EP3353222A1

EP3353222A1 - Thermoplastic polyurethanes

Info

Publication number: EP3353222A1
Application number: EP16766986.0A
Authority: EP
Inventors: Elmar PÖSELT; Dirk Kempfert
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2015-09-24
Filing date: 2016-09-20
Publication date: 2018-08-01
Also published as: US20180265621A1; JP2018528318A; CN108026233A; RU2018114974A3; RU2018114974A; US11168175B2; WO2017050738A1; JP2023029383A; BR112018004019A2

Abstract

The invention relates to a thermoplastic polyurethane that is or can be obtained by reacting at least one polyisocyanate composition, 1,2-ethandiol as a chain extender, and a polyol composition, where no other chain extender is used apart from 1,2-ethandiol; the invention also relates to a method for producing such a thermoplastic polyurethane, and to the use of such a polyurethane for producing injection moulded products, extruded products, films and shaped bodies.

Description

Thermoplastic polyurethanes

The present invention relates to a thermoplastic polyurethane obtainable or obtained by reacting at least one polyisocyanate composition, 1,2-ethanediol as a chain extender and a polyol composition, wherein in addition to 1, 2-ethanediol no further chain extender is used. According to one embodiment, the present invention relates to a thermoplastic polyurethane obtainable or obtained by reacting at least one polyisocyanate composition, 1,2-ethanediol as chain extender and a polyol composition, wherein the polyol composition contains at least polytetrahydrofuran (PTHF) and the polyisocyanate composition comprises at least methylenediphenyl diisocyanate ( MDI). Furthermore, the present invention relates to a process for the preparation of such thermoplastic polyurethanes, and the use of such polyurethanes for the production of injection molded products, extruded products, films and moldings.

Thermoplastic polyurethanes for various applications are known in principle from the prior art. By varying the starting materials different property profiles can be obtained.

For example, WO 2006/082183 A1 discloses a process for the continuous preparation of thermoplastically processable polyurethane elastomers, in which a polyisocyanate, a compound having zerevitinoff-active hydrogen atoms having an average molecular weight of 450 g / mol to 5,000 g / mol, a chain extender and other auxiliary and Additives are implemented. Special property profiles are achieved through special processing.

Also EP 0 922 552 A1 discloses a process for the continuous production of granules of thermoplastic polyurethane elastomers, wherein first by reacting organic diisocyanates, difunctional polyhydroxyl compounds having molecular weights of 500 to 8000 and difunctional chain extenders having molecular weights of 60 to 400 in the presence of Catalysts and optionally auxiliaries and / or additives granules is produced. The use for the production of extrusion, injection molding or calendering, in particular cable sheathing, hoses and / or films is also disclosed.

EP 0 959 104 A1 discloses blends comprising a thermoplastic polyurethane having a Shore hardness of 60 A to 50 D and ethylene-propylene (EPM) rubbers and / or modified ethylene-propylene (EPM) rubbers, which are also used for the production be used by hoses.

WO 98/56845 discloses a thermoplastic polymer obtained by reacting a polyisocyanate, a glycol as a chain extender and a polyether polyol. Various isocyanates, chain extenders and polyols are disclosed. Depending on the type of application, the properties of the thermoplastic polyurethane can be varied by the nature of the starting materials and the proportions used. For example, for use as a hose material, in particular for pneumatic hoses, a high bursting pressure is required even at elevated temperatures. For example, by varying the polyol component, the stability can be influenced. Processing, for example by tempering, can also influence the stability. In addition, existing ester variants which show a bursting pressure of greater than 20 bar at 70 ° C. are opaque to translucent and thus unsuitable for many applications.

For various applications, for example for use as a cable sheath, a high heat resistance of the thermoplastic polyurethane used is also advantageous. A measure of the heat resistance, for example, the determined by TMA onset temperature. For many applications, a high short-term heat distortion resistance is advantageous.

Starting from the prior art, an object of the present invention was accordingly to provide improved materials which show a good bursting pressure even at elevated temperatures in the application for the manufacture of hoses. Another object of the present invention was to provide materials with high heat resistance, in particular high short-term heat resistance.

According to the invention, this object is achieved by a thermoplastic polyurethane obtainable or obtained by reacting at least the components (i) to (iii):

(i) a polyisocyanate composition;

(ii) 1,2-ethanediol as a chain extender;

(Iii) a polyol composition, wherein in addition to 1, 2-ethanediol no further chain extender is used.

The invention also relates to a thermoplastic polyurethane obtainable or obtained by reacting at least the components (i) to (iii):

(i) a polyisocyanate composition;

(ii) 1,2-ethanediol as a chain extender;

(iii) a polyol composition wherein the polyol composition contains at least polytetrahydrofuran (PTHF) and the polyisocyanate composition contains at least methylenediphenyl diisocyanate (MDI), and wherein in addition to 1,2-ethanediol no further chain extender is used. Surprisingly, it has been found that the use of 1,2-ethanediol as sole chain extender, in particular in combination with a defined polyisocyanate composition and a defined polyol composition, gives a thermoplastic polyurethane which has good bursting pressure behavior and high heat distortion resistance. Surprisingly, it has been found that by using 1,2-ethanediol as a chain extender, in particular in combination with the defined polyisocyanate composition and the polyol composition, it was possible to produce a hose which has a bursting pressure of greater than 20 bar at 70.degree. In addition, the hoses show a substantially punctiform bursting behavior. The resulting thermoplastic polyurethanes preferably also have good creep behavior.

