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WO2024243272A2 - Composition polymère d'ignifugeant bromé destinée à être utilisée dans un fil et/ou un câble - Google Patents

Composition polymère d'ignifugeant bromé destinée à être utilisée dans un fil et/ou un câble Download PDF

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Publication number
WO2024243272A2
WO2024243272A2 PCT/US2024/030499 US2024030499W WO2024243272A2 WO 2024243272 A2 WO2024243272 A2 WO 2024243272A2 US 2024030499 W US2024030499 W US 2024030499W WO 2024243272 A2 WO2024243272 A2 WO 2024243272A2
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Prior art keywords
flame retardant
brominated
bromine
composition
retardant composition
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PCT/US2024/030499
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WO2024243272A3 (fr
Inventor
Raghunath ROY
Rajeev S. Mathur
Jonathan P. Mccarney
Wayne HUBERTY
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Albemarle Corp
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Albemarle Corp
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Publication of WO2024243272A2 publication Critical patent/WO2024243272A2/fr
Publication of WO2024243272A3 publication Critical patent/WO2024243272A3/fr
Priority to MX2025013907A priority Critical patent/MX2025013907A/es
Anticipated expiration legal-status Critical
Pending legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K21/00—Fireproofing materials
    • C09K21/06—Organic materials
    • C09K21/08—Organic materials containing halogen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D143/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Coating compositions based on derivatives of such polymers
    • C09D143/04—Homopolymers or copolymers of monomers containing silicon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B7/00—Insulated conductors or cables characterised by their form
    • H01B7/17—Protection against damage caused by external factors, e.g. sheaths or armouring
    • H01B7/29—Protection against damage caused by extremes of temperature or by flame
    • H01B7/295—Protection against damage caused by extremes of temperature or by flame using material resistant to flame

Definitions

  • This invention relates to flame retardant compositions and to polymeric brominated flame retardant compositions for use in wire and/or cable.
  • Conduit, appliance, or automotive wires and cables often only have one polymer layer. This layer must fulfil several functions at the same time, which in other low voltage cables, medium and high voltage cables are fulfilled by separate layers. Accordingly, a polymer composition used for the production of conduit, appliance, or automotive wires, must meet several demanding requirements at the same time, including good insulation behavior, good mechanical properties, in particular good abrasion resistance, good flame retardant properties, good heat deformation resistance, withstand cold temperatures resistance to water and chemicals as well as good processing properties.
  • polyolefins are flame retarded to minimize the spread of fire.
  • polybrominated anionic sty renic polymers are used to flame retard polyolefins, in conjunction with at least one synergist;
  • WO 2001/029124 discloses polyolefins with flame retardants, which include the bis(2,3- dibromopropyl ether) of tetrabromobisphenol -A and the bis(2,3-dibromopropyl ether) of tetrabromobisphenol-S.
  • US 6780348 combinations of a polybromodiphenylalkane and a tetrabromobisphenol-A-bis(bromoalkyl ether) are disclosed.
  • US 8476373 and US 8933159 are directed to brominated anionic chain transfer vinyl aromatic polymers, which can flame retard polyolefins.
  • Fire retardants are used in wire and/or cable formulations to attain the flame performance required for the specific application such as appliances, building and construction, cables in automotives, photovoltaic wires, etc.
  • the insulation coating over the conductor is made to be flame retardant by incorporating various fire-retardant chemistries or technologies (Bromine, Phosphorus, Metal hydroxide (e g.., magnesium hydroxide, aluminum hydroxide, etc.).
  • fire-retardant chemistries are also used in the jacket (layer on top of insulation) formulation.
  • the insulation or jacket could be (1) thermoplastic or (2) thermoset (crosslinked).
  • Non-limiting examples of thermoplastics for insulation or jacket include polyurethanes, polyesters, polyamides, polyolefins, styrenic polymers, chlorinated polyethylene, and combinations thereof.
  • Thermoset formulations for wire and/or cable are commonly formed by crosslinking technologies including (a) Moisture cure, (b) Peroxide cure, or (c) E-beam cure technologies.
  • base polymers suitable for cross-linking include polyolefins, such as polyethylene, and polyolefin copolymers such as poly(ethylene-vinyl acetate) (EVA) and poly(ethylene ethyl acrylate) (EEA), as well as derivatives of polyolefins such as chlorinated polyethylene or silane functionalized polyethylene.
  • non-polymeric brominated flame retardants often have higher melting temperatures than the process conditions, and need to be milled to a very small and uniform particle size (average less than about 10 microns) before they can be used in a wire and/or cable formulations. Higher particle sizes would negatively impact the smoothness of the wire insulation surface.
