Polymer brominated flame retardant composition for use in wires and / or cables

Abstract

The invention relates to a flame retardant composition and a macromolecular brominated flame retardant composition used in wires and / or cables. The brominated flame retardant contains aromatic bound bromine, and in several embodiments is considered as a brominated styrenic polymer. The brominated flame retardant has a weight average molecular weight (Mw) of about 650 to about 75,000 and a bromine content of about 60 wt% or more. The invention also relates to a process for forming a flame retardant composition using different curing methods, including but not limited to electron beam curing and peroxide curing.

Description

TECHNICAL FIELD

[0001] The present invention relates to flame retardant compositions and to high molecular brominated flame retardant compositions for use in wires and / or cables. BACKGROUND

[0002] Conduit, appliance or automotive wires and cables usually have only one polymer layer. This layer has to fulfill several functions at the same time, which in other low voltage cables, medium voltage cables and high voltage cables are fulfilled by separate layers. Therefore, the high molecular compositions used for the production of conduit, appliance or automotive wires have to fulfill several demanding requirements at the same time, including good insulating behavior, good mechanical properties, in particular good abrasion resistance, good flame retardant properties, good heat distortion resistance, ability to withstand low temperatures, water and chemical resistance and good processing properties.

[0003] Many plastics, including polyolefins, are treated with flame retardants to minimize fire spread. In WO 2005 / 095685 and WO 2022 / 031932, polyolefins are flame retarded using a polybrominated anionic styrenic polymer in combination with at least one synergist; WO 2001 / 029124 discloses polyolefins with flame retardants including bis(2,3-dibromopropyl ether) of tetrabromobisphenol-A and bis(2,3-dibromopropyl ether) of tetrabromobisphenol-S. In US 6780348, a combination of polybrominated diphenylalkanes with tetrabromobisphenol-A-bis(bromoalkyl ether) is disclosed. US 8476373 and US 8933159 relate to brominated anionic chain transfer vinyl aromatic polymers which can flame retard polyolefins.

[0004] Fire retardants are used in wire and / or cable formulations to achieve the fire performance required for specific applications such as appliance, building and construction, automotive cables, photovoltaic wires, etc. In these applications, the insulating coating on the conductor is flame retarded by incorporating various fire-retardant chemicals or technologies (bromine, phosphorus, metal hydroxides (e.g., magnesium hydroxide, aluminum hydroxide, etc.)). Such fire-retardant chemicals are also used in jacket (layer on the insulator) formulations. The insulator or jacket can be (1) thermoplastic or (2) thermoset (crosslinked).

[0005] Non-limiting examples of thermoplastic plastics used for the insulator or jacket include polyurethanes, polyesters, polyamides, polyolefins, styrenic polymers, chlorinated polyethylenes, and combinations thereof.

[0006] Thermoset formulations for wire and / or cable are typically formed by crosslinking techniques including (a) moisture cure techniques, (b) peroxide cure techniques, or (c) electron beam cure techniques. Non-limiting examples of base polymers suitable for crosslinking include polyolefins such as polyethylene and polyolefin copolymers such as poly(ethylene-vinyl acetate) (EVA) and poly(ethylene ethyl acrylate) (EEA), and polyolefin derivatives such as chlorinated polyethylene or silane functionalized polyethylene.

[0007] Existing non-high molecular weight brominated flame retardants (BFRs) typically have a higher melting temperature than the process conditions and require milling to a very small and uniform particle size (average less than about 10 microns) before use in wire and / or cable formulations. Higher particle sizes will negatively impact the smoothness of the wire insulation surface. In addition to the expensive and / or time consuming milling process, non-high molecular weight BFRs typically create high extrusion back pressure during compounding.

[0008] Accordingly, the art continues to seek improved flame retardant compositions for use in wire and / or cable. SUMMARY

[0009] The present invention provides a flame retardant composition for use in wire and / or cable comprising a thermoplastic. Non-limiting examples of thermoplastics include polyurethanes, polyesters, polyamides, polyolefins, styrenic polymers, chlorinated polyethylenes, and combinations thereof. The flame retardant is a brominated high molecular weight flame retardant. High molecular weight brominated flame retardants (PBFRs) are based on a polystyrene backbone and synthesized through an aromatic bromination process. These PBFR formulations are suitable for use in a variety of wire and / or cable applications, providing unique properties not previously possible with existing brominated flame retardant technologies.

[0010] Another embodiment of the present invention provides a flame retardant composition for use in wire and / or cable comprising a thermoset formulation. Thermoset formulations for wire and / or cable are typically formed by crosslinking techniques including (a) moisture cure techniques, (b) peroxide cure techniques, or (c) electron beam cure techniques. Non-limiting examples of base polymers suitable for crosslinking include polyolefins such as polyethylene and polyolefin copolymers such as poly(ethylene-vinyl acetate) (EVA) and poly(ethylene ethyl acrylate) (EEA), and polyolefin derivatives such as chlorinated polyethylene or silane functionalized polyethylene. The flame retardant is a brominated high molecular weight flame retardant. High molecular weight brominated flame retardants (PBFRs) are based on a polystyrene backbone and synthesized through an aromatic bromination process. These PBFR formulations are suitable for use in a variety of wire and / or cable applications, providing unique properties not previously possible with existing brominated flame retardant technologies.

[0011] Other embodiments of the present invention include processes for making the flame retardant compositions of the present invention and flame retarded thermoplastic or thermoset compositions and their use as coatings for wires and / or cables.

[0012] These and other embodiments and features of the present invention will be more apparent from the following description, and appended claims. DETAILED DESCRIPTION

[0013] The brominated high molecular weight flame retardants of the present invention have numerous benefits. For example, existing non-high molecular weight BFRs have a higher melting temperature than the process conditions. Therefore, non-high molecular weight BFRs need to be ground to a very small and uniform particle size (average less than about 10 microns) before they can be used in wire and / or cable formulations. However, the high molecular weight flame retardants of the present invention have a glass transition temperature (Tg) that is lower than the typical wire and / or cable processing temperature (Tg less than about 145°C for a processing temperature of about 200°C). Therefore, at the processing temperature, the high molecular weight BFRs will readily melt blend and mix with the other ingredients of the formulation.

[0014] Furthermore, unlike existing high molecular weight BFRs and non-high molecular weight BFRs, the new polymer BFR formulations of the present invention provide lower extrusion back pressure during the compounding and wire extrusion process due to their higher melt index (higher melt index means the polymer flows better at a given pressure and temperature). Therefore, the compounder and cable producer is allowed to extrude at higher production rates (pounds / hour or meters / hour).

