and the particles are identical.
    [0003]
    FOAM according to claim 2, characterized in that at least 65% by weight of the modules that form the polyol component of the matrix and the particles are identical and at least 85% by weight of the modules that form the polyisocyanate component of the matrix and the particles are identical.
    [0004]
    FOAM according to any one of claims 1 to 2, characterized in that the foamed particles have a diameter of 0.1 mm to 10 cm, preferably 0.5 mm to 5 cm, and are spherical or ellipsoid.
    [0005]
    FOAM according to any one of claims 1 to 4, characterized in that the foamed particles have a density of 0.005 to 0.50 g / cm3
    [0006]
    FOAM according to any one of claims 1 to 5, characterized in that the thermoplastic polyurethane of the foamed particles and the matrix polyurethane foam are based on polytetrahydrofuran with an average molecular weight of 600 to 2500 g / mol.
    [0007]
    FOAM according to any one of claims 1 to 5, characterized in that the thermoplastic polyurethane of the foamed particles and the matrix polyurethane foam are based on polyester alcohol with an average molecular weight of 500 to 2500 g / mol.
    [0008]
    FOAM according to any one of claims 1 to 7, characterized in that the matrix is a foam with a density of 0.03 to 0.8 g / cm3
    [0009]
    FOAM according to any one of claims 1 to 8, characterized in that the matrix and particles are present in the combination foam in a weight ratio in the range of 0.1 to 10: 1.
    [0010]
    10. USE OF A COMBINATION FOAM, as defined in any one of claims 1 to 9, characterized in that it occurs as shoe soles, saddles, upholstery, in construction parts in the internal and external areas of automobiles, in balls and sports articles or as a floor covering, especially for sports surfaces, athletics tracks, sports courts, playgrounds and sidewalks.
    [0011]
    11. PROCESS FOR THE PRODUCTION OF COMBINATION FOAMS, as defined in any one of claims 1 to 9, characterized by the reaction of the polyol components and the polyisocyanate components that form the matrix composed of polyurethane foam, and optionally chain extenders, agents crosslinking agents, catalysts, blowing agents, other additives or mixtures thereof in the presence of foamed or to be foamed thermoplastic polyurethane particles.
    [0012]
    12. PROCESS, according to claim 11, characterized in that no external blowing agent is employed.
    [0013]
    13. PROCESS according to any one of claims 11 to 12, characterized in that a polyisocyanate prepolymer with a NOC content of 1% to 20% by weight is first prepared from polyisocyanate components and polyol components of the matrix and optionally chain extenders, crosslinking agents, catalysts, other additives or mixtures thereof, and the isocyanate prepolymer is subsequently mixed with the foamed particles of the thermoplastic polyurethane and the composite is allowed to cure by the action of water.
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    同族专利:
    公开号 | 公开日
    KR20150042242A|2015-04-20|
    EP2882788A1|2015-06-17|
    EP2882788B1|2016-10-12|
    JP6279576B2|2018-02-14|
    CN104704015A|2015-06-10|
    ES2612859T3|2017-05-19|
    PL2882788T3|2017-06-30|
    CN104704015B|2017-05-24|
    KR102096984B1|2020-04-03|
    US20150197617A1|2015-07-16|
    BR112015002711A2|2018-05-22|
    WO2014023794A1|2014-02-13|
    JP2015525822A|2015-09-07|
    US9714332B2|2017-07-25|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US3615972A|1967-04-28|1971-10-26|Dow Chemical Co|Expansible thermoplastic polymer particles containing volatile fluid foaming agent and method of foaming the same|
    AT384714B|1980-07-01|1987-12-28|Distropat Ag|SOLE FOR SHOES|
    DE3405875A1|1984-02-18|1985-08-22|Basf Ag, 6700 Ludwigshafen|METHOD FOR THE PRODUCTION OF CELLED OR COMPACT POLYURETHANE-POLYHANE MOLDED BODIES WITH IMPROVED DEFLECTING PROPERTIES AND INNER MOLD RELEASE AGENT FOR THE POLYISOCYANATE POLYADDITION METHOD|
    DE3607447A1|1986-03-07|1987-09-10|Basf Ag|METHOD FOR PRODUCING MOLDED BODIES WITH A CELLED CORE AND A COMPRESSED EDGE ZONE WITH IMPROVED DEFORMING PROPERTIES|
    DE3631842A1|1986-09-19|1988-03-24|Basf Ag|INNER MOLD RELEASE AGENTS, THE USE THEREOF FOR THE PRODUCTION OF MOLDED BODIES BY THE POLYISOCYANATE POLYADDITIONAL PROCESS AND METHOD FOR THE PRODUCTION OF THE MOLDED BODIES|
    DE4307648A1|1993-03-11|1994-09-15|Basf Ag|Foams based on thermoplastic polyurethanes as well as expandable, particulate, thermoplastic polyurethanes, particularly suitable for the production of foam molded articles|
    US20040039146A1|1998-03-16|2004-02-26|Trent Shidaker|Moisture resistant polyurethane prepolymers|
