Thermoplastic polyurethanes with high temperature stability and uses thereof

Abstract

The present disclosure relates to a thermoplastic polyurethane composition (TPU) comprising the reaction product of an aromatic polyisocyanate and a diol mixture of a first diol and a second diol, where the second diol is at least 15% by weight of the diol mixture. The TPU reaction product also 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 are useful in applications where high temperature stability is desired, such as coating wires and cables or in seals and washers.

Description

Technical Field

[0001] The present disclosure relates to thermoplastic polyurethane (TPU) compositions comprising 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 wt. %. The TPUs of the present disclosure exhibit high temperature stability and have particular use in the formation of cable and / or wire coatings. Background Art

[0002] The use of polyurethanes, including thermoplastic polyurethanes (TPUs), in transmission elements, such as pipes or hoses, or in coated cable systems is known in the prior art. TPUs offer a variety of benefits that extend the durability and service life of transmission elements and cable systems. This is due to excellent wear resistance, high mechanical properties, high impact resistance, low temperature flexibility, good chemical resistance, high resistance to cutting and tearing, and good environmental weathering. When used in transmission elements and cable systems, the prior art shows several demands for TPUs. Some of these demands include, for example, the desire for transmission elements or cable systems used in extremely hot environments or working conditions, such as, for example, meeting the high temperature requirements of Class D cables (ISO 6722) or cables with a thermal rating of 125°C or higher (UL1581).

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

[0004] US Patent No. 11,168,175 B2 discloses a thermoplastic polyurethane obtainable by or through conversion of at least a polyisocyanate composition, ethylene-1,2-diol as a chain extender, and a polyol composition, wherein no other chain extender is used in addition to ethylene-1,2-diol.

[0005] International Publication No. WO 2019 / 002226 discloses a highly heat-resistant thermoplastic polyurethane composition for injection molding or compression molding and a method for preparing the composition, wherein the composition is characterized in that it is a mixture of a diisocyanate compound or a crosslinking agent and a thermoplastic polyurethane, and the thermoplastic polyurethane is synthesized by reacting (A) an ether-containing polyester polyol, (B) a chain extender and (C) a diisocyanate compound.

[0006] Therefore, there is a general need in the art for TPU compositions that can be used in systems requiring high temperature resistance while maintaining other physical properties, such as tensile strength and elongation. Summary of the invention

[0007] The present disclosure relates to a thermoplastic polyurethane composition (also referred to herein as a "TPU composition") comprising a reaction product of an aromatic polyisocyanate, a diol mixture, and a chain extender. The diol mixture used to form the reaction product comprises a first diol selected from one or more of polycarbonate polyols, polycaprolactone diols, and poly(tetramethylene glycol), and a second diol selected from one or more of perfluoropolyethers, hydrogenated polybutadiene diols, and poly(dimethylsiloxane), wherein the second diol is present in the diol mixture in an amount of at least 15% by weight of the diol mixture, and a chain extender. The reaction product of the TPU composition comprises a hard block content of at least 30% by weight.

[0008] Another aspect of the present disclosure relates to a cable or wire coated with a TPU composition, wherein the TPU composition comprises a reaction product of an aromatic polyisocyanate, a diol mixture having a first diol selected from one or more of polycarbonate polyols, polycaprolactone diols, and poly(tetramethylene glycol), and a chain extender, and a second diol selected from one or more of perfluoropolyethers, hydrogenated polybutadiene diols, and poly(dimethylsiloxane), wherein the content of the second diol in the diol mixture is at least 15 weight percent of the diol mixture, and wherein the reaction product of the TPU composition has a hard block content of at least 30 weight percent.

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

[0010] In yet another aspect of the present disclosure, the present invention relates to the use of a TPU composition comprising a reaction product of an aromatic polyisocyanate, a diol mixture having a first diol selected from one or more of polycarbonate polyols, polycaprolactone diols, and poly(tetramethylene glycol)s and a chain extender, and a second diol selected from one or more of perfluoropolyethers, hydrogenated polybutadiene diols, and poly(dimethylsiloxanes), wherein the content of the second diol in the diol mixture is at least 15 wt % of the diol mixture, and wherein the reaction product of the TPU composition has a hard block content of at least 30 wt %, the TPU composition being used to increase the high temperature stability of a coated cable or wire.

[0011] The following implementations of the present subject matter are contemplated:

[0012] 1. A thermoplastic polyurethane composition (TPU) comprising: the reaction product of: an aromatic polyisocyanate; a diol mixture comprising: a first diol selected from one or more of polycarbonate polyols, polycaprolactone diols and poly(tetramethylene glycol), and a second diol selected from one or more of perfluoropolyethers, hydrogenated polybutadiene diols and poly(dimethylsiloxane), wherein the content of the second diol in the diol mixture is at least 15% by weight of the diol mixture; and a chain extender; the reaction product having a hard block content of at least 30% by weight.

[0013] 2. The composition according to embodiment 1, wherein the aromatic polyisocyanate is diphenylmethane diisocyanate.

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

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

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

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

[0018] 7. The composition according to any of the preceding embodiments, wherein the hardblock content is at least 30% by weight of the reaction product.

[0019] 8. The composition according to any of the preceding embodiments, wherein the hardblock content is at least 32% by weight of the reaction product.

[0020] 9. The composition according to any of the preceding embodiments, wherein the hardblock content is at least 33% by weight of the reaction product.

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

[0022] 11. The composition of any one of embodiments 1 to 6, wherein the aromatic polyisocyanate is diphenylmethane diisocyanate, the first diol is a polycarbonate polyol, the second diol is a hydrogenated polybutadiene diol, and the chain extender is 1,3-propylene glycol, and wherein the composition has a hard block content of at least 40 wt%.

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

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

[0025] 14. The composition of any one of the preceding embodiments, wherein the TPU composition has high temperature stability measured by a percent elongation of less than 20% after heating at 200°C for 6 hours.

[0026] 15. The composition of any one of the preceding embodiments, wherein the TPU composition has high temperature stability as measured by a percent elongation of less than 18% after heating at 200°C for 6 hours.

[0027] 16. The composition of any one of the preceding embodiments, wherein the TPU composition has high temperature stability as measured by a percent elongation of less than 6% after heating at 200°C for 6 hours.

[0028] 17. A composition according to any one of embodiments 14 to 16, wherein the elongation percentage is measured by: providing a TPU composition molded into a rectangular plate 1.9 mm to 2.0 mm thick, about 1.0 cm wide and 13.0 cm to 15.0 cm long; placing the plate on a rod; aging the plate at a temperature of 200°C for 6 hours; allowing the plate to cool; and determining the change in length.

[0029] 18. The composition of any one of the preceding embodiments, wherein the TPU has a 60% retention of tensile strength and a 60% retention of ultimate elongation after 6 hours at 200°C as determined by ASTM D412.

[0030] 19. A cable or wire coated with the TPU composition according to any one of the preceding embodiments.

