Flame-retardant thermoplastic composition free of decabromodiphenyl ethane.

Description

1 / 18 DECABROMODIFENYL ETHANE-FREE FLAME-RETARDANT THERMOPLASTIC COMPOSITIONS FIELD OF THE INVENTION

[0001] The present invention relates to methods of replacing decabromodiphenyl ethane brominated flame retardants in thermoplastic polymer compositions and to flame-retardant thermoplastic compositions that are free of decabromodiphenyl ethane. BACKGROUND

[0002] Halogenated flame retardants are well known and widely available. These products are used in various polymer compositions and provide varying levels of flame retardancy for various applications, such as wires and cables. These products can provide good flame retardancy if incorporated in high loads, but these high loads make it difficult to achieve a balance between desired properties, for example, mechanical (such as crush resistance), electrical (such as wet insulation resistance), and extrusion (such as pressure observed in the die).

[0003] Decabromodiphenyl ethane (DBDPE) is a general-purpose, brominated, high-purity, non-DPO (diphenyl oxide) flame retardant for a variety of polymers, including styrenics, engineering polymers, polyolefins, and elastomers, which is commercially available from LANXESS under the trade name Firemaster® 2100R. DBDPE is one of the only universally applicable flame retardants currently in use. DBDPE, however, has come under increasing scrutiny based on regulations. Therefore, there is a desire to have DBDPE-free flame retardant compositions that are suitable for use on a variety of polymers, especially polyolefins, such as those used in wire and cable constructions.

[0004] Several brominated alternatives to DBDPE are sold and have been Petition 870250078591, dated 03 / 09 / 2025, page 11 / 99 2 / 18 proposals for various polymer applications.

[0005] For example, US patent 2020 / 0216650A1 discloses silane-functionalized compositions comprising 16–70% by weight of brominated polymeric flame retardant with a weight-average molecular weight (Mw) equal to or greater than (>) 1,000 g / mol for use in wire and cable constructions. Examples of brominated flame retardants are brominated polyphenyl ether (Emerald Innovation™ 1000) and brominated styrene / butadiene block copolymer (Emerald Innovation™ 3000). The compositions additionally contain 0.3–5% by weight or 10–79% by weight of alkoxysilane.

[0006] US patent 8,420,876 discloses the preparation of oligomeric or polymeric mixtures comprising 1,3-diphenylpropane, 1,3,5-triphenylpentane, 1,3,5,7-tetraphenylheptane and 1,3,5,7,9-pentaphenylnonane with a polydispersity greater than 1.25, suitable for bromination as flame retardants for polyurethane foam applications.

[0007] US patent 8,642,821 discloses processes for producing a brominated flame retardant composition, the process comprising brominating a feed comprising a telomer distribution of styrene and anionic toluene derived from chain transfer in the presence of a catalytic amount of AlBr3 and a solvent. The resulting flame retardants may be suitable for a variety of thermoplastics, although no formulated examples are provided.

[0008] One of the shortcomings of these disclosures is the fact that no burn results were provided, or only horizontal results. The horizontal burn test is a significantly less demanding test than the UL-94 vertical test. There is a need for alternatives to existing DBDPE-free flame retardant compositions that are effective in vertical burn tests.

[0009] It is an object of this disclosure to provide flame retardant compositions that are free of DBDPE and that demonstrate effectiveness in vertical burning tests. It is desirable that these compositions be used in Petition 870250078591, dated 03 / 09 / 2025, page 12 / 99 3 / 18 thermoplastic polyolefin compositions. Thus, it is also an objective to provide thermoplastic polyolefin compositions, such as polyolefins used for wires and cables, which comprise flame retardants that are free of DBDPE. SUMMARY OF THE INVENTION

[0010] This disclosure provides a method for replacing decabromodiphenyl ethane in a flame-retardant thermoplastic composition, particularly those containing polyolefins such as polypropylene or polyethylene. A DBDPE-free thermoplastic polyolefin composition is prepared by combining (a) at least one thermoplastic polyolefin; (b) at least one aromatic brominated flame retardant that is not decabromodiphenyl ethane; and (c) at least one synergist.

