Copolymers and processes for recyclable polymer material using enamine-covalent adaptable networks

Abstract

A polymer composition platform with a wide range of architectures and properties is described. The composition comprises dynamic covalent chemistry to form polymer compositions that may be chemically recycled to monomer constituents at end of life. A composition as described may be copolymerized with a wide range of common polymers to introduce or enhance attributes like recyclability.

Description

COPOLYMERS AND PROCESSES FOR RECYCLABLE POLYMER MATERIAL USING ENAMINE-COVALENT ADAPTABLE NETWORKSTECHNICAL FIELD

[0001] This invention relates generally to the field of polymer materials and more specifically to a new and useful composition, system, and method for materials with diverse properties and multiple applications using Enamine-Covalent Adaptable NetworksBACKGROUND OF THE INVENTION

[0002] Demand for plastics is a pervasive problem. 400 million metric tons of virgin plastics are produced each year with demand expected to double over the coming years. Recycling of plastics unfortunately has many challenges causing it to fall short of the goal of returning plastic materials to the material supply. Large scale recycling requires high energy and temperatures. Almost all plastics cannot be recycled multiple times while preserving performance. Logistical barriers of collection and sorting also cause problems. It’s difficult to sort collected waste and mixed material products are largely deemed not recyclable.SUMMARY

[0003] 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 may be copolymerized with a wide range of common polymers to introduce or enhance attributes like recyclability.BRIEF DESCRIPTION OF DRAWINGS

[0004] FIG. 1 is a variation of a generalized ECAN polymer structure.

[0005] FIG. 2 is a representation of possible component variations of an ECAN polymer structure.

[0007] FIG. 3B is a representation of branched and linear polyamines that may act as components to an ECAN polymer structure.

[0008] FIGS. 4A-C are representations of potential triamine components to an ECAN polymer structure.

[0009] FIGS. 5A-E are representations of potential triamine components to an ECAN polymer structure.

[0010] FIGS. 6A and 6B are representations of potential diamine components to an ECAN polymer structure.

[0011] FIG. 7 is a chart containing representations of several chemical structures which may act as components or additives to an ECAN polymer structure.

[0012] FIGS. 8 and 9 are a representation of the chemical process for creating an ECAN-linked polymer by copolymerizing an ECAN polymer structure with an amine terminated polymer.

[0013] FIG. 10 illustrates a process for making a copolymer of ECAN and a conventional polymer. FIGS. 11A-C are graphs showing various properties of these copolymerized ECAN structures.

[0014] FIG. 12 is a depiction of several amine-terminated polymers suitable for copolymerization with ECAN structures.

[0015] FIG. 13 is an NMR graph depicting the NMR spectra of un-functionalized epoxy.

[0016] FIG. 14 is an NMR graph depicting the NMR spectra of an amine modified epoxy reacted in DMSO with heat.

[0017] FIG. 15 is an NMR graph depicting NMR spectra of diamino functionalized BPA- Epoxy crosslinker and showing the NH2 peak as evidence of the presence of amino groups.2SUBSTITUTE SHEET (RULE 26)DETAILED DESCRIPTION OF THE EMBODIMENTS

[0018] The following description of the embodiments of the invention is not intended to limit the invention to these embodiments but rather to enable a person skilled in the art to make and use this invention.1. Overview

[0019] 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.

[0020] Described herein are compositions and methods of production, processing and / or use for materials using Enamine-Covalent Adaptable Networks (ECANs). ECAN materials can be created using polyketones and polyamines through solvent polymerization, ball milling or reactive extrusion or other processes. In some cases, ECANs act as vi trimers in that they can flow at high temperatures and act like thermosets at low temperatures.

[0021] 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. As used herein, 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. 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 ratesfor multi material products. For instance, 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. Background information is provided in PCT application PCT / US2023 / 066303, which is incorporated in its entirety by reference herein.

[0022] 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) may be used to create a wide range of possible material properties with far-reaching applications. In particular, as described herein, triketones of the ECAN material may be cross-linked using triamines to form a high-performance plastic material. In such variations, 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.

