Bio-based polyol for high-performance polyurethane applications

Abstract

By using as a polyol component and as a copolymer component of poly(farnesene) diol and ε-caprolactone, a polyurethane composition and method having mechanical properties comparable to the most performance-commercial elastomeric materials are described. The poly(farnesene) diol is produced from biobased monomers, and such copolymerization enables the incorporation of renewable materials into high-performance polyurethane materials.

Description

Technical Field

[0001] (Cross - reference to related applications) This disclosure claims the priority and benefit of U.S. Provisional Patent Application No. 63 / 370,534, filed on August 5, 2022, entitled "Bio - based Polyol for High - performance Polyurethane Applications", which is hereby incorporated by reference in its entirety for all purposes.

[0002] In various embodiments, this disclosure generally relates to bio - based polyols for the preparation of high - performance polyurethanes and related applications.

Background Art

[0003] Polyurethane elastomers are versatile materials that combine good mechanical properties with ease of processing and flexibility and are extremely important industrially. For example, polyurethane materials can be processed by conventional thermoplastic techniques, cast to obtain thermosetting materials, foamed to obtain microcellular foams, or dispersed in aqueous or organic media, all with slight adjustments to the formulation.

[0004] For example, the ability to produce high - performance polyurethanes from renewable resources to address issues such as global warming and the depletion of petroleum - based raw materials is a major limitation of this technology. Technical challenges in the purification of bio - based feedstocks to provide products of equivalent quality have hampered development, especially when the demand for such materials is accelerating. There are few commercially available polyols based on renewable raw materials that provide the same high - performance characteristics as petroleum - based products.

[0005] Another recognized limitation of polyurethane technology is the difficulty in manufacturing soft materials (less than 75 Shore A) that can be efficiently produced and maintain their softness over time. The hardness of the resulting polyurethane material is mainly determined by the proportion of the diisocyanate component in the formulation. However, reducing the diisocyanate content (and thus increasing the polyol content) may initially give a soft material, but due to the semi-crystalline nature of the polyol, the hardness increases over time. Reducing the diisocyanate content also means that the degree of crystallinity for promoting the solidification process in manufacturing is lower, and it takes longer to produce polyurethane, making it economically infeasible.

[0006] Several methods for preparing soft polyurethane materials have been disclosed. Canadian Patent No. 1257946 claims the use of specific phthalate and phosphate plasticizers to give a TPU having a hardness of 60 to 80 Shore A. Plasticizers have the disadvantage of migrating from parts that cause problems such as cold hardening, fogging of the surrounding surface, and odor problems. Also, over time, it is a common problem that plasticized products become sticky and the texture becomes unpleasant. Many plasticizers, especially phthalate-based plasticizers, are in the process of being deregulated for environmental and health reasons.

[0007] Previous studies have focused on introducing random copolymers as polyol components to prevent crystallization and maintain softness without using plasticizers. US Patent Application Publication No. 2008 / 0139774 claims the use of branched polyester adipic diol in TPU formulations. The above application teaches that hardness can be maintained at 23 °C (i.e., room temperature) and in the refrigerator for up to 5 days. International Publication No. 2014 / 195211 discloses a plasticizer-free TPU having a hardness of 30 to 55 Shore, based on linear polyester polyols derived from aliphatic dicarboxylic acids and aliphatic diols. However, according to the standard test methods applied to International Publication No. 2014 / 195211, the results of very soft TPU formulations show only properties with a very short lifespan.

[0008] The polycaprolactone copolymerization technology has been used to address the issue of cold curing of polyurethane materials taught in International Publication No. 2020 / 099540. By adopting a block copolymerization technology that incorporates a specific amount of branching into the polycaprolactone copolymer, it has been shown that the material can be kept soft at both room temperature and -4 °C for up to 6 months. However, this technology requires polyurethane processors to fine-tune their processes / formulations to ensure commercially viable production times, and the adoption of this technology has not advanced. This technology also causes environmental problems because it is integrated into the petroleum supply chain.

[0009] To date, the blocks that make up the raw materials of polyurethane elastomers are overwhelmingly based on petroleum-derived chemicals, especially elastomers used in demanding applications where mechanical properties or durability cannot be compromised. Elastomers prepared from renewable sources have difficulty achieving their high-performance properties based on conventional petroleum-based raw materials due to the technical challenges and costs involved in the purification of such feedstocks and the controlled polymerization.

[0010] Polyfarnesen diol (e.g., Krasol® F-3000, Total Cray Valley, Pennsylvania Exxon) has emerged as a useful component of polyurethane elastomers. These materials are derived from trans-beta-farnesene, a bio-based monomer produced by the fermentation of lignocellulosic sugars containing xylose. The resulting polyol can be produced with a narrow polydispersity and high purity. However, when used in elastomer formulations, the manufactured articles lack mechanical strength and have little commercial value in demanding polyurethane applications. They also have poor reactivity with common isocyanates such as MDI.

[0011] Despite the high demand for plastic materials made from renewable raw materials and the aim of reducing the world's dependence on finite resources, there are few commercially viable solutions based on bio-based raw materials that exhibit acceptable processing times, mechanical properties, and durability. Therefore, there is a need for materials that overcome these challenges while maintaining a high bio-based content.

[0012] The availability of new bio-based polymer building blocks also helps to overcome similar technical challenges in polyurethane adhesives, copolyester, and polyamide technologies in a more environmentally sustainable way.

[0013] FR 2,384,810 describes a polyether ester amide obtained by polymerization under autogenous pressure at a temperature of 230 to 300 °C. The reaction mixture consists of one or more polyamide monomers, alpha, omega-dihydroxy (polytetrahydrofuran), or PTMG with a Mn (number average molecular weight) of 160 to 3000 g / mol, and at least one diacid in the presence of water. Then, water is removed from the reaction medium and this is returned to normal or reduced pressure at a temperature of 250 to 280 °C. The resulting product is a block polymer and has good resistance to low temperature impact. However, the polymers obtained according to these patents have a lower melting temperature than those according to the present invention for the same hardness.

[0014] U.S. Patent No. 4,307,227 describes a hot melt type adhesive consisting of 50 to 80% repeating units derived from caprolactam, and a mixture of a primary amine and a dicarboxylic acid of a polyoxyalkylene glycol. The process used (reaction of all components without a catalyst at 220 to 250 °C) does not make it possible to synthesize a product having a Mn of the polyether sequence exceeding 1000 g / mol.

[0015] Patent Application Publications No. 63-035622 and No. 63-277239 relate to polyether block amides obtained by the reaction between one or more sequences of polyoxyalkylene dioxy and a polyoxyalkylene glycol, or an oligoamide of PA-6,6 containing a low-mass diol, in the presence of an esterification catalyst which is a metal tetraalkoxide, under high vacuum at a temperature above 250 °C. By using a low-mass polyoxyalkylene glycol or diol, a product is obtained having a melting point significantly lower than that of the product of the present invention.

[0016] Japanese Patent Application Laid-Open No. 63-182343 relates to a polyether block amide obtained by reacting a PA-6,6 sequence having a diamine terminal and a polyether having a dicarboxylic acid chain terminal in a molten state. The polymers obtained according to the present application have a high melting temperature exceeding 230 °C, which requires a high transformation temperature and thus there is a risk of product degradation during their transformation.