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

[0032] 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. DETAILED DESCRIPTION

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

[0034] Polyisocyanate component :

[0035] The TPU reaction products of the compositions of the present disclosure are prepared using an aromatic polyisocyanate component. In some embodiments, the polyisocyanate component includes one or more aromatic diisocyanates. Examples of suitable aromatic polyisocyanates include, but are not limited to, 4,4'-methylenebis(phenyl isocyanate) (MDI), meta-xylene diisocyanate (XDI), phenylene-1,4-diisocyanate, naphthalene-1,5-diisocyanate, and toluene diisocyanate (TDI); and 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). A mixture 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.

[0036] In some embodiments, the TPU reaction product is substantially free of, or even completely free of, aliphatic polyisocyanates.

[0037] In other embodiments, in addition to the above-mentioned aromatic polyisocyanates, the thermoplastic polyurethane reaction product may include one or more aliphatic diisocyanates. Suitable aliphatic diisocyanates include isophorone diisocyanate (IPDI), 1,6-hexamethylene diisocyanate (HDI), 1,4-cyclohexyl diisocyanate (CHDI), decane-1,10-diisocyanate, lysine diisocyanate (LDI), 1,4-butane diisocyanate (BDI) and dicyclohexylmethane-4,4′-diisocyanate (H12MDI). In some embodiments, a mixture of two or more polyisocyanates can be used.

[0038] Polyol components :

[0039] The TPU reaction product of the composition of the present disclosure is further formed from a polyol or diol. The polyols used in the reaction product of the present invention include polyether polyols, polyester polyols, polycarbonate polyols, polysiloxane polyols, and combinations thereof.

[0040] When present, suitable polyols (which may also be described as hydroxy-terminated intermediates) may include one or more hydroxy-terminated polyesters, one or more hydroxy-terminated polyethers, one or more hydroxy-terminated polycarbonates, one or more hydroxy-terminated polysiloxanes, or mixtures thereof.

[0041] Suitable hydroxyl terminated polyester intermediates include linear polyesters having a number average molecular weight (Mn) of about 500 to about 10,000, about 700 to about 5,000, or about 700 to about 4,000, and an acid number that is typically less than 1.3 or less than 0.5. The molecular weight is determined by measuring the terminal functional groups and is related to the number average molecular weight. The polyester intermediates can be produced by (1) esterification of one or more diols with one or more dicarboxylic acids or anhydrides or (2) transesterification, i.e., the reaction of one or more diols with a dicarboxylic acid ester. In order to obtain linear chains with a predominance of terminal hydroxyl groups, a molar ratio of diol to acid exceeding one mole is generally preferred. Suitable polyester intermediates also include various lactones, such as polycaprolactone, which is typically made from ε-caprolactone and a difunctional initiator such as diethylene glycol. The dicarboxylic acid of the desired polyester can be aliphatic, cycloaliphatic, aromatic, or a combination thereof. Suitable dicarboxylic acids, which may be used alone or in mixtures, generally have a total of 4 to 15 carbon atoms and include: succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, isophthalic acid, terephthalic acid, cyclohexanedicarboxylic acid and the like. Anhydrides of the above dicarboxylic acids may also be used, such as phthalic anhydride, tetrahydrophthalic anhydride, and the like. Adipic acid is a preferred acid. The diols reacted to form the desired polyester intermediate may be aliphatic, aromatic, or a combination thereof, including any of the diols in the chain extender segment described above, and have a total of 2 to 20 or 2 to 12 carbon atoms. Suitable examples include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 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.

[0042] The polyol component may also include one or more polycaprolactone polyester polyols. The polycaprolactone polyester polyols useful in the technology described herein include polyester diols derived from caprolactone monomers. The polycaprolactone polyester polyols are terminated by primary hydroxyl groups. Suitable polycaprolactone polyester polyols can be made from ε-caprolactone and a bifunctional initiator (such as diethylene glycol, 1,4-butanediol or any other diol listed herein. In some embodiments, the polycaprolactone polyester polyol is a linear polyester diol derived from caprolactone monomers.

[0043] Useful examples include CAPA TM 2202A, which is a linear polyester diol having a number average molecular weight (Mn) of 2000; and CAPA TM 2302A, which is a linear polyester diol with an Mn of 3000, both are commercially available from Perstorp Polyols Inc. These materials may also be described as polymers of 2-oxepanone and 1,4-butanediol.

[0044] Polycaprolactone polyester polyol can be made from 2-oxacycloheptanone and diol, wherein diol can be 1,4-butanediol, diethylene glycol, monoethylene glycol, 1,6-hexanediol, 2,2-dimethyl-1,3-propylene glycol or any combination thereof. In some embodiments, the diol for preparing polycaprolactone polyester polyol is linear. In some embodiments, polycaprolactone polyester polyol is made from 1,4-butanediol. In some embodiments, polycaprolactone polyester polyol has a number average molecular weight of 500 to 10,000, or 500 to 5,000, or 1,000 or even 2,000 to 4,000 or even 3000.

[0045] Suitable hydroxyl-terminated polyether intermediates include polyether polyols derived from diols or polyols having a total of 2 to 15 carbon atoms, in some embodiments, alkyl glycols reacted with ethers containing alkylene oxides (typically ethylene oxide or propylene oxide or mixtures thereof) having 2 to 6 carbon atoms. For example, hydroxyl-functional polyethers can be prepared by first reacting propylene glycol with propylene oxide and then reacting with ethylene oxide. The primary hydroxyl groups produced by ethylene oxide are more reactive than secondary hydroxyl groups and are therefore preferred. Available commercial polyether polyols include poly(ethylene glycol) containing ethylene oxide reacted with ethylene glycol, poly(propylene glycol) containing propylene oxide reacted with propylene glycol, poly(tetramethylene ether glycol) containing water reacted with tetrahydrofuran, which can also be described as polytetrahydrofuran and is commonly referred to as PTMEG. In some embodiments, the polyether intermediate includes PTMEG. Suitable polyether polyols also include polyamide adducts of alkylene oxides, and may include, for example, ethylenediamine adducts comprising the reaction product of ethylenediamine and propylene oxide, diethylenetriamine adducts comprising the reaction product of diethylenetriamine and propylene oxide, and similar polyamide type polyether polyols. Copolyethers may also be used in the composition. Typical copolyethers include the reaction products of THF and ethylene oxide or THF and propylene oxide. These may be block copolymers. B and random copolymer R is purchased from BASF. The various polyether intermediates generally have a number average molecular weight (Mn) determined by measuring the terminal functional groups, and the average molecular weight 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 includes a blend of two or more polyethers of different molecular weights, such as 2,000 M n and 1000M n Blends of PTMEG.

