WO2019201698A1

WO2019201698A1 - A moldable reinforced thermoplastic polyurethane, a process for preparing the same, and an article obtained therefrom exhibiting high modulus, low creep and high fatigue life

Info

Publication number: WO2019201698A1
Application number: PCT/EP2019/059053
Authority: WO
Inventors: Mark KUJAWSKI; Mihai Manitiu; Raymond Neff
Original assignee: Basf Se
Priority date: 2018-04-20
Filing date: 2019-04-10
Publication date: 2019-10-24

Abstract

The present invention is directed to a moldable reinforced thermoplastic polyurethane, a process for preparing the same and an article obtained therefrom which exhibits a high modulus, low creep, and high fatigue life.

Description

A moldable reinforced thermoplastic polyurethane, a process for preparing the same, and an article obtained therefrom exhibiting high modulus, low creep and high fatigue life

Background of the invention

Numerous applications require elastomeric materials with high moduli that can be flexed or bent tens of millions of times without failure. Such high fatigue applications require the elastomeric material to withstand these extreme conditions yet maintaining the mechanical properties. Thermoplastic polyurethane (TPU) is one such elastomeric material which is known for its wide range of applications arising due to its mechanical and physical properties.

Generally, a thermoplastic polyurethane or a TPU refers to a multi-phase block polymer created when a polyaddition reaction occurs between an isocyanate and an isocyanate-reactive component. The isocyanate-reactive component includes a polyol. TPUs are generally known as being soft and processable when heated, hard when cooled, and capable of being reprocessed multiple times without losing structural integrity.

TPU is an excellent material, however, the modulus obtained therefrom may not be high enough for some of these high fatigue applications unless the TPU is reinforced. The addition of fillers is an important step to guarantee good mechanical and physical properties. In order to do so, thermoplastic polyurethanes (TPU) are commonly reinforced with fibers, particles, and other solids to obtain a reinforced thermoplastic polyurethane. The solids in the reinforced TPU can increase tensile strength, dimensional stability and other physical and mechanical characteristics of the articles obtained therefrom. For e.g. glass fibers may be combined with a TPU composition to produce a glass fiber-reinforced TPU with high tensile strength and improved rigidity. The glass fibers may take various forms, such as continuous or chopped strands, rovings, woven or non-woven fabrics, and continuous or chopped strand mats.

Although, adding a reinforcement or a filler to TPU drastically increases the modulus of the article obtained therefrom, the fatigue resistance becomes greatly reduced. Moreover, creep recovery is also compromised which results in poor mechanical performance of the article.

Thus, it was an object of the present invention to provide a moldable reinforced TPU which when molded into an article, improves the modulus while maintaining the fatigue life and creep recovery, thereby rendering it suitable for applications such as, but not limited, to a pneumatic tire, non-pneumatic tire, conveyor belt, escalator handrail, footwear and elevator belt. Summary of the invention

Surprisingly, it has been found that a moldable reinforced thermoplastic polyurethane comprising at least one thermoplastic polyurethane and at least one primary reinforcing agent having a weight ratio between the at least one thermoplastic polyurethane and the at least one primary reinforcing agent in the range of 0.01:1.0 to 1.0:1.0 when molded into an article has a fatigue life of at least 10 million cycles at sinusoidal strain of frequency 10 Hz at a displacement of ± 10 mm per cycle at 23°C and a 2% secant modulus at 20°C in the range of 500 M Pa to 3000 MPa determined according to ASTM D412 and can be employed for a wide range of applications such as, but not limited to, a pneumatic tire, non-pneumatic tire, conveyor belt, escalator handrail, footwear and elevator belt.

Accordingly, in one aspect, the present invention is directed to a moldable reinforced thermoplastic polyurethane comprising:

(A) at least one thermoplastic polyurethane, and

(B) at least one primary reinforcing agent,

wherein the weight ratio between the at least one reinforcing agent (B) and the at least one thermoplastic polyurethane (A) is in the range of 0.01:1.0 to 1.0:1.0, and

wherein the moldable reinforced thermoplastic polyurethane when molded into an article has a fatigue life of at least 10 million cycles at sinusoidal strain of frequency 10 Hz at a displacement of ± 10 mm per cycle at 23° C and a 2% secant modulus at 20°C in the range of 500 MPa to 3000 MPa determined according to ASTM D412.

In another aspect, the present invention is directed to a moldable reinforced thermoplastic polyurethane comprising:

(A) at least one thermoplastic polyurethane obtained by reacting the building components: (Al) at least one polyether polyol having a weight average molecular weight Mw in the range of 800 g/mol to 5,000 g/mol determined using size exclusion chromatography,

(A2) at least one diisocyanate, and

(A3) at least one low molecular weight diol having a molecular weight in the range of 60 to 400 g/mol,

and

(B) at least one primary reinforcing agent,

wherein the moldable reinforced thermoplastic polyurethane when molded into an article has a fatigue life of at least 10 million cycles at sinusoidal strain of frequency 10 Hz at a displacement of ± 10 mm per cycle at 23° C and a 2% secant modulus at 20° C in the range of 500 MPa to 3000 MPa determined according to ASTM D412. In another aspect, the present invention is directed to a process for preparing a moldable reinforced thermoplastic polyurethane as above, comprising the steps of:

(a) blending the at least one thermoplastic polyurethane (A) with the at least one primary reinforcing agent (B) in the weight ratio between the at least one reinforcing agent (B) and the at least one thermoplastic polyurethane (A) in the range of 0.01:1.0 to 1.0:1.0, optionally in the presence of the at least one additive (D) to obtain a moldable reinforced thermoplastic polyurethane having a Shore D hardness in the range of 40 to 80 determined according to ASTM D2240, wherein the moldable reinforced thermoplastic polyurethane when molded into an article has a fatigue life of at least 10 million cycles at sinusoidal strain of frequency 10 Hz at a displacement of ± 10 mm per cycle at 23°C and a 2% secant modulus at 20°C in the range of 500 MPa to 3000 MPa determined according to ASTM D412.

In yet another aspect, the present invention is directed to a method of molding an article comprising the steps of:

(a’) melting a moldable reinforced thermoplastic polyurethane as above, and

(b’) molding the moldable reinforced thermoplastic polyurethane of step (a’) to obtain an article having a fatigue life of at least 10 million cycles at sinusoidal strain of frequency 10 Hz at a displacement of ± 10 mm per cycle at 23°C and a 2% secant modulus at 20°C in the range of 500 MPa to 3000 MPa determined according to ASTM D412.

In another aspect, the present invention is directed to a use of the moldable reinforced thermoplastic polyurethane as above or the moldable reinforced thermoplastic polyurethane obtained as above for molding into an article.

In still another aspect, the present invention is directed to an article comprising the moldable reinforced thermoplastic polyurethane as above or the moldable reinforced thermoplastic polyurethane obtained as above or obtained as above.

Brief description of the drawings

Other advantages of the present invention will be readily appreciated, as the same becomes better understood by reference to the following detailed description when considered in connection with the accompanying figures wherein:

Figure 1 is a perspective representation of a geometry comprising moldable reinforced thermoplastic polyurethane according to the invention and used for determining fatigue life and creep recovery.

Figure 2 is another perspective representation of the geometry comprising moldable reinforced thermoplastic polyurethane according to the invention and used for determining fatigue life and creep recovery, as shown in Figure 1. Detailed description of the invention

Before the present compositions and formulations of the invention are described, it is to be understood that this invention is not limited to particular compositions and formulations described, since such compositions and formulation may, of course, vary. It is also to be understood that the terminology used herein is not intended to be limiting, since the scope of the present invention will be limited only by the appended claims.

The terms "comprising", "comprises" and "comprised of" as used herein are synonymous with "including", "includes" or "containing", "contains", and are inclusive or open-ended and do not exclude additional, non-recited members, elements or method steps. It will be appreciated that the terms "comprising", "comprises" and "comprised of" as used herein comprise the terms "consisting of", "consists" and "consists of".

Furthermore, the terms "first", "second", "third" or "(a)", "(b)", "(c)", "(d)" etc. and the like in the description and in the claims, are used for distinguishing between similar elements and not necessarily for describing a sequential or chronological order. It is to be understood that the terms so used are interchangeable under appropriate circumstances and that the embodiments of the invention described herein are capable of operation in other sequences than described or illustrated herein. In case the terms "first", "second", "third" or“(A)”,“(B)” and“(C)” or "(a)", "(b)", "(c)", "(d)", "i", "ii" etc. relate to steps of a method or use or assay there is no time or time interval coherence between the steps, that is, the steps may be carried out simultaneously or there may be time intervals of seconds, minutes, hours, days, weeks, months or even years between such steps, unless otherwise indicated in the application as set forth herein above or below.

In the following passages, different aspects of the invention are defined in more detail. Each aspect so defined may be combined with any other aspect or aspects unless clearly indicated to the contrary. In particular, any feature indicated as being preferred or advantageous may be combined with any other feature or features indicated as being preferred or advantageous.

Reference throughout this specification to "one embodiment" or "an embodiment" means that a particular feature, structure or characteristic described in connection with the embodiment is included in at least one embodiment of the present invention. Thus, appearances of the phrases "in one embodiment" or "in an embodiment" in various places throughout this specification are not necessarily all referring to the same embodiment, but may. Furthermore, the particular features, structures or characteristics may be combined in any suitable manner, as would be apparent to a person skilled in the art from this disclosure, in one or more embodiments. Furthermore, while some embodiments described herein include some but not other features included in other embodiments, combinations of features of different embodiments are meant to be within the scope of the invention, and form different embodiments, as would be understood by those in the art. For example, in the appended claims, any of the claimed embodiments can be used in any combination.

Furthermore, the ranges defined throughout the specification include the end values as well, i.e. a range of 1 to 10 implies that both 1 and 10 are included in the range. For the avoidance of doubt, Applicant shall be entitled to any equivalents according to applicable law.

Thermoplastic polyurethanes or TPUs are an extremely diverse and versatile class of polymeric materials which find wide application in a very broad range of fields. They are generally characterized by the presence of urethane or carbamate group. The diversity of physical and mechanical properties exhibited by the TPUs arises from the ability to incorporate other chemical structures into these polymers. Such structures may be inherently rigid or flexible, or may result in crystallinity or chemical cross-linking.

Generally, the thermoplastic polyurethane is segmented. The segmented TPUs are formed from the reaction of an isocyanate and isocyanate reactive components. The isocyanate reactive component is a hydroxyl group containing compound, such as a long chain polyol. In addition to the polyol, the isocyanate reactive component may also comprise of a short chain diol as a chain extender. The TPUs are regarded as possessing alternating (AB)_n type block copolymeric structure, where A represents a soft segment and B represents a hard segment. Typically, the soft segment is comprised of the long chain polyol while the hard segment is derived from the isocyanate structure linked by the short chain diol. The soft segment primarily influences the elastic nature and low temperature performance, while the hard segments particularly affect the modulus, hardness and upper-use temperature by their ability to remain associated. Thus, to obtain a TPU having desired mechanical performance characteristics, the soft and hard segments need to be adjusted accordingly.

Fillers or reinforcing agents can also be added to the TPUs which result in improved performance characteristics of an article obtained therefrom.

Accordingly, a moldable reinforced thermoplastic polyurethane of the present invention comprises:

(A) at least one thermoplastic polyurethane, and

(B) at least one primary reinforcing agent,

wherein the moldable reinforced thermoplastic polyurethane when molded into an article has a fatigue life of at least 10 million cycles at sinusoidal strain of frequency 10 Hz at a displacement of ± 10 mm per cycle at 23°C and a 2% secant modulus at 20°C in the range of 500 MPa to 3000 MPa determined according to ASTM D412. An aspect of the present invention is directed to a moldable reinforced thermoplastic polyurethane comprising:

(A2) at least one diisocyanate, and

and

(B) at least one primary reinforcing agent,

wherein the moldable reinforced thermoplastic polyurethane when molded into an article has a fatigue life of at least 10 million cycles at sinusoidal strain of frequency 10 Hz at a displacement of ± 10 mm per cycle at 23° C and a 2% secant modulus at 20° C in the range of 500 MPa to 3000 MPa determined according to ASTM D412.

By the term“moldable”, it is referred here that the reinforced thermoplastic polyurethane, as described hereinabove, can be molded into an article.

For the purpose of the present invention, the moldable reinforced thermoplastic polyurethane is characterized in that the at least one thermoplastic polyurethane (A) comprises

(Al) at least one polyether polyol having a weight average molecular weight Mw in the range of 800 g/mol to 5,000 g/mol determined using size exclusion chromatography,

(A2) at least one diisocyanate, and

(A3) at least one low molecular weight diol having a molecular weight in the range of 60 to 400 g/mol.

