Bio-based, recyclable and biodegradable elastomeric materials, methods of manufacture and articles and uses thereof

Abstract

There are provided compositions, systems and methods to fabricate bio-based, recyclable and / or biodegradable elastic materials in the form of fibers, foams and molded objects, as well as various articles made using the same. The elastic materials consist primarily of elastomeric polymers made from transesterification of at least one hard segment, at least one soft segment, and at least one chain extender, without crosslinking or curing at high temperatures.

Description

BIO-BASED, RECYCLABLE AND BIODEGRADABLE ELASTOMERIC MATERIALS, METHODS OF MANUFACTURE AND ARTICLES AND USES THEREOFCROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of priority from U.S. provisional application No. 63 / 684,003, filed August 16, 2024, which is incorporated by reference herein in its entirety.FIELD

[0002] The disclosure relates to bio-based, recyclable and biodegradable elastic materials, methods for preparation of the materials, and applications thereof to form fibers, foams and molded objects. The elastic materials are polymers made of at least one hard segment, soft segment, and chain extender, the hard segment consisting primarily of di-acids and di-alcohols, where the polymers are made without crosslinkers.BACKGROUND

[0003] Polyurethane, including elastane which is better known commercially as spandex, is a class of polymers possessing superior tensile and elongation properties and ranging from hard resins to highly elastic sponge-like materials. It is found in a variety of formats from fibers to foams and used in wide-ranging applications, from bed mattresses to stretchable pants and automobile interiors. However, elastane and polyurethanes in general, are hard to recycle in standard curbside facilities, and their constituent moieties are neither biodegradable nor compostable. Furthermore, isocyanate, one of the crosslinker molecules commonly used in elastane and polyurethanes in general, is a known toxin. Spandex is also not dyeable which is not optimal for garment manufacturing.

[0004] Previously, compostable elastomers such as polybutylene adipate terephthalate (PBAT) have been made. However, these polymers are highly stiff with a low elongation ratio and are not suitable for soft elastomeric applications such as textiles and packaging. Further, the source molecules are petrochemical based.

[0005] Citric acid-based elastomers are well known as well. However, these elastomers suffer from several drawbacks including their brittleness, weak mechanical properties, long curing times and most importantly, their inability to be processed into fibers, resins or foams.

[0006] International (PCT) application publication no. WO 2024 / 130428 describes bio-based and compostable elastomeric materials, methods of manufacture, and articles and uses thereof.1 11310-003 1The elastic materials consist primarily of di-acids and di-alcohols and supporting polymer structures made from reacting a di-alcohol with a di-acid in the presence of a crosslinking agent. However, the stretchable polymers described in WO 2024 / 130428 can have process manufacturing limitations due to the presence of crosslinking agents.

[0007] Chinese Patent Application No. CN108586715A describes a biological poly ester elastomer and preparation method thereof containing dibasic acid component, diol component and branching monomer residues. However, the described polyester is crosslinked, rendering it non-recyclable and non-biodegradable, and limiting its manufacturability as it cannot be melt extruded into fibers. The described polyester is also vulcanized.

[0008] There is a need for a bio-based, recyclable and biodegradable materials that can replace elastane, polyurethanes and / or rubbers without compromising their performance or process attributes.SUMMARY

[0009] The present disclosure relates generally to bio-based, recyclable and biodegradable elastomeric materials which are made from bio-based materials and possess desirable performance tensile and elongation properties as well as process attributes. In some embodiments, elastomeric materials produced in accordance with the methods provided herein can overcome the limitations of the prior art. An object of the present disclosure is to provide elastic materials that preserve the performance and process attributes of polyurethanes and elastane while changing the chemical composition to a bio-based, recyclable, biodegradable and / or compostable material. Composition and process parameters described herein have been chosen to maximize tensile properties, including elongation ratio, while also creating a unique blend of thermoplastic bio-polymers that are made without crosslinking agents and that maintain melt extrusion processability and thermoformability.

[0010] In a first broad aspect of the present disclosure, there is provided a linear elastomeric polymer made from transesterification of at least one hard segment, at least one soft segment, and at least one chain extender, without crosslinking or curing at high temperatures.

[0011] In some embodiments, the polymer of the disclosure is comprised of about 50-60 wt% of soft segments and about 40-50 wt% of hard segments.

[0012] In some embodiments, the polymer of the disclosure has a molecular weight of at least about 7000 Daltons. In other embodiments, the polymer of the disclosure has a molecular weight1 11310-003 2of from 1000 to 7000 Daltons. In another embodiment, the polymer of the disclosure has a molecular weight of about 7000 Daltons.

[0013] Hard segments are generally rigid segments of a polymer comprising di-alcohols and di-acids and possessing an aromatic ring or a short chain alcohol. In some embodiments of polymers of the disclosure, the at least one hard segment is made by reacting one or more dialcohol with a di-acid. Hard segments may comprise or consist of, for example and without limitation, tannic acid, gallic acid, vanillic acid, ellagic acid, hydroxycinnamic acid, malonic acid, isosorbate, 1 ,4 butanediol, neopentylglycol, dimethyl furan-2,5-dicarboxylate (DMFD), dimethyl furanic acid (DMFA), dimethyl ester of furanic acid, 1 ,4-cyclo-hexanedimethanol (CHDM), bifurfuryl alcohol, methyl cinnamate, or a combination thereof.

[0014] In some embodiments of polymers of the disclosure, the at least one hard segment comprises DMFD. In some embodiments of polymers of the disclosure, the at least one hard segment comprises DMFA. In some embodiments of polymers of the disclosure, the at least one hard segment comprises CHDM. In some embodiments of polymers of the disclosure, the at least one hard segment comprises or consists of a mixture of DMFD and CHDM. In some such embodiments, the weight ratio of DMFD:CHDM is about 1-2, about 1.4-1.8, about 1.5-1.7, or about 1.4, about 1 .5, about 1.6, about 1 .7, or about 1.8, or greater than 1 , or greater than 1.5.

