Copolymers and Processes for Recyclable Polymer Materials Using Enamine Covalent Adaptive Networks

Abstract

A platform of polymer compositions having a wide range of structures and properties is described. These compositions utilize dynamic covalent chemistry to form polymer compositions that can be chemically recycled back into monomer components after use. The described compositions can be copolymerized with a wide range of common polymers to introduce or enhance attributes such as recyclability.

Description

TECHNICAL FIELD

[0001] The present invention relates generally to the field of polymer materials, and more specifically, to novel and useful compositions, systems, and methods for materials with diverse properties and multiple uses, utilizing Enamine-Covalent Adaptable Networks. BACKGROUND ART

[0002] The growing demand for plastics has become a widespread problem. 400 million metric tons of virgin plastics are produced each year, and demand is expected to double in the next few years. Unfortunately, the recycling of plastics faces many challenges, and the goal of returning plastic materials to the raw material supply system has not been achieved. Large-scale recycling requires high energy and temperatures. Almost no plastics can be recycled multiple times while maintaining their performance. Logistical barriers in collection and sorting also cause problems. It is difficult to sort the collected waste, and mixed material products are largely considered non-recyclable. SUMMARY OF INVENTION PROBLEMS TO BE SOLVED BY THE INVENTION

[0003] Polymer composition platforms with a wide range of structures and properties are described herein. The compositions utilize dynamic covalent chemistry to form polymer compositions that can be chemically recycled into reusable components after use. The described compositions can be copolymerized with a wide range of common polymers to introduce or enhance attributes such as recyclability. BRIEF DESCRIPTION OF DRAWINGS

[0004] [Figure 1] It is a variation of the generalized ECAN polymer structure. [Figure 2] It is a diagram showing variations of possible components of the ECAN polymer structure. [Figure 3A] This figure shows branched and linear polyamines that can function as building blocks of the ECAN polymer structure. [Figure 3B] This figure shows branched and linear polyamines that can function as building blocks of the ECAN polymer structure. [Figure 4A] This figure shows the potential triamine components of the ECAN polymer structure. [Figure 4B] This figure shows the potential triamine components of the ECAN polymer structure. [Figure 4C] This figure shows the potential triamine components of the ECAN polymer structure. [Figure 5A] This figure shows the potential triamine components of the ECAN polymer structure. [Figure 5B] This figure shows the potential triamine components of the ECAN polymer structure. [Figure 5C] This figure shows the potential triamine components of the ECAN polymer structure. [Figure 5D] This figure shows the potential triamine components of the ECAN polymer structure. [Figure 5E] This figure shows the potential triamine components of the ECAN polymer structure. [Figure 6A] This figure shows the potential diamine components of the ECAN polymer structure. [Figure 6B] This figure shows the potential diamine components of the ECAN polymer structure. [Figure 7] This chart includes diagrams showing several chemical structures that can function as components or additives of the ECAN polymer structure. [Figure 8] This diagram shows the chemical process for creating ECAN-bound polymers by copolymerizing the ECAN polymer structure with amine-terminated polymers. [Figure 9] This diagram shows the chemical process for creating ECAN-bound polymers by copolymerizing the ECAN polymer structure with amine-terminated polymers. [Figure 10] This shows the process for manufacturing copolymers of ECAN and conventional polymers. [Figure 11A] This graph shows the various properties of these copolymerized ECAN structures. [Figure 11B] This graph shows the various properties of these copolymerized ECAN structures. [Figure 11C] This graph shows the various properties of these copolymerized ECAN structures. [Figure 12] This is a description of several amine-terminated polymers suitable for copolymerization with the ECAN structure. [Figure 13] This is an NMR graph depicting the NMR spectrum of a non-functionalized epoxy. [Figure 14] This is an NMR graph depicting the NMR spectrum of an amine-modified epoxy reacted with heat in DMSO. [Figure 15] This NMR graph depicts the NMR spectrum of a diamino-functionalized BPA-epoxy crosslinking agent, showing the NH2 peak as evidence of the presence of an amino group. [Modes for carrying out the invention]

[0005] The following description of embodiments of the present invention is not intended to limit the invention to these embodiments, but rather to enable those skilled in the art to construct and use the invention.

[0006] 1. Overview Enamine Covalent Adaptability Networks (ECAN) and Recyclable Enamine Covalent Adaptability Networks (RECAN) provide novel materials that facilitate chemical recycling and can be adapted to a variety of end products.

[0007] Described herein are compositions and methods of making, processing and / or using materials that employ enamine covalent adaptable networks (ECANs). ECAN materials can be made using polyketones and polyamines through solvent polymerization, ball milling, reactive extrusion, or other processes. In some cases, ECANs function as vitrimers in that they flow at elevated temperatures and behave like thermoset resins at low temperatures.

