EP3902857A1

EP3902857A1 - Particle foams consisting of an aromatic polyester-polyurethane multi-block copolymer

Info

Publication number: EP3902857A1
Application number: EP19829650.1A
Authority: EP
Inventors: Frank Prissok; Elmar Poeselt; Florian PUCH; Dirk Kempfert; Peter Gutmann
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: JP2022515854A; CN113260649B; BR112021011500A2; US20220073693A1; MX2021007936A; WO2020136238A1; TW202031711A; KR20210110634A; CA3124205A1; CN113260649A

Abstract

The present invention relates to an expanded granulate comprising a block copolymer, said block copolymer being obtained or obtainable according to a method comprising the reaction of an aromatic polyester (PE-1), an isocyanate composition (IZ) containing at least one diisocyanate, and a polyol composition (PZ), the polyol composition (PZ) containing at least one aliphatic polyol (P1) with a number-average molecular weight ≥ 500 g/mol, and also relates to a method for producing an expanded granulate of this type. The present invention further relates to the use of an expanded granulate according to the invention for producing a moulded body.

Description

Particle foams made from aromatic polyester-polyurethane multiblock copolymer

description

The present invention relates to foamed granules comprising a block copolymer, the block copolymer being obtained or obtainable according to a process comprising the reaction of an aromatic polyester (PE-1) with an isocyanate composition (IZ) containing at least one diisocyanate and a polyol composition (PZ), wherein the polyol composition (PZ) contains at least one aliphatic polyol (P1)

contains number average molecular weight> 500 g / mol, and a method for producing such a foamed granulate. The present invention further comprises the use of a foamed granulate according to the invention for the production of a

Molded 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.

Polymers based on thermoplastic elastomers (TPE) are already used in various areas. Depending on the application, the properties of the polymer can be modified.

EP 0 656 397 A1 discloses triblock polyaddition products with TPU blocks and polyester blocks which consist of two hard phase blocks, namely the polyester hard phase and the TPU hard phase, consisting of the urethane hard segment, the oligomeric or polymeric reaction product of an organic diisocyanate and a low molecular chain extender, preferably an alkane diol and / or dialkylene glycol and the elastic soft urethane segment, consisting of the higher molecular weight

Polyhydroxyl compound, preferably a higher molecular weight polyester and / or

Polyether diol, which are chemically linked together in blocks by urethane and / or amide bonds. The urethane or amide bonds are made from terminal ones

Hydroxyl or carboxyl groups of the polyester and on the other hand from terminal

Isocyanate groups of the TPU formed. The reaction products can also have further bonds such as, for example, urea bonds, allophanates, isocyanurates and biurets.

EP 1 693 394 A1 describes thermoplastic polyurethanes with polyester blocks and

Processes for their preparation are disclosed. Thereby, thermoplastic polyesters are reacted with a diol and the reaction product obtained is then reacted with isocyanates. In the processes known from the prior art, it is often difficult to adjust the block lengths and thus the properties of the polymer obtained.

Advantageous mechanical properties are to be understood in the context of the present invention with regard to the intended applications. The main application for the subject 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 in which the block structure and thus the desired properties of the polymer and the foamed granules produced therefrom can be adjusted easily. Another object of the present invention was to provide a method for producing the corresponding foamed granules.

According to the invention, this object is achieved by a foamed granulate comprising a block copolymer, the block copolymer being obtained or obtainable according to a process comprising the steps (a) providing an aromatic polyester (PE-1);

(b) reaction of the aromatic polyester (PE-1) with an isocyanate composition (IZ) containing at least one diisocyanate and a polyol composition (PZ), the polyol composition (PZ) at least one aliphatic polyol (P1) with a number average molecular weight> 500 g / mol contains.

It has surprisingly been found that foamed granules made from aromatic polyester-polyol block copolymers combine the advantages of a thermoplastic polyurethane with those of a rigid, high-melting aromatic polyester. It has been found that the foamed granules according to the invention have advantageous properties because the block copolymers used have the advantages of a temperature-stable hard phase and nevertheless temperature-stable products can be produced. The improved phase separation between hard and soft phases in these products results in good mechanical properties of the foamed granules according to the invention, such as high elasticity and good rebound.

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, but in this test it is carried out at 20 mm in order to avoid "strikethrough" of the sample and measuring the substrate, unless otherwise stated.

The present invention relates to foamed granules comprising a block copolymer, the block copolymer being obtained or obtainable according to a process comprising steps (a) and (b). In the context of the invention, a block copolymer is understood to be a polymer which is composed of repeating blocks, for example of two repeating blocks. An important prerequisite for block copolymers suitable according to the invention with good temperature resistance is, in addition to clear phase separation, a sufficient block size of the hard and soft phases, which ensure a wide temperature range for the application. This area of application can be detected by means of DMA (temperature range between glass transition of the soft phase and first softening of the hard phase).

