Ionic liquids used as flame retardant synergistic agents in polyamide polymers

Abstract

The present invention provides a flame-retardant or fire-resistant material comprising a flame retardant for use with a polyamide composition, which maintains a uniform dispersion within the polyamide composition. [Solution] A flame-retardant or fire-resistant material is provided comprising a base material which can be selected from polyamide or nylon, a non-halogenated flame-retardant component, and an ionic liquid flame-retardant component, wherein the ionic liquid compound improves the fire resistance of the material. The flame-retardant or fire-resistant material exhibits desired mechanical properties. In some embodiments, the disclosed flame-retardant or fire-resistant material may also include additional known flame-retardant compounds, such as nitrogen-based or phosphorus-based compounds. In some embodiments, the flame-retardant or fire-resistant material includes a glass fiber filler.

Description

[Technical Field]

[0001] This disclosure, in a broad sense, relates to novel flame-retardant or fire-resistant compounds and compositions for polyamides, and such flame-retardant or fire-resistant compounds and compositions include ionic liquids. [Background technology]

[0002] Flame retardants are chemical additives that can be used in a wide range of consumer products, including plastics, textiles, leather, paper, and rubber. Commonly used chemicals as flame retardants may include inorganic substances, halogen-containing chemicals, nitrogen-containing chemicals, phosphorus-containing chemicals, and silicon-based chemicals. The term "retardant" refers to a classification of use, not a classification of chemical structure.

[0003] Preventive flame protection, including the use of flame retardants, has been practiced since ancient times. For example, alum was used by the ancient Egyptians to reduce flammability. The emergence of synthetic polymers in the 20th century created a need for new flame retardants, as previously used water-soluble inorganic salts were of little or no use in mostly hydrophobic materials. Therefore, modern development efforts have mainly focused on developing polymer-compatible flame retardants.

[0004] Basically, four processes—preheating, decomposition, ignition and combustion, and propagation—are involved in the flammability of polymers. Flame retardants, through physical or chemical action, prevent combustion during specific stages of this process, namely heating, decomposition, ignition, or flame diffusion.

[0005] For example, there are several ways in which the combustion process can be delayed by physical actions such as cooling, forming a protective layer / coating, and / or dilution. During cooling, an endothermic process induced by the flame retardant may cool the material to below the temperature required to maintain the combustion process. By forming a protective layer / coating, the condensed flammable layer may be shielded from the gas phase with a solid or gaseous protective layer. Thus, the condensed phase is cooled, a small amount of pyrolysis gas is generated, oxygen necessary for the combustion process is eliminated, and heat transfer is hindered. In dilution, the fuel in the solid and gas phases may be diluted so as not to exceed the lower ignition limit of the gas mixture by incorporating inert substances (e.g., fillers) and additives that generate inert gases upon decomposition.

[0006] Flame retardants can also inhibit combustion by providing chemical reactions that disrupt the combustion process occurring in the solid and / or gas phases. Regarding reactions in the gas phase, the free radical mechanism of the combustion process occurring in the gas phase is interrupted by the flame retardant. Thus, the exothermic process is stopped, the system is cooled, the supply of flammable gases is reduced, and ultimately, it may be completely suppressed. Regarding reactions in the solid phase, two types of reactions can occur. Firstly, the decomposition of polymers can be promoted by flame retardants, causing significant polymer flow, thereby moving the polymer out of the flame's influence and separating the flame from the polymer. Secondly, flame retardants can cause the formation of a carbon layer on the polymer surface. This can occur, for example, through the dehydrating effect of the flame retardant, which creates double bonds in the polymer. These can then successively form carbonaceous layers through cyclization and crosslinking.

[0007] Bromogenic flame retardants, such as polybrominated diphenyl ethers (PBDEs), were first introduced to the consumer market in the 1970s. They exhibited high compatibility with plastics and textiles and provided excellent flame retardant properties. Bromogenic flame retardants inhibit combustion by volatilizing bromine radicals, which react with high-energy free radicals O· and ·OH produced by combustion, thereby preventing the spread of flames. The most commonly used bromogenic flame retardants are PBDEs and tetrabromobisphenol A (TBBPA).

[0008] Significant efforts are being made to develop halogen-free flame retardants, particularly phosphorus-based flame retardants.

[0009] Other flame retardants have been developed for use in polyamide polymers, but they exhibit similar drawbacks. Melamine cyanurate (MCA) is used as an efficient and cost-effective flame retardant in PA6 and PA66, particularly in unfilled polymers. However, MCA exhibits strong hydrogen bonding and a strong tendency to aggregate. Therefore, its flame retardant performance is unstable. Much research effort has been made to stabilize MCA dispersions in polymers, but to date, these have been largely unsuccessful.

[0010] On the other hand, aluminum diethylphosphinate (ADP) is often used in glass fiber reinforced polyamides. ADP is typically used in combination with melamine polyphosphate (MPP) in general-purpose applications. However, MPP migration often leads to deposition on the injection molding machine surface, resulting in downtime for cleaning and shortening the usable life of the machine and its components. In some applications, ADP is used in combination with aluminum phosphinate (AP) to reduce the migration of flame retardants to the outside of the polymer composition. However, under harsh dual 85 conditions (85% humanity and 85°C), ADP+AP formulations are typically only stable for a maximum of 4 or 5 days, which is far below the 3000-hour stability requirement expected in general-purpose applications.

[0011] It is desirable to develop a flame retardant for use with a polyamide composition that maintains a uniform dispersion in the polyamide composition without any migration from the polyamide or polyamides. The present invention addresses these needs. SUMMARY OF THE INVENTION

[0012] In one embodiment, the present disclosure provides a flame retardant or fire resistant material comprising a substrate that can be selected from polyamides or nylons, a non-halogenated flame retardant component, and an ionic liquid flame retardant component, wherein the ionic liquid flame retardant component comprises a compound having the chemical formula (I):

Chemical formula

[0013] In another embodiment, the disclosed flame-retardant or fire-resistant material may include additional flame-retardant materials, which are not limited to but include inorganic flame retardants, phosphorus-based flame retardants, nitrogen-based flame retardants, silicon-based flame retardants, nanoparticle flame retardants, or any combination thereof. In yet another embodiment, the fire-resistant or flame-retardant material maintains excellent mechanical properties and processability. In yet another embodiment, the disclosed flame-retardant or fire-resistant material may include fillers such as glass fibers. In yet another embodiment, the disclosed ionic liquid (IL) flame retardant does not leach from nylon or polyamide substrates over time. Articles containing the disclosed flame-retardant material are also disclosed. [Modes for carrying out the invention]

[0014] In one embodiment, the ionic liquid has excellent dissolving power for various materials. As disclosed herein, when an ionic liquid (IL) is used in combination with MCA, a small amount of IL can stabilize the MCA dispersion in the polymer. In a further embodiment, the resulting flame retardancy may be very stable. In a further embodiment, the mechanical properties of the polymer may also be maintained or even improved.

[0015] In one embodiment, although we do not wish to be constrained by theory, when IL is dispersed in a polymer, the ionic nature of IL can introduce strong intramolecular forces between the IL molecules and the polymer chains. In a further embodiment, as a result, the migration pathways between polymer chains are blocked. Therefore, in yet another embodiment, when IL is used in combination with ADP / MPP or ADP / AP, the leaching resistance of the flame retardant can be further improved while maintaining or improving the mechanical properties of the polymer.

