WO2020079565A1 - Préimprégné composite renforcé par des fibres continues formé d'un polyester ignifuge - Google Patents

Préimprégné composite renforcé par des fibres continues formé d'un polyester ignifuge Download PDF

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Publication number
WO2020079565A1
WO2020079565A1 PCT/IB2019/058742 IB2019058742W WO2020079565A1 WO 2020079565 A1 WO2020079565 A1 WO 2020079565A1 IB 2019058742 W IB2019058742 W IB 2019058742W WO 2020079565 A1 WO2020079565 A1 WO 2020079565A1
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weight percent
bisphenol
poly
terephthalate
units
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PCT/IB2019/058742
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English (en)
Inventor
Bart VANDORMAEL
Theodosia Kourkoutsaki
Roeland L.H.M. VERLAEK
Vaidyanath Ramakrishnan
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Sabic Global Technologies B.V.
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Publication of WO2020079565A1 publication Critical patent/WO2020079565A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C08J5/249—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs characterised by the additives used in the prepolymer mixture
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
    • C08J5/042—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with carbon fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
    • C08J5/043—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with glass fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/046—Reinforcing macromolecular compounds with loose or coherent fibrous material with synthetic macromolecular fibrous material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/10—Reinforcing macromolecular compounds with loose or coherent fibrous material characterised by the additives used in the polymer mixture
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
    • C08J5/243—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using carbon fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
    • C08J5/244—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using glass fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2469/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
    • 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
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
    • 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
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
    • C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
    • 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
    • C08K5/5399—Phosphorus bound to nitrogen

Definitions

  • Fiber-containing composite materials generally include one or more layers of fiber materials embedded in a matrix material, and can include, for example, unidirectional (UD) tapes and prepregs.
  • UD unidirectional
  • Such composites can have high strength and stiffness as compared, for example, to an extruded plastic sheet without any fiber reinforcement.
  • Composites can also advantageously be light weight, especially as compared to metallic sheets having comparable mechanical properties.
  • Composite materials can be useful for applications in housing parts for electronic applications, as well as in the automotive and aerospace industries.
  • thermoplastic compositions and composites prepared therefrom which can advantageously exhibit good structural performance, flame retardancy, chemical resistance, and heat performance.
  • the present disclosure is directed to thermoplastic compositions including polyester, a phosphorus-containing flame retardant, and optionally one or more of a polycarbonate, an impact modifier, and a flame retardant synergist.
  • the present inventors have discovered that such compositions can be useful for the preparation of fiber reinforced composite materials having desirable properties when the components are present in particular amounts.
  • the fiber reinforced composites and laminates including the thermoplastic composition can exhibit good structural performance, flame retardancy, chemical resistance, and heat performance.
  • an aspect of the present disclosure is a composite.
  • the composite has at least one layer of a fibrous material and a thermoplastic matrix.
  • the fibrous material can be embedded in the thermoplastic matrix.
  • the composite of the present disclosure can be, for example, a unidirectional (UD) composite, for example, a tape or a prepreg.
  • a UD composite is a composite having fibers that extend in substantially one direction.
  • a UD tape or prepreg can be a thin strip or band of continuous UD fibers (as further described below) impregnated with the thermoplastic composition.
  • UD tapes can have a width of 1 to 600 centimeters, and a thickness of less than 1 millimeter.
  • UD tapes can be provided on a spool or reel or in sheet forms, including in bundled sheets.
  • the fibrous material can include glass fibers, carbon fibers, oxide and non-oxide ceramic fibers (e.g., aluminum oxides, silicon oxides, boron oxides, titanium oxides, zirconium oxides, and the like, quartz, basalt, or a combination thereof), polymeric fibers (e.g., aramid fibers, liquid crystal polymer fibers, polyphenylene sulfide fibers, polyether ketone fibers, polyether ether ketone fibers, polyetherimide fibers, poly p-phenylene-2,6-benzobisoxazole, and the like, or a combination thereof), natural fibers (e.g.
  • the fibers can be chopped or woven into fabric.
  • the fibers can also be randomly oriented or can be unidirectional in orientation.
  • the fibrous material can be a continuous fibrous material, a woven fibrous material, a non-crimp fabric, a veil, a random mat, a knitted fibrous material, a nonwoven material (i.e., a fibrous material comprising a plurality of fibers which are interlaid but not in an identifiable manner as in a knitted fabric, formed by, for example, melt blowing processes, melt spinning processes, air laying processes, bonded carded web processes, and the like), or a combination thereof.
  • the fibrous material can be configured as a unidirectional fiber tape having a plurality of parallel fibers arranged therein.
  • the average fiber diameter can be 4 to 500 micrometers (pm). Within this range, the average fiber diameter can be up to 400 pm, or up to 300 pm, or up to 200 pm, or up to 100 pm, or up to 50 pm, or up to 25 pm. Also within this range, the average fiber diameter can be at least 5 pm or at least 10 pm or at least 50 pm, or at least 100 pm. The average fiber diameter can be 4 to 25 pm, particularly preferably in the range from 6 to 18 pm. Preferably, the fibers can have a length that is at least 100 times the fiber diameter.
  • Fibrous materials can vary in size.
  • Woven materials can be woven from glass, ceramic, or polymeric fibers. Fibers can be sized from 100 to 3000 tex (grams per 1000 meters). Woven materials can be made from carbon fibers. Three to 60K fibers can be used, where 1K denotes that 1000 individual fibers have been combined into one yam.
