Surface-modified fibers and articles and methods of making the same

Abstract

Disclosed herein are polymers that may be reacted with a maleimide adduct having a component to produce a functionalized polymer. The functionalized polymer may be configured to impart a specific physical property, such as hydrophobicity, hydrophilicity, and others.

Description

SURFACE-MODIFIED FIBERS AND ARTICLES AND METHODS OF MAKING THESAMECROSS-REFERENCE

[0001] This application claims the benefit of U.S. Provisional Application No. 63 / 539,248, filed September 19, 2023 and U.S. Provisional Application No. 63 / 549,982, filed February 5, 2024, both of which are incorporated herein by reference in their entireties.FIELD

[0002] The present disclosure relates to the functionalization of polymers by reaction of the polymers with another component to impart new functional properties to the polymers.BACKGROUND

[0003] Polyesters and co-polyesters comprising 2,5-furan dicarboxylate have a furan ring (diene) within the chain backbone. Suitable dienophiles for a furan reaction through a Diels- Alder scheme include molecules having electron-deficient single or multiple alkenes and alkynes, and various heteroatom or halogen substituted configurations thereof. Nonexclusive examples of such alkenes include maleic anhydride, maleimide, bismaleimide, tris-maleimide, tetra-maleimide, bio-based bisitaconimide, acrylates, etc. U.S. Patent 10,676,567, incorporated herein by reference, provides a more comprehensive listing of suitable dienophiles for Diels-Alder reaction with the furan moiety.SUMMARY

[0004] The present disclosure is related to functionalized polymers comprising: (a) a linear polymeric unit comprising one or more repeating monomeric units selected from an ester, an amide, an imide, a urethane, a urea, a bio-based monomer, an alkylene, an alkylene terephthalate, or any combination thereof; (b) from 0.1 wt% to 25 wt% of a furan-containing unit interspersed within the linear polymeric unit; and (c) a component linked to the linear polymeric unit that comprises a structure that modulates a physical property of the single chain polymer, wherein the component is present in an amount sufficient to modulate a physical property of the linear polymer unit, as compared to the physical property of the linear polymeric unit without the component, and wherein the physical property is selected from hydrophobicity, durable water repellency, hydrophilicity, moisture wicking, flame retardancy, anti-static properties, anti-microbial properties, soil-releasability, or any combination thereof. In some embodiments, the physical property is hydrophobicity, and the component comprises an aminosilane, a thiosilane, analkylamine, a fatty acid amine, or any combination thereof. In some embodiments, physical property is durable water repellency and the component comprises a silicon compound, a siloxane compound, a hydrocarbon, a nanoparticle providing a lotus effects, or any combination thereof. In some embodiments, the physical property is hydrophilicity and the component comprises an amino-terminated polyethylene glycol, a hydroxy-terminated polyethylene glycol, a thioterminated polyethylene glycol, a sulfonated amine, or any combination thereof. In some embodiments, the physical property is moisture wicking and the component comprises a hydrophilic polymer, polyethylene glycol, polyvinyl alcohol, a hydroscopic agent, a humectant, a salt, a silicone, a surfactant, a microencapsulated phase change material, or any combination thereof. In some embodiments, the physical property is flame retardancy and the component comprises a phosphorous compound, a phosphate, a triphenyl phosphate, a phosphorous-nitrogen compound, ammonium phosphate, ammonium polyphosphate with pentaerythritol, a nitrogenbased compound, melamine, melamine cyanurate, an intumescent flame retardant, a silicon compound, or any combination thereof. In some embodiments, the physical property is an antistatic property and the component comprises a quaternary ammonium, a metallic compound, a metallic salt, a metal oxide, a zinc oxide, a hygroscopic agent, glycerol, a humectant, a surfactant, or any combination thereof. In some embodiments, the physical property is an anti-microbial property and the component comprises a silver-based compound, a quaternary ammonium compound, copper, chitosan, a polyhexamethylene biguanide, or any combination thereof. In some embodiments, the physical property is soil-releasability and the component comprises a silicone, a polyester resin, a cellulose derivative, a cationic surfactant, a silica nanoparticle, a nanoclay, or any combination thereof. In some embodiments, the component is fused to or interspersed within the linear polymeric unit via a Diels-Alder cycloaddition product with the one or more furan- containing units. In some embodiments, the one or more furan-containing units comprises a 2,5- furan dicarboxylic acid residue. In some embodiments, the one or more furan-containing units comprises a 2,5-furan dicarboxylate. In some embodiments, the one or more furan-containing units comprises a 2, 5 -difuranoate moiety.

[0005] The present disclosure provides for single chain polymers comprising: (a) a linear polymeric unit comprising one or more repeating monomeric units selected from an ester, an amide, a urethane, a bio-based monomer, an alkylene, an alkylene terephthalate, or any combination thereof; and (b) one or more furan-containing units interspersed within the linear polymeric unit, wherein the one or more furan-containing units are present in an amount of from 0.1 wt% to 25 wt%.

[0006] Also disclosed herein is a single chain polyamide polymer comprising from 0.1 wt% to 25wt% furan-containing units interspersed therein. In some embodiments, the single chain polyamide polymer is an aramid. In some embodiments, the aramid is poly-paraphenylene terephthalamide or poly(meta-phenyleneisophthalamide). In some embodiments, the single chain polyamide polymer is nylon.

[0007] Also disclosed herein is a single chain polyimide polymer comprising from 0.1 wt% to 25 wt% furan-containing units interspersed therein.

[0008] Also disclosed herein is a single chain polyalkylene polymer comprising from 0.1 wt% to 25 wt% furan-containing units interspersed therein. In some embodiments, the single chain polyalkylene polymer is polyethylene, polytetrafluoroethylene, polypropylene, or polyvinylchloride.

[0009] Also disclosed herein is a single chain polyurethane polymer comprising from 0.1 wt% to 25 wt% furan-containing units interspersed therein.

[0010] Also disclosed herein is a single chain polyurea polymer comprising from 0.1 wt% to 25 wt% furan-containing units interspersed therein.

[0011] Also disclosed herein is a single chain biopolymer comprising from 0.1 wt% to 25 wt% furan-containing units interspersed therein. In some embodiments, the biopolymer is selected from the group consisting of cellulose, chitosan, lignin, starch, polylactic acid, and rubber.

[0012] The present disclosure provides for functionalized polymers that comprises a single chain polymer fused to a maleimide adduct, wherein the single chain polymer comprises one or more repeating monomeric units selected from ester, an amide, an imide, a urethane, a urea, a bio-based monomer, an alkylene, an alkylene terephthalate, or any combination thereof, and wherein the maleimide adduct comprises a component that modulates a physical property of the single chain polymer, with respect to the physical property of the single chain polymer in the absence of the maleimide adduct, wherein the physical property is selected from hydrophobicity, durable water repellency, hydrophilicity, moisture wicking, flame retardancy, anti-static properties, antimicrobial properties, soil-releasability, or any combination thereof. In some embodiments, the maleimide adduct is present in a wt% of from 0.1 wt% to 25 wt%, based on the weight of the functionalized polymer. In some embodiments, the physical property is hydrophobicity, and the component comprises an aminosilane, a thiosilane, an alkylamine, a fatty acid amine, or any combination thereof. In some embodiments, the physical property is durable water repellency and the component comprises a silicon compound, a siloxane compound, a hydrocarbon, a nanoparticle providing a lotus effects, or any combination thereof. In some embodiments, the physical property is hydrophilicity and the component comprises an amino-terminated polyethylene glycol, a hydroxy-terminated polyethylene glycol, a thio-terminated polyethylene glycol, a sulfonatedamine, or any combination thereof. In some embodiments, the physical property is moisture wicking and the component comprises a hydrophilic polymer, polyethylene glycol, polyvinyl alcohol, a hydroscopic agent, a humectant, a salt, a silicone, a surfactant, a microencapsulated phase change material, or any combination thereof. In some embodiments, the physical property is flame retardancy and the component comprises a phosphorous compound, a phosphate, a triphenyl phosphate, a phosphorous-nitrogen compound, ammonium phosphate, ammonium polyphosphate with pentaerythritol, a nitrogen-based compound, melamine, melamine cyanurate, an intumescent flame retardant, a silicon compound, or any combination thereof. In some embodiments, the physical property is an anti-static property and the component comprises a quaternary ammonium, a metallic compound, a metallic salt, a metal oxide, a zinc oxide, a hygroscopic agent, glycerol, a humectant, a surfactant, or any combination thereof. In some embodiments, physical property is an anti-microbial property and the component comprises a silver-based compound, a quaternary ammonium compound, copper, chitosan, a polyhexamethylene biguanide, or any combination thereof. In some embodiments, the physical property is soil-releasability and the component comprises a silicone, a polyester resin, a cellulose derivative, a cationic surfactant, a silica nanoparticle, a nanoclay, or any combination thereof.

[0013] The present disclosure provides for fibers that comprise the functionalized polymer described herein. In some embodiments, the fiber is used to produce an article selected from an a bottle cap, a bottle, cutlery, outdoor apparel, a jacket, pants, footwear, boots, athletic apparel, undergarments, a tent, a backpack, an umbrella, automotive interior material, an awning, outdoor furniture, an electronic device, military clothing, uniforms, a tarpaulin, outdoor covers, curtains, drapes, carpets, table linens, napkins, automotive upholstery, aircraft interior material, public transportation seating material, clean room material, and surface materials.

[0014] The present disclosure provides for yams that comprises the functionalized polymer described herein.

[0015] The present disclosure provides for fabrics that comprises the functionalized polymer described herein.

[0016] The present disclosure provides for plastics that comprises the functionalized polymer described herein.

[0017] The present disclosure provides for moldings that comprises the functionalized polymer described herein.

[0018] The present disclosure provides for films that comprises the functionalized polymer described herein.

[0019] Polyethylene furan-2,5-dicarboxylate (PEF) has been shown to react with a bismaleimideto form crosslinking and branching. If a diamine is reacted with two equivalents of maleic anhydride, the reaction produces a two headed imide with two electron-poor alkenes on each end. This product can then react with two neighboring polymer chains. Illustrated below is a reaction of PEF with maleic anhydride, a dienophile different than generic mal eimides.

