WO2024102687A1

WO2024102687A1 - High resilient thermoplastic polyurethanes and uses thereof

Info

Publication number: WO2024102687A1
Application number: PCT/US2023/078885
Authority: WO
Inventors: Jr. Joseph J. Vontorcik; Daniel PERCIVAL; Ungyeong Jung
Original assignee: Lubrizol Advanced Materials, Inc.
Priority date: 2022-11-08
Filing date: 2023-11-07
Publication date: 2024-05-16

Abstract

The instant disclosure relates to thermoplastic polyurethane (TPU) compositions containing the TPU reaction product of an a polyisocyante comprising a linear aliphatic diisocyanate having from 3 to 12 carbon atoms; a polyol selected from a polycaprolactone and a polyester; and a linear or branched chain extender having main backbone of from 4 to 16 carbon atoms and hydroxyl groups separated by at least two carbon atoms. The TPU of the instant disclosure has from 15 to 50 percent hard segment and an average vertical resiliency measured according to ASTM D2632 of at least 50 percent. The TPU of the instant disclosure exhibit improved vertical resiliency and powder melt time and have a particular use in the printing of three-dimensional (3D) articles.

Description

4754-01

-1-

HIGH RESLIENT THERMOPLASTIC POLYURETHANES AND USES THEREOF

FIELD OF INVENTION

[0001] The instant disclosure relates to thermoplastic polyurethane (TPU) compositions containing the TPU reaction product of an a polyisocyante comprising a linear aliphatic diisocyanate having from 3 to 12 carbon atoms; a polyol selected from a polycaprolactone and a polyester; and a linear or branched chain extender having main backbone of from 4 to 16 carbon atoms and hydroxyl groups separated by at least two carbon atoms. The TPU of the instant disclosure has from 15 to 50 percent hard segment and an average vertical resiliency measured according to ASTM D2632 of at least 50 percent. The TPU of the instant disclosure may exhibit improved vertical resiliency and powder melt time and have a particular use in the printing of three-dimensional (3D) articles.

BACKGROUND OF THE INVENTION

[0002] T his disclosure relates to TPU compositions with one or more of improved vertical resilience and recovety properties while at the same time having decreased 3D printing speed when used to print a 3D article.

[0003] Recovery properties of a polymer, and/or the determination of whether a specific polymer has “fast recovery” properties, is based on how long it takes for an article made of the polymer to return to its original shape after being deformed. For example, how long it takes a shoe sole made of the polymer in question, when it is flexed and/or bent with the application of force, to return to its original shape once the force is released. For many applications, including shoe sole applications, the faster the recovery the better, that is, the faster the article returns to its original shape the better. Thus, materials with fast recovery properties are better suited for such applications.

[0004] Rebound resilience is an indication of hysteretic energy loss that can also be defined by the relationship between storage modulus and loss modulus. The percent rebound measured is inversely proportional to the hysteretic loss. Percentage resilience or rebound resilience is commonly used in quality control testing of polymers and compounding chemicals. Rebound resilience can be determined by a freely falling pendulum hammer and/or ball that is dropped from a given height that impacts a test specimen and imparts to it a certain amount of energy. A portion of that energy is returned 4754-01

-2- by the specimen to the pendulum and may be measured by the extent to which the pendulum rebounds, whereby the restoring force is determined by gravity. 3D printed articles with high rebound resiliency or energy return can be advantageous for athletic footwear applications. The synergistic effect of customizable 3D printed sole components and high rebound resiliency may maximize performance of an athlete.

[0005] In prior compositions, it is seemingly difficult to provide thermoplastic polyurethane compositions with a combination of improved vertical resiliency and recovery while at the same time decreasing the speed of printing 3D articles. Often efforts to improve the recovery properties and/or rebound resilience results in TPU’s having increased or inadequate printing speeds.

[0006] Thus, there is a general need in the state of the art for TPU compositions that can be used in for decreased 3D printing times while at the same time providing sufficient or improved vertical resiliency and/or recovery.

SUMMARY OF THE INVENTION

[0007] The instant disclosure relates to thermoplastic polyurethane (also referred to herein as “TPU”) compositions that include a TPU having from 15 to 50 percent by weight of hard segment and an average vertical resiliency measured according to ASTM D2632 of at least 50 percent. The TPU is formed by the reaction product of a polyisocyante component comprising a linear aliphatic diisocyanate having from 3 to 12 carbon atoms; a polyol component selected from a polycaprolactone and a polyester; and a linear or branched chain extender component having main backbone of from 4 to 16 carbon atoms wherein the carbinol groups are separated by at least two carbon atoms.

[0008] In one embodiment of the instant disclosure, the TPU composition includes a TPU formed by the reaction product of a polyisocyanate component comprising a linear aliphatic diisocyanate is 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 from 20 to 45 weight percent hard segment, an average vertical resiliency measured according to ASTM D2632 of from 20 to 45 weight percent, a tan delta at 1.0 Hz (measured according to D5279) of less than 0.0035. 4754-01

-3-

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

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

[0011] In another aspect of the instant disclosure, the 3D article or part may be selected from a footwear, a prosthetic, an orthopedic, an electronic part, a consumer good, a sporting good, and a toy.

[0012] The following embodiments of the present subject matter are contemplated: [0013] 1. A thermoplastic polyurethane (TPU) composition comprising: a TPU having from 15 to 50 percent hard segment and an average vertical resiliency measured according to ASTM D2632 of at least 50 percent, the TPU formed by the reaction product of: a polyisocyante component comprising a linear aliphatic diisocyanate having from 3 to 12 carbon atoms; a polyol component selected from a poly caprolactone polyol and a polyester polyol; and a linear or branched chain extender component having main backbone of from 4 to 16 carbon atoms with at least two hydroxyl groups wherein the carbinol groups are separated by at least two carbon atoms.

[0014] 2 The composition according to embodiment 1, wherein the linear aliphatic diisocyanate component is selected from 1,6-hexamethylene diisocyanate and pentamethylene diisocyanate, preferably 1,6-hexamethylene diisocyanate.

[0015] 3. The composition according to any one of the preceding embodiments, wherein the polyisocyante component is present in an amount of from 10 to 30 weight percent of the TPU.

[0016] 4. The composition according to any one of the preceding embodiments, wherein the polyisocyante component is present in an amount of from 10 to 25 weight percent of the TPU.

[0017] 5. The composition according to any one of the preceding embodiments, wherein the polyol component is a polycaprolactone.

[0018] 6. The composition according to any one of the preceding embodiments, wherein the polyol component has a molecular weight (M_w) of from 1,000 to 3,500. 4754-01

-4-

[0019] 7 The composition according to embodiment 6, wherein the molecular weight is from 1,500 to 3,250 or 1,850 to 3,250.

[0020] 8. The composition according to any one of the preceding embodiments, wherein the polyol component is present in an amount of from 40 to 80 weight percent of the TPU.

[0021] 9. The composition according to any one of the preceding embodiments, wherein the polyol component is present in an amount of from 50 to 80 weight percent of the TPU.

[0022] 10. The composition according to any one of the preceding embodiments, wherein the polyol component is present in an amount of from 55 to 78 weight percent of the TPU.

[0023] 11. The composition according to any one of the preceding embodiments, wherein the chain extender component is selected from 1,12-dodecanediol, 1,6- hexanediol, and 1,4-butanediol.

[0024] 12. The composition according to any one of the preceding embodiments, wherein the chain extender component is 1,12-dodecanediol.

[0025] 13. The composition according to any one of the preceding embodiments, wherein the chain extender is present in an amount of from 5 to 30 weight percent of the TPU.