It has surprisingly been found that block copolymers of this type can be processed well to give foamed granules, which in turn can be processed well to give moldings which, in particular, have a very good rebound.

According to step (a) of the process for producing the block copolymer, an aromatic polyester (PE-1) is first provided, which is then mixed with a

Isocyanate composition (IZ) containing at least one diisocyanate and one

Polyol composition (PZ) is implemented, the polyol composition (PZ) containing at least one aliphatic polyol (P1) with a number average molecular weight> 500 g / mol. Suitable polyesters (PE-1) are known per se to the person skilled in the art. For example, suitable aromatic polyesters are obtained by transesterification. In the context of the present invention, the polyester (PE-1) can preferably be obtained by transesterification. In the context of the present invention, the term transesterification means that a polyester is reacted with a compound with two zeriwitinoff-active hydrogen atoms, for example a compound with two OH groups or two NH groups or a compound with one OH and one NH group.

According to the invention, the polyester (PE-1) can consist, for example, of at least one

aromatic polyester having a melting point in the range from 160 to 350 ° C. with at least one compound selected from the group consisting of diamines and diols at a temperature of greater than 160 ° C., the compound selected from the group consisting of diamines and diols preferably is used in an amount in the range of 0.02 to 0.3 mol per mol of ester bond in the polyester.

Suitable diamines and diols are known per se to the person skilled in the art. Both diols or diamines with a molecular weight in the range of <500 g / mol or polymeric diols and diamines with a molecular weight in the range of> 500 g / mol are suitable for the purposes of the present invention. The diols and diamines in the context of the present invention are preferably polymeric compounds. According to the invention

Implementation, for example, at a temperature greater than 160 ° C, in particular greater than 200 ° C. The temperature during the reaction to produce the polyester (PE-1) is preferably above the melting point of the polyester used. The reaction is preferably carried out continuously.

According to a further embodiment, the present invention accordingly also relates to foamed granules as described above, the aromatic polyester (PE-1) being obtainable or being obtained by reacting at least one aromatic polyester having a melting point in the range from 160 to 350 ° C. and one Compound selected from the group consisting of diamines and diols or their mixtures.

According to a further embodiment, the present invention also relates to a

foamed granules as described above, the reaction to produce the polyester (PE-1) taking place continuously.

According to the invention, the reaction for the production of the polyester (PE-1) can take place in a suitable apparatus, suitable processes being known per se to the person skilled in the art. According to the invention, it is also possible for additives or auxiliaries to be used in order to accelerate or improve the implementation for the production of the polyester (PE-1). In particular, catalysts can be used. Suitable catalysts for the reaction to produce the polyester (PE-1) are, for example, tributyltin oxide, tin (II) dioctoate, dibutyltin dilaurate, tetrabutoxytitanium (TBOT) or Bi (III) carboxylates.

In particular, the reaction to produce the polyester (PE-1) can be carried out in an extruder. It is also possible according to the invention that the reaction for the production of the polyester (PE-1) takes place in a kneader.

According to a further embodiment, the present invention accordingly also relates to foamed granules as described above, the reaction for the production of the polyester (PE-1) taking place in an extruder.

The implementation for the production of the polyester (PE-1) can, for example, in the case of a

Temperatures in the range from 160 to 350 ° C, preferably in the range from 220 to 300 ° C and in particular from 220 to 280 ° C, more preferably from 230 to 260 ° C and for example with a residence time of 1 second to 15 minutes, preferably with a residence time of 2 seconds to 10 minutes, more preferably with a residence time of 5 seconds to 5 minutes or with a residence time of 10 seconds to 1 minute in

for example flowable, softened or preferably melted state of the polyester and the polymer diol, in particular by stirring, rolling, kneading or preferably extrusion, for example using conventional ones

Plasticizing devices, such as mills, kneaders or extruders,

preferably in an extruder.

The aromatic polyesters preferably used according to the invention for the production of the polyester (PE-1) preferably have a melting point in the range from 160 to 350 ° C., preferably a melting point of greater than 180 ° C. The polyesters suitable according to the invention more preferably have a melting point of greater than 200 ° C., particularly preferably a melting point of greater than 220 ° C. Accordingly, the polyesters suitable according to the invention particularly preferably have a melting point in the range from 220 to 350 ° C.