[0020] While the reaction scheme shows maleic anhydride reacting with PEF, it should be appreciated that the reaction illustrates only one example of a different type of dienophile reacting with a 2,5-furandicarboxylic acid (FDCA) moiety in a polyester. This maleic anhydride reaction is not specific to a PEF homopolymer, and may be implemented with, for example, PETF and other FDCA-containing hermoplastic condensation polymers where the FDCA residue is incorporated into the backbone of the polymer. Alternatively, the maleic anhydride or maleimide reaction may be implemented with a polyester polymer.

[0021] In some embodiments of the present approach, polymers having a backbone with a furan moiety, such as the highly deactivated 2, 5 -difuranoate moiety, are reacted using low energy surface treatment / grafting conditions, without reaching the extreme temperatures needed to produce apolymer melt. It should be appreciated that the present approach contemplates both surface grafting of the polymer backbone (e.g., fiber surface, film surface) and polymer backbone grafting in the bulk of the polymer. Unlike prior art cross-linking reactions of bi-functional bismal eimides to backbone furan-containing groups, which proceed at temperatures high enough to form polymer melts, the present approach advantageously provides embodiments involving backbone grafting of functional side groups at temperatures of 130 °C or less, in water or other solvents, at the polymer interface.

[0022] Under the present approach, the furan-containing moiety in PEF, or other polymers such as poly(butylene) furanoate (PBF), is capable of reacting in a cycloaddition Diels- Alder reaction with an electron poor alkene (also known as a dienophile). It should be appreciated that the present approach may also be used with copolymers including a furanic moiety, such as, for example, polyesters with a furan-containing moiety (e.g., PBTF, PEFT, PETF, etc.). In some embodiments, the present approach may also be used with any condensation polymer (e.g., polyesters, nylons, polyurethanes, etc.). In some embodiments, the present approach may also be used with any condensation polymer (e.g., polyesters, nylons, polyurethanes, etc.) that include FDCA-derived residues or other furan-containing units among potentially numerous other monomer residues. The most common of these alkenes are based on maleic anhydride structures. Maleic anhydride can be reacted with any aliphatic amine to form a maleimide. With sufficient energy and conditions that encourage dehydration of the furan ring oxygen, the reaction proceeds to form a 6-membered aromatic ring in the backbone of the polymer with the imide attached. Functionally, this reaction produces an appending reaction to the polymer backbone. Polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and other terephthalate-based polyesters cannot undergo this post-polymerization reaction.

[0023] In some embodiments, the present approach may take the form of a functionalizable polymer composition with a polymer backbone having a furan-containing moiety, a dienophile binding group providing for furan attachment through a Diels- Alder reaction, and a functional tail connected to the dienophile binding group. In some embodiments the furan-containing moiety is a 2, 5 -difuranoate moiety. In some embodiments the furan-containing moiety is a 2,5-furan dicarboxylic acid residue. In some embodiments the furan-containing moiety is a 2,5-furan dicarboxylate. In some embodiments, the polymer is one or more of a polyester, a polyamide, a polyurethane, a bio-based monomer, a copolymer containing an FDCA-based residue, PETF, polyethylene 2,5-furandicarboxylate, polybutylene 2,5-furandicarboxylate, or PBTF. In some embodiments, the dienophile binding group is one of maleimide or bisitaconimide. In some embodiments, the functional tail is one or more of an aminosilane, a thiosilane, an alkylamine, afatty acid amine, a sulfonated amine, or a functionalized silane.

[0024] Some embodiments of the present approach may take the form of a method for functionalizing a polymer. In some embodiments, a polymer having a backbone with a furan- containing moiety is provided, and a dienophile binding group is attached to the furan moiety through a Diels-Alder reaction. The dienophile binding group is connected to a functional tail, providing a modification, and specifically a surface modification along the polymer backbone. In some embodiments, the functional tail comprises a compound providing a functionality selected from the group consisting of hydrophobicity, durable water repellency, hydrophilicity, wicking, flame retarding, anti-static, and anti-microbial.

[0025] Some embodiments of the present approach may take the form of a method of forming a dienophile binding group for a Diels-Alder reaction. In some embodiments, a functional tail having an amine head group is reacted with maleic anhydride to produce a functional tail connected to a maleimide head group. The functional tail may be, e.g., a compound providing a functionality selected from the group consisting of hydrophobicity, durable water repellency, hydrophilicity, moisture wicking, flame retarding, anti-static, and anti-microbial. For example, if the functionality is hydrophilicity, the compound may be selected from the group consisting of an amino-terminated polyethylene glycol, a hydroxy-terminated polyethylene glycol, a thio-terminated polyethylene glycol, and a sulfonated amine, among other compounds known in the art for producing a hydrophilic functionality. In some embodiments, in which the functionality is hydrophobicity, the compound may be selected from the group consisting of an aminosilane, a thiosilanes, an alkylamine, and a fatty acid amine, among other compounds known in the art for producing a hydrophobic functionality. In some embodiments, in which the functionality is durable water repellency, the compound may be selected from the group consisting of a silicon compound, a siloxane compound, a hydrocarbon, a nanoparticle providing a lotus effects, among other compounds known in the art for producing a water repellant effect. In some embodiments, in which the functionality is soil release, the compound may be selected from the group consisting of a silicone, a polyester resin, a cellulose derivative, a cationic surfactant, a silica nanoparticle, and a nanoclay, among other compounds known in the art for producing the desired effect. In some embodiments, in which the functionality is flame retardancy, the compound may be selected from the group consisting of a phosphorous compound, a phosphate, a triphenyl phosphate, a phosphorous-nitrogen compound, ammonium phosphate, ammonium polyphosphate with pentaerythritol, a nitrogen-based compound, melamine, melamine cyanurate, an intumescent flame retardant, and a silicon compound, among other compounds known in the art for producing the desired effect. In some embodiments, in which the functionality is anti-static properties, thecompound may be selected from the group consisting of a quaternary ammonium, a metallic compound, a metallic salt, a metal oxide, zinc oxide, a hygroscopic agent, glycerol, a humectant, and a surfactant, among other compounds known in the art for producing the desired effect. In some embodiments, in which the functionality is moisture wicking, the compound may be selected from the group consisting of a hydrophilic polymer, polyethylene glycol, polyvinyl alcohol, a hydroscopic agent, a humectant, a salt, a silicone, a surfactant, and a microencapsulated phase change material, among other compounds known in the art for producing the desired effect. In some embodiments, in which the functionality is anti-microbial, the compound may be selected from the group consisting of a silver-based compound, a quaternary ammonium compound, copper, chitosan, and polyhexamethylene biguanide, among other compounds known in the art for producing the desired effect.

[0026] Some embodiments may take the form of a functionalized polymer with a polymer having a backbone with a furan-containing moiety attached to a dienophile binding group through a Diels- Alder reaction. The dienophile binding group is connected to a functional tail, and the functional tail imparts a functionality to the polymer backbone surface. In some embodiments, the functional tail provides the functionalized polymer with at least one behavior selected from the group consisting of durable water repellency, soil releasability, moisture wicking, flame retardancy, antistatic properties, and anti-microbial properties. In some embodiments, the polymer comprises at least one polymer selected from the group consisting of a bio-based polymer, a co-polymer containing an FDCA-based residue, PETF, polyethylene 2,5-furandicarboxylate, polybutylene 2,5- furandi carb oxy late, and PBTF. In some embodiments, the functionalized polymer is formed into one of a yarn or a fabric.

[0027] Some embodiments may take the form of an article comprising the functionalized polymer described above. The article may be, e.g., outdoor apparel, a jacket, pants, footwear, boots, athletic apparel, undergarments, a tent, a backpack, an umbrella, automotive interior material, an awning, outdoor furniture, an electronic device, military clothing, uniforms, a tarpaulin, outdoor covers, curtains, drapes, carpets, table linens, napkins, automotive upholstery, aircraft interior material, public transportation seating material, clean room material, or surface materials.

[0028] Some embodiments of the present approach take the form of a method for preparing a functionalized polymer fabric. In some embodiments, first, a fabric having a polymer with a backbone with a furan-containing moiety is formed. In some embodiments, next, the polymer is reacted with a dienophile binding group having a functional tail to attach the dienophile binding group to the furan-containing moiety through a Diels-Alder reaction, forming a functionalized polymer fabric. In some embodiments, the polymer backbone surface received the modification.In some embodiments, the functional tail provides the functionalized polymer fabric with at least one behavior selected from the group consisting of durable water repellency, soil releasability, moisture wicking, flame retardancy, anti-static properties, and anti-microbial properties. In some embodiments, the polymer comprises at least one polymer selected a bio-based polymer, a copolymer containing an FDCA-based residue, PETF, polyethylene 2,5-furandicarboxylate, polybutylene 2,5-furandicarboxylate, and PBTF. In some embodiments, the functionalized polymer fabric is incorporated into an article such as outdoor apparel, a jacket, pants, footwear, boots, athletic apparel, undergarments, a tent, a backpack, an umbrella, automotive interior material, an awning, outdoor furniture, an electronic device, military clothing, uniforms, a tarpaulin, outdoor covers, curtains, drapes, carpets, table linens, napkins, automotive upholstery, aircraft interior material, public transportation seating material, clean room material, or surface materials. In some embodiments, the functionalized polymer fabric is attached to a second fabric material. In some embodiments, the functionalized polymer fabric may form the backing of a fabric material. In some embodiments, the functionalized polymer fabric may form the face of a fabric material. In some embodiments, the functionalized polymer fabric is blended with a second fabric.BRIEF DESCRIPTION OF THE DRAWINGS

[0029] Novel features of exemplary embodiments are set forth with particularity in the appended claims. A better understanding of the features and advantages will be obtained by reference to the following detailed description that sets forth illustrative embodiments, in which the principles of the disclosed systems and methods are utilized, and the accompanying drawings of which:

[0030] FIG. 1 illustrates the present approach applied using a PETF co-polymer, and a functional group maleimide.

[0031] FIG. 2 illustrates an example of the present approach in which a modified Diels-Alder adduct PETF surface is heat treated to form a modified, aromatized surface PETF.

[0032] FIG. 3A- FIG. 3B are graphs showing a %IPAto wet fabric following a di chloromethane (DCM) washing for PETF-BMI compared to a control (FIG. 3 A) and for PETF-BMI-H2O compared to a control (FIG. 3B).