[0026] 14. The composition according to any one of the preceding embodiments, wherein the chain extender component is present in an amount of from 7 to 25 weight percent of the TPU.

[0027] 15. The composition according to any one of the preceding embodiments, wherein the chain extender component is present in an amount of from 8 to 22 weight percent of the TPU.

[0028] 16. The composition according to any one of the preceding embodiments, wherein the TPU has from 20 to 45 percent hard segment.

[0029] 17. The composition according to any one of the preceding embodiments, wherein the TPU has from 22 to 42 percent hard segment.

[0030] 18. The composition according to any one of the preceding embodiments, wherein the TPU has from 24 to 41 percent hard segment. 4754-01

-5-

[0031] 19. The composition according to any one of the preceding embodiments, wherein the TPU composition further comprises a plasticizer component.

[0032] 20. The composition according to embodiment 19, wherein the plasticizer component is a dialkylether glutarate.

[0033] 21. The composition according to embodiment 19, wherein the plasticizer component is present in an amount of up to 7 weight percent of the TPU composition.

[0034] 22. The composition according to embodiment 19, wherein the plasticizer component is present in an amount of up to 6.5 weight percent of the TPU composition.

[0035] 23. The composition according to embodiment 19, wherein the plasticizer component is present in an amount of up to 5.5 weight percent of the TPU composition.

[0036] 24. The composition according to embodiment 19, wherein the plasticizer component is present in an amount of from 0.5 to 10 weight percent of the TPU composition.

[0037] 25. The composition according to embodiment 19, wherein the plasticizer component is present in an amount of from 1 to 7 weight percent of the TPU composition. [0038] 26. The composition according to any one of the preceding embodiments, wherein the vertical resiliency of the TPU is a least 54 percent.

[0039] 27. The composition according to any one of the preceding embodiments, wherein the TPU has a tan delta at 1.0 Hz (measured according to ASTM D5279) of less than 0.0035.

[0040] 28. The composition according to embodiment 27, wherein the tan delta is less than 0.0032.

[0041] 29. The composition according to embodiment 27, wherein the tan delta is less than 0.0030.

[0042] 30. The composition of any one preceding embodiments, wherein the TPU composition is formed into a powder having a particle size (D90) of less than 140 microns. [0043] 31. The composition according to any one of the preceding embodiments, wherein the particle size is less than 135 microns.

[0044] 32. The composition according to any one of the preceding embodiments, wherein the particle size is less than 132 microns. 4754-01

-6-

[0045] 33. The composition according to any one of the preceding embodiments, wherein the TPU composition is formed into a powder having a powder melt time of less than 30 seconds.

[0046] 34. The composition according to embodiment 30, wherein the powder melt time is less than 25 seconds.

[0047] 35. A 3D printed part prepared from the TPU composition according to any one of the preceding embodiments.

[0048] 36. The 3D printed part according to embodiment 35, wherein the 3D printed part has a rebound resilience measured according to ASTM D7121 of greater than 50.

[0049] 37. The 3D printed part according to embodiment 35, wherein the 3D printed part has a rebound resilience of greater than 55.

[0050] 38. The 3D printed part according to embodiment 35, wherein the 3D printed part has a rebound resilience of greater than 58.

[0051] 39. The 3D printed part according to any one of embodiments 35 to 38, wherein the 3D printed part is selected from a footwear midsole, a prosthetic, an orthopedic, an electronic part, a consumer good, a sporting good, and a toy.

DETAILED DESCRIPTION OF THE INVENTION

[0052] The instant disclosure describes thermoplastic polyurethane compositions that include a TPU having from 15 to 50 percent by weight of hard segment and an average vertical resiliency measured according to ASTM D2632 of at least 50 percent. The TPU is formed by the reaction product of a polyisocyanate component comprising a linear aliphatic diisocyanate component having from 3 to 12 carbon atoms; a polyol component selected from a polycaprolactone and a polyester; and a linear or branched chain extender component having main backbone of from 4 to 16 carbon atoms where the carbinol groups are separated by at least two carbon atoms.

The Polyisocyanate Component:

[0053] The TPU reaction product of the compositions of the instant disclosure are made using an a polyisocyante component comprising a linear aliphatic diisocyanate having from 3 to 12 carbon atoms. Examples of suitable diisocyanates include, without limitation, 1,6-hexamethylene diisocyanate (HDI), 1,4-butane diisocyanate, pentamethylene diisocyanate, 4,4'-Methylenebis(cyclohexyl isocyanate), 1,4- Bis(isocyanatomethyl)cyclohexane, Isophorone diisocyanate, 1,4-Cyclohexane 4754-01

-7- diisocyanate and combinations thereof. In one embodiment, the diisocyanate is 1,6- hexamethylene diisocyanate.

[0054] In some embodiments, the polyisocyanate component may include one or more additional polyisocyanates, which are typically diisocyanates.

[0055] Suitable polyisocyanates which may be used in combination with the linear aliphatic diisocyanate described above may include linear or branched aromatic diisocyanates, branched aliphatic diisocyanates, or combinations thereof. In some embodiments, the polyisocyanate component includes one or more aromatic diisocyanates. In other embodiments, the polyisocyanate component is essentially free of, or even completely free of, aromatic diisocyanates.

[0056] The additional polyisocyanate component may include one or more aromatic diisocyanates. Examples of suitable aromatic polyisocyanates include, but are not limited to, 4,4'-methylenebis(phenyl isocyanate) (MDI), m-xylene diisocyanate (XDI), phenylene- 1,4-diisocyanate, naphthalene-l,5-diisocyanate, and toluene diisocyanate (TDI); as well as aliphatic diisocyanates such as isophorone diisocyanate (IPDI), 1,4- cyclohexyl diisocyanate (CHDI), decane- 1,10-diisocyanate, lysine diisocyanate (LDI), 1,4-butane diisocyanate (BDI), isophorone diisocyanate (IPDI), 3, 3'-dimethyl-4, d'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 includes MDI. In some embodiments, the polyisocyanate includes H12MDI.

[0057] In other embodiments, in addition to the aromatic polyisocyanate and the linear aliphatic diisocyanate described above, polyisocyante component may include one or more additional aliphatic diisocyanates. Suitable aliphatic diisocyanates include isophorone diisocyanate (IPDI), 1,6-hexamethylene diisocyanate (HD I), 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, mixtures of two or more polyisocyanates may be used.

[0058] The polyisocyanate component of the instant TPU compositions may be present in the TPU in an amount of from 10 to 30 weight percent of the TPU. In another 4754-01

-8- embodiment, the polyisocyanate component may be present in the TPU in an amount of from 10 to 25 weight percent of the TPU.

The Polyol Component:

[0059] The TPU reaction product of the compositions of the instant disclosure are further formed from a polyol or diol. Polyols used to form the TPU of the instant TPU compositions are selected from one or more of a polyester polyol and a polycaprolactone. In one embodiment, the polyol is a polycaprolactone. In another embodiment, the polyol is a polyester polyol.

[0060] The average molecular weight (M_w)of the polyol component can be from 1,000 to 3,500. In one embodiment, the average molecular weight of the polyol component is from 1,500 to 3,250. In another embodiment, the average molecular weight of the polyol component is from 1,850 to 3,250

[0061] The average molecular weight of the polyol can be determined by calculating using the following equation:

56.1xl000xFunctionality OH number ’

Functionality, the functionality of the polyol. If it is a diol, the functionality is 2;

OH number', the weight of KOH in milligrams that will neutralize the acetic anhydride capable of reacting by acetylation with one gram of polyol.

