Flame-retardant polydiketoenamine

Abstract

Disclosed are compositions, methods, and articles of manufacture. The compositions are formed by polymerizing monomers, including at least one flame-retardant bis(triketone) monomer and at least one amine monomer. The methods include obtaining at least one flame-retardant bis(triketone) monomer, obtaining at least one amine monomer, and polymerizing the monomers to form a flame-retardant polydiketoenamine. The articles of manufacture include a polymer formed by polymerizing the at least one flame-retardant bis(triketone) monomer and the at least one amine monomer.

Description

Technical Field

[0001] The present disclosure relates to flame-retardant polymers, and more specifically, to flame-retardant polydiketoenamines (PDKs).

Background Art

[0002] Flame-retardant compounds can be added to polymers to provide flame retardancy. Uses for flame-retardant polymers include plastics, foams, synthetic fibers, synthetic rubbers, and the like. Flame retardants in polymers can be broadly classified according to how the flame retardant is incorporated into the polymer matrix. Additive flame retardants are mixed into the polymer during mixing, curing, foaming, extrusion, or other processing techniques. Reactive flame retardants are covalently bonded to the polymer (e.g., by bonding at sites along the polymer chain, being incorporated into the chain as a comonomer, or being used as a crosslinking agent, or a combination thereof). Types of flame retardants that can be additive or reactive flame retardants include organic bromine compounds and organic phosphorus compounds such as phosphates, phosphonates, phosphinates, phosphites, phosphonites, and phosphinate esters.

Summary of the Invention

[0003] Various embodiments relate to compositions formed by polymerizing monomers comprising at least one flame-retardant bis(triketone) monomer and at least one amine monomer. Examples of amine monomers include tris(2-aminoethyl)amine, poly(propylene glycol)bis(2-aminopropyl ether), poly(ethylene glycol)bis(2-aminopropyl ether), poly(ethylene glycol)bis(amine), poly(tetrahydrofuran), dipropylenetriamine, diethylenetriamine, diaminooctane, 4,4'-oxydianiline, and combinations thereof. At least one flame-retardant bis(triketone) monomer may be an organophosphorus compound or an organobromine compound. The monomer may also contain at least one flame-retardant bis(triketone) monomer. In some embodiments, at least one flame-retardant bis(triketone) monomer is derived from a dicarboxyl flame retardant. The amine monomer has at least two primary amine groups.

[0004] Additional embodiments relate to a method comprising obtaining at least one flame-retardant bis(triketone) monomer, obtaining at least one amine monomer, and polymerizing the monomers to form a flame-retardant polydiketoenamine. Polymerization can be carried out in a ball mill. Examples of amine monomers include tris(2-aminoethyl)amine, poly(propylene glycol)bis(2-aminopropyl ether), poly(ethylene glycol)bis(2-aminopropyl ether), poly(ethylene glycol)bis(amine), poly(tetrahydrofuran), dipropylenetriamine, diethylenetriamine, diaminooctane, 4,4'-oxydianiline, and combinations thereof. At least one flame-retardant bis(triketone) monomer can be an organophosphorus compound or an organobromine compound. Obtaining a flame-retardant bis(triketone) monomer may involve reacting a dicarboxyl flame retardant with a diketone compound such as 1,3-diketone. The method also includes obtaining at least one non-flammable bis(triketone) monomer and incorporating it into polymerization.

[0005] Further embodiments relate to manufactured articles comprising polymers formed by polymerizing at least one flame-retardant bis(tricetone) monomer and at least one amine monomer. The at least one flame-retardant bis(tricetone) monomer may be an organophosphorus compound or an organobromine compound. In some embodiments, the at least one flame-retardant bis(tricetone) monomer is derived from a dicarboxyl flame retardant. The amine monomer may have at least two primary amine groups. [Brief explanation of the drawing]

[0006] [Figure 1] This flowchart illustrates a process for forming flame-retardant polydiketoenamines (PDKs) according to some embodiments of the present disclosure. [Figure 2] This is a chemical structure diagram illustrating dicarboxylic acid-functionalized flame retardants according to some embodiments of the present disclosure. [Figure 3] This is a chemical reaction diagram illustrating the process of forming flame-retardant bis(tricetone) monomers according to some embodiments of the present disclosure. [Figure 4] This is a chemical reaction diagram illustrating the process of forming flame-retardant PDK according to some embodiments of the present disclosure. [Modes for carrying out the invention]

[0007] Flame retardants are added to a wide variety of materials to ensure safety and protect them from damage. Examples of materials that often contain flame retardant additives include plastics, paints, coatings, foams, adhesives, synthetic fibers, sound-damping materials, thermal insulation materials, and synthetic rubber.