In one embodiment, the moldable reinforced thermoplastic polyurethane is characterized in that the at least one thermoplastic polyurethane (A) is obtained by reacting the building components: (Al) at least one polyether polyol having a weight average molecular weight Mw in the range of 800 g/mol to 5,000 g/mol determined using size exclusion chromatography,

(A2) at least one diisocyanate, and

The weight average molecular weight, as referred throughout the description and unless indicated otherwise, is determined via size exclusion chromatography procedure with the following parameters:

The at least one thermoplastic polyurethane (A) as described hereinabove, primarily comprises of an isocyanate component and an isocyanate reactive component. The isocyanate reactive component, as described hereinabove, is a hydroxyl group containing component or compound which reacts with the isocyanate component to form the urethane groups in the TPU. The isocyanate reactive component primarily comprises of a polyol which forms the soft segment of the TPU, as described hereinabove. In addition to the polyol, the isocyanate reactive component may also comprise a diol which acts as the chain extender in the hard segment of the TPU.

By the term“polyol”, as described hereinabove and hereinbelow, it is referred to the polymer backbones containing nominally two or more hydroxyl groups, sometimes also referred to as polyalcohols.

The polyol, as the isocyanate reactive component, is a polyether polyol having a weight average molecular weight Mw in the range of 800 g/mol to 5,000 g/mol determined using size exclusion chromatography.

In one embodiment, the at least one polyether polyol (Al) has a weight average molecular weight Mw in the range of 800 g/mol to 4,000 g/mol determined using size exclusion chromatography. In another embodiment, it is in the range of 800 g/mol to 3,000 g/mol determined using size exclusion chromatography. In another embodiment, it is in the range of 800 g/mol to 2,500 g/mol, or 800 g/mol to 2,000 g/mol determined using size exclusion chromatography. In an embodiment, the at least one polyether polyol (Al) has a weight average molecular weight Mw in the range of 900 g/mol to 2,000 g/mol determined using size exclusion chromatography.

I n an embodiment, the moldable reinforced thermoplastic polyurethane is characterized in that the at least one thermoplastic polyurethane (A) is obtained by reacting the building components: (Al) at least one polyether polyol having a weight average molecular weight Mw in the range of 900 g/mol to 2,000 g/mol determined using size exclusion chromatography, (A2) at least one diisocyanate, and

The at least one polyether polyol (Al) that can be employed for the present invention may be made, for example, by reacting an alkylene oxide, such as propylene oxide, with a strong base such as potassium hydroxide, optionally in the presence of water, glycols and the like. Other at least one polyether polyol (Al) which can be utilized include, but are not limited to, those which are produced by polymerization of tetrahydrofuran or epoxides such as epichlorohydrin, ethylene oxide, propylene oxide, butylene oxide, styrene oxide, for example in the presence of Lewis catalysts such as boron trifluoride or other suitable initiator compounds, or by the addition of epoxides, optionally mixed or in succession, onto starter components with reactive hydrogen atoms such as water, alcohols, ammonia, or amines. Suitable initiator compounds contain a plurality of active hydrogen atoms, and include, but are not limited to, water, butanediol, ethylene glycol, propylene glycol (PG), diethylene glycol, triethylene glycol, dipropylene glycol, ethanolamine, diethanolamine, triethanolamine, toluene diamine, diethyl toluene diamine, phenyl diamine, diphenylmethane diamine, ethylene diamine, cyclohexane diamine, cyclohexane dimethanol, resorcinol, bisphenol A, glycerol, trimethylolpropane, 1,2,6-hexanetriol, pentaerythritol, and combinations thereof.

Other suitable at least one polyether polyol (Al) include polyether diols and triols, such as polyoxypropylene diols and triols and poly(oxyethylene-oxypropylene)diols and triols obtained by the simultaneous or sequential addition of ethylene and propylene oxides to di- or tri-functional initiators. Copolymers having oxyethylene contents of from about 5 to about 90% by weight, based on the weight of the polyol component, of which the polyols may be block copolymers, random/block copolymers or random copolymers, can also be used.

In an embodiment, the at least one polyether polyol (Al) is derived from monomers selected from the group consisting of ethylene oxide, propylene oxide, butylene oxide, epichlorohydrin, styrene oxide and tetrahydrofuran. By the term“derived” as used herein, it refers to the building block of the at least one polyether polyol (Al). In other embodiment, it is derived from monomers selected from the group consisting of propylene oxide, butylene oxide, epichlorohydrin, styrene oxide and tetrahydrofuran. In another embodiment, it is derived from monomers selected from the group consisting of butylene oxide, epichlorohydrin, styrene oxide and tetrahydrofuran. I n a particularly preferable embodiment, the at least one polyether polyol (Al) is derived from the monomer of tetrahydrofuran. Tetrahydrofuran is a cyclic ether and is converted into a linear polymer called poly(tetramethylene ether) glycol (PTMEG) which is subjected to polymerization to obtain the TPU, as described hereinabove. The choice of tetrahydrofuran as the at least one polyether polyol (Al) is not limited by the method employed to obtain the same. In fact, commercially available tetrahydrofuran, such as but not limited to, PolyTHF^® from BASF can be used for the purpose of the present invention. A person skilled in the art is well aware of such commercially available tetrahydrofuran.

I n an embodiment, the moldable reinforced thermoplastic polyurethane is characterized in that the at least one thermoplastic polyurethane (A) is obtained by reacting the building components: (Al) at least one polyether polyol derived from the monomer of tetrahydrofuran and having a weight average molecular weight Mw in the range of 800 g/mol to 5,000 g/mol determined using size exclusion chromatography,

(A2) at least one diisocyanate, and

In another preferable embodiment of the present invention, the at least one thermoplastic polyurethane (A) comprises a blend of at least two polyether polyols, as described hereinabove, having, independently of one another, a weight average molecular weight Mw in the range of 800 g/mol to 5,000 g/mol determined using size exclusion chromatography.

The amount of the at least one polyether polyol (Al) in the at least one thermoplastic polyurethane (A), as described hereinabove, is in the range of 1 wt.-% to 80 wt.-%, based on the total weight of the at least one thermoplastic polyurethane (A). In one embodiment, it is in the range of 1 wt.-% to 75 wt.-%, or 4 wt.-% to 75 wt.-%, or 4 wt.-% to 70 wt.-%, or 7 wt.-% to 70 wt.- %, or 7 wt.-% to 65 wt.-% based on the total weight of the at least one thermoplastic polyurethane (A). In other embodiment, it is in the range of 10 wt.-% to 65 wt.-%, or 10 wt.-% to 60 wt.-%, or 12 wt.-% to 60 wt.-%, or 12 wt.-% to 55 wt.-%, or 14 wt.-% to 55 wt.-% based on the total weight of the at least one thermoplastic polyurethane (A). I n another embodiment, it is in the range of 14 wt.-% to 50 wt.-%, or 17 wt.-% to 50 wt.-%, or 17 wt.-% to 45 wt.-%, based on the total weight of the at least one thermoplastic polyurethane (A). I n yet another embodiment, the at least one polyether polyol (Al) is in the range of 20 wt.-% to 45 wt.-%, based on the total weight of the at least one thermoplastic polyurethane (A).

In another embodiment, the at least one polyether polyol (Al) is a combination or blend of the at least one polyether polyol (Al) and a polyether polyol (A ) which are structurally different from each other. By the term“structurally different from each other”, it is referred to the at least one polyether polyol (Al) and the polyether polyol (A ) having, independently of one another, a weight average molecular weight Mw in the range of 800 g/mol to 5,000 g/mol determined using size exclusion chromatography. In one embodiment, the polyether polyol (A ) has a weight average molecular weight Mw in the range of 900 g/mol to 5,000 g/mol determined using size exclusion chromatography. In other embodiment, in the range of 900 g/mol to 4,000 g/mol determined using size exclusion chromatography. I n still other embodiment, in the range of 900 g/mol to 3,000 g/mol determined using size exclusion chromatography. The polyether polyol (A ) is derived from monomers selected from the group consisting of ethylene oxide, propylene oxide, butylene oxide, epichlorohydrin, styrene oxide and tetrahydrofuran. By the term “derived” as used herein, it refers to the building block of the polyether polyol (A ). In one embodiment, the polyether polyol (A ) is derived from tetrahydrofuran in a manner similar to the at least one polyether polyol (Al), as described hereinabove.

I n another embodiment, the moldable reinforced thermoplastic polyurethane is characterized in that the at least one thermoplastic polyurethane (A) is obtained by reacting the building components:

(Al) at least one polyether polyol having a weight average molecular weight Mw in the range of 900 g/mol to 2,000 g/mol determined using size exclusion chromatography,

(A ) a polyether polyol having a weight average molecular weight Mw in the range of 900 g/mol to 3,000 g/mol determined using size exclusion chromatography,

(A2) at least one diisocyanate, and

In yet another embodiment, a further building component comprises at least one polyester polyol (A4). The said at least one polyester polyol (A4) is a reaction product of at least one polyhydric alcohol (A41) with at least one polycarboxylic acid (A42). The at least one polyhydric alcohol (A41) is selected from the group consisting of 1,2-propylene glycol, 1,3-propylene glycol, glycerol, pentaerythritol, trimethylolpropane, 1,4,6-octanetriol, 1,4-butanediol, 1,5-pentanediol, 2,4- pentanediol, 1,6-hexanediol, dodecanediol, octanediol, chloropentanediol, glycerol monallyl ether, glycerol monoethyl ether, diethylene glycol, 2-ethylhexanediol-l,4, cyclohexanediol-1,4, 1,2,6-hexanetriol, 1,3,5-hexanetriol, l,3-bis-(2-hydroxyethoxy) propane, 1,4-butylene glycol, 2,3- butylene glycol, neopentyl glycol, l,4-bis-(hydroxymethyl)cyclohexane and trimethylolethane. While the at least one polycarboxylic acid (A42) is selected from the group consisting of phthalic acid, isophthalic acid, terephthalic acid, tetrachlorophthalic acid, maleic acid, dodecylmaleic acid, octadecenylmaleic acid, fumaric acid, aconitic acid, trimellitic acid, tricarballylic acid, 3,3'- thiodipropionic acid, succinic acid, adipic acid, malonic acid, glutaric acid, pimelic acid, sebacic acid, cyclohexane-1, 2-dicarboxylic acid, l,4-cyclohexadiene-l,2-dicarboxylic acid, 3-methyl-3,5- cyclohexadiene-l,2-dicarboxylic acid and terephthalic acid.

The at least one diisocyanate (A2) in the present invention may have any %NCO content, any number average molecular weight and any viscosity. I n one embodiment, the %NCO content of the at least one diisocyanate (A2) is in the range of 2 wt.-% to 50 wt.-%. Determination of the % NCO contents on percent by weight is accomplished by standard chemical titration analysis known to those skilled in the art. In other embodiment, the %NCO content of the at least one diisocyanate (A2) is in the range of 20 wt.-% to 50 wt.-%. In another embodiment, it is in the range of 25 wt.-% to 40 wt.-%. In a particularly preferable embodiment, the % NCO content of the at least one diisocyanate (A2) is in the range of 30 wt.-% to 35 wt.-%.

For the purpose of the present invention, the at least one diisocyanate (A2) include aliphatic diisocyanate, cycloaliphatic diisocyanate, aromatic diisocyanate and mixtures thereof. Moreover, the at least one diisocyanate (A2) of the present invention is not limited to any particular genus of the diisocyanate. For instance, the at least one diisocyanate (A2) can include monomeric diisocyanate, polymeric diisocyanate and mixture thereof. By the term“polymeric”, it is referred to the polymeric grade or form of the at least one diisocyanate (A2) comprising different oligomers and homologues.