Summary of the Invention

[0017] Surprisingly and unexpectedly, polyurethanes having mechanical properties comparable to the most performance - oriented commercially available elastomeric materials can be obtained by using a copolymer of a diol and a lactone, such as a copolymer of poly(farnesene) diol and ε - caprolactone, as the polyol component. Poly(farnesene) diol is produced from bio - based monomers, and such copolymerization allows for incorporating renewable materials into high - performance polyurethane materials.

[0018] The present disclosure provides a polymer composition and method for producing an A - B - A type copolymer that is a reaction product of a diol and a cyclic lactone or cyclic ether. The disclosed bio - based copolymer advantageously exhibits at least one of commercially desirable processing times, mechanical properties, and / or durability.

[0019] Accordingly, in one aspect, the present specification provides a polymer and method for producing an A - B - A type copolymer having an average molecular weight (Mn) in the range of 1000 to 10,000 g / mol, the copolymer being a reaction product of a diol, such as poly(farnesene) diol, and a cyclic lactone or cyclic ether.

[0020] In any of the aspects or embodiments described herein, poly(farnesene) diol is present in the range of about 10 to about 90 weight % of the total molecular weight of the block copolymer.

[0021] In any of the aspects or embodiments described herein, the cyclic lactone or cyclic ether is present in the range of about 10 to about 90 weight percent of the total molecular weight of the block copolymer.

[0022] In a further aspect, the present specification provides a polyurethane, polyurethane-urea, polyamide, or copolyester composition comprising the polymers described herein.

[0023] In any of the aspects or embodiments described herein, the polyurethane or polyurethane-urea composition comprises an A-B-A type block copolymer having an average molecular weight of 1000 to 10,000 g / mol, and the copolymer is a reaction product of poly(farnesene) diol and a cyclic lactone or cyclic ether, a diisocyanate, and a diol or diamine chain extender. In any of the aspects or embodiments described herein, the poly(farnesene) diol is present in the range of about 10 to about 90 weight percent of the total molecular weight of the block copolymer. In any of the aspects or embodiments described herein, the cyclic lactone or cyclic ether is present in the range of about 10 to about 90 weight percent of the total molecular weight of the block copolymer. In any of the aspects or embodiments described herein, the diol or diamine chain extender has a molecular weight of about 60 to about 600 g / mol. In any of the aspects or embodiments described herein, the molar ratio of isocyanate to hydroxyl (i.e., NCO:OH) is about 0.9:1 to 2:1.

[0024] In any aspect or embodiment described herein, the copolymer described herein is in the range of about 25 to about 95 weight percent of the polyurethane or polyurethane-urea.

[0025] In any aspect or embodiment described herein, the polyurethane or polyurethane-urea comprises a Shore hardness of about 25 Shore A to about 60 Shore D.

[0026] The foregoing general aspects and embodiments are provided by way of example only and are not intended to limit the scope of the present disclosure and the appended claims. Additional objects and advantages related to the compositions, methods, and processes of the present invention will be understood by those skilled in the art in view of the claims, description, and examples. For example, the various aspects and embodiments of the present invention may be utilized in numerous combinations, all of which are explicitly contemplated by this description. The objects and embodiments of these additional advantages are explicitly included within the scope of the present invention. Publications and other materials used herein to illuminate the background of the present invention and, in particular, to provide additional details regarding practice are incorporated by reference.

[0027] The accompanying drawings, which are incorporated herein and form a part thereof, illustrate some embodiments of the present invention and, together with the description, serve to explain the principles of the present invention. The drawings are for the purpose of illustrating embodiments of the present invention only and should not be construed as limiting the present invention. Further objects, features, and advantages of the present invention will become apparent from the following detailed description in conjunction with the accompanying drawings showing exemplary embodiments of the present invention.

Brief Description of the Drawings

[0028]

Figure 1A

Figure 1B

Figure 1C

Modes for Carrying Out the Invention

[0029] Surprisingly and unexpectedly, it has been found that polyurethanes having mechanical properties comparable to the most performant commercially available elastomeric materials can be obtained by using, as the polyol component, a copolymer of a diol and a lactone or an ether, such as a cyclic lactone or a cyclic ether. Additionally, the polyols described herein can be used not only to maintain hardness over time but also in the production of polyurethane materials with a Shore A hardness of 75 or less that can be manufactured with industrially feasible cycle times.

[0030] Unless otherwise specified, all terms have their ordinary meaning as accepted in the field of polymer technology.

[0031] The recitation of a range of values is intended to be merely a concise way of referring individually to each separate value falling within the range, and each separate value is incorporated herein as if it were individually recited. Unless otherwise expressly indicated, all endpoints of ranges are included within the range and are independently combinable.

[0032] As used herein, the articles "a" and "an" are used in this specification to refer to one or more than one (i.e., at least one) of the grammatical objects of an article, unless the context clearly dictates otherwise. By way of example, "an element" means one element or more than one element.

[0033] The term "about" means approximately. When the term "about" is used in conjunction with a numerical range, the range is modified by extending the boundaries above and below the recited numerical values. By way of illustration, the use of the term "about" indicates that values slightly outside the recited value, i.e., values that are plus or minus 0.1% to 10% and are valid and safe, are included in the value. Numerical ranges set forth herein by endpoints include all numbers and fractions subsumed within that range (e.g., 1 to 5 includes 1, 1.5, 2, 2.75, 3, 3.90, 4, and 5).

[0034] As used in this specification and the claims, the phrase "and / or" is to be understood to mean "either or both" of the elements so conjoined, i.e., in some instances the elements are present conjointly and in other instances they are present disjunctively. Multiple elements listed with "and / or" are to be construed in the same fashion, i.e., as "one or more" of the elements so conjoined. Any other elements may optionally be present in addition to or instead of the elements specifically identified in relation to a clause with "and / or", whether or not they are relevant to those elements. Thus, by way of non-limiting example, a reference to "A and / or B" can, in one embodiment, refer to only A (optionally including elements other than B), in another embodiment, refer to only B (optionally including elements other than A), and in yet another embodiment, refer to both A and B (optionally including other elements).

[0035] As used in this specification and the claims, "or" is to 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" is inclusive, i.e., including at least one of the elements, and including the number of elements or two or more of the list, and optionally, additional unlisted items. The term "consisting of" when explicitly indicated, such as "any one" or "exactly one", or when used in the claims, refers to including exactly one of the elements or the list. As used in this document, the term "or" is construed to indicate an exclusive alternative (i.e., "only one of either", "only one of the two", "only one of the two only", "exactly one of either") only when an exclusive condition (such as "either", "either one", "only one of the two", "exactly one of either") precedes it.

[0036] As used herein in the specification and claims, the phrase "at least one" with respect to a list of one or more elements means at least one element selected from one or more of the elements in the list of elements, but does not necessarily include at least one of each and every element specifically listed within the list of elements, and is not to be construed as excluding any combinations of elements in the list of elements. This definition also allows for elements to optionally exist outside of the specifically identified elements within the list of elements that the phrase "at least one" refers to, whether or not related to the specifically identified elements. Thus, by way of 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") may, in one embodiment, refer to at least one A where B does not exist (and other elements outside of B may be included), and in another embodiment, refer to at least one B (optionally including one or more) where A does not exist (and optionally including other elements outside of B). In yet another embodiment, it refers to at least one A (optionally including one or more) and at least one B (optionally including one or more) (optionally including other elements).