    EP1125959A1|2000-02-17|2001-08-22|Mitsui Chemicals, Inc.|Microcellular polyurethane elastomer, and method of producing the same|
    US8501828B2|2004-08-11|2013-08-06|Huntsman Petrochemical Llc|Cure rebond binder|
    CN101128303A|2004-08-12|2008-02-20|太平洋战略咨询有限公司|Method of forming a composite material|
    JP4737967B2|2004-10-13|2011-08-03|株式会社イノアックコーポレーション|Polyurethane foam and method for producing the same|
    EP1979401B1|2006-01-18|2010-09-29|Basf Se|Foams based on thermoplastic polyurethanes|
    EP2109637B1|2007-01-16|2018-07-25|Basf Se|Hybrid systems consisting of foamed thermoplastic elastomers and polyurethanes|
    US9894957B2|2010-11-16|2018-02-20|Basf Se|Damping element in shoe soles|
    US9815931B2|2012-02-28|2017-11-14|Basf Se|Producing rigid polymer foams|
    EP2682427A1|2012-07-06|2014-01-08|Basf Se|Polyurethane-based expandable polymer particle|
    US8961844B2|2012-07-10|2015-02-24|Nike, Inc.|Bead foam compression molding method for low density product|DE102012206094B4|2012-04-13|2019-12-05|Adidas Ag|Soles for sports footwear, shoes and method of making a shoe sole|
    US9610746B2|2013-02-13|2017-04-04|Adidas Ag|Methods for manufacturing cushioning elements for sports apparel|
    DE102013202306B4|2013-02-13|2014-12-18|Adidas Ag|Sole for a shoe|
    DE102013202291B4|2013-02-13|2020-06-18|Adidas Ag|Damping element for sportswear and shoes with such a damping element|
    US9930928B2|2013-02-13|2018-04-03|Adidas Ag|Sole for a shoe|
    DE102013002519B4|2013-02-13|2016-08-18|Adidas Ag|Production method for damping elements for sportswear|
    USD776410S1|2013-04-12|2017-01-17|Adidas Ag|Shoe|
    US20170174818A1|2014-03-26|2017-06-22|Lubrizol Advanced Materials, Inc.|Polyurethane foams and method for producing same|
    DE102014215897B4|2014-08-11|2016-12-22|Adidas Ag|adistar boost|
    DE102014216115A1|2014-08-13|2016-02-18|Adidas Ag|Together cast 3d elements|
    DE102014015411A1|2014-10-20|2016-04-21|Hermann-Frank Müller|concrete slab|
    DE102014016383A1|2014-11-07|2016-05-12|Hermann-Frank Müller|road construction|
    DE102015202013B4|2015-02-05|2019-05-09|Adidas Ag|Process for producing a plastic molding, plastic molding and shoe|
    DE102015206900A1|2015-04-16|2016-10-20|Adidas Ag|Sports Shoe|
    DE102015209795A1|2015-05-28|2016-12-01|Adidas Ag|Ball and method for its production|
    USD783264S1|2015-09-15|2017-04-11|Adidas Ag|Shoe|
    CN105440650B|2015-12-16|2018-10-19|宁波明辉寝具有限公司|A kind of soft polyurethane foam composite material and its production technology|
    US10933609B2|2016-03-31|2021-03-02|The Regents Of The University Of California|Composite foam|
    DE102016209044B4|2016-05-24|2019-08-29|Adidas Ag|Sole form for making a sole and arranging a variety of sole forms|
    CN109312100A|2016-06-29|2019-02-05|株式会社Jsp|Thermoplastic polyurethane foam particle formation body and its manufacturing method and thermoplastic polyurethane foam particle|
    CN106009616A|2016-07-28|2016-10-12|东莞市隆鑫鞋业有限公司|Preparation technique of PUpopcorn shoe sole|
    USD840136S1|2016-08-03|2019-02-12|Adidas Ag|Shoe midsole|
    USD840137S1|2016-08-03|2019-02-12|Adidas Ag|Shoe midsole|
    USD852475S1|2016-08-17|2019-07-02|Adidas Ag|Shoe|
    JP1582717S|2016-09-02|2017-07-31|
    CN106497008A|2016-10-18|2017-03-15|宁波格林美孚新材料科技有限公司|A kind of ultralight PU foaming composite sheet and preparation method thereof|
    DE102016223980A1|2016-12-01|2018-06-07|Adidas Ag|Process for producing a plastic molding, plastic molding and shoe|
    DE102017205830B4|2017-04-05|2020-09-24|Adidas Ag|Process for the aftertreatment of a large number of individual expanded particles for the production of at least a part of a cast sports article, sports article and sports shoe|
    JP6912317B2|2017-08-03|2021-08-04|株式会社ジェイエスピー|Urethane-based thermoplastic elastomer foamed particles|
    DE202017004489U1|2017-08-29|2018-12-02|Ergon International Gmbh|bicycle saddle|
    JP1617832S|2017-09-21|2018-11-12|
    USD899061S1|2017-10-05|2020-10-20|Adidas Ag|Shoe|
    JP6673625B1|2019-05-10|2020-03-25|有限会社 トシ・シミズ|Multi-layer rug mat|
    WO2021170801A1|2020-02-28|2021-09-02|Basf Se|Tpu for inmold assembly of an outer shoe sole on etpu|
    法律状态:
    2018-06-05| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|
    2019-11-26| B06U| Preliminary requirement: requests with searches performed by other patent offices: suspension of the patent application procedure|
    2020-06-09| B09A| Decision: intention to grant|
    2020-09-29| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 08/08/2013, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    DE12179836.7|2012-08-09|
    EP12179836|2012-08-09|
    PCT/EP2013/066613|WO2014023794A1|2012-08-09|2013-08-08|Combination foam|
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