[0008] Commonly used flame retardants in the aforementioned applications include organophosphorus compounds such as organic phosphates, organophosphonates, organophosphinates, organophosphites, and organophosphonites. Organobromine compounds ("brominated flame retardants") are also used as flame retardants. Examples of these include tetrabromobisphenol A, hexabromocyclododecane, and bromodiphenyl ethers. Flame retardants may be additives or reactive. Reactive flame retardants contain functional groups that can form covalent bonds at one or more sites in the polymer matrix, be incorporated into the polymer chain as comonomers, be used as crosslinking agents, or a combination thereof. Additive flame retardants are mixed into the polymer without bonding.

[0009] The advantage of reactive flame retardants is that they do not leach out of materials as easily as additive flame retardants. When flame retardants leach out of materials, it can lead to bioaccumulation of the flame retardant and a decrease in flame retardancy over time. Due to the potential for bioaccumulation, environmental persistence, and toxicity, it has been necessary to reduce or eliminate the use of many additive flame retardants. Therefore, new reactive flame retardants are needed to replace additive flame retardants in polymer applications.

[0010] Reusable plastics made from polydiketoenamines (PDKs), such as polytriketoenamines (PTKs), and similar polymers are attracting attention because they are formed by reversible polymerization. PDKs are formed by polymerizing triketones with aromatic or aliphatic amines. The polymerization reaction results in dynamic covalent diketoenamine bonds, producing only water as a byproduct. These polymers can be readily converted back into triketone and amine monomers (e.g., using concentrated acid). Furthermore, this polymerization and depolymerization can be carried out at room temperature without catalysts, solvents, or additives. The recovered monomers can be used to remanufacture the same polymer without the loss of performance typically seen in conventional recycled plastics. PDK monomers can also be used in other formulations to produce polymers with different properties.

[0011] However, the recovery of PDK monomers can be complicated by the presence of other species bonded to the polymer matrix. For example, the bonds between these compounds and the polymer chain may not be reversible under the same conditions as the polymer itself. Furthermore, if the bonds are cleaved, it may be difficult to recover and reuse the PDK monomers in the presence of other compounds. This specification discloses flame-retardant PDKs formed from amines and flame-retardant bis(tricetone) monomers. Rather than adding flame retardants to PDK, flame-retardant organophosphorus or organobromine bis(tricetone) monomers are formed and polymerized with diamine, triamine, or polyamine monomers or combinations thereof to form flame-retardant PDKs. Flame-retardant PDKs can be reused by recovering the monomers by reversing the polymerization.

[0012] Figure 1 is a flowchart illustrating a process 100 for forming a flame-retardant PDK according to some embodiments of this disclosure. A flame-retardant bis(triketone) monomer is obtained. This is shown in step 110. In this specification, the flame-retardant bis(triketone) monomer is also referred to as a “bis(triketone) flame retardant”. A bis(triketone) flame retardant can be obtained by reacting a dicarboxylate-functionalized derivative of an organophosphorus or organobromine flame retardant (“dicarboxyl flame retardant”) with a diketone (e.g., a cyclic 1,3-diketone). This reaction can be carried out using any suitable reagents and reaction conditions for bonding the diketone at each carboxyl group to form a bis(triketone) monomer. An example of a dicarboxyl flame retardant that can be used is shown in Figure 2. An example of a reaction for forming a bis(triketone) flame retardant is shown in Figure 3. In some embodiments, two or more bis(triketone) flame retardants are obtained in step 110. This is described in detail below.