[0023] Both enamine bonds and imine bonds are reversible and can be reversed (under suitable conditions, e.g., acid) to re-form the original ketones and amines. This means that both moieties can be used to produce circular condensation polymers. As used herein, 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 (via secondary amines) and / or imines (via primary amines). An ECAN material includes a keto amine condensate.

[0024] As shown in FIG. 2, 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 alimited 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. 2.

[0025] 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 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. Examples of triketones include: cyclopropanetrione, cyanuric acid, croconic acid, nihydrine, triuret, mesoxalic acid, dioxosuccinic acid, and / or triketopentane. Additionally, 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), 2,2'-(4,4'-oxybix(benzoly))bis(5,5- dimethylcyclohexane-i, 3-dione) (TK-14), 1,4-Cyclohexanedicarboxylic acid isomer mix (TK15), 2,5-Furandicarboxylic acid (TK16), Trimesic acid (TK17), Citric acid (TK18), Biphenyl-4, 4 '-dicarboxylic acid (TK19) and 2,6-Naphthalenedi carboxylic acid (TK20). Exemplary triketones are provided in Table 1, below.

[0026] 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. Examples of heteroatom triketone are 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).

[0027] In some variations, at least one triketone is a -triketone. In one example, at least one triketone is TK6. In a second example, at least one triketone is TK10. In another example, at least one triketone comprises a TK10 and TK6 mix.

[0028] Table 1, below provides the product code as used herein for some select triketones. Note that some of the compounds are listed as the condensation product of a triketone and an aliphatic acid. Table 1

[0029] The triketone is a rigid molecule and 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 cross-linking reactions. In the context of ECANs, the triketones react with the triamines to form intermolecular 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 maybe the same or may be different.

[0030] 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 important in customizing material properties.

[0031] The system may have at least one polyamine. Polyamine is an organic compound having two or more amino groups. Polyamines include primary and / or secondary amino groups separated by aliphatic and cycloaliphatic chains that can contain different moieties such as aromatic moieties or heteroatoms. Polyamines function as one of the primary (i.e., monomer) building blocks of ECAN material, wherein polyketones and polyamines form enamine and / or imine. The at least one polyamine may comprise any polyamine that can form an enamine 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. Examples of possible polyamines include: aliphatic and / or aromatic, linear and / or branched diamines, also polyamines such as triamine, tetraamine spermidine, spermine, putrescine, cadaverine, aminoterminated 1,2 and 1,4 polybutadienes, ornithine decarboxylase (ODC), diethylenetriamine (DETA), pentamethyldiethylenetriamine, triethylenetetramine (TETA), tetraethylenepentamine (TEPA), pentaethylenehexamine (PEHA), 1,4,7-triazacyclononane, cyclen, cyclam, tris(2- aminoethyl)amine (TREN), tris(aminomethyl)ethane. Selection of monomers andreaction conditions for flexibility, strength, and stability using commercially available polyamines (e.g., DETA (Diethylenetriamine), Ethanamine (Aminoethyl ether), Polyethylenimine (linear and branched), Jeff Amines (Polyetheramines)).

[0032] 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.

[0033] In some embodiments, bio-based diacids and bio-based polyamines can be employed. For instance, dimer diamines having 100% renewable carbon content, such as Priamine (Cargill) dimer diamines can be used. In various embodiments, 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

[0034] 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.Table 2

[0035] 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-i,2-phenylenediamine, N,N,N'-Trimethylethylenediamine, 2,3-Dihydro-iH-imidazo[i,2-a]imidazole and 4-(Piperidin-4-yl)pyridine.

[0036] FIG. 3A provides structures for exemplary aliphatic, polyether, aromatic, 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 usefulwith ECANs. FIGS. 6A and 6B provide examples of aromatic and cycloaliphatic diamines.

[0037] In some variations, 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.

[0038] 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.

[0039] 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. As used herein, 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 maybe aliphatic diamines or aromatic diamines.

[0040] 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). Triamines act as cross-linking agents for ECAN systems. These triamines can be aliphatic or aromatic. Aliphatic triamine comprises a wide range of backbone structure starting from small aliphatic chains n=2 to longchain (n>io) ethylene or polyether amines. Additionally, they can also contain aromatic backbone as part of small molecule or a polymer backbone. The triamine structure and its molecular weights affect select properties of the ECANs. It can be modified to get different ECAN form factors.

