Melt-spun thermoplastic polyurethane fibers and fabrics made therefrom

Abstract

The invention relates to a melt-spun thermoplastic polyurethane fiber made from a thermoplastic polyurethane comprising the reaction product of at least 77.5 wt% poly(butanediol) succinate and up to 22.5 wt% hard segment component, wherein the hard segment component comprises a diisocyanate and a chain extender diol, wherein the molar ratio of isocyanate groups from the diisocyanate to hydroxyl groups from the poly(butanediol) succinate and chain extender diol is 0.9:1 to 1:1. The invention also provides a fabric made from the disclosed fiber.

Description

Background Technology

[0001] Crystalline thermoplastic polyurethane (TPU) materials offer beneficial properties for extruded profiles such as hoses, tubes, sheets, films, and filaments. For example, crystalline TPU materials typically exhibit superior abrasion and solvent resistance compared to their relatively less crystalline counterparts. Furthermore, crystalline TPU materials are generally easier to handle after the polymer melt has been deposited in a molding die. This can increase productivity and provide better quality final products.

[0002] However, (typically crystalline) thermoplastic polyurethane (TPU) materials have generally not been used in extrusion applications because the compositions are often difficult or even impossible to process, as they crystallize in the extrusion equipment and form conglomerates or chunks of solid matter. Furthermore, attempts to prevent crystallization by increasing processing temperatures have not been successful, resulting in thermal decomposition products. What is desirable is crystalline TPU materials that can be processed into articles through extrusion processes, such as high-speed extrusion spinning, which does not have these drawbacks.

[0003] Existing technologies attempt to provide crystalline TPUs that can be processed by extrusion methods, which include adding crystallization-restricting components to the TPU to delay crystallization, thereby avoiding significant solids or crystals in the extruder. This process is described in U.S. Patent 6,995,231. It is also desirable to have crystalline TPU compositions that can be extruded without the need for the addition of additional chemicals to delay crystallization.

[0004] TPU materials have been developed for use in hot melt adhesive (HMA) compositions. These materials are solid at room temperature, become tacky or sticky upon heating, and generally cure rapidly at ambient temperature to develop internal strength and cohesion. Such TPU compositions are described in PCT patent application publication WO2016 / 144676. Due to these properties, TPU materials suitable for use as adhesives are generally considered unsuitable for extrusion processes. However, because these TPUs can possess properties useful for articles, it is desirable to manufacture articles from these TPU materials by extrusion.

[0005] This invention provides a crystalline TPU material that can be extruded to produce extruded articles with improved properties. Summary of the Invention

[0006] This invention relates to a melt-spun fiber and a fabric made therefrom, wherein the fiber comprises a thermoplastic polyurethane comprising a reaction product of poly(butanediol) succinate, diisocyanate, and a chain extender diol. In one embodiment, the fiber is formed from a thermoplastic polyurethane composition comprising: soft segments provided by a crystalline polyol component; and hard segments provided by a diisocyanate and a hydroxyl-terminated chain extender. In another embodiment, the fiber is made from a thermoplastic polyurethane comprising at least 77.5% by weight of poly(butanediol) succinate polyol and 15% to 22.5% by weight of hard segments, wherein the hard segments constitute the total weight of the diisocyanate and the chain extender.

[0007] In another embodiment, the present invention provides a fabric comprising thermoplastic polyurethane fibers, wherein the thermoplastic polyurethane fibers are formed from at least 77.5% by weight of poly(butanediol) succinate polyol and 15% to 22.5% by weight of the reaction product of hard segments, wherein the hard segments constitute the total weight of diisocyanate and chain extender diol.

[0008] These various implementation schemes are described in more detail below. Detailed Implementation

[0009] The features and embodiments of the present invention will be described below with the aid of the following non-limiting description.

[0010] The disclosed technology includes a melt-spun fiber comprising a thermoplastic polyurethane (“TPU”) composition. The TPU composition that can be used to manufacture the melt-spun fiber of the present invention comprises “soft segments” and “hard segments”, wherein the soft segments are derived from a polyol component and the hard segments are derived from a reaction product of a diisocyanate component and a hydroxyl-terminated chain extender. The present invention also includes a fabric comprising the fiber described herein. Each of these components will be described in more detail below.