[0015] Soft segments are generally amorphous, flexible segments of a polymer. In some embodiments of polymers of the disclosure, the at least one soft segment comprises or consists of, for example and without limitation, poly(trimethylene ether) glycol (PO3G), succinic acid, adipic acid, glycerol, sebacid acid, hexane diol, heptane diol, octanediol, decanediol, nonandiol, dodecanediol, itaconic acid, citric acid, or a combination thereof. In some embodiments of polymers of the disclosure, the soft segment comprises or consists of PO3G.

[0016] Chain extenders are generally small, highly reactive bifunctional molecules that increase molecular weight or viscosity of a growing polymer chain at the end of the reaction. In some embodiments of polymers of the disclosure, the at least one chain extender comprises or consists of, for example and without limitation, soybean epoxy, 1 ,4 butanediol, oxacoline, hexamethylene diisocyanate (HDMI), 1 ,10-carbonyl bis caprolactam (CBC), isocyanate, or a combination thereof.

[0017] In some embodiments, the polymer of the disclosure is bio-based, e.g., at least 95%, at least 96%, at least 97%, at least 98%, at least 99%, at least 99.5%, or 100% bio-based.

[0018] In some embodiments, the polymer of the disclosure is biodegradable.1 11310-003 3

[0019] In some embodiments, the polymer of the disclosure is recyclable.

[0020] In some embodiments, the polymer of the disclosure is compostable.

[0021] In some embodiments, the polymer of the disclosure is dyeable.

[0022] In some embodiments, the polymer of the disclosure is recoverable.

[0023] In some embodiments, the polymer of the disclosure polymer can be separated from a blend by increasing pH so that the polymer is hydrolyzed into its monomers. In some such embodiments, the monomers can further react to form a new polymer. In some embodiments, the polymer can be separated from other plastics and fibers via a dissolution process.

[0024] In some embodiments, the polymer of the disclosure demonstrates an elongation ratio of at least 500%, at least 600%, at least 700%, at least 800%, at least 900%, at least 1000%, or about 1000%.

[0025] In some embodiments, the polymer of the disclosure demonstrates a maximum elongation ratio of 1000%.

[0026] In some embodiments, the polymer of the disclosure demonstrates an elongation of at least 10%.

[0027] In some embodiments, the polymer of the disclosure recovers its original length fully upon removal of stress.

[0028] In some embodiments, the polymer of the disclosure can undergo at least 100 cycles of relaxation and elongation without any fatigue.

[0029] In some embodiments, the polymer of the disclosure has a tenacity of at least 5 g / denier.

[0030] In some embodiments, the polymer of the disclosure has a melting point of at least 190 °C.

[0031] In some embodiments, the polymer of the disclosure has dimensions from about 50 denier to about 150 denier or of about 70 denier.

[0032] In some embodiments, the polymer of the disclosure further comprises one or more reinforcing agent which is added to improve stiffness and / or resistance to breaking. Non-limiting examples of reinforcing agents include microcrystalline cellulose, nanocrystalline cellulose, titanium dioxide, kaolin, silica, nanoclay, carbon black, or a combination thereof.1 11310-003 4

[0033] In some embodiments, the polymer of the disclosure is blended with a carrier polymer, for example to obtain a viscosity and / or consistency suitable for processability into fibers or foams. Non-limiting examples of carrier polymers include cellulose, a cellulose derivative, poly(lactic acid), polycaprolactam, starch, or another biopolymer.

[0034] In some embodiments, the polymer of the disclosure is extrudable, e.g., melt extrudable, e.g., capable of being made into a film or a fiber using melt extrusion.

[0035] In some embodiments, the polymer of the disclosure is moldable, e.g., capable of being molded into a solid rubber or a foam.

[0036] In some embodiments, the polymer of the disclosure has one or more of the following properties: stainable and dyeable with dispersion dyes; dyeable, for example in a standard polyester or cotton dyeing process and at standard dyeing temperatures, without melting; moldable into objects, for example by injection molding or 3D printing; capable of being made into a cellular structure or a foam, for example through the introduction of blowing agents; thermoformable at high temperatures; convertable into fibers by extrusion, for example by melt extrusion; and / or convertable into fibers by melt spinning, solution spinning, electrospinning and / or melt blowing. In some embodiments, the polymer of the disclosure polymer can be formed as ultra thin fibers, for example fibers of at least 40 denier, at least 50 denier, at least 60 denier, or at least 70 denier, for example via melt extrusion.

[0037] In some embodiments, the polymer of the disclosure is in the form of a melt extruded fiber suitable for conversion into a knit or woven fabric. In some embodiments, fibers are blended with cotton, polyester and / or nylon. In some embodiments, fibers are capable of being converted into a knit or woven fabric having high stretch, for example, having an elongation of at least 200% and full elastic recovery. For example, fibers can be woven or knit with cotton, polyester or other fibers to form a stretch fabric. In some embodiments, fibers are capable of being separated into monomers using media at high pH, for example pH of 11 to 13. In some such embodiments, the monomers can be reused for spinning a new fiber, thereby allowing recycling of the polymer. In some embodiments, fibers have dimensions ranging from 50 deniers to 150 denier.

[0038] In some embodiments, a stretch fabric comprising polymers of the disclosure can remain intact with no loss of mass or physical properties after 25 wash, rinse and / or drying cycles. In some embodiments, a stretch fabric comprising polymers of the disclosure is dyeable. In some embodiments, a stretch fabric comprising polymers of the disclosure is suitable for use as a spandex or elastane replacement, for example in garments.1 11310-003 5

[0039] In some embodiments, the polymer of the disclosure is suitable for use in place of elastane in garments, undergarments, automobile interiors, medical textiles and / or wound dressings.

