Highly elastic thermoplastic polyurethanes and their uses

Abstract

The present disclosure relates to a thermoplastic polyurethane (TPU) composition containing the reaction product of a polyisocyanate, including a linear aliphatic diisocyanate having 3 to 12 carbon atoms, a polyol selected from polycaprolactone and polyester, and a linear or branched chain extender having a main backbone of 4 to 16 carbon atoms and hydroxyl groups separated by at least two carbon atoms. The TPU of the present disclosure has 15 to 50 percent hard segments and an average vertical modulus of at least 50 percent, as measured according to ASTM D2632. The TPU of the present disclosure exhibits improved vertical modulus and powder melt time, and has particular application in printing three-dimensional (3D) articles.

Description

[Technical Field]

[0001] The present disclosure relates to a thermoplastic polyurethane (TPU) composition containing the reaction product of a polyisocyanate, including a linear aliphatic diisocyanate having 3 to 12 carbon atoms, a polyol selected from polycaprolactone and polyester, and a linear or branched chain extender having a main backbone of 4 to 16 carbon atoms and hydroxyl groups separated by at least two carbon atoms. The TPU of the present disclosure has 15 to 50 percent hard segments and an average vertical modulus of at least 50 percent, as measured according to ASTM D2632. The TPU of the present disclosure exhibits improved vertical modulus and powder melt time and may have particular application in printing three-dimensional (3D) articles. [Background technology]

[0002] The present disclosure relates to TPU compositions that have one or more improved vertical elasticity and recovery properties, but also slower 3D printing speeds when used to print 3D articles.

[0003] The recovery properties of a polymer, and / or the determination of whether a particular polymer has "fast recovery" properties, are based on the time it takes for an article made from the polymer to return to its original shape after being deformed. For example, if a shoe sole made from the polymer of interest is bent and / or curved by the application of a force, it is the time it takes for it to return to its original shape after the force is released. In many applications, including shoe sole applications, the faster the recovery, the better, i.e., the faster the article returns to its original shape. Therefore, materials with fast recovery properties are better suited for such applications.

[0004] Rebound resilience is a measure of hysteresis energy loss, which can also be defined by the relationship between storage modulus and loss modulus. The measured rebound modulus is inversely proportional to hysteresis loss. Elastic modulus or rebound resilience is commonly used in quality control testing of polymers and compounded chemicals. Rebound resilience can be determined by a free-falling pendulum hammer and / or ball falling from a given height, impacting a test specimen and imparting a specific amount of energy to it. A portion of that energy is returned by the specimen to the pendulum, which can be measured by the degree to which the pendulum rebounds, thereby determining the recovery force due to gravity. 3D-printed articles with high rebound resilience can be advantageous for athletic shoe applications. The synergy between customizable 3D-printed sole components and high rebound resilience can maximize athletic performance.

[0005] With conventional compositions, it is seemingly difficult to provide a thermoplastic polyurethane composition with an improved combination of vertical elasticity and recovery while simultaneously reducing the printing speed of 3D articles. Attempts to improve recovery and / or rebound properties often result in faster or inadequate printing speeds for the TPU.

[0006] Thus, there is a general need in the art for TPU compositions that can be used to reduce 3D printing times while providing sufficient or improved vertical elasticity and / or recovery. Summary of the Invention [Means for solving the problem]

[0007] The present disclosure relates to a thermoplastic polyurethane (also referred to herein as "TPU") composition having 15 to 50 weight percent hard segments and an average axial modulus of at least 50 percent as measured according to ASTM D 2632. The TPU is formed by the reaction product of a polyisocyanate component including a linear aliphatic diisocyanate having 3 to 12 carbon atoms, a polyol component selected from polycaprolactone and polyester, and a linear or branched chain extender component having a main backbone of 4 to 16 carbon atoms, wherein the carbinol groups are separated by at least two carbon atoms.

[0008] In one embodiment of the present disclosure, the TPU composition comprises a TPU formed by the reaction product of a polyisocyanate component comprising a linear aliphatic diisocyanate selected from 1,6-hexamethylene diisocyanate and pentamethylene diisocyanate, a polycaprolactone polyol component, and a chain extender component selected from 1,12-dodecanediol, 1,6-hexanediol, and 1,4-butanediol. In such an embodiment, the TPU has 20 to 45 weight percent hard segment, an average dynamic modulus of 20 to 45 weight percent as measured in accordance with ASTM D2632, and a tan delta at 1.0 Hz (measured in accordance with ASTM D5279) of less than 0.0035.

[0009] In one embodiment, the TPU composition can be formed into a powder having a melt time of less than 30 seconds. In another embodiment, the TPU powder can have a particle size (D90) of less than 140 microns.

[0010] Another aspect of the present disclosure relates to a 3D article or part printed from the TPU composition of the present disclosure. In another embodiment, the 3D article or part has a rebound resilience of greater than 50 as measured according to ASTM D7121.

[0011] In another aspect of the present disclosure, the 3D article or part may be selected from footwear, prosthetics, orthopedic parts, electronic parts, consumer goods, sporting goods, and toys.

[0012] The following embodiments of the present subject matter are contemplated. 1. A thermoplastic polyurethane (TPU) composition comprising: a TPU having 1.15 to 50 percent hard segments and an average dynamic modulus of at least 50 percent as measured in accordance with ASTM D2632, the TPU being formed by the reaction product of: a polyisocyanate component comprising a linear aliphatic diisocyanate having 3 to 12 carbon atoms; a polyol component selected from polycaprolactone polyols and polyester polyols; and a linear or branched chain extender component having a main backbone of 4 to 16 carbon atoms with at least two hydroxyl groups, wherein the carbinol groups are separated by at least two carbon atoms. 2. The composition of embodiment 1, wherein the linear aliphatic diisocyanate component is selected from 1,6-hexamethylene diisocyanate and pentamethylene diisocyanate, preferably 1,6-hexamethylene diisocyanate. 3. The composition of any one of embodiments 1 or 2, wherein the polyisocyanate component is present in an amount of 10 to 30 weight percent of the TPU. 4. The composition of any one of embodiments 1-3, wherein the polyisocyanate component is present in an amount of 10 to 25 weight percent of the TPU. 5. The composition of any one of embodiments 1-4, wherein the polyol component is polycaprolactone. 6. The polyol component has a molecular weight (M w 6. The composition of any one of embodiments 1 to 5, wherein 7. The composition of embodiment 6, wherein the molecular weight is 1,500 to 3,250 or 1,850 to 3,250. 8. The composition of any one of embodiments 1-7, wherein the polyol component is present in an amount from 40 to 80 weight percent of the TPU. 9. The composition of any one of embodiments 1-8, wherein the polyol component is present in an amount from 50 to 80 weight percent of the TPU. 10. The composition of any one of embodiments 1-9, wherein the polyol component is present in an amount of 55 to 78 weight percent of the TPU. 11. The composition of any one of embodiments 1-10, wherein the chain extender component is selected from 1,12-dodecanediol, 1,6-hexanediol, and 1,4-butanediol. 12. The composition of any one of embodiments 1-11, wherein the chain extender component is 1,12-dodecanediol. 13. The composition of any one of embodiments 1-12, wherein the chain extender is present in an amount from 5 to 30 percent by weight of the TPU. 14. The composition of any one of embodiments 1-13, wherein the chain extender component is present in an amount of 7 to 25 weight percent of the TPU. 15. The composition of any one of embodiments 1-14, wherein the chain extender component is present in an amount from 8 to 22 weight percent of the TPU. 16. The composition of any one of embodiments 1-15, wherein the TPU has 20 to 45 percent hard segments. 17. The composition of any one of embodiments 1-16, wherein the TPU has 22 to 42 percent hard segments. 18. The composition of any one of embodiments 1-17, wherein the TPU has 24 to 41 percent hard segments. 19. The composition of any one of embodiments 1-18, wherein the TPU composition further comprises a plasticizer component. 20. The composition of embodiment 19, wherein the plasticizer component is a dialkyl ether glutarate. 21. The composition of embodiment 19, wherein the plasticizer component is present in an amount up to 7 weight percent of the TPU composition. 22. The composition of embodiment 19, wherein the plasticizer component is present in an amount up to 6.5 weight percent of the TPU composition. 23. The composition of embodiment 19, wherein the plasticizer component is present in an amount up to 5.5 weight percent of the TPU composition. 24. The composition of embodiment 19, wherein the plasticizer component is present in an amount from 0.5 to 10 weight percent of the TPU composition. 25. The composition of embodiment 19, wherein the plasticizer component is present in an amount from 1 to 7 weight percent of the TPU composition. 26. The composition of any one of embodiments 1-25, wherein the TPU has a vertical elasticity of at least 54 percent. 27. The composition of any one of embodiments 1-26, wherein the TPU has a tan delta at 1.0 Hz (measured according to ASTM D5279) of less than 0.0035. 28. The composition of embodiment 27, wherein tan delta is less than 0.0032. 29. The composition of embodiment 27, wherein tan delta is less than 0.0030. 30. The composition of any one of embodiments 1-29, wherein the TPU composition is formed into a powder having a particle size (D90) of less than 140 microns. 31. The composition of any one of embodiments 1-30, wherein the particle size is less than 135 microns. 32. The composition of any one of embodiments 1-31, wherein the particle size is less than 132 microns. 33. The composition of any one of embodiments 1-32, wherein the TPU composition is formed into a powder having a powder melt time of less than 30 seconds. 34. The composition of embodiment 30, wherein the powder melt time is less than 25 seconds. 35. A 3D printed part prepared from the TPU composition of any one of embodiments 1 to 34. 36. The 3D printed part of embodiment 35, wherein the 3D printed part has a rebound resilience of greater than 50 as measured according to ASTM D7121. 37. The 3D printed part of embodiment 35, wherein the 3D printed part has a rebound resilience of greater than 55. 38. The 3D printed part of embodiment 35, wherein the 3D printed part has a resilience greater than 58. 39. The 3D printed part of any one of embodiments 35-38, wherein the 3D printed part is selected from a footwear midsole, a prosthetic, an orthopedic part, an electronic component, a consumer product, a sporting goods, and a toy. DETAILED DESCRIPTION OF THE INVENTION

