Polymeric brominated flame retardant composition for use in wire and / or cable

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

(19) State Intellectual Property Office (12) Invention Patent Application (10) Application Publication Number (43) Application Publication Date (21) Application Number 202480034191.5 (22) Application Date 2024.05.22 (30) Priority Data 63 / 503798 2023.05.23 US (85) PCT International Application Entering National Phase Date 2025.11.21 (86) PCT International Application Application Data PCT / US2024 / 030523 2024.05.22 (87) PCT International Application Publication Data WO2024 / 243285 EN 2024.11.28 (71) Applicant: Albemarle Corporation Address: North Carolina, USA (72) Inventors: R. Roy, R.S. Mather, J.P. McCartney, W. Huberty (74) Patent Agency: China Patent Agent (Hong Kong) Limited 72001 Patent Attorneys: Yu Miao, Yang Sijie (51) Int.Cl. C07F 9 / 02 (2006.01) C08K 5 / 51 (2006.01) C07F 9 / 28 (2006.01) C08F 220 / 22 (2006.01) C08J 9 / 00 (2006.01) (54) Invention Title: Polymer Brominated Flame Retardant Compositions for Use in Wires and / or Cables (57) Abstract: This invention relates to flame retardant compositions and polymer brominated flame retardant compositions for use in wires and / or cables. The brominated flame retardant contains aromatically bound bromine and, in several embodiments, is considered a brominated styrene 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 higher. The invention also relates to a process for forming a flame retardant composition using various curing methods, including but not limited to electron beam curing and peroxide curing. Claims (3 pages), Description (17 pages), CN 121175321 A, 2025.12.19, CN 1 21 17 53 21 A. 1. A flame retardant composition for use in wires and / or cables, comprising at least one polymeric 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) brominated styrene polymers having a weight-average molecular weight of about 650 to about 75,000 and a bromine content of about 60 wt% or higher, and / or b) brominated anion-transfer vinyl aromatic polymers 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 of about 2000 to about 50,000, preferably...3. The flame retardant composition of claim 1, wherein the brominated flame retardant is a brominated anion chain transfer vinyl aromatic polymer containing about 70 wt% or more bromine, preferably about 72 wt% or more bromine, and about 1000 or more, preferably about 1250 or more bromine. 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 claims 1, wherein the polymeric composition comprises polyurethane, polyester, polyamide, polyolefin, styrene polymer, chlorinated polyethylene, and / or combinations thereof. 6. The flame retardant composition of claim 1, wherein the polymeric composition comprises polyolefins such as polyethylene and polyolefin copolymers such as poly(ethylene-vinyl acetate) (EVA) and poly(ethylene ethyl acrylate) (EEA), as well as 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 comprises the flame retardant composition of any one of the preceding claims. 11. A process for forming a flame retardant composition for use in wires and / or cables, the process comprising: a first step consisting of a combination of i. at least one polymeric composition; ii. at least one brominated flame retardant, wherein the brominated flame retardant contains aromatically bound bromine and is selected from a) a brominated styrene polymer having a weight average molecular weight of about 650 to about 75,000 and a bromine content of about 60 wt% or higher, and / or b) a brominated anion-transfer vinyl aromatic polymer containing about 70 wt% or more bromine; and iii. at least one synergist; and a second step of extruding the mixture from the first step to coat the wires and / or cables. 12. The process for forming a flame retardant composition as described in claim 11, wherein the brominated flame retardant has a weight-average molecular weight (Mw) of about 2,000 to about 50,000, preferably about 8,000 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 as claimed in claim 11, wherein the brominated flame retardant is a brominated anion chain transfer vinyl aromatic polymer, the polymer containing about 70 wt% or more bromine, preferably about 72 wt% or more bromine, and about 1000 or more, preferably about 1250 or more weight-average molecular weight. 14. The process for forming a flame retardant composition as claimed in 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 as claimed in 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 a combination of: i. at least one polymeric 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 styrene polymer having a weight-average molecular weight of about 650 to about 75,000 and a bromine content of about 60 wt% or higher, and / or b) a brominated anion-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 wires and / or cables; and (c) a third step of heating the coated wires and / or cables to a temperature above the decomposition point of the at least one organic peroxide. 17. The process for forming a flame retardant composition as claimed in claim 16, wherein the brominated flame retardant has a weight-average molecular weight (Mw) of about 2,000 to about 50,000, preferably about 8,000 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 as claimed in claim 16, wherein the brominated flame retardant is a brominated anion-transfer vinyl aromatic polymer containing about 70 wt% or more bromine, preferably about 72 wt% or more bromine, and about 1,000 or more, preferably about 1,250 or more weight-average molecular weight. 19. The process for forming a flame retardant composition as claimed in claim 16, wherein the brominated flame retardant has a bromine content of about 67 wt% or more, more preferably about 68 wt% or more. 20. The process for forming a flame retardant composition according to any one of claims 16 to 19, wherein the synergist comprises antimony oxide. 21. The process for forming a flame retardant composition according to 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 a combination of i. at least one polymeric 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 styrene polymer having a weight average molecular weight of about 650 to about 75,000 and a bromine content of about 60 wt% or higher, and / or b) a brominated anion-transfer vinyl aromatic polymer containing about 70 wt% or more bromine; (b) a second step of extruding the mixture from the first step to coat wires and / or cables; and (c) a third step of irradiating the coated wire and / or cable mixture with an effective dose of electron beam irradiation. Claims 2 / 3 Page 3 CN 121175321 A 23. The process for forming a flame retardant composition as claimed in claim 22, wherein the brominated flame retardant has a weight-average molecular weight (Mw) of about 2,000 to about 50,000, preferably about 8,000 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 as claimed in claim 22, wherein the brominated flame retardant is a brominated anion chain transfer vinyl aromatic polymer, the polymer containing about 70 wt% or more bromine, preferably about 72 wt% or more bromine, and about 1,000 or more, preferably about 1,250 or more weight-average molecular weight. 25. The process for forming a flame retardant composition as claimed in claim 22, wherein the brominated flame retardant has a bromine content of about 67 wt% or more, more preferably about 68 wt% or more. 26. The process for forming a flame retardant composition according to any one of claims 22 to 25, wherein the synergist comprises antimony oxide. 27. A coating for wires and / or cables, wherein the coating comprises: a flame retardant composition prepared by the process according to any one of claims 11 to 26. Claims 3 / 3 Page 4 CN 121175321 A Polymer Brominated Flame Retardant Composition for Wires and / or Cables Technical Field