  • Carbon fiber wovens made of 200 tex (3K), 400 tex (6K), 800 tex (12K) or 1600 tex (24K) filament yams can be used.
  • Carbon fiber wovens (e.g., prior to forming the composite material with the thermoplastic composition) can have an average basis weight of 20-1500 g/m 2 , particularly preferably in the range from 20 to 500 g/m 2 .
  • Glass fiber wovens can have an average basis weight of 30 to 1500 g/m 2 , particularly 50 to 600 g/m 2 .
  • Suitable glass fibers can generally be of any cross-sectional shape, including round, flat, oblong, hollow, elliptical, oval, cocoon shape, bean shape, cmciform shape, triangular shape, and the like.
  • the glass fibers can have a circular cross-sectional area and an average filament diameter of 6 to 18 pm, preferably 9 to 17 pm, or a flat shape and noncircular cross-sectional area where the principal cross-sectional axis has an average width of 6 to 40 pm and the secondary cross- sectional axis has an average width of 3 to 20 pm.
  • the glass fibers can be E-glass fibers, A-glass fibers, C-glass fibers, D-glass fibers, S-glass fibers, or R-glass fibers.
  • E glass fibers can be preferred.
  • S-glass fibers can be preferred.
  • Fibers suitable for use in the present disclosure can have a tensile strength of 700 to 5500 MPa, a tensile modulus of 50 to 500 GPa, or both.
  • An exemplary ceramic fiber material comprises polycrystalline alumina fiber, for example available as NEXTEL 610, from 3M.
  • Exemplary woven ceramic fabrics can include, for example, NEXTEL Structural Fabric DF-6 and NEXTEL Structural Fabric DF-l 1 (woven NEXTEL 610 continuous ceramic oxide fiber rovings), available from 3M.
  • NEXTEL fibers are described in US Patent No. 3,795,524, which is incorporated herein by reference in its entirety.
  • the composite further includes a thermoplastic matrix.
  • the thermoplastic matrix includes a thermoplastic composition.
  • the thermoplastic composition includes a polyester, a phosphorus-containing flame retardant, and optionally, one or more of a polycarbonate, an impact modifier, and a flame retardant synergist.
  • the polyester can include, for example, polyesters having repeating units of formula (1) O O
  • J is a divalent group derived from a dihydroxy compound (including a reactive derivative thereof), and can be, for example, a C MO alkylene, a C5-20 cycloalkylene, a Ce-2o arylene, or a
  • polyoxyalkylene in which the alkylene groups contain 2 to 6 carbon atoms, specifically 2, 3, or 4 carbon atoms; and T is a divalent group derived from a dicarboxylic acid (including a reactive derivative thereof), and can be, for example, a C1-20 alkylene, a C5-20 cycloalkylene, or a Ce-20 arylene. Copolyesters containing a combination of different T or J groups can be used.
  • the polyester units can be branched or linear.
  • Polyesters that can be used can include aromatic polyesters, poly((Ci-io alkylene) esters) including poly((Ci-io alkylene) arylates), and poly(C5-20 cycloalkylene diesters).
  • Aromatic polyesters can have a polyester structure according to formula (1), wherein J and T are each aromatic groups as described above.
  • Aromatic polyesters can include poly(isophthalate-terephthalate-resorcinol) esters, poly(isophthalate-terephthalate-bisphenol A) esters, poly[(isophthalate-terephthalate-resorcinol) ester-co- (isophthalate-terephthalate-bisphenol A)] ester, or a combination thereof.
  • poly((Ci- 8 alkylene) arylates) can have a polyester structure according to the above formula, wherein T comprises groups derived from aromatic dicarboxylates, cycloaliphatic dicarboxylic acids, or derivatives thereof. Examples of specifically useful T groups include 1,2-, 1,3-, and l,4-phenylene; 1,4- and 1,5- naphthylenes; cis- or trans-l, 4-cyclohexylene; and the like.
  • the poly((Ci- 8 alkylene) arylate) is a poly((Ci- 8 alkylene) terephthalate).
  • useful alkylene groups J include, for example, ethylene, 1, 4-butylene, and bis-((C2-io alkylene)- disubstituted cyclohexane) including cis- or trans-l, 4-(cyclohexylene)dimethylene.
  • poly((Ci- 8 alkylene) terephthalates) examples include polyethylene terephthalate) (PET), poly(l, 4-butylene terephthalate) (PBT), and poly(n-propylene terephthalate) (PPT). Also useful are poly((Ci- 8 alkylene) naphthoates), such as polyethylene naphthanoate) (PEN), and poly(butylene naphthanoate) (PBN).
  • a poly(cycloalkylene diester) is poly(l,4-cyclohexanedimethylene terephthalate) (PCT). Combinations of the foregoing polyesters can also be used.
  • Copolymers including alkylene terephthalate repeating ester units with other ester groups can also be useful.
  • Specific ester units can include different alkylene terephthalate units, which can be present in the polymer chain as individual units, or as blocks of poly((Ci- 8 alkylene) terephthalates).
  • Copolymers of this type include poly(cyclohexanedimethylene terephthalate)-co-poly(ethylene terephthalate), abbreviated as PETG where the polymer includes greater than or equal to 50 mol% of polyethylene terephthalate), and abbreviated as PCTG where the polymer includes greater than 50 mol% of poly(l,4-cyclohexanedimethylene terephthalate).
