Method for the production of a thermoplastic polyurethane powder by means of precipitation polymerisation

Abstract

The invention relates to a method for producing a thermoplastic polyurethane powder by means of precipitation polymerisation. The method comprises i) providing a solvent mixture which contains at least one first aprotic solvent A1 having a relative permittivity εr between 2 and 20 (at 20 °C and 100 kHz) and a second aprotic polar solvent A2 from the group 1,2-propylene carbonate, gamma-butyrolactone or ethylene carbonate; ii) adding a polyol B having a molecular mass between 60 g / mol and 250 g / mol and a diisocyanate C; iii) reacting B and C in the solvent mixture A at a temperature of at most 150 °C, wherein the resulting polyurethane precipitates as a solid and forms a dispersion; iv) separating the solvent, washing the solid and drying to give the powder. The resulting powder has a molecular mass Mw of ≥ 35000 g / mol, an allophanate content of < 0.25 mol % and a proportion of > 25.0% of particles < 0.500 mm and satisfies a Mz : Mw ratio of < 4.0.

Description

[0001] 2024PF30081-Abroad - 1 -

[0002] Method for producing a thermoplastic polyurethane powder by means of precipitation polymerization

[0003] The present invention relates to a process for producing a thermoplastic polyurethane powder by precipitation polymerization, the thermoplastic polyurethane powder obtained or obtainable by this process, and its use. Furthermore, the invention relates to a molded part obtained or obtainable by processing the thermoplastic polyurethane powder according to the invention.

[0004] State of the art

[0005] The production of polymer powders is of great interest for use in powder sintering processes, as an additive for structured surfaces, or as abrasives and lubricants in cosmetic applications and industry. Powder sintering processes are, in particular, methods in which a layer of powder is first applied, which is then sintered together or the powder particles are fused together in a further step. Such processes are used, for example, for coating metals, polymers, wood, fibers, and other materials, where the surface is impregnated with powder by dipping in a fluidized bed, by spray gun, or via dispersion, and then heated. In addition to epoxy and polyester resins, a wide variety of thermoplastic polymers such as polypropylene, polyamides, PVC, acrylates, and polyurethanes are also used for this purpose.

[0006] A process for the production of thermoplastic polyurethanes (“TPU”) was already described in DE728981C in 1937. TPUs, including one HDI-BDO adduct (HDI = 1,6-hexamethylene diisocyanate; BDO ​​= 1,4-butanediol), which, due to its combination of desirable properties such as high melting point, high modulus of elasticity, and good chemical resistance, was later marketed for a time under the names Perlon U, Igamid U, and Durethan U (O. Bayer, Angew. Chem. 1947, 59, 9, 257-288), are produced by reaction in a solvent (such as chlorobenzene and dioxane). The solvent is usually removed under vacuum. In some cases, the TPUs also precipitated as gels or powders. However, it was later found that the molecular chain lengths achieved were sometimes insufficient to obtain good polymer properties. Higher molecular weight TPU powders based on, for example, BDO-HDI are therefore not accessible.

[0007] However, most polymers, such as polypropylene, polyamide, or thermoplastic polyurethanes, which can be used, for example, for powder coating or powder sintering processes, are produced in melt form. The polymer obtained in this way must be further processed in a 2024PF30081-Abroad - 2 -

[0008] In a process step, the material is brought into powder form, for example, by milling. In the melt production of, for example, aliphatic thermoplastic polyurethanes, the pure monomers, such as 1,4-butanediol (BDO) and 1,6-hexamethylene diisocyanate (HDI), are reacted in a reactor to form an OH-terminated prepolymer. The second stage of the reaction is then carried out in a heavy-duty mixer by adding HDI (in a deficit; concentration ratio approximately 0.98) to the prepolymer to produce the final product (BIOS Final Report No. 1472, ITEM No. 22, pp. 47-48). The disadvantages of this process include the high reaction temperature and the lengthy and inefficient mixing process, which leads to an increase in undesirable side reactions. This melt process can also be carried out in a modified form.In this process, the monomers BDO and HDI are converted to a prepolymer in a loop reactor or, alternatively, in static mixers (Fluitec reactors). This prepolymer then reacts further with HDI in a second reaction step to form the final polymer via reactive extrusion. However, the disadvantages of a relatively high allophane content and the formation of gel particles cannot be avoided even when limiting the conversion (HDI under-concentration, conversion factor 0.98) (WO2021122279). In the melt processes described here as an example, the polymer is obtained as granules after reactive extrusion and must be converted into powder form in a further process step.

[0009] For most polymers, such as polyamides (shown, for example, in EP3491066A1), polypropylene, and the also frequently used thermoplastic polyurethanes (see EP3512687B 1), milling, especially cryogenic milling, is used to convert the granules into a powder. In cryogenic milling, the polymer granules are cooled to a very low temperature with liquid nitrogen and then milled. The desired particle size is separated from the milled material by sieving. The disadvantage of milling processes in general is that the particle shape is not spherical, but very irregular and angular. This negatively affects the flow behavior, and sieving the milled material is more complex. In addition, the particle size distribution during milling is very broad, so the yield is low, or the milling and sieving process has to be repeated several times.Furthermore, cryogenic milling is an expensive process due to the use of liquid nitrogen to adequately cool the polymers.

[0010] A special case is polyamide 12 (or polyamide 11), which is initially produced as PA 12 granules and dissolved under pressure in ethanol at elevated temperature. It is then precipitated and dried under very precisely controlled conditions (see, for example, EP0911142B1). The advantage of this method is that the polymer powder is obtained as relatively spherical particles with a particle size of < 100 pm (free-flowing) and does not require classification (sieving). Disadvantages of the process include the additional work steps and equipment, the associated costs, and the limited or no additives that can be used in the polymer. 2024PF30081-Abroad - 3 -

[0011] The aforementioned processes are expensive due to their complexity and / or their disadvantages for the production of thermoplastic polyurethane powders with long chain lengths in combination with low allophane content and therefore limit the use of thermoplastic polyurethane powders or the processes dependent on them (powder sintering processes; filler for surface structuring) in industry.

[0012] Therefore, there is a need for a process for producing thermoplastic polyurethane powders with high molar masses and low allophane content.

[0013] Object of the invention

[0014] The object of the present invention was therefore to provide a process for producing thermoplastic polyurethane powders with high molar masses and low allophane content. In particular, the process should lead to thermoplastic polyurethane powders with a mean molar mass of > 35,000 g / mol and an allophane content of < 0.25 mol%, based on the total thermoplastic polyurethane powder, as well as > 25.0 wt% of a particle fraction of < 0.500 mm, based on the total thermoplastic polyurethane powder, and / or a ratio of centrifuge material (molar mass Mz) to mean molar mass Mw of < 4.0. Furthermore, the thermoplastic polyurethane powders should be processed into molded parts that are as free as possible from gel particles and / or exhibit good or improved mechanical properties, in particular good elongation at break and a good modulus of elasticity.