[0016] In one embodiment of the flame-retardant material, the material can be selected from the group consisting of resins or plastic products. In another embodiment described above, the flame-retardant composition further includes additives selected from the group consisting of softeners, antifouling agents, and combinations thereof. The vertical fire resistance determined by this test method relates to a specific flame exposure and application time.

[0017] One modified example provides a method for imparting flame retardant properties to a material, which involves mixing a polyamide-based composition, which is a combination of a metal hydroxide, a hydroxide carbonate, a borate, etc., with the material in an amount that yields effective flame retardancy.

[0018] Another modification provides a method for imparting flame retardant properties to a material, which includes mixing a polyamide-based composition combined with an organic flame retardant with the material in an amount that yields effective flame retardancy. Another modification provides a method for imparting flame retardant properties to a material, which includes mixing a polyamide-based composition combined with a halogenated flame retardant with the material in an amount that yields effective flame retardancy. Another modification provides a method for imparting flame retardant properties to a material, which includes mixing a polyamide-based composition combined with a halogenated flame retardant additive, a reactive flame retardant such as a halogenated monomer and a halogenated copolymer with the material in an amount that yields effective flame retardancy.

[0019] Further modifications provide a method for imparting flame retardant properties to a material, comprising mixing a polyamide compound combined with a phosphorus-based flame retardant with the material in an amount that yields effective flame retardancy. Another modification provides a flame retardant composition comprising mixing an ionic liquid combined with red phosphorus, inorganic phosphorus, an organophosphorus compound, an expanding flame retardant system, etc., with the disclosed polyamide compound.

[0020] In certain modifications, a method is provided for imparting flame retardancy to a nylon material, comprising mixing a composition having a nitrogen-based flame retardant disclosed herein with the nylon material in an amount that yields effective flame retardancy. In yet another modification, a method is provided for imparting flame retardancy to a nylon material, comprising mixing a composition of the above chemical formula combined with a silicon-based flame retardant with the nylon material in an amount that yields effective flame retardancy. In yet another modification, a method is provided for imparting flame retardancy to a nylon material, comprising treating the nylon material with a composition of the above formulation combined with silicon, silica, etc., in an amount that yields effective flame retardancy.

[0021] Another modification provides a method for imparting flame retardancy to a nylon material, comprising mixing a composition of the disclosed formulation, combined with nanoparticles, with the material in an amount that yields effective flame retardancy. A specific modification provides a method for imparting flame retardancy to a nylon material, comprising mixing a composition disclosed herein, combined with nanoclay, carbon nanotubes, nanoscale particle additives, etc., with the nylon material in an amount that yields effective flame retardancy.

[0022] Another modification provides a method for imparting flame retardancy to a nylon material, comprising mixing a disclosed ionic liquid, which also functions as a dispersant, with the nylon material in an amount that yields effective flame retardancy. Another modification provides a method for imparting flame retardancy to a nylon material, comprising mixing a disclosed ionic liquid, which also functions as a plasticizer, with the nylon material in an amount that yields effective flame retardancy.

[0023] One modification provides a method for imparting flame retardancy to a nylon material, comprising mixing a disclosed ionic liquid composition, which also functions as an antimicrobial agent, with the nylon material in an amount that yields effective flame retardancy. Another modification provides a method for imparting flame retardancy to a nylon material, comprising mixing a disclosed ionic liquid composition, which also functions as a lubricant, with the material in an amount that yields effective flame retardancy. Yet another modification provides a method for imparting flame retardancy to a nylon material, comprising mixing a disclosed ionic liquid composition, which also functions as a corrosion resistant agent, with the material in an amount that yields effective flame retardancy.

[0024] In one embodiment, the ionic liquid flame retardant composition of the present disclosure may be derived from biomaterials, such as carbohydrates, amino acids, fatty acids, nucleotides, and other organic and inorganic chemicals derived from biomaterials.

[0025] (Ionic liquid) In one embodiment, to replace bromide flame retardants and other compounds that may have toxic bioaccumulative effects, a different class of materials, namely ionic liquids ("ILs"), are disclosed herein and can be used for flame retardant purposes.

[0026] While we do not wish to be limited by theory, ionic liquids are, as is well known in the art, salts in which ions are not sufficiently bonded. At least one ion in the salt has a delocalized charge, and one component is an organic substance that prevents the formation of a stable crystal lattice.

[0027] In one embodiment, ionic liquids have the ability to form a wide range of intermolecular interactions, including strong and weak ionic interactions, hydrogen bonding interactions, van der Waals interactions, dispersive interactions, and π-π interactions. In another embodiment, ionic liquids demonstrate compatibility with a wide variety of materials, including salts, fats, proteins, amino acids, surfactants, oils, inks and plastics, and even DNA. In further embodiments, ionic liquids have been intensively studied for many applications, such as solvents, catalysts, separation, extraction, and biomass processing. In further embodiments, ILs have been used as plasticizers, dispersants, and lubricants. In one embodiment, when used as plasticizers, they exhibit excellent resistance to migration and leaching; this mitigates one of the most important problems with current flame retardant compounds.

[0028] In one embodiment, the ionic liquid is a compound that may contain halogens, nitrogen, sulfur, phosphorus, or some combination of these elements, and thus the compound may be used as a flame retardant, either through a physical or chemical action to inhibit the combustion process, as described above. In one embodiment, functionalization of the ligand or "head," for example, by changing the length of the R group of the ligand, by adding the ligand to different positions on the head, and / or by adding halogens to the ligand or head, further increases the number of possible ionic liquid flame retardants. In one embodiment, the head may be defined as the positively charged central atom or ring of the cation species of the ionic liquid. In one embodiment, the ionic liquid is modified to design biodegradable and non-toxic ionic liquids through the introduction of ether side chains.

[0029] In another embodiment, the ionic liquid may be compounded with other ionic liquids or conventional flame retardants or additives. In further embodiments, these conventional flame retardants may be inorganic flame retardants, halogen-containing flame retardants, phosphorus-based flame retardants, nitrogen-based flame retardants, silicon-based flame retardants, nanoparticles, etc. In further embodiments, the inorganic flame retardant may be a metal hydroxide, a hydroxide carbonate, a borate, etc.; the halogen-containing flame retardant may be a halogen flame retardant additive, a reactive halogenated flame retardant monomer, or a polymer; the phosphorus-based flame retardant may be red phosphorus, an inorganic phosphate, an organophosphorus compound, etc.; the silicon-based flame retardant may be silicon, a silica compound, etc.; and the nanoparticles may be nanoclay, a carbon nanotube, a nanoscale fine particle additive, etc.

[0030] In further embodiments, ionic liquids may also be used as multifunctional additives in polyamide compositions disclosed herein. For example, ionic liquids can be used as lubricants and flame retardants, plasticizers and flame retardants, dispersants and flame retardants, antimicrobial agents and flame retardants, or any combination thereof.

[0031] (Nylon polymer) Nylon, also known as polyamide, is a synthetic polymer having an amide backbone, which links to aliphatic or semi-aromatic side-chain chemical groups. Nylon polymers are thermoplastic and are typically white or colorless. Their properties can be modified through the use of various additives. Nylon is typically divided into families, the two most common of which are known as nylon-XY and nylon-Z. In one embodiment, nylon-XY is derived from diamines having carbon chain length X and dicarboxylic acids having carbon chain length Y. In a further embodiment, an example of nylon-XY is nylon-6,6, derived from hexamethylenediamine and adipic acid. Other examples of nylon-XY polymers include nylon-6,12 and nylon-4,6. In another embodiment, nylon-Z is derived from aminocarboxylic acids having carbon chain length Z. In one embodiment, nylon-6 is an example of a nylon-Z polymer, which can be derived from ring-opening polymerization of caprolactam. Other examples of nylon-Z polymers include nylon-11 and nylon-12.