[0046] Suitable hydroxyl-terminated polycarbonates include those prepared by reacting diols with carbonates. U.S. Patent No. 4,131,731 is incorporated herein by reference for its disclosure of hydroxyl-terminated polycarbonates and their preparations. Such polycarbonates are linear and have terminal hydroxyl groups substantially free of other terminal groups. The basic reactants are diols and carbonates. Suitable diols are selected from alicyclic and aliphatic diols containing 4 to 40, and or even 4 to 12 carbon atoms, and polyoxyalkylene glycols containing 2 to 20 alkoxy groups and 2 to 4 carbon atoms per alkoxy group in each molecule. 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; and alicyclic diols, such as 1,3-cyclohexanediol, 1,4-dihydroxymethylcyclohexane, 1,4-cyclohexanediol-, 1,3-dihydroxymethylcyclohexane-, 1,4-endo-methylene-2-hydroxy-5-hydroxymethylcyclohexane and polyalkylene glycol. The diol used in the reaction can be a single diol or a diol mixture, depending on the desired properties in the finished product. Hydroxyl-terminated polycarbonate intermediates are generally those known in the art and literature. Suitable carbonates are selected from alkylene carbonates composed of 5 to 7 rings. Suitable carbonates used 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-pentenyl carbonate, 1,4-pentenyl carbonate, 2,3-pentenyl carbonate and 2,4-pentenyl carbonate. In addition, suitable herein are dialkyl carbonates, alicyclic carbonates and diaryl carbonates. Dialkyl carbonates can contain 2 to 5 carbon atoms in each alkyl group, and specific examples thereof are diethyl carbonate and dipropyl carbonate. Alicyclic carbonates, especially dialicyclic carbonates, can contain 4 to 7 carbon atoms in each ring structure, and can have 1 to 2 such structures. When one group is alicyclic, the other group can be an alkyl or an aryl. On the other hand, if one group is an aryl, the other can be an alkyl or an alicyclic. Examples of suitable diaryl carbonates are diphenyl carbonate, ditolyl carbonate and dinaphthyl carbonate, which may contain 6 to 20 carbon atoms in each aryl group. In particular, the hydroxyl terminated polycarbonate may be polyhexamethylene carbonate diol, polytetramethylene carbonate diol or a polycarbonate copolymer diol. More particularly, the hydroxyl terminated polycarbonate is polyhexamethylene carbonate diol.

[0047] Suitable polysiloxane polyols include α-ω-hydroxy or amine or carboxylic acid or thiol or epoxy terminated polysiloxanes. Examples include poly(dimethylsiloxane) terminated with hydroxyl or amine or carboxylic acid or thiol or epoxy groups. In some embodiments, the polysiloxane polyol is a hydroxyl terminated polysiloxane. In some embodiments, the polysiloxane polyol has a number average molecular weight in the range of 300 to 5,000 or 400 to 3,000.

[0048] The polysiloxane polyol can be obtained by a dehydrogenation reaction between polysiloxane hydride and an aliphatic polyol or polyoxyalkanol to introduce alcoholic hydroxyl groups into the main chain of the polysiloxane.

[0049] In some embodiments, the polysiloxane may be represented by one or more compounds having the formula:

[0050]

[0051] Among them: Each R 1 and R 2 is independently an alkyl group of 1 to 4 carbon atoms, a benzyl group or a phenyl group; each E is OH or NHR 3 , where R 3 is hydrogen, an alkyl group of 1 to 6 carbon atoms, or a cycloalkyl group of 5 to 8 carbon atoms; a and b are each independently an integer of 2 to 8; and p is an integer between 3 and 50. In the amino-containing polysiloxane, at least one E group is NHR 3 In the hydroxyl-containing polysiloxane, at least one E group is OH. In some embodiments, R 1 and R 2 Both are methyl groups.

[0052] Suitable examples include α,ω-hydroxypropyl terminated poly(dimethylsiloxane) and α,ω-aminopropyl terminated poly(dimethylsiloxane), both of which are commercially available materials. Further examples include copolymers of poly(dimethylsiloxane) materials with poly(alkylene oxides).

[0053] The polyol component, if present, can include poly(ethylene glycol), poly(tetramethylene ether glycol), poly(triethylene oxide), ethylene oxide-terminated poly(propylene glycol), poly(butylene adipate), poly(ethylene adipate), poly(hexylene adipate), poly(tetramethylene-co-hexylene adipate), poly(3-methyl-1,5-pentamethylene adipate), polycaprolactone diol, poly(hexylene carbonate) diol, poly(pentamethylene carbonate) diol, poly(trimethylene carbonate) diol, dimer fatty acid-based polyester polyol, vegetable oil-based polyol, or any combination thereof.

[0054] Examples of dimer fatty acids that can be used to prepare suitable polyester polyols include Priplast, commercially available from Croda. TM Polyester diols / polyols and commercially available from Oleon Polyester diol.

[0055] In some embodiments, the polyol component includes a polyether polyol, a polycarbonate polyol, a polycaprolactone polyol, or any combination thereof.

[0056] In some embodiments, the polyol component includes a polyether polyol. In some embodiments, the polyol component is substantially free of or even completely free of polyester polyols. In some embodiments, the polyol component used to prepare the TPU is substantially free of or even completely free of polysiloxanes.

[0057] 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), copolymers of poly(ethylene glycol) and poly(propylene glycol), epichlorohydrin, or the like, or combinations thereof. In some embodiments, the polyol component includes poly(tetramethylene ether glycol).

[0058] 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 up to 5,000, 4,000, 3,000, 2,500, or even 2,000.

[0059] In some embodiments, the polyol component includes a polycaprolactone polyester polyether polyol, a polyether polyol, a polycaprolactone polyester polyether copolymer polyol, a polyester polyol, or any combination thereof.

[0060] In some embodiments, the polyol component comprises a polycaprolactone polyester polyether polyol, a poly(tetramethylene ether glycol), a polycaprolactone polyester poly(tetramethylene ether glycol) copolymer polyol, polybutylene adipate, polybutylene adipate-hexanediol (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.

[0061] In one embodiment, the thermoplastic polyurethane reaction product is formed by a diol mixture having a first diol and a second diol. In one embodiment, the first diol is selected from one or more of polycarbonate diol, polycaprolactone diol, and 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.

[0062] In one embodiment, the second glycol in the glycol mixture is selected from one or more of perfluoropolyether, hydrogenated polybutadiene glycol, and poly(dimethylsiloxane). In one embodiment, the second glycol is a perfluoropolyether. In another embodiment, the second glycol is a hydrogenated polybutadiene glycol. In one embodiment, the second glycol is a poly(dimethylsiloxane).

[0063] 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).

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

[0065] In one embodiment, the thermoplastic polyurethane composition comprises the reaction product of diphenylmethane diisocyanate, a diol mixture comprising a polycarbonate polyol, and a hydrogenated polybutadiene diol.

[0066] In one embodiment, the thermoplastic polyurethane composition comprises the reaction product of diphenylmethane diisocyanate, a diol mixture comprising a polycarbonate polyol and a poly(dimethylsiloxane).

[0067] In one embodiment, the thermoplastic polyurethane composition comprises the reaction product of diphenylmethane diisocyanate, a diol mixture comprising a polycarbonate polyol, and a perfluoropolyether.

[0068] In one embodiment, the thermoplastic polyurethane composition comprises the reaction product of diphenylmethane diisocyanate, a diol mixture comprising a polycarbonate polyol, and a hydrogenated polybutadiene diol.

[0069] In some embodiments, the second polyol or diol in the diol mixture is at least 15% by weight of the diol mixture. In another embodiment, the second polyol or diol in the diol mixture is at least 18% by weight of the diol mixture. In another embodiment, the second polyol or diol in the diol mixture is at least 20% by weight of the diol mixture. In another embodiment, the second polyol or diol in the diol mixture is at least 22% by weight of the diol mixture.