[0008] ECAN materials may be tunable for a variety of material forms and applications. Furthermore, ECAN materials may be recyclable, where recovery of constituent monomers is possible, and the same or different new RECAN networks can be created. ECAN materials can be degraded into their constituent monomers. These recycled monomers can then be repolymerized to produce the same or different polymeric materials. As used herein, dynamic covalent chemistry means that a polymer can be formed and then degraded back to its original constituent components. This allows ECAN materials to enter a circular cycle where the same monomers are used repeatedly 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 of the monomers used to make it. The versatile material platform of ECAN materials, combined with mixed waste, efficient high-yield recycling, may enable access to new compositions that can increase the recycling rate of multiple material products. For example, a single product such as a running shoe may include fibers (fabrics), one or more adhesives, and an elastomer. When various components of the product are formed using ECAN materials, the product can be depolymerized into constituent monomers such as triketones and polyamines without physical disassembly. Background information is provided in PCT Application No. PCT / US2023 / 066303, which is incorporated herein by reference in its entirety.

[0009] The ECAN material comprises a combination of polyamines, which can be diamines, triamines, tetramines, or multifunctional amines. The selection of the type and concentration of the polyamine relative to the polyketone (a substance having two, three, four, or more keto groups) can be used to create a wide range of possible material properties with a broad spectrum of applications. In particular, as described herein, the triketone of the ECAN material can be crosslinked using a triamine to form a high-performance plastic material. In such variations, the ECAN material may comprise a diamine backbone / chain extension that links two triketones and binds to the amino groups of two triamines. The selection of the types and concentrations of diamines and triamines relative to the triketone is used to adjust or customize the material properties.

[0010] Both enamine bonds and imine bonds are reversible, and can undergo reverse reaction (under appropriate conditions, such as under acid) to reform the original ketone and amine. This means that both moieties can be used to produce cyclic condensation polymers. As used herein, a ketoamine condensate is the product of the reaction of a ketone with a primary or secondary amine, or both, and may comprise both enamine (via secondary amine) and / or imine (via primary amine). The ECAN material comprises a ketoamine condensate.

[0011] As shown in Figure 2, the composition of ECAN may comprise a triketone and one or more polyamines. Different possible component molecules for R1, R2, and R3 can be selectively used, which makes it possible to adjust the resulting ECAN material. The options for R1, R2, and R3 may vary depending on the adjusted properties and the desired form. This may allow various possibilities for R1, R2, and R3, non-limiting examples of which are shown in Figure 2. One structural variation of the ECAN polymer comprises a plurality of triketones, a plurality of triamines, and a plurality of diamines, as represented by the formula shown in Figure 2.

[0012] The system may have at least one polyketone, which may be a triketone. The triketone functions as one of the main (i.e., monomeric) components of ECAN, where the triketone and polyamine form an enamine bond. In Figure 1, the enamine bond is shown as a dashed circle. The triketone may function as a rigid or flexible component in the ECAN components. At least one triketone may be linear or cyclic. In general, at least one triketone may be any triketone capable of forming an enamine or imine bond with a polyamine. Examples of triketones include cyclopropanetrione, cyanuric acid, croconic acid, ninhydrin, triuret, mesooxalic acid, dioxosuccinate, and / or triketopentane. Furthermore, triketones can be formed by the condensation of 1,3-diketones and their derivatives (acetylacetone and derivatives, 1,3-cyclohexanedione, 5,5-dimethyl-1,3-cyclohexanedione (dimedone), barbiturates and derivatives, beta-ketractone and derivatives, etc.) with aliphatic acids (especially adipic acid (TK6), suberic acid (TK8), and dicarboxylic acids such as sebacic acid ((1,10-decandione, 1,10-bis(2-hydroxy-4,4-dimethyl-6-oxo-1-cyclohexen-1-yl)TK10)), or cyclic acids (diphenyl triketone, diphenyl tetraketone, These include products obtained from condensation with 2,2'-terephthaloylbis(5,5-dimethylcyclohexane-1,3-dione) (TK-13), 2,2'-(4,4'-oxybis(benzoyl))bis(5,5-dimethylcyclohexane-1,3-dione) (TK-14), a mixture of 1,4-cyclohexanedicarboxylic acid isomers (TK15), 2,5-franzicarboxylic acid (TK16), trimesic acid (TK17), citric acid (TK18), biphenyl-4,4'-dicarboxylic acid (TK19), and 2,6-naphthalenedicarboxylic acid (TK20), etc. Exemplary triketones are shown in Table 1 below.

[0013] Some embodiments may utilize one or more triketones containing heteroatoms. Heteroatomic triketones can alter the rate of hydrolysis and depolymerization conditions such as time and temperature. The depolymerization rate can be extremely important and beneficial for the selective recovery of monomers. Examples of heteroatomic triketones are 3,3'-(1,10-dihydroxydecane-1,10-diyl)bis(6,6-dimethyldihydro-2H-pyran2,4(3H)-dione), 5,5'-decanedioylbis(2,2-dimethyl-1,3-dioxane-4,6-dione), and 5,5'-(1,10-dihydroxydecane-1,10-diylidene)bis(1,3-dimethylpyrimidine2,4,6(1H,3H,5H)-trione).

[0014] In some variations, at least one triketone is β-tricetone. 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 is a mixture of TK10 and TK6.

[0015] Table 1 below provides the product codes used herein for several selected triketones. Note that some compounds are listed as condensation products of triketones and aliphatic acids. Table 1 [Table 1] [ka]

[0016] Triketones are rigid molecules that react with diamines to form extended main chains, also known as chain extensions. Triamines react with triketones to form crosslinked polymer systems. Crosslinked polymer systems are characterized by a network of polymer chains chemically bonded through crosslinking reactions. In the context of ECAN, triketones react with triamines to form intermolecular bonds between polymer chains, creating a three-dimensional network structure. This crosslinking can affect the overall mechanical strength and stability of the ECAN material. The triketones may be the same or different.