  • non-polymeric BFRs often generate high extrusion back pressure during compounding.
  • thermoplastics for use in wire and/or cable.
  • thermoplastics include polyurethanes, polyesters, polyamides, polyolefins, styrenic polymers, chlorinated polyethylene, and combinations thereof.
  • the flame retardants are brominated polymeric flame retardants.
  • the polymeric brominated fire-retardants (PBFRs) are based on polystyrene backbone and synthesized by aromatic bromination process. These PBFR formulations are suitable for various wire and/or cable applications offering unique properties that were not possible before by the existing brominated fire-retardant technologies.
  • thermoset formulations for use in wire and/or cable.
  • Thermoset formulations for wire and/or cable are commonly formed by crosslinking technologies including (a) Moisture cure, (b) Peroxide cure, or (c) E-beam cure technologies.
  • base polymers suitable for cross-linking include polyolefins, such as polyethylene, and polyolefin copolymers such as poly (ethylene- vinyl acetate) (EVA) and poly(ethylene ethyl acrylate) (EEA), as well as derivatives of polyolefins such as chlorinated polyethylene or silane functionalized polyethylene.
  • the flame retardants are brominated polymeric flame retardants.
  • PBFRs polymeric brominated fire-retardants
  • PBFR formulations are suitable for various wire and/or cable applications offering unique properties that were not possible before by the existing brominated fire-retardant technologies.
  • the benefits of the present brominated polymeric flame retardant are numerous.
  • existing non-polymeric BFRs have higher melting temperature than the process condition.
  • a non-polymeric BFR needs to be milled to a very small and uniform particle size (average less than about 10 microns) before it can be used in a wire and/or cable formulation.
  • the polymeric flame retardant of the present invention has a glass transition temperature (Tg) lower than the ty pical wire and/or cable process temperature (Tg less than about 145 °C vs. process temperatures of about 200 °C).
  • Tg glass transition temperature
  • the polymeric BFR would readily melt-blend and mix with the other ingredients of the formulation.
  • the new polymer BFR formulations of this invention offer lower extrusion back pressure during compounding and wire extrusion process due to its higher melt index (higher melt index means polymer flows better at a given pressure and temperature). Thus, it allows compounder and the cable producer to extrude at higher through-put (Ib/hr, or meter/hr).
  • the polymeric brominated flame retardants of this invention offer higher thermal stability’.
  • the polymeric BFRs claimed in other inventions to be used in wire and/or cable application are often aliphatic brominated polymers as opposed to polymeric BFR of this invention where the bromine is attached to aromatic ring.
  • the 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 time during wire coating and (c) have the possibility for enhanced recyclability.
  • the polymeric brominated flame retardants of this invention enable simplified moisture cure formulations that pass the VW-1 flammability' test for wires and cables under the UL-44 standard.
  • a compounder mixes ⁇ 5% of zinc oxide (ZnO) or another zinc salt in addition to the BFR and typical flame-retardant synergist antimony oxide (ATO).
  • ZnO zinc oxide
  • ATO typical flame-retardant synergist antimony oxide
  • the new polymeric BFRs of this invention enable one to make the moisture cure formulations that pass the VW-1 test without ZnO or another zinc salt.
  • the removal of ZnO or another zinc salt from the formulation allows the formulation to be compatible with more efficient silanol catalyst. This in turn would allow the cable producer to adopt ambient (lower temperature) curing conditions. Otherwise, one must use an expensive sauna cure facility.
  • removal of ZnO or another zinc salt lowers the density of the formulation. The lower density is desirable in the wire and/or cable industry because it translates to lower cost of the overall formulation.
  • the brominated flame retardants in the practice of this invention contain aromatically bound bromine, and in several embodiments are considered to be brominated styrenic polymers.
  • the brominated flame retardants have weight average molecular weights (Mw) of about 650 to about 75,000 and a bromine content of about 60 wt% or more.
  • the styrenic polymers are polystyrenes.
  • Mixtures of two or more brominated flame retardants can be used in the practice of this invention.
  • Mixtures of brominated flame retardants and other non-halogenated flame retardants can also be used in practice of this invention.
  • the brominated flame retardants are brominated anionic styrenic polymers, in which the styrenic polymers were formed via anionic polymerization, typically with an alkyl lithium initiator; these brominated flame retardants generally have a weight average molecular weight (Mw) of about 2000 or more, preferably about 10,000 or more. In some embodiments, the brominated anionic styrenic polymers have aMw 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.
