Novel polyurethane or polyurethaneurea compositions with improved low temperature performance

Abstract

The present application discloses a polyurethane or polyurethaneurea composition with improved low-temperature performance, comprising the reaction product of at least one diisocyanate of the ABA type having a number-average molecular weight of 2500 to 5000 g / mol and at least one block copolymer, the reaction product being formed in the absence of a plasticizer by reacting the reactants in an NCO:OH molar ratio of 0.9:1 to 2:1. The block copolymer is the reaction product of (i) a poly(tetrahydrofuran)diol (the tetrahydrofuran is optionally substituted) in an amount of 40 to 70 weight percent of the total block copolymer molecular weight, and (ii) a cyclic lactone and / or a cyclic ether in an amount of 30 to 60 weight percent of the total block copolymer molecular weight. The present disclosure further discloses a reaction further comprising a diol or diamine chain extender and a composition comprising the polyurethane or polyurethaneurea composition of the present disclosure.

Description

[Technical Field]

[0001] (CROSS-REFERENCE TO RELATED APPLICATIONS) This application claims priority to and the benefit of U.S. Provisional Patent Application No. 63 / 378,055, filed October 1, 2022, the entire contents of which are incorporated herein by reference for all purposes.

[0002] The present disclosure describes novel polyurethane or polyurethaneurea compositions with improved low temperature performance and methods for making same, as well as compositions containing same and methods for using same. [Background technology]

[0003] Polyurethane (PU) elastomers are versatile materials capable of achieving a wide range of mechanical and physical properties. Polyurethane elastomers are known for their viscoelasticity, toughness, and durability under a wide range of environmental conditions. The boundaries of what can be achieved with such materials are constantly being pushed, and their modular nature allows for the manipulation of their chemical structure to achieve desired performance. Maintaining performance at low-temperature extremes is one goal that can be addressed using this technology, resulting in alternatives that are mechanically superior and easier to process compared to silicone elastomers and ethylene propylene diene monomer (EPDM). Improving the low-temperature limit of PU materials while maintaining high-temperature performance—that is, extending a product's usable temperature range—offers a wide range of commercial opportunities, including transportation, aerospace, footwear, manufacturing, construction, and medical markets. The ability to operate at both low and high temperatures is valuable in many end uses, including industrial wheels and rollers, automotive bushings, mechanical seals, and snow sports and other outdoor footwear.

[0004] The low-temperature performance of polyurethane materials is typically evaluated using thermal analysis techniques such as differential scanning calorimetry (DSC) and thermomechanical or dynamic mechanical analysis (DMA). The glass transition temperature (Tg) of a material is often used as an important indicator of low-temperature performance, but not the only indicator. A useful definition of the glass transition temperature of a polymer is the temperature at or above which the molecular structure exhibits macromolecular mobility. For segmented polymers such as polyurethanes, this is the point at which the material transitions from a glassy thermoplastic to a flexible, rubbery state expected of an elastomer. The glass transition can be experimentally determined using either DSC or DMA techniques. With DSC, the glass transition is observed as a step in the baseline of the measurement curve as the material is heated at a constant rate, corresponding to the change in heat capacity of the material as it transitions from a glassy material to one with molecular motion. With DMA, the glass transition is often defined as the maximum value of tan δ.

[0005] Above their glass transition temperature, polyurethane materials exhibit viscoelastic behavior due to their unique segmented, semi-crystalline structure. This means that when a load is applied and then removed, they can store energy, which is returned as an elastic response, or lose the energy as heat. Tan δ, the ratio of the loss modulus to the storage modulus in a DMA experiment, indicates how easily elastic energy is stored or lost during a deformation-relaxation cycle. This represents the material's damping capacity. For this reason, tan δ is also known as the damping coefficient. High-performance elastomers should have a tan δ well below 0.1 above the material's glass transition temperature. To ensure consistent performance at low temperatures, it is desirable for tan δ to be less than 0.1 and stable down to the lowest possible temperature. The minimum use temperature is considered the temperature at which tan δ exceeds 0.1.

[0006] Polycaprolactone is a unique class of polyester polyol used in the production of polyurethane elastomers. Polyurethanes based on polycaprolactone are characterized by best-in-class mechanical properties, excellent durability under harsh environmental conditions, and ease of processing compared to many competing materials. This makes polycaprolactone a popular choice for highly demanding applications, such as industrial seals, gaskets, wheels and rollers, paint protection films, and automotive suspension systems, where the product is exposed to high temperatures, humid environments, UV light, and repeated mechanical deformation. However, like most polyester polyol-based technologies, its performance is limited by its low-temperature limit. This significantly limits its use in industrial applications that require consistent performance at both extremely low and high temperatures.

[0007] Other chemical technologies can be employed to provide low-temperature performance benefits. Poly(tetramethylene ether) glycol (PTMEG) is a popular alternative to polyester polyols such as polycaprolactone when low-temperature performance is important. The glass transition temperature of polyurethane articles made with PTMEG can be reduced by up to 25°C compared to those made with polyester polyols. However, such polyurethanes are known to have lower mechanical strength, poorer high-temperature performance, and are susceptible to degradation by ultraviolet (UV) light. The PTMEG market has also been unstable in recent years, with polyurethane producers experiencing supply shortages and price fluctuations.

[0008] Polycaprolactone copolymers, such as Capa® 7201A, sold by Ingevity Corporation, are also known for their improved low-temperature performance compared to polyester polyols. Capa® 7201A is a 2000 g / mol triblock copolymer of PTMEG and caprolactone, with PTMEG comprising 50% of the polyol weight. Polyurethane articles made with Capa® 7201A typically have glass transition temperatures intermediate between those of polycaprolactone copolymers and PTMEG. While the copolymer uses PTMEG as a raw material, replacing PTMEG homopolymer in polyurethane compositions reduces reliance on this technology by 50%. While offering a compromise between PTMEG and polycaprolactone technologies, Capa® 7201A's low-temperature performance, as measured by glass transition temperature, is still somewhat inferior to PTMEG.

[0009] In addition to improving chemical technology, increasing the molecular weight of the polyol chains in polyurethanes can lower the glass transition temperature. For example, replacing 1000 g / mol of PTMEG with 2000 g / mol of PTMEG in a polyurethane formulation lowers the glass transition temperature. This occurs because the polyol chains have greater mobility, meaning less energy is required for molecular movement. U.S. Patent Application Publication No. 2002 / 0077444, in a patent claiming a method for producing liquid polyurethane prepolymers, describes the use of a polycaprolactone copolymer based on 2294 g / mol of methyl-PTMEG (MePTMEG) and polycaprolactone.

[0010] However, above a certain molecular weight, due to crystallization of the polyol chains, viscoelastic behavior does not manifest until much higher temperatures, despite the low glass transition, i.e., the minimum use temperature is high. This molecular weight limitation on low-temperature performance is observed for both PTMEG and polyurethanes made using polycaprolactone technology. With polyols above 2500 g / mol, a broad glass transition is observed (as a result of the polyol's crystallinity), and the minimum use temperature is significantly higher, despite the low peak Tg.

[0011] Thus, there is a need for polyurethanes with improved low temperature performance. The present disclosure addresses this need with novel polyurethane compositions based on high molecular weight polycaprolactone copolymers that exhibit very low glass transitions and very low minimum use temperatures that overcome the challenges of polyol crystallinity in traditional polyurethane systems. Summary of the Invention

[0012] Surprisingly and unexpectedly, it has been discovered that when copolymers of poly(tetrahydrofuran) or poly(substituted tetrahydrofuran) with cyclic lactones / ethers (e.g., caprolactone), where (i) the copolymer has a molecular weight greater than 2500 g / mol and (ii) the poly(tetrahydrofuran) / poly(substituted tetrahydrofuran) content is at least 40 wt % of the copolymer, are used as the soft segment of a polyurethane article, dramatically improved low-temperature performance is achieved. The glass transition temperatures, as measured by differential scanning calorimetry (DSC) and / or dynamic mechanical analysis (DMA), are comparable to those of poly(tetramethylene ether) glycol (PTMEG), but more importantly, the minimum use temperatures (defined as the lowest temperature at which tan δ is less than 0.1) are extended by up to 25°C. This was surprising and unexpected because polyol crystallization typically increases with increasing molecular weight, raising the minimum use temperature. Polyurethanes based on the copolymers of the present disclosure have not previously been reported because those skilled in the art believed that polyol crystallinity would prevent the formation of useful materials.

[0013] One aspect of the present disclosure relates to a polyurethane or polyurethaneurea composition having improved low temperature performance. In any aspect or embodiment described herein, the polyurethane or polyurethaneurea composition comprises: (a) at least one block copolymer of the ABA type having a number average molecular weight of 2500 to 5000 g / mol, said block copolymer comprising: (i) a poly(tetrahydrofuran) diol, a poly(substituted tetrahydrofuran) diol, or a mixture thereof, present in an amount of about 40 to about 70 weight percent of the total molecular weight of the block copolymer; and (ii) a block copolymer comprising, or which is the reaction product of, a cyclic lactone, a cyclic ether, or a mixture thereof, present in an amount of about 30 to about 60 weight percent of the total molecular weight of the block copolymer; (b) at least one diisocyanate, A polyurethane or polyurethaneurea composition reaction product is formed by reacting (a) with (b) in an NCO:OH molar ratio of about 0.9:1 to about 2:1 (e.g., in the absence of a plasticizer).

[0014] In any aspect or embodiment described herein, the reaction further includes (c) a diol chain extender, a diamine chain extender, or a mixture thereof, each having a molecular weight of from about 60 to about 600, and the polyurethane or polyurethaneurea composition reaction product is formed by reacting (a), (b), and (c) in an NCO:OH molar ratio of from about 0.9:1 to about 2:1 (e.g., in the absence of a plasticizer).

[0015]

[0042] In any aspect or embodiment describe herein, the polyurethane or polyurethaneurea composition comprises: (a) at least one block copolymer of the ABA type having a number average molecular weight of 2500 to 5000 g / mol, said block copolymer comprising: (i) a poly(tetrahydrofuran) diol, a poly(substituted tetrahydrofuran) diol, or a mixture thereof, present in an amount of about 40 to about 70 weight percent of the total molecular weight of the block copolymer; and (ii) a block copolymer comprising, or which is the reaction product of, a cyclic lactone, a cyclic ether, or a mixture thereof, present in an amount of about 30 to about 60 weight percent of the total molecular weight of the block copolymer; (b) at least one diisocyanate; (c) a reaction product of a diol chain extender, a diamine chain extender, or a mixture thereof, each having a molecular weight of about 60 to about 600; A polyurethane or polyurethaneurea composition reaction product is formed by reacting (a), (b), and (c) in an NCO:OH molar ratio of about 0.9:1 to about 2:1 in the absence of a plasticizer.

[0016] In any aspect or embodiment described herein, reactant (b) is present in an amount of about 50 to about 70 weight percent of the total molecular weight of the block copolymer.

[0017] In any aspect or embodiment describe herein, the composition has a hardness of about 30 Shore A to about 60 Shore D.

[0018] In any aspect or embodiment described herein, the NCO:OH molar ratio is from about 0.9:1 to 1.7:1.

[0019] In any aspect or embodiment described herein, the NCO:OH molar ratio is from about 0.95:1 to 1.5:1.

[0020] In any aspect or embodiment described herein, the NCO:OH molar ratio is from about 1:1 to 1.2:1.

[0021]

[0044] In any aspect or embodiment describe herein, the polyurethane or polyurethaneurea composition has a glass transition temperature of less than -60°C as measured by differential scanning calorimetry.

[0022]

[0044] In any aspect or embodiment describe herein, the polyurethane or polyurethaneurea composition has a glass transition temperature of less than -40°C as measured by dynamic mechanical analysis.

[0023] In any aspect or embodiment described herein, reactant (i) comprises or is a poly(substituted tetrahydrofuran)diol. For example, in any aspect or embodiment described herein, reactant (i) comprises or is a poly(substituted tetrahydrofuran)diol, wherein the substitution is C 1-4 Alkyl (e.g., methyl, ethyl, or propyl), C 1-6 Alkoxy (e.g., methoxy or ethoxy), C 2-6 It can include or be substituted with one or more (e.g., 1, 2, 3, 4, 5, 6, or more) substituents independently selected from alkenyl, aromatic (e.g., phenyl, aryl, or heteroaryl), ester, halogen, halide, amide, or ketone.

[0024] In any aspect or embodiment describe herein, the poly(tetrahydrofuran) diol or reactant (i) includes or is poly(tetramethylene ether) glycol (PTMEG).

[0025] In any aspect or embodiment described herein, the poly(substituted tetrahydrofuran) diol or reactant (i) includes or is Me-PTMEG.

[0026] In any aspect or embodiment describe herein, the cyclic lactone includes or is ε-caprolactone.

[0027] In any aspect or embodiment describe herein, the cyclic ether comprises or is ethylene oxide, propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, or a mixture thereof.

[0028] In any aspect or embodiment described herein, the diisocyanate may include or be an aliphatic diisocyanate, an aromatic diisocyanate, or a combination thereof. For example, in any aspect or embodiment described herein, the diisocyanate may be 4,4'-diphenylmethane diisocyanate, isophorone diisocyanate, bimethylene diisocyanate, trimethylene diisocyanate (e.g., 1,3-trimethylene diisocyanate, 2,3-trimethylene diisocyanate, 1,2-trimethylene diisocyanate, 2,2-trimethylene diisocyanate, or a mixture thereof), tetramethylene diisocyanate (e.g., 1,4- Tetramethylene diisocyanate, 1,3-tetramethylene diisocyanate, 1,2-tetramethylene diisocyanate, 2,3-tetramethylene diisocyanate, 1,1-tetramethylene diisocyanate, 2,2-tetramethylene diisocyanate, or mixtures thereof), pentamethylene diisocyanate (e.g., 1,5-pentamethylene diisocyanate, 1,4-pentamethylene diisocyanate, 1,3-pentamethylene diisocyanate, 1,2-pentamethylene diisocyanate, Isocyanates, 2,3-pentamethylene diisocyanate, 2,4-pentamethylene diisocyanate, 3,4-pentamethylene diisocyanate, 3,5-pentamethylene diisocyanate, 1,1-pentamethylene diisocyanate, 2,2-pentamethylene diisocyanate, 3,3-pentamethylene diisocyanate, or mixtures thereof), hexamethylene diisocyanate (e.g., 1,6-hexamethylene diisocyanate, 1,5-hexamethylene diisocyanate, 1,4-Hexamethylene diisocyanate, 1,3-Hexamethylene diisocyanate, 1,2-Hexamethylene diisocyanate, 2,3-Hexamethylene diisocyanate, 2,4-Hexamethylene diisocyanate, 2,5-Hexamethylene diisocyanate, 3,4-Hexamethylene diisocyanate, 3,5-Hexamethylene diisocyanate, 4,5-Hexamethylene diisocyanate, 1,1-Hexamethylene diisocyanate, 2,2-Hexamethylene diisocyanate, 3,3-hexamethylene diisocyanate, or mixtures thereof), heptamethylene diisocyanate (e.g., 1,7-heptamethylene diisocyanate, 1,6-heptamethylene diisocyanate, 1,5-heptamethylene diisocyanate, 1,4-heptamethylene diisocyanate, 1,3-heptamethylene diisocyanate, 1,2-heptamethylene diisocyanate, 2,3-heptamethylene diisocyanate, 2,4-heptamethylene diisocyanate, 2, 5-heptamethylene diisocyanate, 2,6-heptamethylene diisocyanate, 3,3-heptamethylene diisocyanate, 3,4-heptamethylene diisocyanate, 1,1-heptamethylene diisocyanate, 2,2-heptamethylene diisocyanate, 3,3-heptamethylene diisocyanate, 4,4-heptamethylene diisocyanate, or mixtures thereof), toluene diisocyanate (e.g., toluene-2,4-diisocyanate, toluene-2,6 -diisocyanates, or mixtures thereof), naphthylene diisocyanates (e.g., 1,2-naphthylene diisocyanate, 1,3-naphthylene diisocyanate, 1,4-naphthylene diisocyanate, 1,5-naphthylene diisocyanate, 1,6-naphthylene diisocyanate, 1,7-naphthylene diisocyanate, 1,8-naphthylene diisocyanate, or mixtures thereof), cyclohexylmethane diisocyanate (e.g., 1,4-cyclohexyl The compound may comprise or be any of: dicyclohexylmethane diisocyanate (e.g., 4,4'-dicyclohexylmethane diisocyanate, 2,4-cyclohexylmethane diisocyanate, 3,4-cyclohexylmethane diisocyanate, 4,4-cyclohexylmethane diisocyanate, or mixtures thereof); dicyclohexylmethane diisocyanate (e.g., 4,4'-dicyclohexylmethane diisocyanate, 1,4-dicyclohexylmethane diisocyanate, or mixtures thereof);

[0029]

[0041] In any aspect or embodiment describe herein, the diisocyanate includes or is any of 4,4'-diphenylmethane diisocyanate, isophorone diisocyanate, 1,6-hexamethylene diisocyanate, toluene-2,4-diisocyanate, 1,5-naphthylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, or a mixture thereof.