[0032] In one embodiment, the nylon polymer may have various fillers, including, but not limited to, glass fibers. In a further embodiment, the glass fibers are typically incorporated at about 10 wt% to about 40 wt% of the nylon composition. In a further embodiment, a blend of nylon and about 30 wt% glass fibers may be particularly useful in extrusion-based processes. In some embodiments, the addition of glass fibers to nylon can increase strength and durability, but may also provide rigidity. In another embodiment, the addition of glass fibers reduces the thermal expansion coefficient of nylon, making it less susceptible to shape changes with temperature. In yet another embodiment, the addition of glass fibers can improve the impact resistance, chemical resistance, and moldability of the nylon composition. In one embodiment, both unfilled and glass-filled nylon can be good electrical insulators.

[0033] In some embodiments, it may be desirable, depending on the application, to omit glass fillers from the nylon. In one embodiment, the glass may increase the cost, weight, and abrasion of the nylon composition. In another embodiment, glass-filled nylon may exhibit anisotropic behavior, which may be desirable or undesirable depending on the particular application. In some embodiments, glass-filled nylon may be brittle. Therefore, in one embodiment, a person skilled in the art can choose whether or not to use glass fillers in a given nylon composition based on the desired end use of the article produced from that composition.

[0034] In any of these embodiments, the disclosed nylon composition containing an ionic liquid flame retardant may be processed by 3D printing, injection molding, CNC machining, extrusion, or any other method typically used to process thermoplastic polymers.

[0035] In other embodiments, the disclosed nylon composition can be used in a variety of applications where flame-retardant nylon is required, including but not limited to automotive parts, electronic devices, and consumer goods (e.g., electrical appliances, kitchenware). In some embodiments, the disclosed nylon composition can be used in textile applications, including but not limited to clothing, airbags, parachutes, nets, ropes, tents, and conveyor belts.

[0036] Methods are provided for improving the fire resistance of flame-retardant or fire-resistant materials and nylon materials, or for imparting fire resistance to nylon materials. The disclosure provides a fire-resistant composition comprising a polyamide polymer and an ionic liquid compound, wherein the ionic liquid compound improves the fire resistance or flame retardancy of the polyamide polymer while maintaining excellent processability and good mechanical properties in existing equipment. The disclosure also provides a method for preparing a polymer composition having improved flame retardancy by mixing an ionic liquid compound with a polyamide polymer to obtain a flame-retardant or fire-resistant material.

[0037] For convenience, prior to any further description of the present invention, the specific terms used herein, in the examples and in the appended claims are summarized here. These definitions should be read in light of the remainder of the disclosure and understood by those skilled in the art. Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art. Terms used throughout this specification are defined as follows, unless otherwise limited in specific examples:

[0038] The articles "a," "an," and "the" are used to refer to one or more (i.e., at least one) grammatical objects of the article.

[0039] The term "about" is used herein to indicate that the value includes inherent variations in the error of the apparatus, the method used to determine the value, or the variations that exist between the items under consideration.

[0040] When used herein, the terms "optional" and "optionally" mean that the event or situation described thereafter may or may not occur, and that the description includes both cases in which the event or situation occurs and cases in which it does not. For example, "optionally substituted aryl" includes both "aryl" and "substituted aryl" as defined herein.

[0041] As used herein, the term "alkyl" refers to a linear or branched saturated hydrocarbon. Examples of alkyl groups include, but are not limited to, methyl, ethyl, propyl such as propan-1-yl, propan-2-yl(iso-propyl), butane-1-yl, butane-2-yl(sec-butyl), 2-methyl-propan-1-yl(iso-butyl), 2-methyl-propan-2-yl(tert-butyl), pentyl, hexyl, octyl, and decyl.

[0042] As used herein, the term “aryl” refers to a monocyclic aromatic hydrocarbon group or a polycyclic group comprising at least one aromatic hydrocarbon ring. In certain embodiments, the aryl group has 6 to 15 or more ring atoms, or 6 to 12 or more ring atoms, or 6 to 10 or more ring atoms. Examples of aryl groups, but not limited to these, include phenyl, naphthyl, fluorenyl, azlenyl, anthryl, phenanthryl, biphenyl, and terphenyl. The aromatic hydrocarbon ring of the aryl group may be bonded to or condensed to one or more saturated, partially unsaturated, or aromatic rings, such as dihydronaphthyl, indenyl, indanyl, and tetrahydronaphthyl (tetralinyl). The aryl group may optionally be substituted with one or more substituents as described herein.

[0043] As used herein, the term "cycloalkyl" refers to a saturated or unsaturated monocyclic, bicyclic, other polycyclic, or bridging cyclic hydrocarbon group. A cycloalkyl group may have 3 to 22, 3 to 12, or 3 to 8 ring carbons, respectively (C3-C 22 )Cycloalkyl, (C3-C 12 These are called cycloalkyl or (C3-C8)cycloalkyl groups. Cycloalkyl groups may also have one or more carbon-carbon double bonds or carbon-carbon triple bonds.

[0044] The terms “heterocyclyl,” “heterocycle,” or “heterocycle(-)” refer to a cyclic group containing at least one heteroatom as a ring atom. In some embodiments, a heterocyclyl, heterocycle, or heterocycle group contains one to three heteroatoms as ring atoms, the remainder of which are carbon atoms. Examples of heteroatoms include oxygen, sulfur, and nitrogen. In some embodiments, the heterocycle may be a 3 to 10-membered ring structure or a 3 to 7-membered ring, the ring structure containing one to four heteroatoms. A “heterocyclyl,” “heterocycle,” or “heterocycle(-)” may be a single saturated or partially unsaturated non-aromatic ring or a non-aromatic polycyclic system. Examples of heterocyclic compounds include, but are not limited to, azetidine, aziridine, imidazolidine, morpholine, oxirane (epoxide), oxetane, piperazine, piperidine, pyrazolidine, piperidine, pyrrolidine, pyrrolidinone, tetrahydrofuran, tetrahydrothiophene, dihydropyridine, tetrahydropyridine, tetrahydro-2H-thiopyran 1,1-dioxide, quinuclidine, N-bromopyrrolidine, and N-chloropiperidine.

[0045] As used herein, the term “heteroaryl” refers to a monocyclic, bicyclic, or polycyclic aromatic ring system containing one or more heteroatoms, such as nitrogen, oxygen, and sulfur, e.g., one to three heteroatoms. Heteroaryls can also be fused to non-aromatic rings. In various embodiments, as used herein, the term “heteroaryl” refers to a stable 5 to 7-membered monocyclic, stable 9 to 10-membered fused bicyclic, or stable 12 to 14-membered fused tricyclic heterocyclic system containing an aromatic ring containing at least one heteroatom selected from the group consisting of N, O, and S. In some embodiments, at least one nitrogen is present in the aromatic ring. Examples of heteroaryl groups include, but are not limited to, acridine, benzimidazole, benzothiophene, benzofuran, benzoxazole, benzothiazole, carbazole, carboline, cinnoline, furan, imidazole, imidazopyridine, indazole, indole, indoline, indidine, isobenzofuran, isochromene, isoindole, isoindoline, isoquinoline, isothiazole, isoxazole, naphthyridine, oxadiazole, oxazole, perimidine, phenanthoridine, phenanthroline, phenazine, phthalazine, pteridine, purine, pyran, pyrazine, pyrazole, pyridazine, pyridine, pyridone, pyrimidine, pyrrole, pyrrolidine, quinazoline, quinoline, quinoridine, quinoxaline, tetrazole, thiadiazole, thiazole, thiophene, triazole, and xanthene.