  • the brominated anionic styrenic polymers contain 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 polymers contain 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.
  • the brominated anionic styrenic polymers are 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 on the preparation of brominated anionic styrenic polymers is found for example in U.S. Pat. Nos. 7,632,893 and 7,638,583.
  • the brominated flame retardant is a low molecular weight brominated anionic styrenic polymer having a weight average molecular weight (Mw) of about 650 or more, preferably about 950 or more, more preferably about 1000 or more.
  • Mw weight average molecular weight
  • these brominated anionic styrenic polymers have an 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.
  • the low molecular weight brominated anionic styrenic polymers contain 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%, more preferably about 70 wt% to about 75 wt% bromine.
  • the low molecular weight brominated anionic styrenic polymers are brominated anionic polystyrenes.
  • the low molecular weight brominated anionic styrenic polymers are brominated anionic polystyrenes having a weight average molecular weight of about 1000 to about 3000, and about 73 wt% to about 77 wt% bromine.
  • the low molecular weight brominated anionic styrenic polymers can be formed by bromination in an organic solvent or in a sea of bromine (in which bromine is both the brominating agent and the solvent).
  • Information on the preparation of low molecular weight brominated anionic styrenic polymers is found for example in International Patent Publications WO 2017/176740 and WO 2017/184350; these polymers can also be made as described U.S. Pat. Nos. 7,632,893 and 7,638,583.
  • Another brominated flame retardant that can be used in the practice of this invention is sometimes not categorized as a styrenic polymer due to the relatively small number of repeating units in these molecules. Similar to the brominated styrenic polymers, these molecules also contain aromatically-bound bromine, and styrenic repeating units.
  • This brominated flame retardant is a brominated anionic chain transfer vinyl aromatic polymer which contains 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.
  • 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.
  • the brominated anionic chain transfer vinyl aromatic polymers are brominated anionic chain transfer polystyrenes.
  • the brominated anionic chain transfer vinyl aromatic polymers are brominated anionic chain transfer polystyrenes having a weight average molecular weight of about 2000 to about 10,000, and about 72 wt% to about 78 wt% bromine.
  • the brominated anionic chain transfer vinyl aromatic polymers can be formed by bromination in an organic solvent or in a sea of bromine (in which bromine is both the brominating agent and the solvent).
  • Information on the preparation of brominated anionic chain transfer vinyl aromatic polymers is found for example in U.S. Pat. Nos. 8,420,876, 8,796,388, and 8,993,684.
  • the flame retardant additive compositions can 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 derivatives thereof, pentabromodiphenyl oxide, octabromodiphenyl oxide (octabromodiphenyl ether), decabromodiphenyl oxide (decabromodiphenyl ether), 1 ,2-bis(tribromophenoxy)ethane, tetradecabromodiphenoxy benzene, 2,4,6-tribromophenol allyl ether, dibromoneopentyl glycol, tribro
  • tris(tribromophenyl)triazine brominated phenoxytriazines such as tris(tribromophenoxy)triazine, brominated maleimides such as tribromophenyl maleimide, brominated trimethylphenylindan, brominated isocyanurates such as tris(2,3- dibromopropyl)isocyanurate, and tris(tribromoneopentyl) phosphate.
  • Preferred brominated flame retardants to use in admixture with the brominated anionic styrenic polymers and/or brominated anionic chain transfer vinyl aromatic polymers include decabromodiphenyl ethane and N,N-ethylene-bis(tetrabromophthalimide).
  • the embodiments of the present invention include a polymeric composition.
  • the polymeric composition is useful as a thermoplastic material or thermoset material.
  • the polymeric composition, together with the brominated flame retardant, provides a coating to wire and/or cable.
  • Nonlimiting examples of polymeric compositions that are useful as thermoplastics include polyurethanes, polyesters, polyamides, polyolefins, styrenic polymers, chlorinated polyethylene, and combinations thereof.
  • Thermoset formulations for wire and/or cable are commonly formed by crosslinking technologies including (a) Moisture cure, (b) Peroxide cure, or (c) E-beam cure technologies.
  • Non-limiting examples of base polymeric compositions suitable for cross-linking include polyolefins, such as polyethylene, and polyolefin copolymers such as poly (ethylene- vinyl acetate) (EVA) and polyethylene ethyl acrylate) (EEA), as well as derivatives of polyolefins such as chlorinated polyethylene or silane functionalized polyethylene.