  • Poly((C5 i2 cycloalkylene) diester)s can also include poly((C5 i2 cycloalkylene) cyclohexanedicarboxylate)s.
  • poly((C5 i2 cycloalkylene) cyclohexanedicarboxylate)s can also include poly((C5 i2 cycloalkylene) cyclohexanedicarboxylate)s.
  • PCCD poly( 1, 4-cyclohexane-dimethanol- 1,4- cyclohexanedicarboxylate)
  • J is a l,4-cyclohexanedimethylene group derived from l,4-cyclohexanedimethanol
  • T is a cyclohexane ring derived from cyclohexanedicarboxylate or a chemical equivalent thereof, and can include the cis-isomer, the trans-isomer, or a combination thereof.
  • the polyester can be produced from recycled streams.
  • poly(butylene terephthalate) can be derived from recycled polyethylene terephthalate) (PET), for example used PET soft drink bottles.
  • PET polyethylene terephthalate
  • PBT derived from a recycled component contains a polyethylene terephthalate) residue, e.g., a material such as ethylene glycol and isophthalic acid groups (components that are not present in virgin, monomer-based PBT).
  • compositions and articles made from the composition comprising PBT from a recycled stream can exhibit similar performance properties as compositions and articles made from compositions containing monomer-based PBT.
  • Use of PBT from recycled streams can provide a valuable way to effectively use underutilized scrap PET (from post-consumer or post-industrial streams) in PBT- containing compositions, thereby conserving non-renewable resources and reducing the formation of greenhouse gases, e.g., CO2.
  • a PBT that is derived from recycled streams are available under the trade name VALOX iQ PBT from SABIC, including VALOX iQ 315 and VALOX iQ 195.
  • the modified PBT is further described in U.S. Patent No. 7,902,263, which is incorporated herein by reference in its entirety.
  • the modified PBT can be derived from the poly(ethylene terephthalate) component by any method that involves depolymerization of the polyethylene terephthalate) component and polymerization of the depolymerized poly(ethylene terephthalate) component with 1 ,4-butanediol to provide the modified PBT.
  • the modified poly(butylene terephthalate) component can be made by a process that involves depolymerizing a poly(ethylene terephthalate) component selected from the group consisting of poly(ethylene terephthalate) and poly(ethylene terephthalate)copolymers, with a l,4-butanediol component at a temperature from 180° C.
  • a molten mixture containing a component selected from the group consisting of oligomers containing ethylene terephthalate moieties, oligomers containing ethylene isophthalate moieties, oligomers containing diethylene terephthalate moieties, oligomers containing diethylene isophthalate moieties, oligomers containing butylene terephthalate moieties, oligomers containing butylene isophthalate moieties, covalently bonded oligomeric moieties containing at least two of the foregoing moieties, l,4-butanediol, ethylene glycol, and combinations thereof; and agitating the molten mixture at sub-atmospheric pressure and increasing the temperature of the molten mixture to an elevated temperature under conditions sufficient to form a modified PBT
  • the polyester can be a poly((Ci- 8 alkylene) terephthalate).
  • the polyester can be poly(butylene terephthalate), poly(ethylene terephthalate), glycol-modified polyethylene terephthalate), glycol-modified poly(cyclohexylene dimethylene terephthalate), spiro-glycol-modified poly(ethylene terephthalate), poly(cyclohexylene dimethylene terephthalate), poly(trimethylene terephthalate), glycol- modified poly(butylene terephthalate), or a combination thereof.
  • the polyester is poly(butylene terephthalate), poly(ethylene terephthalate), or a combination thereof, preferably a poly(butylene terephthalate).
  • polyesters can include, but are not limited to, poly(butylene terephthalate) sold by SABIC under the trade name VALOX, poly(butylene terephthalate) sold by DuPont under the trade name CRASTIN, polyethylene terephthalate) sold by DuPont under the trade name MYLAR, polycaprolactone sold by DURECT under the trade name LACTEL, poly(lactic acid) sold by Nature Works LLC under the trade name INGEO, copolyester having repeating units derived from dimethyl terephthalate, 2,2,4,4-tetramethyl-l,3-cyclobutanediol, and l,4-cyclohexanedimethanol sold by Eastman Chemical Company under the trade name TRITAN.
  • the polyester can be present in an amount of 30 to 90 wt%, or 35 to 88 wt%, or 35 to 70 wt%, or 37 to 56 wt%, each based on the total weight of the composition.
  • the composition further includes a phosphorus -containing flame retardant.
  • the phosphorus-containing flame retardant can include a phosphate ester, a phosphinate, a phosphazene, a polyphosphonate or a combination thereof.
  • Aromatic phosphates include, for example, phenyl bis(dodecyl) phosphate, phenyl bis(neopentyl) phosphate, phenyl bis(3,5,5'-trimethylhexyl) phosphate, ethyl diphenyl phosphate, 2-ethylhexyl di(p-tolyl) phosphate, bis(2-ethylhexyl) p-tolyl phosphate, tritolyl phosphate, bis(2-ethylhexyl) phenyl phosphate, tri(nonylphenyl) phosphate, bis(dodecyl) p-tolyl phosphate, dibutyl phenyl phosphate, 2-chloroethyl diphenyl phosphate, p-tolyl bis(2,5,5'-trimethylhexyl) phosphate, 2- ethylhexyl diphenyl phosphate,
  • a specific aromatic phosphate is one in which each G is aromatic, for example, triphenyl phosphate, tricresyl phosphate, isopropylated triphenyl phosphate, and the like.