[0015] Unlike previously disclosed high molecular weight BFRs, the high molecular weight brominated flame retardants of the present invention provide higher thermal stability. The high molecular weight BFRs required in other inventions for wire and / or cable applications are typically aliphatic brominated polymers, which is in contrast to the high molecular weight BFRs of the present invention where the bromine is attached to an aromatic ring. Aromatic bromine has higher thermal stability than aliphatic bromine. Higher thermal stability means one can (a) use the formulation at higher processing temperatures, (b) have longer run times during wire coating, and (c) can enhance recyclability.

[0016] The brominated flame retardants in the practice of the present invention contain bromine that is aromatically bound and in several embodiments are considered brominated styrenic polymers. The brominated flame retardants have a weight average molecular weight (Mw) of about 650 to about 75,000 and a bromine content of about 60 wt% or greater. Preferably, the styrenic polymer is polystyrene. Mixtures of two or more brominated flame retardants can be used in the practice of the present invention. Mixtures of brominated flame retardants with other non-halogenated flame retardants can also be used in the practice of the present invention.

[0017] In other embodiments, the brominated flame retardant is a brominated anionic styrenic polymer, wherein the styrenic polymer is formed via anionic polymerization, typically utilizing an alkyl lithium initiator; these brominated flame retardants typically have a weight average molecular weight (Mw) of about 2000 or greater, preferably about 10,000 or greater. In some embodiments, the brominated anionic styrenic polymer has a Mw of about 8000 to about 50,000, preferably about 10,000 to about 30,000, and more preferably about 10,000 to about 20,000.

[0018] Typically, the brominated anionic styrenic polymer contains about 60 wt% or more bromine, preferably about 66 wt% or more bromine, more preferably about 67 wt% or more bromine. In some embodiments, the brominated anionic styrenic polymer contains about 60 wt% to about 72 wt% bromine, more preferably about 66 wt% to about 71 wt% bromine, even more preferably about 67 wt% to about 71 wt% bromine. Preferably, the brominated anionic styrenic polymer is a brominated anionic polystyrene. In some embodiments, the brominated anionic styrenic polymer is a brominated anionic polystyrene having a weight average molecular weight of about 10,000 to about 20,000 and about 67 wt% to about 69 wt% bromine. Information regarding the preparation of brominated anionic styrenic polymers can be found, for example, in U.S. Patent Nos. 7,632,893 and 7,638,583.

[0019] In another embodiment, the brominated flame retardant is a low molecular weight brominated anionic styrenic polymer having a weight average molecular weight (Mw) of about 650 or greater, preferably about 950 or greater, more preferably about 1000 or greater. In some embodiments, these brominated anionic styrenic polymers have a Mw in the range of about 650 to about 10,000, preferably about 750 to about 7500, and more preferably about 1000 to about 4000.

[0020] Typically, the low molecular weight brominated anionic styrenic polymer contains about 60 wt% or more bromine, preferably about 66 wt% or more bromine, more preferably about 70 wt% or more bromine. In some embodiments, these brominated anionic styrenic polymers contain about 60 wt% to about 77 wt% bromine, preferably about 66 wt% to about 77 wt% bromine, more preferably about 70 wt% to about 75 wt% bromine.

[0021] Preferably, the low molecular weight brominated anionic styrenic polymer is a brominated anionic polystyrene. In some embodiments, the low molecular weight brominated anionic styrenic polymer is a brominated anionic polystyrene having a weight average molecular weight of about 1000 to about 3000 and about 73 wt% to about 77 wt% bromine.

[0022] The low molecular weight brominated anionic styrenic polymer can be formed by bromination in an organic solvent or in bromine sea, where bromine is both the brominating agent and the solvent. Information regarding the preparation of low molecular weight brominated anionic styrenic polymers can be found, for example, in International Patent Publications WO 2017 / 176740 and WO 2017 / 184350; these polymers can also be made as described in U.S. Patent Nos. 7,632,893 and 7,638,583.

[0023] Another brominated flame retardant that can be used in the practice of the present application is sometimes not classified as a styrenic polymer due to the relatively small number of repeat units in these molecules. Like the brominated styrenic polymers, these molecules also contain aromatically bound bromine and styrenic repeat units. This brominated flame retardant is a brominated anionic chain transfer vinyl aromatic polymer containing about 70 wt% or more bromine, preferably about 72 wt% or more bromine, and a weight average molecular weight of about 1000 or more, preferably about 1250 or more. In some embodiments, the bromine content is in the range of about 70 wt% to about 79 wt%, preferably about 72 wt% to about 78 wt%, and the Mw is in the range of about 1000 to about 21,000, preferably about 1250 to about 14,000, more preferably about 2000 to about 10,000.

[0024] Preferably, the brominated anionic chain transfer vinyl aromatic polymer is a brominated anionic chain transfer polystyrene. In some embodiments, the brominated anionic chain transfer vinyl aromatic polymer is a brominated anionic chain transfer polystyrene having a weight average molecular weight of about 2000 to about 10,000 and about 72 wt% to about 78 wt% bromine.

[0025] The brominated anionic chain transfer vinyl aromatic polymer can be formed by bromination in an organic solvent or in bromine sea, where bromine is both the brominating agent and the solvent. Information regarding the preparation of brominated anionic chain transfer vinyl aromatic polymers can be found, for example, in U.S. Patent Nos. 8,420,876, 8,796,388, and 8,993,684.

[0026] Mixtures of two or more brominated flame retardants can be used in the practice of the present application. In addition to the brominated anionic styrenic polymer and / or the brominated anionic chain transfer vinyl aromatic polymer, the flame retardant additive composition can also contain one or more other brominated flame retardants. Suitable brominated flame retardants include hexabromocyclohexane, dibromoethyl dibromocyclohexane, monochloropentabromocyclohexane, tetrabromocyclooctane, hexabromocyclododecane, bis(pentabromophenyl)ethane (decabromodiphenylethane), hexabromobenzene, dibromostyrene and derivatives thereof, pentabromodiphenyl ether, octabromodiphenyl ether (octabromodiphenyl oxide), decabromodiphenyl ether (decabromodiphenyl oxide), l,2-bis(tribromophenoxy)ethane, tetradecabromodiphenoxybenzene, 2,4,6-tribromophenol allyl ether, dibromoneopentyl glycol, tribromoneopentyl alcohol, tetrabromobisphenol-A, tetrabromobisphenol A diallyl ether, tetrabromobisphenol-A bis(2,3-dibromopropyl ether), bis(2,4,6-tribromophenoxyethyl) tetrabromobisphenol-A ether, tetrabromobisphenol- bis(2-hydroxyethyl) ether, tetrabromobisphenol-S, tetrabromobisphenol-S bis(2,3- dibromopropyl ether), brominated epoxy oligomers (such as tribromophenol-terminated brominated epoxy oligomers), tetrabromobisphenol-A based brominated carbonate oligomers (such as 2,4,6-tribromophenyl-terminated tetrabromobisphenol-A carbonate oligomers and phenoxy-terminated tetrabromobisphenol-A carbonate oligomers), brominated polystyrene, block copolymers of polystyrene with brominated polybutadiene, poly(dibromophenylene oxide), poly(pentabromobenzyl acrylate), brominated phthalic acid, tetrabromodiallyl phthalate, bis(2-ethylhexyl) tetrabromophthalate, tetrabromophthalimide, N,N-vinyl-bis(tetrabromophthalimide), tetrabromophthalic anhydride, mixed esters of tetrabromophthalic anhydride with diethylene glycol and propylene glycol, N,N'-vinyl-bis-(5,6-dibromonorbornane 2,3-dicarboximide), tris(tribromophenyl)triazine, brominated phenoxytriazines (such as tris(tribromophenoxy)triazine), brominated maleimides (such as tribromophenyl maleimide), brominated trimethylphenyl indenes, brominated isocyanurates (such as tris(2,3-dibromopropyl) isocyanurate), and tris(tribromoneopentyl) phosphate. Preferred brominated flame retardants for use in admixture with the brominated anionic styrenic polymer and / or the brominated anionic chain transfer vinyl aromatic polymer include decabromodiphenylethane and N,N-vinyl-bis(tetrabromophthalimide).

