Patent Application
20220213266
The present invention relates to a composition comprising at least one thermoplastic polyurethane (TPU-1) and a copolyamide (PA-1), prepared by polymerizing at least one lactam, and a monomer mixture (M) comprising at least one C32-C40 dimer acid as component (B1) and at least one C4-C12 diamine as component (B2). The present invention further relates to a process for producing such compositions and to the use of a composition of the invention for production of shaped articles.
Thermoplastic polyurethanes are widely known and are used as materials in many sectors. The properties can be adjusted within wide ranges. Typically, thermoplastic polyurethanes can be processed within a particular temperature range. A problem in the processing is the redissociation of the urethane bond, which, in the course of processing, can lead to degradation of the thermoplastic polyurethanes and to very low melt strengths, and hence to problems in extrusion.
Particularly hard TPUs over and above about 40 D are difficult to process. For processing, the semicrystalline materials firstly have to be melted at high temperatures; secondly, the materials break down at these high temperatures. As a result, materials can be processed only within a very small temperature range. This is a problem especially when different temperatures occur at the nozzle in processes for extrusion of large shaped articles. In that case, there may be instances where the material in the colder zones of the nozzle has not yet completely melted, but is already breaking down in the hotter zones of the nozzle.
Polyamides generally have, in contrast, high melt strength and very wide processing ranges. Polyamides are of particular significance in industry since they feature very good mechanical properties and especially have high strength and toughness, good chemical stability and high abrasion resistance. They are used, for example, for production of fishing line, climbing rope and carpet backing. Furthermore, polyamides find use for production of packing films and packing sheaths.
For packing films and packing sheaths, copolyamides that combine positive properties of different polyamides are frequently also used. The prior art describes various copolyamides.
EP 0 352 562 describes films composed of copolyamides, wherein the copolyamides have been prepared from ε-caprolactam and preferably 1 to 10 parts by weight of a dimer acid and a diamine. DE 28 46 596 describes shaped articles composed of a copolyamide of caprolactam, fatty acid dimers and hexamethylenediamine. Of particular industrial interest are nylon-6 and nylon-6,6, owing to their excellent properties can be used in many sectors. However, nylon-6 and nylon-6,6 have very high melting temperatures.
WO 2018/050487 A1 describes copolyamides, wherein the copolyamide has been prepared by polymerizing at least one lactam (A) and a monomer mixture (M). Additionally described is the production of a polymer film (P) comprising such copolyamides.
Proceeding from the prior art, it was an object of the present invention to provide materials that have improved melt strength and hence a broad processing range, particularly within the hardness range from 40 to 90 D. It was a further object of the present invention to provide materials that have improved melt strength and hence a broad processing range, and are additionally transparent.
This object is achieved in accordance with the invention by a composition (Z-1) comprising at least
It has been found that, surprisingly, copolyamide (PA-1) can be blended with various thermoplastic polyurethanes. The blends have excellent mechanical properties, high toughness and high melt strength. It has also been found that many flame retardants, including flame retardants having relatively low breakdown temperature, can be incorporated directly into a corresponding blend or else into the copolyamide (PA-1). The materials obtained have excellent mechanical properties, high toughness and good flammability performance.
The composition (Z-1) of the invention comprises at least one thermoplastic polyurethane (TPU-1) and a copolyamide (PA-1).
Thermoplastic polyurethanes are known in principle. They are typically produced by reaction of isocyanates and isocyanate-reactive compounds and chain extenders optionally in the presence of at least one catalyst and/or customary auxiliaries and/or additives. Isocyanates, isocyanate-reactive compounds and chain extenders are also referred to, individually or collectively, as formation components.
In the context of the present invention, the customarily used isocyanates and isocyanate-reactive compounds are suitable in principle.
Isocyanate-reactive compounds that may be used in principle include all suitable compounds known to those skilled in the art. According to the invention, at least one diol is preferably used as isocyanate-reactive compound. It is possible here in the context of the present invention to use any suitable diols, for example polyether diols or polyester diols or mixtures of two or more of these.
According to the invention, the thermoplastic polyurethane (TPU-1) is prepared preferably by using a polyol composition typically comprising at least one polyol (P1) as isocyanate-reactive compound. In the context of the present invention, it is possible in principle to use any polyols suitable per se, for example polyesterols, polyetherols and/or polycarbonate diols. For example, the polyol used may have a molecular weight (Mn) in the range from 500 g/mol to 8000 g/mol, and preferably an average functionality with respect to isocyanates of 1.8 to 2.3, preferably 1.9 to 2.2, especially 2. The number-average molecular weight is determined to DIN 55672-1 unless stated otherwise.
The polyol (P1) used preferably has a molecular weight in the range from 600 to 2000 daltons, further preferably a molecular weight in the range from 750 to 5000 daltons, especially a molecular weight of about 1000 daltons.
Polyesters used may be polyesters based on diacids and diols. Diols used are preferably diols having 2 to 10 carbon atoms, for example ethanediol, butanediol or hexanediol, especially butane-1,4-diol or mixtures thereof. Diacids used may be any known diacids, for example linear or branched-chain diacids having four to 12 carbon atoms or mixtures thereof.
It is further possible in the context of the present invention to use polyether polyols, for example those based on commonly known starter substances and customary alkylene oxides, preferably ethylene oxide, propylene oxide and/or butylene oxide, further preferably polyetherols based on 1,2-propylene oxide and ethylene oxide, and especially polyoxytetramethylene glycols. One advantage of the polyether polyols is that they have relatively high hydrolysis stability.
Also suitable are polyetherols having a low level of unsaturation. Polyols having a low level of unsaturation in the context of this invention are especially understood to mean polyether alcohols having a content of unsaturated compounds of less than 0.02 meq/g, preferably less than 0.01 meq/g. Such polyether alcohols are usually prepared by addition of alkylene oxide, especially ethylene oxide, propylene oxide and mixtures thereof, onto the above-described diols or triols in the presence of highly active catalysts.
Such highly active catalysts are preferably cesium hydroxide and multi metal cyanide catalysts, also referred to as DMC catalysts. A frequently and preferentially used DMC catalyst is zinc hexacyanocobaltate. The DMC catalyst can be left in the polyether alcohol after the reaction; it is typically removed, for example by sedimentation or filtration.
In addition, in the context of the present invention, it is possible to use polytetrahydrofurans, for example having an average molecular weight Mn in the range from 400 to 1800 g/mol, preferably from polytetrahydrofurans having an average molecular weight Mn in the range from 600 to 1500 g/mol, more preferably from polytetrahydrofurans having an average molecular weight Mn in the range from 750 to 1250 g/mol, for example in the range from 900 to 1100 g/mol.
It has been found that compositions having a particularly advantageous profile of properties are obtained especially in the case of use of polyols having an average molecular weight in the range from 900 to 1100 g/mol. For instance, the compositions of the invention firstly have a low melting point, and secondly good low-temperature properties.
Examples of suitable polycarbonate diols include polycarbonate diols based on alkanediols. Suitable polycarbonate diols are strictly difunctional OH-functional polycarbonate diols, preferably strictly difunctional OH-functional aliphatic polycarbonate diols. Suitable polycarbonate diols are based, for example, on butane-1,4-diol, pentane-1,5-diol or hexane-1,6-diol, especially butane-1,4-diol, pentane-1,5-diol, hexane-1,6-diol, 3-methylpentane-1,5-diol or mixtures thereof, more preferably butane-1,4-diol, pentane-1,5-diol, hexane-1,6-diol or mixtures thereof. In the context of the present invention, preference is given to using polycarbonate diols based on butane-1,4-diol and hexane-1,6-diol, polycarbonate diols based on pentane-1,5-diol and hexane-1,6-diol, polycarbonate diols based on hexane-1,6-diol and mixtures of two or more of these polycarbonate diols. Suitable polycarbonate diols have, for example, an average molecular weight Mn in the range from 800 to 1200 g/mol.
It has been found that the use of polycarbonate diols affords compositions suitable for those applications having good hydrolysis stability and good aging resistance. For instance, the compositions of the invention, when polycarbonate diols are used as polyols, as well as good low-temperature properties, also have high hydrolysis resistance and good aging resistance.
However, the polymer composition, in the context of the present invention, as well as the polyol (P1), may also comprise one or more chain extenders (KV1) and optionally (KV2) and further isocyanate-reactive compounds. For example, the polyol composition may comprise further polyols having an average molecular weight Mn in the range from 800 to 1200 g/mol.