[0013] This disclosure describes a thermoplastic polyurethane composition comprising a TPU having 15 to 50 weight percent hard segments and an average dynamic modulus of at least 50 percent as measured according to ASTM D 2632. The TPU is formed by the reaction product of a polyisocyanate component including a linear aliphatic diisocyanate component having 3 to 12 carbon atoms, a polyol component selected from polycaprolactone and polyester, and a linear or branched chain extender component having a main backbone of 4 to 16 carbon atoms, wherein the carbinol groups are separated by at least two carbon atoms.

[0014] Polyisocyanate component: The TPU reaction product of the composition of the present disclosure is prepared using a polyisocyanate component comprising a linear aliphatic diisocyanate having 3 to 12 carbon atoms. Examples of suitable diisocyanates include, but are not limited to, 1,6-hexamethylene diisocyanate (HDI), 1,4-butane diisocyanate, pentamethylene diisocyanate, 4,4'-methylenebis(cyclohexylisocyanate), 1,4-bis(isocyanatomethyl)cyclohexane, isophorone diisocyanate, 1,4-cyclohexane diisocyanate, and combinations thereof. In one embodiment, the diisocyanate is 1,6-hexamethylene diisocyanate.

[0015] In some embodiments, the polyisocyanate component may include one or more additional polyisocyanates, typically diisocyanates.

[0016] Suitable polyisocyanates that can be used in combination with the linear aliphatic diisocyanates described above include linear or branched aromatic diisocyanates, branched aliphatic diisocyanates, or combinations thereof. In some embodiments, the polyisocyanate component comprises one or more aromatic diisocyanates. In other embodiments, the polyisocyanate component is essentially free of, or even completely free of, aromatic diisocyanates.

[0017] The additional polyisocyanate component may include one or more aromatic diisocyanates. Examples of suitable aromatic polyisocyanates include 4,4'-methylenebis(phenylisocyanate) (MDI), m-xylene diisocyanate (XDI), phenylene-1,4-diisocyanate, naphthalene-1,5-diisocyanate, and toluene diisocyanate (TDI), as well as isophorone diisocyanate (IPDI), 1,4-cyclohexyl diisocyanate (CHDI), decane-1,10-diisocyanate, lysine diisocyanate (LDI), 1,4-butane diisocyanate (BDI), and isophorone diisocyanate (TDI). Examples of suitable polyisocyanates include, but are not limited to, aliphatic diisocyanates such as 3,3'-dimethyl-4,4'-biphenylene diisocyanate (IPDI), 3,3'-dimethyl-4,4'-biphenylene diisocyanate (TODI), 1,5-naphthalene diisocyanate (NDI), and dicyclohexylmethane-4,4'-diisocyanate (H12MDI). Mixtures of two or more polyisocyanates may be used. In some embodiments, the polyisocyanate is MDI and / or H12MDI. In some embodiments, the polyisocyanate comprises MDI. In some embodiments, the polyisocyanate comprises H12MDI.

[0018] In other embodiments, in addition to the aromatic polyisocyanate and linear aliphatic diisocyanate described above, the polyisocyanate component may contain one or more additional aliphatic diisocyanates. Suitable aliphatic diisocyanates include isophorone diisocyanate (IPDI), 1,6-hexamethylene diisocyanate (HDI), 1,4-cyclohexyl diisocyanate (CHDI), decane-1,10-diisocyanate, lysine diisocyanate (LDI), 1,4-butane diisocyanate (BDI), and dicyclohexylmethane-4,4'-diisocyanate (H12MDI). In some embodiments, a mixture of two or more polyisocyanates may be used.

[0019] The polyisocyanate component of the present TPU composition may be present in the TPU in an amount of 10 to 30 weight percent of the TPU. In another embodiment, the polyisocyanate component may be present in the TPU in an amount of 10 to 25 weight percent of the TPU.

[0020] Polyol component: The TPU reaction product of the composition of the present disclosure is further formed from a polyol or diol. The polyol used to form the TPU of the TPU composition is selected from one or more of polyester polyols and polycaprolactones. In one embodiment, the polyol is polycaprolactone. In another embodiment, the polyol is a polyester polyol.

[0021] The average molecular weight of the polyol component (M w ) can be 1,000 to 3,500. In one embodiment, the average molecular weight of the polyol component is 1,500 to 3,250. In another embodiment, the average molecular weight of the polyol component is 1,850 to 3,250.

[0022] The average molecular weight of the polyol is determined by the following formula:

[0023]

number

[0024] Polycaprolactone polyols useful in the TPU compositions described herein include polyester diols derived from caprolactone monomers, i.e., polycaprolactone. Polycaprolactone polyols are terminated with primary hydroxyl groups. Suitable polycaprolactone polyols can be made from ε-caprolactone and a difunctional initiator, such as diethylene glycol, 1,4-butanediol, or any of the other glycols and / or diols listed herein. In some embodiments, the polycaprolactone polyol is a linear polyester diol derived from caprolactone monomers.

[0025] Useful examples include CAPA™ 2202A, a linear diol with a number average molecular weight (Mn) of 2000, and CAPA™ 2302A, a linear diol with an Mn of 3000, both commercially available from Perstorp Polyols Inc. These materials are also sometimes described as polymers of 2-oxepanone and 1,4-butanediol.

[0026] The polycaprolactone polyol can be prepared from 2-oxepanone and a diol, and the diol can be 1,4-butanediol, diethylene glycol, monoethylene glycol, 1,6-hexanediol, 2,2-dimethyl-1,3-propanediol, or any combination thereof. In some embodiments, the diol used to prepare the polycaprolactone polyol is linear. In some embodiments, the polycaprolactone polyol is prepared from 1,4-butanediol.

[0027] In addition to polycaprolactone polyols, polyester polyols may be used to form the TPU of the TPU composition.

[0028] Suitable polyester polyols generally have an acid value of less than 1.3. In some embodiments, polyester polyols have an acid value of less than 0.5. Polyester polyols include intermediates that can be produced by (1) the esterification reaction of one or more glycols with one or more dicarboxylic acids or anhydrides, or (2) transesterification, i.e., the reaction of one or more glycols with an ester of a dicarboxylic acid. To obtain linear chains with predominantly terminal hydroxyl groups, a mole ratio of glycol to acid greater than 1 mole is generally preferred. Suitable polyester intermediates also include the dicarboxylic acid of the desired polyester, which can be aliphatic, cycloaliphatic, aromatic, or a combination thereof. Suitable dicarboxylic acids, which can be used alone or in mixtures, generally have a total of 4 to 15 carbon atoms and include succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, isophthalic acid, terephthalic acid, cyclohexanedicarboxylic acid, and the like. Anhydrides of the above dicarboxylic acids, such as phthalic anhydride and tetrahydrophthalic anhydride, can also be used. Adipic acid is a preferred acid. The glycols reacted to form the desired polyester intermediate can be aliphatic, aromatic, or combinations thereof, including any of the glycols described in the chain extender section above, having a total of 2 to 20 or 2 to 12 carbon atoms. Suitable examples include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2,2-dimethyl-1,3-propanediol, 1,4-cyclohexanedimethanol, decamethylene glycol, dodecamethylene glycol, and mixtures thereof.