[0011] As used in this article, the weight-average molecular weight (Mw) was measured using polystyrene standards by gel permeation chromatography, and the number-average molecular weight (Mn) was measured by NMR end-group analysis.

[0012] thermoplastic polyurethane

[0013] The TPU compositions that can be used to manufacture the melt-spun fibers of the present invention comprise a polyester polyol component, which can also be described as a hydroxyl-terminated intermediate. In the present invention, the polyol component comprises or consists of a poly(butanediol) succinate polyol.

[0014] Polyester polyol intermediates can be produced by the following reactions: (1) esterification of one or more diols with one or more dicarboxylic acids or anhydrides, or (2) transesterification, i.e., reaction of one or more diols with dicarboxylic acid esters. To obtain a linear chain with predominantly terminal hydroxyl groups, a molar ratio of diol to acid exceeding one mole is generally preferred. For the purposes of this invention, poly(butanediol)succinate is a polyester polyol prepared by the reaction of succinic acid with butanediol (e.g., 1,3-butanediol or 1,4-butanediol). The succinic acid used to form the polyester can be derived from biomass resources, petroleum resources, or mixtures thereof.

[0015] In one useful embodiment, poly(butanediol) succinate may have a number average molecular weight of about 1000 g / mol to about 3000 g / mol, or about 1500 g / mol to about 2500 g / mol, or about 1800 g / mol to about 2200 g / mol, or even about 2000 g / mol.

[0016] In the thermoplastic polyurethane composition used to prepare the fibers of the present invention, the thermoplastic polyurethane comprises at least 77.5% by weight of poly(butanediol) succinate. In another embodiment, the thermoplastic polyurethane comprises 82.5% to 85% by weight of poly(butanediol) succinate. In one embodiment, the soft segments of the thermoplastic polyurethane are substantially composed of or composed of poly(butanediol) succinate. In some embodiments, the thermoplastic polyurethane of the present invention may comprise only trace amounts (e.g., less than 5% by weight, or less than 3% by weight, or even less than 1% by weight) of polyols other than poly(butanediol) succinate.

[0017] In addition to poly(butanediol) succinate containing soft segments, the thermoplastic polyurethane used in this invention also contains hard segments, which are defined as a combination of diisocyanate components and chain extender components.

[0018] The diisocyanate component may comprise one or more diisocyanates. Suitable diisocyanates include aromatic diisocyanates, aliphatic diisocyanates, or combinations thereof. In some embodiments, the polyisocyanate component comprises one or more aromatic diisocyanates. In some embodiments, the polyisocyanate component is substantially free of or even completely free of aliphatic diisocyanates. In other embodiments, the polyisocyanate component comprises one or more aliphatic diisocyanates. In some embodiments, the polyisocyanate component is substantially free of or even completely free of aromatic diisocyanates. In some embodiments, a mixture of aliphatic and aromatic diisocyanates may be suitable.

[0019] Examples of useful polyisocyanates include aromatic diisocyanates such as 4,4'-methylene bis(phenyl) isocyanate (MDI), 3,3'-dimethyl-4,4'-biphenylene diisocyanate (TODI), 1,5-naphthalene diisocyanate (NDI), m-xylene diisocyanate (XDI), phenyl-1,4-diisocyanate, naphthalene-1,5-diisocyanate, and toluene diisocyanate (TDI); and aliphatic diisocyanates such as 1,6-hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), 1,4-cyclohexyl diisocyanate (CHDI), decane-1,10-diisocyanate, lysine diisocyanate (LDI), 1,4-butane diisocyanate (BDI), isophorone diisocyanate (PDI), and dicyclohexylmethane-4,4'-diisocyanate (H12MDI). These diisocyanate isomers may also be applicable. Mixtures of two or more polyisocyanates may be used. In some embodiments, the isocyanate component comprises or is composed of aromatic diisocyanates. In some embodiments, the isocyanate component comprises or is composed of MDI.

[0020] The TPU compositions described herein are made using chain extender components. Suitable chain extenders include diols, diamines, and combinations thereof.