According to the invention, it is also possible to use mixtures of different chain extenders. Chain extenders (KV1) and (KV2) used may be commonly known aliphatic, araliphatic, aromatic and/or cycloaliphatic compounds having a molecular weight, preferably average molecular weight, of 50 g/mol to 499 g/mol, preferably difunctional compounds. Preference is given, for example, to alkanediols having 2 to 10 carbon atoms in the alkylene radical, 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, further preferably unbranched alkanediols, especially propane-1,3-diol, butane-1,4-diol and hexane-1,6-diol.
In a further embodiment, the present invention accordingly also relates to a composition as described above, wherein the chain extender (KV1) and/or the chain extender (KV2) is selected from the group consisting of ethane-1,2-diol, propane-1,3-diol, butane-1,4-diol and hexane-1,6-diol, diethylene glycol, triethylene glycol, hydroquinone bis(2-hydroxyethyl) ether and bis(2-hydroxyethyl) terephthalate.
The chain extender (KV1) in the context of the present invention is further preferably selected from the group consisting of ethane-1,2-diol, propane-1,3-diol, butane-1,4-diol and hexane-1,6-diol. In a further embodiment, the present invention accordingly also relates to a composition as described above, wherein the chain extender (KV1) is butane-1,4-diol.
According to the invention, it is also possible to use further chain extenders in the polyol composition.
It is also possible in accordance with the invention to use a polyhydric alcohol, for example propanediol and/or a further diol, that has been obtained at least partly from renewable raw materials. It is possible here that the polyhydric alcohol has been obtained partly or entirely from renewable raw materials. According to the invention, at least one of the polyhydric alcohols used may be obtained at least partly from renewable raw materials.
What is called bio-propane-1,3-diol is obtainable, for example, from corn and/or sugar. A further option is the conversion of glycerol wastes from biodiesel production. In a further preferred embodiment of the invention, the polyhydric alcohol is propane-1,3-diol that has been at least partly obtained from renewable raw materials.
In a further embodiment, the present invention accordingly relates to a composition as described above, wherein the thermoplastic polyurethane is based to an extent of at least 30% on renewable raw materials. One suitable method of determination is the C14 method, for example.
In the context of the present invention, the organic isocyanates customarily used are suitable in principle. Organic isocyanates used may be aliphatic, cycloaliphatic, araliphatic and/or aromatic isocyanates, more preferably tri-, tetra-, penta-, hexa-, hepta- and/or octamethylene diisocyanate, 2-methylpentamethylene 1,5-diisocyanate, 2-ethylbutylene 1,4-diisocyanate, pentamethylene 1,5-diisocyanate, butylene 1,4-diisocyanate, 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 and/or dicyclohexylmethane 4,4′-, 2,4′- and 2,2′-diisocyanate, diphenylmethane 2,2′-, 2,4′- and/or 4,4′-diisocyanate (MDI), naphthylene 1,5-diisocyanate (NDI), tolylene 2,4- and/or 2,6-diisocyanate (TDI), dimethyl diphenyl 3,3′-diisocyanate, 1,2-diphenylethane diisocyanate and/or phenylene diisocyanate. Particular preference is given to using 4,4′-MDI only.
Accordingly, the present invention, in a further embodiment, also relates to a composition as described above, wherein the thermoplastic polyurethane (TPU-1) is based on an aromatic diisocyanate.
In an alternative embodiment, the present invention, in a further embodiment, also relates to a composition as described above, wherein the thermoplastic polyurethane (TPU-1) is based on an aliphatic diisocyanate.
In a further embodiment, the present invention accordingly relates to a composition as described above, wherein the thermoplastic polyurethane is based on diphenylmethane 4.4′-diisocyanate.
Further suitable aliphatic isocyanates are, for example, hexamethylene diisocyanate (HDI), or 1-isocyanato-4-[(4-isocyanatocyclohexyl) methyl]cyclohexane (H12MDI).
According to the invention, particularly preferred isocyanates are hexamethylene diisocyanate (HDI), diphenylmethane 2,2′-, 2,4′- and/or 4,4′-diisocyanate (MDI) and tolylene 2,4- and/or 2,6-diisocyanate (TDI), or 1-isocyanato-4-[(4-isocyanatocyclohexyl)methyl]cyclohexane (H12MDI), particular preference being given to diphenylmethane 2,2′-, 2,4′- and/or 4,4′-diisocyanate (MDI), especially diphenylmethane 4,4′-diisocyanate.
As well as the isocyanate composition and the polyol composition, the thermoplastic polyurethane (TPU1) may be prepared using further components, for example suitable catalysts or auxiliaries.
In a preferred embodiment, catalysts that accelerate especially the reaction between the NCO groups of the diisocyanates and the hydroxyl groups of the isocyanate-reactive compound and the chain extender are tertiary amines, especially triethylamine, dimethylcyclohexylamine, N-methylmorpholine, N,N′-dimethylpiperazine, 2-(dimethylaminoethoxy)ethanol, diazabicyclo[2.2.2]octane; in another preferred embodiment, these are organic metal compounds such as titanate esters, iron compounds, preferably iron(III) acetylacetonate, tin compounds, preferably tin diacetate, tin dioctoate, tin dilaurate or the dialkyltin salts of aliphatic carboxylic acids, preferably dibutyltin diacetate, dibutyltin dilaurate, or bismuth salts in which bismuth is preferably in oxidation states 2 or 3, especially 3. Salts of carboxylic acids are preferred. Carboxylic acids used are preferably carboxylic acids having 6 to 14 carbon atoms, more preferably having 8 to 12 carbon atoms. Examples of suitable bismuth salts are bismuth(III) neodecanoate, bismuth 2-ethylhexanoate and bismuth octanoate.
The catalysts are preferably used in amounts of 0.0001 to 0.1 parts by weight per 100 parts by weight of the isocyanate-reactive compound. Preference is given to using tin catalysts, especially tin dioctoate.
In addition to catalysts it is also possible to add customary auxiliaries. Examples include surface-active substances, fillers, further flame retardants, nucleation agents, oxidation stabilizers, lubrication and demolding aids, dyes and pigments, optionally stabilizers, for example against hydrolysis, light, heat or discoloration, inorganic and/or organic fillers, reinforcers and plasticizers. Suitable auxiliary and additive substances may be found for example in Kunststoffhandbuch, volume VII, edited by Vieweg and Höchtlen, Carl Hanser Verlag, Munich 1966 (p. 103-113).
Production processes suitable for thermoplastic polyurethanes are disclosed for example in EP 0 922 552 A1. DE 101 03 424 A1 or WO 2006/072461 A1. Production is typically effected on a belt apparatus or in a reactive extruder, but can also be effected on the laboratory scale, for example in a manual casting method. Depending on the physical properties of the components these are all mixed with one another directly or individual components are premixed and/or prereacted, for example to give prepolymers, and only then subjected to polyaddition. In a further embodiment a thermoplastic polyurethane is first produced from the building block components, optionally together with catalyst, into which auxiliaries may optionally also be incorporated. In that case, at least one filler is introduced into this material and distributed homogeneously. Homogeneous distribution is preferably effected in an extruder, preferably in a twin-screw extruder. According to the invention, it is preferable to add the filler in portions, for example a portion of the extruder intake and a further portion of a second dosage site, for example a side feeder. The hardness of the TPUs can be set within relatively broad molar ratios by varying the amounts of the formation components used, typically with rising hardness as the content of chain extender increases.
According to the invention, the mixing ratio of the components used for preparation of the thermoplastic polyurethane may vary within wide ranges. For example, the chain extenders and the polyol used may be used in a molar mixing ratio in the range from 20:1 to 1:1, preferably in the range from 18:1 to 2:1, further preferably in the range from 17:1 to 3:1, more preferably in the range from 15:1 to 4:1.
If the mixtures of different chain extenders are used, the mixing ratio of the chain extenders used may vary within wide ranges. For example, the chain extenders may be used in a molar mixing ratio KV1:KV2 in the range from 20:1 to 3:1, preferably in the range from 15:1 to 4:1, further preferably in the range from 17:1 to 3:1, more preferably in the range from 15:1 to 4:1.
The thermoplastic polyurethane used in accordance with the invention preferably has a hardness in the range from 70 A to 90 D determined according to DIN ISO 7619-1 (Shore A hardness test (3s)), preferably in the range from 80 A to 95 A determined according to DIN ISO 7619-1, more preferably in the range from 80 A to 90 A determined according to DIN ISO 7619-1, especially preferably in the range from 85 A to 90 A determined according to DIN ISO 7619-1.
In a further embodiment, the present invention accordingly also relates to a composition as described above, wherein the thermoplastic polyurethane (TPU-1) has a Shore hardness in the range from 70 A to 90 D determined according to DIN 53505.