[0070] The second polyol or diol mixture can comprise from 15 wt % to 50 wt % of the diol mixture, or from 18 wt % to 45 wt % of the diol mixture, or from 20 wt % to 40 wt % of the diol mixture, or from 22 wt % to 37 wt % of the diol mixture.

[0071] Chain extender components :

[0072] The TPU reaction product of the composition of the present disclosure is further formed by a chain extender. Suitable chain extenders include relatively small polyols, 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 (HEPP), hexamethylene glycol, heptanediol, nonanediol, dodecanediol, 3-methyl-1,5-pentanediol, ethylenediamine, butanediamine, hexamethylenediamine, and hydroxyethylresorcinol (HER), and the like, and mixtures thereof. In some embodiments, the chain extender includes BDO, HDO, 3-methyl-1,5-pentanediol, or a combination thereof. In some embodiments, the chain extender includes BDO. Other diols such as aromatic diols may also be used, but in some embodiments, the TPU as described herein is substantially free of or even completely free of such substances.

[0073] 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.

[0074] In some embodiments, the chain extender component includes 1,4-butanediol, 2-ethyl-1,3-hexanediol, 2,2,4-trimethylpentane-1,3-diol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, 1,3-propylene glycol, 3-methyl-1,5-pentanediol, or a combination thereof. In some embodiments, the chain extender component includes 1,4-butanediol, 3-methyl-1,5-pentanediol, or a combination thereof. In some embodiments, the chain extender component includes 1,4-butanediol.

[0075] In some embodiments, the chain extender component includes a linear alkane diol. In some embodiments, the chain extender component includes 1,4-butanediol, dipropylene glycol, or a combination of the two. In some embodiments, the chain extender component includes 1,4-butanediol. In some embodiments, the chain extender component may include an alkyl diol. Suitable alkyl diols include hydroquinone bis (β-hydroxyethyl) ether (HQEE), 1,4-benzenedimethanol, bisethoxybiphenol, bisphenol A ethoxylate, bisphenol F ethoxylate, and the like. Still other 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 may also be used.

[0076] In some embodiments, the chain extender is selected from one or more of 1,3-propylene glycol, hydroquinone bis(2-hydroxyethyl) ether, and 1,4-butanediol.

[0077] 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.

[0078] 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-propylene glycol.

[0079] 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 hydrogenated polybutadiene diol, and the chain extender is 1,4-butanediol.

[0080] 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.

[0081] In some embodiments, the molar ratio of chain extender to polyol is greater than 1.5. In other embodiments, the molar ratio of chain extender to polyol is at least (or greater than) 1.5, 2.0, 3.5, 3.7, or even 3.8, and / or the molar ratio of chain extender to polyol can be as high as 5.0 or even 4.0.

[0082] Thermoplastic polyurethane compositions of the present disclosure include hard blocks and soft blocks. The hard blocks are derived from the reaction of diisocyanate components and chain extender components. The soft blocks are derived from the reaction of diols and diisocyanates, and their characteristics depend on the type of diols. In one embodiment, based on the gross weight of the thermoplastic polyurethane reaction product, the hard block content of the thermoplastic polyurethane reaction product is at least 30 wt %. In another embodiment, based on the gross weight of the thermoplastic polyurethane reaction product, the hard block content of the thermoplastic polyurethane reaction product is at least 32 wt %. In one embodiment, based on the gross weight of the thermoplastic polyurethane reaction product, the hard block content of the thermoplastic polyurethane reaction product is at least 33 wt %.

[0083] In one embodiment, the thermoplastic polyurethane composition comprises the reaction product of diphenylmethane diisocyanate, a diol mixture comprising a polycarbonate polyol and a perfluoropolyether, and a hydroquinone bis(2-hydroxyethyl) ether chain extender, wherein the reaction product has a hardblock content of at least 33 wt%.

[0084] In another embodiment, the thermoplastic polyurethane composition comprises the reaction product of diphenylmethane diisocyanate, a diol mixture comprising a polycarbonate polyol and a hydrogenated polybutadiene diol, and a 1,3-propylene glycol chain extender, wherein the reaction product has a hardblock content of at least 40 weight percent.

[0085] In another embodiment, the thermoplastic polyurethane composition comprises the reaction product of diphenylmethane diisocyanate, a diol mixture comprising a polycarbonate polyol and a poly(dimethylsiloxane), and a hydroquinone bis(2-hydroxyethyl) ether chain extender, and wherein the composition has a hardblock content of at least 33 weight percent.

[0086] In another embodiment, a thermoplastic polyurethane composition comprises the reaction product of diphenylmethane diisocyanate, a diol mixture comprising a polycarbonate polyol and a hydrogenated polybutadiene diol, and a 1,4-butanediol chain extender, and wherein the composition has a hardblock content of at least 43 weight percent.

[0087] In another embodiment, the thermoplastic polyurethane composition comprises the reaction product of diphenylmethane diisocyanate, a diol mixture comprising a polycarbonate polyol and a hydrogenated polybutadiene diol, and a hydroquinone bis(2-hydroxyethyl) ether chain extender, and wherein the composition has a hardblock content of at least 35 weight percent.

[0088] 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; c) the above chain extender component, wherein the reaction can be carried out in the presence of a catalyst. The reaction can be carried out in a batch or continuous process.

[0089] The process for producing the TPU polymers of the present invention can utilize conventional and hereinafter developed TPU manufacturing equipment and known or hereinafter developed processes. The TPU can be produced in a so-called one-shot, semi-prepolymer or prepolymer process by casting, extrusion or any other method known to those skilled in the art. In one embodiment, the process is a so-called "one-shot" process, in which all three reactants are added to an extruder reactor and reacted.

[0090] Other additives :

[0091] In addition to the TPU reaction product, the thermoplastic polyurethane compositions disclosed herein may also include other optional components.

[0092] Optional additive components may be present during the reaction and / or incorporated into the above-described TPU reaction product to improve processing and other properties. These additives include, but are not limited to, antioxidants, organic phosphites, phosphines and phosphites, hindered amines, organic amines, organic sulfur compounds, lactone and hydroxylamine compounds, biocides, fungicides, antimicrobial agents, compatibilizers, electrically dissipative or antistatic additives, fillers and reinforcing agents (such as titanium dioxide, aluminum oxide, clay and carbon black), flame retardants (such as phosphates, halogenated materials and metal salts of alkylbenzene sulfonic acids), impact modifiers (such as methacrylate-butadiene-styrene ("MBS") and methyl methacrylate butyl acrylate ("MBA")), mold release agents (such as waxes, greases), pigments and colorants, plasticizers, polymers, rheology modifiers (such as monoamines, polyamide waxes, silicones and polysiloxanes), slip additives (such as paraffin waxes, hydrocarbon polyolefins and / or fluorinated polyolefins), and UV stabilizers (which may be hindered amine light stabilizers (HALS) and / or UV light absorbers (UVA) types). Other additives may also be used to enhance the properties of the TPU composition or blended product. All the above-mentioned additives may be used in effective amounts commonly used for these substances.

