Flame retardant thermoplastic polyurethanes (TPUs) based on polypropanediol

Abstract

The present invention relates to a composition comprising a thermoplastic polyurethane that is the reaction product of the components diisocyanate, polypropanediol, and a chain extender, and further comprising a phosphorus-containing flame retardant.

Description

[Technical field]

[0001] The present invention relates to flame retardant thermoplastic polyurethanes based on polypropanediol.

[0002] 2. Description of Related Art Flame retardant thermoplastic polyurethanes are known and described in various disclosures, see, for example, EP 0617079 B2, WO 2020 / 002200, EP 00401675.

[0003] On the other hand, there is a continuing demand in the industry to improve the flame retardancy of the thermoplastic polyurethanes while at the same time maintaining high levels of chemical properties, such as aging and hydrolysis resistance, and mechanical properties.

[0004] For the flame retardancy, various standard measurement methods have been established, for example as DIN EN 13501-1 for the classification of construction products or as DIN EN 45545 for railway applications.

[0005] However, for many other fire tests that do not explicitly measure heat release, it is of great advantage if the material does not release much heat in the event of a fire.

[0006] Often the capability of a material for a particular application is bound by specific properties, especially mechanical resistance, but also hydrolytic stability, aging stability, UV stability, resistance to particular chemicals or oils, temperature range, or processability.

[0007] Summary of the Invention assignment The problem to be solved was to develop new thermoplastic polyurethanes which exhibit a low heat release and have good mechanical properties as well as resistance to aging and hydrolysis.

[0008] solution It has surprisingly been found that flame retardant thermoplastic polyurethane compositions having thermoplastic polyurethanes based on 1,3-polypropanediol (PO3G) polyols have a particularly lower heat release value compared to other polyether polyols.

[0009] At the same time, these PO3G polyol-based polyurethane materials generally exhibit good mechanical properties, aging and hydrolysis resistance, and good flame retardancy.

[0010] Detailed Description of the Invention In embodiment 1, the present invention relates to a thermoplastic polyurethane composition, the thermoplastic polyurethane comprising at least the following components: a) Diisocyanate b) Polypropanediol c) Chain extender and said composition further comprises a flame retardant, preferably said flame retardant comprises phosphorus.

[0011] Thermoplastic Polyurethane The term composition indicates that the composition does not only comprise the thermoplastic polyurethane, but may also comprise several polymers, additives and / or auxiliaries.

[0012] In a preferred embodiment 2, the thermoplastic polyurethane of the thermoplastic polyurethane composition of embodiment 1 is prepared by dissolving an organic isocyanate, preferably a diisocyanate, in a polypropanediol, preferably 0.5×10 3 g / mol~100×10 3 Polypropanediol having a number average molecular weight of 0.05×10 g / mol and a chain extender, preferably 3 g / mol~0.499×10 3 The copolymer is prepared by reacting the copolymer with a chain extender having a molecular weight of 100 g / mol, optionally in the presence of catalysts, auxiliaries and additives, or mixtures thereof.

[0013] The components organic isocyanate, preferably diisocyanate, the polypropanediol and the chain extender, individually or together, are also referred to as components. The components, including the catalyst and / or the auxiliary and / or the additive, are also referred to as feed materials.

[0014] To adjust the hardness and melt index of the thermoplastic polyurethane (TPU), the molar ratio of the amount of the components and the chain extender can be varied, so that the hardness and melt viscosity increase with increasing isocyanate content or with increasing isocyanate and chain extender content, while the melt flow index decreases.

[0015] In a preferred embodiment 3 according to any of the above embodiments or one of their preferred embodiments, the thermoplastic polyurethane composition has a Shore A hardness of less than 95, preferably between 75 and 95.

[0016] In a preferred embodiment 4 according to any of the above embodiments or one of their preferred embodiments, to prepare the thermoplastic polyurethane, the constituents isocyanate, polypropanediol and said chain extender are reacted in the presence of a catalyst and, optionally, auxiliaries and / or additives, in such an amount that the equivalent ratio of the NCO groups of the isocyanate, preferably of the diisocyanate, to the sum of the hydroxyl groups of the polypropanediol and of the chain extender is 0.95-1.10:1, preferably 0.98-1.08:1 and in particular about 1.0-1.05:1. In a highly preferred embodiment, said equivalent ratio is 1.0:1.0.

[0017] In preferred embodiment 5 according to any of the above embodiments or one of their preferred embodiments, the thermoplastic polyurethane has a molecular weight of at least 0.04×10 6 g / mol, more preferably at least 0.06×10 6 g / mol, more preferably at least 0.07×10 6 g / mol, and more preferably at least 0.08×106 The upper limit for the weight average molecular weight of the thermoplastic polyurethane (TPU) is generally determined by its processability and the desired range of properties. Preferably, the weight average molecular weight of the thermoplastic polyurethane is 0.5×10 6 g / mol, more preferably 0.4×10 6 g / mol, more preferably 0.25×10 6 g / mol, and more preferably 0.2×10 6 The average molecular weight and weight average molecular weight as outlined herein are determined by gel permeation chromatography, preferably according to DIN 55672-1, where dimethylformamide (DMF) is used as the solvent.

[0018] Isocyanates In a preferred embodiment 6 according to any of the previous embodiments or one of their preferred embodiments, the isocyanate is an organic isocyanate, more preferably an organic diisocyanate, and even more preferably the isocyanate is selected from the group consisting of aliphatic, cycloaliphatic, araliphatic and aromatic isocyanates, or a mixture thereof.

[0019] In a preferred embodiment, the isocyanate is selected from the group consisting of tri-, tetra-, penta-, hexa-, hepta- and / or octa-methylene diisocyanate, 2-methyl-1,5-pentamethylene diisocyanate, 2-ethyl-1,4-butylene diisocyanate, 1,5-pentamethylene diisocyanate (PDI), 1,4-butylene diisocyanate, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl-cyclohexane (isophorone diisocyanate, IPDI), 1,4-bis(isocyanatomethyl)cyclohexane and / or 1,3-bis(isocyanatomethyl)cyclohexane (HXDI), 2,4-paraphenylene diisocyanate (PPDI), 2,4-tetramethylene xylene diisocyanate, isocyanate (TMXDI), 4,4'-, 2,4'- and 2,2'-dicyclohexylmethane diisocyanate (H12MDI), 1,6-hexamethylene diisocyanate (HDI), 1,4-cyclohexane diisocyanate, 1-methyl-2,4- and / or -2,6-cyclohexane diisocyanate, 2,2'-, 2,4'- and / or 4,4'-diphenylmethane diisocyanate (MDI), 1,5-naphthylene diisocyanate (NDI), 2,4- and / or 2,6-toluene diisocyanate (TDI), 3,3'-dimethyldiphenyl diisocyanate, 1,2-diphenylethane diisocyanate and / or phenylene diisocyanate or mixtures thereof. Aliphatic isocyanates are preferred when the stability against electromagnetic waves, e.g. light, is important, whereas aromatic polyisocyanates are preferred when the high mechanical strength of the polyurethane, especially the thermoplastic polyurethane, is required.Another advantage of aliphatic isocyanates is that they can be produced on a bio-based basis.

[0020] A highly preferred aliphatic isocyanate is 1,5-pentamethylene diisocyanate, which has the added advantage that it can be produced on a biobased basis.

[0021] Highly preferred aromatic isocyanates are 2,2'-, 2,4'-, or 4,4'-diphenylmethane diisocyanate (MDI) or mixtures thereof, and especially preferred is 4,4'-diphenylmethane diisocyanate.