I n an embodiment, the moldable reinforced thermoplastic polyurethane is characterized in that the at least one thermoplastic polyurethane (A) is obtained by reacting the building components: (Al) at least one polyether polyol having a weight average molecular weight Mw in the range of 900 g/mol to 2,000 g/mol determined using size exclusion chromatography,

(A2) at least one aliphatic diisocyanate, and

In another embodiment, the moldable reinforced thermoplastic polyurethane is characterized in that the at least one thermoplastic polyurethane (A) is obtained by reacting the building components:

(A2) at least one cycloaliphatic diisocyanate, and

(A2) at least one aromatic diisocyanate, and

Suitable cycloaliphatic diisocyanates include those in which two isocyanato groups are attached directly and/or indirectly to the cycloaliphatic ring. Aromatic diisocyanates include those in which two isocyanato groups are attached directly and/or indirectly to the aromatic ring. The aliphatic diisocyanate and cycloaliphatic diisocyanate can comprise 6 to 100 carbon atoms linked in a straight chain or cyclized and having two isocyanate reactive end groups. The aliphatic diisocyanate is selected from the group consisting of tetramethylene 1,4-diisocyanate, pentamethylene 1,5-diisocyanate, hexamethylene 1,6-diisocyanate, decamethylene diisocyanate, 1,12-dodecane diisocyanate, 2,2,4-trimethyl-hexamethylene diisocyanate, 2,4,4- trimethyl- hexamethylene diisocyanate and 2-methyl-l,5-pentamethylene diisocyanate.

The cycloaliphatic diisocyanate is selected from the group consisting of cyclobutane-1, 3- diisocyanate, 1,2-, 1,3- and 1,4-cyclohexane diisocyanates, 2,4- and 2,6-methylcyclohexane diisocyanate, 4,4'- and 2,4'-dicyclohexyldiisocyanates, isocyanatomethylcyclohexane isocyanates, isocyanatoethylcyclohexane isocyanates, bis(isocyanatomethyl)cyclohexane diisocyanates, 4,4'- and 2,4'-bis(isocyanato-methyl) dicyclohexane and isophorone diisocyanate.

The aromatic polyisocyanate is selected from the group consisting 2,4- and 2,6- hexahydrotoluenediisocyanate, 1,2-, 1,3-, and 1,4-phenylene diisocyanates, naphthylene-1,5- diisocyanate, 2,4- and 2,6-toluene diisocyanate, 2,4'-, 4,4'- and 2,2-biphenyl diisocyanates, 2,2'- , 2,4'- and 4,4'- diphenylmethane diisocyanate, 1,2-, 1,3- and 1,4-xylylene diisocyanates and m- tetramethylxylyene diisocyanate (TMXDI).

I n one embodiment, the at least one diisocyanate (A2) is selected from the group consisting of 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, tolylene 2,6- diisocyanate, dicyclohexylmethane 2,2’-diisocyanate, dicyclohexylmethane 4,4’-diisocyanate, hexamethylene 1,6-diisocyanate, paraphenylene 2,4-diisocyanate, tetramethylenexylene 2,4- 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, 2,4’-toluene diisocyanate, 2,6’-toluene diisocyanate, and 1,5- naphthalene diisocyanate.

In other embodiment, the at least one diisocyanate (A2) is selected from the group consisting of 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, tolylene 2,6- diisocyanate, dicyclohexylmethane 2,2’-diisocyanate, dicyclohexylmethane 4,4’-diisocyanate, hexamethylene 1,6-diisocyanate, paraphenylene 2,4-diisocyanate, tetramethylenexylene 2,4- diisocyanate, 2 methylpentamethylene 1,5 diisocyanate, 2 ethylbutylene 1,4 diisocyanate, pentamethylene 1,5 diisocyanate and butylene 1,4 diisocyanate.

In still other embodiment, the at least one diisocyanate (A2) is selected from the group consisting of 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, tolylene 2,6- diisocyanate, dicyclohexylmethane 2,2’-diisocyanate, dicyclohexylmethane 4,4’-diisocyanate, hexamethylene 1,6-diisocyanate, paraphenylene 2,4-diisocyanate and tetramethylenexylene 2,4- diisocyanate. In a further embodiment, the at least one diisocyanate (A2) is 4,4'-diphenylmethane diisocyanate (hereinafter referred as MDI). MDI is produced from aniline and formaldehyde feedstocks. Such methods are known to a person skilled in the art. The choice of MDI is not limited to any particular method for preparing the same. Accordingly, the person skilled in the art may obtain MDI by any suitable method. In fact, MDI may be commercially obtained such as, but not limited to, Luprana by BASF.

Accordingly, in one embodiment, the moldable reinforced thermoplastic polyurethane is characterized in that the at least one thermoplastic polyurethane (A) is obtained by reacting the building components:

(A2) 4,4'-diphenylmethane diisocyanate, and

The amount of the at least one diisocyanate (A2) in the at least one thermoplastic polyurethane (A) is in the range of 1 wt.-% to 80 wt.-%, based on the total weight of the at least one thermoplastic polyurethane (A). In one embodiment, it is in the range of 5 wt.-% to 80 wt.-%, or 5 wt.-% to 75 wt.-%, or 10 wt.-% to 75 wt.-%, or 10 wt.-% to 70 wt.-%, or 15 wt.-% to 70 wt.-%, based on the total weight of the at least one thermoplastic polyurethane (A). In other embodiment, it is in the range of 15 wt.-% to 65 wt.-%, or 20 wt.-% to 65 wt.-%, or 20 wt.-% to 63 wt.-%, or 25 wt.-% to 63 wt.-%, or 25 wt.-% to 60 wt.-%, based on the total weight of the at least one thermoplastic polyurethane (A). I n still other embodiment, it is in the range of 30 wt.-% to 60 wt.-%, or 30 wt.-% to 58 wt.-%, or 35 wt.-% to 58 wt.-%, or 40 wt.-% to 58 wt.-%, or 42 wt.-% to 58 wt.-%, based on the total weight of the at least one thermoplastic polyurethane (A). In a further embodiment, the amount of the at least one diisocyanate (A2) is in the range of 45 wt.-% to 55 wt.-%, based on the total weight of the at least one thermoplastic polyurethane (A).

For the purpose of the present invention, suitable chain extenders or isocyanate reactive components as the building components include at least one low molecular weight diol (A3), amines and polyamines. By the term“low molecular weight”, it is referred to the diol having a molecular weight in the range of 60 to 400 g/mol. The chain extenders are compounds stringing together the isocyanate. As already discussed hereinabove, the chains of isocyanate and chain extender represent the hard segment of the at least one thermoplastic polyurethane (A) of the present invention. The end isocyanate units of the hard segments are implicitly connected to the at least one polyether polyols, as described hereinabove. It serves as a spacer between the neighbouring isocyanates. The chain extender structure has a significant effect on the TPU properties because of its ability to drive phase separation, to complement or interfere with a regular hard segment structure and to promote interhard segment hydrogen bonding. Suitable amines and polyamines include aliphatic polyhydric amines such as ethylenediamine, hexamethylenediamine, and isophorone diamine; and aromatic polyhydric amines such as methylene-bis(2-chloroaniline), methy lenebis(di propy la ni li ne), diethyl-toluenediamine, trimethylene glycol di-p-aminobenzoate; alkanolamines such as diethanolamine, triethanolamine and diisopropanolamine.

However, in a preferable embodiment, the at least one low molecular weight diol (A3) is used as the chain extender or isocyanate reactive component in the present invention. Stated another way, the at least one thermoplastic polyurethane (A) of the present invention is the reaction product of the building components the at least one polyether polyol (Al), the at least one diisocyanate (A2) and the at least one low molecular weight diol (A3).

In one embodiment, the at least one low molecular weight diol (A3) has a molecular weight in the range of 60 to 350 g/mol. In other embodiment, in the range of 60 to 300 g/mol. In still other embodiment, in the range of 60 to 250 g/mol. In a further embodiment, the at least one low molecular weight diol (A3) has a molecular weight in the range of 60 to 200 g/mol.

(A2) at least one diisocyanate, and

(A3) at least one low molecular weight diol having a molecular weight in the range of 60 to 200 g/mol.

The at least one low molecular weight diol (A3), as described hereinabove, is selected from the group consisting of ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,3- propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-butylene glycol, 1,5-pentylene glycol, methylpentanediol, 1,6-hexylene glycol, neopentyl glycol, trimethylolpropane, glycerol, pentaerythritol, diglycerol, dextrose, 1,4:3, 6 dianhydrohexitol, hydroquinone bis 2-hydroxyethyl ether and bis-2(hydroxy ethyl)-terephthalate.

In one embodiment, the at least one low molecular weight (A3) is selected from the group consisting of ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,3- propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-butylene glycol, 1,5-pentylene glycol, methylpentanediol, 1,6-hexylene glycol, neopentyl glycol and trimethylolpropane. In other embodiment, it is selected from the group consisting of ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6- hexanediol, 1,4-butylene glycol, 1,5-pentylene glycol, methylpentanediol and 1,6-hexylene glycol. I n still other embodiment, it is selected from the group consisting of ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6- hexanediol, 1,4-butylene glycol and 1,5-pentylene glycol.

I n one embodiment, the at least one low molecu lar weight (A3) is selected from the grou p consisting of propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol and 1,6- hexanediol.

Accordi ngly, in one embodiment, the moldable reinforced thermoplastic polyu rethane is characterized in that the at least one thermoplastic polyu rethane (A) is obtained by reacting the building components:

(Al) at least one polyether polyol havi ng a weight average molecu lar weight Mw in the range of 900 g/mol to 2,000 g/mol determined using size exclusion chromatography,

(A2) at least one diisocyanate, and

(A3) at least one low molecu lar weight diol selected from the group consisting of propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol and 1,6-hexanediol.

The amou nt of the at least one low molecu lar weight diol (A3) in the at least one thermoplastic polyu rethane (A) is such that the weight ratio between the at least one low molecu lar weight diol (A3) and the at least one diisocyanate (A2) is in the range of 0.1: 1.0 to 1.0: 1.0. I n one embodiment, the weight ratio is in the range of 0.11:1.0 to 1.0:1.0, or 0.11:1.0 to 0.95:1.0, or 0.12:1.0 to 0.95:1.0, or 0.12: 1.0 to 0.9:1.0, or 0.13:1.0 to 0.9:1.0. I n other embodiment, it is i n the range of 0.13:1.0 to 0.85:1.0, or 0.14:1.0 to 0.85:1.0, or 0.14:1.0 to 0.8:1.0, or 0.15:1.0 to 0.8:1.0, or 0.15:1.0 to 0.75:1.0. I n still other embodiment, it is in the range of 0.16:1.0 to 0.75:1.0, or 0.16:1.0 to 0.7:1.0, or 0.17:1.0 to 0.7:1.0, or 0.17:1.0 to 0.65:1.0, or 0.18:1.0 to 0.65:1.0, or 0.18:1.0 to 0.60:1.0, or 0.19:1.0 to 0.60:1.0, or 0.19:1.0 to 0.55:1.0, or 0.20:1.0 to 0.55:1.0, or 0.20:1.0 to 0.5:1.0, or 0.20:1.0 to 0.45:1.0. I n yet other embodiment, the weight ratio between the at least one low molecu lar weight diol (A3) and the at least one diisocyanate (A2) is in the range of 0.2:1.0 to 0.4:1.0.

For the purpose of the present invention, the process for preparing the at least one thermoplastic polyu rethane (A), as described hereinabove, does not limit the present invention moldable rei nforced thermoplastic polyurethane, also described hereinabove. That is, to say, that the at least one thermoplastic polyurethane (A) may be obtained by any suitable method by reacting the building com ponents (Al), (A2), (A3) and optionally (A4) at process conditions known to the person skilled in the art. For instance, the at least one thermoplastic polyu rethane (A) may be obtained by, such as but not limited to, a one-shot process or a two-shot process. By the term “one-shot” it is meant that the at least one thermoplastic polyu rethane (A) formation takes place by simultaneous reaction of the at least one polyether polyol (Al), the at least one diisocyanate (A2) and the at least one low molecu lar weight diol (A3). Alternatively, the two-shot process or prepolymer process may also be em ployed, however, such processes general ly require at least one step of reacting the at least one polyether polyol (Al) and the at least one diisocyanate (A2) to obtain a prepolymer fol lowed by reacting the said prepolymer with the low molecu lar weight diol (A3) to obtain the at least one thermoplastic polyu rethane. Moreover, the above processes may optionally take place in the presence of at least one catalyst (A5). Such a choice of the process and the at least one catalyst (A5) is well known to the person skilled in the art and therefore, the present invention is not limited by the same.

In a preferred embodiment, the moldable reinforced thermoplastic polyurethane comprises:

(A2) at least one diisocyanate, and

and

(B) at least one primary reinforcing agent,

In another embodiment, the moldable reinforced thermoplastic polyurethane comprises:

(A) at least one thermoplastic polyurethane obtained by reacting the building components (Al) at least one polyether polyol having a weight average molecular weight Mw in the range of 900 g/mol to 2,000 g/mol determined using size exclusion chromatography,

(A2) at least one diisocyanate, and

and

(B) at least one primary reinforcing agent,

wherein the moldable reinforced thermoplastic polyurethane when molded into an article has a fatigue life of at least 10 million cycles at sinusoidal strain of frequency 10 Hz at a displacement of ± 10 mm per cycle at 40° C and a 2% secant modulus at 20° C in the range of 500 MPa to 3000 MPa determined according to ASTM D412.