[0037] All method steps described in this disclosure can be performed in any order, unless otherwise indicated or clearly inconsistent with the context. The use of any and all examples, or language indicating examples (e.g., "such as") is merely intended to be illustrative and does not limit the claims unless expressly claimed. No language in this specification should be construed as indicating that an element not recited in the claims is essential to the practice of the claims.

[0038] As used herein, the phrase "less than" (e.g., less than about 2) or "less than or equal to" (e.g., less than or equal to about 2) means, respectively, a non-zero numerical value less than that number, or a non-zero numerical value less than or equal to (including) that number.

[0039] In the claims and the above specification, all transitional phrases such as "comprising", "including", "mounting", "having", "containing", "accompanying", "holding", "consisting of", etc. are all open-ended, that is, they should be understood to mean "including but not limited to". As described in Section 2111.03 of the United States Patent and Trademark Office Examination Procedure Manual, only the transitional phrases "consisting of" and "consisting essentially of" are exclusive or semi-exclusive transitional phrases, respectively.

[0040] As used in this specification and the appended claims, terms such as "for example", "for instance", "such as", "including", and the like are intended to introduce examples that clarify a more general subject matter. Unless otherwise specified, these examples are provided only as an aid to understanding the present disclosure and are not intended to limit in any way.

[0041] In this specification, diols and lactones, or polyols or copolymers of, for example, either cyclic lactones or cyclic ethers, are described. The resulting polyols or copolymers are surprisingly and unexpectedly advantageous for the preparation of elastomers, such as polyurethane elastomers. As described above, polyurethanes having mechanical properties comparable to the most performant commercially available elastomer materials can be obtained by using the copolymers described in this specification as the polyol component.

[0042] In one aspect, this specification provides a composition comprising a copolymer of poly(farnesene) diol and a lactone or ether, for example, a cyclic lactone or a cyclic ether.

[0043] Farnesene exists in isomeric forms such as α-farnesene ((E,E)-3,7,11-trimethyl-1,3,6,10-dodecatetraene) and β-farnesene (7,11-dimethyl-3-methylene-1,6,10-dodecatriene), and in (E)-β-farnesene in which one or more hydrogen atoms are substituted (i.e., replaced) by another atom or group of atoms. In any of the aspects or embodiments described herein, poly(farnesene) diol is formed by the polymerization of α-farnesene and / or β-farnesene monomers. In any of the aspects or embodiments described herein, poly(farnesene) diol is formed by the polymerization of monomers selected from the group consisting of (E,E)-α-farnesene, (Z,E)-α-farnesene, (Z,Z)-α-farnesene, cis-β-farnesene, trans-β-farnesene, their hydrogenation reaction products, and combinations thereof. In any of the aspects or embodiments described herein, poly(farnesene) diol is formed by the polymerization of trans-β-farnesene.

[0044] The farnesene monomers used to produce the embodiments of poly(farnesene) diol described herein can be prepared by extraction from insects such as Aphididae or by chemical synthesis from petroleum resources extracted from plants. Thus, it is an advantage that the polymer can be derived from monomers obtained via renewable resources. In certain aspects, this is prepared by culturing microorganisms using a carbon source derived from saccharides. Farnesene resins can be efficiently prepared from farnesene monomers obtained via these sources.

[0045] In any of the aspects or embodiments described herein, the lactone is a cyclic ester. The lactones used to generate various embodiments of the polymers described herein can have a carbon chain length of C2 - C20 atoms. In any of the aspects or embodiments described herein, the carbon atoms in the lactone backbone are independently substituted with an R group on each carbon, where R is selected from H, C1 - C6 aliphatic, aromatic groups (e.g., aryl or heteroaryl), halogen, nitrile, nitro, or ester functional groups, and is represented by the following structure, and n is an integer from 0 to 20. [Chemical formula]

[0046] Specific examples of lactones suitable for use in the polyols or copolymers described and exemplified herein include, for example, α - acetolactone, β - propiolactone, γ - butyrolactone, δ - valerolactone, ε - caprolactone, lactide, or glycolide. In any of the aspects or embodiments described herein, the lactone is selected from α - acetolactone, β - propiolactone, γ - butyrolactone, δ - valerolactone, ε - caprolactone, lactide, glycolide, and combinations thereof. In any of the aspects or embodiments described herein, the lactone is ε - caprolactone.

[0047] Cyclic ethers suitable for use in the polyols or block copolymers described and exemplified herein include, for example, substituted or unsubstituted (non-aromatic) heterocyclic compounds. Ethers having three atoms in the ring are generally called oxiranes, four are oxetanes, five are tetrahydrofurans, and six are tetrahydropyrans. The cyclic ethers used to produce various embodiments of the polymers described herein can have a carbon chain length of C2 - C20 atoms, and the ether carbon atoms can independently be substituted with an R group selected from H, C1 - C6 aliphatic, aromatic, heteroaromatic, halogen, nitrile, nitro, and ester functional groups as shown in the following structure, where n is an integer from 0 to 20. Oxiranes are also known as epoxides. Some preferred cyclic ethers are exemplified by ethylene oxide, propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, tetrahydrofuran, methyltetrahydrofuran.

[0048] In certain embodiments, the present specification provides polyols or copolymers comprising the reaction product of poly(farnesene) diol, such as poly(trans-β-farnesene) diol, and ε-caprolactone. Poly(farnesene) diol is produced from biobased monomers, and such copolymerization allows renewable materials to be incorporated into high-performance polyurethane materials.