[0017] Amine structures (e.g., diamines, triamines, tetraamines, or polyfunctional amines) can offer a wide range of choices. In particular, the selection of the type and concentration of diamines and triamines used with ECAN materials can be important in customizing the material properties.

[0018] The system may have at least one polyamine. A polyamine is an organic compound having two or more amino groups. A polyamine contains primary and / or secondary amino groups separated by aliphatic and alicyclic chains, which may contain different moieties such as aromatic moieties and heteroatoms. The polyamine functions as one of the main (i.e., monomeric) components of the ECAN material, where the polyketone and polyamine form an enamine and / or imine. At least one polyamine may include any polyamine capable of forming an enamine bond with a triketone. The polyamines used herein, including diamines and triamines, may have 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 in various embodiments. Examples of possible polyamines include aliphatic and / or aromatic, linear and / or branched diamines, as well as triamines, tetraamines, spermidine, spermine, putrescine, cadaverine, amino-terminated 1,2 and 1,4 polybutadienes, ornithine decarboxylase (ODC), diethylenetriamine (DETA), pentamethyldiethylenetriamine, triethylenetetramine (TETA), tetraethylenepentamine (TEPA), pentaethylenehexamine (PEHA), 1,4,7-triazacyclononane, cyclene, cyclam, tris(2-aminoethyl)amine (TREN), and tris(aminomethyl)ethane. Selection of monomers and reaction conditions for flexibility, strength, and stability using commercially available polyamines (e.g., DETA (diethylenetriamine), ethaneamine (aminoethyl ether), polyethyleneimine (linear and branched), Jeffamine (polyetheramine)).

[0019] Diamines can be any molecule containing diamines. They can be small molecules with aliphatic or aromatic groups. They can also contain long-chain polyether backchains, polyethylene backchains, or polybutadiene backchains with varying molecular weights. The choice of a particular diamine structure affects the properties of the soft segment of the ECAN polymer, thereby contributing to flexibility and durability. Typical examples may include, but are not limited to, diaminotoluene, dithioaniline, oxydianiline, methylenedianiline, phenylenedioxydianiline, phenylenediamine, hexamethylenediamine, octamethylenediamine, decamethylenediamine, isophoronediamine, diaminoethoxyethane, polyetheramines such as the Jeffamine ED and D series (e.g., ED900, D230, D400, D2000, D4000, JTHF100, JTHF170), amino-terminated polysiloxanes, and / or amino-terminated polybutadienes.

[0020] In some embodiments, bio-based diacids and bio-based polyamines can be used. For example, dimeramines with a 100% renewable carbon content, such as Priamine (Cargill) dimeramine, can be used. In various embodiments, the bio-based components can account for more than 10%, 20%, 30%, 40%, or 50% by mass of the ECAN material.

[0021] Table 2 below provides a list of some polyamines that can be used in the ECAN system. The list includes both the chemical name and the CAS number. [Table 2] JPEG2026534125000005.jpg199158

[0022] Polyamines also include secondary amines such as bis(2-aminopropyl)amine, N,N'-dimethyl-1,3-propanediamine, N-methyl-1,3-propanediamine, triethylenetetramine, diethylenetriamine, N,N'-dimethyl-1,2-phenylenediamine, N,N,N'-trimethylethylenediamine, 2,3-dihydro-1H-imidazo[1,2-a]imidazole, and 4-(piperidine-4-yl)pyridine.

[0023] Figure 3A provides exemplary structures of aliphatic, polyether, aromatic, and alicyclic polyamines. Figure 3B provides examples of branched and linear primary and secondary polyamines. Figures 4A-4C provide exemplary structures of polyethertriamines. Figures 5A-5E provide examples of additional triamines useful for ECAN. Figures 6A and 6B provide examples of aromatic and alicyclic diamines.

[0024] In several variations, the material properties of ECAN can be adjusted or modified by using long-chain diamines and triamines, aromatic triamines, alkyl triamines, alicyclic diamines, aromatic diamines, short-chain diamines and triamines, and / or other polyamine and triketone combinations.

[0025] Diamines function to establish chain extensions. Therefore, the selection of diamines (and / or other polyamines including diamines, triamines, and tetraamines) can affect the stiffness of the main chain. Diamine chain extensions can be of various lengths. The stiffness of ECAN in bulk form is inversely proportional to the length of the triamine and diamine chain extensions. Diamines can be a combination of aliphatic or aromatic groups. The molecular weight of the diamine plays a significant role in tuning the chemical and physical properties of the ECAN network.

[0026] The selection of short-chain diamines may function to promote a more rigid main chain. The selection of long-chain diamines with polymer bonds between amines may function to create soft segments. As used herein, short-chain diamines have a molecular weight of less than 1000, while long-chain diamines have a molecular weight of more than 1000. Diamines may be aliphatic diamines or aromatic diamines.