[0015] Solution to the problem and detailed description of the invention

[0016] The problem was solved by a process for producing a thermoplastic polyurethane powder by precipitation polymerization, comprising the steps: i. Provision

[0017] A) a solvent mixture comprising at least one first aprotic solvent Al) with a relative permittivity s r from 2 to 20, measured at 20 °C and 100 kHz, and at least one second aprotic polar solvent A2) selected from the group comprising or consisting of 1,2-propylene carbonate, gamma-butyrolactone and / or ethylene carbonate;

[0018] B) at least one polyol with a molar mass between 60 g / mol and 250 g / mol;

[0019] C) at least one diisocyanate; 2024PF30081-Foreign - 4 -

[0020] D) optionally a catalyst;

[0021] E) optionally a chain regulator El) and / or an additive E2); ii. Reaction of the polyol B) with the diisocyanate C) in the solvent mixture A) at a temperature of not more than 150 °C, optionally in the presence of the catalyst D), the chain regulator El) and / or the additive E2), to the thermoplastic polyurethane, wherein the thermoplastic polyurethane precipitates as a solid in the solvent mixture A) and forms a dispersion; iii. Separation from the solvent mixture A) and optional washing of the thermoplastic polyurethane with a solvent; and iv. Drying of the thermoplastic polyurethane to the thermoplastic polyurethane powder; wherein the thermoplastic polyurethane powder

[0022] • a mass average with a molar mass Mw of > 35000 g / mol;

[0023] • an allophanate content of < 0.25 mol-%, based on the total thermoplastic polyurethane powder; and

[0024] • > 25.0 wt.% of a particle fraction of < 0.500 mm, based on the total thermoplastic polyurethane powder and / or a ratio of centrifugal mean Mz to mass mean Mw of < 4.0; wherein the mass mean Mw, the allophane content, the particle fraction and the centrifugal mean Mz are each determined by the methods set out below.

[0025] In the course of the development work that led to the present invention, it was surprisingly discovered that the use of a special solvent mixture A), namely comprising at least a first aprotic solvent Al) with a relative permittivity s rfrom 2 to 20, measured at 20 °C and 100 kHz, and at least one second aprotic polar solvent A2) selected from the group comprising or consisting of 1,2-propylene carbonate, gamma-butyrolactone (gamma-butyrolactone) and / or ethylene carbonate, leads to thermoplastic polyurethane powders with high molar masses and low allophane content upon precipitation polymerization. Furthermore, the thermoplastic polyurethane powders according to the invention exhibit > 25.0 wt% of a particle fraction of < 0.500 mm, based on the total thermoplastic polyurethane powder, and / or a ratio of centrifuge mean of molar mass Mz to mass mean of molar mass Mw of < 4.0. 2024PF30081-Abroad - 5 -

[0026] Furthermore, the solvent mixture A) according to the invention does not lead to odorous degradation products during the isolation and processing of the thermoplastic polyurethane powder. It has been found that solvent mixtures containing DMSO as a solvent component also lead to good precipitation polymerizations; however, during isolation and processing, DMSO degradation products are formed, which even in minute concentrations cause an intense odor. This limits its technical applications, as polymers, for example, must be dried before extrusion, and the use of components made from this material in indoor environments is also limited.

[0027] The number-mean molar mass (Mn), mass-mean molar mass (Mw), and centrifuge mean (Mz) of the thermoplastic polyurethane powder are determined by gel permeation chromatography (GPC). For this purpose, the sample to be measured is dissolved in a solution of 3 g potassium trifluoroacetate in 400 cubic centimeters of hexafluoroisopropanol (sample concentration approximately 2 mg / cubic centimeter). The respective GPCs are measured with the following components at a flow rate of 1 cubic centimeter / minute:

[0028] Pump: HPLC pump 515 (Waters GmbH)

[0029] Detector: Smartline RI detector 2300 (Knauer Wissenschaftliche Geräte GmbH)

[0030] Columns: 1 pre-column, 1000 Å PSS PFG 7pm, 300 Å PSS PFG 7pm, 100 Å PSS PFG 7pm in this order (PSS Polymer Standards Service GmbH)

[0031] Degassing: Degasser PSS (PSS Polymer Standards Service GmbH)

[0032] Injection volume: 100 microliters

[0033] Temperature: 23 °C - 25 °C

[0034] Molar mass standard: Polymethyl methacrylate standard kit (PSS Polymer Standards Service GmbH)

[0035] The number mean of the molar mass (Mn or M) n ) is calculated from the data obtained by measuring gel permeation chromatography using the following equation: where:

[0036] M is the molar mass of the polymers of fraction i, such that M < M i+1 for all i, in g / mol, ni is the amount of substance of the polymer of fraction j, in mol.

[0037] The mass average of the molar mass (Mw or M) w ) is also calculated from the data obtained by measuring gel permeation chromatography using the following equation: 2024PF30081-Abroad - 6 - where:

[0038] M is the molar mass of the polymers of fraction i, such that M for all j, in g / mol,

[0039] Tii is the amount of substance of the polymer of fraction j, in mol.

[0040] The centrifuge medium of the molar mass (Mz or M) z ) is calculated from the data obtained by measuring gel permeation chromatography using the following equation: ,n g / mo1 where:

[0041] M is the molar mass of the polymers of fraction i, such that M < M i+1 for all i, in g / mol, ni is the amount of substance of the polymer of fraction j, in mol.

[0042] The allophane content of the thermoplastic polyurethane powder is determined by ¹H-NMR. The measurements are performed with a Bruker AV III HD 600 spectrometer at 600 MHz in DMSO-D6 at 80 °C. The following peaks are evaluated:

[0043] U= CH2-NH 2.98 ppm CH2 for urethane

[0044] 0 = CH2-OH 3.43 ppm CH2 at OH groups

[0045] N= NH 6.6 ppm urethane

[0046] A = NH 8.3-8.4 ppm allophanate

[0047] The allophanate concentration or allophanate content in mol% is calculated according to the following formula:

[0048] Allophanate [mol%] = 100% * A / (A+N)

[0049] The key figure for revenue is derived from the formula:

[0050] KZ = 1 / (1+O / U)

[0051] To determine the particle fraction, approximately 100 g of sample is sieved for 5 minutes using a Haver & Boecker laboratory sieve machine No. 7279 (built in 1978) and the appropriate sieve set (e.g. 0.100 mm, 0.250 mm, 0.500 mm) and the individual fractions are then weighed.

[0052] The tensile test (for determining the elongation at break and the modulus of elasticity / tensile modulus) is carried out within the scope of the invention in accordance with the test method DIN EN ISO 527 using specimen type 2024PF30081-Ausland - 7 -

[0053] 5A (DIN EN ISO 527-2, thickness 2 mm) is performed. The specimens are stored under standard conditions for at least 24 hours prior to the test. Tensile tests are carried out at 22 °C and 50% relative humidity using a Zwick Z010 universal testing machine at a speed of 10 mm / min. The Young's modulus is determined between 0.05% and 0.25% elongation using secant. The specimens can be produced, for example, by drying the thermoplastic polyurethane powder at 80 °C in a drying oven for 4 hours, then processing it on a microextruder (e.g., the Xplore MC 15 HT (15 mL)) and forming it into the required shape using the corresponding injection mold (e.g., a Micro moulder IM 12).

[0054] It is preferred that the first aprotic solvent (Al) comprises or consists of halogenated aromatics, ketones, ethers, esters and carbonates or mixtures thereof, in particular chlorobenzene and / or ortho-dichlorobenzene; cyclopentanone, cyclohexanone; heptan-4-one; benzene, toluene; ethylbenzene; cumene; xylene; acetophenone or mixtures thereof, preferably chlorobenzene.

[0055] The ratio of the first aprotic solvent Al) to the second aprotic polar solvent A2) is preferably 300:1 to 1:9, more preferably 200:1 to 1:1, and even more preferably 100:1 to 8:2.

[0056] Furthermore, it is preferred that the polyol B) comprises or consists of ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, 1,12-dodecanediol or mixtures thereof, wherein the polyol B) preferably contains at least 50.0 wt% 1,4-butanediol, particularly preferably at least 90.0 wt% 1,4-butanediol, based on the total weight of the polyol B).

[0057] The diisocyanate preferably comprises or consists of 1,4-butane diisocyanate, 1,5-pentane diisocyanate, 1,6-hexane diisocyanate, isophorone diisocyanate, 1,1'-methylenebis(4-isocyanatocyclohexane), xylylene diisocyanate, in particular m-xylylene diisocyanate or mixtures thereof, wherein the diisocyanate C) further preferably contains at least 50.0 wt% 1,5-pentane diisocyanate or 1,6-hexane diisocyanate, based on the total weight of the diisocyanate C).