[0001] The present invention relates to flame retardant compositions and polymer brominated flame retardant compositions for wires and / or cables. Background Art

[0002] Conduits, appliances, or automotive wires and cables typically have only one polymer layer. This layer must perform several functions simultaneously, which are performed by separate layers in other low-voltage, medium-voltage, and high-voltage cables. Therefore, polymeric compositions used to produce conduits, appliances, or automotive wires must simultaneously meet several demanding requirements, including good insulation behavior, good mechanical properties, especially good abrasion resistance, good flame retardant properties, good resistance to heat distortion, and tolerance to low temperatures.The plastics exhibit good heat resistance, 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, polybrominated anionic styrene polymers are used in combination with at least one synergist to flame retard polyolefins; WO 2001 / 029124 discloses polyolefins containing 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 that can flame retard polyolefins.

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

[0005] Non-limiting examples of thermoplastic plastics used for insulators or sheaths include polyurethanes, polyesters, polyamides, polyolefins, styrene polymers, chlorinated polyethylene, and combinations thereof.

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

[0007] Existing non-molecular brominated flame retardants (BFRs) typically have melting temperatures higher than the process conditions and require grinding to extremely small and uniform particle sizes (average less than about 10 micrometers) before use in wire and / or cable formulations. Higher particle sizes negatively impact the smoothness of the wire insulation surface. In addition to the expensive and / or time-consuming grinding process, non-molecular BFRs typically generate high extrusion back pressures during blending.

[0008] Therefore, this technology is constantly seeking improved flame retardant compositions for use in wires and / or cables. Summary of the Invention

[0009] The present invention provides flame retardant compositions comprising thermoplastic plastics for use in wires and / or cables. Non-limiting examples of thermoplastic plastics include polyurethanes, polyesters, polyamides, polyolefins, styrene polymers, chlorinated polyethylene, and their specifications.Page 1 / 17, CN 121175321, A combination. The flame retardant is a brominated polymeric flame retardant. Brominated polymeric flame retardants (PBFRs) are based on a polystyrene backbone and synthesized via an aromatic bromination process. These PBFR formulations are suitable for a wide range of wire and / or cable applications, providing unique properties previously unattainable by existing brominated flame retardant technologies.

[0010] Another embodiment of the invention provides a flame retardant composition comprising thermosetting formulations for use in wires and / or cables. Thermosetting formulations for wires and / or cables are typically formed by crosslinking techniques including (a) moisture curing, (b) peroxide curing, or (c) electron beam curing. Non-limiting examples of suitable base polymers for crosslinking include polyolefins such as polyethylene and polyolefin copolymers such as poly(ethylene-vinyl acetate) (EVA) and poly(ethylene ethyl acrylate) (EEA), as well as polyolefin derivatives such as chlorinated polyethylene or silane-functionalized polyethylene. The flame retardant is a brominated polymeric flame retardant. Brominated polymeric flame retardants (PBFRs) are based on a polystyrene backbone and synthesized via an aromatic bromination process. These PBFR formulations are suitable for a wide range of wire and / or cable applications, providing unique properties previously unattainable by existing brominated flame retardant technologies.

[0011] Other embodiments of the invention include processes for preparing the flame retardant compositions and flame-retardant thermoplastic or thermosetting compositions of the invention and their use as coatings for wires and / or cables.

[0012] These and other embodiments and features of the invention will become more apparent in the following description and the appended claims. Detailed Description

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

[0014] Furthermore, unlike existing polymeric BFRs and non-polymeric BFRs, the novel polymeric BFR formulations of the present invention provide lower extrusion back pressures during blending and wire extrusion processes due to their higher melt index (a higher melt index means the polymer flows better at a given pressure and temperature). This allows blenders and cable manufacturers to extrude at higher production rates (lbs / h or meters / h).