[0049] In one aspect, the present disclosure provides an A-B-A type block copolymer having an average molecular weight of from about 1000 to about 10,000 g / mol (including all sub-ranges, e.g., from about 1000 to about 9000 g / mol, from about 1000 to about 8000 g / mol, from about 1000 to about 7000 g / mol, from about 1000 to about 6000 g / mol, from about 1000 to about 5000 g / mol, from about 1000 to about 4000 g / mol, from about 1000 to about 3000 g / mol, from about 1000 to about 2000 g / mol, from about 2000 to about 10,000 g / mol, from about 3000 to about 10,000 g / mol, from about 4000 to about 10,000 g / mol, from about 5000 to about 10,000 g / mol, from about 6000 to about 10,000 g / mol, from about 7000 to about 10,000 g / mol, from about 8000 to about 10,000 g / mol, from about 9000 to about 10,000 g / mol, from about 1500 to about 5000 g / mol, from about 1500 to about 5000 g / mol, from about 2000 to about 5000 g / mol, from about 2500 to about 5000 g / mol, from about 3000 to about 5000 g / mol, from about 3500 to about 5000 g / mol, from about 2500 to about 3500 g / mol, or from about 2000 to about 3000 g / mol), and the block copolymer is a reaction product of poly(farnesene) diol and a cyclic lactone or cyclic ether.In any of the aspects or embodiments described herein, the poly(farnesene) diol is present in the range of about 10 wt% to about 95 wt% or about 10 wt% to about 90 wt% of the total molecular weight of the block copolymer (including all sub-ranges, e.g., about 10 - 95 wt%, about 10 - 85 wt%, about 10 - 80 wt%, about 10 - 75 wt%, about 10 - 70 wt%, about 10 - 65 wt%, about 10 - 60 wt%, about 10 - 55 wt%, about 10 - 50 wt%, about 10 - 45 wt%, about 10 - 40 wt%, about 10 - 35 wt%, about 10 - 30 wt%, about 10 - 25 wt%, about 10 - 20 wt%, about 10 - 15 wt%, about 15 - 95 wt%, about 15 - 90 wt%, about 20 - 95 wt%, about 20 - 90 wt%, about 25 - 95 wt%, about 25 - 90 wt%, about 30 - 95 wt%, about 30 - 90 wt%, about 35 - 95 wt%, about 35 - 90 wt%, about 40 - 95 wt%, about 40 - 90 wt%, about 45 - 95 wt%, about 45 - 90 wt%, about 50 - 95 wt%, or about 50 - 90 wt%), and the cyclic lactone or cyclic ether is present in the range of about 5 wt% to about 90 wt% or about 10 wt% to about 90 wt% of the total molecular weight of the block copolymer (including all sub-ranges, e.g., about 5 - 85 wt%, about 5 - 80 wt%, about 5 - 75 wt%, about 5 - 70 wt%, about 5 - 65 wt%, about 5 - 60 wt%, about 5 - 55 wt%, about 5 - 50 wt%, about 5 - 45 wt%, about 5 - 40 wt%, about 5 - 35 wt%, about 5 - 30 wt%, about 5 - 25 wt%, about 5 - 20 wt%, about 5 - 15 wt%, about 10 - 85 wt%, about 10 - 80 wt%, about 10 - 75 wt%, about 10 - 70 wt%, about 10 - 65 wt%, about 10 - 60 wt%, about 10 - 55 wt%, about 10 - 50 wt%, about 10 - 45 wt%, about 10 - 40 wt%, about 10 - 35 wt%, about 10 - 30 wt%, about 10 - 25 wt%, about 10 - 20 wt%, about 10 - 15 wt%, about 15 - 90 wt%, about 20 - 90 wt%, about 25 - 90 wt%, about 30 - 90 wt%, about 35 - 90 wt%, about 40 - 90 wt%, about 45 - 90 wt%, or about 50 - 90 wt%). In certain embodiments, the poly(farnesene) diol is poly(trans-β-farnesene) diol. In certain embodiments, the lactone or cyclic ether is ε-caprolactone.In certain embodiments, the poly(farnesene) diol is poly(trans-β-farnesene) diol and the lactone or cyclic ether is ε-caprolactone.

[0050] In one aspect, the present specification provides an A-B-A type block copolymer having an average molecular weight of about 1000 to about 10,000 g / mol (including all sub-ranges, for example, about 1000 to about 9000 g / mol, about 1000 to about 8000 g / mol, about 1000 to about 7000 g / mol, about 1000 to about 6000 g / mol, about 1000 to about 5000 g / mol, about 1000 to about 4000 g / mol, about 1000 to about 3000 g / mol, about 1000 to about 2000 g / mol, about 2000 to about 10,000 g / mol, about 3000 to about 10,000 g / mol, about 4000 to about 10,000 g / mol, about 5000 to about 10,000 g / mol, about 6000 to about 10,000 g / mol, about 7000 to about 10,000 g / mol, about 8000 to about 10,000 g / mol, about 9000 to about 10,000 g / mol, about 1500 to about 5000 g / mol, about 1500 to about 5000 g / mol, about 2000 to about 5000 g / mol, about 2500 to about 5000 g / mol, about 3000 to about 5000 g / mol, about 3500 to about 5000 g / mol, about 2500 to about 3500 g / mol, or about 2000 to about 3000 g / mol), and the copolymer is a reaction product of poly(trans-β-farnesene) diol and ε-caprolactone.In any of the aspects or embodiments described herein, poly(trans-β-farnesene) diol is present in an amount of about 10 wt% to about 95 wt% or about 10 wt% to about 90 wt% (including all sub-ranges, e.g., about 10 - 95 wt%, about 10 - 85 wt%, about 10 - 80 wt%, about 10 - 75 wt%, about 10 - 70 wt%, about 10 - 65 wt%, about 10 - 60 wt%, about 10 - 55 wt%, about 10 - 50 wt%, about 10 - 45 wt%, about 10 - 40 wt%, about 10 - 35 wt%, about 10 - 30 wt%, about 10 - 25 wt%, about 10 - 20 wt%, about 10 - 15 wt%, about 15 - 95 wt%, about 15 - 90 wt%, about 20 - 95 wt%, about 20 - 90 wt%, about 25 - 95 wt%, about 25 - 90 wt%, about 30 - 95 wt%, about 30 - 90 wt%, about 35 - 95 wt%, about 35 - 90 wt%, about 40 - 95 wt%, about 40 - 90 wt%, about 45 - 95 wt%, about 45 - 90 wt%, about 50 - 95 wt%, or about 50 - 90 wt%) of the total molecular weight of the block copolymer, and ε-caprolactone is present in an amount of about 5 wt% to about 90 wt% or about 10 wt% to about 90 wt% (and including all sub-ranges, e.g., about 5 - 85 wt%, about 5 - 80 wt%, about 5 - 75 wt%, about 5 - 70 wt%, about 5 - 65 wt%, about 5 - 60 wt%, about 5 - 55 wt%, about 5 - 50 wt%, about 5 - 45 wt%, about 5 - 40 wt%, about 5 - 35 wt%, about 5 - 30 wt%, about 5 - 25 wt%, about 5 - 20 wt%, about 5 - 15 wt%, about 10 - 85 wt%, about 10 - 80 wt%, about 10 - 75 wt%, about 10 - 70 wt%, about 10 - 65 wt%, about 10 - 60 wt%, about 10 - 55 wt%, about 10 - 50 wt%, about 10 - 45 wt%, about 10 - 40 wt%, about 10 - 35 wt%, about 10 - 30 wt%, about 10 - 25 wt%, about 10 - 20 wt%, about 10 - 15 wt%, about 15 - 90 wt%, about 20 - 90 wt%, about 25 - 90 wt%, about 30 - 90 wt%, about 35 - 90 wt%, about 40 - 90 wt%, about 45 - 90 wt%, or about 50 - 90 wt%) of the total molecular weight of the block copolymer. In certain embodiments, poly(farnesene) diol, e.g., poly(trans-β-farnesene) diol, is present in an amount of about 30 wt% to about 90 wt% of the total molecular weight of the block copolymer.In certain embodiments, a lactone, such as ε-caprolactone, is present in an amount of about 10 wt% to about 70 wt% of the total molecular weight of the block copolymer.

[0051] In another aspect, the present disclosure a) at least one block copolymer of the A-B-A type described herein, and b) a reaction product of at least one diisocyanate, comprising a polyurethane or polyurethane-urea composition, c) optionally, a diol or diamine chain extender having a molecular weight of about 60 to 600 g / mol at an NCO:OH molar ratio of 0.9:1 to 2:1, to provide a polyurethane or polyurethane-urea composition.

[0052] In any of the aspects or embodiments of the polyurethane or polyurethane-urea composition, at least one block copolymer is a reaction product of a poly(farnesene) diol and a cyclic lactone or cyclic ether described herein.

