EP3902858A1

EP3902858A1 - Higher-strength etpu

Info

Publication number: EP3902858A1
Application number: EP19829651.9A
Authority: EP
Inventors: Elmar Poeselt; Peter Gutmann; Edgar SCHANDER; Rebecca SPREEN; Christiane Martina DIECKMANN; Dennis JOPP
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2018-12-28
Filing date: 2019-12-27
Publication date: 2021-11-03
Also published as: MX2021007937A; US20220033609A1; CN113316600A; WO2020136239A1; BR112021011630A2; TW202033590A; JP2022515855A; CA3124615A1; KR20210107812A; CN113316600B

Abstract

The present invention relates to an expanded granulate comprising a thermoplastic polyurethane obtainable or obtained by reacting a polyisocyanate composition (IZ), containing at least one aliphatic diisocyanate with a number-average molecular weight of less than 200 g/mol, with at least one chain extender (KV1) and a polyol composition (PZ), and also to a method for producing an expanded granulate of this type. The present invention also relates to the use of an expanded granulate according to the invention for producing a moulded body.

Description

High strength eTPU description

The present invention relates to foamed granules comprising a thermoplastic polyurethane obtainable or obtained by reacting a polyisocyanate composition (IZ) which contains at least one aliphatic diisocyanate with a number average molecular weight less than 200 g / mol, at least one chain extender (KV1), and one

Polyol composition (PZ), and a method for producing such

foamed granules. The present invention further comprises the use of a foamed granulate according to the invention for the production of a shaped body.

Foamed granules, which are also known as particle foams (or particle foams,

Particle foam) and molded articles made therefrom based on thermoplastic polyurethane or other elastomers are known (e.g. WO 94/20568,

WO 2007/082838 A1, WO2017030835, WO 2013/153190 A1 WO2010010010) and can be used in a variety of ways.

A foamed granulate or also a particle foam or particle foam in the sense of the present invention denotes a foam in the form of a particle, the average diameter of the particles being between 0.2 to 20, preferably 0.5 to 15 and in particular between 1 to 12 mm. In the case of non-spherical, e.g. elongated or cylindrical particles mean the longest dimension by diameter.

There is basically a need for foamed granules or particle foams with improved processability to give the corresponding moldings at the lowest possible temperatures while maintaining advantageous mechanical properties. This is particularly relevant for the currently common welding processes in which the

Enter the energy input for welding the foamed granules by means of an auxiliary medium such as water vapor, since better bonding is achieved here and at the same time damage to the material or the foam structure is reduced and at the same time adequate bonding or welding is obtained.

Adequate bonding or welding of the foamed granules is essential in order to obtain advantageous mechanical properties of the molded part produced from the foamed granules. If the foam particles are insufficiently bonded or welded, their properties cannot be used to the full extent, as a result of which the mechanical properties of the molded part obtained are adversely affected overall. The same applies to a weakening of the molded body. Here the mechanical properties at the weakened points are disadvantageous with the same result as mentioned above. The properties of the polymer used must therefore be easily adjustable. Known materials often have a very low modulus of elasticity at room temperature, so that for many applications high densities have to be achieved in order to achieve sufficient rigidity or stability. At the same time, a high rebound and good mechanical properties should be achieved for many applications and the materials should be easy to weld for the production of molded parts from the foamed granulate.

Advantageous mechanical properties are within the scope of the present invention in

To understand with regard to the intended applications. The for the subject of

The main application of the present invention is the application in

Shoe area, wherein the foamed granules can be used for moldings for components of the shoe where cushioning and / or cushioning is relevant, such as Midsoles and insoles.

It was therefore an object of the present invention to provide foamed granules based on polymers which have sufficient rigidity but at the same time have good mechanical properties and are easy to process. Another object of the present invention was to provide a process for producing the corresponding foamed granules.

According to the invention, this object is achieved by a foamed granulate comprising a thermoplastic polyurethane, or obtained by reacting at least components (i) to (iii):

(i) a polyisocyanate composition (IZ);

(ii) at least one chain extender (KV1),

(iii) a polyol composition (PZ), the isocyanate composition containing at least one aliphatic diisocyanate with a number average molecular weight less than 200 g / mol.

It has surprisingly been found that by using the components used according to the invention and in particular the specific isocyanate composition (IZ), foamed granules can be obtained which have a high modulus of elasticity and at the same time have a low softening point, so that the foamed granules are processed well to give moldings can. The foamed granules according to the invention are furthermore distinguished by good mechanical properties, such as, for example, high elasticity and good rebound. Surprisingly, according to the invention, a very good phase separation was achieved with, at the same time, better meltability of the hard phase, so that a harder and at the same time easily processable foamed granulate was obtained. In particular, the compression hardness could be significantly improved compared to conventional materials. In the context of the present invention, the rebound is analogous to DIN 53512, April 2000; the deviation from the norm is the height of the test specimen which should be 12 mm, however this test is carried out with 20 mm to avoid "strikethrough" of the sample and to avoid measuring the substrate, unless otherwise stated.

The present invention relates to a foamed granulate comprising a thermoplastic polyurethane, which can be obtained or obtained by reaction of a

Polyisocyanate composition (IZ), a chain extender (KV1) and one

Polyol composition (PZ). The isocyanate composition (IZ) contains at least one symmetrical diisocyanate with a number average molecular weight less than 200 g / mol.

It has surprisingly been found that thermoplastic polyurethanes of this type can be processed well into foamed granules, which in turn can be processed well into moldings which in particular have a high modulus of elasticity and a very good rebound.

According to the invention, the isocyanate composition (IZ) contains an aliphatic diisocyanate with a number average molecular weight less than 200 g / mol. Suitable isocyanates are known per se to the person skilled in the art. According to the invention, the isocyanate composition (IZ) can also contain further isocyanates.

In the context of the present invention, the aliphatic isocyanate is preferably a linear diisocyanate, in particular a linear diisocyanate with an even number of carbon atoms. According to a further embodiment, the present invention accordingly relates to a foamed granulate as described above, the aliphatic diisocyanate being a linear diisocyanate with an even number of carbon atoms.

The aliphatic diisocyanate is more preferably isomerically pure in the context of the present invention.

A suitable aliphatic diisocyanate with a number average molecular weight less than 200 g / mol is, for example, flexamethylene diisocyanate (HDI).

According to a further embodiment, the present invention accordingly relates to a foamed granulate as described above, the aliphatic diisocyanate

Flexamethylene diisocyanate (Fl Dl) is.

Suitable further isocyanates in the context of the present invention are, in particular, diisocyanates, in particular aliphatic or aromatic diisocyanates, more preferably aromatic diisocyanates. Furthermore, in the context of the present invention, pre-reacted products can be used as the isocyanate component, in which some of the OH components are reacted with an isocyanate in a preceding reaction step. The products obtained are reacted with the remaining OH components in a subsequent step, the actual polymer reaction, and then form the

thermoplastic polyurethane.

Aliphatic and / or cycloaliphatic are customary aliphatic diisocyanates

Diisocyanates used, for example tri-, tetra-, penta-, hexa-, hepta- and / or

Octamethylene diisocyanate, 2-methylpentamethylene-1, 5-diisocyanate, 2-ethyltetramethylene-1, 4-diisocyanate, butylene-1, 4-diisocyanate, trimethylhexamethylene-1, 6-diisocyanate, 1-isocyanato-3,3,5-trimethyl- 5-isocyanatomethyl-cyclohexane (isophorone diisocyanate, IPDI), 1, 4- and / or 1, 3-bis (isocyanatomethyl) cyclohexane (HXDI), 1, 4-cyclohexane diisocyanate, 1-methyl-2,4- and / or 1-methyl-2,6-cyclohexane diisocyanate, 4,4'-, 2,4'- and / or 2,2'-methylene dicyclohexyl diisocyanate (H12MDI).