[0040] In some embodiments, the polymer of the disclosure is suitable for use in place of polyurethane foam in insulation, packaging and / or garment applications.

[0041] In some embodiments, the polymer of the disclosure is suitable for use in place of poly(dimethyl silicone) in molded elastomeric objects, such as phone cases, sealants, household items, mattresses, furniture, and the like.

[0042] In some embodiments, the polymer of the disclosure is suitable for use in place of rubber, e.g., natural or synthetic rubber.

[0043] In another broad aspect, there is provided a fiber comprising one or more polymer of the disclosure. Fibers have the properties as described hereinabove and below. In some embodiments, fibers are biodegradable, recyclable, and / or bio-based. In some embodiments, fibers have an elongation ratio of at least 50% and a maximum elongation ratio of 1000%; can recover their original length fully upon removal of stress; and / or can undergo at least 100 cycles of relaxation and elongation without any fatigue and / or with full elastic recovery and minimal hysteresis. In some embodiments, fibers have a tenacity of at least 5 g / denier and / or a denier size of at least 40.

[0044] In another broad aspect, there is provided a foam comprising one or more polymer of the disclosure. Foams have the properties as described hereinabove and below.

[0045] In another broad aspect, there is provided a molded object comprising one or more polymer of the disclosure. Molded objects have the properties as described hereinabove and below.

[0046] In another broad aspect, there is provided an article comprising one or more polymer, fiber, foam, or molded object of the disclosure. Articles include, for example and without limitation, garments, undergarments, fabrics (e.g., knit or woven fabrics, e.g., stretch fabrics), automobile interiors, medical textiles, wound dressings, insulation, packaging, phone cases, sealants, household items, bed mattresses, and furniture.

[0047] In some embodiments, the bio-based, biodegradable and / or recyclable elastomeric polymer of the disclosure demonstrates an elongation ratio of at least 50%, at least 200%, of up to 600%; or of up to 1000%.1 11310-003 6

[0048] In some embodiments, the bio-based, biodegradable and / or recyclable elastomeric polymer has a tenacity of at least 5 g / denier.

[0049] In some embodiments, the bio-based, biodegradable and / or recyclable elastomeric polymer fiber has a denier size of about 25. In some embodiments, the bio-based, biodegradable and / or recyclable elastomeric polymer fiber has a denier size of about 40. In some embodiments, the bio-based, biodegradable and / or recyclable elastomeric polymer fiber has a denier size of about 25 to about 40.

[0050] In some embodiments, the bio-based, biodegradable and / or recyclable elastomeric polymer can recover its original length fully upon removal of stress.

[0051] In some embodiments, the bio-based, biodegradable and / or recyclable elastomeric polymer can undergo at least 100 cycles of relaxation and elongation without any fatigue.

[0052] In some embodiments, the bio-based, biodegradable and / or recyclable elastomeric polymer is suitable for processing into fibers, e.g., via melt spinning, solution spinning, electrospinning or melt blowing. Fibers may have dimensions of, for example, from 50 to 150 deniers. Fibers can generally be woven or knit with cotton, polyester or other fibers to form a stretch fabric.

[0053] In some embodiments, there is provided a stretch fabric comprising the bio-based, biodegradable and / or recyclable elastomeric polymer described herein. In some such embodiments, the stretch fabric remains intact with no loss of mass or physical properties after 25 wash, rinse and drying cycles.

[0054] In some embodiments, there is provided a knit or woven fabric comprising the biobased, biodegradable and / or recyclable elastomeric polymer described herein. In some such embodiments, the knit or woven fabric further comprises cotton, polyester, nylon, or a combination thereof.

[0055] In some embodiments, the bio-based, biodegradable and / or recyclable elastomeric polymer is suitable for being molded into objects, e.g., via injection molding or 3D printing. For example, bio-based, biodegradable and / or recyclable elastomeric polymers of the disclosure can be made into cellular structures or foams through introduction of blowing agents. In some embodiments, the bio-based, biodegradable and / or recyclable elastomeric polymer is thermoformable at elevated temperatures.1 11310-003 7

[0056] In some embodiments, the bio-based, biodegradable and / or recyclable elastomeric polymer is made partially or entirely of plant-derived molecules.

[0057] In some embodiments, the bio-based, biodegradable and / or recyclable elastomeric polymer is fully biodegradable at the end of its life.

[0058] In some embodiments, the bio-based, biodegradable and / or recyclable elastomeric polymer is fully compostable at the end of its life.

[0059] In some embodiments, the bio-based, biodegradable and / or recyclable elastomeric polymer is fully recyclable at the end of its life. In some such embodiments, the polymer can be broken into its constituent monomers by an increase in pH, and the monomers can then be recovered and re-spun into a new fiber.

[0060] In some embodiments, the bio-based, biodegradable and / or recyclable elastomeric polymer can be separated from a blend via an increase in pH. The increase in pH may, for example, cause hydrolysis of the polymer into its monomers, which can then be further reacted to form a new polymer, thereby promoting recycling. In some such embodiments, the pH is increased to pH of about 11 to about 13, or to pH of 11 , pH of 12, or pH of 13.

[0061] In some embodiments, the bio-based, biodegradable and / or recyclable elastomeric polymer is suitable for use in place of fibers, for example in garments, undergarments, automobile interiors, medical textiles and / or wound dressings.

[0062] In some embodiments, the bio-based, biodegradable and / or recyclable elastomeric polymer is suitable for use in place of polyurethane foam, for example in insulation, packaging and garment applications.