[0053] In any of the embodiments or aspects of the polyurethane or polyurethane-urea composition, at least one block copolymer has an average molecular weight of from about 1000 to 10,000 g / mol (including all sub-ranges, e.g., from about 1000 to about 9000 g / mol, from about 1000 to about 8000 g / mol, from about 1000 to about 7000 g / mol, from about 1000 to about 6000 g / mol, from about 1000 to about 5000 g / mol, from about 1000 to about 4000 g / mol, from about 1000 to about 3000 g / mol, from about 1000 to about 2000 g / mol, from about 2000 to about 10,000 g / mol, from about 3000 to about 10,000 g / mol, from about 4000 to about 10,000 g / mol, from about 5000 to about 10,000 g / mol, from about 6000 to about 10,000 g / mol, from about 7000 to about 10,000 g / mol, from about 8000 to about 10,000 g / mol, from about 9000 to about 10,000 g / mol, from about 1500 to about 5000 g / mol, from about 1500 to about 5000 g / mol, from about 2000 to about 5000 g / mol, from about 2500 to about 5000 g / mol, from about 3000 to about 5000 g / mol, from about 3500 to about 5000 g / mol, from about 2500 to about 3500 g / mol, or from about 2000 to about 3000 g / mol).

[0054] In any embodiments or aspects of the polyurethane or polyurethane-urea composition, the poly(farnesene) diol is in the range of about 10 wt% to about 95 wt% or about 10 wt% to about 90 wt% (including all sub-ranges, e.g., about 10 - 95 wt%, about 10 - 85 wt%, about 10 - 80 wt%, about 10 - 75 wt%, about 10 - 70 wt%, about 10 - 65 wt%, about 10 - 60 wt%, about 10 - 55 wt%, about 10 - 50 wt%, about 10 - 45 wt%, about 10 - 40 wt%, about 10 - 35 wt%, about 10 - 30 wt%, about 10 - 25 wt%, about 10 - 20 wt%, about 10 - 15 wt%, about 15 - 95 wt%, about 15 - 90 wt%, about 20 - 95 wt%, about 20 - 90 wt%, about 25 - 95 wt%, about 25 - 90 wt%, about 30 - 95 wt%, about 30 - 90 wt%, about 35 - 95 wt%, about 35 - 90 wt%, about 40 - 95 wt%, about 40 - 90 wt%, about 45 - 95 wt%, about 45 - 90 wt%, about 50 - 95 wt%, or 50 - 90 wt%) of the total molecular weight of at least one block copolymer, and the cyclic lactone or cyclic ether is in the range of about 5 to about 90 wt% or about 10 to about 90 wt% (including all sub-ranges, e.g., about 5 - 85 wt%, about 5 - 80 wt%, about 5 - 75 wt%, about 5 - 70 wt%, about 5 - 65 wt%, about 5 - 60 wt%, about 5 - 55 wt%, about 5 - 50 wt% of the foam, about 5 - 45 wt%, about 5 - 40 wt%, about 5 - 35 wt%, about 5 - 30 wt%, about 5 - 25 wt%, about 5 - 20 wt%, about 5 - 15 wt%, about 10 - 85 wt%, about 10 - 80 wt%, about 10 - 75 wt%, about 10 - 70 wt%, about 10 - 65 wt%, about 10 - 60 wt%, about 10 - 55 wt%, about 10 - 50 wt%, about 10 - 45 wt%, about 10 - 40 wt%, about 10 - 35 wt%, about 10 - 30 wt%, about 10 - 25 wt%, about 10 - 20 wt%, about 10 - 15 wt%, about 15 - 90 wt%, about 20 - 90 wt%, about 25 - 90 wt%, about 30 - 90 wt%, about 35 - 90 wt%, about 40 - 90 wt%, about 45 - 90 wt%, or about 50 - 90 wt%) of the total molecular weight of at least one block copolymer.

[0055] In any of the embodiments or aspects of the polyurethane or polyurethane-urea composition, the poly(farnesene) diol is poly(trans-β-farnesene) diol. In any of the embodiments or aspects of the polyurethane or polyurethane-urea composition, the lactone or cyclic ether is ε-caprolactone. In any of the embodiments or aspects of the polyurethane or polyurethane-urea composition, the poly(farnesene) diol is poly(trans-β-farnesene) diol and the lactone or cyclic ether is ε-caprolactone.

[0056] In another aspect, the present disclosure a) at least one block copolymer of the A-B-A type having an average molecular weight of about 1000 to 10,000 g / mol, wherein at least one block copolymer is a reaction product of a poly(farnesene) diol, such as poly(trans-β-farnesene) diol, and a cyclic lactone or cyclic ether, such as ε-caprolactone, and the poly(farnesene) diol is present in an amount of about 10 wt% to about 95 wt% or about 10 to about 90 wt% of the total molecular weight of the at least one block copolymer, and the cyclic lactone or cyclic ether is present in an amount of about 5 wt% to about 90 wt% or about 10 to about 90 wt% of the total molecular weight of the at least one block copolymer, the block copolymer; b) comprising a reaction product with at least one diisocyanate, c) optionally, a polyurethane or polyurethane-urea composition comprising a diol or diamine chain extender having a molecular weight of about 60 to 600 g / mol in an NCO:OH molar ratio of 0.9:1 to 2:1.

[0057] In any of the aspects or embodiments of the polyurethane or polyurethane-urea compositions described herein, poly(farnesene) diol, e.g., poly(trans-β-farnesene) diol, is present in an amount of about 30 wt% to about 90 wt% of the total molecular weight of at least one block copolymer. In any of the aspects or embodiments of the polyurethane or polyurethane-urea compositions described herein, lactone, e.g., ε-caprolactone, is present in an amount of about 10 wt% to about 70 wt% of the total molecular weight of at least one block copolymer.

[0058] In certain embodiments, the present specification a) at least one block copolymer of the A-B-A type having an average molecular weight of 1000 to 10,000 g / mol, wherein at least one block copolymer is a reaction product of poly(trans-β-farnesene) diol and ε-caprolactone, and poly(trans-β-farnesene) diol is present in the range of about 10 wt% to about 70 wt% of the total molecular weight of at least one block copolymer, and ε-caprolactone is present in the range of 30 to 90 wt% of the total molecular weight of at least one block copolymer, and b) a reaction product with at least one diisocyanate, c) optionally, a diol or diamine chain extender having a molecular weight of about 60 to 600 at an NCO:OH molar ratio of 0.9:1 to 2:1 to provide a polyurethane or polyurethane-urea composition.

[0059] In any of the aspects or embodiments of the polyurethane or polyurethane-urea compositions described herein, the NCO:OH molar ratio ranges from 0.9:1 to 1.7:1.

[0060] In any of the aspects or embodiments of the polyurethane or polyurethane-urea compositions described herein, the NCO:OH molar ratio ranges from 0.95:1 to 1.5:1.

[0061] In any of the aspects or embodiments of the polyurethane or polyurethane-urea compositions described herein, the molar ratio of NCO:OH ranges from 1:1 to 1.2:1.