[0033] FIG. 4A - FIG. 4B are graphs showing (FIG. 4A) and (FIG. 4B).

[0034] FIG. 5A - FIG. 5B are photographs showing a PETF-C-H2O after two dichloromethane (DCM) washes (FIG. 5A) and a PETF-BMI after two DCM washes (FIG. 5B).DETAILED DESCRIPTION

[0035] The following description is of the best currently contemplated mode of carrying out exemplary embodiments of the present approach. The description is not to be taken in a limiting sense, and is made merely for the purpose of illustrating the general principles described herein.Definitions

[0036] The section headings used herein can be for organizational purposes and are not to be construed as limiting the subject matter described. In some cases, the sectional headings may not be constructed as limiting the subject matter described.

[0037] As used in the specification and claims, the singular form “a”, “an” and “the” include plural references unless the context clearly dictates otherwise. For example, the term “a polypeptide” includes a plurality of polypeptides, including mixtures thereof.

[0038] The term “about” or “approximately” as used herein when referring to a measurable value such as an amount or concentration and the like and, unless stated otherwise, is meant to encompass variations of + / - 20%, which includes + / - 10%, 5%, 1 %, 0.5%, or even 0.1 % of the specified amount.

[0039] As used herein, the term “comprising” is intended to mean that the compositions and methods include the recited elements, but do not exclude others. “Consisting essentially of’ when used to define compositions and methods, shall mean excluding other elements of any essential significance to the combination for the intended use. Thus, a composition consisting essentially of the elements as defined herein would not exclude trace contaminants from the isolation and purification method and pharmaceutically acceptable carriers, such as phosphate buffered saline, preservatives, and the like. “Consisting of’ shall mean excluding more than trace elements of other ingredients and substantial method steps for administering the compositions of this disclosure. Embodiments defined by each of these transition terms are within the scope of this disclosure.

[0040] Many of the PEGylated mal eimides available on the market are expensive ($l,000 / g or more). A key technology enabler for the surface treatment of furanoate poly esters / co-poly esters and other co-polymers containing an FDCA-based residue will be the development of a lower cost route to the dienophiles needed for the various applications listed below. Table 1 provides a sampling of currently available PEGylated maleimides. It should be appreciated that similar types of maleimide functionalized linking agents are available. The list in Table 1 is not a comprehensive list but illustrates aspects of the linking and grafting technology envisioned herein. Maleic anhydride (CAS 108-31-6) is a key building block for maleimide PEGylation, because maleimide and its derivatives stem from the reaction of maleic anhydride with an amine, followed by dehydration.Table 1. Selected PEGylated maleimides available from BroadPharm (San Diego, CA)

[0041] Structural examples of the compounds listed in Table 1 are:(1) PEG-Acid (Mal-PEG4-Acid and Mal-PEG12-Acid shown, respectively.)(2) PEG-NHS Ester (Mal-PEG4-NHS Ester and Mal-PEG12-NHS Ester shown, respectively

[0042] Additional examples and a complete listing of maleimide-based linkers, properties, and uses are available from BroadPharm (San Diego, CA), and its website (broadpharm.com), all of which are incorporated by reference in their entirety. It should be appreciated that hydrophilic, hydrophobic, oleophobic, and oleophilic side groups can be used in embodiments of the present approach. The desired side group can be prepared by reacting an amine head-group containing the functional tail with maleic anhydride to form the corresponding maleimide, as illustrated below:

[0043] The side group may be selected for a desired property, as discussed herein. For example, in some embodiments, phosphorus-rich and / or nitrogen-rich side groups may be selected to provide a flame- retardant effect. In some embodiments, the functional tail could be a long chain (C8-C18) aliphatic tail. In some embodiments, a molecule such as laurel amine (C12 aliphatic tail) could be reacted with maleic anhydride to create the corresponding C12 N-maleimide. In some embodiments, aminopropyl triethoxy silane could be reacted with maleic anhydride to form the corresponding triethoxylsilane functionalized N-substituted maleimide. Almost any primary amine can be converted to the corresponding maleimide, thereby providing the potential to confer the functional aspects of the amine onto the polymer backbone. In their intended applications, the maleimide functionality is directed toward thiol bonding, whereas the opposite terminal portion of the linker targets reactions with other amino acid reactive functional groups.

[0044] Synthetic fibers are not easy to functionalize with reactive (covalent) chemical agents compared with natural fibers. In textile and fiber applications, it is commonly necessary to add chemical post-treatments to alter the final properties of the article (for example, make the fibers hydrophobic, hydrophilic / wicking, soft handle, flame retardant, color-fast, etc.). However, many of these effects can be washed off with laundry cycles / aqueous cleaning. It is desirable to find new ways to covalently append these functional moieties on the backbone of a polymer in fiber form. Polymers that make excellent synthetic textiles like nylon or PET, can normally react at onlytheir polymer end groups. These end groups are few and far between. Having a unique reaction pathway using the furan ring in a PETF or PEF or PBF or PBTF may greatly increase the value of those fibers when treatments needed to be applied and wash-fastness is a concern.

[0045] The monomer, 2,5-furan dicarboxylic acid (FDCA), constitutes an important bio-based commercial monomer for the chemical industry, as many chemical companies re-focus goals to achieve defined sustainability objectives by 2030. In any polycondensation polymer that includes FDCA (e.g., polyester, polyamide, polyurethane, etc.), the incorporation of FDCA introduces a furan ring into the polymer chain. This furan ring can react with a dienophile of sufficient electron deficiency to form a Diels- Alder adduct. Diels-Alder reactions are energetically characterized by a free energy reaction coordinate with a characteristic barrier and energy difference between reactants and products. This reaction coordinate can be affected by strategically pairing the proper electron withdrawing character of the dienophile with the proper electron donating potential of the diene. The Diels-Alder (DA) reaction can be successfully manipulated to yield a retro-Diels-Alder (retro DA) reaction at an appropriate temperature.

[0046] In some embodiments, the reactive molecule of the present approach has at least three primary parts: (1) a functional group providing for furan-containing substrate binding through a Diels-Alder reaction, (2) a linear or multiply branched chain stem connected to the substrate binding group, and (3) one or more functional groups. In some embodiments, a telechelic functional group may be chosen to target specific functional groups for the DA reaction. The maleimide functional group is a special subset of both substrate attachment and telechelic functional groups. The maleimide substrate attachment group is a special instance, as it allows tailoring of the DA-retro DA reaction thermos-reversibility cycling reactions.

[0047] FIG. 1 illustrates the present approach applied using a PETF co-polymer, and a functional group maleimide. FIG. 1 shows the starting copolymer surface and indicates that two steps often occur (when applying enough heat and dehydrating conditions). The first step is the adduct formation (that intermediate surface is not shown in FIG. 1), after further dehydrating conditions the adduct is aromatized to a benzenoid ring structure shown at the bottom of FIG. 1. The aromatization is optional and not necessary to covalently bond the dienophile to the FDCA residue on the surface of the copolymer (PETF in this case). The application of heat drives the cycloaddition reaction, producing a surface-modified PETF with the functional group. In this example the PETF is aromatized.

[0048] FIG. 2 illustrates an example of the present approach in which a modified Diels-Alder adduct PETF surface is heat treated to form a modified, aromatized surface PETF.

[0049] In some embodiments of the present approach, the DA dienophile is applied at atemperature at or above ambient. In some embodiments, the rate of reaction will increase as more thermal energy is applied to the reaction.

[0050] In some embodiments , bisitaconimide may be used as a substrate binding and / or telechelic end group for this approach to yield 100% bio-based solution for performance-enhanced surface modification of PEF polyesters.

[0051] It should be appreciated that the present approach may be used in a wide variety of embodiments. For example, the chemical pathway of the present approach allows for PBF, PEF, or PETF co-polymers to react after the initial polycondensation reaction (e.g., polymerization in autoclave) to modify the backbone either to build viscosity and / or molecular weight via branching and cross-linking, or to join with a mono-functional imide to result in value added side-chain chemistry being covalently added to the backbone.

[0052] As another example, some embodiments may utilize mono-reactivity for modifying the polymer backbone (for example, at polymer surfaces). These embodiments may be valuable in fibers having considerable surface area and small amounts of value-added side chains that add or modify the properties of the final textile / fiber article. For example, a hydrophobic side chain or a hydrophilic side chain may be added to affect the hand or stainability of the fibers (or soil release). In some embodiments, the hydrophobic or hydrophilic side chain is covalently linked to at least one Diels-Alder reactive dienophile to react with a chain backbone furan on the furan-containing polymer substrate. Similarly, flame retardants may be added. In some embodiments of the present approach, the flame-retardant functional group has structure that includes a dienophile group in addition to the flame-retardant functionality to enable Diels- Alder cycloaddition. This allows for the covalent bond with the furan diene in the polymer chain. In some embodiments, the dienophile requires a separate synthesis scheme to ensure energetic matching (as described above) of the furan diene and dienophile to achieve the desired level of thermodynamic stability and flame retardancy. Many conventional textile finishing chemicals that add such functionality do not covalently bond to the fiber polymers and can thus be removed in laundry washing. Synthetic fibers often do not react with textile finishing chemicals (where sometimes natural fibers like cotton can react). The present approach therefore enables a wide range of chemistry.

[0053] In some embodiments, it may be difficult to impart enough energy without remelting the polymer to drive the reactions of the present approach. In some embodiments, there may also be some polymer chain mobility required to allow for resolution of the steric interferences created by the reaction.

[0054] In some embodiments, the present approach may be used to enable bis-reactivity (two maleimides in the additive) for cross-linking or branching polymer chains. In some embodiments,the thermal energy in molten polymer may be sufficient to drive cycloaddition followed by dehydration of the bicyclic ring oxygen to form cross-links and increase melt-viscosity. In some embodiments, the cross-linking or branching will be expected to produce pronounced effects on polymer properties for injection molded or rigid applications.

[0055] In some embodiments, the reactivity of the present approach may be exploited in thermosetting unsaturated polyesters. In some embodiments, these reaction pathways with cycloaddition can be useful in unsaturated polyester resins, such as those used in the fiberglass markets. As another example, FDCA may replace some terephthalic acid in lower molecular weight oligomers / polymers, there could be enhanced thermosetting possibilities depending on specific curing regimes.