Suitable aromatic diisocyanates are, in particular, 1,5-naphthylene diisocyanate (NDI), 2,4- and / or 2,6-tolylene diisocyanate (TDI), 3,3, '- dimethyl-4,4'-diisocyanato-diphenyl (TODI), p-phenylene diisocyanate (PDI), diphenylethane-4,4'-diisocyanate (EDI), methylene diphenyl diisocyanate (MDI), the term MDI being understood to mean 2,2'-, 2,4'- and / or 4,4'-diphenylmethane diisocyanate , 3,3'-dimethyl-diphenyl-diisocyanate, 1, 2-diphenylethane diisocyanate and / or phenylene diisocyanate or H12MDI (4,4'-methylene dicyclohexyl diisocyanate).

In principle, mixtures can also be used. Examples of mixtures are mixtures which, in addition to 4,4'-methylenediphenyl diisocyanate and at least one other

Contains methylene diphenyl diisocyanate. Here the term denotes

Methylene diphenyl diisocyanate 2,2'-, 2,4'- and / or 4,4'-diphenylmethane diisocyanate or a mixture of two or three isomers. Thus e.g. 2,2'- or 2,4'-diphenylmethane diisocyanate or a mixture of two or three isomers are used as further isocyanate. In this embodiment, the polyisocyanate composition can also contain other polyisocyanates mentioned above.

If further isocyanates are used, these are preferably in the isocyanate composition (IZ) in an amount in the range from 0.1 to 20% by weight, more preferably in the range from 0.1 to 10% by weight and particularly preferably in one Contain amount in the range of 0.5 to 5 wt .-%.

Preferred examples of higher-functional isocyanates are triisocyanates, e.g. B.

Triphenylmethane-4,4 ', 4 "-triisocyanate, furthermore the cyanurates of the aforementioned diisocyanates, and also the oligomers obtainable by partial reaction of diisocyanates with water, e.g.

B. the biuretas of the aforementioned diisocyanates, furthermore oligomers which are obtainable by the targeted reaction of semiblocked diisocyanates with polyols which on average have more than two and preferably three or more hydroxyl groups. Aliphatic, cycloaliphatic, araliphatic and / or aromatic isocyanates can be used as organic isocyanates.

Crosslinkers can also be used, for example the above-mentioned higher-functional polyisocyanates or polyols or other higher-functional molecules with a plurality of functional groups reactive toward isocyanates. It is the same in

Within the scope of the present invention it is possible to crosslink the products by an excess of the isocyanate groups used in relation to the hydroxyl groups. Examples of higher-functional isocyanates are tri isocyanates, e.g. B. triphenylmethane 4,4 ', 4 "-triisocyanate and isocyanurates, also the cyanurates of the aforementioned diisocyanates, and the oligomers obtainable by partial reaction of diisocyanates with water, eg.

B. the biuretas of the aforementioned diisocyanates, furthermore oligomers which are obtainable by the targeted reaction of semiblocked diisocyanates with polyols which on average have more than two and preferably three or more hydroxyl groups.

Here, the amount of crosslinker, i.e.

higher functional isocyanates and higher functional polyols or higher functional

Chain extenders are not greater than 3% by weight, preferably less than 1% by weight, more preferably less than 0.5% by weight, based on the total mixture of the components.

Furthermore, the polyisocyanate composition can also contain one or more solvents. Suitable solvents are known to the person skilled in the art. For example, non-reactive solvents such as ethyl acetate, methyl ethyl ketone and hydrocarbons are suitable.

According to the invention, a polyol composition (PZ) is used. According to the invention, the polyol composition (PZ) contains at least one polyol. Suitable polyols are

Generally known to a person skilled in the art and described, for example, in the "Plastics Manual,

Volume 7, Polyurethane ", Carl Hanser Verlag, 3rd edition 1993, Chapter 3.1. Polyesterol or polyetherol are particularly preferably used as polyol (P1). Polycarbonates can also be used. Copolymers can also be used in the context of the present invention. The number average molecular weight of the polyols used according to the invention are preferably in the range from 500 and 5000 g / mol, for example in the range from 550 g / mol and 2000 g / mol, preferably in the range from 600 g / mol and 1500 g / mol, in particular between 650 g / mol and 1000 g / mol.

According to the invention, polyether films are suitable, but also polyester films, block copolymers and hybrid polyols such as e.g. Poly (ester / amide). According to the invention, preferred polyetherols are polyethylene glycols, polypropylene glycols, polyadipates, polycarbonate (diols) and polycaprolactone.

According to a further embodiment, the present invention accordingly relates to a foamed granulate as described above, the polyol composition being a polyol selected from the group consisting of polyether, polyester,

Contains polycaprolactone polyols and polycarbonate polyols.

Suitable polyols are, for example, those which have ethers and ester blocks, such as, for example, polycaprolactone with polyethylene oxide or polypropylene oxide end blocks or else polyether with polycaprolactone end blocks. According to the invention, preferred polyetherols are polyethylene glycols, polypropylene glycols. Polycaprolactone is also preferred.

Mixtures of different polyols can also be used according to the invention.

The polyols or the polyol composition used preferably have an average functionality between 1.8 and 2.3, preferably between 1.9 and 2.2, in particular 2.

The polyols used according to the invention preferably have only primary hydroxyl groups.

According to one embodiment of the present invention, a polyol composition (PZ) is used which contains at least polytetrahydrofuran. According to the invention, the polyol composition can also contain other polyols in addition to polytetrahydrofuran.

According to the invention, polyethers are suitable as further polyols, for example, but also polyesters, block copolymers and hybrid polyols such as e.g. Poly (ester / amide). Suitable

Block copolymers are, for example, those which have ethers and ester blocks, such as, for example, polycaprolactone with polyethylene oxide or polypropylene oxide end blocks or else polyethers with polycaprolactone end blocks. According to the invention, preferred polyetherols are polyethylene glycols, polypropylene glycols. Also preferred as a further polyol

Polycaprolactone.

According to a particularly preferred embodiment, the polytetrahydrofuran has a number average molecular weight Mn in the range from 500 g / mol to 5000 g / mol, more preferably in the range from 550 to 2500 g / mol, particularly preferably in the range from 650 to 2000 g / mol.

The composition of the polyol composition (PZ) can vary within a wide range in the context of the present invention. The polyol composition can also contain mixtures of different polyols.

According to the invention, the polyol composition can also contain a solvent.

Suitable solvents are known per se to the person skilled in the art.

If polytetrahydrofuran is used, the number average molecular weight Mn of the polytetrahydrofuran is preferably in the range from 500 to 5000 g / mol. The number average molecular weight Mn of the polytetrahydrofuran is more preferably in the range from 500 to 1400 g / mol. According to a further embodiment, the present invention also relates to foamed granules as described above, the polyol composition comprising a polyol selected from the group consisting of polytetrahydrofurans with a number average molecular weight Mn in the range from 500 g / mol to 5000 g / mol.

According to a further embodiment, the present invention accordingly relates to a foamed granulate as described above, the polyol composition comprising a polyol selected from the group consisting of polytetrahydrofurans with a number average molecular weight Mn in the range from 500 g / mol to 2000 g / mol.

Mixtures of different polytetrahydrofurans can also be used according to the invention, i.e. Mixtures of polytetrahydrofurans with different molecular weights.

According to the invention, preferred polyether glycols are polyethylene glycols, polypropylene glycols and polytetrahydrofurans, and also their mixed polyether glycols. For example, according to the invention, mixtures of different polytetrahydrofurans can also be used, which are in the

Distinguish molecular weight.

According to the invention, at least one chain extender (KV1) is also used. Suitable chain extenders are known per se to the person skilled in the art. Chain extenders are, for example, compounds with two groups that are reactive toward isocyanate groups, in particular those with a molecular weight of less than 500 g / mol. Suitable chain extenders are, for example, diamines or diols. According to the invention, diols are further preferred. Mixtures of two or more chain extenders can also be used in the context of the present invention.