[0022] Polyol In a preferred embodiment 7 according to any of the above embodiments or one of their preferred embodiments, the polypropanediol is 1,3-polypropanediol. The number average molecular weight of the polypropanediol, preferably the poly-1,3-propanediol, is preferably 0.5×10 3 g / mol~8×10 3 g / mol, more preferably 0.7×10 3 g / mol~4.0×10 3 g / mol, more preferably 0.8×10 3 g / mol~3.2×10 3 g / mol, more preferably 0.8×10 3 g / mol~2.2×10 3 g / mol, more preferably 0.8×10 3 g / mol~1.2×10 3 g / mol.

[0023] Said polypropanediol is a single compound or a mixture of different compounds, wherein said mixture meets the above requirements; preferably said polypropanediol is a single compound, more preferably poly 1,3-propanediol.

[0024] Chain extender Further, a chain extender is used as a component in the synthesis of the thermoplastic polyurethane. In a preferred embodiment 8 according to any of the above embodiments or one of their preferred embodiments, the chain extender is an aliphatic, araliphatic, aromatic or cycloaliphatic compound or a mixture thereof, preferably having a molecular weight of 0.05×10 3 g / mol~0.499×10 3The chain extender preferably has a molecular weight of 100 g / mol. The chain extender preferably has two groups reactive with isocyanates. These groups are also called functional groups. The chain extender is either a single chain extender or a mixture of at least two chain extenders.

[0025] The chain extender is preferably a difunctional compound, and preferred examples are diamines or alkanediols having 2 to 10 carbon atoms in the alkylene group, or mixtures thereof.

[0026] In a preferred embodiment 9 according to any of the above embodiments or one of their preferred embodiments, the chain extender is selected from the group consisting of 1,2-ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, diethylene glycol, di-, tri-, tetra-, penta-, hexa-, hepta-, octa-, nona- and / or deca-alkylene glycols, dipropylene glycol, 1,4-cyclohexanediol, 1,4-dimethanolcyclohexane, neopentyl glycol and hydroquinone bis(β-hydroxyethyl)ether (HQEE) or a mixture thereof.

[0027] In a preferred embodiment 10 according to any of the above embodiments or one of their preferred embodiments, the chain extender is selected from the group consisting of 1,2-ethylene glycol, 1,3-propanediol, 1,4-butanediol, and 1,6-hexanediol, di-, tri-, tetra-, penta-, hexa-, hepta-, octa-, nona- and / or deca-alkylene glycols, preferably the respective oligo- and polyalkylenes or polypropylene glycols, or mixtures thereof.

[0028] In a preferred embodiment 11 according to any of the above embodiments or one of their preferred embodiments, the chain extender is 1,2-ethylenediol, 1,3-propanediol, 1,4-butanediol or 1,6-hexanediol, more preferably 1,3-propanediol or 1,4-butanediol, or a mixture thereof.

[0029] In one highly preferred embodiment 12 according to any of the above embodiments or one of the preferred embodiments thereof, the chain extender is 1,4-butanediol.

[0030] catalyst In particular, a catalyst (d) that promotes the reaction between the NCO groups of the isocyanate (a) and the hydroxyl groups of the polyol and the chain extender is used in a preferred embodiment.

[0031] In a preferred embodiment 13 according to any of the previous embodiments or one of the preferred embodiments thereof, the catalyst is selected from the group consisting of tertiary amines and organometallic compounds or a mixture thereof.

[0032] Preferred tertiary amines are selected from the group consisting of triethylamine, dimethylcyclohexylamine, N-methylmorpholine, N,N'-dimethylpiperazine, 2-(dimethylaminoethoxy)ethanol, diazabicyclo[2.2.2]octane, or mixtures thereof.

[0033] Preferred organometallic compounds are selected from the group consisting of titanates, iron compounds, tin compounds and bismuth salts, or mixtures thereof. A preferred iron compound is iron(III) acetylacetonate. A preferred tin compound is selected from the group consisting of tin diacetate, tin dioctoate, tin dilaurate and dialkyltin salts of aliphatic carboxylic acids, preferably tin dioctoate, or mixtures thereof. A preferred titanate ester is tetrabutyl orthotitanate. In preferred bismuth salts, the bismuth is present in oxidation state 2 or 3, especially 3, and preferred are salts of carboxylic acids, preferably having 6 to 14 carbon atoms, particularly preferably 8 to 12 carbon atoms. Highly preferred bismuth salts are bismuth(III) neodecanoate, bismuth 2-ethylhexanoate or bismuth octanoate, or mixtures thereof.

[0034] In a preferred embodiment 14 according to any of the above embodiments or one of their preferred embodiments, the catalyst is used in an amount of 0.0001 to 0.1 parts by weight per 100 parts by weight of the compound reactive towards isocyanates. In a preferred embodiment 15 according to any of the above embodiments or one of their preferred embodiments, the catalyst is tin dioctoate, more preferably tin(II) 2-ethylhexanoate (SDO), preferably used in an amount of 0.35 to 0.4 parts by weight relative to the composition.

[0035] Auxiliary Agent In a preferred embodiment 16 according to any of the above embodiments or one of their preferred embodiments, additional auxiliaries or additives are contained in the composition besides the flame retardant. In a preferred embodiment, the auxiliaries or additives are selected from surface-active substances, fillers, nucleating agents, oxidation stabilizers, lubrication auxiliaries, mould release auxiliaries, dyes, pigments, stabilizers, preferably stabilizers against hydrolysis, light, heat or discolouration, inorganic fillers, organic fillers, reinforcing agents, plasticisers or mixtures thereof.

[0036] Stabilizers in the sense of the present invention are additives that protect plastics or plastic compositions against harmful environmental influences. Preferred examples are primary and secondary antioxidants, sterically hindered phenols, hindered amine light stabilizers, UV absorbers, hydrolysis inhibitors, quenchers, or mixtures thereof. Examples of commercially available stabilizers are given in Plastics Additives Handbook, 5th edition, edited by H. Zweifel, Hanser Publishers, Munich, 2001 ([1]), p.98-p.136.

[0037] In a preferred embodiment, the ultraviolet absorbing agent is 0.3×10 3 g / mol, specifically 0.39 × 10 3 Further, the preferred UV absorbers have a number average molecular weight of greater than 5×10 3 g / mol, particularly preferably 2×10 3 It has a molecular weight not exceeding g / mol.

[0038] The UV absorber is preferably selected from the group consisting of cinnamates, oxanilides and benzotriazoles or mixtures thereof, and particularly preferred as UV absorber is benzotriazole. Particularly preferred examples of UV absorbers are Tinuvin® 213, Tinuvin® 234, Tinuvin® 312, Tinuvin® 571, Tinuvin® 384 and Eversorb® 82.

[0039] Preferably, the UV absorber is added in an amount of 0.01% to 5% by weight, preferably 0.1% to 2.0% by weight, especially 0.2% to 0.5% by weight, based on the total weight of the composition.

[0040] Often, UV stabilization based on antioxidants and UV absorbers as described above is not sufficient to ensure good stability of the composition against the harmful effects of UV radiation, in which case hindered amine light stabilizers (HALS) are added to the composition in addition to the antioxidants and / or UV absorbers, or as the sole stabilizer.

[0041] Examples of commercially available HALS stabilizers can be found in Plastics Additives Handbook, 5th Edition, H. Zweifel, Hanser Publishers, Munich, 2001, pp. 123-136.

[0042] Particularly preferred hindered amine light stabilizers are bis-(1,2,2,6,6-pentamethylpiperidyl)sebacate (Tinuvin® 765, Ciba Spezialitaetenchemie AG) and the condensation product of 1-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid (Tinuvin® 622). In particular, the condensation product of 1-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid (Tinuvin® 622) is preferred when the titanium content of the finished product is less than 150 ppm by weight, preferably less than 50 ppm by weight, in particular less than 10 ppm by weight, based on the components used.