(A) at least one thermoplastic polyurethane obtained by reacting the building components (Al) at least one polyether polyol having a weight average molecular weight Mw in the range of 900 g/mol to 2,000 g/mol determined using size exclusion chromatography, (A ) a polyether polyol having a weight average molecular weight Mw in the range of 900 g/mol to 3,000 g/mol determined using size exclusion chromatography,

(A2) at least one diisocyanate, and

and

(B) at least one primary reinforcing agent,

(A2) 2,4'-diphenylmethane diisocyanate, and

and

(B) at least one primary reinforcing agent,

wherein the moldable reinforced thermoplastic polyurethane when molded into an article has a fatigue life of at least 10 million cycles at sinusoidal strain of frequency 10 Hz at a displacement of ± 10 mm per cycle at 23°C and a 2% secant modulus at 20° C in the range of 500 MPa to 3000 MPa determined according to ASTM D412.

(A) at least one thermoplastic polyurethane is obtained by reacting the building components: (Al) at least one polyether polyol having a weight average molecular weight Mw in the range of 800 g/mol to 5,000 g/mol determined using size exclusion chromatography,

(A2) 2,4'-diphenylmethane diisocyanate, and

and (B) at least one primary reinforcing agent,

In still another embodiment, the moldable reinforced thermoplastic polyurethane comprises:

(A2) at least one diisocyanate, and

(A3) at least one low molecular weight diol having a molecular weight in the range of 60 to 200 g/mol,

and

(B) at least one primary reinforcing agent,

In yet another embodiment, the moldable reinforced thermoplastic polyurethane comprises:

(A2) at least one diisocyanate, and

(A3) at least one low molecular weight diol selected from the group consisting of propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol and 1,6-hexanediol,

and

(B) at least one primary reinforcing agent,

wherein the moldable reinforced thermoplastic polyurethane when molded into an article has a fatigue life of at least 10 million cycles at sinusoidal strain of frequency 10 Hz at a displacement of ± 10 mm per cycle at 40° C and a 2% secant modulus at 20° C in the range of 500 MPa to 3000 MPa determined according to ASTM D412. The present invention moldable reinforced thermoplastic polyurethane, as described hereinabove, also comprise at least one primary reinforcing agent (B). The at least one thermoplastic polyurethane (A), as described hereinabove, includes a primary reinforcement agent (B) to increase the modulus and improve the creep recovery.

For the purpose of the present invention, the at least one primary reinforcing agent (B) is selected from the group consisting of metal fiber, metalized inorganic fiber, metalized synthetic fiber, glass fiber, polyester fiber, polyamide fiber, graphite fiber, carbon fiber, ceramic fiber, mineral fiber, basalt fiber, inorganic fiber, aramid fiber, kenaf fiber, jute fiber, flax fiber, hemp fiber, cellulosic fiber, sisal fiber and coir fiber.

In one embodiment, the at least one primary reinforcing agent (B) is selected from the group consisting of metal fiber, metalized inorganic fiber, metalized synthetic fiber, glass fiber, polyester fiber, polyamide fiber, graphite fiber, carbon fiber, ceramic fiber, mineral fiber, basalt fiber, inorganic fiber, aramid fiber, kenaf fiber, jute fiber and flax fiber.

I n other embodiment, the at least one primary reinforcing agent (B) is selected from the group consisting of metal fiber, metalized inorganic fiber, metalized synthetic fiber, glass fiber, polyester fiber, polyamide fiber, graphite fiber, carbon fiber, ceramic fiber, mineral fiber, basalt fiber and inorganic fiber.

In still other embodiment, the at least one primary reinforcing agent (B) is selected from the group consisting of metal fiber, metalized inorganic fiber, metalized synthetic fiber, glass fiber, polyester fiber, polyamide fiber, graphite fiber, carbon fiber and ceramic fiber.

In one embodiment, the at least one primary reinforcing agent (B) is a glass fiber. The choice of suitable glass fibers and the process for obtaining the same is known to the person skilled in the art. For instance, the glass fiber as the primary reinforcing agent (B) is made from chopped glass fiber and/or short glass fiber. Moreover, the glass fibers may also be commercially obtained such as, but not limited to, ChopVantage^® by PPG Fiber Glass.

Accordingly, in an embodiment, the moldable reinforced thermoplastic polyurethane comprises:

(A) at least one thermoplastic polyurethane, and

(B) glass fiber,

wherein the weight ratio between the glass fiber (B) and the at least one thermoplastic polyurethane (A) is in the range of 0.01:1.0 to 1.0:1.0, and

wherein the moldable reinforced thermoplastic polyurethane when molded into an article has a fatigue life of at least 10 million cycles at sinusoidal strain of frequency 10 Hz at a displacement of ± 10 mm per cycle at 40° C and a 2% secant modulus at 20° C in the range of 500 MPa to 3000 MPa determined according to ASTM D412. In another embodiment, the moldable reinforced thermoplastic polyurethane comprises:

(A) at least one thermoplastic polyurethane, and

(B) chopped glass fiber,

wherein the weight ratio between the chopped glass fiber (B) and the at least one thermoplastic polyurethane (A) is in the range of 0.01:1.0 to 1.0:1.0, and

(A) at least one thermoplastic polyurethane, and

(B) short glass fiber,

wherein the weight ratio between the short glass fiber (B) and the at least one thermoplastic polyurethane (A) is in the range of 0.01:1.0 to 1.0:1.0, and

wherein the moldable reinforced thermoplastic polyurethane when molded into an article has a fatigue life of at least 10 million cycles at sinusoidal strain of frequency 10 Hz at a displacement of ± 10 mm per cycle at 40° C and a 2% secant modulus at 20° C in the range of 500 MPa to 3,000 MPa determined according to ASTM D412.

For the purpose of the present invention, the at least one primary reinforcing agent (B) may be obtained in any shape and size. For instance, the at least one primary reinforcing agent (B) may be, such as but not limited to, a strand of fiber having a lateral and through-plane dimension or a spherical particle having diameter. The present invention is not limited by the choice of the shape and size of the at least one primary reinforcing agent (B) as the person skilled in the art is well aware of the same.

The at least one primary reinforcing agent (B), as described hereinabove, has an average dimension in the range of 1 pm to 20 pm determined according to ASTM D578-98. By the term “average dimension”, it may be referred to the average size of the at least one primary reinforcing agent (B). For instance, strands of the at least one primary reinforcing agent (B) are typically characterized in terms of the fiber diameter and therefore, the average dimension would be the average fiber diameter.

In an embodiment, the at least one primary reinforcing agent (B) is subjected to a surface treatment agent. The surface treatment agent is also referred to as sizing. The at least one primary reinforcing agent (B) when subjected to a surface treatment agent further improve the mechanical properties. Typically, sizing provides adhesion between the at least one primary reinforcing agent (B) and TPU matrix. Additionally, it facilitates the processing by protecting the at least one primary reinforcing agent (B) from abrasion, integrates multiple fibers into a single strand and ensures adequate wetting by the TPU matrix. In particular, the surface treatment agent is a coupling agent and is selected from the group consisting of a silane coupling agent, titanium coupling agent and aluminate coupling agent. Particularly preferable are the silane coupling agent and are selected from the group consisting of aminosilane, epoxysilane, methyltrimethoxysilane, methyltriethoxysilane, y - glycidoxypropyltrimethoxysilane, vinyltriacetoxysilane and vinyltrimethoxysilane. In a preferable embodiment, the silane coupling agent is epoxysilane or aminosilane.

(A) at least one thermoplastic polyurethane, and

(B) at least one primary reinforcing agent,

wherein the weight ratio between the at least one primary reinforcing agent (B) and the at least one thermoplastic polyurethane (A) is in the range of 0.01:1.0 to 1.0:1.0,

wherein the primary reinforcing agent (B) is subjected to the surface treatment agent and wherein the moldable reinforced thermoplastic polyurethane when molded into an article has a fatigue life of at least 10 million cycles at sinusoidal strain of frequency 10 Hz at a displacement of ± 10 mm per cycle at 40° C and a 2% secant modulus at 20° C in the range of 500 MPa to 3,000 MPa determined according to ASTM D412.

(A) at least one thermoplastic polyurethane, and

(B) glass fiber,

wherein the weight ratio between the glass fiber (B) and the at least one thermoplastic polyurethane (A) is in the range of 0.01:1.0 to 1.0:1.0,

wherein the glass fiber (B) is subjected to the surface treatment agent and

wherein the moldable reinforced thermoplastic polyurethane when molded into an article has a fatigue life of at least 10 million cycles at sinusoidal strain of frequency 10 Hz at a displacement of ± 10 mm per cycle at 40° C and a 2% secant modulus at 20° C in the range of 500 MPa to

3,000 MPa determined according to ASTM D412.

(A) at least one thermoplastic polyurethane, and

(B) at least one primary reinforcing agent,

wherein the primary reinforcing agent (B) is subjected to a coupling agent and

wherein the moldable reinforced thermoplastic polyu rethane when molded into an article has a fatigue life of at least 10 million cycles at sinusoidal strain of frequency 10 Hz at a displacement of ± 10 mm per cycle at 40° C and a 2% secant modulus at 20° C in the range of 500 MPa to

3,000 MPa determined according to ASTM D412. In another embodiment, the moldable reinforced thermoplastic polyurethane comprises:

(A) at least one thermoplastic polyurethane, and

(B) at least one primary reinforcing agent,

wherein the primary reinforcing agent (B) is subjected to a silane coupling agent and wherein the moldable reinforced thermoplastic polyurethane when molded into an article has a fatigue life of at least 10 million cycles at sinusoidal strain of frequency 10 Hz at a displacement of ± 10 mm per cycle at 40° C and a 2% secant modulus at 20° C in the range of 500 MPa to 3,000 MPa determined according to ASTM D412.

(A) at least one thermoplastic polyurethane, and

(B) at least one primary reinforcing agent,

wherein the primary reinforcing agent (B) is subjected to an aminosilane coupling agent and wherein the moldable reinforced thermoplastic polyurethane when molded into an article has a fatigue life of at least 10 million cycles at sinusoidal strain of frequency 10 Hz at a displacement of ± 10 mm per cycle at 40° C and a 2% secant modulus at 20° C in the range of 500 MPa to 3,000 MPa determined according to ASTM D412.

(A) at least one thermoplastic polyurethane, and

(B) at least one primary reinforcing agent,

wherein the primary reinforcing agent (B) is subjected to an epoxysilane coupling agent and wherein the moldable reinforced thermoplastic polyurethane when molded into an article has a fatigue life of at least 10 million cycles at sinusoidal strain of frequency 10 Hz at a displacement of ± 10 mm per cycle at 40° C and a 2% secant modulus at 20° C in the range of 500 MPa to 3,000 MPa determined according to ASTM D412.

(A) at least one thermoplastic polyurethane, and

(B) glass fiber,

wherein the glass fiber (B) is subjected to a silane coupling agent and wherein the moldable reinforced thermoplastic polyurethane when molded into an article has a fatigue life of at least 10 million cycles at sinusoidal strain of frequency 10 Hz at a displacement of ± 10 mm per cycle at 40° C and a 2% secant modulus at 20° C in the range of 500 MPa to 3,000 MPa determined according to ASTM D412.

(A2) at least one diisocyanate, and

(A3) at least one low molecular weight diol selected from the group consisting of propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol and 1,6-hexanediol, and

(B) glass fiber,

wherein the glass fiber (B) is subjected to a silane coupling agent and

The amount of the at least one primary reinforcing agent (B) in the moldable reinforced thermoplastic polyurethane, as described hereinabove, is such that the weight ratio between the at least one reinforcing agent (B) and the at least one thermoplastic polyurethane (A) is in the range of 0.01:1 to 1.0:1.0. In one embodiment, the weight ratio is in the range of 0.01:1.0 to 0.95:1.0, or 0.015:1.0 to 0.95:1.0, or 0.015:1.0 to 0.9:1.0, or 0.02:1.0 to 0.9:1.0, or 0.02:1.0 to 0.85:1.0. In other embodiment, it is in the range of 0.025:1.0 to 0.85:1.0, or 0.025:1.0 to 0.8:1.0, or 0.03:1.0 to 0.8:1.0, or 0.03:1.0 to 0.75:1.0, or 0.035:1.0 to 0.75:1.0. I n yet other embodiment, it is in the range of 0.035:1.0 to 0.7:1.0, or 0.04:1.0 to 0.7:1.0, or 0.04:1.0 to 0.65:1.0, or 0.045:1.0 to 0.65:1.0, or 0.045:1.0 to 0.6:1.0, or 0.045:1.0 to 0.55:1.0, or 0.045:1.0 to 0.5:1.0, or 0.045:1.0 to 0.45:1.0, or 0.045:1.0 to 0.4:1.0, or 0.045:1.0 to 0.35:1.0, or 0.045:1.0 to 0.3:1.0, or 0.045:1.0 to 0.25:1.0. In still other embodiment, the weight ratio between the at least one reinforcing agent (B) and the at least one thermoplastic polyurethane (A) is in the range of 0.045:1.0 to 0.2:1.0.

