Bio-based polyols for high performance polyurethane applications

Abstract

Compositions and methods are described for polyurethanes having mechanical properties comparable to those of commercially available elastomeric materials of the highest performance by employing a copolymer of a poly (farnesene) diol and s-caprolactone as the polyol component. The poly (farnesene) glycol is produced from a bio-based monomer, and such copolymerization allows for the incorporation of renewable materials into high performance polyurethane materials.

Description

[0001] Cross-reference to related applications

[0002] The present disclosure claims priority to and the benefit of U.S. Provisional Application No. 63 / 370,534, filed on August 5, 2022, entitled BIO-BASED POLYOLS FOR HIGH PERFORMANCE POLYURETHANE APPLICATIONS, which is incorporated herein in its entirety for all purposes. Technical Field

[0003] In various embodiments, the present disclosure generally relates to bio-based polyols for preparing high-performance polyurethanes and related applications. Background Art

[0004] Polyurethane elastomers are versatile materials that are of great industrial importance due to their combination of good mechanical properties with ease and flexibility of processing. For example, polyurethane materials can be processed by conventional thermoplastic techniques, cast to obtain thermosets, blow molded to obtain microcellular foams, or dispersed in aqueous or organic media; all with only minor adjustments to the formulation.

[0005] The ability to produce high-performance polyurethanes from renewable resources (e.g., to address the challenges of global warming and dwindling petroleum feedstocks) is a major limitation of the technology. Technical challenges in purifying bio-based feedstocks to obtain products of similar quality have hampered development, especially at a time when demand for such materials is accelerating. Few commercially available polyols based on renewable raw materials have the same high-performance properties as petroleum-based products.

[0006] Another recognized limitation of polyurethane technology is the difficulty in producing soft materials (less than 75 Shore A) that can be efficiently produced and maintain their softness over time. The proportion of the diisocyanate component in the formulation primarily determines the hardness of the resulting polyurethane material. However, reducing the diisocyanate content (and therefore increasing the polyol content) may initially obtain a soft material, but due to the semi-crystalline nature of the polyols, the hardness increases over time. Reducing the diisocyanate content also means that the crystallinity that drives the curing process in production is reduced, and the polyurethane requires longer production time, making this method economically unfeasible.

[0007] Several methods for preparing soft polyurethane materials have been disclosed. Canadian Patent 1257946 claims the use of specific phthalate and phosphate plasticizers to obtain TPUs with a hardness of 60 to 80 Shore A. The disadvantage of plasticizers is migration from the part, resulting in cold hardening, fogging of surrounding surfaces, odor problems, etc. It is also a fairly common problem that the plasticized product becomes sticky and uncomfortable to the touch over time. Many plasticizers, especially those based on phthalates, are being deregulated for environmental and health reasons.

[0008] In order to destroy crystallinity and maintain softness without the use of plasticizers, previous work has focused on introducing random copolymers as polyol components. US2008 / 0139774 claims the use of branched polyester adipate diol esters in TPU formulations. It teaches that the hardness can be maintained for up to 5 days at 23°C (i.e. room temperature) and in a refrigerator. WO 2014 / 195211 discloses a plasticizer-free TPU based on linear polyester polyols derived from aliphatic dicarboxylic acids and aliphatic diols, with a hardness of 30 to 55 Shore. However, according to the standard test protocol applied in WO 2014 / 195211, the results of very soft TPU formulations only show characteristics with very short lifespans.

[0009] As taught in WO 2020 / 099540, polycaprolactone copolymer technology has been used to address the challenge of cold hardening of polyurethane materials. It has been shown that by incorporating a specific amount of branching into polycaprolactone copolymers using block copolymerization technology, the material can remain soft for up to 6 months at room temperature and -4°C. However, this technology requires polyurethane processors to fine-tune their processes / formulations to achieve commercially viable production times, and the adoption of this technology has been slow. This technology is also integrated into the petroleum supply chain; and therefore poses environmental concerns.

[0010] To date, the raw material building blocks of polyurethane elastomers are overwhelmingly based on petroleum-derived chemicals, particularly for elastomers used in demanding applications where mechanical properties or durability cannot be compromised. Due to the technical challenges and expense involved in the purification and controlled polymerization of such raw materials, elastomers made from renewable resources have difficulty achieving the high performance properties of elastomers based on traditional petroleum-based raw materials.

[0011] Polyfarnesene glycol (e.g., Total Cray Valley, Exton, Pennsylvania) F-3000) have become useful building blocks for polyurethane elastomers. These materials are derived from trans-β-farnesene, a bio-based monomer produced by fermentation of lignocellulosic sugars (including xylose). The resulting polyols can be prepared with narrow polydispersity and high purity. However, when used in elastomer formulations, the resulting articles lack mechanical strength and have little commercial value in demanding polyurethane applications. They also have poor reactivity with common isocyanates such as MDI.

[0012] Despite the high demand for plastic materials made from renewable resources - reducing global dependence on finite resources, few commercially available solutions based on bio-based raw materials exhibit commercially acceptable processing times, mechanical properties and durability. Therefore, materials that overcome such challenges while maintaining high bio-based content are needed.

[0013] The availability of new bio-based polymer building blocks can also help overcome similar technical challenges in polyurethane adhesives, copolyesters and polyamide technologies in a more environmentally sustainable manner.

[0014] FR 2,384,810 describes polyetheresteramides obtained by polymerization at a temperature of 230-300° C. under autogenous pressure. The reaction mixture consists of one or more polyamide monomers, α,ω-dihydroxy (polytetrahydrofuran) or PTMG with an Mn (number average molecular weight) of 160-3000 g / mol and at least one diacid in the presence of water. The water is then removed from the reaction medium, which is returned to normal pressure or reduced pressure at a temperature of 250-280° C. The product obtained is a block polymer and has good cold shock resistance. However, for the same hardness, the polymers obtained according to these patents have a lower melting temperature than the polymers according to the invention.

