WO2022024073A1 - Compositions de polycarbonate ignifuge contenant du verre - Google Patents

Compositions de polycarbonate ignifuge contenant du verre Download PDF

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Publication number
WO2022024073A1
WO2022024073A1 PCT/IB2021/056987 IB2021056987W WO2022024073A1 WO 2022024073 A1 WO2022024073 A1 WO 2022024073A1 IB 2021056987 W IB2021056987 W IB 2021056987W WO 2022024073 A1 WO2022024073 A1 WO 2022024073A1
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Prior art keywords
siloxane
flame
composition
copolymer
carbonate
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PCT/IB2021/056987
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English (en)
Inventor
Mark Armstrong
Mark Van Der Mee
Tony Farrell
Remco WIRTZ
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Shpp Global Technologies B.V.
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Priority to CN202180062311.9A priority Critical patent/CN116057111A/zh
Priority to EP21749712.2A priority patent/EP4188983A1/fr
Publication of WO2022024073A1 publication Critical patent/WO2022024073A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/18—Block or graft polymers
    • C08G64/186—Block or graft polymers containing polysiloxane sequences
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
    • C08G77/445—Block-or graft-polymers containing polysiloxane sequences containing polyester sequences
    • C08G77/448—Block-or graft-polymers containing polysiloxane sequences containing polyester sequences containing polycarbonate sequences
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/40—Glass
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0066—Flame-proofing or flame-retarding additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/10—Block- or graft-copolymers containing polysiloxane sequences
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/019—Specific properties of additives the composition being defined by the absence of a certain additive

Definitions

  • compositions that can in some embodiments be essentially free of or free of chlorine and bromine materials are described.
  • the compositions in some embodiments can have a transmission greater than 70 % at a thickness of 1.5 mm measured by ASTM D1003-00 and/or a UL94 rating of V0 at a thickness of 1.5 mm.
  • ECU Electronic control units
  • other electrical devices may have their housings made from flame-retardant materials. These materials may also be transparent, which can be helpful when joining members/pieces of a housing assembly (e.g., ECU) together with laser welding techniques. Further, the transparency can allow a user to view the enclosed volume or weld lines of a given housing assembly.
  • compositions of certain embodiments can have a transmission greater than 70 % at a thickness of 1.5 mm measured by HazeGard (ASTM DI 003-00) and/or a UL94 rating of V0 at a thickness of 1.5 mm. These results can be achieved with limited or no use of halogenated materials such as brominated or chlorinated materials.
  • the compositions can have good IR (laser) transmission, processability parameters (e.g., low injection pressure, short cycle time, small draft angle, and/or low ejection force), chemical resistance properties, and/or low temperature impact properties, which can advantageously increase efficiency and/or durability during processing and/or use of the compositions.
  • processability parameters e.g., low injection pressure, short cycle time, small draft angle, and/or low ejection force
  • chemical resistance properties e.g., low temperature impact properties
  • a flame-retardant composition can contain a first poly(carbonate-siloxane) copolymer, a filler containing glass, and a organophosphorus flame retardant.
  • the first poly(carbonate-siloxane) copolymer can be a random copolymer.
  • the first poly(carbonate-siloxane) copolymer can have a siloxane content of 5 wt. % to 25 wt. %, or 5 wt. % to 10 wt. %, or 5 wt. % to 8 wt. %, or about 6 wt. %, or 15 wt.
  • the first poly(carbonate-siloxane) copolymer can contain less than 0.5 mol. %, or less than 0.2 mol.%, or less than 0.1 mol.%, such as 0 to 0.5 mol. % of siloxane units that are directly coupled to other siloxane units.
  • the first poly(carbonate-siloxane) copolymer can be free of, or essentially free of siloxane units that are directly coupled to other siloxane units.
  • the first poly(carbonate-siloxane) copolymer can have a weight average molecular weight (Mw) of 10,000 to 50,000 g/mol, or 18,000 to 40,000 g/mol, or 20,000 to 35,000 g/mol, as determined by GPC using BPA polycarbonate standards.
  • the first poly(carbonate-siloxane) copolymer can have siloxane unit block length of 10 units to 200 units, or 30 units to 100 units, or 30 units to 50 units.
  • the first poly(carbonate- siloxane) copolymer can have phenolic such as para-cumylphenol end-cap.
  • the first poly(carbonate-siloxane) copolymer can be manufactured using a tube reactor processes.
  • the filler can be glass fiber.
  • the organophosphorus flame retardant can be an oligomeric phosphate ester containing flame retardant, and/or phosphazene containing flame retardants or a combination thereof.
  • the organophosphorus flame retardant can be substantially free of or free of halogen.
  • the flameretardant composition can contain 10 wt % to 85 wt. % or 50 wt. % to 85 wt. %, of the first poly(carbonate-siloxane) copolymer, 10 wt. % to 30 wt. % of the filler, and 1 wt. % to 10 wt. % of the organophosphorus flame retardant.
  • the flame-retardant composition can have a siloxane content of 2 wt. % to 15 wt. %, or 3 wt. % to 15 wt. %, or 3 wt. % to 9 wt. %, based on the total weight of the composition.
  • the flame-retardant composition can optionally contain a polycarbonate polymer.
  • the polycarbonate polymer can be a linear polycarbonate, or a branched polycarbonate, or a combinations thereof.
  • the polycarbonate polymer can be a linear polycarbonate.
  • the polycarbonate polymer can be a branched polycarbonate.
  • the polycarbonate can have a weight average molecular weight (Mw) of 10,000 to 50,000 g/mol, as measured by GPC using BPA polycarbonate standards.
  • the flame-retardant composition can optionally contain 20 wt. % to 79 wt. % or 20 wt. % to 30 wt. % of the polycarbonate polymer.
  • the flame-retardant composition can optionally contain a second poly(carbonate-siloxane) copolymer, having a siloxane content of 15 wt. % to 50 wt. %, 15 wt. % to 25 wt. %, or 18 wt. % to 22 wt. %, or about 20 wt.
  • the siloxane content of the first poly(carbonate-siloxane) copolymer and the second poly(carbonate-siloxane) copolymer can be different. In some aspects, the siloxane content of the first poly(carbonate-siloxane) copolymer can be lower than that of the second poly(carbonate-siloxane) copolymer.
  • the flame-retardant composition can optionally contain 3 wt.
  • the second poly(carbonate-siloxane) copolymer can contain 0.5 mol. % or higher of siloxane units that are directly coupled to other siloxane units.
  • the second poly(carbonate-siloxane) copolymer can have a weight average molecular weight of 10,000 g/mol to 40,000 g/mol, as determined by GPC using BPA polycarbonate standards.
  • the second poly(carbonate-siloxane) copolymer can have siloxane unit block length of 10 units to 200 units, or 30 units to 100 units, or 30 units to 50 units.
  • the second polycarbonatesiloxane) copolymer can have phenolic such as para-cumylphenol end-cap.
  • the flame-retardant composition can optionally contain 0.01 wt. % to 1 wt. % of an anti-drip, such as fluoropolymer containing anti-drip, such as polytetrafluoroethylene (PTFE) containing anti-drip, such as PTFE encapsulated by styrene-acrylonitrile (SAN), known as TSAN.
  • the flame-retardant composition can further contain one or more additives.
  • the one or more additives may include, but are not limited to, scratch-resistance agents, antioxidants, UV absorbers, photochemical stabilizers, fillers, optical brighteners, surfactants, processing aids, mold release agents, pigments, or any combinations thereof.
  • the one or more additive can include an antioxidant and/or a mold release agent.
  • the antioxidant can be a hindered phenolic based antioxidant and/or a phosphite based antioxidant.
  • the mold release agent can be pentaerythritol tetrastearate.
  • the flame-retardant composition can contain 0.01 wt. % to 1 wt.
  • the flame-retardant composition can contain less than 0.1 wt. %, preferably less than 0.05 wt. %, more preferably less than 0.01 wt. %, of each of chlorine and bromine, or is free of each of chlorine and bromine. In some aspects, the flame-retardant composition can contain less than 0.1 wt. %, preferably less than 0.05 wt. %, more preferably less than 0.01 wt. % of halogen, or is free of halogen, such as each of fluorine, chlorine and bromine.
  • the flame-retardant composition can contain 75 wt. % to 85 wt. % of the first poly(carbonate-siloxane) copolymer, 10 wt. % to 20 wt. % of the filler, and 1 wt. % to 10 wt. % of the organophosphorus flame retardant.
  • the flameretardant composition can contain 75 wt. % to 85 wt. % of the first poly(carbonate-siloxane) copolymer, 10 wt. % to 20 wt. % of the filler, 1 wt. % to 10 wt.
  • composition can contain less than 0.1 wt. %, preferably less than 0.05 wt. %, more preferably less than 0.01 wt. % of halogen, or is free of halogen.
  • the flame-retardant composition can contain 75 wt. % to 85 wt.
  • the composition can contain less than 0.1 wt. %, preferably less than 0.05 wt. %, more preferably less than 0.01 wt. % of each of chlorine and bromine, or is free of each of chlorine and bromine.
  • the flame-retardant composition can contain 60 wt. % to 80 wt. % of the first poly(carbonate-siloxane) copolymer, 3 wt. % to 12 wt. % of the second poly(carbonate-siloxane) copolymer, 10 wt. % to 30 wt. % of the filler, and 1 wt. % to 10 wt. % of the organophosphorus flame retardant.
  • the flame-retardant composition can contain 60 wt. % to 80 wt. % of the first poly(carbonate-siloxane) copolymer, 3 wt.
  • composition can contain less than 0.1 wt. %, preferably less than 0.05 wt. %, more preferably less than 0.01 wt.