[0011] The method may further comprise molding the flame-retardant thermoplastic composition into an article. In certain embodiments, the flame-retardant thermoplastic composition is free of an alkoxysilane, an alkoxysilane-functionalized polymer, and / or a silanol condensation catalyst.

[0012] Also described in this document are flame-retardant thermoplastic compositions free of decabromodiphenyl ethane comprising: (a) at least one thermoplastic polyolefin; (b) at least one aromatic brominated flame retardant that is not decabromodiphenyl ethane; and (c) at least one synergist.

[0013] In some embodiments, the flame-retardant thermoplastic composition does not include an alkoxysilane, an alkoxysilane-functionalized polymer, and / or a silanol condensation catalyst.

[0014] Advantageously, the methods and compositions described in this Petition 870250078591, dated 03 / 09 / 2025, p. 13 / 99 The present methods and compositions provide thermoplastic articles that meet the requirements of UL 94 Tests for Flammability of Plastic Materials for Parts in Devices and Appliances, dated December 1, 2021. Preferably, a molded article of the composition has a UL 94 VO rating in a thickness of 0.2 mm to 3.2 mm, such as, for example, in a thickness of about 0.2 mm, about 0.4 mm, about 0.8 mm, about 1.6 mm and about 3.2 mm.

[0015] Flame-retardant thermoplastic methods and compositions may additionally comprise one or more of the following: (d) at least one auxiliary process aid, such as at least one antioxidant and / or at least one heat stabilizer; and (e) at least one inorganic filler, including, but not limited to, talc.

[0016] The flame-retardant thermoplastic composition typically comprises (b) aromatic brominated flame retardant in an amount of about 5% to about 40% by weight and (c) at least one synergist in an amount of about 1% to about 20% by weight, each based on the total weight of the composition.

[0017] Thermoplastic polyolefin may be filled or unfilled. In some embodiments, at least one thermoplastic polyolefin comprises or is polypropylene. In other embodiments, the polyolefin comprises or is polyethylene.

[0018] In certain preferred embodiments, (b) at least one aromatic brominated flame retardant is selected from a phenoxy-terminated carbonate oligomer of tetrabromobisphenol A, a dibromostyrene homopolymer or poly(2,6-dibromophenol oxide). In certain such embodiments, the aromatic brominated flame retardant (b) is a phenoxy-terminated carbonate oligomer of tetrabromobisphenol A.

[0019] In some forms, the ratio between (b) at least one Petition 870250078591, dated 03 / 09 / 2025, p. 14 / 99 5 / 18 aromatic brominated flame retardant and (c) at least one synergist is from about 1:10 to about 10:1, preferably from about 1:1 to about 5:1, more preferably from about 1:1 to about 3:1. In preferred embodiments, the (c) at least one synergist comprises antimony and / or melamine polyphosphate.

[0020] In certain embodiments, (c) at least one synergist comprises an aliphatic brominated flame retardant. In some of these embodiments, the ratio between the aromatic brominated flame retardant and the aliphatic brominated flame retardant is from about 1:1 to about 2:1. In some embodiments, the aromatic brominated flame retardant is a phenoxy-terminated carbonate oligomer of tetrabromobisphenol A, and the aliphatic brominated flame retardant is a brominated styrene / butadiene block copolymer.

[0021] In some particular embodiments, the thermoplastic polymer (a) is uncharged, the synergist (c) comprises an aliphatic brominated flame retardant, and the ratio between the aromatic brominated flame retardant (b) and the aliphatic brominated flame retardant is from about 1:1 to about 2:1. In certain such embodiments, the aromatic brominated flame retardant is a phenoxy-terminated carbonate oligomer of tetrabromobisphenol A, and the aliphatic brominated flame retardant is a brominated styrene / butadiene block copolymer.

[0022] Also described is a method for manufacturing said flame-retardant thermoplastic compositions; and an article containing the thermoplastic polymer composition.