[0015] US Pat. No. 4,307,227 describes a hot melt adhesive consisting of a mixture of 50-80% of dicarboxylic acids and polyoxyalkylene glycols derived from repeating units of caprolactam and primary amines. The process used (all ingredients reacted at 220-250° C. without catalyst) does not allow the synthesis of products with polyether sequences having an Mn greater than 1000 g / mol.

[0016] Patent applications J63-035622 and J63-277239 relate to polyether block amides obtained by reacting an oligoamide of PA-6,6 containing one or more polyoxyalkylenedioxy sequences with a polyoxyalkylene glycol or a low-quality diol under high vacuum at a temperature above 250° C. in the presence of an esterification catalyst which is a metal tetraalkoxide. The use of low-quality polyoxyalkylene glycols or diols results in a product having a melting point significantly lower than that of the product of the present invention.

[0017] Patent application J63-182343 relates to polyether block amides obtained by reacting PA-6,6 sequences with diamine ends and polyether with dicarboxylic acid chain ends in the molten state. The polymers obtained according to this application have a high melting temperature; greater than 230°C, which requires high conversion temperatures and therefore risks degradation of the product during its conversion. Summary of the invention

[0018] It has been surprisingly and unexpectedly discovered that by employing copolymers of diols and lactones, such as copolymers of poly(farnesene) diol and ε-caprolactone as the polyol component, polyurethanes having mechanical properties comparable to the highest performing commercially available elastomeric materials can be obtained. Poly(farnesene) diols are produced from bio-based monomers, and such copolymerization allows the incorporation of renewable materials into high performance polyurethane materials.

[0019] The present disclosure provides polymer compositions and methods for producing ABA type copolymers, which are the reaction products of a diol and a cyclic lactone or cyclic ether. The described bio-based copolymers advantageously exhibit at least one of commercially desirable processing time, mechanical properties and / or durability.

[0020] Thus, in one aspect, the present description provides polymers and methods for producing ABA-type copolymers having an average molecular weight (Mn) of 1000 to 10,000 g / mol, which are the reaction product of a diol (e.g., poly(farnesene) diol) and a cyclic lactone or cyclic ether.

[0021] In any of the aspects or embodiments described herein, the poly(farnesene) glycol is present at about 10 to about 90 wt % of the total molecular weight of the block copolymer.

[0022] In any of the aspects or embodiments described herein, the cyclic lactone or cyclic ether is present at about 10 to about 90 wt % of the total molecular weight of the block copolymer.

[0023] In a further aspect, the present description provides a polyurethane, polyurethane-urea, polyamide or copolyester composition comprising a polymer as described herein.

[0024] In any aspect or embodiment described herein, the polyurethane or polyurethane urea composition comprises an ABA type block copolymer having an average molecular weight of 1000 to 10,000 g / mol, wherein the copolymer is the reaction product of a poly(farnesene) diol and a cyclic lactone or cyclic ether, a diisocyanate, and a diol or diamine chain extender. In any aspect or embodiment described herein, the poly(farnesene) diol is present at about 10 to about 90 wt % of the total molecular weight of the block copolymer. In any aspect or embodiment described herein, the cyclic lactone or cyclic ether is present at about 10 to about 90 wt % of the total molecular weight of the block copolymer. In any aspect or embodiment described herein, the molecular weight of the diol or diamine chain extender is about 60 to about 600 g / mol. In any aspect or embodiment described herein, the molar ratio of isocyanate to hydroxyl (i.e., NCO:OH) is about 0.9:1 to 2:1.

[0025] In any aspect or embodiment described herein, the copolymer as described herein is in the range of about 25 to about 95 wt % of the polyurethane or polyurethane-urea.

[0026] In any aspect or embodiment described herein, the polyurethane or polyurethaneurea comprises a Shore hardness between about 25 Shore A and about 60 Shore D.

[0027] The aforementioned general application aspects and embodiments are given by way of example only and are not intended to limit the scope of the present disclosure and the appended claims. Based on the claims, descriptions and examples of the present invention, one of ordinary skill in the art will appreciate additional goals and advantages associated with the compositions, methods and processes of the present invention. For example, various aspects and embodiments of the present invention may be utilized in numerous combinations, all of which are explicitly contemplated by this specification. These additional advantageous goals and embodiments are explicitly included within the scope of the present invention. Publications and other materials herein that are used to illustrate the background of the present invention and to provide additional details about practice in certain circumstances are incorporated by reference. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate several embodiments of the present invention and, together with the specification, are used to explain the principles of the present invention. The accompanying drawings are only for the purpose of illustrating embodiments of the present invention and should not be construed as limiting the present invention. Additional objects, features and advantages of the present invention will become apparent from the following detailed description in conjunction with the accompanying drawings which show illustrative embodiments of the present invention, in which:

[0029] Figure 1A , 1B 1C and 1C demonstrate the differences in the mechanical properties of some exemplary polymer compositions as described herein. Figure 1AA comparison of the tensile strength (left hand axis) and tear strength (right hand axis) of the polymer compositions is shown. Figure 1B is a comparison of the ultimate elongation of polymer compositions. Figure 1C is a comparison of the elastic moduli of polymer compositions. DETAILED DESCRIPTION

[0030] It has been surprisingly and unexpectedly discovered that by employing copolymers of diols and lactones or ethers, such as cyclic lactones or cyclic ethers, as the polyol component, polyurethanes can be obtained having mechanical properties comparable to the highest performing commercially available elastomeric materials. Additionally, the polyols as described herein can be used to produce polyurethane materials having a Shore A hardness of less than 75 that not only retain their hardness over time, but can also be produced within industrially feasible cycle times.