The selection and relative proportions of the at least one polyether polyol (Al), the at least one diisocyanate (A2), the at least one low molecular weight diol (A3) and the at least one primary reinforcing agent (B), as described hereinabove, impact the physical properties of the resultant moldable reinforced thermoplastic polyurethane and any article formed therefrom in terms of tensile strength, tensile modulus, elongation at break, yield strain, hardness, tear strength, compression set, abrasion resistance, storage modulus, loss modulus, tangent delta, creep resistance, fatigue resistance and other properties such as glass transition. Additionally, the present invention moldable reinforced thermoplastic polyurethane may also further comprise at least one additive (D). The at least one additive (D) is selected from the group consisting of wax, lubricant, ultraviolet light stabilizer, antioxidant, compatibilizer, surfactant, friction modifier, crosslinker, plasticizer, flame retardant and colorant. The choice and amount of the at least one additive (D) is well known to the person skilled in the art. Moreover, the method employed for obtaining the said at least one additive (D) does not limit the present invention and therefore any suitable methods can be used for obtaining the same.

For the purpose of the present invention, it is to be understood that the moldable reinforced thermoplastic polyurethane, as described hereinabove, when molded into an article has the following:

(i) a fatigue life of at least 10 million cycles at sinusoidal strain of frequency 10 Hz at a displacement of ± 10 mm per cycle at 23° C,

(ii) a 2% secant modulus at 20° C in the range of 500 MPa to 3000 MPa determined according to ASTM D412, and

(iii) a creep recovery of less than 14% at 40° C after 48 h.

The moldable reinforced thermoplastic polyurethane also has a Shore D hardness in the range of 40 to 80 determined according to ASTM D2240. In an embodiment, the Shore D hardness is in the range of 50 to 75 determined according to ASTM D2240.

For the purpose of the present invention, the article comprising the moldable reinforced thermoplastic polyurethane, as described hereinabove, and having a fatigue life of at least 10 million cycles at sinusoidal strain of frequency 10 Hz at a displacement of ± 10 mm per cycle at 40° C, a 2% secant modulus at 20° C in the range of 500 MPa to 3000 MPa determined according to ASTM D412, and a creep recovery of less than 14% at 40° C after 48 h can be obtained from molding techniques such as, but not limited to, extrusion or injection molding. Such techniques are well known to the person skilled in the art and accordingly the choice of different moulds for the said techniques along with the typical process conditions can be made depending upon the desired geometry of the final article to be obtained.

Another aspect of the present invention describes a process for preparing the moldable reinforced thermoplastic polyurethane, as described hereinabove, comprising the steps of:

(a) blending the at least one thermoplastic polyurethane (A) with the at least one primary reinforcing agent (B) in the weight ratio between the at least one reinforcing agent (B) and the at least one thermoplastic polyurethane (A) in the range of 0.01:1.0 to 1.0:1.0, optionally in the presence of the at least one additive (D) to obtain a moldable reinforced thermoplastic polyurethane having a Shore D hardness in the range of 40 to 80 determined according to ASTM wherein the moldable reinforced thermoplastic polyurethane when molded into an article has a fatigue life of at least 10 million cycles at sinusoidal strain of frequency 10 Hz at a displacement of ± 10 mm per cycle at 23° C and a 2% secant modulus at 20° C in the range of 500 MPa to 3000 MPa determined according to ASTM D412.

The moldable reinforced thermoplastic polyurethane as obtained in the above process, has a creep recovery of less than 14% at 40° C after 48 h.

In one embodiment, the step (a) of the above described process can be carried out in the presence of any mixing means, such as but not limited to, a batch wise stirrer and reaction vessel, or a continuous stirrer and reaction vessel, or a reaction extruder. The choice of such mixing means is also known to the person skilled in the art.

Yet another aspect of the present invention describes a method of molding the article comprising the steps of:

(a’) melting the moldable reinforced thermoplastic polyurethane, as described hereinabove, and

(b’) molding the moldable reinforced thermoplastic polyurethane of step (a’) to obtain the article having a fatigue life of at least 10 million cycles at sinusoidal strain of frequency 10 Hz at a displacement of ± 10 mm per cycle at 23° C and a 2% secant modulus at 20° C in the range of 500 MPa to 3000 MPa determined according to ASTM D412.

Molding the article in the manner as described hereinabove, results in the article having a creep recovery of less than 14% at 40° C after 48 h.

In step (a’) of the method described hereinabove, the moldable reinforced thermoplastic polyurethane is subjected to melting. In an embodiment, the melting temperature maintained in step (a’) is in the range of 170° C to 220° C.

The moldable reinforced thermoplastic polyurethane obtained in step (a’) is molded to obtain the article in step (b’)· For the purpose of molding in step (b’), any suitable mould or geometry may be selected. Such geometries are well known to the person skilled in the art and the same does not limits the present invention.

In an embodiment, molding techniques such as, but not limited to, injection molding or extrusion may be employed in step (b’)· Such techniques are well known to the person skilled in the art and accordingly the choice of different moulds for the said techniques along with the typical process conditions can be made depending upon the desired geometry of the final article to be obtained. For the purpose of the present invention, the article comprising the moldable reinforced thermoplastic polyurethane, as described hereinabove or hereinbelow, is employed for measuring the fatigue life and creep recovery. Other mechanical properties, such as but not limited to, secant modulus and shore hardness may be measured using the standard techniques available with the person skilled in the art. As discussed hereinabove, the article may be obtained from molding techniques such as but not limited to, injection molding or extrusion and can have any shape and/or size.

In an embodiment, the 2% secant modulus can be determined from test samples which have been annealed at 80° C for 20 hours after molding, then rested at room temperature for at least 24 hours. Tensile testing and dynamic mechanical analysis (DMA) can be conducted on ASTM D412 Die“C” specimen stamped from 2mm thick injection molded test plaques. DMA technique is used to measure the glass transition temperature (Tg) using a film and fiber sample fixture. The test frequency is 10 Hz and the temperature ramp rate is 2° C/min. In order to measure the Tg value, storage modulus (E') and loss modulus (E”) are first determined. The storage modulus (E') represents the stiffness of the polymer material and is proportional to the energy stored during a loading cycle. The loss modulus (E”) is defined as being proportional to the energy dissipated during one loading cycle. It represents, for example, energy lost as heat, and is a measure of vibrational energy that has been converted during vibration and that cannot be recovered. Tg obtained using the E” values are typically lower than -30° C for the present invention.

Calculation of the 2% secant modulus was done by dividing the stress measured at 2% strain by 0.02. However, the fatigue life and creep recovery were tested on a different geometry, such as but not limited to the one described in Figure 1 and Figure 2.

In a particularly preferable embodiment, the article for determining the fatigue life and creep recovery has a geometry as depicted in Figure 1 and Figure 2. For the purpose of the present invention, the geometry may be interchangeably referred as test specimen. The geometry or test specimen is a“V” shaped I-beam with rounded edges. Various reference numerals along with the dimension of the mold for obtaining the geometry are described hereinbelow as:

As referred hereinabove, the terms“flat”,“vertical”,“horizontal”,“inclined” and“rounded” have the typical meanings known to the person skilled in the art. Further, the angles“0” and“P” are subtended with the horizontal and may have any values known to the person skilled in the art, subject to the geometry being “V” shaped. Moreover, the mold dimensions, as described hereinabove, have a tolerance typically of ± 0.005 inches and the geometry obtained using the said mold may contract not more than 3%.

Fatigue life or fatigue testing is defined as the process of progressive localized permanent structural change occurring in a material subjected to conditions that produce fluctuating stresses and strains at some point or points and that may culminate in cracks or complete fracture after a sufficient number of fluctuations. Fatigue life relates to how long an object or material will last before completely failing because of concentrated stresses. It depends on a number of factors, such as but not limited to, the type of material, its structure, its shape and temperature changes. For the purpose of the present invention, the fatigue life can be measured using any suitable instrument. Such an instrument is well known to the person skilled in the art. Nevertheless, a dynamic servo hydraulic tensile testing station may be employed. As described hereinabove, the fatigue life testing is conducted at sinusoidal strain of frequency 10 Hz at a displacement of ± 10 mm per cycle at 23° C and is typically at least 10 million cycles. By the term “displacement of ± 10 mm per cycle”, it is referred to one strain cycle displacing the geometry ± 10 mm from its neutral position i.e. when the geometry is clamped in the instrument at its neutral position, grips open by +10mm, return to neutral, contract to -10mm and again return to neutral. Excellent fatigue life is considered as achieving 10 million strain cycles without breaking, cracking or showing significant hazing or whitening.

Creep recovery is another parameter that is determined using the above described geometry or article. A simple way to express creep is to measure the ability of a material to re-gain its calliper, after being submitted to extensional forces, such as a load or displacement applied to the material, for an extended period of time. In order to determine the creep recovery, a pair of test specimen or a pair of the geometries described hereinabove, were clamped at the top and bottom in series to one another. The pair of test specimens were clamped back-to-back to neutralize any torque generated by the offset load and ensure that the displacement was only along the vertical axis. A constant force was applied to the bottom clamp and the top clamp was fixed in place. Creep testing was conducted at 40° C using an environmental testing chamber. The force to be applied to the pair test specimen for creep testing was determined ahead of time by using a tensile testing station with an environmental test chamber set to 40° C to measure the force required to extend the test specimen by +10 mm at 40° C. This constant force was applied to the test specimens for 48 hours at 40° C, causing the test specimens to elongate. The constant force was then removed and the test specimens were then placed at 23° C for another 24 hours, after which the elongation of the test specimens were recorded. The nonrecoverable deformation, or creep, was defined as the ratio of the initial geometry to the final geometry and was reported as a percentage. Excellent creep resistance was considered as less than 14% nonrecoverable deformation under the prescribed conditions.

Still another aspect of the present invention describes use of the moldable reinforced thermoplastic polyurethane as described hereinabove or the moldable reinforced thermoplastic polyurethane obtained according to the process as described hereinabove, for molding into the article. By the term “molding” as described hereinabove and hereinbelow, it is referred to injection molding or extrusion techniques.

In an embodiment, the moldable reinforced thermoplastic polyurethane is used in applications which require elastomeric materials with high modulus that can be flexed or bent tens of millions of times without failure. Such applications can be, such as but not limited to, a pneumatic tire, non-pneumatic tire, conveyor belt, escalator handrail, footwear and elevator belt.

A further aspect of the present invention describes the article comprising the moldable reinforced thermoplastic polyurethane as described hereinabove or the moldable reinforced thermoplastic polyurethane obtained according to the process described hereinabove or obtained according to the molding method described hereinabove or as used hereinabove. For the purpose of the present invention, the article can be, such as but not limited to, a pneumatic tire, non-pneumatic tire, conveyor belt, escalator handrail, footwear and elevator belt.

Yet another aspect of the present invention describes a process for preparing a pneumatic tire, comprising the steps of:

(PT1) injection molding the moldable reinforced thermoplastic polyurethane as described hereinabove or the moldable reinforced thermoplastic polyurethane obtained according to the process described hereinabove to obtain a pneumatic tire, wherein the non-pneumatic tire has a fatigue life of at least 10 million cycles at sinusoidal strain of frequency 10 Hz at a displacement of ± 10 mm per cycle at 23° C, a 2% secant modulus at 20° C in the range of 500 MPa to 3000 MPa determined according to ASTM D412 and a creep recovery of less than 14% at 40° C after 48 h.

Still another aspect of the present invention describes a process for preparing a non-pneumatic tire, comprising the steps of:

(NP1) injection molding the moldable reinforced thermoplastic polyurethane as described hereinabove or the moldable reinforced thermoplastic polyurethane obtained according to the process described hereinabove to obtain a non-pneumatic tire, wherein the non-pneumatic tire has a fatigue life of at least 10 million cycles at sinusoidal strain of frequency 10 Hz at a displacement of ± 10 mm per cycle at 23° C, a 2% secant modulus at 20° C in the range of 500 MPa to 3000 M Pa determined according to ASTM D412 and a creep recovery of less than 14% at 40° C after 48 h.

