Thermoplastic polyurethane having high-temperature stability and its use

Abstract

The present disclosure relates to a thermoplastic polyurethane composition (TPU) comprising a reaction product of an aromatic polyisocyanate and a diol mixture of a first diol and a second diol, wherein the second diol is at least 15% by weight of the diol mixture. The TPU reaction product further has a hard block content of at least 30% by weight based on the total weight of the TPU reaction product. The TPU compositions disclosed herein have high temperature stability and can be used in applications where high temperature stability is required, such as in the coating of wires and cables or in seals and gaskets.

Description

Technical Field

[0001] The present disclosure relates to a thermoplastic polyurethane (TPU) composition containing a TPU reaction product of an aromatic polyisocyanate, a mixture of diols, and a chain extender, wherein the TPU has a hard block content of at least 30% by weight. The TPU of the present disclosure exhibits high-temperature stability and has specific uses in the formation of coatings for cables and / or wires.

Background Art

[0002] The use of polyurethanes, including thermoplastic polyurethanes (TPUs), in transfer elements such as tubes or hoses, or in coatings of cable systems, is known in the prior art. TPUs offer various benefits for extending the durability and service life of transfer elements and cable systems. This is due to excellent abrasion resistance, high mechanical properties, high impact resistance, low-temperature flexibility, good chemical resistance, high cut and tear resistance, and good environmental weather resistance. The state of the art indicates several requirements for TPUs when used in transfer elements and cable systems. Some of these requirements include, for example, meeting the high-temperature requirements for transfer elements or cable systems used in very high-temperature environments or operating conditions, such as for Class D type cables (ISO 6722) or cables with a heat rating of 125 °C or higher (UL1581).

[0003] U.S. Patent Application Publication No. 2017 / 0210846 (A1) discloses a TPU composition containing an alkylene-substituted spirocyclic compound as a chain extender and a polycarbonate polyol for high-temperature resistance.

[0004] U.S. Patent No. 11,168,175 (B2) discloses a thermoplastic polyurethane that can be obtained by, or is obtained by, at least a polyisocyanate composition, ethane-1,2-diol as a chain extender, and conversion of a polyol composition, and no additional chain extender other than ethane-1,2-diol is used.

[0005] International Publication No. 2019 / 002226 discloses a high heat-resistant thermoplastic polyurethane composition for injection or press molding, and a method for preparing this composition. This composition is characterized in that it is a mixture of a diisocyanate compound or a crosslinking agent and a thermoplastic polyurethane synthesized by brining (A) an ether-containing polyester polyol, (B) a chain extender, and (C) a diisocyanate compound to the reaction. Therefore, there is a general need in the art for TPU compositions that can be used in systems that require high temperature resistance while maintaining other physical properties such as tensile strength and elongation, for example.

Prior Art Documents

Patent Documents

[0006]

Patent Document 1

Patent Document 2

Patent Document 3

Summary of the Invention

[0007] The present disclosure relates to a thermoplastic polyurethane composition (hereinafter also referred to as "TPU composition") comprising a reaction product of an aromatic polyisocyanate, a diol mixture, and a chain extender. The diol mixture used for forming the reaction product includes a first diol selected from one or more of a polycarbonate polyol, a polycaprolactone diol, and a poly(tetrahydrofuran), and the second diol is selected from one or more of a perfluoropolyether, a hydrogenated polybutadiene diol, and a poly(dimethylsiloxane). The content of the second diol in the diol mixture is at least 15% by weight of the diol mixture, and it is a chain extender. The reaction product of the TPU composition includes a hard block content of at least 30% by weight.

[0008] In another aspect of the present disclosure, it is a cable or wire coated with the TPU composition, wherein the TPU composition comprises a reaction product of a diol mixture having a first diol selected from one or more of an aromatic polyisocyanate, a polycarbonate polyol, a polycaprolactone diol, and a poly(tetrahydrofuran), the second diol is selected from one or more of a perfluoropolyether, a hydrogenated polybutadiene diol, and a poly(dimethylsiloxane), the content of the second diol in the diol mixture is at least 15% by weight of the diol mixture, it is a chain extender, and the reaction product of the TPU composition has a hard block content of at least 30% by weight.

[0009] Another aspect of the present disclosure is a seal or gasket formed from a TPU composition, wherein the TPU composition comprises a reaction product of a diol mixture having a first diol selected from one or more of an aromatic polyisocyanate, a polycarbonate polyol, a polycaprolactone diol, and a poly(tetrahydrofuran), the second diol is selected from one or more of a perfluoropolyether, a hydrogenated polybutadiene diol, and a poly(dimethylsiloxane), the content of the second diol in the diol mixture is at least 15% by weight of the diol mixture, a chain extender, and the reaction product of the TPU composition has a hard block content of at least 30% by weight, relating to a seal or gasket.

[0010] In yet another aspect of the present disclosure, there is provided the use of a TPU composition, which comprises a reaction product of a diol mixture having a first diol selected from one or more of an aromatic polyisocyanate, a polycarbonate polyol, a polycaprolactone diol, and a poly(tetrahydrofuran), the second diol is selected from one or more of a perfluoropolyether, a hydrogenated polybutadiene diol, and a poly(dimethylsiloxane), the content of the second diol in the diol mixture is at least 15% by weight of the diol mixture, a chain extender, and the reaction product of the TPU composition has a hard block content of at least 30% by weight for increasing the high temperature stability of a coated cable or wire, relating to the use of the TPU composition.

[0011] The following embodiments of the subject matter are contemplated.

[0012] Embodiment 1. A thermoplastic polyurethane composition (TPU) comprising a reaction product of an aromatic polyisocyanate, a diol mixture, and a chain extender, wherein the diol mixture comprises a first diol selected from one or more of polycarbonate polyol, polycaprolactone diol, and poly(tetrahydrofuran), and a second diol selected from one or more of perfluoropolyether, hydrogenated polybutadiene diol, and poly(dimethylsiloxane), and the content of the second diol in the diol mixture is at least 15% by weight of the diol mixture, and the reaction product has a hard block content of at least 30% by weight.

[0013] Embodiment 2. The composition according to Embodiment 1, wherein the aromatic polyisocyanate is methylene diphenyl diisocyanate.

[0014] Embodiment 3. The composition according to Embodiment 1 or 2, wherein the chain extender is selected from one or more of 1,3-propanediol, hydroquinone bis(2-hydroxyethyl) ether, and 1,4-butanediol.

[0015] Embodiment 4. The composition according to any one of Embodiments 1 to 3, wherein the content of the second diol in the diol mixture is at least 18% by weight of the diol mixture.

[0016] Embodiment 5. The composition according to any one of Embodiments 1 to 4, wherein the content of the second diol in the diol mixture is at least 20% by weight of the diol mixture.

[0017] Embodiment 6. The composition according to any one of Embodiments 1 to 5, wherein the content of the second diol in the diol mixture is at least 22% by weight of the diol mixture.

[0018] Embodiment 7. The composition according to any one of Embodiments 1 to 6, wherein the hard block content is at least 30% by weight of the reaction product.