[0027] For crosslinking, at least one type of triamine may be included in the network. The triamines may all be the same, or there may be multiple triamines (e.g., aliphatic triamines combined with aromatic triamines or short-chain or long-chain triamines). The triamines function as crosslinking agents in the ECAN system. These triamines can be aliphatic or aromatic. Aliphatic triamines include a wide range of backchain structures, from small aliphatic chains n=2 to long-chain (n>10) ethyleneamines or polyetheramines. Furthermore, they can also include aromatic backchains as part of small molecule or polymer backchains. The structure of the triamine and its molecular weight influence some properties of the ECAN. It can be modified to obtain different ECAN form factors.

[0028] The form factor of the ECAN material may determine the choice of triamine. While triamines enable crosslinking, the structural diversity of triamines affects the strength, flexibility, and durability of the final ECAN. For example, elastomeric ECAN can have long-chain triamines in addition to short-chain triamines, increasing the density of soft segments in the ECAN polymer and making it more elastomeric.

[0029] In various embodiments, triamines such as tris(2-aminoethyl)amine, tris(2-aminopropyl)amine, pentane-1,3,5-triamine, benzenetriamine, melamine, triphenylentriamine, tris(4-aminophenyl)amine, 1,3,5-tris(4-aminophenoxy)benzene, and 1,3,5-tris(4-aminophenyl)benzene can be used. In some variations, exemplary multiamines may include, but are not limited to, branched poly(ethyleneimine), cyclomes, and / or cyclenes.

[0030] Triamines may be selected as part of the objective to control the properties of crosslinking. This can then be used to control tensile strength. Triamines have chain length, and the tensile strength of ECAN in bulk form is inversely proportional to the chain length of the triamine. The selection of short-chain triamines may work to promote a strong but brittle ECAN material. The selection of long-chain triamines may work to create a more elastomeric material with lower tensile strength but longer elongation.

[0031] Diamines may include diaminotoluene, dithioaniline, oxydianiline, methylenedianiline, phenylenedioxydianiline, phenylenediamine, hexamethylenediamine, octamethylenediamine, decamethylenediamine, isophoronediamine, diaminoethoxyethane, JTHF100, JTHF170 amino-terminated polysiloxanes, amino-terminated polybutadienes, DETA, HMDA, MDA, ODA, ED900, D230, D400, D2000, D4000, and / or RFD-270, and some examples of potential triamines may include T403, T3000, T5000, and / or TAPB.

[0032] Polyfunctional amines are molecules containing two or more primary or secondary amines. Such molecules can provide multiple crosslinking sites in close proximity. Depending on the crosslinking density, these amines can contribute to improving the strength of the material. Selecting tetrafunctional or higher amines results in a higher density of crosslinking sites, leading to tougher materials that can be adapted not only to existing form factors such as sheets but also to newer form factors such as composites.

[0033] Each system (e.g., diamines and triamines) is typically available in a variety of chain lengths, providing an additional layer of modularity to the design of ECAN systems. Amines can be selected with different numbers of repeating units or components, or otherwise configured. Such variability in chain length can provide flexibility in the property design of the resulting ECAN materials. The chain length of triamines and the main chain length of diamines can be controlled and set independently. Control of molecular weight and / or repeating units can be used when tuning ECAN materials for certain properties. Properties can be controlled using a wide range of chain-length amine repeating units from n=2 to 100.

[0034] The production of ECAN materials can utilize solid-state or liquid-state mixing. While polyamines are typically available as liquids and triketones as solids at room temperature, both compounds can generally be found or obtained in various states (e.g., liquid, gas, or solid). For formulations requiring different states of starting materials, it is assumed that the starting materials are first converted to the appropriate state using standard available techniques. For example, in liquid-liquid formulations, the triketone powder may be melted first before mixing.

[0035] A first method for forming ECAN-based plastics involves blending 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 incorporating small molecule additives. Furthermore, this method may result in a higher degree of mixing of additive components compared to other methods, and a homogeneous mixture of polymer and additives can be achieved in a controllable manner. In one variation, this method may involve facilitating ECAN polymerization through ball milling.

[0036] The systems and methods may offer several potential advantages. The systems and methods are not necessarily limited to offering such advantages, and are presented only as illustrative representations of how the systems and methods may be used. The list of advantages is not intended to be exhaustive, and other advantages may exist as additional or alternatives.

[0037] ECAN materials may have monomers selected to produce a target material form factor with material properties tailored for a specific material form application. A variety of different material forms may be achievable. The material properties of ECAN materials can be modified by controlling the concentration ratios of diamine and triamine components (and / or other polyamine components) and variations in the types of amines. For example, increasing the proportion of a particular type of amine may change the stiffness, flexibility, or strength of the resulting ECAN material. Thus, adjusting the concentrations allows for 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.

[0038] ECAN materials can function as more recyclable plastics. Products made from multiple types of plastics composed of ECAN materials can be collected and reused to form new RECAN plastics. For example, materials used as foam in shoes can be recycled and reused as coatings for automotive applications.

[0039] Related advantages include the fact that ECAN materials can be adapted to different material forms and are recyclable, thus enabling the use of circular materials. ECAN materials can also enable the recovery of materials from waste streams in a certain material form to manufacture the same and / or different forms of materials.

[0040] Figure 7 shows a chart providing examples of triketones, polyamines, plasticizers, solvents, and colorants that can be used in various ECAN systems. These examples are not exhaustive and are provided to illustrate the range of materials that can be employed.