[0043] The HALS compound is preferably used in a concentration of 0.01% to 5% by weight, particularly preferably 0.1% to 1% by weight, in particular 0.15% to 0.3% by weight, based on the total weight of the composition.

[0044] A particularly preferred UV stabilization comprises a mixture of a phenolic stabilizer, a benzotriazole, and a HALS compound in the preferred amounts described above.

[0045] Further information on the abovementioned auxiliaries and additives can be found in the technical literature, for example in Plastics Additives Handbook, 5th Edition, edited by H. Zweifel, Hanser Publishers, Munich, 2001.

[0046] Heating parameters In preferred embodiment 17 of the composition according to any of the previous embodiments or one of the preferred embodiments thereof, the composition has a total heat release (THR), preferably measured according to ISO 5660 Parts 1 and 2 (2002-12), of 35 kW / m on a sample plate of 100 x 100 x 5 mm in a cone calorimeter. 2 Burning at 160MJ / m2 and measured horizontally 2 More preferably, the THR is less than 150 MJ / m 2 Less than 140MJ / m 2 Less than 130MJ / m 2 less than, and most preferably less than 120 MJ / m 2 is less than.

[0047] In preferred embodiment 18 of the composition according to any of the above embodiments or one of their preferred embodiments, the peak heat release rate (pHRR) of the composition is preferably greater than or equal to 600 kW / m, measured according to ISO 5660 Parts 1 and 2 (2002-12) and determined in the cone calorimeter at a plate having a thickness of 5 mm and at 35 kW. 2 Less than 400kW / m 2 Less than 300kW / m 2 is less than.

[0048] Mechanical parameters In a preferred embodiment 19 of the composition according to any of the above embodiments or one of their preferred embodiments, the Shore A hardness of the composition is between 75 and 100, more preferably between 80 and 95. The Shore A hardness is preferably measured according to DIN ISO 7619-1:2016.

[0049] In a preferred embodiment 20 of the composition according to any of the preceding embodiments or one of the preferred embodiments thereof, the tensile strength of the composition, preferably measured according to DIN 53504:2017-03, is greater than 10 MPa, more preferably greater than 15 MPa, even more preferably greater than 20 MPa.

[0050] Flame retardants P-containing flame retardants In one preferred embodiment 21 of the composition according to any of the previous embodiments or one of their preferred embodiments, the flame retardant comprises phosphorus, more preferably a phosphate group. The flame retardant is a single substance or a mixture of at least two flame retardants.

[0051] The amount of the flame retardant in the composition is preferably 5% by weight to 60% by weight, more preferably 5% by weight to 50% by weight, and more preferably 10% by weight to 40% by weight, based on the total composition which is 100% by weight.

[0052] In a preferred embodiment 22 according to any of the previous embodiments or one of the preferred embodiments thereof, the at least one flame retardant in the composition is selected from the group consisting of derivatives of phosphoric acid, derivatives of phosphonic acid, derivatives of phosphinic acid, melamine cyanurate, and metal hydroxides, or a mixture thereof.

[0053] In a preferred embodiment 23 according to any of the previous embodiments or one of their preferred embodiments, the flame retardant comprises phosphorus, more preferably a derivative of phosphoric acid, a derivative of phosphonic acid or a derivative of phosphinic acid, or a mixture thereof.

[0054] In a preferred embodiment 24 according to any of the previous embodiments or one of their preferred embodiments, the composition comprises a phosphate ester as a flame retardant. Preferred embodiments of the phosphate ester are outlined below.

[0055] The phosphate ester is preferably a triester, more preferably a trialkyl phosphate. Other preferred esters are the triaryl phosphates, especially preferred is triphenyl phosphate.

[0056] In another embodiment, the phosphate ester is represented by the general formula (I) [ka] where R represents a substituted alkyl, cycloalkyl, or phenyl group, and n is an integer ranging from 1 to 15.

[0057] When R in the general formula (I) is an alkyl moiety, preferably the alkyl moiety used has 1 to 8 carbon atoms. Cyclohexyl is a preferred example of said cycloalkyl group. In another preferred embodiment, R represents phenyl or alkyl-substituted phenyl.

[0058] Preferably, n is 1 or an integer from 2 to 6, preferably from 3 to 6.

[0059] More preferably, the phosphate ester is selected from the group consisting of resorcinol bisdiphenyl phosphate (RDP), bisphenol A bis(diphenyl phosphate) (BDP), and diphenyl cresyl phosphate (DPK), or the corresponding oligomers, or mixtures thereof. The oligomers preferably have an average degree of oligomerization of n=3-6. Most preferably, the flame retardant comprises resorcinol bis(diphenyl phosphate) (RDP), more preferably in the form of an oligomer having an average degree of oligomerization n=3-6.

[0060] In a preferred embodiment, the phosphorus-containing flame retardant is contained in the composition in an amount of 5% by weight to 60% by weight, with the composition being 100% by weight. The flame retardant, which is a derivative of phosphoric acid, preferably melamine polyphosphate, is preferably contained in an amount of 3% to 30% by weight, more preferably 5% to 10% by weight, based on 100% by weight of the composition. The flame retardant which is a derivative of phosphonic or phosphoric acid is preferably contained in an amount of 2% to 24% by weight, preferably 2% to 10% by weight, based on 100% by weight of the composition.

[0061] The flame retardant which is a derivative of phosphinic acid is preferably contained in an amount of 5% to 30% by weight, preferably 10% to 20% by weight, based on 100% by weight of the composition.

[0062] metal hydroxide In a preferred embodiment 25 according to any of the previous embodiments or one of their preferred embodiments, the flame retardant comprises or is a metal hydroxide or metal oxide hydrate, more preferably the metal is selected from aluminum and magnesium, or is a mixture thereof.

[0063] Preferred metal hydroxides are hydroxides or oxide hydrates, more preferably hydroxides or oxide hydrates of aluminum or hydroxides of magnesium, or mixtures thereof. The advantage of said metal hydroxides is that in a fire they only liberate water and thus do not form any toxic or corrosive smoke products. Furthermore, said hydroxides can reduce smoke density in a fire. However, the disadvantage of said substances is that, firstly, they accelerate the hydrolysis of thermoplastic polyurethanes, and, secondly, they also have a negative effect on the oxidative aging of said polyurethanes.

[0064] In the context of the present invention, the term oxidative aging is used when the mechanical parameters of the thermoplastic polyurethane, such as tensile strength, tensile breaking strain, tear propagation resistance, flexibility, impact resistance, pliability, etc., undergo adverse changes over time. To verify the aging process in the laboratory, the mechanical parameters are first determined before high temperature aging and then after appropriate aging. The preferred aging temperature is 113°C or 121°C, where aging is carried out for 7 days. Other temperatures and times can be used depending on requirements.

[0065] In a preferred embodiment 26 according to any of the previous embodiments or one of the preferred embodiments thereof, the flame retardant comprises aluminum hydroxide or aluminum oxide hydrate or is a mixture thereof.

[0066] In a preferred embodiment, the flame retardant comprising a metal hydroxide or metal oxide hydrate further comprises a phyllosilicate, preferably bentonite.

[0067] In a preferred embodiment 27 according to any of the embodiments 25 or 26 or one of their preferred embodiments, the content of said metal hydroxide is between 10% and 80% by weight. This percentage by weight is based on the total weight of the composition. At higher loading levels, the mechanical properties of the composition are unacceptably impaired. It is therefore advantageous to add other flame retardants, especially those containing phosphorus. In a preferred embodiment, the polyurethane comprises at least one further flame retardant in addition to said metal hydroxide, or said metal oxide hydrate, or a mixture thereof. This further flame retardant is preferably a phosphorus-containing flame retardant. The amount of said metal hydroxide is preferably between 10% and 65% by weight, more preferably between 20% and 50% by weight, and more preferably between 25% and 40% by weight, based on the total weight of the composition, which is 100% by weight.