[0062] The polycaprolactone polyols useful in the instant TPU compositions described herein include polyester diols derived from caprolactone monomers, i.e., polycaprolactones. The polycaprolactone polyols are terminated by primary hydroxyl groups. Suitable polycaprolactone polyols may be made from a- caprolactone and a bifunctional initiator such as di ethylene glycol, 1,4-butanediol, or any of the other glycols and/or diols listed herein. In some embodiments, the polycaprolactone polyols are linear polyester diols derived from caprolactone monomers.

[0063] Useful examples include CAPA™ 2202A, a 2000 number average molecular weight (Mn) linear diol, and CAPA™ 2302 A, a 3000 Mn linear diol, both of which are commercially available from Perstorp Polyols Inc. These materials may also be described as polymers of 2-oxepanone and 1,4-butanediol.

[0064] The polycaprolactone polyols may be prepared from 2-oxepanone and a diol, where the diol may be 1,4-butanediol, di ethylene glycol, monoethylene glycol, 1,6- 4754-01

-9- hexanediol, 2,2-dimethyl-l,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.

[0065] In addition to the polycaprolactone polyol, polyester polyols may also be employed to form the TPU of the TPU composition.

[0066] Suitable polyester polyols generally have an acid number less than 1.3. In some embodiments, the polyester polyol has an acid number of less than 0.5. The polyester polyol includes intermediates that may be produced by (1) an esterification reaction of one or more glycols with one or more dicarboxylic acids or anhydrides or (2) by transesterification reaction, i.e., the reaction of one or more glycols with esters of dicarboxylic acids. Mole ratios generally in excess of more than one mole of glycol to acid are preferred so as to obtain linear chains having a preponderance of terminal hydroxyl groups. Suitable polyester intermediates also include dicarboxylic acids of the desired polyester which can be aliphatic, cycloaliphatic, aromatic, or combinations thereof. Suitable dicarboxylic acids which may be used alone or in mixtures generally have a total of from 4 to 15 carbon atoms and include: succinic, glutaric, adipic, pimelic, suberic, azelaic, sebacic, dodecanedioic, isophthalic, terephthalic, cyclohexane dicarboxylic acid, and the like. Anhydrides of the above dicarboxylic acids such as phthalic anhydride, tetrahydrophthalic anhydride, or the like, can also be used. Adipic acid is a preferred acid. The glycols which are reacted to form a desirable polyester intermediate can be aliphatic, aromatic, or combinations thereof, including any of the glycols described above in the chain extender section, and have a total of from 2 to 20 or from 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-l,3- propanediol, 1,4-cyclohexanedimethanol, decam ethylene glycol, dodecamethylene glycol, and mixtures thereof.

[0067] The polyol component may be present in the TPU in an amount of from 40 to 80, or 50 to 80, or 55 to 78 weight percent of the TPU.

[0068] The TPU composition may further include an additional polyol other than the polycaprolactone and/or polyester polyol described above. When present, the additional polyol may include one or more hydroxyl terminated polyethers, one or more hydroxyl 4754-01

-10- terminated polycarbonates, one or more hydroxyl terminated polysiloxanes, or mixtures thereof.

[0069] Suitable hydroxyl terminated polyether intermediates include polyether polyols derived from a diol or polyol having a total of from 2 to 15 carbon atoms, in some embodiments an alkyl diol or glycol which is reacted with an ether comprising an alkylene oxide having from 2 to 6 carbon atoms, typically ethylene oxide or propylene oxide or mixtures thereof. For example, hydroxyl functional poly ether can be produced by first reacting propylene glycol with propylene oxide followed by subsequent reaction with ethylene oxide. Primary hydroxyl groups resulting from ethylene oxide are more reactive than secondary hydroxyl groups and thus are preferred. Useful commercial polyether polyols include poly(ethylene glycol) comprising ethylene oxide reacted with ethylene glycol, polypropylene glycol) comprising propylene oxide reacted with propylene glycol, poly(tetramethylene ether glycol) comprising water reacted with tetrahydrofuran which can also be described as polymerized tetrahydrofuran, and which is commonly referred to as PTMEG. In some embodiments, the polyether intermediate includes PTMEG. Suitable polyether polyols also include polyamide adducts of an alkylene oxide and can include, for example, ethylenediamine adduct comprising the reaction product of ethylenediamine and propylene oxide, diethylenetriamine adduct comprising the reaction product of diethylenetriamine with propylene oxide, and similar polyamide type polyether polyols. Copolyethers can also be utilized in the described compositions. Typical copolyethers include the reaction product of THF and ethylene oxide or THF and propylene oxide. These are available from BASF as Poly THF® B, a block copolymer, and poly THF® R, a random copolymer. The various polyether intermediates generally have a number average molecular weight (Mn) as determined by assay of the terminal functional groups which is an average molecular weight greater than about 700, such as from about 700 to about 10,000, from about 1,000 to about 5,000, or from about 1,000 to about 2,500. In some embodiments, the polyether intermediate includes a blend of two or more different molecular weight poly ethers, such as a blend of 2,000 M_n and 1000 M_n PTMEG.

[0070] Suitable hydroxyl terminated polycarbonates include those prepared by reacting a glycol with a carbonate. U.S. Patent No. 4,131,731 is hereby incorporated by reference for its disclosure of hydroxyl terminated polycarbonates and their preparation. Such polycarbonates are linear and have terminal hydroxyl groups with essential exclusion 4754-01

-11- of other terminal groups. The essential reactants are glycols and carbonates. 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 with 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-hexan ediol, 2,2,4-trimethyl-l,6-hexanediol, 1,10- decanediol, hydrogenated dilinoleylglycol, hydrogenated dioleylglycol, 3-methyl-l,5- pentanediol; and cycloaliphatic diols such as 1,3 -cyclohexanediol, 1,4- dimethylolcyclohexane, 1,4-cyclohexanediol-, 1,3-dimethylolcyclohexane-, 1,4- endomethylene-2-hydroxy-5-hydroxymethyl cyclohexane, and polyalkylene glycols. The diols used in the reaction may be a single diol or a mixture of diols depending on the properties desired in the finished product. Polycarbonate intermediates which are hydroxyl terminated are generally those known to the art and in the literature. Suitable carbonates are selected from alkylene carbonates composed of a 5 to 7 membered ring. 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 dialkylcarbonates, cycloaliphatic carbonates, and diarylcarbonates. The dialkylcarbonates can contain 2 to 5 carbon atoms in each alkyl group and specific examples thereof are di ethyl carb onate and dipropylcarbonate. Cycloaliphatic carbonates, especially dicycloaliphatic carbonates, can contain 4 to 7 carbon atoms in each cyclic structure, and there can be one or two of such structures. When one group is cycloaliphatic, the other can be either alkyl or aryl. On the other hand, if one group is aryl, the other can be alkyl or cycloaliphatic. Examples of suitable diarylcarbonates, which can contain 6 to 20 carbon atoms in each aryl group, are diphenylcarbonate, ditolyl carb onate, and dinaphthylcarbonate. Particularly, the hydroxyl terminated polycarbonate may be polyhexamethylene carbonate diol, polytetramethylene carbonate diol or a polycarbonate copolymer diol. More particularly, the hydroxyl terminated polycarbonate is a polyhexamethylene carbonate diol.

[0071] Suitable polysiloxane polyols include alpha-omega-hydroxyl or amine or carboxylic acid or thiol or epoxy terminated polysiloxanes. Examples include 4754-01

-12- poly(dimethysiloxane) terminated with a hydroxyl or amine or carboxylic acid or thiol or epoxy group. In some embodiments, the polysiloxane polyols are hydroxyl terminated polysiloxanes. In some embodiments, the polysiloxane polyols have a number-average molecular weight in the range from 300 to 5,000, or from 400 to 3,000.