[0021] Suitable chain extenders include relatively small polyhydroxy compounds, such as lower aliphatic or short-chain diols having 2 to 20, 2 to 12, or 2 to 10 carbon atoms. Suitable examples include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,4-butanediol (BDO), 1,6-hexanediol (HDO), 1,3-butanediol, 1,5-pentanediol, neopentanediol, 1,4-cyclohexanediol (CHDM), 2,2-bis[4-(2-hydroxyethoxy)phenyl]propane (HEPP), 1,4-bis(β-hydroxyethoxy)benzene (HQEE), hexamethylenediol, heptaethylenediol, nonanediol, dodecanediol, 3-methyl-1,5-pentanediol, ethylenediamine, butylenediamine, hexamethylenediamine, and hydroxyethyl resorcinol (HER), and the like, and mixtures thereof. In one embodiment, the chain extender comprises or is composed of 1,4-butanediol.

[0022] In one embodiment of the invention, the TPU used to prepare the fibers of the invention contains 15% to 22.5% by weight hard segments. In another embodiment, the TPU used to prepare the fibers of the invention contains 15% to 17.5% by weight hard segments.

[0023] Optionally, one or more polymerization catalysts may be present during the polymerization reaction of TPU. Generally, any conventional catalyst can be used to react the diisocyanate with the polyol intermediate or chain extender. Examples of suitable catalysts that promote the reaction between the NCO group of the diisocyanate and the hydroxyl groups of the polyol and chain extender are conventional tertiary amines known in the art, such as triethylamine, dimethylcyclohexylamine, N-methylmorpholine, N,N'-dimethylpiperazine, 2-(dimethylaminoethoxy)ethanol, diazabicyclo[2.2.2]octane, and the like, and especially organometallic compounds (e.g., titanium esters), iron compounds (e.g., ferrous acetylacetonate), tin compounds (e.g., stannous diacetate, stannous octate, stannous dilaurate), bismuth compounds (e.g., bismuth trinedecanoate), or dialkyltin salts of aliphatic carboxylic acids (e.g., dibutyltin diacetate, dibutyltin dilaurate), or the like. The amount of catalyst typically used is 0.001 to 0.1 parts by weight per 100 parts by weight of the polyol component. In some embodiments, the reaction that forms the TPU of the present invention is substantially free of or completely free of catalyst.

[0024] The TPU compositions used in this invention can be produced via a "one-shot" method, wherein all components are added together simultaneously or substantially simultaneously to a heated extruder and reacted to form TPU. The equivalence ratio or molar ratio of the total equivalence of the diisocyanate to the hydroxyl-terminated intermediate and the chain extender is typically from about 0.9 to about 1.05, for example, from about 0.95 to about 1, or even from about 0.98 to about 1.0. In one embodiment, the molar ratio of isocyanate groups from the diisocyanate to hydroxyl groups from the poly(butanediol) succinate and the chain extender diol is 0.9:1 to 1:1. In one embodiment, the equivalence ratio may be less than 1.0, such that the TPU has terminal hydroxyl groups to enhance the reaction with the crosslinking agent during the fiber spinning process. The weight average molecular weight (MW) of TPU is typically from about 25,000 g / mol to about 300,000 g / mol, for example from about 50,000 g / mol to about 200,000 g / mol, or even further from about 75,000 g / mol to about 175,000 g / mol, wherein the weight average molecular weight is measured by GPC using polystyrene standards.

[0025] In another embodiment, TPU can be prepared using a prepolymer process. In the prepolymer process, a hydroxyl-terminated intermediate is reacted with an equivalence excess of one or more diisocyanates to form a prepolymer solution containing free or unreacted isocyanates. Subsequently, a chain extender as described herein is added in an equivalence typically equal to that of the isocyanate end groups and any free or unreacted diisocyanate compounds. The overall equivalence ratio of total diisocyanates to the total equivalence of the hydroxyl-terminated intermediate and chain extender is therefore from about 0.95 to about 1.10, for example from about 0.97 to about 1.03, or even from about 0.98 to about 1.0. In one embodiment, the equivalence ratio may be less than 1.0, such that the TPU has terminal hydroxyl groups to enhance the reaction with the crosslinking agent during the fiber spinning process. Generally, the prepolymer process can be carried out in any conventional apparatus, such as an extruder.