[0056] It should be appreciated that the present approach may be applied for films, fibers, and / or molded articles treated wholly or in part through reactive surface modification and covalent grafting compounds. In some embodiments, such compounds may have specific chemical functionalities to impart unique surface properties and characteristics on discrete and / or continuous varying spatial, areal, or linear dimension scales, ranging from several Angstroms to a meter or more in extent.

[0057] Some embodiments of the present approach use physical methods to achieve surface patterning by “printing” with different maleimide dienophiles and then curing the printed furan- containing polymer substrate at an appropriate temperature to drive the Diels-Alder reaction forward. The reactivity at 130 °C between PEF and a 2,000 g / mol PEG-methyl ether maleimide has been demonstrated. In some embodiments, the electronic structure and chemical performance of dienophiles can be manipulated to enhance or lessen Diels-Alder reactivity and reversibility (retro-reaction) through selection of the maleimide stem and telechelic functional group.

[0058] For example, the present approach has been used to show an increased hydrophilicity of a compression-molded PEF film treated with a 2,000 g / mol PEG-methyl ether maleimide at 130 deg C for 2.5 hrs. The resulting treated film was Soxhlet extracted in refluxing water for about 1 hour. The film was dried and a drop of water was added to the film surface. Compared to water droplets applied to untreated PET, PEF, and treated PET that had been similarly extracted, only the maleimide (PEGMEM)-treated PEF exhibited noticeable spreading of the applied water droplet on the surface, indicating increased wettability and hydrophilicity.

[0059] The following are examples of functional residues linked to a maleimide dienophile that may be used to achieve the demonstrative performance applications. In some embodiments, for hydrophilicity / wettability, amino-, hydroxy-, or thio-terminated polyethylene glycols (PEGs), or sulfonated amines are used. In some embodiments, for hydrophobicity: aminosilanes, thiosilanes,alkylamines, or fatty acid amines are used. In some embodiments, antifog agents are used to encourage the spreading of water across films to reduce beading and improve film optical clarity in the presence of water condensation. In some embodiments, both hydrophilic and hydrophobic antifog agents can be employed for effect. In some embodiments, hydrophobic functionality reduces the droplet contact angle and promotes water spreading. In some embodiments, hydrophobic agents force extremely small, fine beads which do not diminish film see-through clarity substantially. In some embodiments, for PEF bottles with improved stress crack resistance, sulfonated amines and functionalized (-NH2, -OH, or -SH) silanes. In some embodiments, for improved self-adhesion in furan-containing polymers: bis-maleimide and multi-maleimide compounds are used. In some embodiments, to achieve adhesion to dissimilar surfaces, monomaleimide with one or more telechelic end groups demonstrating affinity or chemical reactivity (covalent bonding) with the dissimilar polymer surface are used. In some embodiments, hydroxyl, amine, and thiol-terminated maleimide linkers can be used to promote protein adhesion. In some embodiments, thermoreversibility may be achieved by reacting a bis-maleimide or multi- maleimide with a furan-containing polymer where the bis- or multi-maleimide compound is electronically structured to yield the requisite electron withdrawing or donating capacity to limit thermal stability so that the retro-Di els- Alder reaction can proceed at a specified higher temperature. In some embodiments, different maleimide functionalized linkers may be patterned on a surface using printing methods well-known in the art. In some embodiments, patterned application can be accomplished over a wide range of length scales.

[0060] In some embodiments, one or more of these surface treatments can be applied randomly or in pattern on the part as needed to accomplish a technological solution requiring one or more physical or chemical attributes including hydrophilicity, hydrophobicity, lipophilicity, or amphiphilicity in fibers, knitted, woven and non-woven fabrics. Examples include but are not limited to:(1) Improved wetting, wicking, and laundering fabrics.(2) Hydrophobic, water-repellant fabrics for sporting apparel and goods.(3) Oleophobic fabrics and apparel.(4) Stain-resistant fabrics, for enhancing imperviousness to inks, dyes, blood, mustard, ketchup and other condiments, berries, fruits, etc.(5) Enabling the use of chemical (typical acid-type dyes used for nylons) for polyester (carpet, and industrial fibers).(6) Antimicrobial, scent-blocking, or scent-binding properties.

[0061] The person having an ordinary level of skill in the art will recognize that a compound maybe converted to a dienophile for use with a clickable polymer as described herein. For example, as discussed above, primary amine compounds are used due to the ease of converting to the corresponding maleimide. In some embodiments, compounds for providing durable water repellant functionality include, but are not limited to, silicon compounds, siloxane compounds, hydrocarbons, and certain nanoparticles for lotus effects, among others known in the art. Generally, a nanoparticle on a fiber provides nano-roughness similar to the way nature produces extreme hydrophobicity on leaves, such as the famous lotus leaf. In some embodiments, nanoparticles may be modified to be grafted to a maleimide pendant group, which then reacts with fibers at polymer surfaces having a backbone segment with a furan-containing moiety via Diels- Alder cycloaddition as described above. In some embodiments, such fibers are reacted with a trialkoxysilane tail group which then bonds with metal hydroxide nanoparticles added in a subsequent step.

[0062] In some embodiments, the durable water repellant compound is dispersible in water for aqueous application processes, and the resulting fabric has the ability to bead up water from the environment while the fabric is in use and thus shed water easily without water absorbing into the fabric. In some embodiments, this treatment should be durable to withstand standard fabric care and washing for garment maintenance.

[0063] In some embodiments, compounds for providing soil release functionality include, but are not limited to, silicones, polyester resins, cellulose derivatives, cationic surfactants, silica nanoparticles, and nanoclays, among others known in the art. In some embodiments, compounds for providing flame retardant functionality include, but are not limited to, phosphorous compounds, phosphates, triphenyl phosphates, phosphorous-nitrogen compounds, ammonium phosphate, ammonium polyphosphate with pentaerythritol, nitrogen-based compounds, melamine, melamine cyanurate, intumescent flame retardants, and silicon compounds. In some embodiments, anti-static compounds include, but are not limited to, quaternary ammonium compounds, metallic compounds such as metallic salts and metal oxides (e.g., zinc oxide), hygroscopic agents such as glycerol, humectants, and surfactants. In some embodiments, compounds for providing wicking functionality include, but are not limited to, hydrophilic polymers such as polyethylene glycol and polyvinyl alcohol, hydroscopic agents such as humectants, salts, silicones, surfactants, and microencapsulated phase change materials. In some embodiments, compounds for providing antimicrobial functionality include, but are not limited to, silver-based compounds, quaternary ammonium compounds, copper, chitosan, and polyhexamethylene biguanide.

[0064] In some embodiments, knitted or woven fabrics are prepared using the present approach. In some embodiments, fabrics containing a copolymer containing an FDCA-based residue, e.g., PETF2 fibers (i.e., a majority PET copolyester with 2% FDCA residues, having thus replaced thesame amount of moles of terephthalic acid residues in said polymer) are synthesized and used on one or more desired surfaces of an article. In some embodiments, application of the present approach to incorporate the desired functional behavior (e.g., durable water repellency, soil releasability, flame retardancy, anti-static properties, wicking properties, or anti-microbial properties, etc.) through the cycloaddition of the corresponding functional group will give transplanar preference to the added functional group. It should be appreciated that more than one functional group can be used - multiple maleimides may be mixed and matched with separate functional tails on each type. In some embodiments,, the fabric material has a front surface or face, and a rear surface or backing. In some embodiments, the PETF2 fibers may be incorporated into the fabric to form all or a portion of the front surface of the fabric, and all or a majority of the rear surface comprises conventional PET or another non-furanic yam. As an example, a wicking additive in the PETF2 fibers incorporated into the fabric face will give a transplanar preference resulting in moving moisture from the inside to the outside of the fabric. Of course, it should be appreciated that, if desired, the PETF2 fibers may be used to form all or a portion of the rear surface and conventional or other non-furanic yarns forming the remainder. In some embodiments, the face and the backing may contain at least a portion of PETF2 fibers. The person having an ordinary skill in the art may decide where on the fabric the desired functionalized behavior is to be incorporated and include PETF2 fibers at such locations. It should also be appreciated that other polymers having a backbone segment with a furan-containing moiety may be used with or instead of PETF2 without departing from the present approach.

[0065] In some embodiments, the present approach may be used to incorporate durable water repellent functionality to military battle dress uniforms and similar heavy-duty garments. Military uniforms, and battle dress uniform, are blends of polyester / cotton or nylon / cotton. The cotton is present to add some comfort to the wearer and to help reduce the wearer from melt / drip fire issue with 100% polyester. While the cotton is necessary, it also picks up moisture and wets out in hot or wet environments. In some embodiments, because the cotton and polyester filaments are blended within the yarn, the present approach may be used to incorporate a durable water repellent added to a clickable polymer as described herein. In some embodiments, the resulting fabric effectively keeps moisture from being absorbed into the cotton and improves the comfort and wearability of the garment.

[0066] In some embodiments, clickable polymers as described herein may be used to allow fiber- to-fiber cross-linking in polyester and polyester / cotton spun yarns, resulting in a soft cotton yam having considerably improved durability. Polyester and polyester / cotton spun yarns are made through various spinning technologies (such as, e.g., air-jet spinning, ring spinning, open endspinning). With these yarn preparations there are often trade-offs between yarn strength and the softness of hand. For example, the more desirable soft hand tend to be the weaker yarns. In some embodiments, the clickable polymers described herein allow for fiber-to-fiber cross-linking, giving the softer yarn higher yarn strength. In some embodiments, for example, a bis-maleimide reagent - a molecule with two maleimide head groups at each end of a spacer moiety in the molecule - would be a useful reagent. In some embodiments, this would be a polymer surface-to- polymer surface bridging reaction in which two neighboring fibers are surface modified by the same molecule. Bismaleimides are often used as cross-linkers, but in this application, in some embodiments, they are envisioned as surface-to-surface bonding agents.

