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WO2025059659A1 - Matériaux et procédés pour formes de matériau à l'aide de réseaux adaptables énamine-covalents - Google Patents

Matériaux et procédés pour formes de matériau à l'aide de réseaux adaptables énamine-covalents Download PDF

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WO2025059659A1
WO2025059659A1 PCT/US2024/046928 US2024046928W WO2025059659A1 WO 2025059659 A1 WO2025059659 A1 WO 2025059659A1 US 2024046928 W US2024046928 W US 2024046928W WO 2025059659 A1 WO2025059659 A1 WO 2025059659A1
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adhesive
ecan
diamine
polymer
condensation polymer
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WO2025059659A9 (fr
Inventor
Durva NAIK
Deepti GOPALAKRISHNAN
Kezi CHENG
Karan Vivek DIKSHIT
Peter R. CHRISTENSEN
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Flo Materials Inc
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Flo Materials Inc
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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
    • C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen

Definitions

  • a polymer composition platform with a wide range of architectures and properties is herein described.
  • the composition utilizes dynamic covalent chemistry to form polymer compositions that may be chemically recycled to reusable constituents at end of life.
  • a composition as described maybe suitable for use as a fiber, coating, sheet, adhesive, and/or for varied other applications.
  • FIG. 1 is a generalized ECAN polymer structure.
  • FIG. 2 is a representation of different embodiments of an ECAN polymer structure.
  • FIG. 3A is a representation of exemplary amines that may act as components to an ECAN polymer structure.
  • FIG. 3B is a representation of embodiments of branched and linear polyamines that may act as components to an ECAN polymer structure.
  • FIGS. 4A-C are representations of potential triamine components to an ECAN polymer structure.
  • FIGS. 5A-E are representations of potential triamine components to an ECAN polymer structure.
  • FIGS. 6A and 6B are representations of potential diamine components to an ECAN polymer structure.
  • FIG. 7 is a chart containing representations of several chemical structures which may act as components or additives to an ECAN polymer structure.
  • FIG. 8 is a graph showing the relationship between MBC concentration and glass transition temperature in an ECAN polymer structure.
  • FIGS. 9A-C are examples of ECAN polymer fiber structures.
  • FIG. 10A is a stress/strain graph for representative samples of ECAN fiber structures.
  • FIG. 10B shows graphs depicting tensile stress for two different polyamine systems.
  • FIGS. 11A-C are photos of embodiments of elastomeric ECAN polymer.
  • FIG. 11D is a stress strain graph for elastomer embodiments.
  • FIG. 12 is a graph showing the relationship between the force used and the displacement of an ECAN -based pressure-sensitive adhesive.
  • FIGS.13-15 are photographs of a peel-testing apparatus and testing method used to measure properties of adhesive ECAN polymer structures.
  • FIG. 16 is a depiction of the lifecycle of an ECAN polymer adhesive.
  • FIG. 17 illustrates the cyclical nature of forming and depolymerizing keto amine condensate polymers.
  • FIG. 18 is a representation of the circular material lifecycle enabled by use of ECAN/RECAN polymer structures.
  • FIG. 19 is a representation of a potential multi-form ECAN-based product.
  • FIGS. 20A and 20B is a graph depicting the percentage yield of recycling ECAN
  • FIGS. 21A-E are photographs of the process of recycling ECAN polymer structures in the presence of other, non-ECAN materials.
  • FIG. 22A is a copy of the NMR spectra of recovered triketones in mixed plastic systems
  • FIG. 22B is a copy of the NMR spectra of recovered triketones in mixed metal systems
  • Enamine-Covalent Adaptable Networks (ECANs) and Recyclable Enamine- Covalent Adaptable Networks (RECANs) provide new materials that facilitate chemical recycling and can be adapted to a variety of end products.
  • ECANs Enamine-Covalent Adaptable Networks
  • RECANs Recyclable Enamine- Covalent Adaptable Networks
  • ECAN materials can be created using polyketones and polyamines through solvent polymerization, ball milling or reactive extrusion or other processes.
  • ECANs act as thermally activated dynamic covalent networks in that they can flow at high temperatures and act like thermosets at low temperatures.
  • ECAN materials may be tunable for various material forms and applications. Additionally, ECAN materials may be recyclable where recovery of component monomers is possible to create new RECAN networks, that can be the same or different. ECAN materials can be broken down to the monomers from which they are comprised. These recycled monomers can then be re-polymerized to produce the same or different polymer materials. As used herein, dynamic covalent chemistry means that polymers can be formed and then taken apart back into their original components. This allows the ECAN materials to enter a circular cycle whereby the same monomers are used again and again to produce the same, or different, polymers.
  • a circular condensation polymer is a polymer that is formed via a condensation reaction and can be chemically depolymerized to produce at least one monomer from which it was made.
  • Circular condensation polymers can include keto amine condensate(s).
  • the versatile material platform of ECAN materials in combination with mixed waste, efficient high yield recycling may enable access to new compositions that can increase recycling rates for multi material products.
  • a single product such as a running shoe, may include fibers (fabric), one or more adhesives and an elastomer. If the various components of the product are formed using ECAN materials, then the product can be de-polymerized, without physical deconstruction, to component monomers such as triketones and polyamines with multiplicity of primary and/ or secondary amino groups. Background information is provided in PCT application PCT/US2023/066303, which is incorporated in its entirety by reference herein.
  • ECAN materials include combinations of polyamines, which may be diamines, triamines, tetraamines, or multifunctional amines. Selection of the type (s) and concentrations of polyamines with respect to polyketones (substances with two, three, four, or more keto groups) maybe used to create a wide range of possible material properties with far-reaching applications.
  • triketones of the ECAN material may be cross-linked using triamines to form a high-performance plastic material.
  • the ECAN material may include a diamine backbone/chain extension that links two triketones and bonds to amino groups of two triamines. Selection of the types and concentration of diamine and triamine with respect to triketones used to tune or customize material properties.
  • a keto amine condensate is the product of the reaction of a ketone with either a primary or secondary amine, or both, and can include both enamines and/or imines.
  • a composition of an ECAN may comprise a triketone and one or more polyamines.
  • Different possible component molecules may be selectively used for Ri, R2, and R3, which functions to tune the resulting ECAN material.
  • the options for Ri, R2, and R3 may vary depending on tuned properties and desired form. This may enable a variety of possibilities for Ri, R2, and R3, of which a limited example is shown in FIG. 2.
  • One structure variation of an ECAN polymer comprises a plurality of triketones, a plurality of triamines and a plurality of diamines, represented by the formula shown in FIG.
  • the system may have at least one polyketone and the polyketone(s) can be a triketone.
  • Triketones function as one of the primary (i.e., monomer) building blocks of the ECAN, wherein triketones and polyamines form enamine and/ or imine bonds. In FIG. 1, enamine bonds are indicated by the dashed circles.
  • the triketone can function as a rigid or flexible component in the ECAN component.
  • the at least one triketone may comprise a linear or cyclic triketone. Generally, the at least one triketone may comprise any triketone that can form an enamine or imine bond with a polyamine.
  • triketones include: cyclopropanetrione, cyanuric acid, croconic acid, nihydrine, triuret, mesoxalic acid, dioxosuccinic acid, and/or triketopentane.
  • triketones include the product obtained from the condensation of 1,3-diketones and its derivatives, including acetyl acetone and derivatives, 1,3-cyclohexane dione, 5,5-dimethyl-i,3-cyclohexane dione (dimedone), barbituric acid and derivatives, beta-keto lactones and derivatives condensed with aliphatic acids; notably dicarboxylic acids such as adipic acid (TK6), suberic acid (TK8), and sebacic acid ((i,io-Decanedione,i,io-bis(2-hydroxy-4,4-dimethyl-6-oxo-i- cyclohexes-i-yl) TK10), or with cyclic acids, such as diphenyltriketone, diphenyltetraketone, 2,2'-terephthaloylbis(5,5-dimethylcyclohexane-i,3- dione) (TK-13), 2,
  • Some embodiments can employ one or more triketones that include heteroatoms. Triketones with heteroatoms may change the rate of hydrolysis and depolymerization conditions such as time and temperature. The depolymerization rate may be crucial and beneficial for the selective recovery of the monomers.