  • Di- or polyfunctional aromatic phosphate esters are also useful, for example, compounds of the formula
  • each G 2 is independently a hydrocarbyl or hydrocarbyloxy having 1 to 30 carbon atoms, and n is
  • Specific aromatic phosphate esters have two or more phosphorus-containing groups, and are inclusive of acid esters of the formula
  • R 16 , R 17 , R 18 , and R 19 are each independently Ci- 8 alkyl, C5-6 cycloalkyl, Ce-2o aryl, or C7-12 arylalkylene, each optionally substituted by C 1-12 alkyl, specifically by C H alkyl and X is a mono- or poly-nuclear aromatic Ce-3o moiety or a linear or branched C2-30 aliphatic radical, which can be OH- substituted and can contain up to 8 ether bonds, provided that at least one of R 16 , R 17 , R 18 , R 19 , and X is an aromatic group.
  • R 16 , R 17 , R 18 , and R 19 are each independently C H alkyl, naphthyl, phenyl(Ci-4)alkylene, or aryl groups optionally substituted by C H alkyl. Specific aryl moieties are cresyl, phenyl, xylenyl, propylphenyl, or butylphenyl.
  • X is a mono- or polynuclear aromatic Ce-3o moiety derived from a diphenol.
  • n is each independently 0 or 1 ; in some embodiments n is equal to 1.
  • q is from 0.5 to 30, from 0.8 to 15, from 1 to 5, or from 1 to 2.
  • X can be represented by the following divalent groups, or a combination thereof.
  • each of R 16 , R 17 , R 18 , and R 19 can be aromatic, i.e., phenyl, n is 1, and p is 1-5, specifically 1-2.
  • at least one of R 16 , R 17 , R 18 , R 19 , and X corresponds to a monomer used to form the polycarbonate, e.g., bisphenol A or resorcinol.
  • X is derived especially from resorcinol, hydroquinone, bisphenol A, or diphenylphenol
  • R 16 , R 17 , R 18 , R 19 is aromatic, specifically phenyl.
  • a specific phosphate ester of this type is resorcinol bis(diphenyl phosphate), also known as RDP.
  • Another specific class of aromatic organophosphorus compounds having two or more phosphorus-containing groups are compounds of the formula
  • R 16 , R 17 , R 18 , R 19 , n, and q are as defined for formula (19) and wherein Z is C 1-7 alkylidene, C 1-7 alkylene, C 5-12 cycloalkylidene, -O-, -S-, -SO 2 -, or -CO-, specifically isopropylidene.
  • a specific aromatic organophosphorus compound of this type is bisphenol A bis(diphenyl phosphate), also known as BPADP, wherein R 16 , R 17 , R 18 , and R 19 are each phenyl, each n is 1, and q is from 1 to 5, from 1 to 2, or 1.
  • BPADP bisphenol A bis(diphenyl phosphate
  • R 16 , R 17 , R 18 , and R 19 are each phenyl, each n is 1, and q is from 1 to 5, from 1 to 2, or 1.
  • the oligomeric or polymeric counterparts of the above phosphate esters can also be
  • the phosphinate flame retardant can be a metal dialkyl phosphinate.
  • metal dialkylphosphinate refers to a salt including at least one metal cation and at least one dialkylphosphinate anion.
  • the metal dialkylphosphinate has the formula
  • R a and R b are each independently C i -G, alkyl; M is calcium, magnesium, aluminum, or zinc; and d is 2 or 3.
  • R a and R b include methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, and n- pentyl.
  • R a and R b can each be ethyl, M can be zinc, and d can be 2 (that is, the metal dialkylphosphinate can be zinc diethyl phosphinate).
  • the metal dialkylphosphinate can be in particulate form.
  • the metal dialkylphosphinate particles can have a median particle diameter (D50) less than or equal to 40 micrometers, or, more specifically, a D50 less than or equal to 30 micrometers, or, even more specifically, a D50 less than or equal to 25 micrometers, as determined using laser diffraction particle size analysis.
  • D50 median particle diameter
  • the phosphazene can preferably be a bis(phenoxy)phosphazene.
  • bis(phenoxy)phosphazene can be oligomeric or polymeric, and it can be cyclic or linear. In some embodiments, the bis(phenoxy)phosphazene is cyclic and has the structure
  • m is an integer of 3 to 25; x and y are each independently 0, 1, 2, 3, 4, or 5; and each occurrence of R 4 and R 5 is halogen, C1-12 alkyl, or C1-12 alkoxyl.
  • the bis(phenoxy)phosphazene is linear and has the structure
  • n is an integer from 3 to 10,000;
  • Y 1 represents a -P(OPh)4 group or a -P(0)(OPh) 2 group;
  • x and y are each independently 0, 1, 2, 3, 4, or 5; and each occurrence of R 4 and R 5 is halogen, C1-C12 alkyl, or C1-C12 alkoxyl.
  • the polyphosphonate can be as described in US2007/203269, W02007/022008 W02007/065094 W02009/018336, each of which are incorporated herein by reference in their entirety.
  • the polyphosphonate can be a homopolymer.