[0058] The optional catalyst D) can, for example, be selected from typical urethanization catalysts such as those specified in Becker / Braun, Kunststoffhandbuch Band 7, Polyurethane, Kapitel 3.4, or mixtures thereof.

[0059] The optional chain regulator El) may, for example, be selected from the group comprising or consisting of monofunctional zerewitinov H-acidic compounds, monofunctional isocyanates, or mixtures thereof. Examples of the optional chain regulator El) listed under 2024PF30081-Abroad - 8 - include n-octanol, benzyl alcohol, n-octylamine, dioctylamine, >-caprolactam, propanone oxime, butane-1-thiol, acetylacetone, and diethyl malonate.

[0060] The optional additive E2) may, for example, be selected from the group comprising or consisting of stabilizers, dyes and markers or mixtures thereof.

[0061] Dyes are defined here as organic compounds that absorb at least part of the visible light spectrum between 380 nm and 790 nm. Dyes that are dissolved under the reaction conditions specified in step ii. and react with a Zerewitinow H-acidic compound or with an isocyanate group, and are thus covalently bonded to the thermoplastic polyurethane, are particularly preferred.

[0062] Markers, as used here, are compounds that are easily and specifically detectable using analytical methods. These can be, for example, aromatic compounds exhibiting specific UV absorption or UV absorption patterns, or which can be detected by fluorescence spectroscopy. Further examples of markers are isotopically enriched compounds that are readily detectable by NMR spectroscopy or by their radioactivity. Markers that are present in solution under the reaction conditions described in step ii and react with a Zerewitinow H-acidic compound or with an isocyanate group, thus forming a covalent bond with the thermoplastic polyurethane, are particularly preferred.

[0063] Furthermore, it is preferred that

[0064] • 30.0 to 95.0 parts by weight, preferably 60.0 to 90.0 parts by weight of solvent mixture A);

[0065] • 2.0 to 40.0 parts by weight, preferably 3.0 to 20.0 parts by weight of polyol B);

[0066] • 3.0 to 40.0 parts by weight, preferably 5.0 to 25.0 parts by weight of diisocyanate C);

[0067] • 0 to 5.0 parts by weight, preferably 0 to 0.1 parts by weight of catalyst D);

[0068] • 0 to 10.0 parts by weight, preferably 0.001 to 1.5 parts by weight of the chain regulator El);

[0069] • 0 to 20.0 parts by weight, preferably 0.0001 to 3.0 parts by weight of additive E2); are provided, each based on the total amount of solvent mixture A), polyol B), diisocyanate C), catalyst D), chain regulator El) and additive E2), which is normalized to 100 parts by weight.

[0070] The reaction in step ii. preferably takes place at a temperature of 50 °C to 150 °C, more preferably from 100 °C to 145 °C, even more preferably from 120 °C to 140 °C and / or at an isocyanate number of 0.95 to 1.1, more preferably 0.97 to 1.02, even more preferably 0.98 to 2024PF30081-Abroad - 9 -

[0071] 1.0. The dispersion formed in step ii. preferably has a solids content of 5.0 to 50.0 wt.%, more preferably of 15.0 to 45.0 wt.%, and even more preferably of 20.0 to 40.0 wt.%, determined by gravimetric measurement with and without solvent.

[0072] The isocyanate number is calculated by dividing the molar amount of reactive isocyanate groups by the molar amount of reactive Zerewitino H-acidic groups.

[0073] KZ niso / nH-acid

[0074] The reaction in step ii. can also be carried out at a lower or higher pressure than the surrounding atmospheric pressure in the autoclave, for example, if solvents Al) and / or solvent A2) have a lower boiling point than the reaction temperature at approximately 1 bar. It is preferred to carry out the reaction in step ii. at ambient pressure.

[0075] Furthermore, it is preferred that the separation in step iii. is carried out by filtration, centrifugation, and / or evaporation of the solvents. The thermoplastic polyurethane can also be additionally washed with a solvent in step iii. Preferably, this solvent comprises or consists of a solvent with a boiling point between -30 °C and +250 °C (at 1 bar), preferably halogenated aromatics and alkanes, ketones, ethers, esters, alcohols, nitriles, water, and carbonates or mixtures thereof, in particular chlorobenzene, methyl ethyl ketone, acetone, a Cl-C6 alcohol and its esters, dimethyl carbonate, diethyl carbonate, or mixtures thereof, especially chlorobenzene.

[0076] The drying in step iv. is further preferably carried out by moving or mixing the drying material, particularly preferably in a paddle dryer.

[0077] It is also preferred that the thermoplastic polyurethane powder

[0078] • a mass medium with a molar mass Mw of 40000 to 300000 g / mol, preferably of 50000 to 250000 g / mol, particularly preferably of 60000 to 200000 g / mol 1;

[0079] • an allophane content of 0 to 0.20 mol%, preferably of 0.001 to 0.15 mol%, particularly preferably of 0.01 to 0.10 mol%, based on the total thermoplastic polyurethane powder; and / or

[0080] • comprising 30.0 to 100 wt.%, more preferably 40.0 to 90.0 wt.% of a particle fraction of < 0.500 mm, based on the total thermoplastic polyurethane powder and / or a ratio of centrifuge medium of molar mass Mz to mass medium of molar mass Mw of < 3.0, preferably 1.5 to 2.85; 2024PF30081-Abroad - 10 -

[0081] Depending on the choice of powder sintering process and application specifications for the polyurethane powder, powders with different grain sizes are used, but the grain sizes are usually in a range of up to 0.500 mm and smaller.

[0082] Another important aspect of particle size is the formation of the most stable dispersion possible during the reaction and for its processing. After scaling up to industrial levels, the dispersion must be transported by pumps, must not settle prematurely, and should also exhibit good filtration properties. If the particle size is too large, the particles settle too quickly, leading to deposits and increased wear on the pumps.

[0083] The thermoplastic polyurethane according to step iii. and / or the thermoplastic polyurethane powder according to step iv. can / can further be impregnated with a stabilizer from a stabilizer solution. For this purpose, the thermoplastic polyurethane according to step iii. and / or the thermoplastic polyurethane powder according to step iv. is preferably dispersed in the stabilizer solution and then separated and dried. The stabilizer solution preferably comprises or consists of

[0084] • a solvent selected from the group comprising or consisting of solvents of the group consisting of chlorinated aromatics; aromatics; aliphatics; esters; ethers; alcohols; water; ketones; nitriles; carbonates; or mixtures thereof, or preferably the solvent(s) (Al) from step i., wherein the solvent(s) preferably have a boiling point of < 250 °C at 1 bar; and

[0085] • a stabilizer dissolved therein, selected from the group comprising or consisting of sterically hindered phenol derivatives, organic phosphine, phosphite and / or phosphonate derivatives (generally also called phosphorus-based stabilizers), sulfur-containing antioxidants, 2,2,6,6-tetramethylpiperidine derivatives, benzotriazole derivatives, triazine derivatives, hydroxybenzophenone derivatives, cyanoacrylate derivatives, oxalinide derivatives or mixtures thereof; wherein the weight fraction of the stabilizer is preferably from 0.001 to 10.0 wt.%, more preferably from 0.05 to 5.0 wt.%, based on the total weight of the stabilizer solution.

[0086] Preferably, the stabilizer solution contains phosphorus(III) compounds as phosphorus-based stabilizers, which are oxidized to phosphorus(V) compounds upon heating in the presence of oxygen. Organic phosphites, phosphine compounds, and phosphonates, particularly organic phosphites and phosphonates, are also preferably used. 2024PF30081-Abroad - 11 -

[0087] Particularly preferred is the phosphorus-based stabilizer selected from at least one compound according to the structures (1), (2), (3), (4), (5) and (6). 2024PF30081-Abroad - 12 -

[0088] The compound (1) is classified as CAS: 31570-04-4 and is commercially available under the name Irgafos™ 168 from BASF (Germany).