  • heteroatom triketone examples include 3,3'-(i,io- dihydroxydecane-i,io-diyl)bis(6,6-dimethyldihydro-2H-pyran2,4(3H)-dione), 5, 5'-decanedioylbis(2,2-dimethyl-i,3-dioxane-4, 6-dione), 5,5'-(i,io- dihydroxydecane-i,io-diylidene)bis(i,3-dimethylpyrimidine2,4,6(iH,3H,5H)- trione).
  • at least one triketone is a P-triketone.
  • at least one triketone is TK6.
  • at least one triketone is TK10.
  • at least one triketone comprises a TK10 and TK6 mix.
  • Table 1 below provides the product code as used herein for some diacids used to obtain select triketones. Note that some of the compounds are listed as the condensation product of a triketone and an aliphatic acid.
  • the triketone reacts with a diamine to form a more extended backbone, also referred to as a chain extension.
  • the triamine reacts with the triketone to form a cross-linked polymer system.
  • a cross-linked polymer system characterizes a network of polymer chains that are chemically bonded together through crosslinking reactions.
  • the triketones react with the triamines to form covalent bonds between the polymer chains, creating a three- dimensional network structure. This cross-linking may impact the overall mechanical strength and stability of the ECAN material.
  • the triketones may be the same or maybe different.
  • the amine structure (e.g., of the diamines, triamine, tetraamines, or multifunctional amines) may have a wide range of options. In particular, selection of the type and concentration of diamines and triamines used with the ECAN material maybe used in customizing material properties.
  • the system may have at least one polyamine.
  • Polyamine is an organic compound having two or more amino groups. Polyamines function as one of the primary (i.e., monomer) building blocks of ECAN material, wherein polyketones and polyamines form enamine and/ or imine bonds.
  • the at least one polyamine may comprise any polyamine that can form a enamine or an imine bond with triketone.
  • Polyamines used herein, including di and triamines can have, in various embodiments, molecular weights of less than 200, less than 500, less than 1000, less than 2000, less than 3000, greater than 200, greater than 500, greater than 1000, greater than 2000 or greater than 3000 g/mol.
  • polyamines examples include: aliphatic, cyclo aliphatic and/or aromatic, linear and/or branched polyamines such as triamine, tetraamine spermidine, tri-functional primary amines (Hexatran), carbolines, polyethertriamines, polyoxylpropylenetriamine, spermine, putrescine, cadaverine, ornithine decarboxylase (ODC), diethylenetriamine (DETA), 4,4'- methylbiscyclohexylamine (MBC) pentamethyldiethylenetriamine, triethylenetetramine (TETA), tetraethylenepentamine (TEPA), pentaethylenehexamine (PEHA), 1,4,7-triazacyclononane, cyclen, cyclam, tris(2-aminoethyl)amine (TREN) and tris(aminomethyl)ethane.
  • ODC diethylenetriamine
  • DETA diethylenetriamine
  • MMC 4,4'- methylbiscycl
  • Diamines can be any diamine containing molecule. They could be small molecules with aliphatic or aromatic groups. They can also contain long-chain polyether or polyethylene, or polybutadienes backbones with variable molecular weights. Choice of a specific diamine structure affects the soft segment characteristics of the ECAN polymers, contributing to flexibility, and durability.
  • Representative examples may include, but are not limited to: - diaminotoluene, dithioaniline, oxydinaline, methylene dianiline, phenylene dioxydianiline, phenylene diamine, hexamethylene diamine, octamethyelene diamine, decamethyelene diamine, isophorone diamine, diaminoethoxy ethane, polyether amines such as the Jeffamine ED, and D series, e.g., ED900, D230, D400, D2000, D4000, JTHF100, JTHF170 amino terminated polysiloxanes, and/or amino terminated polybutadiene.
  • bio-based diacids and polyamines can be employed.
  • linear aliphatic polyamines having 100% renewable carbon content such as Priamine (Cargill) dimer diamines can be used.
  • the bio-based component can comprise more than 10, more than 20, more than 30, more than 40 or more than 50% of the ECAN material by mass
  • Table 2 below provides a list of some of the polyamines that can be used in ECAN systems. The list includes both chemical names and CAS Number.
  • Polyamines also include secondary amines, such as Bis(2-aminopropyl)amine, N,N'-Dimethyl-i,3-propanediamine, N-Methyl-i,3-propanediamine,
  • Triethylenetetramine Diethylenetriamine, N,N'-Dimethyl-1,2- phenylenediamine, N,N,N'-Trimethylethylenediamine, 2,3-Dihydro-iH- imidazo[i,2-a]imidazole and 4-(Piperidin-4-yl)pyridine.
  • FIG. 3 A provides structures for exemplary aliphatic, polyether, aromatic and cycloaliphatic polyamines.
  • FIG. 3B provides examples of branched and linear primary and secondary polyamines.
  • FIGS. 4A-4C provide structures for exemplary polyether triamines.
  • FIGS. 5A-5E provide examples of additional triamines useful with ECANs.
  • FIGS. 6A and 6B provide examples of aromatic and cycloaliphatic diamines.
  • the ECAN material properties may be tuned or adjusted by using long chain di- and triamines, aromatic triamines, alkyl triamines, cycloaliphatic diamines, aromatic diamines, short di- and triamines, and/or other polyamine and triketone combinations.
  • the diamine functions to establish chain extension.
  • the selection of the diamine (and/or other polyamines including di, tri, and tetra amines) may thereby function to influence backbone rigidity.
  • the chain extension of the diamine can be various lengths.
  • the stiffness of the ECAN in a bulk form is inversely proportional to the triamines and diamine chain extension length.
  • Diamines can be a combination of aliphatic or aromatic groups.
  • the molecular weight of the diamines has a large role to play in the tuning of chemical and physical properties of ECAN networks.
  • Selection of a short-chain diamine may function to promote a more rigid backbone. Selection of a long-chain diamine with polymeric linkages between the amines may function to create a soft segment.
  • short-chain diamines have a molecular weight of less than 1000 while long chain diamines have a molecular weight of greater than 1000.
  • the diamines may be aliphatic diamines or aromatic diamines.
  • At least one type of triamine may be included in the network for crosslinking.
  • the triamines can be all the same or there can be multiple triamines (e.g., combining aliphatic triamines with aromatic triamines or short or long triamines).
  • an ECAN material may dictate the choice of triamines. While triamines enable cross-linking, the structural diversity of triamines affects the strength, flexibility and durability of the final ECAN.
  • an elastomeric ECAN may have long-chain triamines in addition to short-chain triamines, to enable a higher density of soft segments in the ECAN polymer, making it more elastomeric.
  • Various embodiments can employ triamines such as: Tris (2-aminoethyl) amine, Tris (2-aminopropyl) amine, Pentane-1,3,5 triamine, Benzene triamines, Melamine, Triphenylene triamine, Tris (4-aminophenyl) amine, i,3,5-Tris(4-aminophenoxy)benzene, i,3,5-Tris(4-aminophenyl)benzene.
  • exemplary multiamines may include but are not limited to branched poly (ethylene imine), Cyclam, and/ or Cyclen.
  • the triamines may be selected in part to control the nature of cross-linking. This may in turn be used in controlling tensile strength.
  • the triamines have chain length, wherein tensile strength of the ECAN in bulk form is inversely proportional to the triamine chain length. Selection of a short-chain triamine may function to promote a strong but brittle ECAN material. Selection of a long-chain triamine may function to make more elastomeric materials with lower tensile strength but longer elongation.
  • Diamines can include Diaminotoluene, Dithioaniline, Oxydinaline, Methylene dianiline, Phenylene dioxydianiline, Phenylene diamine, hexamethylene diamine, octamethyelene diamine, decamethyelene diamine, isophorone diamine, diaminoethoxy ethane, JTHF100, JTHF170 amino terminated polysiloxanes, amino terminated polybutadiene, DET, HMDA, MDA, ODA, ED900, D230, D400, D2000, D4000, and/or RFD-270, and some examples of potential triamines can include T403, T3000, T5000, and/or TAPB.
  • Multifunctional amines are molecules containing 2 or more primary or secondary amines. Such molecules may provide multiple cross-linking sites in close proximity. Depending on the cross-link density these amines can contribute to higher strength of material. Choosing a tetra or greater functional amines, provides a higher density of cross-linking sites, leading to a tougher material that could fit in newer form factors like composites as well as existing form factors like sheets.