[0063] In some embodiments, the bio-based, biodegradable and / or recyclable elastomeric polymer is suitable for use in place of poly(dimethyl silicone) in molded elastomeric objects, for example in phone cases, sealants, or household items such as, without limitation, bed mattresses or furniture.

[0064] In some embodiments, there is provided a foam comprising the bio-based, biodegradable and / or recyclable elastomeric polymer described herein. In some embodiments, foams of the disclosure further comprise a surfactant, such as without limitation castor oil, which can increase density and / or uniformity of the foam.

[0065] In some embodiments, there is provided a molded object comprising the bio-based, biodegradable and / or recyclable elastomeric polymer described herein.1 11310-003 8

[0066] In some embodiments, there is provided a fiber comprising the bio-based, biodegradable and / or recyclable elastomeric polymer described herein.

[0067] In some embodiments, there is provided an article comprising the bio-based, biodegradable and / or recyclable elastomeric polymer described herein. Non-limiting examples of such articles include garments, undergarments, woven fabrics, knit fabrics, stretch fabrics, automobile interiors, medical textiles, wound dressings, insulation, packaging, phone cases, sealants, household items, bed mattresses, furniture, and the like.

[0068] In an embodiment, there is provided a biodegradable, recyclable, compostable, and / or bio-based elastomeric fiber which has an elongation ratio of at least 50%, up to 600%, or up to a maximum elongation ratio of 1000%; can recover its original length fully upon removal of stress; and can undergo at least 100 cycles of relaxation and elongation without any fatigue. In some such embodiments, the elastomeric fiber has a tenacity of at least 5 g / denier. In some such embodiments, the elastomeric fiber has a denier size of at least about 40. In some such embodiments, the elastomeric fiber has a denier size of at least about 70. In some such embodiments, the elastomeric fiber comprises a linear elastomeric polymer made from transesterification of at least one hard segment, at least one soft segment, and at least one chain extender, without crosslinking or curing at high temperatures. In some embodiments, the polymer is comprised of about 50-60 wt% of soft segments and about 40-50 wt% of hard segments and / or has a molecular weight of about 7000 Daltons or higher, as described herein.

[0069] In an embodiment, there is provided an elastomeric polymer which provides a sustainable alternative to or replacement for elastane. In some such embodiments, the elastomeric polymer is composed entirely of natural biomolecules, e.g., 100% bio-based, biodegradable and / or recyclable.

[0070] In an embodiment, there is provided a bio-based, biodegradable and / or recyclable elastomeric polymer.

[0071] In an embodiment, there is provided a bio-based, biodegradable and / or recyclable elastomeric polymer which has an elongation ratio of 200%.

[0072] In an embodiment, there is provided a bio-based, biodegradable and / or recyclable elastomeric polymer which has an elongation ratio of up to 600%.

[0073] In an embodiment, there is provided a bio-based, biodegradable and / or recyclable elastomeric polymer which has a tenacity of at least 5 g / denier.1 11310-003 9

[0074] In an embodiment, there is provided a bio-based, biodegradable and / or recyclable elastomeric fiber which has a denier size of about 25 to about 40, about 25, or about 40.

[0075] In an embodiment, there is provided a bio-based, biodegradable and / or recyclable elastomeric polymer which has full elastic recovery.

[0076] In an embodiment, there is provided a bio-based, biodegradable and / or recyclable elastomeric polymer which is stable through multiple wash cycles.

[0077] In an embodiment, there is provided a bio-based, biodegradable and / or recyclable elastomeric polymer which can be processed via adapted melt spinning.

[0078] In an embodiment, there is provided a bio-based, biodegradable and / or recyclable elastomeric polymer formed by extrusion, following by curing with LIV light.

[0079] In an embodiment, there is provided a bio-based, biodegradable and / or recyclable elastomeric polymer that can be formed as ultra thin fibers (e.g., fibers of at least 40 denier, at least 70 denier), e.g., via melt or dry spinning.

[0080] In an embodiment, there is provided a bio-based, biodegradable, recyclable and / or compostable elastomeric polymer which can be easily separated from a blend at end of life via mild hydrolysis. For example and without limitation, an increase in pH can cause hydrolysis of the polymer into its monomers. Recovered monomers can further react to form a new polymer and can be reprocessed into fibers without degradation, thereby promoting recycling.

[0081] Fibers, foams, and molded objects comprising the bio-based, biodegradable and / or recyclable elastomeric polymers of the disclosure are also provided.

[0082] Articles comprising the bio-based, biodegradable and / or recyclable elastomeric polymers of the disclosure, as well as fibers, foams, and molded objects thereof, are also provided.

[0083] More aspects and features of the technology are described in the detailed description below.DETAILED DESCRIPTION

[0084] The terminology used in the description of the various described embodiments herein is for the purpose of describing particular embodiments only and is not intended to be limiting.

[0085] In order to provide a clear and consistent understanding of the terms used in the present specification, a number of definitions are provided below. Moreover, unless defined1 11310-003 10otherwise, all technical and scientific terms as used herein have the same meaning as commonly understood to one of ordinary skill in the art to which this invention pertains.Definitions

[0086] As used herein, the use of the word “a” or “an” when used in conjunction with the term “comprising” in the claims and / or the specification may mean “one”, but it is also consistent with the meaning of “one or more”, “at least one”, and “one or more than one”. Similarly, the word “another” may mean at least a second or more.

[0087] As used herein, the words “comprising” (and any form of comprising, such as “comprise” and “comprises”), “having” (and any form of having, such as “have” and “has”), “including” (and any form of including, such as “include” and “includes”) and “containing” (and any form of containing, such as “contain” and “contains”), are inclusive or open-ended and do not exclude additional, unrecited elements or process steps.