[0068] The specific surface area of ​​the metal hydroxide is preferably 2 m 2 / g~150m2 / g, more preferably 2m 2 / g~9m 2 / g, more preferably 3m 2 / g~8m 2 / g, and particularly preferably 3m 2 / g~5m 2 / g.

[0069] The specific surface area is preferably determined by the BET method in accordance with DIN ISO 9277:2003-05 using nitrogen.

[0070] Coating of the metal hydroxide or the metal oxide hydrate In another preferred embodiment 28 according to any of the above embodiments 25 to 27 or one of the preferred embodiments thereof, the metal hydroxide or both are at least partially covered with a coating.

[0071] The coating at least partially covers the surface of the metal hydroxide or metal oxide hydrate. The coating is equivalent to the often used phrase "surface treatment". The coating either adheres purely physically onto the metal hydroxide, either by interlocking effects or van der Waals forces, or has a chemical bond to the metal hydroxide. This is achieved primarily by covalent interactions.

[0072] Surface treatments or surface modifications to provide a coating around the part to be encapsulated, in this case the metal hydroxide or the metal oxide hydrate, are described in detail in the literature. "Particulate-Filled Polymer Composites" (2nd Edition), edited by Rothon, Roger N., 2003, Smithers Rapra Technology is a basic reference describing suitable materials as well as coating techniques. Chapter 4 is particularly relevant. Suitable materials are commercially available, for example, from Nabaltec, Schwandorf, or Martinswerke, Bergheim, both Germany.

[0073] Preferred coating materials are saturated or unsaturated polymers with acid functionality, preferably at least one acrylic acid or at least one anhydride, preferably maleic anhydride, which bond particularly well to the surface of the metal hydroxide.

[0074] Said polymer comprises one polymer or a mixture of polymers, preferably one polymer. Preferred polymers are polymers of monoolefins or diolefins, or mixtures thereof, copolymers of monoolefins and diolefins with each other or with other vinyl monomers, or polystyrene, or poly(p-methylstyrene), or poly(α-methylstyrene), or copolymers of styrene or α-methylstyrene with dienes or acrylic acid derivatives, or graft copolymers of styrene or α-methylstyrene, or halogen-containing polymers, or polymers derived from α- or β-unsaturated acids or their derivatives, or copolymers of one of these monomers with each other or with other unsaturated monomers, or mixtures thereof.

[0075] Another preferred coating material is a monomeric organic acid or derivative thereof. The acid is preferably a saturated acid, more preferably an aliphatic acid, more preferably a saturated fatty acid.

[0076] Preferred fatty acids contain 10 to 30 carbon atoms, preferably 12 to 22 carbon atoms, especially 16 to 20 carbon atoms, and more preferably have no double bonds. Stearic acid is very particularly preferred.

[0077] Preferred fatty acid derivatives are their salts, preferably the salts are calcium, aluminium, magnesium or zinc salts. Particularly preferred are the calcium salts, in particular calcium stearate.

[0078] Organosilane Coating Another preferred material for the coating around the metal hydroxide or metal oxide hydrate is an organosilane, preferably having the following structure: (R) 4-n -Si-X n , where n=1, 2, or 3. X is a hydrolyzable group that reacts with the surface of the metal hydroxide, also called a coupling group. X is preferably a halogen, preferably chlorine, and the coupling agent is accordingly trichlorosilane, dichlorosilane, or monochlorosilane. More preferably, the coupling group X is an alkoxy group, more preferably a methoxy group or an ethoxy group, or a mixture thereof. It is preferred that the moiety R is a hydrocarbon moiety, and that the organosilane compound is selected so as to have good compatibility with the thermoplastic polyurethane.

[0079] The moiety R is preferably attached to the silicon by a hydrolytically stable carbon-silicon bond and is either reactive or inert. A preferred example of a reactive moiety R is an unsaturated hydrocarbon moiety, more preferably an allyl moiety. It is preferred that the moiety R is inert and more preferably that the saturated hydrocarbon moiety has 2 to 30 carbon atoms, preferably has 6 to 20 carbon atoms, and particularly preferably has 8 to 18 carbon atoms, and is more preferably a branched or linear aliphatic hydrocarbon moiety.

[0080] The organosilane compound contains only one moiety R and has the general formula: R-Si-(X)3 where X is preferably a halogen, preferably chlorine, and the coupling reagent is accordingly trichlorosilane, dichlorosilane, or monochlorosilane. It is more preferred that the coupling group X is an alkoxy group, more preferably a methoxy group or an ethoxy group, or a mixture thereof.

[0081] It is highly preferred that the moiety is a hexadecyl group, preferably having a methoxy or ethoxy coupling group, so that the organosilane is a hexadecylsilane.

[0082] The amount of the silane applied to the metal hydroxide is 0.1% to 5% by weight, more preferably 0.5% to 1.5% by weight, and particularly preferably about 1% by weight, based on the total amount of the metal hydroxide or metal oxide hydroxide.

[0083] The amount of the carboxylic acid or carboxylic acid derivative applied to the metal hydroxide is 0.1% by weight to 5% by weight, more preferably 1.5% by weight to 5% by weight, and particularly preferably 3% by weight to 5% by weight, based on the total amount of the metal hydroxide.

[0084] It is preferred that more than 50%, more preferably more than 70%, more preferably more than 90% of the metal hydroxide particles, which are at least partially surrounded by a coating and which are preferably in powder form, have a maximum dimension of less than 10 μm, preferably less than 5 μm, particularly preferably less than 3 μm, while at least 50%, preferably at least 70%, more preferably at least 90% of the particles have at least one maximum dimension of more than 0.1 μm, more preferably more than 0.5 μm, and particularly preferably more than 1 μm.

[0085] The inventive composition preferably uses a pre-coated metal hydroxide or metal oxide hydrate, which is the only way to avoid undesirable side reactions between the coating material and the components of the composition, and is a particularly effective way to provide the advantage of inhibiting the oxidative degradation of the thermoplastic polyurethane. In a preferred embodiment, the coating of the metal hydroxide or metal oxide hydrate is carried out in the feed zone of the extruder, after which the polyurethane is added in the downstream part of the extruder.

[0086] In a preferred embodiment 29 according to any of the above embodiments 1 to 28 or one of their preferred embodiments, the composition comprises as flame retardant a phosphoric acid ester as outlined and preferred herein, and a metal hydroxide as outlined and preferred herein. In a more preferred embodiment 30, the flame retardant comprises a metal hydroxide or a metal oxide hydrate, where the metal is selected from aluminum and magnesium, and a derivative of phosphoric acid as preferred below. Very preferably, the phosphoric acid ester is selected from the group consisting of resorcinol bisdiphenyl phosphate (RDP), bisphenol A bis(diphenyl phosphate) (BDP), and diphenyl cresyl phosphate (DPK), or the corresponding oligomers, or mixtures thereof. The oligomer preferably has an average degree of oligomerization of n=3 to 6.

[0087] In a preferred embodiment 31 according to any of the above embodiments 1 to 28 or one of their preferred embodiments, the flame retardant comprises aluminum hydroxide or aluminum oxide hydrate as preferred herein, and resorcinol bis(diphenyl phosphate) (RDP), more preferably in oligomeric form, more preferably having an average degree of oligomerization of n=3 to 6.

[0088] In a preferred embodiment 32 according to any of the embodiments 1 to 28 or one of their preferred embodiments, the flame retardant comprises a metal hydroxide or metal oxide hydrate, or a mixture thereof, more preferably the metal is selected from aluminum and magnesium, or a mixture thereof, the phosphate ester is selected from the group consisting of resorcinol bisdiphenylphosphate (RDP), bisphenol A bis(diphenylphosphate) (BDP), and diphenylcresyl phosphate (DPK), or a corresponding oligomer, or a mixture thereof, wherein the oligomer preferably has an average degree of oligomerization of n=3 to 6, and the flame retardant further comprises a derivative of a phosphinic acid as preferred herein, most preferably aluminum diethylphosphinate.