[0030] In any aspect or embodiment described herein, the diol chain extender includes or is an aliphatic diol or an aromatic diol. For example, in any aspect or embodiment described herein, the diol chain extender can be an alkylene oxide or a glycol, ethylene glycol, propanediol (e.g., 1,3-propanediol, 1,2-propanediol, 1,1-propanediol, 2,2-propanediol, or a mixture thereof), butanediol (e.g., 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, 2,3-butanediol, 1,1-butanediol, 2,2-butanediol, or a mixture thereof), or a mixture of alkylene oxides such as ethylene glycol, propanediol (e.g., 1,3-propanediol, 1,2-propanediol, 1,1-propanediol, 2,2-propanediol, or a mixture thereof), butanediol (e.g., 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, 2,3-butanediol, 1,1-butanediol, 2,2-butanediol, or a mixture thereof). or mixtures thereof), pentanediols (e.g., 1,5-pentanediol, 1,4-pentanediol, 1,3-pentanediol, 1,2-pentanediol, 2,3-pentanediol, 2,4-pentanediol, 3,4-pentanediol, 3,5-hexanediol, 1,1-pentanediol, 2,2-pentanediol, 3,3-pentanediol, or mixtures thereof), hexanediols (e.g., 1,6-hexanediol, 1,5-hexanediol, 1,4-hexanediol, 1,3-hexanediol, hexanediol, 1,2-hexanediol, 2,3-hexanediol, 2,4-hexanediol, 2,5-hexanediol, 3,4-hexanediol, 3,5-hexanediol, 4,5-hexanediol, 1,1-hexanediol, 2,2-hexanediol, 3,3-hexanediol, or mixtures thereof), heptanediols (e.g., 1,7-heptanediol, 1,6-heptanediol, 1,5-heptanediol, 1,4-heptanediol, 1,3-heptanediol, 1,2-heptanediol, 2 ,3-heptadiol, 2,4-heptadiol, 2,5-heptadiol, 2,6-heptadiol, 3,3-heptadiol, 3,4-heptadiol, 1,1-heptadiol, 2,2-heptadiol, 3,3-heptadiol, 4,4-heptadiol, or mixtures thereof), dihydroxybenzenes (e.g., 1,2-dihydroxybenzene, 1,3-dihydroxybenzene, 1,4-dihydroxybenzene, or mixtures thereof), di(hydroxyethyl)-hydroxyquinones (e.g., 1,4-di-(beta hydroxyethyl)-hydroxyquinone, 2,5-di-(hydroxyethyl)-hydroxyquinone, 2,3-di-(hydroxyethyl)-hydroxyquinone, 3,5-di-(hydroxyethyl)-hydroxyquinone, or mixtures thereof), di(hydroxymethyl)-hydroxyquinone (e.g., 2,5-di-(hydroxyethyl)-hydroxyquinone, 2,3-di-(hydroxymethyl)-hydroxyquinone, 3,5-di-(hydroxymethyl)-hydroxyquinone, or mixtures thereof), di-(hydroxyethyl)-bisphenol A (e.g., 1,4-di-(beta hydroxyethyl)-bisphenol A, 1,3-di-(beta hydroxyethyl)-bisphenol A, The compound may comprise or be any of 1,2-di-(beta hydroxyethyl)-bisphenol A, 1,5-di-(beta hydroxyethyl)-bisphenol A, 2,3-di-(beta hydroxyethyl)-bisphenol A, 2,4-di-(beta hydroxyethyl)-bisphenol A, 2,5-di-(beta hydroxyethyl)-bisphenol A, 2,6-di-(beta hydroxyethyl)-bisphenol A, 3,4-di-(beta hydroxyethyl)-bisphenol A, 3,5-di-(beta hydroxyethyl)-bisphenol A, or mixtures thereof.

[0031]

[0044] In any aspect or embodiment describe herein, the diol chain extender includes or is any of ethylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,4-di-(beta hydroxyethyl)-hydroxyquinone, 1,4-di-(beta hydroxyethyl)-bisphenol A, or a mixture thereof.

[0032]

[0044] In any aspect or embodiment described herein, the diamine chain extender is diaminodiphenylmethane (e.g., 2,2'-diaminodiphenylmethane, 2,3'-diaminodiphenylmethane, 2,4'-diaminodiphenylmethane, 2,5'-diaminodiphenylmethane, 2,6'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 3,5'-diaminodiphenylmethane, 3,6'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 4,5'-diaminodiphenylmethane, 4,6'-diaminodiphenyl methane, 5,6'-diaminodiphenylmethane, or mixtures thereof), dichloro-diaminodiphenylmethane (e.g., 2,2'-dichloro-3,3'-diaminodiphenylmethane, 2,2'-dichloro-4,4'-diaminodiphenylmethane, 5,5'-dichloro-3,3'-diaminodiphenylmethane, 2,2'-dichloro-6,6'-diaminodiphenylmethane, 2,2'-dichloro-3,4'-diaminodiphenylmethane, 2,2'-dichloro-3,5'-diaminodiphenylmethane, 2,2'-dichloro-3,6'-diaminodiphenylmethane Nilmethane, 2,2'-dichloro-4,5'-diaminodiphenylmethane, 2,2'-dichloro-4,6'-diaminodiphenylmethane, 2,2'-dichloro-5,6'-diaminodiphenylmethane, 3,3'-dichloro-2,2'-diaminodiphenylmethane, 3,3'-dichloro-4,4'-diaminodiphenylmethane, 3,3'-dichloro-5,5'-diaminodiphenylmethane, 3,3'-dichloro-6,6'-diaminodiphenylmethane, 3,3'-dichloro-2,5'-diaminodiphenylmethane, 3,3'-dichloro-4,5'-diamino aminodiphenylmethane, 3,3'-dichloro-6,5'-diaminodiphenylmethane, 3,3'-dichloro-4,2'-diaminodiphenylmethane, 3,3'-dichloro-4,6'-diaminodiphenylmethane, 4,4'-dichloro-2,2'-diaminodiphenylmethane, 4,4'-dichloro-3,3'-diaminodiphenylmethane, 4,4'-dichloro-5,5'-diaminodiphenylmethane, 4,4'-dichloro-6,6'-diaminodiphenylmethane, 4,4'-dichloro-2,3'-diaminodiphenylmethane, 4,4'-dichloro-2,5'-Diaminodiphenylmethane, 4,4'-dichloro-2,6'-diaminodiphenylmethane, 4,4'-dichloro-3,5'-diaminodiphenylmethane, 4,4'-dichloro-3,6'-diaminodiphenylmethane, 4,4'-dichloro-5,6'-diaminodiphenylmethane, 5,5'-dichloro-2,2'-diaminodiphenylmethane, 5,5'-dichloro-3,3'-diaminodiphenylmethane, 5,5'-dichloro-4,4'-diaminodiphenylmethane, 5,5'-dichloro-6,6'-diaminodiphenylmethane, 5,5'-dichloro -2,3'-diaminodiphenylmethane, 5,5'-dichloro-2,4'-diaminodiphenylmethane, 5,5'-dichloro-2,6'-diaminodiphenylmethane, 5,5'-dichloro-3,4'-diaminodiphenylmethane, 5,5'-dichloro-3,6'-diaminodiphenylmethane, 5,5'-dichloro-4,6'-diaminodiphenylmethane, 6,6'-dichloro-2,2'-diaminodiphenylmethane, 6,6'-dichloro-3,3'-diaminodiphenylmethane, 6,6'-dichloro-4,4'-diaminodiphenylmethane, 6,6'-di chloro-5,5'-diaminodiphenylmethane, 6,6'-dichloro-2,3'-diaminodiphenylmethane, 6,6'-dichloro-2,4'-diaminodiphenylmethane, 6,6'-dichloro-2,5'-diaminodiphenylmethane, 6,6'-dichloro-3,4'-diaminodiphenylmethane, 6,6'-dichloro-3,5'-diaminodiphenylmethane, 6,6'-dichloro-4,5'-diaminodiphenylmethane, or mixtures thereof), diaminobenzenes (e.g., 1,4-diaminobenzene, 1,2-diaminobenzene, 1,3-diaminodiphenylmethane, dimethoxy-diaminobiphenyl (e.g., 2,2'-dimethoxy-3,3'-diaminobiphenyl, 2,2'-dimethoxy-4,4'-diaminobiphenyl, 5,5'-dimethoxy-3,3'-diaminobiphenyl, 2,2'-dimethoxy-6,6'-diaminobiphenyl, 2,2'-dimethoxy-3,4'-diaminobiphenyl, 2,2'-dimethoxy-3,5'-diaminobiphenyl, 2,2'-dimethoxy-3,6'-diaminobiphenyl, 2,2'-dimethoxy-4,5'-diaminobiphenyl, 2,2'-Dimethoxy-4,6'-diaminobiphenyl, 2,2'-dimethoxy-5,6'-diaminobiphenyl, 3,3'-dimethoxy-2,2'-diaminobiphenyl, 3,3'-dimethoxy-4,4-diaminobiphenyl, 3,3'-dimethoxy-5,5'-diaminobiphenyl, 3,3'-dimethoxy-6,6'-diaminobiphenyl, 3,3'-dimethoxy-2,5'-diaminobiphenyl, 3,3'-dimethoxy-4,5'-diaminobiphenyl, 3,3'-dimethoxy-6,5'-diaminobiphenyl, 3,3'-dimethoxy-4,2'-diaminobiphenyl 4,4'-dimethoxy-2,2'-diaminobiphenyl, 4,4'-dimethoxy-3,3'-diaminobiphenyl, 4,4'-dimethoxy-5,5'-diaminobiphenyl, 4,4'-dimethoxy-6,6'-diaminobiphenyl, 4,4'-dimethoxy-2,3'-diaminobiphenyl, 4,4'-dimethoxy-2,5'-diaminobiphenyl, 4,4'-dimethoxy-2,6'-diaminobiphenyl, 4,4'-dimethoxy-3,5'-diaminobiphenyl, 4,4'-dimethoxy 4,4'-dimethoxy-5,6'-diaminobiphenyl, 5,5'-dimethoxy-2,2'-diaminobiphenyl, 5,5'-dimethoxy-3,3'-diaminobiphenyl, 5,5'-dimethoxy-4,4'-diaminobiphenyl, 5,5'-dimethoxy-6,6'-diaminobiphenyl, 5,5'-dimethoxy-2,3'-diaminobiphenyl, 5,5'-dimethoxy-2,4'-diaminobiphenyl, 5,5'-dimethoxy-2,6'-diaminobiphenyl, 5,5'-dimethoxy-3,4'-diaminobiphenyl Nyl, 5,5'-dimethoxy-3,6'-diaminobiphenyl, 5,5'-dimethoxy-4,6'-diaminobiphenyl, 6,6'-dimethoxy-2,2'-diaminobiphenyl, 6,6'-dimethoxy-3,3'-diaminobiphenyl, 6,6'-dimethoxy-4,4'-diaminobiphenyl, 6,6'-dimethoxy-5,5'-diaminobiphenyl, 6,6'-dimethoxy-2,3'-diaminobiphenyl, 6,6'-dimethoxy-2,4'-diaminobiphenyl, 6,6'-dimethoxy-2,5'-diaminobiphenyl, 6,6'-dimethoxy-3,4'-diaminobiphenyl, 6,6'-dimethoxy-3,5'-diaminobiphenyl, 6,6'-dimethoxy-4,5'-diaminobiphenyl, or mixtures thereof), dimethyl-diaminobiphenyls (e.g., 2,2'-dimethyl-3,3'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 5,5'-dimethyl-3,3'-diaminobiphenyl, 2,2'-dimethyl-6,6'-diaminobiphenyl, 2,2'-dimethyl-3,4'-diaminobiphenyl, 2,2'-dimethyl-3,5'-diaminobiphenyl, 2, 2'-dimethyl-3,6'-diaminobiphenyl, 2,2'-dimethyl-4,5'-diaminobiphenyl, 2,2'-dimethyl-4,6'-diaminobiphenyl, 2,2'-dimethyl-5,6'-diaminobiphenyl, 3,3'-dimethyl-2,2'-diaminobiphenyl, 3,3'-dimethyl-4,4-diaminobiphenyl, 3,3'-dimethyl-5,5'-diaminobiphenyl, 3,3'-dimethyl-6,6'-diaminobiphenyl, 3,3'-dimethyl-2,5'-diaminobiphenyl, 3,3'-dimethyl-4,5'-diaminobiphenyl, 3,3 '-Dimethyl-6,5'-diaminobiphenyl, 3,3'-dimethyl-4,2'-diaminobiphenyl, 3,3'-dimethyl-4,6'-diaminobiphenyl, 4,4'-dimethyl-2,2'-diaminobiphenyl, 4,4'-dimethyl-3,3'-diaminobiphenyl, 4,4'-dimethyl-5,5'-diaminobiphenyl, 4,4'-dimethyl-6,6'-diaminobiphenyl, 4,4'-dimethyl-2,3'-diaminobiphenyl, 4,4'-dimethyl-2,5'-diaminobiphenyl, 4,4'-dimethyl-2,6'-diaminobiphenyl, 4, 4'-dimethyl-3,5'-diaminobiphenyl, 4,4'-dimethyl-3,6'-diaminobiphenyl, 4,4'-dimethyl-5,6'-diaminobiphenyl, 5,5'-dimethyl-2,2'-diaminobiphenyl, 5,5'-dimethyl-3,3'-diaminobiphenyl, 5,5'-dimethyl-4,4'-diaminobiphenyl, 5,5'-dimethyl-6,6'-diaminobiphenyl, 5,5'-dimethyl-2,3'-diaminobiphenyl, 5,5'-dimethyl-2,4'-diaminobiphenyl, 5,5'-dimethyl-2,6'-diaminobiphenyl, 5,5'-dimethyl-3,4'-diaminobiphenyl, 5,5'-dimethyl-3,6'-diaminobiphenyl, 5,5'-dimethyl-4,6'-diaminobiphenyl, 6,6'-dimethyl-2,2'-diaminobiphenyl, 6,6'-dimethyl-3,3'-diaminobiphenyl, 6,6'-dimethyl-4,4'-diaminobiphenyl, 6,6'-dimethyl-5,5'-diaminobiphenyl, 6,6'-dimethyl-2,3'-diaminobiphenyl, 6,6'-dimethyl-2,4'-diaminobiphenyl, 6,6'-dimethyl-2,5'-diaminobiphenyl, 6 ,6'-dimethyl-3,4'-diaminobiphenyl, 6,6'-dimethyl-3,5'-diaminobiphenyl, 6,6'-dimethyl-4,5'-diaminobiphenyl, or mixtures thereof), diaminobiphenyls (e.g., 2,2'-diaminobiphenyl, 2,3'-diaminobiphenyl, 2,4'-diaminobiphenyl, 2,5'-diaminobiphenyl, 2,6'-diaminobiphenyl, 3,4'-diaminobiphenyl, 3,5'-diaminobiphenyl, 3,6'-diaminobiphenyl, 4,4'-diaminobiphenyl, 4,5'-diaminobiphenyl , 4,6'-diaminobiphenyl, 5,6'-diaminobiphenyl, or mixtures thereof), dichloro-diaminobiphenyls (e.g., 2,2'-dichloro-3,3'-diaminobiphenyl, 2,2'-dichloro-4,4'-diaminobiphenyl, 5,5'-dichloro-3,3'-diaminobiphenyl, 2,2'-dichloro-6,6'-diaminobiphenyl, 2,2'-dichloro-3,4'-diaminobiphenyl, 2,2'-dichloro-3,5'-diaminobiphenyl, 2,2'-dichloro-3,6'-diaminobiphenyl, 2,2'-dichloro-4, 5'-Diaminobiphenyl, 2,2'-dichloro-4,6'-diaminobiphenyl, 2,2'-dichloro-5,6'-diaminobiphenyl, 3,3'-dichloro-2,2'-diaminobiphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl, 3,3'-dichloro-5,5'-diaminobiphenyl, 3,3'-dichloro-6,6'-diaminobiphenyl, 3,3'-dichloro-2,5'-diaminobiphenyl, 3,3'-dichloro-4,5'-diaminobiphenyl, 3,3'-dichloro-6,5'-diaminobiphenyl, 3,3'-dichloro-4,2'-diaminobiphenyl, 3,3'-dichloro-4,6'-diaminobiphenyl, 4,4'-dichloro-2,2'-diaminobiphenyl, 4,4'-dichloro-3,3'-diaminobiphenyl, 4,4'-dichloro-5,5'-diaminobiphenyl, 4,4'-dichloro-6,6'-diaminobiphenyl, 4,4'-dichloro-2,3'-diaminobiphenyl, 4,4'-dichloro-2,5'-diaminobiphenyl, 4,4'-dichloro-2,6'-diaminobiphenyl, 4,4'-dichloro-3,5'-diaminobiphenyl, 4,4'-dichloro-3,6'-diaminobiphenyl, 4,4'-dichloro-5,6'-diaminobiphenyl, 5,5'-dichloro-2,2'-diaminobiphenyl, 5,5'-dichloro-3,3'-diaminobiphenyl, phenyl, 5,5'-dichloro-4,4'-diaminobiphenyl, 5,5'-dichloro-6,6'-diaminobiphenyl, 5,5'-dichloro-2,3'-diaminobiphenyl, 5,5'-dichloro-2,4'-diaminobiphenyl, 5,5'-dichloro-2,6'-diaminobiphenyl, 5,5'-dichloro-3,4'-diaminobiphenyl, 5,5'-dichloro-3,6'-diaminobiphenyl, 5,5'-dichloro-4,6'-diaminobiphenyl, 6,6'-dichloro-2,2'-diaminobiphenyl, 6,6'-dichloro-3,3'-diaminobiphenyl phenyl, 6,6'-dichloro-4,4'-diaminobiphenyl, 6,6'-dichloro-5,5'-diaminobiphenyl, 6,6'-dichloro-2,3'-diaminobiphenyl, 6,6'-dichloro-2,4'-diaminobiphenyl, 6,6'-dichloro-2,5'-diaminobiphenyl, 6,6'-dichloro-3,4'-diaminobiphenyl, 6,6'-dichloro-3,5'-diaminobiphenyl, 6,6'-dichloro-4,5'-diaminobiphenyl, or mixtures thereof), or mixtures thereof.