  • the flame-retardant composition can contain 60 wt. % to 80 wt. % of the first poly(carbonate-siloxane) copolymer, 3 wt. % to 12 wt. % of the second poly(carbonate-siloxane) copolymer, 10 wt. % to 30 wt. % of the filler, 1 wt. % to 10 wt. % of the organophosphorus flame retardant, 0.01 wt. % to 1 wt. % of the mold release agent, 0.01 wt. % to 0.5 wt.
  • the composition can contain less than 0.1 wt. %, preferably less than 0.05 wt. %, more preferably less than 0.01 wt. % of each of chlorine and bromine, or is free of each of chlorine and bromine.
  • the flame-retardant composition can contain 60 wt. % to 70 wt. % of the first poly(carbonate-siloxane) copolymer, 3 wt. % to 12 wt. % of the second poly(carbonate-siloxane) copolymer, 20 wt. % to 30 wt. % of the filler, and 1 wt. % to 10 wt. % of the organophosphorus flame retardant.
  • the flame-retardant composition can contain 60 wt. % to 70 wt. % of the first poly(carbonate-siloxane) copolymer, 3 wt.
  • composition can contain less than 0.1 wt. %, preferably less than 0.05 wt.
  • the flame-retardant composition can contain 60 wt. % to 70 wt. % of the first poly(carbonate-siloxane) copolymer, 3 wt. % to 12 wt. % of the second poly(carbonate-siloxane) copolymer, 20 wt. % to 30 wt. % of the filler, 1 wt. % to 10 wt. % of the organophosphorus flame retardant, 0.01 wt. % to 1 wt. % of the mold release agent, 0.01 wt.
  • the flame-retardant composition can contain 70 wt. % to 80 wt.
  • the flame-retardant composition can contain 70 wt. % to 80 wt. % of the first poly(carbonate-siloxane) copolymer, 3 wt. % to 12 wt. % of the second poly(carbonate-siloxane) copolymer, 10 wt. %.
  • composition can contain less than 0.1 wt. %, preferably less than 0.05 wt. %, more preferably less than 0.01 wt. % of halogen, or is free of halogen.
  • the flame-retardant composition can contain 70 wt. % to 80 wt. % of the first poly(carbonate-siloxane) copolymer, 3 wt. % to 12 wt. % of the second poly(carbonate-siloxane) copolymer, 10 wt. % to 20 wt. % of the filler, 1 wt. % to 10 wt. % of the organophosphorus flame retardant, 0.01 wt. % to 1 wt. % of the mold release agent, 0.01 wt. % to 0.5 wt. % of the hindered phenolic based antioxidant, and 0.01 wt.
  • composition can contain less than 0.1 wt. %, preferably less than 0.05 wt. %, more preferably less than 0.01 wt. % of each of chlorine and bromine, or is free of each of chlorine and bromine.
  • the flame-retardant composition can contain 50 wt. % to 65 wt. % of the first poly(carbonate-siloxane) copolymer, 20 wt. % to 30 wt. % of the polycarbonate polymer, such as one or more bisphenol A polycarbonate polymers , 10 wt. % to 20 wt. % of the filler, and 1 wt. % to 10 wt. % of the organophosphorus flame retardant.
  • the flame-retardant composition can contain 50 wt. % to 65 wt. % of the first poly(carbonate-siloxane) copolymer, 20 wt.
  • composition can contain less than 0.1 wt. %, preferably less than 0.05 wt.
  • the flame-retardant composition can contain 50 wt. % to 65 wt. % of the first poly(carbonate-siloxane) copolymer, 20 wt. % to 30 wt. % of the polycarbonate polymer, such as one or more bisphenol A polycarbonate polymers, 10 wt. % to 20 wt. % of the filler, 1 wt. % to 10 wt. % of the organophosphorus flame retardant, 0.01 wt. % to 1 wt. % of the mold release agent, 0.01 wt.
  • composition can contain less than 0.1 wt %, preferably less than 0.05 wt. %, more preferably less than 0.01 wt. % of each of chlorine and bromine, or is free of each of chlorine and bromine.
  • compositions, or molded articles of the compositions, with a thickness of 1.5 mm can have i) a transmission of higher than 70%, measured by HazeGard (ASTM D1003-00), ii) a laser transmission higher than 70% at a X of 908 nm, measured by HazeGard (ASTM D1003-00), and iii) a UL94 rating of V0 at 1.5 mm thickness, or any combination thereof.
  • compositions, or molded articles of the compositions can have a UL94 rating of V0 at a thickness 1.2 mm.
  • compositions, or molded articles of the compositions can have a UL94 rating of V0 at a thickness 1 mm.
  • the composition can have a melt volume rate (MVR.) of greater than 3.1 cc/10 min, preferably 5.0 cc/10 min to 13.7 cc/10 min as measured at 300 °C, 1.2 kg, 300 sec, in accordance with ISO 1133.
  • MVR. melt volume rate
  • the composition can have a combination of, or all of the properties mentioned in this paragraph.
  • the flame-retardant compositions of certain embodiments can be extruded, blow- molded, injection-molded, rotational molded and/or thermoformed compositions.
  • the flame-retardant composition can be comprised in or formed into an article of manufacture.
  • the article of manufacture can be transparent.
  • the article of manufacture can be an automobile part, an electronic housing, electronic housing component, an electrical housing, electrical housing component, a personal equipment part, or a home appliance component.
  • the article of manufacture can be an electronic or electrical housing, or an electronic or electrical housing component.
  • the article of manufacture can be an extruded, a blow-molded, an injection-molded article, a rotational molded and/or thermoformed article.
  • wt.% refers to a weight percentage of a component, a volume percentage of a component, or molar percentage of a component, respectively, based on the total weight, the total volume of material, or total moles, that includes the component.
  • 10 grams of component in 100 grams of the material is 10 wt.% of component.
  • ppm refer to parts per million by weight, based on the total weight, of material that includes the component.
  • A, B, and/or C includes: A alone, B alone, C alone, a combination of A and B, a combination of A and C, a combination of B and C, or a combination of A, B, and C.
  • A, B, and/or C includes: A alone, B alone, C alone, a combination of A and B, a combination of A and C, a combination of B and C, or a combination of A, B, and C.
  • “and/or” operates as an inclusive or.
  • the flame-retardant composition(s) can “comprise,” “consist(s) essentially of,” or “consist of’ particular ingredients, components, compositions, etc. disclosed throughout the specification.
  • a basic and novel characteristic in some embodiments can include transparent glass filled flame-retardant compositions having a light transmission greater than 70 % at a thickness of 1.5 mm and/or a UL94 rating of V0 at a thickness of 1.5 mm.
  • the discovery can include a flame retardant thermoplastic composition containing 10 wt. % to 85 wt. %, of a first poly(carbonate-siloxane) copolymer, 10 wt. % to 30 wt. % of a filler containing glass, and 1 wt. % to 10 wt. % of a organophosphorus flame retardant.
  • the first poly(carbonate-siloxane) copolymer can have a siloxane content of 5 wt. % to 25 wt.
  • the first poly(carbonate-siloxane) copolymer can have a siloxane content of 15 wt. % to 25 wt. % based on the weight of the copolymer and have less than 0.5 mol. % of siloxane units that are directly coupled to other siloxane units.
  • the total siloxane content of the flame-retardant composition can be 2 wt. % to 15 wt. %.
  • compositions of certain embodiments can be free of or essentially free of chlorine and bromine and can have a transmission greater than 70 % at a thickness of 1.5 mm measured in accordance with ASTM D 1003 and a UL94 rating of V0 at a thickness of 1.5 mm.
  • the flame-retardant compositions in certain embodiments can contain i) 10 wt. % to 85 wt. %, 50 wt. % to 85 wt. %, or 50 wt. % to 65 wt. %, or 60 wt. % to 80 wt. %, or 60 wt. % to 70 wt. %, or 70 wt. % to 80 wt. %, or 75 wt. % to 85 wt. %, or at least any one of, equal to any one of, or between any two of 10, 20, 30, 40, 50, 55, 60, 65, 70, 75, 80 and 85 wt.
  • % of the first poly(carbonate-siloxane) copolymer ii) 10 wt. % to 30 wt. %, or 10 wt.% to 20 wt.% or 20 wt.% to 30 wt.% or at least any one of, equal to any one of, or between any two 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24 25, 26, 27, 28, 29 and 30 wt. % of the filler, and iii) 1 wt. % to 10 wt. %, preferably 1 wt. % to 8 wt. %, or at least any one of, equal to any one of, or between any two 1, 2, 3, 4, 5, 6, 7, 8, 9, and 10 wt.
  • the flame-retardant composition contains less than 0.1 wt. %, preferably less than 0.05 wt. %, more preferably less than 0.01 wt. % of each of chlorine and bromine, or is free of each of chlorine and bromine. In some aspects, the flame-retardant composition contains less than 0.1 wt. %, preferably less than 0.05 wt. %, more preferably less than 0.01 wt. %, of halogen, or most preferably is free of halogen, such as each of chlorine, bromine, and/or fluorine.
  • the total siloxane content of the flame-retardant composition can be 2 wt.
  • the poly(carbonate-siloxane) copolymers can include carbonate units and siloxane units.
  • Suitable carbonate units also referred to as carbonate blocks
  • the carbonate units can be derived from a dihydroxy compound such as an aromatic dihydroxy compound of formula (2) or a bisphenol of formula (3)
  • each R b can be independently a halogen atom such bromine, a C1-10 hydrocarbyl group such as a C1-10 alkyl, a halogen- substituted C1-10 alkyl, a Ce-io aryl, or a halogen-substituted Ce-io aryl, and n can be integers of 0 to 4.
  • each R b can be independently bromine, a C1-3 alkyl, a halogen-substituted C1-3 alkyl, and n can be 0 to 1.