[0041] The form factor of an ECAN material may dictate the choice of triamines. While triamines enable cross-linking, the structural diversity of triamines affects thestrength, flexibility and durability of the final ECAN. For example, 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.

[0042] 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, 1,3,5-Tris(4- aminophenoxy)benzene, i,3,5-Tris(4-aminophenyl)benzene. In some variations, exemplary multiamines may include but are not limited to branched poly (ethylene imine), Cyclam, and / or Cyclen.

[0043] 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.

[0044] 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, DETA, 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.

[0045] 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.

[0046] Each system (e.g., diamines and triamines) is typically available in various chain lengths, providing an additional layer of modularity in designing the ECAN system. 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. The triamine chain lengths and the diamine backbone lengths may be controlled and set independently. Control of molecular weight and / or repeating units maybe used in tuning an ECAN material for a property. A wide range of chain length amine repeating units from n=2 to 100 can be used to control properties.

[0047] Production of ECAN material may use solid state mixing or liquid state mixing. Typically 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). For formulations that require a different state of the starting material, it is assumed that 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.

[0048] A first method for ECAN based plastic formation comprises: blending the additive components with one, or both, monomer components; and liquid-liquid 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. In one variation, the method may include promoting ECAN polymerization through ball milling.

[0049] 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.

[0050] 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 not limited to: sheets, films, fibers, foams, adhesives, coatings, and / or sealants.

[0051] ECAN materials can serve as a more recyclable plastic. Multi-plastic products composing the ECAN materials maybe recovered and reused in formation of new RECAN plastics. For example, a material used as foam in a shoe can be recycled and reused as a coating in automotive use case.

[0052] As a related benefit, with ECAN materials being both tunable to different material forms and recyclable, 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.

[0053] 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.

[0054] Colorants include both dyes and pigments. Additional additives include antioxidants, UV absorbers, conductivity enhancers, viscosity modifiers, rheology modifiers, thermal conductivity enhancers and colorants including pigments and dyes.

[0055] Many ECAN polymers can provide chemically recyclable alternatives to non- chemically recylable polymers. For example, 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.

[0056] In various embodiments, for example, a cured ECAN sheet may have a tensile strength at break of greater than io, greater than 20, greater than 25 or greater than 30 MPa. Similarly, elongation at break (strain %) maybe greater than 5, 10, 25, greater than 50, or greater than 75%. Young’s modulus maybe 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 110, or above 12O°C. In addition, the temperature for workable thermal processing can be less than 200 or less than 15O°C.

[0057] A list of exemplary plasticizers is provided below, 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 0.01 to 1%, 0.1 to 1%, 0.1 to 2% or 1 to 5%.2. ECAN copolymerization with amino terminated and amino functionalized polymers

[0058] In some cases, ECANs may be used in forming and tuning materials of a pure ECAN form (ketone(s) and polyamine(s)). In some other cases, ECANs may be used to form and tune materials of a mixed ECAN -polymer form. Described herein are examples wherein ECANs can copolymerize with other polymers such that the ECANs can chain extend and crosslink these polymers and introduce recyclability in specialty polymers (e.g. - polyamides, polyureas, polybutadiene, and polysiloxanes). This maybe used to create ECAN blended materials (copolymer) where other materials / polymers interface with ECANs. In this way an ECAN may be used as an additive that has similar properties and is physically and chemically compatible. For example, an ECAN-polyamide material could be formed where ECAN material is used as an additive to nylon. Due to the recyclability of ECAN materials, this may result in a nylon like material that has enhanced recyclabilityresulting from the ECAN additive. For example, the triketone can be recovered from the copolymer by hydrolyzing the copolymer with acid bath.

[0059] ECANs can interface with polymers possessing amine groups as reactive monomer units or telechelic amines on polymers such as polyamides, polyureas, polysiloxanes, and polybutadiene. Polymers not including amine groups can be derivatized by adding amine groups to make them compatible with ECANs.

