Enhanced hydrolysis protection of thermoplastic polyurethane by a combination of a carbodiimide and surfactant

Abstract

The present invention relates to a composition (C) comprising a thermoplastic elastomer (TPE-1) as component (C1); a carbodiimide (CD) in an amount of from 0.1 to 5% by weight based on the sum of components of composition (C); and an additive composition (AC) in an amount of from 0.1 to 2% by weight based on the sum of components of composition (C), comprising at least one additive (A); wherein the additive composition (AC) has an HLB value of greater than 4.0, determined according to the organic conception diagram method and a process for preparing said composition. Furthermore, the present invention relates to the use of the composition according to the present invention for the preparation of an article and the use of a mixture (M1) comprising a carbodiimide (CD) and an additive composition (AC) comprising at least one additive (A) as a stabilizer for a composition comprising a thermoplastic elastomer, wherein the additive composition (AC) has an HLB value of greater than 4.0, determined according to the organic conception diagram method.

Description

[0001] 240082W001

[0002] Enhanced hydrolysis protection of thermoplastic polyurethane by a combination of a carbodiimide and surfactant

[0003] The present invention relates to a composition (C) comprising a thermoplastic elastomer (TPE-1 ) as component (C1); a carbodiimide (CD) in an amount of from 0.1 to 5% by weight based on the sum of components of composition (C); and an additive composition (AC) in an amount of from 0.1 to 2% by weight based on the sum of components of composition (C), comprising at least one additive (A); wherein the additive composition (AC) has an HLB value of greater than 4.0, determined according to the organic conception diagram method and a process for preparing said composition. Furthermore, the present invention relates to the use of the composition according to the present invention for the preparation of an article and the use of a mixture (M 1 ) comprising a carbodiimide (CD) and an additive composition (AC) comprising at least one additive (A) as a stabilizer for a composition comprising a thermoplastic elastomer, wherein the additive composition (AC) has an HLB value of greater than 4.0, determined according to the organic conception diagram method.

[0004] Thermoplastic elastomers have been known for a long time. Processes for producing thermoplastic elastomers are already known from the prior art. Their technical importance is based on the combination of high-quality mechanical properties with the advantages of cost-effective thermoplastic processing. By using different chemical components, a wide range of mechanical properties can be achieved.

[0005] In particular thermoplastic elastomers comprising ester bonds or comprising additives which are based on esters are sensitive towards hydrolysis.

[0006] However, it is known that this negative effect can be largely compensated for by the addition of a carbodiimide to the compositions.

[0007] For example US2020071486A1 and EP0381897A1 disclose compositions containing a polyester-based NCO prepolymer with urethane groups, a monomeric aromatic carbodiimide (Stabaxol I: bis(2,6-diisopropylphenyl)carbodiimide) and ethyl p-toluenesulfonate.

[0008] In general, carbodiimides have already proven to be effective hydrolysis inhibitors for thermoplastics, including thermoplastic ester-based polyurethanes. However, carbodiimides have the disadvantage of being very expensive and decomposing at higher temperatures during processing or developing toxic gases (emission of isocyanates). Therefore, there was a need for compositions with improved hydrolysis resistance, which make it possible to reduce the amount of carbodiimides used while maintaining the hydrolysis resistance of the polymer.

[0009] This object is achieved in accordance with the invention by a composition (C) comprising 240082W001

[0010] - 2 -

[0011] (a) a thermoplastic elastomer (TPE-1) as component (C1);

[0012] (b) a carbodiimide (CD) in an amount of from 0.1 to 5% by weight based on the sum of components of composition (C);

[0013] (c) an additive composition (AC) in an amount of from 0.1 to 2% by weight based on the sum of components of composition (C), comprising at least one additive (A); wherein the additive composition (AC) has an HLB value of greater than 4.0, determined according to the organic conception diagram method.

[0014] It has been found that, surprisingly, the specific combination of the components according to the present invention results in compositions comprising thermoplastic elastomers which have an improved hydrolysis stability and allow to reduce the amount of carbodiimide used. Preferably, additive (A) is a nonionic compound.

[0015] The composition according to the present invention comprises components (a), (b) and (c) and may also comprise further components.

[0016] Composition (C) comprises a carbodiimide (CD) in an amount of from 0.1 to 5% by weight based on the sum of components of composition (C). In the context of the present invention, the term carbodiimide encompasses polycarbodiimides as well as mono-carbodiimides or oligo-carbodiimides. Carbodiimides which may be used in the composition according to the present invention are in principle known. Suitable carbodiimides are for example disclosed in DE-A 4 318 979, DE-A 4442724 and EP-A 460481 . According to the present invention, also mixtures of two or more carbodiimides may be used.

[0017] Furthermore, suitable carbodiimides man be selected from carbodiimides and / or oligomeric polycarbodiimides as disclosed in EP0628541 , preferably carbodiimides and / or oligomeric polycarbodiimides of the formula (I) in which

[0018] R is the same or different and is selected from the group of saturated or unsaturated alcohols, -NCO-, -NHCONHR1-, -NHC0NR1R2- and -NHC00R3- radicals, where R1and R2are the same or different and represent an alkyl, cycloalkyl or aralkyl radical and

[0019] R3is R1or an alkoxypolyoxyalkylene radical and 240082W001

[0020] - 3 - n is an integer from 0 to 10.

[0021] The composition (C) further comprises an additive composition (AC) in an amount of from 0.1 to 2% by weight based on the sum of components of composition (C), comprising at least one additive (A), wherein the additive composition (AC) has an HLB value of greater than 4.0, determined according to the organic conception diagram method. Preferably, the additive composition consists of the at least one additive (A). Suitable additives (A) preferably have a an HLB value of greater than 4.0, determined according to the organic conception diagram method. Preferably, the additive (A) is selected from surfactants. According to a further embodiment, the present invention is directed to the composition (C) as disclosed above, wherein the HLB value of the additive (A) is 4.0 or greater, preferably in the range of from 4.0 to 22.0, determined according to the organic conception diagram method.