[0093] These additional additives can be incorporated into the components for preparing the TPU reaction product or into the reaction mixture for preparing the TPU reaction product, or into the TPU composition after the TPU reaction product is prepared. In another method, all materials can be mixed with the TPU reaction product and then melted, or they can be directly incorporated into the melt of the TPU reaction product.

[0094] It is generally preferred to incorporate one or more antioxidants into the TPU reaction product and / or TPU composition described above. These can 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 phenols, organic phosphites, phosphines and phosphites, hindered amines, organic amines, organic sulfur compounds, lactones and hydroxylamine compounds. For applications where transparency is required, the antioxidant is preferably soluble in the TPU reaction product described above, or dispersed therein as very fine droplets or particles. Many suitable antioxidant materials are commercially available. These include Irganox TM 1010, Irganox TM MD1024, Irgaphos TM 168. Irgaphos TM 126 (all available from BASF Specialty Chemicals), etc. Antioxidants can be used in conventional amounts, such as 0.1 wt % to 3 wt %, or 0.2 wt % to 2 wt %, or 0.3 wt % to 1.1 wt %, in the TPU composition.

[0095] The TPU compositions of the present disclosure may also include from 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 include from about 1% to about 6% by weight of an antimicrobial and / or biocide material, from about 2% to about 4% by weight of an antimicrobial and / or biocide material, and many percentages therebetween. In the context of the present formulation, the terms "antimicrobial" and / or "biocide" are intended to include, but are not limited to, fungicides, herbicides, insecticides, antimicrobials, including all forms of carbonates, silicates, sulfates and halides and borates of sodium, potassium, calcium, zinc, copper and barium; zinc carboxylates; boric acid; sodium dichromate; copper chromium arsenate (CCA); copper chromate borate (CBC); ammoniacal copper arsenate (ACA); ammoniacal copper zinc arsenate (ACZA); copper chromium fluoride (CFK); copper chromium fluoroborate (CCFB); copper Chromium phosphate (CCP); propiconazole tebuconazole; organic chlorides such as pentachlorophenol (PCP); quaternary ammonium compounds (MC); 8-hydroxyquinoline copper or potassium persulfate copper; tri-n-butyltin oxide (TBTO); tri-n-butyltin naphthenate (TBTN); didecyldimethylammonium bromide (DDAB); didecyldimethylammonium chloride (DDAC); silver ions, mercuric ions, carbamates, isothiazolinones, chlorinated phenoxy and polyhexamethylene biguanide hydrochloride, barium metaborate monohydrate, borates and mixtures thereof. Preferred compositions of the present invention are water-insoluble and contain inorganic biocides.

[0096] The TPU compositions disclosed herein may also include a compatibilizer. Useful compatibilizers include maleated thermoplastics, thermoplastic elastomeric block copolymers, crystallizable copolymers of propylene and ethylene or other higher alpha-olefins, chlorinated thermoplastics, ionomers, maleated elastomeric copolymers, and mixtures thereof.

[0097] Suitable compatibilizers may also include modified polyolefins, including modified thermoplastics and modified rubbers. In one or more embodiments, these modified polyolefins include at least one functional group connected thereto. In one or more embodiments, these functional groups may include carboxylic acids; C1-C8 carboxylates such as methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, butoxycarbonyl, pentyloxycarbonyl, hexyloxycarbonyl, heptyloxycarbonyl, octyloxycarbonyl and isomeric forms thereof; carboxylic anhydride; carboxylates formed by neutralizing carboxylic acid groups with metal ions of groups I, II, III, IV-A and VII of the periodic table, exemplarily including sodium ions, potassium ions, lithium ions, magnesium ions, calcium ions, iron ions, nickel ions, zinc ions and aluminum ions and mixtures thereof; amides; epoxy resins; hydroxyl groups; amino groups; and C2-C6 acyloxy groups, such as acetoxy, propionyloxy or butyryloxy groups. In one or more embodiments, these functional groups may be part of unsaturated monomer precursors that may be copolymerized with olefin monomers or grafted onto polyolefins to form modified polyolefins.

[0098] Functional 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 derived from the polymerization of α-olefins and α,β-ethylenically unsaturated carboxylic acids.

[0099] Suitable modified polyolefins include those disclosed in US Pat. Nos. 6,001,484, 6,072,003, 3,264,272, and 3,939,242, which are incorporated herein by reference.

[0100] In one or more embodiments, the mer units of the polyolefin containing functional groups may be present in the polyolefin in an amount of about 0.05 mol % to about 5 mol %. For example, in the case of maleated polyethylene, about 0.005 mol % to about 5 mol % of the mer units contain maleic acid residues pendant to the backbone.

[0101] In one or more embodiments, useful modified polyolefins are available under the trade name OPTEMA TM TC120 and TC220 (ExxonMobil), which are copolymers of ethyl methacrylate, and POLYBONDTM (Chemtura) or FUSABOND TM (DuPont), which are maleated polypropylenes.

[0102] Maleated elastomeric copolymers include copolymers of ethylene, α-olefins and one or more dienes, wherein the copolymers are reacted with maleic anhydride to provide further functionality. These copolymers are available under the trade name EXXELOR TM (ExxonMobil) The compatibilizers as disclosed herein may be used in the TPU composition in conventional amounts such as 0.1 wt % to 50 wt %, or 0.3 wt % to 30 wt %, or 0.5 wt % to 20 wt %.

[0103] The TPU compositions disclosed herein may also include an antistatic agent. Many antistatic agents are known in the art. Sometimes, the antistatic agent is applied to the surface of a polymer article made of the TPU composition by spraying or dipping.

[0104] Low molecular weight antistatic agents are sometimes blended with the above TPU compositions rather than coated on the surface. Such low molecular weight antistatic agents include: ethoxylated fatty amines, esters or amides, such as those 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 alkyl sulfonates, sulfates, 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.

[0105] The low molecular weight antistatic agent blended into the above-mentioned TPU composition is generally an organic compound comprising a hydrophobic component and a hydrophilic component. The hydrophobic component generally provides compatibility with the polymer, thereby connecting the two materials together. The hydrophilic component generally absorbs moisture and evenly distributes the water on the surface of a particular polymer. This water film formed on the surface increases the surface conductivity through an ion conduction process, thereby increasing the electrostatic charge dissipation rate. Therefore, conventional low molecular weight internal antistatic agents generally do not improve the volume conductivity of the polymer, and are generally sensitive to atmospheric humidity, generally providing poor performance at low humidity.

[0106] Internal low molecular weight antistatic agents are generally designed to migrate from the interior of the above-mentioned TPU composition to the surface during or after molding. Gradual surface migration can be advantageous because it can replace any antistatic agent at the surface lost due to evaporation, cleaning or wear. However, migration must occur at an appropriate rate. If it is too fast, migration can cause frosting, surface smearing and molding difficulties; if it is too slow, the antistatic properties will be unstable because any lost antistatic agent cannot be replaced in time. Slow migration is a common problem in polymers with high crystallinity such as polypropylene, and migration after molding may take up to about a month to achieve maximum antistatic performance.