[0013] Next, an amine monomer having two or more primary amine groups is obtained. This is shown in step 120. In this specification, "amine" or "amine monomer" means diamines, triamines, polyamines, and combinations thereof, unless otherwise specified. In some embodiments, the selected amine is tris(2-aminoethyl)amine (TREN). However, any suitable aliphatic or aromatic amine monomer having at least two amine groups can be used. Examples of these amines include poly(propylene glycol)bis(2-aminopropyl ether), poly(ethylene glycol)bis(2-aminopropyl ether), poly(ethylene glycol)bis(amine), poly(tetrahydrofuran), dipropylenetriamine, diethylenetriamine, diaminooctane, 4,4'-oxydianiline, and the like. In some embodiments, two or more amines are obtained in process 100. For example, the amine monomer may be a mixture of TREN and 4,4'-oxydianiline.

[0014] A bis(tricetone) flame retardant is reacted with an amine monomer to form a flame-retardant PDK. This is shown in step 130. In some embodiments, the polymerization involves two or more amine monomers or two or more bis(tricetone) flame retardant monomers or both. Polymerization can be carried out by mechanically grinding selected amounts of monomers in a ball mill. In such cases, the reaction can be carried out at room temperature in the absence of organic solvents. However, in some embodiments, polymerization can be carried out by other techniques, such as in solution with stirring at room temperature. Techniques for forming flame-retardant PDKs are discussed in more detail with respect to Figure 4.

[0015] The properties of flame-retardant PDK can be adjusted by changing the components and conditions of the polymerization reaction in step 130. For example, the type and amount of amine monomer can be changed, as can the type and amount of bis(tricetone) flame retardant. Furthermore, non-flame-retardant bis(tricetone) monomers can be added to the reaction mixture to form copolymers (e.g., terpolymers) with amine repeating units, flame-retardant repeating units, and non-flammable ketone repeating units (see below). Additional monomers or additives, or both, that can be added (e.g., during ball milling or solvent system reactions, additional processing steps, etc.) may include any suitable polymer additives / components known to those skilled in the art (e.g., crosslinkers, dyes, pigments, plasticizers, stabilizers, etc.).

[0016] In some embodiments, the flame-retardant PDK formed in step 130 can be reacted with a strong acid. This depolymerization reaction is not illustrated herein. The reaction between flame-retardant PDK and a strong acid (e.g., sulfuric acid, hydrochloric acid, nitric acid, etc.) reverses the polymerization reaction, allowing the monomers obtained in steps 110 and 120 to be recovered. This monomer recovery reaction can be carried out at room temperature, and the monomers can be used to form new materials (e.g., flame-retardant PDK, other PDKs, other polymers and compounds, etc.). In other embodiments, the flame-retardant PDK does not react with a strong acid.

[0017] Figure 2 is a chemical structure diagram illustrating dicarboxylate-functionalized flame retardants by some embodiments of the present disclosure. Each dicarboxylate-functionalized flame retardant ("dicarboxyl flame retardant") contains two carboxyl substituents (Y). The phenyl-Y bond, represented by a dashed line to the center of the phenyl ring, indicates that the carboxyl substituent can be attached at any available position on each phenyl ring (e.g., meta, ortho, or para). In this specification, "carboxyl substituent" may refer to a carboxyl group (-COOH) or another substituent containing an alkyl (R) group and a carboxyl group. In some embodiments, Y is a substituent such as -ORCOOH or -RCOOH. For example, Y is -O(CH2) n COOH, -O(C6H4)COOH, -(CH2) n The R group may be a substituent such as COOH, where n is an integer of 1 or more. Examples of R groups include linear alkyl groups, branched alkyl groups, cyclic alkyl groups, and aromatic groups. In some embodiments, the R group may contain a heteroatom. Examples of alkyl groups that can be included in the carboxyl substituent will be discussed in more detail below.

[0018] In some embodiments, the dicarboxyl flame retardant is a dicarboxyl derivative of triphenyl phosphate 210, or a dicarboxyl derivative of tritril phosphate such as tri-o-tolyl phosphate or tri-m-tolyl phosphate or both (not shown). Further examples of dicarboxyl flame retardants include a dicarboxyl derivative of resorcinol bis(diphenyl phosphate) 220; a dicarboxyl derivative of bisphenol A bis(diphenyl phosphate) 230; a similar compound such as pentanediic acid, 3-(2-carboxy-6-oxide-6H-dibenz[c,e][1,2]oxaphosphorin-6-yl)-1-methyl ester 240 (wherein Y=-COOH) or Y=-RCOOH; a dicarboxyl derivative of 6H-dibenz[c,e][1,2]oxaphosphorin-6-oxide 250; and a dicarboxyl derivative of trialkyl phosphate 260 (wherein n is an integer of 1 or more).