Polyesters suitable according to the invention for the production of the polyester (PE-1) are known per se and contain at least one aromatic ring bound in the

Polycondensate backbone derived from an aromatic dicarboxylic acid. The aromatic ring can optionally also be substituted, for example by

Halogen atoms, e.g. Chlorine or bromine and / or by linear or branched alkyl groups with preferably 1 to 4 carbon atoms, in particular 1 to 2 carbon atoms, such as e.g. a methyl, ethyl, iso- or n-propyl and / or an n-, iso- or tert-butyl group. The polyesters can be made by aromatic polycondensation

Dicarboxylic acids or mixtures of aromatic and aliphatic and / or

cycloaliphatic dicarboxylic acids and the corresponding ester-forming derivatives, such as dicarboxylic acid anhydrides, mono- and / or diesters with expediently a maximum of 4 Carbon atoms in the alcohol residue, with aliphatic dihydroxy compounds at elevated temperatures, for example from 160 to 260 ° C, in the presence or absence of

Esterification catalysts.

As polyesters, the polyalkylene terephthalates of alkane diols with 2 to 6 carbon atoms have proven particularly outstanding, in particular aromatic polyesters selected from the group consisting of polybutylene terephthalate (PBT), polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), so that preferably polyethylene terephthalate and particularly preferably polybutylene terephthalate or Mixtures of polyethylene terephthalate and

Find polybutylene terephthalate.

According to a further embodiment, the present invention accordingly also relates to a foamed granulate as described above, the aromatic polyester for producing the polyester (PE-1) being selected from the group consisting of polybutylene terephthalate (PBT), polyethylene terephthalate (PET) and polyethylene naphthalate (PEN) ), where too

Recycled products made of polyester and blends can be used.

For example, polyethylene terephthalates or polybutylene terephthalates derived from recycling processes can be used in the context of the present invention.

Suitable molecular weight ranges (Mn) of the polyester used to produce the polyester (PE-1) are, according to the invention, in the range from 2,000 to 100,000, particularly preferably in the range from 10,000 to 50,000.

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 the aromatic polyester (PE-1) according to step (b) with a

Isocyanate composition (IZ) containing at least one diisocyanate and one

Implemented polyol composition (PZ), the polyol composition (PZ) containing at least one aliphatic polyol (P1) with a number average molecular weight> 500 g / mol.

According to the invention, the polyol composition contains at least one aliphatic polyol (P1) with a number average molecular weight> 500 g / mol. In the context of the present invention, the polyol composition can contain further components, for example further polyols or solvents. According to a further embodiment, the polyol composition (PZ) contains a diol (D1) with a number average molecular weight <500 g / mol. According to a further embodiment, the present invention accordingly also relates to foamed granules as described above, the polyol composition containing a diol (D1) with a number-average molecular weight <500 g / mol.

Suitable aliphatic polyols (P1) or other polyols are known to the person skilled in the art

generally known and described, for example, in "Kunststoff Handbuch, Volume 7, Polyurethane", Carl Hanser Verlag, 3rd edition 1993, chapter 3.1. Polyester poly or polyether polyol are particularly preferably used as polyols. You can also

Polycarbonates are used. Copolymers can also be used in the context of the present invention. Polyether polyols and polyester polyols are particularly preferred. 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.

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, for example, as further polyols, 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. For example, the content of the first polyol (P1) can be in the range from 15% to 85%, preferably in the range from 20% to 80%, more preferably in the range from 25% to 75%.

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 a

thermoplastic polyurethane as described above, wherein the polyol composition is 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.

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

According to a further embodiment, the present invention accordingly also relates to foamed granules as described above, the polyol (P1) being selected from the group consisting of polyether, polyester, polycarbonate alcohol and

Hybrid polyols.

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.

Suitable diols (D1) are also known in principle to the person skilled in the art. According to the invention, the diol (D1) has a molecular weight of <500 g / mol. For example, aliphatic, araliphatic, aromatic and / or cycloaliphatic diols with a molecular weight of 50 g / mol to 220 g / mol can be used according to the invention. Are preferred

Alkanediols with 2 to 10 carbon atoms in the alkylene radical, in particular di-, tri-, tetra-, penta-, hexa-, hepta-, octa-, nona- and / or decaalkylene glycols. For the present invention, 1,2-ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol are particularly preferred. 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 diol (D1).

According to a further embodiment, the present invention accordingly also relates to foamed granules as described above, the diol (D1) being selected from the group consisting of 1, 2-ethylene glycol, 1, 3-propanediol, 1, 4-butanediol and 1, 6-hexanediol.

According to step (b), an isocyanate composition (IZ) is also used. Suitable isocyanates are known per se to the person skilled in the art. Diisocyanates, in particular aliphatic or aromatic, are particularly suitable in the context of the present invention

Diisocyanates, more preferably aromatic diisocyanates.