Another aspect of the present invention describes a process for preparing a conveyor belt, comprising the steps of:

(CB1) extruding the moldable reinforced thermoplastic polyurethane as described hereinabove or the moldable reinforced thermoplastic polyurethane obtained according to the process described hereinabove to obtain a conveyor belt, wherein the conveyor belt has a fatigue life of at least 10 million cycles at sinusoidal strain of frequency 10 Hz at a displacement of ± 10 mm per cycle at 23° , a 2% secant modulus at 20° C in the range of 500 MPa to 3000 MPa determined according to ASTM D412 and a creep recovery of less than 14% at 40° C after 48 h.

Yet another aspect of the present invention describes a process for preparing an escalator handrail, comprising the steps of:

(EH1) extruding the moldable reinforced thermoplastic polyurethane as described hereinabove or the moldable reinforced thermoplastic polyurethane obtained according to the process described hereinabove to obtain an escalator handrail, wherein the escalator handrail has a fatigue life of at least 10 million cycles at sinusoidal strain of frequency 10 Hz at a displacement of ± 10 mm per cycle at 40° C, a 2% secant modulus at 20° C in the range of 500 MPa to 3000 MPa determined according to ASTM D412 and a creep recovery of less than 14% at 40° C after 48 h.

Still another aspect of the present invention describes a process for preparing a footwear, comprising the steps of:

(FW1) injection molding the moldable reinforced thermoplastic polyurethane as described hereinabove or the moldable reinforced thermoplastic polyurethane obtained according to the process described hereinabove to obtain a footwear, wherein the footwear has a fatigue life of at least 10 million cycles at sinusoidal strain of frequency 10 Hz at a displacement of ± 10 mm per cycle at 23° C, a 2% secant modulus at 20° C in the range of 500 MPa to 3000 MPa determined according to ASTM D412 and a creep recovery of less than 14% at 40° C after 48 h. Another aspect of the present invention describes a process for preparing an elevator belt, comprising the steps of:

(RG) extruding the moldable reinforced thermoplastic polyurethane as described hereinabove or the moldable reinforced thermoplastic polyurethane obtained according to the process described hereinabove to obtain an elevator belt, wherein the elevator belt has a fatigue life of at least 10 million cycles at sinusoidal strain of frequency 10 Hz at a displacement of ± 10 mm per cycle at 23° C, a 2% secant modulus at 20° C in the range of 500 MPa to 3000 MPa determined according to ASTM D412 and a creep recovery of less than 14% at 40° C after 48 h.

The present invention is illustrated in more detail by the following embodiments and combinations of embodiments which result from the corresponding dependency references and links:

1. A moldable reinforced thermoplastic polyurethane comprising:

(A) at least one thermoplastic polyurethane, and

(B) at least one primary reinforcing agent,

2. The thermoplastic polyurethane according to embodiment 1, characterized in that the at least one thermoplastic polyurethane (A) is obtained by reacting the building components:

(A2) at least one diisocyanate, and

3. The thermoplastic polyurethane according to embodiment 2, characterized in that the at least one polyether polyol (Al) has a weight average molecular weight Mw in the range of 800 g/mol to 2,000 g/mol determined using size exclusion chromatography.

4. The thermoplastic polyurethane according to embodiment 2 or 3, characterized in that the at least one polyether polyol (Al) is derived from monomers selected from the group consisting of ethylene oxide, propylene oxide, butylene oxide, epichlorohydrin, styrene oxide and tetrahydrofuran. 5. The thermoplastic polyurethane according to one or more of embodiments 2 to 4, characterized in that the polyether polyol (Al) is derived from tetrahydrofuran.

6. The thermoplastic polyurethane according to one or more of embodiments 2 to 5, characterized in that the amount of the at least one polyether polyol (Al) is in the range of 1 wt.- % to 80 wt.-%, based on the total weight of the at least one thermoplastic polyurethane (A).

7. The thermoplastic polyurethane according to one or more of embodiments 2 to 6, characterized in that the at least one diisocyanate (A2) is selected from the group consisting of 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, tolylene 2,6- diisocyanate, dicyclohexylmethane 2,2’-diisocyanate, dicyclohexylmethane 4,4’-diisocyanate, hexamethylene 1,6-diisocyanate, paraphenylene 2,4-diisocyanate, tetramethylenexylene 2,4- 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, 2,4’-toluene diisocyanate, 2,6’-toluene diisocyanate, and 1,5- naphthalene diisocyanate.

8. The thermoplastic polyurethane according to embodiment 7, characterized in that the at least one diisocyanate (A2) is 2,4'-diphenylmethane diisocyanate.

9. The thermoplastic polyurethane according to one or more of embodiments 2 to 8, characterized in that the amount of the at least one diisocyanate (A2) is in the range of 1 wt.-% to 80 wt.-%, based on the total weight of the at least one thermoplastic polyurethane (A).

10. The thermoplastic polyurethane according to one or more embodiments 2 to 9, characterized in that the at least one low molecular weight diol (A3) has a molecular weight in the range of 60 g/mol to 200 g/mol.

11. The thermoplastic polyurethane according to one or more of embodiments 2 to 10, characterized in that the at least one low molecular weight diol (A3) is selected from the group consisting of ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,3- propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-butylene glycol, 1,5-pentylene glycol, methylpentanediol, 1,6-hexylene glycol, neopentyl glycol, trimethylolpropane, glycerol, pentaerythritol, diglycerol, dextrose, 1,4:3, 6 dianhydrohexitol, hydroquinone bis 2-hydroxyethyl ether and bis-2(hydroxy ethyl)-terephthalate.

12. The thermoplastic polyurethane according to one or more of embodiments 2 to 11, characterized in that the weight ratio between the at least one low molecular weight diol (A3) and the at least one diisocyanate (A2) is in the range of 0.1:1.0 to 1:1.0. 13. The thermoplastic polyurethane according to one or more of embodiments 1 to 12, characterized in that a further building component comprises at least one polyester polyol (A4).

14. The thermoplastic polyurethane according to embodiment 13, characterized in that the polyester polyol (A4) is a reaction product of at least one polyhydric alcohol (A41) with at least one polycarboxylic acid (A42).

15. The thermoplastic polyurethane according to embodiment 14, characterized in that the at least one polyhydric alcohol (A41) is selected from the group consisting of 1,2-propylene glycol, 1,3-propylene glycol, glycerol, pentaerythritol, trimethylolpropane, 1,4,6-octanetriol, 1,4- butanediol, 1,5-pentanediol, 2,4-pentanediol, 1,6-hexanediol, dodecanediol, octanediol, chloropentanediol, glycerol monallyl ether, glycerol monoethyl ether, diethylene glycol, 2- ethylhexanediol-1,4, cyclohexanediol-1,4, 1,2,6-hexanetriol, 1,3,5-hexanetriol, 1,3-bis- (2- hydroxyethoxy) propane, 1,4-butylene glycol, 2,3-butylene glycol, neopentyl glycol, 1,4-bis- (hydroxymethyl)cyclohexane and trimethylolethane.

16. The thermoplastic polyurethane according to embodiment 14, characterized in that the at least one polycarboxylic acid (A42) is selected from the group consisting of phthalic acid, isophthalic acid, terephthalic acid, tetrachlorophthalic acid, maleic acid, dodecylmaleic acid, octadecenylmaleic acid, fumaric acid, aconitic acid, trimellitic acid, tricarballylic acid, 3,3'- thiodipropionic acid, succinic acid, adipic acid, malonic acid, glutaric acid, pimelic acid, sebacic acid, cyclohexane-1, 2-dicarboxylic acid, l,4-cyclohexadiene-l,2-dicarboxylic acid, 3-methyl-3,5- cyclohexadiene-l,2-dicarboxylic acid and terephthalic acid.

17. The thermoplastic polyurethane according to one or more of embodiments 2 to 16, characterized in that the at least one polyether polyol (Al) is a combination of the at least one polyether polyol (Al) and a polyether polyol (A ) which are structurally different from each other.

18. The thermoplastic polyurethane according to embodiment 17, characterized in that the polyether polyol (A ) has a weight average molecular weight Mw in the range of 800 g/mol to 5,000 g/mol determined using size exclusion chromatography.

19. The thermoplastic polyurethane according to embodiment 17 or 18, characterized in that the polyether polyol (A ) has a weight average molecular weight Mw in the range of 900 g/mol to 3,000 g/mol determined using size exclusion chromatography.

20. The thermoplastic polyurethane according to one or more of embodiments 17 to 19, characterized in that the polyether polyol (A ) is derived from monomers selected from the group consisting of ethylene oxide, propylene oxide, butylene oxide, epichlorohydrin, styrene oxide and tetrahydrofuran. 21. The thermoplastic polyurethane according to embodiment 19, characterized in that the polyether polyol (A ) is derived from tetrahydrofuran.

22. The thermoplastic polyurethane according to one or more of embodiments 2 to 21 further comprising at least one catalyst (A5).

23. The thermoplastic polyurethane according to one or more of embodiments 1 to 22, characterized in that the at least one primary reinforcing agent (B) is selected from the group consisting of metal fiber, metalized inorganic fiber, metalized synthetic fiber, glass fiber, polyester fiber, polyamide fiber, graphite fiber, carbon fiber, ceramic fiber, mineral fiber, basalt fiber, inorganic fiber, aramid fiber, kenaf fiber, jute fiber, flax fiber, hemp fiber, cellulosic fiber, sisal fiber and coir fiber.

24. The thermoplastic polyurethane according to embodiment 23, characterized in that the at least one primary reinforcing agent (B) is a glass fiber.

25. The thermoplastic polyurethane according to embodiment 22 or 23, characterized in that the glass fiber is made from chopped glass fiber and/or short glass fiber.

26. The thermoplastic polyurethane according to one or more of embodiments 1 to 26, characterized in that the at least one primary reinforcing agent (B) has an average dimension in the range of 1 pm to 20 pm determined according to ASTM D578-98.

27. The thermoplastic polyurethane according to one or more of embodiments 1 to 27, characterized in that the at least one primary reinforcing agent (B) is subjected to a surface treatment agent.

28. The thermoplastic polyurethane according to embodiment 27, characterized in that the surface treatment agent is a coupling agent selected from the group consisting of a silane coupling agent, titanium coupling agent and aluminate coupling agent.

29. The thermoplastic polyurethane according to embodiment 28, characterized in that the surface treatment agent is a silane coupling agent selected from the group consisting of aminosilane, epoxysilane, methyltrimethoxysilane, methyltriethoxysilane, y - glycidoxypropyltrimethoxysilane, vinyltriacetoxysilane and vinyltrimethoxysilane.

30. The thermoplastic polyurethane according to embodiment 29, characterized in that the silane coupling agent is epoxysilane or aminosilane. 31. The thermoplastic polyurethane according to one or more of embodiments 1 to 30 further comprising at least one additive (D).

32. The thermoplastic polyurethane according to claim 31, characterized in that the at least one additive (D) is selected from the group consisting of wax, lubricant, ultraviolet light stabilizer, antioxidant, compatibilizer, surfactant, friction modifier, crosslinker, plasticizer, flame retardant and colorant.

33. The thermoplastic polyurethane according to one or more of embodiments 1 to 32, characterized in that the moldable reinforced thermoplastic polyurethane when molded into an article has a creep recovery of less than 14% at 40° C after 48 h.

34. The thermoplastic polyurethane according to one or more of embodiments 1 to 33, characterized in that the article is obtained by injection molding or extrusion.

35. A process for preparing a moldable reinforced thermoplastic polyurethane according to one or more of embodiments 1 to 34, comprising the steps of:

(a) blending the at least one thermoplastic polyurethane (A) with the at least one primary reinforcing agent (B) in the weight ratio between the at least one reinforcing agent (B) and the at least one thermoplastic polyurethane (A) in the range of 0.01:1.0 to 1.0:1.0, optionally in the presence of the at least one additive (D) to obtain a moldable reinforced thermoplastic polyurethane having a Shore D hardness in the range of 40 to 80 determined according to ASTM D2240,

36. The process according to embodiment 35, characterized in that the moldable reinforced thermoplastic polyurethane when molded into an article has a creep recovery of less than 14% at 40° C after 48 h.

