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WO2025064709A1 - Fibres modifiées en surface et articles et leurs procédés de fabrication - Google Patents

Fibres modifiées en surface et articles et leurs procédés de fabrication Download PDF

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Publication number
WO2025064709A1
WO2025064709A1 PCT/US2024/047538 US2024047538W WO2025064709A1 WO 2025064709 A1 WO2025064709 A1 WO 2025064709A1 US 2024047538 W US2024047538 W US 2024047538W WO 2025064709 A1 WO2025064709 A1 WO 2025064709A1
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Prior art keywords
polymer
functionalized polymer
physical property
furan
combination
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WO2025064709A8 (fr
Inventor
Isaac Keene Iverson
Ronald D. Moffitt
Ryan L. Smith
Tanja M. GRUBER
Shane O'TOOLE
Michael J. Simko
Makoto MASUNO
Evgeny Beletskiy
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Origin Materials Operating Inc
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Origin Materials Operating Inc
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Publication of WO2025064709A8 publication Critical patent/WO2025064709A8/fr
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/181—Acids containing aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/333—Polymers modified by chemical after-treatment with organic compounds containing nitrogen
    • C08G65/33331—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing imide group
    • C08G65/33337—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing imide group cyclic

Definitions

  • 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.
  • 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
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the one or more furan-containing units comprises a 2,5- furan dicarboxylic acid residue.
  • the one or more furan-containing units comprises a 2,5-furan dicarboxylate.
  • the one or more furan-containing units comprises a 2, 5 -difuranoate moiety.
  • 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%.
  • a single chain polyamide polymer comprising from 0.1 wt% to 25 wt% furan-containing units interspersed therein.
  • the single chain polyamide polymer is an aramid.
  • the aramid is poly-paraphenylene terephthalamide or poly(meta-phenyleneisophthalamide).
  • the single chain polyamide polymer is nylon.
  • a single chain polyalkylene polymer comprising from 0.1 wt% to 25 wt% furan-containing units interspersed therein.
  • the single chain polyalkylene polymer is polyethylene, polytetrafluoroethylene, polypropylene, or polyvinylchloride.
  • Also disclosed herein is a single chain polyurea polymer comprising from 0.1 wt% to 25 wt% furan-containing units interspersed therein.
  • biopolymer comprising from 0.1 wt% to 25 wt% furan-containing units interspersed therein.
  • the biopolymer is selected from the group consisting of cellulose, chitosan, lignin, starch, polylactic acid, and rubber.
  • 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.
  • the maleimide adduct is present in a wt% of from 0.1 wt% to 25 wt%, based on the weight of the functionalized polymer.
  • the physical property is hydrophobicity, and the component comprises an aminosilane, a thiosilane, an alkylamine, a fatty acid amine, or any combination thereof.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the present disclosure provides for fibers that comprise the functionalized polymer described herein.
  • 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.
  • the present disclosure provides for yams that comprises the functionalized polymer described herein.
  • the present disclosure provides for fabrics that comprises the functionalized polymer described herein.
  • the present disclosure provides for plastics that comprises the functionalized polymer described herein.
  • the present disclosure provides for moldings that comprises the functionalized polymer described herein.
  • PEF Polyethylene furan-2,5-dicarboxylate
  • reaction scheme shows maleic anhydride reacting with PEF
  • 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.
  • the maleic anhydride or maleimide reaction may be implemented with a polyester polymer.
  • 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 a polymer melt.
  • 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.
  • 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.
  • the furan-containing moiety in PEF is capable of reacting in a cycloaddition Diels- Alder reaction with an electron poor alkene (also known as a dienophile).
  • PEF poly(butylene) furanoate
  • 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.).
  • the present approach may also be used with any condensation polymer (e.g., polyesters, nylons, polyurethanes, etc.).
  • 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.
  • 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.
  • 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.
  • the furan-containing moiety is a 2, 5 -difuranoate moiety.
  • the furan-containing moiety is a 2,5-furan dicarboxylic acid residue.
  • the furan-containing moiety is a 2,5-furan dicarboxylate.
  • 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.
  • the dienophile binding group is one of maleimide or bisitaconimide.
  • the functional tail is one or more of an aminosilane, a thiosilane, an alkylamine, a fatty acid amine, a sulfonated amine, or a functionalized silane.
  • Some embodiments of the present approach may take the form of a method for functionalizing a polymer.
  • 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.
  • 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.
  • Some embodiments of the present approach may take the form of a method of forming a dienophile binding group for a Diels-Alder reaction.
  • 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.
  • 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.
  • the compound in which the functionality is hydrophobicity, 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.
  • the compound in which the functionality is durable water repellency, 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.
  • the compound in which the functionality is soil release, 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.
  • the compound in which the functionality is flame retardancy, 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.
  • 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.
  • the compound in which the functionality is anti-static properties, 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.
  • the compound in which the functionality is moisture wicking, 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.
  • the functionality 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.