[0026] Optional additive components may be present during the polymerization reaction and / or incorporated into the aforementioned TPU elastomers to improve processing and other properties. These additives include, but are not limited to, antioxidants, organophosphites, phosphine and phosphonates, hindered amines, organic amines, organosulfur compounds, lactones and hydroxylamine compounds, biocides, fungicides, antimicrobial agents, compatibilizers, dissipative or antistatic additives, fillers and reinforcing agents (e.g., titanium dioxide, alumina, clay, and carbon black), flame retardants (e.g., phosphates, halogenated materials, and metal salts of alkylbenzene sulfonates), and impact modifiers (e.g., butadiene-styrene methacrylate (“MBS”) and methyl methacrylate propylene). Butyl ester (“MBA”), mold release agents (e.g., waxes, fats, and oils), pigments and colorants, plasticizers, polymers, rheology modifiers (e.g., monoamines, polyamide waxes, silicones, and polysiloxanes), slip additives (e.g., paraffin waxes, hydrocarbon polyolefins, and / or fluorinated polyolefins), and UV stabilizers (which may belong to the hindered amine light stabilizer (HALS) and / or UV light absorber (UVA) types). Other additives may be used to enhance the properties of TPU compositions or blends. All of the above additives may be used in the conventionally effective amounts of these substances.

[0027] These additional additives may be incorporated into the components used to prepare the TPU resin, into the reaction mixture used to prepare the TPU resin, or incorporated after the manufacture of the TPU resin. In another method, all materials may be mixed with the TPU resin and then melted, or they may be directly incorporated into the melt of the TPU resin.

[0028] In one embodiment, the TPU composition of the present invention will be clear and / or transparent. For example, the TPU composition of the present invention may have a clarity greater than 80% as measured according to the procedure in ASTM D1003. In another embodiment, the thermoplastic polyurethane has a melt onset temperature of 100°C to 120°C, which is determined by thermomechanical analysis of a 10-mil sample using a TAQ400 TMA instrument. In another embodiment, the thermoplastic polyurethane composition has a melt index greater than 25 g / 10 min at 190°C as measured according to the procedure in ASTM D1238.

[0029] thermoplastic polyurethane fiber

[0030] Melt-spun TPU fibers are produced by melting a TPU composition in an extruder. The TPU melt is fed to a spinning nozzle. The melt exits the nozzle to form fibers, which are then cooled and wound onto a bobbin.

[0031] The melt spinning process begins with feeding a pre-formed TPU polymer into an extruder. The TPU is melted in the extruder. After leaving the extruder and mixer, the molten TPU polymer flows into a manifold. The manifold splits the melt flow into different streams, each fed to multiple spinning nozzles. Typically, there are melt pumps for each different stream exiting the manifold, each pump feeding several spinning nozzles. The spinning nozzles will have small orifices that force the melt through and exit as fibers. The size of the orifices in the spinning nozzle will depend on the desired fiber size (denier). The fiber is drawn or stretched as it exits the spinning nozzle and is cooled before being wound onto a bobbin. The fiber is stretched by winding the bobbin at a higher speed than the fiber exiting the spinning nozzle. For melt-spun TPU fibers, the bobbin is typically wound at a rate greater than the speed at which the fiber exists at the spinning nozzle, for example, in some embodiments, 4 to 8 times the speed at which the fiber exits the spinning nozzle, but may be slower or faster depending on the specific equipment. The typical bobbin winding speed can vary between 100 and 3000 meters per minute, but for TPU melt-spun fibers, a more common speed is 1500 to 2500 meters per minute. A finished oil, such as silicone oil, is usually added to the fiber surface after cooling and just before winding into the bobbin.

[0032] The spinning temperature (the temperature of the polymer melt in the spinning nozzle) should be higher than the melting point of the polymer. In this invention, due to the crystalline nature of TPU, the spinning temperature can be 80°C to 100°C higher than the melting point of the polymer. The spinning temperature for the fibers produced by this invention is greater than 190°C, and preferably about 190°C to about 220°C, or even about 190°C to about 210°C.

[0033] The melt-spun TPU fibers of this invention can be manufactured as monofilament or multifilament yarns. Furthermore, melt-spun TPU fibers can be produced in various deniers. The term "denier" is defined as the mass (in grams) of 9000 meters of fiber, yarn, or filament. It describes the linear density (mass per unit length) of the fiber, yarn, or filament, and is measured according to ASTM D1577 Option B. Typical melt-spun TPU fibers are produced in denier sizes less than 240, more typically from 10 to less than 240 denier, with 100 and 160 denier being commonly used sizes.

[0034] According to ASTM D2256, the melt-spun TPU fibers manufactured according to the present invention also have a limiting elongation of at least 50% (e.g., 50% to 200%).