[0089] Compound (2) is classified as CAS: 237-249-1 and is commercially available under the name Brüggolen™ H10 from Brüggeman (Germany).

[0090] The compound (3) is classified as CAS: 26741-53-7 and is commercially available under the name Irgafos™ 126 from BASF (Germany).

[0091] Compound (4) is classified as CAS: 603-35-0 and is commercially available under the name Triphenylphosphine from BASF (Germany).

[0092] The compound (5) is classified as CAS: 80693-00-1 and is commercially available under the name ADK Stab™ PEP 36 from Adeka (Japan).

[0093] The compound (6) is classified as CAS: 126050-54-2 and is commercially available under the name ADK Stab™ HP-10 from Adeka (Japan).

[0094] Another suitable stabilizer containing phosphorus(III) is AddWorks™ LXR 568 MP from Clariant (Switzerland).

[0095] It is preferred that the phosphorus-based stabilizer is selected from the group comprising or consisting of compounds according to structures (1), (2), (4), (6) or mixtures thereof. The compound according to structure (1) and / or (2) is particularly preferred as the phosphorus-based stabilizer. These phosphorus-based stabilizers result in a particularly high tensile strength of the manufactured molded body. 2024PF30081-Abroad - 13 -

[0096] The stabilizer solution may also contain a sterically hindered phenol. Mixtures of several such components and different stabilizers can also be used.

[0097] Preferably, the sterically hindered phenol is a compound of the general structure (7a) or (7b) where n means 1, 2, 3 or 4,

[0098] Ri, R2 and R3 each independently represent Ci to C4 alkyl or hydrogen

[0099] X represents a direct bond or an organic residue with Ci- to Ceo-, and the organic residue may contain oxygen and / or nitrogen.

[0100] R4 represents a direct bond, carbon, Ci-Cs alkyl, aryl or a structure according to formula (8a), (8b) or (8c).

[0101] Particularly preferred is the sterically hindered phenol selected from at least one compound according to structures (9), (10), (11) and (12). 2024PF30081-Abroad - 14 -

[0102] Compound (9) is classified as CAS: 6683-19-8 and is commercially available under the name ADK Stab™ AO-60 from Adeka (Japan). 2024PF30081-Foreign - 15 -

[0103] Compound (10) is classified as CAS: 85-60-9 and is commercially available under the name Songnox™ 4425 from Songwon Industrial Group (South Korea).

[0104] Compound (11) is classified as CAS: 23128-74 and is commercially available under the name Songnox™ 1098 from Songwon Industrial Group (South Korea).

[0105] The compound (12) is classified as CAS: 36443-68-2 and is commercially available under the name Irganox™ 245 from BASF (Germany).

[0106] Furthermore, the stabilizer solution can optionally contain a sulfur-containing antioxidant. Mixtures of several such components can also be used.

[0107] For example, a sulfur-containing antioxidant can have a structure according to RI-CH2-(S) X -CH2-R2, where x = 1 or 2 and where Ri and R2 can be the same or different and represent aromatic or aliphatic groups. Preferably, Ri and R2 are aliphatic groups, which can be linear or branched and can contain functional groups.

[0108] Examples of commercially available sulfur-containing antioxidants include dilauryl 3,3'-thiodipropionate (CAS 123-28-4), distearyl 3,3'-thiodipropionate (CAS 693-36-7), ditridecylthiodipropionate (CAS 10595-72-9); pentaerythritoltetrakis ([β-laurylthiopropionate (CAS 29598-76-3), 2,2'-thiodiethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] (CAS 41484-35-9), dimyristylthiodipropionate (CAS 16545-54-3) and distearyl disulfides (CAS 2500-88-1), as well as mixtures of these substances.

[0109] Alternatively, the sulfur-containing antioxidant can also comprise one or more diphenyl thioesters such as 4,4'-thiobis(2-t-butyl-5-methylphenol) (CAS 96-69-5) and 2,2'-thiobis(6-t-butyl-4-methylphenol) (CAS 90-66-4).

[0110] Pentaerythritoltetrakis ([β-laurylthiopropionate] (CAS 29598-76-3) (structure (13)) is particularly preferred as a sulfur-containing antioxidant. 2024PF30081-Abroad - 16 -

[0111] Furthermore, it is preferred that the thermoplastic polyurethane powder, after the aforementioned impregnation, contains 0.005 to 2.0 wt.% of the stabilizer from the stabilizer solution, based on the total weight of the thermoplastic polyurethane powder. The thermoplastic polyurethane powder obtained after impregnation preferably has a b-value of < 4.0, more preferably of 0.1 to 2.5, determined in the CIE Lab color space using a spectrophotometer with illuminant D 65 at 8° according to DIN EN ISO 11664-4.Furthermore, it is preferred that the thermoplastic polyurethane powder exhibits a change in the b-value (Ab) after exposure to a temperature of 120 °C for a duration of 96 h and / or 155 °C for a duration of 6 h, each under an air atmosphere, of < 3.5, preferably of 0.1 to 2.8, more preferably of 0.2 to 2.0, wherein the b-value in the CIE Lab color space is determined by means of a spectrophotometer with the illuminant D 65 at 8° according to DIN EN ISO 11664-4 and the change in the b-value is obtained by subtracting the b-value before the temperature exposure from the b-value after the temperature exposure.It was surprisingly found that the aforementioned impregnation according to the invention reduces the yellowing of the thermoplastic polyurethane powder, even after exposure to heat. This yellowing can otherwise be very pronounced in thermoplastic polyurethane powders produced by solvent processes, particularly aliphatic thermoplastic polyurethane powders, due to the drying step (German Plastics Practice, 1946, p. 304). The b-value in the CIE Lab color space, as explained above, is used within the scope of the invention as a measure of the yellowing or the "whiteness" of the polyurethane powder. The CIE Lab color space consists of the L-value, the a-value, and the aforementioned b-value. "L" defines the lightness, "a" the red / green value, and "b" the yellow / blue value.To determine the b-value, a color measurement of the respective sample (approximately 3 mm powder layer between two coverslips for microscopy) is performed using a portable spectrophotometer (Konica Minolta CM5) with illuminant D 65 at 8° (observer angle) and diffuse illumination according to DIN EN ISO 11664-4. The powder's color is measured in reflectance and expressed in the CIE Lab color space using the L, a, and b values. The b-value is calculated from the measured spectral reflectance curve using the instrument's software.

[0112] Furthermore, the invention relates to a thermoplastic polyurethane powder obtained or obtainable according to the inventive method. As already explained above, these thermoplastic polyurethane powders have a high average molar mass in combination with a low allophane content. If they have also been additionally impregnated according to the invention, they also exhibit less yellowing after exposure to temperature, in particular after drying at 80°C or above.

[0113] Furthermore, the invention relates to the use of the thermoplastic polyurethane powder according to the invention in an extrusion process, injection molding process, powder sintering process, 2024PF30081-Abroad - 17 -

[0114] Solvent and / or melt processes, especially for the production of molded parts and / or coatings.

[0115] Furthermore, the invention relates to a molded part obtained or produced by processing the thermoplastic polyurethane powder according to the invention. Preferably, the molded part is free of gel particles. The gel particles are detected by a so-called gel determination. In this process, the thermoplastic polyurethane powder is injection-molded into a standard rod (dimensions 80 mm x 10 mm x 4 mm). The rod is placed with its flat side on a light table. The gel particles are visible to the naked eye in transmitted light as bright spots in the otherwise homogeneous sample. In addition, the circular depressions on the smooth surface of the specimens, which are created by gel particles near the surface, are counted. To account for minor injection molding defects, the sample is considered free of gel particles if the total number of counted gel particles (X) is less than 5, slightly contaminated if 5 < X < 15, highly contaminated if 15 < X < 30, and very highly contaminated if X > 30.