[0019] In addition to the exemplified organic phosphate compounds, dicarboxyl flame retardants may include, in some embodiments, dicarboxyl derivatives of organic phosphonates, organic phosphinates, organic phosphites, and organic phosphonites. Furthermore, dicarboxyl flame retardants may include various flame-retardant organic bromine compounds such as dicarboxyl derivative 270 of tetrabromobisphenol-A or other brominated flame retardants. Examples of brominated flame retardants that can be used are discussed in more detail above. In some embodiments, carboxyl flame retardants having more than two carboxyl groups may be used.

[0020] Figure 3 is a chemical reaction diagram showing a process 300 for forming a flame-retardant bis(tricetone) monomer according to several embodiments of the present disclosure. A solution of dimedone 320 and triphenylphosphate dicarboxyl flame retardant 310 is prepared in dichloromethane (DCM). A mixture of N,N'-dicyclohexylcarbodiimide (DCC) and 4-dimethylaminopyridine (DMAP) is then added to the solution. The resulting mixture is reacted at room temperature (e.g., about 25°C). In some embodiments, the reaction mixture is stirred for about 10 minutes, but any appropriate time can be selected for the reaction (e.g., until the reaction is deemed complete). This reaction forms triphenylphosphate bis(tricetone) flame retardant 330.

[0021] The illustrated triphenylphosphate bis(triketone) flame retardant 330 is derived from the triphenylphosphate dicarboxyl flame retardant 310, but other dicarboxyl flame retardants can be used in process 300 (e.g., the dicarboxyl flame retardant shown in Figure 2). Furthermore, alternative diketones (e.g., other cyclic diketones, 1,3-diketones, etc.) can replace dimedone 320 in some embodiments. The resulting reaction can produce bis(triketone) flame retardants similar to the illustrated bis(triketone) flame retardant 330, depending on the selection of the dicarboxyl flame retardant and diketone. For example, process 300 can be carried out using dicarboxyltetrabromobisphenol A270 (Figure 2) and dimedone 320, yielding a bis(triketone) brominated flame retardant (not shown).

[0022] Figure 4 is a chemical reaction diagram showing a process 400 for forming a flame - retardant PDK according to some embodiments of the present disclosure. In process 400, triphenyl phosphate bis(triketone) flame retardant 330 (Figure 3) and TREN 410 are reacted in a ball mill that mechanically grinds the monomers together to form a flame - retardant PDK 420. This solvent - free polymerization reaction can be carried out at room temperature. The flame - retardant PDK 420 contains at least two flame - retardant repeating units and at least two TREN repeating units. The number of repeating units depends on the amount of monomers and the polymerization reaction time. For example, the number of each repeating unit can be an integer between 2 and 1,000,000 (e.g., about 2 - 25,000, about 500 - 25,000, about 1,000 - 25,000, about 2,000 - 25,000, about 5,000 - 25,000, about 25,000 - 50,000, about 50,000 - 500,000, etc.). In Figure 4, the bonds between TREN nitrogen atoms and additional flame - retardant repeating units are represented by wavy lines.

[0023] In some embodiments, the flame - retardant PDK can be formed using techniques other than ball milling. For example, a bis(triketone) flame retardant (e.g., triphenyl phosphate bis(triketone) flame retardant 330) can be dissolved in dimethylformamide (DMF) and stirred at room temperature. Then, TREN 410 or another diamine, triamine, or polyamine, or a combination thereof can be added to the solution to form a viscous solution. The viscous solution can be heated (e.g., up to about 110°C) while stirring in an open container to evaporate water. In some embodiments, these reaction conditions are maintained for about 1 hour, but the time can be varied. Then, the reaction mixture can be cooled to room temperature, purified (e.g., by diluting the mixture with dichloromethane and precipitating the polymer product from diethyl ether), and dried.