[0062] The carbamate-functionalized polymer is produced by the reaction of an isocyanate monomer. In any of the aspects or embodiments of the polyurethane or polyurethane-urea compositions described herein, the isocyanate monomer is tolylene diisocyanate (2,4 or 2,6-tolylene diisocyanate or a mixture thereof) (TDI), phenylene diisocyanate (m-, p-phenylene diisocyanate or a mixture thereof), 4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate (NDI), diphenylmethane diisocyanate (4,4'-, 2,4'- or 2,2'-diphenylmethane diisocyanate or a mixture thereof) (MDI), 4,4'-toluidine diisocyanate (TODI), and 4,4'-diphenyl ether diisocyanate, 1,2-xylylene diisocyanate (o-XDI), 1,3-xylylene diisocyanate (m-XDI), and 1,4-xylylene diisocyanate (p-XDI), 1,2-hydrogenated xylylene diisocyanate (o-H6XDI), 1,3-hydrogenated xylylene diisocyanate (m-H6XDI), and 1,4-hydrogenated xylylene diisocyanate (p-H6XDI), tetramethylxylylene diisocyanate (1,3- or 1,4-tetramethylxylylene diisocyanate or a mixture thereof) (TMXDI), and ω,ω'-diisocyanate-1,4-diethylbenzene, trimethylene diisocyanate, 1,2-propylene diisocyanate, butylene diisocyanate (tetramethylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, and 1,3-butylene diisocyanate), 1,5-pentamethylene diisocyanate (PDI), 1,6-hexamethylene diisocyanate (also known as: hexamethylene diisocyanate) (HDI), 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, and 2,6-diisocyanate methyl caproate, 1,3-cyclopentane diisocyanate, 1,3-cyclopentene diisocyanate, cyclohexane diisocyanate (1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate), 3-isocyanatomethyl-3,5,5-Trimethylcyclohexyl isocyanate (also known as isophorone diisocyanate) (IPDI), methylene bis(cyclohexyl isocyanate) (hereinafter, bis(isocyanatocyclohexyl)methane) (4,4’-, 2,4- or 2,2’-methylene bis(cyclohexyl isocyanate), its trans,trans-isomer, trans,cis-isomer, cis,cis-isomer, or a mixture thereof) (H12MDI), methylcyclohexane diisocyanate (methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate), norbornane diisocyanate (various isomers or a mixture thereof) (NBDI), 4,4’-diphenylmethane diisocyanate, isophorone diisocyanate, 1,6-hexamethylene diisocyanate, 1,5-naphthylene diisocyanate, 4,4’-dicyclohexylmethane diisocyanate and combinations thereof, or is selected from them.,

[0063] In any of the embodiments or aspects of the polyurethane or polyurethane-urea compositions described herein, the diisocyanate is selected from the group consisting of 4,4’-diphenylmethane diisocyanate, isophorone diisocyanate, 1,6-hexamethylene diisocyanate, 1,5-naphthylene diisocyanate, 4,4’-dicyclohexylmethane diisocyanate.

[0064] In any of the embodiments or aspects of the polyurethane or polyurethane-urea compositions described herein, the chain extender is a multifunctional molecule, such as a low molecular weight diol or diamine. In certain embodiments, they react with the diisocyanate functional groups to increase the polyurethane molecular weight and increase the block length of the hard segments.

[0065] In any of the aspects or embodiments of the polyurethane or polyurethane-urea compositions described herein, the diol chain extender comprises a polyhydroxy compound, such as a lower aliphatic or short-chain glycol having 2 to 20, or 2 to 12, or 2 to 10 carbon atoms. In certain embodiments, the diol chain extender is selected from the group consisting of, or comprising, diethylene glycol, propylene glycol, dipropylene glycol, 1,3-butanediol, 1,5-pentanediol, neopentyl glycol, 1,4-cyclohexanedimethanol (CHDM), 2,2-bis[4-(2-hydroxyethoxy)phenyl]propane (HEPP), heptanediol, nonanediol, dodecanediol, ethylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,4-di-(beta-hydroxyethyl)-hydroxyquinone, 1,4-di-(beta-hydroxyethyl)-bisphenol A, and combinations thereof.

[0066] In any of the aspects or embodiments of the polyurethane or polyurethane-urea compositions described herein, the diol chain extender is selected from the group consisting of, or comprising, ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,4-di-(beta-hydroxyethyl)-hydroxyquinone, 1,4-cyclohexanedimethanol, 1,4-di-(beta-hydroxyethyl)-bisphenol A, and combinations thereof.

[0067] In any of the aspects or embodiments of the polyurethane or polyurethane-urea compositions described herein, the chain extender comprises, or is, a diamine chain extender. In any of the aspects or embodiments of the polyurethane or polyurethane-urea compositions described herein, the diamine chain extender comprises, or is selected from the group consisting 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, and combinations thereof.

[0068] In any of the aspects or embodiments of the polyurethane or polyurethane-urea compositions described herein, the composition is used to be processed as 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 or two-component polyurethane coating, or a polyurethane sealant.

[0069] In any of the aspects or embodiments of the polyurethane or polyurethane-urea compositions described herein, the composition is processed as a thermoplastic polyurethane, a hot cast elastomer, or an elastomeric foam.

[0070] In any of the aspects or embodiments of the polyurethane or polyurethane-urea compositions described herein, the composition is processed as a thermoplastic polyurethane or a hot cast elastomer.

[0071] In various embodiments, the compositions and methods are described for producing high performance commercial elastomeric materials using a copolymer of poly(farnesene) diol and ε-caprolactone as the polyol component. Poly(farnesene) diol is produced from biobased monomers, and such copolymerization enables the incorporation of renewable materials into high performance polyurethane materials.

[0072] In any of the aspects or embodiments described herein, using the polyol or copolymer described herein, a polyurethane material having a hardness of less than 75 Shore A can be produced that not only retains hardness over time but can also be produced with industrially feasible cycle times.

[0073] Shore values are measured by a Shore durometer, a device typically used to measure the hardness of polymeric, elastomeric, and rubbery materials. The scale ranges from 0 to 100. The higher the number on the scale, the greater the resistance to indentation and thus the harder the material. A lower number indicates lower resistance and a softer material.

[0074] In any of the aspects or embodiments described herein, a polyurethane material having a hardness of less than 65 Shore can be produced using the polyol or copolymer described herein.

[0075] In any of the aspects or embodiments described herein, a polyurethane material having a hardness of less than 50 Shore can be produced using the polyol or copolymer described herein.

[0076] In any of the aspects or embodiments described herein, a polyurethane material having a hardness of less than 45 Shore can be produced using the polyol or copolymer described herein.

[0077] In any of the aspects or embodiments described herein, a polyurethane material having a Shore hardness of less than 35 can be produced using a polyol or copolymer described herein.

[0078] In any of the aspects or embodiments described herein, a polyurethane material having a Shore hardness of less than 25 can be produced using a polyol or copolymer described herein.

[0079] The entire disclosure of U.S. Patent No. 3784520 is incorporated herein by reference for chemicals and methods for preparing copolycaprolactone-farnesene diol polyester polymers.

[0080] In another aspect, the present specification provides a) at least one block copolymer of the A-B-A type described herein, and b) at least one polyamide of an oligomer of structure D-(E-D)x or Fy-D-Fz, wherein D is an alpha-omega diacid, E is an alpha-omega diamine, F is a lactam and / or an alpha amino omega acid, and x, y, and z are integers of 1 or more, a copolyamide-polyester composition.

[0081] In any of the aspects or embodiments of the copolyamide-polyester composition, at least one block copolymer of the A-B-A type has an average molecular weight of about 1000 g / mol to about 10,000 g / mol, the copolymer is a reaction product of poly(farnesene) diol and a cyclic lactone or cyclic ether, the poly(farnesene) diol is present in the range of about 10 wt% to about 90 wt% of the total molecular weight of at least one block copolymer, and the cyclic lactone or cyclic ether is present in the range of about 10 wt% to about 90 wt% of the total molecular weight of at least one block copolymer.