37. A method of molding an article comprising the steps of:

(a’) melting a moldable reinforced thermoplastic polyurethane according to one or more of embodiments 1 to 34, and

(b’) molding the moldable reinforced thermoplastic polyurethane of step (a’) to obtain an article having a fatigue life of at least 10 million cycles at sinusoidal strain of frequency 10 Hz at a displacement of ± 10 mm per cycle at 23° C and a 2% secant modulus at 20° C in the range of 500 MPa to 3000 MPa determined according to ASTM D412. 38. The method according to embodiment 37, characterized in that in step (b’) injection molding or extrusion takes place.

39. The method according to embodiment 37 or 38, characterized in that the article has a creep recovery of less than 14% at 40° C after 48 h.

40. Use of the moldable reinforced thermoplastic polyurethane according to one or more of embodiments 1 to 34 or the moldable reinforced thermoplastic polyurethane obtained according to embodiment 35 or 36 for molding into an article.

41. The use according to embodiment 40, characterized in that the molding is selected from the group consisting of injection molding or extrusion.

42. The use according to embodiment 40 or 41, characterized in that the article is selected from the group consisting of a pneumatic tire, non-pneumatic tire, conveyor belt, escalator handrail, footwear and elevator belt.

43. An article comprising the moldable reinforced thermoplastic polyurethane according to one or more of embodiments 1 to 34 or the moldable reinforced thermoplastic polyurethane obtained according to embodiment 35 or 36 or obtained according to one or more of embodiments 37 to 39.

44. A moldable reinforced thermoplastic polyurethane comprising:

(A) at least one thermoplastic polyurethane, and

(B) at least one primary reinforcing agent,

45. The thermoplastic polyurethane according to embodiment 45, characterized in that the at least one thermoplastic polyurethane (A) is obtained by reacting the building components:

(A2) at least one diisocyanate, and

(A3) at least one low molecular weight diol having a molecular weight in the range of 60 to 400 g/mol. 46. The thermoplastic polyurethane according to embodiment 45, characterized in that the at least one polyether polyol (Al) is derived from monomers selected from the group consisting of ethylene oxide, propylene oxide, butylene oxide, epichlorohydrin, styrene oxide and tetrahydrofuran.

47. The thermoplastic polyurethane according to embodiment 45 or 46, characterized in that the at least one diisocyanate (A2) is selected from the group consisting of 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, tolylene 2,6-diisocyanate, dicyclohexylmethane 2,2’-diisocyanate, dicyclohexylmethane 4,4’-diisocyanate, hexamethylene 1,6-diisocyanate, paraphenylene 2,4-diisocyanate, tetramethylenexylene 2,4-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, 2,4’-toluene diisocyanate, 2,6’-toluene diisocyanate, and 1,5- naphthalene diisocyanate.

48. The thermoplastic polyurethane according to one or more of embodiments 45 to 47, characterized in that the at least one low molecular weight diol (A3) is selected from the group consisting of ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,3- propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-butylene glycol, 1,5-pentylene glycol, methylpentanediol, 1,6-hexylene glycol, neopentyl glycol, trimethylolpropane, glycerol, pentaerythritol, diglycerol, dextrose, 1,4:3, 6 dianhydrohexitol, hydroquinone bis 2-hydroxyethyl ether and bis-2(hydroxy ethyl)-terephthalate.

49. The thermoplastic polyurethane according to one or more of embodiments 44 to 48, characterized in that a further building component comprises at least one polyester polyol (A4).

50. The thermoplastic polyurethane according to one or more of embodiments 45 to 49, characterized in that the at least one polyether polyol (Al) is a combination of the at least one polyether polyol (Al) and a polyether polyol (A ) which are structurally different from each other.

51. The thermoplastic polyurethane according to embodiment 50, characterized in that the polyether polyol (A ) has a weight average molecular weight Mw in the range of 800 g/mol to 5,000 g/mol determined using size exclusion chromatography.

52. The thermoplastic polyurethane according to one or more of embodiments 44 to 51, characterized in that the at least one primary reinforcing agent (B) is selected from the group consisting of metal fiber, metalized inorganic fiber, metalized synthetic fiber, glass fiber, polyester fiber, polyamide fiber, graphite fiber, carbon fiber, ceramic fiber, mineral fiber, basalt fiber, inorganic fiber, aramid fiber, kenaf fiber, jute fiber, flax fiber, hemp fiber, cellulosic fiber, sisal fiber and coir fiber. 53. The thermoplastic polyurethane according to one or more of embodiments 44 to 52, characterized in that the at least one primary reinforcing agent (B) has an average dimension in the range of 1 pm to 20 pm determined according to ASTM D578-98.

54. The thermoplastic polyurethane according to one or more of embodiments 44 to 53, characterized in that the at least one primary reinforcing agent (B) is subjected to a surface treatment agent.

55. The thermoplastic polyurethane according to embodiment 54, characterized in that the surface treatment agent is a coupling agent selected from the group consisting of a silane coupling agent, titanium coupling agent and aluminate coupling agent.

56. The thermoplastic polyurethane according to one or more of embodiments 44 to 55, characterized in that the moldable reinforced thermoplastic polyurethane when molded into an article has a creep recovery of less than 14% at 40° C after 48 h.

57. The thermoplastic polyurethane according to one or more of embodiments 44 to 56, characterized in that the article is obtained by injection molding or extrusion.

58. A process for preparing a moldable reinforced thermoplastic polyurethane according to one or more of embodiments 44 to 57, comprising the step of:

59. A method of molding an article comprising the steps of:

(a’) melting a moldable reinforced thermoplastic polyurethane according to one or more of embodiments 44 to 57, and

(b’) molding the moldable reinforced thermoplastic polyurethane of step (a’) to obtain an article having a fatigue life of at least 10 million cycles at sinusoidal strain of frequency 10 Hz at a displacement of ± 10 mm per cycle at 40° C and a 2% secant modulus at 20° C in the range of 500 MPa to 3000 MPa determined according to ASTM D412. 60. Use of the moldable reinforced thermoplastic polyurethane according to one or more of embodiments 44 to 57 or the moldable reinforced thermoplastic polyurethane obtained according to embodiment 58 for molding into an article.

61. An article comprising the moldable reinforced thermoplastic polyurethane according to one or more of embodiments 44 to 57 or the moldable reinforced thermoplastic polyurethane obtained according to embodiment 58 or obtained according to embodiment 59.

62. A moldable reinforced thermoplastic polyurethane comprising:

(A) at least one thermoplastic polyurethane obtained by reacting the building components:

(A2) at least one diisocyanate, and

(A3) at least one low molecular weight diol having a molecular weight in the range of

60 to 400 g/ mol,

and

(B) at least one primary reinforcing agent,

63. The thermoplastic polyurethane according to embodiment 62, characterized in that the at least one polyether polyol (Al) is derived from monomers selected from the group consisting of ethylene oxide, propylene oxide, butylene oxide, epichlorohydrin, styrene oxide and tetrahydrofuran.

64. The thermoplastic polyurethane according to embodiment 62 or 63, characterized in that the at least one diisocyanate (A2) is selected from the group consisting of 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, tolylene 2,6-diisocyanate, dicyclohexylmethane 2,2’-diisocyanate, dicyclohexylmethane 4,4’-diisocyanate, hexamethylene 1,6-diisocyanate, paraphenylene 2,4-diisocyanate, tetramethylenexylene 2,4-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, 2,4’-toluene diisocyanate, 2,6’-toluene diisocyanate, and 1,5- naphthalene diisocyanate. 65. The thermoplastic polyurethane according to one or more of embodiments 62 to 64, characterized in that the at least one low molecular weight diol (A3) is selected from the group consisting of ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,3- propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-butylene glycol, 1,5-pentylene glycol, methylpentanediol, 1,6-hexylene glycol, neopentyl glycol, trimethylolpropane, glycerol, pentaerythritol, diglycerol, dextrose, 1,4:3, 6 dianhydrohexitol, hydroquinone bis 2-hydroxyethyl ether and bis-2(hydroxy ethyl)-terephthalate.

66. The thermoplastic polyurethane according to one or more of embodiments 62 to 65, characterized in that a further building component comprises at least one polyester polyol (A4).

67. The thermoplastic polyurethane according to one or more of embodiments 62 to 66, characterized in that the at least one polyether polyol (Al) is a combination of the at least one polyether polyol (Al) and a polyether polyol (A ) which are structurally different from each other.

68. The thermoplastic polyurethane according to embodiment 67, characterized in that the polyether polyol (A ) has a weight average molecular weight Mw in the range of 800 g/mol to 5,000 g/mol determined using size exclusion chromatography.

69. The thermoplastic polyurethane according to one or more of embodiments 62 to 68, characterized in that the at least one primary reinforcing agent (B) is selected from the group consisting of metal fiber, metalized inorganic fiber, metalized synthetic fiber, glass fiber, polyester fiber, polyamide fiber, graphite fiber, carbon fiber, ceramic fiber, mineral fiber, basalt fiber, inorganic fiber, aramid fiber, kenaf fiber, jute fiber, flax fiber, hemp fiber, cellulosic fiber, sisal fiber and coir fiber.

70. The thermoplastic polyurethane according to one or more of embodiments 62 to 69, characterized in that the at least one primary reinforcing agent (B) has an average dimension in the range of 1 pm to 20 pm determined according to ASTM D578-98.

71. The thermoplastic polyurethane according to one or more of embodiments 62 to 70, characterized in that the at least one primary reinforcing agent (B) is subjected to a surface treatment agent.

72. The thermoplastic polyurethane according to embodiment 71, characterized in that the surface treatment agent is a coupling agent selected from the group consisting of a silane coupling agent, titanium coupling agent and aluminate coupling agent.

73. The thermoplastic polyurethane according to one or more of embodiments 62 to 72, characterized in that the moldable reinforced thermoplastic polyurethane when molded into an article has a creep recovery of less than 14% at 40° C after 48 h determined by the method defined in the description.

74. The thermoplastic polyurethane according to one or more of embodiments 62 to 73, characterized in that the article is obtained by injection molding or extrusion.

75. A process for preparing a moldable reinforced thermoplastic polyurethane according to one or more of embodiments 62 to 74, comprising the step of:

76. A method of molding an article comprising the steps of:

(a’) melting a moldable reinforced thermoplastic polyurethane according to one or more of embodiments 62 to 74, and

(b’) molding the moldable reinforced thermoplastic polyurethane of step (a’) to obtain an article having a fatigue life of at least 10 million cycles at sinusoidal strain of frequency 10 Hz at a displacement of ± 10 mm per cycle at 40° C and a 2% secant modulus at 20° C in the range of 500 MPa to 3000 MPa determined according to ASTM D412.

77. Use of the moldable reinforced thermoplastic polyurethane according to one or more of embodiments 62 to 74 or the moldable reinforced thermoplastic polyurethane obtained according to embodiment 75 for molding into an article.

78. An article comprising the moldable reinforced thermoplastic polyurethane according to one or more of embodiments 62 to 74 or the moldable reinforced thermoplastic polyurethane obtained according to embodiment 75 or obtained according to embodiment 76. Examples

Compounds

Polyol

- Polyol 1 Polytetrahydrofuran with Mn = 1000 g/mol

- Polyol 2 Polytetrahydrofuran with Mn = 2000 g/mol

Diisocyanate 4,4'-diphenylmethane diisocyanate (MDI) having NCO content of 33.5 wt.-%

Chain extender 1,3-propanediol

were obtained from BASF

Primary reinforcing agent Chopped fiber glass with silane sizing and having an average fiber diameter of 10 pm

was obtained from PPG Fiber Glass

Standard methods

2% secant modulus ASTM D412

Shore D hardness ASTM D2240

Average dimension ASTM D578-98

The weight average molecular weight, Mw, was determined using size exclusion chromatography procedure with the following parameters:

Column PLgel 5pm Guard column, 100000 and 500 A columns at 80° C

Mobile phase Dimethylformamide (DMF) with 0.05 wt.-% Li Br

Flow rate 0.8 mL/min

Sample injection 100 pL of 1 mg/mL

Detector Differential refractometer at 38° C

Calibration EasiCal polystyrene standards with molecular weights of

M = 10,000 Da to 70,00,000 Da

General synthesis of moldable reinforced thermoplastic polyurethane TPU resins were prepared in either batch processes or continuous processes. For batch processes, in a 2 L metal container, polyol chain extender, and additives such as waxes or heat stabilizers were mixed with a mechanical stirrer. The container was then subsequently covered and placed inside a hot air oven preheated at 85° C. The preheated mixture was taken out of the oven and, in a separate vessel, polyisocyanate was heated to a temperature of 55° C. Once the temperature of the polyol mixture reached 80° C, the preheated polyisocyanate was added and the mixture stirred at 300 rpm. When the reacting materials reached 110C due to the exothermic reaction, the mixture was poured into a teflon frame kept over a hot plate having a temperature of 120° C to obtain a TPU slab. Once the TPU slab turned solid, it was removed from the hot plate and subsequently annealed inside a hot oven at 100° C for 20 h. The TPU was allowed to cool gradually, followed by being shredded to small granulates. The granulates were dried at 110° C for 3 h.