  • polyolefins such as polyethylene
  • polyolefin copolymers such as poly (ethylene- vinyl acetate) (EVA) and polyethylene ethyl acrylate) (EEA)
  • EVA polyethylene ethyl acrylate
  • Optional ingredients that can be present in the flame retardant compositions include inorganic compounds, antioxidants, impact modifiers, compatibilizers, halogenated polyethlyenes, pigments, flame retardant synergists, anti-dripping agents, dyes, light stabilizers, UV stabilizers, fillers, antifoaming agents, antimicrobial agents, biocidal agents, buffers, pH stabilizers, fixing agents, anti-static agents, soil repellants, water repellants, optical brighteners, plasticizers, emulsifiers, acid scavengers, radical scavengers, metal scavengers or deactivators, processing aids, mold release agents, lubricants, anti-blocking agents, antistatic agents, slip additives, blowing agents, antifogging agents, reinforcing agents, coupling agent, nucleating agents, other flame retardants, and other thermal stabilizers.
  • Preferred optional ingredients include inorganic compounds, antioxidants, impact modifiers, compatibilizers, halogenated polyethlyenes, and pigments.
  • one or more antioxidants, one or more compatibilizers, one or more impact modifiers, one or more halogenated polyethlyenes, and/or one or more pigments are present in the additive composition.
  • at least one inorganic compound and one or more other optional ingredients selected from antioxidants, impact modifiers, compatibilizers, and halogenated polyethlyenes are present in the flame retardant additive composition.
  • Inorganic compounds are a preferred type of optional ingredient.
  • the phrase "inorganic component" refers to one or more inorganic compounds which contain one or more metal atoms that do not have a hydrocarbyl group bound directly to the metal atom(s). More preferably, at least one inorganic compound is present in the flame-retardant additive composition.
  • Suitable inorganic compounds include talc, ammonium phosphate, ammonium phosphinate, antimony trioxide, antimony pentoxide, antimony phosphate, aluminum phosphinate, aluminum diethyl phosphinate, sodium antimonate, calcium stearate, calcium borate, calcium phosphinate, magnesium hydroxide, magnesium aluminum hydroxide carbonate, zinc borate, zinc oxide, zinc stannate, zinc sulfide, zinc phosphate, zinc phosphinate, zinc diethyl phosphinate, zinc molybdate.
  • tin(IV) oxide titanium dioxide, titanium phosphate, a-zirconium phosphate, wollastonite, hydrotalcite, silane-modified aluminum silicate, glass fibers, and clays including smectites such as montmorillonite, bentonite, nontronite, hectorite, laponite, beidellite, volkonskoite, sauconite, stevensite, and saponite; kaolins such as halloysite; micas such as ledikite; rectorite; tarasovite; kenyaite; permutite; vermiculites; attapulgites; and illites.
  • smectites such as montmorillonite, bentonite, nontronite, hectorite, laponite, beidellite, volkonskoite, sauconite, stevensite, and saponite
  • kaolins such as halloysite
  • micas such as ledikite; rec
  • the inorganic compound(s) is about 5 wt% or more and preferably about 10 wt% or more, or about 5 wt% to about 40 wt%, preferably about 5 wt% to about 30 wt%, more preferably about 10 wt% to about 25 wt%, based on the total weight of the additive composition.
  • these values refer to the combined amount of inorganic compounds present in the additive composition.
  • Antioxidants that can be used in the practice of this invention include phenolic antioxidants, thioesters, aromatic amines, phosphonites, and phosphite antioxidants. Suitable antioxidants include 2,6-di-tert-butyl-4-methyl phenol.
  • antioxidants include tetrakis(3-(4-hydroxy-3.5-di-tert- butylphenyl)propionyloxymethyl)methane and tris-(2.4-di-tert-butylphenyl) phosphite; more preferred is a combination of tetrakis(3-(4-hydroxy-3,5-di-tert- butylphenyl)propionyloxymethyl)methane and tris-(2,4-di-tert-butylphenyl) phosphite.
  • impact modifiers are rubbers or elastomers. Suitable impact modifiers in the practice of this invention include ethylene octene copolymers and ethylene hexene copolymers. Ethylene octene copolymers are preferred impact modifiers in the practice of this invention. Mixtures of impact modifiers can be used if desired.
  • Compatibilizers are sometimes thermoplastic elastomers, maleated copolymers of olefin homopolymers or copolymers, or in sztM-formed macromolecule catalysts.
  • Compatibilizers suitable for use in the practice of this invention include styrene ethylene butadiene copolymers, especially styrene ethylene/butylene linear triblock copolymers, maleic anhydride modified polypropylene homopolymers, and a sodium ionomer of ethylene/methacrylic acid copolymer. Mixtures of compatibilizers can be used.