[0072] Polysiloxane polyols may be obtained by the dehydrogenation reaction between a polysiloxane hydride and an aliphatic polyhydric alcohol or polyoxyalkylene alcohol to introduce the alcoholic hydroxy groups onto the polysiloxane backbone.

[0073] In some embodiments, the polysiloxanes may be represented by one or more compounds having the following formula:

in which: each R¹ and R² are independently a 1 to 4 carbon atom alkyl group, a benzyl, or a phenyl group; each E is OH or NHR³ where R³ is hydrogen, a 1 to 6 carbon atoms alkyl group, or a 5 to 8 carbon atoms cyclo-alkyl group; a and b are each independently an integer from 2 to 8; c is an integer from 3 to 50. In amino-containing polysiloxanes, at least one of the E groups is NHR³. In the hydroxyl -containing polysiloxanes, at least one of the E groups is OH. In some embodiments, both R¹ and R² are methyl groups.

[0074] Suitable examples include alpha-omega-hydroxypropyl terminated poly(dimethysiloxane) and alpha-omega-amino propyl terminated poly(dimethysiloxane), both of which are commercially available materials. Further examples include copolymers of the poly(dimethysiloxane) materials with a poly(alkylene oxide).

[0075] The additional polyol component, when present, may include polyethylene glycol), poly(tetramethylene ether glycol), poly(trimethylene oxide), ethylene oxide capped poly (propylene glycol), poly(butylene adipate), poly(ethylene adipate), poly(hexam ethylene adipate), poly(tetramethylene-co-hexam ethylene adipate), poly(3- methyl-l,5-pentamethylene adipate), polycaprolactone diol, poly(hexamethylene carbonate) glycol, poly(pentamethylene carbonate) glycol, poly (trimethylene carbonate) glycol, dimer fatty acid based polyester polyols, vegetable oil based polyols, or any combination thereof. 4754-01

-13-

[0076] Examples of dimer fatty acids that may be used to prepare suitable polyester polyols include Priplast™ polyester glycols/polyols commercially available from Croda and Radia® polyester glycols commercially available from Oleon.

[0077] In some embodiments, the polyol component is free of or essentially free additional polyols other than the polycaprolactone or polyester polyol. In one embodiment, the TPU is free of or essentially free polyols other than the polycaprolactone or polyester polyol described above. In one embodiment, the TPU composition includes a polycaprolactone polyol and is free of any additional polyol(s).

[0078] In some embodiments, the polyol component includes ethylene oxide, propylene oxide, butylene oxide, styrene oxide, poly(tetramethylene ether glycol), polypropylene glycol), poly(ethylene glycol), copolymers of poly(ethylene glycol) and polypropylene glycol), epichlorohydrin, and the like, or combinations thereof. In some embodiments, the polyol component includes poly(tetramethylene ether glycol).

The Chain Extender Component:

[0079] The TPU reaction product of the compositions of the instant disclosure are further formed from a chain extender component. The chain extender component includes a linear or branched chain extender having a main backbone of from 4 to 16 carbon atoms with at least two hydroxyl groups where the carbinol groups are separated by at least two carbon atoms. “Main backbone” as used herein refers to the longest carbon to carbon chain in the chain extender component. Further, “carbinol group” refers to a -C(OH)- moiety.

[0080] Suitable chain extenders include relatively small polyhydroxy compounds, for example lower aliphatic or short chain glycols having from 4 to 16, or 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 (UDO), 1,3 -butanediol, 1,5-pentanediol, neopentylglycol, hexamethylenediol, heptanediol, nonanediol, dodecanediol, 3-methyl-l,5-pentanediol, and the like, as well as mixtures thereof. In some embodiments, the chain extender includes BDO, HDO, 3-methyl-l,5-pentanediol, or a combination thereof. In some embodiments, the chain extender includes BDO. Other glycols may be used, but in some embodiments, the TPU composition described herein are essentially free of or even completely free of such materials.

[0081] In some embodiments, the chain extender component includes 1,4-butanediol, 2-ethyl- 1,3 -hexanediol, 2,2,4-trimethyl, 1,6-hexanediol, dimethylol, 3-methyl-l,5- 4754-01

-14- pentanediol or combinations thereof. In some embodiments, the chain extender component includes 1,4-butanediol, 3-methyl-l,5-pentanediol or combinations thereof. In some embodiments, the chain extender component includes 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.

[0082] In some embodiments, the mole ratio of the chain extender is present in an amount of from 5 to 30, or 7 to 25 or 8 to 22 weight percent of the TPU. In one embodiment, the chain extender component is present in an amount of from 8 to 22 weight percent of the TPU.

[0083] The thermoplastic polyurethane composition of the instant disclosure includes hard blocks and soft blocks. The hard block is derived by a reaction of diisocyanate component and chain extender component. Hard block may also be referred herein as ‘hard segment’. The soft block, also referred as ‘soft segment’ is derived by reaction of a diol with diisocyanate, and the characteristic thereof depends on the kind of the 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 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 can have a hard block content is from 15 to 50 weight percent of the TPU. In one embodiment, the hard block content is from 20 to 45 weight percent of the TPU. In another embodiment, the hard block content is from 22 to 42 weight percent of the TPU. In one embodiment, the hard block content is from 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.

[0084] The TPU composition can have a TPU having from 15 to 50 percent hard segment and an average vertical resiliency measured according to ASTM D2632 of at least 50 percent, the TPU formed by the reaction product of 1,6-hexamethylene diisocyanate, poly caprolactone and 1,12 dodecanediol. In particular the hard segment can be from 24 to 41, or from 24 to 32, or from 22 to 26 or from 30 to 34 weight percent of the TPU.

[0085] The TPU composition as described herein may be prepared by reacting a) the polyisocyanate component described above; b) the polyol component described above; and c) the chain extender component described above, where the reaction may be carried 4754-01

-15- out in the presence of a catalyst. The reaction may be carried in either a batch or continuous process.

[0086] The TPU compositions described herein may also be characterized by having recovery properties indicated by a dynamic mechanical analysis (“DMA”) value. The values are measured by completing a dynamic frequency sweep using a Rheometrics ARES system on a rectangle torsion mode samples measuring 20 mm by 12.7 mm by 2.0 mm at a temperature of 23° C, as strain of 0.1% and frequencies from 0.1 to 100 Hz. The resulting values give an indication of the sample’s recovery properties, where a smaller tan delta value at a given frequency represent 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.

[0087] The TPU compositions described herein further may be characterized by their resilience by vertical rebound as measured by ASTM D2632. ASTM D2362 is a standard testing to evaluate resiliency of TPU and resiliency is a critical parameter in, for example, athletic footwear applications. In one embodiment, the vertical resiliency of the TPU composition is at least 50 percent. In another embodiment, the vertical resiliency of the TPU composition is at least 54 percent.

[0088] The TPU compositions described herein when formed into a powder may have a melt time. Melt time is measured by spreading 0.2 mm thick TPU powder on a steel plate and heating the TPU using an electrical heater until melting is exhibited. The melting may be observed by using a high-speed camera to record a video of the melting process. The recorded movie is converted to one image per second frames and the frames were analyzed to determine the time the TPU sample was fully molten. The time the TPU was fully molten is reported as “powder melt time” for 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. Particularly, the melt time is less than 20.

[0089] TPU powder melt time is an important feature of TPU powders used in 3D printing applications.