[0067] In some embodiments, the present approach may be employed to impart soil repellent finishes on, e.g., carpets, rugs, and other fibers. For example, a carpet composed of face fibers comprising at least 1 wt% furan-containing moieties in the fiber polymer may be treated with a soil repellency finish comprising a maleimide head group and a silane functional tail. In some embodiments, the composition of polymer fiber would be about 1 wt% - 2 wt% furan-containing residues in the fiber polymer matrix, although the range may be from about 0.1 wt% up to about 25 wt% furan-containing residues by weight in the polymer used to make the synthetic fibers. In some embodiments, the desired strength of the surface modification and the economic viability are the largest factors for determining a composition suitable for a particular embodiment.

[0068] In some embodiments, the fibers are further treated with silica-based particles that can covalently attach to form a siloxane bridge to the grafted maleimide fiber surface.

[0069] As another example of one of the aforementioned applications of the present approach, enzymes may be bound to PEF fibers and non-woven materials for a variety of fabric applications. In some embodiments, an enzyme may be bound to the surface of, e.g., PEF fibers and non-woven materials to carry out a catalyzed reaction, provided that the substrates for the enzyme(s) are present in the solution, and conditions amenable to enzyme functionality. In some embodiments, for instance, an enzyme having perhydrolysis activity for the in-situ production of peracids may be bound to a fabric. In some embodiments, peracids are effective antimicrobial agents and bleaching agents. In some embodiments, one application is in-situ sterilization and bleaching of white fabric.

[0070] The present approach has a wide range of potential applications. In some embodiments, the durable water repellent functionality may be useful in, for example, outdoor apparel, jackets, and pants, footwear, tents and camping hear, backpacks and other fabric containers, umbrellas, sports equipment such as gloves, hats, and bags, automotive interiors, awnings and outdoor furniture, electronic devices, military attire and applications, workwear and uniforms, tarpaulinsand covers, medical apparel. In some embodiments, soil release functionality may be useful in athletic apparel, casual apparel, tents and camping gear, automotive interiors, awnings and outdoor furniture, workwear and uniforms, medical apparel, home furnishings, carpets and rugs, table linens and napkins, public transportation seating, pet bedding, restaurant and hospitality, and aircraft interiors and equipment. In some embodiments, flame retardant functionality may be useful in, for example, automotive interiors, electronic devices, military applications and attire, workwear and uniforms, home furnishings, curtains and drapes, public transportation seating, restaurant and hospitality products, and aircraft interiors and equipment. In some embodiments, anti-static functionality may be useful in, for example, electronic devices, workwear and uniforms, aircraft interiors and equipment, clean rooms, computer, server, and telecommunications surfaces, and automotive and pharmaceutical manufacturing. In some embodiments, wicking functionality may be useful in, for example, outdoor apparel, jackets, and pants, footwear and boots, athletic apparel, casual apparel, undergarments, sports equipment, such as gloves, hats, and bags, military equipment and attire, workwear and uniforms, medical apparel, and bedding and sleepwear. In some embodiments, anti -microbial functionality may be useful in, for example, outdoor apparel, jackets, and pants, footwear and boots, athletic apparel, casual apparel, undergarments, tents and camping gear, sports equipment, such as gloves, hats, and bags, automotive interiors, military equipment and attire, workwear and uniforms, medical apparel, home furnishings, bedding and sleepwear, public transportation seating, and pet bedding. Of course, these examples are not intended to be limiting and are provided to illustrate the wide range of applications for the present approach.

[0071] It should be appreciated that another of methods for applying the chemical treatments described above are available. For example, these include, but are not limited to,• Dipping, immersion applications;• Coating, painting, spraying applications;• Printing applications;• Photogravure applications;• Rotogravure applications;• Flexographic applications;• Offset applications;• Digital applications;• Ink Jet applications;• Laser applications; and• Thermal Transfer applications.Exemplary embodiments

[0072] In some embodiments, the present disclosure provides functionalizable polymercompositions comprising: a polymer having backbone with a furan-containing moiety, a dienophile binding group providing for furan attachment through a Diels-Alder reaction, and a functional tail connected to the dienophile binding group. In some embodiments, the furan- containing moiety is a 2,5-furan dicarboxylic acid moiety. In some embodiments, the furan- containing moiety is a 2,5-furan dicarboxylate. In some embodiments, the furan-containing moiety is a 2, 5 -difuranoate moiety. In some embodiments, the polymer is selected from the group consisting of a polyester, a polyamide, a polyurethane, a bio-based monomer, a copolymer containing an FDCA-based residue, PETF, polyethylene 2,5-furandicarboxylate, polybutylene 2,5- furandi carb oxy late, and PBTF. In some embodiments, the dienophile binding group is one of maleimide or bisitaconimide. In some embodiments, the functional tail is selected from the group consisting of an aminosilane, a thiosilane, an alkylamine, a fatty acid amine, a sulfonated amine, and a functionalized silane. In some embodiments, the present disclosure provides methods for functionalizing a polymer, the methods comprising: providing a polymer having a backbone with a furan-containing moiety; attaching a dienophile binding group to the furan-containing moiety through a Diels- Alder reaction, wherein the dienophile binding group is connected to a functional tail. In some embodiments, the functional tail comprises a compound providing a functionality selected from the group consisting of hydrophobicity, durable water repellency, hydrophilicity, wicking, flame retarding properties, anti-static properties, and anti-microbial properties.

[0073] In some embodiments, the present disclosure provides for methods of forming a dienophile binding group for a Diels- Alder reaction, the method comprising: reacting a functional tail having an amine head group with maleic anhydride to produce a functional tail connected to a maleimide head group. In some embodiments, the functional tail comprises a compound providing a functionality selected from the group consisting of hydrophobicity, durable water repellency, hydrophilicity, moisture wicking, flame retarding properties, anti-static properties, and antimicrobial properties. In some embodiments, the functionality is hydrophilicity, and the compound is selected from the group consisting of an amino-terminated polyethylene glycol, a hydroxyterminated polyethylene glycol, a thio-terminated polyethylene glycol, and a sulfonated amine In some embodiments, the functionality is hydrophobicity, and the compound is selected from the group consisting of an aminosilane, a thiosilanes, an alkylamine, and a fatty acid amine. In some embodiments, the functionality is durable water repellency, and the compound is selected from the group consisting of a silicon compound, a siloxane compound, a hydrocarbon, a nanoparticle providing a lotus effects, among others known in the art. In some embodiments, the functionality is soil releasability, and the compound is selected from the group consisting of a silicone, a polyester resin, a cellulose derivative, a cationic surfactant, a silica nanoparticle, and a nanoclay.In some embodiments, the functionality is flame retardant, and the compound is selected from the group consisting of a phosphorous compound, a phosphate, a triphenyl phosphate, a phosphorous- nitrogen compound, ammonium phosphate, ammonium polyphosphate with pentaerythritol, a nitrogen-based compound, melamine, melamine cyanurate, an intumescent flame retardant, and a silicon compound. In some embodiments, the functionality is anti-static, and the compound is selected from the group consisting of a quaternary ammonium, a metallic compound, a metallic salt, a metal oxide, zinc oxide, a hygroscopic agent, glycerol, a humectant, and a surfactant. In some embodiments, the functionality is moisture wicking, and the compound is selected from the group consisting of a hydrophilic polymer, polyethylene glycol, polyvinyl alcohol, a hydroscopic agent, a humectant, a salt, a silicone, a surfactant, and a microencapsulated phase change material. In some embodiments, the functionality is anti-microbial, and the compound is selected from the group consisting of a silver-based compound, a quaternary ammonium compound, copper, chitosan, and polyhexamethylene biguanide.

[0074] In some embodiments, the present disclosure provides functionalized polymers comprising: a polymer having a backbone with a furan-containing moiety attached to a dienophile binding group through a Diels- Alder reaction, wherein the dienophile binding group is connected to a functional tail. In some embodiments, the functional tail provides the functionalized polymer with at least one behavior selected from the group consisting of durable water repellency, soil releasability, moisture wicking, flame retardancy, anti-static properties, and anti-microbial properties. In some embodiments, the polymer comprises at least one polymer selected from the group consisting of a bio-based polymer, or a polymer comprising a bio-based monomer, a copolymer containing an FDCA-based residue, PETF, polyethylene 2,5-furandicarboxylate, polybutylene 2,5-furandicarboxylate, and PBTF. In some embodiments, the functionalized polymer is formed into one of a yarn and a fabric.

[0075] In some embodiments, the present disclosure provides for an article comprising a functionalized polymer disclosed herein. In some embodiments, the article is selected from the group consisting of outdoor apparel, a jacket, pants, footwear, boots, athletic apparel, undergarments, a tent, a backpack, an umbrella, automotive interior material, an awning, outdoor furniture, an electronic device, military clothing, uniforms, a tarpaulin, outdoor covers, curtains, drapes, carpets, table linens, napkins, automotive upholstery, aircraft interior material, public transportation seating material, clean room material, and surface materials.

[0076] In some embodiments, the present disclosure provides for methods for preparing a functionalized polymer fabric, the method comprising: forming a fabric having a polymer with a backbone with a furan-containing moiety; reacting the polymer with a dienophile binding grouphaving a functional tail to attach the dienophile binding group to the furan-containing moiety through a Diels-Alder reaction, forming a functionalized polymer fabric; wherein the functional tail provides the functionalized polymer fabric with at least one behavior selected from the group consisting of durable water repellency, soil releasability, moisture wicking, flame retardancy, antistatic properties, and anti-microbial properties. In some embodiments, the polymer comprises at least one polymer selected from the group consisting of a bio-based polymer or a polymer comprising a bio-based monomer, a copolymer containing an FDCA-based residue, PETF, polyethylene 2,5-furandicarboxylate, polybutylene 2,5-furandicarboxylate, or PBTF. In some embodiments, the functionalized polymer fabric is incorporated into an article selected from the group consisting of outdoor apparel, a jacket, pants, footwear, boots, athletic apparel, undergarments, a tent, a backpack, an umbrella, automotive interior material, an awning, outdoor furniture, an electronic device, military clothing, uniforms, a tarpaulin, outdoor covers, curtains, drapes, carpets, table linens, napkins, automotive upholstery, aircraft interior material, public transportation seating material, clean room material, and surface materials. In some embodiments, the functionalized polymer fabric is attached to a second fabric material. In some embodiments, the functionalized polymer fabric forms the backing of a fabric material. In some embodiments, the functionalized polymer fabric forms the face of a fabric material. In some embodiments, the functionalized polymer fabric is blended with a second fabric.EXAMPLES

[0077] For a better understanding of the present disclosure and of its many advantages, the following examples are given by way of illustration and without limiting the scope of this disclosure.Example 1

[0078] Hydrophilic PEF materials were demonstrated using the present approach. PET and PEF films were prepared and dipped in a hot aqueous solution of a maleimide with a PEG tail group for 2 hours. Samples of undipped PET and PEF films were retained as controls. All films were then subjected to extensive hot water washing a soxhlet extractor to remove any physically adsorbed reagent that might provide a temporary hydrophilic effect. The films were then analyzed by surface Attenuated Total Reflectance-Fourier Transform Infrared (ATR-FTIR). The resulting spectrum for the PEF undipped and PEF reacted film indicates that the PEF film dipped in the maleimide solution had a covalently bonded PEG tail group.