[0019] Embodiment 8. The composition according to any one of Embodiments 1 to 7, wherein the hard block content is at least 32% by weight of the reaction product.

[0020] Embodiment 9. The composition according to any one of Embodiments 1 to 8, wherein the hard block content is at least 33% by weight of the reaction product.

[0021] Embodiment 10. The aromatic polyisocyanate is methylene diphenyl diisocyanate, the first diol is a polycarbonate polyol, the second diol is a perfluoropolyether, the chain extender is hydroquinone bis(2-hydroxyethyl) ether, and the composition has a hard block content of at least 33% by weight. The composition according to any one of Embodiments 1 to 6.

[0022] Embodiment 11. The aromatic polyisocyanate is methylene diphenyl diisocyanate, the first diol is a polycarbonate polyol, the second diol is a hydrogenated polybutadiene diol, the chain extender is 1,3-propanediol, and the composition has a hard block content of at least 40% by weight. The composition according to any one of Embodiments 1 to 6.

[0023] Embodiment 12. The aromatic polyisocyanate is methylene diphenyl diisocyanate, the first diol is a polycarbonate polyol, the second diol is poly(dimethylsiloxane), the chain extender is hydroquinone bis(2-hydroxyethyl) ether, and the composition has a hard block content of at least 33% by weight. The composition according to any one of Embodiments 1 to 6.

[0024] Embodiment 13. The composition according to any one of Embodiments 1 to 6, wherein the aromatic polyisocyanate is methylene diphenyl diisocyanate, the first diol is a polycarbonate polyol, the second diol is a hydrogenated polybutadiene diol, the chain extender is 1,4-butanediol, and the composition has a hard block content of at least 43% by weight.

[0025] Embodiment 14. The composition according to any one of Embodiments 1 to 13, wherein the TPU composition has high temperature stability measured at less than 20% elongation percentage after heating at 200 °C for 6 hours.

[0026] Embodiment 15. The composition according to any one of Embodiments 1 to 14, wherein the TPU composition has high temperature stability measured at less than 18% elongation percentage after heating at 200 °C for 6 hours.

[0027] Embodiment 16. The composition according to any one of Embodiments 1 to 15, wherein the TPU composition has high temperature stability measured at less than 6% elongation percentage after heating at 200 °C for 6 hours.

[0028] Embodiment 17. The composition according to any one of Embodiments 14 to 16, wherein the elongation percentage is measured by providing a TPU composition formed into a rectangular plaque having a thickness of 1.9 - 2.0 mm, a width of about 1.0 cm, and a length of 13.0 - 15.0 cm, placing the plaque on a rod, aging the plaque at a temperature of 200 °C for 6 hours, cooling the plaque, and determining the change in length.

[0029] Embodiment 18. The composition according to any one of Embodiments 1 to 17, wherein the TPU has a tensile strength retention rate of 60% and an ultimate elongation retention rate of 60% determined by ASTM D412 after 6 hours at 200 °C.

[0030] Embodiment 19. A cable or wire coated with the TPU composition according to any one of Embodiments 1 to 18.

[0031] Embodiment 20. A seal or gasket formed from the TPU composition according to any one of Embodiments 1 to 18.

[0032] Embodiment 21. Use of the TPU composition according to any one of Embodiments 1 to 18 for increasing the high-temperature stability of a coated cable or wire, seal or gasket.

Mode for Carrying Out the Invention

[0033] The present disclosure relates to a thermoplastic polyurethane (also referred to herein as "TPU") composition. The TPU composition disclosed herein generally comprises a TPU reaction product ("TPU reaction product") of an aromatic polyisocyanate, a diol mixture, a chain extender, and optionally, other additives. Polyisocyanate component:

[0034] The TPU reaction product of the composition of the present disclosure is prepared using an aromatic polyisocyanate component. In some embodiments, the polyisocyanate component comprises one or more aromatic diisocyanates. Examples of suitable aromatic polyisocyanates include 4,4'-methylenebis(phenyl isocyanate) (MDI), m-xylene diisocyanate (XDI), phenylene-1,4-diisocyanate, naphthalene-1,5-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 (PDI), 3,3'-dimethyl-4,4'-biphenylene diisocyanate (TODI), 1,5-naphthalene diisocyanate (NDI), and dicyclohexylmethane-4,4'-diisocyanate (H12MDI), but are not limited thereto. 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.

[0035] In some embodiments, the TPU reaction product essentially does not contain or even completely does not contain aliphatic polyisocyanates.

[0036] In other embodiments, in addition to the aromatic polyisocyanates described above, the thermoplastic polyurethane reaction product may include one or more aliphatic diisocyanates. Suitable aliphatic diisocyanates include aliphatic diisocyanates such as 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. Polyol component:

[0037] The TPU reaction product of the compositions of the present disclosure is further formed from a polyol or diol. Suitable polyols for use in this reaction product include polyether polyols, polyester polyols, polycarbonate polyols, polysiloxane polyols, and combinations thereof.

[0038] Suitable polyols, which may also be described as hydroxyl - terminated intermediates when present, include one or more hydroxyl - terminated polyesters, one or more hydroxyl - terminated polyethers, one or more hydroxyl - terminated polycarbonates, one or more hydroxyl - terminated polysiloxanes, or mixtures thereof.

[0039] Suitable hydroxyl-terminated polyester intermediates can include linear polyesters having a number average molecular weight (Mn) of from about 500 to about 10,000, from about 700 to about 5,000, or from about 700 to about 4,000, and generally have an acid value of less than 1.3 or less than 0.5. The molecular weight is determined by assay of the end functional groups and is related to the number average molecular weight. The polyester intermediate can be produced by (1) an esterification reaction of one or more glycols with one or more dicarboxylic acids or anhydrides, or (2) a transesterification reaction, i.e., a reaction of one or more glycols with an ester of a dicarboxylic acid. In order to obtain a linear chain with a predominance of terminal hydroxyl groups, generally, the molar ratio of glycol to acid is preferably greater than 1 mole. Also, suitable polyester intermediates include various lactones such as polycaprolactone typically made from ε-caprolactone and a difunctional initiator such as diethylene glycol. The dicarboxylic acids of the desired polyester can be aliphatic, alicyclic, aromatic, or combinations thereof. Suitable dicarboxylic acids that 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, etc. Anhydrides of the above dicarboxylic acids such as phthalic anhydride, tetrahydrophthalic anhydride, etc. can also be used. Adipic acid is the preferred acid. The glycols that react to form the desired polyester intermediate can be aliphatic, aromatic, or combinations thereof, include any of the glycols described in the section on chain extenders above, and have 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.

[0040] The polyol component may also include one or more polycaprolactone polyester polyols. Polycaprolactone polyester polyols useful in the techniques described herein include polyester diols derived from caprolactone monomers. The polycaprolactone polyester polyols are terminated with primary hydroxyl groups. Suitable polycaprolactone polyester 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 polyester polyol is a linear polyester diol derived from caprolactone monomers.