  • R a and R b each can be independently a halogen, Ci-
  • p and q each can be independently integers of 0 to 4, such that when p or q is less than 4, the valence of each carbon of the ring is filled by hydrogen; and X a can be a single bond, -O-, -S(O)-, -S(O)2-, -C(O)-, a Cun alkylidene of formula -C(R c )(R d ) - wherein R c and R d each can be independently hydrogen or C1-10 alkyl.
  • R a and R b each can be independently Ci-e alkyl or C1-3 alkoxy, and p and q each can be independently 0 to 1, and.
  • p and q is each 0, or p and q is each 1;
  • R a and R b are each a C1-3 alkyl group, preferably methyl, disposed meta to the hydroxy group on each Ce arylene group;
  • X a is a bridging group connecting the two hydroxy-substituted aromatic groups, where the bridging group and the hydroxy substituent of each Ce arylene group are disposed para to each other on the Ce arylene group, where X a can be a substituted or unsubstituted C3-18 cycloalkylidene; a C1-25 alkylidene of the formula - C(R c )(R d ) - wherein R c and R d each can be independently hydrogen, C1-12 alkyl,
  • aromatic dihydroxy compound of formula (2) can include but are not limited to resorcinol; substituted resorcinol compounds such as 5-methyl resorcinol, 5-ethyl resorcinol, 5-propyl resorcinol, 5-butyl resorcinol, 5-t-butyl resorcinol, 5-phenyl resorcinol, 5- cumyl resorcinol, 2,4,5,6-tetrafluoro resorcinol, 2,4,5,6-tetrabromo resorcinol, or the like; catechol; hydroquinone; or substituted hydroquinones such as 2-methyl hydroquinone, 2-ethyl hydroquinone, 2-propyl hydroquinone, 2-butyl hydroquinone, 2-t-butyl hydroquinone, 2- phenyl hydroquinone, 2-cumyl hydroquinone, 2,3,5,6-tetramethyl hydroquinone, 2,3,5,6
  • Examples of bisphenols of formula (3) can include 4,4’ -dihydroxybiphenyl, 1,6- dihydroxynaphthalene, 2,6-dihydroxynaphthalene, bi s(4-hydroxyphenyl)m ethane, bis(4- hydroxyphenyl)diphenylmethane, bis(4-hydroxyphenyl)- 1 -naphthylmethane, 1 ,2-bis(4- hydroxyphenyl)ethane, l,l-bis(4-hydroxyphenyl)-l -phenyl ethane, 2-(4-hydroxyphenyl)-2-(3- hydroxyphenyl)propane, bis(4-hydroxyphenyl)phenylmethane, 2,2-bis(4-hydroxy-3- bromophenyl)propane, 1, 1 -bi s (hydroxyphenyl)cyclopentane, 1 , 1
  • the compound of formula (2) or formula (3) can include resorcinol, 2,2-bis(4-hydroxyphenyl) propane (bisphenol A or BPA), 3,3-bis(4-hydroxyphenyl) phthalimidine, 2-phenyl-3,3’-bis(4-hydroxyphenyl) phthalimidine (also known as N-phenyl phenolphthalein bisphenol, “PPPBP”, or 3,3-bis(4-hydroxyphenyl)-2-phenylisoindolin-l-one), l,l-bis(4-hydroxy-3-methylphenyl) cyclohexane, or l,l-bis(4-hydroxyphenyl)-3,3,5- trimethylcyclohexane (TMC bisphenol).
  • BPA 2,2-bis(4-hydroxyphenyl) propane
  • PPPBP 3,3-bis(4-hydroxyphenyl) phthalimidine
  • 2-phenyl-3,3’-bis(4-hydroxyphenyl) phthalimidine also known as N-phenyl
  • the carbonate units can have the formula of formula (la) [0037]
  • the siloxane units (also referred to as polysiloxane blocks) are optionally of formula (4) wherein each R can be independently a C1-13 monovalent organic group.
  • each R can be independently a C1-13 alkyl, C-C13 alkoxy, C2-13 alkenyl, C2-13 alkenyloxy, C3-6 cycloalkyl, C3-6 cycloalkoxy, Ce-14 aryl, Ce-io aryloxy, C7-13 arylalkylene, C7-13 arylalkylenoxy, C7-13 alkylarylene, or C7-13 alkylarylenoxy.
  • the foregoing groups can be fully or partially halogenated with one or more of fluorine, chlorine, bromine, or iodine.
  • R can be unsubstituted by a halogen.
  • a combination of the foregoing R groups can be used in the same poly(carbonate-siloxane) copolymer.
  • each R can be independently a C1-3 alkyl, C1-3 alkoxy, C3-6 cycloalkyl, C3-5 cycloalkoxy, Ce-14 aryl, Ce-io aryloxy, C7 arylalkylene, C7 arylalkylenoxy, C7 alkylarylene, or C7 alkylarylenoxy.
  • each R can be independently methyl, trifluoromethyl, or phenyl.
  • E in formula (4) can vary widely depending on the type and relative amount of each component in the polycarbonate composition, the desired properties of the composition, and like considerations. Generally, E has an average value of 10 to 200, preferably 10 to 100, more preferably 20 to 60, still more preferably 30 to 50.
  • the siloxane units are of formula (5) wherein E is as defined for formula (4); each R can be the same or different, and is as defined for formula (4); and each Ar can be the same or different, and can be independently a substituted or unsubstituted C6-C30 arylene, wherein the bonds can be directly connected to an aromatic moiety.
  • Ar groups in formula (5) independently can be derived from a C6-C30 dihydroxyarylene compound, for example a dihydroxy compound of formula (2) or formula (3).
  • Exemplary dihydroxyarylene compounds can be l,l-bis(4-hydroxyphenyl) methane, 1,1- bis(4-hydroxyphenyl) ethane, 2,2-bis(4-hydroxyphenyl) propane, 2,2-bis(4-hydroxyphenyl) butane, 2,2-bis(4-hydroxyphenyl) octane, l,l-bis(4-hydroxyphenyl) propane, l,l-bis(4- hydroxyphenyl) n-butane, 2,2-bis(4-hydroxy-l -methylphenyl) propane, 1 , l-bis(4- hydroxyphenyl) cyclohexane, bis(4-hydroxyphenyl sulfide), or l,l-bis(4-hydroxy-t- butylphenyl) propane.
  • siloxane units of formula (5) include those of the formulas (6a) and (6b) wherein E is as described as described above.
  • E can have an average value 10 to 200, preferably 10 to 100, more preferably 30 to 50.
  • the siloxane units can be of formula (7) wherein R and E are as described for formula (4), and each R 5 can be independently a divalent Ci-30 hydrocarbylene group, and wherein the polymerized polysiloxane unit is the reaction residue of its corresponding dihydroxy compound.
  • the siloxane units can be polydiorganosiloxane blocks of formula (8): wherein R and E are as defined for formula (4).
  • R and E are as defined for formula (4).
  • Each R 6 in formula (8) can be the same or different, and can be independently a divalent C2-8 aliphatic group.
  • Each M in formula (8) can be the same or different, and can be independently a halogen, cyano, nitro, C1-8 alkylthio, Ci-s alkyl, C1-8 alkoxy, C2-8 alkenyl, C2-8 alkenyloxy, C3-8 cycloalkyl, C3-8 cycloalkoxy, Ce-io aryl, Ce-io aryloxy, C7-12 arylalkylene, C7-12 arylalkylenoxy, C7-12 alkylarylene, or C7-12 alkylarylenoxy.
  • Each m can independently be 0, 1, 2, 3, or 4.
  • M can be a halogen such as bromo or chloro, an alkyl such as methyl, ethyl, or propyl, an alkoxy such as methoxy, ethoxy, or propoxy, or an aryl such as phenyl, chlorophenyl, or tolyl;
  • R 6 can be a dimethylene, trimethylene or tetramethylene; and
  • R can be a C1-8 alkyl haloalkyl such as trifluoropropyl, cyanoalkyl, or aryl such as phenyl, chlorophenyl or tolyl.
  • R in formula (8), can be methyl, or a combination of methyl and trifluoropropyl, or a combination of methyl and phenyl.
  • R in formula (8), R is methyl, M is methoxy, m is one, and R 6 is a divalent C1-3 aliphatic group.
  • Preferred polydiorganosiloxane blocks are of the formulas or a combination thereof, wherein E has an average value of 10 to 100, preferably 20 to 60, more preferably 30 to 50, or 40 to 50.
  • Suitable siloxane units have been described, for example, in WO 2008/042500 Al, WO 2010/076680 Al, and WO 2016/174592 Al, each of which are incorporated into the present application by reference.
  • An end-capping agent is generally used to terminate polymer chains.
  • the endcapping agent (i.e. chain stopper) for the first and/or second poly(carbonate-siloxane) copolymers independently can be a monohydroxy compound, a mono-acid compound, or a mono-ester compound.
  • Exemplary end-capping agents include phenols such as phenol, p- cyanophenol, and C1-C22 alkyl-substituted phenols such as p-cumyl-phenol, resorcinol monobenzoate, and p-and tertiary-butyl phenol, monoethers of diphenols, such as pmethoxyphenol, monoesters of diphenols such as resorcinol monobenzoate, functionalized chlorides of aliphatic monocarboxylic acids such as acryloyl chloride and methacryoyl chloride, and mono-chloroformates such as phenyl chloroformate, alkyl-substituted phenyl chloroformates, p-cumyl phenyl chloroformate, and toluene chloroformate. Phenol and paracumylphenol are specifically mentioned. Combinations of different end groups can be used.