[0027] In addition, for the brominated flame retardants discussed above, embodiments of the present application include a polymeric composition. The polymeric composition can be used as a thermoplastic or a thermoset. The polymeric composition and the brominated flame retardant together provide a coating for wire and / or cable. Non-limiting examples of polymeric compositions that can be used as thermoplastics include polyurethanes, polyesters, polyamides, polyolefins, styrenic polymers, chlorinated polyethylenes, and combinations thereof. Thermoset formulations for wire and / or cable are typically formed by crosslinking techniques including (a) moisture cure techniques, (b) peroxide cure techniques, or (c) electron beam cure techniques. Non-limiting examples of base polymeric compositions suitable for crosslinking include polyolefins such as polyethylene and polyolefin copolymers such as poly(ethylene-vinyl acetate) (EVA) and poly(ethylene ethyl acrylate) (EEA), and polyolefin derivatives such as chlorinated polyethylene or silane-functionalized polyethylene.

[0028] Optional ingredients that can be present in the flame retardant composition include inorganic compounds, antioxidants, impact modifiers, compatibilizers, halogenated polyethylenes, pigments, flame retardant synergists, anti-drip agents, dyes, light stabilizers, UV stabilizers, fillers, antifoams, antibacterial agents, biocides, buffers, pH stabilizers, fixatives, antistatic agents, antifouling agents, water repellents, optical brighteners, plasticizers, emulsifiers, acid scavengers, radical scavengers, metal scavengers or passivators, processing aids, mold release agents, lubricants, antiblocking agents, antistatic agents, slip additives, blowing agents, anti-fog agents, reinforcing agents, coupling agents, nucleating agents, other flame retardants, and other thermal stabilizers.

[0029] Preferred optional ingredients include inorganic compounds, antioxidants, impact modifiers, compatibilizers, halogenated polyethylenes, and pigments. In some preferred embodiments, one or more antioxidants, one or more compatibilizers, one or more impact modifiers, one or more halogenated polyethylenes, and / or one or more pigments are present in the additive composition. In some preferred embodiments, at least one inorganic compound is present in the flame retardant additive composition and one or more other optional ingredients selected from the group consisting of antioxidants, impact modifiers, compatibilizers, and halogenated polyethylenes.

[0030] Inorganic compounds are a preferred type of optional ingredient. As used throughout this document, the phrase "inorganic component" means one or more inorganic compounds containing one or more metal atoms that do not have a hydrocarbyl group directly bonded to the metal atom. More preferably, at least one inorganic compound is present in the flame retardant additive composition.

[0031] In the practice of the present application, suitable inorganic compounds, some of which act as synergists, include talc, ammonium phosphates, ammonium phosphinates, antimony trioxide, antimony pentoxide, antimony phosphate, aluminum phosphinates, diethyl aluminum phosphinates, sodium antimonate, calcium stearate, calcium borate, calcium phosphinate, magnesium hydroxide, aluminum magnesium hydroxide carbonate, zinc borate, zinc oxide, zinc stannate, zinc sulfide, zinc phosphate, zinc phosphinate, diethyl zinc phosphinate, zinc molybdate, tin (IV) oxide, titanium dioxide, titanium phosphate, alpha-zirconium phosphate, wollastonite, hydrotalcite, silane-modified aluminum silicate, glass fibers, and clays, including smectites such as montmorillonite, bentonite, nontronite, hectorite, saponite, beidellite, cronstedtite, sauconite, stevensite, and szaibelyite; kaolins such as halloysite; micas such as illite; ledikite; talcose; kenyaite; zeolite A; vermiculite; attapulgite; and hectorite. Mixtures of two or more inorganic compounds can be used, if desired, and in some embodiments, more than one inorganic compound is preferred.

[0032] When present in the flame retardant composition, the inorganic compound is about 10 wt% or more, preferably about 15 wt% or more, more preferably about 25 wt% or more, or from about 10 wt% to about 70 wt%, preferably from about 15 wt% to about 60 wt%, more preferably from about 15 wt% to about 60 wt%, based on the total weight of the additive composition. When more than one inorganic compound comprises the inorganic component of the additive composition, these values refer to the combined amount of inorganic compounds present in the additive composition.

[0033] Antioxidants that can be used in the practice of the present application include phenolic antioxidants, thioesters, aromatic amines, phosphonites, and phosphites. Suitable antioxidants include 2,6-di-tert-butyl-4-methylphenol, tetrakis(3-(4-hydroxy-3,5-di-tert-butylphenyl)propionyloxy- methyl)methane, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-s-triazine-2,4,6(1 H,3H,5H)trione, 3,5-di-tert-butyl-4-hydroxyhydrocinnamate, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4- hydroxybenzyl)benzene, 4,4'-methylenebis(2,6-di-tert-butyl-phenol), ethylenebis(oxyethylene)bis-(3-(5-tert-butyl-4-hydroxy-m-tolyl)-propionate), N,N'-(hexane-1,6-diyl)bis(3-(3,5-di-tert-butyl-4- hydroxyphenyl)propionamide), 3,5-di-tert-butyl-4-hydroxybenzoic acid hexadecyl ester, 2,2'-thiodiethylbis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], C 13 to C 15C9 to C13 linear and branched alkyl esters of 3-(3',5'-di-tert-butyl-4'- hydroxyphenyl)propionic acid 11 C9 to C13 linear and branched alkyl esters of 3-(3',5'-di-tert-butyl-4'- hydroxyphenyl)propionic acid

[0034] Generally, the impact modifier is a rubber or elastomer. Suitable impact modifiers in the practice of the present application include ethylene octene copolymers and ethylene hexene copolymers. In the practice of the present application, ethylene octene copolymers are the preferred impact modifier. If desired, mixtures of impact modifiers can be used.