[0089] The metal hydroxide, the metal oxide hydrate, or a mixture thereof is contained in the composition in an amount of 10% by weight to 60% by weight, preferably 33% by weight to 60% by weight, based on the total weight of the composition.

[0090] In a preferred embodiment 33 according to any of the previous embodiments, preferably according to embodiments 1 to 22 or according to one of the preferred embodiments thereof, the flame retardant comprises a derivative of phosphoric acid, more preferably a phosphoric acid ester.

[0091] The phosphate ester is preferably a triester, more preferably a trialkyl phosphate. Other preferred esters are the triaryl phosphates, especially preferred is triphenyl phosphate.

[0092] In another embodiment, the phosphate ester is represented by the general formula (I) [ka] where R represents a substituted alkyl, cycloalkyl, or phenyl group, and n is an integer ranging from 1 to 15. When R in the general formula (I) is an alkyl moiety, preferably the alkyl moiety used has 1 to 8 carbon atoms. Cyclohexyl is a preferred example of said cycloalkyl group. In another preferred embodiment, R represents phenyl or alkyl-substituted phenyl.

[0093] Preferably, n is 1 or an integer from 2 to 6, preferably from 3 to 6.

[0094] More preferably, the phosphate ester is selected from the group consisting of resorcinol bisdiphenyl phosphate (RDP), bisphenol A bis(diphenyl phosphate) (BDP), and diphenyl cresyl phosphate (DPK), or the corresponding oligomers, or mixtures thereof. The oligomers preferably have an average degree of oligomerization of n=3-6. Most preferably, the flame retardant comprises resorcinol bis(diphenyl phosphate) (RDP), more preferably in the form of an oligomer having an average degree of oligomerization n=3-6.

[0095] The phosphate derivative is preferably contained in the composition in an amount within a range of 2% by weight to 15% by weight, and more preferably within a range of 2% by weight to 10% by weight, based on the total weight of the composition.

[0096] In a preferred embodiment 34 of the composition according to any of the previous embodiments, preferably according to embodiments 1 to 22 or 33, or according to one of the preferred embodiments thereof, the flame retardant comprises melamine cyanurate. The melamine cyanurate is contained in the composition in an amount ranging from 5% to 40% by weight, preferably from 20% to 30% by weight, relative to the total amount of the composition.

[0097] In preferred embodiment 35, the composition according to any of the previous embodiments, preferably according to embodiments 1-22 or 33-34 or according to any of the preferred embodiments thereof, comprises a derivative of melamine cyanurate and phosphoric acid, more preferably the phosphoric acid ester is selected from the group consisting of 1,3-phenylene bis(diphenyl) phosphate, 1,3-phenylene bis(dixylenyl) phosphate, or a corresponding oligomer, or a mixture thereof. The oligomer preferably has an average degree of oligomerization of n=3-6.

[0098] In a preferred embodiment 36, the composition according to any of the previous embodiments, preferably according to embodiments 1 to 22 or 33 to 35 or according to any of the preferred embodiments thereof, comprises melamine cyanurate and resorcinol bis(diphenyl phosphate) (RDP), more preferably the RDP is in the form of an oligomer having an average degree of oligomerization of n = 3 to 6. RDP is preferably present in the composition in an amount ranging from 2% to 15% by weight, preferably from 2% to 10% by weight, relative to the total amount of the composition, and the melamine cyanurate in an amount ranging from 5% to 40% by weight, preferably from 20% to 30% by weight, relative to the total amount of the composition.

[0099] Phosphinic Acid Derivatives In a preferred embodiment 37, the composition according to any of the above embodiments or one of the preferred embodiments thereof comprises a derivative of phosphinic acid.

[0100] One preferred phosphinic acid derivative has the general formula (II) R1R2(P=O)OR3, where all three radicals R1, R2 and R3 are the same in one preferred embodiment or different from each other in another preferred embodiment. The radicals R1, R2 and R3 are preferably hydrogen or organic radicals, which are aliphatic in one preferred embodiment and aromatic in another preferred embodiment, and more preferably have 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and more preferably the alkyl radicals are selected from methyl, ethyl, propyl, butyl, pentyl, heptyl, octyl, nonyl, decyl radicals or mixtures thereof.

[0101] In one preferred embodiment, the organic ester is an alkyl ester, in another preferred embodiment an aryl ester. Very preferably, all hydroxy groups of the phosphinic acid are esterified. Preferably, at least one of the organic groups is aliphatic, and more preferably, all of the organic groups are aliphatic.

[0102] In a preferred embodiment, R1, R2 or R3 has 1 to 3 carbon atoms or is hydrogen. In a preferred embodiment, R1 and R2 are ethyl moieties, and more preferably in this embodiment, R3 is also an ethyl group or a methyl group. In a preferred embodiment, R1, R2 and R3 are simultaneously either an ethyl group or a methyl group.

[0103] In another preferred embodiment, R1, R2 and R3 are each a hydrogen atom.

[0104] Phosphinate Another preferred embodiment of the phosphinic acid derivatives are phosphinates. Phosphinates are salts of phosphinic acid with organic or inorganic cations. The groups R1 and R2 of formula (II) are either aliphatic or aromatic and preferably have 1 to 20, more preferably 1 to 10, more preferably 1 to 3 carbon atoms. Preferably, at least one of the groups R1 or R2 is aliphatic, more preferably R1 and R2 are aliphatic, and very preferably R1 and R2 are ethyl groups. In another preferred embodiment, R1 and R2 are hydrogen.

[0105] Preferred salts of phosphinic acid are metal hypophosphites, such as alkali metal salts, alkaline earth metal salts, aluminum salts, calcium salts, titanium salts, zinc salts, or mixtures thereof, more preferred are aluminum or zinc salts, or mixtures thereof, more preferred is aluminum.

[0106] The most preferred phosphinate is aluminum diethylphosphinate.

[0107] Favourable combinations In a preferred embodiment 38 of the composition according to any of the above embodiments, preferably according to one of the above embodiments 1 to 22 or according to one of their preferred embodiments, the flame retardant comprises a derivative of melamine cyanurate and phosphoric acid, preferably the preferred ones mentioned above, and a derivative of phosphinic acid, preferably the preferred ones mentioned above.

[0108] In a highly preferred embodiment 39 of the composition according to any of the previous embodiments, preferably according to one of the embodiments 1 to 22 or according to one of the preferred embodiments thereof, the flame retardant comprises melamine cyanurate and resorcinol bis(diphenyl phosphate) (RDP), more preferably RDP in the form of an oligomer having an average degree of oligomerization n=3 to 6, and aluminum diethylphosphinate.

[0109] Melamine Polyphosphate In a preferred embodiment 40 of the composition according to any of the previous embodiments, preferably according to embodiments 1 to 22 or according to one of the preferred embodiments thereof, the flame retardant comprises melamine polyphosphate, which is another preferred derivative of phosphoric acid.

[0110] Preferably, the melamine polyphosphate has a phosphorus content in the range of 7% to 20% by weight, preferably in the range of 10% to 17% by weight, more preferably in the range of 12% to 14% by weight, based on the total weight of the melamine polyphosphate.

[0111] In preferred embodiment 41 according to any of the above embodiments, preferably according to embodiments 1 to 22 or 40 or according to one of their preferred embodiments, the melamine polyphosphate is present in the composition in an amount of 2% to 35% by weight, in particular in the range of 3% to 30% by weight, more preferably in the range of 4% to 25% by weight, more preferably in the range of 5% to 20% by weight, even more preferably in the range of 5% to 10% by weight, based on the weight of the total composition, which is 100% by weight.