[0031] Unless otherwise specified, all terms have the ordinary meanings accepted in the polymer technology field.

[0032] Unless otherwise indicated, the recitation of a range of values ​​is intended merely to serve as a shorthand method of referring individually to each individual value falling within the range, and each individual value is incorporated into the specification as if individually recited. Unless otherwise expressly indicated, the endpoints of all ranges are included in the range and are independently combinable.

[0033] As used herein and in the appended claims, the articles "a" and "an" are used herein to refer to one or more than one (i.e., at least one) of the grammatical objects of the article unless the context clearly indicates otherwise. For example, "an element" means one element or more than one element.

[0034] The term "about" means approximately. When the term "about" is used in conjunction with a numerical range, the term modifies the range by extending the limits above and below the numerical values ​​set forth. Illustratively, the use of the term "about" indicates a value slightly exceeding the referenced value, i.e., plus or minus 0.1% to 10%, which is also effective and safe, and is included in the value. The numerical ranges recited herein by endpoints include all numbers and fractions (e.g., 1 to 5, including 1, 1.5, 2, 2.75, 3, 3.90, 4, and 5) that fall within the range.

[0035] As used herein in the specification and in the claims, the phrase "and / or" should be understood to mean "either or both" of the elements so combined, i.e., elements that exist together in some cases and separately in other cases. Multiple elements listed with "and / or" should be interpreted in the same manner, i.e., "one or more" of the elements so combined. In addition to the elements specifically identified by the "and / or" clause, other elements may optionally be present, whether related or unrelated to those specifically identified. Thus, as a non-limiting example, in one embodiment, when used in conjunction with open language such as "comprising", a reference to "A and / or B" may refer only to A (optionally including elements other than B); in another embodiment, only to B (optionally including elements other than A); in yet another embodiment, to both A and B (optionally including other elements); etc.

[0036] As used herein in this specification and in the claims, "or" shall 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" shall be interpreted as inclusive, that is, including at least one of the number of elements or the list and (as the case may be) additional unlisted items, as well as more than one. Only terms that clearly indicate the contrary, such as "only one of..." or "exactly one of..." or when used in the claims, "consisting of..." will refer to including exactly one element of a plurality of elements or a list of elements. In general, the term "or" as used herein should only be interpreted as indicating exclusive alternatives (i.e., "one or the other, but not both") when preceded by an exclusive term, such as "any one of," "one of...", "only one of...", or "exactly one of...".

[0037] As used herein in this specification and claims, the phrase "at least one" with respect to a list of one or more elements should be understood to mean at least one element selected from any one or more elements in the list of elements, but not necessarily including at least one element of each element specifically listed in the list of elements, and not excluding any combination of elements in the list of elements. This definition also allows that elements other than the elements specifically identified in the list of elements referred to by the phrase "at least one" may optionally be present, whether or not related to those elements specifically identified. Thus, as a non-limiting example, in one embodiment, "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 refer to at least one that optionally includes more than one A, does not have B (and optionally includes elements other than B); in another embodiment, may refer to at least one that optionally includes more than one B, does not have A (and optionally includes elements other than A); in yet another embodiment, may refer to at least one that optionally includes more than one A, and optionally includes more than one B (and optionally includes other elements); etc.

[0038] Unless otherwise indicated or otherwise clearly contradicted by context, all method steps described in this disclosure may be performed in any order. The use of any and all examples or language indicating examples (e.g., "such as") is intended to be illustrative only and does not limit the scope of the claims unless expressly claimed. No language in this specification should be construed to indicate that any unclaimed element is necessary to practice the embodiments of the claims.

[0039] 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) followed by a number means a non-zero number that is less than the stated number or a non-zero number that is less than or equal to the stated number, respectively.

[0040] In the claims and the foregoing description, all transitional phrases such as "comprising," "including," "carrying," "having," "containing," "involving," "holding," "consisting of," etc. shall be understood as open-ended, i.e., meaning 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 described in Section 2111.03 of the 10 United States Patent Office Manual of Patent Examining Procedures.

[0041] As used in the specification and the appended claims, the terms "for example / for instance", "such as", "including", etc. are intended to introduce examples that further illustrate a more general subject matter. Unless otherwise specified, these examples are provided merely to aid in understanding the present disclosure and are not meant to be limiting in any way.

[0042] Described herein are polyols or copolymers of diols and lactones or one of them, such as cyclic lactones or cyclic ethers. The resulting polyols or copolymers have surprising and unexpected advantages for preparing elastomers (e.g., polyurethane elastomers). As described above, by using copolymers as described herein as the polyol component, polyurethanes having mechanical properties comparable to the highest performance commercially available elastomeric materials can be obtained.

[0043] In one aspect, the disclosure provides a composition comprising a copolymer of a poly(farnesene) glycol and a lactone or ether, such as a cyclic lactone or cyclic ether.

[0044] 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), as well as (E)-β-farnesene in which one or more hydrogen atoms have been replaced (i.e., substituted) by another atom or group of atoms. In any aspect or embodiment described herein, the poly(farnesene) diol is formed by polymerization of α-farnesene and / or β-farnesene monomers. In any aspect or embodiment of the aspects or embodiments described herein, the poly(farnesene) diol is formed by 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, hydrogenation reaction products thereof, and combinations thereof. In any of the aspects or embodiments described herein, the poly(farnesene) diol is formed by polymerization of trans-β-farnesene.