[0015] Unlike previously disclosed polymeric BFRs, the polymeric brominated flame retardant of the present invention provides higher thermal stability.The polymeric BFRs claimed in other inventions for wire and / or cable applications are typically aliphatic brominated polymers, which is the opposite of the polymeric BFRs of this invention (wherein bromine is attached to an aromatic ring). Aromatic bromines have higher thermal stability than aliphatic bromines. Higher thermal stability means that one can (a) use the formulation at higher processing temperatures, (b) have longer run times during wire coating, and (c) enhance recyclability.

[0016] The brominated flame retardants in the practice of this invention contain aromatically bound bromine and are considered, in several embodiments, brominated styrene 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 higher. Preferably, the styrene polymer is polystyrene. In the practice of this invention, mixtures of two or more brominated flame retardants can be used. In the practice of this invention, mixtures of brominated flame retardants with other non-halogenated flame retardants can also be used.

[0017] In other embodiments, the brominated flame retardant is a brominated anionic styrene polymer, wherein the styrene 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 styrene 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 styrene 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 styrene polymer contains about 60 wt% to about 72 wt% bromine, more preferably about 66 wt% to about 71 wt% bromine, and even more preferably about 67 wt% to about 71 wt% bromine. Preferably, the brominated anionic styrene polymer is brominated anionic polystyrene. In some embodiments, the brominated anionic styrene polymer is 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 styrene 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 styrene 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 styrene polymers have a molecular weight (Mw) in the range of about 650 to about 10,000, preferably about 750 to about 7,500, and more preferably about 1,000 to about 4,000.

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

[0021] Preferably, the low molecular weight brominated anionic styrene polymer is brominated anionic polystyrene. In some embodiments, the low molecular weight brominated anionic styrene polymer is brominated anionic polystyrene having a weight-average molecular weight of about 1,000 to about 3,000 and about 73 wt% to about 77 wt% bromine.

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

[0023] Another brominated flame retardant that can be used in the practice of the present invention is sometimes not classified as a styrene polymer, due to the relatively small number of repeating units in these molecules. Similar to brominated styrene polymers, these molecules also contain aromatically bonded bromine and styrene repeating 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 Mw is in the range of about 1,000 to about 21,000, preferably about 1,250 to about 14,000, more preferably about 2,000 to about 10,000.

[0024] Preferably, the brominated anion chain transfer vinyl aromatic polymer is brominated anion chain transfer polystyrene. In some embodiments, the brominated anion chain transfer vinyl aromatic polymer is brominated anion chain transfer polystyrene having a weight average molecular weight of about 2,000 to about 10,000 and about 72 wt% to about 78 wt% bromine.

[0025] The brominated anion chain transfer vinyl aromatic polymer can be obtained by reacting it in an organic solvent or in a brominated environment (wherein...Bromine is used as both a brominating agent and a solvent to form the brominated flame retardant. Information regarding the preparation of brominated anion 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] In practice, mixtures of two or more brominated flame retardants can be used. In addition to the brominated anion styrene polymers and / or the brominated anion chain transfer vinyl aromatic polymers, the flame retardant composition may also contain one or more other brominated flame retardants. Suitable brominated flame retardants include hexabromocyclohexane, dibromocyclohexane, etc. (See page 3 / 17 of CN 121175321 A for details). Ethyl dibromocyclohexane, monochloropentabromocyclohexane, tetrabromocyclooctane, hexabromocyclododecane, bis(pentabromophenyl)ethane (decabromodiphenyl ethane), hexabromobenzene, dibromostyrene and its derivatives, pentabromodiphenyl ether, octabromodiphenyl ether (octabromodiphenyl ether), decabromodiphenyl ether (decabromodiphenyl ether), 1,2-bis(tribromophenoxy)ethane, tetradecylbromodiphenoxybenzene, 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 and brominated polybutadiene, poly(dibromophenylene ether), poly(pentabromoprene acrylate), brominated phthalic acid, diallyl tetrabromophthalate, bis(2-ethylhexyl) tetrabromophthalate, tetrabromophthalimide, N,N-vinyl- Bis(tetrabromophthalimide), tetrabromophthalic anhydride, a mixture of tetrabromophthalic anhydride with diethylene glycol and propylene glycol, N,N'-vinyl-bis(5,6-dibromonorbornene-2,3-dicarboximide), tris(tribromophenyl)triazine, brominated phenoxytriazine (such as tris(tribromophenoxy)triazine), brominated maleic anhydride (such as tribromophenyl maleic anhydride), trimethylphenyl indene bromide, brominated isocyanurates (such as tris(2,3-dibromopropyl) isocyanurate), and tris(tribromoneopentyl) phosphate. Preferred brominated flame retardants used in combination with the brominated anionic styrene polymers and / or the brominated anionic chain-transfer vinyl aromatic polymers include decabromodiphenyl ethane and N,N-vinyl-bis(tetrabromophthalimide).

[0027] Additionally, embodiments of the present invention, regarding the brominated flame retardant discussed above, include a polymeric composition. This polymeric composition can be used as a thermoplastic or thermosetting material. The polymeric composition, together with the brominated flame retardant, provides a coating for wires and / or cables. Non-limiting examples of polymeric compositions that can be used as thermoplastics include polyurethanes, polyesters, polyamides, polyolefins, styrene-based polymers, chlorinated polyethylene, and combinations thereof. Thermosetting formulations for wires and / or cables are typically formed using crosslinking techniques, including (a) moisture curing, (b) peroxide curing, or (c) electron beam curing. 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), as well as polyolefin derivatives such as chlorinated polyethylene or silane-functionalized polyethylene.