[0088] The term “about” is used to indicate that a value includes an inherent variation of error for the device or the method being employed to determine the value.

[0089] As used herein, when content is indicated as being present on a "weight basis" or at a “weight percent (wt%)” or “by weight,” the content is measured as the percentage of the weight of component(s) indicated by dry basis (by taking moisture percentage in each component into account), relative to the total weight of all components present in a composition.

[0090] The term “derivative” as used herein, is understood as being a substance similar in structure to another compound but differing in some slight structural detail.

[0091] As used herein, the term "polymer" refers to a material that includes a set of macromolecules. Macromolecules included in a polymer can be the same or can differ from one another in some fashion. A macromolecule can have any of a variety of skeletal structures, and can include one or more types of monomeric units. In particular, a macromolecule can have a skeletal structure that is linear or non-linear. Examples of non-linear skeletal structures include branched skeletal structures, such those that are star branched, comb branched, or dendritic branched, and network skeletal structures. A macromolecule included in a homopolymer typically includes one type of monomeric unit, while a macromolecule included in a copolymer typically includes two or more types of monomeric units. Examples of copolymers include statistical copolymers, random copolymers, alternating copolymers, periodic copolymers, block copolymers, radial copolymers, and graft copolymers.1 11310-003 11

[0092] In some instances, a reactivity and a functionality of a polymer can be altered by addition of a set of functional groups, such as acid anhydride groups, amino groups and their salts, N-substituted amino groups, amide groups, carbonyl groups, carboxy groups and their salts, cyclohexyl epoxy groups, epoxy groups, glycidyl groups, hydroxy groups, isocyanate groups, urea groups, aldehyde groups, ester groups, ether groups, alkenyl groups, alkynyl groups, thiol groups, disulfide groups, silyl or silane groups, groups based on glyoxals, groups based on aziridines, groups based on active methylene compounds or other b-dicarbonyl compounds (e.g., 2,4- pentandione, malonic acid, acetylacetone, ethylacetone acetate, malonamide, acetoacetamide and its methyl analogues, ethyl acetoacetate, and isopropyl acetoacetate), halo groups, hydrides, or other polar or H bonding groups and combinations thereof. Such functional groups can be added at various places along the polymer, such as randomly or regularly dispersed along the polymer, at ends of the polymer, on the side, end or any position on the crystallizable side chains, attached as separate dangling side groups of the polymer, or attached directly to a backbone of the polymer. Also, a polymer can be capable of cross-linking, entanglement, or hydrogen bonding in order to increase its mechanical strength or its resistance to degradation under ambient or processing conditions.

[0093] “Polymerization” is a process of reacting monomer molecules together in a chemical reaction to form three-dimensional networks or polymer chains. Many forms of polymerization are known, and different systems exist to categorize them, as are known in the art.

[0094] As can be appreciated, a polymer can be provided in a variety of forms having different molecular weights, since a molecular weight (MW) of the polymer can be dependent upon processing conditions used for forming the polymer. Accordingly, a polymer can be referred to as having a specific molecular weight or a range of molecular weights. As used herein with reference to a polymer, the term "molecular weight (MW)" can refer to a number average molecular weight or a weight average molecular weight. Polymers are often referred to in terms of their average MW, for example PEG1000 refers to PEG of average MW of 1000. Polymers may also be referred to in terms of their degree of polymerization (“n”), which can range, generally, from as low as 40 to as high as 5000. In some cases, polymers of different molecular weights may be mixed to give a composition having desired properties. It should be understood that polymers of any molecular weight, or mixtures of polymers of different molecular weights, may be used, as long as the resulting composition has the desired properties or is generally suitable for the uses described herein, as will be determined by the skilled artisan using known techniques.1 11310-003 12

[0095] As used herein, the term “copolymer” refers to polymers having two or more different divalent monomer units.

[0096] As used herein, the term "chemical bond" refers to a coupling of two or more atoms based on an attractive interaction, such that those atoms can form a stable structure. Examples of chemical bonds include covalent bonds and ionic bonds. Other examples of chemical bonds include hydrogen bonds and attractive interactions between carboxy groups and amine groups. As used herein, the term "covalent bond" means a form of chemical bonding that is characterized by the sharing of pairs of electrons between atoms, or between atoms and other covalent bonds. Attraction-to-repulsion stability that forms between atoms when they share electrons is known as covalent bonding. Covalent bonding includes many kinds of interactions, including sigmabonding, pi-bonding, metal-metal bonding, agostic interactions, and three-center two-electron bonds.

[0097] As used herein, the term "reactive function" means a chemical group (or a moiety) capable of reacting with another chemical group to form a covalent or an electrovalent bond, examples of which are given above. Preferably, such reaction is doable at relatively low temperatures, e.g. below 200 °C, more preferably below 100 °C, and / or at conditions suitable to handle delicate substrates, e.g. textiles. A reactive function could have various chemical natures. For example, a reactive function could be capable of reacting and forming electrovalent bonds or covalent bonds with reactive functions of various substrates, e.g., cotton, wool, fur, leather, polyester, or textiles made from such materials, as well as other base materials.

[0098] As used herein, the term “compostable” refers to organic matter that breaks down completely into non-toxic components (e.g., water, carbon dioxide, and biomass) by biological processes during composting and that does not harm the environment, i.e., leaves no toxic residue. As used herein, the term “biodegradable” means a material that breaks down and decomposes in the environment. While all compostable material is biodegradable, not all biodegradable material is compostable. Unlike compostable items which don’t leave toxic residue behind because they are already organic, certain biodegradable products can take several years to break down and in some cases can leave toxic waste behind.