[0023] It should be understood that both the previous general description and the detailed description below are merely illustrative and explanatory and are not limiting of the invention, as claimed. DETAILED DESCRIPTION

[0024] This disclosure relates to methods for replacing decabromodiphenyl ethane in a flame-retardant thermoplastic composition. The thermoplastic polymer may be a polyester, polyamide, polystyrene, including Petition 870250078591, dated 03 / 09 / 2025, p. 15 / 99 6 / 18 High-impact polystyrene (HIPS), polyolefin, polycarbonate, polyurethane, polyphenylene ether, or other thermoplastic polymer. More than one thermoplastic polymer (thermoplastic polymer blends) may be used, such as blends of polyphenylene ether / styrenic resin, polyvinyl chloride / acrylonitrile butadiene styrene (ABS), or other impact-modified polymers such as methacrylonitrile and α-methylstyrene containing ABS, and polyester / ABS or polycarbonate / ABS. The thermoplastic polymer may be unreinforced or reinforced, for example, glass-reinforced, such as a glass-filled polyester (e.g., glass-filled polyalkylene terephthalate) or a glass-filled polyamide.

[0025] Illustrative polymers are: olefin polymers, crosslinked or not, for example, homopolymers of ethylene, propylene and butylene; copolymers of two or more of these alkene monomers and copolymers of one or more of these alkene monomers and other copolymerizable monomers, for example, ethylene / propylene copolymers, ethylene / ethyl acrylate copolymers and ethylene / propylene copolymers, ethylene / acrylate copolymers and ethylene / vinyl acetate copolymers; polymers of olefinically unsaturated monomers, for example, polystyrene, for example, high-impact polystyrene and styrene copolymers, polyurethanes. Preferably, the polyolefin is polypropylene and / or polyethylene.

[0026] At least one thermoplastic polymer (i) is frequently present in the flame-retardant thermoplastic composition in an amount of about 30 to about 95% by weight, as well as about 40 to about 90% by weight or about 50 to about 90% by weight, based on the total weight of the flame-retardant thermoplastic composition.

[0027] Aromatic brominated flame retardant is not DBDPE and is generally a brominated aromatic polymer or oligomer.

[0028] Exemplary brominated flame retardants that can be used in the compositions described in this document include aromatic and aliphatic brominated flame retardants, such as a block copolymer of Petition 870250078591, dated 03 / 09 / 2025, p. 16 / 99 7 / 18 styrene / butadiene brominated (e.g., Emerald Innovation™ 3000), a phenoxy-terminated carbonate oligomer of tetrabromobisphenol A (e.g., BC-58™), a dibromostyrene homopolymer (e.g., Firemaster® PBS-64 HW), 1,1'-(isopropylene)bis[3,5-dibromo-4-(2,3-dibromo-2-methylpropoxy)benzene] (SR-130), ethylenebistetrabromophthalimide (SAYTEX® BT93), a brominated triazine, such as tris(tribromophenoxy)triazine (e.g., FR245), poly(2,6-dibromophenol oxide) (UNIPLEX FRP 64), polybromostyrene copolymerized with another monomer (e.g., Firemaster® CP-44HF) and combinations of the same.

[0029] In certain preferred embodiments, the aromatic brominated flame retardant is selected from a phenoxy-terminated carbonate oligomer of tetrabromobisphenol A, a dibromostyrene homopolymer or poly(2,6-dibromophenol oxide).

[0030] The amount of aromatic brominated flame retardant (b) used in the flame-retardant thermoplastic composition will be the amount required to obtain the desired flame retardancy. In general, the composition and the resulting product may contain from about 1 to about 40% by weight, preferably from about 5 to about 40% by weight, as from about 15 to about 30% by weight or from about 5 to about 25% by weight of a brominated flame retardant. Standard polymer blends containing an aromatic brominated flame retardant, which are blended with additional amounts of substrate polymer or bonding agent, typically contain even higher concentrations of the flame retardant, for example, up to 95% by weight or more.

[0031] In certain cases, a combination of brominated flame retardants can be used in a thermoplastic formulation. The combination used may depend on the thermoplastic material. For example, it has been surprisingly found that the combination of an aromatic brominated flame retardant, such as a phenoxy-terminated carbonate oligomer of tetrabromobisphenol A, can show a synergistic effect when combined. Petition 870250078591, dated 03 / 09 / 2025, page 17 / 99 8 / 18 with an aliphatic brominated flame retardant, such as a brominated styrene / butadiene block copolymer, in polypropylene and polyethylene. In this case, the aliphatic brominated flame retardant will act as a synergist (component c) for the aromatic brominated flame retardant (component b).