[0116] Types of embodiment:

[0117] The invention relates in particular to the following embodiments:

[0118] According to a first embodiment, the invention relates to a process for producing a thermoplastic polyurethane powder by means of precipitation polymerization, comprising the steps: i. Provision

[0119] A) a solvent mixture comprising at least one first aprotic solvent Al) with a relative permittivity s r from 2 to 20, measured at 20 °C and 100 kHz, and at least one second aprotic polar solvent A2) selected from the group comprising or consisting of 1,2-propylene carbonate, gamma-butyrolactone and / or ethylene carbonate;

[0120] B) at least one polyol with a molar mass between 60 g / mol and 250 g / mol;

[0121] C) at least one diisocyanate;

[0122] D) optionally a catalyst;

[0123] E) optionally a ketene regulator El) and / or an additive E2); ii. Reaction of the polyol B) with the diisocyanate C) in the solvent mixture A) at a temperature of not more than 150 °C, optionally in the presence of the catalyst D), the ketene regulator El) and / or the additive E2), to the 2024PF30081-Foreign - 18 - thermoplastic polyurethane, wherein the thermoplastic polyurethane precipitates as a solid in the solvent mixture A) and forms a dispersion; iii. Separation from the solvent mixture A) and optional washing of the thermoplastic polyurethane with a solvent; and iv. Drying of the thermoplastic polyurethane to the thermoplastic polyurethane powder; wherein the thermoplastic polyurethane powder

[0124] • a mass average with a molar mass Mw of > 35000 g / mol;

[0125] • an allophanate content of < 0.25 mol-%, based on the total thermoplastic polyurethane powder; and

[0126] • > 25.0 wt.% of a particle fraction of < 0.500 mm, based on the total thermoplastic polyurethane powder and / or a ratio of centrifugal medium of molar mass Mz to mass mean of molar mass Mw of < 4.0; wherein the mass mean of molar mass Mw, the allophane content, the particle fraction and the centrifugal medium of molar mass Mz are each determined by the methods set out in this description.

[0127] According to a second embodiment, the invention relates to a process according to the first embodiment, characterized in that the first aprotic solvent (Al) comprises or consists of halogenated aromatics, ketones, ethers, esters and carbonates or mixtures thereof, in particular chlorobenzene and / or ortho-dichlorobenzene; cyclopentanone, cyclohexanone; heptan-4-one; benzene; toluene; ethylbenzene; cumene; xylene; acetophenone or mixtures thereof, preferably chlorobenzene.

[0128] According to a third embodiment, the invention relates to a method according to the first or second embodiment, characterized in that the ratio of the first aprotic solvent Al) to the second aprotic polar solvent A2) is 300:1 to 1:9, preferably 200:1 to 1:1, more preferably 100:1 to 8:2.

[0129] According to a fourth embodiment, the invention relates to a process according to one of the preceding embodiments, characterized in that the polyol B) comprises or consists of ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, 1,12-dodecanediol, or mixtures thereof, wherein the polyol B) preferably contains at least 50.0 wt.% 1,4-butanediol, particularly preferably at least 90.0 wt.% 1,4-butanediol, based on the total weight of the polyol B) and / or the diisocyanate C) 1,4-butane diisocyanate, 1,5-pentane diisocyanate, 1,6-hexane diisocyanate, 2024PF30081-Abroad - 19 -

[0130] Isophorone diisocyanate, 1, l'-methylenebis(4-isocyanatocyclohexane), xylylene diisocyanate, in particular m-xylylene diisocyanate or mixtures thereof, wherein the diisocyanate C) preferably contains at least 50.0 wt% 1,5-pentane diisocyanate or 1,6-hexane diisocyanate, based on the total weight of the diisocyanate C).

[0131] According to a fifth embodiment, the invention relates to a process according to one of the preceding embodiments, characterized in that the reaction in step ii. takes place at a temperature of 50 °C to 150 °C, preferably from 100 °C to 145 °C, more preferably from 120 °C to 140 °C and / or at an isocyanate number of 0.95 to 1.1, preferably 0.97 to 1.02, more preferably 0.98 to 1.0.

[0132] According to a sixth embodiment, the invention relates to a method according to one of the preceding embodiments, characterized in that the dispersion formed in step ii. has a solids content of 5.0 to 50.0 wt.%, preferably 15.0 to 45.0 wt.%, more preferably 20.0 to 40.0 wt.%, determined by gravimetric measurement with and without solvent.

[0133] According to a seventh embodiment, the invention relates to a method according to one of the preceding embodiments, characterized in that

[0134] • a mass medium with a molar mass Mw of 40000 to 300000 g / mol, preferably of 50000 to 250000 g / mol, particularly preferably of 60000 to 200000 g / mol;

[0135] • an allophane content of 0 to 0.20 mol%, preferably of 0.001 to 0.15 mol%, particularly preferably of 0.01 to 0.10 mol%, based on the total thermoplastic polyurethane powder; and / or

[0136] • of 30.0 to 100.0 wt.%, more preferably of 40.0 to 90.0 wt.% of a particle fraction of < 0.500 mm, based on the total thermoplastic polyurethane powder and / or a ratio of centrifugal mass Mz to mass Mw of < 3.0, preferably of 1.5 to 2.85; has.

[0137] According to an eighth embodiment, the invention relates to a method according to one of the preceding embodiments, characterized in that the thermoplastic polyurethane according to step iii. and / or the thermoplastic polyurethane powder according to step iv. is impregnated with a stabilizer from a stabilizer solution, wherein for this purpose the thermoplastic polyurethane according to step iii. and / or the thermoplastic polyurethane powder according to step iv. is dispersed in the stabilizer solution and subsequently separated and dried.

[0138] According to a ninth embodiment, the invention relates to a method according to the eighth embodiment, characterized in that the stabilizer solution 2024PF30081-Abroad - 20 -

[0139] • a solvent selected from the group comprising or consisting of solvents from the group consisting of chlorinated aromatics; aromatics; aliphatics; esters; ethers; alcohols; water; ketones; nitriles; carbonates; or mixtures thereof, or preferably the solvent(s) (Al) from step i., wherein the solvent(s) preferably have a boiling point of < 250 °C at 1 bar; and

[0140] • a stabilizer dissolved therein, selected from the group comprising or consisting of sterically hindered phenol derivatives, organic phosphine, phosphite and / or phosphonate derivatives, sulfur-containing antioxidants, 2,2,6,6-tetramethylpiperidine derivatives, benzotriazole derivatives, triazine derivatives, hydroxybenzophenone derivatives, cyanoacrylate derivatives, oxalinide derivatives or mixtures thereof; comprising or consisting of, wherein the weight fraction of the stabilizer is preferably from 0.001 to 10.0 wt.%, more preferably from 0.05 to 5.0 wt.%, based on the total weight of the stabilizer solution.

[0141] According to a tenth embodiment, the invention relates to a method according to the eighth or ninth embodiment, characterized in that the thermoplastic polyurethane powder contains 0.005 to 2.0 wt.% of the stabilizer from the stabilizer solution, based on the total weight of the thermoplastic polyurethane powder.