[0022] It has been found that suitable additives (A) may be characterized by the general formula

[0023] Ri-O-(CH2CH2O)n-R2or

[0024] Ri-O-(CH2CH3CH2O)n-(CH2CH2O)n-R2wherein Ri or R2=H, or alkyl chain with carbon number from 1 to 18, could contain 1 or more unsaturated group and / or 1 or more branched group and / or 1 or more ring group and / or 1 or more OH group or the general formula

[0025] Ri - COO - (CH2CH2O)n - H

[0026] Ri - COO - (CH2CH2O)n - CO - R2wherein Ri or R2= alkyl chain with carbon number from 1 to 18, could contain 1 or more unsaturated group and / or 1 or more branched group and / or 1 or more ring group and / or 1 or more OH group.

[0027] Suitable additives (A) may for example be selected from surfactants such as for example polyethylene glycols, polyethylene glycol oleate, polyethylene glycol ricinoleate, sorbitan stearate, glyceryl laurate, and fatty alcohol alkoxylates. According to a further embodiment, the present invention is directed to the composition (C) as disclosed above, wherein the additive (A) is selected from the group consisting of polyethylene glycols, polyethylene glycol oleate, polyethylene glycol ricinoleate, sorbitan stearate, glyceryl laurate, and fatty alcohol alkoxylates.

[0028] Suitable polyethylene glycols may for example have a molecular weight Mw in the range of from 200 to 1000 g / mol, preferably in the range of from 400 to 800 g / mol. 240082W001

[0029] - 4 -

[0030] Suitable fatty alcohol alkoxylates may for example, have a molecular weight Mw in the range of from 400 to 3300 g / mol, preferably in the range of from 600 to 2500 g / mol, more preferable in the range of from 800 to 2000 g / mol.

[0031] The composition (C) further comprises a thermoplastic elastomer (TPE-1) as component (C1). Thermoplastic elastomers include, for example, thermoplastic polyurethanes (TPU), thermoplastic polyester elastomers (e.g., polyether esters and polyester esters), thermoplastic copolyamides (e.g., polyether copolyamides) or thermoplastic styrene-butadiene block copolymers.

[0032] In a preferred embodiment the thermoplastic elastomer is a thermoplastic polyurethane, more preferable a thermoplastic polyurethane based on a polyester. According to a further embodiment, the present invention is directed to the composition (C) as disclosed above, wherein the thermoplastic elastomer (TPE-1) is a thermoplastic polyurethane, preferably a thermoplastic polyurethane based on a polyester.

[0033] Suitable thermoplastic polyurethanes are in principle known. The thermoplastic polyurethane present in the composition typically is the reaction product of at least one diisocyanate, at least one polyol, and at least one chain extender.

[0034] According to the present invention, it is also possible to use mixtures of two or more polyols. Suitable polyols are in principle known to the person skilled in the art. Preferably, the polyol is a polyesterpolyol. Preferably in accordance with the invention, the polyol is selected from the group consisting of polyester polyols and more preferably from linear polyester polyols.

[0035] Suitable polyester polyols, especially polyester diols, may be prepared, for example, from dicarboxylic acids having 2 to 12 carbon atoms, preferably 4 to 10 carbon atoms, and polyhydric alcohols. Examples of useful dicarboxylic acids include: aliphatic dicarboxylic acids, such as succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid and sebacic acid, or aromatic dicarboxylic acids, such as phthalic acid, isophthalic acid and terephthalic acid. The dicarboxylic acids may be used individually or in the form of mixtures, for example in the form of a mixture of succinic acid, sebacic acid and adipic acid. For preparation of the polyester diols, it may possibly be advantageous to use, rather than the dicarboxylic acids, the corresponding dicarboxylic acid derivatives such as carboxylic diesters having 1 to 4 carbon atoms in the alcohol radical, for example dimethyl terephthalate or dimethyl adipate, carboxylic anhydrides, for example succinic anhydride, glutaric anhydride or phthalic anhydride, or carbonyl chlorides. Examples of polyhydric alcohols are glycols having 2 to 10, preferably 2 to 6, carbon atoms, for example ethylene glycol, diethylene glycol, butane-1 ,4-diol, pentane-1,5-diol, hexane-1 ,6-diol, decane-1, 10-diol, 2,2-dimethylpropane-1,3-diol, propane-1, 3- diol, 2-methylpropane-1 ,3-diol, 3-methylpentane-1 ,5-diol or dipropylene glycol. The polyhydric alcohols may be used individually or as mixtures, for example in the form of a butane-1, 4-diol and / or propane-1, 3-diol mixture. In addition, it is also possible to include small amounts of up to 3% by weight of the total reaction mixture of higher-functionality polyols of low molecular weight, for example 1,1,1 -trimethylolpropane or pentaerythritol. Preference is given in accordance with the invention to the use of exclusively bifunctional starting compounds. 240082W001

[0036] - 5 -

[0037] The molecular weight of the polyol used may vary within wide ranges. Suitable examples include polyols that have an average molecular weight in the range from 500 to 3500 g / mol, further preferably in the range from 800 to 3000 g / mol.

[0038] According to the invention, polyol may also be a polyetherpolyol, for example a polyetherpolyol such as polytetramethylene ether glycol, polyethylene glycol, or polypropylene glycol and copolymers thereof.

[0039] According to the present invention, it is also possible to use mixtures of two or more polyols for the preparation of the thermoplastic polyurethane. The polyols used or the polyol composition preferably have an average functionality in the range from 1.7 and 2.3, preferably in the range from 1.9 and 2.1, especially 2.