  • Preferred compatibilizers include styrene ethylene/butylene linear triblock copolymers.
  • Halogenated polyethylenes are polyethylenes containing halogen atoms. Suitable halogenated polyethylene includes polytetrafluoroethylene and chlorinated polyethylene. Mixtures of halogenated polyethylenes can be used.
  • Pigments are substances that impart coloration to a polymer, and are generally used only when a color for polymeric brominated flame retardant compositions for use in wire and/or cable is desired.
  • suitable pigments in the practice of this invention include a mixed oxide of chromium, antimony, and titanium (Brow n 24), a mixed compound of chromium, nickel, and titanium (Yellow 53), l,8-bis(phenylthio)anthracene- 9, 10-dione (Solvent Yellow 163).
  • titanium dioxide, and carbon black titanium dioxide, zinc sulphide, iron oxides, lead chromates and lead chromate molybdates, cadmium, chromium oxides. Mixtures of two or more pigments can be used.
  • One embodiment of the present invention is a flame retardant composition for use in wire and/or cable which comprises 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 styrenic polymers which have weight average molecular weights 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 which have weight average molecular weights of about 650 to about 75,000 and which contains about 70 wt% or more bromine.
  • the brominated flame retardant contains aromatically-bound bromine and is selected from a) brominated styrenic polymers which have weight average molecular weights of about 650 to about 75,000 and a bromine content of about 60 wt% or more, and/or b) a bro
  • Optional ingredients that are often present in the flame retarded polyolefin compositions are as described above.
  • Suitable polymeric compositions are those polymeric composition useful as a thermoplastic material or thermoset material.
  • Non-limiting examples of polymeric compositions that are useful as thermoplastics include polyurethanes, polyesters, polyamides, polyolefins, styrenic polymers, chlorinated polyethylene, and combinations thereof.
  • Thermoset formulations for wire and/or cable are commonly formed by crosslinking technologies including (a) Moisture cure, (b) Peroxide cure, or (c) E-beam cure technologies.
  • 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 derivatives of polyolefins such as chlorinated polyethylene or silane functionalized polyethylene.
  • polyolefins such as polyethylene
  • polyolefin copolymers such as poly (ethylene- vinyl acetate) (EVA) and poly (ethylene ethyl acrylate) (EEA)
  • EVA ethylene- vinyl acetate
  • ESA ethylene ethyl acrylate
  • the brominated flame retardants in the practice of this invention contain aromatically bound bromine, and in several embodiments are considered to be brominated styrenic polymers.
  • the brominated flame retardants have weight average molecular weights (Mw) of about 650 to about 75,000 and a bromine content of about 60 wt% or more.
  • the styrenic polymers are polystyrenes.
  • Mixtures of two or more brominated flame retardants can be used in the practice of this invention.
  • Mixtures of brominated flame retardants and other non-halogenated flame retardants can also be used in practice of this invention.
  • the brominated flame retardants are brominated anionic styrenic polymers, in which the styrenic polymers were formed via anionic polymerization, typically with an alkyl lithium initiator; these brominated flame retardants generally have a weight average molecular weight (Mw) of about 2000 or more, preferably about 1 ,000 or more. In some embodiments, the brominated anionic styrenic polymers have aMw 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.
  • the brominated anionic styrenic polymers contain 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 polymers contain 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.
  • the brominated anionic styrenic polymers are 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 on the preparation of brominated anionic styrenic polymers is found for example in U.S. Pat. Nos. 7,632,893 and 7,638,583.
  • the brominated flame retardant is a low molecular weight brominated anionic styrenic polymer having a weight average molecular weight (Mw) of about 650 or more, preferably about 950 or more, more preferably about 1000 or more.
  • Mw weight average molecular weight
  • these brominated anionic styrenic polymers have an 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.
  • the low molecular weight brominated anionic styrenic polymers contain 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%, more preferably about 70 wt% to about 75 wt% bromine.
  • the low molecular weight brominated anionic styrenic polymers are brominated anionic polystyrenes.
  • the low molecular weight brominated anionic styrenic polymers are brominated anionic polystyrenes having a weight average molecular weight of about 1000 to about 3000, and about 73 wt% to about 77 wt% bromine.
  • the low molecular w eight brominated anionic styrenic polymers can be formed by bromination in an organic solvent or in a sea of bromine (in which bromine is both the brominating agent and the solvent).