[0029] The polyol component may be present in the TPU in an amount from 40 to 80, or from 50 to 80, or from 55 to 78 weight percent of the TPU.

[0030] The TPU composition may further comprise additional polyols other than the polycaprolactone and / or polyester polyols described above. If present, the additional polyols may comprise one or more hydroxyl-terminated polyethers, one or more hydroxyl-terminated polycarbonates, one or more hydroxyl-terminated polysiloxanes, or mixtures thereof.

[0031] Suitable hydroxyl-terminated polyether intermediates include polyether polyols derived from alkyl diols or glycols reacted with diols or polyols having a total of 2 to 15 carbon atoms, in some embodiments alkylene oxides having 2 to 6 carbon atoms, typically ethers containing ethylene oxide or propylene oxide, or mixtures thereof. For example, hydroxyl-functional polyethers can be produced by first reacting propylene glycol with propylene oxide and then with ethylene oxide. Primary hydroxyl groups, resulting from ethylene oxide, are preferred because they are more reactive than secondary hydroxyl groups. Useful commercially available polyether polyols include poly(ethylene glycol), which contains ethylene oxide reacted with ethylene glycol; poly(propylene glycol), which contains propylene oxide reacted with propylene glycol; and poly(tetramethylene ether glycol), which contains water reacted with tetrahydrofuran (sometimes described as polymerized tetrahydrofuran and commonly referred to as PTMEG). In some embodiments, the polyether intermediate comprises PTMEG. Suitable polyether polyols also include polyamide adducts of alkylene oxides, such as ethylenediamine adducts, which include the reaction product of ethylenediamine and propylene oxide; diethylenetriamine adducts, which include the reaction product of diethylenetriamine and propylene oxide; and similar polyamide-type polyether polyols. Copolyethers can also be utilized in the described compositions. Typical copolyethers include the reaction products of THF and ethylene oxide or THF and propylene oxide. These are available from BASF as block copolymers, PolyTHF® B, and random copolymers, PolyTHF® R. The various polyether intermediates generally have number-average molecular weights (Mn), as determined by assay of terminal functional groups, that are greater than about 700, such as about 700 to about 10,000, about 1,000 to about 5,000, or about 1,000 to about 2,500.In some embodiments, the polyether intermediate is 2,000M. n and 1000M n and blends of two or more polyethers of different molecular weights, such as a blend of PTMEG.

[0032] Suitable hydroxyl-terminated polycarbonates include those prepared by reacting a glycol with a carbonate. U.S. Pat. No. 4,131,731 is incorporated herein by reference for its disclosure of hydroxyl-terminated polycarbonates and their preparation. Such polycarbonates are linear and essentially have terminal hydroxyl groups, excluding other end groups. The essential reactants are a glycol and a carbonate. Suitable glycols are selected from cycloaliphatic and aliphatic diols containing 4 to 40 and / or even 4 to 12 carbon atoms, and from polyoxyalkylene glycols containing 2 to 20 alkoxy groups per molecule, each alkoxy group containing 2 to 4 carbon atoms. Suitable diols include aliphatic diols containing 4 to 12 carbon atoms, such as 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 2,2,4-trimethyl-1,6-hexanediol, 1,10-decanediol, hydrogenated dilinoleyl glycol, hydrogenated dioleyl glycol, and 3-methyl-1,5-pentanediol, and alicyclic diols, such as 1,3-cyclohexanediol, 1,4-dimethylolcyclohexane, 1,4-cyclohexanediol, 1,3-dimethylolcyclohexane, 1,4-endomethylene-2-hydroxy-5-hydroxymethylcyclohexane, and polyalkylene glycols. The diol used in the reaction can be a single diol or a mixture of diols, depending on the properties desired in the final product. Hydroxyl-terminated polycarbonate intermediates are generally known in the art and in the literature. Suitable carbonates are selected from alkylene carbonates composed of 5- to 7-membered rings. Suitable carbonates for use herein include ethylene carbonate, trimethylene carbonate, tetramethylene carbonate, 1,2-propylene carbonate, 1,2-butylene carbonate, 2,3-butylene carbonate, 1,2-ethylene carbonate, 1,3-pentylene carbonate, 1,4-pentylene carbonate, 2,3-pentylene carbonate, and 2,4-pentylene carbonate.Also suitable herein are dialkyl carbonates, alicyclic carbonates, and diaryl carbonates. Dialkyl carbonates can contain 2 to 5 carbon atoms in each alkyl group; specific examples include diethyl carbonate and dipropyl carbonate. Alicyclic carbonates, particularly bicyclic aliphatic carbonates, can contain 4 to 7 carbon atoms in each ring structure, with one or two such structures present. When one group is alicyclic, the other can be either alkyl or aryl. On the other hand, when one group is aryl, the other can be alkyl or alicyclic. Examples of suitable diaryl carbonates, which can contain 6 to 20 carbon atoms in each aryl group, are diphenyl carbonate, ditolyl carbonate, and dinaphthyl carbonate. In particular, the hydroxyl-terminated polycarbonate can be polyhexamethylene carbonate diol, polytetramethylene carbonate diol, or polycarbonate copolymer diol. More particularly, the hydroxyl-terminated polycarbonate is polyhexamethylene carbonate diol.

[0033] Suitable polysiloxane polyols include alpha-omega-hydroxyl-, amine-, carboxylic acid-, thiol-, or epoxy-terminated polysiloxanes. Examples include poly(dimethysiloxanes) terminated with hydroxyl-, amine-, carboxylic acid-, thiol-, or epoxy groups. In some embodiments, the polysiloxane polyol is a hydroxyl-terminated polysiloxane. In some embodiments, the polysiloxane polyol has a number average molecular weight ranging from 300 to 5,000 or 400 to 3,000.

[0034] Polysiloxane polyols can be obtained by introducing alcoholic hydroxy groups into the polysiloxane skeleton through a dehydrogenation reaction between a polysiloxane hydride and an aliphatic polyhydric alcohol or a polyoxyalkylene alcohol.

[0035] In some embodiments, the polysiloxane has the following formula:

[0036] [ka] and In the formula, each R 1 and R 2 are independently an alkyl group of 1 to 4 carbon atoms, a benzyl group, or a phenyl group, and each E is OH or NHR 3 (In the formula, R 3 is hydrogen, an alkyl group of 1 to 6 carbon atoms, or a cycloalkyl group of 5 to 8 carbon atoms), a and b are each independently an integer of 2 to 8, and c is an integer of 3 to 50. In the amino-containing polysiloxane, at least one of the E groups is NHR 3 In hydroxyl-containing polysiloxanes, at least one of the E groups is OH. In some embodiments, R 1 and R 2 are both methyl groups.

[0037] Suitable examples include alpha-omega-hydroxypropyl-terminated poly(dimethysiloxane) and alpha-omega-aminopropyl-terminated poly(dimethysiloxane), both of which are commercially available materials. Further examples include copolymers of poly(dimethysiloxane) materials with poly(alkylene oxides).

[0038] Additional polyol components, if present, may include poly(ethylene glycol), poly(tetramethylene ether glycol), poly(trimethylene oxide), end-ethylene oxide-capped poly(propylene glycol), poly(butylene adipate), poly(ethylene adipate), poly(hexamethylene adipate), poly(tetramethylene-co-hexamethylene adipate), poly(3-methyl-1,5-pentamethylene adipate), polycaprolactone diol, poly(hexamethylene carbonate) glycol, poly(pentamethylene carbonate) glycol, poly(trimethylene carbonate) glycol, dimeric fatty acid-based polyester polyol, vegetable oil-based polyol, or any combination thereof.

[0039] Examples of dimer fatty acids that may be used to prepare suitable polyester polyols include Priplast™ polyester glycol / polyols available from Croda and Radia® polyester glycols available from Oleon.