[0090] The TPU compositions of the instant disclosure may be further formed into a TPU powder having a suitable particle size. The TPU powder may be formed by 4754-01

-16- conventional means such as cryogenic grinding. In one embodiment, the particle size (D90), which is size value where 90% of volumetric particle population belongs to when 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.

[0091] The process to produce the TPU polymer of this invention can utilize conventional and hereafter developed TPU manufacturing equipment and known or hereafter developed processes. The TPU may be produced in the so-called one-shot, semiprepolymer or prepolymer method, by casting, extrusion or any other process known to the person skilled in the art. In one embodiment, the process is a so-called “one-shot” process where all three reactants are added to an extruder reactor and reacted.

[0092] The TPU compositions of the instant 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 layers of the TPU composition on a supporting structure. The layers may then be cured to finally form a 3D printed article. The 3D compositions disclosed herein feature decreased powder melt times which permit faster printing of 3D articles. Further, the articles formed from the instant TPU compositions exhibit similar to better vertical rebound and resiliency (as described above) over current 3D printing materials of similar makeup. In some embodiments, the 3D printed article may have a rebound resilience of greater than 55 or greater than 58 or greater than 60.

[0093] The articles formed from the 3D printing the instantly disclosed TPU composition may include a footwear midsole, a prosthetic, an orthopedic, an electronic part, a consumer good, a sporting good, and a toy. The types of articles that may be 3D printed using the instant TPU compositions are not limited, and more specific examples of 3D printed articles may include cook and storage ware, furniture, automotive components, toys, sportswear, medical devices, personalized medical articles, replicated medical implants, dental articles, sterilization containers, drapes, gowns, filters, hygiene products, diapers, films, sheets, tubes, pipes, wire jacketing, cable jacketing, agricultural films, geomembranes, sporting equipment, cast film, blown film, profiles, boat and water craft components, crates, containers, packaging, labware, office floor mats, instrumentation sample holders, liquid storage containers, packaging material, medical tubing and valves, 4754-01

-17- a footwear component, a sheet, a tape, a carpet, an adhesive, a wire sheath, a cable, a protective apparel, an automotive part, a coating, a foam laminate, an overmolded article, an automotive skin, an awning, a tarp, a leather article, a roofing construction article, a steering wheel, a powder coating, a powder slush molding, a consumer durable, a grip, a handle, a hose, a hose liner, a pipe, a pipe liner, a caster wheel, a skate wheel, a computer component, a belt, an applique, a footwear component, a conveyor or timing belt, a glove, a fiber, a fabric, or a garment.

[0094] Additional articles that may be 3D printed with the instant TPU compositions include, jewelry, customized keep shakes and/or collectibles, such as but not limited to coins medallions, frames and picture frames, eyewear frames, keys, cups, mugs, miniatures and models, wrist bands, personalized action figures, and the like.

Other Additives:

[0095] The TPU compositions disclosed herein, in addition to the TPU reaction product, may further contain other optional components.

[0096] Optional additive components may be present during the reaction, and/or incorporated into the TPU reaction product described above to improve processing and other properties. These additives include but are not limited to antioxidants, organic phosphites, phosphines and phosphonites, hindered amines, organic amines, organo sulfur compounds, lactones and hydroxylamine compounds, biocides, fungicides, antimicrobial agents, compatibilizers, electro-dissipative or anti-static 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 alkyl benzenesulfonates, 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 paraffinic waxes, hydrocarbon polyolefins and/or fluorinated polyolefins, and UV stabilizers, which may be of the hindered amine light stabilizers (HALS) and/or UV light absorber (UVA) types. Other additives may be used to enhance the performance of the TPU composition or blended product. All of the additives described above may be used in an effective amount customary for these substances. In some embodiments, the additives can be used in the TPU composition at amounts up to and including 1.0 wt % of the TPU composition. 4754-01

-18-

[0097] These additional additives can be incorporated into the components of, or into the reaction mixture for, the preparation of the TPU reaction product, or after making the TPU reaction product, in the TPU compositions. In another process, all the 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.

[0098] In one embodiment, the TPU compositions described herein further include a plasticizer. The type of plasticizer used can be any of the known plasticizers for use in TPU. The most common plasticizer types used are phthalates with butyl benzyl phthalate being the most preferred. Plasticizers used in the present invention can include phthalate based plasticizers, such as, di-n-butylphthalate, di-2-ethylhexyl phthalate (DOP), di-n- octyl phthalate, diisodecyl phthalate, diisooctyl phthalate, octyldecyl phthalate, butylbenzyl phthalate, and di-2-ethyhexyl phosphate isophthalate; aliphatic ester-based plasticizers, such as di-2-ethylhexyl adipate (DOA), di-n-decyl adipate, diisodecyl adipate, dibutyl sebacate, and di-2-ethylhexyl sebacate; pyrometallitate-based plasticizers, such as trioctyl trimellitate and tridecyl trimellitate; phosphate-based plasticizers, such as tributyl phosphate, tri-2-ethylhexyl phosphate, 2-ethylhexyldiphenyl phosphate, and tricresyl phosphate; epoxy-based plasticizers, such as epoxy-based soybean oil; and polyester- based polymer plasticizers. For applications that are sensitive from the toxicological point of view, such as children’s toys and food contact, di -isononyl -cyclohexane- 1,2- dicarboxylate (Hexamoll® DINCH® from BASF) may be used as the plasticizer. A single plasticizer may be used or a combination of two or more plasticizers may be used. The selection of the desired plasticizer will depend on the end use application of the TPU polymer, as is well understood by those skilled in the art of formulating TPU.

[0099] In one embodiment, the plasticizer is a dialkylether 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 from 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 from 1 to 7 weight percent of the 4754-01

-19-

TPU composition, more particularly from 4 to 6 weight percent of the TPU composition of the plasticizer.

[0100] The TPU composition can have a TPU having from 15 to 50 percent hard segment and an average vertical resiliency measured according to ASTM D2632 of at least 50 percent, the TPU formed by the reaction product of 1,6-hexamethylene diisocyanate, polycaprolactone and 1,12-dodecanediol and from 1 to 7 weight percent of the TPU composition of the plasticizer. Particularly the amount of plasticizer is from 4 to 6 weight percent of the TPU composition.

[0101] The TPU composition can have a TPU having from 20 to 45 percent hard segment and an average vertical resiliency measured according to ASTM D2632 of at least 50 percent, the TPU formed by the reaction product of 1,6-hexamethylene diisocyanate, polycaprolactone and 1,12-dodecanediol and from 1 to 7 weight percent of the TPU composition of the plasticizer. Particularly the amount of plasticizer is from 4 to 6 weight percent of the TPU composition.

[0102] It is usually preferable to incorporate one or more antioxidants into the TPU reaction product and/or TPU compositions described above. These may be added during the reaction to form the TPU reaction product, blended into the previously-formed polymer described above, or added to the TPU composition. Suitable antioxidants include phenolic types, organic phosphites, phosphines and phosphonites, hindered amines, organic amines, organo sulfur compounds, lactones and hydroxylamine compounds. For applications in which transparency is wanted, the antioxidant is preferably soluble in the TPU reaction product described above, or dispersable therein as very fine droplets or particles. Many suitable antioxidant materials are available commercially. These include Irganox™ 1010, Irganox™ MD1024, Irgaphos™ 168, Irgaphos™ 126, all available from BASF Specialty Chemicals, and the like. Antioxidants may be used in the TPU compositions in conventional amounts, such as, 0.1 to 3 weight percent, or 0.2 to 2 weight percent, or 0.3 to 1.1 weight percent.