[0079] Samples of four films (z.e., dipped and undipped PET films, and dipped and undipped PEF films) were then dried and then subjected to water droplet contact angle measurement. The contactangles for the dipped and undipped PET films did not change, but the PEF film dipped in maleimide / PEG tail group solution showed a dramatic hydrophilic effect. Because of the hydrophilic nature of the PEG tail group, the water droplets on the dipped PEF films did not bead like the droplets on the PET and undipped PEF films. Table 2 summarizes the advancing and receding contact angle measurements as determined using a goniometer. As can be seen, the PEF film dipped in maleimide / PEG tail is much more hydrophilic than the undipped PEF film control. This embodiment of the present approach therefore produced a PEF film with a covalently bound PEG tail group on the modified surface that could, e.g., survive numerous laundry cycles if applied to textiles, among other potential benefits.Table 2. Contact angle measurements for control and demonstrative PEF filmExample 2. Scouring of Fabric

[0080] In some embodiments, prior to treating a polymer with a maleimide adduct, the polymer is subjected to a scouring process. In some embodiments, the scouring is done to remove any oils and dirt on the surface of the polymer fabric that may be present from a prior spinning or knitting process.

[0081] In some embodiments, the polymer fabric is scoured by soaking the polymer in a solution containing a scouring agent (such as, e.g., Sera wash, soda ash, Rucogen FWK, etc.) at temperatures up to 130 °C. In some embodiments, the polymers are soaked in a solution of a scouring agent at a temperature of less than 80 °C. In some embodiments, the polymers are soaked in a solution of a scouring agent at a temperature of from 60 ° to 75 °C. In some embodiments, the polymers are soaked in a solution of a scouring agent for a duration of from 5 minutes to 180 minutes.

[0082] In some embodiments, scouring agents solutions can further contain a surfactant, an alkali agent, a chelating agent, a dispersant, a wetting agent, or any combination thereof. In some embodiments, the fabric is rinsed with water after the scouring process and dried.Example 3. Application Of Maleimide Functional Chemistry To Polyester Fabrics, without a furan-containing moiety incorporated therein

[0083] Polyester fabrics are produced according to standard industry methods, and are optional scoured, as described above. The polyester fabric is then saturated with a solution containing a maleimide adduct, with a functional tail intended to impart functional properties (e.g., hydrophilicity, hydrophobicity, anti-static properties, anti-microbial properties, anti-soil properties, oleophobicity, etc.).

[0084] As described above, any solvent is contemplated for solubilizing the maleimide adduct. In some embodiments, the solvent is water. In some embodiments, the solution contains the maleimide adduct at concentrations of less than 0.01 wt%. In some embodiments, the solution contains the maleimide adduct at a concentration from 0.3 wt% to 1.3 wt%. In some embodiments, the fabric is exposed to the maleimide adduct containing solution for a duration of from 2 minutes to 180 minutes. In some embodiments, the fabric is exposed to the maleimide adduct for a duration of from 15 minutes to 60 minutes. In some embodiments, the temperature of the solution during the treatment of the fabrics is from 20 ° to 170 °C. In some embodiments, the temperature of the solution during treatment of the fabric is at a temperature of from 120 °C to 150 °C. After treatment, the wet pick up of the fabric is optionally reduced by squeegee of the fabric through a nip roller, with a target wet pick up of from 50 wt% to 100 wt%. In some embodiments, the target wet pick up is from 60 wt% to 70 wt%. In some embodiments, the fabric is then dried in an oven at temperatures ranging from 100 °C to 170 °C. In some embodiments, the fabric is dried in an oven at a temperature ranging from 130 °C to 145 °C. In some embodiments, the fabric is dried for a duration of from 2 minutes to 120 minutes. In some embodiments, the fabric is dried for a duration of from 2 minutes to 15 minutes. At this point, the fabric is ready for testing of its functional properties (such as wicking, hydrophobicity, etc.).

[0085] Without wishing to be bound to theory, the present process is dependent on the selection and use of a maleimide adduct as the functional species, wherein the concentration, treatment time, treatment temperature, drying temperature, or any combination thereof are technical parameters that generate the resulting fabric with a modified property.Example 4. Application Of Maleimide Functional Chemistry To Furan-Containing Polyester Fabrics

[0086] Polyester fabrics containing furanoate groups in the backbone of the polymer were reacted with maleimide adducts to demonstrate embodiments of the present disclosure. The furanoate groups are present in any amount, and in a range such that the polyester fabric retains its original properties, in additional to new functionalities imparted by reaction with the maleimide adducts. The polyester fabrics produced and tested contain furanoate moi eties in a range from 1 wt% to 10 wt% of furanoate.

[0087] In this example, a polyester-furanoate (PETF) fabric is saturated with a solution containing a maleimide with a tail (also referred to herein as a maleimide adduct; i.e., a maleimide with a functional group appended to the maleimide) that is intended to impart one or more functional properties (such as hydrophilicity, hydrophobicity, anti-static properties, anti-microbial properties, anti-soil properties, oleophobicity, etc.).

[0088] The solvent of the solution can be any solvent capable of solvating the maleimide adduct of choice. In some embodiments, the solvent is water. The solution contains the maleimide adduct at concentrations > 0.01 wt%. In some embodiments, the maleimide adduct is present in the solution in a concentration of from 0.3 wt% to 1.3 wt%. The polyester fabric is exposed to the maleimide adduct containing solution for 2 minutes to 180 minutes. In some embodiments, the polymer is exposed to the maleimide adduct solution for 15 minutes to 60 minutes. The temperature of the solution during the treatment of the fabrics ranges from 20 ° to 170 °C. In some embodiments, the temperature of the solution during treatment of the fabric ranges from 120 °C to 150 °C. After treatment, the wet pick up (i.e., absorbed moisture) of the fabric is optionally reduced or removed by squeegee (i.e., squeezing) of the fabric through a nip roller. In some embodiments, a target wet pick up of the fabric ranges from 50 wt% to 100 wt%. In some embodiments, a target wet pick up of the fabric ranges from 60 wt% to 70 wt%. The fabric is then dried in an oven at temperatures ranging from 100 °C to 170 °C. In some embodiments, the fabric is dried in an oven at temperatures ranging from 130 °C to 145 °C. In some embodiments, the fabric is dried for a period from 2 minutes to 120 minutes. In some embodiments, the fabric is dried for a period of from 2 minutes to 15 minutes. At this point, the fabric is ready for testing of its functional properties (e.g., wicking, hydrophobicity, etc.).

[0089] Without departing from the scope of the present disclosure, embodiments described herein provides for numerous methods for functionalizing polymer materials, depending on the selectionand use of a maleimide adduct as the functional species having a particular functional property. In some embodiments the functionalizing of polymer material will be impacted by optimization of the maleimide adduct concentration, a treatment time, a treatment temperature, a drying temperature, or any combination thereof, to generate the resulting fabric with a modified properties.

[0090] In some embodiments, functional chemistries are applied to polymer by a padding method. In some embodiments, functional chemistries are applied to a polymer by an exhaust” method. Each of these methods, as described below, differ in the temperature and time (duration) of treatment.1 , Padding

[0091] A fabric is dipped into a low temperature (e.g., less than 60 °C or at room temperature) solution for a short duration (e.g., less than about 5 minutes). The fabric is then squeegeed using a nip roller to reduce the wet pick of the fabric. The fabric is then dried according to a time / temperatures as disclosed herein.2, Exhaust

[0092] A fabric is heated in a closed system at a temperature from 120 °C to 150 °C, or at a temperature of 130 °C, for up to 3 hours, potentially in conjunction with a dying process. After this treatment, the fabric is optionally rinsed and then dried as disclosed herein.3, Maleimide

[0093] A general structure of the maleimide comprises a cyclic portion (i.e., a maleimide head of the formula shown below) that is linked to a “functional tail” moiety( / .c., an R1group), that is chosen to impart performance on the target polymer / fiber.