[0033]

[0041] In any aspect or embodiment describe herein, the diamine chain extender includes or is any of 4,4'-diaminodiphenylmethane, 3,3'-dichloro-4,4'-diaminodiphenylmethane, 1,4-diaminobenzene, 3,3'-dimethoxy-4,4-diaminobiphenyl, 3,3'-dimethyl-4,4-diaminobiphenyl, 4,4'-diaminobiphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl, or a mixture thereof.

[0034] In any aspect or embodiment described herein, reactant (i) is present in an amount of about 50 to about 70 weight percent of the total molecular weight of the block copolymer.

[0035]

[0041] In any aspect or embodiment describe herein, the composition is a thermoplastic polyurethane, a hot cast elastomer, a cold cast elastomer, a microcellular polyurethane foam, a polyurethane dispersion in an aqueous or organic medium, a polyurethane adhesive, a one-component polyurethane coating, a two-component polyurethane coating, an additive manufacturing composition / resin, or a polyurethane sealant.

[0036]

[0047] In any aspect or embodiment describe herein, the block copolymer comprises, or is a reaction product of, poly(tetramethylene ether) glycol and ε-caprolactone.

[0037] Further aspects of the present disclosure relate to a thermoplastic polyurethane, a hot cast elastomer, a cold cast elastomer, a microcellular polyurethane foam, a polyurethane dispersion in an aqueous or organic medium, a polyurethane adhesive, a one-component polyurethane coating, a two-component polyurethane coating, an additive manufacturing composition / resin, or a polyurethane sealant comprising the polyurethane or polyurethaneurea composition of the present disclosure.

[0038] Additional aspects of the present disclosure relate to a thermoplastic polyurethane, a hot cast elastomer, a cold cast elastomer, a microcellular polyurethane foam, a polyurethane dispersion in an aqueous or organic medium, a polyurethane adhesive, a one-component polyurethane coating, a two-component polyurethane coating, an additive manufacturing composition / resin, or a polyurethane sealant comprising the polyurethane or polyurethaneurea composition of the present disclosure, wherein the polyurethane or polyurethaneurea composition is (a) at least one block copolymer of the ABA type having a number average molecular weight of 2500 to 5000 g / mol, said block copolymer comprising: (i) a poly(tetrahydrofuran) diol, a poly(substituted tetrahydrofuran) diol, or a mixture thereof, present in an amount of about 40 to about 70 weight percent of the total molecular weight of the block copolymer; and (ii) a block copolymer comprising, or which is the reaction product of, a cyclic lactone, a cyclic ether, or a mixture thereof, present in an amount of about 30 to about 60 weight percent of the total molecular weight of the block copolymer; (b) at least one diisocyanate, A polyurethane or polyurethaneurea composition reaction product is formed by reacting (a) with (b) in an NCO:OH molar ratio of about 0.9:1 to about 2:1 (e.g., in the absence of a plasticizer).

[0039] In any aspect or embodiment described herein, the reaction further includes (c) a diol chain extender, a diamine chain extender, or a mixture thereof, each having a molecular weight of from about 60 to about 600, and the polyurethane or polyurethaneurea composition reaction product is formed by reacting (a), (b), and (c) in an NCO:OH molar ratio of from about 0.9:1 to about 2:1 in the absence of a plasticizer.

[0040] In any aspect or embodiment describe herein, the composition is processed as a thermoplastic polyurethane, a hot cast elastomer, or a cold cast elastomer.

[0041] In any aspect or embodiment describe herein, the composition is processed as a thermoplastic polyurethane or a hot cast elastomer. DETAILED DESCRIPTION OF THE INVENTION

[0042] Described herein are polyurethane or polyurethaneurea compositions with surprising and unexpectedly improved low-temperature performance. In particular, when copolymers of poly(tetrahydrofuran) or poly(substituted tetrahydrofuran) with cyclic lactones / ethers (e.g., caprolactone) are used as the soft segment of polyurethane articles, low-temperature performance has been found to be dramatically improved when (i) the copolymer has a molecular weight greater than 2500 g / mol, and (ii) the poly(tetrahydrofuran) / poly(substituted tetrahydrofuran) content is at least 40 wt. % of the copolymer. The glass transition temperatures, as measured by differential scanning calorimetry (DSC) and / or dynamic mechanical analysis (DMA), are comparable to those of poly(tetramethylene ether) glycol (PTMEG), but more importantly, the minimum use temperature (defined as the lowest temperature at which tan δ is less than 0.1) is extended by up to 25°C. This was a surprising and unexpected effect, since polyol crystallization typically increases with increasing molecular weight, raising the minimum use temperature. Polyurethanes based on copolymers have not been reported previously, likely due to the belief that polyol crystallinity would prevent the formation of useful materials.

[0043] The contents of all references, patents, pending patent applications, and published patents cited throughout this disclosure are expressly incorporated herein by reference. The headings used herein are for organizational purposes only and are not intended to be used to limit the scope of the description or claims that may be had by reference to the entire specification.

[0044] The following terms are used to describe the present disclosure. Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure belongs. The terms used herein are for the purpose of describing particular embodiments only and are not intended to limit the disclosure. If a term is not specifically defined herein, the term will be given the art-recognized meaning by those of ordinary skill in the art who apply the term in connection with its use in describing the present disclosure.

[0045] Where a range of values ​​is given, unless the context clearly indicates otherwise (e.g., in the case of a group including a number of carbon atoms, the number of each carbon atom falling within the range is given), it is understood that each intervening value, to the tenth of the unit of the lower limit, between the upper and lower limit of that range and any other stated or intervening value in that stated range is encompassed in the disclosure. The upper and lower limits of these smaller ranges may independently be included in the smaller ranges and are also encompassed within the disclosure, subject to any specifically excluded limit in the stated range. When the stated range includes one or both of the limits, ranges excluding either / both of those included limits are also included in the disclosure.

[0046] As used in this specification and the appended claims, the articles "a," "an," and "the" and similar referents should be construed to cover both the singular and the plural (e.g., "one or more," or "at least one") of the grammatical object of the article unless otherwise indicated herein or clearly contradicted by context. By way of example, "an element" means one element or more than one element.

[0047] As used in this specification and the claims, the term "and / or" should be understood to mean "either or both" of the elements so conjoined, i.e., elements that are conjunctively present in some instances and disjunctively present in other instances. Multiple elements listed with "and / or" should be construed in the same manner, i.e., "one or more" of the elements so conjoined. Other elements, whether related or unrelated to the elements specifically identified in the "and / or" clause, may optionally be present. Thus, as a non-limiting example, a reference to "A and / or B" may, in one embodiment, refer to A only (optionally including elements other than B); in another embodiment, refer to B only (optionally including elements other than A); in yet another embodiment, refer to both A and B (optionally including other elements); and so forth.

[0048] As used herein and in the claims, "or" should be understood to have the same meaning as "and / or" as defined above. For example, when separating items in a list, "or" or "and / or" should be interpreted as being inclusive, i.e., including at least one element, but also including two or more of a number or list of elements, and possibly additional unlisted items. When expressly indicated or used in the claims, such as "any one" or "exactly one," the term "consisting of" refers to the inclusion of exactly one element of a number or list of elements. As used herein, the term "or" should be interpreted as indicating exclusive alternatives ("either / or, but not both") only when preceded by a condition of exclusivity (e.g., "either / or," "either / or only," "exactly either / or," etc.).

[0049] As used herein in the specification and claims, the phrase "at least one" in reference to a list of one or more elements should be understood to mean at least one element selected from one or more of the elements in the list of elements, but not necessarily including at least one of each and every element specifically listed within the list of elements, and not excluding any combinations of elements in the list of elements. This definition also allows for the optional presence of elements other than those specifically identified in the list of elements to which the phrase "at least one" refers, whether related or unrelated to the specifically identified elements. Thus, as a non-limiting example, "at least one of A and B" (or, equivalently, "at least one of A or B" or, equivalently, "at least one of A and / or B" can refer, in one embodiment, to at least one A with no B (which may include elements other than B); in another embodiment, to at least one B (optionally including one or more) and no A (optionally including elements other than B); and in yet another embodiment, to at least one A (optionally including one or more) and at least one B (optionally including one or more) (optionally including other elements).

[0050] In the claims and the above specification, all transitional phrases such as "comprises," "includes," "mounts," "has," "contains," "accompanying," "holds," "consisting of," and the like, are to be understood to be open-ended, i.e., to mean "including, but not limited to." Only the transitional phrases "consisting of" and "consisting essentially of" shall be closed or semi-closed transitional phrases, respectively, as set forth in Section 2111.03 of the United States Manual of Patent Examining Procedures.

[0051] It should also be understood that for particular methods or processes described herein that include multiple steps or acts, the order of the method steps or acts is not necessarily limited to the order in which the method steps or acts are recited, unless otherwise indicated by context. Thus, all methods described herein can be performed in any suitable order unless otherwise indicated herein or clearly contradicted by context. Furthermore, all methods described herein and having more than one step can be performed by more than one person or patent practicing entity. Thus, a person or patent practicing entity can perform method step (a), another person or patent practicing entity can perform method step (b), and yet another person or patent practicing entity can perform method step (c). The use of any and all examples or exemplary language (e.g., "etc.") provided herein is intended merely to better clarify the invention of this disclosure and does not pose a limitation on the scope of the invention as otherwise claimed.

[0052] Groupings of alternative elements or embodiments of the invention disclosed herein are not to be construed as limitations. Each group member may be referred to and claimed individually or in any combination with other members of the group or other elements found herein. It is anticipated that one or more members of a group may be included in, or excluded from, a group for purposes of convenience and / or patentability. When such inclusion or exclusion occurs, the specification is deemed to include the modified group, and therefore fulfills the written description of all Markush groups used in the appended claims.

[0053] The term "substituted" or "optionally substituted" is intended to mean, independently (i.e., when more than one substituent occurs in a formula, each substituent is selected independently of the other substituents), one or more (e.g., 1, 2, 3, 4, 5, 6, or more) substituents at a carbon (or nitrogen) position anywhere on a molecule or compound within the context, and possible substituents include, but are not limited to, hydroxyl, thiol, carboxyl, cyano (C≡N), nitro (NO), halogen, C 1-6 or C 2-4 Haloalkyl, C 1-6 or C 1-4 alkyl, 6- to 16- or 6- to 12-membered aryl (e.g., a 6-, 7-, or 8-membered monocyclic aromatic ring, a 10- to 16-membered aryl having multiple fused rings, phenyl, substituted phenyl, benzyl, substituted benzyl, or benzoyl), 5- to 16- or 5- to 12-membered heteroaryl (e.g., an aryl having one or more heteroatoms independently selected from N, O, S, or P, or a 5-, 6-, 7-, or 8-membered monocyclic ring or a 10- to 16-membered heteroaryl having multiple fused rings), C 1-6 or C 1-4 Alkoxy, ketone, thioether (preferably C1-C6 alkyl or aryl), C 1-6 or C 1-4 acyl, ester or thioester (preferably C1-C6 alkyl or aryl), including alkylene ester (so that the attachment is on the alkylene group rather than to the ester functionality, which is preferably substituted with a C1-C6 alkyl or aryl group), halogen (e.g., F, Cl, Br), C 1-6 or C 1-4 Alkanols, amides, amines (5- or 6-membered cyclic alkyleneamines, C 1-6 or C 1-4 Alkylamine, or C 1-6 Alkylene-NR1R2 or C 1-4alkylene -NR1R2, where the alkyl group may be optionally substituted with one or more hydroxyl groups and / or one or more halogen groups), an optionally substituted -N(C0-C6 alkyl)C(O)(O-C1-C6 alkyl) group, keto, carboxyl, C 1-6 Esters (oxyesters or carbonylesters), C 1-6 Keto, -OC(O)-NR1R2 or -N(R1)-C(O)-O-R1, -(CH2) n OH, -(CH2) n SH, -(CH2) n COOH, C1-C6 alkyl, -(CH2) n O-(C1-C6 alkyl), -(CH2) n C(O)-(C1-C6 alkyl), -(CH2) n OC(O)-(C1-C6 alkyl), -(CH2) n C(O)O-(C1-C6 alkyl), -(CH2) n NHC(O)-R1, -(CH2) n C(O)-NR1R2, -(OCH2) n OH, -(CHO) n COOH, C1-C6 alkyl, -(OCH2) n O-(C1-C6 alkyl), -(CHO) n C(O)-(C1-C6 alkyl), -(OCH2) n NHC(O)-R1, -(CHO) n C(O)-NR1R2, -S(O)2-R S , -S(O)-R S (R S is C1-C6 alkyl or -(CH2) m -NR1R2 groups), where each n is independently 0, 1, 2, 3, 4, 5, or 6; and R1 and R2 are each independently H or C. 1-6and alkyl groups (which may be optionally substituted with one or two hydroxyl groups and / or zero, one, two, or three halogen groups). Various optionally substituted moieties may be substituted with three or more substituents, preferably three or fewer, preferably one or two substituents. Note that in compounds at certain positions of molecular substitution, where substitution is required (primarily due to valence) but substitution is not indicated, the substituent is to be interpreted or understood to be H unless otherwise suggested by the context of the substitution.

[0054] As used herein, "any" or "optionally" means that the subsequently described event or circumstance may or may not occur, and that the description includes instances where the event or circumstance occurs and instances where it does not.

[0055] The present disclosure describes polyurethane or polyurethaneurea compositions with improved low temperature performance, compositions comprising the polyurethane or polyurethaneurea compositions of the present disclosure, and methods of making and using the compositions of the present disclosure.

[0056] One aspect of the present disclosure relates to a polyurethane or polyurethaneurea composition having improved low temperature performance. In any aspect or embodiment described herein, the polyurethane or polyurethaneurea composition comprises: (a) at least one block copolymer of the ABA type having a number average molecular weight of 2500 to 5000 g / mol, said block copolymer comprising: (i) a poly(tetrahydrofuran) diol, a poly(substituted tetrahydrofuran) diol, or a mixture thereof, present in an amount of about 40 to about 70 weight percent of the total molecular weight of the block copolymer; and (ii) a block copolymer comprising, or which is the reaction product of, a cyclic lactone, a cyclic ether, or a mixture thereof, present in an amount of about 30 to about 60 weight percent of the total molecular weight of the block copolymer; (b) at least one diisocyanate, A polyurethane or polyurethaneurea composition reaction product is formed by reacting (a) with (b) in an NCO:OH molar ratio of about 0.9:1 to about 2:1 (e.g., in the absence of a plasticizer).

[0057] In any aspect or embodiment described herein, the reaction further includes (c) a diol chain extender, a diamine chain extender, or a mixture thereof, each having a molecular weight of from about 60 to about 600, and the polyurethane or polyurethaneurea composition reaction product is formed by reacting (a), (b), and (c) in an NCO:OH molar ratio of from about 0.9:1 to about 2:1 (e.g., in the absence of a plasticizer).