[0103] TPU compositions of the present disclosure may also contain about 0.10 to about 10.0% by weight of an antimicrobial and/or biocide material. In alternative embodiments of the present invention, the composition may contain about 1 to about 6% by weight of an antimicrobial and/or biocide material, about 2 to about 4% by weight of an antimicrobial and/or biocide material, as well as numerous percentages in between. The 4754-01

-20- terms “antimicrobial” and/or “biocide” in the context of this formulation is intended to include, but is not limited to fungicides, herbicides, insecticides, antimicrobial agents comprising sodium, potassium, calcium, zinc, copper, and barium salts of carbonate, silicate, sulfate, halide, and borate in all forms; zinc carboxylates; boric acids; sodium di chromate; 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 tebuconazole; organo-chloride such as pentachlorophenol (PCP); quaternary ammonium compounds (MC); copper 8-hydroxy quinoline or copper oxene; tri- n-butyltin oxide (TBTO); tri-n-butyltin naphthenate (TBTN); didecyldimethylammonium bromide (DDAB); didecyldimethylammonium chloride (DDAC); silver ions, mercury ions, carbamates, isothiazolones, chlorinated phenoxy and polyhexamethylene beguanidide hydrochlorides, barium metaborate monohydrate, borate salts and mixtures thereof. Preferred compositions of the present invention are water insoluble and comprise inorganic biocides.

[0104] The TPU compositions disclosed herein may further include a compatibilizer. Useful compatibilizers include maleated thermoplastics, thermoplastic elastomer block copolymers, crystallizable copolymers of propylene with ethylene or other higher a- olefins, chlorinated thermoplastics, ionomers, maleated elastomeric copolymers, and mixtures thereof.

[0105] Suitable compatibilizers may also include modified polyolefins which include modified thermoplastics and modified rubbers. In one or more embodiments, these modified polyolefins include at least one functional group attached thereto. In one or more embodiments, these functional groups can include carboxylic acid; Cl to C8 carboxylate ester such as carbomethoxy, carboethoxy, carbopropoxy, carbobutoxy, carbopentoxy, carbohexoxy, carboheptoxy, carboctoxy, and isomeric forms thereof; carboxylic acid anhydride; carboxylate salts formed from the neutralization of carboxylic acid group(s) with metal ions from Groups I, II, III, IV-A and VII of the periodic table, illustratively including sodium, potassium, lithium, magnesium, calcium, iron, nickel, zinc, and aluminum, and mixtures thereof; amide; epoxy; hydroxy; amino; and C2 to C6 acyloxy such as acetoxy, propionyloxy, or butyryloxy. In one or more embodiments, these functional groups may be part of an unsaturated monomer precursor that can be 4754-01

-21- copolymerized with an olefin monomer or grafted onto a polyolefin to form the modified polyolefin.

[0106] 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, the ionic hydrocarbon polymers from the polymerization of a-olefins with a,P-ethylenically unsaturated carboxylic acids. [0107] Suitable modified polyolefins include those disclosed in U.S. Patent Nos. 6,001,484, 6,072,003, 3,264,272, and 3,939,242, which are incorporated herein by reference.

[0108] In one or more embodiments, the mer units of the polyolefin containing the functional groups can be present in the polyolefin in an amount from about 0.05 to about 5 mole percent. For example, in the case of maleated polyethylene, from about 0.005 to about 5 mole percent of the mer units include the residue of maleic acid pendent to the backbone.

[0109] In one or more embodiments, useful modified polyolefins can be obtained under the tradename OPTEMA™ TCI 20 and TC220 (ExxonMobil), which are ethylmethacrylate copolymers, and POLYBOND™ (Chemtura), or FUSABOND™ (DuPont), which are maleated polypropylenes.

[0110] Maleated elastomeric copolymers include copolymers of ethylene, an a-olefin, and one or more dienes, where the copolymer is reacted with maleic anhydride to provide further functionality. These copolymers are commercially available under the tradename EXXELOR™ (ExxonMobil). Compatibilizer as disclosed herein may be used in the TPU compositions in conventional amounts, such as, 0.1 to 50 weight percent, or 0.3 to 30 weight percent, or 0.5 to 20 weight percent.

[OHl] The TPU compositions disclosed herein may further include an antistatic agent. A number of antistatic agents are known in the art. Sometimes, the antistatic agent is applied to the surface of a polymeric article made from the TPU composition by means of spraying or dipping.

[0112] Low molecular weight antistatic agents are also sometimes blended with the TPU composition described above rather than coated on the surface. Such low molecular weight antistatic agents include: ethoxylated fatty amines, ester, or amides such as those 4754-01

-22- described in U.S. Patents 3,631,162; 3,591,563; 3,575,903; 3,441,552; 3,441,552; and 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. Patents 3,933,871; 3,862,045; 3,850,818; 3,395,100; 3,324,091; and 3,272,648; or alkylsulphonates, sulphates or phosphates such as those described in U.S. Patents 3,475,203 and 3,446,651, and Japanese Patents 82- 30,756; 82-202,338; and 73-14,651.

[0113] Low molecular weight antistatic agents blended into the TPU compositions described above are generally organic compounds comprising a hydrophobic component and a hydrophilic component. The hydrophobic component generally provides compatibility with the polymer and thereby links the two materials together. The hydrophilic component generally absorbs moisture and causes water to be uniformly distributed on the surface of the particular polymer. This water film formed on the surface increases surface conductivity by means of an ion conduction process, thereby increasing the rate of static charge dissipation. Consequently, conventional low molecular weight internal antistats generally do not improve volume conductivity of the polymer and are generally sensitive to atmospheric humidity, typically providing poor performance at low humidity.

[0114] Internal, low molecular weight antistatic agents are generally designed to migrate from the interior of the TPU compositions described above to the surface during or after molding. Gradual surface migration can be advantageous, since it can replace any antistatic agent at the surface which is lost due to evaporation, cleaning or wear. However, the migration must occur at the proper rate. If it is too fast, the migration can cause blooming, surface smearing and molding difficulties; if it is too slow, the antistatic properties will be erratic, since any lost antistatic agent is not promptly replaced. Slow migration is a problem prevalent in polymers having high crystallinity, such as polypropylene, and migration may take up to about a month after molding to reach maximum antistatic performance.

[0115] Additional representative anti-static agents that may be included in the mixture include quarternary ammonium compounds such as disclosed in U.S. Patent No. 5,933,693, including but not limited to quarternary ammonium salts of alkyl sulfuric acid and carboxylic acid; metallic salts of lithium, sodium, potassium, ammonium, calcium, and barium; complexes of metallic salts with polyhydric alcohols and their derivatives, 4754-01

-23- such as 1,4 butanediol, ethylene glycol, propylene glycol and polyethylene glycol, and complexes of metallic salts with mono-ols such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; hexahalogenated ionic compounds such as disclosed in U.S. Patent No. 5,677,357, including hexahalogenated phosphate compounds, such as potassium hexafluorophosphate, sodium hexafluorophosphate and ammonium hexafluorophosphate.

[0116] Metallic salt anti-static additives may be used in the composition such as the metallic salt that is carried by diglyme (2 -methoxyethylether) and a triol, a polyether or butanediol.

[0117] Some antistatic agents, such as quaternary ammonium salts, are not able to withstand processing temperatures required in conventional fabricating or molding steps for some polymers. Additionally, conventional low molecular weight antistatic agents often tend to lose their antistatic effectiveness due to evaporation, or they cause undesirable odors or promote cracking or crazing.