[0107] Additional representative antistatic agents that may be included in the mixture include quaternary ammonium compounds such as those disclosed in U.S. Pat. No. 5,933,693, including but not limited to quaternary ammonium salts of alkyl sulfates and carboxylates; metal salts of lithium, sodium, potassium, ammonium, calcium and barium; complexes of metal salts with polyols and their derivatives such as 1,4-butanediol, ethylene glycol, propylene glycol and polyethylene glycol, and complexes of metal salts with monohydric alcohols such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; hexahalogenated ion compounds such as those disclosed in U.S. Pat. No. 5,677,357, including hexahalophosphate compounds such as potassium hexafluorophosphate, sodium hexafluorophosphate and ammonium hexafluorophosphate.

[0108] Metal salt antistatic additives may be used in the composition, such as metal salts carried by diglyme (2-methoxyethyl ether) and triols, polyethers or butanediols.

[0109] Some antistatic agents (such as quaternary ammonium salts) cannot withstand the processing temperatures required in the conventional manufacturing or molding steps of some polymers. In addition, conventional low molecular weight antistatic agents tend to lose their antistatic effect due to evaporation, or they cause undesirable odors or promote cracking or crazing.

[0110] The TPU compositions disclosed herein may also include fillers or reinforcing agents. Fillers include a wide range of particulate materials, including talc, marble, granite, carbon black, graphite, aramid, silica-alumina, zirconium oxide, bentonite, antimony trioxide, coal-based fly ash, clay, feldspar, nepheline, pyrogenic silica, aluminum oxide, magnesium oxide, zinc oxide, barium sulfate, aluminum silicate, calcium silicate, titanium dioxide, titanate, chalk, ground glass, silicon dioxide or glass, glass microspheres, glass beads or glass fibers. The glass fiber used can be made of E, A or C glass, and preferably has a sizing agent and a coupling agent. Its diameter is typically 6 μm to 20 μm. Continuous filament fibers (rovings) or chopped glass fibers (short fibers) with a length of 1 mm to 10 mm, preferably 3 mm to 6 mm, can be used.

[0111] The filler may also be a metal hydroxide, such as magnesium hydroxide, potassium hydroxide, and aluminum hydroxide; a metal carbonate, such as magnesium carbonate and calcium carbonate; a metal sulfide and sulfate, such as molybdenum disulfide and barium sulfate; a metal borate, such as barium borate, barium metaborate, zinc borate, zinc metaborate; a metal anhydride, such as aluminum anhydride; or aluminum trihydrate.

[0112] Boron nitride and various recycled and regrinded thermoset polyurethane and / or polyurea polymers may also be used.

[0113] Representative fillers include, but are not limited to, clays such as diatomaceous earth, kaolin, and montmorillonite; calcite; diatomaceous earth; asbestos; ground minerals; and lithopone. These fillers are typically used in conventional manners and in conventional amounts, e.g., 5 wt % or less to 50 wt % or more, based on the weight of the composition.

[0114] Reinforcement materials include high aspect ratio materials such as flakes and fibers, which can be flakes and fibers of glass, aramid, various other polymers, etc. Additional materials that can be used include mineral fibers, whiskers, alumina fibers, mica, powdered quartz, metal fibers, carbon fibers, and wollastonite. Reinforcers are typically used in an amount of 5 to 50 weight percent based on the entire layer or composition.

[0115] Fillers useful in some formulations include flame resistant fillers which may include antimony oxide, decabromobiphenyl oxide, alumina trihydrate, magnesium hydroxide, borates, and halogenated compounds.

[0116] 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 for shielding electromagnetic waves can be added. Aluminum flakes (K-102 from Transmet) are particularly suitable for EMI (electromagnetic interference) purposes. The composition can also be mixed with additional carbon fibers, carbon black, especially conductive carbon black, or nickel-coated carbon fibers.

[0117] Other miscellaneous fillers include wood fiber / flour / chips, rubber powder, cotton, starch, clay, synthetic fibers (eg, polyolefin fibers), and carbon fibers.

[0118] The content of filler depends on the filler density; the higher the filler density, the more filler can be added to the formulation without significantly affecting the volume fraction of the filler. Therefore, the content of filler is discussed herein as a percentage of filler weight based on the total formulation weight. In the formulations disclosed herein, the filler content is in the range of about 0.1% to about 80%, preferably about 5% to about 50% (except carbon black, which is generally used in an amount of about 0.1% to about 5%), more preferably about 5% to about 40%, especially about 8% to about 30%.

[0119] The TPU composition disclosed herein may also include a flame retardant. The flame retardant may be, but is not necessarily, an intumescent material. Examples include phenyl didodecyl 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-ethylhexyl) p-tolyl phosphate, tricresyl phosphate, bis(2-ethylhexyl)-phenyl phosphate, tri(nonylphenyl) phosphate, phenyl methyl hydrogen phosphate, didodecyl p-tolyl phosphate, tricresyl phosphate, triphenyl phosphate, dibutylphenyl phosphate, p-tolyl bis(2,5,5'-trimethylhexyl) phosphate, 2-ethylhexyl diphenyl phosphate and diphenyl hydrogen phosphate. Preferred flame retardants are bisphenol-A bis(diphenyl phosphate), resorcinol bis(diphenyl phosphate) and cresol bis(diphenyl phosphate).

[0120] Other examples of flame retardants include brominated organic compounds, such as brominated diols. They may contain 5 to 20 carbon atoms, and in some embodiments, 5 to 10 or even 5 carbon atoms, and may contain quaternary carbon atoms. The additive may be present in an amount sufficient to provide the desired flame retardancy, and in other embodiments, may be present in 0% to 15% by weight of the overall composition, or even in 0% to 10%, 0.1% to 7%, or 0.2% to 5% by weight of the overall composition.

[0121] Other examples include brominated organic compounds. Suitable examples include brominated diols, brominated monohydric 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 glycol, tri(tribromoneopentyl)phosphate, and 4,4'-isopropylidenebis[2-(2,6-dibromophenoxy)ethanol].

[0122] In some embodiments, the flame retardant additive includes a metal salt of a halogen borate, a metal salt of a halogen phosphate, or a combination thereof. In some embodiments, a combination of flame retardants is used. Additional examples of flame retardant additives include metal salts of organic sulfonates, such as sodium salts of alkylbenzene sulfonates, and in some embodiments, flame retardant additives include nitrogen-containing compounds. Flame retardants can be added to TPU compositions in conventional amounts. In certain embodiments, the flame retardant may be present in the TPU composition in an amount of 0% to 30% by weight based on the total weight of the TPU composition. In certain embodiments, the flame retardant may be present in the TPU composition in an amount of 0.1% to 20% by weight based on the total weight of the TPU composition. In certain embodiments, the flame retardant may be present in the TPU composition in an amount of 0.5% to 15% by weight based on the total weight of the TPU composition.

[0123] Industrial Applicability :

[0124] In many applications, it is desirable or even critical that the TPU used to make the article exhibit good heat resistance. For example, it is often important for wires and cables and seals or gaskets used in industrial applications to have these desired properties.