According to the invention, the thermoplastic polyurethane is obtained or is obtainable by reacting the components (i) to (iii). A polyisocyanate composition, a polyol composition and 1, 2-ethanediol are implemented as a chain extender. According to the invention, no further chain extender is used in addition to 1,2-ethanediol.

In another embodiment, a polyisocyanate composition containing at least methylene diphenyl diisocyanate (MDI) is reacted with a polyol composition containing at least polytetrahydrofuran (PTHF) and 1,2-ethanediol as a chain extender.

The polyol composition used contains at least one polyol in the context of the present invention. Polyols are generally known to the person skilled in the art and are described, for example, in "Kunststoffhandbuch, Volume 7, Polyurethanes", Carl Hanser Verlag, 3rd edition 1993, Chapter 3.1. Particular preference is given to using polyesterols or polyetherols as polyols. Likewise, polycarbonates can be used. Copolymers can also be used in the context of the present invention. The number-average molecular weight of the polyols used according to the invention is preferably between 0.5 × 10 ³ g / mol and 8 × 10 ³ g / mol, preferably between 0.6 × 10 ³ g / mol and 5 × 10 ³ g / mol, in particular between 0.8 × 10 ³ g / mol, and 3 × 10 ³ g / mol.

According to the invention, polyethers are suitable, for example polytetrahydrofuran, but also polyesters, block copolymers and hybrid polyols, e.g. Poly (ester / amide). Preferred polyetherols according to the invention are polyethylene glycols, polypropylene glycols, polyadipates, polycarbonates (diol) s and polycaprolactone.

For example, the polyol composition contains at least one polytetrahydrofuran. Accordingly, according to a further embodiment, the present invention relates to a thermoplastic polyurethane as described above, wherein the polyol composition used contains at least one polytetrahydrofuran. According to a particularly preferred embodiment, the polyol used has a molecular weight Mn in the range of 500 g / mol to 1500 g / mol, preferably in the range of 600 g / mol to 1400 g / mol, more preferably in the range of 650 g / mol to 1000 g / mol. Accordingly, according to another embodiment, the present invention relates to a thermoplastic polyurethane as described above, wherein at least one polyol contained in the polyol composition has a molecular weight Mn in the range of 500 g / mol to 1500 g / mol. Polyester polyols may also be used in the context of the present invention, preferably polyesters having a molecular weight Mn in the range from 500 g / mol to 2500 g / mol, more preferably in the range from 550 g / mol to 1800 g / mol, particularly preferably in the range from 600 g / mol to 1200 g / mol. According to the invention, it is also possible to use mixtures of different polyols. The polyol composition may also contain two or more polyols. Preferably, the polyols used or the polyol composition have an average functionality between 1, 8 and 2.3, preferably between 1, 9 and 2.2, in particular 2. Preferably, the polyols used in the invention have only primary hydroxyl groups.

According to one embodiment of the present invention, at least one polyol composition containing at least polytetrahydrofuran is used as component (iii) for the preparation of the thermoplastic polyurethane. According to the invention, the polyol composition in addition to polytetrahydrofuran also contain other polyols.

According to the invention, for example, further polyethers are suitable, but also polyesters, block copolymers and hybrid polyols, such as e.g. Poly (ester / amide). Preferred polyetherols according to the invention are polyethyleneglycols, polypropylene glycols and polycaprolactone. According to a further embodiment, the present invention relates to a thermoplastic polyurethane as described above, wherein the polyol used contains at least one polytetrahydrofuran and at least one polyol selected from the group consisting of polyethylene glycol, polypropylene glycol, polyadipates, polycarbonate (diols) and polycaprolactones.

Furthermore, according to a further embodiment, the present invention relates to a thermoplastic polyurethane as described above, wherein the polyol composition contains at least one polytetrahydrofuran and at least one further polyol selected from the group consisting of polyethylene glycol, polypropylene glycol and polycaprolactone.

The composition of the polyol composition can vary widely within the scope of the present invention. For example, the content of polytetrahydrofuran in Range from 15% to 85%, preferably in the range of 20% to 80%, more preferably in the range of 25% to 75%.

According to the invention, the polyol composition may also contain a solvent. Suitable solvents are known per se to the person skilled in the art.

If polytetrahydrofuran is used, the molecular weight Mn of the polytetrahydrofuran is preferably in the range from 650 to 1400 g / mol. More preferably, the molecular weight Mn of the polytetrahydrofuran is in the range of 750 to 1400 g / mol.

According to a further embodiment, the present invention relates to a thermoplastic polyurethane as described above, wherein the polytetrahydrofuran has a molecular weight Mn in the range of 650 g / mol to 1400 g / mol. In particular, when using a polytetrahydrofuran having a molecular weight Mn in the range of 650 g / mol to 1400 g / mol, good material properties or a good property profile are obtained for use as a pneumatic hose.