[0035] Furthermore, according to ASTM D3418 measurements, the melt-spun TPU fibers manufactured according to the present invention can also have a melt initiation of 100° to 120°. The fibers manufactured according to the present invention will shrink by less than 20%.

[0036] fabric

[0037] The TPU fibers of the present invention can be used alone or in combination with other natural or synthetic fibers by knitting or weaving to prepare fabrics that can be used in a variety of articles.

[0038] In one embodiment, the melt-spun TPU fibers of the present invention can be woven into fabrics. In another embodiment, the melt-spun TPU fibers of the present invention can be combined with one or more different TPU fibers to form fabrics. In yet another embodiment, the melt-spun TPU fibers of the present invention can be combined with other fibers (e.g., cotton, nylon, or polyester) to manufacture various end-use articles.

[0039] For example, fabrics according to the invention may combine the melt-spun TPU fibers of the invention with yarns of less elasticity than the TPU fibers of the invention (also referred to herein as "stiff yarns"). Stiff yarns may include, for example, polyester, nylon, cotton, wool, acrylic, polypropylene, or viscose rayon. Stiff yarns may also include, for example, other TPU fibers (not of the invention) of less elasticity than the TPU fibers of the invention. In one embodiment, the stiff yarn has a limiting elongation of 10% to 200%, for example 10% to 75%, or even 10% to 60%, or even 10% to 50%, or even 10% to 30%, and the melt-spun TPU fibers of the invention have a limiting elongation of at least 50%, for example 50% to 200%. Each fiber component may be included in the composition in an amount from 1% by weight to 99% by weight. The percentage by weight of melt-spun TPU fibers in the end-use application may vary depending on the desired function. For example, woven fabrics may comprise 1% to 8% by weight of melt-spun TPU fibers, underwear 2% to 5% by weight, swimwear and sportswear 8% to 30% by weight, compression garments 10% to 45% by weight, and medical tubing 35% to 60% by weight, with the remainder being rigid, inelastic fibers. Fabrics made from these two fiber materials can be constructed using various processes, including but not limited to circular knitting, warp knitting, braiding, braiding, non-woven, or combinations thereof. In one embodiment, fabrics made from the fibers of the present invention may be heat-treated to fuse the TPU fibers and form a monolayer. When measured according to ASTM D1052, this construction will withstand up to 300,000 cycles of cracking at –5°C.

[0040] The various properties of the fibers and fabrics manufactured according to the present invention can be measured according to the following measurement methods: Denier is a measure of linear density and is measured according to ASTM D1577 Option B; The tenacity of TPU fibers is measured by denier-standardized tensile strength and also according to ASTM D2256. The ultimate elongation of TPU fibers is the elongation at break, and it is measured according to ASTM D2256. The shrinkage rate of the fiber was measured by the following method: using a one-meter-long filament (free standing), and exposing the filament to 70°C in an oven for 90 seconds, to compare the filament length before and after exposure to the elevated temperature. TMA melt initiation is measured by heating the sample to its melt, causing it to deform due to the force applied by the probe. The TMA instrument detects and records the change in sample height with temperature; the shift in sample height indicates softening (or the melt initiation point of the polymer). The melt initiation point is measured on a thermal analysis (TA) Q400 unit with a puncture probe, a temperature range of 50°C to 210°C, a heating rate of 5°C per minute, and a preload and applied force of 0.05 N and 0.02 N, respectively. Hardness was measured according to ASTM D2240; The melting point Tm of the soft segment (TM-SS) is measured according to ASTM D3418. Melt flow index is measured according to ASTM D1238; Haze, clarity, and transparency are measured according to ASTM D1003.

[0041] The present invention will be better understood by referring to the following embodiments.

[0042] Example

[0043] Table 1 lists the TPU compositions used in the manufacture of fibers in this invention. Unless otherwise noted, the hard segments used in all embodiments are made of 4,4'-methylenebis(phenyl isocyanate) and 1,4-butanediol.

[0044] Table 1

[0045] 1 The chain extender in Example 2 was a mixture of 1,4-butanediol and neopentyl glycol.

[0046] Fibers were prepared using TPU materials selected from Table 1.