[0040] Suitable polyols are described, for example, in "Kunststoffhandbuch [Plastics Handbook], volume 7, Polyurethane [Polyurethanes]”, Carl Hanser Verlag, 3rd edition 1993, chapter 3.1.

[0041] According to the invention, the polyol composition may also comprise a solvent. Suitable solvents are known per se to those skilled in the art.

[0042] According to the invention, a chain extender is used for the preparation of the thermoplastic polyurethane. Suitable chain extenders are known per se to those skilled in the art.

[0043] Chain extenders used are compounds having at least two groups reactive toward isocyanates. Groups reactive toward isocyanates may especially be NH, OH or else SH groups. Suitable examples are diamines or else diols or water. Preference is given to using at least one chain extender selected from the group consisting of compounds having at least two isocyanate-reactive groups having a molecular weight of < 500 g / mol.

[0044] Chain extenders used may, for example, be commonly known aliphatic, araliphatic, aromatic and / or cycloaliphatic compounds having a molecular weight of 50 to 499 g / mol, preferably bifunctional compounds, for example alkanediols having 2 to 10 carbon atoms in the alkylene radical, for example diols selected from the group consisting of C2 to C6 diols, preferably butane-1 ,4-diol, hexane-1 ,6-diol and / or di-, tri-, tetra-, penta-, hexa-, hepta-, octa-, nona- and / or decaalkylene glycols having 3 to 8 carbon atoms, preferably unbranched alkanediols, especially propane-1, 3- diol, butane-1, 4-diol and hexane-1, 6-diol. It is further preferably possible here to use aliphatic, araliphatic, aromatic and / or cycloaliphatic diols having a molecular weight of 50 g / mol to 220 g / mol. Preference is given to alkanediols having 2 to 12 carbon atoms in the alkylene radical, especially di-, tri-, tetra-, penta-, hexa-, hepta-, octa-, nona- and / or decaalkylene glycols. For the present invention, particular preference is given to ethanediol, propanediol, butanediol,. pentanediol, hexanediol, or mixtures thereof.

[0045] It is also possible in accordance with the invention to use mixtures of two or more chain extenders. 240082W001

[0046] - 6 -

[0047] The employed amount of the chain extender and the polyol composition may be varied within broad ranges. For example, in the context of the present invention, the chain extender may be used in an amount in the range from 1 :40 to 10:1, based on the polyol used.

[0048] Typically, a polyisocyanate, in particular a diisocyanate is used for the preparation of the thermoplastic polyurethane. Preferred diisocyanates within the context of the present invention are aliphatic or aromatic diisocyanates, especially aromatic diisocyanates.

[0049] In addition, in the context of the present invention, prereacted products may be used as isocyanate components, in which a polyol is reacted with an isocyanate in a preceding reaction step. The products obtained have essentially isocyanate end groups and may be used in accordance with the invention.

[0050] Aliphatic diisocyanates used are customary aliphatic and / or cycloaliphatic diisocyanates, for example tri-, tetra-, penta-, hexa-, hepta- and / or octamethylene diisocyanate, 2-methylpentamethylene 1 ,5-diisocyanate, 2- ethyltetramethylene 1 ,4-diisocyanate, hexamethylene 1,6-diisocyanate (HDI), pentamethylene 1 ,5-diisocyanate, butylene 1 ,4-diisocyanate, trimethylhexamethylene 1,6-diisocyanate, 1,3-Bis(isocyanatemethyl) cyclohexan (H6XDI), 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (isophorone diisocyanate, IPDI), 1,4- and / or 1,3- bis(isocyanatomethyl)cyclohexane (HXDI), cyclohexane 1 ,4-diisocyanate, 1 -methylcyclohexane 2,4- and / or 2,6- diisocyanate, methylene dicyclohexyl 4,4'-, 2,4'- and / or 2,2'-diisocyanate (H12MDI).

[0051] Preferred aliphatic polyisocyanates are hexamethylene 1,6-diisocyanate (HDI), pentamethylene 1 ,5-diisocyanate, 1- isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane and methylene dicyclohexyl 4,4'-, 2,4'- and / or 2,2'- diisocyanate (H12MDI).

[0052] Suitable aromatic diisocyanates are especially naphthylene 1 ,5-diisocyanate (NDI), tolylene 2,4- and / or 2,6- diisocyanate (TDI), diphenylmethane 2,2'-, 2,4'- and / or 4,4'-diisocyanate (MDI), 3,3'-dimethyl-4,4'- diisocyanatodiphenyl (TODI), xylylene diisocyanates (XDI), p-phenylene diisocyanate (PDI), diphenylethane 4,4'- diisocyanate (EDI), diphenylmethane diisocyanate, 3,3’-dimethyldiphenyl diisocyanate, diphenylethane 1,2- diisocyanate and / or phenylene diisocyanate.

[0053] It is also possible in the context of the present invention to use higher-functionality isocyanates, by way of example triisocyanates, for example triphenylmethane 4,4’, 4”-triisocy anate, and also the cyanurates of the aforementioned diisocyanates, and the oligomers obtainable by partial reaction of diisocyanates with water, for example the biurets of the aforementioned diisocyanates, and additionally oligomers obtainable by controlled reaction of semiblocked diisocyanates with polyols having an average of more than two and preferably three or more hydroxyl groups. 240082W001

[0054] - 7 -

[0055] For example, the polyisocyanate may be selected from the group consisting of diphenylmethane 2,2'-, 2,4'- and 4,4'-diisocyanate (MDI), tolylene 2,4- and 2,6-diisocyanate (TDI), hexamethylene diisocyanate (HDI), 1-isocyanato-4- [(4-isocyanatocyclohexyl)methyl]cyclohexane (H12MDI) or naphthalene 1 ,5-diisocyanate (NDI).