[0032] Examples of additional flame retardant synergists (c) include antimony, melamine condensation products (e.g., melam, melem, melon), melamine cyanurate, reaction products of melamine with polyphosphoric acid (e.g., dimelamine pyrophosphate, melamine polyphosphate), reaction products of melamine condensation products with polyphosphoric acid (e.g., melem polyphosphate, melam polyphosphate, melon polyphosphate), melamine-poly(metal phosphate) (e.g., melamine-poly(zinc phosphate), a triazine-based compound, as a reaction product of trichlorotriazine, piperazine and morpholine, e.g., poly-[2,4(piperazine-1,4-yl)-6-(morpholine-4-yl)-1,3,5-triazine] / piperazine (e.g., MCA® PPM Triazine HF), an organic phosphinate, such aluminum dialkylphosphinate, for example, aluminum diethylphosphinate (Exolit® OP); and aluminum hydrogen phosphite (Al2(HPO3)3).

[0033] In certain embodiments, a synergist is a nitrogen-containing synergist. Suitable nitrogen-containing synergists may be chosen from, for example, melamine derivatives, such as melamine and its condensation products (melam, melem, melon or similar compounds with higher condensation levels), melamine cyanurate and phosphorus / nitrogen compounds, such as dimelamine phosphate, dimelamine pyrophosphate, melamine phosphate, melamine pyrophosphate, melamine polyphosphate, melam polyphosphate, melon polyphosphate and melem polyphosphate and mixed polysalts thereof.

[0034] Examples of suitable additional flame retardants as a synergist include halogenated flame retardants, alkyl or aryl phosphine oxide flame retardants, alkyl or aryl phosphate flame retardants, alkyl or aryl phosphonates, alkyl or aryl phosphinates, and alkyl acid salts. Petition 870250078591, dated 03 / 09 / 2025, page 18 / 99 9 / 18 or aryl phosphine. Frequently, the additional flame retardant is an alkyl or aryl phosphate (e.g., triphenyl phosphate, bisphenol-A bis(diphenyl phosphate), resorcinol bis(diphenyl phosphate), or resorcinol bis(doxylenyl phosphate).

[0035] In some embodiments, the synergist is a phosphorus-based flame retardant. For example, when an aromatic brominated flame retardant, such as a phenoxy-terminated carbonate oligomer of tetrabromobisphenol A, was used with unfilled polyethylene, a synergistic result with melamine polyphosphate was found. Alternative phosphorus-based flame retardants are expected to have a similar effect.

[0036] In other embodiments, when mineral-filled polyethylene was used, an aliphatic brominated flame retardant, such as a dibromo-styrene homopolymer, was used as a synergist.

[0037] In preferred embodiments, it is advantageous to use the brominated flame retardants disclosed herein in combination with antimony-based synergists, for example, Sb2O3. In general, the flame retardant products of this invention will be used with the antimony-based synergists in a weight-to-weight ratio ranging from about 1:1 to 7:1 and, preferably, from about 1:1 to about 3:1.

[0038] As demonstrated in this document, the use of a nitrogen-containing synergist or nitrogen-containing flame retardant is not necessary to obtain excellent flame retardant performance and processing stability in thermoplastic polymer applications when using the combination of aromatic bromine-containing flame retardant and synergist of the present disclosure. Thus, in some embodiments, the thermoplastic flame retardant composition of the present disclosure does not include a nitrogen-containing synergist or nitrogen-containing flame retardant.

[0039] The amount of synergist will typically range from about 1 to about 20% by weight, as will about 10 to about 15% by weight of the thermoplastic composition. Petition 870250078591, dated 03 / 09 / 2025, p. 19 / 99 10 / 18

[0040] The thermoplastic composition may consist essentially of or consist of components (a), (b) and (c) and, optionally, any one or a combination of components (d) and (e).

[0041] Auxiliary process aids (d) and filler (e) are typically employed in an amount less than 10 percent by weight of the flame-retardant thermoplastic composition, for example, generally less than 5 percent by weight, such as 3% by weight or less. Non-limiting examples of auxiliary process aids (d) include antioxidants, UV stabilizers, lubricants, impact modifiers, plasticizers, acid scavengers (e.g., carbodi-imides or epox), phosphine suppressants, pigments, dyes, optical brighteners, antistatic agents, anti-drip agents, e.g., PTFE, and other additives used to improve the properties of the resin.