[0024] Furthermore, by performing process 400 to polymerize other dicarboxylic flame retardants or amines, or both, various flame-retardant PDKs can be formed. For example, the bis(triketone) flame retardant 330 shown in FIG. 4 can be replaced with other bis(triketone) flame retardants. Examples of other bis(triketone) flame retardants that can be used are discussed in more detail with respect to FIG. 3. Additionally, TREN 410 can be replaced or combined with other diamines, triamines, or polyamines. Examples of amines that can be used are discussed in detail with respect to FIG. 1. Further, other bis(triketone) monomers can be included in the polymerization with the bis(triketone) flame retardant 330 and TREN 410. For example, a flame-retardant terpolymer can be formed from a mixture of bis(triketone) monomers (not shown) generated by reacting the bis(triketone) flame retardant 330, TREN 410, and diketone with a dicarboxylic acid such as adipic acid, suberic acid, or sebacic acid. These non-flame-retardant bis(triketone) monomers can be formed under reaction conditions such as those of process 300 (FIG. 3).

[0025] In addition to the compounds and reactions discussed with respect to FIGS. 1-4, organophosphorus flame-retardant monomers and organobromine bis(triketone) flame-retardant monomers having other functional groups and structures can be formed and reacted with diamines, triamines, or polyamines, or combinations thereof, to form flame-retardant PDKs. For example, the bis(triketone) flame retardant or amine, or both, can be formed with additional moieties such as epoxides, hydroxyls, propylene carbonates, alkyl halides, esters, alkynes, amines, isocyanates, acid chlorides, chloroformates, alkyls, etc. As used herein, "alkyl" may be straight-chain, branched, or cyclic and is C1-C 100This refers to a group. Examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, octyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cyclooctyl. In some embodiments, the alkyl group is unsaturated (e.g., alkenes and alkynes).

[0026] Additional examples of parts that may be included in the compounds shown herein may include substituted analogs of cyclic alkyl groups. In the case of cyclic compounds, alkyl groups may be aromatic or non-aromatic. In this specification, the term “aromatic” also means pseudo-aromatic heterocycles, which are heterocycle substituents that have properties and structure (nearly planar) similar to aromatic heterocycle ligands but are not aromatic by definition. Examples of cyclic aromatic alkyl groups that can be used include six-carbon aromatic rings (phenyl) and their substituted variants (e.g., 2-methylphenyl, xylyl, tolyl, etc.), C4-C 60 Aromatic ring, C4~C 20 Examples include aromatic rings. A cyclic group may optionally contain a heteroatom (e.g., nitrogen, oxygen, or sulfur) that substitutes for at least one carbon atom in the cyclic structure.

[0027] The compounds described herein may contain one or more chiral centers. Unless otherwise specified, the disclosed structures encompass all stereoisomers, conformational isomers, rotational isomers, isomers, and enantiomers of the represented compounds. Furthermore, polymers or other materials containing the disclosed compounds may include, in addition to the individual stereoisomers, racemic forms of the compounds, as well as mixtures containing any of these. Substituents of the compounds described herein may be involved in additional chemical reactions, transformations, or interactions, including synthesis, decomposition, single or double substitution or both, oxidation / reduction, acid / base, nucleophilic substitution, electrophilic substitution and radical substitution, addition / elimination reactions, crosslinking reactions, and polymerization reactions.

[0028] If isomers named after alkyl, alkenyl, alkoxy, aryl, or other functional groups exist (e.g., n-butyl, isobutyl, sec-butyl, and tert-butyl), referring to a member of that group without specifying a particular isomer (e.g., butyl) is intended to include all isomers within that family (e.g., n-butyl, isobutyl, sec-butyl, and tert-butyl). Furthermore, unless otherwise specified, a reference to one member of the group (e.g., n-butyl) includes the remaining isomers within the family (e.g., isobutyl, sec-butyl, and tert-butyl).

[0029] Unless otherwise specified, chemical reactions are carried out under ambient conditions or with minimal heating without a special atmosphere or headspace, and can be carried out using standard organic solvents to control the mixing properties such as viscosity and flow index. Standard procedures for quenching, solvent removal, and purification of the reaction are performed. Room temperature is approximately 15°C to 30°C unless otherwise specified. Ranges given herein (e.g., time, concentration, temperature, etc.) include all numbers at both endpoints and between the endpoints. Unless otherwise specified, the use of “about,” “approximately,” or tilde (~) in relation to a range applies to both ends of the range (e.g., “approximately 1g to 5g” should be interpreted as “approximately 1g to approximately 5g”). Modifying terms such as “about,” “approximately,” and “~” indicate + / - 10% of the endpoints of the stated value, range of values, or range of one or more values.