[0125] The TPU reaction products of the present disclosure impart high temperature stability, sometimes referred to as heat resistance, to the TPU compositions of the present invention over currently known TPU compositions. Within the scope of the present disclosure, the term "high temperature stability" relates to the ability of the product to resist high temperatures. Therefore, it may also be referred to as "heat resistance."

[0126] Based on the detailed examples, one skilled in the art can routinely repeat the measurements to objectively determine whether the TPU composition exhibits high temperature stability.

[0127] For example, to measure high temperature stability, the TPU composition can be compression molded into a rectangular plate 1.9 mm to 2.0 mm thick and 1.0 cm wide and 13.0 cm to 15.0 cm long. The plate is placed on a rod and aged at a temperature of 200°C for 6 hours. The aging conditions are the conditions specified in ISO6722. After cooling, the elongation percentage of the plate is measured. High temperature stability can be measured as an elongation percentage of less than 20%. For example, when heated at 200°C for 6 hours, when the elongation percentage is less than 20%, the TPU composition is considered to exhibit high temperature stability. The elongation percentage can be measured by determining the change in length according to the following formula:

[0128]

[0129] In some embodiments, the percent elongation is less than 18%, or less than 18%, or less than 6%, or less than 3%.

[0130] The tensile strength retention and ultimate elongation retention of the TPU can be further evaluated. The TPU composition can be prepared and aged according to the aging conditions listed above, i.e., aging at 200°C for 6 hours. Thereafter, the tensile strength retention and ultimate elongation retention are measured according to ASTM D412. In one embodiment, both the tensile strength retention and ultimate elongation retention are greater than 60%. In another embodiment, both the tensile strength retention and ultimate elongation retention are greater than 65%.

[0131] In another aspect, the TPU composition can be prepared as above and aged at 180° C. for 168 hours. In such an embodiment, both the tensile strength retention and the ultimate elongation retention are greater than 65%.

[0132] The compositions of the present invention are particularly useful for forming articles such as coatings for wire and cable and seals or gaskets.

[0133] 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 compositions, in particular the high heat resistance of the TPU compositions described herein, cables or wires coated with the TPU compositions of the present invention can be used in mining and power generation, which can be offshore, solar-based, wind turbine or hydroelectric. In other embodiments, cables or wires coated with the TPU compositions can be used in constructions where they are used for security, data, terminal, communication and signal wiring. In other embodiments, cables or wires coated with the TPU compositions can be used in automotive, train, subway, ship and aviation industries.

[0134] In some embodiments, the TPU compositions of the present disclosure can be used to make seals and gaskets. Seals and gaskets can be used in internal combustion engines, heavy equipment, appliances, and countless other applications that also require heat resistance.

[0135] Articles containing the various TPU compositions described above include any article that will be exposed to elevated temperatures during its use, particularly such articles that have not been prepared in the past using thermoplastic polyurethanes because such materials have had insufficient high temperature resistance or performance.

[0136] Example :

[0137] Different TPU samples were prepared according to the formulations shown in Table 1.

[0138] Table 1A: Formulation information of selected TPU samples

[0139]

[0140] Table 1B: Formulation information of selected TPU samples

[0141]

[0142]

[0143] The polycarbonate is polyhexamethylene carbonate diol.

[0144] The samples were compression molded into 1.9 mm to 2.0 mm thick plates. The plates were then cut into rectangular strips of about 1.0 cm wide and 13.0 cm to 15.0 cm long. The rectangular strips were placed on a rod in a 200°C oven for 6 hours with the middle portion in contact with the rod so that most of the sample was free to extend. This aging condition is one of the conditions specified in ISO6722.

[0145] High temperature stability is determined by measuring the change in length of a rectangular sample after exposure to 200°C for 6 hours and calculated according to the following formula:

[0146]

[0147] The results are shown in Table 2. After exposure to high temperature, Example 1 dripped and broke, while the other examples according to the TPU compositions disclosed herein showed much better dimensional stability, maintaining the initial shape much better than the benchmark.

[0148] Table 2: Length changes of samples after exposure to 200°C for 6 hours

[0149]

[0150] The polycarbonate is polyhexamethylene carbonate diol.

[0151] Examples 1 and 8 were also aged at 200°C for 6 hours as specified in ISO 6722, and the tensile strength retention and ultimate elongation retention were determined according to ASTM D412 and are shown in Table 4. For the 200°C / 6 hour condition, Example 8 showed greater than 60% retention of tensile strength and ultimate elongation, while Example 1 melted.

[0152] Table 4: Tensile strength and ultimate elongation retention of Examples 8 and 1

[0153]

[0154] Example 8 was additionally aged at 180° C. for 168 hours as specified in UL 1581. The tensile property retention is shown in Table 5. Compared to Comparative Example 1, Example 8 showed higher retention of tensile strength and ultimate elongation.

[0155] Table 5: Tensile property retention rate of Example 8 of the present invention at 180°C for 168 hours

[0156]

[0157] Unless otherwise specified herein, references to treat rates or amounts of components present in the lubricating compositions disclosed herein are on an oil-free basis, i.e., the amount of active matter. Additionally, unless otherwise specified, "weight %" as used herein shall refer to weight percent based on the total weight of the composition on an oil-free basis.

[0158] The present disclosure is not limited to the specific embodiments described in this application, and these embodiments are intended to illustrate various aspects. Without departing from the spirit and scope of the present invention, many modifications and changes can be made, which will be apparent to those skilled in the art. In addition to those listed herein, according to the foregoing description, functionally equivalent methods and components within the scope of the present disclosure will be apparent to those skilled in the art. Such modifications and changes are intended to fall within the scope of the appended claims. The present disclosure is only limited by the terms of the appended claims and the full range of equivalents given by such claims. It should be understood that the present disclosure is not limited to specific methods, reagents, compounds or compositions, which can certainly vary. It should also be understood that the terms used herein are only used for the purpose of describing specific embodiments and are not intended to be limited.

[0159] Although various compositions, methods, and apparatus are described as "comprising" various components or steps (interpreted to mean "including, but not limited to"), the compositions, methods, and apparatus may also "consist essentially of" or "consist of" the various components and steps, and such terms should be interpreted as limiting a substantially closed group of members.

[0160] With respect to the use of substantially any plural and / or singular terms herein, those skilled in the art may translate from the plural to the singular and / or from the singular to the plural as appropriate, depending on the context and / or application. For clarity, various singular / plural arrangements may be expressly set forth herein.