[0060] In one formulation example, ECAN-Polyurea [ECAN-PU] - Isocyanate terminated polyethers serve as a soft segment. Isocyanate groups react with alkyl diamines to form an amine terminated polyurea segment. See FIGS. 8 and 9. Triketones can react with the resulting telechelic amine moiety to form an ECAN-polyurea, with a linear uncross-linked molecular architecture. The resultant ECAN-PU possesses all the properties of PU with the added benefit of being recyclable through mechanical and chemical methods. FIG. 10 provides one embodiment of a method for making an ECAN-PU. A polyurea is first dissolved in dichloromethane. One or more selected ketones are then added on an equivalents basis to form the ECAN- PU. After removal of solvent, the dried ECAN-PU is available in pure form.

[0061] The mass ratio of triketone to amine terminated polymer is typically the result of the relative sizes and molecular weights of the triketone molecule and amineterminated polymer that it is reacting with. On a mass basis, the ratio of triketone to amine terminated polymer can be, for example, greater than 1:10, greater than 1:7, greater than 1:2, greater than 1:1. In the same and other embodiments, the ratio can be less than 1:10, less than 1:7, less than 1:2, less than 1:1, FIG. 8 provides the reaction mechanism for adding amine groups to an isocyanate to produce end capped polyurea. The polyurea is then reacted with a polyketone to produce an ECAN material.

[0062] As an example, in one experiment, TK-10 triketone (i,io-Decanedione,i,io-bis(2- hydroxy-4,4-dimethyl-6-oxo-i-cyclohexes-i-yl)) is reacted with an amine end capped polypropylene glycol diisocyanate (MW ~2ooo g / mol). All the reactions may be carried out in a planetary centrifugal mixer (such as a Thinky mixer) at ambient conditions.

[0063] A reaction between PPG diisocyanate and a diamine (for example, HMDA or MDA) can be carried out in a molar ratio [NC0]:[NH2] of 1:2. The reaction mechanism is shown FIG. 8 where the R groups are generic structures. Double molar amounts of diamine can be used to ensure the isocyanate groups were reacted and only amine end functional groups were available to react with the triketone. Diamine HMDA or MDA can be added to a solution of PPG diisocyanate in DCM and reacted at RT and 1000 rpm for 5 minutes to obtain amine end capped polyurea (PU-NH2). The reaction mixture may exhibit higher viscosity indicating an increase in molecular weight. TK-10 triketone, in equal (calculated) molar amounts, can be added to the PU-NH2 + DCM mixture and reacted at RT and 1000 rpm for 5 minutes. That addition may cause a further increase in viscosity, indicating a molecular weight buildup. It is expected that TK-10 serves as a chain extender between the different PU-NH2 chains.

[0064] The characteristics of the HMDA product were analyzed and are provided in FIGS.11A-C. FIG. 11A illustrates that the heating and cooling cycles exhibit a Tg at -55 °C. FIG. 11B illustrates the rubber-flow transitions observed in the rheological temperature sweeps, and FIG. 11C depicts frequency sweeps that demonstrate rubbery behavior at room temperature and flow at 200 °C. Frequency sweeps showthat the material is in a molten state at 200 °C but has rubber-like properties at RT. These experimental results indicate that the material is behaving as a thermoplastic ECAN PU.

[0065] To produce a copolymer such as ECAN-PU, the process can be carried to completion at room temperature in solvent using a mixing device such as a planetary centrifugal mixer. In one embodiment, 1 mole equivalent of poly (propylene glycol) diisocyanate (MW > 500 g / mol) is reacted with 2 molar equivalents of hexamethylenediamine (MW = 116.21 g / mol) in dichloromethane, although other solvents can be used and the reaction in some cases can be completed neat, without a solvent. The reaction can be carried out using a mixer such as a planetary centrifugal mixer operating at room temperature at a speed of >1000 rpm for >1 minute. The reaction produced an amine terminated polyurea which can readily react with a triketone. Specifically, 1 molar equivalent of triketone is added to the reaction container and the same conditions (>1000 rpm, >1 minute, RT) for mixing. Upon complete mixing, the material is placed in a vacuum oven for drying at room temperature or greater. One embodiment of this process is shown in FIG. 16.

[0066] In addition to polyurethanes, triketones can interface with other amine end capped polymers such as amine terminated nylons, silicones, butadienes, epoxies, urethanes and other performance polymer systems. FIG. 12 provides exemplary structures for amine terminated polyamides, amine terminated polybutadiene and amine terminated polydimethyl siloxane.