[0056] In a further embodiment, the present invention therefore also relates to a process for producing a polyurethane as described above, wherein the polyisocyanate is selected from the group consisting of diphenylmethane 2,2'-, 2,4'- and 4,4'-diisocyanate (MDI), tolylene 2,4- and 2,6-diisocyanate (TDI), hexamethylene diisocyanate (HDI), 1- isocyanato-4-[(4-isocyanatocyclohexyl)methyl]cyclohexane (H12MDI) or naphthalene 1 ,5-diisocyanate (NDI). The polyisocyanate (I2) is preferably selected from the group consisting of diphenylmethane 2,2'-, 2,4'- and 4,4'- diisocyanate (MDI), tolylene 2,4- and 2,6-diisocyanate (TDI), hexamethylene diisocyanate (HDI), 1-isocyanato-4-[(4- isocyanatocyclohexyl)methyl]cyclohexane (H12MDI) and naphthalene 1,5-diisocyanate (NDI).

[0057] In case mixtures of two isocyanates are used, the isocyanates are typically used in a ratio of 1 :20 to 1 :3.

[0058] The molecular weight of the thermoplastic polyurethane may vary within wide ranges. It is particularly advantageous for the thermoplastic polyurethane to have a molecular weight in the range from 20 000 to 500 000 g / mol, determined by means of GPC, more preferably in the range from 50 000 to 300 000 g / mol., in particular in the range of from 80 000 to 250 000 g / mol, preferably in the range of from 90 000 to 200 000 g / mol.

[0059] According to the invention, further additives may be added to the composition. It is also possible in accordance with the invention to use combinations of two or more additives.

[0060] Examples of auxiliaries and additives include surface-active substances, flame retardants, nucleating agents, oxidation stabilizers, antioxidants, lubricants and demolding aids, dyes and pigments, stabilizers, for example against light, heat or discoloration, inorganic and / or organic fillers, reinforcers and plasticizers. Suitable auxiliaries and additives can be found, for example, in Kunststoffhandbuch, volume VII, edited by Vieweg and Hbchtlen, Carl Hanser Verlag, Munich 1966 (p. 103-113).

[0061] Suitable processes for preparing a composition comprising a thermoplastic elastomer and additives are in principle known.

[0062] If the carbodiimide and the additive are added to a reaction mixture, this can in principle be done at any stage of the manufacturing process of a thermoplastic elastomer.

[0063] In an alternative embodiment, component (b) and component (c) are mixed with a thermoplastic elastomer.

[0064] If the mixture of components (b) and (c) is added to a thermoplastic elastomer which has al-ready substantially reacted, this can be done, for example, by compounding or swelling. 240082W001

[0065] - 8 -

[0066] According to a further aspect, the present invention is also directed to a process for preparing a composition comprising a thermoplastic elastomer (TPE-1 ), a carbodiimide (CD), and an additive composition (AC) as disclosed above, comprising

[0067] (I) mixing the thermoplastic elastomer (TPE-1), the carbodiimide (CD) and the additive composition (AC).

[0068] The mixing can be conducted in apparatuses that are known per se to the person skilled in the art, for example heatable / coolable stirred tanks or reaction extruders. The reaction typically is conducted at temperatures known per se to the person skilled in the art, for example at a temperature in the range from 20 to 250°C, preferably in the range from 40 to 130°C, further preferably at a temperature in the range from 70 to 90°C.

[0069] According to the present invention, it is also possible to mix the carbodiimide (CD) and the additive composition (AC) in a first mixing step and add the resulting mixture to the thermoplastic elastomer (TPE-1).

[0070] According to the invention, it is also possible for the process to comprise further steps, for example a pretreatment of the components or an after-treatment of the composition obtained, for example a heat treatment or shaping steps to form an article.

[0071] According to a further aspect, the present invention is also directed to the use of the composition (C) as disclosed above for the preparation of an article.

[0072] With regard to the preferred embodiments, reference is made to the above statements relating to the process of the invention. In a further embodiment, the present invention therefore also relates to a polyurethane as described above, wherein the polyurethane is thermoplastic.

[0073] The composition of the invention and the composition obtained or obtainable by a process of the invention can be processed further by processes known to the person skilled in the art to give the desired films, moldings, rolls, fibers, automobile trim, hoses, cable connectors, bellows, trailing cables, cable sheaths, gaskets, belts or damping elements, for example injection molding, calendering or extrusion.

[0074] The composition produced in accordance with the invention may advantageously be used especially in all applications specific to thermoplastic elastomers, in particular thermoplastic polyurethanes. The present invention therefore also relates to the use of the composition obtainable or obtained by a process as described above or of a composition as described above for production of shaped bodies, adhesives, coatings, hoses, films, nonwoven articles or fibers. 240082W001

[0075] - 9 -

[0076] According to a further aspect, the present invention is also directed to the use of a composition as disclosed above or a composition prepared according to the process as disclosed above for the production of shaped bodies, coatings, tubes, rolls, belts, damping elements, cable sheaths, hoses, films, nonwoven articles or fibers, foamed parts, particle foams, added manufacturing filaments, 3D printing, extrusion parts, injection molding parts, agriculture, construction applications.

[0077] According to a further aspect, the present invention is also directed to the use of a mixture (M 1 ) comprising a carbodiimide (CD) and an additive composition (AC) comprising at least one additive (A) as a stabilizer for a composition comprising a thermoplastic elastomer, wherein the additive composition (AC) has an HLB value of greater than 4.0, determined according to the organic conception diagram method.