[0041] Useful examples include CAPA™ 2202A, a linear polyester diol with a number average molecular weight (Mn) of 2000, and CAPA™ 2302A, a linear polyester diol with a Mn of 3000, 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.

[0042] The polycaprolactone polyester polyol can be prepared from 2-oxepanone and a diol, where 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 polyester polyol is linear. In some embodiments, the polycaprolactone polyester polyol is prepared from 1,4-butanediol. In some embodiments, the polycaprolactone polyester polyol has a number average molecular weight of 500-10,000, or 500-5,000, or 1,000-, or even 2,000-4,000, or even 3000.

[0043] Suitable hydroxyl-terminated polyether intermediates include diols or polyols having a total of 2 to 15 carbon atoms, and in some embodiments, alkylene oxides having 2 to 6 carbon atoms, typically alkyl diols or glycols that react with ethers containing ethylene oxide or propylene oxide or mixtures thereof. Derived polyether polyols. For example, a hydroxyl-functional polyether can be produced by first reacting propylene glycol with propylene oxide and then with ethylene oxide. Primary hydroxyl groups obtained from ethylene oxide are preferred because they are more reactive than secondary hydroxyl groups. Useful commercially available polyether polyols include poly(ethylene glycol) containing ethylene oxide reacted with ethylene glycol, poly(propylene glycol) containing propylene oxide reacted with propylene glycol, and poly(tetramethylene ether glycol) containing water reacted with tetrahydrofuran (also described as polymerized tetrahydrofuran and generally 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 containing the reaction product of ethylenediamine and propylene oxide, diethylenetriamine adducts containing the reaction product of diethylenetriamine and propylene oxide, and similar polyamide-type polyether polyols. Copolymers can also be utilized in the described compositions. Typical copolymers include the reaction products of THF and ethylene oxide or THF and propylene oxide. These are available from BASF as the block copolymer PolyTHF® B and the random copolymer polyTHF® R. The various polyether intermediates generally have a number average molecular weight (Mn) determined by assay of the terminal functional groups that is 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 2,000 M. n and 1,000 M n and includes blends of two or more polyethers of different molecular weights, such as blends of PTMEG.

[0044] Suitable hydroxyl-terminated polycarbonates include those prepared by reacting glycols with carbonates. U.S. Patent No. 4,131,731 is incorporated herein by reference for the disclosure of hydroxyl-terminated polycarbonates and their preparation. Such polycarbonates are linear and have essentially terminal hydroxyl groups except for other terminal groups. The essential reactants are glycols and carbonates. Suitable glycols are selected from alicyclic and aliphatic diols containing 4 to 40 and / or further 4 to 12 carbon atoms, and 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, 3-methyl-1,5-pentanediol, etc., 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 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, dialkyl carbonates, cycloaliphatic carbonates, and diaryl carbonates are also suitable herein. The dialkyl carbonate can contain 2 to 5 carbon atoms in each alkyl group, and specific examples thereof are diethyl carbonate and dipropyl carbonate. The cycloaliphatic carbonate, particularly the bicyclic aliphatic carbonate, can contain 4 to 7 carbon atoms in each cyclic structure, and one or two such structures can exist. When one group is cycloaliphatic, the other can be either alkyl or aryl. On the other hand, when one group is aryl, the other can be either alkyl or cycloaliphatic. Examples of suitable diaryl carbonates that 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 a polycarbonate copolymer diol. More specifically, the hydroxyl-terminated polycarbonate is polyhexamethylene carbonate diol.

[0045] Suitable polysiloxane polyols include alpha-omega-hydroxyl or amine or carboxylic acid or thiol or epoxy-terminated polysiloxanes. Examples include poly(dimethylsiloxane) having a hydroxyl or amine or carboxylic acid or thiol or epoxy group as a terminal group. In some embodiments, the polysiloxane polyol is a hydroxyl-terminated polysiloxane. In some embodiments, the polysiloxane polyol has a number average molecular weight in the range of 300 to 5,000 or 400 to 3,000.

[0046] The polysiloxane polyol can be obtained by introducing an alcoholic hydroxyl group into the polysiloxane backbone by a dehydrogenation reaction between a polysiloxane hydride and an aliphatic polyhydric alcohol or a polyoxyalkylene alcohol.

[0047] In some embodiments, the polysiloxane can be represented by one or more compounds having the following formula [Chemical formula] In the formula, each R 1 and R 2 is, independently, an alkyl group having 1 to 4 carbon atoms, benzyl, or a phenyl group, and each E is OH or NHR 3 (wherein R 3 is hydrogen, an alkyl group having 1 to 6 carbon atoms, or a cycloalkyl group having 5 to 8 carbon atoms), and 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 the hydroxyl-containing polysiloxane, at least one of the E groups is OH. In some embodiments, both R 1 and R 2 are methyl groups.

[0048] Suitable examples include alpha-omega-hydroxypropyl-terminated poly(dimethylsiloxane) and alpha-omega-aminopropyl-terminated poly(dimethylsiloxane), both of which are commercially available materials. Further examples include copolymers of poly(dimethylsiloxane) materials and poly(alkylene oxide).

[0049] As the polyol component, when present, poly(ethylene glycol), poly(tetramethylene ether glycol), poly(trimethylene oxide), 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, dimer fatty acid-based polyester polyol, vegetable oil-based polyol, or any combination thereof may be mentioned.

[0050] Examples of dimer fatty acids that can be used in the preparation of suitable polyester polyols include Priplast™ polyester glycol / polyol commercially available from Croda and Radia® polyester glycol commercially available from Oleon.

[0051] In some embodiments, the polyol component includes a polyether polyol, a polycarbonate polyol, a polycaprolactone polyol, or any combination thereof.

[0052] In some embodiments, the polyol component includes a polyether polyol. In some embodiments, the polyol component does not essentially or even completely include a polyester polyol. In some embodiments, the polyol component used to prepare the TPU does not substantially or even completely include a polysiloxane.

[0053] In some embodiments, the polyol component includes ethylene oxide, propylene oxide, butylene oxide, styrene oxide, poly(tetramethylene ether glycol), poly(propylene glycol), poly(ethylene glycol), poly(ethylene glycol), a copolymer of poly(ethylene glycol) and poly(propylene glycol), epichlorohydrin, etc., or a combination thereof. In some embodiments, the polyol component includes poly(tetramethylene ether glycol).

[0054] In some embodiments, the polyol has a number average molecular weight of at least 900. In other embodiments, the polyol has a number average molecular weight of at least 900, 1,000, 1,500, 1,750, and / or a maximum of 5,000, 4,000, 3,000, 2,500, or even 2,000.

[0055] In some embodiments, the polyol component comprises a polycaprolactone polyester polyether polyol, a polyether polyol, a polycaprolactone polyester polyether copolymer polyol, a polyester polyol, or any combination thereof.

[0056] In some embodiments, the polyol component comprises a polycaprolactone polyester polyether polyol, poly(tetramethylene ether glycol), a polycaprolactone polyester poly(tetramethylene ether glycol) copolymer polyol, polybutylene adipate, polybutylene - hexylene adipate (an adipate made from a mixture of 1,4 - butanediol and 1,6 - hexanediol), or any combination thereof. In some embodiments, the polyol component comprises a polycaprolactone polyester poly(tetramethylene ether glycol) copolymer polyol.