[0067] In another formulation example. ECAN-Epoxy can be formed through reacting with diamino functionalized epoxy. Epoxide groups (Poly(ethylene glycol) diglycidyl ether) react with alkyl triamines under heat in DMSO solvent to form a diamine terminated epoxy segment. The diamine epoxy can react with triketones to form ECAN-epoxy. The reaction is modeled below. FIG. 13 provides the NMR spectra of un-functionalized epoxy. FIG. 14 provides the NMR spectra of the resulting amine modified epoxy reacted in DMSO with heat. The spectra indicate successful attachment of the triamine to the epoxy backbone. The terminal aminegroups allow for the formation of enamine and / or imine with ketones, resulting in an ECAN-epoxy copolymer.

[0068] In another formulation example. ECAN-BPA-Epoxy can be formed using diamine terminated epoxy. Epoxide groups (polyfbisphenol A) diglycidyl ether) react with alkyl triamines under heat in DMSO solvent to form a diamine terminated epoxy segment, with good MW agreement (calculated MW -1293 g / mol and expected MW -1367). The diamine epoxy can react with triketones to form ECAN-BPA- epoxy.

[0069] FIG. 15 is a copy of NMR spectra of diamino functionalized BPA-Epoxy crosslinker and shows the NH2 peak as evidence of the presence of amino groups. In addition to a triketone and the amine end-capped polymer, the ECAN copolymer can also incorporate polyamines that are used to produce pure ECAN materials. For example, a copolymer can include a triketone, an amine terminated polyurethane, a diamine and / or a triamine.

[0070] In one aspect, example 1 is a copolymer comprising a keto amine condensate including a polyketone, a polyamine, and an amine terminated or amine functionalized_polymer, the amine terminated or amine functionalized polymer selected from at least one of amine terminated_or amine functionalized polyurethane, polyamide, polydimethylsiloxane, silicone, butadiene, epoxy and polyimide. Example 2 is the copolymer of example 1 wherein the polyketone is a triketone. Example 3 is the copolymer of example 1 wherein the triketone is TK-6, TK-10, or a combination thereof. Example 4 is The copolymer of example 1 wherein the triketone ketone is selected from at least one of cyclopropanetrione, cyanuric acid, croconic acid, nihydrine, triuret, mesoxalic acid, dioxosuccinic acid, and / or triketopentane. Additionally, triketones include the product obtained from the condensation of 1,3-diketones and its derivatives, such as 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 (TK10), or with cyclic acids, such as 1,4-Cyclohexanedicarboxylic acid, isomer mix (TK15), 2,5-Furandicarboxylic acid(TK16), Trimesic acid (TK17), Citric acid (TK18), Biphenyl-4,4'-dicarboxylic acid (TK19), 2,6-Naphthalenedicarboxylic acid (TK20) diphenyltriketone, diphenyltetraketone, i,io-Decanedione,i,io-bis(2-hydroxy-4,4-dimethyl-6-oxo-i- cyclohexes-i-yl) (TK-10), 2,2'-terephthaloylbis(5,5-dimethylcyclohexane-i,3- dione) (TK-13), 2,2'-(4,4'-oxybix(benzoly))bis(5,5-dimethylcyclohexane-i,3- dione) (TK-14). Example 5 is The copolymer of example 1 comprising a heteroatom triketone. Example 6 is The copolymer of example 5 wherein the heteroatom triketone is selected from at least one of: 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), and 5,5'-(i,io-dihydroxydecane-i,io- diylidene)bis(i,3-dimethylpyrimidine2,4,6(iH,3H,5H)-trione). Example 7 is the copolymer of any of examples 1-6 wherein the ratio of triketone to amine terminated polymer on a mass basis is less than 10:1, less than 5:1, less than 2:1, less than 1:1, less than 1:2, less than 1:5, less than 1:7 or less than 1:10. Example 8 is The copolymer of example 7 comprising a diamine or triamine different from the amine terminated or amine funtionalized polymer. Example 9 is the copolymer of example 7 wherein the copolymer is a circular condensation copolymer. Example 10 is the copolymer of example 7 including at least one of heat stabilizers, light stabilizers, plasticizers, rheology modifiers, flame retardants, conductivity enhancers, anti-static additives and colorants. Example 11 is a fiber, elastomer, adhesive or sheet comprising the copolymer of any of example 1-10. Example 12 is the copolymer of example 1-6 wherein the amine -terminated polymer is a polyurea. Example 13 is the copolymer of any of examples 1-6 wherein the amine- terminated polymer is an epoxy. Example 14 is The copolymer of example 1, 12, or 13 wherein the polyamine is selected from polyetheramines, aromatic amines, aliphatic amines, cycloaliphatic amines and polyimines. Example 15 is the copolymer of example 14 wherein the polyamine comprises at least one of HMDA, MDA, ODA, ED900, D230, D400, D2000, D4000, RFD-270, T403, T3000, T5000, and TAPB.