[0045] The farnesene monomers used to produce the embodiments of the poly(farnesene) diols described herein can be prepared by chemical synthesis from petroleum resources extracted from insects (such as Aphididae) or plants. Therefore, the advantage is that the polymer can be derived from monomers obtained from renewable resources. In some aspects, it is prepared by culturing microorganisms using carbon sources derived from sugars. Farnesene resins can be effectively prepared from farnesene monomers obtained from these sources.

[0046] In any aspect or embodiment of aspect described herein or embodiment, lactone is cyclic ester.The lactone of each embodiment for producing polymkeric substance described herein can have the carbon chain length between C2 and C20 atom.In any aspect or embodiment of aspect described herein or embodiment, the carbon atom in lactone main chain is replaced by R group independently on each carbon, and wherein R is selected from H, C1-C6 aliphatic group, aromatic group (for example, aryl or heteroaryl), halogen, nitrile, nitro or ester functional group, as shown in the following structure, wherein n is 0 to 20 integer.

[0047]

[0048] Specific examples of lactones suitable for use in the polyols or copolymers described and exemplified herein include, for example, α-acetone, β-propiolactone, γ-butyrolactone, δ-valerolactone, ε-caprolactone, lactide or glycolide. In any aspect or embodiment of the aspects or embodiments described herein, the lactone is selected from α-acetone, β-propiolactone, γ-butyrolactone, δ-valerolactone, ε-caprolactone, lactide, glycolide and combinations thereof. In any aspect or embodiment of the aspects or embodiments described herein, the lactone is ε-caprolactone.

[0049] 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 with three atoms on the ring are generally referred to as oxiranes, those with four atoms are referred to as oxetanes, those with five atoms are referred to as tetrahydrofurans, and those with six atoms are referred to as tetrahydropyrans. The cyclic ethers of various embodiments for producing the polymers described herein may have a carbon chain length between C2 and C20 atoms, wherein the ether carbon atoms are independently selected from H, C1-C6 aliphatic, aromatic, heteroaromatic, halogen, nitrile, nitro and ester functional groups R groups optionally substituted, as shown in the following structure, wherein n is an integer between 0 and 20. Oxiranes are also referred to as epoxides. Some preferred cyclic ethers are exemplified by ethylene oxide, propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, tetrahydrofuran, and methyltetrahydrofuran.

[0050] In certain embodiments, the present specification provides a polyol or copolymer comprising the reaction product of a poly(farnesene) glycol (e.g., poly(trans-β-farnesene) glycol) and ε-caprolactone. The poly(farnesene) glycol is produced from bio-based monomers, and such copolymerization allows the incorporation of renewable materials into high-performance polyurethane materials.

[0051] In one aspect, the present description provides an ABA type block copolymer having an average molecular weight of about 1000 to about 10,000 g / mol (and including all subranges, 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 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 / ml, about 2500 to about 5000 g / mol, about 3000 to about 5000 g / mol, about 3500 to about 5000 g / ml, about 2500 to about 3500 g / mol, or about 2000 to about 3000 g / mol).In any aspect or embodiment described herein, the poly(farnesene) glycol is present in about 10 wt % to about 95 wt % or about 10 wt % to about 90 wt % (and including all subranges, 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 10-3 0wt%, about 10-25wt%, about 10-20wt%, about 10-15wt%, about 15-95wt%, about 15-90wt%, about 20-95wt%, about 20-90wt%, about 25-95wt%, about 25-90wt%, about 30-95wt%, about 30-90wt%, about 35-95wt%, about 35-90wt%, about 40-95wt%, about 40-90wt%, about 45-95wt%, about 45-90wt%, about 50-95wt% or about 50-90wt%), and the cyclic lactone or cyclic ether accounts for a block total of %, 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 10-85 wt %, about 10-80 wt %, about 10-80 wt %, about 10- In some embodiments, the poly(farnesene) glycol is poly(trans-β-farnesene) glycol. In some embodiments, the lactone or cyclic ether is ε-caprolactone. In certain embodiments, the poly(farnesene) glycol is poly(trans-β-farnesene) glycol and the lactone or cyclic ether is ε-caprolactone.

[0052] In one aspect, the present description provides an ABA type block copolymer having an average molecular weight of about 1000 to about 10,000 g / mol (and including all subranges, 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 5 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 / ml, about 2500 to about 5000 g / mol, about 3000 to about 5000 g / mol, about 3500 to about 5000 g / ml, about 2500 to about 3500 g / mol, or about 2000 to about 3000 g / mol).In any aspect or embodiment described herein, the poly(trans-β-farnesene) diol is present in the block copolymer at about 10 wt% to about 95 wt% or about 10 wt% to about 90 wt% (and including all subranges, 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 10-30wt%, about 10-25wt%, about 10-20wt%, about 10-15wt%, about 15-95wt%, about 15-90wt%, about 20-95wt%, about 20-90wt%, about 25-95wt%, about 25-90wt%, about 30-95wt%, about 30-90wt%, about 35-95wt%, about 35-90wt%, about 40-95wt%, about 40-90wt%, about 45-95wt%, about 45-90wt%, about 50-95wt% or about 50-90wt%), and ε-caprolactone accounts for 8% of the embedded % to about 90 wt % or about 10 wt % to about 90 wt % (and including all subranges, 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) glycol, e.g., poly(trans-β-farnesene) glycol, is present in an amount from about 30 wt% to about 90 wt% of the total molecular weight of the block copolymer. In certain embodiments, the lactone, such as epsilon-caprolactone, is present in an amount from about 10 wt % to about 70 wt % of the total molecular weight of the block copolymer.

[0053] In another aspect, the present disclosure provides a polyurethane or polyurethane-urea composition comprising the reaction product of:

[0054] a) at least one ABA type block copolymer as described herein;

[0055] b) at least one diisocyanate; and

[0056] c) optionally a diol or diamine chain extender having a molecular weight of about 60 to 600 g / mol and 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, the at least one block copolymer is the reaction product of a poly(farnesene) glycol and a cyclic lactone or cyclic ether as described herein.