  • Blends of poly(carbonate-siloxane) copolymers such as blends of random and block poly(carbonate-siloxane) copolymers can be used using the second poly(carbonate-siloxane) copolymer
  • the first poly(carbonate-siloxane) copolymer and/or second poly(carbonate-siloxane) copolymers independently can contain repeating carbonate units, and repeating siloxane units (5), (6), (7), (8), or a combination comprising at least one of the foregoing, wherein E, e.g. siloxane unit block length, has an average value of 10 to 100, or 20 to 60, or 30 to 60, or 40 to 60, or 40 to 50.
  • the first and/or second poly(carbonate-siloxane) copolymers independently can contain repeating carbonate units derived from bisphenol A, and repeating siloxane units (6a), (6b), (8a), (8b ), (8c), or a combination comprising at least one of the foregoing (specifically of formula 8a), wherein E, e.g. siloxane unit block length, has an average value of 10 to 100, or 20 to 60, or 30 to 60, or 40 to 60, or 40 to 50.
  • the first and/or second poly(carbonate-siloxane) copolymers can be phenolic endcapped, such as paracumylphenol(PCP) endcapped.
  • the first poly(carbonate-siloxane) copolymer can have a siloxane content of 5 wt. % to 25 wt. %, or 5 wt. % to 10 wt. %, or 5 wt. % to 8 wt. %, or about 6 wt. %, or 15 wt. % to 25 wt. %, or 18 wt. % to 22 wt. %, or about 20 wt. %, or at least any one of, equal to any one of, or between any two of 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24 and 25 wt. %.
  • siloxane content of a poly(carbonate-siloxane) copolymer means the content of siloxane units based on the total weight of the copolymer.
  • the first poly(carbonate-siloxane) copolymer can have a weight average molecular weight (Mw) of 10,000 to 50,000 g/mol, or 18,000 to 40,000 g/mol, or 20,000 to 35,000 g/mol, as measured by gel permeation chromatography using a crosslinked styrene-divinyl benzene column, at a sample concentration of 1 milligram per milliliter, and as calibrated with bisphenol A polycarbonate standards.
  • Mw weight average molecular weight
  • a poly(carbonate-siloxane) copolymer there are potentially three types of linkages between the carbonate blocks (C) and siloxane blocks (S). Illustratively these linkages are C- C, S-S, and C-S.
  • the first polysiloxane-polycarbonate contains less than 0.5 mol. % of the siloxane units directly coupled to another siloxane unit, specifically less than 0.2 mol. % of the siloxane units are directly coupled to another siloxane unit, more specifically less than 0.1 mol. %, or 0 mol. % of the siloxane units are directly coupled to another siloxane unit.
  • a composition with relatively high optical transparency and laser transparency is obtained by using such poly(carbonate-siloxane) copolymer.
  • the C-C, S-S, and C-S linkages can be determined via nuclear magnetic resonance (NMR) spectroscopy.
  • the first poly(carbonate-siloxane) copolymers can be manufactured using one or more of the tube reactor processes described in U.S. Patent Application Publication No. 2004/0039145, or the process described in U.S. Patent No. 6,723,864, or the process described in U.S. Patent No. 8,466,249.
  • the first poly(carbonate-siloxane) copolymers can have a EE/EB ratio less than 0.05.
  • EE/EB ratio refers to the molar ratio of the siloxane (such as polydiorganosiloxane) units directly coupled to another siloxane (such as polydiorganosiloxane) unit (EE) relative to, the siloxane (such as polydiorganosiloxane) units directly coupled to a carbonate (such as BPA) unit (EB) for the poly(carbonate-siloxane) copolymer (such as PDMS-BPA) copolymer.
  • the EE/EB ratio can be determined via nuclear magnetic resonance spectroscopy (NMR).
  • the second polycarbonatesiloxane) copolymers can manufactured using interfacial polymerization process.
  • the second poly(carbonate-siloxane) copolymers can have a EE/EB ratio equal to or greater than 0.05.
  • the flame-retardant composition can optionally contain 3 wt % to 15 wt. % or at least any one of, equal to any one of, or between any two of 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14 and 15 wt. % of the second poly(carbonate-siloxane) copolymer.
  • the second poly(carbonate-siloxane) copolymer can have a siloxane content of 15 wt. % to 50 wt. %, 15 wt. % to 25 wt. %, or 18 wt. % to 22 wt. %, or about 20 wt. %, or 35 wt. % to 45 wt.
  • % or 38 wt. % to 42 wt. %, or about 40 wt. % or at least any one of, equal to any one of, or between any two of 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49 and 50 wt. %.
  • the second poly(carbonate-siloxane) copolymer can have a weight average molecular weight (Mw) of 10,000 to 50,000 Da, or 10,000 to 40,000 Da or 18,000 to 35,000 Da as measured by gel permeation chromatography using a crosslinked styrene-divinyl benzene column, at a sample concentration of 1 milligram per milliliter, and as calibrated with bisphenol A polycarbonate standards.
  • the second poly(carbonate-siloxane) contains 0.5 mol. % or greater, such as 20 mol. % to 60 mol. %, such as 30 mol. % to 50 mol. %, of the siloxane units directly coupled to another siloxane unit.
  • the flame-retardant composition can include the first poly(carbonate-siloxane) copolymer and second poly(carbonate-siloxane) copolymer at a weight ratio 80:3 to 10:60.
  • the flame-retardant composition can include a filler or a reinforcing agent.
  • the filler can be a glass filler.
  • Glass fillers may include, for example, silicate spheres, cenospheres, aluminosilicate (armospheres), or the like, and/or fiberglass.
  • the glass filler may take any shape, for example as glass spheres, glass fibers, glass whiskers, or glass flakes.
  • the filler can contain glass fibers.
  • the fibers can be long fibers or short fibers that are continuous, chopped, woven, or the like.
  • the short fibers refers to a population of fibers having an average fiber length of less than or equal to 5 mm.
  • the long fibers refers to a population of fibers having an average fiber length greater than 5 mm, including for example, a population of fibers having a fiber length in the range of 5 to 20 mm, or 5 to 15 mm.
  • the fibers can have a length from 0.2 to 20 mm, preferably 0.2 to 10 mm, more preferably 0.7 to 7 mm.
  • the fibers can have various cross-sections, such as a round (or circular), flat, bilobe, triangular, rectangular, square, pentagonal, hexagonal, heptagonal, octagonal, nonagonal, decagonal or irregular section. Fibers having other cross-sections of other shapes can readily be used.
  • the average diameter of the fibers can be from 1 to 25 micrometers (gm), preferably 3 to 20 pm, more preferably 4 to 18 pm, even more preferably 5 to 17 pm.
  • the glass fibers can include a plurality of chopped glass fibers.
  • glass refers to a material, natural or synthetic, which contains silicon dioxide (SiCh) or silica as its main material.
  • the glass fibers may be textile glass fibers such as E, A, C, ECR, R, S, D, and/or NE glass fibers, and are desirably E type glass fibers.
  • the more caustic glasses such as soda lime glass, which can sometimes cause polycarbonate degradation and foaming, can be excluded or glass with low amounts of sodium and calcium can be used.
  • the fibers can further include a coating agent (i.e., sizing).
  • the coating agent can provide for a coated fiber that is bonding or non-bonding with polycarbonate or polycarbonate copolymer. Bonding fibers have a sizing on the surface of the fibers that is compatible with polycarbonate or polycarbonate copolymer, whereas non-bonding fibers have a sizing on their surface that does not promote strong adhesion to polycarbonate or the polycarbonate copolymer.
  • the non-bonding/bonding characteristics of the fibers can be controlled, for example, by coating the fibers with coatings such as an epoxide, polyvinyl acetate, particular polyester resins, starch, acrylic resins, melamine, polyvinyl chloride, polyethylene oxide, polyurethane, polyepoxide, poly(arylene ether) (e.g., phenoxide), polyvinyl alcohol, or a silane coupling agent, to change the bonding properties between the fibers and the polycarbonate or polycarbonate copolymer in the composition.
  • coatings such as an epoxide, polyvinyl acetate, particular polyester resins, starch, acrylic resins, melamine, polyvinyl chloride, polyethylene oxide, polyurethane, polyepoxide, poly(arylene ether) (e.g., phenoxide), polyvinyl alcohol, or a silane coupling agent, to change the bonding properties between the fibers and the polycarbonate or polycarbonate
  • bonding coating agents are epoxide, poly epoxide, poly(vinyl acetate), polyester, starch, poly(acrylic acid), poly(meth)acrylate, melamine, poly(vinyl chloride), poly (alkylene oxide) such as poly(C 1-3 alkylene oxide), poly (arylene ether), polyurethane, poly(vinyl alcohol), Ci-e organosilanes, or a combination thereof.
  • the bonding coating agent can be a phenolic epoxy resin, an epoxylated carboxylic acid derivative (e.g., a reaction product of an ester of a polycarboxylic acid having one or more unesterified carboxyl groups with a compound including more than one epoxy group), an epoxidized diene polymer, an epoxidized polyene polymer, or a combination thereof.
  • an epoxylated carboxylic acid derivative e.g., a reaction product of an ester of a polycarboxylic acid having one or more unesterified carboxyl groups with a compound including more than one epoxy group
  • an epoxidized diene polymer e.g., an epoxidized polyene polymer, or a combination thereof.
  • Multiple bonding coating agents can be used.
  • non-bonding coating agents include polyolefins, for example, a polyolefin wax, such as a natural or artificial olefin wax.
  • the polyolefin wax can be polyethylene wax, polypropylene wax, polybutylene wax, or copolymers thereof such as polyethylene-propylene wax and polyethylene-butylene wax.
  • An exemplary polyolefinic wax is polyethylene wax.
  • Alpha olefin-ethylene copolymers can also be useful as coating waxes.