[0099] As used herein, the term “bio-based” refers to materials made from substances derived from organic matter, i.e., biomaterials, plants, biomass, waste feedstock, food waste or other renewable agricultural, marine, and forestry materials. In some embodiments, a bio-based polymer is made partially or entirely of plant-derived molecules.1 11310-003 13

[0100] As used herein, the term “hard segment” refers to a rigid segment of a polymer comprising di-alcohols and di-acids and generally possessing an aromatic ring or a short chain alcohol. Examples of hard segments in accordance with elastomeric polymers of the disclosure include, without limitation, segments comprising or consisting of tannic acid, gallic acid, vanillic acid, ellagic acid, hydroxycinnamic acid, malonic acid, isosorbate, 1 ,3 propanediol, 1 ,4 butanediol, neopentylglycol, dimethyl furan-2,5-dicarboxylate (DMFD), dimethyl furanic acid (DM FA), dimethyl ester of furanic acid, 1 ,4-cyclo-hexanedimethanol (CHDM), bifurfuryl alcohol, methyl cinnamate, neopentyl glycol, lactic acid, isosobic acid, lactide, caprolactam, and combinations thereof. In some embodiments, the hard segment comprises or consists of DMFD and / or CHDM.

[0101] As used herein, the term “soft segment” refers to an amorphous, flexible segment of a polymer. Examples of soft segments in accordance with elastomeric polymers of the disclosure include, without limitation, segments comprising poly(trimethylene ether) glycol (PO3G), succinic acid, adipic acid, glycerol, sebacid acid, hexane diol, heptane diol, octanediol, decanediol, nonandiol, dodecanediol, itaconic acid, citric acid, and combinations thereof. In some embodiments, the soft segment comprises or consists of PO3G.

[0102] As used herein, the term “chain extender” refers to a small, highly reactive bifunctional molecule that increases molecular weight or viscosity of a growing polymer chain at the end of the reaction. Examples of chain extenders in accordance with elastomeric polymers of the disclosure include, without limitation, soybean epoxy, 1 ,4 butanediol, oxacoline, hexamethylene diisocyanate (HDMI), 1 , 10-carbonyl bis caprolactam (CBC), isocyanate, and combinations thereof

[0103] As used herein, the term “recoverable” refers to the ability of an elastomeric polymer to be recovered, recycled and / or reused. In some embodiments, an elastomeric polymer can be separated from other components of a material or blend by increasing the pH so that the polymer is hydrolyzed into its monomers, which can then be reacted again to form a new polymer. In alternative embodiments, an elastomeric polymer can be separated from other materials such as plastics and fibers via a dissolution process.EXAMPLES

[0104] The present invention will be more readily understood by referring to the following examples, which are provided to illustrate the invention and are not to be construed as limiting the scope thereof in any manner.

[0105] Unless defined otherwise or the context clearly dictates otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary1 11310-003 14skill in the art to which this invention belongs. It should be understood that any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the invention.

[0106] Example 1. Elastomeric polymer preparation.

[0107] Introduction. The elastomeric polymer prepared herein is based on a family of biodegradable polyesters and represents a new generation of synthetic biomaterials. It includes highly biocompatible and biodegradable bio-based components.

[0108] Protocol. For elastomeric polymer preparation, components were mixed in a vessel according to their respective molar amount. Standard reaction conditions for polymerization were used. The obtained elastomeric polymer was washed several times with water to remove unreacted monomers.

[0109] Tables 1-7 show composition, preparation and characteristics of exemplary elastomeric polymers of the disclosure. The following abbreviations are used: DMFD: Dimethyl furan-2,5- dicarboxylate; CHDM: Cyclohexane dimethanol; PO3G: Polytrimethylene ether glycol; TBOT: Titanium butoxide; PBO: lead oxide; HDI: hexamethylene diisocyanate.Table 1. Exemplary elastomeric polymer 1 prepared in accordance with certain embodiments.1 11310-003 15Table 2. Exemplary elastomeric polymer 2 prepared in accordance with certain embodiments.Table 3. Exemplary elastomeric polymer 3 prepared in accordance with certain embodiments.Table 4. Exemplary elastomeric polymer 4 prepared in accordance with certain embodiments.Table 5. Exemplary elastomeric polymer 5 prepared in accordance with certain embodiments.1 11310-003 16Table 6. Exemplary elastomeric polymer 6 prepared in accordance with certain embodiments.Table 7. Exemplary elastomeric polymer 7 prepared in accordance with certain embodiments.1 11310-003 17

[0110] Example 2. Characterization of elastomeric polymers.

[0111] Spandex reference. It is an object of the present technology to replace conventional spandex (e.g., elastane, Lycra™) with a recyclable, biodegradable, and / or bio-based elastomer. Spandex is a polyurethane-based fiber mostly produced by melt or solvent spinning from macro glycols and cyclic diisocyanates. Its physical properties can be adjusted by the components used.

[0112] A typical, conventional spandex monofilament can display the following properties: elongation at break of 200 to 550%; tenacity of 0.9 g / denier; elastic modulus of 0.05 g / denier; 95% strain recovery over cycles at 100% elongation; 10% hysteresis at rest after 5 cycles at 200% elongation; and / or permanent deformation of 10 to 17% after 50,000 cycles.

[0113] Testing procedures. Elastomeric polymers were tested as described here.

[0114] Tensile measurements are made using an Instron universal testing machine equipped with a 50 N loading cell. Specimens are cut into straight segments approximately 4 mm wide, 1.5 mm thick, and 10 cm long. The specimens are held by two 25 mm clamps placed 30 mm apart. Tensile load is measured while extending the material at a constant 50 mm / min. Tensile stress, tensile strain, and Young’s modulus are calculated using the Instron Blue Hill™ software.1 11310-003 18

[0115] Elastic recovery is assessed by measuring 10 consecutive extension-relaxation cycles. The specimen is extended at 100 % / min up to 50% strain, and then allowed to relax at the same rate back to 0%. The maximum tensile stress for each cycle is recorded.