[0118] The TPU compositions disclosed herein may further include a filler or reinforcing agent. Fillers include a wide range 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, milled glass, silica or glass, glass microspheres, glass beads or glass fibers. The glass fibers used may be made from E, A or C glass and have preferably been provided with a size and with a coupling agent. Their diameter is generally from 6 to 20 pm. Use may be made either of continuous-filament fibers (rovings) or of chopped glass fibers (staple) whose length is from 1 to 10 mm, preferably from 3 to 6 mm.

[0119] The fillers may also be metal hydroxides, e.g., magnesium hydroxide, potassium hydroxide and aluminum trihydroxide; metal carbonates such as magnesium carbonate and calcium carbonate; metal sulfides and sulfates such as molybdenum disulfide and barium sulfate; metal borates such as barium borate, meta-barium borate, zinc borate and meta-zinc borate; metal anhydride such as aluminum anhydride; or aluminum trihydrate.

[0120] Boron nitride and various reclaimed and reground thermoset polyurethane and/or polyurea polymers may also be used. 4754-01

-24-

[0121] Representative fillers include but are not limited to clay such as diatomite, kaolin and montmorillonite; huntite; celite; asbestos; ground minerals; and lithopone. These fillers are typically used a conventional manner and in conventional amounts, e.g., from 5 wt% or less to 50 wt% or more based on the weight of the composition.

[0122] Reinforcements include high aspect ratio materials such as platelets and fibers, which can be of glass, aramid, various other polymers, and the like. Additional materials which may be used include mineral fibers, whiskers, alumina fibers, mica, powdered quartz, metal fibers, carbon fibers and wollastonite. Reinforcing agents, are usually used in amounts of from 5 to 50% by weight, based on the entire layer or composition.

[0123] Fillers which are useful in some formulations include ignition resistance fillers which can include antimony oxide, decabromobiphenyl oxide, alumina trihydrate, magnesium hydroxide, borates, and halogenated compounds.

[0124] In addition, metal flakes (e.g., aluminum flakes from Transmet Corp.), metal powders, metal fibers, metal-coated fillers, e.g., nickel-coated glass fibers, and also other additives which screen electromagnetic waves, may be added. Aluminum flakes (K-102 from Transmet) are particularly suitable for EMI (electromagnetic interference) purposes. The compositions may also be mixed with additional carbon fibers, carbon black, in particular conductivity black, or nickel-coated carbon fibers.

[0125] Other miscellaneous fillers include wood fibers/flours/chips, rubber dust, cotton, starch, clay, synthetic fibers (e.g., polyolefin fibers), and carbon fibers.

[0126] The level of the filler depends upon the filler density; the higher the filler density, the more of it which can be added to the formulation without appreciably affecting the volume fraction of that filler. Accordingly, the level of the filler is discussed herein in terms of weight percent 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% (except for carbon black, which is typically used at levels from about 0.1% to about 5 %), more preferably from about 5% to about 40%, and especially from about 8% to about 30%.

[0127] The TPU compositions disclosed herein may further include a flame retardant. The flame retardants may be, but not necessarily, intumescent. Examples include phenylbisdodecyl phosphate, phenylbisneopentyl phosphate, phenyl ethylene hydrogen phosphate, phenyl-bis-3,5,5'-trimethylhexyl phosphate), ethyldiphenyl phosphate, 2- 4754-01

-25- ethylhexyl di(p-tolyl) phosphate, diphenyl hydrogen phosphate, bis(2-ethyl-hexyl) p- tolylphosphate, 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-ethylhexyldiphenyl phosphate, and diphenyl hydrogen phosphate. The preferred flame retardants are bisphenol-A bis(diphenyl phosphate), resorcinol bis(diphenyl phosphate), and cresol bis(diphenyl phosphate).

[0128] Further examples of flame retardants include a brominated organic compound, for example, a brominated diol. It may contain from 5 to 20 carbon atoms, and in some embodiments 5 to 10, or even 5 carbon atoms, and may contain a quaternary carbon atom. The additive may be present in an amount sufficient to provide the desired flame retardancy, and in other embodiments may be present from 0 to 15 percent by weight of the overall composition, or even from 0 to 10, from 0.1 to 7, or from 0.2 to 5 percent by weight of the overall composition.

[0129] Further examples include brominated organic compounds. Suitable examples include brominated diols, brominated mono-alcohols, 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] .

[0130] In some embodiments, the flame retardant additive includes a metal salt of a halogen borate, metal salt of halogen phosphate, or a combination thereof. In some embodiments, combinations of retardants are used. Additional examples of flame retardant additives include a metal salt of organic sulfonate, for example, a sodium salt of an alkyl benzene sulfonate and in some embodiments, the flame retardant additive includes a nitrogen-containing compound. Flame retardants may be added to the TPU composition in conventional amounts. In some embodiments, the flame retardant may be present in the TPU compositions at an amount of from 0 weight percent 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 compositions at an amount of from 0.1 weight percent to 20 weight 4754-01

-26- percent based on the total weight of the TPU composition. In one embodiment, the flame retardant may be present in the TPU compositions at an amount of from 0.5 weight percent to 15 weight percent based on the total weight of the TPU composition.

EXAMPLES

Examples 1 to 11

[0131] A series of thermoplastic polymers, including those of the present technology were prepared as disclosed in Table 1.

TABLE 1

Abbreviations: HDI, Hexametylene Diisocyanate; MDI, 4,4'-methylenebis(phenyl isocyanate); UVp, UV protectant; AO, antioxidant; HS, hard segment.

* Comparative examples.

[0132] The UVp was oxanilide based chemical and AOs were phenol and phosphite based chemicals.

[0133] The plasticizer use was dialkylether glutarate. 4754-01

- l-

Example 12 - Material properties

[0134] Test samples were prepared by reacting the components as disclosed in Table 1 and forming the samples by molding.

[0135] The following properties were determined:

Average vertical resiliency rebound (%) according to ASTM D2632.

- Recovery properties indicated by a dynamic mechanical analysis (“DMA”) value. The values are measured by completing a dynamic frequency sweep using a Rheometrics ARES system on a rectangle torsion mode samples measuring 20 mm by 12.7 mm by 2.0 mm at a temperature of 23° C, as strain of 0.1% and frequencies from 0.1 to 100 Hz. Tan delta was measured according to ASTM D5279.

TABLE 2

[0136] The inventive examples exhibited significantly higher rebound resiliency as well as lower tan delta values when measured in various frequency settings. These properties indicate the inventive examples can provide very high energy return when used as a 3D printed object.

Example 13 - Properties of TPU powders

[0137] Powders were prepared by reacting the components as disclosed in Table 1 and cryogenic grinding via pin-mill and air classification. 4754-01

-28-

[0138] Particle size D90 was determined by using a particle size analyzer, LS230 Particle Size Analyzer from Beckman Coulter according to ISO 13320. Less than 2 g of powder is mixed with a reference oil at 23 °C and loaded into the particle size analyzer. Then, the particle size analyzer measures particle size by polarization intensity differential scattering technology. After analysis, it provides volumetric distribution of particles and D90 is size value where 90% of particle population belongs to.

[0139] Melt time is measured by spreading 0.2 mm thick TPU powder on a steel plate and heating the TPU using an electrical heater until melting is exhibited. The melting may be observed by using a high-speed camera to record a video of the melting process. The recorded movie is converted to one image per second frames and the frames were analyzed to determine the time the TPU sample was fully molten. The time the TPU was fully molten is reported as “powder melt time” for the sample.

TABLE 3

[0140] Preferred examples provided significantly shorter powder melt time than 30 seconds. This indicates preferred examples have more efficient melt and coalescence behavior, which ultimately leads to shorter printing time and higher throughput.