[0082] In any of the embodiments or aspects of the copolyamide-polyester composition, D, E, and F are independently selected from C2-C12 aliphatic or aromatic groups.

[0083] In any of the embodiments or aspects of the copolyamide-polyester composition, the copolyamide-polyester composition has the structure Fy-D-Fz, where F is C11, D is C12, and y and z are integers from 1 to 5.

[0084] In another aspect, this specification provides a) at least one block copolymer of the A-B-A type described herein, and b) at least one diacid, and c) a copolyester composition produced as a reaction product of at least one short-chain diol having a molecular weight of less than 250 g / mol.

[0085] In any of the embodiments or aspects of the copolyester composition, the composition has an average molecular weight of about 1000 g / mol to about 10,000 g / mol, the copolymer is a reaction product of poly(farnesene) diol and a cyclic lactone or cyclic ether, the poly(farnesene) diol is present in the range of about 10 wt% to about 90 wt% of the total molecular weight of at least one block copolymer, and the cyclic lactone or cyclic ether is present in the range of about 10 wt% to about 90 wt% of the total molecular weight of at least one block copolymer.

[0086] In any of the embodiments or aspects of the copolyester composition, the block copolymer is from about 90 wt% to about 25 wt% of the copolyester composition.

[0087] In any of the embodiments or aspects of the copolyester composition, the short-chain diol is less than 25 wt% of the copolyester composition.

[0088] In any of the embodiments or aspects of the copolyester composition, the diol is 1,4-butanediol.

Example

[0089] Material The polycaprolactone polyol was produced by reacting ε - caprolactone with trans - β - farnesene diol Krasol® F3000 (Total Cray Valley, Pennsylvania, Exxon) in a molar ratio (ring - opening polymerization), and polycaprolactone was obtained according to Table 1.

Table 1

[0090] The reaction was carried out at 180 °C in the presence of stannous octoate (DABCO T9) as a catalyst and monitored by GC measurement of residual ε - caprolactone. The reaction was terminated when the amount of residual ε - caprolactone was less than 0.5%.

[0091] The polyols used as comparative materials are CAPA® 2201A (Ingevity, UK), a typical polyol used in high - performance polyurethane applications, and Krasol® F3000 (Total Cray Valley, France), a polyfarnesene diol produced using 100% recycled raw materials.

[0092] Examples and comparative examples of the described compositions and methods were prepared via a hot - cast manufacturing process (Examples 1 - 6) and a thermoplastic polyurethane (TPU) manufacturing process (Examples 7 - 23).

[0093] Examples 1 - 6 To prepare the hot-cast polyurethane elastomer material according to Table 2, first the necessary polyol was added dropwise to melt 4,4'-diphenylmethane diisocyanate and reacted at 80 °C for 2 hours. As a result, a polyurethane prepolymer with 3.98% NCO was obtained. To this, 1,4-butanediol was added according to 97% stoichiometry or an isocyanate index of 103, and the mixture was homogenized for 2 minutes using a vortex mixer. Then, the reaction mixture was poured onto a coated metal plate adjusted at 120 °C for 1 hour. Thereafter, the cast sheet was placed in an oven at 120 °C for 16 hours, then demolded and cooled to 23 °C.

Table 2

[0094] The mechanical properties of the polyurethane material were measured according to ISO 37 (Type 2) (Ultimate Tensile strength, Elongation) and ASTM D 624 Type C (Tear strength).

[0095] The tensile test was carried out according to ISO 37 using a Type 2 specimen (a dumbbell-shaped test piece with a thickness of 2.0 mm + / - 0.2 mm and a test length of 20 mm + / - 0.5 mm). The test piece was cut from a 2.0 mm polyurethane sheet using a die cutter and then conditioned at 23 °C / relative humidity 50% for 7 days before the test. A ZwickRoell Proline Z010 tensile testing machine equipped with a pincer grip and a 10 kN load cell was used to deform the test piece in tensile mode at a speed of 200 mm / min until the test piece broke. The tensile strength is defined as the stress megapascal (MPa or N / mm 2 ) recorded at the break of the sample. The maximum elongation rate is defined as the increase rate of the test length at break. The elastic modulus is defined as the average stress / strain of the first 0.25% elongation of the material and is a measure of the resistance of the material to deformation.

[0096] The tear strength test was conducted in accordance with ASTM D 624 using a die C / right-angle specimen (a non-notched specimen with a tab end at a right angle of 90° on one side) with a thickness of 2.0 mm + / - 0.2 mm. The specimens were cut from a 2.0 mm polyurethane sheet using a die cutter and then conditioned at 23 °C / 50% relative humidity for 7 days prior to testing. The specimens were deformed in tensile mode at a crosshead speed of 500 mm / min using a ZwickRoell Proline Z010 tensometer equipped with pincer grips and a 10 kN load cell until the specimens were completely broken. The tear strength is defined as the force required to cause rupture of the specimen divided by the thickness of the specimen at the value where rupture occurred.

[0097] In each of the exemplary polyols (i.e., Examples 1-4), a significant improvement in maximum tensile strength, maximum elongation, tear strength, and modulus of elasticity was shown compared to a reference polyol (Comparative Example 5) having a 100% renewable raw material content (Comparative Example 5). Surprisingly, it was found that the performance of premium polyols such as CAPA® 2201A can be achieved while maintaining a renewable content of more than 50% in the polyol (e.g., bio-based farnesene).

Table 3

[0098] Figures 1A, 1B, and 1C further illustrate the differences in mechanical properties of the compositions described herein compared to currently available materials. Figure 1A shows the comparison, tensile strength (left axis) and tear strength (right axis). Figure 1B shows the maximum elongation of the comparison. Figure 1C shows the comparison modulus of elasticity.

[0099] To prepare the thermoplastic polyurethane elastomer material according to Table 4, one-shot bulk polymerization was carried out. The polyol, extender (1,4-butane), antioxidant (BHT derivative), and diisocyanate were weighed in a reactor. When using aromatic diisocyanate, no catalyst was used. When using aliphatic isocyanate, a Sn(IV)-based catalyst was used. The weights of the polyol, extender, and diisocyanate for a stoichiometry (NCO to OH ratio) of 1.02. The reactants were mixed until a 5 °C temperature rise was achieved. The reaction mixture was transferred to a tray and cured in an oven for at least 3 hours. The size of the cooled plate was reduced and melt processed to obtain test samples. [Table 4] [Table 5]

[0100] The data presented in Table 5 further supports the invention of the present disclosure.

[0101] The content of all references, patents, pending patent applications, and published patents cited throughout this application are hereby expressly incorporated by reference into this specification.

[0102] One of ordinary skill in the art will recognize, or be able to ascertain, many equivalents to the specific embodiments of the invention described herein using only routine experimentation. 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 in no way intended to limit the invention. Various modifications or alterations may be proposed to one of ordinary skill in the art, which 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 the components may be varied to optimize the desired effects, additional components may be added, and / or similar components may be substituted for one or more of the described components. Additional advantageous features and functions related to the systems, methods, and processes of the invention will be apparent from the appended claims. Further, one of ordinary skill in the art will recognize, or be able to ascertain, many equivalents to the specific embodiments of the invention described herein using only routine experimentation. Such equivalents are intended to be encompassed by the following claims.