According to a further embodiment, the present invention relates to a thermoplastic polyurethane as described above, wherein the polyol composition used is free of polytetrahydrofuran (PTHF) and in the implementation no polytetrahydrofuran (PTHF) is used as a further component. For example, the present invention relates to a thermoplastic polyurethane as described above, wherein in addition to 1, 2-ethanediol no further chain extender is used, the polyol composition is free of polytetrahydrofuran (PTHF) and in the implementation no polytetrahydrofuran (PTHF) used as a further component becomes.

According to the invention, 1,2-ethanediol is used as a chain extender and no further chain extender is used. In the context of the present invention, a chain extender is understood as meaning a compound which has at least two isocyanate-reactive functional groups, for example hydroxyl groups, amino groups or thiol groups, and has a molecular weight Mw of less than 300 g / mol , In the context of the present invention, the polyol composition is also free of such compounds.

In the context of the present invention, the amount of chain extender and polyol composition used can vary within wide limits. For example, component (iii) and component (ii) are used in a molar ratio of (iii) to (ii) of 1 to 0.7, 1 to 2.7, and 1 to 7.3.

According to the invention, a polyisocyanate cyanate composition is used to prepare the thermoplastic polyurethane. The polyisocyanate composition contains at least one polyisocyanate. According to the invention, the polyisocyanate composition can also contain two or more polyisocyanates. For example, in the context of the present invention for the preparation of the thermoplastic polyurethane, a polyisocyanate composition is used which contains at least methylene diphenyl diisocyanate (MDI). According to the invention, the term methylene diphenyl diisocyanate means 2,2'-, 2,4'- and / or 4,4'-diphenylmethane diisocyanate or a mixture of two or three isomers. Thus, 2,2'-, 2,4'- and / or 4,4'-diphenylmethane diisocyanate can be used according to the invention or a mixture of two or three isomers. According to the invention, the polyisocyanate composition may also contain further polyisocyanates. According to the invention, it is thus also possible for the isocyanate composition to contain methylene diphenyl diisocyanate and at least one further polyisocyanate. However, according to the invention it is also possible that the isocyanate composition contains only methylene diphenyl diisocyanate.

According to the invention, a polyisocyanate cyanate composition which does not contain any methylenediphenyl diisocyanate (MDI) can also be used for the preparation of the thermoplastic polyurethane.

Accordingly, according to another embodiment, the present invention relates to a thermoplastic polyurethane as described above, wherein the polyisocyanate composition used is free of methylenediphenyl diisocyanate (MDI). In this case, if the polyisocyanate composition used is free from methylene diphenyl diisocyanate (MDI), preferably no methylene diphenyl diisocyanate (MDI) is used as further component in the reaction. Preferred polyisocyanates in the context of the present invention are diisocyanates, in particular aliphatic or aromatic diisocyanates, more preferably aromatic diisocyanates.

Furthermore, in the context of the present invention, pre-reacted prepolymers can be used as isocyanate components in which some of the OH components are reacted with an isocyanate in an upstream reaction step. These prepolymers are reacted in a subsequent step, the actual polymer reaction, with the remaining OH components and then form the thermoplastic polyurethane. The use of prepolymers offers the possibility to also use OH components with secondary alcohol groups.

The aliphatic diisocyanates used are conventional 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-isocyanato-3, 3,5-trimethyl-5-isocyanatomethylcyclohexane (isophorone diisocyanate, IPDI), 1, 4 and / or 1, 3-bis (isocyanatomethyl) cyclohexane (HXDI), 1, 4- Cyclohexane diisocyanate, 1-methyl-2,4- and / or 1-methyl-2,6-cyclohexane diisocyanate, 4,4'-, 2,4'- and / or 2,2'-Methylendicyclohexyldiisocyanat (H 12MDI).

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

Preferred aliphatic polyisocyanates are hexamethylene-1,6-diisocyanate (HDI), 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane and 4,4'-, 2,4'- and / or 2,2 '- methylene dicyclohexyl diisocyanate (H 12MDI); 4,4'-, 2,4'- and / or 2,2'-methylenedicyclohexyl diisocyanate (H 12MDI) and 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane or mixtures thereof are particularly preferred.

According to a further embodiment, the present invention relates to a thermoplastic polyurethane as described above, wherein the polyisocyanate composition used comprises at least one polyisocyanate selected from the group consisting of methylene diphenyl diisocyanate (MDI), hexamethylene 1,6-diisocyanate (HDI) and 4,4 '. , 2,4'- and 2,2'-methylenedicyclohexyl diisocyanate (H12MDI). The polyisocyanate composition used as polyisocyanate particularly preferably contains methylene diphenyl diisocyanate (MDI).

Suitable aromatic diisocyanates are, in particular, 1,5-naphthylene diisocyanate (NDI), 2,4- and / or 2,6-toluene diisocyanate (TDI), 3,3'-dimethyl-4,4'-diisocyanato-diphenyl (TODI), p-phenylene diisocyanate (PDI), diphenylethane-4,4'-diisoyanate (EDI), diphenylmethane diisocyanate, 3,3'-dimethyl-diphenyl-diisocyanate, 1, 2-diphenylethane-diisocyanate and / or phenylene-diisocyanate.