[0116] Physical properties. Tensile properties, cyclability, and elastic recovery are assessed.

[0117] (1) Tensile properties. Tensile measurements are used to determine elastic properties such as Young’s modulus, Tensile stress at yield, and Tensile strain at yield.

[0118] (2) Cyclability. T esting is conducted to see if the elastic force is maintained over cycles. For spandex, about 95% of elastic strain is maintained over cycles.

[0119] (3) Elastic recovery. Testing can be used to see if test materials instantaneously return to their original length after a stretch-relax cycle The tensile set of the materials can be measured following a procedure based on ASTM D412.

[0120] Example 3. Characterization of fibers made from elastomeric polymers of the disclosure.

[0121] Fiber characteristics for test elastomeric polymers are shown in Table 8. Fibers were prepared by polycondensation followed by melt extrusion. For all samples, hard segments were comprised of DMFD : CHDM -1.5-1.65 : 1 , and soft segments were comprised of PO3G.Sample 1 : ratio of soft to hard was 1 to 1 ; Sample 2: ratio of soft to hard was 6 to 4; Sample 3: ratio of soft to hard was 6 to 4 with higher molecular weight of the soft segment.Table 8. Fiber characteristics in accordance with certain embodiments.

[0122] Although this invention is described in detail with reference to embodiments thereof, these embodiments are offered to illustrate but not to limit the invention. It is possible to make1 11310-003 19other embodiments that employ the principles of the invention and that fall within its spirit and scope as defined by the claims appended hereto.

[0123] Based upon the foregoing, those skilled in the art will readily recognize that various modifications and changes may be made to the various embodiments without strictly following the exemplary embodiments and applications illustrated and described herein. Such modifications do not depart from the true spirit and scope of various aspects of the disclosure, including aspects set forth in the claims.

[0124] The contents of all documents and references cited herein are hereby incorporated by reference in their entirety.1 11310-003 20

Claims

CLAIMSWhat is claimed is:

1. A linear elastomeric polymer made from transesterification of at least one hard segment, at least one soft segment, and at least one chain extender, without crosslinking or curing at high temperatures.

2. The polymer of claim 1 , wherein the polymer is comprised of about 50-60 wt% of soft segments and about 40-50 wt% of hard segments.

3. The polymer of claim 1 or 2, wherein the at least one hard segment is made by reacting one or more di-alcohol with a di-acid.

4. The polymer of any one of claims 1 to 3, wherein the at least one hard segment comprises or consists of tannic acid, gallic acid, vanillic acid, ellagic acid, hydroxycinnamic acid, malonic acid, isosorbate, 1 ,4 butanediol, neopentylglycol, dimethyl furan-2,5-dicarboxylate (DMFD), dimethyl furanic acid (DMFA), dimethyl ester of furanic acid, 1,4-cyclo- hexanedimethanol (CHDM), bifurfuryl alcohol, methyl cinnamate, or a combination thereof.

5. The polymer of claim 4, wherein the at least one hard segment comprises of consists of a mixture of DMFD and CHDM.

6. The polymer of claim 5, wherein the weight ratio of DMFD:CHDM is about 1-2, about 1.4-1.8, about 1.5-1.7, or about 1.4, about 1.5, about 1.6, about 1.7, or about 1.8, or greater than 1, or greater than 1.5.

7. The polymer of any one of claims 1 to 6, wherein the at least one soft segment comprises or consists of poly(trimethylene ether) glycol (PO3G), succinic acid, adipic acid, glycerol, sebacid acid, hexane diol, heptane diol, octanediol, decanediol, nonandiol, dodecanediol, itaconic acid, citric acid, or a combination thereof.

8. The polymer of claim 7, wherein the at least one soft segment comprises or consists of PO3G.

9. The polymer of any one of claims 1 to 8, wherein the at least one chain extender comprises or consists of soybean epoxy, 1,4 butanediol, oxacoline, hexamethylene diisocyanate (HDMI), 1 ,10-carbonyl bis caprolactam (CBC), isocyanate or a combination thereof.

10. The polymer of any one of claims 1 to 9, wherein the polymer has a molecular weight of at least 7000 Daltons, or from 1000 to 7000 Daltons, or about 7000 Daltons.1 11310-003 2111. The polymer of any one of claims 1 to 10, wherein the polymer is extrudable.

12. The polymer of claim 11, wherein the polymer can be extruded into a film or a fiber.

13. The polymer of any one of claims 1 to 10, wherein the polymer can be molded into a solid rubber or a foam.

14. The polymer of any one of claims 1 to 13, wherein the polymer is at least 95% biobased.

15. The polymer of claim 14, wherein the polymer is 95%, 96%, 97%, 98%, 99%, 99.5%, or 100% bio-based.

16. The polymer of any one of claims 1 to 15, wherein the polymer is biodegradable and / or compostable.

17. The polymer of any one of claims 1 to 16, wherein the polymer is recyclable.

18. The polymer of any one of claims 1 to 17, wherein the polymer is dyeable.

19. The polymer of any one of claims 1 to 18, wherein the polymer is recoverable.

20. The polymer of any one of claims 1 to 19, wherein the polymer can be separated from a blend by increasing pH so that the polymer is hydrolyzed into its monomers, optionally wherein the monomers can further react to form a new polymer; or, wherein the polymer can be separated from other plastics and fibers via a dissolution process.

21. The polymer of any one of claims 1 to 20, wherein the polymer demonstrates an elongation ratio of at least 500%, at least 600%, at least 700%, at least 800%, at least 900%, at least 1000%, or about 1000%.