Furthermore, in the context of the present invention, prereacted products can be used as isocyanate components 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, hexamethylene-1, 6-diisocyanate (HDI), pentamethylene-1, 5-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).

Preferred aliphatic polyisocyanates are hexamethylene-1,6-diisocyanate (HDI), 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl-cyclohexane and 4,4'-, 2,4'- and / or 2,2 '- methylene dicyclohexyl diisocyanate (H12MDI).

Preferred aliphatic polyisocyanates are hexamethylene-1,6-diisocyanate (HDI), 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl-cyclohexane and 4,4'-, 2,4'- and / or 2,2 '- methylene dicyclohexyl diisocyanate (H12MDI); 4,4′-, 2,4′- and / or 2,2′-methylene dicyclohexyl diisocyanate (H12MDI) and 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl-cyclohexane or mixtures thereof are particularly preferred.

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.

Further examples of mixtures are polyisocyanate compositions containing

4,4'-MDI and 2,4'-MDI, or

4,4'-MDI and 3,3, '- dimethyl-4,4'-diisocyanato-diphenyl (TODI) or

4,4'-MDI and H12MDI (4,4'-methylene dicyclohexyl diisocyanate or

4,4'-MDI and TDI; or

4,4'-MDI and 1,5-naphthylene diisocyanate (NDI).

According to the invention, three or more isocyanates can also be used. The polyisocyanate composition usually contains 4,4'-MDI in an amount of 2 to 50% based on the total polyisocyanate composition and the further isocyanate in an amount of 3 to 20% based on the total polyisocyanate composition.

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 (a).

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 triisocyanates, 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 (a) and higher-functional polyols or chain extenders not more 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 a further embodiment, the present invention accordingly also relates to foamed granules as described above, the diisocyanate being selected from the group consisting of 2,2'-, 2,4'- and / or 4,4'-diphenylmethane diisocyanate (MDI) , 2,4- and / or 2,6-tolylene diisocyanate (TDI), 4,4'-, 2,4'- and / or 2,2'-

Methylene dicyclohexyl diisocyanate (H12MDI), hexamethylene diisocyanate (HDI) and 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl-cyclohexane (IPDI).

The proportions of the components used are preferably selected in accordance with step (b) such that the proportion of the aromatic polyester used is in the range from 10 to 60%, based on the mass of the components used.

According to a further embodiment, the present invention accordingly also relates to foamed granules as described above, the diisocyanate in a molar amount of at least 0.9, based on the alcohol groups, the sum of the components of the polyol composition (PZ) and the aromatic polyester (PE-1 ) is used.

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 block copolymer, the block copolymer being obtained or obtainable according to a process comprising the steps

(a) providing an aromatic polyester (PE-1);

(b) reaction of the aromatic polyester (PE-1) with a

Isocyanate composition (IZ) containing at least one diisocyanate and a polyol composition (PZ), the

Polyol composition (PZ) contains at least one aliphatic polyol (P1) with a number average molecular weight> 500 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 one needed for the positioning 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 methods are, for example, customary mixing methods with the aid of a kneader, continuously or batchwise, or an extruder such as, for example

co-rotating twin screw extruder.

In the case of compatibilizers or auxiliary substances such as stabilizers, these can also be incorporated into the components when the components are frozen.

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 conventional auxiliary substances 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.

In this step some of the usual U-additives mentioned above can be added to the mixture. The particle foams 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, instead of a vessel with a volume of 0.5 l, a vessel with a volume of 10 l is used, since this is particularly true for foam particles with low density and high mass a measurement with only 0.5 I volume is too imprecise.

As stated above, the diameter of the individual particles of the foamed granulate 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 is with

Diameter means the longest dimension:

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.

One embodiment of the above-mentioned method comprises impregnating the granules with a blowing agent under pressure and then expanding 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 in the absence of water.

Suitable suspension aids are e.g. 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, in particular C4-10 alkanes, for example the isomers of butane, pentane, hexane, heptane and octane, particularly preferably isopentane. 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. The melt strand foams up and the particle foams 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 set. 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 granulate can be produced directly from the granulate in that the corresponding granulate is 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 e.g. those described in W02014150122 or e.g. 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 Hildebrand 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 corresponding moldings can be produced by methods known to those skilled in the art.

A preferred method for producing a molded foam 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 steam, hot air (as described, for example, in EP1979401 B1) or energy radiation (microwaves or radio waves). The temperature when the foamed granules are fused is preferably below or close to the melting temperature of the polymer from which the foamed granules were produced. Accordingly, 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 / residence 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 preparation. Here, the corresponding foamed granules are contacted with a carrier liquid containing a dye, the carrier liquid (TF) being a

Has 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 when the foamed granules are produced. For example, the dye can be added to the extruder when the foamed granules are produced 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) .