[0047] Table 2

[0048] All documents mentioned above are incorporated herein by reference, including any prior applications claiming priority, whether or not specifically listed above. Reference to any document does not imply an admission that such document conforms to the prior art or constitutes common sense to anyone skilled in the art of any jurisdiction. Except as expressly indicated in the embodiments, or whether otherwise explicitly stated, all numerical quantities of materials, reaction conditions, molecular weights, carbon numbers, and the like specified in this specification should be understood to be modified by the word "about." It should be understood that the upper and lower limits, ranges, and ratios set forth herein can be combined independently. Similarly, the scope and quantity of each element of the invention can be used in conjunction with the scope or quantity of any of the other elements.

[0049] As used herein, the transitional term "comprising," "containing," or "characterized in" is inclusive or open-ended and does not exclude additional, undescribed elements or method steps. However, in the various descriptions of "comprising" herein, the term is intended to also cover the phrases "consistently composed of" and "composed of" as alternative embodiments, wherein "composed of" excludes any unspecified elements or steps, and "consistently composed of" allows for the inclusion of additional, undescribed elements or steps that do not substantially affect the essential and novel features of the composition or method under consideration.

[0050] While certain representative embodiments and details have been shown for the purpose of illustrating the invention, it will be apparent to those skilled in the art that various changes and modifications can be made therein without departing from the scope of the invention. In this regard, the scope of the invention is limited only by the following claims.

Claims

1. A melt-spun fiber, wherein the fiber comprises: A thermoplastic polyurethane comprising a reaction product of at least 77.5% by weight poly(butanediol) succinate and up to 22.5% by weight a hard segment component, wherein the hard segment component comprises a diisocyanate and a chain extender diol, wherein the molar ratio of isocyanate groups from the diisocyanate to hydroxyl groups from the poly(butanediol) succinate and the chain extender diol is from 0.9:1 to 1:

1.

2. The fiber according to claim 1, wherein the poly(butanediol) succinate has a number average molecular weight of 1000 g / mol to 3000 g / mol, or 1500 g / mol to 2500 g / mol, or 1800 g / mol to 2200 g / mol, or 2000 g / mol, as measured by NMR end-group analysis.

3. The fiber according to any one of the preceding claims, wherein the thermoplastic polyurethane has a clarity greater than 80% as measured by ASTM D1003.

4. The fiber according to any one of the preceding claims, wherein the thermomechanical analysis determines that the thermoplastic polyurethane has a melt initiation of 100°C to 120°C.

5. The fiber according to any one of the preceding claims, wherein the thermoplastic polyurethane has a melt index greater than 25 g / 10 min at 190°C / 10 kg, as measured by ASTM D1238.

6. The fiber according to any one of the preceding claims, wherein the thermoplastic polyurethane comprises 15% to 17.5% by weight of hard segments.

7. The fiber of claim 6, wherein the thermoplastic polyurethane comprises 82.5% to 85% by weight of poly(butanediol) succinate.

8. The fiber according to any one of the preceding claims, wherein the fiber is free of nano-silica.

9. The fiber according to any one of the preceding claims, wherein the diisocyanate comprises or is composed of 4,4'-diphenylmethane diisocyanate.

10. The fiber according to any one of the preceding claims, wherein the chain extender diol is selected from the group consisting of: ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,3-butanediol, 1,5-pentanediol, neopentanediol, 1,4-cyclohexanediol, 2,2-bis[4-(2-hydroxyethoxy)phenyl]propane, 1,4-bis(β-hydroxyethoxy)benzene, hexamethylenediol, heptahydrate, nonanediol, dodecanediol, 3-methyl-1,5-pentanediol, ethylenediamine, butylenediamine, hexamethylenediamine, and hydroxyethyl resorcinol, or mixtures thereof.

11. The fiber according to any one of the preceding claims, wherein the chain extender diol comprises or is composed of 1,4-butanediol.

12. A fabric comprising: Thermoplastic polyurethane fiber, wherein the thermoplastic polyurethane comprises at least 77.5% by weight of poly(butanediol) succinate and up to 22.5% by weight of a hard segment component, wherein the hard segment component comprises diisocyanate and chain extender diol, wherein the molar ratio of isocyanate groups from the diisocyanate to hydroxyl groups from the poly(butanediol) succinate and chain extender diol is 0.9:1 to 1:

1.

13. The fabric according to claim 12, wherein the poly(butanediol) succinate has a number average molecular weight of 1000 g / mol to 3000 g / mol, or 1500 g / mol to 2500 g / mol, or 1800 g / mol to 2200 g / mol, or 2000 g / mol, as measured by NMR end-group analysis.