For preparation of the thermoplastic polyurethanes of the invention, the formation components are preferably reacted in the presence of catalysts and optionally auxiliaries and/or additives in such amounts that the ratio of equivalence of NCO groups in the diisocyanates to the sum total of the hydroxyl groups in the further formation components is 0.9 to 1.1:1, preferably 0.95 to 1.05:1 and especially about 0.95 to 1.00:1.
Preference is given in accordance with the invention to using thermoplastic polyurethanes where the thermoplastic polyurethane has an average molecular weight (Mw) in the range from 50 000 to 500 000 Da. The upper limit for the average molecular weight (Mw) of the thermoplastic polyurethanes is generally determined by processibility and by the spectrum of properties desired. Further preferably, the thermoplastic polyurethane has an average molecular weight (Mw) in the range from 50 000 to 250 000 Da, especially preferably in the range from 50 000 to 150 000 Da.
It is also possible in accordance with the invention for the composition to comprise two or more thermoplastic polyurethanes differing for example in their average molecular weight or in their chemical composition. For example, the composition of the invention may comprise a first thermoplastic polyurethane TPU-1 and a second thermoplastic polyurethane TPU-2, for example a thermoplastic polyurethane TPU-1 based on an aliphatic diisocyanate and a further TPU-2 based on an aromatic diisocyanate.
TPU-1 is prepared here using an aliphatic isocyanate, and TPU-2 using an aromatic isocyanate.
Organic isocyanates used to prepare the TPU-1 are preferably aliphatic or cycloaliphatic isocyanates, more preferably tri-, tetra-, penta-, hexa-, hepta- and/or octamethylene diisocyanate, 2-methylpentamethylene 1,5-diisocyanate, 2-ethylbutylene 1,4-diisocyanate, pentamethylene 1,5-diisocyanate, butylene 1,4-diisocyanate, 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 and/or dicyclohexylmethane 4,4′-, 2,4′- and 2,2′-diisocyanate.
In a further embodiment, the present invention therefore relates to a composition as described above, wherein the thermoplastic polyurethane TPU-1 is based on at least one aliphatic diisocyanate selected from the group consisting of hexamethylene diisocyanate and di(isocyanatocyclohexyl)methane.
Organic isocyanates (a) used for the preparation of TPU-2 are preferably araliphatic and/or aromatic isocyanates, more preferably diphenylmethane 2,2′-, 2,4′- and/or 4,4′-diisocyanate (MDI), naphthylene 1,5-diisocyanate (NDI), tolylene 2.4- and/or 2,6-diisocyanate (TDI), dimethyl diphenyl 3,3′-diisocyanate, 1,2-diphenylethane diisocyanate and/or phenylene diisocyanate. Particular preference is given to using 4,4′-MDI.
In a further embodiment, the present invention therefore relates to a composition as described above, wherein the thermoplastic polyurethane TPU-2 is based on diphenylmethane diisocyanate (MDI).
Isocyanate-reactive compounds used with preference for TPU-1 and TPU-2 are a polycarbonate diol or a polytetrahydrofuran polyol. Suitable polytetrahydrofuran polyols have, for example, a molecular weight in the range from 500 to 5000, preferably 500 to 2000, more preferably 800 to 1200.
According to the invention, TPU-1 and TPU-2 are prepared preferably by using at least one polycarbonate diol, preferably an aliphatic polycarbonate diol. Examples of suitable polycarbonate diols include polycarbonate diols based on alkanediols. Suitable polycarbonate diols are strictly difunctional OH-functional polycarbonate diols, preferably strictly difunctional OH-functional aliphatic polycarbonate diols. Suitable polycarbonate diols are based, for example, on butanediol, pentanediol or hexanediol, especially butane-1,4-diol, pentane-1,5-diol, hexane-1,6-diol, 3-methylpentane-1,5-diol or mixtures thereof, more preferably butane-1,4-diol, pentane-1,5-diol, hexane-1,6-diol or mixtures thereof. Preference is given in the context of the present invention to using polycarbonate diols based on butanediol and hexanediol, polycarbonate diols based on pentanediol and hexanediol, polycarbonate diols based on hexanediol and mixtures of two or more of these polycarbonate diols.
It is preferable when the polycarbonate diols used for preparation of TPU-1 and TPU-2 have a number-average molecular weight Mn in the range from 500 to 4000 determined by GPC, preferably in the range from 650 to 3500 determined by GPC, more preferably in the range from 800 to 3000 determined by GPC.
Chain extenders which may be used for preparation of TPU-1 and TPU-2 preferably include aliphatic, araliphatic, aromatic and/or cycloaliphatic compounds having a molecular weight of 0.05 kg/mol to 0.499 kg/mol, preferably difunctional compounds, for example diamines and/or alkanediols having 2 to 10 carbon atoms in the alkylene radical, di-, tri-, tetra-, penta-, hexa-, hepta-, octa-, nona- and/or decaalkylene glycols having 3 to 8 carbon atoms, especially 1,2-ethylene glycol, propane-1,3-diol, butane-1,4-diol, hexane-1,6-diol, preferably corresponding oligo- and/or polypropylene glycols, and it is also possible to use mixtures of the chain extenders. The compounds (c) preferably have primary hydroxyl groups only, and very particularly preference is given to using mixtures of butane-1,4-diol with a further chain extender selected from the compounds recited above, for example mixtures comprising butane-1,4-diol and a second chain extender in a molar ratio in the range from 100:1 to 1:1, preferably in a range from 95:1 to 5:1, more preferably in a range from 90:1 to 10:1.
In a further embodiment, the present invention therefore relates to a composition as described above, wherein the thermoplastic polyurethane is prepared using, as chain extender, a mixture of butane-1,4-diol and a further chain extender.
According to the invention, TPU-1 preferably has a hardness in the range from 85 A to 70 D determined according to DIN ISO 7619-1, preferably in the range from 95 A to 70 D determined according to DIN ISO 7619-1, more preferably in the range from 55 D to 65 D determined according to DIN ISO 7619-1.
According to the invention, TPU-2 preferably has a hardness in the range from 70 A to 70 D determined according to DIN ISO 7619-1, more preferably in the range from 80 A to 60 D determined according to DIN ISO 7619-1, more preferably in the range from 80 A to 90 A determined according to DIN ISO 7619-1.
In a further embodiment, the present invention therefore relates to a composition as described above, wherein the thermoplastic polyurethane TPU-1 has a Shore hardness in the range from 85 A to 65 D determined according to DIN ISO 7619-1. In a further embodiment, the present invention therefore relates to a composition as described above, wherein the thermoplastic polyurethane TPU-2 has a Shore hardness in the range from 70 A to 65 D determined according to DIN ISO 7619-1.
TPU-1 preferably has a molecular weight of more than 100 000 Da; TPU-2 preferably has a molecular weight in the range from 150 000 to 300 000 Da. The upper limit for the number-average molecular weight of the thermoplastic polyurethanes is generally determined by processibility and also the desired spectrum of properties.
In a further embodiment, the present invention therefore relates to a composition as described above, wherein the thermoplastic polyurethane TPU-1 has a molecular weight in the range from 100 000 Da to 400 000 Da. In a further embodiment, the present invention therefore relates to a composition as described above, wherein the thermoplastic polyurethane TPU-2 has a molecular weight in the range from 150 000 Da to 300 000 Da.
The composition of the invention comprises, for example, the at least one thermoplastic polyurethane TPU-1 and the at least one thermoplastic polyurethane TPU-2 in a sum total amount in the range from 5% by weight to 95% by weight based on the overall composition, especially in the range from 20% by weight to 80% by weight based on the overall composition, preferably in the range from 25% by weight to 75% by weight, more preferably in the range from 30% by weight to 70% by weight, based in each case on the sum total of components (I) and (II).
The thermoplastic polyurethanes may be prepared batchwise or continuously by the known processes, for example using reactive extruders or the belt process, by the “one-shot” process or the prepolymer process, preferably by the “one-shot” process. In these processes, the components to be reacted may be mixed with one another successively or simultaneously, with immediate onset of the reaction. In the extruder process, the formation components are introduced into the extruder individually or as a mixture, for example reacted preferably at temperatures of 100° C. to 280° C., more preferably 140° C. to 250° C., and the polyurethane obtained is then extruded, cooled, and pelletized.
The composition of the invention comprises the at least one thermoplastic polyurethane (TPU1) in an amount in the range from 5% by weight to 95% by weight based on the overall composition, especially in the range from 20% by weight to 80% by weight based on the overall composition, preferably in the range from 25% by weight to 75% by weight, based in each case on the sum total of components (I) and (II).