  • Each system e.g., diamines and triamines
  • the amines can be selected or otherwise configured with different numbers of repeating units or building blocks. Such variability in chain lengths may provide flexibility in the designating properties of resulting ECAN materials.
  • ECAN material may use solid state mixing or liquid state mixing.
  • polyamines are available as liquids and triketones are available typically as solids at room temperature; but both these compounds may be generally found and/or acquired in a state (e.g., liquid, gas, solid).
  • a state e.g., liquid, gas, solid.
  • the starting material is initially converted into the appropriate state using standard available techniques. For example, for liquid-liquid mixing formulation, a triketone powder may be initially melted prior to mixing.
  • a first method for ECAN based plastic formation comprises: blending the additive components with one, or both, monomer components; and liquidliquid mixing of the ECAN monomer components. This method may be particularly useful for implementations that incorporate small molecule additives. Additionally, this method may result in a high degree of mixing of additive components as compared to other methods, such that a homogeneous mixture of polymer and additive can be controllably achieved. [0059] I n one variation, the method may include promoting ECAN polymerization through ball milling.
  • the system and method may provide a number of potential benefits.
  • the system and method are not limited to always providing such benefits and are presented only as exemplary representations for how the system and method may be put to use.
  • the list of benefits is not intended to be exhaustive and other benefits may additionally or alternatively exist.
  • ECAN materials may have monomers selected to produce a targeted material form factor with material properties tuned for particular material form applications.
  • a variety of different material forms may be achievable. Controlling the concentration ratios and amine type variations for diamines and triamine components (and/ or other polyamine components), the material properties of an ECAN material can be modified. For example, increasing the proportion of a particular amine type can lead to changes in the rigidity, flexibility, or strength of the resulting ECAN material. Thus, tailoring the concentration allows for the customization of the final properties based on the desired application.
  • Possible form factors may include, but are not limited to: sheets, films, fibers, foams, adhesives, coatings, and/or sealants.
  • compositions disclosed herein may refer directly to elastomers, sheets, films, fibers, foams, adhesives, coatings, or sealants, however such examples and compositions may be applicable to any form of ECAN, including elastomers, sheets, films, fibers, foams, adhesives, coatings, and/or sealants.
  • ECAN materials can serve as a more recyclable plastic.
  • Multi-plastic products composing the ECAN materials may be recovered and reused in formation of new RECAN plastics.
  • a material used as foam in a shoe can be recycled and reused as a coating in automotive use case.
  • ECAN materials may enable circular material use. ECAN materials may enable reclaiming materials from waste stream from one material form to produce material of the same and/or different forms.
  • FIG. 7 A chart providing examples of triketones, polyamines, plasticizers, solvents, and colorants that can be used in various ECAN systems is provided in FIG. 7. These examples are not exhaustive and are provided to show the variety of materials that can be employed.
  • Colorants include both dyes and pigments. Additional additives include antioxidants, UV absorbers, conductivity enhancers, viscosity modifiers, rheology modifiers.
  • ECAN polymers can provide chemically recyclable alternatives to non- chemically recyclable polymers.
  • ECANs can replicate the properties of cellulose acetate in a form that be chemically recycled to its monomer constituents.
  • the ECAN materials disclosed herein can exhibit various properties equal to, or exceeding, the properties of conventional polymers such as cellulose acetate. These properties include, for instance, tensile strength, elongation, modulus, viscoelastic properties, glass transition temperature and thermal processing and degradation temperatures.
  • a cured ECAN sheet may have a tensile strength at break of greater than 10, greater than 20, greater than 25 or greater than 30 MPa.
  • elongation at break (strain %) may be greater than 5, 10, 25, greater than 50, or greater than 75%.
  • Young’s modulus may be greater than 0.1, greater than 0.5, greater than 1.0 or greater than 1.5 GPa.
  • Glass transition temperature, Tg can be above 30, 50, above 75, above 85 , above 95, above no, or above 12O°C.
  • the temperature for workable thermal processing can be less than 200 or less than 15O°C.
  • ECAN materials can provide a chemically recyclable substitute for cellulose acetate that can accept additives such as plasticizers and colorants, as are used in the eyewear industry.
  • the frames can be produced from an ECAN material by, for example, compression molding, extrusion or reactive extrusion.
  • ECANs may be used in the production of a wide variety of material forms potentially including but not limited to sheets/fihns, fibers, foams, elastomers, adhesives, sealants, coatings and/ or multimaterial forms.
  • the ECAN material as discussed may be tuned to different material properties.
  • ECAN 1 may include 100 mol% TREN.
  • ECAN 1.2 includes 100 mol% T403.
  • ECAN 1.3 may include 5 mol% D230 and 95 mol% T403, and may optionally include a coloring agent, which may be a dye or a pigment.
  • a variation containing an aromatic triamine may include 1-30 mol% of a triamine, some examples of which may be TAPB, TAP A, and/or TPB, 10-20 mol% of a diamine, some examples of which may be MDA, D2000, and/or ED900, and 50-89 mol% of a triamine, such as TREN and/or T403.
  • a combination of TREN and T403 maybe used as triamines in the composition.
  • the ratio of TREN to T403 may preferably be 50-90 mol% TREN and 10-50 mol% T403, 70 mol% TREN and 30 mol% T403.
  • a small additive of diamines such as 5%, 7.5%, or 10% of weight maybe added to the triamine composition.
  • Such additive maybe D2000, IPDA, HMDA or THF170, JTHF, or another diamine, and the addition of such diamines may have effects on the Tg, yield stress, and elongation % of the composition.
  • a composition may also include additives.
  • additives may comprise monoamine additives, which may affect material properties of the composition.
  • An additive of 1 mol% may comprise monoamines including but not limited to APTS, BzA, PEA, M-600, M-1000, M2095, and/or M-3085.
  • additives may comprise dyes, such as disperse dyes, pigments, such as inorganic pigments, and/or antioxidants, such as HALS.
  • Additives may be present alone or together in the composition, and may comprise 1%, 2%, 2.5%, 5%, 10%, or another amount by weight of the composition.
  • Table 8 shows exemplary ECAN formulations with TREN and T403 as triamine combinations with a polyether diamine along with additives and colorants.
  • Table 9 shows colors do not significantly change the mechanical properties of ECANs.
  • the tabulated properties of several compositions containing dyes, pigments, and antioxidant additives are described in the tables below:
  • any general type of additive may be incorporated that will provide desired properties for either the precursor product or the end-product.
  • additive types include heat stabilizers, light stabilizers, plasticizers, rheology modifiers, flame retardants, conductivity enhancers, anti-static additives and colorants. These and/ or other additive types may be incorporated as desired by implementation.
  • the at least one additive may include heat (and/or light) stabilizers. Heat/light stabilizers may function as a precursor additive that enables mixing of system components while preventing the ECAN system from undesired breakdown or decomposition during formation and processing. For example, heated mixing may enable formation of the ECAN system using reactive extrusion.
  • heat/light stabilizers may enable ECAN formation using other techniques. Additionally or alternatively, heat/light stabilizers may controllably improve the heat/light sensitivity of the end-product. Additionally or alternatively, heat/light stabilizers may prevent (or reduce) damage (usually through oxidation) to the polymer during precursor processing and/ or for the end-product. Examples of heat/light stabilizers include: hindered organo-phosphites and hindered amines (HALS) and others.
  • the at least one additive may include plasticizers. Plasticizers may function to provide the desired material properties to the final end-product.
  • plasticizers may change thermomechanical properties of the system such as: rigidity, density, glass transition temperature, melting temperature, storage modulus, loss modulus, elastic modulus, tensile modulus, hardness, gel fraction, crosslink density, luster, opacity, refractive index, tensile strength, impact resistance, thermal conductivity, electrical conductivity, etc.
  • plasticizers may provide a high mechanical integrity, while decreasing brittleness, enabling the end-product to be flexible, pliable, and processable. This may enable the final ECAN end-product to be shaped using industry standard techniques (e.g., compression molding, CNC machining, extrusion, melt spinning, injection molding, etc.).
  • the desired "plasticity" of the end-product may include blending of one, or more, non-reactive small molecules.