  • Information on the preparation of low molecular w eight brominated anionic styrenic polymers is found for example in International Patent Publications WO 2017/176740 and WO 2017/184350; these polymers can also be made as described U.S. Pat. Nos. 7,632,893 and 7,638,583.
  • Another brominated flame retardant that can be used in the practice of this invention is sometimes not categorized as a styrenic polymer due to the relatively small number of repeating units in these molecules. Similar to the brominated styrenic polymers, these molecules also contain aromatically -bound bromine, and styrenic repeating units.
  • This brominated flame retardant is a brominated anionic chain transfer vinyl aromatic polymer which contains 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.
  • 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.
  • the brominated anionic chain transfer vinyl aromatic polymers are brominated anionic chain transfer polystyrenes.
  • the brominated anionic chain transfer vinyl aromatic polymers are brominated anionic chain transfer polystyrenes having a weight average molecular weight of about 2000 to about 10,000, and about 72 wt% to about 78 wt% bromine.
  • the brominated anionic chain transfer vinyl aromatic polymers can be formed by bromination in an organic solvent or in a sea of bromine (in which bromine is both the brominating agent and the solvent).
  • Information on the preparation of brominated anionic chain transfer vinyl aromatic polymers is found for example in U.S. Pat. Nos. 8,420,876, 8,796,388, and 8,993,684.
  • the flame retardant additive compositions can 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 derivatives thereof, pentabromodiphenyl oxide, octabromodiphenyl oxide (octabromodiphenyl ether), decabromodiphenyl oxide (decabromodiphenyl ether), 1 ,2-bis(tribromophenoxy)ethane, tetradecabromodiphenoxy benzene, 2,4,6-tribromophenol allyl ether, dibromoneopentyl glycol, tribro
  • brominated epoxy oligomer such as tribromophenol endcapped brominated epoxy oligomers
  • brominated carbonate oligomers based on tetrabromobisphenol-A such as 2,4,6-tribromophenyl terminated tetrabromobisphenol-A carbonate oligomer and phenoxy-terminated tetrabromobisphenol-A carbonate oligomer
  • brominated polystyrenes block copolymers of polystyrene and brominated polybutadiene.
  • poly(dibromophenylene oxide), poly(pentabromobenzyl acrylate), brominated phthalic acids diallyl tetrabromophthalate, bis(2-ethylhexyl) tetrabromophthalate, tetrabromophthalimide, N,N-ethylene-bis(tetrabromophthalimide), tetrabromophthalic anhydride, a mixed ester of tetrabromophthalic anhydride with diethylene glycol and propylene glycol, N,N'-ethylene-bis-(5,6-dibromonorbomane 2,3-dicarboximide), tris(tribromophenyl)triazine, brominated phenoxytriazines such as tris(tribromophenoxy)triazine, brominated maleimides such as tribromophenyl maleimide, brominated trimethylphenylindan, brominated isocyanurates such as tris
  • Preferred brominated flame retardants to use in admixture with the brominated anionic styrenic polymers and/or brominated anionic chain transfer vinyl aromatic polymers include decabromodiphenyl ethane and N,N-ethylene-bis(tetrabromophthalimide).
  • One embodiment for a process for forming a flame retardant composition for use in wire and/or cable comprises: A first step comprising of combining 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 styrenic polymers which have weight average molecular weights 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 which contains 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
  • a further embodiment for a process for forming a flame retardant composition comprises a first step comprising of combining 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 styrenic polymers which have weight average molecular weights 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 which contains about 70 wt% or more bromine; and at least one silanol catalyst.
  • a second step of extruding the mixture of the first step to coat a wire and/or cable.
  • a third step of exposing the mixture of the first step to either or both elevated temperature and external moisture such that the article reaches a desired degree of crosslinking.
  • a further embodiment for a process for forming a flame retardant composition which process comprises a first step comprising of combining 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 styrenic polymers which have weight average molecular weights 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 which contains about 70 wt% or more bromine.
  • a second step of extruding the mixture of the first step to coat a wire and/or cable.
  • a third step of electron-beam irradiating the mixture of the coated wire and/or cable with an effective dose of electron-beam irradiation is selected from a) brominated styrenic polymers which have weight average molecular weights of about 650 to about 75,000 and a
  • the brominated flame retardants and polymeric compositions include those discussed above.
  • the individual components can be blended separately and/or in subcombinations with the substrate or host polymer in appropriate proportions.
  • the flame retardant additive composition is typically about 40 wt% or more of the flame retarded polyolefin composition, or about 40 wt% to about 80 wt% of the flame retarded polyolefin composition, based on the total weight of the flame retarded polyolefin composition.