[0058] In any of the aspects or embodiments of the polyurethane or polyurethane-urea compositions, the at least one block copolymer has an average molecular weight of about 1000 to 10,000 g / mol (and including all subranges, e.g., 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). 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 / ml, about 2500 to about 5000 g / mol, about 3000 to about 5000 g / mol, about 3500 to about 5000 g / ml, about 2500 to about 3500 g / mol, or about 2000 to about 3000 g / mol).

[0059] In any of the aspects or embodiments of the polyurethane or polyurethane-urea compositions, the poly(farnesene) glycol is present in an amount of about 10 wt % to about 95 wt % or about 10 wt % to about 90 wt % (and including all subranges, 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 %) of the total molecular weight of the at least one block copolymer. %, about 10-35wt%, about 10-30wt%, about 10-25wt%, about 10-20wt%, about 10-15wt%, about 15-95wt%, about 15-90wt%, about 20-95wt%, about 20-90wt%, about 25-95wt%, about 25-90wt%, about 30-95wt%, about 30-90wt%, about 35-95wt%, about 35-90wt%, about 40-95wt%, about 40-90wt%, about 45-95wt%, about 45-90wt%, about 50-95wt% or about 50-90wt%), and the The cyclic lactone or cyclic ether is present in an amount of about 5 to about 90 wt % or about 10 to about 90 wt % (and including all subranges, 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 10-75wt%, about 10-70wt%, about 10-65wt%, about 10-60wt%, about 10-55wt%, about 10-50wt%, about 10-45wt%, about 10-40wt%, about 10-35wt%, about 10-30wt%, about 10-25wt%, about 10-20wt%, about 10-15wt%, about 15-90wt%, about 20-90wt%, about 25-90wt%, about 30-90wt%, about 35-90wt%, about 40-90wt%, about 45-90wt% or about 50-90wt%).

[0060] In any of the aspects or embodiments of the polyurethane or polyurethane-urea compositions, the poly(farnesene) diol is poly(trans-β-farnesene) diol. In any of the aspects or embodiments of the polyurethane or polyurethane-urea compositions, the lactone or cyclic ether is ε-caprolactone. In any of the aspects or embodiments of the polyurethane or polyurethane-urea compositions, the poly(farnesene) diol is poly(trans-β-farnesene) diol and the lactone or cyclic ether is ε-caprolactone.

[0061] In another aspect, the present disclosure provides a polyurethane or polyurethane-urea composition comprising the reaction product of:

[0062] a) at least one ABA-type block copolymer having an average molecular weight of about 1000 to 10,000 g / mol, wherein the at least one block copolymer is the reaction product of a poly(farnesene) glycol (e.g., poly(trans-β-farnesene) glycol) and a cyclic lactone or cyclic ether (e.g., ε-caprolactone), and wherein the poly(farnesene) glycol is present at 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 at 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;

[0063] b) at least one diisocyanate; and

[0064] c) optionally a diol or diamine chain extender having a molecular weight of about 60 to 600 g / mol and an NCO:OH molar ratio of 0.9:1 to 2:1.

[0065] In any of the aspects or embodiments of the polyurethane or polyurethane-urea compositions described herein, the poly(farnesene) glycol, e.g., poly(trans-β-farnesene) glycol, is present in an amount from about 30 wt % to about 90 wt % of the total molecular weight of the at least one block copolymer. In any of the aspects or embodiments of the polyurethane or polyurethane-urea compositions described herein, the lactone, e.g., ε-caprolactone, is present in an amount from about 10 wt % to about 70 wt % of the total molecular weight of the at least one block copolymer.

[0066] In certain embodiments, the present description provides a polyurethane or polyurethane-urea composition comprising the reaction product of:

[0067] a) at least one ABA type block copolymer having an average molecular weight of 1000 to 10,000 g / mol, wherein the at least one block copolymer is the reaction product of poly(trans-β-farnesene) diol and ε-caprolactone, wherein the poly(trans-β-farnesene) diol is present in an amount of about 10 wt % to about 70 wt % of the total molecular weight of the at least one block copolymer, and the ε-caprolactone is present in an amount of 30-90 wt % of the total molecular weight of the at least one block copolymer;

[0068] b) at least one diisocyanate; and

[0069] c) optionally a diol or diamine chain extender having a molecular weight of 60 to 600 g / mol and an NCO:OH molar ratio of 0.9:1 to 2:1.

[0070] In any of the aspects or embodiments of the polyurethane or polyurethane-urea compositions described herein, the NCO:OH molar ratio is in the range of 0.9:1 to 1.7:1.

[0071] In any of the aspects or embodiments of the polyurethane or polyurethane-urea compositions described herein, the NCO:OH molar ratio is in the range of 0.95:1-1.5:1.

[0072] In any of the aspects or embodiments of the polyurethane or polyurethane-urea compositions described herein, the NCO:OH molar ratio is in the range of 1:1 to 1.2:1.