[0078] It has been found that the use of the specific combination of the carbodiimide (CD) and an additive composition (AC) comprising at least one additive (A) as disclosed above allows to prepare thermoplastic elastomer compositions, in particular thermoplastic polyurethanes which have improved hydrolysis stability when only using small amounts of carbodiimide.

[0079] Further embodiments of the present invention are apparent from the claims and the examples. It will be appreciated that the features of the object / processes / uses according to the invention that are mentioned above and elucidated below are usable not only in the combination specified in each case but also in other combinations without departing from the scope of the invention. Thus, for example, the combination of a preferred feature with a particularly preferred feature or of a feature not characterized further with a particularly preferred feature etc. is also encompassed implicitly even if this combination is not mentioned explicitly.

[0080] The present invention is illustrated in more detail by the following embodiments and combinations of embodiments which are apparent from the corresponding dependency references and other references. In particular, it should be noted that in every case where a range of embodiments is mentioned, for example in the context of an expression such as "the process according to any of embodiments 1 to 4”, each embodiment in this range is deemed to be explicitly disclosed to those skilled in the art, i.e. the wording of this expression is to be understood by those skilled in the art as synonymous with "the process according to any of embodiments 1 , 2, 3 and 4”.

[0081] 1 . Composition (C) comprising

[0082] (a) a thermoplastic elastomer (TPE-1 ) as component (C1);

[0083] (b) a carbodiimide (CD) in an amount of from 0.1 to 5% by weight based on the sum of components of composition (C);

[0084] (c) an additive composition (AC) in an amount of from 0.1 to 2% by weight based on the sum of components of composition (C), comprising at least one additive (A); 240082W001

[0085] - 10 - wherein the additive composition (AC) has an HLB value of greater than 4.0, preferably in the range of from 4.0 to 22.0, determined according to the organic conception diagram method.

[0086] 2. The composition according to embodiment 1, wherein the thermoplastic elastomer (TPE-1) is a thermoplastic polyurethane, preferably a thermoplastic polyurethane based on a polyester.

[0087] 3. The composition according to embodiment 1 or 2, wherein the HLB value of the additive (A) is 4.0 or greater, preferably in the range of from 4.0 to 22.0, determined according to the organic conception diagram method.

[0088] 4. The composition according to any one of embodiments 1 to 3, wherein the additive (A) is characterized by the general formula

[0089] Ri-O-(CH2CH2O)n-R2or

[0090] Ri-O-(CH2CH3CH2O)n-(CH2CH2O)n-R2wherein Ri or R2=H, or alkyl chain with carbon number from 1 to 18, could contain 1 or more unsaturated group and / or 1 or more branched group and / or 1 or more ring group and / or 1 or more OH group or the general formula

[0091] Ri - COO - (CH2CH2O)n - H

[0092] Ri - COO - (CH2CH2O)n - CO - R2wherein Ri or R2= alkyl chain with carbon number from 1 to 18, could contain 1 or more unsaturated group and / or 1 or more branched group and / or 1 or more ring group and / or 1 or more OH group.

[0093] 5. The composition according to any one of embodiments 1 to 3, wherein the additive (A) is selected from the group consisting of polyethylene glycols, polyethylene glycol oleate, polyethylene glycol ricinoleate, sorbitan stearate, glyceryl laurate, and fatty alcohol alkoxylates.

[0094] 6. Composition (C) comprising

[0095] (a) a thermoplastic elastomer (TPE-1) as component (C1);

[0096] (b) a carbodiimide (CD) in an amount of from 0.1 to 5% by weight based on the sum of components of composition (C);

[0097] (c) an additive composition (AC) in an amount of from 0.1 to 2% by weight based on the sum of components of composition (C), comprising at least one additive (A); 240082W001

[0098] - 11 - wherein the additive composition (AC) has an HLB value of greater than 4.0, preferably in the range of from 4.0 to 22.0, determined according to the organic conception diagram method, wherein the thermoplastic elastomer (TPE-1) is a thermoplastic polyurethane, preferably a thermoplastic polyurethane based on a polyester and wherein the additive (A) is selected from the group consisting of polyethylene glycols, polyethylene glycol oleate, polyethylene glycol ricinoleate, sorbitan stearate, glyceryl laurate, and fatty alcohol alkoxylates.

[0099] 7. A process for preparing a composition comprising a thermoplastic elastomer (TPE-1), a carbodiimide (CD), and an additive composition (AC) according to any one of embodiments 1 to 6, comprising

[0100] (I) mixing the thermoplastic elastomer(TPE-l), the carbodiimide (CD) and the additive composition (AC).

[0101] 8. A process for preparing a composition comprising a thermoplastic elastomer (TPE-1), a carbodiimide (CD), and an additive composition (AC), comprising

[0102] (I) mixing the thermoplastic elastomer(TPE-l) as component (C1), the carbodiimide (CD) in an amount of from 0.1 to 5% by weight based on the sum of components of composition (C) and the additive composition (AC) in an amount of from 0.1 to 2% by weight based on the sum of components of composition (C), comprising at least one additive (A) wherein the additive composition (AC) has an HLB value of greater than 4.0, preferably in the range of from 4.0 to 22.0, determined according to the organic conception diagram method.

[0103] 9. The process according to embodiment 8, wherein the thermoplastic elastomer (TPE-1) is a thermoplastic polyurethane, preferably a thermoplastic polyurethane based on a polyester.

[0104] 10. The process according to embodiment 8 or 9, wherein the HLB value of the additive (A) is 4.0 or greater, preferably in the range of from 4.0 to 22.0, determined according to the organic conception diagram method.