Preferred examples of higher functional isocyanates are triisocyanates, e.g. B. triphenylmethane-4,4 ', 4 "-triisocyant, furthermore the cyanurates of the abovementioned diisocyanates, as well as the oligomers obtainable by partial reaction of diisocyanates with water, for example the bisurethe of the abovementioned diisocyanates, furthermore oligomers, which can be obtained by targeted reaction of semi-blocked diisocyanates with polyols which have on average more than two and preferably three or more hydroxyl groups.

According to the invention, the polyisocyanate composition may also contain one or more solvents. Suitable solvents are known to the person skilled in the art. Suitable examples are non-reactive solvents such as ethyl acetate, methyl ethyl ketone and hydrocarbons.

In addition, crosslinkers, for example the above-mentioned higher-functional polyisocyanates or polyols or also other higher-functional molecules having a plurality of isocyanate-reactive functional groups, can also be used in the context of the present invention. According to the invention, the components (i) to (iii) are used in a ratio such that the molar ratio of the sum of the functionalities of the polyol composition used and chain extenders to the sum of the functionalities of the isocyanate composition used ranges from 1 to 0, 8 to 1 to 1, 3 is located. The ratio is preferably in the range from 1 to 0.9 to 1 to 1.2, more preferably in the range from 1 to 0.965 to 1 to 1:05, particularly preferably in the range from 1 to 0.98 to 1 to 1, 03 ,

According to a further embodiment, the present invention relates to a thermoplastic polyurethane as described above, wherein the molar ratio of the sum of the functionalities of the polyol composition used and chain extenders to the sum of the functionalities of the isocyanate composition used in the range of 1 to 0.8 to 1 to 1, 3 is located.

Another size taken into account in the reaction of components (i) to (iii) is the isocyanate index. Here, the index is defined by the ratio of the total isocyanate groups used in the reaction of component (i) to the isocyanate-reactive groups, ie in particular the groups of components (ii) and (iii). With a figure of 1000, an isocyanate group of component (i) has an active hydrogen atom. For ratios above 1000, more isocyanate groups exist than isocyanate-reactive groups. The ratio in the reaction of components (i) to (iii) is preferably in the range from 965 to 1100, for example in the range from 970 to 110, more preferably in the range from 970 to 1050, particularly preferably in the range from 980 to 1030 ,

According to a further embodiment, the present invention relates to a thermoplastic polyurethane as described above, wherein the ratio in the reaction in the range of 965 to 1 100 is.

According to the invention, further additives can be added in the reaction of components (i) to (iii), for example catalysts or auxiliaries and additives. Additives and auxiliaries are known per se to the person skilled in the art. Combinations of several additives can also be used according to the invention.

In the context of the present invention, the term additive is understood in particular as meaning catalysts, auxiliaries and additives, in particular stabilizers, nucleating agents, fillers or crosslinkers.

Suitable additives or additives are for example stabilizers, nucleating agents, fillers such as silicates or crosslinkers such as polyfunctional aluminosilicates. According to a further embodiment, the present invention accordingly relates to a thermoplastic polyurethane as described above, wherein the thermoplastic polyurethane contains at least one additive. As auxiliaries and additives may be mentioned, for example, surface-active substances, flame retardants, nucleating agents, oxidation stabilizers, antioxidants, lubricants and mold release aids, dyes and pigments, stabilizers, eg. For example, against hydrolysis, light, heat or discoloration, inorganic and / or organic fillers, reinforcing agents and plasticizers. Suitable auxiliaries and additives can be found, for example, in Kunststoffhandbuch, Volume VII, edited by Vieweg and Hochtlen, Carl Hanser Verlag, Munich 1966 (S103 - 1 13) are removed.

Suitable catalysts are also known in principle from the prior art. Suitable catalysts are, for example, organic metal compounds selected from the group consisting of tin, titanium, zirconium, hafnium, bismuth, zinc, aluminum and iron organyls, such as tin organyl compounds, preferably tin dialkyls such as dimethyltin or Diethyltin, or tin organyl compounds of aliphatic carboxylic acids, preferably tin diacetate, tin dilaurate, dibutyltin diacetate, dibutyltin dilaurate, bismuth compounds such as bismuth-alkyl compounds or the like, or iron compounds, preferably iron (MI) acetylacetonate or the metal salts of the carboxylic acids such as Tin isooctoate, tin dioctoate, titanic acid ester or bismuth (III) neodecanoate.

According to a preferred embodiment, the catalysts are selected from tin compounds and bismuth compounds, more preferably tin alkyl compounds or bismuth-halo compounds. Particularly suitable are the tin isooctoate and bismuth neodecanoate.

The catalysts are usually used in amounts of 0 to 2000 ppm, preferably 1 ppm to 1000 ppm, more preferably 2 ppm to 500 ppm, and most preferably from 5 ppm to 300 ppm.