Suitable diols are known in principle to the person skilled in the art. According to the invention, the diol preferably has a molecular weight of <500 g / mol. For example, according to the invention, aliphatic, araliphatic, aromatic and / or cycloaliphatic diols with a molecular weight of 50 g / mol to 220 g / mol can be used as chain extenders. Alkanediols having 2 to 10 carbon atoms in the alkylene radical are preferred, in particular di-, tri-, tetra-, penta-, flexa-, flepta-, octa-, nona- and / or decaalkylene glycols. For the present

Invention are particularly preferably 1, 2-ethylene glycol, 1, 3-propanediol, 1, 4-butanediol, 1, 6-flexanediol.

Also branched compounds such as 1,4-cyclohexyldimethanol, 2-butyl-2-ethylpopanediol, neopentyl glycol, 2,2,4-trimethyl-1,3-pentanediol, pinacol, 2-ethyl-1,3-hexanediol or 1,4- Cyclohexanediol are suitable in the context of the present invention as chain extenders (KV1).

According to a further embodiment, the present invention accordingly relates to a foamed granulate as described above, the chain extender (KV1) being selected is from the group consisting of 1,3-propanediol, 1,2-ethanediol, 1,4-butanediol, 1,6-hexanediol and HQEE.

The proportions of the components used are preferably selected in accordance with step (b) in such a way that a hard segment content in the range from 10 to 40% is obtained.

Unless stated otherwise, the weight-average molecular weights Mw of the thermoplastic block copolymers, dissolved in HFIP (hexafluoroisopropanol), are determined by means of GPC in the context of the present invention. The molecular weight is determined using two GPC columns connected in series (PSS-Gel; 100A; 5m; 300 ^* 8mm, Jordi-Gel DVB; MixedBed; 5m; 250 ^* 10mm; column temperature 60 ° C; flow 1 mL / min; Rl- Detector). The calibration is carried out with polymethyl methacrylate (EasyCal; PSS, Mainz), HFIP is used as the solvent.

According to a further aspect, the present invention also relates to a method for producing a foamed granulate. The present invention relates to a

A method for producing a foamed granulate comprising the steps

(i) providing a composition (Z1) containing a thermoplastic

Polyurethane, the thermoplastic polyurethane being obtained or obtainable Reaction of at least components (a) to (c):

(a) a polyisocyanate composition (IZ);

(b) at least one chain extender (KV1),

(c) a polyol composition (PZ), the isocyanate composition containing at least one aliphatic diisocyanate with a number average molecular weight less than 200 g / mol;

(ii) impregnating the composition (Z1) with a blowing agent under pressure;

(iii) expanding the composition (Z1) by means of pressure drop.

In the context of the present invention, the composition (Z1) can be used in the form of a melt or in the form of a granulate.

With regard to preferred embodiments of the method, suitable feedstocks or mixing ratios, reference is made to the above statements, which apply accordingly.

The method according to the invention can include further steps, for example

Temperature adjustments.

The unexpanded needed for the production of the foamed granulate

Polymer mixture of the composition (Z1) is known from the Individual components and optionally further components such as, for example

Processing aids, stabilizers, compatibilizers or pigments. Suitable processes are, for example, conventional mixing processes using a kneader, continuously or batchwise, or an extruder such as, for example

co-rotating twin screw extruder.

In the case of compatibilizers or auxiliaries such as stabilizers, these can already be incorporated into the components during the manufacture.

Usually the individual components are mixed before the mixing process

put together or dosed into the apparatus that takes over the mixing. In the case of an extruder, the components are all metered into the feed and conveyed together into the extruder, or individual components are added via a side metering.

Processing takes place at a temperature at which the components are in a plasticized state. The temperature depends on the softening or

Melting ranges of the components, but must be below the decomposition temperature of each component. Additives such as pigments or fillers or other of the above-mentioned customary auxiliaries are not melted in, but are incorporated in the solid state.

In this case, further embodiments are possible using conventional methods, the processes used in the production of the starting materials being able to be directly incorporated into the production. So it would be e.g. possible in the case of the belt process, directly at the end of the belt, in which the material is fed into an extruder in order to obtain lens granules, which incorporate the styrene polymer, the toughness modifier and fillers or dyes.

In this step, some of the usual excipients mentioned above can be added to the mixture.

The foamed granules according to the invention generally have a bulk density of 50 g / l to 200 g / l, preferably 60 g / l to 180 g / l, particularly preferably 80 g / l to 150 g / l. The

Bulk density is measured analogously to DIN ISO 697, whereby when determining the above values, in contrast to the norm, a 10 I volume vessel is used instead of a 0.5 I volume vessel, since a particularly low density, high mass foam particle Measurement with only 0.5 I volume is too imprecise.

As stated above, the diameter of the foamed granules is between 0.5 to 30; preferably 1 to 15 and in particular between 3 to 12 mm. In the case of non-spherical, e.g. elongated or cylinder-shaped foamed granules means the longest dimension by diameter.

The foamed granules can be produced by the customary methods known in the prior art (i) providing a composition (Z) according to the invention;

(ii) impregnating the composition with a blowing agent under pressure;

(iii) expanding the composition by means of pressure drop.

The amount of blowing agent is preferably 0.1 to 40, in particular 0.5 to 35 and particularly preferably 1 to 30 parts by weight, based on 100 parts by weight of the amount of composition (Z) used.

An embodiment of the above method comprises

(i) providing a composition (Z) according to the invention in the form of granules;

(ii) impregnation of the granules with a blowing agent under pressure;

(iii) expanding the granules by means of a drop in pressure.

Another embodiment of the above-mentioned method comprises a further step:

(ii) impregnation of the granules with a blowing agent under pressure;

(iii-a) reducing the pressure to normal pressure without foaming the granules, if necessary

by reducing the temperature beforehand

(iii-b) foaming of the granules by increasing the temperature.

The non-expanded granulate preferably has an average minimum diameter of 0.2-10 mm (determined via 3D evaluation of the granulate, e.g. via dynamic image analysis using an optical measuring device called PartAn 3D from Microtrac).

The individual granules generally have an average mass in the range from 0.1 to 50 mg, preferably in the range from 4 to 40 mg and particularly preferably in the range from 7 to 32 mg. This average mass of the granules (particle weight) is determined as an arithmetic mean by weighing 3 granulate particles three times.

An embodiment of the above-mentioned method comprises the impregnation of the

Granules with a blowing agent under pressure and subsequent expansion of the granules in steps (I) and (II):

(I) Impregnation of the granules in the presence of a blowing agent under pressure at elevated temperatures in a suitable, closed reaction vessel (e.g. autoclave)

(II) sudden relaxation without cooling

The impregnation in step (I) can take place in the presence of water and optionally suspension auxiliaries or only in the presence of the blowing agent and

Absence of water. Suitable suspension auxiliaries are, for example, water-insoluble inorganic stabilizers, such as tricalcium phosphate, magnesium pyrophosphate, metal carbonates; also polyvinyl alcohol and surfactants, such as sodium dodecylaryl sulfonate. They are usually used in amounts of 0.05 to 10% by weight, based on the composition according to the invention.

Depending on the pressure selected, the impregnation temperatures are in the range from 100 ° C. to 200 ° C., the pressure in the reaction vessel being between 2-150 bar, preferably between 5 and 100 bar, particularly preferably between 20 and 60 bar

Impregnation time is generally 0.5 to 10 hours.

The implementation of the process in suspension is known to the person skilled in the art and e.g.

described in detail in W02007 / 082838.

When carrying out the process in the absence of the blowing agent, care must be taken to avoid aggregation of the polymer granules.

Suitable blowing agents for carrying out the process in a suitable closed reaction vessel are e.g. organic liquids and gases used in the

Processing conditions are in a gaseous state, such as hydrocarbons or inorganic gases or mixtures of organic liquids or gases and inorganic gases, which can also be combined.