Accordingly, the present invention also relates, in a further embodiment, to a composition as described above, wherein the proportion of the thermoplastic polyurethane (TPU-1) in the composition is in the range from 5% to 95% by weight, based on the sum total of components (I) and (II).
The sum of components (I) and (II) here adds up to 100% by weight in each case.
In addition, the composition (Z-1) of the invention comprises at least one copolyamide (PA-1). The proportion of the copolyamide (PA-1) in the composition may vary within wide ranges and is, for example, in the range from 5% by weight to 95% by weight based on the overall composition, especially in the range from 20% by weight to 80% by weight based on the overall composition, preferably in the range from 25% by weight to 75% by weight, based in each case on the sum total of components (I) and (II).
Accordingly, the present invention also relates, in a further embodiment, to a composition as described above, wherein the proportion of the copolyamide (PA-1) in the composition is in the range from 5% to 95% by weight, based on the sum total of components (I) and (II).
In the context of the present invention, “at least one copolyamide” is understood to mean either exactly one copolyamide or a mixture of two or more copolyamides.
According to the invention, the copolyamide (PA-1) is obtainable by polymerizing the components (A) at least one lactam, and (B) a monomer mixture (M) comprising components (B1) at least one C32-C40 dimer acid and (B2) at least one C4-C12 diamine.
According to the invention, the ratio of components (A) and (B) used may vary within wide ranges. Suitable copolyamides are described, for example, in WO 2018/050487 A1. The copolyamide (PA-1) is preferably obtainable by polymerizing the following components:
(A) 15% to 84% by weight of at least one lactam,
(B) 16% to 85% by weight of a monomer mixture (M) comprising the following components:
(B1) at least one C32-C40 dimer acid and
(B2) at least one C4-C12 diamine,
where the percentages by weight of components (A) and (B) are each based on the sum total of the percentages by weight of components (A) and (B).
In the context of the present invention, the terms “component (A)” and “at least one lactam” are used synonymously and therefore have the same meaning.
The same applies to the terms “component (B)” and “a monomer mixture (M)”. These terms are likewise used synonymously in the context of the present invention and therefore have the same meaning.
In the context of the present invention, “at least one lactam” means either exactly one lactam or a mixture of two or more lactams. Preference is given to exactly one lactam.
According to the invention, the at least one copolyamide is preferably prepared by polymerizing 15% to 84% by weight of component (A) and 16% to 85% by weight of component (B), preference being given to preparing the copolyamide by polymerizing 40% to 83% by weight of component (A) and 17% to 60% by weight of component (B), and the at least one copolyamide especially preferably being prepared by polymerizing 60% to 80% by weight of component (A) and 20% to 40% by weight of component (B), where the percentages by weight of components (A) and (B) are each based on the sum total of the percentages by weight of components (A) and (B).
Preferably, the sum total of the percentages by weight of components (A) and (B) is 100% by weight.
In the context of the present invention, the percentages by weight of components (A) and (B) are based on the percentages by weight of components (A) and (B) prior to the polymerization, i.e. when components (A) and (B) have not yet reacted with one another. During the polymerization, the weight ratio of components (A) and (B) may change if appropriate.
According to the invention, the copolyamide is prepared by polymerizing components (A) and (B). The polymerization of components (A) and (B) is known per se to those skilled in the art. Typically, the polymerization of components (A) and (B) is a condensation reaction. During the condensation reaction, component (A) reacts with components (B1) and (B2) present in component (B) and if appropriate with component (B3) which is described further down and may likewise be present in component (B). This forms amide bonds between the individual components. Typically, component (A) is at least partly in open-chain form, i.e. as the amino acid, during the polymerization.
The polymerization of components (A) and (B) can take place in the presence of a catalyst. Suitable catalysts are all catalysts known to those skilled in the art that catalyze the polymerization of components (A) and (B). Such catalysts are known to those skilled in the art. Preferred catalysts are phosphorus compounds, for example sodium hypophosphite, phosphorous acid, triphenylphosphine or triphenyl phosphite.
The polymerization of components (A) and (B) forms the copolyamide, which therefore gains structural units derived from component (A) and structural units derived from component (B). Structural units derived from component (B) comprise structural units derived from components (B1) and (B2) and, optionally, from component (B3).
The polymerization of components (A) and (B) forms the copolyamide as a copolymer. The copolymer may be a random copolymer but it may likewise be a block copolymer.
In a block copolymer there is formation of blocks of units derived from component (B), and blocks of units derived from component (A). These alternate. In a random copolymer, there is alternation of structural units derived from component (A) with structural units derived from component (B). This alternation takes place randomly; for example, two structural units derived from component (B) may be followed by one structural unit derived from component (A), which is followed in turn by one structural unit derived from component (B), which is then followed by a structural unit comprising three structural units derived from component (A).
The at least one copolyamide (PA-1) is preferably a random copolymer.
The present invention therefore also provides a polymer film in which the at least one copolyamide is a random copolymer.
The preparation of the at least one copolyamide preferably comprises the following steps:
Suitable reaction conditions are described, for example, in WO 2018/050487 A1.
The polymerization in step a) may take place in any reactor known to those skilled in the art. Preference is given to stirred tank reactors. It is also possible to use auxiliaries for improving reaction management that are known to those skilled in the art, for example defoamers such as polydimethylsiloxane (PDMS).
In step b), the at least one first copolyamide obtained in step a) may be pelletized by any methods known to those skilled in the art, for example by strand pelletization or underwater pelletization.
The extraction in step c) may be effected by any methods known to those skilled in the art.
During the extraction in step c), by-products formed in step a) during the polymerization of components (A) and (B) are typically extracted from the at least one pelletized copolyamide.
In step d), the at least one extracted copolyamide obtained in step c) is dried. Processes for drying are known to those skilled in the art. According to the invention, the at least one extracted copolyamide is dried at a temperature (Tr). The temperature (Tr) is preferably above the glass transition temperature (TGC) of the at least one copolyamide and below the melting temperature (TMC) of the at least one copolyamide.
The drying in step d) is typically effected for a period in the range from 1 to 100 hours, preferably in the range from 2 to 50 hours and especially preferably in the range from 3 to 40 hours.
The at least one copolyamide typically has a glass transition temperature (TGC). The glass transition temperature (TGC) is for example in the range from 20 to 50° C., preferably in the range from 23 to 47° C. and especially preferably in the range from 25 to 45° C., determined according to ISO 1 1357-2: 2014.
Component (A) in the context of the present invention is at least one lactam. Lactams are known per se to those skilled in the art. Preference is given in accordance with the invention to lactams having 4 to 12 carbon atoms.
In the context of the present invention, “lactams” are understood to mean cyclic amides having preferably 4 to 12 carbon atoms, more preferably 5 to 8 carbon atoms, in the ring. Suitable lactams are selected for example from the group consisting of 3-aminopropanolactam (propio-3-lactam; β-lactam; β-propiolactam), 4-aminobutanolactam (butyro-4-lactam; γ-lactam; γ-butyrolactam), 5-aminopentanolactam (2-piperidinone; δ-lactam; δ-valerolactam), 6-aminohexanolactam (hexano-6-lactam; ε-lactam; ε-caprolactam), 7-aminoheptanolactam (heptano-7-lactam; ζ-lactam; ζ-heptanolactam), 8-aminooctanolactam (octano-8-lactam; η-lactam; η-octanolactam), 9-aminononanolactam (nonano-9-lactam; θ-lactam; θ-nonanolactam), 10-aminodecanolactam (decano-10-lactam; ω-decanolactam), 11-aminoundecanolactam (undecano-11-lactam; ω-undecanolactam) and 12-aminododecanolactam (dodecano-12-lactam; ω-dodecanolactam).
According to the invention, the lactams may be unsubstituted or at least monosubstituted. If at least monosubstituted lactams are used, the nitrogen atom and/or the ring carbon atoms thereof may bear one, two or more substituents selected independently from the group consisting of C5- to C10-alkyl. C5- to C6-cycloalkyl, and C5- to C10-aryl.
Suitable C5- to C10-alkyl substituents are, for example, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, and tert-butyl. A suitable C5- to C6-cycloalkyl substituent is, for example, cyclohexyl. Preferred C5- to C10-aryl substituents are phenyl and anthranyl.
Preference is given to using unsubstituted lactams, preference being given to γ-lactam (γ-butyrolactam), δ-lactam (δ-valerolactam) and ε-lactam (ε-caprolactam). Particular preference is given to δ-lactam (δ-valerolactam) and ε-lactam (ε-caprolactam), and ε-caprolactam is especially preferred.