The properties of the thermoplastic polyurethanes according to the invention can vary within wide ranges, depending on the application. The thermoplastic polyurethanes according to the invention have for example a Shore hardness in the range of 60 A to 80 D, determined according to DIN 53505, preferably in the range of 80 A to 74 D, determined according to DIN 53505, more preferably in the range of 85A to 60 D, determined according to DIN 53505, particularly preferably in the range of 95 A to 58 D, determined according to DIN 53505.

According to a further embodiment, the present invention relates to a thermoplastic polyurethane as described above, wherein the thermoplastic polyurethane has a Shore hardness in the range of 60 A to 80 D, determined according to DIN 53505.

According to a further aspect, the present invention also relates to a process for the preparation of a thermoplastic polyurethane, comprising the reaction of components (i) to (iii):

(i) a polyisocyanate composition; (ii) 1,2-ethanediol as a chain extender;

Furthermore, the present invention also relates to a process for the preparation of a thermoplastic polyurethane comprising the reaction of components (i) to (iii):

(i) a polyisocyanate composition;

(ii) 1,2-ethanediol as a chain extender;

(iii) a polyol composition wherein the polyol composition contains at least polytetrahydrofuran (PTHF) and the polyisocyanate composition contains at least methylenediphenyl diisocyanate (MDI) and wherein in addition to 1,2-ethanediol no further chain extender is used.

With regard to preferred embodiments of the method, suitable starting materials or mixing ratios, reference is made to the above statements, which apply accordingly. The reaction of components (i) to (iii) can in principle be carried out under known reaction conditions. The reaction can be carried out batchwise or else continuously, for example in a belt process or a reaction extrusion process. Suitable methods are described, for example, in EP 0 922 552 A1 or WO 2006/082183 A1.

According to a preferred embodiment, the reaction of components (i) to (iii) is carried out at elevated temperatures as room temperature.

According to the invention, the heating can take place in any suitable manner known to the person skilled in the art.

In this case, for example, in a reaction by means of reaction extrusion process, the reaction is conducted such that the zone temperature is in the range of 170 ° C to 245 ° C, preferably in the range of 180 ° C to 235 ° C, more preferably in the range of 190 ° C to 230 ° C.

Accordingly, according to another embodiment, the present invention also relates to a process for producing a thermoplastic polyurethane as described above, wherein the reaction is carried out by a reaction extrusion method and the zone temperature is in the range of 170 ° C to 245 ° C.

According to the invention, it is also possible that the method comprises further steps, for example a pretreatment of the components or an aftertreatment of the resulting thermoplastic polyurethane. Accordingly, the present invention relates to a further ren embodiment also a method for producing a thermoplastic polyurethane as described above, wherein after the reaction, the resulting thermoplastic polyurethane is annealed. The thermoplastic polyurethane according to the invention or a thermoplastic polyurethane obtained or obtainable by a process according to the invention can be used in many ways. In particular, the thermoplastic polyurethanes according to the invention are suitable for the production of molded parts and films, more preferably for the production of hoses.

Furthermore, the present invention therefore also relates to the use of a thermoplastic polyurethane as described above or of a thermoplastic polyurethane obtainable or obtained by a process according to the invention for the production of injection-molded products, extruded products, films, and moldings. According to a further embodiment, the present invention relates to the use as described above, wherein the shaped body is a hose. Here, the high bursting pressure of the thermoplastic polyurethanes according to the invention is advantageous.

The present invention also relates to the injection molding products, extruded products, films or moldings obtained by a process according to the invention, for example hoses, cable sheathing or conveyor belts.

In the context of the present invention, it is also possible for the resulting injection-molded products, extruded products, films or moldings to be subjected to an aftertreatment.

Further, the present invention relates to a hose comprising a thermoplastic polyurethane as described above or a thermoplastic polyurethane obtainable or obtained by a method as described above.

In this case, the hose can have further components. In particular, the tube may be multi-layered and reinforced by conventional means. Suitable for reinforcement are, for example, fibers or fabrics, for example those made of glass, textiles or metals.

According to a further embodiment, the present invention accordingly relates to a hose as described above, wherein the hose is constructed in multiple layers.

According to a further embodiment, the present invention accordingly relates to a hose as described above, wherein the hose is reinforced by fibers or fabrics. In the context of the present invention, it is further possible that in the production of a shaped article according to the invention, in particular a film or a tube, color pigments or liquid organic dyes are added. Furthermore, it is possible within the scope of the present invention for the shaped body, for example the film or the tube, to undergo an after-treatment, for example crosslinking. According to a further embodiment, the present invention accordingly relates to a film or a tube as described above, wherein the film or the tube has been subjected to a post-treatment.

As the examples prove, can be obtained with a thermoplastic polyurethane of the invention, a hose that can be used for pneumatic applications and after annealing at the dimensions 5.8 ^* 8.2 mm at a Shore hardness of 98A a bursting pressure at 70 ° C of greater than 20 bar.

Other preferred applications are as cable sheathing or for the production of conveyor belts. The high heat resistance of the thermoplastic polyurethanes according to the invention is advantageous for use as a cable sheath. In the context of the present invention, the heat resistance is determined by means of the TMA onset temperature.