[0142] According to an eleventh embodiment, the invention relates to a method according to one of the preceding embodiments, characterized in that

[0143] • 30.0 to 95.0 parts by weight, preferably 60.0 to 90.0 parts by weight of solvent mixture A);

[0144] • 2.0 to 40.0 parts by weight, preferably 3.0 to 20.0 parts by weight of polyol B);

[0145] • 3.0 to 40.0 parts by weight, preferably 5.0 to 25.0 parts by weight of diisocyanate C);

[0146] • 0 to 5.0 parts by weight, preferably 0 to 0.1 parts by weight of catalyst D);

[0147] • 0 to 10.0 parts by weight, preferably 0.001 to 1.5 parts by weight of the ketene regulator El);

[0148] • 0 to 20.0 parts by weight, preferably 0.0001 to 3.0 parts by weight of additive E2); are provided, each based on the total amount of solvent mixture A), polyol B), diisocyanate C), catalyst D), ketene regulator El) and additive E2), which is normalized to 100 parts by weight.

[0149] According to a twelfth embodiment, the invention relates to a thermoplastic polyurethane powder obtained or obtainable by a method according to one of embodiments 1 to 11.

[0150] According to a thirteenth embodiment, the invention relates to the use of a thermoplastic polyurethane powder according to embodiment 12 in an extrusion process, 2024PF30081-Abroad - 21 -

[0151] Injection molding processes, powder sintering processes, solvent and / or melt processes, especially for the production of molded parts and / or coatings.

[0152] According to a fourteenth embodiment, the invention relates to a molded part obtained or obtainable by processing a thermoplastic polyurethane powder according to embodiment 12. According to a fifteenth embodiment, the invention relates to a molded part according to the fourteenth embodiment, characterized in that the molded part is free of gel particles, wherein "free of gel particles" is defined and determined as set out in this description.

[0153] 2024PF30081-Abroad - 22 -

[0154] The present invention will be explained in more detail with reference to the following examples.

[0155] Measurement methods:

[0156] The following measurement methods were used:

[0157] GPC method for determining number mean of molar mass Mn, mass mean of molar mass Mw and centrifuge mean of molar mass Mz:

[0158] Determination by gel permeation chromatography (GPC). For this purpose, the sample to be measured was dissolved in a solution of 3 g potassium trifluoroacetate in 400 cubic centimeters of hexafluoroisopropanol (sample concentration approx. 2 mg / cubic centimeter). The respective GPCs were measured with the following components at a flow rate of 1 cubic centimeter / minute:

[0159] Pump: HPLC pump 515 (Waters GmbH);

[0160] Detector: Smartline RI detector 2300 (Knauer Wissenschaftliche Geräte GmbH);

[0161] Columns: 1 guard column, 1000 Ä PSS PFG 7pm, 300 Ä PSS PFG 7pm, 100 Ä PSS; PFG

[0162] 7pm in this order (PSS Polymer Standards Service GmbH);

[0163] Degassing: Degasser PSS (PSS Polymer Standards Service GmbH);

[0164] Injection volume: 100 microliters;

[0165] Temperature: 23 °C - 25 °C;

[0166] Molar mass standard: Polymethyl methacrylate standard kit (PSS Polymer Standards Service GmbH).

[0167] The number-mean molar mass (M n ) was calculated from the data obtained by measuring gel permeation chromatography using the following equation: where:

[0168] M is the molar mass of the polymers of fraction i, such that M < M i+1 for all i, in g / mol, ni is the amount of substance of the polymer of fraction i, in mol.

[0169] The mass average of the molar mass (M w ) was also calculated from the data obtained by measuring gel permeation chromatography using the following equation: where:

[0170] M is the molar mass of the polymers of fraction i, such that M < M i+1 For all i, in g / mol, ni is the amount of substance of the polymer of fraction i, in mol. 2024PF30081-Abroad - 23 -

[0171] The centrifuge reagent of the molar mass (M z ) was calculated from the data obtained by measuring gel permeation chromatography using the following equation: ,n g / mo1 where:

[0172] M is the molar mass of the polymers of fraction i, such that M < M i+1 for all i, in g / mol, ni is the amount of substance of the polymer of fraction j, in mol.

[0173] Allophane content:

[0174] The allophanate content was determined using ¹H NMR. The measurements were performed with a Bruker

[0175] AV III HD 600 spectrometer at 600 MHz in DMSO-D6 at 80 °C.

[0176] The following peaks were evaluated:

[0177] U=CH2-NH 2.98 ppm CH2for urethane

[0178] O=CH2-OH 3.43 ppm CH2 at OH groups

[0179] N=NH 6.6 ppm urethane

[0180] A = NH 8.3 - 8.4 ppm allophanate

[0181] The aliphatic allophanate concentration in mol% was calculated using the following formula:

[0182] Allophanate [mol%] = 100% * A / (A+N)

[0183] The key figure for revenue is derived from the formula:

[0184] KZ = 1 / (1+O / U)

[0185] 2024PF30081-Abroad - 24 -

[0186] Production of test specimens for tensile tests

[0187] The polymer was dried at 80 °C in a drying oven for 4 h and then processed on a microextruder MC 15 HT (15 mL) from Xplore and brought into the required shape with the associated injection molding part Micro moulder IM 12.

[0188] Determination of the modulus of elasticity / tensile modulus and the elongation at break:

[0189] The tensile test was performed according to the test method DIN EN ISO 51 using specimen type 5A (DIN EN ISO 527-2, 2 mm thick). The specimens were stored under standard conditions for at least 24 hours prior to the test. The tensile tests were carried out at 22 °C and 50% relative humidity using a Zwick Z010 universal testing machine at a speed of 10 mm / min. The modulus of elasticity (tensile modulus) was determined between 0.05% and 0.25% elongation using a secant.

[0190] Isocyanate titration:

[0191] By back titration of n-butylamine with 0.1 N hydrochloric acid after addition of an excess of amine to an isocyanate solution using a Metrohm, 751 GPD titrino 685 Dosimat and 728 stirrer.

[0192] Gel determination:

[0193] The respective polymer powder was injection-molded into a standard rod (dimensions 80 mm x 10 mm x 4 mm). The rod was placed flat-side down on a light table. The gel particles were visible to the naked eye as bright spots in the otherwise homogeneous sample when illuminated with transmitted light. Additionally, the circular depressions on the smooth surface of the specimens, caused by gel particles near the surface, were counted. To account for minor injection molding defects, a sample with a total number of gel particles counted (X < 5) was considered free of gels, a sample with a total of 5 < X < 15 was considered slightly contaminated, a sample with a total of 15 < X < 30 was considered highly contaminated, and a sample with a total of X > 30 was considered very highly contaminated.

[0194] Sieving:

[0195] 100 g of sample was sieved for 5 min using a Haver & Boecker laboratory sieve machine No. 7279 (built in 1978) and the corresponding sieve sets (0.100 mm, 0.250 mm and 0.500 mm) and the individual fractions were then weighed.

[0196] Materials:

[0197] The following materials were used for components A) to E): 2024PF30081-Abroad - 25 -

[0198] First aprotic solvent (Al):

[0199] • Chlorobenzene of analytical grade, sourced from Azelis Deutschland GmbH, relative permittivity: 8 r = 5.6 (see Literature 1.) below)

[0200] • o-Dichlorobenzene (oDCB) 99%, sourced from Acros Organics, relative permittivity: 8 r = 9.9 (see literature 1.) below)

[0201] Second aprotic polar solvent A2):

[0202] • 1,2-Propylene carbonate 99%, sourced from Merck, relative permittivity: s r = 65 (see literature 2.) below)

[0203] • Gamma-butyrolactone > 99%, sourced from TCI, relative permittivity: s r = 42.3 (see literature 3.) below)

[0204] • Ethylene carbonate > 98%, sourced from Sigma-Aldrich, relative permittivity: s r = 90 (see literature 4.) below)

[0205] References: 1.) DK Handbook, Endress+Hauser Messtechnik GmbH&Co. (1999); 2.) Barthel et al J. Chem. Eng. Data 2000, 45, 6, 1007-1011; 3.) MouMouzias et al J. Chem. Eng. Data 1999, 44, 6, 1273-1278; 4.) Stich, Michael Dissertation 2018, page 12, Technical University of Ilmenau.