According to the invention, component (B) is a monomer mixture (M). The monomer mixture (M) comprises components (B1), at least one C32-C40 dimer acid, and (B2), at least one C4-C12 diamine.
In the context of the present invention, a monomer mixture (M) is understood to mean a mixture of two or more monomers, where at least components (B1) and (B2) are present in the monomer mixture (M).
In the context of the present invention, the terms “component (B1)” and “at least one C32-C40 dimer acid” are used synonymously and therefore have the same meaning. The same applies to the terms “component (B2)” and “at least one C4-C12 diamine”.
These terms are likewise used synonymously in the context of the present invention and therefore have the same meaning.
The monomer mixture (M) comprises, for example, in the range from 45 to 55 mol % of component (B1) and in the range from 45 to 55 mol % of component (B2), based in each case on the sum total of the molar percentages of components (B1) and (B2), preferably based on the total molar amount of component (B).
Preferably, component (B) comprises in the range from 47 to 53 mol % of component (B1) and in the range from 47 to 53 mol % of component (B2), based in each case on the sum total of the molar percentages of components (B1) and (B2), preferably based on the total molar amount of component (B).
More preferably, component (B) comprises in the range from 49 to 51 mol % of component (B1) and in the range from 49 to 51 mol % of component (B2), based in each case on the sum total of the molar percentages of components (B1) and (B2), preferably based on the total molar amount of component (B).
The sum total of the molar percentages of components (B1) and (B2) present in component (B) typically adds up to 100 mol %.
Component (B) may also additionally comprise a component (B3), at least one C4-C20 diacid. In the context of the present invention, the terms “component (B3)” and “at least one C4-C20 diacid” are used synonymously and therefore have the same meaning.
When component (B) additionally comprises component (B3), it is preferable that component (B) comprises in the range from 25 to 54.9 mol % of component (B1), in the range from 45 to 55 mol % of component (B2) and in the range from 0.1 to 25 mol % of component (B3), based in each case on the total molar amount of component (B).
More preferably, component (B) in that case comprises in the range from 13 to 52.9 mol % of component (B1), in the range from 47 to 53 mol % of component (B2) and in the range from 0.1 to 13 mol % of component (B3), based in each case on the total molar amount of component (B).
Further preferably, component (B) in that case comprises in the range from 7 to 50.9 mol % of component (B1), in the range from 49 to 51 mol % of component (B2) and in the range from 0.1 to 7 mol % of component (B3), based in each case on the total molar amount of component (B).
When component (B) additionally comprises component (B3), the molar percentages of components (B1), (B2) and (B3) typically add up to 100 mole percent.
The monomer mixture (M) may further comprise water.
Components (B1) and (B2) and optionally (B3) of component (B) can react with one another to obtain amides. This reaction is known per se to those skilled in the art. Therefore, component (B) may comprise components (B1) and (B2) and optionally (B3) in fully reacted form, in partly reacted form or in unreacted form. Preferably, component (B) comprises components (B1), (B2) and optionally (B3) in unreacted form.
In the context of the present invention, “in unreacted form” thus means that component (B1) is present as the at least one C32-C40 dimer acid and component (B2) as the at least one C4-C12 diamine, and component (B3), if present, as the at least one C4-C20 diacid.
If components (B1) and (B2) and any (B3) present have at least partly reacted with one another, components (B1) and (B2) and any (B3) present are at least partly in amide form.
According to the invention, component (B1) is at least one C32-C40 dimer acid. In the context of the present invention. “at least one C32-C40 dimer acid” means either exactly one C32-C40 dimer acid or a mixture of two or more C32-C40 dimer acids.
Dimer acids are also referred to as dimer fatty acids. C32-C40 dimer acids are known per se to those skilled in the art and are typically prepared by dimerizing unsaturated fatty acids. This dimerization may be catalyzed by aluminas, for example. Suitable unsaturated fatty acids for preparing the at least one C32-C40 dimer acid are known to those skilled in the art and are, for example, unsaturated C16 fatty acids, unsaturated C16 fatty acids and unsaturated C20 fatty acids.
Component (B1) is therefore preferably prepared proceeding from unsaturated fatty acids selected from the group consisting of unsaturated C16 fatty acids, unsaturated C18 fatty acids and unsaturated C20 fatty acids, particular preference being given to the unsaturated C18 fatty acids. An example of a suitable unsaturated C16-fatty acid is palmitoleic acid ((9Z)-hexadeca-9-enoic acid).
Suitable unsaturated C18 fatty acids are, for example, selected from the group consisting of petroselinic acid ((6Z)-octadeca-6-enoic acid), oleic acid ((9Z)-octadeca-9-enoic acid), elaidic acid ((9E)-octadeca-9-enoic acid), vaccenic acid ((11E)-octadeca-11-enoic acid), linoleic acid ((9Z,12Z)-octadeca-9,12-dienoic acid), alpha-linolenic acid ((9Z,12Z,15Z)-octadeca-9,12,15-trienoic acid), gamma-linolenic acid ((6Z,9Z,12Z)-octadeca-6,9,12-trienoic acid), calendulic acid ((8E,10E,12Z)-octadeca-8,10,12-trienoic acid), punicic acid ((9Z,11E,13Z)-octadeca-9,11,13-trienoic acid),
alpha-eleostearic acid ((9Z,11E,13E)-octadeca-9,11,13-trienoic acid) and beta-eleostearic acid ((9E,11E,13E)-octadeca-9,11,13-trienoic acid). Particular preference is given to unsaturated cis fatty acids selected from the group consisting of petroselinic acid ((6Z)-octadeca-6-enoic acid), oleic acid ((9Z)-octadeca-9-enoic acid), elaidic acid ((9E)-octadeca-9-enoic acid), vaccenic acid ((11E)-octadeca-11-enoic acid), linoleic acid ((9Z,12Z)-octadeca-9,12-dienoic acid).
Suitable unsaturated C20 fatty acids are for example selected from the group consisting of gadoleic acid ((9Z)-eicosa-9-enoic acid), icosenoic acid ((11Z)-eicosa-11-enoic acid), arachidonic acid ((5Z,8Z,11Z,14Z)-eicosa-5,8,11,14-tetraenoic acid) and timnodonic acid ((5Z,8Z,11Z,14Z,17Z)-eicosa-5,8,11,14,17-pentaenoic acid).
Component (B1) is especially preferably at least one C36 dimer acid.
The at least one C36-dimer acid is preferably prepared from unsaturated cis fatty acids. The C36 dimer acid is more preferably prepared proceeding from cis fatty acids selected from the group consisting of petroselinic acid ((6Z)-octadeca-6-enoic acid), oleic acid ((9Z)-octadeca-9-enoic acid), elaidic acid ((9E)-octadeca-9-enoic acid),
vaccenic acid ((11E)-octadeca-11-enoic acid) and linoleic acid ((9Z,12Z)-octadeca-9,12-dienoic acid).
The preparation of component (B1) from unsaturated fatty acids can additionally form trimer acids; residues of unreacted unsaturated fatty acid may also remain.
The formation of trimer acids is known to those skilled in the art.
Preferably in accordance with the invention, component (B1) comprises at most 0.5% by weight of unreacted unsaturated fatty acid and at most 0.5% by weight of trimer acid, more preferably at most 0.2% by weight of unreacted unsaturated fatty acid and at most 0.2% by weight of trimer acid, based in each case on the total weight of component (B1).
Dimer acids (also known as dimerized fatty acids or dimer fatty acids) thus refer generally, and especially in the context of the present invention, to mixtures that are prepared by oligomerization of unsaturated fatty acids. They are preparable, for example, by catalytic dimerization of plant-derived unsaturated fatty acids, using unsaturated C16- to C20-fatty acids in particular as starting materials. The bond formation proceeds primarily by the Diels-Alder mechanism, and results, depending on the number and position of the double bonds in the fatty acids used to prepare the dimer acids, in mixtures of primarily dimeric products having cycloaliphatic, linear aliphatic, branched aliphatic, and also C6 aromatic hydrocarbon groups between the carboxyl groups. Depending on the mechanism and/or any subsequent hydrogenation, the aliphatic radicals may be saturated or unsaturated and the proportion of aromatic groups may also vary. The radicals between the carboxylic acid groups then comprise 32 to 40 carbon atoms for example. They are preferably prepared using fatty acids having 18 carbon atoms, so that the dimeric product thus has 36 carbon atoms. The radicals which join the carboxyl groups of the dimer fatty acids preferably comprise no unsaturated bonds and no aromatic hydrocarbon radicals.