  • 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.
  • 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.
  • 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.
  • the functionalized polymer is formed into one of a yarn or a fabric.
  • 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.
  • 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.
  • 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.
  • 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.
  • the functionalized polymer fabric is attached to a second fabric material.
  • the functionalized polymer fabric may form the backing of a fabric material.
  • the functionalized polymer fabric may form the face of a fabric material.
  • the functionalized polymer fabric is blended with a second fabric.
  • FIG. 1 illustrates the present approach applied using a PETF co-polymer, and a functional group maleimide.
  • 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.
  • 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).
  • DCM di chloromethane
  • FIG. 4A - FIG. 4B are graphs showing (FIG. 4A) and (FIG. 4B).
  • a polypeptide includes a plurality of polypeptides, including mixtures thereof.
  • 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)
  • PEG-Acid Mal-PEG4-Acid and Mal-PEG12-Acid shown, respectively.
  • PEG-NHS Ester Mal-PEG4-NHS Ester and Mal-PEG12-NHS Ester shown, respectively
  • maleimide-based linkers [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:
  • the side group may be selected for a desired property, as discussed herein.
  • phosphorus-rich and/or nitrogen-rich side groups may be selected to provide a flame- retardant effect.
  • the functional tail could be a long chain (C8-C18) aliphatic tail.
  • a molecule such as laurel amine (C12 aliphatic tail) could be reacted with maleic anhydride to create the corresponding C12 N-maleimide.
  • aminopropyl triethoxy silane could be reacted with maleic anhydride to form the corresponding triethoxylsilane functionalized N-substituted maleimide.
  • 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.
  • 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.
  • Synthetic fibers are not easy to functionalize with reactive (covalent) chemical agents compared with natural fibers.
  • 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.).
  • many of these effects can be washed off with laundry cycles / aqueous cleaning.
  • Polymers that make excellent synthetic textiles like nylon or PET can normally react at only their 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.
  • 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.
  • FDCA 2,5-furan dicarboxylic acid
  • 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.
  • 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.
  • 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.
  • 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.
  • the PETF is aromatized.
  • 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.
  • the DA dienophile is applied at a temperature at or above ambient. In some embodiments, the rate of reaction will increase as more thermal energy is applied to the reaction.
  • 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.
  • the present approach may be used in a wide variety of embodiments.
  • 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.
  • 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.
  • a hydrophobic side chain or a hydrophilic side chain may be added to affect the hand or stainability of the fibers (or soil release).
  • 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.
  • flame retardants may be added.
  • 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.
  • 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.
  • the present approach may be used to enable bis-reactivity (two maleimides in the additive) for cross-linking or branching polymer chains.
  • 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.
  • the cross-linking or branching will be expected to produce pronounced effects on polymer properties for injection molded or rigid applications.
  • thermosetting unsaturated polyesters may be exploited in thermosetting unsaturated polyesters.
  • these reaction pathways with cycloaddition can be useful in unsaturated polyester resins, such as those used in the fiberglass markets.
  • FDCA may replace some terephthalic acid in lower molecular weight oligomers/polymers, there could be enhanced thermosetting possibilities depending on specific curing regimes.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • PEGMEM maleimide
  • 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.
  • sulfonated amines and functionalized (-NH2, -OH, or -SH) silanes for PEF bottles with improved stress crack resistance: sulfonated amines and functionalized (-NH2, -OH, or -SH) silanes.
  • sulfonated amines and functionalized (-NH2, -OH, or -SH) silanes for improved self-adhesion in furan-containing polymers: bis-maleimide and multi-maleimide compounds are used.
  • monomaleimide with one or more telechelic end groups demonstrating affinity or chemical reactivity (covalent bonding) with the dissimilar polymer surface are used.
  • Stain-resistant fabrics for enhancing imperviousness to inks, dyes, blood, mustard, ketchup and other condiments, berries, fruits, etc.
  • a compound may be converted to a dienophile for use with a clickable polymer as described herein.
  • primary amine compounds are used due to the ease of converting to the corresponding maleimide.
  • 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.
  • a nanoparticle on a fiber provides nano-roughness similar to the way nature produces extreme hydrophobicity on leaves, such as the famous lotus leaf.
  • 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.
  • such fibers are reacted with a trialkoxysilane tail group which then bonds with metal hydroxide nanoparticles added in a subsequent step.
  • 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.
  • this treatment should be durable to withstand standard fabric care and washing for garment maintenance.
  • 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.
  • 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.
  • 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.
  • 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.
  • compounds for providing antimicrobial functionality include, but are not limited to, silver-based compounds, quaternary ammonium compounds, copper, chitosan, and polyhexamethylene biguanide.
  • knitted or woven fabrics are prepared using the present approach.
  • 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 the same amount of moles of terephthalic acid residues in said polymer) are synthesized and used on one or more desired surfaces of an article.