[0112] In a preferred embodiment 42, the composition according to any of the previous embodiments, preferably according to embodiments 1 to 22 or 40 to 41 or according to one of the preferred embodiments thereof, is free of melamine cyanurate. "Free of melamine cyanurate" preferably means that the composition comprises less than 5% by weight, more preferably less than 1% by weight, more preferably less than 0.5% by weight, more preferably less than 0.01% by weight, more preferably less than 50 ppm by weight, preferably less than 20 ppm by weight of melamine cyanurate. In a highly preferred embodiment, the composition comprises 0 ppm of melamine cyanurate.

[0113] In one preferred embodiment 43 of the composition according to any of the above embodiments, preferably according to embodiments 1 to 22 or 40 to 42 or according to one of the preferred embodiments thereof, the flame retardant comprises a derivative of phosphinic acid, more preferably the flame retardant comprises the melamine polyphosphates and derivatives of phosphinic acid as outlined above and preferred, preferably as outlined below and preferred.

[0114] The derivatives of said phosphinic acids are preferably selected from salts containing organic or inorganic cations or from organic esters.

[0115] Phosphinic esters have the general formula R1R2(P=O)OR3, where all three organic groups R1, R2 and R3 may be the same or different. The groups R1, R2 and R3 are either aliphatic or aromatic and preferably have 1 to 20, more preferably 1 to 10, more preferably 1 to 3 carbon atoms. Preferably, at least one of the groups is aliphatic, preferably all of the groups are aliphatic, very particularly preferably R1 and R2 are ethyl groups. More preferably, R3 is also aliphatic, more preferably an ethyl or methyl group. In a preferred embodiment, R1, R2 and R3 are simultaneously ethyl or methyl groups.

[0116] Other preferred derivatives of phosphinic acid are phosphinates, i.e. salts of phosphinic acid having the general formula: R1R2(P=O)O-. The R1 and R2 groups are either aliphatic or aromatic. More preferably, R1 and R2 independently have 1 to 20 carbon atoms, preferably 1 to 10, more preferably 1 to 3 carbon atoms. Preferably, at least one of the R1 or R2 groups is aliphatic, preferably both groups are aliphatic, and very preferably R1 and R2 are ethyl groups. Preferred salts of phosphinic acid are aluminium, calcium or zinc salts, or mixtures thereof, more preferably aluminium or zinc salts.

[0117] In a preferred embodiment 44 of the composition according to any of the previous embodiments, preferably according to embodiments 1 to 22 or 40 to 43 or according to one of the preferred embodiments thereof, the flame retardant comprises diethylaluminum phosphinate, preferably in an amount of 3% to 30% by weight, relative to the total amount of the composition. Even more preferably, the flame retardant comprises diethylaluminum phosphinate and melamine polyphosphate.

[0118] In preferred embodiment 45 of the composition according to any of the previous embodiments, preferably according to embodiments 1 to 22 or 40 to 44 or according to one of the preferred embodiments thereof, the derivative of phosphinic acid is an alkali metal hypophosphite. The salt is preferably an alkali metal salt, an alkaline earth metal salt or a mixture thereof. Preferred earth metal salts are selected from aluminum salts, titanium salts, zinc salts or mixtures thereof. More preferably, the flame retardant comprises an aluminum hypophosphite salt or a calcium hypophosphite salt or a mixture thereof.

[0119] In a preferred embodiment, the content of the phosphinic acid derivative in the composition is in the range of 5 wt% to 45 wt% based on the total composition, particularly 7 wt% to 40 wt% based on the total composition, more preferably in the range of 8 wt% to 38 wt%, more preferably in the range of 10 wt% to 35 wt%, more preferably in the range of 12 wt% to 32 wt%, and particularly preferably in the range of 15 wt% to 30 wt%.

[0120] In preferred embodiment 46 of the composition according to any of the preceding embodiments, preferably according to embodiments 1 to 22 or 40 to 45 or according to one of the preferred embodiments thereof, the total amount of the flame retardant is from 5% to 50% by weight, more preferably from 7% to 40% by weight, based on the weight of the total composition.

[0121] In a preferred embodiment, the flame retardant has an average particle size D50 in the range of 0.1 μm to 100 μm, preferably 0.5 μm to 60 μm, particularly preferably 3 μm to 50 μm. The particles preferably have an average particle size D99 of less than 100 μm, more preferably less than 90 μm. The flame retardant more preferably has an average particle size D50 in the range of 0.1 μm to 100 μm and an average particle size D99 of less than 100 μm. The particle size distribution is unimodal, otherwise polymodal, more preferably bimodal.

[0122] The melamine polyphosphate preferably consists of particles having a mean particle size D50 typically within the range of 0.1 μm to 100 μm, preferably 0.5 μm to 60 μm, particularly preferably 1 μm to 10 μm.

[0123] In a preferred embodiment, the aluminum diethylphosphinate has an average particle size D50 in the range of 20 μm to 80 μm, preferably 20 μm to 40 μm.

[0124] In a preferred embodiment 47, the composition according to one of the above embodiments, preferably according to embodiments 1 to 22 or 40 to 46 or according to one of the preferred embodiments thereof, comprises a further flame retardant.

[0125] In a preferred embodiment 48 according to one of the above embodiments, preferably according to embodiments 1 to 22, or 40 to 47, or according to one of their preferred embodiments, the flame retardant comprises melamine polyphosphate as outlined above and preferred, a salt of phosphinic acid or a derivative of phosphinic acid as outlined above and preferred, and at least one further flame retardant.

[0126] This further flame retardant is either a single substance or a mixture of at least two flame retardants. Highly preferably, the further flame retardant is liquid at 21°C.

[0127] Preferably, said further flame retardant comprises a further phosphorus-containing flame retardant, more preferably a derivative of phosphoric acid or a derivative of phosphonic acid, or a mixture thereof. This improves the processability of said composition. The composition preferably contains said further flame retardant, preferably said further phosphorus-containing flame retardant. Preferably, the amount of all phosphorus-containing flame retardants in said composition is in the range of 2% by weight to 10% by weight, based on the total amount of said composition.

[0128] It is preferred if the phosphoric acid derivative or phosphonic acid derivative is a salt, preferably a salt with an organic or inorganic cation, or an organic ester. An organic ester is a derivative of a phosphorus-containing acid in which at least one oxygen atom directly bonded to the phosphorus is esterified with an organic group. In a preferred embodiment, the organic ester is an alkyl ester, in another preferred embodiment an aryl ester or a mixed alkyl / aryl ester. It is particularly preferred if all hydroxyl groups of the corresponding phosphorus-containing acid are esterified. Examples of preferred phosphoric acid esters include 1,3-phenylene bis(diphenyl)phosphate, 1,3-phenylene bis(dixylenyl)phosphate and the corresponding oligomer products having an average degree of oligomerization of n=3-6. A preferred resorcinol is resorcinol bis(diphenyl phosphate) (RDP). This resorcinol is preferably in oligomeric form. Further preferred phosphorus-containing flame retardants are bisphenol A bis(diphenyl phosphate) (BDP) and diphenyl cresyl phosphate (DPC). Bisphenol A bis(diphenyl phosphate) (BDP) is preferably in the form of an oligomer.

[0129] The preferred embodiments of the flame retardant or mixture of flame retardants result in better flame retardant performance combined with generally better mechanical properties of the composition.

[0130] In preferred embodiment 49, the composition according to one of the above embodiments or its preferred embodiment or one of its preferred embodiments has a phenol content of less than 100 ppm by weight, preferably less than 50 ppm by weight, more preferably less than 20 ppm by weight, and particularly preferably less than 10 ppm by weight, based on the total weight of the composition.For more details, see also WO 2015 / 121504, which is incorporated herein by reference.The advantage is that the composition has better hydrolysis resistance.