  • the polyphosphonate homopolymer is typically the product of bisphenol A and tetraphenyl phosphonium phenolate, such as FRX-100, the synthesis of which is described in US2011/0237695, which is incorporated herein by reference in its entirety.
  • the phosphorus-containing flame retardant can be present in a total amount of 5 to 50 wt%, based on the total weight of the composition. Within this range, the phosphorus -containing flame retardant can be present in an amount of 10 to 50 wt%, or 20 to 50 wt%.
  • the phosphorus- containing flame retardant can comprise 15 to 35 wt%, preferably 20 to 30 wt% of the phosphinate, 5 to 30 wt%, preferably 20 to 30 wt% of the phosphate ester, 3 to 10 wt% of the phosphazene, or 15 to 50 wt%, preferably 25 to 45 wt% of the polyphosphonate, based on the total weight of the composition, provided that the total amount of phosphorus-containing flame retardant is in the range of 5 to 50 wt%.
  • the composition can include 5 to 30 wt% of the phosphate ester.
  • the composition can include 20 to 30 wt% of the phosphate ester.
  • the composition can include 3 to 10 wt% of the phosphazene, 25 to 45 wt% of the polyphosphonate, or both.
  • the composition can include 15 to 35 wt% of the phosphinate.
  • the composition can exclude flame retardants other than the phosphorus -containing flame retardants described above.
  • Halogenated flame retardants can be excluded from the present composition.
  • Non-brominated and non-chlorinated phosphorus-containing flame retardants can be preferred.
  • the composition can optionally further include one or more of a polycarbonate, an impact modifier, and a flame retardant synergist.
  • the polycarbonate is present in the composition.
  • “Polycarbonate” as used herein means a homopolymer or copolymer having repeating structural carbonate units of formula (2) wherein at least 60 percent of the total number of R 1 groups are aromatic, or each R 1 contains at least one Ce-3o aromatic group.
  • each R 1 can be derived from a dihydroxy compound such as an aromatic dihydroxy compound of the formula p
  • each R h is independently a halogen atom, for example bromine, a CMO hydrocarbyl group such as a CMO alkyl, a halogen-substituted CMO alkyl, a G-io aryl, or a halogen-substituted G-io aryl, and n is 0 to 4.
  • R a and R b are each independently a halogen, C 2 alkoxy, or C 2 alkyl, and p and q are each 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.
  • p and q is each 0, or p and q is each 1, and R a and R b are each a C M alkyl group, specifically methyl, disposed meta to the hydroxy group on each 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 G, arylene group are disposed ortho, meta, or para (specifically para) to each other on the G, arylene group, for example, a single bond, -0-, -S-, -S(O)-, -S(0) 2 -, -C(O)-, or a C 8 organic group, which can be cyclic or acyclic, aromatic or non-aromatic, and can further comprise heteroatoms such as halogens, oxygen, nitrogen, sulfur, silicon, or phosphorous.
  • dihydroxy compounds that can be used are described, for example, in WO 2013/175448 Al, US 2014/0295363, and WO 2014/072923, each of which are incorporated herein by reference in their entirety.
  • Specific dihydroxy compounds 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, and 1,1- bis(4-hydroxyphenyl)-3 ,3 , 5 -trimethylcyclohexane (isophorone bisphenol) .
  • BPA 2,2-bis(4-hydroxyphenyl) propane
  • BPA bisphenol A
  • 2-phenyl-3,3’-bis(4-hydroxyphenyl) phthalimidine also known as N-phenyl phenolphthalein bisphenol,“PPP
  • Polycarbonate as used herein also includes copolymers including carbonate units and ester units (“poly(ester-carbonate)s,” also known as polyester-polycarbonates). Poly(ester-carbonate)s further contain, in addition to recurring carbonate chain units described above, repeating ester units of formula (1) as described above.
  • Specific dihydroxy compounds for use in the poly(ester-carbonate)s include aromatic dihydroxy compounds (e.g., resorcinol), bisphenols (e.g., bisphenol A), a C M aliphatic diol such as ethane diol, n-propane diol, i-propane diol, 1, 4-butane diol, 1, 4-cyclohexane diol, 1,4- hydroxymethylcyclohexane, or a combination thereof.
  • aromatic dihydroxy compounds e.g., resorcinol
  • bisphenols e.g., bisphenol A
  • C M aliphatic diol such as ethane diol, n-propane diol, i-propane diol, 1, 4-butane diol, 1, 4-cyclohexane diol, 1,4- hydroxymethylcyclohexane, or a combination thereof.
  • Aliphatic dicarboxylic acids that can be used include C5-20 aliphatic dicarboxylic acids (which includes the terminal carboxyl groups), specifically linear G- 1 2 aliphatic dicarboxylic acid such as decanedioic acid (sebacic acid); and alpha, omega-Cn dicarboxylic acids such as dodecanedioic acid (DDDA).
  • Aromatic dicarboxylic acids that can be used include terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid, 1, 4-cyclohexane dicarboxylic acid, or a combination thereof.
  • a combination of isophthalic acid and terephthalic acid wherein the weight ratio of isophthalic acid to terephthalic acid is 91:9 to 2:98 can be used.
  • ester units for use in the poly(ester-carbonate)s include ethylene terephthalate units, n-proplyene terephthalate units, n-butylene terephthalate units, ester units derived from isophthalic acid, terephthalic acid, and resorcinol (ITR ester units), and ester units derived from sebacic acid and bisphenol A.