Suitable hydrocarbons are, for example, halogenated or non-halogenated, saturated or unsaturated aliphatic hydrocarbons, preferably non-halogenated, saturated or unsaturated aliphatic hydrocarbons.

Preferred organic blowing agents are saturated, aliphatic hydrocarbons, in particular those with 3 to 8 carbon atoms, such as butane or pentane.

Suitable inorganic gases are nitrogen, air, ammonia or carbon dioxide, preferably nitrogen or carbon dioxide or mixtures of the above-mentioned gases.

In a further embodiment, the impregnation of the granules with a blowing agent under pressure comprises the process and subsequent expansion of the granules in steps (a) and (ß):

(a) Impregnation of the granules in the presence of a blowing agent under pressure at elevated temperatures in an extruder

(ß) granulation of the mass emerging from the extruder under conditions that

Prevent uncontrolled foaming.

Suitable blowing agents in this process variant are volatile organic compounds with a boiling point at normal pressure of 1013 mbar from -25 ° C to 150 ° C, in particular -10 ° C to 125 ° C. Hydrocarbons (preferably halogen-free) are particularly suitable, especially C4-10- Alkanes, for example the isomers of butane, pentane, hexane, heptane and octane, particularly preferably isobutane. Other possible blowing agents are more sterically demanding compounds such as alcohols, ketones, esters, ethers and organic carbonates

Here, the composition in step (ii) is mixed in an extruder while melting with the blowing agent under pressure, which is fed to the extruder. The

blowing agent mixture is under pressure, preferably with a moderately controlled

Back pressure (e.g. underwater pelletizing) pressed and granulated. Here, the melt strand foams and the foamed granules are obtained by granulation.

The implementation of the process via extrusion is known to the person skilled in the art and e.g. described in detail in W02007 / 082838 and WO 2013/153190 A1.

All conventional screw machines can be considered as extruders, in particular

Single-screw and twin-screw extruders (e.g. type ZSK from Werner & Pfleiderer), co-kneaders, Kombiplast machines, MPC kneading mixers, FCM mixers, KEX kneading screw extruders and shear roller extruders, such as those e.g. in Saechtling (ed.), plastic paperback, 27.

Edition, Hanser-Verlag Munich 1998, chap. 3.2.1 and 3.2.4. The extruder is usually operated at a temperature at which the composition (Z1) is in the form of a melt, for example at 120 ° C. to 250 ° C., in particular 150 to 210 ° C. and a pressure after the blowing agent has been added of 40 to 200 bar, preferably 60 to 150 bar, particularly preferably 80 to 120 bar in order to ensure homogenization of the blowing agent with the melt.

This can be carried out in an extruder or an arrangement of one or more extruders. For example, in a first extruder

Components are melted and blinded, and a blowing agent is injected. In the second extruder, the impregnated melt is homogenized and the temperature and or the pressure are adjusted. If, for example, three extruders are combined with one another, the mixing of the components and the injection of the blowing agent can also be divided into two different process parts. If, as is preferred, only one extruder is used, all process steps, melting, mixing, injection of the

Blowing agent, homogenization and adjusting the temperature and or the pressure carried out in an extruder.

Alternatively, according to the methods described in WO 2014/150122 or WO 2014/150124 A1, the corresponding, possibly even already colored, foamed granules can be produced directly from the granules in that the corresponding granules are coated with a

supercritical fluid is soaked, is removed from the supercritical fluid followed by

(i ’) immersing the article in a heated fluid or

(ii ‘) irradiating the article with energetic radiation (e.g. infrared or

Microwave radiation). Suitable supercritical liquids are, for example, those described in WO2014150122 or, for example carbon dioxide, nitrogen dioxide, ethane, ethylene, oxygen or nitrogen, preferably carbon dioxide or nitrogen.

The supercritical liquid can also contain a polar liquid with a Flildebrand solubility parameter equal to or greater than 9 MPa-1/2.

Here, the supercritical fluid or the heated fluid may also contain a dye, whereby a colored, foamed article is obtained.

Another object of the present invention is a molded article produced from the foamed granules according to the invention.

The fixing position of the corresponding shaped bodies can be known according to the person skilled in the art

Methods are done.

A preferred method for locating a foam molded part comprises the following steps:

(A) introducing the foamed granules according to the invention in an appropriate form,

(B) Fusion of the foamed granules according to the invention from step (i).

The fusion in step (B) is preferably carried out in a closed form, the fusion being able to take place by means of water vapor, industrial air (as described for example in EP1979401 B1) or energetic radiation (microwaves or radio waves).

The temperature at which the foamed granules are fused is preferably below or close to the melting temperature of the polymer from which the particle foam was produced. For the common polymers, the temperature for fusing the foamed granules is between 100 ° C and 180 ° C, preferably between 120 and 150 ° C.

Here, temperature profiles / dwell times can be determined individually, e.g. in analogy to the methods described in US20150337102 or EP2872309B1.

The welding via energetic radiation generally takes place in the frequency range of microwaves or radio waves, possibly in the presence of water or other polar liquids, such as e.g. microwave-absorbing polar groups

Hydrocarbons (such as esters of carboxylic acids and diols or triols or glycols and liquid polyethylene glycols) and can be analogous to those in EP3053732A or

W016146537 described procedures take place. As stated above, the foamed granules can also contain dyes. Dyes can be added in various ways.

In one embodiment, the foamed granules produced can be colored after production. Here, the corresponding foamed granules are contacted with a carrier liquid containing a dye, the carrier liquid (TF) having a polarity that is suitable for sorption of the carrier liquid into the foamed granulate. This can be carried out in analogy to the methods described in the EP application with the application number 17198591.4.

Suitable dyes are, for example, inorganic or organic pigments. Suitable natural or synthetic inorganic pigments are, for example, carbon black, graphite,

Titanium oxides, iron oxides, zirconium oxides, cobalt oxide compounds, chromium oxide compounds, copper oxide compounds. Suitable organic pigments are, for example, azo pigments and polycyclic pigments.

In a further embodiment, the color can be added during the production of the foamed granulate. For example, the dye can be added to the extruder in the production of the foamed granules by extrusion.

Alternatively, already colored material can be used as the starting material for the production of the foamed granulate, which is extruded or - expanded in a closed vessel according to the above-mentioned methods.

Furthermore, in the process described in WO2014150122, the supercritical liquid or the heated liquid can contain a dye.

As stated above, the molded parts according to the invention have advantageous properties for the above-mentioned applications in the shoe or sports shoe sector.

The tensile and compression properties of the molded articles produced from the foamed granules are characterized in that the tensile strength is above 600 kPa (DIN EN ISO 1798, April 2008) and the elongation at break is above 100% (DIN EN ISO 1798, April 2008) and the compressive stress is above 15 kPa at 10% compression (analogous to DIN EN ISO 844, November 2014; the deviation from the norm lies in the height of the sample with 20 mm instead of 50 mm and thus the adjustment of the test speed to 2 mm / min ).

The resilience of the molded articles made from the foamed granules is above 55% (analogous to DIN 53512, April 2000; the deviation from the norm is

Test specimen height which should be 12 mm, but is carried out with 20 mm in this test in order to avoid "strikethrough" the sample and measuring the substrate). As stated above, the density and compression properties of the manufactured ones

Shaped bodies in a context. The density of the molded parts produced is advantageously between 75 to 375 kg / m ³ , preferably between 100 to 300 kg / m ³ , particularly preferably between 150 to 200 kg / m ³ (DIN EN ISO 845, October 2009).

The ratio of the density of the molded part to the bulk density of the invention

foamed granules are generally between 1.5 and 2.5, preferably between 1.8 and 2.0.