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.

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.

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 e.g.

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 flart phase made from 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 flart phase due to their predetermined block structure, which results from the structure of molecules which are already polymeric and thus long-chain, 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.

Owing to the good mechanical properties and the good temperature behavior, the foamed granules 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 or a foamed granulate according to the invention, obtained or obtainable by a process according to the invention for the production of moldings, the molded body 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 or foamed granules according to the invention, obtained or obtainable by a process according to the invention for the production of molded articles, the molded article being 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.

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

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

Within the scope of the present invention, the matrix consists of a polymer (PM). For the purposes of the present invention, suitable as matrix material are, for example, elastomers or 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 mean a mixture which consists of 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 designated exists. 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 a 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 the production of the polymer (PM), in particular an ethylene-vinyl acetate copolymer or a polyurethane, are

Expert known per se.

In a preferred embodiment, the hybrid materials according to the invention are integral foams, in particular integral foams based on polyurethane. 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 molds. The molds are usually made of metal, e.g. Aluminum or steel. These procedures are described, for example, by Piechota and Röhr in "IntegralschaumstofF, 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 have g / cm ³ . The degrees of compaction for the production of the shaped bodies 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. Connections that are considered

They 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 C 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. Examples include: inorganic fillers such as silicate minerals, for example layered silicates such as antigorite, bentonite, serpentine, hornblende, 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 sulphide, zinc sulphide and glass etc. Preferably used are kaolin (china clay), aluminum silicate and coprecipitates made of barium sulphate and aluminum silicate as well as natural and synthetic fibrous minerals such as wollastonite, metal and in particular glass fibers of various lengths, which can optionally be sized. As organic Fillers are possible, for example: 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 flybrid materials according to the invention, in particular flybrid materials with a matrix of cellular polyurethane, are distinguished by a very good flow of the matrix material with the foamed granulate according to the invention. This breaks an inventive

Flybrid 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 suitable, for example, as floor coverings, in particular as coverings for playgrounds, athletic 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 can be found in the claims and the 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 block copolymer, the block copolymer being obtained or obtainable according to a process comprising the steps

(a) providing an aromatic polyester (PE-1);

(b) reaction of the aromatic polyester (PE-1) with a

Isocyanate composition (IZ) containing at least one diisocyanate and optionally a polyol composition (PZ), the polyol composition (PZ) at least one aliphatic polyol (P1) with a number average

Contains molecular weight> 500 g / mol. 2. Foamed granules according to embodiment 1, wherein the polyol composition contains a diol (D1) with a number average molecular weight <500 g / mol.

3. Foamed granules according to one of the embodiments 1 or 2, wherein the

aromatic polyester (PE-1) is obtainable or is obtained by reacting at least one aromatic polyester with a melting point in the range from 160 to 350 ° C. and at least one diol (D2) at a temperature of greater than 200 ° C.

4. Foamed granules according to embodiment 3, the reaction taking place continuously.

5. Foamed granules according to embodiment 3 or 4, the reaction taking place in an extruder.

6. Foamed granules according to one of the embodiments 3 to 5, the

aromatic polyester is selected from the group consisting of

Polybutylene terephthalate (PBT), polyethylene terephthalate (PET) and polyethylene naphthalate (PEN).

7. Foamed granules according to one of the embodiments 2 to 6, the diol (D1) being selected from the group consisting of 1,2-ethylene glycol, 1,3-propanediol, 1,4-butanediol and 1,6-hexanediol.

8. Foamed granules according to one of the embodiments 1 to 7, the polyol (P1) being selected from the group consisting of polyether, polyester, polycarbonate alcohols and hybrid polyols.

9. Foamed granules according to one of the embodiments 1 to 7, wherein the

Diisocyanate in a molar amount of at least 0.9 based on the

Alcohol groups of the sum of the components of the polyol composition (PZ) and the aromatic polyester (PE-1) is used.

10. Foamed granules according to one of the embodiments 1 to 9, wherein the

Diisocyanate is selected from the group consisting of 2,2'-, 2,4'- and / or 4,4'-diphenylmethane diisocyanate (MDI), 2,4- and / or 2,6-tolylene diisocyanate (TDI), 4, 4'-, 2,4'- and / or 2,2'-methylene dicyclohexyl diisocyanate (H12MDI),

Hexamethylene diisocyanate (HDI) and 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (IPDI).