  • plasticizers include: citrates (triethyl citrate, acetyl triethyl citrate, acetyl tributyl citrate), phthalates (dimethyl phthalate, diethyl phthalate, dibutyl phthalate, butyl benzyl phthalate), trimellitates (trimethyl trimellitate, triethyl trimellitate and tributyl trimellitate), esters of orthophosphoric acid (triphenyl phosphate, tricresyl phosphate, ethylhexyl diphenyl phosphate, isodecyl diphenyl phosphate), benzoates (diethylene glycol dibenzoate, dipropylene glycol dibenzoate), adipates (dimethyl adipate), tartrates, oleates, sebacates, azelates,
  • plasticizers A list of exemplary plasticizers is provided in Table 10, along with their structures. Different ECAN systems can use different types and amounts of plasticizers. In some cases, the plasticizer can be added to the ECAN in amounts, wt/wt, of o.oi to 0.1%, o.i to 1%, o.i to 2% or 1 to 5%.
  • Plasticizers may also be or include colorants, excess short chain monomers (e.g., excess amines that are not fully crosslinked), and/ or reactive diluents such as difunctional polyetheramine.
  • colorants such as 1% of reactive red dye
  • a solvent based method for adding plasticizers may include a formulation process comprising: providing ig triketone (e.g., TK-6, TK-10); adding compatible solvent (e.g., Chloroform, DMF or DCM) to triketone; heating (e g., heating between 9O-2OO°C) and stirring or mixing to fully dissolve; then adding desired plasticizer (e.g., 0.1-25% w/w TEC) to mixture, and adding polyamine with excess amine to triketone (e.g., o.24mL of TREN) ; processing with vacuum oven (e.g., at 80C at 2ohrs); and pressing at ⁇ i.ig into desired shape.
  • ig triketone e.g., TK-6, TK-10
  • compatible solvent e.g., Chloroform, DMF or DCM
  • heating e.g., heating between 9O-2OO°C
  • desired plasticizer e.g. 0.1-25% w/w TEC
  • an ECAN variation suitable for melt spinning fibers may include 10-30 Mol% of at least one cycloaliphatic diamine; 1-50% Mol% of at least one long chain triamine >iooog/mol; 1-50 Mol% of at least one aromatic triamine (e.g., TAPB), and at least one triketone.
  • ECAN -based elastomeric polymer may be created that can be melt-spun into fibers in the 12O-I6O°C range.
  • FIGS. 8A-8C are copies of photographs that show various stages of fiber production.
  • an ECAN may include at least one triketone; 4O-8oMol% of at least one short chain triamine having a molecular weight less than 500 g/Mol; and 2O-6oMol% of at least one long chain triamine having a molecular weight greater than looog/Mol.
  • a structural adhesive (high Tg rigid at room temperature) ECAN may include at least one triketone; 20-75 Mol% of at least one aromatic triamine; and 25-80 Mol% of at least one short chain polyether triamine. In another variation, it may include at least one cycloaliphatic diamine; at least one short chain polyether triamine; In an adhesive material form, a pressure sensitive adhesive ECAN may include at least one triketone; at least one long chain aliphatic, aromatic triamine, and at least one long chain polyether triamine.
  • a set of differing ECAN material forms may be used in combination to create a product comprised of multiple material forms but made of a ECAN material.
  • a system and method described herein for multi-form products may function to create a mono-material product comprised of two or more material forms made of ECAN material. In other words, a product may be derived from the same monomers despite being produced into multiple material forms, each with differing material properties.
  • a resulting system may include a product component of two or more interfacing material surfaces made of a ECAN material, wherein the two material surfaces maybe ECAN materials distinctly tuned with differing material properties.
  • the two or more material surfaces are preferably surfaces of ECAN materials of one or more material forms.
  • the material forms may be specially tuned and produced for different material properties.
  • one material maybe a sheet made of ECAN material and a second material may be a rubber made of ECAN material.
  • a third material can be the adhesive between the sheet and rubber.
  • a product may be formed from multiple material forms such as sheets/films, fibers, elastomers, foams, adhesives, sealants, coatings and/or multimaterial forms.
  • a method for production may include interfacing a material surface of the first ECAN material to a material surface of the second ECAN material. More specifically, the method may include forming a first ECAN material of a first form, forming at least a second ECAN material of a second form, interfacing a material surface of the first ECAN material to a material surface of the second ECAN material.
  • a shoe By interfacing multiple different ECAN materials highly complex products may be produced. As shown in FIG. 12, a shoe may serve as a highly complex product involving the interfacing of multiple material forms, but which could all be achievable through a mono-material ECAN production and recycling process.
  • ECANs can allow for the control of one or more physical properties without adversely affecting other properties as would typically occur. These properties include Tg, Modulus, yield stress, and elongation.
  • diamine selection can be employed to adjust Tg while maintaining, or even increasing, yield stress and modulus.
  • incorporation of a specific diamine can increase Tg by, 10, 20, 30 or more degrees while affecting the modulus by less than 10, less than 5 or less than 2%.
  • a cycloaliphatic diamine e.g., MBC (4,4'-methylbiscyclohexylamine)
  • MBC 4,4'-methylbiscyclohexylamine
  • Another mechanism of control of physical properties can be implemented by increasing the concentration of polyether and/or linear aliphatic diamine. For example, as shown in Table 10, a higher concentration of polyether and linear aliphatic diamine can increase the elongation of ECANs.
  • ECANs can be used to produce fibers.
  • compositions and methods of production, processing and/or use for fiberbased materials using ECANs are provided herein.
  • the compositions and methods thereof involve melt spinning of fibers with ECANs.
  • Such fibers may function as alternative fiber materials that could be used in place of or in combination with nylon.
  • the ECAN fibers maybe used in knit and non woven material forms and applications.
  • the ECAN material and production process may be tuned to make the resulting ECAN fiber, as shown in FIG. 9A-C, a suitable replacement or substitute for nylon 6,6, nylon 6, and/ or nylon 11, allowing products made from these traditional materials to be more recyclable.
  • ECAN materials may be manufacturable at wide range of temperatures (e.g., room temperature to 200°C).
  • Various ECAN formulations may be used to create fibers.
  • An ECAN variation suitable for melt spinning fibers may, in one exemplary variation, include 10- 30 Mol% of at least one cycloaliphatic polyether amine; 1-50% Mol% of at least one long chain triamine >iooog/mol; at least one aromatic triamine and at least one triketone.
  • ECAN -based elastomeric polymer may be created that can be melt-spun into fibers in the 12O-I6O°C range.
  • T-403 (shown in FIG. 4A) is a polyetheramine characterized by repeating oxypropylene units in the backbone. T-403 is a trifunctional primary amine having an average molecular weight of approximately 440. T-403 includes amine groups that are located on secondary carbon atoms at the ends of aliphatic polyether chains.
  • an ECAN variation suitable for spinning melt fibers may be composed of, for example, 50-95% triamine, 1 to 10% long chain triamine and 5 to 25% low MW and/or high MW polyethertriamine.
  • the amines used can be 40 to 60% T-403, 20 to 40% TAPB, 1 to 10% T5000, and 10 to 20% RFD-270.
  • Specific polyamines useful in fiber production include T-3000 (shown in FIG. 4B) and T-5000 (as shown in FIG. 4C) which are triamines with approximately a 3000 and 5000 molecular weight respectively.
  • D2000 is a polyetheramine characterized by repeating oxypropylene units.
  • D2000 is a difunctional, primary amine with average molecular weight of about 2000.
  • the primary amine groups are located on secondary carbon atoms at the end of the aliphatic polyether chains.
  • D4000 is a polyetheramine characterized by repeating oxypropylene units in the backbone.
  • D4000 includes a difunctional, primary amine with an average molecular weight of about 4ooog/mol.
  • the primary amine groups are located on secondary carbon atoms at the end of aliphatic polyether chains.
  • the ECAN fiber material may include RFD-270.
  • One exemplary ECAN material composition such as shown below may be formed into fiber.
  • the triamine may have a molecular weight equal or greater than looog/mol. In some variations, the molecular weight range of the triamine may range 100-10,000 Dalton.
  • an ECAN suitable for melt long-chain triamines as discussed may include triamines such as T-3000 or T-5000.