Claims

1. An A-B-A type block copolymer comprising a reaction product of poly(farnesene) diol and a cyclic lactone or cyclic ether, wherein the poly(farnesene) diol is present in the range of about 10 wt% to 95 wt% (e.g., about 10 wt% to about 90 wt%) of the total molecular weight of the copolymer, the cyclic lactone or cyclic ether is present in the range of about 5 wt% to about 90 wt% (e.g., about 10 wt% to about 90 wt%) of the total molecular weight of the copolymer, and the copolymer has an average molecular weight of about 1000 g / mol to about 10,000 g / mol.

2. The copolymer according to claim 1, wherein the poly(farnesene) diol is a polymer comprising at least one monomer selected from (E,E)-α-farnesene, (Z,E)-α-farnesene, (Z,Z)-α-farnesene, cis-β-farnesene, trans-β-farnesene, hydrogenated derivatives thereof, and combinations thereof.

3. The copolymer according to claim 1, wherein the cyclic lactone is at least one of α-acetolactone, β-propiolactone, γ-butyrolactone, δ-valerolactone, ε-caprolactone, lactide, glycolide, or combinations thereof.

4. The copolymer according to claim 3, wherein the cyclic lactone is ε-caprolactone.

5. The copolymer according to claim 1, wherein the cyclic ether is at least one of ethylene oxide, propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, tetrahydrofuran, methyltetrahydrofuran, or combinations thereof.

6. The copolymer according to claim 1 or claim 5, wherein the poly(farnesene) diol is present in the range of about 10 wt% to about 60 wt% of the total molecular weight of the block copolymer.

7. A polymer composition comprising a reaction product of the copolymer according to claim 1 and at least one of a diacid, diisocyanate, urea, dinitrile, or combinations thereof, thereby forming a polyester, polyurethane, polyurethane-urea, polyamide, or polyamide material.

8. As the reaction product, a) At least one block copolymer of the A-B-A type having an average molecular weight of 1000 to 10,000 g / mol, wherein the at least one block copolymer is a reaction product of poly(farnesene) diol and a cyclic lactone or cyclic ether, and the poly(farnesene) diol is present in the range of about 10 wt% to about 95 wt% (e.g., about 10 wt% to about 90 wt%) of the total molecular weight of the at least one block copolymer, and the cyclic lactone or cyclic ether is present in the range of about 5 wt% to about 95 wt% (e.g., about 10 wt% to about 90 wt%) of the total molecular weight of the at least one block copolymer, a copolymer, and b) comprising a reaction product with at least one diisocyanate, c) optionally, a diol or diamine chain extender having a molecular weight of about 60 g / mol to about 600 g / mol and an NCO:OH molar ratio of about 0.9:1 to about 2:1, a polymer composition.

9. The polymer composition according to claim 8, wherein the poly(farnesene) diol is a polymer comprising at least one monomer selected from (E,E)-α-farnesene, (Z,E)-α-farnesene, (Z,Z)-α-farnesene, cis-β-farnesene, trans-β-farnesene, hydrogenated derivatives thereof, and combinations thereof.

10. The polymer composition according to claim 8, wherein the cyclic lactone is at least one of α-acetolactone, β-propiolactone, γ-butyrolactone, δ-valerolactone, ε-caprolactone, lactide, glycolide, or combinations thereof.

11. The polymer composition according to claim 10, wherein the cyclic lactone is ε-caprolactone.

12. The polymer composition according to claim 8, wherein the cyclic ether is at least one of ethylene oxide, propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, tetrahydrofuran, methyltetrahydrofuran, or combinations thereof.

13. The polymer composition according to claim 8 or 12, wherein the poly(farnesene) diol is present in the range of about 10 wt% to about 60 wt% of the total molecular weight of the at least one block copolymer.

14. The polymer composition according to claim 8, wherein the at least one block copolymer is included in the range of about 25% to about 95% by weight of the polymer composition, and the polymer composition is polyurethane or polyurethane-urea.

15. The polymer composition according to claim 8, wherein the polymer composition has a Shore hardness of about 25 Shore A to about 60 Shore D.

16. The polymer composition according to claim 8, wherein the diisocyanate is selected from the group consisting of 4,4'-diphenylmethane diisocyanate, isophorone diisocyanate, 1,6-hexamethylene diisocyanate, 1,5-naphthylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, and combinations thereof.

17. The polymer composition according to claim 8, wherein the diol chain extender is selected from the group consisting of ethylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,4-di-(beta-hydroxyethyl)-hydroxyquinone, 1,4-cyclohexanedimethanol, 1,4-di-(beta-hydroxyethyl)-bisphenol A, and combinations thereof.

18. The polymer composition according to claim 8, wherein the diamine chain extender is selected from the group consisting 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, and combinations thereof.

19. The polymer composition according to claim 8, wherein the polymer composition is at least one of 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 or two-component polyurethane coating, an additive manufacturing material, or a polyurethane sealant.

20. A copolyamide-polyester composition produced as the following reaction product: a) At least one block copolymer of the A-B-A type having an average molecular weight of about 1000 g / mol to about 10,000 g / mol, wherein the copolymer is a reaction product of poly(farnesene) diol and a cyclic lactone or cyclic ether, and the poly(farnesene) diol is present in the range of about 10 wt% to about 95 wt% (e.g., about 10 wt% to about 90 wt%) of the total molecular weight of the at least one block copolymer, and the cyclic lactone or cyclic ether is present in the range of about 10 wt% to about 95 wt% (e.g., about 10 wt% to about 90 wt%) of the total molecular weight of the at least one block copolymer, a copolymer, and b) A copolyamide-polyester composition produced as a reaction product of at least one polyamide of an oligomer having a structure D-(E-D)x or Fy-D-Fz, wherein D is an alpha-omega diacid, E is an alpha-omega diamine, F is a lactam and / or an alpha amino omega acid, and x, y, and z are integers of 1 or more.

21. The copolyamide-polyester composition according to claim 20, wherein D, E, and F are independently selected from C2-C12 aliphatic or aromatic groups.

22. The copolyamide-polyester composition according to claim 21, wherein the copolyamide-polyester composition has a structure of Fy-D-Fz, F is C11, D is C12, and y and z are integers from 1 to 5.

23. A copolyester composition, comprising a) At least one block copolymer of the A-B-A type having an average molecular weight of about 1000 g / mol to about 10,000 g / mol, wherein the copolymer is a reaction product of poly(farnesene) diol and a cyclic lactone or cyclic ether, and the poly(farnesene) diol is present in the range of about 10 wt% to about 95 wt% (e.g., about 10 wt% to about 90 wt%) of the total molecular weight of the at least one block copolymer, and the cyclic lactone or cyclic ether is present in the range of about 10 wt% to about 95 wt% (e.g., about 10 wt% to about 90 wt%) of the total molecular weight of the at least one block copolymer, a copolymer, and b) At least one diacid, and c) A copolyester composition produced as a reaction product with at least one short-chain diol, wherein the molecular weight of the short-chain diol is less than 250 g / mol. **Claim 24** The copolyester composition according to claim 23, wherein the block polymer is from about 90% to about 25% by weight of the copolyester composition. **Claim 25** The copolyester composition according to claim 23, wherein the short-chain diol is less than 25% by weight of the copolyester composition. **Claim 26** The copolyester composition according to claim 23, wherein the diacid is terephthalic acid. **Claim 27** The copolyester composition according to claim 23, wherein the diol is 1,4-butanediol.

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