In the context of the present invention, preference is thus given to using Cie fatty acids in the preparation. It is particularly preferable to use linolenic acid, linoleic acid and/or oleic acid.
Depending on reaction management the above-described oligomerization affords mixtures which comprise primarily dimeric, but also trimeric, molecules and also monomeric molecules and other by-products. Purification by distillation is customary. Commercial dimer acids generally comprise at least 80% by weight of dimeric molecules, up to 19% by weight of trimeric molecules, and not more than 1% by weight of monomeric molecules and of other by-products.
It is preferable to use dimer acids that consist to an extent of at least 90% by weight, preferably to an extent of at least 95% by weight, most preferably to an extent of at least 98% by weight, of dimeric fatty acid molecules.
The proportions of monomeric, dimeric, and trimeric molecules and of other by-products in the dimer acids may be determined by gas chromatography (GC), for example. The dimer acids are converted to the corresponding methyl esters by the boron trifluoride method (cf. DIN EN ISO 5509) before GC analysis and then analyzed by GC.
In the context of the present invention it is thus a fundamental feature of “dimer acids” that production thereof comprises oligomerization of unsaturated fatty acids. This oligomerization gives rise principally, in other words to an extent preferably of at least 80% by weight, more preferably to an extent of at least 90% by weight, even more preferably to an extent of at least 95% by weight and more particularly to an extent of at least 98% by weight, to dimeric products. The fact that the oligomerization thus forms predominantly dimeric products comprising exactly two fatty acid molecules justifies this designation, which is in any case commonplace. An alternative expression for the relevant term “dimer acids” is thus “mixture comprising dimerized fatty acids”.
The dimer acids to be used are obtainable as commercial products. Examples include Radiacid 0970, Radiacid 0971, Radiacid 0972, Radiacid 0975, Radiacid 0976, and Radiacid 0977 from Oleon, Pripol 1006, Pripol 1009, Pripol 1012, and Pripol 1013 from Croda, Empol 1008. Empol 1012. Empol 1061, and Empol 1062 from BASF SE, and Unidyme 10 and Unidyme TI from Arizona Chemical.
Component (B1) has, for example, an acid number in the range from 190 to 200 mg KOH/g.
According to the invention, component (B2) is at least one C4-C12 diamine. In the context of the present invention, “at least one C4-C12 diamine” means either exactly one C4-C12 diamine or a mixture of two or more C4-C12 diamines. In the context of the present compound. “C4-C12 diamine” is understood to mean aliphatic and/or aromatic compounds having four to twelve carbon atoms and two amino groups (—NH2 groups). The aliphatic and/or aromatic compounds may be unsubstituted or additionally at least monosubstituted. If the aliphatic and/or aromatic compounds are additionally at least monosubstituted, they may bear one, two or more substituents that do not take part in the polymerization of components (A) and (B). Such substituents are for example alkyl or cycloalkyl substituents.
These are known per se to those skilled in the art. The at least one C4-C12 diamine is preferably unsubstituted.
Examples of suitable components (B2) are selected from the group consisting of 1,4-diaminobutane (butane-1,4-diamine; tetramethylenediamine; putrescine), 1,5-diaminopentane (pentamethylenediamine; pentane-1,5-diamine; cadaverine), 1,6-diaminohexane (hexamethylenediamine; hexane-1,6-diamine), 1-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane (decamethylenediamine), 1,11-diaminoundecane (undecamethylenediamine) and 1,12-diaminododecane (dodecamethylenediamine).
Preferably, component (B2) is selected from the group consisting of tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, decamethylenediamine and dodecamethylenediamine.
According to the invention, any component (B3) present in component (B) is at least one C4-C20 diacid. In the context of the present invention, “at least one C4-C20 diacid” means either exactly one C4-C20 diacid or a mixture of two or more C4-C20 diacids.
In the context of the present invention, “C4-C20 diacid” is understood to mean aliphatic and/or aromatic compounds having two to eighteen carbon atoms and two carboxyl groups (—COOH groups). The aliphatic and/or aromatic compounds may be unsubstituted or additionally at least monosubstituted. If the aliphatic and/or aromatic compounds are additionally at least monosubstituted, they may bear one, two or more substituents that do not take part in the polymerization of components (A) and (B). Such substituents are for example alkyl or cycloalkyl substituents. These are known to those skilled in the art. The at least one C4-C20 diacid is preferably unsubstituted.
Suitable components (B3) are for example selected from the group consisting of butanedioic acid (succinic acid), pentanedioic acid (glutaric acid), hexanedioic acid (adipic acid), heptanedioic acid (pimelic acid), octanedioic acid (suberic acid), nonanedioic acid (azelaic acid), decanedioic acid (sebacic acid), undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid and hexadecanedioic acid.
Preferably, component (B3) is selected from the group consisting of pentanedioic acid (glutaric acid), hexanedioic acid (adipic acid), decanedioic acid (sebacic acid) and dodecanedioic acid.
According to the invention, the composition (Z1) can be produced, for example, by mixing the individual components, for example the thermoplastic polyurethane (TPU1) and the polyamide (PA1), for example in a suitable apparatus such as an extruder or a kneader. The composition (Z1) can be produced here under conditions known per se.
According to the invention, it is also possible to use further additives, for example flame retardants or fillers. Suitable fillers, plasticizers or flame retardants are known per se to the person skilled in the art.
In a further embodiment, the present invention accordingly relates to a composition (Z1) as described above, wherein the composition comprises at least one flame retardant.
In a further embodiment, the present invention also relates to a composition (Z1) as described above, wherein the composition comprises at least one filler.
In the context of the present invention, preference can be given to using flame retardants selected from the group consisting of metal hydroxides, nitrogen-containing flame retardants and phosphorus-containing flame retardants. Preference is given in accordance with the invention to flame retardants selected from the group consisting of melamine cyanurate, magnesium hydroxide and phosphorus-containing flame retardants.
In a further embodiment, the present invention also relates to a composition (Z1) as described above, wherein the flame retardant is selected from the group consisting of metal hydroxides, nitrogen-containing flame retardants and phosphorus-containing flame retardants.
In a further embodiment, the present invention also further relates to a composition as described above, wherein the composition comprises at least one flame retardant selected from the group consisting of melamin cyanurate, magnesium hydroxide and phosphorus-containing flame retardants.
Also suitable in the context of the present invention, for example, are mixtures of different flame retardants, for example mixtures comprising one or more phosphorus-containing flame retardants.
Accordingly, the present invention, in a further embodiment, also relates to a composition as described above, wherein the composition comprises at least one first phosphorus-containing flame retardant (F1) selected from the group consisting of derivatives of phosphoric acid and derivatives of phosphonic acid, and at least one further phosphorus-containing flame retardant (F2) selected from the group consisting of derivatives of phosphinic acid.
Suitable flame retardants are, for example, also metal hydroxides. In the event of fire, metal hydroxides released exclusively water and therefore do not form any toxic or corrosive smoke gas products. Furthermore, these hydroxides are capable of reducing smoke gas density in the event of fire. However, a disadvantage of these substances is that, in some cases, they promote the hydrolysis of thermoplastic polyurethanes and also affect the oxidative aging of the polyurethanes.
Suitable hydroxides in the context of the present invention are preferably those of magnesium, calcium, zinc and/or aluminum or mixtures thereof. More preferably, the metal hydroxide is selected from the group consisting of aluminum hydroxides, aluminum oxide hydroxides, magnesium hydroxide and a mixture of two or more of these hydroxides.
The compositions of the invention may also comprise a phosphorus-containing flame retardant. According to the invention, it is possible in principle to use any known phosphorus-containing flame retardants for thermoplastic polyurethanes.
Preference is given, in the context of the present invention, to using derivatives of phosphoric acid, derivatives of phosphonic acid or derivatives of phosphinic acid or mixtures of two or more of these derivatives. In a further preferred embodiment, the phosphorus-containing flame retardant is liquid at 21° C.
Preferably, the derivatives of phosphoric acid, phosphonic acid or phosphinic acid are salts with an organic or inorganic cation or organic esters. Organic esters are derivatives of the phosphorus-containing acids in which at least one oxygen atom bonded directly to the phosphorus has been esterified with an organic radical. In a preferred embodiment the organic ester is an alkyl ester, and in another preferred embodiment an aryl ester. More preferably, all hydroxyl groups of the corresponding phosphorus-containing acid have been esterified.
Suitable organic phosphate esters are, for example, the triesters of phosphoric acid, such as trialkyl phosphates and especially triaryl phosphates, for example resorcinol bis(diphenyl phosphate).