[0042] The thermoplastic composition may comprise one or more heat stabilizers. Examples of suitable heat stabilizers include metal hydroxides, oxides, oxide hydrates, borates, molybdates, carbonates, sulfates, phosphates, silicates, siloxanes, stannates, mixed oxide-hydroxides, oxide-hydroxide-carbonates, hydroxide-silicates, hydroxide-borates, preferably where the metal is zinc, magnesium, calcium or manganese, generally zinc. For example, one or more heat stabilizers may be chosen from among zinc borate, zinc stannate, zinc molybdate complex (e.g., Kemgard® 911B), zinc molybdate / magnesium hydroxide complex (e.g., Kemgard® MZM), zinc molybdate / magnesium silicate complex (e.g., Kemgard® 911C), calcium molybdate / zinc complex (e.g., Kemgard® 911A) and zinc phosphate complex (e.g., Kemgard® 981), montmorillonite, kaolinite, halloysite and hydrotalcite.When present, the amount of at least one heat stabilizer is frequently from 0.1 to 5% by weight, based on the total weight of the flame-retardant thermoplastic composition.

[0043] At least one inorganic filler may be present in Petition 870250078591, dated 03 / 09 / 2025, page 20 / 99 11 / 18 flame-retardant thermoplastic composition. As is known in the art, an inorganic filler can reduce the molding shrinkage coefficient and the linear expansion coefficient of a resulting molded article and improve the high and low thermal shock properties. Various fillers in the form of fiber or non-fiber (e.g., powder, plate) can be used depending on the desired article. Some examples of fibrous fillers, which are types of inorganic fillers, may be those such as glass fiber, glass fiber with non-circular cross-section, such as flat fiber, carbon fiber, silica fiber, alumina silica fiber, zirconia fiber, boron nitride fiber, silicon nitride fiber, boron fiber, potassium titanate fiber, and even metallic fibrous substances such as stainless steel, aluminum, titanium, copper, and brass. The typical fibrous filler is glass fiber or carbon fiber.Alternatively, inorganic fillers can be powdered fillers, such as carbon black, graphite, silica, quartz powder, glass beads, glass powder, calcium silicate, kaolin, talc, clay, diatomaceous earth, silicates such as wollastonite, metal oxides such as iron oxide, titanium oxide, zinc oxide and alumina, metal hydroxides, metal carbonates such as calcium carbonate and magnesium carbonate, metal sulfates such as calcium sulfate and barium sulfate, silicon carbide, silicon nitride, boron nitride and various metal powders. Another example of inorganic fillers is plate-shaped fillers such as mica, glass flakes and various metal foils. These inorganic fillers can be used separately or in combination of two or more. In use, inorganic fillers are desirably pre-treated with a sizing agent or surface treatment agent, if necessary.

[0044] When present, the amount of at least one inorganic filler (e) in the flame-retardant thermoplastic composition is frequently from 1 to 50% by weight, for example, from 5 to 50% by weight, from 10 to 40% by weight, or from 15 to 30% by weight, based on the total weight of the flame-retardant thermoplastic composition.

[0045] Thermoplastic articles formed from formulations containing a thermoplastic polymer and a flame-retardant composition. Petition 870250078591, dated 03 / 09 / 2025, page 21 / 99 The 12 / 18 brominated compound described in this document can be produced conventionally, for example, by injection molding, extrusion molding, compression molding and similar methods. Blow molding may also be suitable in certain cases.

[0046] The desired product is, in one example, a molded article of the composition, which achieves the UL 94 V0 classification in a thickness of 0.4 mm, 0.8 mm, 1.6 mm or between 0.2 mm and about 3.2 mm.

[0047] To obtain excellent flame performance (UL 94 V0) for thin-walled articles (e.g., 0.8 mm or less), it is necessary to achieve short flame extinguishing times while avoiding flame dripping during the UL 94 test. A short flame extinguishing time is typically achieved by using flame retardants, while flame splashing can be avoided by adding anti-drip agents.