[0105] 11 . The process according to any one of embodiments 8 to 10, wherein the additive (A) is characterized by the general formula

[0106] Ri-O-(CH2CH2O)n-R2 or

[0107] Rl-O-(CH2CH3CH2O)n-(CH2CH2O)n-R2 240082W001

[0108] - 12 - wherein Ri or R2=H, or alkyl chain with carbon number from 1 to 18, could contain 1 or more unsaturated group and / or 1 or more branched group and / or 1 or more ring group and / or 1 or more OH group or the general formula

[0109] Ri - COO - (CH2CH2O)n - H

[0110] Ri - COO - (CH2CH2O)n - CO - R2wherein Ri or R2= alkyl chain with carbon number from 1 to 18, could contain 1 or more unsaturated group and / or 1 or more branched group and / or 1 or more ring group and / or 1 or more OH group..

[0111] 12. The process according to any one of embodiments 8 to 10, wherein the additive (A) is selected from the group consisting of polyethylene glycols, polyethylene glycol oleate, polyethylene glycol ricinoleate, sorbitan stearate, glyceryl laurate, and fatty alcohol alkoxylates.

[0112] 13. Use of the composition according to any one of embodiments 1 to 6 for the preparation of an article.

[0113] 14. Use of the composition (01) for the preparation of an article, the composition comprising

[0114] (a) a thermoplastic elastomer (TPE-1) as component (01);

[0115] (b) a carbodiimide (CD) in an amount of from 0.1 to 5% by weight based on the sum of components of composition (C);

[0116] (c) an additive composition (AC) in an amount of from 0.1 to 2% by weight based on the sum of components of composition (C), comprising at least one additive (A); wherein the additive composition (AC) has an HLB value of greater than 4.0, preferably in the range of from 4.0 to 22.0, determined according to the organic conception diagram method.

[0117] 15. The use according to embodiment 14, wherein the thermoplastic elastomer (TPE-1) is a thermoplastic polyurethane, preferably a thermoplastic polyurethane based on a polyester.

[0118] 16. The use according to embodiment 14 or 15, wherein the HLB value of the additive (A) is 4.0 or greater, preferably in the range of from 4.0 to 22.0, determined according to the organic conception diagram method.

[0119] 17. The use according to any one of embodiments 14 to 16, wherein the additive (A) is characterized by the general formula 240082W001

[0120] - 13 -

[0121] Ri-O-(CH2CH2O)n-R2or

[0122] Ri-O-(CH2CH3CH2O)n-(CH2CH2O)n-R2wherein Ri or R2=H, or alkyl chain with carbon number from 1 to 18, could contain 1 or more unsaturated group and / or 1 or more branched group and / or 1 or more ring group and / or 1 or more OH group or the general formula

[0123] Ri - COO - (CH2CH2O)n - H

[0124] Ri - COO - (CH2CH2O)n - CO - R2wherein Ri or R2= alkyl chain with carbon number from 1 to 18, could contain 1 or more unsaturated group and / or 1 or more branched group and / or 1 or more ring group and / or 1 or more OH group..

[0125] 18. The use according to any one of embodiments 14 to 16, wherein the additive (A) is selected from the group consisting of polyethylene glycols, polyethylene glycol oleate, polyethylene glycol ricinoleate, sorbitan stearate, glyceryl laurate, and fatty alcohol alkoxylates.

[0126] 19. Article comprising a composition according to any one of embodiments 1 to 6.

[0127] 20. Use of a mixture (M1) comprising a carbodiimide (CD) and an additive composition (AC) comprising at least one additive (A) as a stabilizer for a composition comprising a thermoplastic elastomer, preferably for enhancing at least one property for a composition comprising the thermoplastic elastomer, wherein the additive composition (AC) has an HLB value of greater than 4.0, preferably in the range of from 4.0 to 22.0, determined according to the organic conception diagram method.

[0128] 21 . Composition (C) comprising

[0129] (a) a thermoplastic elastomer (TPE-1) as component (C1);

[0130] (b) a carbodiimide (CD) in an amount of from 0.1 to 5% by weight based on the sum of components of composition (C);

[0131] (c) an additive composition (AC) in an amount of from 0.1 to 2% by weight based on the sum of components of composition (C), comprising at least one additive (A); wherein the additive composition (AC) has an HLB value of greater than 4.0, preferably in the range of from 4.0 to 22.0, determined according to the organic conception diagram method as described in method example 1, and 240082W001

[0132] - 14 - wherein the additive (A) is characterized by the general formula

[0133] Ri-O-(CH2CH2O)n-R2or

[0134] Ri-O-(CH2CH3CH2O)n-(CH2CH2O)n-R2wherein Ri or R2=H, or alkyl chain with carbon number from 1 to 18, could contain 1 or more unsaturated group and / or 1 or more branched group and / or 1 or more ring group and / or 1 or more OH group or the general formula

[0135] Ri - COO - (CH2CH2O)n - H

[0136] Ri - COO - (CH2CH2O)n - CO - R2wherein Ri or R2= alkyl chain with carbon number from 1 to 18, could contain 1 or more unsaturated group and / or 1 or more branched group and / or 1 or more ring group and / or 1 or more OH group

[0137] 22. The composition according to embodiment 21, wherein the thermoplastic elastomer (TPE-1) is a thermoplastic polyurethane, preferably a thermoplastic polyurethane based on a polyester.

[0138] 23. The composition according to embodiment 21 or 22, wherein the HLB value of the additive (A) is 4.0 or greater, preferably in the range of from 4.0 to 22.0, determined according to the organic conception diagram method as described in method example 1 .

[0139] 24. The composition according to any one of embodiments 21 to 23, wherein the additive (A) is selected from the group consisting of polyethylene glycols, polyethylene glycol oleate, polyethylene glycol ricinoleate, sorbitan stearate, glyceryl laurate, and fatty alcohol alkoxylates.