[0131] Manufacturing method Another aspect of the present invention and embodiment 50 is the preparation of said composition comprising a thermoplastic polyurethane according to any of the above embodiments, preferably according to embodiments 1 to 22, 23 to 32, 33 to 39, or 40 to 49, or according to one of the preferred embodiments thereof.

[0132] The composition comprising the thermoplastic polyurethane in an embodiment including all the features of one of the embodiments outlined above or one of the preferred embodiments thereof is produced discontinuously or continuously. Preferred methods for producing thermoplastic polyurethane are the reactive extruder method, the belt-line method or the "one-shot" method, preferably the "one-shot" method or the reactive extruder method, most preferably the reactive extruder method.

[0133] These methods are used either by direct mixing of the components or alternatively by applying a prepolymer method.

[0134] The polyisocyanate prepolymer can be obtained by reacting an excess amount of the above polyisocyanate with the polypropanediol at a temperature of 30°C to 100°C, preferably at 8 x 10°C.

[0135] In the "one-shot" process, the components diisocyanate and polypropanediol, as well as the chain extender, are mixed with each other. This is done either sequentially or simultaneously, in a preferred embodiment in the presence of the catalyst. In the extruder process, the components diisocyanate and diol are mixed with the chain extender in a preferred embodiment, and also with the catalyst in a further preferred embodiment. The mixing in the reactive extrusion process is preferably carried out at a temperature of 100°C to 280°C, preferably 140°C to 250°C. The thermoplastic polyurethane obtained is preferably in the form of granules or powder. Auxiliaries and additives may be added during the synthesis of the thermoplastic polyurethane or are added to the thermoplastic polyurethane. The latter is preferred. This is especially the case when the additives or auxiliaries are not inert to the isocyanate, the chain extender, the compound reactive with isocyanate, or the catalyst.

[0136] In one embodiment, the coagent is added during the synthesis of the thermoplastic polyurethane. In another preferred embodiment, the coagent is added to the thermoplastic polyurethane after its synthesis.

[0137] In a preferred embodiment, the synthesis of the thermoplastic polyurethane is carried out in an extruder, more preferably a twin-screw extruder is used, which is operated with positive pressure transport, thus allowing more accurate setting of the temperature and throughput on the extruder.

[0138] Preferably, the thermoplastic polyurethane is prepared in a first step and the further components of the composition, preferably the flame retardant, are added by at least one further step. Preferably, the further components are mixed with the thermoplastic polyurethane in an extruder.

[0139] In a preferred embodiment 51, the thermoplastic polyurethane composition according to one of the above embodiments 1 to 49, preferably according to embodiments 1 to 22, 23 to 32, 33 to 39 or 40 to 49 or according to one of its preferred embodiments, or obtainable by a process according to embodiment 50 or one of its preferred embodiments, is in the form of pellets or powder. The pellets or powder in a preferred embodiment are compact materials. In another preferred embodiment, the pellets are expanded materials, also called expanded beads or expanded powders. Beads or expanded beads in a preferred embodiment refer to particles having a maximum dimension of 1 mm to 5 cm. Powder in a preferred embodiment refer to particles having a maximum size of 1 mm. Preferably, the size of the powder is less than 1×10 -6 m~1mm.

[0140] Another aspect and embodiment 52 of the present invention are therefore expanded beads made of said composition according to one of the above embodiments 1 to 49, preferably according to embodiments 1 to 22, 23 to 32, 33 to 39 or 40 to 49 or according to one of its preferred embodiments, or obtained by a process according to embodiment 50 or one of its preferred embodiments.

[0141] The foamed beads, as well as the molded bodies produced therefrom, can be used in a variety of applications (see, for example, WO 94 / 20568, WO 2007 / 082838 A1, WO 2017 / 030835, WO 2013 / 153190 A1, WO 2010 / 010010 (WO2010010010)), which are incorporated herein by reference.

[0142] Use to manufacture goods Another aspect and embodiment 53 of the present invention is the use of said composition according to one of the above embodiments 1 to 49, preferably according to embodiments 1 to 22, 23 to 32, 33 to 39 or 40 to 49 or according to one of its preferred embodiments, or obtained by a process according to embodiment 50 or one of its preferred embodiments, for manufacturing an article.

[0143] In preferred embodiments, the composition is injection molded, calendered, powder sintered, or extruded to form an article.

[0144] Yet another aspect of the present invention and embodiment 54 is the article as described above made with a composition according to one of the above embodiments 1 to 49, preferably according to embodiments 1 to 22, 23 to 32, 33 to 39, or 40 to 49, or according to one of its preferred embodiments, or obtained by a process according to embodiment 50 or one of its preferred embodiments. Preferably said article is selected from the group consisting of cables, cases, mobile phones, coatings, covers, vibration-damping elements, bellows, sheets, fibers, membrane mouldings, roofing or flooring for buildings or vehicles, nonwovens, gaskets, packaging materials, rolls, shoe soles, shoe intermediate layers, hoses, cables, cable connectors, cable sheaths, pillows, laminates, telephones, profiles, straps, saddles, foams from additional foaming of the compound, plug connections, televisions, cable routing, solar cell modules, linings in automobiles, wiper blades, elevator load bearing members, roping arrangements, machines, drive belts, preferably for moving walkways, handrails for moving walkways, modifiers for thermoplastic materials, meaning substances that affect the properties of another material. Each of these articles is itself a preferred embodiment, also called an application.

[0145] In a highly preferred embodiment, the article is a cable sheath.

[0146] Foaming In a preferred embodiment, the composition in the article is compact, meaning that its density is greater than 0.9 kg / L.

[0147] In another preferred embodiment, the composition in these articles is foamed. In one preferred embodiment, the foamed article is produced by interlocking foamed beads or foamed powder. In other words, the article is produced by pre-foamed precursors, which are preferably foamed beads or foamed powder.

[0148] In yet another embodiment, the foamed article is produced, preferably by injection molding, calendaring, powder sintering, or extrusion, from a compact composition further comprising a foaming agent.

[0149] The blowing agent used to expand the beads or the powder or the compact material is either a chemical blowing agent or a physical blowing agent. The bulk density of the foamed article is preferably from 50 g / L to 800 g / L, more preferably from 50 g / L to 500 g / L, more preferably from 50 g / L to 250 g / L, particularly preferably from 60 g / L to 200 g / L. The density is preferably measured according to DIN ISO 697.

[0150] Examples of suitable blowing agents are organic liquids and gases that remain liquid under processing conditions.

[0151] Preferred organic blowing agents are saturated aliphatic hydrocarbons, particularly those having 3 to 8 carbon atoms, more preferred examples being butane or pentane. Preferred inorganic gases are nitrogen, air, ammonia and carbon dioxide, or mixtures thereof, preferably nitrogen or carbon dioxide, or mixtures thereof. EXAMPLES

[0152] The examples show that the use of PO3G polyol results in a lower calorific value.

[0153] Example 1 - Feedstock TPU1: A TPU based on Weylchem's Velvetol H1000 (polypropanediol) with a molecular weight of 1000, 1,4-butanediol, methylenediphenyl 4,4-diisocyanate (MDI) with a Shore hardness of 85A.

[0154] TPU2: A TPU with a Shore hardness of 85A based on polytetrahydrofuran polyol (PTHF) having a molecular weight of 1000, 1,4-butanediol, and MDI, commercially available as Elastollan 1185A10 from BASF Polyurethanes GmbH, Germany.