[0040] In some embodiments, the polyol component is free of, or essentially free of, additional polyols other than polycaprolactone or polyester polyols. In one embodiment, the TPU is free of, or essentially free of, polyols other than the polycaprolactone or polyester polyols described above. In one embodiment, the TPU composition comprises polycaprolactone polyols and does not include any additional polyols.

[0041] In some embodiments, the polyol component comprises ethylene oxide, propylene oxide, butylene oxide, styrene oxide, poly(tetramethylene ether glycol), poly(propylene glycol), poly(ethylene glycol), poly(ethylene glycol), copolymers of poly(ethylene glycol) and poly(propylene glycol), epichlorohydrin, etc., or combinations thereof. In some embodiments, the polyol component comprises poly(tetramethylene ether glycol).

[0042] Chain extender component The TPU reaction product of the composition of the present disclosure is further formed from a chain extender component. The chain extender component includes a linear or branched chain extender having a backbone of 4 to 16 carbon atoms with at least two hydroxyl groups, the carbinol groups separated by at least two carbon atoms. As used herein, "backbone" refers to the longest carbon-carbon chain in the chain extender component. Additionally, "carbinol group" refers to the -C(OH)- moiety.

[0043] Suitable chain extenders include relatively small polyhydroxy compounds, such as lower aliphatic or short-chain glycols having 4 to 16, 4 to 12, or 4 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, neopentyl glycol, hexamethylenediol, heptanediol, nonanediol, dodecanediol, 3-methyl-1,5-pentanediol, and the like, as well as mixtures thereof. In some embodiments, the chain extender includes BDO, HDO, 3-methyl-1,5-pentanediol, or a combination thereof. In some embodiments, the chain extender includes BDO. While other glycols can be used, in some embodiments, the TPU compositions described herein are essentially free of, or even completely free of, such materials.

[0044] In some embodiments, the chain extender component comprises 1,4-butanediol, 2-ethyl-1,3-hexanediol, 2,2,4-trimethyl-1,6-hexanediol, dimethylol, 3-methyl-1,5-pentanediol, or a combination thereof. In some embodiments, the chain extender component comprises 1,4-butanediol, 3-methyl-1,5-pentanediol, or a combination thereof. In some embodiments, the chain extender component comprises one or more of 1,12-dodecanediol, 1,6-hexanediol, and 1,4-butanediol. In another embodiment, the chain extender component is 1,12-dodecanediol.

[0045] In some embodiments, the molar ratio of the chain extender is present in an amount from 5 to 30, or from 7 to 25, or from 8 to 22 weight percent of the TPU. In one embodiment, the chain extender component is present in an amount from 8 to 22 weight percent of the TPU.

[0046] The thermoplastic polyurethane compositions of the present disclosure comprise a hard block and a soft block. The hard block is derived from the reaction of a diisocyanate component with a chain extender component. The hard block may also be referred to herein as a "hard segment." The soft block, also referred to as a "soft segment," is derived from the reaction of a diol with a diisocyanate, and its properties depend on the type of diol. In one embodiment, the hard block content of the TPU is at least 15 weight percent or at least 20 weight percent, based on the total weight of the TPU. In another embodiment, the hard block content of the TPU is at least 22 weight percent, based on the total weight of the TPU. In one embodiment, the hard block content of the TPU is at least 24 weight percent, based on the total weight of the TPU. The TPU may have a hard block content of 15 to 50 weight percent of the TPU. In one embodiment, the hard block content is 20 to 45 weight percent of the TPU. In another embodiment, the hard block content is 22 to 42 weight percent of the TPU. In one embodiment, the hard block content is 24 to 41 weight percent of the TPU. In one embodiment, the hard block content is from 24 to 32, or from 22 to 26, or from 30 to 34 weight percent of the TPU.

[0047] The TPU composition can have a TPU having 15 to 50 percent hard segment and an average dynamic modulus of at least 50 percent as measured according to ASTM D2632, where the TPU is formed from the reaction product of 1,6-hexamethylene diisocyanate, polycaprolactone, and 1,12 dodecanediol. Specifically, the hard segment can be 24 to 41, or 24 to 32, or 22 to 26, or 30 to 34 weight percent of the TPU.

[0048] The TPU compositions described herein can be prepared by reacting a) the polyisocyanate component described above, b) the polyol component described above, and c) the chain extender component described above, which can be carried out in the presence of a catalyst. The reaction can be carried out in either a batch or continuous process.

[0049] The TPU compositions described herein may also be characterized by recovery properties as indicated by dynamic mechanical analysis (DMA) values. DMA values ​​are measured using a Rheometrics ARES system by completing a dynamic frequency sweep on a 20 mm x 12.7 mm x 2.0 mm rectangular torsion mode specimen at a temperature of 23°C, a strain of 0.1%, and a frequency of 0.1 to 100 Hz. The resulting value provides an indication of the specimen's recovery properties, with a lower tan delta value at a given frequency representing better recovery. In one embodiment, the TPU composition has a tan delta at 1.0 Hz (measured according to ASTM D5279) of less than 0.0035. In another embodiment, the tan delta is less than 0.0032. In yet another embodiment, the tan delta is less than 0.0030.

[0050] The TPU compositions described herein may be further characterized by their resilience as measured by vertical rebound according to ASTM D2632. ASTM D2362 is a standard test for evaluating the resilience of TPUs, which is an important parameter in, for example, athletic shoe applications. In one embodiment, the TPU composition has a vertical resilience of at least 50 percent. In another embodiment, the TPU composition has a vertical resilience of at least 54 percent.

[0051] The TPU compositions described herein may have a melt time when formed into a powder. The melt time is measured by spreading a 0.2 mm thick TPU powder on a steel plate and using an electric heater to heat the TPU until melting is observed. Melting can be observed by using a high-speed camera to record a video of the melting process. The recorded video is converted to one image per second, and the frames are analyzed to determine the time when the TPU sample is completely melted. The time when the TPU is completely melted is reported as the "powder melt time" of the sample. In some embodiments, the TPU compositions described herein have a powder melt time of less than 30 seconds. In another embodiment, the powder melt time is less than 25 seconds. In particular, the melt time is less than 20 seconds.

[0052] The melting time of TPU powder is an important characteristic of TPU powders used in 3D printing applications.

[0053] The TPU composition of the present disclosure may be further formed into a TPU powder having a suitable particle size. The TPU powder may be formed by conventional means, such as cryogenic grinding. In one embodiment, the particle size (D90), the size value to which 90% of the particle volume population belongs, as measured according to ISO-13320, is less than 140 microns. In another embodiment, the particle size is less than 135 microns. In one embodiment, the particle size is less than 132 microns.

[0054] The process for producing the TPU polymer of the present invention can utilize conventional and future developed TPU manufacturing equipment and known or future developed processes. The TPU can be produced by the so-called one-shot, semi-prepolymer, or prepolymer process, by casting, extrusion, or any other process known to those skilled in the art. In one embodiment, the process is the so-called "one-shot" process, in which all three reactants are added to an extruder reactor and reacted.

[0055] The TPU compositions of the present disclosure are particularly useful in 3D printing applications. For 3D printing, the TPU composition is dispensed from a dispensing head having a set of nozzles to deposit a layer of the TPU composition onto a support structure. The layer can then be cured to ultimately form a 3D-printed article. The 3D compositions disclosed herein feature reduced powder melting times, which allows for faster printing of 3D articles. Furthermore, articles formed from the present TPU compositions exhibit similar to better vertical rebound and resilience (as described above) than current 3D printing materials of similar composition. In some embodiments, the 3D-printed articles may have a rebound resilience greater than 55, or greater than 58, or greater than 60.

[0056] The article formed by 3D printing the TPU composition disclosed herein can include footwear midsoles, prosthetics, orthopedic parts, electronic components, consumer goods, sporting goods, and toys.The type of article that can be 3D printed using this TPU composition is not limited, and more specific examples of 3D printed articles include cooking and storage items, furniture, automobile parts, toys, sportswear, medical devices, personalized medical items, replica medical implants, dental items, sterilization containers, coverings, surgical gowns, filters, hygiene products, diapers, films, sheets, tubes, pipes, wire jackets, cable jackets, agricultural films, geomembranes, sporting equipment, cast films, blown films, profiles, boat and marine parts, crates, containers, packaging, laboratory equipment, office floor mats, instrument sample holders, Examples may include liquid storage containers, packaging materials, medical tubing and valves, footwear parts, sheets, tapes, carpets, adhesives, wire sheathing, cables, protective clothing, automotive parts, coatings, foam laminates, overmolded articles, automotive skins, awnings, tarps, leather articles, roofing building articles, handles, powder coatings, powder slush moldings, consumer durables, grips, handles, hoses, hose liners, pipes, pipe liners, caster wheels, skate wheels, computer parts, belts, appliques, footwear parts, conveyor or timing belts, gloves, fibers, fabrics, or clothing.