[0035] The compatibilizer is sometimes a maleic anhydride copolymer of a thermoplastic elastomer, an olefin homopolymer or copolymer, or a macromolecular catalyst formed in situ. Compatibilizers suitable for use in the practice of the present application include styrene ethylene butadiene copolymers, especially styrene ethylene / butylene linear triblock copolymers, maleic anhydride modified polypropylene homopolymers, and sodium ionomers of ethylene / methacrylic acid copolymers. Mixtures of compatibilizers can be used. Preferred compatibilizers include styrene ethylene / butylene linear triblock copolymers.

[0036] The halogenated polyethylene is a polyethylene containing halogen atoms. Suitable halogenated polyethylenes include polytetrafluoroethylene and chlorinated polyethylene. Mixtures of halogenated polyethylenes can be used.

[0037] Pigments are substances that impart color to polymers and are generally used only when color is desired for the high molecular brominated flame retardant composition used in the wire and / or cable. Non-limiting examples of suitable pigments for practicing the present application include mixed oxides of chromium, antimony, and titanium (Brown 24), mixed compounds of chromium, nickel, and titanium (Yellow 53), 1,8-bis(phenylthio)anthracene-9,10-dione (Solvent Yellow 163), titanium dioxide, and carbon black, titanium dioxide, zinc sulfide, iron oxide, lead chromate and lead molybdate, cadmium, chromium oxide. Mixtures of two or more pigments can be used.

[0038] Flame retardant high molecular composition for wire and / or cable One embodiment of the present application is a flame retardant composition for use in wire and / or cable comprising at least one high molecular composition; at least one brominated flame retardant; and at least one synergist in an amount greater than about 0.0 wt%; wherein the brominated flame retardant contains aromatically bound bromine and is selected from a) a brominated styrenic polymer having a weight average molecular weight of about 650 to about 75,000 and a bromine content of about 60 wt% or more, and / or b) a brominated anionic chain transfer vinyl aromatic polymer having a weight average molecular weight of about 650 to about 75,000 and containing about 70 wt% or more bromine.

[0039] Optional ingredients normally present in flame retardant polyolefin compositions are described above.

[0040] Suitable high molecular compositions are those that can be used as thermoplastic or thermoset materials. Non-limiting examples of high molecular compositions that can be used as thermoplastics include polyurethanes, polyesters, polyamides, polyolefins, styrenic polymers, chlorinated polyethylenes, and combinations thereof. Thermoset formulations for wires and / or cables are typically formed by crosslinking techniques including (a) moisture cure techniques, (b) peroxide cure techniques, or (c) electron beam cure techniques. Non-limiting examples of base high molecular compositions suitable for crosslinking include polyolefins such as polyethylene and polyolefin copolymers such as poly(ethylene-vinyl acetate) (EVA) and poly(ethylene ethyl acrylate) (EEA), and polyolefin derivatives such as chlorinated polyethylene or silane functionalized polyethylene.

[0041] Brominated flame retardants in the practice of the present application contain aromatic bound bromine and in several embodiments are considered brominated styrenic polymers. The brominated flame retardants have a weight average molecular weight (Mw) of about 650 to about 75,000 and a bromine content of about 60 wt% or greater. Preferably, the styrenic polymer is polystyrene. Mixtures of two or more brominated flame retardants can be used in the practice of the present application. Mixtures of brominated flame retardants with other non-halogenated flame retardants can also be used in the practice of the present application.

[0042] In other embodiments, the brominated flame retardant is a brominated anionic styrenic polymer, wherein the styrenic polymer is formed via anionic polymerization, typically using an alkyl lithium initiator; these brominated flame retardants typically have a weight average molecular weight (Mw) of about 2000 or greater, preferably about 10,000 or greater. In some embodiments, the brominated anionic styrenic polymer has a Mw of about 8000 to about 50,000, preferably about 10,000 to about 30,000, and more preferably about 10,000 to about 20,000.

[0043] Generally, the brominated anionic styrenic polymer contains about 60 wt% or more bromine, preferably about 66 wt% or more bromine, more preferably about 67 wt% or more bromine. In some embodiments, the brominated anionic styrenic polymer contains about 60 wt% to about 72 wt% bromine, more preferably about 66 wt% to about 71 wt% bromine, even more preferably about 67 wt% to about 71 wt% bromine. Preferably, the brominated anionic styrenic polymer is a brominated anionic polystyrene. In some embodiments, the brominated anionic styrenic polymer is a brominated anionic polystyrene having a weight average molecular weight of about 10,000 to about 20,000 and about 67 wt% to about 69 wt% bromine. Information regarding the preparation of brominated anionic styrenic polymers can be found, for example, in U.S. Patent Nos. 7,632,893 and 7,638,583.

[0044] In another embodiment, the brominated flame retardant is a low molecular weight brominated anionic styrenic polymer having a weight average molecular weight (Mw) of about 650 or greater, preferably about 950 or greater, more preferably about 1000 or greater. In some embodiments, these brominated anionic styrenic polymers have a Mw in the range of about 650 to about 10,000, preferably about 750 to about 7500, and more preferably about 1000 to about 4000.

[0045] Generally, the low molecular weight brominated anionic styrenic polymer contains about 60 wt% or more bromine, preferably about 66 wt% or more bromine, more preferably about 70 wt% or more bromine. In some embodiments, these brominated anionic styrenic polymers contain about 60 wt% to about 77 wt% bromine, preferably about 66 wt% to about 77 wt% bromine, more preferably about 70 wt% to about 75 wt% bromine.

[0046] Preferably, the low molecular weight brominated anionic styrenic polymer is a brominated anionic polystyrene. In some embodiments, the low molecular weight brominated anionic styrenic polymer is a brominated anionic polystyrene having a weight average molecular weight of about 1000 to about 3000 and about 73 wt% to about 77 wt% bromine.

[0047] The low molecular weight brominated anionic styrenic polymers can be formed by bromination in an organic solvent or in bromine sea, where bromine is both the brominating agent and the solvent. Information regarding the preparation of low molecular weight brominated anionic styrenic polymers can be found, for example, in International Patent Publication Nos. WO 2017 / 176740 and WO 2017 / 184350; these polymers can also be made as described in U.S. Patent Nos. 7,632,893 and 7,638,583.

[0048] Another brominated flame retardant that can be used in the practice of the present application is sometimes not classified as a styrenic polymer because the number of repeat units in these molecules is relatively low. Like the brominated styrenic polymers, these molecules also contain aromatically bound bromine and styrenic repeat units. This brominated flame retardant is a brominated anionic chain transfer vinyl aromatic polymer containing about 70 wt% or more bromine, preferably about 72 wt% or more bromine, and a weight average molecular weight of about 1000 or more, preferably about 1250 or more. In some embodiments, the bromine content is in the range of about 70 wt% to about 79 wt%, preferably about 72 wt% to about 78 wt%, and the Mw is in the range of about 1000 to about 21,000, preferably about 1250 to about 14,000, more preferably about 2000 to about 10,000.