[0140] 25. A process for preparing a composition comprising a thermoplastic elastomer (TPE-1), a carbodiimide (CD), and an additive composition (AC) according to any one of embodiments 1 to 4, comprising

[0141] (I) mixing the thermoplastic elastomer(TPE-l), the carbodiimide (CD) and the additive composition (AC).

[0142] 26. Use of the composition according to any one of embodiments 21 to 24 for the preparation of an article. 240082W001

[0143] - 15 -

[0144] 27. Use of a mixture (M1) comprising a carbodiimide (CD) and an additive composition (AC) comprising at least one additive (A) as a stabilizer for a composition comprising a thermoplastic elastomer, preferably for enhancing at least one property for a composition comprising the thermoplastic elastomer, wherein the additive composition (AC) has an HLB value of greater than 4.0, preferably in the range of from 4.0 to 22.0, determined according to the organic conception diagram method as described in method example 1 , wherein the additive (A) is characterized by the general formula

[0145] Ri-O-(CH2CH2O)n-R2 or

[0146] Rl-O-(CH2CH3CH2O)n-(CH2CH2O)n-R2 wherein Ri or R2=H, or alkyl chain with carbon number from 1 to 18, could contain 1 or more unsaturated group and / or 1 or more branched group and / or 1 or more ring group and / or 1 or more OH group or the general formula

[0147] Ri - COO - (CH2CH2O)n - H

[0148] Ri - COO - (CH2CH2O)n - CO - R2wherein Ri or R2= alkyl chain with carbon number from 1 to 18, could contain 1 or more unsaturated group and / or 1 or more branched group and / or 1 or more ring group and / or 1 or more OH group.

[0149] The following examples serve to illustrate the invention without having a limiting effect.

[0150] Examples

[0151] 1. Starting Materials Used :

[0152] Polyol 1 is Lupraphen®6600 / 1 , molar mass=2000 g / mol, OH number=51.5 - 51.6 Polyol 2 is Lupraphen®6607 / 1 , molar mass=2000 g / mol, OH number=56.0 - 56.3 Chain extender (CE) 1 is 1 ,4-butanediol, molar mass=90.10 g / mol

[0153] Isocyanate 1 is diphenylmethane 4,4'-diisocyanat (4,4'-MDI), molar mass=250.26 g / mol Hydrolysis stabilizer 1 is a carbodiimide-based hydrolysis stabilizer (Elastostab® H01) Surfactant 240082W001

[0154] - 16 -

[0155] 2. Process

[0156] Polymer polyol 1 is reacted together with chain extender 1 and isocyanate 1. Hydrolysis stabilizer 1 is likewise added to the reaction mixture. The resultant reaction mixture is poured out onto a heatable plate and reacted to completion for 10 minutes at 120° C. The resultant polymer sheet is then conditioned for 24 hours at 80° C. The polymer sheet is then granulated, and the granules are molded by the injection molding process to give a test sheet.

[0157] 3. Example 1 (Comparison / without additives)

[0158] 63.31% by weight of polymer polyol 1, 7.71% by weight of CE 1, and 28.98% by weight of isocyanate 1 are reacted by process.

[0159] Table 1, 2 shows the results.

[0160] 4. Example 2 (Comparison / Hydrolysis stabilizer without surfactant)

[0161] 62.72% by weight of polymer polyol 1, 7.64% by weight of CE 1, 29.02% by weight of isocyanate 1, and 0.63% by weight of hydrolysis stabilizer are reacted by process.

[0162] Table 1, 2 shows the results.

[0163] 5. Example 3 (in accordance with the invention)

[0164] 62.31% by weight of polymer polyol 1, 7.78% by weight of CE 1, 29.04% by weight of isocyanate 1, 0.62% by weight of hydrolysis stabilizer, and 0.25% of surfactant 1 are reacted by process.

[0165] Table 1, 2 shows the results.

[0166] 6. Example 4 (in accordance with the invention) 240082W001

[0167] - 17 -

[0168] 62.31% by weight of polymer polyol 1, 7.78% by weight of CE 1, 29.04% by weight of isocyanate 1, 0.62% by weight of hydrolysis stabilizer, and 0.25% of surfactant 2 are reacted by process.

[0169] Table 1, 2 shows the results.

[0170] 7. Example 5 (in accordance with the invention)

[0171] 62.31% by weight of polymer polyol 1, 7.78% by weight of CE 1, 29.04% by weight of isocyanate 1, 0.62% by weight of hydrolysis stabilizer, and 0.25% of surfactant 3 are reacted by process.

[0172] Table 1, 2 shows the results.

[0173] 8. Example 6 (Comparison / without additives)

[0174] 64.77% by weight of polymer polyol 2, 7.19% by weight of CE 1, and 28.05% by weight of isocyanate 1 are reacted by process.

[0175] Table 3, 4 shows the results.

[0176] 9. Example 7 (Comparison / Hydrolysis stabilizer without surfactant)

[0177] 64.15% by weight of polymer polyol 2, 7.12% by weight of CE 1, 28.09% by weight of isocyanate 1, and 0.64% by weight of hydrolysis stabilizer are reacted by process.

[0178] Table 3, 4 shows the results.

[0179] 10. Example 8 (in accordance with the invention)

[0180] 64.20% by weight of polymer polyol 2, 7.03% by weight of CE 1, 27.87% by weight of isocyanate 1, 0.64% by weight of hydrolysis stabilizer, and 0.26% of surfactant 1 are reacted by process.

[0181] Table 3, 4 shows the results.

[0182] 11 . Example 9 (in accordance with the invention)

[0183] 64.20% by weight of polymer polyol 2, 7.03% by weight of CE 1, 27.87% by weight of isocyanate 1, 0.64% by weight of hydrolysis stabilizer, and 0.26% of surfactant 2 are reacted by process. 240082W001

[0184] - 18 -

[0185] Table 3, 4 shows the results.