[0073] The carbamate-functional polymer is produced by the reaction of isocyanate monomers. In any aspect or embodiment of the aspects or embodiments of the polyurethane or polyurethane-urea composition described herein, the isocyanate monomer comprises or is selected from the group consisting of toluene diisocyanate (2,4- or 2,6-toluene diisocyanate or mixtures thereof) (TDI), phenylene diisocyanate (meta-, p-phenylene diisocyanate or mixtures thereof), 4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate (NDI), diphenylmethane diisocyanate (4,4'-, 2,4'- or 2,2'-diphenylmethane diisocyanate or mixtures thereof) (MDI), 4,4'-toluidine diisocyanate (TODI) and 4,4'-diphenyl ether diisocyanate, 1,2-dimethyl phenylene diisocyanate (o-XDI), 1,3-xylene diisocyanate (m-XDI) and 1,4-xylene diisocyanate (p-XDI), 1,2-hydrogenated xylene diisocyanate (o-H6XDI), 1,3-hydrogenated xylene diisocyanate (m-H6XDI) and 1,4-hydrogenated xylene 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, butane diisocyanate (tetramethylene diisocyanate, 1,2-butanediisocyanate) isocyanate, 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-diisocyanatomethylhexanoate, 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) Acid ester) (also known as bis(isocyanatocyclohexyl)methane) (4,4'-, 2,4- or 2,2'-methylenebis(cyclohexyl isocyanate), their trans, trans isomers, trans, cis isomers, cis, cis isomers or mixtures thereof) (H12MDI), methylcyclohexane diisocyanate (methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate), norbornane diisocyanate (various isomers or mixtures thereof) (NBDI), 4,4'-diphenylmethane diisocyanate, isophorone diisocyanate, 1,6-hexamethylene diisocyanate, 1,5-naphthalene diisocyanate, 4,4-dicyclohexylmethane diisocyanate and combinations thereof.

[0074] In any of the aspects or embodiments 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-naphthalene diisocyanate, 4,4-dicyclohexylmethane diisocyanate.

[0075] In any aspect or embodiment of the polyurethane or polyurethane-urea composition described herein, the chain extender is a multifunctional molecule such as a low molecular weight diol or diamine. In certain embodiments, they react with diisocyanate functionality to build polyurethane molecular weight and increase the block length of the hard segment.

[0076] In any aspect or embodiment of the polyurethane or polyurethane-urea composition described herein, the diol chain extender comprises a polyol, such as a lower aliphatic or short chain diol having 2-20, 2-12, or 2-10 carbon atoms. In certain embodiments, the diol chain extender comprises or is selected from the group consisting of 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-bis-(β-hydroxyethyl)-hydroxyquinone, 1,4-bis-(β-hydroxyethyl)-bisphenol A, and combinations thereof.

[0077] In any of the aspects or embodiments of the polyurethane or polyurethane-urea compositions described herein, the diol chain extender comprises or is selected from the group consisting of ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,4-bis-(β-hydroxyethyl)-hydroxyquinone, 1,4-cyclohexanedimethanol, 1,4-bis-(β-hydroxyethyl)-bisphenol A, and combinations thereof.

[0078] 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.

[0079] In any of the aspects or embodiments of the polyurethane or polyurethane-urea compositions described herein, the composition is used for processing into 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.

[0080] In any of the aspects or embodiments of the polyurethane or polyurethane-urea compositions described herein, the composition is processed into a thermoplastic polyurethane, a thermocast elastomer, or an elastomeric foam.

[0081] In any of the aspects or embodiments of the polyurethane or polyurethane-urea compositions described herein, the composition is processed into a thermoplastic polyurethane or a thermocast elastomer.

[0082] In various embodiments, compositions and methods are described for producing high performance commercially available elastomeric materials by employing copolymers of poly(farnesene) glycol and ε-caprolactone as the polyol component. Poly(farnesene) glycol is produced from bio-based monomers, and such copolymerization allows the incorporation of renewable materials into high performance polyurethane materials.

[0083] In any of the aspects or embodiments described herein, the polyol or copolymer can be used to produce a polyurethane material having a Shore A hardness of less than 75 that not only maintains its hardness over time but can also be produced within an industrially feasible cycle time.

[0084] The Shore value is measured by a Shore durometer, a device used to measure the hardness of materials, typically polymers, elastomers, and rubbers. The scale ranges from 0-100. Higher numbers on the scale indicate greater resistance to indentation, and therefore a harder material. Lower numbers indicate less resistance, and a softer material.

[0085] In any of the aspects or embodiments described herein, the polyol or copolymer as described herein can be used to produce a polyurethane material having a Shore hardness of less than 65.

[0086] In any of the aspects or embodiments described herein, the polyol or copolymer as described herein can be used to produce a polyurethane material having a Shore hardness of less than 50.

[0087] In any of the aspects or embodiments described herein, the polyol or copolymer as described herein can be used to produce a polyurethane material having a Shore hardness of less than 45.

[0088] In any of the aspects or embodiments described herein, the polyol or copolymer as described herein can be used to produce a polyurethane material having a Shore hardness of less than 35.

[0089] In any of the aspects or embodiments described herein, the polyol or copolymer as described herein can be used to produce a polyurethane material having a Shore hardness of less than 25.

[0090] The entire disclosure of US 3,784,520A regarding chemicals and processes for making copolylactone-farnesene diol polyester polymers is incorporated herein by reference.

[0091] In another aspect, the present description provides a copolyamide-polyester composition produced as the reaction product of:

[0092] a) at least one ABA type block copolymer as described herein; and

[0093] b) at least one polyamide of an oligomer of structure D-(ED)x or Fy-D-Fz, wherein D is an α-ω diacid, E is an α-ω diamine and F is a lactam or / and an α-amino ω acid, and x, y and z are integers equal to or greater than 1.

[0094] In any aspect or embodiment of the copolyamide-polyester composition, the at least one ABA-type block copolymer has an average molecular weight of about 1000 g / mol to about 10,000 g / mol, wherein the copolymer is the reaction product of a poly(farnesene) glycol and a cyclic lactone or a cyclic ether, and wherein the poly(farnesene) glycol is present at 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 at about 10 wt % to about 90 wt % of the total molecular weight of the at least one block copolymer.