[0057] In one embodiment, the thermoplastic polyurethane reaction product is formed from a diol mixture having a first diol and a second diol. In one embodiment, the first diol is selected from one or more of a polycarbonate diol, a polycaprolactone diol, and a poly(tetrahydrofuran) diol. In one embodiment, the first diol is a polycarbonate diol. In another embodiment, the first diol is a polycaprolactone diol. In yet another embodiment, the first diol is a poly(tetrahydrofuran) diol.

[0058] In one embodiment, the second diol in the diol mixture is selected from one or more of a perfluoropolyether, a hydrogenated polybutadiene diol, and a poly(dimethylsiloxane). In one embodiment, the second diol is a perfluoropolyether. In another embodiment, the second diol is a hydrogenated polybutadiene diol. In one embodiment, the second diol is a poly(dimethylsiloxane).

[0059] In one embodiment, the first diol is a polycarbonate polyol and the second diol is a perfluoropolyether. In another embodiment, the first diol is a polycarbonate polyol and the second diol is a hydrogenated polybutadiene diol. In yet another embodiment, the first diol is a polycarbonate polyol and the second diol is a poly(dimethylsiloxane).

[0060] In one embodiment, the thermoplastic polyurethane composition comprises a reaction product of a diol mixture comprising methylene diphenyl diisocyanate, a polycarbonate polyol, and a perfluoropolyether.

[0061] In one embodiment, the thermoplastic polyurethane composition comprises a reaction product of a diol mixture comprising methylene diphenyl diisocyanate, a polycarbonate polyol, and a hydrogenated polybutadiene diol.

[0062] In one embodiment, the thermoplastic polyurethane composition comprises a reaction product of a diol mixture comprising methylene diphenyl diisocyanate, a polycarbonate polyol, and a poly(dimethylsiloxane).

[0063] In one embodiment, the thermoplastic polyurethane composition comprises a reaction product of a diol mixture comprising methylene diphenyl diisocyanate, a polycarbonate polyol, and a perfluoropolyether.

[0064] In one embodiment, the thermoplastic polyurethane composition comprises a reaction product of a diol mixture comprising methylene diphenyl diisocyanate, a polycarbonate polyol, and a hydrogenated polybutadiene diol.

[0065] In some embodiments, the second polyol or diol in the diol mixture is at least 15 wt% of the diol mixture. In another embodiment, the second polyol or diol in the diol mixture is at least 18 wt% of the diol mixture. In another embodiment, the second polyol or diol in the diol mixture is at least 20 wt% of the diol mixture. In another embodiment, the second polyol or diol in the diol mixture is at least 22 wt% of the diol mixture.

[0066] The second polyol or diol mixture can range from 15 to 50 wt% of the diol mixture, or from 18 to 45 wt% of the diol mixture, or from 20 to 40 wt% of the diol mixture, or from 22 to 37 wt% of the diol mixture.

[0067] Chain extender component The TPU reaction product of the compositions of the present disclosure is further formed from a chain extender. Suitable chain extenders include relatively small polyhydroxy compounds, such as lower aliphatic or short-chain glycols having 2 to 20, or 2 to 12, or 2 to 10 carbon atoms. Suitable examples include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,4-butanediol (BDO), 1,6-hexanediol (HDO), 1,3-butanediol, 1,5-pentanediol, neopentyl glycol, 1,4-cyclohexanedimethanol (CHDM), 2,2-bis[4-(2-hydroxyethoxy)phenyl]propane (hydroxyethoxy phenyl propane, HEPP), hexamethylene diol, heptanediol, nonanediol, dodecanediol, 3-methyl-1,5-pentanediol, ethylenediamine, butanediamine, hexamethylenediamine, and hydroxyethyl resorcinol (HER), etc., 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 is BDO. Other glycols such as aromatic glycols can also be used, but in some embodiments, the TPU described herein does not essentially contain such materials or even does not contain them at all.

[0068] In some embodiments, the chain extender used to prepare the TPU includes a cyclic chain extender. Suitable examples include CHDM, HEPP, HER, and combinations thereof. In some embodiments, the chain extender used to prepare the TPU includes an aromatic cyclic chain extender, such as HEPP, HER, or a combination thereof. In some embodiments, the chain extender used to prepare the TPU includes an aliphatic cyclic chain extender, such as CHDM.

[0069] In some embodiments, the chain extender component comprises 1,4-butanediol, 2-ethyl-1,3-hexanediol, 2,2,4-trimethylpentane-1,3-diol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, 1,3-propanediol, 3-methyl-1,5-pentanediol, or combinations thereof. In some embodiments, the chain extender component comprises 1,4-butanediol, 3-methyl-1,5-pentanediol, or combinations thereof. In some embodiments, the chain extender component comprises 1,4-butanediol.

[0070] In some embodiments, the chain extender component comprises a linear alkylene diol. In some embodiments, the chain extender component comprises 1,4-butanediol, dipropylene glycol, or a combination of the two. In some embodiments, the chain extender component comprises 1,4-butanediol. In some embodiments, the chain extender component may comprise an alkykaryl diol. Suitable alkyaryl diols include hydroquinone bis(β-hydroxyethyl)ether (HQEE), 1,4-benzenedimethanol, bisethoxybiphenol, bisphenol A ethoxylate, bisphenol F ethoxylate, and the like. Further suitable chain extenders are 1,3-bis(2-hydroxyethyl)benzene and 1,2-bis(2-hydroxyethoxy)benzene. Mixtures of any of the above chain extenders can also be utilized.

[0071] In some embodiments, the chain extender is selected from one or more of 1,3-propanediol, hydroquinone bis(2-hydroxyethyl)ether, and 1,4-butanediol.

[0072] In one embodiment, the first diol is a polycarbonate polyol, the second diol is a perfluoropolyether, and the chain extender is hydroquinone bis(2-hydroxyethyl)ether.

[0073] In one embodiment, the first diol is a polycarbonate polyol, the second diol is a hydrogenated polybutadiene diol, and the chain extender is 1,3-propanediol.

[0074] In one embodiment, the first diol is a polycarbonate polyol, the second diol is poly(dimethylsiloxane), and the chain extender is hydroquinone bis(2-hydroxyethyl) ether. In one embodiment, the first diol is a polycarbonate polyol, the second diol is a hydrogenated polybutadiene diol, and the chain extender is 1,4-butanediol.

[0075] In one embodiment, the first diol is a polycarbonate polyol, the second diol is a hydrogenated polybutadiene diol, and the chain extender is hydroquinone bis(2-hydroxyethyl) ether.

[0076] In some embodiments, the molar ratio of the chain extender to the polyol is greater than 1.5. In other embodiments, the molar ratio of the chain extender to the polyol is at least 1.5, 2.0, 3.5, 3.7, or even 3.8 (or greater), and / or the molar ratio of the chain extender to the polyol can be up to 5.0, or even 4.0.