[0058]

[0042] In any aspect or embodiment describe herein, the polyurethane or polyurethaneurea composition comprises: (a) at least one block copolymer of the ABA type having a number average molecular weight of 2500 to 5000 g / mol, said block copolymer comprising: (i) a poly(tetrahydrofuran) diol, a poly(substituted tetrahydrofuran) diol, or a mixture thereof, present in an amount of about 40 to about 70 weight percent of the total molecular weight of the block copolymer; and (ii) a block copolymer comprising, or which is the reaction product of, a cyclic lactone, a cyclic ether, or a mixture thereof, present in an amount of about 30 to about 60 weight percent of the total molecular weight of the block copolymer; (b) at least one diisocyanate; (c) a reaction product of a diol chain extender, a diamine chain extender, or a mixture thereof, each having a molecular weight of about 60 to about 600; A polyurethane or polyurethaneurea composition reaction product is formed by reacting (a), (b), and (c) in an NCO:OH molar ratio of about 0.9:1 to about 2:1 (e.g., in the absence of a plasticizer).

[0059] In any aspect or embodiment described herein, the at least one ABA-type block copolymer has a number average molecular weight of about 2500 to about 5000 g / mol. For example, in any aspect or embodiment described herein, the at least one ABA-type block copolymer has a number average molecular weight of about 2500 to about 5000 g / mol, about 2500 to about 4500 g / mol, about 2500 to about 4000 g / mol, about 2500 to about 3500 g / mol, about 3000 to about 5000 g / mol, about 3000 to about 4500 g / mol, about 3000 to about 4000 g / mol, about 3500 to about 5000 g / mol, about 3500 to about 4500 g / mol, or about 4000 to about 5000 g / mol.

[0060] In any aspect or embodiment described herein, the poly(tetrahydrofuran)diol, poly(substituted tetrahydrofuran)diol, or mixture thereof is present in an amount of about 40 to about 70 weight percent of the total molecular weight of the block copolymer. For example, in any aspect or embodiment described herein, the poly(tetrahydrofuran)diol, poly(substituted tetrahydrofuran)diol, or mixture thereof is present in an amount of about 40 to about 70 weight percent, about 40 to about 65 weight percent, about 40 to about 60 weight percent, about 40 to about 55 weight percent, about 45 to about 70 weight percent, about 45 to about 65 weight percent, about 45 to about 60 weight percent, about 50 to about 70 weight percent, about 50 to about 65 weight percent, or about 55 to about 75 weight percent of the total molecular weight of the block copolymer. In any aspect or embodiment described herein, reactant (i) is present in an amount of about 50 to about 70 weight percent of the total molecular weight of the block copolymer.

[0061] In any aspect or embodiment described herein, the cyclic lactone, cyclic ether, or mixture thereof is present in an amount of about 30 to about 60% by weight of the total molecular weight of the block copolymer. For example, in any aspect or embodiment described herein, the cyclic lactone, cyclic ether, or mixture thereof is present in an amount of about 30 to about 60%, about 30 to about 55%, about 30 to about 50%, about 30 to about 45%, about 35 to about 60%, about 35 to about 55%, about 35 to about 50%, about 40 to about 60%, about 40 to about 55%, or about 45 to about 50% by weight of the total molecular weight of the block copolymer.

[0062] In any aspect or embodiment described herein, reactant (b) is present in an amount of about 50 to about 70 weight percent of the total molecular weight of the block copolymer. For example, in any aspect or embodiment described herein, reactant (b) is present in an amount of about 50 to about 70 weight percent, about 50 to about 65 weight percent, about 50 to about 60 weight percent, about 55 to about 70 weight percent, about 55 to about 65 weight percent, or about 60 to about 70 weight percent of the total molecular weight of the block copolymer.

[0063] In any aspect or embodiment described herein, the composition has a hardness of about 30 Shore A to about 60 Shore D. For example, in any aspect or embodiment described herein, the composition may have a hardness of about 30 Shore A to about 60 Shore D, about 30 Shore A to about 50 Shore D, about 30 Shore A to about 40 Shore D, about 30 Shore A to about 30 Shore D, about 30 Shore A to about 70 Shore A, about 30 Shore A to about 60 Shore A, about 40 Shore A to about 60 Shore D, about 40 Shore A to about 50 Shore D, about 40 Shore A to about 40 Shore D, about 40 Shore A to about 30 Shore D, or about 40 Shore A to about 70 Shore D. Shore A, about 50 Shore A to about 60 Shore D, about 50 Shore A to about 50 Shore D, about 50 Shore A to about 40 Shore D, about 50 Shore A to about 30 Shore D, about 50 Shore A to about 70 Shore A, about 60 Shore A to about 60 Shore D, about 60 Shore A to about 50 Shore D, about 60 Shore A to about 40 Shore D, about 60 Shore A to about 30 Shore D, about 70 Shore A to about 60 Shore D, about 70 Shore A to about 50 Shore D, or about 30 Shore D to about 60 Shore D.

[0064] In any aspect or embodiment described herein, the NCO:OH molar ratio is about 0.9:1 to 1.7:1. In any aspect or embodiment described herein, the NCO:OH molar ratio is about 0.95:1 to 1.5:1. In any aspect or embodiment described herein, the NCO:OH molar ratio is about 1:1 to 1.2:1.

[0065] In any aspect or embodiment described herein, the polyurethane or polyurethaneurea composition has a glass transition temperature, as measured by differential scanning calorimetry, of less than −60° C. For example, in any aspect or embodiment described herein, the polyurethane or polyurethaneurea composition has a glass transition temperature, as measured by dynamic mechanical analysis, of less than −60° C., −55° C., −50° C., −45° C., −40° C., −35° C., or −30° C.

[0066] In any aspect or embodiment described herein, reactant (i) comprises or is a poly(substituted tetrahydrofuran) diol. For example, in any aspect or embodiment described herein, reactant (i) is a poly(substituted tetrahydrofuran) diol, wherein the substitution is C 1-4 Alkyl (e.g., methyl, ethyl, or propyl), C 1-6 Alkoxy (e.g., methoxy or ethoxy), C 2-6 and one or more (e.g., 1, 2, 3, 4, 5, 6, or more) substitutions independently selected from alkenyl, aromatic (e.g., phenyl, aryl, or heteroaryl), ester, halogen, halide, amide, or ketone. In any aspect or embodiment described herein, the poly(tetrahydrofuran) diol or reactant (i) comprises or is poly(tetramethylene ether) glycol (PTMEG). In any aspect or embodiment described herein, the poly(substituted tetrahydrofuran) diol or reactant (i) comprises or is Me-PTMEG.

[0067] In any aspect or embodiment describe herein, the cyclic lactone includes or is ε-caprolactone.

[0068] In any aspect or embodiment describe herein, the cyclic ether comprises or is ethylene oxide, propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, or a mixture thereof.

[0069] In any aspect or embodiment described herein, the diisocyanate may include or be an aliphatic diisocyanate, an aromatic diisocyanate, or a combination thereof. For example, in any aspect or embodiment described herein, the diisocyanate may be 4,4'-diphenylmethane diisocyanate, isophorone diisocyanate, bimethylene diisocyanate, trimethylene diisocyanate (e.g., 1,3-trimethylene diisocyanate, 2,3-trimethylene diisocyanate, 1,2-trimethylene diisocyanate, 2,2-trimethylene diisocyanate, or a mixture thereof), tetramethylene diisocyanate (e.g., 1,4- Tetramethylene diisocyanate, 1,3-tetramethylene diisocyanate, 1,2-tetramethylene diisocyanate, 2,3-tetramethylene diisocyanate, 1,1-tetramethylene diisocyanate, 2,2-tetramethylene diisocyanate, or mixtures thereof), pentamethylene diisocyanate (e.g., 1,5-pentamethylene diisocyanate, 1,4-pentamethylene diisocyanate, 1,3-pentamethylene diisocyanate, 1,2-pentamethylene diisocyanate, Isocyanates, 2,3-pentamethylene diisocyanate, 2,4-pentamethylene diisocyanate, 3,4-pentamethylene diisocyanate, 3,5-pentamethylene diisocyanate, 1,1-pentamethylene diisocyanate, 2,2-pentamethylene diisocyanate, 3,3-pentamethylene diisocyanate, or mixtures thereof), hexamethylene diisocyanate (e.g., 1,6-hexamethylene diisocyanate, 1,5-hexamethylene diisocyanate, 1,4-Hexamethylene diisocyanate, 1,3-Hexamethylene diisocyanate, 1,2-Hexamethylene diisocyanate, 2,3-Hexamethylene diisocyanate, 2,4-Hexamethylene diisocyanate, 2,5-Hexamethylene diisocyanate, 3,4-Hexamethylene diisocyanate, 3,5-Hexamethylene diisocyanate, 4,5-Hexamethylene diisocyanate, 1,1-Hexamethylene diisocyanate, 2,2-Hexamethylene diisocyanate, 3,3-hexamethylene diisocyanate, or mixtures thereof), heptamethylene diisocyanate (e.g., 1,7-heptamethylene diisocyanate, 1,6-heptamethylene diisocyanate, 1,5-heptamethylene diisocyanate, 1,4-heptamethylene diisocyanate, 1,3-heptamethylene diisocyanate, 1,2-heptamethylene diisocyanate, 2,3-heptamethylene diisocyanate, 2,4-heptamethylene diisocyanate, 2, 5-heptamethylene diisocyanate, 2,6-heptamethylene diisocyanate, 3,3-heptamethylene diisocyanate, 3,4-heptamethylene diisocyanate, 1,1-heptamethylene diisocyanate, 2,2-heptamethylene diisocyanate, 3,3-heptamethylene diisocyanate, 4,4-heptamethylene diisocyanate, or mixtures thereof), toluene diisocyanate (e.g., toluene-2,4-diisocyanate, toluene-2,6 -diisocyanates, or mixtures thereof), naphthylene diisocyanates (e.g., 1,2-naphthylene diisocyanate, 1,3-naphthylene diisocyanate, 1,4-naphthylene diisocyanate, 1,5-naphthylene diisocyanate, 1,6-naphthylene diisocyanate, 1,7-naphthylene diisocyanate, 1,8-naphthylene diisocyanate, or mixtures thereof), cyclohexylmethane diisocyanate (e.g., 1,4-cyclohexyl The compound may comprise or be any of: dicyclohexylmethane diisocyanate (e.g., 4,4'-dicyclohexylmethane diisocyanate, 2,4-cyclohexylmethane diisocyanate, 3,4-cyclohexylmethane diisocyanate, 4,4-cyclohexylmethane diisocyanate, or mixtures thereof); dicyclohexylmethane diisocyanate (e.g., 4,4'-dicyclohexylmethane diisocyanate, 1,4-dicyclohexylmethane diisocyanate, or mixtures thereof);

[0070]

[0047] In any aspect or embodiment describe herein, the diisocyanate is 4,4'-diphenylmethane diisocyanate, isophorone diisocyanate, bimethylene diisocyanate, 1,3-trimethylene diisocyanate, 2,3-trimethylene diisocyanate, 1,2-trimethylene diisocyanate, 2,2-trimethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,3-tetramethylene diisocyanate, 1,2-tetramethylene diisocyanate, 2,3-tetramethylene diisocyanate, 1,1- Tetramethylene diisocyanate, 2,2-tetramethylene diisocyanate, 1,5-pentamethylene diisocyanate, 1,4-pentamethylene diisocyanate, 1,3-pentamethylene diisocyanate, 1,3-pentamethylene diisocyanate, 2,3-pentamethylene diisocyanate, 2,4-pentamethylene diisocyanate, 3,4-pentamethylene diisocyanate, 3,5-pentamethylene diisocyanate, 1,1-pentamethylene diisocyanate, 2,2-pentamethylene diisocyanate, 3,3-pentamethylene Diisocyanate, 1,6-hexamethylene diisocyanate, 1,5-hexamethylene diisocyanate, 1,4-hexamethylene diisocyanate, 1,3-hexamethylene diisocyanate, 1,2-hexamethylene diisocyanate, 2,3-hexamethylene diisocyanate, 2,4-hexamethylene diisocyanate, 2,5-hexamethylene diisocyanate, 3,4-hexamethylene diisocyanate, 3,5-hexamethylene diisocyanate, 4,5-hexamethylene diisocyanate, 1,1-hexamethylene diisocyanate nate, 2,2-hexamethylene diisocyanate, 3,3-hexamethylene diisocyanate, 1,7-heptamethylene diisocyanate, 1,6-heptamethylene diisocyanate, 1,5-heptamethylene diisocyanate, 1,4-heptamethylene diisocyanate, 1,3-heptamethylene diisocyanate, 1,2-heptamethylene diisocyanate, 2,3-heptamethylene diisocyanate, 2,4-heptamethylene diisocyanate, 2,5-heptamethylene diisocyanate, 2,6-heptamethylene diisocyanate, 3,3-heptamethylene diisocyanate, 3,4-heptamethylene diisocyanate, 1,1-heptamethylene diisocyanate, 2,2-heptamethylene diisocyanate, 3,3-heptamethylene diisocyanate, 4,4-heptamethylene diisocyanate, toluene-2,4-diisocyanate, toluene-2,6-diisocyanate, 1,2-naphthylene diisocyanate, 1,3-naphthylene diisocyanate, 1,4-naphthylene diisocyanate, 1,5-naphthylene diisocyanate, 1 The compound may comprise or be any of: 1,6-naphthylene diisocyanate, 1,7-naphthylene diisocyanate, 1,8-naphthylene diisocyanate, 1,4-cyclohexylmethane diisocyanate, 2,4-cyclohexylmethane diisocyanate, 3,4-cyclohexylmethane diisocyanate, 4,4-cyclohexylmethane diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 1,4-dicyclohexylmethane diisocyanate, or mixtures thereof.

[0071]

[0041] In any aspect or embodiment describe herein, the diisocyanate includes or is any of 4,4'-diphenylmethane diisocyanate, isophorone diisocyanate, 1,6-hexamethylene diisocyanate, toluene-2,4-diisocyanate, 1,5-naphthylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, or a mixture thereof.

[0072] In any aspect or embodiment described herein, the diol chain extender includes or is an aliphatic diol or an aromatic diol. For example, in any aspect or embodiment described herein, the diol chain extender can be an alkylene oxide or a glycol, ethylene glycol, propanediol (e.g., 1,3-propanediol, 1,2-propanediol, 1,1-propanediol, 2,2-propanediol, or a mixture thereof), butanediol (e.g., 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, 2,3-butanediol, 1,1-butanediol, 2,2-butanediol, or a mixture thereof), or a mixture of alkylene oxides such as ethylene glycol, propanediol (e.g., 1,3-propanediol, 1,2-propanediol, 1,1-propanediol, 2,2-propanediol, or a mixture thereof), butanediol (e.g., 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, 2,3-butanediol, 1,1-butanediol, 2,2-butanediol, or a mixture thereof). or mixtures thereof), pentanediols (e.g., 1,5-pentanediol, 1,4-pentanediol, 1,3-pentanediol, 1,2-pentanediol, 2,3-pentanediol, 2,4-pentanediol, 3,4-pentanediol, 3,5-hexanediol, 1,1-pentanediol, 2,2-pentanediol, 3,3-pentanediol, or mixtures thereof), hexanediols (e.g., 1,6-hexanediol, 1,5-hexanediol, 1,4-hexanediol, 1,3-hexanediol, hexanediol, 1,2-hexanediol, 2,3-hexanediol, 2,4-hexanediol, 2,5-hexanediol, 3,4-hexanediol, 3,5-hexanediol, 4,5-hexanediol, 1,1-hexanediol, 2,2-hexanediol, 3,3-hexanediol, or mixtures thereof), heptanediols (e.g., 1,7-heptanediol, 1,6-heptanediol, 1,5-heptanediol, 1,4-heptanediol, 1,3-heptanediol, 1,2-heptanediol, 2 ,3-heptadiol, 2,4-heptadiol, 2,5-heptadiol, 2,6-heptadiol, 3,3-heptadiol, 3,4-heptadiol, 1,1-heptadiol, 2,2-heptadiol, 3,3-heptadiol, 4,4-heptadiol, or mixtures thereof), dihydroxybenzenes (e.g., 1,2-dihydroxybenzene, 1,3-dihydroxybenzene, 1,4-dihydroxybenzene, or mixtures thereof), di(hydroxyethyl)-hydroxyquinones (e.g., 1,4-di-(beta hydroxyethyl)-hydroxyquinone, 2,5-di-(hydroxyethyl)-hydroxyquinone, 2,3-di-(hydroxyethyl)-hydroxyquinone, 3,5-di-(hydroxyethyl)-hydroxyquinone, or mixtures thereof), di(hydroxymethyl)-hydroxyquinone (e.g., 2,5-di-(hydroxyethyl)-hydroxyquinone, 2,3-di-(hydroxymethyl)-hydroxyquinone, 3,5-di-(hydroxymethyl)-hydroxyquinone, or mixtures thereof), di-(hydroxyethyl)-bisphenol A (e.g., 1,4-di-(beta hydroxyethyl)-bisphenol A, 1,3-di-(beta hydroxyethyl)-bisphenol A, The bisphenol A may be, or may be, any of 1,2-di-(beta hydroxyethyl)-bisphenol A, 1,5-di-(beta hydroxyethyl)-bisphenol A, 2,3-di-(beta hydroxyethyl)-bisphenol A, 2,4-di-(beta hydroxyethyl)-bisphenol A, 2,5-di-(beta hydroxyethyl)-bisphenol A, 2,6-di-(beta hydroxyethyl)-bisphenol A, 3,4-di-(beta hydroxyethyl)-bisphenol A, 3,5-di-(beta hydroxyethyl)-bisphenol A, or mixtures thereof.