[0048] The following examples are illustrative of the flame-retardant thermoplastic formulations of this disclosure. EXAMPLES

[0049] A twin-screw extruder was used to compose the formulations shown in Table 1 at a barrel temperature of 200-220 °C. The amount of brominated flame retardant was 30% by weight to evaluate its suitability as a substitute for DBDPE in the exemplary polyolefins used in wire and cable articles. An injection molding machine was used to prepare samples of various thicknesses at 200-220 °C and a mold temperature of 50-60 °C. The formulations were evaluated for flame retardant activity in the UL-94 vertical burn test and processing stability. V-0 refers to the highest rating; V-2 refers to the lowest rating before rejection. Table 1 Polypropylene with talc filler containing 15-30% by weight of aromatic BrFRs Petition 870250078591, dated 03 / 09 / 2025, p. 22 / 99 13 / 18 % of FR in PP with 20% talc load UL94 at 1.6 mm (48 h) UL94 at 1.6 mm (7 days) 30 PBS-64HW / 10 ATO V-0 V-0 15 PBS-64HW / 15 EI3000 / 10 ATO failed failed 30 PBS-64HW / 1 ZnB / 10 ATO V-0 V-0 30 PBS-64HW / 2 ZnB / 10 ATO V-0 V-0 15 PBS-64HW / 15 EI3000 / 1 ZnB / 10 ATO failed failed 15 PBS-64HW / 15 EI3000 / 2 ZnB / 10 ATO failed failed 30 BC-58 / 10ATO V-0 V-2 15 BC-58 / 15 EI 3000 / 10 ATO failed failed 30CP-44HF / 10 ATO V-2 V-2 15 CP-44HF / 15 EI 3000 / 10 ATO failed failed PBS-64HW = Firemaster® PBS-64 HW (LANXESS) ATE = antimony trioxide EI3000 = Emerald Innovation™ 3000 (LANXESS) ZnB = zinc borate BC-58 = BC-58™ (LANXESS) CP-44HF = Firemaster® CP-44HF (LANXESS)

[0050] As shown in Table 1, the inclusion of 30% by weight of various brominated aromatic flame retardants (BrFR) with antimony trioxide in inorganically filled polypropylene achieved UL-94 V-0 at 1.6 mm thickness, while the same result was not observed for 15% by weight of aromatic BrFR. Supplementation of the aromatic flame retardant with an aliphatic flame retardant did not result in adequate flame retardancy. Table 2 Unfilled polypropylene with 15-30% by weight of aromatic BrFR Petition 870250078591, dated 03 / 09 / 2025, page 23 / 99 14 / 18 Percentage of FR in PP without load UL94 at 3.2mm (48 h) UL94 at 3.2mm (7 days) 30 BC-58 / 10ATO failed failed 15 BC-58 / 15 EI3000 / 10 ATO V-0 N / A 20 BC-58 / 10 EI3000 / 10 ATO V-0 N / A 22.5 BC-58 / 7.5 EI3000 / 10 ATO V-0 N / A 30 EI3000 / 10 ATO failed failed 30 PBS-64HW / 10 ATO failed failed 30 FRP-64P / 10 ATO failed failed PBS-64HW = Firemaster® PBS-64 HW (LANXESS) ATE = antimony trioxide EI3000 = Emerald Innovation™ 3000 (LANXESS) BC-58 = BC-58™ (LANXESS) N / A: Not available

[0051] In contrast to the talc-filled polypropylene of Example 1, the unfilled polypropylene did not benefit from the inclusion of 30% aromatic brominated flame retardant with antimony synergist. However, when the aromatic flame retardant was supplemented with aliphatic brominated flame retardant, where the ratio between the aromatic brominated flame retardant and the aliphatic brominated flame retardant was greater than 1:1, the aromatic brominated flame retardants with antimony synergist achieved UL-94 V-0 at 1.6 mm thickness. Table 3 Unfilled polyethylene with 15-30% by weight of aromatic BrFR % FR in PE without load UL94 at 1.6 mm (48 h) UL94 at 1.6 mm (7 days) 30 BC-58 / 10 ATO V-0 V-0 15 BC-58 / 15 EI3000 / 10 ATO V-0 V-0 27.6 BC-58 / 11.1 ATO / 5.6MPP V-0 at 2mm V-0 at 2mm Petition 870250078591, dated 03 / 09 / 2025, page 24 / 99 15 / 18 % FR in PE unloaded UL94 at 1.6 mm (48 h) UL94 at 1.6 mm (7 days) 30 FRP-64P / 10 ATO V-0 at 3.2 mm V-2 at 1.6 mm V-0 at 3.2 mm V-2 at 1.6 mm ATE = antimony trioxide EI3000 = Emerald Innovation™ 3000 (LANXESS) BC-58 = BC-58™ (LANXESS) MPP = melamine polyphosphate FR64P = UNIPLEX™ FRP-64P (LANXESS)