[0206] Polyol B):

[0207] • 1,4-Butanediol (BDO) (Company: Ashland), Purity: > 99% wt.%.

[0208] Diisocyanate C):

[0209] • 1,6-Hexamethylene diisocyanate (HDI) (Company: Covestro AG), purity: > 99% wt.%.

[0210] Chain regulator El):

[0211] • n-Octanol of analytical grade, sourced from Arcos Organics, purity: > 99% wt.%;

[0212] Additive E2):

[0213] Irganox™ 245 from BASF

[0214] Irgafos™ 168 from BASF 2024PF30081-Abroad - 26 -

[0215] Experimental procedure and results:

[0216] Experiment 1: HDI and BDO in chlorobenzene (solvent Al) and various solvents

[0217] A2 (hereinafter also referred to as co-solvent)

[0218] 1200 mL of a mixture of chlorobenzene and co-solvent (10:1), 100.9 g (1.12 mol) of BDO, 1.43 g (11 mmol) of n-octanol, and 94.9 g (0.565 mol) of HDI were placed in a 2 L reaction vessel equipped with a thermometer, reflux condenser, and mechanical stirrer at 20 °C. The mixture was slowly heated on an oil bath until reflux occurred, and another 94.9 g (0.565 mol) of HDI was added via a dropping funnel while stirring until the mixture refluxed gently. After the addition was complete, the mixture was heated at reflux for a further 5 hours. The polymer precipitated as a white powder. The mixture was cooled to 20 °C and filtered (Nutsche), and the residue was washed twice with 150 mL of chlorobenzene and twice with 150 mL of acetone. The powders from experiments Id, le, and If were additionally washed as a final step with a solution of 1.0 g Irganox 245 and 1.0 g Irgafos 168 in 150 mL of chlorobenzene.The white solid was first dried in air and then under vacuum at 120 °C until constant weight was achieved. No allophane (< 0.1 mol%) was found in the NMR spectrum of the inventive examples Id, le, and If, as well as reference example 1c. The inventive spray bodies showed no gel particles. Subsequently, the product was separated into four particle fractions by vibratory sieving with sieve inserts of 0.100 mm, 0.250 mm, and 0.500 mm. The results are summarized in Table 1.

[0219] Table 1 2024PF30081-Abroad - 27 -

[0220] The patent replication experiments 1a) (DE728981C) and 1b) (German Plastics Practice 1947, 289) using chlorobenzene or a mixture of chlorobenzene / o-dichlorobenzene yielded thermoplastic polyurethanes that did not reach the necessary molar mass Mw > 35000 g / mol to exhibit practically usable mechanical properties of the polymer. Molded parts made from these materials were very brittle. This was confirmed by testing their fracture behavior (experiments 1a and 1b).

[0221] The use of a solvent mixture of chlorobenzene and DMSO (reference example 1c) did indeed lead to an increase in the molar mass Mw to > 35000 g / mol and an improvement in the mechanical properties of the molded parts made from the resulting thermoplastic polyurethane powder. However, it was found that an intense, unpleasant odor was detectable during the synthesis of the thermoplastic polyurethane powder and during its isolation and processing. This odor was also present in the resulting thermoplastic polyurethane powder and the polymer granules obtained from it by extrusion.

[0222] In contrast, experiments Id, le, and If according to the invention, using chlorobenzene and 1,2-propylene carbonate, gamma-butyrolactone, or ethylene carbonate as co-solvents, also yielded higher molar masses (> 35,000 g / mol) – in some cases significantly higher molar masses than reference example 1c – with simultaneously low allophane content, a particle fraction with a particle size < 0.500 mm of > 25 wt.%, and a ratio of centrifuge medium of molar mass Mz to mass medium of molar mass Mw of < 4.0. Furthermore, the molded bodies obtained or recovered from the thermoplastic polyurethane powders according to the invention also exhibited significantly better mechanical properties than the non-inventive examples. [2024PF30081-Abroad - 28 -]

[0223] In contrast to the reference example, no unpleasant odor was produced during synthesis, isolation, processing, and extrusion. The resulting powder and granules were also largely odorless.

[0224] The powders of experiments Id, le and If treated with the additives Irganox 245 and Irgafos 168 showed no visible yellowing after drying, while the untreated powders of experiments la, 1b and 1c showed clear yellowing.

[0225] Experiments 2 (not according to the invention):

[0226] In the following experiments 2a and 2b (not according to the invention), the precipitation polymerization is investigated only in the solvent propylene carbonate or > -butyrolactone.

[0227] Experiment 2a: HDI+BDO in 1,2-propylene carbonate

[0228] 1000 mL of propylene carbonate, 178.2 g (1.98 mol) of BDO, 2.60 g (20 mmol) of n-octanol, and 168.0 g (1.00 mol) of HDI were placed in a 2 L reaction vessel equipped with a thermometer, reflux condenser, and mechanical stirrer at 20 °C, and the mixture was heated to 135 °C in an oil bath. An additional 168.0 g (1.00 mol) of HDI was added dropwise using a dropping funnel while stirring, ensuring that the internal temperature of the mixture did not exceed 135 °C. After the addition was complete, the mixture was heated for a further 5 hours at 135 °C, during which time the polymer began to precipitate. The reaction mixture was cooled, the solid was filtered off (using a Büchner funnel), and the residue was washed three times with 250 mL of propylene carbonate. The filter cake was subsequently dried under vacuum at 120 °C. The yield was 480 g (92%) as a large, white lump. Sieving revealed a fines fraction with a particle size < 0.500 mm of less than 5 wt%. The NMR spectrum showed 0.2 mol% allophanate.The GPC yielded Mw: 85606 g / mol; Mn: 17210 g / mol; Mz: 189611 g / mol.

[0229] Experiment 2b: HDI+BDO in γ-Butyrolactone

[0230] 1000 mL of gamma-butyrolactone, 178.2 g (1.98 mol) of BDO, 2.60 g (20 mmol) of n-octanol, and 168.0 g (1.00 mol) of HDI were placed in a 2 L reaction vessel equipped with a thermometer, reflux condenser, and mechanical stirrer at 20 °C. The mixture was then heated to 135 °C on an oil bath. A further 168.0 g (1.00 mol) of HDI was then added rapidly using a dropping funnel while stirring, maintaining a temperature of approximately 135 °C. After the addition was complete, the mixture was heated to 135 °C for another 5 hours. The mixture was cooled, and the polymer precipitated as a large clump adhering to the stirrer. A small portion of the polymer clump was separated, washed with acetone, and dried for GPC and NMR analysis. 2024PF30081-Abroad - 29 -

[0231] The NMR spectrum revealed 0.1 mol% allophanate. GPC yielded Mw: 137707 g / mol; Mn: 23203 g / mol; Mz: 295338 g / mol. Sieving, and thus determination of the particle size, was not possible. Experiments 2a and 2b, which are not in accordance with the invention, show that the use of the second aprotic polar solvent A2) as the sole solvent is also insufficient to obtain the thermoplastic polyurethane powders according to the invention. The use of both 1,2-propylene carbonate (experiment 2a) and μ-butyrolactone (experiment 2b) resulted in a polymer clump, not a powder. Therefore, the particle fraction was either undeterminable or the particle fraction with a particle size < 0.500 mm was significantly less than 25 wt%.

[0232] This shows that it is precisely the solvent mixture according to the invention that leads to a thermoplastic polyurethane powder with higher molar masses (> 35000 g / mol) and simultaneously low allophane content, a particle fraction with a particle size < 0.500 mm of > 25 wt.% and a ratio of centrifugal medium of molar mass Mz to mass medium of molar mass Mw of < 4.0 as well as molded bodies obtainable or obtained therefrom with improved mechanical properties.