[0057] Additional articles that can be 3D printed with the present TPU compositions include jewelry, customized keep shakes and / or collectibles (such as, but not limited to, coins, medals, frames and picture frames, eyeglass frames, keys, cups, mugs, miniatures and models, wristbands, personalized action figures, etc.).

[0058] Other additives: The TPU compositions disclosed herein may further contain other optional ingredients in addition to the TPU reaction product.

[0059] Optional additive components may be present during the reaction and / or incorporated into the above TPU reaction products to improve processing and other properties. These additives include antioxidants; organic phosphites, phosphines, and phosphonites; hindered amines, organic amines, organic sulfur compounds, lactones, and hydroxylamine compounds, biocides, fungicides, antimicrobial agents, compatibilizers, electrically dissipative or antistatic additives; fillers and reinforcing agents, such as titanium dioxide, alumina, clay, and carbon black; flame retardants, such as phosphates, halogenated materials, and metal salts of alkylbenzene sulfonates; impact modifiers, such as methacrylate-butadiene-styrene ("MBS") and methylmethacrylate butylacrylate ("MBA"); mold release agents, such as waxes, fats and oils, pigments and colorants, plasticizers, polymers; rheology modifiers, such as monoamines, polyamide waxes, silicones, and polysiloxanes; slip additives, such as paraffin waxes, hydrocarbon polyolefins, and / or fluorinated polyolefins; and hindered amine light stabilizers. Examples of suitable additives include, but are not limited to, UV stabilizers, which may be of the HALS (Highly Active Inorganic Starch) and / or UV light absorber (UVA) type. Other additives may be used to improve the performance of the TPU composition or blend product. All of the above additives may be used in conventional effective amounts for these materials. In some embodiments, the additives may be used in the TPU composition in an amount of 1.0 wt.% or less of the TPU composition.

[0060] These additional additives can be incorporated into the components or reaction mixture to prepare the TPU reaction product, or they can be incorporated into the TPU composition after the TPU reaction product has been made. In an alternative process, all materials can be mixed with the TPU reaction product and then melted, or they can be incorporated directly into the melt of the TPU reaction product.

[0061] In one embodiment, the TPU composition described herein further comprises a plasticizer. The type of plasticizer used can be any of the known plasticizers for use in TPUs. The most common type of plasticizer used is phthalate, with butyl benzyl phthalate being the most preferred. Plasticizers that can be used in the present invention include phthalate-based plasticizers such as di-n-butyl phthalate, di-2-ethylhexyl phthalate (DOP), di-n-octyl phthalate, diisodecyl phthalate, diisooctyl phthalate, octyldecyl phthalate, butyl benzyl phthalate, and di-2-ethylhexyl isophthalate phosphate; di-2-ethylhexyl adipate (DOA), di-n-decyl adipate, diisodecyl adipate, dibutyl sebacate; Examples of suitable plasticizers include aliphatic plasticizers such as methyl acrylate and di-2-ethylhexyl sebacate; pyrometallitate plasticizers such as trioctyl trimellitate and tridecyl trimellitate; phosphate plasticizers such as tributyl phosphate, tri-2-ethylhexyl phosphate, 2-ethylhexyl diphenyl phosphate, and tricresyl phosphate; epoxy plasticizers such as epoxy soybean oil; and polyester polymer plasticizers. For toxicologically sensitive applications, such as children's toys and contact with food, di-isononyl-cyclohexane-1,2-dicarboxylate (Hexamoll® DINCH® manufactured by BASF) may be used as a plasticizer. A single plasticizer may be used, or a combination of two or more plasticizers may be used. The selection of the desired plasticizer depends on the end use of the TPU polymer, as is well understood by those skilled in the art of TPU formulation.

[0062] In one embodiment, the plasticizer is a dialkyl ether glutarate. The plasticizer component may be present in the TPU composition in an amount of up to 7 weight percent of the TPU composition. In another embodiment, the plasticizer component may be present in the TPU composition in an amount of up to 6.5 weight percent of the TPU composition. In one embodiment, the plasticizer component may be present in the TPU composition in an amount of up to 5.5 weight percent of the TPU composition. In one embodiment, the plasticizer may be present in the TPU composition in an amount of 0.5 to 10 weight percent of the TPU composition. In another embodiment, the plasticizer may be present in the TPU composition in an amount of 1 to 7 weight percent of the TPU composition, more specifically, 4 to 6 weight percent plasticizer of the TPU composition.

[0063] The TPU composition can have a TPU having 15 to 50 percent hard segment and an average dynamic modulus of at least 50 percent as measured according to ASTM D2632, the TPU being formed from the reaction product of 1,6-hexamethylene diisocyanate, polycaprolactone, and 1,12-dodecanediol, and 1 to 7 weight percent of the TPU composition of a plasticizer. Specifically, the amount of plasticizer is 4 to 6 weight percent of the TPU composition.

[0064] The TPU composition can have a hard segment content of 20 to 45 percent and an average dynamic modulus of at least 50 percent as measured according to ASTM D2632, the TPU being formed from the reaction product of 1,6-hexamethylene diisocyanate, polycaprolactone, and 1,12-dodecanediol, and 1 to 7 weight percent of the TPU composition of a plasticizer. Specifically, the amount of plasticizer is 4 to 6 weight percent of the TPU composition.

[0065] It is usually preferable to incorporate one or more antioxidants into the TPU reaction product and / or TPU composition. These can be added during the reaction to form the TPU reaction product, blended into the preformed polymer, or added to the TPU composition. Suitable antioxidants include phenolic types, organic phosphites, phosphines, and phosphonites, hindered amines, organic amines, organic sulfur compounds, lactones, and hydroxylamine compounds. For applications where transparency is desired, the antioxidant is preferably soluble in the TPU reaction product or dispersible therein as very fine droplets or particles. Many suitable antioxidant materials are commercially available. These include Irganox™ 1010, Irganox™ MD1024, Irgaphos™ 168, and Irgaphos™ 126, all available from BASF Specialty Chemicals. The antioxidants may be used in conventional amounts in the TPU composition, such as 0.1 to 3 weight percent, or 0.2 to 2 weight percent, or 0.3 to 1.1 weight percent.

[0066] The TPU compositions of the present disclosure may also contain from about 0.10 to about 10.0 wt. % of an antimicrobial and / or biocidal material. In alternative embodiments of the present invention, the compositions may contain from about 1 to about 6 wt. % of an antimicrobial and / or biocidal material, from about 2 to about 4 wt. % of an antimicrobial and / or biocidal material, and many percentages therebetween.The terms "antimicrobial" and / or "biocide" in the context of this formulation include all forms of sodium, potassium, calcium, zinc, copper, and barium salts of carbonates, silicates, sulfates, halogens, and borates; zinc carboxylates; boric acid; sodium dichromate; copper chrome arsenate (CCA); chromated copper borate (CBC); ammoniacal copper arsenate (ACA); ammoniacal copper zinc arsenate (ACZA); copper chromium fluoride (CFK); copper chromium fluoroborate (CCFB); copper chromium phosphorous (CCP); propiconazole and tebuconazole; organic chlorides such as pentachlorophenol (PCP); quaternary ammonium compounds. Compound (MC); copper 8-hydroxyquinoline or copper oxene; tri-n-butyltin oxide (TBTO); tri-n-butyltin naphthenate (TBTN); didecyldimethylammonium bromide (DDAB); didecyldimethylammonium chloride (DDAC); fungicides, herbicides, insecticides, and antimicrobial agents including silver ion, mercury ion, carbamates, isothiazolones, chlorinated phenoxy and polyhexamethylene biguanidide hydrochloride, barium metaborate monohydrate, borates, and mixtures thereof. Preferred compositions of the present invention are water-insoluble and include an inorganic biocide.