[0046] All numerical ranges in this specification include all numerical values ​​and all numerical ranges within the numerical ranges described. As a non-limiting example, (C1-C6)alkyl also includes any one of C1, C2, C3, C4, C5, C6, (C1-C2), (C1-C3), (C1-C4), (C1-C5), (C2-C3), (C2-C4), (C2-C5), (C2-C6), (C3-C4), (C3-C5), (C3-C6), (C4-C5), (C4-C6), and (C5-C6)alkyl.

[0047] As used herein, the terms “halo,” “halide,” and “halogen” refer to an atom selected from fluorine, chlorine, bromine, and iodine.

[0048] As used herein, the term “thermoplastic” refers to a polymer that becomes plastic or flexible when heated and hardens or solidifies when cooled, and this process can be repeated. In some embodiments, thermoplastic materials may have high molecular weights, and polymer chains associate by intermolecular forces that may weaken with increasing temperature. In one embodiment, thermoplastic resins can be molded or reshaped and molded. On the other hand, the term “thermosetting” refers to a polymer that forms irreversible chemical bonds during curing. In one embodiment, a cured thermosetting polymer decomposes rather than melts when heated and does not reform when cooled. In one embodiment, the polymer composition described herein is not thermosetting and does not contain a thermosetting polymer. In further embodiments, some categories of polymers, such as polyurethane, may include both thermosetting and thermoplastic types.

[0049] As used herein, the term “recycled” refers to polymer materials or plastics that have been reprocessed into new products. Recycled polymers or plastics may be waste from the initial processing step or materials after consumer or industrial use. In one embodiment, polymers and polymer compositions useful herein can be recycled. In another embodiment, “mechanical recycling” of plastics and / or polymers occurs when plastics and / or polymers are remelted and remolded. In some embodiments, mechanical recycling may further include regrinding the plastic either before or after remelting. In some embodiments, mechanical recycling may cause polymer decomposition, which may result in a decrease in processing performance, such as an undesirable change in melt flow rate, compared to unused polymers. In another embodiment, thermoplastic materials exposed to thermal and / or mechanical stress may become weak and brittle and / or otherwise prone to degradation. In one embodiment, polymers, polymer compositions, and thermoplastic materials useful herein may be recycled materials or blends of recycled and unused materials.

[0050] In one embodiment, a flame-retardant or fire-resistant material comprising a substrate, a non-halogenated flame-retardant component, and an ionic liquid flame-retardant component is disclosed herein, wherein the ionic liquid flame-retardant component comprises a compound having chemical formula (I): [ka] Here A is P, and each of R1, R2, R3 and R4 may be unsubstituted or substituted with halogen, nitro, trifluoromethyl, trifluoromethoxy, methoxy, carboxy, -NH2, -OH, -SH, -NHCH3, -N(CH3)2, cyano, -SMe, and -SO3H, (C1-C 20 )alkyl, aryl, (C3-C 10 ) Heterocyclyl, (C3-C 10 )Cycloalkyl, (C3-C 10) Independently selected from the group consisting of heterocyclyl(C1-C8)alkyl, aryl(C1-C8)alkyl, heteroaryl, and heteroaryl(C1-C8)alkyl. - is a halide, [B(R)4] - , OH - SCN - , RPO4 - ,(RO)2P(=O)O - , RSO4 - , RSO3 - ROSO3 - [N(CN)2] - ...RCOO] - [NO3] - [PF6] - [BF4] - (RSO2)2N - Selected from the group consisting of oxalates, dicarboxylates and tricarboxylates, formates, phosphates and aluminates, where each R may be unsubstituted or substituted with halogen, nitro, methoxy, carboxy, -NH2, -OH, -SH, -NHCH3, -N(CH3)2, -SMe and cyano, (C1-C 20 )alkyl, aryl, (C3-C 10 ) Heterocyclyl, (C3-C 10 )Cycloalkyl, (C3-C 10 ) Independently selected from the group consisting of heterocyclyl(C1-C8)alkyl, aryl(C1-C8)alkyl, heteroaryl, and heteroaryl(C1-C8)alkyl.

[0051] And in one embodiment, X - is a halide, [B(R)4] - , OH - SCN - , RPO4 - ,(RO)2P(=O)O - , RSO4 - , RSO3 - ROSO3 - [N(CN)2] - ...RCOO] - [NO3] -[PF6] - [BF4] - (RSO2)2N - Selected from the group consisting of oxalates, dicarboxylates and tricarboxylates, formates, phosphates and aluminates, where each R may be unsubstituted or substituted with halogen, nitro, methoxy, carboxy, -NH2, -OH, -SH, -NHCH3, -N(CH3)2, -SMe and cyano, (C1-C 20 )alkyl, aryl, (C3-C 10 ) Heterocyclyl, (C3-C 10 )Cycloalkyl, (C3-C 10 ) Independently selected from the group consisting of heterocyclyl(C1-C8)alkyl, aryl(C1-C8)alkyl, heteroaryl, and heteroaryl(C1-C8)alkyl.

[0052] In another embodiment, each of R1, R2, R3, or R4 is independently (C1-C 20 ) Selected from the group consisting of alkyl, aryl, and aryl(C1-C8)alkyl; X - (CN)2N - RCOO - , halides, OH - SH - 5CN - [PF6] - [BF4] - , RSO3 - , RSO3 - , RSO3 - ROSO3 - ,(RO)2P(=O)O - and (RSO2)2N - Selected from the group consisting of, where R may optionally be substituted with a halogen, (C1-C 20 ) Selected from the group consisting of alkyl, aryl, and aryl, (C1-C8)alkyl.

[0053] In one embodiment, the substrate may be a polyamide polymer. In a further embodiment, the polyamide polymer may be a nylon-XY polymer or a nylon-Z polymer. In one embodiment, the nylon-XY polymer may be nylon-6,6; nylon-6,12; nylon-4,6; or any combination thereof. In another embodiment, the nylon-Z polymer may be nylon-6, nylon-11, nylon-12, or any combination thereof.

[0054] In one embodiment, the polyamide may be a natural or synthetic polyamide. In another embodiment, the polyamide may be an aliphatic polyamide or an aromatic polyamide, or may contain both aromatic and aliphatic segments (i.e., it may be a polyphthalamide). In yet another embodiment, if the polyamide contains an aliphatic segment, the aliphatic segment may have about 1 to about 10 carbon atoms, or may have 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 carbon atoms, or any combination of the aforementioned values, or a range encompassing any of the aforementioned values. In one embodiment, the polyamide is nylon 3 (poly(propiolactam)), nylon 6 (poly(caprolactam)), nylon 8 (polycapryllactam), nylon 10 (poly(decano-10-lactam)), nylon 11 (poly(undecano-11-lactam)), nylon 12 (poly(dodecano-12-lactam)), nylon 4,6 (poly(tetramethyleneadipamide)), nylon 6,6 (poly(hexamethyleneadipamide)), nylon 6,9 (poly The polyamides may be poly(hexamethylene azeramide), nylon 6,10 (poly(hexamethylene sebamid)), nylon 6,12 (poly(hexamethylene dodecanediamide)), nylon 10,10 (poly(decamethylene sebamid)), poly(hexamethylene isophthalamide), poly(hexamethylene teraphthalamide), poly(m-phenylene teraphthalamide), poly(nonane methylene teraphthalamide), para-aramid, or any combination thereof. In alternative embodiments, the thermoplastic polymer may be one or more polyamides listed herein.