[0077] The thermoplastic polyurethane composition of the present disclosure includes a hard block and a soft block. The hard block is derived from the reaction of a diisocyanate component and a chain extender component. The soft block is derived from the reaction of a diol and a diisocyanate, and its properties depend on the type of diol. In one embodiment, the hard block content of the thermoplastic polyurethane reaction product is at least 30% by weight based on the total weight of the thermoplastic polyurethane reaction product. In another embodiment, the hard block content of the thermoplastic polyurethane reaction product is at least 32% by weight based on the total weight of the thermoplastic polyurethane reaction product. In one embodiment, the hard block content of the thermoplastic polyurethane reaction product is at least 33% by weight based on the total weight of the thermoplastic polyurethane reaction product.

[0078] In one embodiment, the thermoplastic polyurethane composition includes a reaction product of methylene diphenyl diisocyanate, a diol mixture including a polycarbonate polyol and a perfluoropolyether, and a hydroquinone bis(2-hydroxyethyl) ether chain extender, and the reaction product has a hard block content of at least 33% by weight.

[0079] In another embodiment, the thermoplastic polyurethane composition includes a reaction product of methylene diphenyl diisocyanate, a diol mixture including a polycarbonate polyol and a hydrogenated polybutadiene diol, and a 1,3-propanediol chain extender, and the reaction product has a hard block content of at least 40% by weight.

[0080] In another embodiment, the thermoplastic polyurethane composition includes a reaction product of methylene diphenyl diisocyanate, a diol mixture including a polycarbonate polyol and a poly(dimethylsiloxane), and a hydroquinone bis(2-hydroxyethyl) ether chain extender, and the composition has a hard block content of at least 33% by weight.

[0081] In another embodiment, the thermoplastic polyurethane composition comprises a reaction product of methylene diphenyl diisocyanate, a diol mixture comprising a polycarbonate polyol and a hydrogenated polybutadiene diol, and a 1,4-butanediol chain extender, and the composition has a hard block content of at least 43 wt%.

[0082] In another embodiment, the thermoplastic polyurethane composition comprises a reaction product of methylene diphenyl diisocyanate, a diol mixture comprising a polycarbonate polyol and a hydrogenated polybutadiene diol, and a hydroquinone bis(2-hydroxyethyl) ether chain extender, and the composition has a hard block content of at least 35 wt%.

[0083] The reaction product of the thermoplastic polyurethane composition described herein can be prepared by reacting a) the above polyisocyanate component, b) the above polyol component, and c) the above chain extender component, and the reaction can be carried out in the presence of a catalyst. The reaction can be carried out either in a batch or continuous process.

[0084] 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 method, semi-prepolymer method, or prepolymer method, 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.

[0085] Other additives: The thermoplastic polyurethane composition disclosed herein may further contain other optional components in addition to the TPU reaction product.

[0086] Optional additive components may be present during the reaction and / or may be incorporated into the above TPU reaction product 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, antibacterial agents, compatibilizers, electrical dissipation or antistatic additives, fillers and reinforcing agents (e.g., titanium dioxide, alumina, clay, and carbon black), flame retardants (e.g., phosphates, halogenated materials, and metal salts of alkylbenzene sulfonates), impact modifiers (e.g., methacrylate-butadiene-styrene (“MBS”) and methyl methacrylate butyl acrylate (“MBA”)), release agents (e.g., waxes, fats and oils, pigments and colorants, plasticizers, polymers), rheology modifiers (e.g., monoamines, polyamide waxes, silicones, and polysiloxanes), slip additives (e.g., paraffin wax, hydrocarbon polyolefins, and / or fluorinated polyolefins), and UV stabilizers (which may be of the hindered amine light stabilizer (HALS) and / or UV light absorber (UVA) type), but are not limited thereto. 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 their customary effective amounts.

[0087] These additional additives can be incorporated into the components of the reaction mixture or into the reaction mixture to prepare the TPU reaction product, or can be incorporated into the TPU composition after the TPU reaction product has been made. In another process, all of 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.

[0088] Generally, it is preferred to incorporate one or more antioxidants into the above TPU reaction product and / or TPU composition. These can be added during the reaction to form the TPU reaction product, blended into the pre-formed polymer as described above, 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 above 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, Irgaphos™ 126, etc., all available from BASF Specialty Chemicals. The antioxidant can 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, etc.

[0089] The TPU composition of the present disclosure may also contain from about 0.10 to about 10.0 weight % of an antibacterial agent and / or biocide material. In alternative embodiments of the present invention, the composition may contain from about 1 to about 6 weight % of an antibacterial agent and / or biocide material, from about 2 to about 4 weight % of an antibacterial agent and / or biocide material, and numerous percentages therebetween.The terms "antimicrobial agent" and / or "biocide" in the context of this formulation are intended to include, but not be limited to, sodium, potassium, calcium, zinc, copper, and barium salts of all forms of carbonates, silicates, sulfates, halides, 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 tebuconazole; organic chlorides such as pentachlorophenol (PCP); quaternary ammonium compounds (MC); copper 8-hydroxyquinoline or copper oxine; tri-n-butyltin oxide (TBTO); tri-n-butyltin naphthenate (TBTN); didecyldimethylammonium bromide (DDAB); didecyldimethylammonium chloride (DDAC); silver ions, mercury ions, carbamates, isothiazolones, chlorinated phenoxys, and polyhexamethylene biguanide hydrochloride, barium metaborate monohydrate, borates, and mixtures thereof, including fungicides, herbicides, insecticides, and antimicrobial agents. Preferred compositions of the present invention are water-insoluble and contain inorganic biocides.

[0090] The TPU compositions disclosed herein may further include a compatibilizer. Useful compatibilizers include maleated thermoplastic resins, thermoplastic elastomer block copolymers, crystalline copolymers of propylene and ethylene or other higher α-olefins, chlorinated thermoplastic resins, ionomers, maleated elastomer copolymers, and mixtures thereof.

[0091] Suitable compatibilizers may also include modified polyolefins including modified thermoplastic resins and modified rubbers. In one or more embodiments, these modified polyolefins include at least one functional group bonded thereto. In one or more embodiments, these functional groups include C1-C8 carboxylic acid esters such as carboxylic acid, carbomethoxy, carboethoxy, carbopropoxy, carbobutoxy, carbopentoxy, carbohexoxy, carboheptoxy, carbooctoxy, and their isomeric forms, carboxylic acid anhydrides, sodium, potassium, lithium, magnesium, calcium, iron, nickel, zinc, and aluminum, and carboxylates formed from the neutralization of carboxylic acid groups by metal ions from Groups I, II, III, IV-A, and VII of the periodic table, including mixtures thereof, amides, epoxies, hydroxy, amino, and C2-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 copolymerized with an olefin monomer or grafted onto a polyolefin to form a modified polyolefin.

[0092] Functionalized 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, and ionic hydrocarbon polymers from the polymerization of α-olefins and α,β-ethylenically unsaturated carboxylic acids.

[0093] 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.