Claims

2024PF30081-Abroad - 30 - Patent claims 1. Method for producing a thermoplastic polyurethane powder by precipitation polymerization, comprising the steps of: i. Provision A) a solvent mixture comprising at least one first aprotic solvent Al) with a relative permittivity s r from 2 to 20, measured at 20 °C and 100 kHz, and at least one second aprotic polar solvent A2) selected from the group comprising or consisting of 1,2-propylene carbonate, gamma-butyrolactone and / or ethylene carbonate; B) at least one polyol with a molar mass between 60 g / mol and 250 g / mol; C) at least one diisocyanate; D) optionally a catalyst; E) optionally a chain regulator El) and / or an additive E2); ii. Reaction of the polyol B) with the diisocyanate C) in the solvent mixture A) at a temperature of not more than 150 °C, optionally in the presence of the catalyst D), the chain regulator El) and / or the additive E2), to the thermoplastic polyurethane, wherein the thermoplastic polyurethane precipitates as a solid in the solvent mixture A) and forms a dispersion; iii. Separation from the solvent mixture A) and optional washing of the thermoplastic polyurethane with a solvent; and iv. Drying of the thermoplastic polyurethane to the thermoplastic polyurethane powder; wherein the thermoplastic polyurethane powder • a mass average with a molar mass Mw of > 35000 g / mol; • an allophanate content of < 0.25 mol-%, based on the total thermoplastic polyurethane powder; and • > 25.0 wt.% of a particle fraction of < 0.500 mm, based on the total thermoplastic polyurethane powder and / or a ratio of centrifugal medium of molar mass Mz to mass mean of molar mass Mw of < 4.0; wherein the mass mean of molar mass Mw, the allophane content, the particle fraction and the centrifugal medium of molar mass Mz are each determined using the methods set out in the description. 2024PF30081-Abroad - 31 - 2. The method according to claim 1, characterized in that the first aprotic solvent (Al) comprises or consists of halogenated aromatics, ketones, ethers, esters and carbonates or mixtures thereof, in particular chlorobenzene and / or ortho-dichlorobenzene; cyclopentanone, cyclohexanone; heptan-4-one; benzene; toluene; ethylbenzene; cumene; xylene; acetophenone or mixtures thereof, preferably chlorobenzene.

3. Method according to claim 1 or 2, characterized in that the ratio of the first aprotic solvent Al) to the second aprotic polar solvent A2) is 300:1 to 1:9, preferably 200:1 to 1:1, more preferably 100:1 to 8:

2.

4. A method according to any one of the preceding claims, characterized in that the polyol B) comprises or consists of ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, 1,12-dodecanediol, or mixtures thereof, wherein the polyol B) preferably contains at least 50.0 wt.% 1,4-butanediol, particularly preferably at least 90.0 wt.% 1,4-butanediol, based on the total weight of the polyol B) and / or the diisocyanate C) comprises 1,4-butane diisocyanate, 1,5-pentane diisocyanate, 1,6-hexane diisocyanate, isophorone diisocyanate, 1,1'-methylenebis(4-isocyanatocyclohexane), xylylene diisocyanate, in particular m-xylylene diisocyanate. or mixtures thereof, wherein the diisocyanate C) preferably contains at least 50.0 wt% 1,5-pentane diisocyanate or 1,6-hexane diisocyanate, based on the total weight of the diisocyanate C).

5. Method according to one of the preceding claims, characterized in that the reaction in step ii. takes place at a temperature of 50 °C to 150 °C, preferably from 100 °C to 145 °C, more preferably from 120 °C to 140 °C and / or at an isocyanate number of 0.95 to 1.1, preferably 0.97 to 1.02, more preferably 0.98 to 1.

0.

6. Method according to one of the preceding claims, characterized in that the dispersion formed in step ii. has a solids content of 5.0 to 50.0 wt.%, preferably 15.0 to 45.0 wt.%, more preferably 20.0 to 40.0 wt.%, determined by gravimetric measurement with and without solvent.

7. Method according to one of the preceding claims, characterized in that the thermoplastic polyurethane powder is a bulk material with a molar mass Mw of 40000 to 300000 g / mol, preferably of 50000 to 250000 g / mol, particularly preferably of 60000 to 200000 g / mol; 2024PF30081-Abroad - 32 - • an allophane content of 0 to 0.20 mol%, preferably of 0.001 to 0.15 mol%, particularly preferably of 0.01 to 0.10 mol%, based on the total thermoplastic polyurethane powder; and / or • of 30.0 to 100.0 wt.%, more preferably of 40.0 to 90.0 wt.% of a particle fraction of < 0.500 mm, based on the total thermoplastic polyurethane powder and / or a ratio of centrifuge medium of molar mass Mz to mass medium of molar mass Mw of < 3.0, preferably of 1.5 to 2.85; has.

8. Method according to one of the preceding claims, characterized in that the thermoplastic polyurethane according to step iii. and / or the thermoplastic polyurethane powder according to step iv. is impregnated with a stabilizer from a stabilizer solution, wherein for this purpose the thermoplastic polyurethane according to step iii. and / or the thermoplastic polyurethane powder according to step iv. is dispersed in the stabilizer solution and subsequently separated and dried.

9. Method according to claim 8, characterized in that the stabilizer solution • a solvent selected from the group comprising or consisting of solvents from the group consisting of chlorinated aromatics; aromatics; aliphatics; esters; ethers; alcohols; water; ketones; nitriles; carbonates; or mixtures thereof, or preferably the solvent(s) (Al) from step i., wherein the solvent(s) preferably have a boiling point of < 250 °C at 1 bar; and • a stabilizer dissolved therein, selected from the group comprising or consisting of sterically hindered phenol derivatives, organic phosphine, phosphite and / or phosphonate derivatives, sulfur-containing antioxidants, 2,2,6,6-tetramethylpiperidine derivatives, benzotriazole derivatives, triazine derivatives, hydroxybenzophenone derivatives, cyanoacrylate derivatives, oxalinide derivatives or mixtures thereof; comprising or consisting of, wherein the weight fraction of the stabilizer is preferably from 0.001 to 10.0 wt.%, more preferably from 0.05 to 5.0 wt.%, based on the total weight of the stabilizer solution.

10. Method according to claim 8 or 9, characterized in that the thermoplastic polyurethane powder contains 0.005 to 2.0 wt.% of the stabilizer from the stabilizer solution, based on the total weight of the thermoplastic polyurethane powder. 2024PF30081-Abroad - 33 - 1.

1. Method according to one of the preceding claims, characterized in that • 30.0 to 95.0 parts by weight, preferably 60.0 to 90.0 parts by weight of solvent mixture A); • 2.0 to 40.0 parts by weight, preferably 3.0 to 20.0 parts by weight of polyol B); • 3.0 to 40.0 parts by weight, preferably 5.0 to 25.0 parts by weight of diisocyanate C); • 0 to 5.0 parts by weight, preferably 0 to 0.1 parts by weight of catalyst D); • 0 to 10.0 parts by weight, preferably 0.001 to 1.5 parts by weight of the chain regulator El); • 0 to 20.0 parts by weight, preferably 0.0001 to 3.0 parts by weight of additive E2); are provided, each based on the total amount of solvent mixture A), polyol B), diisocyanate C), catalyst D), chain regulator El) and additive E2), which is normalized to 100 parts by weight.

12. Thermoplastic polyurethane powder, obtained or obtainable by a process according to any one of claims 1 to 11.

13. Use of a thermoplastic polyurethane powder according to claim 12 in an extrusion process, injection molding process, powder sintering process, solvent and / or melt process, in particular for the production of molded parts and / or coatings.

14. Molded part obtained or obtainable by processing a thermoplastic polyurethane powder according to claim 12.

15. Molded part according to claim 14, characterized in that the molded part is free of gel particles, wherein "free of gel particles" is defined and determined as set out in the description.

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