[0094] The R1group is referred to herein as a functional tail. In some embodiments, the maleimide adduct can have multiple tails and / or multiple head groups (i.e., maleimides), e.g., a two-headed maleimide with PEG tail, a one-headed maleimide with PEG tail, a two-headed maleimide with hydrophobic tail, a three-headed maleimide with macromolecule tail, etc. In all cases, the functional tail of the maleimide is selected to impart one or more specific functional properties to the fabric. Those properties may include:, for example, hydrophobicity for water-repellant fabricsfor sporting apparel and goods; hydrophilicity for improved wetting, wicking, and laundering fabrics; oleophobic properties for fabrics and apparel; stain-resistant properties for fabrics with emphasis on enhancing imperviousness to inks, dyes, blood, mustard, ketchup and other condiments, berries, fruits, etc.; antimicrobial properties, for example for scent-blocking or scentbinding; and anti-soil properties for prevention of dirt build up in carpets.Example 5. Hydrophilic treatment example“Padding” treatment samples:

[0095] After scouring with iso-propyl alcohol (IPA), PETF-6 (4.05 g) fabric was submerged in 100 ml of 1 wt.% PEG-PPG-bis-mal eimide / deionized water (DI) water solution at room temperature and stirred for 2 min. The soaked fabrics were dewatered by hand squeezing, and the resulted wet fabric had a 110-120 % mass gain. Afterwards, the wet fabric was dried in an oven at 145 °C for 60 min. The resulting fabrics was denoted as “PETF6-PPbm-tRT(2)-dl45(60).”“Exhaust” treatment samples:

[0096] After scouring with IPA, PETF-6 (3.44 g) fabric was submerged in 200 ml of 1 wt.% PEG- PPG-bis-mal eimide / DI water solution and sealed in a pressure flask. A thermocouple was inserted in the solution to monitor the temperature. The flask of solution and fabrics were stirred (with a magnetic stir bar) and heated to 130 °C with an oil bath and held for 75 min, before cooling to room temperature using an ice bath. The soaked fabrics were dewatered by hand squeezing, and the resulting wet fabrics had a 100-110 % mass gain. Afterwards, the wet fabrics were dried in an oven at 145 °C for 15 min. The resulting fabric was denoted as “PETF6-PPbm-tl30(75)- dl45(I5).”Control samples:

[0097] Scoured PETF-6 fabrics were submerged in 200 ml of DI water and sealed in a pressure flask. A thermocouple was inserted into the solution to monitor the temperature. The flask of solution and fabrics was stirred (with a magnetic stir bar) and heated to 130 °C with an oil bath and held for 75 min, before cooling to room temperature using an ice bath. The soaked fabrics were dewatered by hand squeezing and dried at room temperature overnight. The resulted fabric was denoted as “PETF6-water-tl30(75).”Hydrophilicity test (wicking test):

[0098] Hydrophilicity of the fabrics were evaluated by the water wicking height (along wale direction) after dipping one end of the dry fabrics in water for 10 min and measuring the height of the water line.Fabric washing cycle:

[0099] Each washing cycle includes 4 batches of washing. In every batch, the fabrics (6~12 g) were added in 700 ml DI water at 40 °C and stirred for 5 min. After the 4 batches of washing (total 2800 ml water and 20 min), the fabrics were dewatered by hand squeezing and laid flat for overnight drying.Test results:

[0100] Table 2 and FIG. 3A and FIG. 3B summarize wicking test results of the PETF6 fabrics after padding and exhaust treatments, together with the control PETF6 fabrics without mal eimide treatment.

[0101] The control PETF6 fabric has very weak hydrophilicity, with only 1.6-2.1 water wicking height. As shown in FIG. 3A, the padding treatment improves the wicking properties of PETF6 fabric. The wicking properties of the padding treated samples gradually degraded after 5 washing cycles. The exhaust treatment, as shown in Fig. 3B, improves the wicking properties of PETF6 fabric even more than the padding treatment. The wicking properties of the exhaust treated fabric remained stable after 5 washing cycles.Table 3. The water wicking height of different fabrics at 10 min.Example 6. Hydrophobic treatment example

[0102] Scoured PETF-6 fabric (1.02 g) was submerged in 100 mL 0.3 wt% bis-maleimide solution in di chloromethane for 2 min. The soaked fabric was removed and air dried for 15 min, followed by heat-treatment in a 150 °C oven for 15 min (sample labeled “PETF-BMI”). A control PETF sample was soaked in DCM solution without maleimide and dried under the same conditions (sample labeled “PETF-C”). Both samples were cut in half, and one of each halves was heated in 10 mL DI water in pressure relief vials, placed in 130 °C aluminum block hotplate for 60 min. After cooling, fabrics were squeezed to remove excess water and dried in a 105 °C oven for 15 min. These samples were labeled “PETF-BMI-H2O” and “PETF-C-H2O” for maleimide treated and untreated control, respectively.

[0103] Hydrophobicity of the fabric was measured by applying 20 L droplets of aqueous iso-propanol (IPA) solutions to the fabric. Three droplets of each IPA concentration were added. The concentration of IPA was increased in 5% increments until the fabric was entirely wetted with droplets within 3 min. The lowest % IPA needed to wet the fabric was used as hydrophobicity ranking of the fabrics. Higher ranking indicated higher fabric hydrophobicity, as shown in FIG.4A and FIG. 4B

[0104] After droplet tests fabrics were dried at ambient conditions overnight. To evaluate hydrophobic coating anchoring to the fabrics they were washed with dichloromethane (DCM, 50 mL) for 5 min with occasional agitation in a beaker. After washing the fabrics were air dried for 15 min, followed by heating at 105 °C for 15 min. Droplet tests to measure hydrophobicity were repeated after each wash, as shown in Table 4, below.Table 4. Results of droplet test to measure hydrophobicity

[0105] Hydrophobicity resistance to dichloromethane washing indicated covalent bonding of the hydrophobic treatment to the polyester fabric accomplished by bis-maleimide deposition on PETF fabric followed by treated fabric water heat treatment.

[0106] FIG. 5A shows a PETF-C-H2O fabric after two DCM washes. The fabric was entirely wetted with three DI water droplets (0% IPA) after 3 min , and instantly with three 5% IPA droplets. Fig. 5B shows a PETF-BMI fabric after two DCM washes. The fabric was entirely wetted with three 15% IPA droplets instantly, but not with 10% IPA although at a low contact angle.Prophetic Example. Dyeability modification of polymer fabrics

[0107] The following prophetic examples discloses methods to shown an application of a maleimide with an amine tail to a greige PETF fabric to enable a measurable / demonstrable difference in permanent dyeability of the fabric towards anionic dyes. Without wishing to be bound to theory, normal PET fabrics are generally resistant to absorbing negatively charged dyestuff when dyed in aqueous conditions. The disclosed prophetic example can be used to comparing corresponding griege PET knit fabrics made at the same time and on the same knitting equipment.Materials

[0108] Amino terminated alkyl maleimide (1 gram), which is a monomaleimide of hexamethylene diamine:

[0109] Red Dye 40 (also known as "Allura Red AC"Methods

[0110] Determine solubility level of the amino-terminated alkyl maleimide adduct and dissolve it in pH 4-5 water, starting with 100 mg of the ammonium terminated maleimide in 10 mL of pH 4- 5 water.[oni] Cut polymer fabric to 2 cm x 8 cm strips. Make sure the fabric is scoured to remove any lubricating oils before cutting into strips - fabric can be scoured as previously described herein above. In some embodiments, the fabrics can be rinsed with acetone and then n-hexane and allowed to air dry. The acetone can be evaporated to look for lubricating oil residues (as can the hexane). Weigh the fabric swatches (2 x 8 cm) - post scour and record all weights of fabrics to nearest 0.001 grams. Dip each fabric swatch in the pH 4-5 aqueous solution (in a petri dish or shallow beaker) for 60 seconds. In some embodiments, the solution can be warmed to 50 °C. Also create a blank solvent control aqueous solution at similar pH (4-5).Controls Per PETF test fabric

[0112] Run a control experiment with PET fabric (for each condition where the PETF fabric was used). Also run a set of dipping controls where the PETF and PET fabrics are dipped in solvent- only controls for the same time and temperature. Set aside an undipped set of fabric controls (PETF and PET swatch) to be placed in the oven alongside the dipped test items and dipped solvent only controls. Remove each of the fabrics from petri dish (or beaker) and squeeze between two pieces of plate glass (or other method of consistently squeezing fabric swatches while flat). Weigh the fabric post squeeze to establish a "wet pick-up" % (target enough squeezing to produce between 50 - 100% wet pick up).

[0113] Place in convection oven at 150 °C for about 3 min to see if the fabrics in that solvent driesin time, targeting taking the fabrics out no more than 30 sec after the last of the water has evaporated. Place all three sets of fabrics in the oven for the same time and at the same temperature (PETF and PET+mal eimide Dip; PETF and PET solvent-only dip; no dip controls of PETF; and PET swatches). Weigh the fabrics again - upon cooling.Rinse fabrics to remove physically absorbed amine reagent

[0114] Place fabrics in a small beaker. Add 50 mL of DI Water (making sure the pH of water is below 7). Allow to sit for 1 hour with occasional gentle agitation with a glass rod. Drain the water and repeat 3 times more.

[0115] Optionally, look for free amine groups still coming out in the rinse solution. The following diagnostic test can be run: after the end of each 1 hour water soak, take a 5 mL sample of the water and separate from the fabric. Add a drop of 50% NaOH solution to raise the pH of the water sample above pH 9. Apply a drop of this basic solution to a TLC plate and then expose to ninhydrin and develop with heat gun. Look for color chain consistent with free amine in solution. This would indicate that ungrafted reagent is still rinsing off the fabric.

[0116] Pour off the remaining rinse water from the beaker. Remove the fabrics and squeeze between two pieces of plate glass with fabric swatches completely flat. Airdry the fabrics to a constant weight. Compare the weight to the initial weight before dipping and after dipping / curing. An oven drying (at mild conditions of 65 °C) can be deployed as necessary.Testing Fabrics for Acid Dyeability

[0117] Dissolve 25 mg of Allura Red AC (aka Red Dye 40) in 25 mL of DI water (or 100 mg of dye in 25 mL of DI water) Dip half the length of the 8 cm fabric swatch in the solution and allow to sit for 5 min. Drape the other end of the fabric over the side of the beaker. Remove the fabric and wash with DI water. This can be done with copious quantities from a squirt bottle. Alternatively, if a color remains, deploy 50 mL of 40 °C water and 1 hour soaking with multiple water changes as done for the original rinsing post oven step. Report any visual differences between the PETF and PET control fabrics and record with pictures. Optionally, use a LAB Color meter to measure the color space of the stained and unstained ends of each fabric. Without wishing to be bound by theory, the PETF fabrics treated with the ammonium terminated maleimide should show red dye pick up and the PET control fabrics should have the red staining removed by washing.Prophetic Example. Film Bridging Adhesives

[0118] The following prophetic examples describes a method to show application of a bis- maleimide (BMI) applied to a surface of a PETF film, that will then act as an adhesive when another PETF film is pressed on top of that surface, with the BMI acting as a bridging agent. Adhesion between the two films can be tested by lap-shear testing and also observed qualitatively by hand lap-shear observations. This can be compared to PET control films.Hydrophobic bismaleimides

[0119] The following bis-maleimides can be tested in parallel: (i) BMI-3000 (powder); (ii) BMI- 689 (liquid); and (iii) BMI-1700 (liquid).