Further embodiments of the present invention can be taken from the claims and the examples. It is understood that the features of the subject / method / uses according to the invention mentioned above and those explained below can be used not only in the particular combination indicated, but also in other combinations, without departing from the scope of the invention. So z. Also, the combination of a preferred feature with a particularly preferred feature, or a non-further characterized feature with a particularly preferred feature, etc. implicitly encompasses, even if this combination is not explicitly mentioned.

Listed below are exemplary embodiments of the present invention, which are not limitative of the present invention. In particular, the present invention also encompasses those embodiments which result from the back references given below and thus combinations.

1 . Thermoplastic polyurethane obtainable or obtained by reacting at least components (i) to (iii): a polyisocyanate composition;

1, 2-ethanediol as a chain extender;

a polyol composition, wherein in addition to 1, 2-ethanediol no further chain extender is used. Thermoplastic polyurethane according to embodiment 1, wherein the polyol composition used contains at least one polyol selected from the group consisting of polytetrahydrofuran (PTHF), polyethylene glycol, polypropylene glycol, polyadipates, polycarbonate (diols) and polycaprolactones.

Thermoplastic polyurethane according to embodiment 2, wherein the polytetrahydrofuran has a molecular weight Mn in the range of 650 g / mol to 1400 g / mol.

Thermoplastic polyurethane according to one of embodiments 1 to 3, wherein the polyisocyanate composition used comprises at least one polyisocyanate selected from the group consisting of methylenediphenyl diisocyanate (MDI), hexamethylene-1,6-diisocyanate (HDI) and 4,4'-, 2,4'- and 2,2'-methylenedicyclohexyl diisocyanate (H12MDI).

Thermoplastic polyurethane according to one of embodiments 1 to 4, wherein the molar ratio of the sum of the functionalities of the polyol composition used and chain extenders to the sum of the functionalities of the isocyanate composition used in the range of 1 to 0.8 to 1 to 1.3.

A thermoplastic polyurethane according to any one of embodiments 1 to 5, wherein the ratio in the reaction is in the range of 965 to 1100.

Thermoplastic polyurethane according to any one of embodiments 1 to 6, wherein at least one polyol contained in the polyol composition has a molecular weight Mn in the range of 500 g / mol to 1500 g / mol.

Thermoplastic polyurethane according to one of embodiments 1 to 7, wherein the thermoplastic polyurethane has a Shore hardness in the range of 60 A to 80 D, determined according to DIN 53505.

Process for the preparation of a thermoplastic polyurethane, comprising the reaction of components (i) to (iii):

(i) a polyisocyanate composition;

(ii) 1,2-ethanediol as a chain extender;

(Iii) a polyol composition, wherein in addition to 1, 2-ethanediol no further chain extender is used. Use of a thermoplastic polyurethane according to any one of embodiments 1 to 8 or a thermoplastic polyurethane obtainable or obtained according to one Process according to embodiment 9 for the production of injection molded products, extrusion products, films and moldings.

1 1. Use according to embodiment 10, wherein the shaped body is a hose.

12. A hose comprising a thermoplastic polyurethane according to any of embodiments 1 to 8 or a thermoplastic polyurethane obtainable or obtained by a process according to embodiment 9. 13. Thermoplastic polyurethane obtainable or obtained by reacting at least components (i) to (iii):

(i) a polyisocyanate composition;

(ii) 1,2-ethanediol as a chain extender;

(iii) a polyol composition wherein in addition to 1,2-ethanediol no further chain extender is used, the polyol composition containing at least polytetrahydrofuran (PTHF) and the polyisocyanate composition containing at least methylene diphenyl diisocyanate (MDI).

14. A thermoplastic polyurethane according to embodiment 13, wherein the polytetrahydrofuran has a molecular weight Mn in the range of 650 g / mol to 1400 g / mol.

15. Thermoplastic polyurethane according to any one of embodiments 13 or 14, wherein the molar ratio of the sum of the functionalities of the polyol composition used and chain extender to the sum of the functionalities of the isocyanate composition used in the range of 1 to 0.8 to 1 to 1.3.

16. The thermoplastic polyurethane according to any one of Embodiments 13 to 15, wherein the ratio in the reaction is in the range of 965 to 1100.

17. Thermoplastic polyurethane according to one of embodiments 13 to 16, wherein the thermoplastic polyurethane has a Shore hardness in the range of 60 A to 80 D, determined according to DIN 53505.

18. Process for the preparation of a thermoplastic polyurethane, comprising the reaction of components (i) to (iii):

(i) a polyisocyanate composition;

(ii) 1,2-ethanediol as a chain extender;

(iii) a polyol composition, wherein in addition to 1, 2-ethanediol no further chain extender is used, wherein the polyol composition contains at least polytetrahydrofuran (PTHF) and the polyisocyanate composition contains at least methylene diphenyl diisocyanate (MDI).

19. Use of a thermoplastic polyurethane according to any of embodiments 13 to 17 or a thermoplastic polyurethane obtainable or obtained according to one

Process according to embodiment 18 for the production of injection molded products, extrusion products, films and moldings.