[0186] 12. Example 10 (In Accordance with the Invention) 64.20% by weight of polymer polyol 2, 7.03% by weight of CE 1 , 27.87% by weight of isocyanate 1 , 0.64% by weight of hydrolysis stabilizer, and 0.26% of surfactant 3 are reacted by process.

[0187] Table 3, 4 shows the results.

[0188] Table 1

[0189] Table 2

[0190] Table 3 240082W001

[0191] - 19-

[0192] Table 4 240082W001

[0193] - 20 -

[0194] 13. Method example 1 - determination of the HLB value according to the organic conception diagram method

[0195] The HLB value of a component can be determined using the organic conception diagram method developed by Nihon Emulsion Co., Ltd. (https: / / www.nihon-emulsion.co.jp / en / tech / organic.html).

[0196] According to the Organic Conception Diagram method, the property of a compound in terms of physical chemistry is considered in such a way that the property that depends much on Van Der Waals force is called "Organic nature" and the one that depends much on electric affinity is called "Inorganic nature".

[0197] Thus considering the property of a compound is expressed by a combination of two characteristic values, organic value = OV and inorganic value = IV which are inherent to each compound. By using the data available for chemical groups and radicals from Nihon Emulsion Co. Ltd, the values can be determined for a given structure (https: / / www.nihon-emulsion.co.jp / shared / pdf / tech / organic_and_lnorganic_values_en.pdf).

[0198] Using the inorganic value and the organic value, the HLB value of a compound can be calculated using equation (1) and (2):

[0199] (1) inorganic value (IV)Zorganic value (OV) = IOB

[0200] (2) HLB = IOBx10

[0201] Literature cited

[0202] US2020071486A1

[0203] EP0381897A1

[0204] DE-A 4318979

[0205] DE-A 4442724

[0206] EP-A 460481

[0207] EP0628541

[0208] "Kunststoffhandbuch [Plastics Handbook], volume 7, Polyurethane [Polyurethanes]”, Carl Hanser Verlag, 3rd edition 1993, chapter 3.1

[0209] Kunststoffhandbuch, volume VII, edited by Vieweg and Hdchtlen, Carl Hanser Verlag, Munich 1966 (p. 103-113)

Claims

240082W001- 21 -Claims1 . Composition (C) comprising(a) a thermoplastic elastomer (TPE-1) as component (C1);(b) a carbodiimide (CD) in an amount of from 0.1 to 5% by weight based on the sum of components of composition (C);(c) an additive composition (AC) in an amount of from 0.1 to 2% by weight based on the sum of components of composition (C), comprising at least one additive (A); wherein the additive composition (AC) has an HLB value of greater than 4.0, preferably in the range of from 4.0 to 22.0, determined according to the organic conception diagram method as described in method example 1, and wherein the additive (A) is characterized by the general formulaRi-O-(CH2CH2O)n-R2 orRl-O-(CH2CH3CH2O)n-(CH2CH2O)n-R2 wherein Ri or R2=H, or alkyl chain with carbon number from 1 to 18, could contain 1 or more unsaturated group and / or 1 or more branched group and / or 1 or more ring group and / or 1 or more OH group or the general formulaRi - COO - (CH2CH2O)n - HRi - COO - (CH2CH2O)n - CO - R2wherein Ri or R2= alkyl chain with carbon number from 1 to 18, could contain 1 or more unsaturated group and / or 1 or more branched group and / or 1 or more ring group and / or 1 or more OH group2. The composition according to claim 1, wherein the thermoplastic elastomer (TPE-1) is a thermoplastic polyurethane, preferably a thermoplastic polyurethane based on a polyester.

3. The composition according to claim 1 or 2, wherein the HLB value of the additive (A) is 4.0 or greater, preferably in the range of from 4.0 to 22.0, determined according to the organic conception diagram method as described in method example 1.240082W001- 22 -4. The composition according to any one of claims 1 to 3, wherein the additive (A) is selected from the group consisting of polyethylene glycols, polyethylene glycol oleate, polyethylene glycol ricinoleate, sorbitan stearate, glyceryl laurate, and fatty alcohol alkoxylates.

5. A process for preparing a composition comprising a thermoplastic elastomer (TPE-1 ), a carbodiimide (CD), and an additive composition (AC) according to any one of claims 1 to 4, comprising(I) mixing the thermoplastic elastomer(TPE-l), the carbodiimide (CD) and the additive composition (AC).

6. Use of the composition according to any one of claims 1 to 4 for the preparation of an article.

7. Use of a mixture (M1) comprising a carbodiimide (CD) and an additive composition (AC) comprising at least one additive (A) as a stabilizer for a composition comprising a thermoplastic elastomer, preferably for enhancing at least one property for a composition comprising the thermoplastic elastomer, wherein the additive composition (AC) has an HLB value of greater than 4.0, preferably in the range of from 4.0 to 22.0, determined according to the organic conception diagram method as described in method example 1, wherein the additive (A) is characterized by the general formulaRi-O-(CH2CH2O)n-R2 orRl-O-(CH2CH3CH2O)n-(CH2CH2O)n-R2 wherein Ri or R2=H, or alkyl chain with carbon number from 1 to 18, could contain 1 or more unsaturated group and / or 1 or more branched group and / or 1 or more ring group and / or 1 or more OH group or the general formulaRi - COO - (CH2CH2O)n - HRi - COO - (CH2CH2O)n - CO - R2wherein Ri or R2= alkyl chain with carbon number from 1 to 18, could contain 1 or more unsaturated group and / or 1 or more branched group and / or 1 or more ring group and / or 1 or more OH group.

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