  • the triamines may additionally include at least one triamine selected from the group consisting of T-403 and TAPB (e.g. encounter i,3,5-tris(4-aminophenyl)benzene), Tris(2-aminoethyl)amine , Tris(p-aminophenyl)amine, and/ or i,3,5-Tris(4-aminophenyl)benzene.
  • the ECAN fibers may have various potential benefits compared to other similar fiber materials. As a first potential benefit, ECAN fiber materials maybe a more eco-friendly option to nylon 6,6 and nylon 11 in apparel, carpets, automotive, industrial, marine applications.
  • ECAN formulations can be varied to possess greater amounts of polyether amines to ensure high elongation is possible. Such variations may use a combination of short triamines to provide strength along with long chain triamines to improve elongation.
  • ECAN fiber materials may have a comparable or superior elongation at break performance.
  • ECAN fiber can have a high Young’s Modulus (200-i300MPa) and may have 50-300% elongation depending on the formulation.
  • Young’s Modulus 200-i300MPa
  • Nylon 6,6 fibers have an elongation at break of 50% and modulus of 3 GPa while nylon 11 have an elongation of 230% and modulus of 1 GPa.
  • Tg of ECAN fiber formulations can be tuned using a different amount of triamines.
  • Aromatic triamines may ensure high Tg whereas polyetheramines may lead to a softer structure with low Tg.
  • ECAN fibers may have a high range in glass transition temperatures, potentially ranging between -5O°C to 4O°C depending on formulation of the ECAN.
  • ECANs can be recycled to retrieve the original monomers and polymerized to synthesize a new material with the same, differing, and/or better properties. Additionally, while nylon cannot be heated to high temperatures (>180 °C) to reform the material due to its propensity for degradation, ECANs can be reheated and remolded to achieve any form factor of choice.
  • a method for producing ECAN fiber may include supplying an ECAN material, where the ECAN material may have a composition described herein; melting the ECAN material; extruding, pumping, and/or moving the melted ECAN material through a spinneret to form initial filaments.
  • the ECAN material may be supplied as granules, chips or other form factor for feeding into a hopper or other container that feeds into an extruder or other component where the material is initially melted.
  • ECANs have a wide range of operating temperature in the extruder (100-250C) allowing multiple different formulations to be spun into fibers depending on the specifications needed.
  • the ECAN material when passed through the spinneret forms continuous filaments or threads.
  • the fibers may be cooled and then drawn or stretched, which may align the polymer chains and improve strength and other properties of the fiber.
  • the resulting fiber may then be wound.
  • the fiber may also be used in creating ECAN -fiber based structures such as ECAN fabrics or weaves.
  • Coatings are ubiquitous in products available on the market. From high- performance coatings in automotive, textiles, packaging etc., different polymers like polyurethane, PVC, siloxanes, epoxies are used for their abrasion resistance, weather, UV, chemical and corrosion resistance.
  • ECANs can be formulated to mimic highly conformable elastomeric coatings.
  • the ECAN material may be produced into an elastomer or elastomeric coating that could mimic and be used in place of Polyurethane (PU) or Polydimethylsiloxane (PDMS).
  • PU Polyurethane
  • PDMS Polydimethylsiloxane
  • Polyetheramines promote the softness of the elastomeric ECANs. Additionally, selection of diamines within an ECAN material may play a critical role in promoting an elastomer form. Triketones may also have an impact on properties.
  • ECAN composition may be used in targeting different material properties like glass transition temperature, Young’s modulus, yield strength, elongation, and degradation temperature.
  • various polyamines may result in properties such as: Tg ⁇ -50 to 30, °C, yield stress >0.1 - 100 MPa, Elongation >100%, degradation temperature > 350 °C.
  • One variation may be prepared that combines short chain triamines Huntsman T403 and long chain triamines Huntsman T3000 and T5000 (>1%) which perform as double network polymers.
  • an ECAN material comprising at least one triamine that is selected from the group consisting of T3000 and T5000 and having greater than iMol% ( Figure attached) may result in an elastomeric properties suitable for an elastomer form or elastomeric coating.
  • formulations may be created that are suited for roll to roll coatings, dip coating, brush coating, spray coating. These methods allow multiple methods of applying a coating to different substrates for the end consumer.
  • An ECAN material in an elastomer or elastomeric coating form may exhibit multiple properties beneficial to use as a novel elastomer or coating option for many applications.
  • ECAN elastomer coatings can be applied on flexible surfaces.
  • the ECAN elastomeric form may have low tensile stress ( ⁇ 10 MPa) and high elongation (>100%) with temperature resistance >350 °C.
  • the ECAN elastomeric form maybe able to achieve ECAN coatings of 25 um or greater thickness.
  • the ECAN elastomeric form may also be applied as layer by layer deposition to create multilayer coatings.
  • Each coating layer may be formulated and adjusted to exhibit different properties to create a multilayer coating for various applications in textiles, automotive, protective coatings for industry and homes.
  • ECAN formulations in addition to use as a coating may be used as elastomeric soft polymers that resemble silicones and PU elastomers.
  • the mechanical properties of PU elastomers vary according to the desired application and the formulation of PU.
  • the modulus can vary from 0.00114- 3.54 GPA while the elongation at break lies in the range of 0.4-1300%.
  • TOPCOAT PU-270 the elongation at break is 130% while the ultimate tensile strength is 20.5 MPa.
  • An ECAN variation suitable for elastomers and elastomeric coatings may, in one exemplary variation, include 90 Mol% T-403 and 10 Mol% methylenedianiline (MDA).
  • Another ECAN variation suitable for elastomers and elastomeric coatings may include 90-99 Mol% T-403 and 1-10 Mol% T3000. See FIG. 10B.
  • Yet another ECAN variation suitable for elastomers & elastomeric coatings may include 90-99 Mol% T-403 and 1-10 Mol% T5000. See Fig. 10B.
  • FIG. 11A is a photo of Ci, C2 and C3 after drying at 6°C on a hot plate.
  • FIG. 11B is a photo of Ci, C2 and C3 after drying at room temperature.
  • FIG. 11C is a photo of Ci, C2 and C3 after drying in vacuum oven.
  • Thermal properties of elastomeric formulations may also be affected by the manner in which the compositions are dried. Tg can vary based on whether formulations are dried under room temperature, elevated temperature >6oC, and whether vacuum was applied to the samples.
  • polyetheramines polyether diamines or triamines
  • a low molecular weight polyethertriamine can be used with a high molecular weight polyether triamine.
  • the low and high molecular weight components are used in molar ratios of from 0.5:99.5 to 5:95; from 0.5:99.5 to 3:97, from 1.0:99 to 2.5:97.5, from 10:90, from 20:80.
  • two or more different high MW polyetheramines can be used with o, 1, 2 or more low MW polyetheramines.
  • a low MW polyethertriamine (T403) and a high MW polyether triamine (T5000) at a molar ratio of 99:1 and a low MW polyether triamine (T403) and a high MW polyether triamine (T3000) at a molar ratio of 97.5:2.5 were shown to exhibit good elastomeric properties.
  • Siloxane diamines with different molecular weights (248 and 950) may be mixed with a linear aliphatic polyamine (such as Priamine 1071) in different molar ratios [(Mw 248 - 20 mol% ) and (Mw 950 - 10, 20, 50 mol%)] at concentration of 50 %w/v and casting thickness of 500 pm.
  • a linear aliphatic polyamine such as Priamine 1071
  • ECAN-based adhesives include both structural adhesives and pressure sentistive adhesives. By controlling the rate of chain extension and cross-linking, ECAN materials may be tuned to build adhesive formulations.
  • the adhesive maybe a strong/structural adhesive ECAN form that functions to mimic epoxybased and/ or other forms of strong, structural adhesives.
  • the adhesive may be a reversable adhesive ECAN form that functions to mimic acrylate-based milder pressure sensitive adhesives.
  • sample preparation has a great impact on peel testing.
  • PSA cured with both an upper and lower substrate layer shows higher adhesion force compared to open cured PSA which has inconsistent results due to entrapment of bubbles.
  • biobased adhesive 60 wt. %) exhibits good adhesion force. Initial force of adhesion is greater than petroleum based, meaning that the biobased alternative can be employed without any loss of adhesive force.
  • ECAN sample TT5 is made by combining triketone TK10 + 50% aromatic triamine (TAPB) + 50% long chain polyether triamine T5000).