[0094] In one or more embodiments, the mer units of the functional group-containing polyolefin can be present in the polyolefin in an amount of about 0.05 to about 5 mole percent. For example, in the case of maleated polyethylene, about 0.005 to about 5 mole percent of the mer units contain residues of maleic acid pendant from the backbone.

[0095] In one or more embodiments, useful modified polyolefins are available under the trade names OPTEMA™ TC120 and TC220 (ExxonMobil), which are ethyl methacrylate copolymers, and POLYBOND™ (Chemtura) or FUSABOND™ (DuPont), which are maleated polypropylenes.

[0096] Maleated elastomer copolymers include copolymers of ethylene, an α-olefin, and one or more dienes, which react 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 0.1 to 50 weight percent, or 0.3 to 30 weight percent, or 0.5 to 20 weight percent.

[0097] The TPU compositions disclosed herein can further include an antistatic agent. Numerous antistatic agents are known in the art. Sometimes, the antistatic agent is applied to the surface of the polymeric article made from the TPU composition by spraying or dipping.

[0098] The low molecular weight antistatic agent may be blended with the above TPU composition rather than being coated on the surface. Such low molecular weight antistatic agents include ethoxylated fatty amines, esters, or amides such as those described in U.S. Patent Nos. 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. Patent Nos. 3,933,871, 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. Patent Nos. 3,475,203 and 3,446,651, and Patent Nos. 82-30,756, 82-202,338, and 73-14,651.

[0099] The low molecular weight antistatic agent blended into the above TPU composition is generally an organic compound containing a hydrophobic component and a hydrophilic component. The hydrophobic component generally provides compatibility with the polymer, thereby binding the two materials together. The hydrophilic component generally absorbs moisture and evenly distributes water on the surface of a particular polymer. This water film formed on the surface increases the surface conductivity by an ion conduction process, thereby increasing the rate of electrostatic charge dissipation. As a result, conventional low molecular weight internal antistatic agents generally do not improve the volume conductivity of the polymer, are generally sensitive to atmospheric humidity, and typically provide poor performance at low humidity.

[0100] Internal low molecular weight antistatic agents are generally designed to move from the inside to the surface of the above TPU composition during or after molding. Progressive surface migration can be advantageous because it can replace any antistatic agent on the surface that has been lost by evaporation, washing, or abrasion. However, the migration must occur at an appropriate rate. If the rate is too fast, the migration can cause blooming, surface smearing, and molding difficulties, and if it is too slow, any lost antistatic agent cannot be quickly replaced, resulting in unstable antistatic properties. Slow migration is a problem that spreads to polymers with high crystallinity such as polypropylene, and the migration may take up to about one month after molding to reach maximum antistatic performance.

[0101] Additional representative antistatic agents that may be included in the mixture include, but are not limited to, quaternary ammonium salts of alkyl sulfates and carboxylic acids, quaternary ammonium compounds as disclosed in U.S. Patent No. 5,933,693, metal salts of lithium, sodium, potassium, ammonium, calcium, and barium, complexes of metal salts with polyhydric alcohols such as 1,4-butanediol, ethylene glycol, propylene glycol, and polyethylene glycol and their derivatives, and complexes of metal salts with monohydric alcohols such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether, and hexahalogenated ionic compounds as disclosed in U.S. Patent No. 5,677,357, including hexahalogenated phosphoric acid compounds such as potassium hexafluorophosphate, sodium hexafluorophosphate, and ammonium hexafluorophosphate.

[0102] Metal salt antistatic additives such as metal salts supported by diglyme (2-methoxyethyl ether) and triol, polyether, or butanediol can be used in the composition.

[0103] Some antistatic agents, such as quaternary ammonium salts, cannot withstand the processing temperatures required for some conventional fabrication or molding steps for some polymers. Additionally, conventional low molecular weight antistatic agents often tend to lose their antistatic effect by evaporation, or cause undesirable odors, or promote cracking or splitting.

[0104] The TPU compositions disclosed herein may further comprise a filler or a reinforcing agent. Examples of fillers include a wide range of particulate materials such as 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, titanate, chalk, ground glass, silica or glass, glass microspheres, glass beads or glass fibers. The glass fibers used can be made of E, A, or C glass, and preferably are sized and provided with a coupling agent. Their diameters are generally 6-20 μm. Either continuous filament fibers (rovings) with a length of 1-10 mm, preferably 3-6 mm, or chopped glass fibers (staples) can be used.

[0105] The filler can also be 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, metaboric acid barium, zinc borate, zinc metaborate; a metal anhydride such as aluminum anhydride; or an aluminum trihydrate.

[0106] Boron nitride and various recycled and reground thermosetting polyurethanes and / or polyureapolymer can also be used.

[0107] 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 methods and in conventional amounts, for example, from 5 wt% or less to 50 wt% or more based on the weight of the composition.

[0108] Reinforcing agents include high aspect ratio materials such as platelets and fibers, which can be glass, aramid, and various other polymers. Additional materials that can be used include mineral fibers, whiskers, alumina fibers, mica, powdered quartz, metal fibers, carbon fibers, and wollastonite. Reinforcing agents are typically used in an amount of 5 to 50 wt% based on the layer or the entire composition.

[0109] Fillers useful in some formulations include fire-resistant fillers that can include antimony oxide, decabromobiphenyl oxide, alumina trihydrate, magnesium hydroxide, borates, and halogenated compounds.

[0110] 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 that shield electromagnetic waves may be added. Aluminum flakes (K-102 from Transmet) are particularly suitable for EMI (electromagnetic interference) purposes. The composition may also be mixed with additional carbon fibers, carbon black, particularly conductive black, or nickel-coated carbon fibers.

[0111] Other miscellaneous fillers include wood fiber / powder / chips, rubber dust, cotton, starch, clay, synthetic fibers (e.g., polyolefin fibers), and carbon fibers.

[0112] The level of the filler depends on the density of the filler. The higher the density of the filler, the more filler can be added to the formulation without perceptibly affecting the volume fraction of the filler. Thus, the level of the filler is considered herein in terms of the weight percentage of the 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 typically used at levels of about 0.1% to about 5%), more preferably from about 5% to about 40%, particularly from about 8% to about 30%.

[0113] The TPU compositions disclosed herein may further comprise a flame retardant. The flame retardant may or may not be 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, phenyl methyl hydrogen phosphate, di(dodecyl) p-tolyl phosphate, tricresyl phosphate, triphenyl phosphate, dibutyl phenyl 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).

[0114] Further examples of flame retardants include brominated organic compounds such as brominated diols. It may contain 5 to 20 carbon atoms, in some embodiments 5 to 10 carbon atoms, 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, or in other embodiments may be present from 0 to 15 weight percent, or even from 0 to 10, 0.1 to 7, or 0.2 to 5 weight percent of the total composition.

[0115] As a further example, brominated organic compounds can be mentioned. Suitable examples include brominated diols, brominated monoalcohols, brominated ethers, brominated esters, brominated phosphates, and combinations thereof. Suitable brominated organic compounds can 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'-isopropylidene bis[2-(2,6-dibromophenoxy)ethanol].