  • the molar ratio of ester units to carbonate units in the poly(ester-carbonate)s can vary broadly, for example 1:99 to 99:1, or 10:90 to 90: 10, or 25:75 to 75:25, or 2:98 to 15:85.
  • the molar ratio of ester units to carbonate units in the poly(ester-carbonate)s can vary from 1:99 to 30:70, or 2:98 to 25:75, or 3:97 to 20:80, or 5:95 to 15:85.
  • the polycarbonate can be a linear homopolymer containing bisphenol A carbonate units (BPA-PC), commercially available under the trade name LEXAN from SABIC; or a branched, cyanophenol end-capped bisphenol A homopolycarbonate produced via interfacial polymerization, containing 3 mol% l,l,l-tris(4-hydroxyphenyl)ethane (THPE) branching agent, commercially available under the trade name LEXAN CFR from SABIC.
  • BPA-PC bisphenol A carbonate units
  • LEXAN branched, cyanophenol end-capped bisphenol A homopolycarbonate produced via interfacial polymerization, containing 3 mol% l,l,l-tris(4-hydroxyphenyl)ethane (THPE) branching agent
  • the polycarbonate can be a poly(carbonate-siloxane) copolymer including bisphenol A carbonate units and siloxane units, for example blocks containing 5 to 200 dimethylsiloxane units, such as those commercially available under the trade name EXL from SABIC.
  • poly(aromatic ester-carbonate)s comprising bisphenol A carbonate units and isophthalate-terephthalate-bisphenol A ester units, also commonly referred to as poly(carbonate-ester)s (PCE) or poly(phthalate-carbonate)s (PPC), depending on the relative ratio of carbonate units and ester units.
  • PCE poly(carbonate-ester)s
  • PPC poly(phthalate-carbonate)s
  • Another specific poly(ester-carbonate) comprises resorcinol isophthalate and terephthalate units and bisphenol A carbonate units.
  • poly(ester-carbonate-siloxane)s comprising bisphenol A carbonate units, isophthalate-terephthalate-bisphenol A ester units, and siloxane units, for example blocks containing 5 to 200 dimethylsiloxane units, such as those commercially available under the trade name FST from SABIC.
  • Poly(aliphatic ester-carbonate)s can be used, such as those comprising bisphenol A carbonate units and sebacic acid-bisphenol A ester units, such as those commercially available under the trade name LEXAN HFD from SABIC.
  • a specific copolycarbonate includes bisphenol A and bulky bisphenol carbonate units, i.e., derived from bisphenols containing at least 12 carbon atoms, for example 12 to 60 carbon atoms or 20 to 40 carbon atoms.
  • copolycarbonates examples include copolycarbonates comprising bisphenol A carbonate units and 2-phenyl-3,3’-bis(4-hydroxyphenyl) phthalimidine carbonate units (a BPA-PPPBP copolymer, commercially available under the trade name XHT from SABIC), a copolymer comprising bisphenol A carbonate units and l,l-bis(4-hydroxy-3-methylphenyl)cyclohexane carbonate units (a BPA-DMBPC copolymer commercially available under the trade name DMC from SABIC), and a copolymer comprising bisphenol A carbonate units and isophorone bisphenol carbonate units
  • the polycarbonates can have an intrinsic viscosity, as determined in chloroform at 25 °C, of 0.3 to 1.5 deciliters per gram (dl/gm). specifically 0.45 to 1.0 dl/gm.
  • the polycarbonates can have a weight average molecular weight (Mw) of 10,000 to 200,000 Daltons, specifically 20,000 to 100,000 Daltons, as measured by gel permeation chromatography (GPC), using a crosslinked styrene- divinylbenzene column and calibrated to bisphenol A homopolycarbonate references.
  • GPC samples are prepared, for example, at a concentration of 1 milligram per milliliter, and are eluted at a flow rate of 1.5 milliliters per minute.
  • the polycarbonate can include a homopolycarbonate including repeating units derived from bisphenol A, a copolycarbonate including repeating units derived from bisphenol A and siloxane units, a copolycarbonate including bisphenol A carbonate units and 2-phenyl-3,3’-bis(4-hydroxyphenyl) phthalimidine carbonate units, a copolycarbonate including bisphenol A carbonate units and sebacic acid- bisphenol A ester units, a poly(ester-carbonate-siloxane) including bisphenol A carbonate units, isophthalate-terephthalate-bisphenol A ester units, and siloxane units, a copolycarbonate including units derived from bisphenol A and l,l-bis(4-hydroxy-3-methylphenyl)cyclohexane, a (isophthalate- terephthalate-resorcinol)-carbonate copolyester, or a combination thereof.
  • Polycarbonate as used herein can also include post-consumer recycled polycarbonate (PCR-PC).
  • PCR-PC post-consumer recycled polycarbonate
  • post-consumer recycled polycarbonate refers to polycarbonate that has reached the intended end user or consumer, is no longer being used for the intended purpose, and which has been collected or reclaimed after utilization by the end-user or consumer, e.g. collected apart or separated from the normal consumer waste streams.
  • the polycarbonate can be included in the composition in an amount of 3 to 30 wt%, or 5 to 25 wt%, or 10 to 25 wt%, based on the total weight of the composition.