[0095] In any aspect or embodiment of the copolyamide-polyester composition, D, E and F are independently selected from C2-C12 aliphatic groups or aromatic groups.

[0096] In any aspect or embodiment of the copolyamide-polyester composition, the copolyamide-polyester composition has the structure Fy-D-Fz, wherein F is C11, D is C12, and y and z are integers between 1 and 5.

[0097] In another aspect, the present specification provides a copolyester composition produced as the reaction product of:

[0098] a) at least one ABA type block copolymer as described herein;

[0099] b) at least one diacid; and

[0100] c) at least one short-chain diol, wherein the molecular weight of the short-chain diol is <250 g / mol.

[0101] In any aspect or embodiment of the copolyester composition, the composition has an average molecular weight of about 1000 g / mol to about 10,000 g / mol, wherein the copolymer is the reaction product of a poly(farnesene) glycol and a cyclic lactone or cyclic ether, and wherein the poly(farnesene) glycol is present at 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 at about 10 wt % to about 90 wt % of the total molecular weight of the at least one block copolymer.

[0102] In any aspect or embodiment of the copolyester composition, the block copolymer comprises from about 90 wt % to about 25 wt % of the copolyester composition.

[0103] In any aspect or embodiment of the copolyester composition, the short chain diol comprises less than 25 wt % of the copolyester composition.

[0104] In any aspect or embodiment of the copolyester composition, the diol is 1,4-butanediol.

[0105] Examples

[0106] Material

[0107] By reacting ε-caprolactone with trans-β-farnesenediol F3000 (Total Craywood, Exton, PA) was reacted (ring-opening polymerization) at molar ratios to produce polycaprolactone according to Table 1 to produce polycaprolactone polyols.

[0108] Table 1

[0109] Exemplary Polyol Formulations Example 1 Example 2 Example 3 Example 4 Caprolactone content (wt%) 14 29 40 48 Molecular weight of copolymer (g / mol) 3200 3900 4500 5300 Hydroxyl value (mgKOH / g) 35.2 28.9 24.5 21.3 Viscosity (mPa.s) 110.9 153.4 248.7 380

[0110] The reaction was carried out at 180°C in the presence of stannous octoate (DABCO T9) as a catalyst and monitored by GC determination of residual ε-caprolactone. The reaction was terminated when the amount of residual ε-caprolactone was less than 0.5%.

[0111] The polyols used as comparative materials are 2201A (Ingevity, United Kingdom), a typical polyol used in high-performance polyurethane applications, and F3000 (Total Cray Valley, France), a polyfarnesene diol made from 100% renewable raw materials.

[0112] Examples of the described compositions and methods as well as comparative examples were prepared by a hot casting production process (Examples 1-6) and a thermoplastic polyurethane (TPU) production process (Examples 7-23).

[0113] Examples 1-6

[0114] To prepare the hot-cast polyurethane elastomer material according to Table 2, the required polyol was first added dropwise to the molten 4,4'-diphenylmethane diisocyanate and reacted at 80°C for 2 hours. This produced a polyurethane prepolymer with an NCO of 3.98%. 1,4-Butanediol was added thereto according to a stoichiometric amount of 97% or an isocyanate index of 103, and the mixture was homogenized for 2 minutes using a vortex mixer. The reaction mixture was then poured onto a coated metal plate that had been conditioned at 120°C for 1 hour. The cast plate was then placed in an oven at 120°C for 16 hours, then demolded and cooled to 23°C.

[0115] Table 2

[0116]

[0117] *Comparative example.

[0118] The mechanical properties of the polyurethane materials were determined according to ISO 37 (Type 2) (ultimate tensile strength, elongation) and ASTM D 624 Type C (tear strength).

[0119] Tensile tests were performed according to ISO 37 using Type 2 specimens (dumbbell-shaped test pieces with a thickness of 2.0 mm + / - 0.2 mm and a test length of 20 mm + / - 0.5 mm). The test pieces were cut from 2.0 mm polyurethane sheets using a die cutter and then conditioned for a period of 7 days at 23°C / 50% relative humidity before testing. The test pieces were deformed in tension mode at a transverse rate of 200 mm / min using a ZwickRoell Proline Z010 tensiometer equipped with a pincer grip and a 10 kN load cell until the test piece broke. The ultimate tensile strength is defined as the stress recorded at sample break, expressed in megapascals (MPa or N / mm 2 ) units. Ultimate elongation is defined as the percentage increase in test length at break. The elastic modulus is defined as the average stress / strain of a material at the initial 0.25% elongation and is a measure of a material's resistance to deformation.

[0120] Tear strength testing was performed according to ASTM D 624 using a die C / right angle specimen (uncut test piece with a 90° right angle on one side and a tab end) with a thickness of 2.0 mm + / - 0.2 mm. Test pieces were cut from 2.0 mm polyurethane sheets using a die cutter and then conditioned for a period of 7 days at 23°C / 50% relative humidity before testing. The test piece was deformed in tension mode at a transverse rate of 500 mm / min using a ZwickRoell Proline Z010 tensiometer equipped with a clamp and a 10 kN load cell until the test piece was completely torn. Tear strength is defined as the force required to rupture the test piece divided by the thickness of the test piece.

[0121] In each of the exemplary polyols (i.e., "Examples 1-4"), the ultimate tensile strength, ultimate elongation, tear strength, and elastic modulus all showed significant improvements compared to the reference polyol having 100% renewable content (Comparative Example 5). It was surprisingly found that it is possible to achieve 2201A, while maintaining over 50% renewable content (e.g., bio-based farnesene) in the polyol.