22. The polymer of any one of claims 1 to 20, wherein the polymer demonstrates a maximum elongation ratio of 1000%.

23. The polymer of any one of claims 1 to 22, wherein the polymer demonstrates an elongation of at least 10%.

24. The polymer of any one of claims 1 to 23, wherein the polymer recovers its original length fully upon removal of stress.

25. The polymer of any one of claims 1 to 24, wherein the polymer can undergo at least 100 cycles of relaxation and elongation without any fatigue.

26. The polymer of any one of claims 1 to 25, wherein the polymer has a tenacity of at least 5 g / denier.1 11310-003 2227. The polymer of any one of claims 1 to 26, wherein the polymer has a melting point of at least 190 °C.

28. The polymer of any one of claims 1 to 27, wherein the polymer has dimensions from about 50 denier to about 150 denier or of about 70 denier.

29. The polymer of any one of claims 1 to 28, further comprising one or more reinforcing agent which is added to improve stiffness and / or resistance to breaking.

30. The polymer of claim 29, wherein the one or more reinforcing agent comprises microcrystalline cellulose, nanocrystalline cellulose, titanium dioxide, kaolin, silica, nanoclay, carbon black, or a combination thereof.

31. The polymer of any one of claims 1 to 30, wherein the polymer is blended with a carrier polymer to obtain a viscosity and consistency suitable for processability into fibers or foams.

32. The polymer of claim 31 , wherein the carrier polymer is cellulose, a cellulose derivative, poly(lactic acid), polycaprolactam, starch, or another biopolymer.

33. The polymer of any one of claims 1 to 32, wherein the polymer has one or more of the following properties:- stainable and dyeable with dispersion dyes;- dyeable, for example in a standard polyester or cotton dyeing process, without melting;- moldable into objects, for example by injection molding or 3D printing;- capable of being made into a cellular structure or a foam, for example through the introduction of blowing agents;- thermoformable at high temperatures;- convertable into fibers by extrusion, for example by melt extrusion, optionally wherein said fibers are of about 70 denier; and / or- convertable into fibers by melt spinning, solution spinning, electrospinning and / or melt blowing.

34. The polymer of any one of claims 1 to 33, wherein the polymer can be processed into fibers via melt spinning, solution spinning, electrospinning, melt blowing or melt extrusion.

35. The polymer of any one of claims 1 to 34, wherein the polymer can be formed as ultra thin fibers, for example fibers of at least 40 denier, at least 50 denier, at least 60 denier, or at least 70 denier, for example via melt extrusion.1 11310-003 2336. The polymer of any one of claims 1 to 35, wherein the polymer is in the form of a melt extruded fiber suitable for conversion into a knit or woven fabric.

37. The polymer of any one of claims 33 to 36, wherein the fiber is blended with cotton, polyester or nylon.

38. The polymer of any one of claims 33 to 37, wherein the fiber has one or more of the following properties:- capable of being converted into a knit or woven fabric having high stretch, for example an elongation of at least 200% and full elastic recovery; and- capable of being separated into monomers using media at high pH, for example pH of 11 to 13, wherein the monomers can be reused for spinning a new fiber, thereby allowing recycling of the polymer.

39. The polymer of any one of claims 33 to 38, wherein said fibers have dimensions ranging from 50 deniers to 150 denier.

40. The polymer of any one of claims 33 to 39, wherein said fibers can be woven or knit with cotton, polyester or other fibers to form a stretch fabric.

41. The polymer of claim 40, wherein the stretch fabric remains intact with no loss of mass or physical properties after 25 wash, rinse and / or drying cycles.

42. The polymer of any one of claims 1 to 41 , wherein the polymer is suitable for use in place of elastane in garments, undergarments, automobile interiors, medical textiles and / or wound dressings.

43. The polymer of any one of claims 1 to 41 , wherein the polymer is suitable for use in place of polyurethane foam in insulation, packaging and / or garment applications.

44. The polymer of any one of claims 1 to 41 , wherein the polymer is suitable for use in place of poly(dimethyl silicone) in molded elastomeric objects.

45. The polymer of claim 44, wherein the molded elastomeric objects are phone cases, sealants or household items.

46. The polymer of claim 45, wherein the household items are bed mattresses or furniture.

47. The polymer of any one of claims 1 to 46, wherein the polymer is suitable for use in place of rubber.

48. The polymer of claim 47, wherein the rubber is natural or synthetic rubber.1 11310-003 2449. A fiber comprising the polymer of any one of claims 1 to 48.

50. A foam comprising the polymer of any one of claims 1 to 48.

51. A molded object comprising the polymer of any one of claims 1 to 48.

52. An article comprising the polymer of any one of claims 1 to 48, the fiber of claim 49, the foam of claim 50, or the molded object of claim 51.

53. The article of claim 52, wherein the article is a garment, an undergarment, an automobile interior, a medical textile, a wound dressing, insulation, packaging, a phone case, a sealant, a household item, a bed mattress, or furniture.

54. The article of claim 52 or 53, wherein the article is a knit or woven fabric.

55. The article of claim 54, wherein the knit or woven fabric is a stretch fabric.

56. A biodegradable, recyclable, and bio-based elastomeric fiber comprising the polymer of any one of claims 1 to 48.

57. The elastomeric fiber of claim 56, wherein the fiber has an elongation ratio of at least 50% and a maximum elongation ratio of 1000%, can recover its original length fully upon removal of stress, and can undergo at least 100 cycles of relaxation and elongation without any fatigue and / or with full elastic recovery and minimal hysteresis.

58. The elastomeric fiber of claim 57, wherein the polymer has a tenacity of at least 5 g / denier and / or wherein the fiber has a denier size of at least 40.1 11310-003 25

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