  • ECAN sample Pi is TK10 reacted with 100% linear aliphatic polyamine (dimer diamine) adhesives. Table 17 provides maximum load and peel load for each formulation, using ASTM D1876.
  • FIG. 13 is a photograph showing ECAN TT5 between two Kapton substrate layers.
  • FIG. 16 illustrates the circular chemical recycling system enabled by ECANs.
  • An ECAN PSA can be employed with traditional polymer, cardboard or paper packaging and can be depolymerized in situ without removing the packaging. The monomers are recovered by acid hydrolysis, for example, and can then be re-used to make the same or different ECAN polymer. The non-ECAN components can be conventionally thermally recycled or otherwise disposed of.
  • Cycloaliphatic diamines and small molecule triamines may be used to create structural adhesives that can bind metals.
  • mol% of the components of the ECAN may be Triamine 1- 0-50%, Triamine 2- 0-50%, Diamines 1-10%.
  • An ECAN material for a structural adhesive form may, in one exemplary variation, include 25-75 mol% cycloaliphatic diamine and 25-75 mol% short chain triamine, wherein polyamines to triketones have an eq. ratio of 0.8-1.2, 0.9-1.1 or 0.99-1.01.
  • the diamine may be a diamine such as RFD-270.
  • the triamine may, for example, be a triamine such as T-403.
  • Such a resulting material may exhibit adhesive properties make it tough to remove and could be used on materials such as aluminum and stainless steel.
  • Such a composition may include 75 mol% RFD-270 and 25 mol% T403 as a ratio of polyamines, with a 1:1 ratio of polyamines to triketones in the composition.
  • T-403 (shown in FIG. 4A) is a polyetheramine characterized by repeating oxypropylene units in the backbone. T-403 is a trifunctional primary amine having an average molecular weight of approximately 440. T-403 includes amine groups that are located on secondary carbon atoms at the ends of aliphatic polyether chains.
  • a bio-based pressure sensitive ECAN adhesive may be formed by the polymerization of the bio-based linear aliphatic polyamine , and the triketone TK-10 at an eq. ratio of 1:1.
  • the linear aliphatic polyamine may comprise 25, 50, 75, 100, or another number Mol% of the polyamines, with the remaining o, 20, 50, 75, or another number Mol% of the polyamines comprising T5000, or another triamine.
  • the polyamines and the triketones are preferably polymerized at an eq ration of 1:1.
  • HMDA/OMDA HMDA/OMDA + linear aliphatic polyamine
  • Another example useful in adhesives employs 0-50% aromatic triamine and o- 50% long chain polyethertriamine which leads to a material which in its free form state serves as a pressure sensitive adhesive, in heat cured state it serves as a structural adhesive.
  • the small molecule triamine may be TAPB, and the long chain triamine is T5000.
  • a ECAN material in a reversible, pressure sensitive adhesive form behaves like a Command Strip made by 3M, wherein, upon heat or pressure, the ECAN- based adhesive could be removed cleanly. Furthermore, an ECA -based adhesive could be recycled to reclaim original monomers. This is an important as yet unavailable feature of commercial adhesives.
  • ECAN materials described herein are chemically recyclable and are considered to be circular keto amine based condensation polymers.
  • a circular condensation polymer is a polymer produced via a condensation reaction that can be recycled at the monomer level so that monomers can be reused to produce new polymers, or other materials.
  • ECAN formulations can undergo dynamic amine exchange also known as catalyst free transamination at elevated temperatures (above Tg). This allows ECANs to be recycled through thermal reforming processes, i.e., reactive extrusion, compression molding as typically performed on thermoplastics.
  • circular condensation polymers can be hydrolyzed with a strong acid.
  • Strong acids include acids such as nitric, phosphoric and sulfuric acid, HC1.
  • sulfuric acid is the acid of choice.
  • a circular condensation polymer is reacted with H2SO4 at an elevated temperature.
  • the H2SO4 is provided at 1.0-2.0 M, 2.0-3.0 M, 3.0 to 4.0M, 4.0-5.0M, 5.0-6.0M or greater than 6M.
  • Temperature can be, for example, room temperature, 3O-4O°C, 4O-5O°C, 50- 6o°C, 6O-7O°C, 7O-8O°C or 8o-9O°C, or greater than 90C.
  • the depolymerization of enamine and/ or imine bonds can be hydrolyzed by an acid.
  • the acid can be an acid such as sulfuric acid.
  • the ratio of polymer to acid, on a wt/wt basis can be, for example, 5-30%, 30-60% or 50-90%.
  • the H2SO4 acid concentration may be 2.5 M, with 25% solution concentration, at 60C, for horr. such a system may result in > 80% yield.
  • the acid can be recycled to process additional batches, or the system can be operated on a continuous basis.
  • the circular condensation polymer can be comminuted prior to introducing it to the acid, and average particle size can be less than 5 cm, less than 2.5 cm, less than 1 cm or less than 0.5 cm. In other embodiments, the particle size can greater than 0.5 cm, greater than 1.0 cm, greater than 2.5 cm, greater than 5 cm or greater than 10 cm.
  • the mixture can be agitated, by, for example, mixing, shaking or applying ultrasound.
  • Reaction times can be, for example, greater than 30 minutes, greater than or equal to 1 hr, greater than or equal to 3 hr, greater than or equal to 6 hr, less than 6 hr, less than 4 hr, less then 2 hr, less then 1 hr or less than 30 minutes.
  • ECAN based adhesives can be removed via acid hydrolysis, as described elsewhere herein.
  • ECAN based adhesives can also be thermally removed cleanly from a surface.
  • the ECAN adhesive is heated to greater than 40, 60, 80, 100, 150, 200, 250 or 3OO°C to soften the material through catalyst-free, dynamic transamination at elevated temperatures to where adjoined substrates can be separated without damage and the ECAN adhesive can be removed entirely from both surfaces.
  • the temperature can be lowered after reaction in order to facilitate separation and solidification of some of the components.
  • the temperature of the mixture can be lowered to less than o°C, -io°C, - 15°C or -20°C.
  • FIG. 17 The circular recycling of products produced with ECANs is illustrated in FIG. 17 which shows that monomers can be recycled in intersecting single plastic and multiplastic systems.
  • FIG. 18 provides a diagram depicting the circular nature of forming and depolymerizing enamine and/or imine bonds in ECAN systems.
  • any mixed material system involving multiple ECANs, ECANS with other plastics, and/or ECANs with metals will lead to precipitation of triketone and dissolution of amines.
  • the ECANs can be processed in conditions where other materials like plastic and metals are unaffected. Filtration enables triketone recovery at different temperatures and acid conditions. Filtrate can be distilled at different temperatures to recover multiple amines. Depending on their structure, amine molecules have different boiling points. A recycling process may leverage this to recover substantially all the amines in the filtrate. In this way, a recycling process may recover both triketones and polyamines to use it for ECANs of same or different form factors.
  • the recycling yield may be tuned by adjusting the molarity, pH, and temperature of the acid bath. Different formulations of ECANs may affect the molarity and temperature required for optimal recycling. Recycling processes may be scaled up without appreciable drop in efficacy, though recycling of mixed materials may require more processing than recycling of isolated ECAN materials.
  • the recyclability of ECANs may enable an input ECAN material(s) to be recycled into an output RECAN material(s).
  • a method for recycling may include receiving an input ECAN -based material, processing the item for ECAN recycling, recovering, separating, and washing monomers, and optionally reforming an output RECAN material from the recovered monomers.
  • the input ECAN materials may be of a first ECAN material form, and the resulting RECAN material form may be the same or different ECAN material form.
  • multiple ECAN material forms may be processed for recycling either as standalone forms or as a multi-form ECAN- based item.
  • the output RECAN materials may be a single RECAN material form or a plurality of different output RECAN material forms.
  • ECANs may be processed in mixed material waste streams. ECANS maybe processed alongside other plastics and/or metals.
  • ECANs also extends to the different material forms the compositions may be formed into. ECANs of varied forms may be recycled together using the same process, and the depolymerized constituent monomers from varied ECAN compositions may be recovered from the resultant material.
  • a ECAN -based fiber may be processed together with an ECAN- based elastomer or adhesive. This property enables the easy recycling of composite products which may comprise ECAN fibers, elastomers, coatings, foams, sheets, and adhesives.