[0049] Preferably, the brominated anionic chain transfer vinyl aromatic polymer is a brominated anionic chain transfer polystyrene. In some embodiments, the brominated anionic chain transfer vinyl aromatic polymer is a brominated anionic chain transfer polystyrene having a weight average molecular weight of about 2000 to about 10,000 and about 72 wt% to about 78 wt% bromine.

[0050] The brominated anionic chain transfer vinyl aromatic polymer can be formed by bromination in an organic solvent or in bromine sea, where bromine is both the brominating agent and the solvent. Information regarding the preparation of brominated anionic chain transfer vinyl aromatic polymers can be found, for example, in U.S. Patent Nos. 8,420,876, 8,796,388, and 8,993,684.

[0051] Mixtures of two or more brominated flame retardants can be used in the practice of the present application. In addition to the brominated anionic styrenic polymer and / or the brominated anionic chain transfer vinyl aromatic polymer, the flame retardant additive composition can also contain one or more other brominated flame retardants. Suitable brominated flame retardants include hexabromocyclohexane, dibromoethyl dibromocyclohexane, monochloropentabromocyclohexane, tetrabromocyclooctane, hexabromocyclododecane, bis(pentabromophenyl)ethane (decabromodiphenylethane), hexabromobenzene, dibromostyrene and derivatives thereof, pentabromodiphenyl ether, octabromodiphenyl ether (octabromodiphenyl oxide), decabromodiphenyl ether (decabromodiphenyl oxide), l,2-bis(tribromophenoxy)ethane, tetradecabromodiphenoxybenzene, 2,4,6-tribromophenol allyl ether, dibromoneopentyl glycol, tribromoneopentyl alcohol, tetrabromobisphenol-A, tetrabromobisphenol A diallyl ether, tetrabromobisphenol-A bis(2,3-dibromopropyl ether), bis(2,4,6-tribromophenoxyethyl) tetrabromobisphenol-A ether, tetrabromobisphenol- bis(2-hydroxyethyl) ether, tetrabromobisphenol-S, tetrabromobisphenol-S bis(2,3- dibromopropyl ether), brominated epoxy oligomers (such as tribromophenol-terminated brominated epoxy oligomers), tetrabromobisphenol-A based brominated carbonate oligomers (such as 2,4,6-tribromophenyl-terminated tetrabromobisphenol-A carbonate oligomers and phenoxy-terminated tetrabromobisphenol-A carbonate oligomers), brominated polystyrene, block copolymers of polystyrene with brominated polybutadiene, poly(dibromophenylene oxide), poly(pentabromobenzyl acrylate), brominated phthalic acid, tetrabromodiallyl phthalate, bis(2-ethylhexyl) tetrabromophthalate, tetrabromophthalimide, N,N-vinyl-bis(tetrabromophthalimide), tetrabromophthalic anhydride, mixed esters of tetrabromophthalic anhydride with diethylene glycol and propylene glycol, N,N'-vinyl-bis-(5,6-dibromonorbornane 2,3-dicarboximide), tris(tribromophenyl)triazine, brominated phenoxytriazines (such as tris(tribromophenoxy)triazine), brominated maleimides (such as tribromophenyl maleimide), brominated trimethylphenyl indenes, brominated isocyanurates (such as tris(2,3-dibromopropyl) isocyanurate), and tris(tribromoneopentyl) phosphate. Preferred brominated flame retardants for use in admixture with the brominated anionic styrenic polymer and / or the brominated anionic chain transfer vinyl aromatic polymer include decabromodiphenylethane and N,N-vinyl-bis(tetrabromophthalimide).

[0052] Process for forming a flame retardant composition for use in wire and / or cable One embodiment of a process for forming a flame retardant composition for use in wire and / or cable, the process comprising: a first step consisting of combining: at least one high molecular composition; at least one brominated flame retardant, wherein the brominated flame retardant contains aromatically bound bromine and is selected from a) a brominated styrenic polymer having a weight average molecular weight of about 650 to about 75,000 and a bromine content of about 60 wt% or more, and / or b) a brominated anionic chain transfer vinyl aromatic polymer containing about 70 wt% or more bromine; and at least one synergist, and then extruding the mixture of the first step to coat a wire and / or cable Yet another embodiment of a process for forming a flame retardant composition, the process comprising: a first step consisting of combining: at least one high molecular composition; at least one brominated flame retardant, wherein the brominated flame retardant contains aromatically bound bromine and is selected from a) a brominated styrenic polymer having a weight average molecular weight of about 650 to about 75,000 and a bromine content of about 60 wt% or more, and / or b) a brominated anionic chain transfer vinyl aromatic polymer containing about 70 wt% or more bromine; and at least one organic peroxide. A second step of extruding the mixture of the first step to coat a wire and / or cable. And a third step of heating the coated wire and / or cable to a temperature above the decomposition point of the at least one organic peroxide.

[0053] Yet another embodiment of a process for forming a flame retardant composition, the process comprising: a first step consisting of combining: at least one high molecular composition; at least one synergist; at least one brominated flame retardant, wherein the brominated flame retardant contains aromatically bound bromine and is selected from a) a brominated styrenic polymer having a weight average molecular weight of about 650 to about 75,000 and a bromine content of about 60 wt% or more, and / or b) a brominated anionic chain transfer vinyl aromatic polymer containing about 70 wt% or more bromine. A second step of extruding the mixture of the first step to coat a wire and / or cable. And a third step of electron beam irradiating the mixture of the coated wire and / or cable with an effective dose of electron beam irradiation.

[0054] The brominated flame retardant and the high molecular composition include those discussed above. When preparing the compositions of the present invention, the individual components can be admixed with the substrate or host polymer individually and / or in sub-combinations in the appropriate proportions.

[0055] When the flame retardant polyolefin composition is formed from the flame retardant additive composition, the flame retardant additive composition is typically about 40 wt% or more of the flame retardant polyolefin composition, or about 40 wt% to about 80 wt% of the flame retardant polyolefin composition, based on the total weight of the flame retardant polyolefin composition.

[0056] Various methods can be used to prepare the compositions of the present application. The blending of the brominated flame retardant with other ingredients can be carried out on a blending apparatus such as a single screw extruder, a twin screw extruder, or a Buss kneader. Preferably, the blending uses an extruder, more preferably a twin screw extruder. Other ingredients used in the practice of the present application can be added in the initial feed throat of the extruder, or the ingredients can be added further downstream to the extruder. In the extruder, many of the ingredients are typically melted as they are mixed together. The extrudate from the extruder is typically converted into pellets or granules by either cooling the strand of extruded polymer and subdividing the solidified strand into pellets or granules, or by simultaneously subjecting the extrudate to die face pelletization and water or air cooling. If desired, the compositions of the present application can be formulated as a powder or granular admixture of the ingredients of the composition.