[0041] Colorants include both dyes and pigments. Additional additives include antioxidants, UV absorbers, conductivity enhancers, viscosity modifiers, rheology modifiers, thermal conductivity enhancers, and colorants containing pigments and dyes.

[0042] Many ECAN polymers can provide chemically recyclable alternatives to chemically non-recyclable polymers. For example, ECAN can replicate the properties of cellulose acetate in a form that is chemically recyclable to its monomer components. The ECAN materials disclosed herein can exhibit a variety of properties equivalent to or exceeding those of conventional polymers such as cellulose acetate. These properties include, for example, tensile strength, elongation, modulus of elasticity, viscoelastic properties, glass transition temperature, and thermal working and decomposition temperatures.

[0043] In various embodiments, for example, a cured ECAN sheet may have a tensile strength at break greater than 10 MPa, 20 MPa, 25 MPa, or 30 MPa. Similarly, the elongation at break (strain %) may be greater than 5%, 10%, 25%, 50%, or 75%. The Young's modulus may be greater than 0.1 GPa, 0.5 GPa, 1.0 GPa, or 1.5 GPa. The glass transition temperature is T g The temperature may be above 30°C, above 50°C, above 75°C, above 85°C, above 95°C, above 110°C, or above 120°C. Furthermore, the practical heat processing temperature may be below 200°C or below 150°C.

[0044] A list of exemplary plasticizers, along with their structures, is shown below. Different ECAN systems may use different types and amounts of plasticizers. In some cases, plasticizers may be added to ECAN in amounts of 0.01–1%, 0.1–1%, 0.1–2%, or 1–5% wt / wt. [Table 3]

[0045] 2. ECAN copolymerization with amine-terminated polymers and amine-functionalized polymers In some cases, ECAN may be used to form and prepare materials in pure ECAN forms (ketones and polyamines). In other cases, ECAN may be used to form and prepare materials in mixed ECAN-polymer forms. This specification describes examples in which ECAN can copolymerize with other polymers, and ECAN can chain-extend and crosslink these polymers, introducing recyclability to specialty polymers (e.g., polyamides, polyureas, polybutadienes, and polysiloxanes). This may be used to create ECAN blend materials (copolymers) in which other materials / polymers interact with ECAN. In this way, ECAN may be used as an additive having similar properties and being physically and chemically compatible. For example, ECAN-polyamide materials can be formed in which the ECAN material is used as an additive to nylon. Due to the recyclability of the ECAN material, this may result in a nylon-like material with enhanced recyclability due to the ECAN additive. For example, triketones can be recovered from copolymers by hydrolysis of the copolymer in an acid bath.

[0046] ECAN can interact with polymers that have amine groups as reactive monomer units, or polymers that have telechelic amines on polymers such as polyamides, polyureas, polysiloxanes, and polybutadienes. Polymers that do not contain amine groups can be derivatized by adding amine groups to make them compatible with ECAN.

[0047] In one formulation example, ECAN-polyurea [ECAN-PU], the isocyanate-terminated polyether functions as a soft segment. The isocyanate group reacts with an alkyldiamine to form an amine-terminated polyurea segment. See Figures 8 and 9. A triketone can react with the resulting telechelic amine moiety to form ECAN-polyurea having a linear, uncrosslinked molecular structure. The resulting ECAN-PU possesses all the properties of PU, with the added advantage of being recyclable through mechanical and chemical methods. Figure 10 provides one embodiment of a method for preparing ECAN-PU. The polyurea is first dissolved in dichloromethane. Then, one or more selected ketones are added on an stoichiometric basis to form ECAN-PU. After removal of the solvent, the dried ECAN-PU is available in pure form. [ka]

[0048] The mass ratio of triketone to amine-terminated polymer is typically a result of the relative size and molecular weight of the reacting triketone molecule and amine-terminated polymer. 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, or 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, or less than 1:1. Figure 8 provides a reaction mechanism for producing a terminally capped polyurea by adding an amine group to an isocyanate. This polyurea is then reacted with a polyketone to produce the ECAN material.

[0049] As an example, in one experiment, TK-10 triketone (1,10-decandione, 1,10-bis(2-hydroxy-4,4-dimethyl-6-oxo-1-cyclohexen-1-yl)) is reacted with amine-terminated polypropylene glycol diisocyanate (approximately 2000 g / mol MW). All reactions can be carried out under ambient conditions using a planetary centrifugal mixer (such as a Thinky mixer).

[0050] The reaction between PPG diisocyanate and a diamine (e.g., HMDA or MDA) can be carried out in a molar ratio of [NCO]:[NH2] of 1:2. The reaction mechanism is shown in Figure 8, where the R group is a common structure. Using twice the molar amount of diamine ensures that the isocyanate group reacts and only amine-terminal functional groups that can react with the triketone are present. By adding the diamine HMDA or MDA to a solution of PPG diisocyanate in DCM and reacting at room temperature and 1000 rpm for 5 minutes, amine-terminated polyurea (PU-NH2) can be obtained. The reaction mixture may exhibit a higher viscosity, indicating an increase in molecular weight. Equal (calculated) molar amounts of TK-10 triketone can be added to the PU-NH2 + DCM mixture and reacted at room temperature and 1000 rpm for 5 minutes. This addition may cause a further increase in viscosity, indicating an increase in molecular weight. TK-10 is expected to function as a chain extender between different PU-NH2 chains.