[0055] In one embodiment, in a flame-retardant or fire-resistant material, the base material is present in an amount of about 80 wt% to about 95 wt% of the flame-retardant or fire-resistant material.

[0056] In one embodiment, the non-halogenated flame retardant component may include inorganic flame retardants, phosphorus-based flame retardants, nitrogen-based flame retardants, silicon-based flame retardants, nanoparticle flame retardants, or any combination thereof. In another embodiment, the non-halogenated flame retardant component may be selected from melamine cyanurate (MCA), aluminum diethylphosphinate (ADP), aluminum phosphate (AP), or any combination thereof. In one embodiment, the total amount of flame retardants, including the non-halogenated flame retardant in combination with an ionic liquid flame retardant, may be about 5 wt% to about 20 wt%, or about 8 wt% to about 16 wt%, or about 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or about 20 wt% of the flame retardant material. In one embodiment, in a flame-retardant or fire-resistant material, the weight ratio of a non-halogenated flame retardant component to an ionic liquid flame retardant component is about 21:1 to about 4:1, or about 21:1, about 17:1, about 15:1, or about 4:1. In one embodiment, the ionic liquid flame retardant component may be tributyl(ethyl)phosphonium 4-methylbenzenesulfonate.

[0057] In one embodiment, the flame-retardant or fire-resistant material has an UL94 flammability rating of at least V2 or at least V0. In one embodiment, the flame-retardant or fire-resistant material has a flammability rating of at least about 5 kJ / m³ 2 The above-mentioned impact strength with a Charpy notch conforms to ISO 179.

[0058] In one embodiment, a filler material comprising a flame-retardant or fire-resistant material and a filler material is disclosed herein. In another embodiment, the filler material may be glass fiber. In one embodiment, the filler material is present in an amount of about 10 wt% to about 40 wt% relative to the amount of the flame-retardant or fire-resistant material. In one embodiment, the filler material is present in an amount of about 30 wt% relative to the amount of the flame-retardant or fire-resistant material. In one embodiment, the filler material has an UL94 flammability rating of at least V2 or at least V0. In one embodiment, the filler material is maintained without blooming for at least 3000 hours at 85°C and 85% relative humidity.

[0059] In one embodiment, disclosed herein is a flame-retardant or fire-resistant material wherein the base material is nylon-6,6, the non-halogenated flame retardant component is MCA, and the ionic liquid flame retardant component is tributylethylphosphonium 4-methylbenzenesulfonate. In one embodiment, disclosed herein is a flame-retardant or fire-resistant material wherein the base material is nylon-6,6, the non-halogenated flame retardant component is MCA, and the ionic liquid flame retardant component is tributylethylphosphonium 4-methylbenzenesulfonate. In one embodiment, disclosed herein is a filler material wherein the base material is nylon-6,6, the non-halogenated flame retardant component is a combination of ADP and AP, and the ionic liquid flame retardant component is tributylethylphosphonium 4-methylbenzenesulfonate. In one embodiment, disclosed herein is a filler material wherein the base material is nylon-6, the non-halogenated flame retardant component is a combination of ADP and AP, and the ionic liquid flame retardant component is tributylethylphosphonium 4-methylbenzene sulfonate.

[0060] Furthermore, this specification discloses articles comprising the disclosed flame-retardant or fire-resistant materials and / or the disclosed filler materials.

[0061] In alternative embodiments, the nylon polymer is a single polymer and not a blend of two or more different nylon polymers.

[0062] In yet another embodiment, the thermoplastic polymer may be a blend of at least one recycled polymer and at least one unused polymer. In yet another embodiment, the at least one recycled polymer and the at least one unused polymer may be the same or different polymers. In yet another embodiment, if the thermoplastic polymer is a blend of at least one recycled polymer and at least one unused polymer, the blend may include about 1% to about 99% recycled polymer and about 99% to about 1% unused polymer, or about 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or about 99% recycled polymer and about 99, 95, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10, 5, or about 1% unused polymer, or any combination of the aforementioned values, or a range encompassing any of the aforementioned values. In yet another embodiment, at least one recycled polymer, at least one unused polymer, or both may be a blend of two or more different thermoplastic polymers as described above. In yet another embodiment, the thermoplastic polymer is not a blend of recycled and unused polymers, but instead comprises either 100% of one or more recycled polymers or one or more unused polymers.

[0063] In another embodiment, the Disclosure provides a method for preparing a polymer composition having an improved fire resistance, comprising the step of mixing a polyamide polymer in an optional range of about 80 wt% to about 95 wt%, between about 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, or about 95 wt%, or between the aforementioned values, or any combination of the aforementioned values, or a range encompassing any of the aforementioned values, with a flame retardant in an optional range of about 5 wt% to about 20 wt%, or between about 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or about 20 wt%, or any combination of the aforementioned values, or a range encompassing any of the aforementioned values, which includes both a non-halogenated flame retardant and a compound having formula (I). In one embodiment, as used herein, the term "flame retardant" refers to a composite material comprising both a non-halogenated flame retardant and a compound having formula (I).

[0064] In one embodiment, in the flame-retardant or fire-resistant material, the weight ratio of the non-halogenated flame-retardant component to the ionic liquid flame-retardant component is about 21:1 to about 4:1, or about 21:1, about 17:1, about 15:1, or about 4:1. Therefore, in one embodiment, when carrying out the method, the non-halogenated flame-retardant material (e.g., APP, AP, MCA) and the compound having formula (I) can be mixed before being added to the substrate, or added separately to the substrate, or added separately to two different parts of the substrate or two different nylon polymers. In further embodiments, the order of addition is not important as long as the composition is properly mixed and the final flame-retardant or fire-resistant material has the components in the indicated proportions.

[0065] In one embodiment, a flame retardant can be added during the process of manufacturing the polyamide polymer. In a further embodiment, if the polyamide polymer is a blend of two or more polyamide polymers, the flame retardant can be added to one polymer or two or more polymers. In some embodiments, if the polyamide polymer contains a portion of recycled material and a portion of unused polymer, the flame retardant can be added to the unused polymer during the manufacturing of the unused polymer.

[0066] In another embodiment, the flame retardant may be added after the thermoplastic polymer has already been manufactured. Furthermore, in this embodiment, mixing may be required to ensure uniform dispersion of the flame retardant throughout the polyamide composition.

[0067] In yet another embodiment, if the polyamide composition comprises a mixture of unused polymers and recycled polymers, the flame retardant can be added to the recycled polymers after or during any recycling process, or the same or a different flame retardant can be added to the unused polymers during the manufacturing process. In yet another embodiment, if the polymer composition comprises a mixture of unused polymers and recycled polymers, the flame retardant can be added to the recycled polymers after any recycling process, or the flame retardant can be added to the unused polymers during the manufacturing process. In this embodiment, once the unused polymers and recycled polymers are mixed, it is expected that the flame retardant will be dispersed throughout the polymer composition as the mixing of the unused polymers and recycled polymers takes place.

[0068] In one embodiment, the preparation of the polymer compositions disclosed herein is achieved by simply mixing the raw materials under conditions suitable for the formation of a tight mixture. Such conditions include, but are not limited to, solution mixing or melt mixing in a single-screw or twin-screw extruder, mixing bowl, rolls, kneader, or similar mixing apparatus that can apply shear to the components. In one embodiment, a twin-screw extruder is used.