Especially suitable in accordance with the invention are salts of the respective derivatives of phosphoric acid, phosphonic acid or phosphinic acid, more preferably phosphinate salts. Suitable examples in the context of the present invention are melamine polyphosphate or diethylaluminum phosphinate.
In addition, it is also possible in the context of the present invention to use nitrogen-containing flame retardants. According to the invention, it is possible in principle to use any known nitrogen-containing flame retardants for thermoplastic polyurethanes.
Suitable flame retardants in the context of the present invention are, for example, also melamine derivatives such as, in particular, melamine polyphosphate or melamine cyanurate.
In the context of the present invention, it is also possible that the composition, as well as the thermoplastic polyurethane, comprises mixtures of various flame retardants, for example a melamine derivative and a derivative of phosphoric acid, or a melamine derivative and a derivative of phosphinic acid, or a melamine derivative, a derivative of phosphoric acid and a derivative of phosphinic acid.
The melamine derivative may preferably be a melamine cyanurate. Accordingly, the present invention, in a further embodiment, may also relate to a composition comprising, as well as the thermoplastic polyurethane, for example, a melamine cyanurate and a derivative of phosphoric acid, or a melamine cyanurate and a derivative of phosphinic acid, or a melamine cyanurate, a derivative of phosphoric acid and a derivative of phosphinic acid. For example, the composition of the invention comprises at least one thermoplastic polyurethane, at least melamine cyanurate, at least one first phosphorus-containing flame retardant (F1) selected from the group consisting of derivatives of phosphoric acid and derivatives of phosphonic acid and at least one further phosphorus-containing flame retardant (F2) selected from the group consisting of derivatives of phosphinic acid.
Preferably, the composition, aside from the melamine cyanurate, the at least one phosphorus-containing flame retardant (F1) and the at least one phosphorus-containing flame retardant (F2), does not comprise any further flame retardants. Further preferably, the composition of the invention comprises melamine cyanurate, exactly one phosphorus-containing flame retardant (F1) selected from the group consisting of derivatives of phosphoric acid and derivatives of phosphonic acid and exactly one phosphorus-containing flame retardant (F2) selected from the group consisting of derivatives of phosphinic acid.
Accordingly, the present invention, in a further embodiment, also relates to a composition as described above, wherein the phosphorus-containing flame retardant (F1) is a phosphinate.
In a further embodiment, the present invention also further relates to a composition as described above, wherein the phosphinate is selected from the group consisting of aluminum phosphinates or zinc phosphinates.
In addition, the present invention, in a further embodiment, also relates to a composition as described above, wherein the phosphorus-containing flame retardant (F2) is a phosphoric ester.
In a further embodiment, the present invention also relates to a composition as described above, wherein the flame retardant (F1) is selected from the group consisting of resorcinol bis(diphenyl phosphate) (RDP), bisphenol A bis(diphenyl phosphate) (BDP) and diphenyl cresyl phosphate (DPK).
The proportion of the flame retardant (F) in the composition is, for example, in the range from 2.5% to 40% by weight, based on the overall composition, preferably in the range from 5% to 30% by weight, based on the overall composition, more preferably in the range from 10% to 20% by weight, based on the overall composition.
In a further embodiment, the present invention accordingly also relates to a composition as described above, wherein the flame retardant (F) is present in an amount in the range from 2.5% to 40% by weight, based on the overall composition.
In one embodiment, for preparation of the compositions of the invention, thermoplastic polyurethane and flame retardant are processed in one step. In other preferred embodiments, for production of the compositions of the invention, a reaction extruder, a belt system or other suitable apparatus is firstly used to produce a thermoplastic polyurethane, preferably in pellet form, into which at least one further flame retardant is then introduced in at least one further step, or else two or more steps.
The mixing of the thermoplastic polyurethane with the at least one flame retardant is effected, for example, in a mixing unit which is preferably an internal kneader or an extruder, preferably a twin-screw extruder. In another preferred embodiment using an extruder, the flame retardant introduced is liquid at the temperature that exists downstream of the addition thereof to the extruder in flow direction.
The composition of the invention may further comprise a filler (FS1). According to the invention, the chemical nature and form of the filler (FS1) may vary within wide ranges, provided that compatibility with the composition (Z1) is sufficient. The filler (FS1) should be chosen here such that the form and particle size of the filler enable sufficient miscibility and homogeneous distribution in the composition.
Suitable fillers are for example glass fibers, glass beads, carbon fibers, aramid fibers, potassium titanate fibers, fibers of liquid-crystal polymers, organic fibrous fillers or inorganic reinforcing materials. Organic fibrous fillers are for example cellulose fibers, hemp fibers, sisal or kenaf. Inorganic reinforcing materials are, for example, ceramic fillers, such as aluminum nitride and boron nitride, or mineral fillers, such as asbestos, talc, wollastonite, microvit, silicates, chalk, calcined kaolins, mica and quartz flour. Preferably in accordance with the invention, the filler (FS1) is selected from the group consisting of glass fibers, carbon fibers, aramid fibers, potassium titanates fibers, fibers of liquid-crystalline polymers, metal fibers, polyester fibers, polyamide fibers, organic fibrous fillers and inorganic fibrous fillers.
In a further embodiment, the present invention accordingly also relates to a composition as described above, wherein the filler (FS1) is selected from the group consisting of glass fibers, carbon fibers, aramid fibers, potassium titanates fibers, fibers of liquid-crystalline polymers, metal fibers, polyester fibers, polyamide fibers, organic fibrous fillers and inorganic fibrous fillers.
Fibrous fillers are preferred in the context of the present invention. In a further embodiment, the present invention accordingly also relates to a composition as described above, wherein the filler (FS1) is fibrous.
The dimensions of the fillers used may vary within customary ranges. The filler used preferably has a length in the range from 3 mm to 4 mm and a diameter in the range from 1 μm to 20 μm, each determined in accordance with ASTM D578-98. In a further embodiment, the present invention accordingly also relates to a composition as described above, wherein the filler (FS1) has a length in the range from 3 mm to 4 mm and a diameter in the range from 1 μm to 20 μm, each determined in accordance with ASTM D578-98.
The fillers, for example the fibrous fillers, may have been pretreated for better compatibility with the thermoplastic, for example with a silane compound.
Preference is given to using inorganic fibrous fillers. When using inorganic fibrous fillers, a greater reinforcing effect and a higher heat resistance are observed.
According to the invention, the composition may also comprise two or more fillers.
The proportion of the filler (FS1) in the composition is, for example, in the range from 40% to 60% by weight, based on the overall composition, preferably in the range from 45% to 55% by weight, based on the overall composition, more preferably in the range from 48% to 52% by weight, based on the overall composition.
In a further embodiment, the present invention accordingly also relates to a composition as described above, wherein the filler (FS1) is present in an amount in the range from 40% to 60% by weight, based on the overall composition.
According to the invention, the composition may comprise further components, for example demolding aids, UV protection, antioxidant or color pigments.
In a further aspect, the present invention also relates to a process for producing a composition (Z-1). The present invention relates to a process for producing a composition (Z-1), comprising the following steps:
This process of the invention comprises at least steps (a) and (b). The process may comprise further steps, for example drying steps or temperature adjustments. According to the invention, it is also possible to add further components, for example the aforementioned auxiliaries and additives.
In a further aspect, the present invention accordingly relates to a process as described above, wherein the components used are dried, for example at a temperature in the range from 80 to 100° C. For example, the drying can be effected at a temperature in the range from 80 to 100° C. for a period of 2 to 4 hours.
According to the invention, in step (b), the copolyamide (PA-1) and the thermoplastic polyurethane (TPU-1) are mixed. This can be effected in apparatuses known per se to the person skilled in the art, for example in an extruder. Suitable extruders and process conditions are known per se to the person skilled in the art. For example, the mixing in an extruder can be effected at a temperature in the range from 180 to 240° C., preferably at a temperature in the range from 190° C. to 230° C., more preferably at a temperature in the range from 200° C. to 225° C.
Suitable dwell times in the extruder are, for example, in the range from 5 to 20 minutes, preferably 10 to 15 minutes.
With regard to the preferred embodiments, reference is made to the above details of the components used with preference.
Suitable processes for producing the composition are known per se to the person skilled in the art. In the context of the present invention, processes known per se are typically used for compounding.
For example, the composition can be produced in an extruder in a manner known per se, for example in a twin-screw extruder. According to the invention, it is preferable to add the filler in portions, for example a portion of the extruder intake and a further portion of a second dosage site, for example a side feeder. The temperature here is preferably in the range from 160 to 230° C. In the context of the present invention, the extruder can be operated, for example, at a speed in the range from 150 to 300 revolutions per minute.