[0073]

[0044] In any aspect or embodiment describe herein, the diol chain extender is selected from the group consisting of ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,1-propanediol, 2,2-propanediol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, 2,3-butanediol, 1,1-butanediol, 2,2-butanediol, 1,5-pentanediol, 1,4-pentanediol, 1,3-pentanediol, 1,2-pentanediol, 2,3-pentanediol, 2,4-pentanediol, 3,4-pentanediol, Diol, 3,5-hexanediol, 1,1-pentanediol, 2,2-pentanediol, 3,3-pentanediol, 1,6-hexanediol, 1,5-hexanediol, 1,4-hexanediol, 1,3-hexanediol, 1,2-hexanediol, 2,3-hexanediol, 2,4-hexanediol, 2,5-hexanediol, 3,4-hexanediol, 3,5-hexanediol, 4,5-hexanediol, 1,1-hexanediol, 2,2-hexanediol, 3,3-hexanediol, 1,7-heptanediol, 1 ,6-heptadiol, 1,5-heptadiol, 1,4-heptadiol, 1,3-heptadiol, 1,2-heptadiol, 2,3-heptadiol, 2,4-heptadiol, 2,5-heptadiol, 2,6-heptadiol, 3,3-heptadiol, 3,4-heptadiol, 1,1-heptadiol, 2,2-heptadiol, 3,3-heptadiol, 4,4-heptadiol, 1,2-dihydroxybenzene, 1,3-dihydroxybenzene, 1,4-dihydroxybenzene, 1,4-di-(beta-hydroxyethyl)-hydroxy Quinones, 2,5-di-(hydroxyethyl)-hydroxyquinone, 2,3-di-(hydroxyethyl)-hydroxyquinone, 3,5-di-(hydroxyethyl)-hydroxyquinone, 2,5-di-(hydroxyethyl)-hydroxyquinone, 2,3-di-(hydroxymethyl)-hydroxyquinone, 3,5-di-(hydroxymethyl)-hydroxyquinone, 1,4-di-(beta hydroxyethyl)-bisphenol A, 1,3-di-(beta hydroxyethyl)-bisphenol A, 1,2-di-(beta hydroxyethyl)-bisphenol A, 1,The bisphenol A may be, or may contain, 5-di-(beta hydroxyethyl)-bisphenol A, 2,3-di-(beta hydroxyethyl)-bisphenol A, 2,4-di-(beta hydroxyethyl)-bisphenol A, 2,5-di-(beta hydroxyethyl)-bisphenol A, 2,6-di-(beta hydroxyethyl)-bisphenol A, 3,4-di-(beta hydroxyethyl)-bisphenol A, 3,5-di-(beta hydroxyethyl)-bisphenol A, or mixtures thereof.

[0074]

[0044] In any aspect or embodiment describe herein, the diol chain extender includes or is any of ethylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,4-di-(beta hydroxyethyl)-hydroxyquinone, 1,4-di-(beta hydroxyethyl)-bisphenol A, or a mixture thereof.

[0075]

[0044] In any aspect or embodiment described herein, the diamine chain extender is diaminodiphenylmethane (e.g., 2,2'-diaminodiphenylmethane, 2,3'-diaminodiphenylmethane, 2,4'-diaminodiphenylmethane, 2,5'-diaminodiphenylmethane, 2,6'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 3,5'-diaminodiphenylmethane, 3,6'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 4,5'-diaminodiphenylmethane, 4,6'-diaminodiphenyl methane, 5,6'-diaminodiphenylmethane, or mixtures thereof), dichloro-diaminodiphenylmethane (e.g., 2,2'-dichloro-3,3'-diaminodiphenylmethane, 2,2'-dichloro-4,4'-diaminodiphenylmethane, 5,5'-dichloro-3,3'-diaminodiphenylmethane, 2,2'-dichloro-6,6'-diaminodiphenylmethane, 2,2'-dichloro-3,4'-diaminodiphenylmethane, 2,2'-dichloro-3,5'-diaminodiphenylmethane, 2,2'-dichloro-3,6'-diaminodiphenylmethane Nilmethane, 2,2'-dichloro-4,5'-diaminodiphenylmethane, 2,2'-dichloro-4,6'-diaminodiphenylmethane, 2,2'-dichloro-5,6'-diaminodiphenylmethane, 3,3'-dichloro-2,2'-diaminodiphenylmethane, 3,3'-dichloro-4,4'-diaminodiphenylmethane, 3,3'-dichloro-5,5'-diaminodiphenylmethane, 3,3'-dichloro-6,6'-diaminodiphenylmethane, 3,3'-dichloro-2,5'-diaminodiphenylmethane, 3,3'-dichloro-4,5'-diamino aminodiphenylmethane, 3,3'-dichloro-6,5'-diaminodiphenylmethane, 3,3'-dichloro-4,2'-diaminodiphenylmethane, 3,3'-dichloro-4,6'-diaminodiphenylmethane, 4,4'-dichloro-2,2'-diaminodiphenylmethane, 4,4'-dichloro-3,3'-diaminodiphenylmethane, 4,4'-dichloro-5,5'-diaminodiphenylmethane, 4,4'-dichloro-6,6'-diaminodiphenylmethane, 4,4'-dichloro-2,3'-diaminodiphenylmethane, 4,4'-dichloro-2,5'-Diaminodiphenylmethane, 4,4'-dichloro-2,6'-diaminodiphenylmethane, 4,4'-dichloro-3,5'-diaminodiphenylmethane, 4,4'-dichloro-3,6'-diaminodiphenylmethane, 4,4'-dichloro-5,6'-diaminodiphenylmethane, 5,5'-dichloro-2,2'-diaminodiphenylmethane, 5,5'-dichloro-3,3'-diaminodiphenylmethane, 5,5'-dichloro-4,4'-diaminodiphenylmethane, 5,5'-dichloro-6,6'-diaminodiphenylmethane, 5,5'-dichloro -2,3'-diaminodiphenylmethane, 5,5'-dichloro-2,4'-diaminodiphenylmethane, 5,5'-dichloro-2,6'-diaminodiphenylmethane, 5,5'-dichloro-3,4'-diaminodiphenylmethane, 5,5'-dichloro-3,6'-diaminodiphenylmethane, 5,5'-dichloro-4,6'-diaminodiphenylmethane, 6,6'-dichloro-2,2'-diaminodiphenylmethane, 6,6'-dichloro-3,3'-diaminodiphenylmethane, 6,6'-dichloro-4,4'-diaminodiphenylmethane, 6,6'-di chloro-5,5'-diaminodiphenylmethane, 6,6'-dichloro-2,3'-diaminodiphenylmethane, 6,6'-dichloro-2,4'-diaminodiphenylmethane, 6,6'-dichloro-2,5'-diaminodiphenylmethane, 6,6'-dichloro-3,4'-diaminodiphenylmethane, 6,6'-dichloro-3,5'-diaminodiphenylmethane, 6,6'-dichloro-4,5'-diaminodiphenylmethane, or mixtures thereof), diaminobenzenes (e.g., 1,4-diaminobenzene, 1,2-diaminobenzene, 1,3-diaminodiphenylmethane, dimethoxy-diaminobiphenyl (e.g., 2,2'-dimethoxy-3,3'-diaminobiphenyl, 2,2'-dimethoxy-4,4'-diaminobiphenyl, 5,5'-dimethoxy-3,3'-diaminobiphenyl, 2,2'-dimethoxy-6,6'-diaminobiphenyl, 2,2'-dimethoxy-3,4'-diaminobiphenyl, 2,2'-dimethoxy-3,5'-diaminobiphenyl, 2,2'-dimethoxy-3,6'-diaminobiphenyl, 2,2'-dimethoxy-4,5'-diaminobiphenyl, 2,2'-Dimethoxy-4,6'-diaminobiphenyl, 2,2'-dimethoxy-5,6'-diaminobiphenyl, 3,3'-dimethoxy-2,2'-diaminobiphenyl, 3,3'-dimethoxy-4,4-diaminobiphenyl, 3,3'-dimethoxy-5,5'-diaminobiphenyl, 3,3'-dimethoxy-6,6'-diaminobiphenyl, 3,3'-dimethoxy-2,5'-diaminobiphenyl, 3,3'-dimethoxy-4,5'-diaminobiphenyl, 3,3'-dimethoxy-6,5'-diaminobiphenyl, 3,3'-dimethoxy-4,2'-diaminobiphenyl 4,4'-dimethoxy-2,2'-diaminobiphenyl, 4,4'-dimethoxy-3,3'-diaminobiphenyl, 4,4'-dimethoxy-5,5'-diaminobiphenyl, 4,4'-dimethoxy-6,6'-diaminobiphenyl, 4,4'-dimethoxy-2,3'-diaminobiphenyl, 4,4'-dimethoxy-2,5'-diaminobiphenyl, 4,4'-dimethoxy-2,6'-diaminobiphenyl, 4,4'-dimethoxy-3,5'-diaminobiphenyl, 4,4'-dimethoxy 4,4'-dimethoxy-5,6'-diaminobiphenyl, 5,5'-dimethoxy-2,2'-diaminobiphenyl, 5,5'-dimethoxy-3,3'-diaminobiphenyl, 5,5'-dimethoxy-4,4'-diaminobiphenyl, 5,5'-dimethoxy-6,6'-diaminobiphenyl, 5,5'-dimethoxy-2,3'-diaminobiphenyl, 5,5'-dimethoxy-2,4'-diaminobiphenyl, 5,5'-dimethoxy-2,6'-diaminobiphenyl, 5,5'-dimethoxy-3,4'-diaminobiphenyl Nyl, 5,5'-dimethoxy-3,6'-diaminobiphenyl, 5,5'-dimethoxy-4,6'-diaminobiphenyl, 6,6'-dimethoxy-2,2'-diaminobiphenyl, 6,6'-dimethoxy-3,3'-diaminobiphenyl, 6,6'-dimethoxy-4,4'-diaminobiphenyl, 6,6'-dimethoxy-5,5'-diaminobiphenyl, 6,6'-dimethoxy-2,3'-diaminobiphenyl, 6,6'-dimethoxy-2,4'-diaminobiphenyl, 6,6'-dimethoxy-2,5'-diaminobiphenyl, 6,6'-dimethoxy-3,4'-diaminobiphenyl, 6,6'-dimethoxy-3,5'-diaminobiphenyl, 6,6'-dimethoxy-4,5'-diaminobiphenyl, or mixtures thereof), dimethyl-diaminobiphenyls (e.g., 2,2'-dimethyl-3,3'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 5,5'-dimethyl-3,3'-diaminobiphenyl, 2,2'-dimethyl-6,6'-diaminobiphenyl, 2,2'-dimethyl-3,4'-diaminobiphenyl, 2,2'-dimethyl-3,5'-diaminobiphenyl, 2, 2'-dimethyl-3,6'-diaminobiphenyl, 2,2'-dimethyl-4,5'-diaminobiphenyl, 2,2'-dimethyl-4,6'-diaminobiphenyl, 2,2'-dimethyl-5,6'-diaminobiphenyl, 3,3'-dimethyl-2,2'-diaminobiphenyl, 3,3'-dimethyl-4,4-diaminobiphenyl, 3,3'-dimethyl-5,5'-diaminobiphenyl, 3,3'-dimethyl-6,6'-diaminobiphenyl, 3,3'-dimethyl-2,5'-diaminobiphenyl, 3,3'-dimethyl-4,5'-diaminobiphenyl, 3,3 '-Dimethyl-6,5'-diaminobiphenyl, 3,3'-dimethyl-4,2'-diaminobiphenyl, 3,3'-dimethyl-4,6'-diaminobiphenyl, 4,4'-dimethyl-2,2'-diaminobiphenyl, 4,4'-dimethyl-3,3'-diaminobiphenyl, 4,4'-dimethyl-5,5'-diaminobiphenyl, 4,4'-dimethyl-6,6'-diaminobiphenyl, 4,4'-dimethyl-2,3'-diaminobiphenyl, 4,4'-dimethyl-2,5'-diaminobiphenyl, 4,4'-dimethyl-2,6'-diaminobiphenyl, 4, 4'-dimethyl-3,5'-diaminobiphenyl, 4,4'-dimethyl-3,6'-diaminobiphenyl, 4,4'-dimethyl-5,6'-diaminobiphenyl, 5,5'-dimethyl-2,2'-diaminobiphenyl, 5,5'-dimethyl-3,3'-diaminobiphenyl, 5,5'-dimethyl-4,4'-diaminobiphenyl, 5,5'-dimethyl-6,6'-diaminobiphenyl, 5,5'-dimethyl-2,3'-diaminobiphenyl, 5,5'-dimethyl-2,4'-diaminobiphenyl, 5,5'-dimethyl-2,6'-diaminobiphenyl, 5,5'-dimethyl-3,4'-diaminobiphenyl, 5,5'-dimethyl-3,6'-diaminobiphenyl, 5,5'-dimethyl-4,6'-diaminobiphenyl, 6,6'-dimethyl-2,2'-diaminobiphenyl, 6,6'-dimethyl-3,3'-diaminobiphenyl, 6,6'-dimethyl-4,4'-diaminobiphenyl, 6,6'-dimethyl-5,5'-diaminobiphenyl, 6,6'-dimethyl-2,3'-diaminobiphenyl, 6,6'-dimethyl-2,4'-diaminobiphenyl, 6,6'-dimethyl-2,5'-diaminobiphenyl, 6 ,6'-dimethyl-3,4'-diaminobiphenyl, 6,6'-dimethyl-3,5'-diaminobiphenyl, 6,6'-dimethyl-4,5'-diaminobiphenyl, or mixtures thereof), diaminobiphenyls (e.g., 2,2'-diaminobiphenyl, 2,3'-diaminobiphenyl, 2,4'-diaminobiphenyl, 2,5'-diaminobiphenyl, 2,6'-diaminobiphenyl, 3,4'-diaminobiphenyl, 3,5'-diaminobiphenyl, 3,6'-diaminobiphenyl, 4,4'-diaminobiphenyl, 4,5'-diaminobiphenyl , 4,6'-diaminobiphenyl, 5,6'-diaminobiphenyl, or mixtures thereof), dichloro-diaminobiphenyls (e.g., 2,2'-dichloro-3,3'-diaminobiphenyl, 2,2'-dichloro-4,4'-diaminobiphenyl, 5,5'-dichloro-3,3'-diaminobiphenyl, 2,2'-dichloro-6,6'-diaminobiphenyl, 2,2'-dichloro-3,4'-diaminobiphenyl, 2,2'-dichloro-3,5'-diaminobiphenyl, 2,2'-dichloro-3,6'-diaminobiphenyl, 2,2'-dichloro-4, 5'-Diaminobiphenyl, 2,2'-dichloro-4,6'-diaminobiphenyl, 2,2'-dichloro-5,6'-diaminobiphenyl, 3,3'-dichloro-2,2'-diaminobiphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl, 3,3'-dichloro-5,5'-diaminobiphenyl, 3,3'-dichloro-6,6'-diaminobiphenyl, 3,3'-dichloro-2,5'-diaminobiphenyl, 3,3'-dichloro-4,5'-diaminobiphenyl, 3,3'-dichloro-6,5'-diaminobiphenyl, 3,3'-dichloro-4,2'-diaminobiphenyl, 3,3'-dichloro-4,6'-diaminobiphenyl, 4,4'-dichloro-2,2'-diaminobiphenyl, 4,4'-dichloro-3,3'-diaminobiphenyl, 4,4'-dichloro-5,5'-diaminobiphenyl, 4,4'-dichloro-6,6'-diaminobiphenyl, 4,4'-dichloro-2,3'-diaminobiphenyl, 4,4'-dichloro-2,5'-diaminobiphenyl, 4,4'-dichloro-2,6'-diaminobiphenyl, 4,4'-dichloro-3,5'-diaminobiphenyl, 4,4'-dichloro-3,6'-diaminobiphenyl, 4,4'-dichloro-5,6'-diaminobiphenyl, 5,5'-dichloro-2,2'-diaminobiphenyl, 5,5'-dichloro-3,3'-diaminobiphenyl, phenyl, 5,5'-dichloro-4,4'-diaminobiphenyl, 5,5'-dichloro-6,6'-diaminobiphenyl, 5,5'-dichloro-2,3'-diaminobiphenyl, 5,5'-dichloro-2,4'-diaminobiphenyl, 5,5'-dichloro-2,6'-diaminobiphenyl, 5,5'-dichloro-3,4'-diaminobiphenyl, 5,5'-dichloro-3,6'-diaminobiphenyl, 5,5'-dichloro-4,6'-diaminobiphenyl, 6,6'-dichloro-2,2'-diaminobiphenyl, 6,6'-dichloro-3,3'-diaminobiphenyl and / or mixtures thereof).