  • the polyolefin wax may also include a polar co-monomer such as an unsaturated carboxylic acid, carboxylic ester, or carboxylic acid salt.
  • Other exemplary polyolefin coating agents include paraffin and higher alkyl (e.g., greater than Cs) siloxy and silanol compounds. Multiple non-bonding coating agents can be used.
  • the coating agent can further include a coupling agent to improve the adhesion between the coating agent and the fibers.
  • the coupling agent can be a functionalized silane such as a tri(Ci-s alkoxy)monoamino silane, tri(Ci-6 lkoxy)diamino silane, tri(Ci-6 alkoxy)(Ci-6 alkyl ureido) silane, tri(Ci-6 alkoxy)(epoxy Ci-6 alkyl) silane, tri(Ci- 6 alkoxy)(glycidoxy Ci-6 alkyl) silane, tri(Ci-s alkoxy)(mercapto Ci-6 alkyl) silane, or a combination thereof.
  • the coupling agent can be (3 -aminopropyl )tri ethoxy silane, (3-glycidoxypropyl)trimethoxysilane, (2-(3,4-epoxycyclohexyl)ethyl)triethoxysilane, (3- mercaptopropyl)trimethoxysilane, (3-(2-aminoethylamino)propyl)triethoxysilane, (3- ureidopropyl)triethoxysilane, or a combination thereof.
  • Particularly useful are aminopropyltriethoxysilane and glycidylpropyltrimethoxysilane.
  • Preferred functionality of the functionalized silane is epoxy functionality or amine functionality.
  • coating agent materials that can be included in the coating agent are anti-static agents, lubricants, wetting agents, or the like.
  • the amount of coating agent can be from 0.1 to 5 wt % based on the weight of the fibers.
  • the coating agent may be applied to the fibers by suitable means, such as immersing the fibers in the coating agent or contacting the fibers with an aqueous emulsion, or suspension of the coating.
  • suitable coating methods include using an aqueous dispersion of the sizing applied to the uncoated fiber by a roller in a continuous fashion, which can be followed by a heat treatment or curing step.
  • the fibers can be provided in the form of monofilament or multifilament fibers and can be used either alone or in combination with other types of fiber, for example, co-weaving or core/sheath, side-by-side, skin-core type or matrix and fibril constructions, or by other methods including those known to one skilled in the art of fiber manufacture.
  • Exemplary cowoven structures include, for example, glass fiber-carbon or the like.
  • Fibers can be supplied in the form of, for example, rovings, woven fibrous reinforcements, such as 0-90 degree fabrics or the like; non-woven fibrous reinforcements such as continuous strand mat, chopped strand mat, tissues, papers and felts or the like; or three-dimensional reinforcements such as braids.
  • Filaments can be made by standard processes, e.g., by steam or air blowing, flame blowing and mechanical pulling.
  • the preferred filaments for plastic reinforcement are made by mechanical pulling.
  • fiber diameter between 6 to 20 micrometers (pm) can be used with a diameter of from 10 to 15 pm being preferred.
  • the flame-retardant composition can optionally contain 20 wt. % to 79 wt. %, or 20 wt. % to 75 wt. %, or 20 wt. % to 50 wt. % or 20 wt. % to 30 wt. % or at least any one of, equal to any one of, or between any two of 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 35, 40, 45, 50, 55, 60, 65, 70 and 75 wt. % of a polycarbonate.
  • the polycarbonate can be linear or branched polycarbonate. In some aspects, the polycarbonate can be linear polycarbonate. In some aspects, the polycarbonate can be branched polycarbonate. In some aspects, combinations comprising linear polycarbonates and branched polycarbonates can be used.
  • the polycarbonate can include carbonate units as shown in formula (1).
  • the carbonate units of the polycarbonate can be derived from a dihydroxy compound such as an aromatic dihydroxy compound of formula (2) or a bisphenol of formula (3).
  • the polycarbonate can contain carbonate units derived from bisphenol A, e.g. a bisphenol A polycarbonate polymer.
  • the polycarbonate can be a bisphenol A polycarbonate homopolymer.
  • the polycarbonate such as the bisphenol A polycarbonate homopolymer can be manufactured by processes such as interfacial polymerization and melt polymerization, which are known, and are described, for example, in WO 2013/175448 Al and WO 2014/072923 Al.
  • the polycarbonate can be a linear or branched polycarbonate.
  • Branched polycarbonate can be prepared by adding a branching agent during polymerization, for example trimellitic acid, trimellitic anhydride, trimellitic trichloride, tris-hydroxyphenylethane, isatin- bis-phenol, tris-phenol TC (l,3,5-tris((phydroxyphenyl)isopropyl)benzene ), tris-phenol PA ( 4( 4(1, l-bis(p-hydroxyphenyl)-ethyl) alpha, alpha-dimethyl benzyl)phenol), 4-chloroformyl phthalic anhydride, trimesic acid, and/or benzophenone tetracarboxylic acid.
  • a branching agent for example trimellitic acid, trimellitic anhydride, trimellitic trichloride, tris-hydroxyphenylethane, isatin- bis-phenol, tris-phenol TC (l,3,
  • the branching agents can be added at a level of 0.05 to 4.0 wt. %.
  • the branched polycarbonate can contain carbonate units derived from bisphenol A.
  • the branched polycarbonate can be a homopolymer containing carbonate units derived from bisphenol A.
  • the linear polycarbonate can be a homopolymer containing carbonate units derived from bisphenol A.
  • the polycarbonate can have a weight average molecular weight of 10,000 to 100,000 g/mol, specifically 10,000 to 50,000 Daltons, as measured by gel permeation chromatography (GPC), using a crosslinked styrenedivinylbenzene column and calibrated to bisphenol A homopolycarbonate references.
  • the end-capping agent (i.e. chain stopper) for the polycarbonate can be a monohydroxy compound, a mono-acid compound, or a mono-ester compound.
  • Exemplary end-capping agents include phenols such as phenol, p-cyanophenol, and C1-C22 alkyl-substituted phenols such as p-cumyl-phenol, resorcinol monobenzoate, and p-and tertiary-butyl phenol, monoethers of diphenols, such as pmethoxyphenol, monoesters of diphenols such as resorcinol monobenzoate, functionalized chlorides of aliphatic monocarboxylic acids such as acryloyl chloride and methacryoyl chloride, and mono-chloroformates such as phenyl chloroformate, alkyl-substituted phenyl chloroformates, p-cumyl phenyl chloroformate, and toluene chloroformate. Phenol and paracumylphenol are specifically mentioned. Combinations of different end groups can be used.
  • the polycarbonate can be paracumyl
  • the polycarbonates and/or poly(carbonate-siloxane) copolymers described herein can optionally contain post-consumer recycle (PCR), e g. derived from previously manufactured articles (e.g., soda bottles, water bottles, and the like), and/or biobased components.
  • PCR post-consumer recycle
  • the flame-retardant composition contain an organophosphorus flame retardant.
  • the organophosphorus flame retardant can be non-halogenated.
  • non-halogenated flame retardant refers to flame retardants that do not intentionally contain halogens such as Cl or Br. It is understood, however, that in facilities that process multiple products a certain amount of cross contamination can occur resulting in halogen levels typically on the parts per million by weight scale. With this understanding it can be readily appreciated that “non- halogenated flame retardant” may be defined as having a halogen content of less than or equal to about 1000 parts per million by weight (ppm), less than or equal to about 500 ppm, or less than or equal to about 250 ppm.
  • the organophosphorus flame retardant can include melamine polyphosphate, melamine salt of pentaerythritol acid phosphate, dimethylmethylphosphonate, aluminum diethylphosphinate, and phosphate esters (triphenyl phosphate, triaryl phosphate (e.g., trpiphenyl phosphate (TPP), triethyl phosphate, dimethyl methylphosphonate, resorcinol bis(diphenyl phosphate) (RDP)), phosphorus containing polyols, 10-(2,5-dihydroxyphenyl)- 10H-9-oxa- 10-phospha-phenanthrene- 10-oxide, phosphorus-containing lactone-modified polyesters, ethylene glycol bis(diphenyl phosphate), neopentylglycol bis(diphenyl phosphate), or any combination thereof oligomeric phosphate ester containing flame retardant (e.g.
  • FyroflexTM Sol-DP available from ICL-IP, Inc., Ardsley, N.Y.
  • These flame retardants can be used alone or in conjunction with other flame retardants.
  • a combination of organophosphorus flame retardants can be used.
  • Two of the G groups may be joined together to provide a cyclic group, for example, diphenyl pentaerythritol diphosphate, which is described by Axelrod in U.S. Pat. No. 4,154,775.
  • aromatic phosphates may be, for example, phenyl bis(dodecyl)phosphate, phenyl bis(neopentyl)phosphate, phenyl bis(3,5,5 F -trimethylhexyl)phosphate, ethyl diphenyl phosphate, 2-ethylhexyl di(p- tolyljphosphate, bis(2-ethylhexyl) p-tolyl phosphate, tritolyl phosphate, bis(2- ethylhexyljphenyl phosphate, tri(nonylphenyl)phosphate, bis(dodecyl) p-tolyl phosphate, dibutyl phenyl phosphate, p-tolyl bis(2,5,5'-trimethylhexyl)phosphate, 2-ethylhexyl diphenyl phosphate, or the like.
  • a specific aromatic phosphate is one in which each G is aromatic, for
  • Di- or polyfunctional aromatic phosphorus-containing compounds are also useful, for example, phosphate compounds of the formulas below or
  • each G 1-7 are independently a hydrogen, hydrocarbon having 1 to about 30 carbon atoms or hydrocarbonoxy having 1 to about 30 carbon atoms; each Y is hydrogen; m 0 to 4, and n is 1 to about 30.