11. A method for producing a foamed granulate comprising the steps (i) providing a composition (Z1) containing a block copolymer, the block copolymer being obtained or obtainable according to a process comprising the steps

(a) providing an aromatic polyester (PE-1);

(b) reaction of the aromatic polyester (PE-1) with a

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

(iii) expanding the composition (Z1) by means of pressure drop. Method according to embodiment 11, wherein the polyol composition contains a diol (D1) with a number average molecular weight <500 g / mol. Method according to one of the embodiments 11 or 12, wherein the aromatic polyester (PE-1) is obtainable or is obtained by reacting at least one aromatic polyester having a melting point in the range from 160 to 350 ° C. and at least one diol (D2) at one temperature of greater than 200 ° C. Method according to embodiment 13, wherein the reaction takes place continuously. Method according to embodiment 13 or 14, wherein the reaction takes place in an extruder. Method according to one of the embodiments 13 to 15, wherein the aromatic polyester is selected from the group consisting of polybutylene terephthalate (PBT), polyethylene terephthalate (PET) and polyethylene naphthalate (PEN). Method according to one of the embodiments 12 to 16, wherein the diol (D1) is selected from the group consisting of 1,2-ethylene glycol, 1,3-propanediol, 1,4-butanediol and 1,6-hexanediol. Method according to one of the embodiments 1 1 to 17, wherein the polyol (P1) is selected from the group consisting of polyether, polyester,

Polycarbonate alcohols and hybrid polyols. Method according to one of the embodiments 11 to 18, wherein the diisocyanate in a molar amount of at least 0.9 based on the alcohol groups of the sum the components of the polyol composition (PZ) and the aromatic polyester (PE-1) is used.

20. The method according to any one of embodiments 1 1 to 19, wherein the diisocyanate

is selected from the group consisting of 2,2'-, 2,4'- and / or 4,4'-diphenylmethane diisocyanate (MDI), 2,4- and / or 2,6-tolylene diisocyanate (TDI), 4,4 '-, 2,4'- and / or 2, 2'-methylene dicyclohexyl diisocyanate (H12MDI),

21. Foamed granules obtained or obtainable by a process according to one of the embodiments 11 to 20.

22. Use of a foamed granulate according to one of the embodiments 1 to 10 or 21 for the production of a shaped body.

23. Use according to embodiment 22, wherein the molded body is produced by welding or gluing the particles together.

24. Use according to embodiment 22 or 23, 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.

25. Use of foamed particles according to one of the embodiments 1 to 10 or 21 in balls and sports equipment or as flooring and wall cladding, in particular for sports areas, athletic tracks, sports halls, children's playgrounds and walkways.

26. Hybrid material containing a matrix of a polymer (PM) and a foamed granulate according to one of the embodiments 1 to 10 or 21 or a foamed granulate obtainable or obtained by a method according to one of the

Embodiments 1 1 to 20.

27. Hybrid material according to embodiment 26, wherein the polymer (PM) is an EVA.

28. Hybrid material according to embodiment 26, wherein the polymer (PM)

is thermoplastic polyurethane.

29. Hybrid material according to embodiment 26, wherein the polymer (PM)

Polyurethane foam is.

30. Hybrid material according to embodiment 26, 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:

Polyester 1: Polybutylene terephthalate (PBT) with a weight average

Molecular weight of 60,000 g / mol

Polyol 2: polyether polyol with an OH number of 174.7 and exclusively

primary OH groups (based on tetramethylene oxide, functionality: 2)

Polyol 3: polyether polyol with an OH number of 1 12.2 and exclusively

primary OH groups (based on tetramethylene oxide, functionality: 2)

Polyol 4: mixture of polyol 3 53.33% and polyol 5 46.67%

Polyol 5: polyether polyol with an OH number of 55.8 and exclusively primary

OH groups (based on tetramethylene oxide, functionality: 2)

Polyol 6: polyester polyol with an OH number of 56 and exclusively primary

OH groups (based on hexanediol, butanediol and adipic acid, functionality: 2)

Polyol 7: polyester polyol with an OH number of 38 and exclusively primary

OH groups (based on methyl propanediol butanediol adipate, functionality: 2)

Chain extender 1: 1, 4-butanediol

Isocyanate 1: aromatic isocyanate (4,4 ‘methylene diphenyl diisocyanate)

Isocyanate 2: aliphatic isocyanate (1, 6-hexamethylene diisocyanate)

Catalyst 1: tin-Il-dioctoate (pure)

Antioxidant 1: sterically hindered phenol

Hydrolysis stabilizer 1: polymeric carbodiimide

Hydrolysis stabilizer 2: epoxidized soybean oil

Hydrolysis stabilizer 3: polymeric carbodiimide

Wax 1: amide wax

TPU crosslinker 1: Thermoplastic polyurethane with an NCO content of 8.5% and a functionality of 2.05 by adding oligomeric MDI Example of polymer synthesis Description of the urethane-containing polymer production - general description

The examples polymer 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. Examples of urethane-containing polymer 1 to 4

The polybutylene terephthalate, Ultradur B4500 from BASF SE, was metered into the first zone. After the PBT had melted, a monomeric diol, in the examples polymer 1 to 4, 1, 4-butanediol, or else a low molecular weight polyol, and optionally a catalyst, was fed into the third zone to transesterify the PBT. After the transesterification, the other reaction components, such as diisocyanate and longer-chain polyols, were added in the fifth zone. The addition of further additives, as above

described, takes place in zone 8.