[0076]

[0049] In any aspect or embodiment described herein, the diamine chain extender is selected from the group consisting of 2,2'-diaminodiphenylmethane, 2,3'-diaminodiphenylmethane, 2,4'-diaminodiphenylmethane, 2,5'-diaminodiphenylmethane, 2,6'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 3,5'-diaminodiphenylmethane, 3,6'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 4,5'-diaminodiphenylmethane, 4,6'-diaminodiphenylmethane, 5,6'-diaminodiphenyl Methane, 2,2'-dichloro-3,3'-diaminodiphenylmethane, 2,2'-dichloro-4,4'-diaminodiphenylmethane, 5,5'-dichloro-3,3'-diaminodiphenylmethane, 2,2'-dichloro-6,6'-diaminodiphenylmethane, 2,2'-dichloro-3,4'-diaminodiphenylmethane, 2,2'-dichloro-3,5'-diaminodiphenylmethane, 2,2'-dichloro-3,6'-diaminodiphenylmethane, 2,2'-dichloro-4,5'-diaminodiphenylmethane, 2,2'-dichloro-4,6'-diaminodi Phenylmethane, 2,2'-dichloro-5,6'-diaminodiphenylmethane, 3,3'-dichloro-2,2'-diaminodiphenylmethane, 3,3'-dichloro-4,4'-diaminodiphenylmethane, 3,3'-dichloro-5,5'-diaminodiphenylmethane, 3,3'-dichloro-6,6'-diaminodiphenylmethane, 3,3'-dichloro-2,5'-diaminodiphenylmethane, 3,3'-dichloro-4,5'-diaminodiphenylmethane, 3,3'-dichloro-6,5'-diaminodiphenylmethane, 3,3'-dichloro-4,2'-di Aminodiphenylmethane, 3,3'-dichloro-4,6'-diaminodiphenylmethane, 4,4'-dichloro-2,2'-diaminodiphenylmethane, 4,4'-dichloro-3,3'-diaminodiphenylmethane, 4,4'-dichloro-5,5'-diaminodiphenylmethane, 4,4'-dichloro-6,6'-diaminodiphenylmethane, 4,4'-dichloro-2,3'-diaminodiphenylmethane, 4,4'-dichloro-2,5'-diaminodiphenylmethane, 4,4'-dichloro-2,6'-diaminodiphenylmethane, 4,4'-dichloro-3,5'-Diaminodiphenylmethane, 4,4'-dichloro-3,6'-diaminodiphenylmethane, 4,4'-dichloro-5,6'-diaminodiphenylmethane, 5,5'-dichloro-2,2'-diaminodiphenylmethane, 5,5'-dichloro-3,3'-diaminodiphenylmethane, 5,5'-dichloro-4,4'-diaminodiphenylmethane, 5,5'-dichloro-6,6'-diaminodiphenylmethane, 5,5'-dichloro-2,3'-diaminodiphenylmethane, 5,5'-dichloro-2,4'-diaminodiphenylmethane, 5,5'-dichloro 2,6'-diaminodiphenylmethane, 5,5'-dichloro-3,4'-diaminodiphenylmethane, 5,5'-dichloro-3,6'-diaminodiphenylmethane, 5,5'-dichloro-4,6'-diaminodiphenylmethane, 6,6'-dichloro-2,2'-diaminodiphenylmethane, 6,6'-dichloro-3,3'-diaminodiphenylmethane, 6,6'-dichloro-4,4'-diaminodiphenylmethane, 6,6'-dichloro-5,5'-diaminodiphenylmethane, 6,6'-dichloro-2,3'-diaminodiphenylmethane, 6,6'- Dichloro-2,4'-diaminodiphenylmethane, 6,6'-dichloro-2,5'-diaminodiphenylmethane, 6,6'-dichloro-3,4'-diaminodiphenylmethane, 6,6'-dichloro-3,5'-diaminodiphenylmethane, 6,6'-dichloro-4,5'-diaminodiphenylmethane, 1,4-diaminobenzene, 1,2-diaminobenzene, 1,3-diaminobenzene, 2,2'-dimethoxy-3,3'-diaminobiphenyl, 2,2'-dimethoxy-4,4'-diaminobiphenyl, 5,5'-dimethoxy-3,3'-diaminobiphenyl nyl, 2,2'-dimethoxy-6,6'-diaminobiphenyl, 2,2'-dimethoxy-3,4'-diaminobiphenyl, 2,2'-dimethoxy-3,5'-diaminobiphenyl, 2,2'-dimethoxy-3,6'-diaminobiphenyl, 2,2'-dimethoxy-4,5'-diaminobiphenyl, 2,2'-dimethoxy-4,6'-diaminobiphenyl, 2,2'-dimethoxy-5,6'-diaminobiphenyl, 3,3'-dimethoxy-2,2'-diaminobiphenyl, 3,3'-dimethoxy-4,4-diaminobiphenyl, 3,3'-dimethoxy-5,5'-Diaminobiphenyl, 3,3'-dimethoxy-6,6'-diaminobiphenyl, 3,3'-dimethoxy-2,5'-diaminobiphenyl, 3,3'-dimethoxy-4,5'-diaminobiphenyl, 3,3'-dimethoxy-6,5'-diaminobiphenyl, 3,3'-dimethoxy-4,2'-diaminobiphenyl, 3,3'-dimethoxy-4,6'-diaminobiphenyl, 4,4'-dimethoxy-2,2'-diaminobiphenyl, 4,4'-dimethoxy-3,3'-diaminobiphenyl, 4,4'-dimethoxy-5,5'-diaminobiphenyl, 4,4 '-Dimethoxy-6,6'-diaminobiphenyl, 4,4'-dimethoxy-2,3'-diaminobiphenyl, 4,4'-dimethoxy-2,5'-diaminobiphenyl, 4,4'-dimethoxy-2,6'-diaminobiphenyl, 4,4'-dimethoxy-3,5'-diaminobiphenyl, 4,4'-dimethoxy-3,6'-diaminobiphenyl, 4,4'-dimethoxy-5,6'-diaminobiphenyl, 5,5'-dimethoxy-2,2'-diaminobiphenyl, 5,5'-dimethoxy-3,3'-diaminobiphenyl, 5,5'-dimethoxy-4,4'-diaminobiphenyl Biphenyl, 5,5'-dimethoxy-6,6'-diaminobiphenyl, 5,5'-dimethoxy-2,3'-diaminobiphenyl, 5,5'-dimethoxy-2,4'-diaminobiphenyl, 5,5'-dimethoxy-2,6'-diaminobiphenyl, 5,5'-dimethoxy-3,4'-diaminobiphenyl, 5,5'-dimethoxy-3,6'-diaminobiphenyl, 5,5'-dimethoxy-4,6'-diaminobiphenyl, 6,6'-dimethoxy-2,2'-diaminobiphenyl, 6,6'-dimethoxy-3,3'-diaminobiphenyl, 6,6'-dimethoxy 4,4'-diaminobiphenyl, 6,6'-dimethoxy-5,5'-diaminobiphenyl, 6,6'-dimethoxy-2,3'-diaminobiphenyl, 6,6'-dimethoxy-2,4'-diaminobiphenyl, 6,6'-dimethoxy-2,5'-diaminobiphenyl, 6,6'-dimethoxy-3,4'-diaminobiphenyl, 6,6'-dimethoxy-3,5'-diaminobiphenyl, 6,6'-dimethoxy-4,5'-diaminobiphenyl, 2,2'-dimethyl-3,3'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 5,5'-dimethyl-3,3'-diaminobiphenyl, 2,2'-dimethyl-6,6'-diaminobiphenyl, 2,2'-dimethyl-3,4'-diaminobiphenyl, 2,2'-dimethyl-3,5'-diaminobiphenyl, 2,2'-dimethyl-3,6'-diaminobiphenyl, 2,2'-dimethyl-4,5'-diaminobiphenyl, 2,2'-dimethyl-4,6'-diaminobiphenyl, 2,2'-dimethyl-5,6'-diaminobiphenyl, 3,3'-dimethyl-2,2'-diaminobiphenyl, 3,3'-dimethyl-4,4-diaminobiphenyl, 3, 3'-dimethyl-5,5'-diaminobiphenyl, 3,3'-dimethyl-6,6'-diaminobiphenyl, 3,3'-dimethyl-2,5'-diaminobiphenyl, 3,3'-dimethyl-4,5'-diaminobiphenyl, 3,3'-dimethyl-6,5'-diaminobiphenyl, 3,3'-dimethyl-4,2'-diaminobiphenyl, 3,3'-dimethyl-4,6'-diaminobiphenyl, 4,4'-dimethyl-2,2'-diaminobiphenyl, 4,4'-dimethyl-3,3'-diaminobiphenyl, 4,4'-dimethyl-5,5'-diaminobiphenyl, 4, 4'-dimethyl-6,6'-diaminobiphenyl, 4,4'-dimethyl-2,3'-diaminobiphenyl, 4,4'-dimethyl-2,5'-diaminobiphenyl, 4,4'-dimethyl-2,6'-diaminobiphenyl, 4,4'-dimethyl-3,5'-diaminobiphenyl, 4,4'-dimethyl-3,6'-diaminobiphenyl, 4,4'-dimethyl-5,6'-diaminobiphenyl, 5,5'-dimethyl-2,2'-diaminobiphenyl, 5,5'-dimethyl-3,3'-diaminobiphenyl, 5,5'-dimethyl-4,4'-diaminobiphenyl, 5, 5'-Dimethyl-6,6'-diaminobiphenyl, 5,5'-dimethyl-2,3'-diaminobiphenyl, 5,5'-dimethyl-2,4'-diaminobiphenyl, 5,5'-dimethyl-2,6'-diaminobiphenyl, 5,5'-dimethyl-3,4'-diaminobiphenyl, 5,5'-dimethyl-3,6'-diaminobiphenyl, 5,5'-dimethyl-4,6'-diaminobiphenyl, 6,6'-dimethyl-2,2'-diaminobiphenyl, 6,6'-dimethyl-3,3'-diaminobiphenyl, 6,6'-dimethyl-4,4'-diaminobiphenyl, 6,6'-Dimethyl-5,5'-diaminobiphenyl, 6,6'-dimethyl-2,3'-diaminobiphenyl, 6,6'-dimethyl-2,4'-diaminobiphenyl, 6,6'-dimethyl-2,5'-diaminobiphenyl, 6,6'-dimethyl-3,4'-diaminobiphenyl, 6,6'-dimethyl-3,5'-diaminobiphenyl, 6,6'-dimethyl-4,5'-diaminobiphenyl, 2,2'-diaminobiphenyl, 2,3'-diaminobiphenyl, 2,4'-diaminobiphenyl, 2,5'-diaminobiphenyl, 2,6'-diaminobiphenyl , 3,4'-diaminobiphenyl, 3,5'-diaminobiphenyl, 3,6'-diaminobiphenyl, 4,4'-diaminobiphenyl, 4,5'-diaminobiphenyl, 4,6'-diaminobiphenyl, 5,6'-diaminobiphenyl, 2,2'-dichloro-3,3'-diaminobiphenyl, 2,2'-dichloro-4,4'-diaminobiphenyl, 5,5'-dichloro-3,3'-diaminobiphenyl, 2,2'-dichloro-6,6'-diaminobiphenyl, 2,2'-dichloro-3,4'-diaminobiphenyl, 2,2'-dichloro-3,5'-diaminobiphenyl Aminobiphenyl, 2,2'-dichloro-3,6'-diaminobiphenyl, 2,2'-dichloro-4,5'-diaminobiphenyl, 2,2'-dichloro-4,6'-diaminobiphenyl, 2,2'-dichloro-5,6'-diaminobiphenyl, 3,3'-dichloro-2,2'-diaminobiphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl, 3,3'-dichloro-5,5'-diaminobiphenyl, 3,3'-dichloro-6,6'-diaminobiphenyl, 3,3'-dichloro-2,5'-diaminobiphenyl, 3,3'-dichloro-4,5' -diaminobiphenyl, 3,3'-dichloro-6,5'-diaminobiphenyl, 3,3'-dichloro-4,2'-diaminobiphenyl, 3,3'-dichloro-4,6'-diaminobiphenyl, 4,4'-dichloro-2,2'-diaminobiphenyl, 4,4'-dichloro-3,3'-diaminobiphenyl, 4,4'-dichloro-5,5'-diaminobiphenyl, 4,4'-dichloro-6,6'-diaminobiphenyl, 4,4'-dichloro-2,3'-diaminobiphenyl, 4,4'-dichloro-2,5'-diaminobiphenyl, 4,4'-dichloro-2,6'-Diaminobiphenyl, 4,4'-dichloro-3,5'-diaminobiphenyl, 4,4'-dichloro-3,6'-diaminobiphenyl, 4,4'-dichloro-5,6'-diaminobiphenyl, 5,5'-dichloro-2,2'-diaminobiphenyl, 5,5'-dichloro-3,3'-diaminobiphenyl, 5,5'-dichloro-4,4'-diaminobiphenyl, 5,5'-dichloro- 6,6'-diaminobiphenyl, 5,5'-dichloro-2,3'-diaminobiphenyl, 5,5'-dichloro-2,4'-diaminobiphenyl, 5,5'-dichloro-2,6'-diaminobiphenyl, 5,5'-dichloro-3,4'-diaminobiphenyl, 5,5'-dichloro-3,6'-diaminobiphenyl, 5,5'-dichloro-4,6'-diaminobiphenyl, 6,6'-di, The compound may comprise or be any of chloro-2,2'-diaminobiphenyl, 6,6'-dichloro-3,3'-diaminobiphenyl, 6,6'-dichloro-4,4'-diaminobiphenyl, 6,6'-dichloro-5,5'-diaminobiphenyl, 6,6'-dichloro-2,3'-diaminobiphenyl, 6,6'-dichloro-2,4'-diaminobiphenyl, 6,6'-dichloro-2,5'-diaminobiphenyl, 6,6'-dichloro-3,4'-diaminobiphenyl, 6,6'-dichloro-3,5'-diaminobiphenyl, 6,6'-dichloro-4,5'-diaminobiphenyl, or mixtures thereof.

[0077]

[0041] In any aspect or embodiment describe herein, the diamine chain extender includes or is any of 4,4'-diaminodiphenylmethane, 3,3'-dichloro-4,4'-diaminodiphenylmethane, 1,4-diaminobenzene, 3,3'-dimethoxy-4,4-diaminobiphenyl, 3,3'-dimethyl-4,4-diaminobiphenyl, 4,4'-diaminobiphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl, or a mixture thereof.

[0078]

[0047] In any aspect or embodiment describe herein, the block copolymer comprises, or is a reaction product of, poly(tetramethylene ether) glycol and ε-caprolactone.

[0079] A further aspect of the present disclosure relates to a thermoplastic polyurethane comprising the polyurethane or polyurethaneurea composition of the present disclosure.

[0080] An additional aspect of the present disclosure relates to hot cast elastomers comprising the polyurethane or polyurethaneurea compositions of the present disclosure.

[0081] Yet another aspect of the present disclosure relates to cold-cast elastomers comprising the polyurethane or polyurethaneurea compositions of the present disclosure.

[0082] Another aspect of the present disclosure relates to microcellular polyurethane foams comprising the polyurethane or polyurethaneurea compositions of the present disclosure.

[0083] A still further aspect of the present disclosure relates to a polyurethane dispersion in an aqueous or organic medium comprising the polyurethane or polyurethaneurea composition of the present disclosure.

[0084] An additional aspect of the present disclosure relates to polyurethane adhesives comprising the polyurethane or polyurethaneurea compositions of the present disclosure.

[0085] A further aspect of the present disclosure relates to a one-component polyurethane coating comprising the polyurethane or polyurethaneurea composition of the present disclosure.