[0052] Unlike the unfilled polypropylene of Example 2, unfilled polyethylene achieved UL-94 V-0 at 1.6 mm thickness with the inclusion of 30% aromatic brominated flame retardant with antimony synergist, as well as with a 1:1 ratio between the aromatic brominated flame retardant and the aliphatic brominated flame retardant.

[0053] It was concluded that DBDPE can be successfully replaced in polyolefin formulations by other aromatic and aliphatic brominated flame retardants when used with antimony alone or with other synergists. The examples use polyolefins. However, it is conceivable that the flame retardant compositions disclosed may be suitable for other polymers such as HIPS (high impact polystyrene) and ABS (acrylonitrile butadiene styrene). In these cases, it may be necessary to adjust the amount of aliphatic and aromatic flame retardant used to replace DBDPE and / or the amount of synergist.

[0054] The invention may comprise, consist of, or essentially consist of the materials and / or procedures described in this document. In particular, the following embodiments are within the scope of this disclosure: 1. A flame-retardant thermoplastic composition that is free of decabromodiphenyl ethane comprising: (a) a thermoplastic polyolefin polymer; Petition 870250078591, dated 03 / 09 / 2025, page 25 / 99 16 / 18 (b) an aromatic brominated flame retardant that is not decabromodiphenyl ethane; and (c) a synergist for the aromatic brominated flame retardant. 2. The flame-retardant thermoplastic composition of embodiment 1, wherein a molded article of the composition has a UL 94 V0 rating in a thickness between 0.2 mm and 3.2 mm. 3. The flame-retardant thermoplastic composition of embodiments 1 or 2, wherein the aromatic brominated flame retardant is a phenoxy-terminated carbonate oligomer of tetrabromobisphenol A, a dibromostyrene homopolymer, or poly(2,6-dibromophenol oxide). 4. A flame-retardant thermoplastic composition according to any of the embodiments 1-3, wherein the synergist comprises antimony and / or melamine polyphosphate. 5. A flame-retardant thermoplastic composition according to any of the embodiments 1-5, wherein the ratio between the aromatic brominated flame retardant and the synergist is about 1:10 to 10:1. 6. A flame-retardant thermoplastic composition according to any one of embodiments 1 to 5, wherein the aromatic brominated flame retardant is about 5 to 40% by weight of the composition. 7. A flame-retardant thermoplastic composition according to any of the embodiments 1-6, wherein the synergist is about 1% to 20% by weight of the composition. 8. The flame-retardant thermoplastic composition, according to any of embodiments 1-7, additionally comprises at least one auxiliary processing aid, such as an antioxidant or heat stabilizer. 9. The flame-retardant thermoplastic composition, according to any of embodiments 1 to 8, additionally comprises an inorganic filler. 10. The flame-retardant thermoplastic composition according to Petition 870250078591, dated 03 / 09 / 2025, page 26 / 99 17 / 18 any of the modalities 1-8, in which the synergist comprises an aliphatic brominated flame retardant. 11. The flame-retardant thermoplastic composition according to embodiment 10, wherein the ratio between the aromatic brominated flame retardant and the aliphatic brominated flame retardant is from about 1:1 to about 2:1. 12. A flame-retardant thermoplastic composition, according to embodiment 11, in which the thermoplastic polymer is unfilled. 13. A flame-retardant thermoplastic composition according to any of the embodiments 10-12, wherein the aromatic brominated flame retardant is a phenoxy-terminated tetrabromobisphenol A carbonate oligomer, and the aliphatic brominated flame retardant is a brominated styrene / butadiene block copolymer. 14. A flame-retardant thermoplastic composition according to any of the embodiments 1-5, wherein the thermoplastic polymer is filled. 15. A method for preparing a decabromodiphenyl ethane-free flame-retardant thermoplastic composition comprising combining: (a) a polyolefin thermoplastic polymer; (b) an aromatic brominated flame retardant that is not decabromodiphenyl ethane; and (c) a synergist for the aromatic brominated flame retardant. 16. The method of embodiment 15, in which the aromatic brominated flame retardant is a phenoxy-terminated carbonate oligomer of tetrabromobisphenol A, a dibromostyrene homopolymer or poly(2,6-dibromophenol oxide). 17. The method according to embodiments 15 or 16, in which the synergist comprises antimony and / or melamine polyphosphate. 18. The method according to any of the embodiments 15-17, wherein the ratio between the aromatic brominated flame retardant and the synergist Petition 870250078591, dated 03 / 09 / 2025, p. 27 / 99 18 / 18 is approximately 1:1 to 3:1. 19. The method according to any of the embodiments 15-18, wherein the thermoplastic polymer is unfilled, the synergist comprises an aliphatic brominated flame retardant and the ratio between the aromatic brominated flame retardant and the aliphatic brominated flame retardant is from about 1:1 to about 2:1. 20. The method according to embodiment 19, wherein the aromatic brominated flame retardant is a phenoxy-terminated carbonate oligomer of tetrabromobisphenol A, and the aliphatic brominated flame retardant is a brominated styrene / butadiene block copolymer. Petition 870250078591, dated 03 / 09 / 2025, p. 28 / 99