The housing temperatures for zone 1 are 150 ° C. The melting of the PBT and the transesterification in zones 2 - 5 take place at temperatures of 250 - 300 ° C. The polymer is built up in zones 6 - 12 at housing temperatures of 240 - 210 ° C. The melt is discharged and underwater pelletized with

Melt temperatures of 210 - 230 ° C. The screw speed is between 180 and 240 1 / min. The throughput is in the range of 150 - 220 kg / h.

Following the synthesis, the polymer obtained is underwater or

Strand granulated and then dried. Examples of urethane-containing polymer 5 to 7

The polyester (PBT) is fed into the first housing of a twin-screw extruder, ZSK58 from Coperion with a process length of 48D. After the polyester has melted, the polyol and, if appropriate, the catalyst contained therein are added to the housing 3. The transesterification takes place at housing temperatures of 250-300 ° C before the diisocyanate is added to the reaction mixture in the fifth housing. Downstream, the molar mass build-up takes place at housing temperatures of 190 - 230 ° C. Following the synthesis, the polymer obtained is granulated underwater or strand and then dried.

The amounts used are summarized in Table 1. Table 1: Examples of synthesis:

The properties of the thermoplastic polyurethanes produced by the continuous synthesis are summarized in Table 2. Table 2: Examples of properties:

3. Example of foam particle production

To produce the expanded particles from the products (Table 1), a twin-screw extruder with a screw diameter of 44 mm and a ratio of length to diameter of 42 with a subsequent melt pump, a start-up valve with a screen changer, a perforated plate and an underwater pelletizer was used. 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 crosslinker 1 was used for some experiments

added.

This crosslinker is a thermoplastic polyurethane that comes in a separate

Extrusion process with 4,4'-diphenylmethane diisocyanate with an average functionality of 2.05 was added. The residual NCO content is> 5%.

The polymer used in each case and the crosslinking agent 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 underwater pelletizing (UWG)

Granules were cut 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 3. The polymers always form 100 parts while the blowing agents are also counted, so that total compositions above 100 parts are obtained.

Table 3: 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 devices as well as the pressure in the cutting chamber of the UWG are listed in Table 4.

Table 4: 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 products are listed in Table 5.

Table 5: Data on the expanded polymer

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 fill level of 80%, the phase ratio being 0.31.

Polymer 3 can be seen here as the solid phase and the mixture of water with calcium carbonate and a surface-active substance as the liquid phase. This mixture was placed in the gas-tight kettle which had previously been flushed with nitrogen Blowing agent (butane) with the amount given in Table 6 based on the solid phase (polymer 3). The kettle was heated with stirring of the solid / liquid phase and pressurized nitrogen at a temperature of 50 ° C. up to a pressure of 8 bar. The heating was then continued until the desired impregnation temperature (IMT) was reached. When the impregnation temperature and the impregnation pressure were reached, the boiler was released via a valve after a given holding time. The exact setting parameters of the tests and the bulk densities achieved are listed in Table 6.

Table 6: Setting parameters and bulk density of the impregnated polymer 3

4. Welding and mechanics

4.1 Fierposition of the molded body by steam welding

The expanded granules were then welded on a molding machine from Kurtz ersa GmbHFI (Energy Foamer) to square plates with a side length of 200 mm and a thickness of 10 mm or 20 mm by exposure to water vapor. The differ in the plate thickness

Welding parameters only with regard to cooling. The welding parameters of the different materials were chosen such 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 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 7 as steam pressures. The plates are stored in the oven for 4 hours at 70 ° C.

Table 7: Steaming conditions (vapor pressures)

4.2 Production of the Shaped Bodies by Radio Frequency Welding The expanded granules were then processed on a molding machine from the company

Kurtz ersa GmbH (RF-Foamer) welded to square plates with a side length of 200 mm and 10 mm thickness by radio frequency waves. For this purpose, approx. 100 g of the particles were weighed out and poured into a Teflon mold and painted as flat as possible. The mold was closed with a Teflon plate to 10 mm and the expanded granules were compressed. The radio frequency welding at 24 MHz was started, the set voltage (setpoint: 5.9 to 6.5 kV) was reached in 2 seconds. The particles were welded at this tension for 30 to 50 seconds. The mold warmed up to approx. 100 ° C due to the radiation of the particles. The mold was then cooled to 40 to 50 ° C. at room temperature without external cooling before the welded plate was removed. The machine parameters are summarized in Table 8. Before the plates are mechanically tested, they are stored in the oven for 4 hours at 70 ° C.