  • the tabulated results from processing a representative sample of material of an ECAN suitable for material sheets are described in the table below.
  • ECANS may also be recycled among other, non-ECAN material, which may include metals, other polymers, and other materials.
  • the recycling process will depolymerize the ECANs and cause the constituent monomers to precipitate and be recoverable, while leaving other, non ECAN, materials that do not react with the acid bath untouched.
  • the tabulated results of an exemplary processing of a mixed-waste stream including ECANs, other plastics, and other metal waste are described in the table below:
  • ECANs maybe recycled into equivalent or even higher quality materials. Unlike plastic recycling processes that result in materials of lower grade/ quality, the recycling process of ECANs extract source components in an original form, opening up options in how they are used.
  • a method for recycling may include receiving a mono-material, multi -form item constructed of ECAN -based materials, processing the item for ECAN recycling, recovering, separating, and washing monomers. The monomers may then be used in reforming ECAN material forms from the recovered monomers.
  • ECAN materials maybe used to address material demands for different elements of a shoe, and yet still be recyclable as a mono-material product.
  • the shoe can include a fabric upper, an elastomer sole (lower) and an adhesive holding the upper and lower together. If comprised of ECAN materials, the entire shoe can be recycled in a single operation even though it includes different types of extruded, molded, spun and coated materials.
  • a mono-material, multi-form item may include ECAN-based materials of two or more forms and/or tuned for different material properties.
  • the different material forms may, for example, include ECAN-bulk solid materials (e.g., sheets, films, blocks, and the like), fiber or fiber-based materials, coatings, multilayered structures, sealants, elastomer materials, foams, and/or adhesives.
  • the item may include ECAN-based materials of different classes of material forms.
  • the item may include sheets of ECAN material, ECAN fiber-based materials, and/or ECAN adhesives.
  • the item may include different varieties of the same class of material form.
  • the item may include two varieties of ECAN fiber, where the different varieties use different material formulations.
  • Circular condensation polymers such as ECAN materials need not be in pure form in order to chemically recycle them.
  • products that include ECAN materials as well as additives, metals, glass, other polymers and/ or food stuffs can be chemically recycled to extract, e.g., triketone from the ECAN component.
  • ECAN components can be chemically recycled in a single step.
  • a consumer product may include an elastomer adhered to a fabric with an adhesive. If the elastomer, fabric and adhesive are comprised of ECAN materials, they can be chemically recycled without needing to first segregate the components. If all three components are made using the same triketone, then the pure triketone can be derived from all three of the components. Any non-chemically recyclable components will not be reacted, but they will not interfere with the recycling of the ECAN materials.
  • ECAN 1 and ECAN 1.3 were recycled under different concentrations of polymer and acid to determine the ease and completeness with which the materials can be recycled.
  • ECAN 1 was recycled at 5, 10, 15, 20, 25, and 30% concentration by weight in 6M H 2 SO 4 at 95°C. While yields were comparable in most cases (FIG. 20A, ECAN 1; FIG. 20B, ECAN 1.3 ), 25% and 30% concentrations led to very low total volume. Analysis by NMR of materials recovered consistently showed > 70% purity (FIGS. 22A and 22B).
  • ECAN 1 purity increased with increasing concentration of ECAN in acid solution while ECAN 1.3 provided higher purity monomer at lower concentrations (Table 22).
  • FIGS. 13A and 13B provides a bar graph showing the recycled triketone yield at various ECAN concentrations for ECAN 1 and ECAN 1.3.
  • ECAN 1 depolymerizes within 20 minutes at 90°C. Temperatures tested included 40°C, 6o°C, 8o°C and 96°C. The sulfuric acid was provided at 25% (2.5 M H2SO4) based on previous experiments. Results are provided in Table 6. Note that 4O°C took a longer time to solubilize initially, and the ECAN particles were visible even after 60 minutes. All other temperatures showed a fast start to dissolution. 4O°C provided the lowest yield. Results indicate that a temperature from 6o°C to 8o°C may be preferred to 96°C. This indicates that circular recycling can be done at temperatures below about 80 °C, but above room temperature.
  • ECANs lend themselves to efficient chemical recycling even in the presence of non-recyclable materials.
  • Metals included steel, aluminum, and samarium cobalt.
  • Plastics included polypropylene, Teflon, PVC, polyethylene, rubber, polyester and nylon.
  • Sulfuric acid was provided at 2.5 M, 25% concentration, and depolymerization was carried out at 6o°C. As shown below, recoveries of triketone was greater than 50% without damage to any of the plastics and metals. (Table 25).
  • FIGS. 11A-C are photographs of recovered TK-10 triketone from mixtures of an ECAN and traditional plastics.
  • FIG. 21A is TK-10 recovered from a mixture of ECAN, polypropylene, Teflon, PVC, polyethylene and rubber.
  • FIG. 21B is TK-10 from a mixed plastic of ECAN, polyester and nylon.
  • FIG. 21C is TK-10 recovered from a mixture of ECAN and mixed metals.
  • FIGS. 21D and 21E are photographs of recovered TK-10 from samples of an ECAN coating and ECAN fibers, respectively.
  • FIG. 22A provides NMR spectra of recovered triketone from a mixed plastics system. Results show high purity triketone with minimal impurities, despite being depolymerized in the presence of legacy plastics.
  • FIG. 22B provides NMR spectra of recovered triketone from a mixed metals system. Results show high purity triketone with minimal impurities, despite being depolymerized in the presence of a variety of metals.
  • triketone recovery yield was evaluated at various freezing periods at -18-°C .
  • the freezing times evaluated were: o, ih, 3I1, and overnight in 2.5 M H2SO4.
  • NMR shows higher yield than expected.
  • NMR of 3I1 freezing time showed that the recycling yield was 95%.
  • purity was lower than expected at 67.6%.
  • yield was more than expected as well, indicating that there may be residual material in the recovered triketone.
  • example one is a circular condensation polymer comprising a polyketone and at least one of a diamine, a triamine, and a polyamine having primary and secondary amino functionalities, wherein the polymer exhibits a Tg of greater than 40°C, 6o°C or 8o°C and a Young’s modulus of greater than 0.5, 1 or 2 GPa.
  • Example 2 is The circular condensation polymer of example 1 wherein the ketone is a triketone comprising:
  • Example 3 is the polymer of example 1 comprising an aliphatic diamine from C2 to C12.
  • Example 4 is the polymer of example 2 wherein the diamine comprises an alkyl diamine.
  • Example 5 is the polymer of example 3 wherein the diamine is at least one of a linear alkyl and a cyclo alkyl.
  • Example 6 is the polymer of example 4 wherein the diamine comprises a polyaromatic or cycloaliphatic diamine
  • example 7 is the polymer of example 1 comprising an aromatic diamine.
  • Example 8 is the polymer of example 1 wherein the polyamine crosslinker comprises tris(2-aminoethyl)amine and/or T403 polyetheramine triamine and/or Hexatran.
  • Example 9 is the polymer of example 1 further comprising at least one of a pigment, a dye, a plasticizer, a viscosity modifier, an antioxidant and a UV stabilizer, plasticizers, UV/heat stabilizers, flame retardants, fillers, reinforcements, processing aids, impact modifiers, surface modifiers, optical additives, anti-yellow agents, condensation control agents.
  • Example 10 is the polymer of example 1 exhibiting an elongation at break of greater than 5%, greater than 25%, greater than 50% or greater than 100%.
  • Example 11 is a sheet comprising the polymer of any of the preceding examples.
  • Example 12 is an eyewear frame comprising the polymer of any of examples 1-9.
  • Example 13 is a triketone obtained by hydrolyzing with an acid the polymer of any of examples 1-9.
  • Example 14 is an amine obtained by hydrolyzing with an acid the polymer of any of examples 1- 9.
  • Example 15 is a circular condensation polymer produced from either the triketone of example 13, the amine of example 14, or both.
  • Example 16 is a condensation polymer different from the condensation polymer of example 1 produced from either the triketone of example 13, the amine of example 14, or both.
  • Example 17 is the circular condensation polymer of any of the preceding example wherein the triketone comprises a P-triketon.