[0028] Optional components that may be present in the flame retardant composition include inorganic compounds, antioxidants, impact modifiers, compatibilizers, halogenated polyethylene, pigments, flame retardant synergists, anti-drip agents, dyes, light stabilizers, UV stabilizers, fillers, defoamers, antibacterial agents, insecticides, buffers, pH stabilizers, fixatives, antistatic agents, antifouling agents, waterproofing agents, optical brighteners, plasticizers, emulsifiers, acid scavengers, free radical scavengers, metal scavengers or passivators, processing aids, mold release agents, lubricants, anti-blocking agents, antistatic agents, slip additives, foaming agents, antifogging agents, reinforcing agents, coupling agents, nucleating agents, other flame retardants, and other heat stabilizers.

[0029] Preferred optional components include inorganic compounds, antioxidants, impact modifiers, compatibilizers, halogenated polyethylene, 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, the flame retardant additive composition contains at least one inorganic compound and one or more other optional components selected from antioxidants, impact modifiers, compatibilizers, and halogenated polyethylenes.

[0030] Inorganic compounds are a preferred type of optional component. As used throughout this document, the phrase "inorganic component" refers to one or more inorganic compounds containing one or more metal atoms that do not have a hydrocarbon group directly bonded to a metal atom. More preferably, the flame retardant additive composition contains at least one inorganic compound. Specification 4 / 17 pages 8 CN 121175321 A

[0031] In the practice of the invention, suitable inorganic compounds (some of which act as synergists) include talc, ammonium phosphate, ammonium phosphonate, antimony trioxide, antimony pentoxide, antimony phosphate, aluminum phosphonate, diethyl aluminum phosphonate, sodium antimonate, stearic acidCalcium, calcium borate, calcium phosphite, magnesium hydroxide, magnesium aluminum hydroxide carbonate, zinc borate, zinc oxide, zinc stannate, zinc sulfide, zinc phosphate, zinc phosphite, diethyl zinc phosphite, zinc molybdate, tin(IV) oxide, titanium dioxide, titanium phosphate, zirconium α-phosphate, wollastonite, hydrotalcite, silane-modified aluminum silicate, glass fiber, and clay, including montmorillonite such as montmorillonite, bentonite, chloropyrite, hydropyrite, lithium soapstone, bedesite, chromium bentonite, zinc montmorillonite, magnesia, and soapstone; kaolinite such as halloysite; mica such as illite; rettoite; tarazite; sodium hydroxysilicate; synthetic zeolite; vermiculite; attapulgite; and illite. Mixtures of two or more inorganic compounds may 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 about 10 wt% to about 70 wt%, preferably about 15 wt% to about 60 wt%, more preferably 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 invention include phenolic antioxidants, thioesters, aromatic amines, phosphites, and phosphites. Suitable antioxidants include 2,6-di-tert-butyl-4-methylphenol, tetrakis(3-(4-hydroxy-3,5-di-tert-butylphenyl)propionyloxymethyl)methane, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzene)-s-triazine-2,4,6(1H,3H,5H)trione, 3,5-di-tert-butyl-4-hydroxyhydrocinnamate, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzene), 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- (2,2'-di-tert-butyl-4-hydroxyphenyl)propionamide), hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, 2,2'-thiodiethylbis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], C13 to C15 straight-chain and branched alkyl esters of 3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate, C9 to C11 straight-chain and branched alkyl esters of 3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate, 2,2'-methylenebis(6-tert-butyl-4-methylphenol), 2,2'-ethylidenebis(4,6-di-tert-butylphenol), (1,1-Di(tert-butyl)-4-hydroxyphenyl)methyl)ethylphosphonate, reaction product of N-phenyl-aniline with 2,4,4-trimethylpentene, dimyristate thiodipropionate, di(octadecyl)disulfide, pentaerythritol tetra(β-lauryl thiopropionate), 3,3'-thiodipropionate dioctadecyl ester, 3,3'-thiodipropionate didodecyl ester, tri-(2,4-di-tert-butylphenyl) phosphite, bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphate, (2-butyl-2-ethyl-1,3-propanediol)phosphite (2,4,6-tri-tert-butylphenyl) ester, 4,4'-biphenylene diphosphite tetra(2,4-di-tert-butylphenyl) ester, di(octadecyl) pentaerythritol diphosphate, bis(2,4-bisisophenylpropylphenyl) pentaerythritol diphosphate A 1:1:2 combination of phosphate esters, tris(dipropylene glycol) phosphite, poly(dipropylene glycol) phenyl phosphite, diphenyl isodecanyl phosphite, phenyl diisodecyl phosphite, hepta(dipropylene glycol) triphosphate, tris(nonylphenyl) phosphite, bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, 2,2'-ethylidene bis(4,6-di-tert-butylphenyl)fluorophosphite, 2,2'-methylene bis(4,6-di-tert-butylphenyl)octyl phosphite, trilauryl trithiophosphite, 1,2-bis(3,5-di-tert-butyl-4-hydroxycinnamoyl)hydrazine and calcium (3,5-di-tert-butyl-4-hydroxyphenyl)methylethoxyphosphinide, polyethylene wax, and tris(2,4-di-tert-butylphenyl) phosphite. Mixtures of two or more antioxidants may be used. Preferred antioxidants include tetrakis(3-(4-hydroxy-3,5-di-tert-butylphenyl)propionyloxymethyl)methane and tri-(2,4-di-tert-butylphenyl) phosphite; more preferably, a combination of tetrakis(3-(4-hydroxy-3,5-di-tert-butylphenyl)propionyloxymethyl)methane and tri-(2,4-di-tert-butylphenyl) phosphite.