[0069] In any of these embodiments, the polymer composition may be completely free of additional substances not disclosed herein, or may contain less than about 10%, or less than about 9, 8, 7, 6, 5, 4, 3, 2, 1, 0.5, or 0.25% of additional substances not disclosed herein. In one embodiment, the polymer composition may be free of or substantially free of any fluorochemical liquor repellents or fluorochemical liquor repellent additives. In one embodiment, fluorochemical liquor repellent additives or fluorochemical liquor repellents that may be excluded from the disclosed polymer composition may include, but are not limited to, those comprising at least one fluorochemical group, for example, at least one fluoroaliphatic or fluoroalicyclic group. In another embodiment, the fluorochemicals of the polymers and oligomers to be excluded may include one or more fluorochemical groups containing perfluorinated carbon chains having 3 to about 20 carbon atoms, more preferably about 4 to about 12 carbon atoms.

[0070] In another embodiment, the polymer composition may include, but is not limited to, commercially available core-shell impact modifiers, linear or crosslinked copolymers or terpolymers, or may not include or substantially include such impact modifiers.

[0071] (Properties and their determination) In one embodiment, flammability can be measured by a standard test method such as UL94, published by Underwriters Laboratories, for example. In another embodiment, the UL94 test can measure both the ability of a plastic component to extinguish or spread a flame after ignition and / or the drip behavior of a plastic component in response to a small open flame or radiant heat source. In one embodiment, the UL94 standard can be used to evaluate the minimum thickness at which a plastic sample stops burning when held in a vertical orientation. A V2 sample stops burning in 10 seconds or less with dripping, while a V1 sample stops burning in less than 30 seconds without dripping. In yet another embodiment, a V0 sample stops burning in less than 10 seconds without dripping. In one embodiment, a plastic composition tested herein, including a mixture of conventional flame retardants and ionic liquid flame retardants, is evaluated as a V0 sample under the UL94 standard.

[0072] In another embodiment, Charpy impact strength can be measured by a standard test method such as ISO 179. In a further embodiment, this test can be used to estimate the brittleness or toughness of a sample under a given set of test conditions and to determine comparative data between similar material species. In one embodiment, the Charpy impact strength of a nylon composition containing a combination of a conventional flame retardant and an ionic liquid flame retardant is similar to or better than a control sample that does not contain a flame retardant, and significantly improved compared to a control sample containing only a conventional flame retardant.

[0073] In one embodiment, various methods can be used to evaluate blooming on a plastic surface. In a further embodiment, blooming (also known as efflorescence) can occur when components of a plastic composition migrate to the surface of the material, when an additive is incompatible with the polymer or other additives, or when the plastic material is stored inappropriately. In one embodiment, an acceptable nylon formulation does not show blooming for at least 3000 hours when held at 85°C and 85% relative humidity.

[0074] [Embodiment] (Embodiment 1) A flame-retardant or fire-resistant material comprising a substrate, a non-halogenated flame-retardant component, and an ionic liquid flame-retardant component, wherein the ionic liquid flame-retardant component comprises a compound having the formula (I). [Chemical formula] A is P, and each of R1, R2, R3, and R4 may be unsubstituted or substituted with halogen, nitro, trifluoromethyl, trifluoromethoxy, methoxy, carboxy, -NH2, -OH, -SH, -NHCH3, -N(CH3)2, cyano, -SMe, and -SO3H, independently selected from the group consisting of (C1-C 20 ) alkyl, aryl, (C3-C 10 ) heterocyclyl, (C3-C 10 ) cycloalkyl, (C3-C 10 ) heterocyclyl(C1-C8)alkyl, aryl(C1-C8)alkyl, heteroaryl, and heteroaryl(C1-C8)alkyl, and X - is a halide, [B(R)4] - , OH - , SCN - , RPO4 - , (RO)2P(=O)O - , RSO4 - , RSO3 - , ROSO3 - , [N(CN)2] - , [RCOO] - , [NO3]- [PF6] - [BF4] - (RSO2)2N - Selected from the group consisting of oxalates, dicarboxylates and tricarboxylates, formates, phosphates and aluminates, where each R may be unsubstituted or substituted with halogen, nitro, methoxy, carboxy, -NH2, -OH, -SH, -NHCH3, -N(CH3)2, -SMe and cyano, (C1-C 20 )alkyl, aryl, (C3-C 10 ) Heterocyclyl, (C3-C 10 )Cycloalkyl, (C3-C 10 A flame-retardant or fire-resistant material independently selected from the group consisting of heterocyclyl(C1-C8)alkyl, aryl(C1-C8)alkyl, heteroaryl, and heteroaryl(C1-C8)alkyl.

[0075] (Embodiment 2) X - is a halide, [B(R)4] - , OH - SCN - , RPO4 - ,(RO)2P(=O)O - , RSO4 - , RSO3 - ROSO3 - [N(CN)2] - ...RCOO] - [NO3] - [PF6] - [BF4] - (RSO2)2N - Selected from the group consisting of oxalates, dicarboxylates and tricarboxylates, formates, phosphates and aluminates, where each R may be unsubstituted or substituted with halogen, nitro, methoxy, carboxy, -NH2, -OH, -SH, -NHCH3, -N(CH3)2, -SMe and cyano, (C1-C 20 )alkyl, aryl, (C3-C 10 ) Heterocyclyl, (C3-C10 )Cycloalkyl, (C3-C 10 A flame-retardant or fire-resistant material according to Embodiment 1, independently selected from the group consisting of heterocyclyl(C1-C8)alkyl, aryl(C1-C8)alkyl, heteroaryl, and heteroaryl(C1-C8)alkyl.

[0076] (Embodiment 3) Each of R1, R2, R3, or R4 operates independently, (C1-C 20 ) Selected from the group consisting of alkyl, aryl, and aryl(C1-C8)alkyl; X - (CN)2N - RCOO - , halides, OH - SH - 5CN - [PF6] - [BF4] - , RSO3 - , RSO3 - , RSO3 - ROSO3 - ,(RO)2P(=O)O - and (RSO2)2N - A group consisting of (C1-C) is selected, where R can be optionally substituted with a halogen. 20 A flame-retardant or fire-resistant material according to Embodiment 1, selected from the group consisting of alkyl, aryl, and aryl, (C1-C8)alkyl.

[0077] (Embodiment 4) The flame-retardant or fire-resistant material according to Embodiment 1, wherein the base material comprises a polyamide polymer.

[0078] (Embodiment 5) The flame-retardant or fire-resistant material according to Embodiment 5, wherein the polyamide polymer includes a nylon-XY polymer or a nylon-Z polymer.

[0079] (Embodiment 6) The flame-retardant or fire-resistant material according to Embodiment 5, wherein the nylon-XY polymer includes nylon-6,6; nylon-6,12; nylon-4,6; or any combination thereof.

[0080] (Embodiment 7) The flame-retardant or fire-resistant material according to Embodiment 5, wherein the nylon-Z polymer includes nylon-6, nylon-11, nylon-12, or any combination thereof.

[0081] (Embodiment 8) The flame-retardant or fire-resistant material according to Embodiment 1, wherein the base material is present in an amount of about 80 wt% to about 95 wt% of the flame-retardant or fire-resistant material.

[0082] (Embodiment 9) The flame-retardant or fire-resistant material according to Embodiment 1, wherein the non-halogenated flame-retardant component includes an inorganic flame retardant, a phosphorus-based flame retardant, a nitrogen-based flame retardant, a silicon-based flame retardant, a nanoparticle flame retardant, or any combination thereof.