The invention further relates to the use of an inventive

foamed granulate for the production of a molded article for shoe midsoles, shoe insoles, shoe combination soles, bicycle saddles, bicycle tires, damping elements, upholstery, mattresses, underlays, handles, protective films, in components in the interior and exterior of automobiles, in balls and sports equipment or as flooring, in particular for sports surfaces , Track and field tracks, sports halls, children's playgrounds and sidewalks.

Preference is given to using a foamed granulate according to the invention for providing a molded article for midsoles, insoles for shoes,

Shoe soles or cushion elements for shoes.

FH here the shoe is preferably a street shoe, sports shoe, sandals, boots or safety shoe, particularly preferably a sports shoe.

The present invention accordingly also relates to a molded body, the molded body being a shoe combination sole for shoes, preferably for street shoes,

Sports shoes, sandals, boots or safety shoes, particularly preferred sports shoes.

The present invention accordingly also relates to a molded article, the molded article being an midsole for shoes, preferably for street shoes, sports shoes, sandals, boots or safety shoes, particularly preferably sports shoes.

The present invention accordingly also relates to a molded article, the molded article being an insert for shoes, preferably for street shoes, sports shoes, sandals, boots or safety shoes, particularly preferably sports shoes.

The present invention accordingly also relates to a molded article, the molded article being a cushioning element for shoes, preferably for street shoes, sports shoes, sandals, boots or safety shoes, particularly preferably sports shoes.

FH here the padding element can e.g. be used in the heel area or forefoot area.

Another object of the present invention is therefore also a shoe in which the molded body according to the invention as a midsole, midsole or cushioning in, for example Heel area, forefoot area is used, the shoe preferably a

Street shoe, sports shoe, sandal, boots or safety shoe, a sports shoe is particularly preferred.

In another aspect, the present invention also relates to foamed granules obtained or obtainable by a process according to the invention.

The block copolymers used according to the invention usually have a hard phase made of aromatic polyester and a soft phase. The block copolymers used according to the invention have a good phase separation between the elastic soft phase and the rigid hard phase due to their predetermined block structure, which results from the structure of inherently polymeric and thus long-chain molecules such as a polytetrahydrofuran and a polybutylene terephthalate building block. This good phase separation manifests itself in a property which is referred to as high, snappiness, but which is very difficult to characterize with physical methods and which is particularly advantageous

Properties of the foamed granules according to the invention leads.

Because of the good mechanical properties and the good temperature behavior, the polymer foams according to the invention are particularly suitable for the production of moldings. Moldings can be produced from the foamed granules according to the invention, for example by welding or gluing.

According to a further aspect, the present invention also relates to the use of a foamed granulate according to the invention or of a foamed granulate obtained or obtainable by a process according to the invention for the production of moldings. According to a further embodiment, the present invention also relates to the use of a foamed granulate according to the invention or of a foamed granulate obtained or obtainable by a process according to the invention for the production of molded articles, the molded article being produced by welding or gluing the particles together.

The moldings obtained according to the invention are suitable, for example, for the production of shoe soles, parts of a shoe sole, bicycle saddles, upholstery, mattresses, underlays, handles, protective films, components in the interior and exterior of automobiles, in balls and

Sports equipment or as flooring and wall cladding, in particular for sports areas, athletic tracks, sports halls, children's playgrounds and sidewalks.

According to a further embodiment, the present invention also relates to the use of a foamed granulate according to the invention or of a foamed granulate obtained or obtainable by a method according to the invention for the production of molded articles, the molded article being a shoe sole, part of a shoe sole Bicycle saddle, an upholstery, a mattress, pad, handle, protective film, a component in the automotive interior and exterior.

According to a further aspect, the present invention also relates to the use of the foamed granules or foamed particles according to the invention in balls and sports equipment or as flooring and wall covering, in particular for sports areas, athletic tracks, sports halls, children's playgrounds and walkways.

According to a further aspect, the present invention also relates to a hybrid material containing a matrix made of a polymer (PM) and a foamed granulate according to the present invention. Materials comprising a foamed granulate and a matrix material are referred to as hybrid materials in the context of this invention. The matrix material can consist of a compact material or also of a foam.

Polymers (PM) suitable as matrix material are known per se to the person skilled in the art. For example, ethylene-vinyl acetate copolymers, epoxy-based binders or even polyurethanes are suitable in the context of the present invention. Polyurethane foams or compact polyurethanes such as, for example, are suitable according to the invention

thermoplastic polyurethanes.

According to the invention, the polymer (PM) is selected such that there is sufficient adhesion between the foamed granules and the matrix in order to obtain a mechanically stable hybrid material.

The matrix can completely or partially surround the foamed granulate.

According to the invention, the hybrid material can contain further components, for example further fillers or granules. According to the invention, the hybrid material can also contain mixtures of different polymers (PM). The hybrid material can too

Contain mixtures of foamed granules.

Foamed granules which can be used in addition to the foamed granules according to the present invention are known per se to the person skilled in the art. Foamed granules made of thermoplastic polyurethanes are particularly suitable for the purposes of the present invention.

According to one embodiment, the present invention accordingly also relates to a

Hybrid material containing a matrix of a polymer (PM), a foamed granulate according to the present invention and a further foamed granulate made of a thermoplastic polyurethane.

In the context of the present invention, the matrix consists of a polymer (PM). Elastomers or, for example, are suitable as matrix material in the context of the present invention Foams, in particular foams based on polyurethanes, for example elastomers such as ethylene-vinyl acetate copolymers or thermoplastic polyurethanes.

Accordingly, the present invention also relates to a hybrid material as described above, wherein the polymer (PM) is an elastomer. Furthermore, the present invention relates to a hybrid material as described above, the polymer (PM) being selected from the group consisting of ethylene-vinyl acetate copolymers and thermoplastic polyurethanes.

According to one embodiment, the present invention also relates to a hybrid material containing a matrix of an ethylene-vinyl acetate copolymer and a foamed granulate according to the present invention.

According to a further embodiment, the present invention relates to a hybrid material containing a matrix of an ethylene-vinyl acetate copolymer, a foamed granulate according to the present invention and a further foamed granulate, for example made of a thermoplastic polyurethane.

According to one embodiment, the present invention relates to a hybrid material containing a matrix made of a thermoplastic polyurethane and a foamed granulate according to the present invention.

According to a further embodiment, the present invention relates to a hybrid material containing a matrix made of a thermoplastic polyurethane, a foamed granulate according to the present invention and a further foamed granulate, for example made of a thermoplastic polyurethane.

Suitable thermoplastic polyurethanes are known per se to the person skilled in the art. Suitable thermoplastic polyurethanes are described, for example, in "Kunststoff Handbuch, Volume 7, Polyurethane", Carl Hanser Verlag, 3rd edition 1993, chapter 3.

In the context of the present invention, the polymer (PM) is preferably a polyurethane.

Polyurethane in the sense of the invention includes all known elastic polyisocyanate polyaddition products. These include, in particular, massive polyisocyanate polyadducts, such as viscoelastic gels or thermoplastic polyurethanes, and elastic foams based on polyisocyanate polyadducts, such as

Soft foams, semi-rigid foams or integral foams. Furthermore, in the context of the invention, polyurethanes are to be understood as meaning elastic polymer blends containing polyurethanes and other polymers, and foams made from these polymer blends. The matrix is preferably a hardened, compact polyurethane binder, an elastic polyurethane foam or a viscoelastic gel.

In the context of the present invention, a polyurethane binder is understood to be a mixture which comprises at least 50% by weight, preferably at least 80% by weight and in particular at least 95% by weight of a prepolymer containing isocyanate groups, hereinafter referred to as isocyanate prepolymer. The viscosity of the polyurethane binder according to the invention is preferably in a range from 500 to 4000 mPa.s, particularly preferably from 1000 to 3000 mPa.s, measured at 25 ° C. according to DIN 53 018.

In the context of the invention, polyurethane foams are understood to be foams according to DIN 7726.

The density of the matrix material is preferably in the range from 1.2 to 0.01 g / cm 3.