[0067] The TPU compositions disclosed herein may further comprise a compatibilizer. Useful compatibilizers include maleated thermoplastics, thermoplastic elastomeric block copolymers, crystalline copolymers of propylene and ethylene or other higher α-olefins, chlorinated thermoplastics, ionomers, maleated elastomeric copolymers, and mixtures thereof.

[0068] Suitable compatibilizers may also include modified polyolefins, including modified thermoplastics and modified rubbers. In one or more embodiments, these modified polyolefins contain at least one functional group attached thereto. In one or more embodiments, these functional groups may include carboxylic acid; C1-C8 carboxylic acid esters, such as carbomethoxy, carboethoxy, carbopropoxy, carbobutoxy, carbopentoxy, carbohexoxy, carboheptoxy, carboxyloxy, and their isomeric forms; carboxylic anhydrides; carboxylates formed from the neutralization of carboxylic acid groups with metal ions from Groups I, II, III, IV-A, and VII of the Periodic Table, including, by way of example, sodium, potassium, lithium, magnesium, calcium, iron, nickel, zinc, and aluminum, and mixtures thereof; amide; epoxy; hydroxy; amino; and C2-C6 acyloxy, such as acetoxy, propionyloxy, or butyryloxy. In one or more embodiments, these functional groups may be part of unsaturated monomer precursors that may be copolymerized with olefin monomers or grafted onto polyolefins to form modified polyolefins.

[0069] Functionalizing monomers or agents include acrylic acid, methacrylic acid, maleic acid, maleic anhydride, acrylamide, methacrylamide, glycidyl acrylate, glycidyl methacrylate, vinyl acetate, vinyl butyrate, methyl acrylate, ethyl acrylate, butyl acrylate, 2-hydroxyethyl acrylate, sodium acrylate, zinc acrylate, ionic hydrocarbon polymers from the polymerization of α-olefins with α,β-ethylenically unsaturated carboxylic acids.

[0070] Suitable modified polyolefins include those disclosed in US Pat. Nos. 6,001,484, 6,072,003, 3,264,272, and 3,939,242, which are incorporated herein by reference.

[0071] In one or more embodiments, the functionalized polyolefin mer units may be present in the polyolefin in an amount of from about 0.05 to about 5 mole percent, e.g., in the case of maleated polyethylene, from about 0.005 to about 5 mole percent of the mer units comprise residues of maleic acid pendant to the backbone.

[0072] In one or more embodiments, useful modified polyolefins are available under the tradenames OPTEMA™ TC120 and TC220 (ExxonMobil), which are ethyl methacrylate copolymers, and POLYBOND™ (Chemtura) or FUSABOND™ (DuPont), which are maleated polypropylenes.

[0073] Maleated elastomeric copolymers include copolymers of ethylene, α-olefins, and one or more dienes that are reacted with maleic anhydride to provide additional functionality. These copolymers are commercially available under the trade name EXXELOR™ (ExxonMobil). The compatibilizers disclosed herein can be used in conventional amounts in the TPU composition, such as from 0.1 to 50 weight percent, or from 0.3 to 30 weight percent, or from 0.5 to 20 weight percent.

[0074] The TPU composition disclosed herein can further comprise an antistatic agent. Numerous antistatic agents are known in the art. Sometimes, the antistatic agent is applied to the surface of the polymer article made from the TPU composition by spraying or dipping.

[0075] The low molecular weight antistatic agent may be blended with the TPU composition rather than being coated on the surface.Such low molecular weight antistatic agent includes ethoxylated fatty amines, esters, or amines such as those described in U.S. Patent Nos. 3,631,162, 3,591,563, 3,575,903, 3,441,552, 3,441,552, 3,270,650, 3,468,702, 3,454,494, 3,365,437, 3,223,545, and 3,206,429; quaternary ammonium salts such as those described in U.S. Pat. Nos. 3,862,045, 3,850,818, 3,395,100, 3,324,091, and 3,272,648; or alkyl sulfonates, sulfates, or phosphates such as those described in U.S. Pat. Nos. 3,475,203 and 3,446,651, and Japanese Patent Application Laid-Open Nos. 57-030756, 57-202338, and 48-014651.

[0076] The low-molecular-weight antistatic agents blended into the TPU compositions are generally organic compounds containing hydrophobic and hydrophilic components. The hydrophobic component generally provides compatibility with the polymer, thereby binding the two materials together. The hydrophilic component generally absorbs moisture and distributes it evenly over the surface of the particular polymer. This water film formed on the surface increases surface conductivity through an ionic conduction process, thereby increasing the rate of static charge dissipation. As a result, conventional low-molecular-weight internal antistatic agents generally do not improve the volume conductivity of the polymer and are generally sensitive to atmospheric humidity, typically providing poor performance at low humidity.

[0077] Internal low-molecular-weight antistatic agents are generally designed to migrate from the interior of the TPU composition to the surface during or after molding. Gradual surface migration can be advantageous because it can replace any surface antistatic agent lost through evaporation, washing, or abrasion. However, migration must occur at an appropriate rate. If the rate is too fast, migration can cause blooming, surface smearing, and molding difficulties. If the rate is too slow, any lost antistatic agent cannot be replaced quickly enough, resulting in unstable antistatic properties. Slow migration is a prevalent problem with polymers with high crystallinity, such as polypropylene, and migration can take up to about one month after molding to reach maximum antistatic performance.

[0078] Additional representative antistatic agents that may be included in the mixture include, but are not limited to, quaternary ammonium compounds such as those disclosed in U.S. Pat. No. 5,933,693, including quaternary ammonium salts of alkyl sulfates and carboxylic acids; metal salts of lithium, sodium, potassium, ammonium, calcium, and barium; complexes of metal salts with polyhydric alcohols and their derivatives, such as 1,4-butanediol, ethylene glycol, propylene glycol, and polyethylene glycol, and complexes of metal salts with monools, such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; and hexahalogenated ion compounds such as those disclosed in U.S. Pat. No. 5,677,357, including hexahalogenated phosphate compounds such as potassium hexafluorophosphate, sodium hexafluorophosphate, and ammonium hexafluorophosphate.

[0079] Metal salt antistatic additives such as diglyme (2-methoxyethyl ether) and metal salts carried by triols, polyethers, or butanediols can be used in the composition.

[0080] Some antistatic agents, such as quaternary ammonium salts, cannot withstand the processing temperatures required for conventional fabrication or molding steps for some polymers. Additionally, conventional low molecular weight antistatic agents often tend to lose their antistatic effectiveness through evaporation, or cause undesirable odors, or promote cracking or crazing.

[0081] The TPU compositions disclosed herein may further comprise a filler or reinforcing agent. Fillers include a wide variety of particulate materials, including talc, marble, granite, carbon black, graphite, aramid, silica-alumina, zirconia, bentonite, antimony trioxide, coal-based fly ash, clay, feedspar, nepheline, fumed silica, alumina, magnesium oxide, zinc oxide, barium sulfate, aluminum silicate, calcium silicate, titanium dioxide, titanates, chalk, crushed glass, silica or glass, glass microspheres, glass beads, or glass fibers. The glass fibers used may be made of E, A, or C glass, preferably sized and coupled with a coupling agent. Their diameter is generally 6 to 20 μm. Either continuous filament fibers (roving) or chopped glass fibers (staple) having lengths of 1 to 10 mm, preferably 3 to 6 mm, may be used.

[0082] The filler may also be, for example, a metal hydroxide such as magnesium hydroxide, potassium hydroxide, and aluminum trihydroxide; a metal carbonate such as magnesium carbonate and calcium carbonate; a metal sulfide and sulfate such as molybdenum disulfide and barium sulfate; a metal borate such as barium borate, barium metaborate, zinc borate, and zinc metaborate; a metal anhydride such as aluminum anhydride; or aluminum trihydrate.

[0083] Boron nitride and various reclaimed and reground thermoset polyurethane and / or polyurea polymers may also be used.

[0084] Representative fillers include, but are not limited to, clays such as diatomaceous earth, kaolin, and montmorillonite; huntite; celite; asbestos; ground minerals; and lithopone. These fillers are typically used in conventional manners and in conventional amounts, for example, from 5% by weight or less to 50% by weight or more based on the weight of the composition.

[0085] Reinforcing agents include high aspect ratio materials such as platelets and fibers, which may be glass, aramid, various other polymers, etc. Additional materials that may be used include mineral fibers, whiskers, alumina fibers, mica, powdered quartz, metal fibers, carbon fibers, and wollastonite. Reinforcing agents are typically used in amounts of 5 to 50 weight percent based on the total layer or composition.