[0116] In some embodiments, the flame retardant additive includes a metal salt of a boric acid halogen, a metal salt of a phosphoric acid halogen, or a combination thereof. In some embodiments, a combination of retardants is used. Further examples of flame retardant additives can include metal salts of organic sulfonates, such as the sodium salt of alkylbenzene sulfonate, and in some embodiments, the flame retardant additive includes a nitrogen-containing compound. The flame retardant can be added to the TPU composition in a conventional amount. In some embodiments, the flame retardant may be present in the TPU composition in an amount of 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 composition in an amount of 0.1 weight percent 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 weight percent to 15 weight percent, based on the total weight of the TPU composition.

Industrial Applicability

[0117] In many applications, it is desirable or even essential for the TPU used in manufacturing articles to exhibit good heat resistance. For example, for wires and cables used in industrial applications, as well as seals or gaskets, possessing these desirable properties is usually important.

[0118] The TPU reaction product of the present disclosure imparts high-temperature stability (sometimes referred to as heat resistance) to this TPU composition, which is superior to currently known TPU compositions. Within the scope of the present disclosure, the term "high-temperature stability" relates to the ability of the product to withstand high temperatures. Thus, it can also be referred to as "heat resistance".

[0119] Based on detailed examples, those skilled in the art can repeatedly perform assays regularly to objectively determine whether a TPU composition exhibits high-temperature stability.

[0120] For example, to measure high-temperature stability, the TPU composition can be compression molded into plaques with a rectangular shape, a thickness of 1.9 - 2.0 mm, a width of 1.0 cm, and a length of 13.0 - 15.0 cm. The plaques are placed on a rod and aged at a temperature of 200 °C for 6 hours. These aging conditions are those specified in ISO6722. After cooling, the plaques are measured for the percentage of elongation. High-temperature stability can be measured as a percentage of elongation of less than 20%. For example, a TPU composition is considered to exhibit high-temperature stability when the percentage of elongation when heated at 200 °C for 6 hours is less than 20%. The percentage of elongation can be measured by determining the change in length according to the following formula.

Number

[0121] In some embodiments, the percentage of elongation is less than 18%, or less than 18%, or less than 6%, or less than 3%.

[0122] The TPU can be further evaluated for the retention rate of tensile strength and the retention rate of ultimate elongation. The TPU composition may be prepared and aged according to the above aging conditions (i.e., 6 hours at 200 °C). Thereafter, the retention rate of tensile strength and the retention rate of ultimate elongation are measured according to ASTM D412. In one embodiment, both the retention rate of tensile strength and the retention rate of ultimate elongation exceed 60%. In another embodiment, both the retention rate of tensile strength and the retention rate of ultimate elongation exceed 65%.

[0123] In another aspect, the TPU composition may be prepared as described above and aged at 180 °C for 168 hours. In such embodiments, both the retention rate of tensile strength and the retention rate of ultimate elongation exceed 65%.

[0124] The present composition finds particularly useful applications for coatings for wires and cables and for forming articles such as seals or gaskets.

[0125] In some embodiments, the TPU compositions of the present disclosure can be used to coat wires and cables. Due to the good mechanical and physical properties of the TPU composition, particularly the high heat resistance of the TPU compositions described herein, cables or wires coated with the present TPU composition can be used in mining and power generation, which can be offshore, solar-based, wind turbines, or hydroelectric power. In other embodiments, cables or wires coated with the TPU composition can be used in buildings where they are used for security, data, terminal, communication, and signal wiring. In other embodiments, cables or wires coated with the TPU composition can be used in the automotive, train, subway, boat, and aviation industries.

[0126] In some embodiments, the TPU compositions of the present disclosure can be used to manufacture seals and gaskets. Seals and gaskets can be used in internal combustion engines, heavy machinery, and electrical appliances, and can also be used in countless other applications where heat resistance is required.

[0127] Articles containing the various TPU compositions described above include any article that is exposed to high temperatures during its use, particularly such articles that have not been made using thermoplastic polyurethane in the past because such materials have insufficient high-temperature resistance or performance.

Examples

[0128] According to the formulations shown in Table 1, different TPU samples were prepared.

Table 1A

Table 1B

[0129] The polycarbonate was polyhexamethylene carbonate diol.

[0130] The samples were compression molded into plaques with a thickness of 1.9 - 2.0 mm. The plaques were then cut into rectangular strips with a width of approximately 1.0 cm and a length of 13.0 - 15.0 cm. The rectangular strips were placed on rods in an oven at 200 °C for 6 hours, with the central part in contact with the rods so that most of the sample could freely extend. This aging condition is one of the conditions specified in ISO 6722.

[0131] The high-temperature stability was determined by measuring the change in the length of the rectangular samples after exposure to 200 °C for 6 hours and calculated according to the following formula.

Equation

[0132] The results are shown in Table 2. Example 1 is dripping and damaged, but other examples with the TPU compositions disclosed herein show much better dimensional stability after exposure to high temperatures and maintain their original shape much better than the reference.

Table 2

[0133] The polycarbonate was polyhexamethylene carbonate diol.

[0134] Examples 1 and 8 were also aged at 200 °C for 6 hours (as defined in ISO 6722), and the retention rates of tensile strength and elongation at break were determined according to ASTM D412 and are shown in Table 4. For the 200 °C / 6-hour condition, Example 8 showed a retention rate higher than 60% of the tensile strength and elongation at break while Example 1 was melted.

Table 4

[0135] Example 8 was additionally aged at 180 °C for 168 hours as defined in UL1581. The retention rates of the tensile properties are shown in Table 5. Example 8 showed a higher retention rate of tensile strength and elongation at break than Comparative Example 1.

Table 5

[0136] Unless otherwise specified herein, references to the treatment rate or amount of a component present in the lubricating compositions disclosed herein are cited on an oil-free basis, i.e., based on the amount of the active substance. Further, unless otherwise specified, "wt%" as used herein refers to the weight percent based on the total weight of the composition on an oil-free basis.

[0137] This disclosure is not limited to the specific embodiments described in this application and is intended as an exemplification of various aspects. As will be apparent to those skilled in the art, many modifications and variations can be made without departing from the spirit and scope of the invention. In addition to those listed herein, functionally equivalent methods and components within the scope of this disclosure 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. This disclosure should be limited only by the terms of such claims and the full scope of equivalents to which such claims are entitled. This disclosure is not limited to a particular method, reagent, compound, or composition, which can, of course, vary. It should also be understood that the terms used herein are for the purpose of describing particular embodiments only and are not intended to be limiting.

[0138] Various compositions, methods, and devices are described with respect to including (which is to be interpreted as meaning including but not limited to) various components or steps, but the compositions, methods, and devices can also consist essentially of or consist of various components and steps, and such terms should be interpreted as defining essentially closed-member groups.

[0139] Regarding the use of substantially any plural and / or singular terms herein, those skilled in the art can convert from plural to singular and / or from singular to plural as appropriate for the context and / or application. Various singular / plural conversions may be explicitly described herein for clarity.