[0083] (Embodiment 10) The flame-retardant or fire-resistant material according to Embodiment 9, wherein the non-halogenated flame-retardant component comprises melamine cyanurate (MCA), aluminum diethylphosphinate (ADP), aluminum phosphate (AP), or any combination thereof.

[0084] (Embodiment 11) The flame-retardant or fire-resistant material according to Embodiment 1, wherein the non-halogenated flame-retardant component and the ionic liquid flame-retardant component together constitute about 5 wt% to about 20 wt% of the flame-retardant or fire-resistant material.

[0085] (Embodiment 12) The flame-retardant or fire-resistant material according to Embodiment 1, wherein the ionic liquid flame-retardant component comprises tributyl(ethyl)phosphonium 4-methylbenzene sulfonate.

[0086] (Embodiment 13) The flame-retardant or fire-resistant material according to Embodiment 1, wherein the non-halogenated flame-retardant component is present in a ratio of about 21:1 to about 4:1 with respect to the ionic liquid flame-retardant component.

[0087] (Embodiment 14) The flame-retardant or fire-resistant material according to Embodiment 1, wherein the flame-retardant or fire-resistant material has at least a V2 UL94 flammability rating.

[0088] (Embodiment 15) The flame-retardant or fire-resistant material according to Embodiment 14, wherein the flame-retardant or fire-resistant material has at least a UL94 flammability rating of V0.

[0089] (Embodiment 16) The aforementioned flame-retardant or fire-resistant material contains at least about 5 kJ / m³ 2 The flame-retardant or fire-resistant material according to Embodiment 1, having impact strength with a Charpy notch in accordance with ISO 179.

[0090] (Embodiment 17) A filling material comprising the flame-retardant or fire-resistant material and the filler described in Embodiment 1.

[0091] (Embodiment 18) The filler material according to Embodiment 17, wherein the filler material includes glass fibers.

[0092] (Embodiment 19) The filler material of Embodiment 17, wherein the filler material is present in an amount of about 10 wt% to about 40 wt% relative to the amount of flame-retardant or fire-resistant material.

[0093] (Embodiment 20) The filler material according to Embodiment 19, wherein the filler material is present in an amount of about 30 wt% relative to the amount of flame-retardant or fire-resistant material.

[0094] (Embodiment 21) The filler material according to Embodiment 1, wherein the filler material has at least a V2 UL94 flammability rating.

[0095] (Embodiment 22) The filler material according to Embodiment 1, wherein the filler material has at least a V0 UL94 flammability rating.

[0096] (Embodiment 23) The filler material according to Embodiment 17, wherein the filler material is maintained without blooming for at least 3000 hours at 85°C and 85% relative humidity.

[0097] (Embodiment 24) The flame-retardant or fire-resistant material according to Embodiment 1, wherein the base material contains nylon-6,6, the non-halogenated flame retardant component contains MCA, and the ionic liquid flame retardant component contains tributylethylphosphonium-4-methylbenzenesulfonate.

[0098] (Embodiment 25) The flame-retardant or fire-resistant material according to Embodiment 1, wherein the base material contains nylon-6, the non-halogenated flame-retardant component contains MCA, and the ionic liquid flame-retardant component contains tributylethylphosphonium-4-methylbenzenesulfonate.

[0099] (Embodiment 26) The filler material according to Embodiment 18, wherein the base material contains nylon-6,6, the non-halogenated flame retardant component contains a combination of ADP and AP, and the ionic liquid flame retardant component contains tributylethylphosphonium 4-methylbenzene sulfonate.

[0100] (Embodiment 27) The filler material according to embodiment 18, wherein the base material contains nylon-6, the non-halogenated flame retardant component contains a combination of ADP and AP, and the ionic liquid flame retardant component contains tributylethylphosphonium 4-methylbenzene sulfonate.

[0101] (Embodiment 28) An article comprising the flame-retardant or fire-resistant material described in Embodiment 1.

[0102] (Embodiment 29) An article comprising the filling material described in Embodiment 17. [Examples]

[0103] This disclosure is illustrated herein by examples, which are intended to illustrate the workings of the disclosure and not to limit its scope in any way. Unless otherwise defined, all technical and scientific terms used herein have the same meanings as those commonly understood by those skilled in the art to which this disclosure belongs. Similar or equivalent methods and materials may be used in carrying out the disclosed methods and compositions, but exemplary methods, apparatus, and materials are described herein.

[0104] [Example 1] In this example, tributyl(ethyl)phosphonium 4-methylbenzenesulfonate (CAS registry number 119520-10-4) was used as an ionic liquid flame retardant. The nylon used was PA66 (EPR27, manufactured by Shenma, Dongguan, China). Table 1 shows the amount (wt%) of MCA and / or ionic liquid used relative to the polymer wt%.

[0105] Drying was carried out at 100°C for 4 to 6 hours. The extrusion temperature was 240 to 270°C, the injection temperature was 270 to 280°C, and the mold temperature was 80°C. The flame retardancy and mechanical properties are shown in Table 1.

[0106] [Table 1]

[0107] [Example 2] In this example, tributyl(ethyl)phosphonium 4-methylbenzenesulfonate (CAS registry number 119520-10-4) was used as an ionic liquid flame retardant. The nylon used was PA6 (PA6-J2700, manufactured by Hangzhou Juheshun New Material Co. Ltd., Hangzhou, China). Table 2 shows the amount (wt%) of MCA and / or ionic liquid used relative to the polymer wt%.

[0108] Drying was carried out at 100°C for 4 to 6 hours. The extrusion temperature was 220 to 240°C, the injection temperature was 240 to 260°C, and the mold temperature was 70 to 80°C. The flame retardancy and mechanical properties are shown in Table 2.

[0109] [Table 2]

[0110] [Example 3] In this example, tributyl(ethyl)phosphonium 4-methylbenzenesulfonate (CAS registry number 119520-10-4) was used as an ionic liquid flame retardant. The nylon used was PA66 (EPR27, manufactured by Shenma, Dongguan, China). Table 3 shows the amounts (wt%) of ADP, AP, and / or ionic liquids used relative to the polymer wt%. 30 wt% of glass fiber (Megalith EDR14-2000-988A, manufactured by Evergreen Chemicals Co., Changzhou, China) was used as a filler.

[0111] Drying was carried out at 90°C for 4 to 6 hours. The extrusion temperature was 240 to 285°C, the injection temperature was 270 to 285°C, and the mold temperature was 80 to 100°C. The flame retardancy and leaching properties are shown in Table 3.

[0112] [Table 3]

[0113] [Example 4] In this example, tributyl(ethyl)phosphonium 4-methylbenzenesulfonate (CAS registry number 119520-10-4) was used as an ionic liquid flame retardant. The nylon used was PA6 (PA6-J2700, manufactured by Hangzhou Juheshun New Material Co. Ltd., Hangzhou, China). Table 4 shows the amounts (wt%) of ADP, AP, and / or ionic liquids used relative to the polymer wt%. 30 wt% of glass fiber (Megalith EDR14-2000-988A, manufactured by Evergreen Chemicals Co., Changzhou, China) was used as a filler.

[0114] Drying was carried out at 90°C for 4 to 6 hours. The extrusion temperature was 220 to 250°C, the injection temperature was 230 to 250°C, and the mold temperature was 80°C. The flame retardancy and leaching properties are shown in Table 4.