  • compositions of this invention can be prepared using compounding equipment such as a single screw extruder, a twin screw extruder, or a Buss kneader.
  • compounding equipment such as a single screw extruder, a twin screw extruder, or a Buss kneader.
  • the compounding uses an extruder, more preferably a twin-screw extruder.
  • the other ingredients utilized in the practice of this invention can be added in the initial feed port of the extruder or they can be added to the extruder further downstream. In an extruder, many ingredients typically melt as they are mixed together.
  • the extrudate from the extruder is typically converted into granules or pellets either by cooling strands of the extruding polymer and subdividing the solidified strands, or by subjecting the extrudate to concurrent die-faced pelletizing and water-cooling or air-cooling.
  • the compositions of this invention can be formulated as powder or granular blends of the ingredients of the composition.
  • masterbatches comprising a polymeric composition and at least one brominated flame retardant can be formed.
  • a masterbatch is usually a mixture having a high concentration of the brominated flame retardant relative to the thermoplastic. Normally, the masterbatch is later blended with more polymeric composition to form the product with the desired ratios of brominated flame retardant, other ingredients, and polymeric composition. Masterbatches can be used in thermoset formulations.
  • these compositions of the present invention are useful as coatings for wire and/or cable.
  • Fire retardants are used in wire and/or cable formulation to meet the flame performance required for the specific application such as appliances, building and construction, cables in automotives, photovoltaic wires, etc.
  • the insulation coating over the conductor is made to be flame retardant by incorporating various fire-retardant chemistries or technologies (Br, P, Metal hydroxide, etc.).
  • fire-retardant chemistries are also used in the jacket (layer on top of insulation) formulation.
  • the insulation or jacket could be (1) thermoplastic or (2) thermoset (crosslinked).
  • Thermoplastic and thermoset formulation could have polyolefin (PP, PE) as the base polymer. Beyond polyolefin, the base polymer could also be polyurethane and chlorinated polyethylene.
  • Polyolefin can be crosslinked typically by (a) Moisture cure, (b) Peroxide cure, (c) E-beam cure technologies.
  • the composition is prepared in a compounding extruder that mixes and evenly distributes and disperses all the ingredients.
  • the extruded compound is then formed into pellets.
  • pellets are then fed into a wireline extruder to coat the wire.
  • the coated wire will be crosslinked in a second step based on the curing chemistry.
  • the curing chemistries suitable for the invention include curing by moisture. For moisture cure, the coated wire would be placed in a Sauna bath at increased temperature and moisture.
  • compositions discussed above would further include a silanol catalyst to promote moisture curing.
  • Silanol catalysts known in the art for crosslinking alkoxysilane polymers can be employed for the compositions of the invention.
  • Such catalysts include organic bases, carboxylic acids and organometallic compounds including organic titanates and complexes or carboxylates of lead, cobalt, iron, nickel, zinc and tin.
  • Tin carboxylates are particularly useful silanol catalysts for the compositions of the invention.
  • the composition can be exposed to either or both elevated temperature and external moisture and if an elevated temperature, it is typically between ambient and up to but below the melting point of the polymer for a period such that the article reaches a desired degree of crosslinking.
  • the temperature of any post-shaping cure should be above 0° C.
  • UL-VW-1 bum test The VW-1 Bum Test is conducted by subjecting three or six samples of a specific coated conductor to the protocol of UL 2556. This involves five 15- second applications of a 125 mm flame impinging on at an angle 20° on a vertically oriented specimen 610 mm (24 in) in length. A strip of kraft paper 12.5 ⁇ 1 mm (0.5 ⁇ 0.1 in) is affixed to the specimen 254 ⁇ 2 mm (10 ⁇ 0. 1 in) above the impingement point of the flame.
  • 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 being 235 ⁇ 6 mm (9.25 ⁇ 0.25 in) below the point at which the tip of the blue inner cone of the flame impinges on the specimen.
  • Test failure is based upon the criteria of either burning the 25% of the kraft paper tape flag, ignition of the cotton batting or if the specimen bums longer than 60 seconds on any of the five flame applications.
  • the length of uncharred insulation (“no char to flag length”) is measured at the completion of the test.
  • the VW-1 cotton ignited indicates if falling material ignited the cotton bed.
  • Each sample was formed by mixing and melting together all of the ingredients in a twin screw extruder (ZSK30 (30 mm). Wemer & Pfleiderer Coperion GmbH), each ingredient being fed separately in powder form.