Table 8: Parameters for radio frequency welding

4.3 Mechanics

Table 8a:

Table 8b:

5.Measurement methods:

For the material characterization, i.a. The following measurement methods are used: DSC, DMA, TMA, NMR, FT-IR, GPC

Mechanics (TPU)

Shore hardness D DIN 7619-1: 2012-02

E-module DIN 53504: 2017-03

Tensile strength DIN 53504: 2017-03

Elongation at break DIN 53504: 2017-03

Tear resistance DIN ISO 34-1, B: 2016-09

Abrasion DIN 4649: 2014-03

Mechanics (expanded polymer)

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

Literature cited

WO 94/20568 A1

WO 2007/082838 A1

WO 2017/030835 A1

WO 2013/153190 A1

WO 2010/010010 A1

EP 0 656 397 A1

EP 1 693 394 A1

"Plastic Handbook", Volume 7, Polyurethane ", Carl Hanser Verlag, 3rd edition 1993, Chapter 3.1 WO 2014/150122 A1

WO 2014/150124 A1

EP 1979401 B1

US 2015/0337102 A1

EP 2 872 309 B1

EP 3 053 732 A1 1

WO 2016/146537

Piechota and Röhr in "Integral foam, Carl-Hanser-Verlag, Munich, Vienna, 1975, or in the plastics manual, volume 7, polyurethane, 3rd edition, 1993, chapter 7

Claims

1. Foamed granules comprising a block copolymer, the block copolymer

is obtained or is obtainable according to a method comprising the steps

(a) providing an aromatic polyester (PE-1);

(b) reaction of the aromatic polyester (PE-1) with a

Contains molecular weight> 500 g / mol.

2. Foamed granules according to claim 1, wherein the polyol composition contains a diol (D1) with a number average molecular weight <500 g / mol.

3. Foamed granules according to one of claims 1 or 2, wherein the aromatic polyester (PE-1) is obtainable or is obtained by reacting at least one aromatic polyester with a melting point in the range from 160 to 350 ° C and at least one diol (D2) at a temperature greater than 200 ° C.

4. Foamed granules according to claim 3, wherein the reaction takes place continuously.

5. Foamed granules according to claim 3 or 4, wherein the reaction in one

Extruder is done.

6. Foamed granules according to one of claims 3 to 5, wherein the aromatic polyester is selected from the group consisting of polybutylene terephthalate (PBT), polyethylene terephthalate (PET) and polyethylene naphthalate (PEN).

7. Foamed granules according to one of claims 2 to 6, wherein the diol (D1)

is selected from the group consisting of 1,2-ethylene glycol, 1,3-propanediol, 1,4-butanediol and 1,6-hexanediol.

8. Foamed granules according to one of claims 1 to 7, wherein the polyol (P1) is selected from the group consisting of polyether, polyester,

Polycarbonate alcohols and hybrid polyols.

9. Foamed granules according to one of claims 1 to 7, wherein the diisocyanate is used in a molar amount of at least 0.9 based on the alcohol groups of the sum of the components of the polyol composition (PZ) and the aromatic polyester (PE-1).

10. Foamed granules according to one of claims 1 to 9, wherein the diisocyanate is selected from the group consisting of 2,2'-, 2,4'- and / or 4,4'-diphenylmethane diisocyanate (MDI), 2,4- and / or 2,6-tolylene diisocyanate (TDI), 4,4'-, 2,4'- and / or 2,2'-methylene dicyclohexyl diisocyanate (H12MDI),

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

(b) providing an aromatic polyester (PE-1);

(b) reaction of the aromatic polyester (PE-1) with a

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

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

12. Foamed granules obtained or obtainable by a process according to claim 1 1.

13. Use of a foamed granulate according to one of claims 1 to 10 or 12 for the production of a shaped body.

14. Use according to claim 13, wherein the production of the shaped body by means

The particles are welded or glued together.

15. Use according to claim 13 or 14, wherein the molded body is a 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.

16. Use of foamed particles according to one of claims 1 to 10 or 12 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.

17. Hybrid material containing a matrix of a polymer (PM) and a foamed granulate according to one of claims 1 to 10 or 12 or a foamed granulate obtainable or obtained by a method according to claim 11.