14. The fabric according to claim 12 or 13, wherein the fiber shrinkage is less than 20%.

15. The fabric according to any one of claims 12 to 14, wherein the thermoplastic polyurethane has a clarity greater than 80% as measured by ASTM D1003.

16. The fabric according to any one of claims 12 to 15, wherein the thermoplastic polyurethane comprises 15% to 17.5% by weight of hard segments.

17. The fabric according to any one of claims 12 to 16, wherein the thermoplastic polyurethane comprises 82.5% to 85% by weight of poly(butanediol) succinate.

18. The fabric according to any one of claims 12 to 17, wherein the thermomechanical analysis determines that the thermoplastic polyurethane has a melt initiation of 100°C to 120°C.

19. The fiber according to any one of claims 12 to 18, wherein the thermoplastic polyurethane has a melt index greater than 25 g / 10 min at 190 °C / 10 kg, as measured by ASTM D1238.

20. The fabric according to any one of claims 12 to 19, wherein the fibers are free of nano-silica.

21. The fabric according to any one of claims 12 to 20, wherein the diisocyanate comprises or is composed of 4,4'-diphenylmethane diisocyanate.

22. The fabric according to any one of claims 12 to 21, wherein the chain extender diol comprises or is composed of 1,4-butanediol.

23. The fabric according to any one of claims 12 to 22, wherein the fibers have a denier of 100 to 2500, or 100 to 2000, as measured by ASTM D1577 Option B.

24. The fabric according to any one of claims 12 to 23, wherein the fabric further comprises a second fiber, wherein the second fiber is selected from nylon fiber, polyester fiber, polypropylene fiber, or mixtures thereof.

25. The fabric according to any one of claims 12 to 24, wherein the fabric further comprises a second thermoplastic polyurethane fiber.

26. The fabric according to any one of claims 12 to 25, wherein the film formed from said fabric withstands 300,000 cycles of cracking at -5°C as measured by ASTM D1052.

27. A melt-spun fiber, wherein the fiber comprises: A thermoplastic polyurethane comprising 82.5 wt% to 85 wt% poly(butanediol) succinate and 15 wt% to 17.5 wt% hard segment component, wherein the hard segment component comprises 4,4'-diphenylmethane diisocyanate and 1,4-butanediol, wherein the molar ratio of isocyanate groups from the diisocyanate to hydroxyl groups from the poly(butanediol) succinate and chain extender diol is 09:1 to 1:1, and wherein the thermoplastic polyurethane has a clarity greater than 80% as measured by ASTM D1003, a melt initiation at 100°C to 120°C as measured by thermomechanical analysis, and a melt index greater than 25 g / 10 min at 190°C / 10 kg as measured by ASTM D1238.

28. The fiber according to claim 27, wherein the poly(butanediol) succinate has a number average molecular weight of 1000 g / mol to 3000 g / mol, or 1500 g / mol to 2500 g / mol, or 1800 g / mol to 2200 g / mol, or 2000 g / mol, as measured by NMR end-group analysis.

29. A fabric comprising: Thermoplastic polyurethane fiber, wherein the thermoplastic polyurethane comprises 82.5 wt% to 85 wt% poly(butanediol) succinate and 15 wt% to 17.5 wt% of a hard segment component, wherein the hard segment component comprises 4,4'-diphenylmethane diisocyanate and 1,4-butanediol, wherein the molar ratio of isocyanate groups from the diisocyanate to hydroxyl groups from the poly(butanediol) succinate and the chain extender diol is 1:09 to 1:1, and wherein the thermoplastic polyurethane has a clarity greater than 80% as measured by ASTM D1003, a melt initiation at 100°C to 120°C as measured by thermomechanical analysis, and a melt index greater than 25 g / 10 min at 190°C / 10 kg as measured by ASTM D1238, and wherein the fiber shrinkage is less than 20%.

30. The fabric of claim 29, wherein the fabric further comprises a second fiber, wherein the second fiber is selected from nylon fiber, polyester fiber, polypropylene fiber, or mixtures thereof.

31. The fabric according to claim 29 or 30, wherein the film formed from said fabric withstands 300,000 cycles of cracking at -5°C as measured by ASTM D1052.

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