The matrix material is particularly preferably an elastic foam or an integral foam with a density in the range from 0.8 to 0.1 g / cm 3, in particular from 0.6 to 0.3 g / cm 3, or compact material, for example a hardened polyurethane binder .

Foams in particular are suitable as matrix material. Hybrid materials that contain a matrix material made of a polyurethane foam preferably have good adhesion between the matrix material and the foamed granulate.

According to one embodiment, the present invention also relates to a hybrid material containing a matrix made of a polyurethane foam and a foamed granulate according to the present invention.

According to a further embodiment, the present invention relates to a hybrid material containing a matrix made of a polyurethane foam, a foamed granulate according to the present invention and a further foamed granulate, for example made of a thermoplastic polyurethane.

According to one embodiment, the present invention relates to a hybrid material containing a matrix of a polyurethane integral foam and a foamed granulate according to the present invention.

According to a further embodiment, the present invention relates to a hybrid material containing a matrix made of an integral polyurethane foam, a foamed granulate according to the present invention and a further foamed granulate, for example made of a thermoplastic polyurethane.

A hybrid material according to the invention, containing a polymer (PM) as a matrix and a foamed granulate according to the invention can be produced, for example, by mixing the components used to produce the polymer (PM) and the foamed granulate, if appropriate, with other components and converting them to the hybrid material, the The reaction is preferably carried out under conditions under which the foamed granulate is essentially stable. Suitable processes and reaction conditions for producing the polymer (PM), in particular an ethylene-vinyl acetate copolymer or a polyurethane, are known per se to the person skilled in the art.

In a preferred embodiment, the hybrid materials according to the invention are integral foams, in particular integral foams based on polyurethanes. Suitable processes for producing integral foams are known per se to the person skilled in the art. The integral foams are preferably produced by the one-shot process with the help of low pressure or high pressure technology in closed, suitably temperature-controlled molding tools. The molds are usually made of metal, e.g. Aluminum or steel. These procedures are described, for example, by Piechota and Röhr in "Integral Foam, Carl-Hanser-Verlag, Munich, Vienna, 1975, or in the Kunststoff-Handbuch, Volume 7, Polyurethane, 3rd Edition, 1993, Chapter 7.

If the hybrid material according to the invention comprises an integral foam, the amount of the reaction mixture introduced into the mold is dimensioned such that the molded bodies obtained from integral foams have a density of 0.08 to 0.70 g / cm 3, in particular 0.12 to 0.60 g / cm3. The degrees of compaction for the production of the moldings with a compacted edge zone and cellular core are in the range from 1.1 to 8.5, preferably from 2.1 to 7.0.

It is thus possible to produce hybrid materials with a matrix of a polymer (PM) and the foamed granules according to the invention contained therein, in which there is a homogeneous distribution of the foamed particles. The foamed granulate according to the invention can easily be used in a process for producing a hybrid material, since the individual particles are free-flowing due to their small size and do not impose any special processing requirements. Techniques for homogeneous distribution of the foamed granulate, such as slow rotation of the mold, can be used.

If necessary, auxiliaries and / or additives can also be added to the reaction mixture for producing the hybrid materials according to the invention. Examples include surface-active substances, foam stabilizers, cell regulators, release agents, fillers, dyes, pigments, hydrolysis protection agents, odor-absorbing substances and fungistatic and bacteriostatic substances.

As surface-active substances there are e.g. Compounds into consideration which serve to support the homogenization of the starting materials and, if appropriate, are also suitable for regulating the cell structure. Examples include emulsifiers, such as the sodium salts of castor oil sulfates or of fatty acids, and salts of fatty acids with amines, e.g. oleic acid diethylamine, stearic acid diethanolamine, ricinoleic acid diethanolamine, salts of sulfonic acids, e.g. Alkali or ammonium salts of dodecylbenzene or

Dinaphthylmethane disulfonic acid and ricinoleic acid; Foam stabilizers, such as siloxane Oxalkylene copolymers and other organopolysiloxanes, ethoxylated alkylphenols, ethoxylated fatty alcohols, paraffin oils, castor oil or. Ricinoleic acid esters, Turkish red oil and peanut oil, and cell regulators such as paraffins, fatty alcohols and dimethylpolysiloxanes. To

Oligomeric acrylates with polyoxyalkylene and fluoroalkane residues are also suitable for improving the emulsifying action, the cell structure and / or stabilizing the foam

Page groups.

Examples of suitable release agents include: reaction products of fatty acid esters with polyisocyanates, salts from amino groups-containing polysiloxanes and fatty acids, salts from saturated or unsaturated (cyclo) aliphatic carboxylic acids with at least 8 carbon atoms and tertiary amines, and in particular internal release agents such as carboxylic acid esters and / or -amides produced by esterification or amidation of a mixture

Montanic acid and at least one aliphatic carboxylic acid with at least 10 carbon atoms with at least difunctional alkanolamines, polyols and / or polyamines

Molecular weights of 60 to 400, mixtures of organic amines, metal salts of stearic acid and organic mono- and / or dicarboxylic acids or their anhydrides or mixtures of an imino compound, the metal salt of a carboxylic acid and optionally a carboxylic acid.

Fillers, in particular reinforcing fillers, are understood to be the conventional organic and inorganic fillers, reinforcing agents, weighting agents, agents for improving the abrasion behavior in paints, coating agents, etc., which are known per se. The following may be mentioned by way of example: inorganic fillers such as silicate minerals, for example layered silicates such as antigorite, bentonite, serpentine, tinsel, amphibole, chrisotile, talc; Metal oxides such as kaolin, aluminum oxides, titanium oxides, zinc oxide and iron oxides, metal salts such as chalk, heavy spar and inorganic pigments such as

Cadmium sulfide, zinc sulfide as well as glass etc. Kaolin (china clay), aluminum silicate and coprecipitates of barium sulfate and aluminum silicate and natural and synthetic fibrous minerals such as wollastonite, metal and in particular glass fibers of various lengths, which can optionally be sized, are preferably used. Examples of suitable organic fillers are: carbon black, melamine, rosin,

Cyclopentadienyl resins and graft polymers as well as cellulose fibers, polyamide, polyacrylonitrile, polyurethane, polyester fibers based on aromatic and / or aliphatic dicarboxylic acid esters and in particular carbon fibers.

The inorganic and organic fillers can be used individually or as mixtures.

In a hybrid material according to the invention, the volume fraction of the foamed granulate is preferably 20 volume percent and more, particularly preferably 50

Volume percent and more preferably 80 volume percent and more and in particular 90 volume percent and more, each based on the volume of the invention

Hybrid system. The hybrid materials according to the invention, in particular hybrid materials with a matrix of cellular polyurethane, are distinguished by very good adhesion of the matrix material to the foamed granules according to the invention. This breaks an inventive

Hybrid material preferably not at the interface between matrix material and foamed granulate. This makes it possible to produce hybrid materials that are opposite

conventional polymer materials, especially conventional polyurethane materials with the same density have improved mechanical properties, such as tear resistance and elasticity.

The elasticity of hybrid materials according to the invention in the form of integral foams is preferably greater than 40% and particularly preferably greater than 50% according to DIN 53512.

Furthermore, the hybrid materials according to the invention, in particular those based on integral foams, show high rebound elasticities with low density. In particular

Integral foams based on hybrid materials according to the invention are therefore outstandingly suitable as materials for shoe soles. This gives light and comfortable soles with good durability properties. Such materials are particularly considered

Midsoles suitable for sports shoes.

The hybrid materials according to the invention with a cellular matrix are, for example, suitable for upholstery, for example of furniture, and mattresses.

Hybrid materials with a matrix made of a viscoelastic gel are particularly characterized by increased viscoelasticity and improved elastic properties. These materials are therefore also suitable as upholstery materials, for example for seats, especially saddles such as bicycle saddles or motorcycle saddles.