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

[0035] Compatibilizers are sometimes thermoplastic elastomers, maleic copolymers of olefin homopolymers or copolymers, or in-situ formed macromolecular catalysts. Suitable compatibilizers for use in the practice of this invention include styrene-ethylene-butadiene copolymers, particularly linear triblock copolymers of styrene-ethylene / butene, maleic anhydride-modified polypropylene homopolymers, and sodium ionomers of ethylene / methacrylic acid copolymers. Mixtures of compatibilizers may be used. Preferred compatibilizers include linear triblock copolymers of styrene-ethylene / butene.

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

[0037] Pigments are substances that impart color to polymers and are generally used only when color is required for polymeric brominated flame retardant compositions in wires and / or cables. Non-limiting examples of suitable pigments for practicing the invention 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, as well as carbon black, titanium dioxide, zinc sulfide, iron oxide, lead chromate and lead chromate molybdate, cadmium, and chromium oxide. Mixtures of two or more pigments may be used.

[0038] Flame-retardant polymeric compositions for use in wires and / or cables. One embodiment of the present invention is a flame-retardant composition for use in wires and / or cables, comprising at least one polymeric 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) brominated styrene polymers having a weight-average molecular weight of about 650 to about 75,000 and a bromine content of about 60 wt% or higher, and / or b) brominated anion-transfer vinyl aromatic polymers having a weight-average molecular weight of about 650 to about 75,000 and containing about 70 wt% or more bromine.

[0039] Optional components commonly present in flame-retardant polyolefin compositions are as described above.

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

[0041] The brominated flame retardants used in the practice of the invention contain aromatically bound bromine and are considered, in several embodiments, brominated styrene 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 higher. Preferably, the styrene polymer is polystyrene. Mixtures of two or more brominated flame retardants may be used in the practice of the invention. Mixtures of brominated flame retardants with other non-halogenated flame retardants may also be used in the practice of the invention.

[0042] In other embodiments, the brominated flame retardant is a brominated anionic styrene polymer, wherein the styrene 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 styrene 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] Typically, the brominated anionic styrene 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 styrene polymer contains about 60 wt% to about 72 wt% bromine, more preferably about 66 wt% to about 71 wt% bromine, and even more preferably about 67 wt% to about 71 wt% bromine. Preferably, the brominated anionic styrene polymer is brominated anionic polystyrene. In some embodiments, the brominated anionic styrene polymer is 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 styrene 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 styrene 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 styrene polymers have a molecular weight (Mw) in the range of about 650 to about 10,000, preferably about 750 to about 7,500, and more preferably about 1,000 to about 4,000.

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

[0046] Preferably, the low molecular weight brominated anionic styrene polymer is brominated anionic polystyrene. In some embodiments, the low molecular weight brominated anionic styrene polymer is brominated anionic polystyrene having a weight-average molecular weight of about 1,000 to about 3,000 and about 73 wt% to about 77 wt% bromine.

[0047] The low molecular weight brominated anionic styrene polymers can be formed by bromination in an organic solvent or in a brominated container (where bromine is both the brominating agent and the solvent). Information on the preparation of low molecular weight brominated anionic styrene polymers can be found, for example, in International Patent Publications WO 2017 / 176740 and WO 2017 / 184350; these polymers can also be manufactured as described in U.S. Patents 7,632,893 and 7,638,583.

[0048] Another brominated flame retardant that can be used in the practice of the present invention is sometimes not classified as a styrene polymer because these molecules have a relatively small number of repeating units. Similar to brominated styrene polymers, these molecules also contain aromatically bonded bromine and styrene repeating units. Such a 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 Mw is in the range of about 1,000 to about 21,000, preferably about 1,250 to about 14,000, more preferably about 2,000 to about 10,000.

[0049] Preferably, the brominated anion chain transfer vinyl aromatic polymer is brominated anion chain transfer polystyrene. In some embodiments, the brominated anion chain transfer vinyl aromatic polymer is brominated anion chain transfer polystyrene having a weight average molecular weight of about 2,000 to about 10,000 and about 72 wt% to about 78 wt% bromine.