[0140] Generally, the terms used herein, particularly those used in the appended claims (e.g., the body of the appended claims), will be understood by those skilled in the art to be generally intended as "open" terms (e.g., the term "comprising" should be interpreted as "comprising 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 introductions of claim recitations is intended, such intent will be explicitly recited in the claim, and it will be further understood by those skilled in the art that where no such recitation exists, no such intent exists. For example, for purposes of illustration, the following appended claims may include the use of 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 article "a" or "an", even if the same claim includes introductory phrases "one or more" or "at least one" and indefinite articles such as "a" or "an", limits any particular claim including such introduced claim recitation to embodiments including only one such recitation (e.g., "a" and / or "an" should be interpreted to mean "at least one" or "one or more"), and the same is true for the use of definite articles used to introduce claim recitations. In addition, even where a specific number of introductions of claim recitations 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., an explicit recitation of "two recitations" without other modifying phrases means at least two recitations, or two or more recitations). Further, where a convention similar to "at least one of A, B, and C, etc." is used, generally such construction is intended in the sense that those skilled in the art will understand the convention (e.g., "a system having at least one of A, B, and C" includes, but is not limited to, a system having only A, only B, only C, 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 a construction 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, a system having only A, only B, only C, A and B together, A and C together, B and C together, and / or A, B, and C together). It will be further understood by one of ordinary skill in the art that substantially any disjunctive word and / or phrase presenting two or more alternative terms is intended to contemplate the possibility of including one of the terms, any of the terms, or both terms, regardless of whether in the specification, claims, or drawings. For example, the phrase "A or B" would be understood to include the possibility of "A" or "B" or "A and B".

[0141] In addition, where a feature or aspect of the present disclosure may be described with respect to a Markush group, one of ordinary skill in the art will recognize that the present disclosure thereby also describes with respect to any individual member or subgroup of members of the Markush group.

[0142] As will be understood by those skilled in the art, for all purposes, such as providing a written description, all ranges disclosed herein include any and all possible sub-ranges and combinations of those sub-ranges. Any recited range can be readily recognized as being such that the same range can be adequately described and enabled to be decomposed into at least equal halves, thirds, quarters, fifths, tenths, etc. of the range. By way of non-limiting example, each range discussed herein can be readily decomposed into lower thirds, middle thirds, and upper thirds, etc. As will be understood by those skilled in the art, all language such as "up to", "at least", etc. includes the recited number and refers to a range that can then be decomposed into sub-ranges as discussed above. Finally, as will be understood by those skilled in the art, ranges include each and every member. Thus, for example, a group having from 1 to 3 weight % refers to a group having 1, 2, or 3 weight %. Similarly, a group having from 1 to 5 weight % refers to a group having 1, 2, 3, 4, or 5 weight %, etc., including all points therebetween.

[0143] Further, when ranges are provided regarding processing speed, such ranges are intended to include processing speed for individual components and / or mixtures of components. Thus, for example, a range of 1 to 3 weight % is intended to mean that a given component can be present in the range of 1 to 3 weight %, or that a mixture of similar components can be present in the range of 1 to 3 weight %.

[0144] Although the invention has been described in connection with its preferred embodiments, it should be understood that various modifications will be apparent to those skilled in the art upon reading this specification. Accordingly, 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

1. A thermoplastic polyurethane composition (TPU), Aromatic polyisocyanates and, A mixture of diols, A first diol selected from one or more of polycarbonate polyols, polycaprolactone diols, and poly(tetrahydrofurans), A diol mixture comprising: a second diol selected from one or more perfluoropolyethers, hydrogenated polybutadienediols, and poly(dimethisiloxanes), wherein the content of the second diol in the diol mixture is at least 15% by weight of the diol mixture; The chain extender and the reaction product are included. A thermoplastic polyurethane composition (TPU) wherein the reaction product has a hard block content of at least 30% by weight.

2. The composition according to claim 1, wherein the aromatic polyisocyanate is methylenediphenyl diisocyanate.

3. The composition according to claim 1, wherein the chain extender is selected from one or more of 1,3-propanediol, hydroquinone bis(2-hydroxyethyl) ether, and 1,4-butanediol.

4. The composition according to claim 1, wherein the content of the second diol in the diol mixture is at least 18% by weight of the diol mixture.

5. The composition according to claim 1, wherein the content of the second diol in the diol mixture is at least 20% by weight of the diol mixture.

6. The composition according to claim 1, wherein the content of the second diol in the diol mixture is at least 22% by weight of the diol mixture.

7. The composition according to claim 1, wherein the hard block content is at least 30% by weight of the reaction product.

8. The composition according to claim 1, wherein the hard block content is at least 32% by weight of the reaction product.

9. The composition according to claim 1, wherein the hard block content is at least 33% by weight of the reaction product.

10. The composition according to claim 1, wherein the aromatic polyisocyanate is methylenediphenyl diisocyanate, the first diol is a polycarbonate polyol, the second diol is a perfluoropolyether, the chain extender is hydroquinone bis(2-hydroxyethyl) ether, and the composition has a hard block content of at least 33% by weight.

11. The composition according to claim 1, wherein the aromatic polyisocyanate is methylenediphenyl diisocyanate, the first diol is a polycarbonate polyol, the second diol is a hydrogenated polybutadiene diol, the chain extender is 1,3-propanediol, and the composition has a hard block content of at least 40% by weight.

12. The composition according to claim 1, wherein the aromatic polyisocyanate is methylenediphenyl diisocyanate, the first diol is a polycarbonate polyol, the second diol is poly(dimethisiloxane), the chain extender is hydroquinone bis(2-hydroxyethyl) ether, and the composition has a hard block content of at least 33% by weight.

13. The composition according to claim 1, wherein the aromatic polyisocyanate is methylenediphenyl diisocyanate, the first diol is a polycarbonate polyol, the second diol is a hydrogenated polybutadiene diol, the chain extender is 1,4-butanediol, and the composition has a hard block content of at least 43% by weight.

14. The composition according to claim 1, wherein the TPU composition has high-temperature stability measured at less than 20% elongation after heating at 200°C for 6 hours.

15. The composition according to claim 1, wherein the TPU composition has high-temperature stability measured at less than 18% elongation percentage after heating at 200°C for 6 hours.

16. The composition according to claim 1, wherein the TPU composition has high-temperature stability measured at less than 6% elongation after heating at 200°C for 6 hours.

17. The composition according to claim 14, wherein the elongation percentage is measured by providing a TPU composition molded into a rectangular plaque having a thickness of 1.9 to 2.0 mm, a width of about 1.0 cm, and a length of 13.0 to 15.0 cm, placing the plaque on a rod, aging the plaque at a temperature of 200°C for 6 hours, cooling the plaque, and determining the change in length.

18. The composition according to claim 1, wherein the TPU has a 60% retention rate of tensile strength and a 60% retention rate of ultimate elongation as determined by ASTM D412 after 6 hours at 200°C.

19. A cable or wire coated with the TPU composition described in claim 1.

20. A seal or gasket formed from the TPU composition described in claim 1.