  • suitable di- or polyfunctional aromatic phosphorus- containing compounds include resorcinol tetraphenyl diphosphate (RDP), the bis(diphenyl)phosphate of hydroquinone and the bis(diphenyl)phosphate of bisphenol-A (BPADP), respectively, their oligomeric and polymeric counterparts, and the like. Methods for the preparation of the aforementioned di- or polyfunctional aromatic compounds are described in British Patent No. 2,043,083.
  • the organophosphorus flame retardant comprises one or more metal salts of phosphinates and phosphonates (so-called “metallophosphorous” flame retardants).
  • the metal component of the metal phosphinate or phosphonate salt can be a cation of Mg, Ca, Al, Sb, Sn, Ge, Ti, Zn, Fe, Zr, Ce, Bi, Sr, Mn, Li, Na, or K.
  • the phosphinate or phosphonate component can be dimethylphosphinate, diethylphosphinate, di-n- propylphosphinate, di-n-butylphosphinate, di-n-hexylphosphinate, dicyclohexylphosphinate, di-2-ethylhexylphosphinate, diphenylphosphinate, di-o-tolylphosphinate, dimethylphosphonate, diethylphosphonate, di-n-propylphosphonate, di-n-butylphosphonate, di-n-hexylphosphonate, dicyclohexylphosphonate, di-2-ethylhexylphoshate, diphenylphosphonate, di-o-tolylphosphonate, dimethylphosphate, diethylphosphate, di-n- propylphosphate, di-n-butylphosphate, di-n-hexylphosphate, di
  • a preferred metallophosphorus flame retardant is aluminum tris(diethylphosphinate).
  • Preparation of metallophosphorus flame retardants is described, for example, in U.S. Pat. Nos. 6,255,371 and 6,547,992 to Schlosser et al., and U.S. Pat. Nos. 6,355,832 and 6,534,673 to Weferling et al.
  • the organophosphorus flame retardant does not contain any halogens.
  • the organophosphorus flame retardant is phosphazene or phosphazene compound such as a phenoxyphosphazene oligomer.
  • the phosphazene compound comprises at least one species of the compound selected from the group consisting of a cyclic phenoxyphosphazene represented by the formula (23) below; a chainlike phenoxyphosphazene represented by the formula (24) below; and a crosslinked phenoxyphosphazene compound obtained by crosslinking at least one species of phenoxyphosphazene selected from those represented by the formulae (23) and (24) below, with a crosslinking group represented by the formula (25) below: where in the formula (23), m represents an integer of 3 to 25, Ri and R2 are the same or different and are independently a hydrogen, a hydroxyl, a C7-30 aryl group, a Cl-12 alkoxy, or a Cl-12 alkyl.
  • the phenoxyphosphazenes may also have a crosslinking group represented by the formula (25) below: where in the formula (25), A represents — C(CHs)2 — , — SO2 — , — S — , or — O — , and q is 0 or 1.
  • the phenoxyphosphazene compound has a structure represented by the formula (26) where Ri to Re can be the same of different and can be an aryl, an alkyl such as a C1-12 alkyl, a C1-12 alkoxy, , or a combination thereof.
  • Ri, R2, Rs, R4, Rs and Re can be phenyl group.
  • phenoxyphosphazenes are FP-110 manufactured and distributed by Fushimi Pharmaceutical Co., Ltd., LY202® manufactured and distributed by Lanyin Chemical Co., Ltd., and SPB-100® manufactured and distributed by Otsuka Chemical Co., Ltd.
  • the cyclic phenoxyphosphazene compound represented by the formula (23) may be exemplified by compounds such as phenoxy cyclotriphosphazene, octaphenoxy cyclotetraphosphazene, and decaphenoxy cyclopentaphosphazene, obtained by allowing ammonium chloride and phosphorus pentachloride to react at 120 to 130 °C to obtain a mixture containing cyclic and straight chain chlorophosphazenes, extracting cyclic chlorophosphazenes such as hexachloro cyclotriphosphazene, octachlorocyclotetraphosphazene, and decachloro cyclopentaphosphazene, and then substituting it with a phenoxy group.
  • the cyclic phenoxyphosphazene compound may be a compound in which m in the formula (23) represents an integer of 3 to 8.
  • the chainlike phenoxyphosphazene compound represented by the formula (24) is exemplified by a compound obtained by subjecting hexachloro cyclotriphosphazene, obtained by the above-described method, to ring-opening polymerization at 220 to 250 °C, and then substituting thus obtained chainlike dichlorophosphazene having a degree of polymerization of 3 to 10000 with phenoxy groups.
  • the chain-like phenoxyphosphazene compound has a value of n in the formula (24) of 3 to 1000, specifically 5 to 100, and more specifically 6 to 25.
  • the crosslinked phenoxyphosphazene compound may be exemplified by compounds having a crosslinked structure of a 4,4'-diphenylene group, such as a compound having a crosslinked structure of a 4,4'-sulfonyldiphenylene (bisphenol S residue), a compound having a crosslinked structure of a 2,2-(4,4'-diphenylene) isopropylidene group, a compound having a crosslinked structure of a 4,4'-oxydiphenylene group, and a compound having a crosslinked structure of a 4,4'-thiodiphenylene group.
  • a 4,4'-diphenylene group such as a compound having a crosslinked structure of a 4,4'-sulfonyldiphenylene (bisphenol S residue), a compound having a crosslinked structure of a 2,2-(4,4'-diphenylene) isopropylidene group, a compound having a crosslinked structure of a 4,4'-oxydiphen
  • the phenylene group content of the crosslinked phenoxyphosphazene compound is generally 50 to 99.9 wt%, and specifically 70 to 90 wt%, based on the total number of phenyl group and phenylene group contained in the cyclic phosphazene compound represented by the formula (23) and/or the chainlike phenoxyphosphazene compound represented by the formula (24).
  • the crosslinked phenoxyphosphazene compound may be particularly preferable if it doesn't have any free hydroxyl groups in the molecule thereof.
  • the phosphazene compound comprises the cyclic phosphazene.
  • the organophosphorus flame retardant can be an oligomeric phosphate ester containing flame retardant, or a phosphazene containing flame retardant, or any combination thereof.
  • the flame-retardant composition can contain 1 to 10 wt. %, or 1 to 8 wt. %, of the organophosphorus flame retardant such as the oligomeric phosphate ester containing flame retardant, and/or phosphazene containing flame retardant.
  • the flame-retardant composition can optionally contain anti-drips.
  • the anti-drip can be a fibril forming fluoropolymer such as polytetrafluoroethylene (PTFE).
  • PTFE polytetrafluoroethylene
  • the PTFE can be encapsulated by a rigid copolymer such as styrene-acrylonitrile copolymer (SAN).
  • SAN styrene-acrylonitrile copolymer
  • TSAN styrene-acrylonitrile copolymer
  • Encapsulated fluoropolymers can be made by polymerizing the encapsulating polymer in the presence of the fluoropolymer, for example an aqueous dispersion.
  • TSAN can provide significant advantages over PTFE, in that TSAN can be more readily dispersed in the composition.
  • the TSAN can contain 35 to 65 wt. % of PTFE and 35 to 65 wt. % of SAN, based on the total weight of TSAN.
  • the SAN can comprise 60 wt. % to 90 wt. % of styrene and 10 wt. % to 40 wt. % of acrylonitrile.
  • the fluoropolymer can be pre-blended in some manner with a second polymer, such as for, example, an aromatic polycarbonate or SAN to form an agglomerated material for use as an antidrip. Either method can be used to produce an encapsulated fluoropolymer.
  • the flame-retardant composition can optionally include 0.01 to 1 wt. %, of the anti-drip, such as TSAN.
  • the flame-retardant composition can be free of, or essentially free of, or contains less 0.01 wt. % or less than 0.005 wt. % of flame retardant salts such as alkali metal salts of perfluorinated Cl -Cl 6 alkyl sulfonates such as potassium perfluorobutane sulfonate (Rimar salt), potassium perfluoroctane sulfonate, tetraethylammonium perfluorohexane sulfonate, potassium diphenylsulfone sulfonate (KSS), and the like, sodium benzene sulfonate, sodium toluene sulfonate (NATS) and the like.
  • flame retardant salts such as alkali metal salts of perfluorinated Cl -Cl 6 alkyl sulfonates such as potassium perfluorobutane sulfonate (Rimar salt), potassium
  • the flame-retardant composition can further include one or more additives.
  • the one or more additives may include, but are not limited to, scratch-resistance agents, reinforcing agents, heat stabilizers, plasticizers, lubricants, anti-static agents, stabilizers, antioxidants, flame retardants, UV absorbers, photochemical stabilizers, optical brighteners, surfactants, processing aids, mold release agents, colorants, pigments, biocidal agents or any combinations thereof.
  • the one or more additive includes antioxidants, silver containing biocidal agents and/or mold release agents.
  • Non-limiting examples of antioxidants include sterically hindered phenolic compounds, aromatic amines, a phosphite compound, carbon black and the like.
  • Non-limiting examples of the anti-oxidant phosphite compound include organophosphites such as tris(nonyl phenyl)phosphite, tris(2,4-di-t- butylphenyl)phosphite, bis(2,4-di-t- butylphenyl)pentaerythritol diphosphite, distearyl pentaerythritol diphosphate or any combinations thereof.
  • Non-limiting examples of phenolic antioxidants include 2,6-di-ter/- butyl-4-methylphenol (CAS No. 128-37-0), pentaerythritol-tetrakis(3-(3,5-di-/e/7-butyl-4- hydroxyphenyl)propionate (CAS No. 6683-19-8), octadecyl 3-(3',5'-di-ter/-butyl-4- hydroxyphenyl)propionate (CAS No. 2082-79-3), l,3,5-trimethyl-2,4,6-tris-(3,5-di-ter/-butyl- 4-hydroxybenzyl)benzene (CAS No.