[0050] The brominated anion chain transfer vinyl aromatic polymer can be formed by bromination in an organic solvent or in a brominated bromine (where bromine is both a brominating agent and a solvent). Information regarding the preparation of brominated anion-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] In practice of the invention, mixtures of two or more brominated flame retardants may be used. In addition to the brominated anion-transfer vinyl polymers and / or the brominated anion-transfer vinyl aromatic polymers, the flame retardant composition may also contain one or more other brominated flame retardants. Suitable brominated flame retardants include hexabromocyclohexane, dibromoethyldibromocyclohexane, monochloropentabromocyclohexane, tetrabromocyclooctane, hexabromocyclododecane, bis(pentabromophenyl)ethane (decabromodiphenyl ethane), hexabromobenzene, dibromostyrene and its derivatives, pentabromodiphenyl ether, octabromodiphenyl ether (octabromodiphenyl ether), decabromodiphenyl ether, and others. (See specification 7 / 17 pages, 11 CN 121175321 A)Benzene ether (decabromodiphenyl ether), 1,2-bis(tribromophenoxy)ethane, tetradecylbromodiphenoxybenzene, 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-encapsulated...) End-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 and brominated polybutadiene, poly(dibromophenylene ether), poly(pentabromophenyl acrylate), brominated phthalic acid, diallyl tetrabromophthalate, bis(2-ethylhexyl) tetrabromophthalate, tetrabromophthalimide, N,N-vinyl- Bis(tetrabromophthalimide), tetrabromophthalic anhydride, a mixture of tetrabromophthalic anhydride with diethylene glycol and propylene glycol, N,N'-vinyl-bis(5,6-dibromonorbornene-2,3-dicarboximide), tris(tribromophenyl)triazine, brominated phenoxytriazine (such as tris(tribromophenoxy)triazine), brominated maleic anhydride (such as tribromophenyl maleic anhydride), trimethylphenyl indene bromide, brominated isocyanurates (such as tris(2,3-dibromopropyl) isocyanurate), and tris(tribromoneopentyl) phosphate. Preferred brominated flame retardants used in combination with the brominated anionic styrene polymers and / or the brominated anionic chain-transfer vinyl aromatic polymers include decabromodiphenyl ethane and N,N-vinyl-bis(tetrabromophthalimide).

[0052] A process for forming a flame retardant composition for wires and / or cables. One embodiment of a process for forming a flame retardant composition for wires and / or cables includes: a first step comprising: at least one polymeric composition; at least one brominated flame retardant, wherein the brominated flame retardant contains aromatically bound bromine and is selected from a) brominated styrene polymers having a weight average molecular weight of about 650 to about 75,000 and a bromine content of about 60 wt% or higher, and / or b) brominated anion-transfer vinyl aromatic polymers containing about 70 wt% or more bromine; and at least one synergist; and then extruding the mixture from the first step to coat the wires and / or cables. Another embodiment of a process for forming a flame retardant composition includes: a first step comprising: at least one polymeric composition; at least one brominated flame retardant, wherein the brominated flame retardant contains aromatically bound bromine and is selected from a) brominated styrene polymers having a weight average molecular weight of about 650 to about 75,000 and a bromine content of about 60 wt% or higher, and / or b) brominated anion-transfer vinyl aromatic polymers containing about 70 wt% or more bromine; and at least one synergist; and then extruding the mixture from the first step to coat the wires and / or cables.The mixture comprises an aromatically bound bromine selected from a) brominated styrene polymers having a weight-average molecular weight of about 650 to about 75,000 and a bromine content of about 60 wt% or higher, and / or b) brominated anion-transfer vinyl aromatic polymers containing about 70 wt% or more bromine; and at least one organic peroxide. A second step involves extruding the mixture from the first step to coat the wire and / or cable. A third step involves heating the coated wire and / or cable to a temperature above the decomposition point of the at least one organic peroxide.

[0053] Another embodiment of a process for forming a flame retardant composition includes: a first step comprising a combination of: at least one polymeric 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) brominated styrene polymers having a weight-average molecular weight of about 650 to about 75,000 and a bromine content of about 60 wt% or higher, and / or b) brominated anion-transfer vinyl aromatic polymers containing about 70 wt% or more bromine. A second step involves extruding the mixture from the first step to coat wires and / or cables. A third step involves irradiating the coated wire and / or cable mixture with an effective dose of electron beam irradiation.

[0054] The brominated flame retardant and the polymeric composition include those brominated flame retardants and polymeric compositions discussed above. When preparing the compositions of the present invention, individual components may be blended individually and / or in a sub-combination manner with a substrate or host polymer in appropriate proportions. Specification 8 / 17 pages 12 CN 121175321 A

[0055] When the flame-retardant polyolefin composition is formed from a 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 invention. Blending of the brominated flame retardant with other components can be carried out on blending equipment (such as a single-screw extruder, a twin-screw extruder, or a Buss kneader). Preferably, blending is performed using an extruder, more preferably, a twin-screw extruder. Other components used in the practice of the present invention can be added at the initial feed port of the extruder, or the components can be added further downstream to the extruder. In the extruder, many components are typically melted when they are mixed together. Extrudate from an extruder is typically converted into granules or pellets by cooling the extruded polymer strands and further subdividing the cured strands into pellets or pellets, or by simultaneously subjecting the extrudate to die-cutting and water or air cooling. If desired, the compositions of the present invention can be formulated as powders or granular blends of the components of the composition.