20. Use according to embodiment 19, wherein the shaped body is a hose. 21. A tube comprising a thermoplastic polyurethane according to any of embodiments 13 to 17 or a thermoplastic polyurethane obtainable or obtained by a method according to embodiment 18.

The following examples are illustrative of the invention, but are in no way limiting as to the subject matter of the present invention.

EXAMPLES

1 . Production Example I

The following starting materials were used:

Polyol 1: Polyether polyol having an OH number of 174.7 and excluding primary OH groups (based on tetramethylene oxide, functionality: 2)

Polyol 2: Polyether polyol with an OH number of 1 12.2 and excluding primary OH groups (based on tetramethylene oxide, functionality: 2)

Polyol 3: Mixture of Polyol 2 53.33% and Polyol 4 46.67% Polyol 4: Polyether polyol with an OH number of 55.8 and excluding primary

OH groups (based on tetramethylene oxide, functionality: 2) Polyol 5: Polyester polyol with an OH number of 140 and excluding primary

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

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

KV 1: 1, 2-ethanediol

KV2: 1,4-butanediol

Catalyst 1: stannous isooctoate (10% in dioctyl adipate)

1 .1 Example of discontinuous synthesis:

A thermoplastic polyurethane (TPU) was synthesized from 4,4'-diphenylmethane diisocyanate, chain extender 1, 2-ethanediol and polytetrahydrofuran having a number average molecular weight of 1 kg / mol with stirring in a reaction vessel. The starting temperature was 80 ° C. After reaching a reaction temperature of 110 ° C., the solution was poured out onto a heating plate heated to 125 ° C. and the resulting TPU

Granulated plate after annealing (15 h, 80 ° C). The measured values were produced by injection molding plates or tubes, wherein the zone temperatures of the extruders used were between 190 ° C and 235 ° C.

The synthesis and properties of thermoplastic polyurethanes obtained are summarized in Tables 1 and 2.

Table 1: Examples of synthesis:

Table 2: Examples of properties:

Example 1 Example 2 Example 3 Example 4 Shore D 59 47 47 56

Modulus of elasticity [MPa] 90 69 50

Tensile strength [MPa] 39 27 22 53

Elongation at break [%] 420 570 510 420

Tearing resistance [kN / m] 135 72 67 1 13

Compression set

(72h / 23 ° C / 30min) [%] 37 33 27 21

Compression set

(24h / 70 ° C / 30min) [%] 55 51 47 35

Compression set

(24h / 100 ° C / 30min) [%] 75 73 67 54

Abrasion [mm ³ ] 94 140 127 36

Bursting pressure unannealed 5.8 ^* 51, 5 33.7 33.8 22.4

8.2 mm hoses at 23 ° C [bar]

Bursting pressure of unannealed 5.8 ^* 22.8 20.2 21, 9 12.1

8.2 mm hoses at 70 ° C [bar]

Bursting pressure annealed 5.8 ^* 8.2 53.5 35.1 36.7 27.5

mm hoses at 23 ° C [bar]

Bursting pressure annealed 5.8 ^* 8.2 28.2 24.1 25.6 14.7

mm hoses at 70 ° C [bar]

Creep behavior [%] 1 1, 41 4.64

Vicat determination (10N, 120 ° C / h) 140.3 1 1 1, 8

[° C]

TMA Onset Temperature 195 200 233 177

(ΔΤ 20 ° C / min) [° C]

Tube optic translucent translucent opaque transparent

1 .2 Example of continuous synthesis 1 .2.1 Reaction extrusion process:

In the first housing of a twin-screw extruder type ZSK 92 from Werner & Pfleiderer, Stuttgart with a process length of 56 D, a mixture of the chain extender 1, 2-ethanediol, polytetrahydrofuran and a catalyst with an initial temperature of 150 ° C on the one hand and separately the 4,4'-

Diphenylmethane diisocyanate with an original temperature of 65 ° C, and optionally dosed a phenolic antioxidant. The speed of the twin screw was 230 min ^-1 . The temperature setting values of the housings were 200 ° C downstream in the first worm third, 170 ° C in the second worm third, and 190 ° C in the third and last wrench thirds. The output was 850 kg / h. After the melt discharge by underwater granulation and integrated centrifugal drying, the granules were finally dried at about 80 to 90 ° C. The granules were then further processed by injection molding into test specimens or by extrusion to form hoses. The tubing was extruded on a 45 gauge Arenz extruder with 3-zone screw with 9.8 mm die and a 6.9 mm mandrel. The zone temperatures were between 180 and 225 ° C. The hose geometry was adjusted by varying the take-off speed and pressure in a water bath with vacuum calibration.

The synthesis and properties of thermoplastic polyurethanes prepared by continuous synthesis are summarized in Table 3 and Table 4.