  • the flame-retardant composition can include 0.01 wt. % to 0.5 wt.
  • % of a hindered phenolic based antioxidant such as octadecyl-3- [3,5-di-tert-butyl-4-hydroxyphenyl]propionate, and/or 0.01 wt. % to 0.5 wt. % of a phosphite based antioxidant such as tris(2,4-di-t- butylphenyl)phosphite.
  • plasticizers such as dioctyl-4,5-epoxy- hexahydrophthalate; tris-(octoxycarbonylethyl)isocyanurate; tristearin; di- or polyfunctional aromatic phosphates such as resorcinol tetraphenyl diphosphate (RDP), the bis(diphenyl) phosphate of hydroquinone and the bi s(di phenyl) phosphate of bisphenol A; poly-alpha- olefins; epoxidized soybean oil; silicones, including silicone oils; esters, for example, fatty acid esters such as alkyl stearyl esters, e.g., methyl stearate, stearyl stearate, pentaerythritol tetrastearate, and the like; combinations of methyl stearate and hydro
  • Non-limiting examples of a lubricant such as mold release agent include glycerol monostearate, pentaeiythritol tetrastearate, or a combination that includes at least one of the foregoing, preferably wherein the mold release agent is glycerol monostearate.
  • the flame-retardant composition can include 0.01 to 1 wt. % of a mold release agent such as pentaerythritol tetrastearate.
  • the flame-retardant composition can contain biocidal agents.
  • the biocidal agents can be metal containing biocidal agents, such as Ag, Cu, Al, Sb, As, Ba, Bi, B, Au, Pb, Hg, Ni, Th, Sn, Zn containing biocidal agents.
  • the biocidal agent can be Ag containing biocidal agent.
  • Suitable Ag containing biocidal agent can contain silver ions, colloidal silver, silver salts, silver complexes, silver proteins, silver nanoparticles, silver functionalized clay, zeolites containing silver ions or any combinations thereof.
  • Silver salts and/or silver complexes can include silver acetate, silver benzoate, silver carbonate, silver ionate, silver iodide, silver lactate, silver laureate, silver nitrate, silver oxide, silver palpitate, silver sulfadiazine, silver sulfate, silver chloride, or any combinations thereof.
  • the flame-retardant composition can contain Ag containing biocidal agent(s) in amounts such that and the silver content in the flame-retardant composition can be 0.01 wt. % to 5 wt. %.
  • the flame-retardant compositions of certain embodiments can be made by various methods known in the art such as extrusion, injection molding or like.
  • the components such as one or any foregoing components described herein, can be mixed together and then melt-blended to form the flame-retardant composition.
  • the melt blending of the components can include use of shear force, extensional force, compressive force, ultrasonic energy, electromagnetic energy, thermal energy or combinations comprising at least one of the foregoing forces or forms of energy.
  • the one or any foregoing components described herein may be first dry blended with each other, or dry blended with any combination of foregoing components, then fed into an extruder from one or multi-feeders, or separately fed into an extruder from one or multi-feeders.
  • the filler can be first processed into a masterbatch, then fed into an extruder. The components may be fed into the extruder from a throat hopper or any side feeders.
  • the extruders used may have a single screw, multiple screws, intermeshing co-rotating or counter rotating screws, non-intermeshing co-rotating or counter rotating screws, reciprocating screws, screws with pins, screws with screens, barrels with pins, rolls, rams, helical rotors, co-kneaders, disc-pack processors, various other types of extrusion equipment, or combinations comprising at least one of the foregoing.
  • the extruder can generally be operated at a temperature higher than that necessary to cause the composition to melt and flow. In some aspects, the temperature of the melt in the extruder barrel can be maintained as low as possible in order to avoid excessive thermal degradation of the components.
  • the melted composition exits extruder through small exit holes in a die.
  • the extrudate can be quenched in a water bath and pelletized.
  • the pellets so prepared can be of any desired length (e.g., one- fourth inch long or less). Such pellets can be used for subsequent molding, shaping, or forming.
  • Mixtures including any combination of the foregoing mentioned components may be subjected to multiple blending and forming steps if desirable.
  • the composition may first be extruded and formed into pellets.
  • the pellets may then be fed into a molding machine where it may be formed into any desirable shape or product.
  • the flame-retardant composition emanating from a single melt blender may be formed into sheets or strands and subjected to post-extrusion processes such as annealing, uniaxial or biaxial orientation.
  • the flame-retardant composition(s) in certain embodiments can be comprised in an article of manufacture. Aspects of the disclosure also relate to articles including the flameretardant composition described herein.
  • the article is a film, a sheet, a molded article, a welded article, a filament or a powder.
  • the composition is incorporated into a film.
  • the film may include at least one film layer that includes the flame-retardant composition.
  • the article can be transparent.
  • the article can be shaped, formed, casted, or molded article.
  • the article can be a molded article (e.g. injection molding, extrusion, rotational molding, or blow molding), a thermoformed article, an extruded film, an extruded sheet, a honeycomb structure, one or more layers of a multi-layer.
  • the article can be a consumer product.
  • the article can an electronic housing (e.g. ), or electronic housing component, such as laser weldable electrical housing, electrical housing component, electronic housing, or electronic housing component.
  • the article can be an electronic housing for an adapter, a cell phone, a smart phone, a GPS device, a laptop computer, a tablet computer, an e-reader, a copier, radar, lidar, an electrical junction box, an electrical connector, an electrical vehicle charger, an outdoor electrical enclosure, a smart meter enclosure, a smart grid power node, a photovoltaic frame, a miniature circuit breaker or a solar apparatus
  • the article can be a component of a consumer electronic device selected from gaming console, a gaming controller, a portable gaming device, a cellular telephone, a television, a personal computer, a tablet computer, a laptop computer, a personal digital assistant, a portable media player, a, a digital camera, a portable music player, an appliance, a power tool, a robot, a toy, a greeting card, a home entertainment system, and active loudspeaker, or a soundbar.
  • a consumer electronic device selected from gaming console, a gaming controller, a portable gaming device, a cellular telephone, a television, a personal computer, a tablet computer, a laptop computer, a personal digital assistant, a portable media player, a, a digital camera, a portable music player, an appliance, a power tool, a robot, a toy, a greeting card, a home entertainment system, and active loudspeaker, or a soundbar.
  • the article can be an automotive, scooter, and motorcycle exterior and interior component such as panels, quarter panels, rocker panels, trim, fenders, battery covers, doors, deck-lids, trunk lids, hoods, bonnets, roofs, bumpers, fascia, grilles, mirror housings, pillar appliques, cladding, body side moldings, wheel covers, hubcaps, door handles, spoilers, window frames, headlamp bezels, headlamps, tail lamps, tail lamp housings, tail lamp bezels, license plate enclosures, or roof racks, or running boards.
  • Aspect 1 is directed to a flame-retardant composition containing 10 wt. % to 85 wt. % of a first poly(carbonate-siloxane) copolymer, wherein the first poly(carbonate- siloxanejcopolymer is a random copolymer with less than 0.5 mol. % of siloxane units that are directly coupled to other siloxane units, and wherein the composition comprises a total siloxane content of 2 wt. % to 15 wt. %; 10 wt. % to 30 wt. % of a filler comprising glass, preferably a glass fiber; 1 wt. % to 10 wt.
  • Aspect 2 is directed to the flame-retardant composition of aspect 1, wherein the first poly(carbonate-siloxane) copolymer has a siloxane content of 5 wt. % to 25 wt. %, based on the total weight of the first poly(carbonate-siloxane) copolymer.
  • Aspect 3 is directed to the fl me-retardant composition of aspects 1 or 2, wherein the composition contains less than 0.1 wt. %, preferably less than 0.05 wt. %, more preferably less than 0.01 wt. % of each of chlorine and bromine, or is free of each of chlorine and bromine.
  • Aspect 4 is directed to the flame-retardant composition of any one of aspects 1 to 3, wherein the composition contains less than 0.1 wt. %, preferably less than 0.05 wt. %, more preferably less than 0.01 wt. %, of halogen, or most preferably is free of halogen.
  • Aspect 5 is directed to the flameretardant composition of any one of aspects 1 to 4, further containing 3 wt. % to 15 wt. % of a second poly(carbonate-siloxane) copolymer, wherein the copolymer has a siloxane content of 15 wt. % to 50 wt. %.
  • Aspect 6 is directed to the flame-retardant composition of any one of aspects 1 to 5, further containing 20 wt. % to 79 wt. % of a polycarbonate.
  • Aspect 7 is directed to the flame-retardant composition of any one of aspects 1 to 6, further containing 0.01 wt. % to 1 wt. % of an antioxidant, 0.01 wt.
  • Aspect 8 is directed to the flame-retardant composition of any one of aspects 1 to 3 and 5 to 7, containing 75 wt. % to 85 wt. % of the first polycarbonatesiloxane) copolymer; 10 wt. % to 20 wt. % of the filler comprising glass; and 1 wt. % to 10 wt. % of the organophosphorus flame retardant.
  • Aspect 9 is directed to the flame-retardant composition of aspect 8, wherein the composition contains less than 0.1 wt.
  • aspects 10 is directed to the flame-retardant composition of aspect 8, further containing 0.01 wt. % to 1 wt. % of the mold release, 0.01 wt. % to 0.5 wt. % of a hindered phenolic based antioxidant, and 0.01 wt. % to 0.5 wt. % of a phosphite based antioxidant, wherein the composition contains less than 0.1 wt. %, preferably less than 0.05 wt. %, more preferably less than 0.01 wt.