  • polycarbonate can be included in an amount of 10 to less than 25 wt%, or 10 to 24 wt%, or 10 to 23 wt%.
  • the composition can include the impact modifier.
  • impact modifiers include natural rubber, fhioroelastomers, ethylene-propylene rubber (EPR), ethylene-butene rubber, ethylene- propylene-diene monomer rubber (EPDM), acrylate rubbers, hydrogenated nitrile rubber (HNBR), silicone elastomers, styrene-butadiene -styrene (SBS), styrene -butadiene rubber (SBR), styrene-(ethylene- butene)-styrene (SEBS), acrylonitrile-butadiene-styrene (ABS), acrylonitrile-ethylene-propylene-diene- styrene (AES), styrene-isoprene-styrene (SIS), styrene-(ethylene-propylene)-styrene (SEPS), methyl methacrylate-butad
  • a specific type of impact modifier is an elastomer-modified graft copolymer comprising (i) an elastomeric (i.e., rubbery) polymer substrate having a Tg less than l0°C, more specifically less than -l0°C, or more specifically -40° to -80°C, and (ii) a rigid polymeric superstrate grafted to the elastomeric polymer substrate.
  • an elastomeric (i.e., rubbery) polymer substrate having a Tg less than l0°C, more specifically less than -l0°C, or more specifically -40° to -80°C, and (ii) a rigid polymeric superstrate grafted to the elastomeric polymer substrate.
  • Materials suitable for use as the elastomeric phase include, for example, conjugated diene rubbers, for example polybutadiene and polyisoprene; copolymers of a conjugated diene with less than 50 wt.% of a copolymerizable monomer, for example a monovinylic compound such as styrene, acrylonitrile, n-butyl acrylate, or ethyl acrylate; olefin rubbers such as ethylene propylene copolymers (EPR) or ethylene-propylene-diene monomer rubbers (EPDM); ethylene-vinyl acetate rubbers; silicone rubbers; elastomeric Ci-s alkyl (meth)acrylates; elastomeric copolymers of Ci-s alkyl (meth)acrylates with butadiene or styrene; or combinations of at least one of the foregoing elastomers.
  • conjugated diene rubbers for example
  • Materials suitable for use as the rigid phase include, for example, monovinyl aromatic monomers such as styrene and alpha- methyl styrene, and monovinylic monomers such as acrylonitrile, acrylic acid, methacrylic acid, and the Ci- 6 esters of acrylic acid and methacrylic acid, specifically methyl methacrylate.
  • monovinyl aromatic monomers such as styrene and alpha- methyl styrene
  • monovinylic monomers such as acrylonitrile, acrylic acid, methacrylic acid, and the Ci- 6 esters of acrylic acid and methacrylic acid, specifically methyl methacrylate.
  • Specific elastomer-modified graft copolymers include those formed from styrene- butadiene-styrene (SBS), styrene-butadiene rubber (SBR), styrene-ethylene-butadiene-styrene (SEBS), ABS (acrylonitrile-butadiene-styrene), acrylonitrile-ethylene-propylene-diene-styrene (AES), styrene- isoprene-styrene (SIS), methyl methacrylate -butadiene -styrene (MBS), and styrene-acrylonitrile (SAN).
  • the impact modifier comprises ABS (acrylonitrile-butadiene-styrene), styrene- acrylonitrile (SAN), or a combination thereof.
  • Other impact modifiers can include poly(ether-ester) impact modifiers, such as those containing high molecular weight poly(caprolactone) or poly(tetrahydrofuran), such as poly(butylene terephthalate)-poly(tetrahydrofuran) block copolymers commercially available from DuPont under the tradename HYTREL and poly(cyclohexamethylene) cyclohexylene dicarboxylate-poly(tetrahydrofuran) block copolymers commercially-available from Eastman under the tradename ECDEL.
  • poly(ether-ester) impact modifiers such as those containing high molecular weight poly(caprolactone) or poly(tetrahydrofuran), such as poly(butylene terephthalate)-poly(tetrahydrofuran) block copolymers commercially available from DuPont under the tradename HYTREL and poly(cyclohexamethylene) cyclohexylene dicarboxylate-poly
  • the impact modifier can be included in the composition in an amount of 1 to 10 wt%, based on the total weight of the composition. Within this range, the impact modifier can be present in an amount of 2 to 8 wt%, or 3 to 7 wt%.
  • the flame retardant synergist can be present in the composition.
  • the flame retardant synergist can be a nitrogen-containing flame retardant synergist, for example including a nitrogen- containing heterocyclic base and a phosphate or pyrophosphate or polyphosphate acid.
  • the nitrogen- containing flame retardant synergist can have the formula
  • g is 1 to 10,000, and the ratio of f to g is 0.5:1 to 1.7: 1, or 0.7: 1 to 1.3: 1, or 0.9:1 to 1.1: 1. It will be understood that this formula includes species in which one or more protons are transferred from the phosphate group(s) to the melamine group(s).
  • the nitrogen-containing flame retardant synergist is melamine phosphate (CAS Reg. No. 20208-95-1).
  • g the nitrogen-containing flame retardant synergist is melamine pyrophosphate (CAS Reg. No. 15541 60-3).
  • g is, on average, greater than 2
  • the nitrogen-containing flame retardant synergist is a melamine polyphosphate (CAS Reg.
  • the nitrogen-containing flame retardant synergist can be melamine pyrophosphate, melamine polyphosphate, or a combination thereof.