[0086] Fillers that are useful in some formulations include ignition-resistant fillers, which can include antimony oxide, decabromobiphenyl oxide, alumina trihydrate, magnesium hydroxide, borate salts, and halogenated compounds.

[0087] Additionally, metal flakes (e.g., aluminum flakes from Transmet Corp.), metal powders, metal fibers, metal-coated fillers, such as nickel-coated glass fibers, and other additives that shield electromagnetic waves may also be added. Aluminum flakes (K-102 from Transmet Corp.) are particularly suitable for EMI (electromagnetic interference) purposes. The composition may also be mixed with additional carbon fibers, carbon black, especially conductive black, or nickel-coated carbon fibers.

[0088] Other miscellaneous fillers include wood fiber / flour / chips, rubber dust, cotton, starch, clay, synthetic fibers (eg, polyolefin fibers), and carbon fiber.

[0089] The filler level depends on the density of the filler; the denser the filler, the more filler can be added to the formulation without appreciably affecting the filler volume fraction. Thus, filler levels are discussed herein in terms of the weight percent of filler based on the total formulation weight. In the formulations disclosed herein, the filler content ranges from about 0.1% to about 80%, preferably from about 5% to about 50% (excluding carbon black, which is typically used at levels of about 0.1% to about 5%), more preferably from about 5% to about 40%, and particularly from about 8% to about 30%.

[0090] The TPU compositions disclosed herein may further comprise a flame retardant. The flame retardant may be, but is not necessarily, intumescent. Examples include phenyl bisdodecyl phosphate, phenyl bisneopentyl phosphate, phenyl ethylene hydrogen phosphate, phenyl-bis-3,5,5'-trimethylhexyl phosphate, ethyl diphenyl phosphate, 2-ethylhexyl di(p-tolyl) phosphate, diphenyl hydrogen phosphate, bis(2-ethyl-hexyl)p-tolyl phosphate, tritolyl phosphate, bis(2-ethylhexyl)-phenyl phosphate, tri(nonylphenyl) phosphate, phenylmethyl hydrogen phosphate, di(dodecyl)p-tolyl phosphate, tricresyl phosphate, triphenyl phosphate, dibutylphenyl phosphate, p-tolyl bis(2,5,5'-trimethylhexyl) phosphate, 2-ethylhexyl diphenyl phosphate, and diphenyl hydrogen phosphate. Preferred flame retardants are bisphenol-A bis(diphenyl phosphate), resorcinol bis(diphenyl phosphate), and cresol bis(diphenyl phosphate).

[0091] Further examples of flame retardants include brominated organic compounds, such as brominated diols. The brominated organic compounds may contain 5 to 20 carbon atoms, in some embodiments 5 to 10, or even 5 carbon atoms, and may contain quaternary carbon atoms. The additive may be present in an amount sufficient to provide the desired flame retardancy, and in other embodiments, may be present in an amount of 0 to 15 weight percent of the total composition, or even 0 to 10, 0.1 to 7, or 0.2 to 5 weight percent of the total composition.

[0092] Further examples include brominated organic compounds. Suitable examples include brominated diols, brominated monoalcohols, brominated ethers, brominated esters, brominated phosphates, and combinations thereof. Suitable brominated organic compounds may include tetrabromobisphenol-A, hexabromocyclododecane, poly(pentabromobenzyl acrylate), pentabromobenzyl acrylate, tetrabromobisphenol A-bis(2,3-dibromopropyl ether), tribromophenol, dibromoneopentyl glycol, tribromoneopentyl alcohol, tris(tribromoneopentyl)phosphate, and 4,4'-isopropylidenebis[2-(2,6-dibromophenoxy)ethanol].

[0093] In some embodiments, the flame retardant additive comprises a metal salt of a halogen borate, a metal salt of a halogen phosphate, or a combination thereof. In some embodiments, a combination of retarders is used. Further examples of flame retardant additives include metal salts of organic sulfonates, such as the sodium salt of alkylbenzene sulfonate, and in some embodiments, the flame retardant additive comprises a nitrogen-containing compound. The flame retardant may be added to the TPU composition in conventional amounts. In some embodiments, the flame retardant may be present in the TPU composition in an amount of 0 to 30 weight percent, based on the total weight of the TPU composition. In another embodiment, the flame retardant may be present in the TPU composition in an amount of 0.1 to 20 weight percent, based on the total weight of the TPU composition. In one embodiment, the flame retardant may be present in the TPU composition in an amount of 0.5 to 15 weight percent, based on the total weight of the TPU composition. [Example]

[0094] Examples 1 to 11 A series of thermoplastic polymers, including those of the present technology, were prepared as disclosed in Table 1.

[0095] [Table 1] Abbreviations: HDI, hexamethylene diisocyanate; MDI, 4,4'-methylenebis(phenylisocyanate); UVp, UV protectant; AO, antioxidant; HS, hard segment. * Comparative example.

[0096] UVp was an oxanilide-based chemical, and AO was a phenol and phosphite-based chemical.

[0097] Dialkyl ether glutarate was used as the plasticizer.

[0098] Example 12 - Material Properties Test samples were prepared by reacting the ingredients disclosed in Table 1 and forming the sample by molding.

[0099] The following properties were measured: -Average vertical rebound (%) according to ASTM D2632. - Recovery properties as indicated by Dynamic Mechanical Analysis ("DMA") values. Values ​​are measured using a Rheometrics ARES system by completing a dynamic frequency sweep from 0.1 to 100 Hz at 0.1% strain on a 20 mm x 12.7 mm x 2.0 mm rectangular torsion mode specimen at a temperature of 23°C. Tan delta was measured in accordance with ASTM D5279.

[0100] [Table 2]

[0101] Examples of the present invention exhibited significantly higher rebound resilience as well as lower tan delta values ​​when measured at various frequency settings. These properties indicate that examples of the present invention can provide very high energy return when used as 3D printed objects.

[0102] Example 13 - Properties of TPU powder The powders were prepared by reacting the ingredients disclosed in Table 1 and cryogenically grinding via pin milling and air classification.

[0103] The particle size D90 was determined by using a particle size analyzer (LS230 particle size analyzer manufactured by Beckman Coulter) according to ISO 13320. Less than 2g of powder was mixed with reference oil at 23°C and loaded into the particle size analyzer. The particle size analyzer then measures the particle size by polarized intensity differential scattering technology. After analysis, it provides the volume distribution of particles, and D90 is the size value to which 90% of the particle population belongs.

[0104] Melting time is measured by spreading a 0.2 mm thick TPU powder on a steel plate and using an electric heater to heat the TPU until melting is observed. Melting can be observed by using a high-speed camera to record video of the melting process. The recorded video is converted to one image per second, and the frames are analyzed to determine the time when the TPU sample is completely melted. The time when the TPU is completely melted is reported as the "powder melting time" of the sample.

[0105] [Table 3]

[0106] The preferred embodiment provided powder melting times significantly shorter than 30 seconds, indicating that the preferred embodiment has more efficient melting and coalescence behavior, ultimately resulting in shorter printing times and higher throughput.

[0107] Example 14 - Properties of 3D printed parts The 3D printed parts were prepared by using a Hewlett Packard Multijet Fusion 3D printer.

[0108] Rebound resilience was determined according to ASTM D7121.

[0109] UTS is the ultimate tensile strength measured according to ASTM D2632, and EAB is the elongation at break, also measured according to ASTM D2632. To assess the isotropy of the 3D printed objects, tensile specimens were printed parallel to both the horizontal and vertical axes of the print bed and tested according to ASTM D2632. The respective ratios between the vertical axis property and the horizontal axis property (UTS-ISOTRO% and EAB-ISOTRO%) were then calculated to represent the isotropy of the 3D printed objects.

[0110] [Table 4]

[0111] Isotropic behavior of 3D printed objects is often difficult to achieve due to the layer-by-layer buildup of 3D printing technology. Examples 4, 6, and 9 exhibit significantly improved isotropic tensile properties compared to the remaining examples. In other words, the 3D printed objects printed in Examples 4, 6, and 9 have uniform and consistent mechanical and physical properties regardless of printing direction. Furthermore, these examples exhibit high rebound resilience, a desirable property for footwear components.