[0120] For each Maleimide case, dissolve the hydrophobic maleimide in DCM (as described herein for hydrophobic testing). Other organic solvents that dissolve these three BMIs can also be explored. Make 5% w / w solutions of the three different BMI

[0121] The following film strips can be used (based on wt% furanoate incorporated therein): (i) PETF 10%; (ii) PETF30%; and (iii) a PET Control.Method

[0122] Films do not need any scouring or surface pre-treatment. Cut the film strips into 2 cm x 6 cm strips. For each film composition type apply the following procedure:

[0123] Place 3 film strips on a flat surface. To each of the respective film strips, apply 0.25 mL of one of the BMI solutions listed above. Note, this volume is approximate and can be fine-tuned depending on the polymer fabric strips used. Apply the liquid on the right side of each of the films such that the left half of each film is not wetted. Take another piece of the same film strip and place it on the wetted right half of the treated film strip such that half of the film strip overlaps. The liquid in between the two strips should spread out, like water between to glass slides. Place a 0.5 kg weight on the sandwich pair of strips (or appropriate weight depending on the size of the fabric strips, as needed). Wipe up excess DCM solution and wait for the remaining DCM between the two films to evaporate. After 2 hours at room temperature, pull laterally on the two uncoated ends of the film-strip sandwich and see if any qualitative adhesion is observed.

[0124] Official readings can be taken with an INSTRON, to detect qualitative bridging of the two film strips. Alternatively, the film sandwich can be placed in warm oven at a temperature from 35 °C to 50 °C.

[0125] Record any qualitative differences between the PET vs the two types of PETF films andwhen testing the three different BMI with each pair of strips tested.

[0126] The present approach may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the claims of the application rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.

Claims

CLAIMSWhat is claimed is:

1. A functionalized polymer comprising:(a) a linear polymeric unit comprising one or more repeating monomeric units selected from an ester, an amide, an imide, a urethane, a urea, a bio-based monomer, an alkylene, an alkylene terephthalate, or any combination thereof;(b) from 0.1 wt% to 25 wt% of furan-containing units interspersed within the linear polymeric unit; and(c) a component linked to the linear polymeric unit that comprises a structure that modulates a physical property of the single chain polymer, wherein the component is present in an amount sufficient to modulate a physical property of the linear polymer unit, as compared to the physical property of the linear polymeric unit without the component, and wherein the physical property is selected from hydrophobicity, durable water repellency, hydrophilicity, moisture wicking, flame retardancy, anti-static properties, antimicrobial properties, soil-releasability, or any combination thereof.

2. The functionalized polymer of claim 1, wherein the physical property is hydrophobicity, and the component comprises an aminosilane, a thiosilane, an alkylamine, a fatty acid amine, or any combination thereof.

3. The functionalized polymer of claim 1, wherein the physical property is durable water repellency and the component comprises a silicon compound, a siloxane compound, a hydrocarbon, a nanoparticle providing a lotus effects, or any combination thereof.

4. The functionalized polymer of claim 1, wherein the physical property is hydrophilicity and the component comprises an amino-terminated polyethylene glycol, a hydroxy-terminated polyethylene glycol, a thio-terminated polyethylene glycol, a sulfonated amine, or any combination thereof.

5. The functionalized polymer of claim 1, wherein the physical property is moisture wicking and the component comprises a hydrophilic polymer, polyethylene glycol, polyvinyl alcohol, a hydroscopic agent, a humectant, a salt, a silicone, a surfactant, a microencapsulated phase change material, or any combination thereof.

6. The functionalized polymer of claim 1, wherein the physical property is flame retardancyand the component comprises a phosphorous compound, a phosphate, a triphenyl phosphate, a phosphorous-nitrogen compound, ammonium phosphate, ammonium polyphosphate with pentaerythritol, a nitrogen-based compound, melamine, melamine cyanurate, an intumescent flame retardant, a silicon compound, or any combination thereof.

7. The functionalized polymer of claim 1, wherein the physical property is an anti-static property and the component comprises a quaternary ammonium, a metallic compound, a metallic salt, a metal oxide, a zinc oxide, a hygroscopic agent, glycerol, a humectant, a surfactant, or any combination thereof.

8. The functionalized polymer of claim 1, wherein the physical property is an anti-microbial property and the component comprises a silver-based compound, a quaternary ammonium compound, copper, chitosan, a polyhexamethylene biguanide, or any combination thereof.

9. The functionalized polymer of claim 1, wherein the physical property is soil-releasability and the component comprises a silicone, a polyester resin, a cellulose derivative, a cationic surfactant, a silica nanoparticle, a nanoclay, or any combination thereof.

10. The functionalized polymer of any one of claims 1-9, wherein component is linked to the linear polymeric unit via a Diels-Alder cycloaddition product with the one or more furan- containing units.

11. The functionalized polymer of any one of claims 1-10, wherein the one or more furan- containing units comprises a 2, 5 -difuranoate moiety.

12. The functionalized polymer of any one of claims 1-10, wherein the one or more furan- containing units comprise a 2,5-furan dicarboxylic acid moiety.

13. The functionalized polymer of any one of claims 1-10, wherein the one or more furan- containing units comprise a 2,5-furan di carb oxy late.

14. A functionalized polymer that comprises a single chain polymer fused to a maleimide adduct, wherein the single chain polymer comprises one or more repeating monomeric units selected from an ester, an amide, an imide, a urethane, a urea, a bio-based monomer, an alkylene, an alkylene terephthalate, or any combination thereof, and wherein the maleimide adduct comprises a component that modulates a physicalproperty of the single chain polymer, with respect to the physical property of the single chain polymer in the absence of the maleimide adduct, wherein the physical property is selected from hydrophobicity, durable water repellency, hydrophilicity, moisture wicking, flame retardancy, anti-static properties, antimicrobial properties, soil-releasability, or any combination thereof.

15. The functionalized polymer of claim 14, wherein the maleimide adduct is present in a wt% of from 0.1 wt% to 25 wt%, based on the weight of the functionalized polymer.

16. The functionalized polymer of claim 14, wherein the physical property is hydrophobicity, and the component comprises an aminosilane, a thiosilane, an alkylamine, a fatty acid amine, or any combination thereof.

17. The functionalized polymer of claim 14, wherein the physical property is durable water repellency and the component comprises a silicon compound, a siloxane compound, a hydrocarbon, a nanoparticle providing a lotus effects, or any combination thereof.

18. The functionalized polymer of claim 14, wherein the physical property is hydrophilicity and the component comprises an amino-terminated polyethylene glycol, a hydroxyterminated polyethylene glycol, a thio-terminated polyethylene glycol, a sulfonated amine, or any combination thereof.

19. The functionalized polymer of claim 14, wherein the physical property is moisture wicking and the component comprises a hydrophilic polymer, polyethylene glycol, polyvinyl alcohol, a hydroscopic agent, a humectant, a salt, a silicone, a surfactant, a microencapsulated phase change material, or any combination thereof.

20. The functionalized polymer of claim 14, wherein the physical property is flame retardancy and the component comprises a phosphorous compound, a phosphate, a triphenyl phosphate, a phosphorous-nitrogen compound, ammonium phosphate, ammonium polyphosphate with pentaerythritol, a nitrogen-based compound, melamine, melamine cyanurate, an intumescent flame retardant, a silicon compound, or any combination thereof.

21. The functionalized polymer of claim 14, wherein the physical property is an anti-static property and the component comprises a quaternary ammonium, a metallic compound, a metallic salt, a metal oxide, a zinc oxide, a hygroscopic agent, glycerol, a humectant, asurfactant, or any combination thereof.

22. The functionalized polymer of claim 14, wherein the physical property is an anti-microbial property and the component comprises a silver-based compound, a quaternary ammonium compound, copper, chitosan, a polyhexamethylene biguanide, or any combination thereof.

23. The functionalized polymer of claim 14, wherein the physical property is soil-releasability and the component comprises a silicone, a polyester resin, a cellulose derivative, a cationic surfactant, a silica nanoparticle, a nanoclay, or any combination thereof.

24. A fiber that comprises the functionalized polymer of any one of claims 1-23.

25. The fiber of claim 24, wherein the fiber is present in an article selected from an a bottle cap, a bottle, cutlery, outdoor apparel, a jacket, pants, footwear, boots, athletic apparel, undergarments, a tent, a backpack, an umbrella, automotive interior material, an awning, outdoor furniture, an electronic device, military clothing, uniforms, a tarpaulin, outdoor covers, curtains, drapes, carpets, table linens, napkins, automotive upholstery, aircraft interior material, public transportation seating material, clean room material, and surface materials.

26. A yarn that comprises the functionalized polymer of any one of claims 1-23.

27. A fabric that comprises the functionalized polymer of any one of claims 1-23.

28. Aplastic that comprises the functionalized polymer of any one of claims 1-23.

29. A molding that comprises the functionalized polymer of any one of claims 1-23.

30. A film that comprises the functionalized polymer of any one of claims 1-23.

31. A single chain polyamide polymer comprising from 0.1 wt% to 25 wt% furan-containing units interspersed therein.

32. The single chain polyamide polymer of claim 31, wherein the single chain polyamide polymer is an aramid.

33. The single chain polyamide polymer of claim 32, wherein the aramid is polyparaphenylene terephthalamide or poly(meta-phenyleneisophthalamide).

34. The single chain polyamide polymer of claim 31, wherein the single chain polyamidepolymer is nylon.

35. A single chain polyimide polymer comprising from 0.1 wt% to 25 wt% furan-containing units interspersed therein.

36. A single chain polyalkylene polymer comprising from 0.1 wt% to 25 wt% furan-containing units interspersed therein.

37. The single chain polyalkylene polymer of claim 36, wherein the single chain polyalkylene polymer is polyethylene, polytetrafluoroethylene, polypropylene, or polyvinylchloride.

38. A single chain polyurethane polymer comprising from 0.1 wt% to 25 wt% furan-containing units interspersed therein.

39. A single chain polyurea polymer comprising from 0.1 wt% to 25 wt% furan-containing units interspersed therein.

40. A single chain biopolymer comprising from 0.1 wt% to 25 wt% furan-containing units interspersed therein, wherein the biopolymer is selected from the group consisting of cellulose, chitosan, lignin, starch, polylactic acid, and rubber.

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