[0057] In certain embodiments, a masterbatch can be formed comprising the high molecular composition and at least one brominated flame retardant. A masterbatch is typically a mixture having a high concentration of the brominated flame retardant relative to the thermoplastic. Typically, the masterbatch is later admixed with more of the high molecular composition to form a product having the desired ratio of brominated flame retardant, other ingredients, and high molecular composition. The masterbatch can be used in thermoset formulations.

[0058] Forming a coating for wire and / or cable In particular, the compositions of the present application are useful as coatings for wire and / or cable. Fire retardant agents are used in wire and / or cable formulations to meet the fire performance requirements of specific applications such as appliances, building and construction, automotive cables, photovoltaic wire, etc. In these applications, the insulating coating on the conductor is made flame retardant by incorporating various fire retardant chemicals or technologies (Br, P, metal hydroxides, etc.). Such fire retardant chemicals are also used in jacket (layer on the insulator) formulations. The insulator or jacket can be (1) thermoplastic or (2) thermoset (crosslinked). The thermoplastic and thermoset formulations can have polyolefins (PP, PE) as the base polymer. In addition to polyolefins, the base polymer can also be polyurethane and chlorinated polyethylene. The polyolefins can typically be crosslinked by (a) moisture cure technology, (b) peroxide cure technology, (c) electron beam cure technology.

[0059] Typically, the compositions are prepared in a blending extruder that mixes and evenly distributes and disperses all of the ingredients. The extruded compound is then formed into pellets. Typically, the pellets are then fed into a cable extruder to coat the wire. For thermoset wire, the coated wire will be crosslinked in a second step based on cure chemistry.

[0060] Suitable curing chemistries for the present invention include curing by electron beam and curing by peroxide. For peroxide curing, the strand will pass through a continuous cure tube at elevated temperature. For electron beam curing, the strand will pass through an electron beam chamber.

[0061] For peroxide curing, any process known in the art will be suitable for this purpose. Generally and for example, the curing system can include an organic peroxide introduced into the blend at a temperature below the decomposition point of the peroxide, such as 2,5-dimethyl-2,5-di-(tert-butylperoxy)hexane, dicumyl peroxide, VUL-CUP® or DiCup®, and the crosslinking can include heating the blend to a temperature above the decomposition point of the peroxide. The crosslinking in one embodiment can include a continuous cure process downstream of the extruder. The crosslinking in another embodiment can include an Engel process, in which the blend is rammed to form a crosslinked extrudate by maintaining a pressure head above the decomposition temperature of the peroxide after the peroxide is introduced.

[0062] For electron beam curing, any process known in the art will be suitable for this purpose. For example, the method can include electron beam irradiation of the flame retardant composition with an effective dose of electron beam irradiation. The effective or absorbed dose of electron beam radiation can be 49 to 201 kilojoules of energy per kilogram of EBC formulation (kJ / kg), or 49 to 160 kJ / kg, or 80 to 201 kJ / kg, or 80 to 160 kJ / kg, or 50 to 80 kJ / kg, or 100 to 140 kJ / kg, or 160 to 201 kJ / kg. 100 kJ / kg equals 10 megarads (Mrad) / kg, which equals 100,000 grays. 1 gray = 1 joule per kilogram (J / kg) = 100 rads. The electron beam irradiation step can be performed at any suitable temperature, such as 10°C to 50°C (e.g., 23°C ± 1°C), in any suitable atmosphere, such as air or molecular nitrogen. The irradiation can be performed continuously or intermittently, alternatingly continuously.

[0063] Examples - Overview Ingredients Ingredients for making the flame retardant compositions are provided in the examples. In the tables, some of the ingredients used are referred to by their trade name.

[0064] Analytical Methods Known analytical methods can be used or adapted for use in analyzing the properties of the brominated flame retardants and their polyolefin compositions used in the practice of the invention. The following methods are used to measure the properties of the formed brominated flame retardants and / or the flame retardant polyolefin compositions, if applicable.

[0065] Analytical methods for or suitable for testing high molecular BFRs are described in WO 2022 / 031932 Al, which is incorporated herein by reference.

[0066] UL-VW-1 Flame Test. VW-1 burn testing was performed by subjecting three or six samples of a particular coated conductor to the protocol of UL 2556. This involves applying a 125 mm flame for 15 seconds five times, the flame impinging on a vertically oriented test specimen 610 mm (24 inches) in length at a 20° angle. A strip of 12.5 ± 1 mm (0.5 ± 0.1 inch) Kraft paper is affixed to the specimen 254 ± 2 mm (10 ± 0.1 inches) above the flame impingement point. A continuous horizontal layer of cotton is placed on the floor of the test chamber centered on the vertical axis of the test specimen, with the upper surface of the cotton 235 ± 6 mm (9.25 ± 0.25 inches) below the point at which the tip of the blue inner cone of the flame impinges on the specimen. Test failure is based on the following criteria: 25% burn of the Kraft paper strip, ignition of the cotton batting, or burning of the specimen for more than 60 seconds under any of the five flame applications. As an additional measure of burn performance, the length of the uncharred insulation is measured at the completion of the test (“uncharred to flag length”). Igniting VW-1 cotton indicates whether the falling material ignites the cotton bed.

[0067] Each sample was formed by mixing and melting all ingredients together in a twin-screw extruder (ZSK30 (30 mm), Werner & Pfleiderer Coperion GmbH), each ingredient fed separately as a powder.

[0068] In all of the following tables, the amount of each ingredient and the amount of bromine are reported in wt%.

[0069] Example 1 Coated wire and / or cable formulations as shown in Table 1 below were prepared according to the description contained herein. A 14 AWG tinned copper wire with a 0.030 inch insulation was used for the wire construction. The brominated fire retardant coated wire was sent through a 60 foot long steam filled steel tube to complete the peroxide cure process. The cured cable was then used for the following tests. Table 1 shows peroxide crosslinkable fire retardant formulations. In Example 1, a high molecular brominated flame retardant was used according to the disclosure contained herein. Comparative Example 1 contains a commercially available SAYTEX ® 8010 small molecule brominated flame retardant. Example 2 uses a commercially available high molecular aromatic brominated flame retardant SAYTEX ® HP 3010.