Example 14 - Properties of 3D printed parts

[0141] 3D printed parts were prepared by using a multi -jet fusion 3D printer from Hewlett Packard. 4754-01

-29-

[0142] Rebound resilience was determined according to ASTM D7121.

[0143] UTS is ultimate tensile strength, which is measured according to ASTM

D2632, and EAB is elongation at break that is also measured according to ASTM D2632. To evaluate isotropic nature of 3D printed object, tensile specimens were printed in parallel to both horizontal and vertical axis of print bed and tested per ASTM D2632. Then, respective ratios (UTS-ISOTRO% and EAB-ISOTRO%) between vertical and horizontal axis properties were calculated to represent isotropic nature of 3D printed object.

TABLE 4

[0144] Isotropic behavior of 3D printed object is often challenging to obtain due to layer-to-layer construction of 3D printing technology. Ex. Nos. 4, 6 and 9 show significantly enhanced isotropic tensile properties than the rest of examples. In other words, 3D printed objects that are printed with Ex. Nos. 4, 6 and 9 have uniform and consistent mechanical and physical properties regardless of printing orientation. In addition, these examples exhibit high rebound resilience which is a preferred property for footwear components.

[0145] Embodiments will be further illustrated by the following examples, which set forth particularly advantageous embodiments. While the examples are provided to illustrate certain embodiments, they are not intended to be limiting. 4754-01

-30-

[0146] Unless otherwise stated herein, reference to treat rates or amounts of components present in the lubricating compositions disclosed herein are quoted on an oil free basis, i.e., amount of active. Further, unless otherwise stated, “wt. %” as used herein shall refer to the weight percent based on the total weight of the composition on an oil-free basis.

[0147] The present disclosure is not to be limited in terms of the particular embodiments described in this application, which are intended as illustrations of various aspects. Many modifications and variations can be made without departing from its spirit and scope, as will be apparent to those skilled in the art. Functionally equivalent methods and components within the scope of the disclosure, in addition to those enumerated herein, will be apparent to those skilled in the art from the foregoing descriptions. 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 this disclosure is not limited to particular methods, reagents, compounds, or compositions, which can, 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.

[0148] While various compositions, methods, and devices are described in terms of “comprising” various components or steps (interpreted as meaning “including, but not limited to”), the compositions, methods, and devices can also “consist essentially of’ or “consist of’ the various components and steps, and such terminology should be interpreted as defining essentially closed-member groups.

[0149] With respect to the use of substantially any plural and/or singular terms herein, those having skill in the art can translate from the plural to the singular and/or from the singular to the plural as is appropriate to the context and/or application. The various singular/plural permutations may be expressly set forth herein for sake of clarity.

[0150] It will be understood by those within the art that, in general, terms used herein, and especially in the appended claims (e.g., bodies of the appended claims) are generally intended as “open” terms (e.g., the term “including” should be interpreted as “including but not limited to,” the term “having” should be interpreted as “having at least,” the term “includes” should be interpreted as “includes but is not limited to,” etc.). It will be further 4754-01

-31- understood by those within the art that if a specific number of an introduced claim recitation is intended, such an intent will be explicitly recited in the claim, and in the absence of such recitation, no such intent is present. For example, as an aid to understanding, the following appended claims may contain usage 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 the introduction of a claim recitation by the indefinite articles “a” or “an” limits any particular claim containing such introduced claim recitation to embodiments containing only one such recitation, even when the same claim includes the introductory phrases “one or more” or “at least one” and indefinite articles such as “a” or “an” (e.g., “a” and/or “an” should be interpreted to mean “at least one” or “one or more”); the same holds true for the use of definite articles used to introduce claim recitations. In addition, even if a specific number of an introduced claim recitation is explicitly recited, those skilled in the art will recognize that such recitation should be interpreted to mean at least the recited number (e.g., the bare recitation of “two recitations,” without other modifiers, means at least two recitations, or two or more recitations). Furthermore, in those instances where a convention analogous to “at least one of A, B, and C, etc.” is used, in general, such a construction is intended in the sense one having skill in the art would understand the convention (e.g., “a system having at least one of A, B, and C” would include but not be limited to systems that have A alone, B alone, C alone, A and B together, A and C together, B and C together, and/or A, B, and C together, etc.). In those instances where a convention analogous to “at least one of A, B, or C, etc.” is used, in general, such a construction is intended in the sense one having skill in the art would understand the convention (e.g., “a system having at least one of A, B, or C” would include but not be limited to systems that have A alone, B alone, C alone, 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 those within the art that virtually any disjunctive word and/or phrase presenting two or more alternative terms, whether in the description, claims, or drawings, should be understood to contemplate the possibilities of including one of the terms, either of the terms, or both terms. For example, the phrase “A or B” will be understood to include the possibilities of “A” or “B” or “A and B.”

[0151] In addition, where features or aspects of the disclosure may be described in terms of Markush groups, those skilled in the art will recognize that the disclosure is also 4754-01

-32- thereby described in terms of any individual member or subgroup of members of the Markush group.

[0152] As will be understood by one skilled in the art, for any and all purposes, such as in terms of providing a written description, all ranges disclosed herein also encompass any and all possible subranges and combinations of subranges thereof. Any listed range can be easily recognized as sufficiently describing and enabling the same range being 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 also be understood by one skilled in the art all language such as “up to,” “at least,” and the like include the number recited and refer to ranges which can be subsequently broken down into subranges as discussed above. Finally, as will be understood by one skilled in the art, a range includes each individual member. Thus, for example, a group having 1-3 wt. % refers to groups having 1, 2, or 3 wt.%. Similarly, a group having 1 to 5 wt. % refers to groups having 1, 2, 3, 4, or 5 wt. %, and so forth, including all points therebetween.

[0153] Moreover, where a recited range for a treat rate is provided, it is contemplated that such range shall include treat rates for individual components and/or a mixture of components. Thus, for example, a range of 1 to 3 wt % contemplates that a given component may be present in a range of 1 to 3 wt % or that a mixture of similar components can be present in a range from 1 to 3 wt %.

[0154] 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. Therefore, it is to be understood that the invention disclosed herein is intended to cover such modifications as fall within the scope of the appended claims.

Claims

4754-01 -33- What is claimed is:

1. A thermoplastic polyurethane (TPU) composition comprising: a TPU having from 15 to 50 percent hard segment and an average vertical resiliency measured according to ASTM D2632 of at least 50 percent, the TPU formed by the reaction product of: a polyisocyante component comprising a linear aliphatic diisocyanate having from 3 to 12 carbon atoms; a polyol component selected from a poly caprolactone polyol and a polyester polyol; and a linear or branched chain extender component having main backbone of from 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 according to 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 according to either claim 1 or claim 2, wherein the polyisocyante component is present in an amount of from 10 to 30 weight percent of the TPU.

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

5. The composition according to any one of claims 1 to 4, wherein the polyol component has a molecular weight (M_w) of from 1,000 to 3,500.

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

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

9. The composition according to any one of claims 1 to 8, wherein the TPU composition further comprises a plasticizer component. 4754-01

-34-

10. The composition according to claim 9, wherein the plasticizer component is a dialkylether glutarate.

11. The composition according to either 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 according to any one of claims 1 to 11, wherein the vertical resiliency of the TPU is a least 54 percent.

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

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

15. The composition according to 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. A 3D printed part prepared from the TPU composition according to any one of claims 1 to 15.

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

18. The 3D printed part according to either claim 16 or claim 17, wherein the 3D printed part is selected from a footwear midsole, a prosthetic, an orthopedic, an electronic part, a consumer good, a sporting good, and a toy.