[0030] The processes and accompanying drawings discussed herein should not be construed as limiting. Those skilled in the art will recognize that various techniques can be used to change the conditions, components, methods, etc., that ultimately produce the flame-retardant polydiketoenamine. It is also possible to arbitrarily change the conditions throughout the process. Furthermore, in some embodiments, as will be understood by those skilled in the art, the process can be added, omitted, or performed in a different order, but still remain within the scope of this disclosure. It should also be noted that the process can be performed by a single entity or multiple entities. For example, a first entity can form a bis(tricetone) flame retardant, and a second entity can perform the polymerization process.

Claims

1. At least one flame-retardant bis(tricetone) monomer, at least one amine monomer and A flame-retardant polydiketoenamine composition formed by polymerizing monomers containing, The at least one flame-retardant bis(triketone) monomer is derived from a dicarboxyl flame retardant selected from the group consisting of: dicarboxyl derivatives of triphenyl phosphate; dicarboxyl derivatives of tri-o-tolyl phosphate or tri-m-tolyl phosphate; dicarboxyl derivatives of resorcinol bis(diphenyl phosphate); dicarboxyl derivatives of bisphenol A bis(diphenyl phosphate); pentanediic acid; 3-(2-carboxy-6-oxide-6H-dibenz[c,e][1,2]oxaphosphorin-6-yl)-1-methyl ester compounds; dicarboxyl derivatives of 6H-dibenz[c,e][1,2]oxaphosphorin-6-oxide; and dicarboxyl derivatives of trialkyl phosphate, wherein a diketone is bonded to the carboxyl group of the dicarboxyl flame retardant, and the bis(triketone) monomer is derived from a dicarboxyl flame retardant selected from the group consisting of: dicarboxyl derivatives of triphenyl phosphate; dicarboxyl derivatives of triphenyl phosphate; The at least one amine monomer is selected from the group consisting of tris(2-aminoethyl)amine, poly(propylene glycol)bis(2-aminopropyl ether), poly(ethylene glycol)bis(2-aminopropyl ether), poly(ethylene glycol)bis(amine), dipropylenetriamine, diethylenetriamine, diaminooctane, 4,4'-oxydianiline, and combinations thereof. Flame-retardant polydiketoenamine composition.

2. The flame-retardant polydiketoenamine composition according to claim 1, wherein the at least one flame-retardant bis(tricetone) monomer is a triphenylphosphate bis(tricetone) flame retardant.

3. The flame-retardant polydiketoenamine composition according to claim 1 or 2, wherein the at least one amine monomer is tris(2-aminoethyl)amine.

4. The objective is to obtain at least one flame-retardant bis(tricketone) monomer by reacting a dicarboxyl flame retardant selected from the group consisting of a dicarboxyl derivative of triphenyl phosphate; a dicarboxyl derivative of tri-o-tolyl phosphate or tri-m-tolyl phosphate; a dicarboxyl derivative of resorcinol bis(diphenyl phosphate); a dicarboxyl derivative of bisphenol A bis(diphenyl phosphate); pentanediic acid; 3-(2-carboxy-6-oxide-6H-dibenz[c,e][1,2]oxaphosphorin-6-yl)-1-methyl ester compound; a dicarboxyl derivative of 6H-dibenz[c,e][1,2]oxaphosphorin-6-oxide; and a dicarboxyl derivative of trialkyl phosphate with a diketone compound. To obtain at least one amine monomer, Polymerizing the at least one flame-retardant bis(tricetone) monomer and the at least one amine monomer to form a flame-retardant polydiketoenamine, Methods that include...

5. The method according to claim 4, wherein the at least one flame-retardant bis(tricetone) monomer is a triphenylphosphate bis(tricetone) flame retardant.

6. The method according to claim 4 or 5, wherein the at least one amine monomer is tris(2-aminoethyl)amine.

7. The method according to any one of claims 4 to 6, wherein the polymerization is carried out in a ball mill.

8. The method according to any one of claims 4 to 7, wherein the diketone compound is a 1,3-diketone.

9. Articles containing flame-retardant polymers, The flame-retardant polymer comprises the flame-retardant polydiketoenamine composition described in any one of claims 1 to 3, in an article.

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