Hybrid materials with a compact matrix are for example used as floor coverings,

Particularly suitable as a covering for playgrounds, athletics tracks, sports fields and sports halls.

The properties of the hybrid materials according to the invention can depend on

Polymer (PM) used vary widely and can be varied within wide limits in particular by varying the size, shape and nature of the expanded granulate, or by adding other additives, for example also other non-foamed granules such as plastic granules, for example rubber granules .

The hybrid materials according to the invention have a high durability and resilience, which is particularly noticeable through high tensile strength and elongation at break. In addition, hybrid materials according to the invention have a low density. Further embodiments of the present invention are the claims and the

Take examples. It is understood that the above and the

features explained below of the invention

Object / method / uses can be used not only in the respectively specified combination, but also in other combinations without leaving the scope of the invention. So z. B. also implicitly includes the combination of a preferred feature with a particularly preferred feature, or a feature that is not further characterized with a particularly preferred feature, etc., even if this combination is not expressly mentioned.

Exemplary embodiments of the present invention are listed below, but these do not restrict the present invention. In particular, the present invention also encompasses those embodiments which result from the references referred to below and thus combinations.

1. Foamed granules comprising a thermoplastic polyurethane obtainable or obtained by reacting at least components (i) to (iii):

(i) a polyisocyanate composition (IZ);

(ii) at least one chain extender (KV1),

2. Foamed granules according to embodiment 1, wherein the aliphatic diisocyanate is a linear diisocyanate with an even number of carbon atoms.

3. Foamed granules according to embodiment 1 or 2, the aliphatic

Diisocyanate is flexamethylene diisocyanate (HDI).

4. Foamed granules according to one of the embodiments 1 to 3, wherein the

Chain extender (KV1) is selected from the group consisting of 1, 3-propanediol, 1, 2-ethanediol, 1, 4-butanediol, 1, 6-flexanediol and FIQEE.

5. Foamed granules according to one of the embodiments 1 to 4, the

Polyol composition a polyol selected from the group consisting of

Contains polyether, polyester, polycaprolactone polyols and polycarbonate polyols.

6. Foamed granules according to one of the embodiments 1 to 5, the

Polyol composition a polyol selected from the group consisting of

Contains polytetrahydrofurans with a number average molecular weight Mn in the range from 500 g / mol to 2000 g / mol. 7. A method for producing a foamed granulate comprising the steps

(i) Provision of a composition (Z1) comprising a thermoplastic polyurethane, the thermoplastic polyurethane being obtained or obtainable. Reaction of at least components (a) to (c):

(a) a polyisocyanate composition (IZ);

(b) at least one chain extender (KV1),

(ii) impregnating the composition (Z1) with a blowing agent under pressure;

(iii) expanding the composition (Z1) by means of pressure drop.

8. The method according to embodiment 2, wherein the aliphatic diisocyanate is a linear diisocyanate with an even number of carbon atoms.

9. The method according to embodiment 1 or 2, wherein the aliphatic diisocyanate

Hexamethylene diisocyanate (HDI).

10. The method according to any one of embodiments 1 to 3, wherein the chain extender (KV1) is selected from the group consisting of 1,3-propanediol, 1,2-ethanediol, 1,4-butanediol, 1,6-hexanediol and HQEE.

1 1. Method according to one of the embodiments 1 to 4, wherein the

Polyol composition a polyol selected from the group consisting of

12. The method according to one of the embodiments 1 to 5, wherein the

Polyol composition a polyol selected from the group consisting of

Contains polytetrahydrofurans with a number average molecular weight Mn in the range from 500 g / mol to 2000 g / mol.

13. Foamed granules obtained or obtainable by a process according to one of the embodiments 7 to 12.

14. Use of a foamed granulate according to one of the embodiments 1 to 6 or 13 for the production of a shaped body.

15. Use according to embodiment 14, wherein the molded body is produced by welding or gluing the particles together. 16. Use according to embodiment 14 or 15, wherein the molded body

Shoe sole, part of a shoe sole, a bicycle saddle, an upholstery, a mattress, pad, handle, protective film, a component in the automotive interior and exterior.

17. Use of a foamed granulate according to one of the embodiments 1 to 6 or 13 in balls and sports equipment or as flooring and wall covering, in particular for sports areas, athletic tracks, sports halls, children's playgrounds and walkways.

18. Hybrid material containing a matrix of a polymer (PM) and a foamed granulate according to one of the embodiments 1 to 6 or 13 or a foamed granulate obtainable or obtained by a method according to one of the

Embodiments 7 to 12.

19. Hybrid material according to embodiment 18, wherein the polymer (PM) is an EVA.

20. Hybrid material according to embodiment 18, wherein the polymer (PM)

is thermoplastic polyurethane.

21. Hybrid material according to embodiment 18, wherein the polymer (PM)

Polyurethane foam is.

22. Hybrid material according to embodiment 18, wherein the polymer (PM) is a polyurethane integral foam.

The following examples serve to illustrate the invention but are in no way limitative of the subject matter of the present invention.

EXAMPLES

1. The following feedstocks were used:

Polyol 1: polyether polyol with an OH number of 1 12.2 and exclusively primary

OH groups (based on tetramethylene oxide, functionality: 2) chain extender 1: 1, 4-butanediol

Isocyanate 1: aliphatic isocyanate (1, 6-hexamethylene diisocyanate)

Isocyanate 2: aromatic isocyanate (4,4'-methylene diphenyl isocyanate)

Catalyst 1: tin-Il-dioctoate (50% in DOA)

Catalyst 2: tin-Il-dioctoate (10% in DOA)

Antioxidant 1: sterically hindered phenol Antioxidant 2: sterically hindered phenol

TPU crosslinker 1: Thermoplastic polyurethane with an NCO content of 8.5% and a functionality of 2.05 by adding oligomeric MDI

2. Production of the TPU

The examples TPU 1 to 4 listed below were produced in a twin-screw extruder, ZSK58 MC, from Coperion with a process length of 48D (12 housings). The melt was discharged from the extruder using a gear pump. After melt filtration, the polymer melt was processed into granules by means of underwater granulation, which were continuously dried in a heating fluidized bed at 40-90 ° C.

The polyol, the chain extender and the diisocyanate and possibly a catalyst were metered into the first zone. Additional additives, as described above, are fed in zone 8.

The housing temperatures are in the range of 150 - 230 ° C. The melt is discharged and underwater pelletized at melt temperatures of 210 - 230 ° C. The screw speed is between 180 and 240 1 / min. The throughput is in the range of 180 - 220 kg / h.

The amounts used are summarized in Table 1.

Table 1: Examples of synthesis:

3. Manufacture of the eTPU

3.1 To produce the expanded particles from the thermoplastic polyurethanes (Table 1), a twin-screw extruder with a screw diameter of 44 mm and a length to diameter ratio of 42 with a subsequent melt pump, a start-up valve with screen changer, a perforated plate and an underwater pelletizer. The thermoplastic polyurethane was dried at 80 ° C. for 3 h before processing in order to obtain a residual moisture content of less than 0.02% by weight. In addition to the thermoplastic polyurethane, a TPU was added to which 4,4'-diphenylmethane diisocyanate with an average functionality of 2.05 was added in a separate extrusion process.

The thermoplastic polyurethane used in each case and the TPU crosslinker 1 were each metered separately into the feed of the twin-screw extruder via gravimetric metering devices.

After the materials had been metered into the feed of the twin-screw extruder, they were melted and mixed. The blowing agents C02 and N2 were then added via an injector. The remaining extruder length was used for the homogeneous incorporation of the blowing agents into the polymer melt. After the extruder, the polymer / blowing agent mixture was pressed into a perforated plate (LP) by means of a gear pump (ZRP) via a start-up valve with a screen changer (AV), separated into strands in the perforated plate into strands which were flowed through with a tempered liquid and under pressure in the cutting chamber the underwater pelletizer (UWG) cut into pellets and transported away with the water and thereby expanded.