[0051] The properties of the HMDA product were analyzed and are shown in Figures 11A-C. Figure 11A illustrates the Tg observed at -55°C during heating and cooling cycles. Figure 11B illustrates the rubber-to-flow transition observed by rheological temperature sweep, and Figure 11C depicts frequency sweep demonstrating rubbery behavior at room temperature and flowability at 200°C. The frequency sweep shows that the material is molten at 200°C but possesses rubbery properties at room temperature. These experimental results indicate that the material behaves as thermoplastic ECAN PU.

[0052] To produce copolymers such as ECAN-PU, the process can be completed at room temperature in a solvent using a mixing apparatus such as a planetary centrifugal mixer. In one embodiment, 1 molar 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, but other solvents can be used, and in some cases the reaction can be completed neat without a solvent. The reaction can be carried out at room temperature using a mixer such as a planetary centrifugal mixer operating at a speed of over 1000 rpm for more than 1 minute. The reaction produces an amine-terminated polyurea that readily reacts with triketone. Specifically, 1 molar equivalent of triketone is added to the reaction vessel and mixed under the same conditions (over 1000 rpm, more than 1 minute, room temperature). After complete mixing, the material is placed in a vacuum oven to dry at room temperature or above. One embodiment of this process is shown in Figure 16.

[0053] In addition to polyurethanes, triketones can interact with other amine-terminated polymers, such as amine-terminated nylons, silicones, butadienes, epoxys, urethanes, and other high-performance polymer systems. Figure 12 provides exemplary structures of amine-terminated polyamides, amine-terminated polybutadienes, and amine-terminated polydimethylsiloxanes.

[0054] In another formulation example, ECAN-epoxy can be formed by reaction with a diamino-functionalized epoxy. The epoxide group (poly(ethylene glycol) diglycidyl ether) reacts with an alkyltriamine under heating in DMSO solvent to form a diamine-terminated epoxy segment. The diamine epoxy can then react with a triketone to form ECAN-epoxy. The reaction model is shown below. Figure 13 provides the NMR spectrum of the unfunctionalized epoxy. Figure 14 provides the NMR spectrum of the amine-modified epoxy obtained by reaction under heating in DMSO. The spectra show successful bonding of the triamine to the epoxy backbone. The terminal amine group enables the formation of enamines and / or imines with the ketone, resulting in the ECAN-epoxy copolymer. [ka]

[0055] In another formulation example, ECAN-BPA-epoxy can be formed using a diamine-terminated epoxy. The epoxide group (poly(bisphenol A) diglycidyl ether) reacts with an alkyltriamine under heating in DMSO solvent to form a diamine-terminated epoxy segment with good MW match (calculated MW approximately 1293 g / mol and expected MW approximately 1367 g / mol). The diamine epoxy can react with a triketone to form ECAN-BPA-epoxy. [ka] [ka]

[0056] Figure 15 is a copy of the NMR spectrum of a diamino-functionalized BPA-epoxy crosslinking agent, showing an NH2 peak as evidence of the presence of an amino group. In addition to triketone and amine-terminated capped polymers, ECAN copolymers can also incorporate polyamines used to produce pure ECAN materials. For example, copolymers may contain triketones, amine-terminated polyurethanes, diamines, and / or triamines.