[0086] Yet another aspect of the present disclosure relates to a two-component polyurethane coating comprising the polyurethane or polyurethaneurea composition of the present disclosure.

[0087] Another aspect of the present disclosure relates to additive manufacturing compositions / resins comprising the polyurethane or polyurethaneurea compositions of the present disclosure.

[0088] A still further aspect of the present disclosure relates to a polyurethane sealant comprising the polyurethane or polyurethaneurea composition of the present disclosure.

[0089] Additional aspects of the present disclosure relate to a thermoplastic polyurethane, a hot cast elastomer, a cold cast elastomer, a microcellular polyurethane foam, a polyurethane dispersion in an aqueous or organic medium, a polyurethane adhesive, a one-component polyurethane coating, a two-component polyurethane coating, an additive manufacturing composition / resin, or a polyurethane sealant comprising the polyurethane or polyurethaneurea composition described herein. For example, the polyurethane or polyurethaneurea composition is (a) at least one block copolymer of the ABA type having a number average molecular weight of 2500 to 5000 g / mol, said block copolymer comprising: (i) a poly(tetrahydrofuran) diol, a poly(substituted tetrahydrofuran) diol, or a mixture thereof, present in an amount of about 40 to about 70 weight percent of the total molecular weight of the block copolymer; and (ii) a block copolymer comprising, or which is the reaction product of, a cyclic lactone, a cyclic ether, or a mixture thereof, present in an amount of about 30 to about 60 weight percent of the total molecular weight of the block copolymer; (b) a reaction product with at least one diisocyanate; A polyurethane or polyurethaneurea composition reaction product is formed by reacting (a) with (b) in an NCO:OH molar ratio of about 0.9:1 to about 2:1 (e.g., in the absence of a plasticizer).

[0090] In any aspect or embodiment described herein, the reaction further includes (c) a diol chain extender, a diamine chain extender, or a mixture thereof, each having a molecular weight of from about 60 to about 600, and the polyurethane or polyurethaneurea composition reaction product is formed by reacting (a), (b), and (c) in an NCO:OH molar ratio of from about 0.9:1 to about 2:1 (e.g., in the absence of a plasticizer).

[0091] In any aspect or embodiment describe herein, the composition is processed as a thermoplastic polyurethane, a hot cast elastomer, or a cold cast elastomer.

[0092] In any aspect or embodiment describe herein, the composition is processed as a thermoplastic polyurethane or a hot cast elastomer. [Example]

[0093] Polycaprolactone copolymers were produced by reacting ε-caprolactone (component A) with PTMEG or Me-PTMEG (component B) in a ring-opening polymerization according to the formulations in Table 1 .

[0094] The reaction was carried out at 180°C in the presence of stannous octoate (DABCO® T-9, Evonik Nutrition & Care GmbH, Essen, Germany) as a catalyst and monitored by gas chromatography (GC) measurement of residual ε-caprolactone. The reaction was terminated when the amount of residual ε-caprolactone was less than 0.5%.

[0095] [Table 1] * Comparative Example

[0096] To prepare the polyurethane elastomer material according to Table 2, the required polyol was first added dropwise to molten 4,4'-diphenylmethane diisocyanate and allowed to react at 80°C until the target NCO content was achieved. To this, 1,4-butanediol was added according to 97% stoichiometry or 103 isocyanate index, and the mixture was homogenized using a vortex mixer for 2 minutes. The reaction mixture was then poured onto a coated metal plate conditioned at 120°C for 1 hour. The cast sheet was then placed in a 120°C oven for 16 hours, after which it was demolded and cooled to 23°C.

[0097] [Table 2] * Comparative Example **Hard segment content was kept the same for each sample to allow direct comparison of PUs prepared with polyols of different molecular weights.

[0098] The thermal properties of the polyurethane elastomers were determined using DSC and the thermomechanical properties were determined using DMA.

[0099] A Discovery DSC 25 (TA Instruments, New Castle, Delaware, USA) equipped with a liquid nitrogen cooling system was used to determine the phase transitions of polyurethane samples. The instrument was calibrated with indium to determine melting temperature and enthalpy. 2-5 mg samples were sealed in Tzero® aluminum pans (TA Instruments, New Castle, Delaware, USA). Thermograms were generated using the following heating-cooling-heating cycle: 1. Heat from -120°C to 230°C-250°C (depending on polyol class and / or molecular weight) at a rate of 20°C / min. 2. Cool to -120°C at a rate of 10°C / min. 3. Reheat to 230-250°C at a heating rate of 20°C / min.

[0100] Thermograms were analyzed using TRIOS software (TA Instruments, New Castle, DE, USA) to determine the glass transition temperature (Tg).

[0101] The thermomechanical properties of polyurethane elastomers were measured using a Discovery DMA 850 (TA Instruments, New Castle, Delaware, USA). The instrument was operated in single cantilever mode, with a 20 mm (length) × 12 mm (width) × 2 mm (thickness) specimen held between a fixed clamp and a movable clamp (test length: 4 mm). Temperature scans were performed from -100 °C to 200 °C at a rate of 3 °C / min and a constant frequency of 1 Hz. Strain mode was used, with a displacement amplitude of 50 μm.

[0102] The glass transition temperature, measured by DMA, was determined as the peak of the tan δ curve. The minimum use temperature was determined as the lowest temperature at which tan δ was less than 0.1.

[0103] [Table 3] * Comparative Example Not According to the Invention

[0104] The data support the surprising and unexpected effects discussed herein.

[0105] The foregoing general fields of application are provided merely as examples and are not intended to limit the scope of the present disclosure and the appended claims. Additional objects and advantages associated with the compositions, methods, and processes of the present disclosure will be understood by those skilled in the art in light of the claims, description, and examples. For example, the various aspects and embodiments of the present disclosure may be utilized in numerous combinations, all of which are expressly contemplated by this description. These additional aspects and embodiments are expressly included within the scope of the present disclosure. Publications and other materials used herein to illuminate the context of the present disclosure, particularly to provide additional details regarding practice, are incorporated by reference.

[0106] Thus, those skilled in the art will recognize or be able to ascertain using no more than routine experimentation, many equivalents to the specific embodiments of the present disclosure described herein. Such equivalents are intended to be encompassed by the following claims. It is understood that the detailed examples and embodiments described herein are provided for illustrative purposes only and are not to be construed as limiting the present disclosure in any way. Various modifications or variations therein will be suggested to those skilled in the art and are within the spirit and scope of this application and are considered to be within the scope of the appended claims. For example, the relative amounts of components may be varied to optimize the desired effect, additional components may be added, and / or similar components may be substituted for one or more of the components described. Additional advantageous features and functions associated with the systems, methods, and processes of the present disclosure will be apparent from the appended claims. Moreover, those skilled in the art will recognize or be able to ascertain using no more than routine experimentation, many equivalents to the specific embodiments of the present disclosure described herein. Such equivalents are intended to be encompassed by the following claims.

Claims

1. 1. A polyurethane or polyurethaneurea composition having improved low temperature performance, said composition comprising: (a) at least one block copolymer of A-B-A type having a number average molecular weight of 2500 to 5000 g / mol, said block copolymer comprising: (i) a poly(tetrahydrofuran)diol, a poly(substituted tetrahydrofuran)diol, or a mixture thereof, present in an amount of about 40 to about 70 weight percent of the total molecular weight of the block copolymer; and (ii) a block copolymer comprising, or being the reaction product of, a cyclic lactone, a cyclic ether, or mixtures thereof, present in an amount of about 30 to about 60 weight percent of the total molecular weight of the block copolymer; (b) at least one diisocyanate; A composition wherein the polyurethane or polyurethaneurea composition reaction product is formed by reacting (a) and (b) in an NCO:OH molar ratio of about 0.9:1 to about 2:

1.

2. 10. The composition of claim 1, wherein the reaction further comprises (c) a diol chain extender, a diamine chain extender, or a mixture thereof, each having a molecular weight of from about 60 to about 600, and the polyurethane or polyurethaneurea composition reaction product is formed by reacting (a), (b), and (c) in an NCO:OH molar ratio of from about 0.9:1 to about 2:1 in the absence of a plasticizer.

3. The composition of claim 1 or 2, wherein reactant (b) is present in an amount of about 50 to about 70 weight percent of the total molecular weight of the block copolymer.

4. The composition of any one of claims 1 to 3, wherein the composition has a hardness ranging from about 30 Shore A to about 60 Shore D.

5. The composition of any one of claims 1 to 4, wherein the NCO:OH molar ratio is from about 0.9:1 to about 1.7:1 (e.g., from about 0.95:1 to about 1.5:1).

6. The composition of any one of claims 1 to 5, wherein the NCO:OH molar ratio is from about 1:1 to about 1.2:

1.

7. The composition of any one of claims 1 to 6, wherein the composition has a glass transition temperature of less than -60°C as measured by differential scanning calorimetry.

8. The composition of any one of claims 1 to 7, wherein the composition has a glass transition temperature of less than -40°C as measured by dynamic mechanical analysis.

9. The composition of any one of claims 1 to 8, wherein reactant (i) comprises or is a poly(substituted tetrahydrofuran) diol.

10. Reactant (i) is C １－４ alkyl (e.g., methyl, ethyl, or propyl), C １－６ Alkoxy (e.g., methoxy or ethoxy), C ２－６ 9. The composition of any one of claims 1 to 8, comprising or consisting of a poly(substituted tetrahydrofuran)diol having one or more (e.g., 1, 2, 3, 4, 5, 6, or more) substitutions independently selected from alkenyl, aromatic (e.g., phenyl, aryl, or heteroaryl), ester, halogen, halide, amide, or ketone.

11. The composition of any one of claims 1 to 8, wherein reactant (i) comprises or is poly(tetramethylene ether) glycol (PTMEG) or Me-PTMEG.

12. The composition according to any one of claims 1 to 11, wherein the cyclic lactone is ε-caprolactone.

13. The composition of any one of claims 1 to 11, wherein the cyclic ether is ethylene oxide, propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, or a mixture thereof.

14. The composition of any one of claims 1 to 13, wherein the diisocyanate comprises or is an aliphatic diisocyanate, an aromatic diisocyanate, or a combination thereof.

15. The diisocyanate may be 4,4'-diphenylmethane diisocyanate, isophorone diisocyanate, bimethylene diisocyanate, trimethylene diisocyanate (e.g., 1,3-trimethylene diisocyanate, 2,3-trimethylene diisocyanate, 1,2-trimethylene diisocyanate, 2,2-trimethylene diisocyanate, or a mixture thereof), tetramethylene diisocyanate (e.g., 1,4-tetramethylene diisocyanate, 1,3-tetramethylene diisocyanate, 1,2-tetramethylene diisocyanate, 2,3-tetramethylene diisocyanate, 1,1-tetramethylene diisocyanate, 2,2-tetramethylene diisocyanate, or mixtures thereof), pentamethylene diisocyanate (e.g., 1,5-pentamethylene diisocyanate, 1,4-pentamethylene diisocyanate, 1,3-pentamethylene diisocyanate, 1,2-pentamethylene diisocyanate, 2,3-pentamethylene diisocyanate, 2,4-pentamethylene diisocyanate, 3,4-pentamethylene diisocyanate, 3,5-pentamethylene diisocyanate, isocyanates, 1,1-pentamethylene diisocyanate, 2,2-pentamethylene diisocyanate, 3,3-pentamethylene diisocyanate, or mixtures thereof), hexamethylene diisocyanate (e.g., 1,6-hexamethylene diisocyanate, 1,5-hexamethylene diisocyanate, 1,4-hexamethylene diisocyanate, 1,3-hexamethylene diisocyanate, 1,2-hexamethylene diisocyanate, 2,3-hexamethylene diisocyanate, 2,4-hexamethylene diisocyanate, 2,5-hexamethylene diisocyanate, methylene diisocyanate, 3,4-hexamethylene diisocyanate, 3,5-hexamethylene diisocyanate, 4,5-hexamethylene diisocyanate, 1,1-hexamethylene diisocyanate, 2,2-hexamethylene diisocyanate, 3,3-hexamethylene diisocyanate, or mixtures thereof), heptamethylene diisocyanate (e.g., 1,7-heptamethylene diisocyanate, 1,6-heptamethylene diisocyanate, 1,5-heptamethylene diisocyanate, 1,4-heptamethylene diisocyanate, 1,3-heptamethylene diisocyanate, 1,2-heptamethylene diisocyanate, 2,3-heptamethylene diisocyanate, 2,4-heptamethylene diisocyanate, 2,5-heptamethylene diisocyanate, 2,6-heptamethylene diisocyanate, 3,3-heptamethylene diisocyanate, 3,4-heptamethylene diisocyanate, 1,1-heptamethylene diisocyanate, 2,2-heptamethylene diisocyanate methylene diisocyanate, 3,3-heptamethylene diisocyanate, 4,4-heptamethylene diisocyanate, or mixtures thereof), toluene diisocyanate (e.g., toluene-2,4-diisocyanate, toluene-2,6-diisocyanate, or mixtures thereof), naphthylene diisocyanate (e.g., 1,2-naphthylene diisocyanate, 1,3-naphthylene diisocyanate, The composition of any one of claims 1 to 13, comprising or being any of 1,4-naphthylene diisocyanate, 1,5-naphthylene diisocyanate, 1,6-naphthylene diisocyanate, 1,7-naphthylene diisocyanate, 1,8-naphthylene diisocyanate, or mixtures thereof), cyclohexylmethane diisocyanate (e.g., 1,4-cyclohexylmethane diisocyanate, 2,4-cyclohexylmethane diisocyanate, 3,4-cyclohexylmethane diisocyanate, 4,4-cyclohexylmethane diisocyanate, or mixtures thereof), dicyclohexylmethane diisocyanate (e.g., 4,4'-dicyclohexylmethane diisocyanate, 1,4-dicyclohexylmethane diisocyanate, or mixtures thereof), or mixtures thereof.

16. The composition of any one of claims 1 to 13, wherein the diisocyanate is 4,4'-diphenylmethane diisocyanate, isophorone diisocyanate, 1,6-hexamethylene diisocyanate, toluene-2,4-diisocyanate, 1,5-naphthylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, or a mixture thereof.

17. The composition of any one of claims 2 to 16, wherein the diol chain extender comprises or is an aliphatic diol or an aromatic diol.

18. The diol chain extender may be selected from the group consisting of alkylene oxides or glycols, ethylene glycol, propanediols (e.g., 1,3-propanediol, 1,2-propanediol, 1,1-propanediol, 2,2-propanediol, or mixtures thereof), butanediols (e.g., 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, 2,3-butanediol, 1,1-butanediol, 2,2-butanediol, or mixtures thereof), pentanediols (e.g., 1,5-pentanediol, 1,4-pentanediol, hexanediol (e.g., 1,6-hexanediol, 1,5-hexanediol, 1,4-hexanediol, 1,3-hexanediol, 1,2-pentanediol, 2,3-pentanediol, 2,4-pentanediol, 3,4-pentanediol, 3,5-hexanediol, 1,1-pentanediol, 2,2-pentanediol, 3,3-pentanediol, or a mixture thereof), hexanediol (e.g., 1,6-hexanediol, 1,5-hexanediol, 1,4-hexanediol, 1,3-hexanediol, 1,2-hexanediol, 2,3-hexanediol, 2,4-hexanediol, 2,5-hexanediol), , 3,4-hexanediol, 3,5-hexanediol, 4,5-hexanediol, 1,1-hexanediol, 2,2-hexanediol, 3,3-hexanediol, or mixtures thereof), heptadiols (e.g., 1,7-heptadiol, 1,6-heptadiol, 1,5-heptadiol, 1,4-heptadiol, 1,3-heptadiol, 1,2-heptadiol, 2,3-heptadiol, 2,4-heptadiol, 2,5-heptadiol, 2,6-heptadiol, 3,3-heptadiol, 3,4-heptadiol, dihydroxybenzenes (e.g., 1,2-dihydroxybenzene, 1,3-dihydroxybenzene, 1,4-dihydroxybenzene, or mixtures thereof), di(hydroxyethyl)-hydroxyquinones (e.g., 1,4-di-(beta-hydroxyethyl)-hydroxyquinone, 2,5-di-(hydroxyethyl)-hydroxyquinone, 2,3-di-(hydroxyethyl)-hydroxyquinone, 3,di-(hydroxymethyl)-hydroxyquinone (e.g., 2,5-di-(hydroxyethyl)-hydroxyquinone, 2,3-di-(hydroxymethyl)-hydroxyquinone, 3,5-di-(hydroxymethyl)-hydroxyquinone, or mixtures thereof), di-(hydroxyethyl)-bisphenol A (e.g., 1,4-di-(beta hydroxyethyl)-bisphenol A, 1,3-di-(beta hydroxyethyl)-bisphenol A, 1,2-di-(beta hydroxyethyl)-bisphenol A, 1,5 17. The composition of any one of claims 2 to 16, comprising or consisting of 2,3-di-(beta hydroxyethyl)-bisphenol A, 2,4-di-(beta hydroxyethyl)-bisphenol A, 2,5-di-(beta hydroxyethyl)-bisphenol A, 2,6-di-(beta hydroxyethyl)-bisphenol A, 3,4-di-(beta hydroxyethyl)-bisphenol A), 3,5-di-(beta hydroxyethyl)-bisphenol A, or mixtures thereof.