  • aspects 11 is directed to the flame-retardant composition of aspect 8, further containing 0.01 wt. % to 1 wt. % of the mold release, 0.01 wt. % to 0.5 wt. % of a hindered phenolic based antioxidant, 0.01 wt. % to 0.5 wt. % of a phosphite based antioxidant, and 0.01 wt. % to 1 wt. % of the anti-drip, wherein the composition contains less than 0.1 wt. %, preferably less than 0.05 wt. %, more preferably less than 0.01 wt.
  • Aspect 12 is directed to the flame-retardant composition of any one of aspects 1 to 3 and 5 to 7, containing 60 wt. % to 80 wt. % of the first poly(carbonate-siloxane) copolymer; 3 wt. % to 12 wt. % of the second poly(carbonate-siloxane) copolymer; 10 wt. % to 30 wt. % of the filler comprising glass; and 1 wt. % to 10 wt. % of the organophosphorus flame retardant.
  • Aspect 13 is directed to the flame-retardant composition of aspect 12, wherein the composition contains less than 0.1 wt. %, preferably less than 0.05 wt. %, more preferably less than 0.01 wt. %, of halogen, or most preferably is free of halogen.
  • Aspect 14 is directed to the flameretardant composition of aspect 12, further containing 0.01 wt. % to 1 wt. % of the mold release, 0.01 wt. % to 0.5 wt. % of a hindered phenolic based antioxidant, and 0.01 wt. % to 0.5 wt. % of a phosphite based antioxidant, wherein the composition contains less than 0.1 wt.
  • Aspect 15 is directed to the flame-retardant composition of aspect 12, further containing 0.01 wt. % to 1 wt. % of the mold release, 0.01 wt. % to 0.5 wt. % of a hindered phenolic based antioxidant, 0.01 wt % to 0.5 wt. % of a phosphite based antioxidant, and 0.01 wt. % to 1 wt. % of the anti-drip, wherein the composition contains less than 0.1 wt.
  • Aspect 16 is directed to the flameretardant composition of any one of aspects 1 to 3 and 5 to 7, containing 70 wt. % to 80 wt. % of the first poly(carbonate-siloxane) copolymer; 3 wt. % to 12 wt. % of the second poly(carbonate-siloxane) copolymer; 10 wt. % to 20 wt. % of the filler comprising glass; and 1 wt. % to 10 wt. % of the organophosphorus flame retardant.
  • Aspect 17 is directed to the flame-retardant composition of aspect 16, wherein the composition contains less than 0.1 wt. %, preferably less than 0.05 wt. %, more preferably less than 0.01 wt. %, of halogen, or most preferably is free of halogen.
  • Aspect 18 is directed to the flame-retardant composition of aspect 16, further containing 0.01 wt. % to 1 wt. % of the mold release, 0.01 wt. % to 0.5 wt. % of a hindered phenolic based antioxidant, and 0.01 wt. % to 0.5 wt. % of a phosphite based antioxidant, wherein the composition contains less than 0.1 wt.
  • Aspect 19 is directed to the flame-retardant composition of aspect 16, further containing 0.01 wt. % to 1 wt. % of the mold release, 0.01 wt. % to 0.5 wt. % of a hindered phenolic based antioxidant, 0.01 wt. % to 0.5 wt. % of a phosphite based antioxidant, and 0.01 wt. % to 1 wt. % of the anti-drip, wherein the composition contains less than 0.1 wt.
  • Aspect 20 is directed to the flame-retardant composition of any one of aspects 1 to 3 and 5 to 7, containing 50 wt. % to 65 wt. % of the first poly(carbonate-siloxane) copolymer; 20 wt. % to 30 wt. % of one or more bisphenol A polycarbonate polymers; 10 wt. % to 20 wt. % of the filler comprising glass; and 1 wt. % to 10 wt. % of the organophosphorus flame retardant.
  • Aspect 21 is directed to the flame-retardant composition of aspect 20, wherein the composition contains less than 0.1 wt. %, preferably less than 0.05 wt. %, more preferably less than 0.01 wt. %, of halogen, or most preferably is free of halogen.
  • Aspect 22 is directed to the flame-retardant composition of aspect 20, further containing 0.01 wt. % to 1 wt. % of the mold release, 0.01 wt. % to 0.5 wt. % of a hindered phenolic based antioxidant, and 0.01 wt. % to 0.5 wt. % of a phosphite based antioxidant, wherein the composition contains less than 0.1 wt.
  • Aspect 23 is directed to the flame-retardant composition of aspect 20, further containing 0.01 wt. % to 1 wt. % of the mold release, 0.01 wt. % to 0.5 wt. % of a hindered phenolic based antioxidant, 0.01 wt. % to 0.5 wt. % of a phosphite based antioxidant, and 0.01 wt. % to 1 wt. % of the anti-drip, wherein the composition contains less than 0.1 wt.
  • Aspect 24 is directed to the flame-retardant composition of any one of aspects 1 to 23, having a laser transmission greater than 70 % at a 980 nm at a thickness of 1.5 mm.
  • Aspect 25 is directed to the flameretardant composition of any one of aspects 1 to 24, wherein the composition is an extruded, a blow-molded, an injection-molded, rotational molded, and/or thermoformed article.
  • Aspect 26 is directed to the flame-retardant composition of any one of aspects 1 to 25, wherein the composition is comprised in an article of manufacture.
  • Aspect 27 is directed to the flameretardant composition of aspect 26, wherein the article of manufacture is an electronic housing, or electronic housing component.
  • the EE/EB ratio refers to the molar ratio of the polydiorganosiloxane units directly coupled to another polydiorganosiloxane unit (EE) relative to the polydiorganosiloxane units directly coupled to a BPA unit (EB) for the PDMS-BPA polycarbonate copolymer.
  • the EE/EB ratio was determined via nuclear magnetic resonance spectroscopy (NMR).
  • compositions were prepared by pre-blending all constituents in a dry -blend and tumble mixed for 15 minutes.
  • the pre-blend was fed directly to a co-rotation twin screw extruder under the conditions shown in Table IB.
  • the extrudate was pelletized and dried in a dehumidifying dryer at about 120° C for about 2-4 hours.
  • the dried pellets were injection molded in an ENGEL molding machine to form appropriate test samples under the conditions shown in Table IB.
  • Example compositions and their properties are shown in Tables 2, 3, 4 and 5
  • MVR Melt volume rate
  • Table 2 Varying flame retardants.
  • Table 2 shows that the addition of flame retardant salts like Rimar (Cl) and KSS (C2) in combination with small quantities of anti drip (TSAN) result in V0 performance at 1.5 mm thickness, but have relatively poor transmission with values of 54 and 34% respectively.
  • organophosphorus flame retardant additives e.g. Sol-DP and phosphazene are used in polycarbonate -siloxane compositions with glass fiber, unexpectedly high transmission values, above 70% are achieved (E3-E7), with (E4) and without (E3, E5-E7) anti-drip. All compositions are able to achieve a V0 rating at 1.5 mm and when increasing the organophosphorus flame retardant loading even at 1.2 mm (E5).
  • compositions of Table 3 show replacing part of the polycarbonate-siloxane with an equivalent amount of a BPA polycarbonate, while keeping the total siloxane content of the composition above 3 wt. %, still maintains high transmission (greater than 70 %) allows tuning the composition for properties like flow using PC homopolymers as blend components .
  • Composition E9 and E3 have substantially low halogen content.
  • Table 4 Replacing the first polycarbonate-siloxane with a second polycarbonate-siloxane polycarbonate
  • compositions of Table 4 show replacing part of the polycarbonate-siloxane with an equivalent amount of the second PC-siloxane polycarbonate, while keeping the total siloxane content of the composition above 3 wt. %, still good transmission (greater than 70 %) can be obtained. This allows adjusting the composition for properties like flow and impact using combinations of different PC-siloxane copolymers without affecting the high transmission and V0 rating at 1.5 mm . Results presented in tables 2, 3 and 4 shows transmission depends largely on type of flame retardants used. Composition E12, E13 and E3 have substantially low halogen content.
  • Method of examples described herein can be machine or computer implemented at least in part. Some examples can include a computer-readable medium or machine-readable medium encoded with instructions operable to configure an electronic device to perform methods as described in the above examples.
  • An implementation of such methods can include code, such as microcode, assembly language code, a higher-level language code, or the like. Such code can include computer readable instructions for performing various methods. The code may form portions of computer program products. Further, in an example, the code can be tangibly stored on one or more volatile, nontransitory, or non-volatile tangible computer- readable media, such as during execution or at other times.
  • Examples of these tangible computer-readable media can include, but are not limited to, hard disks, removable magnetic disks, removable optical disks (e.g., compact disks and digital video disks), magnetic cassettes, memory cards or sticks, random access memories (RAMs), read only memories (ROMs), and the like.

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Abstract

L'invention concerne des compositions ignifuges, des procédés de fabrication des compositions, et des composites contenant les compositions. La composition ignifuge peut contenir de 10 % en poids à 85 % en poids d'un premier copolymère de poly(carbonate-siloxane), 10 % en poids à 30 % en poids d'une charge contenant du verre, de préférence une fibre de verre, et 1 % en poids à 10 % en poids d'un agent ignifuge organophosphoré. Le premier copolymère de poly(carbonate-siloxane) peut être un copolymère statistique avec moins de 0,5 % en moles d'unités siloxane qui sont directement couplées à d'autres unités siloxane, et contient une teneur en siloxane de 5 % en poids à 25 % en poids. La composition a une teneur totale en siloxane de 2 % en poids à 15 % en poids et la composition a une transmission supérieure à 70 % à une épaisseur de 1,5 mm et/ou un indice UL94 de V0 à une épaisseur de 1,5 mm.
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