[0071] In another aspect, example 15 is a method of making a copolymer, the method comprising: covalently bonding a telechelic amine terminated or aminefunctionalized polymer segment and a polyamine to a polyketone via-enamine and / or imine bonds to produce the copolymer. Example 16 is the method of example 15 wherein the non-amine terminated polymer segment is selected from polyurethane, polyamide, polydimethylsiloxane, silicone, butadiene, epoxy and polyimide. Example 17 is the method of example 15 wherein the triketone is selected from cyclopropanetrione, cyanuric acid, croconic acid, nihydrine, triuret, mesoxalic acid, dioxosuccinic acid, and / or triketopentane; the product obtained from the condensation of 1,3-diketones and its derivatives, such as 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 (TK10), or with cyclic acids, such as 1,4-Cyclohexanedicarboxylic acid, isomer mix (TK15), 2,5-Furandicarboxylic acid (TK16), Trimesic acid (TK17), Citric acid (TK18), Biphenyl-4,4'-dicarboxylic acid (TK19), 2, 6 -Naphthalenedicarboxylic acid (TK20) diphenyltriketone, diphenyltetraketone, i,io-Decanedione,i,io-bis(2-hydroxy-4,4-dimethyl-6-oxo-i- cyclohexes-i-yl) (TK-10), 2,2'-terephthaloylbis(5,5-dimethylcyclohexane-i,3- dione) (TK-13), 2,2'-(4,4'-oxybix(benzoly))bis(5,5-dimethylcyclohexane-i,3- dione) (TK-14). Example 18 is the method of example 15 wherein the polyamine is selected from at least one of short chain polyetheramines, long chain polyether amines, aromatic di and tri amines and linear triamines. Example 19 is the method of example 15 or 18 comprising depolymerizing the copolymer to produce the triketone. Example 20 is the method of any of examples 15-19 comprising adding an additive to the copolymer, the additive selected from at least one of heat stabilizers, light stabilizers, plasticizers, rheology modifiers, flame retardants, conductivity enhancers, anti-static additives and colorants. Example 21 is the method of any of examples 15-20 comprising reacting a non-amine terminated polymer segment with a diamine to form the amine terminated polymer segment.

[0072] As used herein, 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 may be used interchangeably without departing from the teaching of the embodiments and variations herein.

[0073] As a person skilled in the art will recognize from the previous detailed description and from the figures and claims, modifications and changes can be made to the embodiments of the invention without departing from the scope of this invention as defined in the following claims.

[0074] What is claimed is:

Claims

CLAIMS:

1. A copolymer comprising a keto amine condensate including a polyketone, a polyamine, and an amine terminated or amine functionalized.polymer, the amine terminated or amine functionalized polymer selected from at least one of amine terminated or amine functionalized polyurethane, polyamide, polydimethylsiloxane, silicone, butadiene, epoxy and polyimide.