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

[0058] Formation of coatings for wires and / or cables In particular, these compositions of the present invention can be used as coatings for wires and / or cables. Flame retardants are used in wire and / or cable formulations to meet the fire resistance requirements of specific applications (such as appliances, building and construction, automotive cables, photovoltaic cables, etc.). In these applications, the insulating coating on the conductor is flame retardant by incorporating various fire retardant chemicals or technologies (Br, P, metal hydroxides, etc.). Such fire retardant chemicals are also used in sheath (layer on the insulator) formulations. The insulator or sheath can be (1) thermoplastic or (2) thermosetting (crosslinked). Thermoplastic and thermosetting formulations can use polyolefins (PP, PE) as the base polymer. Besides polyolefins, the base polymer can also be polyurethane and chlorinated polyethylene. Polyolefins can typically be crosslinked using (a) moisture curing, (b) peroxide curing, and (c) electron beam curing.

[0059] Typically, the composition is prepared in a blending extruder where all components are mixed and uniformly distributed and dispersed. The extruded compound is then formed into pellets. Typically, the pellets are then fed into a cable extruder for coating the wire. For thermosetting wires, the coated wire will be crosslinked in a second step based on curing chemistry.

[0060] The curing chemistry suitable for this invention includes curing by electron beam and curing by peroxide. For peroxide curing, the wire will pass through a continuous vulcanizing tube at high temperature. For electron beam curing, the wire will pass through an electron beam chamber.

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

[0062] For electron beam curing, any process known in this art will be suitable for this purpose. For example, methods may include...This includes irradiating the flame retardant composition with an effective dose of electron beam radiation. The effective or absorbed dose of electron beam radiation can be 49 to 201 kJ / kg 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 / kg, which equals 100,000 grays. 1 gray = 1 joule / kg (J / kg) = 100 grays. The electron beam irradiation step can be carried out at any suitable temperature, such as 10°C to 50°C (e.g., 23°C ± 1°C), and in any suitable atmosphere, such as air or molecular nitrogen. Irradiation can be performed continuously or intermittently, or alternately continuously.

[0063] Example – Summary Ingredients The ingredients used to manufacture the flame retardant composition are provided in the examples. Some of the ingredients used are mentioned by their trade names in the tables.

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

[0065] Analytical methods used or suitable for determining polymeric BFRs are described in WO 2022 / 031932 A1, which is incorporated herein by reference.

[0066] UL-VW-1 Burning Test. The VW-1 burning test is performed by subjecting three or six samples of a specific coated conductor to the UL 2556 protocol. This involves applying a 125 mm flame for 15 seconds five times, with the flame impacting a vertically oriented specimen of 610 mm (24 inches) in length at a 20° angle. A 12.5 ± 1 mm (0.5 ± 0.1 inch) strip of kraft paper was fixed to the specimen at a distance of 254 ± 2 mm (10 ± 0.1 inch) above the flame impact point. A continuous horizontal layer of cotton was placed on the floor of the test chamber, centered on the vertical axis of the test specimen, with the upper surface of the cotton below the point where the tip of the blue inner cone of the flame struck the specimen at 235 ± 6 mm (9.25 ± 0.25 inch). Test failure was based on the following criteria: 25% burning of the kraft paper with the flag, ignition of the cotton wadding, or burning of the specimen for more than 60 seconds under any of the five flame applications. As an additional measure of flammability, the length of the unburned insulation (“no char to flag length”) was measured at the end of the test. Ignition of the VW-1 cotton indicated whether the falling material ignited the cotton bed.

[0067] Each sample was tested by extrusion in a twin-screw extruder (ZSK30 (30 mm), Werner & Pfleiderer Coperion).All ingredients are mixed and melted together in GmbH, and each ingredient is fed separately in powder form.

[0068] In all 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. 14 AWG tinned copper wire with 0.030-inch insulation was used for the wire construction. The wire coated with the brominated flame retardant was fed through a 60-foot steam-filled steel pipe to complete the peroxide curing process. The cured cable was then used for the following tests. Table 1 shows peroxide crosslinkable flame retardant formulations. In Example 1, a polymeric brominated flame retardant was used according to the disclosure contained herein. Comparative Example 1 contains the commercially available SAYTEX® 8010 small molecule brominated flame retardant. Example 2 uses the commercially available polymeric aromatic brominated flame retardant SAYTEX® HP 3010.

[0070] Table 1. Composition of Peroxide-Cureable Flame Retardant Formulations, Page 10 / 17, 14 CN 121175321 A

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

[0072] Example 2: A second example of producing coated wires and / or cables by electron beam curing. 14 AWG copper wire with 0.030-inch insulation was used for the wire construction. Electron beam curable flame retardant formulations (Table 3) were irradiated with 20 Mrad to produce cured wires. The cured cables were then used for the following tests. Table 3 shows various electron beam curable flame retardant formulations. And Table 4 shows the wire extrusion running conditions, die pressure readings, and wire surface quality. Comparative Example 1 is the 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 Specification 11 / 17 pages 15 CN 121175321 A

[0074] Table 4

[0075] Table 5

[0076] The process conditions illustrate the benefits of Example 2, as the example provides lower die pressure during wire extrusion while maintaining key VW-1 and thermal creep properties. Such improvements are important for customers with lower energy consumption and the possibility of higher line speeds (higher yields). Specification 12 / 17 pages 16 CN 121175321 A

[0077] Example 3 An example of producing coated wires and / or cables by electron beam curing. 14 AWG tinned copper wire with 0.030-inch insulation was used for the wire construction. An electron beam curable flame retardant formulation (Table 3) was 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 flame retardant formulations.The materials. And Table 7 shows the wire extrusion operating conditions, die pressure readings, and wire surface quality. A comparative example is the commercially available SAYTEX®-8010 small molecule brominated flame retardant. Examples 3-1 to 3-5 use high molecular weight brominated flame retardants manufactured according to the disclosure contained herein.