19. 17. The composition of any one of claims 2 to 16, wherein the diol chain extender is ethylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,4-di-(beta hydroxyethyl)-hydroxyquinone, 1,4-di-(beta hydroxyethyl)-bisphenol A, or a mixture thereof.

20. the diamine chain extender is diaminodiphenylmethane (e.g., 2,2'-diaminodiphenylmethane, 2,3'-diaminodiphenylmethane, 2,4'-diaminodiphenylmethane, 2,5'-diaminodiphenylmethane, 2,6'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 3,5'-diaminodiphenylmethane, 3,6'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 4,5'-diaminodiphenylmethane, 4,6'-diaminodiphenylmethane, 5,6'-diaminodiphenylmethane, or or mixtures thereof), dichloro-diaminodiphenylmethane (e.g., 2,2'-dichloro-3,3'-diaminodiphenylmethane, 2,2'-dichloro-4,4'-diaminodiphenylmethane, 5,5'-dichloro-3,3'-diaminodiphenylmethane, 2,2'-dichloro-6,6'-diaminodiphenylmethane, 2,2'-dichloro-3,4'-diaminodiphenylmethane, 2,2'-dichloro-3,5'-diaminodiphenylmethane, 2,2'-dichloro-3,6'-diaminodiphenylmethane, 2,2'-dichloro-4,5'-diaminodiphenyl Phenylmethane, 2,2'-dichloro-4,6'-diaminodiphenylmethane, 2,2'-dichloro-5,6'-diaminodiphenylmethane, 3,3'-dichloro-2,2'-diaminodiphenylmethane, 3,3'-dichloro-4,4'-diaminodiphenylmethane, 3,3'-dichloro-5,5'-diaminodiphenylmethane, 3,3'-dichloro-6,6'-diaminodiphenylmethane, 3,3'-dichloro-2,5'-diaminodiphenylmethane, 3,3'-dichloro-4,5'-diaminodiphenylmethane, 3,3'-dichloro-6,5'-di Aminodiphenylmethane, 3,3'-dichloro-4,2'-diaminodiphenylmethane, 3,3'-dichloro-4,6'-diaminodiphenylmethane, 4,4'-dichloro-2,2'-diaminodiphenylmethane, 4,4'-dichloro-3,3'-diaminodiphenylmethane, 4,4'-dichloro-5,5'-diaminodiphenylmethane, 4,4'-dichloro-6,6'-diaminodiphenylmethane, 4,4'-dichloro-2,3'-diaminodiphenylmethane, 4,4'-dichloro-2,5'-diaminodiphenylmethane, 4,4'-dichloro-2,6'-diaminodiphenylmethane, 4,4'-dichloro-3,5'-diaminodiphenylmethane, 4,4'-dichloro-3,6'-diaminodiphenylmethane, 4,4'-dichloro-5,6'-diaminodiphenylmethane, 5,5'-dichloro-2,2'-diaminodiphenylmethane, 5,5'-dichloro-3,3'-diaminodiphenylmethane, 5,5'-dichloro-4,4'-diaminodiphenylmethane, 5,5'-dichloro-6,6'-diaminodiphenylmethane, 5,5'-dichloro-2,3'-diaminodiphenylmethane, 5,5'-dichloro 2,4'-diaminodiphenylmethane, 5,5'-dichloro-2,6'-diaminodiphenylmethane, 5,5'-dichloro-3,4'-diaminodiphenylmethane, 5,5'-dichloro-3,6'-diaminodiphenylmethane, 5,5'-dichloro-4,6'-diaminodiphenylmethane, 6,6'-dichloro-2,2'-diaminodiphenylmethane, 6,6'-dichloro-3,3'-diaminodiphenylmethane, 6,6'-dichloro-4,4'-diaminodiphenylmethane, 6,6'-dichloro-5,5'-diaminodiphenylmethane, 6,6'- dichloro-2,3'-diaminodiphenylmethane, 6,6'-dichloro-2,4'-diaminodiphenylmethane, 6,6'-dichloro-2,5'-diaminodiphenylmethane, 6,6'-dichloro-3,4'-diaminodiphenylmethane, 6,6'-dichloro-3,5'-diaminodiphenylmethane, 6,6'-dichloro-4,5'-diaminodiphenylmethane, or mixtures thereof), diaminobenzenes (e.g., 1,4-diaminobenzene, 1,2-diaminobenzene, 1,3-diaminobenzene, or mixtures thereof), dimethoxy-diaminobenzenes (e.g., 1,4-diaminobenzene, 1,2-diaminobenzene, 1,3-diaminobenzene, or mixtures thereof), Aminobiphenyls (e.g., 2,2'-dimethoxy-3,3'-diaminobiphenyl, 2,2'-dimethoxy-4,4'-diaminobiphenyl, 5,5'-dimethoxy-3,3'-diaminobiphenyl, 2,2'-dimethoxy-6,6'-diaminobiphenyl, 2,2'-dimethoxy-3,4'-diaminobiphenyl, 2,2'-dimethoxy-3,5'-diaminobiphenyl, 2,2'-dimethoxy-3,6'-diaminobiphenyl, 2,2'-dimethoxy-4,5'-diaminobiphenyl, 2,2'-dimethoxy-4,6'-diaminobiphenyl, 2,2'-dimethoxy-5,6'-diaminobiphenyl, 3,3'-dimethoxy-2,2'-diaminobiphenyl, 3,3'-dimethoxy-4,4-diaminobiphenyl, 3,3'-dimethoxy-5,5'-diaminobiphenyl, 3,3'-dimethoxy-6,6'-diaminobiphenyl, 3,3'-dimethoxy-2,5'-diaminobiphenyl, 3,3'-dimethoxy-4,5'-diaminobiphenyl, 3,3'-dimethoxy-6,5'-diaminobiphenyl, 3,3'-dimethoxy-4,2'-diaminobiphenyl, 3,3'-dimethoxy-4,6'-diaminobiphenyl 4,4'-dimethoxy-2,2'-diaminobiphenyl, 4,4'-dimethoxy-3,3'-diaminobiphenyl, 4,4'-dimethoxy-5,5'-diaminobiphenyl, 4,4'-dimethoxy-6,6'-diaminobiphenyl, 4,4'-dimethoxy-2,3'-diaminobiphenyl, 4,4'-dimethoxy-2,5'-diaminobiphenyl, 4,4'-dimethoxy-2,6'-diaminobiphenyl, 4,4'-dimethoxy-3,5'-diaminobiphenyl, 4,4'-dimethoxy-3,6'-diaminobiphenyl, 4,4'-dimethoxy 5,5'-dimethoxy-5,6'-diaminobiphenyl, 5,5'-dimethoxy-2,2'-diaminobiphenyl, 5,5'-dimethoxy-3,3'-diaminobiphenyl, 5,5'-dimethoxy-4,4'-diaminobiphenyl, 5,5'-dimethoxy-6,6'-diaminobiphenyl, 5,5'-dimethoxy-2,3'-diaminobiphenyl, 5,5'-dimethoxy-2,4'-diaminobiphenyl, 5,5'-dimethoxy-2,6'-diaminobiphenyl, 5,5'-dimethoxy-3,4'-diaminobiphenyl, 5,5'-dimethoxy-3,6'-diaminobiphenyl nyl, 5,5'-dimethoxy-4,6'-diaminobiphenyl, 6,6'-dimethoxy-2,2'-diaminobiphenyl, 6,6'-dimethoxy-3,3'-diaminobiphenyl, 6,6'-dimethoxy-4,4'-diaminobiphenyl, 6,6'-dimethoxy-5,5'-diaminobiphenyl, 6,6'-dimethoxy-2,3'-diaminobiphenyl, 6,6'-dimethoxy-2,4'-diaminobiphenyl, 6,6'-dimethoxy-2,5'-diaminobiphenyl, 6,6'-dimethoxy-3,4'-diaminobiphenyl, 6,6'-dimethoxy-3,5'-diaminobiphenyl, 6,6'-dimethoxy-4,5'-diaminobiphenyl, or a mixture thereof), dimethyl-diaminobiphenyl (e.g., 2,2'-dimethyl-3,3'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 5,5'-dimethyl-3,3'-diaminobiphenyl, 2,2'-dimethyl-6,6'-diaminobiphenyl, 2,2'-dimethyl-3,4'-diaminobiphenyl, 2,2'-dimethyl-3,5'-diaminobiphenyl, 2,2'-dimethyl-3,6'-diaminobiphenyl, 2,2 '-dimethyl-4,5'-diaminobiphenyl, 2,2'-dimethyl-4,6'-diaminobiphenyl, 2,2'-dimethyl-5,6'-diaminobiphenyl, 3,3'-dimethyl-2,2'-diaminobiphenyl, 3,3'-dimethyl-4,4-diaminobiphenyl, 3,3'-dimethyl-5,5'-diaminobiphenyl, 3,3'-dimethyl-6,6'-diaminobiphenyl, 3,3'-dimethyl-2,5'-diaminobiphenyl, 3,3'-dimethyl-4,5'-diaminobiphenyl, 3,3'-dimethyl-6,5'-diaminobiphenyl, 3,3 '-dimethyl-4,2'-diaminobiphenyl, 3,3'-dimethyl-4,6'-diaminobiphenyl, 4,4'-dimethyl-2,2'-diaminobiphenyl, 4,4'-dimethyl-3,3'-diaminobiphenyl, 4,4'-dimethyl-5,5'-diaminobiphenyl, 4,4'-dimethyl-6,6'-diaminobiphenyl, 4,4'-dimethyl-2,3'-diaminobiphenyl, 4,4'-dimethyl-2,5'-diaminobiphenyl, 4,4'-dimethyl-2,6'-diaminobiphenyl, 4,4'-dimethyl-3,5'-diaminobiphenyl, 4, 4'-dimethyl-3,6'-diaminobiphenyl, 4,4'-dimethyl-5,6'-diaminobiphenyl, 5,5'-dimethyl-2,2'-diaminobiphenyl, 5,5'-dimethyl-3,3'-diaminobiphenyl, 5,5'-dimethyl-4,4'-diaminobiphenyl, 5,5'-dimethyl-6,6'-diaminobiphenyl, 5,5'-dimethyl-2,3'-diaminobiphenyl, 5,5'-dimethyl-2,4'-diaminobiphenyl, 5,5'-dimethyl-2,6'-diaminobiphenyl, 5,5'-dimethyl-3,4'-diaminobiphenyl, 5,5'-dimethyl-3,6'-diaminobiphenyl, 5,5'-dimethyl-4,6'-diaminobiphenyl, 6,6'-dimethyl-2,2'-diaminobiphenyl, 6,6'-dimethyl-3,3'-diaminobiphenyl, 6,6'-dimethyl-4,4'-diaminobiphenyl, 6,6'-dimethyl-5,5'-diaminobiphenyl, 6,6'-dimethyl-2,3'-diaminobiphenyl, 6,6'-dimethyl-2,4'-diaminobiphenyl, 6,6'-dimethyl-2,5'-diaminobiphenyl, 6,6'-dimethyl-3,4'-diaminobiphenyl, 6 ,6'-dimethyl-3,5'-diaminobiphenyl, 6,6'-dimethyl-4,5'-diaminobiphenyl, or mixtures thereof), diaminobiphenyls (e.g., 2,2'-diaminobiphenyl, 2,3'-diaminobiphenyl, 2,4'-diaminobiphenyl, 2,5'-diaminobiphenyl, 2,6'-diaminobiphenyl, 3,4'-diaminobiphenyl, 3,5'-diaminobiphenyl, 3,6'-diaminobiphenyl, 4,4'-diaminobiphenyl, 4,5'-diaminobiphenyl, 4,6'-diaminobiphenyl, 5,6'-diamino biphenyl, or mixtures thereof), dichloro-diaminobiphenyls (e.g., 2,2'-dichloro-3,3'-diaminobiphenyl, 2,2'-dichloro-4,4'-diaminobiphenyl, 5,5'-dichloro-3,3'-diaminobiphenyl, 2,2'-dichloro-6,6'-diaminobiphenyl, 2,2'-dichloro-3,4'-diaminobiphenyl, 2,2'-dichloro-3,5'-diaminobiphenyl, 2,2'-dichloro-3,6'-diaminobiphenyl, 2,2'-dichloro-4,5'-diaminobiphenyl, 2,2'-dichloro-4, 6'-diaminobiphenyl, 2,2'-dichloro-5,6'-diaminobiphenyl, 3,3'-dichloro-2,2'-diaminobiphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl, 3,3'-dichloro-5,5'-diaminobiphenyl, 3,3'-dichloro-6,6'-diaminobiphenyl, 3,3'-dichloro-2,5'-diaminobiphenyl, 3,3'-dichloro-4,5'-diaminobiphenyl, 3,3'-dichloro-6,5'-diaminobiphenyl, 3,3'-dichloro-4,2'-diaminobiphenyl, 3,3'-dichloro-4,6'-diaminobiphenyl, 4,4'-dichloro-2,2'-diaminobiphenyl, 4,4'-dichloro-3,3'-diaminobiphenyl, 4,4'-dichloro-5,5'-diaminobiphenyl, 4,4'-dichloro-6,6'-diaminobiphenyl, 4,4'-dichloro-2,3'-diaminobiphenyl, 4,4'-dichloro-2,5'-diaminobiphenyl, 4,4'-dichloro-2,6'-diaminobiphenyl, 4,4'-dichloro-3,5'-diaminobiphenyl, 4,4'-dichloro-3,6'-diaminobiphenyl, 4,4'-dichloro-5,6'-diaminobiphenyl, 5,5'-dichloro-2,2'-diaminobiphenyl, 5,5'-dichloro-3,3'-diaminobiphenyl, 5,5'-dichloro-4,4'-diaminobiphenyl, Phenyl, 5,5'-dichloro-6,6'-diaminobiphenyl, 5,5'-dichloro-2,3'-diaminobiphenyl, 5,5'-dichloro-2,4'-diaminobiphenyl, 5,5'-dichloro-2,6'-diaminobiphenyl, 5,5'-dichloro-3,4'-diaminobiphenyl, 5,5'-dichloro-3,6'-diaminobiphenyl, 5,5'-dichloro-4,6'-diaminobiphenyl, 6,6'-dichloro-2,2'-diaminobiphenyl, 6,6'-dichloro-3,3'-diaminobiphenyl, 6,6'-dichloro-4,4'-diamino 20. The composition of any one of claims 2 to 19, comprising or consisting of any of the following: 6,6'-dichloro-5,5'-diaminobiphenyl, 6,6'-dichloro-2,3'-diaminobiphenyl, 6,6'-dichloro-2,4'-diaminobiphenyl, 6,6'-dichloro-2,5'-diaminobiphenyl, 6,6'-dichloro-3,4'-diaminobiphenyl, 6,6'-dichloro-3,5'-diaminobiphenyl, 6,6'-dichloro-4,5'-diaminobiphenyl, or mixtures thereof.

21. 20. The composition of any one of claims 2 to 19, wherein the diamine chain extender is 4,4'-diaminodiphenylmethane, 3,3'-dichloro-4,4'-diaminodiphenylmethane, 1,4-diaminobenzene, 3,3'-dimethoxy-4,4-diaminobiphenyl, 3,3'-dimethyl-4,4-diaminobiphenyl, 4,4'-diaminobiphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl, or mixtures thereof.

22. The composition of any one of claims 1 to 21, wherein reactant (i) is present in an amount of about 50 to about 70 weight percent of the total molecular weight of the block copolymer.

23. 23. The composition of any one of claims 1 to 22, wherein the composition is a thermoplastic polyurethane, a hot cast elastomer, a cold cast elastomer, a microcellular polyurethane foam, a polyurethane dispersion in an aqueous or organic medium, a polyurethane adhesive, a one-component polyurethane coating, a two-component polyurethane coating, an additive manufacturing composition / resin, or a polyurethane sealant.

24. 23. A thermoplastic polyurethane, hot cast elastomer, cold cast elastomer, microcellular polyurethane foam, polyurethane dispersion in aqueous or organic medium, polyurethane adhesive, one-component polyurethane coating, two-component polyurethane coating, additive manufacturing composition / resin, or polyurethane sealant comprising the polyurethane or polyurethaneurea composition of any one of claims 1 to 22.

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