  • the fabric material has a front surface or face, and a rear surface or backing.
  • 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.
  • 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.
  • 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.
  • the face and the backing may contain at least a portion of PETF2 fibers.
  • 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.
  • the present approach may be used to incorporate a durable water repellent added to a clickable polymer as described herein.
  • the resulting fabric effectively keeps moisture from being absorbed into the cotton and improves the comfort and wearability of the garment.
  • 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 end spinning). 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.
  • the clickable polymers described herein allow for fiber-to-fiber cross-linking, giving the softer yarn higher yarn strength.
  • 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.
  • the present approach may be employed to impart soil repellent finishes on, e.g., carpets, rugs, and other fibers.
  • 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.
  • 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.
  • the desired strength of the surface modification and the economic viability are the largest factors for determining a composition suitable for a particular embodiment.
  • the fibers are further treated with silica-based particles that can covalently attach to form a siloxane bridge to the grafted maleimide fiber surface.
  • enzymes may be bound to PEF fibers and non-woven materials for a variety of fabric applications.
  • 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.
  • an enzyme having perhydrolysis activity for the in-situ production of peracids may be bound to a fabric.
  • peracids are effective antimicrobial agents and bleaching agents.
  • one application is in-situ sterilization and bleaching of white fabric.
  • 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, tarpaulins and covers, medical apparel.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the present disclosure provides functionalizable polymer compositions 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.
  • the furan- containing moiety is a 2,5-furan dicarboxylic acid moiety.
  • the furan- containing moiety is a 2,5-furan dicarboxylate.
  • the furan-containing moiety is a 2, 5 -difuranoate moiety.
  • 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.
  • the dienophile binding group is one of maleimide or bisitaconimide.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the functionalized polymer is formed into one of a yarn and a fabric.
  • the present disclosure provides for an article comprising a functionalized polymer disclosed herein.
  • 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.
  • 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 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; 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.
  • 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.
  • 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.
  • the functionalized polymer fabric is attached to a second fabric material.
  • the functionalized polymer fabric forms the backing of a fabric material.
  • the functionalized polymer fabric forms the face of a fabric material.
  • the functionalized polymer fabric is blended with a second fabric.
  • 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.
  • scouring agents solutions can further contain a surfactant, an alkali agent, a chelating agent, a dispersant, a wetting agent, or any combination thereof.
  • the fabric is rinsed with water after the scouring process and dried.
  • any solvent is contemplated for solubilizing the maleimide adduct.
  • the solvent is water.
  • 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%.
  • 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.
  • 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.).
  • 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
  • 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.
  • 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.).
  • 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
  • one or more functional properties such as hydrophilicity, hydrophobicity, anti-static properties, anti-microbial properties, anti-soil properties, oleophobicity, etc.
  • the solvent of the solution can be any solvent capable of solvating the maleimide adduct of choice.
  • the solvent is water.
  • the solution contains the maleimide adduct at concentrations > 0.01 wt%.
  • 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.
  • 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.
  • the temperature of the solution during treatment of the fabric ranges from 120 °C to 150 °C.
  • 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.
  • a target wet pick up of the fabric ranges from 50 wt% to 100 wt%.
  • 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.
  • 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.).
  • embodiments described herein provides for numerous methods for functionalizing polymer materials, depending on the selection and use of a maleimide adduct as the functional species having a particular functional property.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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 R 1 group), that is chosen to impart performance on the target polymer/fiber.
  • the R 1 group is referred to herein as a functional tail.
  • 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.
  • 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 fabrics for 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.
  • 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.
  • DI deionized water
  • the soaked fabrics were dewatered by hand squeezing, and the resulted wet fabric had a 110-120 % mass gain.
  • 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).”
  • 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).”
  • 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).”
  • 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.
  • IPA aqueous iso- propanol
  • 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.
  • 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.
  • 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.
  • 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.
  • Red Dye 40 also known as “Allura Red AC”
  • LAB Color meter to measure the color space of the stained and unstained ends of each fabric.
  • 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.
  • the following film strips can be used (based on wt% furanoate incorporated therein): (i) PETF 10%; (ii) PETF30%; and (iii) a PET Control.
  • 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:

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Abstract

L'invention concerne des polymères qui peuvent être mis à réagir avec un produit d'addition maléimide contenant un composant afin de produire un polymère fonctionnalisé. Le polymère fonctionnalisé peut être conçu pour conférer une propriété physique spécifique, telle que l'hydrophobie, l'hydrophilie et autres.
PCT/US2024/047538 2023-09-19 2024-09-19 Fibres modifiées en surface et articles et leurs procédés de fabrication Pending WO2025064709A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040102585A1 (en) * 2000-08-04 2004-05-27 Steinmetz Alan Lawrence Graft polymers or graft copolymers
US20150203619A1 (en) * 2011-06-22 2015-07-23 Byk-Chemie Gmbh Surface-active comb copolymers
US20200369685A1 (en) * 2019-05-20 2020-11-26 Massachusetts Institute Of Technology Boronic ester prodrugs and uses thereof
US20210230781A1 (en) * 2018-06-08 2021-07-29 Cummins Filtration Ip, Inc. Cross-linked non-wovens produced by melt blowing reversible polymer networks

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040102585A1 (en) * 2000-08-04 2004-05-27 Steinmetz Alan Lawrence Graft polymers or graft copolymers
US20150203619A1 (en) * 2011-06-22 2015-07-23 Byk-Chemie Gmbh Surface-active comb copolymers
US20210230781A1 (en) * 2018-06-08 2021-07-29 Cummins Filtration Ip, Inc. Cross-linked non-wovens produced by melt blowing reversible polymer networks
US20200369685A1 (en) * 2019-05-20 2020-11-26 Massachusetts Institute Of Technology Boronic ester prodrugs and uses thereof

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