[0070] Table 1. Composition of peroxide curable fire retardant formulations

[0071] Table 2 below shows various properties of peroxide cured wire

[0072] Example 2 A second example of producing coated wire and / or cable by electron beam curing. 14 AWG copper wire with a 0.030 inch insulation was used for wire construction. The electron beam curable fire retardant formulations (Table 3) were irradiated with 20 Mrad to produce cured wire. The cured cable was then used for the following tests. Table 3 shows various electron beam curable fire retardant formulations. And Table 4 shows wire extrusion run conditions, die pressure readings, and wire surface quality. Comparative Example 1 is a commercially available SAYTEX ® -8010 small molecule brominated flame retardant. Example 1 is a high molecular weight brominated flame retardant manufactured according to the disclosure contained herein.

[0073] Table 3

[0074] Table 4

[0075] Table 5

[0076] The process conditions show the benefits of having Example 2, as the example provides lower die pressure during wire extrusion while maintaining key VW-1 and hot creep performance. Such improvements are important for lower energy usage customers and the possibility of higher line speeds (higher throughput).

[0077] Example 3 An example of producing coated wire and / or cable by electron beam curing. 14 AWG tinned copper wire with a 0.030 inch insulation was used for wire construction. The electron beam curable fire retardant formulations (Table 3) were irradiated with 15 Mrad to produce cured wire. The cured cable was then used for the following tests. Table 6 shows various electron beam curable fire retardant formulations. And Table 7 shows wire extrusion run conditions, die pressure readings, and wire surface quality. Comparative Example is a commercially available SAYTEX ® -8010 small molecule brominated flame retardant. Examples 3-1 to 3-5 use a high molecular weight brominated flame retardant manufactured according to the disclosure contained herein.

[0078] Table 6

[0079] Table 7

[0080] Table 8

[0081] Example 4 Example of producing coated wire and / or cable by electron beam curing. A 14 AWG tinned copper wire with a 0.030 inch insulation was used for the wire construction. The electron beam curable flame retardant formulations (Table 3) were irradiated with 15 Mrad to produce cured wire. The cured cable was then used for the following tests. Table 9 shows various electron beam curable flame retardant formulations. And Table 10 shows wire extrusion run conditions, die pressure readings, and wire surface quality. Comparative example is a commercially available SAYTEX® ® -8010 small molecule brominated flame retardant. Example uses a high molecular weight brominated flame retardant made according to the disclosure contained herein.

[0082] Table 9

[0083] Table 10

[0084] Table 11

[0085] Example 5 Examples of blended flame retardant and polypropylene are shown below. The compounds are made according to the disclosure contained herein. The PP-BFR formulations above were blended in a 30 mm twin screw extruder at 200 °C at 175 rpm. The blended material was cooled and pelletized. The BFR wt% was adjusted to maintain a constant Br% (16.5) for each formulation.

[0086] Example 6 Example of producing coated wire and / or cable by polypropylene cable insulation and using the example in polypropylene cable insulation. The insulation is made according to the disclosure contained herein. Each of the examples from Example 5 are used herein. A 0.75 inch single screw extruder with a 3: 1 Maddock screw head was used to extrude a 30 mil BFR-PP compound insulation on 14 AWG copper wire at a line speed of 5 meters per minute. The resulting wire was analyzed. As can be seen in the following table, it is noted that the BFR of the present invention provides the following benefits: 1. Die pressure is 30% lower, which indicates better melt flowability than non-high molecular BFR.

[0087] 2. Provides horizontal burn performance compared to commercially available S-8010 / BT-93W 3. While all BFRs provide crush performance > 10 KN (maximum limit of the instrument). The present invention provides better crush performance.

[0088] Example 7 Example of producing coated wire and / or cable with thermoplastic cable jacket and using the same in thermoplastic cable jacket. Jacket is manufactured according to the disclosure contained herein. TPU-BFR compound is produced on a WP twin screw extruder at 200°C at 200 rpm. High molecular BFR and non-high molecular (S-8010, BT-93W) BFR are used in the formulation, keeping Br% (16.5%) and Br / ATO ratio constant.

[0089] Example 9 Example of producing thermoplastic tape. TPU-FR pellets blended on WP are dried at 100°C for 4 hours, after which tape is produced in a single screw extruder. Tape produced from TPU-BFR compound: Single screw extruder conditions used: 0.75 inch single screw extruder with 2:1 PE screw; 160°C / 190°C / 190°C / 190°C; 20 / 40 / 20 screen pack; 45 rpm; 30 mil tape thickness. As can be seen below, the BFR of the present invention provides better elongation at break and better tear strength compared to non-high molecular S-8010, while providing V2 fire performance.

[0090] Components referred to in the specification or claims hereof by chemical name or formula, whether in single or plural form, are identified as they exist prior to contact with another substance referred to by chemical name or chemical type (e.g., another component, a solvent, or the like). It is immaterial what chemical changes, transformations, and / or reactions, if any, occur in the resulting mixture or solution, as such changes, transformations, and / or reactions are the natural result of bringing the specified components together under the conditions called for pursuant to the present disclosure. Thus, the components are identified as ingredients to be brought together in performing a desired operation or in forming a desired composition. Moreover, even though the claims hereinafter can refer to substances, components, and / or ingredients by name, it is precisely the time at which the named substance, component, or ingredient exists immediately prior to its first contact, admixture, or mixture with one or more other substances, components, and / or ingredients according to the present disclosure. The fact that the substance, component, or ingredient can have lost its original identity through chemical reaction or transformation during the course of the contacting, admixing, or mixing operation, if conducted pursuant to the present disclosure and with the ordinary skill of a chemist, is thus of no practical concern.

[0091] The present application can comprise, consist of, or consist essentially of the materials and / or processes recited herein.

[0092] As used herein, the term "about" in reference to the amount of an ingredient in the compositions of the present application or used in the methods of the present application, means that variations of ± 10%, ± 5%, ± 1%, ± 0.5%, or even ± 0.1% are expected and / or allowed on the basis of a typical measurement and liquid handling procedures used in the real world to manufacture concentrates or use solutions. The term about also encompasses amounts that differ due to the different equilibrium conditions for the composition that result from a different initial mixture of the ingredients used in the manufacture of said composition or the practice of said method. Whether or not modified by the term "about", the claim includes equivalents of the amounts.

[0093] The articles "a" and "an" as used in the present disclosure aren't intended to be limiting and should generally be interpreted as "one or more" unless explicitly indicated to the contrary by the context. The use of the term "or" in the context of "A or B" or "A and / or B" is intended to encompass both "A and B" and "A or B" unless otherwise specifically indicated by the context.

[0094] The present application is susceptible to considerable variation in form and may be carried out by specific details. Therefore, the foregoing description is not intended to be limiting, and should not be construed as imposing limitations upon the overall scope of the present application.

Claims

1. A flame retardant composition for use in wire and / or cable comprising at least one high molecular composition; at least one brominated flame retardant; and at least one synergist in an amount greater than about 0.0 wt%; wherein the brominated flame retardant contains aromatic bound bromine and is selected from a) a brominated styrenic polymer having a weight average molecular weight of about 650 to about 75,000 and a bromine content of about 60 wt% or more, and / or b) a brominated anionic chain transfer vinyl aromatic polymer having a weight average molecular weight of about 650 to about 75,000 and containing about 70 wt% or more bromine.