[0155] Melapur MC 15 ED: Melamine cyanurate (1,3,5-triazine-2,4,6(1H,3H,5H)-trione, in combination with 1,3,5-triazine-2,4,6-triamine (1:1)), CAS number: 37640-57-6, BASF SE, 67056 Ludwigshafen, Germany, particle size D99%≦50μm, D50%≦4.5μm, moisture content %(w / w)<0.2.

[0156] Fyrolflex RDP: Resorcinol bis(diphenyl phosphate), CAS number: 125997-21-9, Supresta Netherlands BV, Officepark De Hoef, Hefweg 1, 3821 AE Amersfoort, The Netherlands, Viscosity at 25°C = 700 mPas, Acid number < 0.1 mg KOH / g, Water content % (w / w) < 0.1.

[0157] Exolit OP 1230: Aluminium diethylphosphinate, CAS number: 225789-38-8, Clariant Produkte (Deutschland) GmbH, Chemiepark Knapsack, 50351 Hürth, moisture content % (w / w) <0.2, average particle size (D50) 20-40 μm. Melapur 200 / 70: Melamine polyphosphate (nitrogen content 42-44 wt%, phosphorus content 12-14 wt%), CAS number: 218768-84-4, BASF SE, Germany, particle size D99%≦70μm, average particle size D50%≦10μm, moisture content %(w / w)<0.3.

[0158] Styrolution PS 485N, CAS number: 9003-55-8, Polymer (C8H8C4H6) x , styrene butadiene copolymer, HIPS, INEOS Styrolution Group GmbH, Mainzer Landstraße 50, DE-60325 Frankfurt, Melt volume rate, 200°C / 5kg (ISO 1133):4cm 3 / 10min.

[0159] Cloisite 20A: Organically modified nanodisperse layered silicate based on natural bentonite, BYK-Chemie GmbH, Abelstraße 45, D-46483 Wesel, powder, density 1.80 g / m 3 , particle size D50 = 10 μm, moisture content < 2.5%, lamellar spacing 2.7 nm.

[0160] Apyral 40 HS1: Aluminum hydroxide with a hydrophobic surface coating based on approx. 1% hexadecylsilane, Nabaltec AG, Alsstrasse 50 - 52, D-92421 Schwandorf, Al(OH)3 content [%] ≈ 99.5, particle size (laser scattering) [μm] D50: 1.4, specific surface area (BET) [m 2 / g]:3.5.

[0161] Example 2 - Preparation of the composition Tables 1-7 below list the compositions, where the individual feedstocks are listed in weight percent (wt%). The compounds, also referred to as compositions, were each produced using a Berstorff Model ZE 40 A twin-screw extruder having a section length of 35 D, divided into 10 zones. Temperature profile: HZ1 (supply section) 175℃~185℃ HZ2 180℃~190℃ HZ3 185℃~195℃ HZ4 185℃~195℃ HZ5 (nozzle) 180℃~190℃ Screw speed: 100 rpm Pressure: Approx. 10~30bar Strand cooling: water bath (10°C).

[0162] Table 1 [Table 1]

[0163] Table 2 [Table 2]

[0164] Table 3 [Table 3]

[0165] Table 4 [Table 4]

[0166] Table 5 [Table 5]

[0167] Table 6 [Table 6]

[0168] Table 7 [Table 7]

[0169] Third example - mechanical properties The compound was extruded into a film having a thickness of 1.6 mm using an Arenz type single screw extruder equipped with a 3-zone screw with a mixing section (screw ratio 1:3).The MFR of the granules used, the density of the corresponding test pieces according to DIN EN ISO 1133-1:2011, the Shore hardness according to DIN ISO 7619-1:2016, the tensile strength according to DIN EN ISO 527-2 / 5A / 200:2012, the tear resistance and the elongation at break according to DIN ISO 34-1, B:2016 were measured.

[0170] Example 4 - Flame retardant To evaluate the flame retardancy, test specimens with a thickness of 5 mm were subjected to a radiation intensity of 35 kW / m in a cone calorimeter according to ISO 5660 Parts 1 and 2 (2002-12). 2 The cone measurements are performed in horizontal direction at 100° C. Test specimens with dimensions 100×100×5 mm for the cone measurements were injection molded using an Arburg 520S with a screw diameter of 30 mm. The key parameters for the cone measurements for the different materials are shown in Tables 5 and 6. The inventive examples show significantly lower THR (total heat release) values ​​compared to the comparative examples.

[0171] Tables 8 to 10 below show the values ​​of the mechanical properties determined according to Example 3 and the flame retardancy determined according to Example 4 of the compositions specified in Tables 1 to 7.

[0172] Table 8 [Table 8]

[0173] Table 9 [Table 9]

[0174] Table 10

Table 10

Claims

1. A composition comprising thermoplastic polyurethane, wherein the thermoplastic polyurethane comprises at least the following components a) Diisocyanate b) Polypropanediol c) Chain extenders It is a reaction product of, The composition further comprises a flame retardant, wherein the flame retardant comprises phosphorus.

2. The composition according to claim 1, wherein the polypropanediol is 1,3-polypropanediol.

3. The total heat generation (THR), measured according to ISO 5660 Parts 1 and 2 (2002-12), was 160 MJ / m³ when measured at 35 kW on a 5 mm plate in a cone calorimeter. ２ Less than 150 MJ / m², more preferably 150 MJ / m² ２ Less than, more preferably 140 MJ / m ２ Less than 130 MJ / m ２ Less than, and most preferably 120 MJ / m ２ The composition according to claim 1, wherein the composition is less than [amount missing].

4. The composition according to claim 1, wherein the tensile strength measured according to DIN 53504:2017-03 is greater than 10 MPa, more preferably greater than 15 MPa, and even more preferably greater than 20 MPa.

5. The composition according to claim 1, wherein the Shore A hardness of the composition is 75 to 100, more preferably 80 to 95.

6. The composition according to claim 1, wherein the flame retardant is a derivative of phosphoric acid, phosphonic acid, or phosphinic acid, or a mixture thereof, more preferably comprising a phosphoric acid ester.

7. The composition according to claim 1, wherein the flame retardant comprises resorcinol bis(diphenyl phosphate) (RDP).

8. The composition according to claim 1, wherein the flame retardant comprises a metal hydroxide or a metal oxide hydrate.

9. The composition according to claim 8, wherein the metal is selected from aluminum and magnesium, or a mixture thereof.

10. The composition according to claim 1, wherein the flame retardant comprises aluminum hydroxide or aluminum oxide hydrate, or a mixture thereof.

11. The composition according to claim 8, wherein the metal hydroxide or the metal oxide hydrate or both are at least partially covered with a coating.

12. The composition according to claim 1, wherein the flame retardant comprises a derivative of phosphoric acid, more preferably a phosphoric acid ester, and more preferably the phosphoric acid ester is selected from the group consisting of resorcinol bis-diphenyl phosphate (RDP), bisphenol A bis(diphenyl phosphate) (BDP), and diphenyl cresyl phosphate (DPK), or a mixture thereof.

13. The composition according to claim 12, wherein the flame retardant further comprises melamine cyanurate.

14. The composition according to claim 13, wherein the flame retardant further comprises a derivative of phosphinic acid, more preferably a metal salt of a phosphinic acid derivative, and more preferably the metal is selected from aluminum, calcium, and zinc, or a mixture thereof.

15. The composition according to claim 1, wherein the flame retardant comprises melamine polyphosphate.

16. The composition according to claim 15, wherein the flame retardant further comprises a derivative of phosphinic acid, more preferably a metal salt of the phosphinic acid derivative.

17. The composition according to claim 16, wherein the metal is selected from aluminum, calcium, and zinc, or a mixture thereof.

18. The composition according to claim 1, wherein the flame retardant comprises aluminum diethyl phosphine.

19. A cable comprising the composition according to any one of claims 1 to 18.