Table 3: Examples of synthesis:

Table 4: Examples of properties:

Example 5 Example 6 Example 7

Shore D 53 55 50

Modulus of elasticity [MPa] 75 72 32

Tensile strength [MPa] 25 32 30

Elongation at break [%] 520 500 450

Tearing resistance [kN / m] 84 102 88

Compression set 30

(72h / 23 ° C / 30min) [%] 31 38

Compression set 50

(24h / 70 ° C / 30min) [%] 55 64

Compression set 71 69 100

(24h / 100 ° C / 30min) [%]

Abrasion [mm ³ ] 138 80 79

Bursting pressure of untempered 5.8 30.5 30.9 36.9

^* 8.2 mm hoses at 23 ° C

[bar] Bursting pressure of untempered 5.8 19.7 19.6 17.6

^* 8.2 mm hoses at 70 ° C

[bar]

Bursting pressure annealed 5.8 ^* 31, 1 32.3 40

8.2 mm hoses at 23 ° C

[bar]

Bursting pressure annealed 5.8 ^* 22.3 22.6 19.2

8.2 mm hoses at 70 ° C

[bar]

Creep behavior [%] 5,79 5,35

Vicat determination (10N, 145.8, 155.8

120 ° C / h) [° C]

TMA Onset Temperature 209 21 1

(ΔΤ 20 ° C / min) [° C]

Tube optic translucent translucent opaque. Measurement Methods: For material characterization, i.a. the following measuring methods are used:

DSC, DMA, TMA, NMR, FT-IR, GPC, burst pressure measurement

Shore hardness D DIN 7619-1,

Tensile strength DIN 53 504,

Elongation at break DIN 53504,

Tear strength DIN 53 515,

Abrasion DIN 4649

Vicat DIN EN ISO 306

Compression set DIN ISO 815

Creep behavior DIN EN ISO 899-1

E-module DIN 53 504 (S1 tie rod)

The creep behavior was determined by stretching a tempered (20 h / 100 ° C) S1 tensile bar by 5%. The force or tension that occurs for the first time at this stretch is maintained at room temperature for 12 hours. After relaxation, the difference in length is determined.

Claims

claims

1 . Thermoplastic polyurethane obtainable or obtained by reacting at least components (i) to (iii):

(i) a polyisocyanate composition;

(ii) 1,2-ethanediol as a chain extender;

2. The thermoplastic polyurethane according to claim 1, wherein the polyol composition used contains at least one polyol selected from the group consisting of polytetrahydrofuran (PTHF), polyethylene glycol, polypropylene glycol, polyadipates, polycarbonates (diols) and polycaprolactones.

3. A thermoplastic polyurethane according to claim 2, wherein the polytetrahydrofuran has a molecular weight Mn in the range of 650 g / mol to 1400 g / mol.

4. A thermoplastic polyurethane according to any one of claims 1 to 3, wherein the polyisocyanate composition used at least one polyisocyanate selected from the group consisting of methylene diphenyl diisocyanate (MDI), hexamethylene-1, 6-diisocyanate (HDI) and 4,4'-, 2,4 'and 2,2'-methylenedicyclohexyl diisocyanate (H12MDI).

5. A thermoplastic polyurethane according to any one of claims 1 to 4, wherein the polyol used contains at least one polytetrahydrofuran.

6. A thermoplastic polyurethane according to any one of claims 1 to 5, wherein the polyol composition contains at least one polytetrahydrofuran and at least one further polyol selected from the group consisting of polyethylene glycol, polypropylene glycol and polyalkolactone.

7. A thermoplastic polyurethane according to any one of claims 1 to 6, wherein a polyisocyanate composition is used which contains at least methylene diphenyl diisocyanate (MDI).

The thermoplastic polyurethane according to any one of claims 1 to 7, wherein the polyol composition contains at least polytetrahydrofuran (PTHF) and the polyisocyanate composition contains at least methylene diphenyl diisocyanate (MDI). Thermoplastic polyurethane according to one of claims 1 to 8, wherein the molar ratio of the sum of the functionalities of the polyol composition used and chain extender to the sum of the functionalities of the isocyanate composition used in the range of 1 to 0.8 to 1 to 1.3.

0. Thermoplastic polyurethane according to any one of claims 1 to 9, wherein the characteristic number in the reaction in the range of 965 to 1 100.

Thermoplastic polyurethane according to one of claims 1 to 10, wherein at least one polyol contained in the polyol composition has a molecular weight Mn in the range of 500 g / mol to 1500 g / mol.

Thermoplastic polyurethane according to one of claims 1 to 1 1, wherein the thermoplastic polyurethane has a Shore hardness in the range of 60 A to 80 D, determined according to DIN 53505.

A process for producing a thermoplastic polyurethane, which comprises reacting components (i) to (iii): a polyisocyanate composition;

1, 2-ethanediol as a chain extender;

a polyol composition, wherein in addition to 1, 2-ethanediol no further chain extender is used.

Use of a thermoplastic polyurethane according to one of claims 1 to 12 or of a thermoplastic polyurethane obtainable or obtained by a process according to claim 13 for the production of injection-molded products, extruded products, films and moldings.

Use according to claim 14, wherein the shaped body is a hose.

16. A hose comprising a thermoplastic polyurethane according to one of claims 1 to 12 or a thermoplastic polyurethane obtainable or obtained by a process according to claim 13.