[0122] Table 3

[0123]

[0124] *Comparative example not according to the present invention

[0125] Figure 1A , 1B and 1C further demonstrate the difference in mechanical properties according to the compositions as described herein compared to currently available materials. Figure 1A A comparison of tensile strength (left hand axis) and tear strength (right hand axis) is shown. Figure 1B A comparison of the ultimate elongation is shown. Figure 1C A comparison of the elastic moduli is shown.

[0126] To prepare the thermoplastic polyurethane elastomer material according to Table 4, a bulk polymerization was performed. The polyol, extender (1,4-butane), antioxidant (BHT derivative) and diisocyanate were weighed into the reactor. When aromatic diisocyanates were used, no catalyst was used. When aliphatic isocyanates were used, a Sn(IV)-based catalyst was used. The weights of the polyol, extender and diisocyanate had a stoichiometry (NCO to OH ratio) of 1.02. The reactants were mixed until the temperature rose by 5°C. The reaction mixture was transferred to a tray and cured in an oven for a minimum of 3 hours. The cooled slabs were reduced in size and melt processed into test specimens.

[0127] Table 4

[0128]

[0129]

[0130] *AL is H12MDI, AR is MDI

[0131] **Comparative example.

[0132] Table 5

[0133]

[0134] *Comparative example.

[0135] The data presented in Table 5 further support the invention of the present disclosure.

[0136] The contents of all references, patents, pending patent applications, and issued patents cited throughout this application are hereby expressly incorporated herein by reference.

[0137] Those skilled in the art will recognize or be able to determine using only routine experiments, many equivalent forms of the specific embodiments of the invention described herein. Such equivalent forms are intended to be covered by the appended claims. It should be understood that the detailed examples and embodiments described herein are given for illustrative purposes only and are in no way considered to be limitations of the present invention. Various modifications or changes thereto will be considered by those skilled in the art, and are included in the spirit and scope of the present application and are considered to be within the scope of the appended claims. For example, the relative amounts of the ingredients may be changed to optimize the desired effect, other ingredients may be added, and / or one or more of the ingredients may be replaced with similar ingredients. Other advantageous features and functions associated with the systems, methods and processes of the present invention will be apparent from the appended claims. In addition, those skilled in the art will recognize or be able to determine using only routine experiments many equivalent forms of the specific embodiments of the invention described herein. Such equivalent forms are intended to be covered by the appended claims.

Claims

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

2. The copolymer of claim 1, wherein the poly(farnesene) diol is a polymer comprising at least one monomer selected from the group consisting of: (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 of claim 1, wherein the cyclic lactone is at least one of α-acetone, β-propiolactone, γ-butyrolactone, δ-valerolactone, ε-caprolactone, lactide, glycolide, or a combination thereof. The copolymer according to claim 3 , wherein the cyclic lactone is ε-caprolactone.

5. The copolymer of 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 a combination thereof.

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

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

8. A polymer composition comprising as a reaction product: a) at least one ABA type block copolymer having an average molecular weight of 1000 to 10,000 g / mol, the at least one block copolymer being the reaction product of a poly(farnesene) glycol and a cyclic lactone or cyclic ether, wherein the poly(farnesene) glycol is present in an amount 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 an amount 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; b) at least one diisocyanate; and c) optionally a diol or diamine chain extender having a molecular weight of about 60 g / mol to about 600 g / mol and a NCO:OH molar ratio of about 0.9:1 to about 2:

1.

9. The polymer composition of claim 8, wherein the poly(farnesene) diol is a polymer comprising at least one monomer selected from the group consisting of: (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 of claim 8, wherein the cyclic lactone is at least one of α-acetone, β-propiolactone, γ-butyrolactone, δ-valerolactone, ε-caprolactone, lactide, glycolide, or a combination thereof.

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

12. The polymer composition of 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 a combination thereof.

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

14. The polymer composition of claim 8, wherein the at least one block copolymer comprises from about 25 wt% to about 95 wt% of the polymer composition, and wherein the polymer composition is a polyurethane or a polyurethane-urea.

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

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

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

18. The polymer composition of 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 of 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 reaction product of: a) at least one ABA type block copolymer having an average molecular weight of from about 1000 g / mol to about 10,000 g / mol, wherein the copolymer is the reaction product of a poly(farnesene) glycol and a cyclic lactone or cyclic ether, and wherein the poly(farnesene) glycol is present at about 10 wt % to about 95 wt % (e.g., from 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 at about 5 wt % to about 90 wt % (e.g., from about 10 wt % to about 90 wt %) of the total molecular weight of the at least one block copolymer; and b) at least one polyamide of an oligomer of structure D-(ED)x or Fy-D-Fz, wherein D is an α-ω diacid, E is an α-ω diamine and F is a lactam or / and an α-amino ω acid, and x, y and z are integers equal to or greater than 1.

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

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

23. A copolyester composition produced as the reaction product of: a) at least one ABA type block copolymer having an average molecular weight of from about 1000 g / mol to about 10,000 g / mol, wherein the copolymer is the reaction product of a poly(farnesene) glycol and a cyclic lactone or cyclic ether, and wherein the poly(farnesene) glycol is present at about 10 wt % to about 95 wt % (e.g., from 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 at about 5 wt % to about 90 wt % (e.g., from about 10 wt % to about 90 wt %) of the total molecular weight of the at least one block copolymer; b) at least one diacid; and c) at least one short-chain diol, wherein the molecular weight of the short-chain diol is <250 g / mol.

24. The copolyester composition of claim 23, wherein the block polymer comprises from about 90 wt% to about 25 wt% of the copolyester composition.

25. The copolyester composition of claim 23, wherein the short chain diol comprises less than 25 wt% of the copolyester composition.

26. The copolyester composition of claim 23, wherein the diacid is terephthalic acid.

27. The copolyester composition of claim 23, wherein the diol is 1,4-butanediol.

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