  • Example 18 is the circular condensation polymer of any of the preceding example comprising an additive selected from heat stabilizers, light stabilizers, plasticizers, rheology modifiers, flame retardants, conductivity enhancers, anti-static additives and colorants.
  • example 19 is a pressure sensitive adhesive comprising a circular condensation polymer including a triketone, a diamine and a polyamine, the diamine and polyamine being different and each bonded to the triketone via formation of an enamine bond or an imine bond, wherein the adhesive exhibits a T-peel strength of greater than 3, 7, 8, 10 or 15 N for a 50 pm layer at a rate of 254 mm/min.
  • Example 20 is the pressure sensitive adhesive of example 19 wherein the polymer comprises at least 3, 5, 10 or 20 % biobased compounds on a molar basis.
  • Example 21 is the pressure sensitive adhesive of example 19 wherein the diamine is a difunctional linear diamine and the polyamine comprises at least 3 functional amine groups.
  • Example 22 is the pressure sensitive adhesive of example 19 wherein the polyamine comprises N(CH2CH2NH2)n — (NHCH2CH2)n— segments.
  • Example 23 is the pressure sensitive adhesive of example 19 or 22, wherein the polyamine comprises a polypropylene or polyethelenepolyethylene glycol based polyetheramine.
  • Example 24 is the pressure sensitive adhesive of example 19 wherein the triketone comprises cyclic moiet.
  • Example 25 is the pressure sensitive adhesive of example 19 comprising a first short chain aliphatic triamine, a second short chain aromatic triamine and a long chain aliphatic triamine.
  • Example 26 is the pressure sensitive adhesive of example lqcomprising about 50% TAPE and about 50% T5000, on an equivalent basis.
  • Example 26 is the pressure sensitive adhesive of example 19 wherein the polymer comprises:
  • example 26 is a structural adhesive comprising a circular condensation polymer including a triketone, a cycloaliphatic ether diamine, and a short chain polyamine.
  • Example 27 is the structural adhesive of example 26 wherein the cycloaliphatic ether diamine comprises cycloaliphatic segments and polyetheramine segments.
  • Example 28 is the structural adhesive of example 26 wherein the cycloaliphatic segments and polyetheramine segments are in a molar ratio of 3:1 and/or an equivalents ratio of 1:1.32.
  • Example 29 is the structural adhesive of example 26 or 27 wherein the short chain polyamine comprises a polypropylene glycol (PPG)-based polyetheramine.
  • PPG polypropylene glycol
  • Example 30 is the structural adhesive of example 26, 27, or 28, wherein the chemically recyclable polymer comprises, on a molar basis, 25-75% cycloaliphatic diamine and 25-75% short chain triamine, and wherein the ratio of polyamines to triketones is about 1:1 on an equivalents basis.
  • Example 31 is a process comprising curing the structural adhesive of example 26 on a surface and removing the structural adhesive from the surface by depolymerizing the cured structural adhesive.
  • Example 32 is the process of example 31 comprising depolymerizing the cured structural adhesive to produce at least one of the triketone, cycloaliphatic ether diamine or short chain polyamine.
  • Example 33 is the process of example 31 wherein at least one of the triketone, cycloaliphatic ether diamine or short chain polyamine is recovered at greater than 50%, greater than 75%, greater than 90% or greater than 95% of the originally used component.
  • example 34 is an elastomeric coating comprising a circular condensation polymer including a triketone, a diamine and a polyetheramine, wherein the coating has a Tg of less than 5O°C and an elongation at break of greater than 100, 300, 400 or 500.
  • Example 35 is the elastomeric coating of example 34 wherein the elastomeric coating exhibits one or more of: a Young’s Modulus of greater than 1, 10, 100, 250, 500, 1000, 2000 or 3000 MPa; a yield stress of greater than 0.1, 1.0 or 10 MPa; and a degradation temperature of greater than 300 °C.
  • Example 36 is the elastomeric coating of example 34 comprising a short chain triamine and a long chain triamine.
  • Example 37 is the elastomeric coating of example 36 wherein the long chain polyether triamine has a molecular weight of greater than or equal to 3,000.
  • Example 38 is the elastomeric coating of example 34 including an amine component comprising between 85 and 95% T-403 and 5 and 15% 4,4’-methylenedianiline, on an equivalents basis.
  • Example 39 is the elastomeric coating of example 34 including an amine component comprising between 85 and 95% T-403 and between 5 and 15% T3000, on an equivalents basis.
  • Example 40 is the elastomeric coating of any of examples 34-39, the coating having a thickness of greater than 25pm, greater than 50 pm or greater than 100 pm.
  • Example 41 is the elastomeric coating of any of examples 34-40 wherein the coating has a thickness of less than 25 pm, less than 50 pm, less than 100 pm or less than 500 pm.
  • Example 42 is the elastomeric coating of any of examples 34-41 wherein the elongation at break is greater than 1, 10, 50, 100, 500 or 1000%.
  • example 43 is a fiber comprising a circular condensation polymer, the polymer comprising a ditopic triketone, the ditopic triketone selected from the structure:
  • Example 44 is the fiber of example 43 wherein the polymer comprises from 10-30% aliphatic diamines and 1-50% long chain triamines.
  • Example 45 is the fiber of example 43 or 44 wherein 40 to 60% T-403, 20-40% TAPB, 1 to 10% T5000 and 10 to 20% RFD-270 .
  • Example 46 is the fiber of example 43 or 44 having a Tg of greater than -5O°C, -25°C, o°C, 20°C, 4O°C or 6o°C.
  • Example 47 is the fiber of any of examples 43-46 comprising a monoamine.
  • Example 48 is the fiber of example 47 comprising 0.5 to 2.5% monoamine on a molar basis.
  • Example 49 is the fiber of example 47 wherein the monoamine comprises APTS.
  • Example 50 is the fiber any of examples 43-49 comprising at least one of heat: stabilizers, light stabilizers, plasticizers, rheology modifiers, flame retardants, conductivity enhancers, anti-static additives and colorants.
  • Example 51 is a thread or fabric comprising the fiber of any of examples 70-76.
  • Example 52 is A method of recycling a circular condensation polymer, the method comprising: combining the circular condensation polymer with at least 25% by weight of sulfuric acid, the sulfuric acid at a concentration of 2.0 M or greater; allowing the sulfuric acid to hydrolyze at least some of the enamine bonds in the circular condensation polymer; and separating monomeric triketone from other components.
  • Example 53 is the method of example 52 wherein hydrolyzing occurs at a temperature greater than 4O°C, 5O°C or 6o°C.
  • Example 54 is the method of example 52 wherein the circular condensation polymer is one component of a mixed component product including a metal and/or a non-circular condensation polymer.
  • Example 55 is the method of example 52 wherein the circular condensation polymer is one component of a mixed component product including at least two of: a circular condensation polymeric elastomer component; a circular condensation polymeric adhesive component; and a circular condensation polymeric fiber component.
  • Example 56 is the method of example 55 wherein a monomeric triketone is recovered from at least two of the polymeric components.
  • Example 57 is the method of example 56 wherein at least 50%, at least 60%, at least 70%, at least 80% or at least 90% of the mass of the mixed component product.
  • Example 58 is the method of any of examples 52-57 wherein the mixed component product is a running shoe.
  • first, second, third, etc. are used to characterize and distinguish various elements, components, regions, layers and/ or sections. These elements, components, regions, layers and/or sections should not be limited by these terms. Use of numerical terms may be used to distinguish one element, component, region, layer and/or section from another element, component, region, layer and/or section. Use of such numerical terms does not imply a sequence or order unless clearly indicated by the context. Such numerical references maybe used interchangeably without departing from the teaching of the embodiments and variations herein.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polyamides (AREA)

Abstract

L'invention concerne une plateforme de composition polymère ayant une large gamme d'architectures et de propriétés. La composition utilise une chimie covalente dynamique pour former des compositions polymères qui peuvent être chimiquement recyclées en des constituants monomères à la fin de leur vie. Les polymères peuvent être fabriqués sous la forme de fibres, d'élastomères, de revêtements, d'adhésifs, de feuilles, etc., qui sont plus facilement et efficacement recyclés que les plastiques communs.
PCT/US2024/046928 2023-09-15 2024-09-16 Matériaux et procédés pour formes de matériau à l'aide de réseaux adaptables énamine-covalents Pending WO2025059659A1 (fr)

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