2. The copolymer of claim 1 wherein the polyketone is a triketone.

3. The copolymer of claim 2 wherein the triketone is TK-6, TK-10 or a combination thereof.

4. The copolymer of claim 1 wherein the keto amine condensate comprises both enamine and imine bonds.

5. The copolymer of claim 1 wherein the polyketone.is selected from at least one of: cyclopropanetrione, cyanuric acid, croconic acid, nihydrine, triuret, mesoxalic acid, dioxosuccinic acid, and / or triketopentane; 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 '-t erepht h a loylbi s(5 ,5 - dimethylcyclohexane-i, 3-dione) (TK-13), 2,2'-(4,4'-oxybix(benzoly))bis(5,5- dimethylcyclohexane-i, 3-dione) (TK-14), 1,4-Cyclohexanedicarboxylic acid isomer mix (TK15), 2,5-Furandicarboxylic acid (TK16), Trimesic acid (TK17), Citric acid (TK18), Biphenyl-4, 4 '-dicarboxylic acid (TK19) and 2,6-Naphthalenedi carboxylic acid (TK20).

6. The copolymer of claim 1 comprising a heteroatom triketone.

7. The copolymer of claim 6 wherein the heteroatom triketone is selected from at least one of: 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), and 5,5'-(i,io-dihydroxydecane-1, io-diylidene)bis(i,3-dimethylpyrimidine2, 4, 6(1H,3H,5H)- trione).

8. The copolymer of any of claims 1-7 wherein the ratio of polyketone to amine terminated polymer on a mass basis is less than 10:1, less than 5:1, less than 2:1, less than 1:1 or less than 1:2 or less than 1:5 or less than 1:7 or less than 1:10.

9. The copolymer of claim 8 comprising a diamine or triamine different from the amine terminated or amine functionalized polymer.

10. The copolymer of claim 8 wherein the copolymer is a circular condensation polymer.

11. The copolymer of claim 8 including at least one of a pigment, a dye, a plasticizer, a viscosity modifier, an antioxidant, a UV stabilizer, a plasticizer, a UV / heat stabilizer, a flame retardant, a filler, a reinforcement, a processing aid, a impact modifier, a surface modifier, an optical additive, an anti-yellow agent and a condensation control agent.

12. A fiber, elastomer, adhesive, coating or sheet comprising the copolymer of any of claims 1-7.

13. The copolymer of claim 1-7 wherein the amine-terminated polymer is a polyurea.

14. The copolymer of any of claims 1-7 wherein the amine-terminated polymer is an epoxy.

15. The copolymer of claim 1, 13 or 14 wherein the polyamine is selected from polyetheramines, aromatic amines, aliphatic amines and cycloaliphatic amines.

16. The copolymer of claim 15 wherein the polyamine comprises at least one of HMD A, MDA, ODA, ED900, D230, D400, D2000, D4000, RFD-270, T403, T3000, T5000, and TAPB.

17. A method of making a copolymer, the method comprising: covalently bonding a telechelic amine terminated or amine functionalized polymer segment and a polyamine to a polyketone via-enamine and / or imine bonds to produce the copolymer.

18. The method of claim 17 wherein the non-amine terminated polymer segment is selected from polyurethane, polyamide, polydimethylsiloxane, silicone, butadiene, epoxy and polyimide.19- The method of claim 17 wherein the triketone is selected from: cyclopropanetrione, cyanuric acid, croconic acid, nihydrine, triuret, mesoxalic acid, dioxosuccinic acid, and / or triketopentane; 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), 2,2'-(4,4'-oxybix(benzoly))bis(5,5- dimethylcyclohexane-i, 3-dione) (TK-14), 1,4-Cyclohexanedicarboxylic acid isomer mix (TK15), 2,5-Furandicarboxylic acid (TK16), Trimesic acid (TK17), Citric acid (TK18), Biphenyl-4, 4 '-dicarboxylic acid (TK19) and 2,6-Naphthalenedi carboxylic acid (TK20).

20. The method of claim 17 wherein the polyamine is selected from at least one of short chain polyetheramines, long chain polyether amines, aromatic di and tri amines and linear triamines.

21. The method of claim 17 or 20 comprising depolymerizing the copolymer to produce the triketone.

22. The method claim 21 comprising adding an additive to the copolymer, the additive selected from at least one of heat stabilizers, light stabilizers, plasticizers, rheology modifiers, flame retardants, conductivity enhancers, anti-static additives and colorants.

23. The method of claim 21 comprising reacting a non-amine terminated polymer segment with a diamine or triamine to form the amine terminated or amine functionalized polymer segment.

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