[0161] It will be understood by those skilled in the art that, in general, the terms used herein and in particular in the appended claims (e.g., the bodies of the appended claims) are generally intended to be "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 "comprising" should be interpreted as "comprising, but not limited to", etc.). It will be further understood by those skilled in the art that if a specific number of an introduced claim recitation is intended, such an intent will be explicitly stated in the claim, and in the absence of such a statement, such an intent is absent. For example, to aid understanding, the following appended claims may contain the use of the introductory phrases "at least one" and "one or more" to introduce claim recitations. However, the use of such phrases should not be interpreted as implying that the introduction of a claim recitation by the indefinite article "a", "an" will limit any particular claim containing such introduced claim recitation to an embodiment containing only one such recitation, even when the same claim includes the introductory phrases "one or more" or "at least one" and an indefinite article such as "a", "an" (e.g., "a", "an" should be interpreted as meaning "at least one" or "one or more"); the same is true for the use of definite articles used to introduce claim recitations. In addition, even if a specific number of introduced claim expressions is explicitly stated, those skilled in the art will recognize that such expressions should be interpreted as meaning at least the stated number (e.g., the unmodified expression "two expressions," without other modifiers, means at least two expressions or two or more expressions). In addition, in those cases where a convention similar to "at least one of A, B, and C, etc." is used, generally speaking, such a structure is intended to have the meaning that a person skilled in the art will understand the convention (e.g., "a system having at least one of A, B, and C" will include, but is not limited to, systems having only A, only B, only C, A and B, A and C, B and C, and / or A, B, and C, etc.). In those cases where a convention similar to "at least one of A, B, or C, etc." is used, generally speaking, such a structure is intended to have the meaning that a person skilled in the art will understand the convention (e.g., "a system having at least one of A, B, or C" will include, but is not limited to, systems having only A, only B, only C, A and B, A and C, B and C, and / or A, B, and C, etc.). Those skilled in the art will further understand that, whether in the specification, claims or drawings, in fact, any disjunctive word and / or phrase presenting two or more alternative terms should be understood to contemplate the possibility of including one of the terms, any of the terms, or both of the terms. For example, the phrase "A or B" will be understood to include the possibility of "A" or "B" or "A and B".

[0162] 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 thereby described in terms of any individual member or subgroup of members of the Markush group.

[0163] As will be understood by those 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 sub-ranges and combinations of sub-ranges thereof.Any listed range can be easily considered to fully describe and enable the same range to be decomposed into at least equal half, one-third, one-quarter, one-fifth, one-tenth, etc. As a non-limiting example, each range discussed herein can be easily decomposed into lower third, middle third, and upper third, etc. As will be understood by those skilled in the art, all languages ​​(such as "at most", "at least", etc.) include the numbers stated, and refer to the ranges that can be subsequently decomposed into sub-ranges as described above. Finally, as will be understood by those skilled in the art, ranges include each individual member.Therefore, for example, a group with 1% to 3% by weight refers to a group with 1%, 2%, or 3% by weight. Similarly, a group with 1% to 5% by weight refers to a group with 1%, 2%, 3%, 4%, or 5% by weight, etc., including all points therebetween.

[0164] Furthermore, when a stated range is provided for a treat rate, it is contemplated that the range shall include treat rates for individual components and / or mixtures of components. Thus, for example, a range of 1 wt % to 3 wt % contemplates that a given component may be present in the range of 1 wt % to 3 wt % or that a mixture of similar components may be present in the range of 1 wt % to 3 wt %.

[0165] Although the present invention has been explained with respect to its preferred embodiment, it should be understood that various modifications thereof will become apparent to those skilled in the art upon reading this specification. Therefore, it should be understood that the invention disclosed herein is intended to cover these modifications falling within the scope of the appended claims.

Claims

1. A thermoplastic polyurethane composition (TPU), comprising: The following reaction products: Aromatic polyisocyanates; A diol mixture, the diol mixture comprising: a first diol, the first diol being selected from one or more of polycarbonate polyol, polycaprolactone diol and poly(tetrahydrofuran), and a second glycol selected from one or more of a perfluoropolyether, a hydrogenated polybutadiene glycol, and a poly(dimethylsiloxane), wherein the second glycol is present in the glycol mixture in an amount of at least 15% by weight of the glycol mixture; and Chain extenders; The reaction product has a hardblock content of at least 30 weight percent.

2. The composition of claim 1, wherein the aromatic polyisocyanate is diphenylmethane diisocyanate.

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

4. The composition of any one of the preceding claims, wherein the content of the second diol in the diol mixture is at least 18% by weight of the diol mixture.

5. The composition of any one of the preceding claims, wherein the content of the second diol in the diol mixture is at least 20% by weight of the diol mixture.

6. The composition of any one of the preceding claims, wherein the content of the second diol in the diol mixture is at least 22% by weight of the diol mixture.

7. The composition of any one of the preceding claims, wherein the hardblock content is at least 30 wt% of the reaction product.

8. The composition of any one of the preceding claims, wherein the hardblock content is at least 32% by weight of the reaction product.

9. The composition of any one of the preceding claims, wherein the hardblock content is at least 33 wt% of the reaction product.

10. The composition of any one of claims 1 to 6, wherein the aromatic polyisocyanate is diphenylmethane diisocyanate, the first diol is a polycarbonate polyol, the second diol is a perfluoropolyether, and the chain extender is hydroquinone bis(2-hydroxyethyl) ether, and wherein the composition has a hard block content of at least 33 wt%.

11. The composition of any one of claims 1 to 6, wherein the aromatic polyisocyanate is diphenylmethane diisocyanate, the first diol is a polycarbonate polyol, the second diol is a hydrogenated polybutadiene diol, and the chain extender is 1,3-propylene glycol, and wherein the composition has a hard block content of at least 40 wt%.

12. The composition of any one of claims 1 to 6, wherein the aromatic polyisocyanate is diphenylmethane diisocyanate, the first diol is a polycarbonate polyol, the second diol is poly(dimethylsiloxane), and the chain extender is hydroquinone bis(2-hydroxyethyl) ether, and wherein the composition has a hard block content of at least 33 wt%.

13. The composition of any one of claims 1 to 6, wherein the aromatic polyisocyanate is diphenylmethane diisocyanate, the first diol is a polycarbonate polyol, the second diol is a hydrogenated polybutadiene diol, and the chain extender is 1,4-butanediol, and wherein the composition has a hard block content of at least 43 wt%.

14. The composition of any one of the preceding claims, wherein the TPU composition has high temperature stability as measured by a percent elongation of less than 20% after heating at 200°C for 6 hours.

15. The composition of any one of the preceding claims, wherein the TPU composition has high temperature stability as measured by a percent elongation of less than 18% after heating at 200°C for 6 hours.

16. The composition of any one of the preceding claims, wherein the TPU composition has high temperature stability as measured by a percent elongation of less than 6% after heating at 200°C for 6 hours.

17. The composition of any one of claims 14 to 16, wherein the percent elongation is measured by: providing a TPU composition molded into a rectangular plate 1.9 mm to 2.0 mm thick, about 1.0 cm wide and 13.0 cm to 15.0 cm long; placing the plate on a rod; aging the plate at a temperature of 200° C. for 6 hours; allowing the plate to cool; and determining the change in length.

18. The composition of any one of the preceding claims, wherein the TPU has a 60% retention of tensile strength and a 60% retention of ultimate elongation after 6 hours at 200°C as determined by ASTM D412.

19. A cable or wire coated with a TPU composition according to any one of the preceding claims.

20. A seal or gasket formed from the TPU composition of any one of claims 1 to 18.

21. Use of a TPU composition according to any one of claims 1 to 18 for increasing the high temperature stability of a coated cable or wire, seal or gasket.

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