The separation of the expanded particles from the process water is ensured by means of a centrifugal dryer.

The total throughput of the extruder, polymers and blowing agent was 40 kg / h. The amounts of the polymers used and of the blowing agents are listed in Table 2. The polymers always form 100 parts while the blowing agents are also counted, so that total compositions above 100 parts are obtained.

Table 2: Proportions of the metered polymers and blowing agents, where the polymers / solids always give 100 parts and the blowing agents are also counted

The temperatures used for the extruder and the downstream equipment as well as the pressure in the cutting chamber of the UWG are listed in Table 3. Table 3: Temperature data of the system parts

After the expanded granules have been separated from the water by means of a centrifugal dryer, the expanded granules are dried at 60 ° C. for 3 hours in order to remove the remaining surface water and any moisture present in the particles and not to falsify further analysis of the particles.

The resulting bulk densities after drying for the individual expanded thermoplastic polyurethanes are listed in Table 4.

Table 4: Data on the eTPU

3.2 In addition to processing in the extruder, expanded particles were also processed in the

Impregnation kettle manufactured. For this purpose, the vessel was filled with a solid / liquid phase with a filling level of 80%, the phase ratio being 0.32.

The solid phase is the TPU1 or TPU2 and the liquid phase is the mixture of water with calcium carbonate and a surface-active substance. The blowing agent (butane) was injected onto this mixture in the gas-tight vessel, which had previously been flushed with nitrogen, in the amount given in Table 5, based on the solid phase (TPU1 or TPU 2). The kettle was stirred while the

Solid / liquid phase heated and at a temperature of 50 ° C defined nitrogen pressed up to a pressure of 8 bar. Then it was up to the desired

Impregnation temperature (IMT) heated further. When the impregnation temperature and the impregnation pressure were reached, the boiler was released via a valve after a given holding time. The exact manufacturing parameters of the tests as well as the achieved

Bulk densities are listed in Table 5.

Table 5: Manufacturing parameters and bulk density of the impregnated materials TPU 1 and TPU 2

4. Welding and mechanics 4.1 Manufacture of the molded body by steam welding

The expanded granules were then made into square plates with a on an automatic molding machine from Kurtz ersa GmbH (Energy Foamer)

Side length of 200 mm and a thickness of 10 mm or 20 mm thickness

Welded upon application of water vapor. With the plate thickness, the welding parameters differ only in terms of cooling. The

Welding parameters of the different materials were chosen so that the plate side of the final molded part, that of the movable side (Mil) of the

Facing the tool had the smallest possible number of collapsed eTPU particles. Due to the movable side of the tool, the gap was also steamed. Regardless of the test, a cooling time of 120 s with a plate thickness of 20 mm and 100 s with a 10 mm thick plate was always set at the end of the fixed (Ml) and the movable side of the tool. The respective steaming conditions are listed in Table 6 as steam pressures. The plates are stored in the oven for 4 hours at 70 ° C.

Table 6: Steaming conditions (vapor pressures)

Table 7: Mechanical properties

4.2 Comparative tests of resilience To emphasize the better resilience of the material used, two TPU's (TPU3 and TPU4) were foamed, which have a hard phase made of MDI but have the same Shore hardness as the TPU 1 or TPU 2, also in the impregnation process as described above. For this purpose, the vessel was filled with a solid / liquid phase with a filling level of 80%, the phase ratio being 0.32.

The solid phase is the TPU3 or TPU4 and the liquid phase is the mixture of water with calcium carbonate and a surface-active substance. The blowing agent (butane) was pressed onto this mixture in the gas-tight kettle which had previously been flushed with nitrogen in the amount given in Table 8, based on the solid phase (TPU3 or TPU4). The kettle was stirred while the

Impregnation temperature (IMT) heated further. When the impregnation temperature and of the impregnation pressure was released via a valve after a given holding time.

Table 8: Manufacturing parameters and bulk density of the impregnated materials

Side length of 200 mm and a thickness of 20 mm thickness welded by exposure to water vapor. The welding parameters of the different materials were chosen so that the plate side of the final molded part, which was facing the movable side (Mil) of the tool, had the smallest possible number of collapsed eTPU particles. Regardless of the test, a cooling time of 40 s was always set at the end of the fixed (Ml) and the movable side of the tool. The respective vapor deposition conditions are listed in Table 9. The plates are then stored in the oven for 4 hours at 70 ° C.

Table 9: Welding parameters

The resilience was then determined for all samples according to DIN EN ISO

8307: 2008-03 determined (Table 10)

Table 10: Mechanical analysis

Measurement methods: For material characterization, the following measurement methods can be used:

DSC, DMA, TMA, NMR, FT-IR, GPC

Mechanics (eTPU)

Density DIN EN ISO 845: 2009-10 tear resistance DIN EN ISO 8067: 2009-06

Dimensional stability test ISO 2796: 1986-08

Tensile test ASTM D5035: 2011

Rebound resilience DIN 53512: 2000-4 (Table 7)

DIN EN ISO 8307: 2008-03 (table 10)

Literature cited:

WO 94/20568 A1

WO 2007/082838 A1

WO 2017/030835 A1

WO 2013/153190 A1

WO 2010/010010

"Plastic Handbook, Volume 7, Polyurethane", Carl Hanser Verlag, 3rd edition 1993, chapter 3.1. WO 2007/082838 A1

WO 2013/153190 A1

Saechtling (ed.), Plastic paperback, 27th edition, Hanser-Verlag Munich 1998, chap. 3.2.1 and 3.2.4

WO 2014/150122 A1

WO 2014/150124 A1

EP 1 979 401 B1

US 2015/0337102 A1

EP 2 872 309B1

EP 3 053 732 A1

WO 2016/146537 A1

Claims

(i) a polyisocyanate composition (IZ);

(ii) at least one chain extender (KV1),

2. Foamed granules according to claim 1, wherein the aliphatic diisocyanate

is linear diisocyanate with an even number of carbon atoms.

3. Foamed granules according to claim 1 or 2, wherein the aliphatic diisocyanate is hexamethylene diisocyanate (HDI).

4. Foamed granules according to one of claims 1 to 3, wherein the

Chain extender (KV1) is selected from the group consisting of 1, 3-propanediol, 1, 2-ethanediol, 1, 4-butanediol, 1, 6-hexanediol and HQEE.

5. Foamed granules according to one of claims 1 to 4, wherein the

Polyol composition a polyol selected from the group consisting of

6. Foamed granules according to one of claims 1 to 5, wherein the

Polyol composition a polyol selected from the group consisting of

7. A method for producing a foamed granulate comprising the steps

(i) providing a composition (Z1) containing a thermoplastic

(a) a polyisocyanate composition (IZ);

(b) at least one chain extender (KV1),

(c) a polyol composition (PZ), the isocyanate composition containing at least one aliphatic diisocyanate with a number average molecular weight less than 200 g / mol; (ii) impregnating the composition (Z1) with a blowing agent under pressure;

(iii) expanding the composition (Z1) by means of pressure drop. 8. Foamed granules obtained or obtainable by a process according to claim

7.

9. Use of a foamed granulate according to one of claims 1 to 6 or 8 for the production of a shaped body.

10. Use according to claim 9, wherein the production of the shaped body by means

The particles are welded or glued together.

11. Use according to claim 9 or 10, wherein the molded body is a shoe sole, part of a shoe sole, a bicycle saddle, padding, a mattress, pad, handle,

Protective film, a component in the automotive interior and exterior.

12. Use of a foamed granulate according to one of claims 1 to 6 or 8 in balls and sports equipment or as flooring and wall covering, in particular for sports areas, athletic tracks, sports halls, children's playgrounds and walkways.

13. Hybrid material containing a matrix of a polymer (PM) and a foamed granulate according to one of claims 1 to 6 or 8 or a foamed granulate obtainable or obtained by a method according to claim 7.