[0115] [Table 4]

[0116] [Example 5] Several experiments were conducted using MPP as a flame retardant (data not shown). However, migration of MPP was worse than that of AP and / or ADP. Ionic liquids such as those disclosed herein can significantly improve migration resistance, but these compositions did not meet the requirement of not blooming for 3000 hours at 85°C and 85% relative humidity.

Claims

1. The material comprises a base material, a non-halogenated flame retardant component, and an ionic liquid flame retardant component, wherein the ionic liquid flame retardant component contains a compound having formula (I). 【Chemistry 1】 A is P, R １ , ８ , ３ , １０ , ８ , ８ , １ , １ , R ２ , R ３ and R ４ each of which may be unsubstituted or substituted with halogen, nitro, trifluoromethyl, trifluoromethoxy, methoxy, carboxy, -NH ２ , -OH, -SH, -NHCH ３ , -N(CH ３ )( ２ , cyano, -SMe, and -SO ３ H, and is independently selected from the group consisting of (C １ -C ２０ )alkyl, aryl, (C ３ -C １０ )heterocyclyl, (C ３ -C １０ )cycloalkyl, (C ３ -C １０ )heterocyclyl(C １ -C ８ )alkyl, aryl(C １ -C ８ )alkyl, heteroaryl and heteroaryl(C １ -C ８ )alkyl X － is a halide [B(R) ４ ] － , OH － SCN － RPO ４ － (RO) ２ P(=O)O － RSO ４ － RSO ３ － ROSO ３ － [N(CN) ２ ] － [RCOO] － [NO ３ ] － [PF ６ ] － [BF ４ ] － (RSO ２ ) ２ N － Selected from the group consisting of oxalates, dicarboxylates and tricarboxylates, formates, phosphates, and aluminates, where R may be unsubstituted or a halogen, nitro, methoxy, carboxy, or -NH ２ , -OH, -SH, -NHCH ３ , -N(CH ３ ) ２ , may be substituted with -SMe and cyano, (C １ -C ２０ ) alkyl, aryl, (C ３ -C １０ ) Heterocyclyl, (C ３ -C １０ ) Cycloalkyl, (C ３ -C １０ ) Heterocyclyl (C １ -C ８ ) alkyl, aryl (C １ -C ８ ) alkyl, heteroaryl and heteroaryl (C １ -C ８ ) Independently selected from the group consisting of alkyl groups, Flame-retardant or fire-resistant material.

2. X － is a halide, [B(R) ４ － OH － SCN － RPO ４ － (RO) ２ P(=O)O － RSO ４ － RSO ３ － ROSO ３ － [N(CN) ２ － [RCOO] － [NO ３ － [PF ６ － [BF ４ － (RSO ２ ) ２ N － , oxalate, dicarboxylate and tricarboxylate, formate, phosphate, and aluminate, and each R may be unsubstituted or substituted with halogen, nitro, methoxy, carboxy, -NH ２ , -OH, -SH, -NHCH ３ , -N(CH ３ ) ２ , -SMe and cyano, (C １ -C ２０ )alkyl, aryl, (C ３ -C １０ )heterocyclyl, (C ３ -C １０ )cycloalkyl, (C ３ -C １０ )heterocyclyl(C １ -C ８ )alkyl, aryl(C １ -C ８ )alkyl, heteroaryl and heteroaryl(C １ -C<​​​​​​

3. R １ , R ２ , R ３ or R ４ Each of them operates independently, (C １ -C ２０ ) alkyl, aryl, and aryl (C １ -C ８ ) Selected from the group consisting of alkyl groups; X － (CN) ２ N － RCOO － , halides, OH － SH － , CN － [PF ６ ] － [BF ４ ] － RSO ３ － RSO ３ － RSO ３ － ROSO ３ － (RO) ２ P(=O)O － and (RSO ２ ) ２ N － A selection is made from the group consisting of, where R can be optionally substituted with a halogen, (C １ -C ２０ ) alkyl, aryl, and aryl (C １ -C ８ A flame-retardant or fire-resistant material according to claim 1, selected from the group consisting of alkyl groups.

4. The flame-retardant or fire-resistant material according to claim 1, wherein the base material comprises a nylon-XY polymer, a nylon-Z polymer, or any combination thereof.

5. The flame-retardant or fire-resistant material according to claim 4, wherein the nylon-XY polymer comprises nylon-6,6; nylon-6,12; nylon-4,6; or any combination thereof.

6. The flame-retardant or fire-resistant material according to claim 4, wherein the nylon-Z polymer comprises nylon-6, nylon-11, nylon-12, or any combination thereof.

7. The flame-retardant or fire-resistant material according to claim 1, wherein the base material is present in an amount of about 80 wt% to about 95 wt% of the flame-retardant or fire-resistant material.

8. The flame-retardant or fire-resistant material according to claim 1, wherein the non-halogenated flame-retardant component includes an inorganic flame retardant, a phosphorus-based flame retardant, a nitrogen-based flame retardant, a silicon-based flame retardant, a nanoparticle flame retardant, or any combination thereof.

9. The flame-retardant or fire-resistant material according to claim 1, wherein the non-halogenated flame-retardant component and the ionic liquid flame-retardant component are present together in an amount of about 5 wt% to about 20 wt% of the flame-retardant or fire-resistant material.

10. The flame-retardant or fire-resistant material according to claim 1, wherein the non-halogenated flame-retardant component is present in a ratio of about 21:1 to about 4:1 with respect to the ionic liquid flame-retardant component.

11. The flame-retardant or fire-resistant material according to claim 1, wherein the flame-retardant or fire-resistant material has at least a UL94 flammability rating of V2.

12. The aforementioned flame-retardant or fire-resistant material has a load of at least about 5 kJ / m³ ２ The flame-retardant or fire-resistant material according to claim 1, having impact strength with a Charpy notch in accordance with ISO 179.

13. A filler comprising the flame-retardant or fire-resistant material described in claim 1 and a filler containing glass fibers.

14. The filler material according to claim 13, wherein the filler material is present in an amount of about 10 wt% to about 40 wt% relative to the amount of flame-retardant or fire-resistant material.

15. The filler material according to claim 1, wherein the filler material has at least a UL94 flammability rating of V2.

16. The filler material according to claim 13, wherein the filler material is maintained without blooming for at least 3,000 hours at 85°C and 85% relative humidity.

17. The flame-retardant or fire-resistant material according to claim 1, wherein the base material comprises nylon-6,6, the non-halogenated flame-retardant component comprises melamine cyanurate (MCA), and the ionic liquid flame-retardant component comprises tributylethylphosphonium 4-methylbenzene sulfonate.

18. The flame-retardant or fire-resistant material according to claim 1, wherein the base material comprises nylon-6, the non-halogenated flame-retardant component comprises melamine cyanurate (MCA), and the ionic liquid flame-retardant component comprises tributylethylphosphonium 4-methylbenzene sulfonate.

19. The filler material according to claim 13, wherein the base material comprises nylon-6,6, the non-halogenated flame retardant component comprises a combination of aluminum diethylphosphinate (ADP) and aluminum phosphate (AP), and the ionic liquid flame retardant component comprises tributylethylphosphonium 4-methylbenzene sulfonate.

20. The filler material according to claim 13, wherein the base material contains nylon-6, the non-halogenated flame retardant component contains a combination of aluminum diethylphosphinate (ADP) and aluminum phosphate (AP), and the ionic liquid flame retardant component contains tributylethylphosphonium 4-methylbenzene sulfonate.

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