[0112] The embodiments are further described by the following examples, which set forth particularly advantageous embodiments. The examples are provided to illustrate certain embodiments and are not intended to be limiting.

[0113] Unless otherwise stated herein, references to treat rates or amounts of components present in the lubricating compositions disclosed herein are quoted on an oil-free basis, i.e., based on the amount of active material. Further, unless otherwise stated, "wt. %" as used herein shall refer to weight percent based on the total weight of the composition on an oil-free basis.

[0114] The present disclosure is not limited with respect to the specific embodiments described in this application, which are intended as illustrations of various aspects. It will be apparent to those skilled in the art that many modifications and variations can be made without departing from the spirit and scope of the present invention. Functionally equivalent methods and components within the scope of the present disclosure, in addition to those enumerated herein, will be apparent to those skilled in the art from the foregoing description. Such modifications and variations are intended to fall within the scope of the appended claims. The present disclosure is to be limited only by the terms of the appended claims, along with the full scope of equivalents to which such claims are entitled. It is to be understood that the present disclosure is not limited to particular methods, reagents, compounds, or compositions, which may, of course, vary. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only, and is not intended to be limiting.

[0115] Although various compositions, methods, and devices are described in terms of "comprising" (which may be interpreted to mean "including, but not limited to") various components or steps, the compositions, methods, and devices may also "consist essentially of" or "consist of" the various components and steps, and such terminology should be interpreted as defining essentially closed-member groups.

[0116] With respect to the use of virtually any plural and / or singular term herein, those of skill in the art will be able to convert from plural to singular and / or from singular to plural as appropriate to the context and / or application. Various singular / plural conversions may be expressly set forth herein for clarity.

[0117] In general, it will be understood by those skilled in the art that the terms used herein, and particularly the terms used in the appended claims (e.g., the body of the appended claims), are generally intended as "open" terms (e.g., the term "comprising" should be interpreted as "including but not limited to," the term "having" should be interpreted as "having at least," the term "including" should be interpreted as "including but not limited to," etc.). Where a specific number of introduced claim recitations is intended, such intention will be explicitly set forth in the claim; in the absence of such recitation, it will be further understood by those skilled in the art that no such intention exists. For example, as an aid to understanding, the following appended claims may include the use of the introductory phrases "at least one" and "one or more" to introduce claim recitations. However, the use of such phrases should not be construed to imply that introducing a claim recitation with the indefinite article "a" or "an" limits any particular claim containing such an introduced claim recitation to embodiments containing only one such recitation, even if the same claim includes the introductory phrase "one or more" or "at least one" and an indefinite article such as "a" or "an" (e.g., "a" and / or "an" should be construed to mean "at least one" or "one or more"). The same is true for the use of definite articles used to introduce claim recitations. Additionally, even when a specific number of introduced claim recitations is explicitly recited, those skilled in the art will recognize that such recitation should be construed to mean at least the recited number (e.g., an express recitation of "two recitations" without other modifiers means at least two recitations, or more than two recitations). Furthermore, when a convention similar to "at least one of A, B, and C, etc." is used, generally such configurations are intended in the sense that one of ordinary skill in the art would understand the convention (e.g., "a system having at least one of A, B, and C" includes, but is not limited to, systems having A only, B only, C only, A and B together, A and C together, B and C together, and / or A, B, and C together, etc.).When a convention similar to "at least one of A, B, or C, etc." is used, generally such configuration is intended in the sense that one of ordinary skill in the art would understand the convention (e.g., "a system having at least one of A, B, or C" includes, but is not limited to, systems having A only, B only, C only, A and B together, A and C together, B and C together, and / or A, B, and C together, etc.). It will be further understood by one of ordinary skill in the art that virtually any disjunctive word and / or phrase presenting two or more alternative terms, regardless of the specification, claims, or drawings, should be understood to contemplate the possibility of including one of the terms, either of the terms, or both terms. For example, the phrase "A or B" would be understood to include the possibilities of "A" or "B" or "A and B."

[0118] Additionally, where features or aspects of the present disclosure may be described in terms of a Markush group, those skilled in the art will recognize that the present disclosure is also thereby described in terms of any individual member or subgroup of members of the Markush group.

[0119] As will be understood by those skilled in the art, for any and all purposes, including with respect to providing a written description, all ranges disclosed herein encompass any and all possible subranges and combinations thereof. Any recited range can be readily recognized as fully descriptive and allowing that same range to be broken down into at least equal halves, thirds, quarters, fifths, tenths, etc. As a non-limiting example, each range discussed herein can be readily broken down into a lower third, middle third, and upper third, etc. As will be understood by those skilled in the art, all terms such as "up to," "at least," etc. refer to ranges that are inclusive of the recited numbers and can then be broken down into subranges, as discussed above. Finally, as will be understood by those skilled in the art, a range includes each individual member. Thus, for example, a group having 1-3% by weight refers to groups having 1, 2, or 3% by weight. Similarly, a group having 1-5% by weight refers to groups having 1, 2, 3, 4, or 5% by weight, etc., including all points in between.

[0120] Furthermore, when a stated range of treatment rates is provided, it is intended that such range includes the treatment rates for individual components and / or mixtures of components. Thus, for example, a range of 1-3 wt. % contemplates that a given component may be present in the range of 1-3 wt. %, or that a mixture of similar components may be present in the range of 1-3 wt. %.

[0121] While the invention has been explained in relation to its preferred embodiments, it is to be understood that various modifications thereof will become apparent to those skilled in the art upon reading the specification. It is therefore to be understood that the invention disclosed herein is intended to cover such modifications as fall within the scope of the appended claims.

Claims

1. 1. A thermoplastic polyurethane (TPU) composition comprising: a TPU having 15 to 50 percent hard segment and an average dynamic modulus of at least 50 percent as measured in accordance with ASTM D2632, said TPU comprising: a polyisocyanate component comprising a linear aliphatic diisocyanate having 3 to 12 carbon atoms; a polyol component selected from polycaprolactone polyols and polyester polyols; a linear or branched chain extender component having a backbone of 4 to 16 carbon atoms with at least two hydroxyl groups, wherein the carbinol groups are separated by at least two carbon atoms; and

2. The composition of claim 1, wherein the linear aliphatic diisocyanate component is selected from 1,6-hexamethylene diisocyanate and pentamethylene diisocyanate, preferably 1,6-hexamethylene diisocyanate.

3. The composition of claim 1 or claim 2, wherein the polyisocyanate component is present in an amount of 10 to 30 weight percent of the TPU.

4. The composition of any one of claims 1 to 3, wherein the polyol component is polycaprolactone.

5. The polyol component has a molecular weight (M ｗ The composition according to any one of claims 1 to 4, wherein

6. The composition of any one of claims 1 to 5, wherein the polyol component is present in an amount of 40 to 80 weight percent of the TPU.

7. The composition of any one of claims 1 to 6, wherein the chain extender component is selected from 1,12-dodecanediol, 1,6-hexanediol, and 1,4-butanediol.

8. The composition of any one of claims 1 to 7, wherein the chain extender is present in an amount of 5 to 30 percent by weight of the TPU.

9. The composition of any one of claims 1 to 8, wherein the TPU composition further comprises a plasticizer component.

10. 10. The composition of claim 9, wherein the plasticizer component is a dialkyl ether glutarate.

11. 11. The composition of claim 9 or claim 10, wherein the plasticizer component is present in an amount of up to 7 weight percent of the TPU composition.

12. The composition of any one of claims 1 to 11, wherein the dynamic modulus of the TPU is at least 54 percent.

13. The composition of any one of claims 1 to 12, wherein the TPU has a tan delta at 1.0 Hz (measured in accordance with ASTM D5279) of less than 0.0035.

14. The composition of any one of claims 1 to 13, wherein the TPU composition is compacted into a powder having a particle size (D90) of less than 140 microns.

15. The composition of any one of claims 1 to 15, wherein the TPU composition is formed into a powder having a powder melt time of less than 30 seconds.

16. 3D printed parts prepared from the TPU composition of any one of claims 1 to 15.

17. 17. The 3D printed part of claim 16, wherein the 3D printed part has a rebound resilience of greater than 50 measured according to ASTM D7121.

18. 18. The 3D printed part of claim 16 or claim 17, wherein the 3D printed part is selected from a footwear midsole, a prosthetic, an orthopedic part, an electronic component, a consumer product, a sporting goods, and a toy.

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