2. The flame retardant composition of claim 1, wherein the brominated flame retardant has a weight average molecular weight (Mw) of about 2000 to about 50,000, preferably about 8000 to about 50,000, more preferably about 10,000 to about 30,000, and most preferably about 10,000 to about 20,000.

3. The flame retardant composition of claim 1, wherein the brominated flame retardant is a brominated anionic chain transfer vinyl aromatic polymer containing about 70 wt% or more bromine, preferably about 72 wt% or more bromine, and a weight average molecular weight of about 1000 or more, preferably about 1250 or more.

4. The flame retardant composition of claim 1, wherein the brominated flame retardant has a bromine content of about 67 wt% or more, more preferably about 68 wt% or more.

5. The flame retardant composition of any one of claim 1, wherein the high molecular composition comprises polyurethanes, polyesters, polyamides, polyolefins, styrenic polymers, chlorinated polyethylenes, and / or combinations thereof.

6. The flame retardant composition of claim 1, wherein the high molecular composition comprises polyolefins such as polyethylene and polyolefin copolymers such as poly(ethylene-vinyl acetate) (EVA) and poly(ethylene ethyl acrylate) (EEA), and polyolefin derivatives such as chlorinated polyethylene or silane functionalized polyethylene.

7. The flame retardant composition of any one of claims 1 to 6, further comprising an organic peroxide.

8. The flame retardant composition of claim 7, wherein the organic peroxide comprises dicumyl peroxide or 2,5-dimethyl-2,5-di-(tert-butylperoxy)hexane.

9. The flame retardant composition of any one of claims 1 to 8, wherein the synergist comprises antimony oxide.

10. A coated wire and / or cable, wherein the coating consists of the flame retardant composition of any one of the preceding claims.

11. A process for forming a flame retardant composition for use in wire and / or cable, the process comprising: a first step consisting of combining i. at least one high molecular composition; ii. at least one brominated flame retardant, wherein the brominated flame retardant contains aromatically bound bromine and is selected from a) a brominated styrenic polymer having a weight average molecular weight of about 650 to about 75,000 and a bromine content of about 60 wt% or more, and / or b) a brominated anionic chain transfer vinyl aromatic polymer containing about 70 wt% or more bromine; and iii. at least one synergist; extruding the mixture of the first step to coat wire and / or cable.

12. The process for forming a flame retardant composition of claim 11, wherein the brominated flame retardant has a weight average molecular weight (Mw) of about 2000 to about 50,000, preferably about 8000 to about 50,000, more preferably about 10,000 to about 30,000, and most preferably about 10,000 to about 20,000.

13. The process for forming a flame retardant composition of claim 11, wherein the brominated flame retardant is a brominated anionic chain transfer vinyl aromatic polymer, the polymer containing about 70 wt% or more bromine, preferably about 72 wt% or more bromine, and a weight average molecular weight of about 1000 or more, preferably about 1250 or more.

14. The process for forming a flame retardant composition of claim 11, wherein the brominated flame retardant has a bromine content of about 67 wt% or more, more preferably about 68 wt% or more.

15. The process for forming a flame retardant composition of any one of claims 11 to 14, wherein the synergist comprises antimony oxide.

16. A process for forming a flame retardant composition, the process comprising: (a) a first step consisting of combining i. at least one high molecular composition; ii. at least one synergist; iii. at least one brominated flame retardant, wherein the brominated flame retardant contains aromatically bound bromine and is selected from a) a brominated styrenic polymer having a weight average molecular weight of about 650 to about 75,000 and a bromine content of about 60 wt% or more, and / or b) a brominated anionic chain transfer vinyl aromatic polymer containing about 70 wt% or more bromine; and iv. at least one organic peroxide (b) a second step of extruding the mixture of the first step to coat wire and / or cable (c) a third step of heating the coated wire and / or cable to a temperature above the decomposition point of the at least one organic peroxide.

17. The process for forming a flame retardant composition of claim 16, wherein the brominated flame retardant has a weight average molecular weight (Mw) of about 2000 to about 50,000, preferably about 8000 to about 50,000, more preferably about 10,000 to about 30,000, and most preferably about 10,000 to about 20,000.

18. The process for forming a flame retardant composition of claim 16, wherein the brominated flame retardant is a brominated anionically chain transferred vinyl aromatic polymer containing about 70 wt% or more bromine, preferably about 72 wt% or more bromine, and a weight average molecular weight of about 1000 or greater, preferably about 1250 or greater.

19. The process for forming a flame retardant composition of claim 16, wherein the brominated flame retardant has a bromine content of about 67 wt% or greater, more preferably about 68 wt% or greater.

20. The process for forming a flame retardant composition of any one of claims 16 to 19, wherein the synergist comprises antimony oxide.

21. The process for forming a flame retardant composition of any one of claims 16 to 20, wherein the organic peroxide comprises dicumyl peroxide or 2,5-dimethyl-2,5-di(tert- butylperoxy)hexane.

22. A process for forming a flame retardant composition, the process comprising: (a) a first step consisting of combining i. at least one high molecular composition; ii. at least one synergist; iii. at least one brominated flame retardant, wherein the brominated flame retardant contains aromatic bound bromine and is selected from a) a brominated styrenic polymer having a weight average molecular weight of about 650 to about 75,000 and a bromine content of about 60 wt% or greater, and / or b) a brominated anionically chain transferred vinyl aromatic polymer containing about 70 wt% or more bromine; (b) a second step of extruding the mixture of the first step to coat wire and / or cable (c) a third step of electron beam irradiating the mixture of coated wire and / or cable with an effective dose of electron beam irradiation.

23. The process for forming a flame retardant composition of claim 22, wherein the brominated flame retardant has a weight average molecular weight (Mw) of about 2000 to about 50,000, preferably about 8000 to about 50,000, more preferably about 10,000 to about 30,000, and most preferably about 10,000 to about 20,000.

24. The process for forming a flame retardant composition of claim 22, wherein the brominated flame retardant is a brominated anionically chain transferred vinyl aromatic polymer containing about 70 wt% or more bromine, preferably about 72 wt% or more bromine, and a weight average molecular weight of about 1000 or greater, preferably about 1250 or greater.

25. The process for forming a flame retardant composition of claim 22, wherein the brominated flame retardant has a bromine content of about 67 wt% or greater, more preferably about 68 wt% or greater.

26. The process for forming a flame retardant composition of any one of claims 22 to 25, wherein the synergist comprises antimony oxide.

27. A coated wire and / or cable wherein the coating is comprised of the following: A flame retardant composition made from the process of any one of claims 11 to 26.

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