[0057] In one embodiment, Example 1 is a copolymer comprising a ketoamine condensate containing a polyketone, a polyamine, and an amine-terminated polymer or amine-functionalized polymer, wherein the amine-terminated polymer or amine-functionalized polymer is selected from at least one of amine-terminated polyurethane or amine-functionalized polyurethane, amine-terminated polyamide or amine-functionalized polyamide, amine-terminated polydimethylsiloxane or amine-functionalized polydimethylsiloxane, amine-terminated silicone or amine-functionalized silicone, amine-terminated butadiene or amine-functionalized butadiene, amine-terminated epoxy or amine-functionalized epoxy, and amine-terminated polyimide or amine-functionalized 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 a copolymer of Example 1, wherein the triketone is selected from at least one of cyclopropanetrione, cyanuric acid, croconic acid, ninhydrin, triuret, mesooxalic acid, dioxosuccinate, and / or triketopentane.Furthermore, triketones can be formed by the condensation of 1,3-diketones and their derivatives (such as acetylacetone and its derivatives, 1,3-cyclohexanedione, 5,5-dimethyl-1,3-cyclohexanedione (dimedone), barbituric acid and its derivatives, beta-ketractone and its derivatives) with aliphatic acids (especially dicarboxylic acids such as adipic acid (TK6), suberic acid (TK8), and sebacic acid (TK10)), or by the condensation of 1,3-diketones and their derivatives (such as acetylacetone and its derivatives, 1,3-cyclohexanedicarboxylic acid, 5,5-dimethyl-1,3-cyclohexanedicarboxylic acid (TK16), trimesic acid (TK17), and citric acid (TK18)). These include products obtained from condensation with biphenyl-4,4'-dicarboxylic acid (TK19), 2,6-naphthalenedicarboxylic acid (TK20), diphenyl triketone, diphenyl tetraketone, 1,10-decandione, 1,10-bis(2-hydroxy-4,4-dimethyl-6-oxo-1-cyclohexen-1-yl) (TK-10), 2,2'-terephthaloylbis(5,5-dimethylcyclohexane-1,3-dione) (TK-13), 2,2'-(4,4'-oxybis(benzoyl))bis(5,5-dimethylcyclohexane-1,3-dione) (TK-14), etc. Example 5 is a copolymer of Example 1 containing a heteroatom triketone. Example 6 is a copolymer of Example 5, wherein the heteroatom triketone is selected from at least one of 3,3'-(1,10-dihydroxydecane-1,10-diyl)bis(6,6-dimethyldihydro-2H-pyran2,4(3H)-dione), 5,5'-decanedioylbis(2,2-dimethyl-1,3-dioxane-4,6-dione), and 5,5'-(1,10-dihydroxydecane-1,10-diylidene)bis(1,3-dimethylpyrimidine2,4,6(1H,3H,5H)-trione). Example 7 is a copolymer of any of Examples 1-6, wherein the ratio of triketone to amine-terminated polymer 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 on a mass basis. Example 8 is a copolymer of Example 7 that contains a diamine or triamine different from the amine-terminated polymer or amine-functionalized polymer. Example 9 is a copolymer of Example 7 in which the copolymer is a cyclic condensation copolymer.Example 10 is a copolymer of Example 7 comprising at least one of the following: a heat stabilizer, a light stabilizer, a plasticizer, a rheology modifier, a flame retardant, a conductivity enhancer, an antistatic additive, and a colorant. Example 11 is a fiber, elastomer, adhesive, or sheet comprising any copolymer of Examples 1-10. Example 12 is a copolymer of Examples 1-6 in which the amine-terminated polymer is polyurea. Example 13 is a copolymer of Examples 1-6 in which the amine-terminated polymer is epoxy. Example 14 is a copolymer of Example 1, 12, or 13 in which the polyamine is selected from polyetheramines, aromatic amines, aliphatic amines, alicyclic amines, and polyimines. Example 15 is a copolymer of Example 14 in which the polyamine comprises at least one of HMDA, MDA, ODA, ED900, D230, D400, D2000, D4000, RFD-270, T403, T3000, T5000, and TAPB.

[0058] In another embodiment, Example 15 is a method for producing a copolymer, which involves covalently bonding a telechelic amine-terminated polymer segment or an amine-functionalized 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 nonamine-terminated polymer segment is selected from polyurethane, polyamide, polydimethylsiloxane, silicone, butadiene, epoxy, and polyimide. Example 17 shows the condensation of triketones with cyclopropanetrione, cyanuric acid, croconic acid, ninhydrin, triuret, mesooxalic acid, dioxosuccinic acid, and / or triketopentane, as well as 1,3-diketones and their derivatives (such as acetylacetone and its derivatives, 1,3-cyclohexanedione, 5,5-dimethyl-1,3-cyclohexanedione (dimedone), barbituric acid and its derivatives, beta-ketractone and its derivatives), and aliphatic acids (especially dicarboxylic acids such as adipic acid (TK6), suberic acid (TK8), and sebacic acid (TK10)), or cyclic acids (1,4-cyclohexanedicarboxylic acid isomer mixture (TK15), 2,5-frangic acid). The method in Example 15 is selected from products obtained by condensation with acids (TK16), trimesic acid (TK17), citric acid (TK18), biphenyl-4,4'-dicarboxylic acid (TK19), 2,6-naphthalenedicarboxylic acid (TK20), diphenyl triketone, diphenyl tetraketone, 1,10-decandione, 1,10-bis(2-hydroxy-4,4-dimethyl-6-oxo-1-cyclohexen-1-yl) (TK-10), 2,2'-terephthaloylbis(5,5-dimethylcyclohexane-1,3-dione) (TK-13), 2,2'-(4,4'-oxybis(benzoyl))bis(5,5-dimethylcyclohexane-1,3-dione) (TK-14), etc. Example 18 is the method of Example 15, wherein the polyamine is selected from at least one of short-chain polyetheramines, long-chain polyetheramines, aromatic diamines and triamines, and linear triamines. Example 19 is the method of Example 15 or 18, which includes depolymerizing the copolymer to produce a triketone.Example 20 is any method from Examples 15-19, comprising adding an additive to the copolymer, the additive being selected from at least one of heat stabilizers, light stabilizers, plasticizers, rheology modifiers, flame retardants, conductivity enhancers, antistatic additives, and colorants. Example 21 is any method from Examples 15-20, comprising reacting a non-amine-terminated polymer segment with a diamine to form an amine-terminated polymer segment.

[0059] As used herein, the terms 1st, 2nd, 3rd, 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. The 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. Unless explicitly indicated by the context, the use of such numerical terms does not imply order or sequence. Such numerical references may be used interchangeably without departing from the teachings of the embodiments and variations herein.

[0060] As those skilled in the art will recognize from the preceding detailed description and from the drawings and claims, modifications and changes can be made to embodiments of the present invention without departing from the scope of the invention as defined in the following claims.