  • the resultant 14 AWG copper wire with 0.030-inch insulation thickness was immediately cooled in a water trough before winding down in a wire spool.
  • the wire spool was then submerged in 90 °C water for 12 hours to complete the moisture curing process.
  • the cured wire was then tested for flame performance (VW-1).
  • Table 7 [0072] The VW-1 data above (table 2) shows that in the absence of added synergist (ZnO), the flame retardants of the present invention can offer VW-1 flame performance. However, a similar formulation with non-polymeric S-8010 does not offer these unique properties. [0073] Components referred to by chemical name or formula anywhere in the specification or claims hereof, whether referred to in the singular or plural, are identified as they exist prior to coming into contact with another substance referred to by chemical name or chemical type (e.g., another component, a solvent, or etc.).
  • chemical name or chemical type e.g., another component, a solvent, or etc.
  • the invention may comprise, consist, or consist essentially of the materials and/or procedures recited herein.
  • the term "about" modifying the quantify of an ingredient in the compositions of the invention or employed in the methods of the invention refers to variation in the numerical quantify that can occur, for example, through typical measuring and liquid handling procedures used for making concentrates or use solutions in the real world; through inadvertent error in these procedures; through differences in the manufacture, source, or purify of the ingredients employed to make the compositions or carry out the methods; and the like.
  • the term about also encompasses amounts that differ due to different equilibrium conditions for a composition resulting from a particular initial mixture. Whether or not modified by the term "about”, the claims include equivalents to the quantities.

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  • Life Sciences & Earth Sciences (AREA)
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Abstract

La présente invention concerne des compositions ignifuges et des compositions polymères d'ignifugeant bromé destinées à être utilisées dans un fil et/ou un câble. Les ignifugeants bromés contiennent du brome lié de manière aromatique et, dans plusieurs modes de réalisation, sont considérés comme étant des polymères styréniques bromés. Les ignifugeants bromés présentent des masses moléculaires moyennes en poids (Mw) d'environ 650 à environ 75 000 et une teneur en brome d'environ 60 % en poids ou plus. La présente invention concerne en outre un processus de formation d'une composition ignifuge comprenant : une première étape consistant à combiner au moins une composition polymère ; au moins un agent synergiste ; au moins un ignifugeant bromé, l'ignifugeant bromé contenant du brome lié de manière aromatique et étant sélectionné parmi a) des polymères styréniques bromés qui présentent des masses moléculaires moyennes en poids d'environ 650 à environ 75 000 et une teneur en brome d'environ 60 % en poids ou plus, et/ou b) un polymère aromatique vinylique de transfert de chaîne anionique bromé qui contient environ 70 % en poids ou plus de brome ; et au moins un catalyseur silanol ; une deuxième étape consistant à extruder le mélange de la première étape pour revêtir un fil et/ou un câble ; et une troisième étape consistant à exposer le mélange de la première étape à une température élevée, à une humidité externe ou aux deux, de sorte que l'article atteigne un degré souhaité de réticulation.
PCT/US2024/030499 2023-05-23 2024-05-22 Composition polymère d'ignifugeant bromé destinée à être utilisée dans un fil et/ou un câble Pending WO2024243272A2 (fr)

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PCT/US2024/030523 Pending WO2024243285A2 (fr) 2023-05-23 2024-05-22 Composition polymère bromée ignifuge pour utilisation dans les fils et/ou les câbles

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JP5896626B2 (ja) * 2011-06-08 2016-03-30 リケンテクノス株式会社 シラン架橋性難燃ポリオレフィンとシラノール触媒樹脂組成物からなる電線成形体の製造方法
CA2869814C (fr) * 2012-04-27 2016-06-14 Borealis Ag Composition de polymere retardatrice d'inflammation
WO2014098930A1 (fr) * 2012-12-17 2014-06-26 3M Innovative Properties Company Câble twinaxial ignifuge
TW201439287A (zh) * 2013-01-20 2014-10-16 Sekisui Chemical Co Ltd 阻燃性胺甲酸乙酯樹脂組成物
US20150337125A1 (en) * 2014-05-23 2015-11-26 Albemarle Corporation Brominated Flame Retardants and their use in Thermoplastic and Thermosetting Flammable Materials
EP4023713A1 (fr) * 2017-08-10 2022-07-06 Dow Global Technologies LLC Compositions comprenant un ignifuge polymère bromé
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WO2024243285A2 (fr) 2024-11-28
MX2025013908A (es) 2025-12-01
WO2024243285A3 (fr) 2025-04-10
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