For continuous processes, the polyols, chain extenders, additives, and isocyanates were maintained in individual tanks to preheat them. When the materials were at their required temperatures they were dosed into a vessel that mixes the ingredients such as a mixpot or a reaction extruder. The ingredients can be added individually, together, at one location, or over multiple locations to improve the reaction. The polymerization takes place either on a conveyor belt or inside a reaction extruder barrel and was then shredded into granulates or pelletized underwater. Pellets and granulates were cured and dried before use the same as the batch process.

Once the pellets or granulates were cured and dried, they were mixed with the reinforcement using a twin-screw compounder or other method familiar to those skilled in the art. They were then pelletized or granulated, cured, and dried to make them ready for molding into articles or test samples.

Table 1 below reports the amount of different components present in the moldable reinforced thermoplastic polyurethane.

Table 1

In order to determine the 2% secant modulus, test samples were annealed at 80° C for 20 hours after molding, then rested at room temperature for at least 24 hours. Tensile testing and dynamic mechanical analysis were conducted on ASTM D412 Die“C” specimen stamped from 2mm thick injection molded test plaques. Calculation of the 2% secant modulus was done by dividing the stress measured at 2% strain by 0.02. Table 2 summarizes the results obtained.

Procedure for obtaining the sample for creep recovery and fatigue life

The test specimen for creep and fatigue testing was a V-shaped I-beam with round edges (see Figure 1 and Figure 2) with the following dimensions of the mold:

The mold dimensions, as described hereinabove, have a tolerance typically of ± 0.005 inches and the test specimen obtained using the said mold contracts not more than 3%.

The fatigue resistance was measured using a dynamic servo hydraulic tensile testing station. Testing was conducted at 23° C at a frequency of 10 Hz. One strain cycle displaces the test specimen ± 10 mm from its neutral position. Excellent fatigue life was considered as achieving 10 million strain cycles under the prescribed conditions without breaking, cracking, or showing significant hazing or whitening. The pair of test specimen were clamped at the top and bottom. The pair of test specimens were clamped back-to-back to neutralize any torque generated by the offset load and ensure that the displacement was only along the vertical axis. A constant force was applied to the bottom clamp and the top clamp was fixed in place. The force to be applied to the pair test specimen for creep testing was determined ahead of time by using a tensile testing station to measure the force required to extend the test specimen 10 mm. This force was applied to the test specimens for 48 hours, causing the test specimens to elongate. The constant force was then removed and the test specimens were then placed at 23° C for another 24 hours, after which the height of the test specimens were recorded. The nonrecoverable deformation, or creep, was defined as the ratio of the initial geometry to the final geometry and was reported as a percentage. Excellent creep resistance was considered as less than 14% nonrecoverable deformation under the prescribed conditions. Table 2 below summarizes the results obtained.

Table 2

+ implies that the sample testing was stopped while the fatigue life was still increasing with no signs of failure

It was observed that the 1,3-propanediol formed a tighter hard phase network of the thermoplastic polyurethane resin. The tighter hard phase resulted in an unexpected and unique advantage in that it increased the modulus of the TPU, which subsequently allowed lower loadings of the reinforcement to be required to reach the same modulus target of the moldable reinforced thermoplastic polyurethane. Having less reinforcement further improved the fatigue resistance of the articles comprised of the moldable reinforced thermoplastic polyurethane.

Claims

1. A moldable reinforced thermoplastic polyurethane comprising:

(A) at least one thermoplastic polyurethane, and

(B) at least one primary reinforcing agent,

2. The thermoplastic polyurethane according to claim 1, characterized in that the at least one thermoplastic polyurethane (A) is obtained by reacting the building components:

(Al) at least one polyether polyol having a weight average molecular weight Mw in the range of 800 g/mol to 5,000 g/mol determined using size exclusion chromatography, (A2) at least one diisocyanate, and

3. The thermoplastic polyurethane according to claim 2, characterized in that the at least one polyether polyol (Al) is derived from monomers selected from the group consisting of ethylene oxide, propylene oxide, butylene oxide, epichlorohydrin, styrene oxide and tetrahydrofuran.

4. The thermoplastic polyurethane according to claim 2 or 3, characterized in that the at least one diisocyanate (A2) is selected from the group consisting of 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, tolylene 2,6-diisocyanate, dicyclohexylmethane 2,2’-diisocyanate, dicyclohexylmethane 4,4’-diisocyanate, hexamethylene 1,6-diisocyanate, paraphenylene 2,4-diisocyanate, tetramethylenexylene

2.4-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, 2,4’-toluene diisocyanate, 2,6’-toluene diisocyanate, and 1,5-naphthalene diisocyanate.

5. The thermoplastic polyurethane according to one or more of claims 2 to 4, characterized in that the at least one low molecular weight diol (A3) is selected from the group consisting of ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,3-propanediol,

1.4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-butylene glycol, 1,5-pentylene glycol, methylpentanediol, 1,6-hexylene glycol, neopentyl glycol, trimethylolpropane, glycerol, pentaerythritol, diglycerol, dextrose, 1,4:3, 6 dianhydrohexitol, hydroquinone bis 2- hydroxyethyl ether and bis-2(hydroxy ethyl)-terephthalate.

6. The thermoplastic polyurethane according to one or more of claims 1 to 5, characterized in that a further building component comprises at least one polyester polyol (A4).

7. The thermoplastic polyurethane according to one or more of claims 2 to 6, characterized in that the at least one polyether polyol (Al) is a combination of the at least one polyether polyol (Al) and a polyether polyol (A ) which are structurally different from each other.

8. The thermoplastic polyurethane according to claim 7, characterized in that the polyether polyol (A ) has a weight average molecular weight Mw in the range of 800 g/mol to 5,000 g/mol determined using size exclusion chromatography.

9. The thermoplastic polyurethane according to one or more of claims 1 to 8, characterized in that the at least one primary reinforcing agent (B) is selected from the group consisting of metal fiber, metalized inorganic fiber, metalized synthetic fiber, glass fiber, polyester fiber, polyamide fiber, graphite fiber, carbon fiber, ceramic fiber, mineral fiber, basalt fiber, inorganic fiber, aramid fiber, kenaf fiber, jute fiber, flax fiber, hemp fiber, cellulosic fiber, sisal fiber and coir fiber.

10. The thermoplastic polyurethane according to one or more of claims 1 to 9, characterized in that the at least one primary reinforcing agent (B) has an average dimension in the range of 1 pm to 20 pm determined according to ASTM D578-98.

11. The thermoplastic polyurethane according to one or more of claims 1 to 10, characterized in that the at least one primary reinforcing agent (B) is subjected to a surface treatment agent.

12. The thermoplastic polyurethane according to claim 11, characterized in that the surface treatment agent is a coupling agent selected from the group consisting of a silane coupling agent, titanium coupling agent and aluminate coupling agent.

13. The thermoplastic polyurethane according to one or more of claims 1 to 12, characterized in that the moldable reinforced thermoplastic polyurethane when molded into an article has a creep recovery of less than 14% at 40° C after 48 h.

14. The thermoplastic polyurethane according to one or more of claims 1 to 13, characterized in that the article is obtained by injection molding or extrusion.

15. A process for preparing a moldable reinforced thermoplastic polyurethane according to one or more of claims 1 to 14, comprising the step of:

wherein the moldable reinforced thermoplastic polyurethane when molded into an article has a fatigue life of at least 10 million cycles at sinusoidal strain of frequency 10 Hz at a displacement of ± 10 mm per cycle at 40° C and a 2% secant modulus at 20° C in the range of 500 MPa to 3000 M Pa determined according to ASTM D412.

16. A method of molding an article comprising the steps of:

(a’) melting a moldable reinforced thermoplastic polyurethane according to one or more of claims 1 to 14, and

17. Use of the moldable reinforced thermoplastic polyurethane according to one or more of claims 1 to 14 or the moldable reinforced thermoplastic polyurethane obtained according to claim 15 for molding into an article.

18. An article comprising the moldable reinforced thermoplastic polyurethane according to one or more of claims 1 to 14 or the moldable reinforced thermoplastic polyurethane obtained according to claim 15 or obtained according to claim 16.

19. A moldable reinforced thermoplastic polyurethane comprising:

(A2) at least one diisocyanate, and

(A3) at least one low molecular weight diol having a molecular weight in the range of 60 to 400 g/ mol,

and (B) at least one primary reinforcing agent,

20. The thermoplastic polyurethane according to claim 19, characterized in that the at least one polyether polyol (Al) is derived from monomers selected from the group consisting of ethylene oxide, propylene oxide, butylene oxide, epichlorohydrin, styrene oxide and tetrahydrofuran.

21. The thermoplastic polyurethane according to claim 19 or 20, characterized in that the at least one diisocyanate (A2) is selected from the group consisting of 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, tolylene 2,6-diisocyanate, dicyclohexylmethane 2,2’-diisocyanate, dicyclohexylmethane 4,4’-diisocyanate, hexamethylene 1,6-diisocyanate, paraphenylene 2,4-diisocyanate, tetramethylenexylene

22. The thermoplastic polyurethane according to one or more of claims 19 to 21, characterized in that the at least one low molecular weight diol (A3) is selected from the group consisting of ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,3-propanediol,

23. The thermoplastic polyurethane according to one or more of claims 19 to 22, characterized in that a further building component comprises at least one polyester polyol (A4).

24. The thermoplastic polyurethane according to one or more of claims 19 to 23, characterized in that the at least one polyether polyol (Al) is a combination of the at least one polyether polyol (Al) and a polyether polyol (A ) which are structurally different from each other.

25. The thermoplastic polyurethane according to claim 24, characterized in that the polyether polyol (A ) has a weight average molecular weight Mw in the range of 800 g/mol to 5,000 g/mol determined using size exclusion chromatography.

26. The thermoplastic polyurethane according to one or more of claims 19 to 25, characterized in that the at least one primary reinforcing agent (B) is selected from the group consisting of metal fiber, metalized inorganic fiber, metalized synthetic fiber, glass fiber, polyester fiber, polyamide fiber, graphite fiber, carbon fiber, ceramic fiber, mineral fiber, basalt fiber, inorganic fiber, aramid fiber, kenaf fiber, jute fiber, flax fiber, hemp fiber, cellulosic fiber, sisal fiber and coir fiber.

27. The thermoplastic polyurethane according to one or more of claims 19 to 26, characterized in that the at least one primary reinforcing agent (B) has an average dimension in the range of 1 pm to 20 pm determined according to ASTM D578-98.

28. The thermoplastic polyurethane according to one or more of claims 19 to 27, characterized in that the at least one primary reinforcing agent (B) is subjected to a surface treatment agent.

29. The thermoplastic polyurethane according to claim 28, characterized in that the surface treatment agent is a coupling agent selected from the group consisting of a silane coupling agent, titanium coupling agent and aluminate coupling agent.

30. The thermoplastic polyurethane according to one or more of claims 19 to 29, characterized in that the at least one reinforcing agent (B) is glass fiber that is subjected to a silane coupling agent.

31. The thermoplastic polyurethane according to one or more of claims 19 to 30, characterized in that the moldable reinforced thermoplastic polyurethane when molded into an article has a creep recovery of less than 14% at 40° C after 48 h determined by the method defined in the description.

32. The thermoplastic polyurethane according to one or more of claims 19 to 31, characterized in that the article is obtained by injection molding or extrusion.

33. A process for preparing a moldable reinforced thermoplastic polyurethane according to one or more of claims 19 to 32, comprising the step of:

34. A method of molding an article comprising the steps of:

(a’) melting a moldable reinforced thermoplastic polyurethane according to one or more of claims 19 to 32, and

35. Use of the moldable reinforced thermoplastic polyurethane according to one or more of claims 19 to 32 or the moldable reinforced thermoplastic polyurethane obtained according to claim 33 for molding into an article.

36. An article comprising the moldable reinforced thermoplastic polyurethane according to one or more of claims 19 to 32 or the moldable reinforced thermoplastic polyurethane obtained according to claim 33 or obtained according to claim 34.