Claims

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

2. The copolymer according to claim 1, wherein the polyketone is a triketone.

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

4. The copolymer according to claim 1, wherein the ketoamine condensate contains both enamine and imine bonds.

5. The aforementioned polyketone is Condensation of cyclopropanetrione, cyanuric acid, croconic acid, ninhydrin, triuret, mesooxalic acid, dioxosuccinic acid, and / or triketopentane, as well as 1,3-diketones and their derivatives (such as acetylacetone and its derivatives, 1,3-cyclohexanedione, 5,5-dimethyl-1,3-cyclohexanedione (dimedone), barbituric acid and its derivatives, beta-ketractone and its derivatives) with aliphatic acids (especially adipic acid (TK6), suberic acid (TK8), and dicarboxylic acids such as sebacic acid ((1,10-decandione, 1,10-bis(2-hydroxy-4,4-dimethyl-6-oxo-1-cyclohexen-1-yl)TK10)), and The copolymer according to claim 1, wherein is selected from at least one of the products obtained by condensation with a cyclic acid (such as diphenyl triketone, diphenyl tetraketone, 2,2'-terephthaloylbis(5,5-dimethylcyclohexane-1,3-dione) (TK-13), 2,2'-(4,4'-oxybis(benzoyl))bis(5,5-dimethylcyclohexane-1,3-dione) (TK-14), a mixture of 1,4-cyclohexanedicarboxylic acid isomers (TK15), 2,5-franzicarboxylic acid (TK16), trimesic acid (TK17), citric acid (TK18), biphenyl-4,4'-dicarboxylic acid (TK19), and 2,6-naphthalenedicarboxylic acid (TK20)).

6. The copolymer according to claim 1, comprising a heteroatom triketone.

7. The aforementioned heteroatom triketone is The copolymer according to claim 6, selected from at least one of 3,3'-(1,10-dihydroxydecane-1,10-diyl)bis(6,6-dimethyldihydro-2H-pyran2,4(3H)-dione), 5,5'-decanedioylbis(2,2-dimethyl-1,3-dioxane-4,6-dione), and 5,5'-(1,10-dihydroxydecane-1,10-diylidene)bis(1,3-dimethylpyrimidine2,4,6(1H,3H,5H)-trione).

8. The copolymer according to any one of claims 1 to 7, wherein the ratio of polyketone to amine-terminated polymer 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 on a mass basis.

9. The copolymer according to claim 8, comprising a diamine or triamine different from the amine-terminated polymer or amine-functionalized polymer.

10. The copolymer according to claim 8, wherein the copolymer is a recyclable condensation polymer.

11. The copolymer according to claim 8, comprising at least one of the following: pigments, dyes, plasticizers, viscosity modifiers, antioxidants, UV stabilizers, plasticizers, UV / heat stabilizers, flame retardants, fillers, reinforcing materials, processing aids, impact modifiers, surface modifiers, optical additives, anti-yellowing agents, and condensation control agents.

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

13. The copolymer according to any one of claims 1 to 7, wherein the amine-terminated polymer is polyurea.

14. The copolymer according to any one of claims 1 to 7, wherein the amine-terminated polymer is epoxy.

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

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

17. A method for producing copolymers, A 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 a copolymer.

18. The method according to claim 17, wherein the nonamine-terminated polymer segment is selected from polyurethane, polyamide, polydimethylsiloxane, silicone, butadiene, epoxy, and polyimide.

19. The aforementioned triketone is Cyclopropanetrione, cyanuric acid, croconic acid, ninhydrin, triuret, mesooxalic acid, dioxosuccinic acid, and / or triketopentane, as well as 1,3-diketones and their derivatives (such as acetylacetone and its derivatives, 1,3-cyclohexanedione, 5,5-dimethyl-1,3-cyclohexanedione (dimedone), barbituric acid and its derivatives, beta-ketractone and its derivatives), and aliphatic acids (especially adipic acid (TK6), suberic acid (TK8), and dicarboxylic acids such as sebacic acid ((1,10-decandione, 1,10-bis(2-hydroxy-4,4-dimethyl-6-oxo-1-cyclohexen-1-yl)TK10)) and The method according to claim 17, selected from products obtained by condensation of or with cyclic acids (such as diphenyl triketone, diphenyl tetraketone, 2,2'-terephthaloylbis(5,5-dimethylcyclohexane-1,3-dione) (TK-13), 2,2'-(4,4'-oxybis(benzoyl))bis(5,5-dimethylcyclohexane-1,3-dione) (TK-14), a mixture of 1,4-cyclohexanedicarboxylic acid isomers (TK15), 2,5-franzicarboxylic acid (TK16), trimesic acid (TK17), citric acid (TK18), biphenyl-4,4'-dicarboxylic acid (TK19), and 2,6-naphthalenedicarboxylic acid (TK20).

20. The method according to claim 17, wherein the polyamine is selected from at least one of short-chain polyetheramines, long-chain polyetheramines, aromatic diamines and triamines, and linear triamines.

21. The method according to claim 17 or 20, comprising depolymerizing a copolymer to produce a triketone.

22. The method according to claim 21, comprising adding an additive to the copolymer, wherein the additive is selected from at least one of a heat stabilizer, a light stabilizer, a plasticizer, a rheology modifier, a flame retardant, a conductivity enhancer, an antistatic additive, and a colorant.

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

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