The present invention further relates to a composition obtained or obtainable by a process of the invention.
The present invention also relates to the use of the composition (Z1) of the invention or of a composition obtained or obtainable by a process of the invention for production of a shaped article.
In a further aspect, the present invention also further relates to shaped articles comprising a composition of the invention according to or a composition obtained or obtainable by a process of the invention.
The present invention also relates to the use of the composition of the invention comprising at least one flame-retardant thermoplastic polyurethane as described above for production of coatings, damping elements, bellows, films or fibers, molded articles, floors for buildings and transport, random-laid webs, preferably seals, rollers, shoe soles, hoses, cables, cable connectors, cable sheathings, cushions, laminates, profiles, belts, saddles, foams, plug connectors, trailing cables, solar modules, automotive trim. Use for the production of cable sheathings is preferred. Production is preferably effected from pellet materials by injection molding, calendering, powder sintering or extrusion and/or by additional foaming of the composition of the invention.
On account of their good mechanical properties and good thermal characteristics, the thermoplastic polyurethanes of the invention and the compositions of the invention are especially suitable for production of films, moldings, wheels/rollers, fibers, automotive trim, hoses, cable plugs, bellows, trailing cables, cable sheathings, seals, belts or damping elements.
The present invention thus also provides films, moldings, wheels/rollers, fibers, automotive trim, hoses, cable plugs, bellows, trailing cables, cable sheathings, seals, belts or damping elements comprising a thermoplastic polyurethane as described above or a composition as described above.
Further embodiments of the present invention can be found in the claims and the examples. It will be appreciated that the features of the subject matter/process of the invention or of the uses of the invention recited hereinabove and elucidated hereinbelow may be used 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.
Illustrative embodiments of the present invention are detailed hereinbelow, but are not intended to limit the present invention. In particular, the present invention also encompasses those embodiments that result from the dependency references and hence combinations specified hereinbelow.
The examples that follow serve to illustrate the invention, but are in no way limiting in respect of the subject matter of the present invention.
Ultramid RX2298®: copolymer of nylon-6 and nylon-6,36 (PA 6/6.36) from BASF SE®, sold under the Ultramid RX2298® brand name, having a viscosity number to DIN 53727 (0.005 g/ml H2SO4) of 28 ml/g, an MVR (230° C./10 kg) of 115 cm3/10 min, a melting temperature of 201° C. and a density of 1.054 g/cm3.
Elastollan 1180 A10: TPU of Shore hardness 80 A from BASF Polyurethanes GmbH, Elastogranstrasse 60, 49448 Lemförde, based on polytetrahydrofuran polyol (PTHF) having a molecular weight of 1000 g/mol, butane-1,4-diol, diphenylmethane 4,4′-diisocyanate.
Elastollan 1160 D12: TPU of Shore hardness 60 D from BASF Polyurethanes GmbH, Elastogranstrasse 60, 49448 Lemförde, based on polytetrahydrofuran polyol (PTHF) having a molecular weight of 1000, butane-1,4-diol, MDI.
Elastollan 1278 D11U: TPU of Shore hardness 78 D from BASF Polyurethanes GmbH, Elastogranstrasse 60, 49448 Lemförde, based on polytetrahydrofuran polyol (PTHF) having a molecular weight of 1000, butane-1,4-diol, MDI.
Elastollan 1283 D11U: TPU of Shore hardness 83 D from BASF Polyurethanes GmbH, Elastogranstrasse 60, 49448 Lemförde, based on polytetrahydrofuran polyol (PTHF) having a molecular weight of 1000, butane-1,4-diol. MDI.
Elastollan 685 A10: TPU of Shore hardness 85 A from BASF Polyurethanes GmbH, Elastogranstrasse 60, 49448 Lemförde, based on butanediol adipate ester, butane-1,4-diol, MDI.
Elastollan B60 D11: TPU of Shore hardness 85 A from BASF Polyurethanes GmbH, Elastogranstrasse 60, 49448 Lemförde, based on butanediol adipate ester, butane-1,4-diol, MDI.
Elastollan AC85 A12: TPU of Shore hardness 60 A from BASF Polyurethanes GmbH, Elastogranstrasse 60, 49448 Lemförde, based on polyester polyol (adipic acid, butane-1,4-diol and hexane-1,6-diol) having a molecular weight of 2000, butane-1,4-diol, hexamethylene diisocyanate.
Elastollan L1160 D10N: TPU of Shore hardness 60 D from BASF Polyurethanes GmbH, Elastogranstrasse 60, 49448 Lemförde, based on polytetrahydrofuran polyol (PTHF) having a molecular weight of 1000 g/mol, 1,4-butanediol, 4,4′-diisocyanatodicyclohexylmethane.
Exolit OP 1230: Aluminum diethylphosphinate, CAS #: 225789-38-8, Clariant Produkte (Deutschland) GmbH, Chemiepark Knapsack, 50351 HOrth, water content % (w/w) <0.2, average particle size (D50) 20-40 μm.
Fyrolflex RDP: Resorcinol bis(diphenyl phosphate), CAS #: 125997-21-9, Supresta Netherlands B.V., Office Park De Hoef, Hoefseweg 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.
Melapur MC 15 ED: Melamine cyanurate (1,3,5-triazine-2,4,6(1H,3H,5H)-trione, compound with 1,3,5-triazine-2,4,6-triamine (1:1)), CAS #: 37640-57-6, BASF SE, 67056 Ludwigshafen, GERMANY, particle size D99% </=50 μm, D50%<=4.5 μm, water content % (w/w)<0.2.
Melapur MC 200/70: Melamine polyphosphate (nitrogen content 42-44% by wt., phosphorous content 12-14% by wt.)), CAS #: 218768-84-4. BASF SE, 67056 Ludwigshafen, GERMANY, particle size D99% </=70 μm, average particle diameter D50%<=10 μm, water content % (w/w)<0.3.
Chopvantage HP3550 EC10-3,8: Glass fibers from PPG Industries Fiber Glass, Energieweg 3, 9608 PC Westerbroek, The Netherlands. E glass, filament diameter 10 μm, length 3.8 mm.
The tables that follow list compositions in which the individual constituents are stated in parts by weight (PW). The mixtures were each produced with a Berstorff ZE 40 A twin-screw extruder with screw length 35 D divided into 10 barrel sections. Pelletization was effected using standard underwater pelletization apparatus from Gala (UWG).
Density, Shore hardness, tensile strength, tear propagation resistance, abrasion and elongation at break were determined on films having a thickness of 1.6 mm. The films were extruded with an Arenz single-screw extruder having a three-zone screw with a mixing section (screw ratio 1:3). The films were assessed in accordance with their appearance.
UL 94V and HB flame tests were conducted either on 1.6 mm films or on 2 mm injection-molded plaques.
Moduli of elasticity, impact resistances and notched impact resistances were determined on injection-molded test specimens. For this purpose, test specimens were produced on an Arburg 520S having a screw diameter of 30 mm.
Burst pressures were determined on hoses having an external diameter of 8.0 mm and an internal diameter of 5.5 mm. The hoses were extruded with a Kuhne single-screw extruder having a three-zone screw with a mixing section (screw ratio 1:3).
The results are summarized in the tables that follow.
Blends produced from Elastollan 1180 A10 and Ultramid RX2298.
Blends produced from Elastollan 1160 D10 and Ultramid RX2298.
Blends produced from Elastollan 1178 D11U and Ultramid RX2298.
Blends produced from Elastollan 1183 D11U and Ultramid RX2298.
It was possible to obtain a film only for one mixture. Shore hardness was determined on injection moldings in this case.
Blends produced from Elastollan 685 A10 and Ultramid RX2298.
Blends produced from Elastollan B60 D11 and Ultramid RX2298.
Blends produced from Elastollan AC85 A12 and Ultramid RX2298.
Blends produced from Elastollan L1160 D12 and Ultramid RX2298.
Mixtures produced from Ultramid RX2298, Exolit OP 1230 and melamine cyanurate 15ED.
Various illustrative mixtures produced from Ultramid RX2298, AC85 A12, 1160 D0, Exolit OP 1230, Fyrolflex RDP, melamine polyphosphate MC 200/70 and melamine cyanurate MC 15ED.
Various illustrative mixtures produced from Ultramid RX2298, AC85 A12, 1160 D10, Exolit OP 1230, Fyrolflex RDP, melamine polyphosphate MC 200/70 and melamine cyanurate MC 15ED.
| Number | Date | Country | Kind |
|---|---|---|---|
| 19171847.7 | Apr 2019 | EP | regional |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/EP2020/061844 | 4/29/2020 | WO | 00 |