Claims

1 / 2 CLAIMS 1. A flame-retardant thermoplastic composition that is free of decabromodiphenyl ethane, characterized by comprising: (a) a polyolefin thermoplastic polymer; (b) an aromatic brominated flame retardant selected from a phenoxy-terminated carbonate oligomer of tetrabromobisphenol A and a dibromostyrene homopolymer; and (c) an aliphatic brominated flame retardant, wherein the ratio of the aromatic brominated flame retardant to the aliphatic brominated flame retardant is from about 1:1 to about 3:

1.

2. Flame-retardant thermoplastic composition according to claim 1, characterized in that a molded article of the composition has a UL 94 VO rating at a thickness of between 0.2 mm and 3.2 mm.

3. Flame-retardant thermoplastic composition according to claims 1 or 2, characterized in that the composition further comprises antimony and / or melamine polyphosphate.

4. Thermoplastic flame-retardant composition, according to any one of claims 1-3, characterized in that the aromatic brominated flame retardant is about 5-40% by weight of the composition.

5. Thermoplastic flame-retardant composition, according to any one of claims 1-4, characterized in that the aliphatic brominated flame retardant is about 1% by weight to about 20% by weight of the composition.

6. Flame-retardant thermoplastic composition, according to any one of claims 1-5, characterized by further comprising at least one auxiliary processing aid, such as an antioxidant or a heat stabilizer. Petition 870250086859, dated 09 / 25 / 2025, page 8 / 12 2 / 2 7. Thermoplastic flame-retardant composition, according to any one of claims 1-6, characterized in that the ratio between the aromatic brominated flame retardant and the aliphatic brominated flame retardant is from about 1:1 to about 2:

1.

8. Flame-retardant thermoplastic composition according to any one of claims 1-7, characterized in that the thermoplastic polymer is unfilled polypropylene or unfilled polyethylene.

9. Thermoplastic flame-retardant composition, according to any one of claims 1-8, characterized in that the aromatic brominated flame retardant is a phenoxy-terminated tetrabromobisphenol A carbonate oligomer, and the aliphatic brominated flame retardant is a brominated styrene / butadiene block copolymer.

10. Method for preparing a decabromodiphenyl ethane-free flame-retardant thermoplastic composition according to claims 8 or 9, characterized by comprising combining in an extruder: (a) the thermoplastic polyolefin polymer; (b) the aromatic brominated flame retardant; (c) the aliphatic brominated flame retardant; (d) antimony and / or melamine polyphosphate; and (e) any auxiliary process aid. Petition 870250086859, dated 09 / 25 / 2025, page 9 / 12