[0078] Table 6

[0079] Table 7

[0080] Table 8

[0081] Example 4 An example of producing coated wires and / or cables by electron beam curing. 14 AWG tinned copper wire with 0.030-inch insulation was used for the wire construction. An electron beam curable flame retardant formulation (Table 3) was irradiated with 15 Mrad to produce a cured wire. The cured cable was then used for the following tests. Table 9 shows the various electron beam curable flame retardant formulations. And Table 10 shows the wire extrusion operating conditions, die pressure readings, and wire surface quality. A comparative example is the commercially available instruction manual, page 13 / 17, CN 121175321 A, SAYTEX®-8010, a small molecule brominated flame retardant. The example uses a high molecular weight brominated flame retardant manufactured according to the disclosure contained herein.

[0082] Table 9

[0083] Table 10

[0084] Table 11

[0085] Example 5 Examples of blended flame retardants and polypropylene are shown below. The compounds were manufactured according to the disclosure contained herein. The above PP-BFR formulations were blended at 200°C and 175 rpm in a 30 mm twin-screw extruder. The blended material was cooled and allowed to stand before pelleting. The BFR wt% was adjusted to maintain a constant Br% (16.5) for each formulation. Instruction manual, pages 14 / 17, 18, CN 121175321 A

[0086] Example 6: An example of producing coated wire and / or cable using polypropylene cable insulation and using the example in polypropylene cable insulation. The insulation is manufactured according to the disclosure contained herein. Each of the examples from Example 5 is used herein. 30 mils of BFR-PP compound insulation were extruded on 14 AWG copper wire at a linear rate of 5 meters per minute using a 0.75-inch single-screw extruder with a 3:1 Maddock screw head. The resulting wire was analyzed. As can be seen in the table below, it should be noted that the BFR of the present invention provides the following benefits: 1. 30% lower die pressure, which indicates better melt flowability than non-polymer BFRs.

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

[0088] Example 7: An example of producing coated wires and / or cables using thermoplastic cable sheaths and in thermoplastic cable sheathsUsing the example described. The sheath is manufactured according to the disclosure contained herein. The TPU-BFR compound is produced at 200°C and 200 rpm on a WP twin-screw extruder. Polymer BFR and non-polymer (S-8010, BT-93W) BFR are used in the formulation to keep the Br% (16.5%) and Br / ATO ratio constant. Specification 15 / 17 pages 19 CN 121175321 A

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

[0090] Any component mentioned anywhere in the specification or claims by a chemical name or chemical formula, whether in the singular or plural form, is identified as being present prior to contact with another substance (e.g., another component, solvent, or etc.) mentioned by a chemical name or chemical type. What kind of chemical change, transformation and / or reaction (if any) occurs in the resulting mixture or solution is irrelevant, as such change, transformation and / or reaction is a natural result of bringing the specified components together under the conditions claimed in this disclosure. Therefore, the components are identified as those that are to be aggregated together when performing the desired operation or forming the desired composition. Furthermore, even though the claims below may refer to substances, components, and / or ingredients in the present tense (“comprising,” “is,” etc.), the mentioned substances, components, or ingredients are present precisely before their first contact, blending, or mixing with one or more other substances, components, and / or ingredients according to this disclosure. Therefore, there is practically no need to worry about the fact that substances, components, or ingredients may have lost their original properties through chemical reactions or transformations during the contact, blending, or mixing operation (if performed according to this disclosure and using the general skills of a chemist).

[0091] The invention may include, consist of, or substantially consist of the materials and / or procedures listed herein.

[0092] As used herein, the term “about” modifying the amount of an ingredient used in the composition or method of the invention refers, for example, by a typical measurement and liquid handling procedure used in the real world to produce concentrates or use solutions; by thisOmissions or errors in the procedure; differences in the manufacture, source, or purity of the ingredients used to make the composition or carry out the method; and variations in numerical quantities that may occur. The term "about" also covers quantities that differ due to different equilibrium conditions of the composition produced from a particular initial mixture. Whether or not modified by the term "about," the claims include equivalent quantities.

[0093] Unless otherwise expressly indicated, the articles "a" or "an" as used herein are not intended to be limiting and should not be construed as limiting the specification or claims to the single element referred to by the words. Rather, unless otherwise expressly indicated by the text, the articles "a" or "an" as used herein are intended to cover one or more such elements.

[0094] The invention is susceptible to considerable variation in its practice. Therefore, the foregoing description is not intended to be limiting and should not be construed as limiting the invention to the specific examples presented above. Specification 17 / 17 pages 21 CN 121175321 A

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.