  • g can have an average value of greater than 2 to 10,000, or 5 to
  • melamine polyphosphate When the nitrogen-containing flame retardant synergist is melamine polyphosphate, g can have an average value of greater than 2 to 500.
  • Methods for preparing melamine phosphate, melamine pyrophosphate, and melamine polyphosphate are known in the art, and all are commercially available.
  • melamine polyphosphates can be prepared by reacting polyphosphoric acid and melamine, as described, for example, in U.S. Pat. No. 6,025,419, or by heating melamine pyrophosphate under nitrogen at 290°C to constant weight, as described in U.S. Patent No. 6,015,510, both of which are incorporated herein by reference in their entirety.
  • the nitrogen-containing flame retardant synergist can include melamine cyanurate.
  • the flame retardant synergist can include silica, preferably nanosilica.
  • the nanosilica can include a solid silica.
  • the nanosilica can include at least one of a fused silica or a fumed silica.
  • the nanosilica can include at least one of a crystalline silica or an amorphous silica.
  • Examples of solid silica include attapulgite, e.g., Min-U-GelTM commercially available from Active Minerals International, UltrasilTM commercially available from Degussa Corporation, and DavisilTM-643 commercially available from Sigma- Aldrich.
  • the nanosilica can include a high purity nanosilica, where‘high purity nanosilica’ is a nanosilica that has greater than or equal to 70 wt%, or greater than or equal to 80 wt%, 90 to 100 wt% of silica oxide, based on the total weight of the nanosilica.
  • the nanosilica can have a D50 particle size by volume of 5 to 50 nanometers (nm), or 5 to 40 nm, or 15 to 25 nm, as determined using laser light scattering particle size analysis techniques.
  • the nanosilica can have a hydrophobic coating.
  • the hydrophobic coating can include at least one of an organosiloxane or an organosilane.
  • the organosiloxane can include at least one of an oligomeric linear siloxane (such as polydimethylsiloxane or polyphenylmethylsiloxane) or a cyclic siloxane (such as octamethyltetrasiloxane or hexamethyltrisiloxane).
  • the hydrophobic coating can include a polysiloxane graft that can be comprise an organosiloxane (such as polydimethylsiloxane) grafted onto a surface of the nanosilica.
  • the organosilane can include at least one of
  • phenyltrimethoxysilane diphenyldimethoxysilane, polyethyleneglycoltrimethoxysilane,
  • phenethyltrimethoxysilane gamma-methacryloxypropyltrimethoxysilane, gamma- aminopropyltrimethoxysilane, glycidyloxypropyltrimethoxysilane, N-aminoethyl-3- aminopropyltrimethoxysilane, aminoethylaminopropylmethyldimethoxysilane,
  • diphenyldiethoxysilane polyethyleneglycoltriethoxysilane, phenyltriethoxysilane, gamma- methacryloxypropyltriethoxysilane, gamma-aminopropyltriethoxysilane,
  • hydrophobic coating component can be added to the silica prior to or during formation of the composition.
  • Other flame retardant synergists can also be optionally included in the composition in conventional amounts and as understood by those having skill in the field.
  • Examples include silicone, metal oxides such as boehmite, aluminum oxide, iron oxide, titanium oxide, manganese oxide, magnesium oxide, zirconium oxide, zinc oxide, molybdenum oxide, cobalt oxide, bismuth oxide, chromium oxide, tin oxide, antimony oxide, nickel oxide, copper oxide and tungsten oxide, metal powder such as aluminum, iron, titanium, manganese, zinc, molybdenum, cobalt, bismuth, chromium, tin, antimony, nickel, copper and tungsten, metal salts such as zinc borate, zinc metaborate, barium metaborate, zinc carbonate, magnesium carbonate, calcium carbonate, and barium carbonate, clays, talc, or a combination thereof.
  • the aforementioned optional flame retardant synergists can be excluded from the composition.
  • the flame retardant synergist can be present in an amount of 0.5 to 20 wt%, based on the total weight of the composition. Within this range, the flame retardant synergist can be present in an amount of 10 to 20 wt%, or 12 to 18 wt%. In some embodiments, when the flame retardant synergist is nitrogen-containing flame retardant synergist, it can be present in the composition in an amount of 5 to 20 wt%, based on the total weight of the composition.
  • the silica when the flame retardant synergist is silica, can be present in the composition in an amount of 0.5 to 5 wt%, or 0.5 to 3 wt%, or 0.5 to 2 wt%, or 0.5 to 1.5 wt%, based on the total weight of the composition.
  • the thermoplastic composition can include various additives ordinarily incorporated into polymer compositions of this type, with the proviso that the additive(s) are selected so as to not significantly adversely affect the desired properties of the thermoplastic composition.
  • additives can be mixed at a suitable time during the mixing of the components for forming the composition.
  • Additives can include, fillers, reinforcing agents, antioxidants, heat stabilizers, light stabilizers, ultraviolet (UV) light stabilizers, plasticizers, lubricants, mold release agents, antistatic agents, colorants such as such as titanium dioxide, carbon black, and organic dyes, surface effect additives, radiation stabilizers, flame retardants, and anti-drip agents.
  • a combination of additives can be used, for example a combination of an antioxidant, a UV stabilizer, a transesterification stabilizer, a mold release agent, an antistat agent, a nucleant, a pigment, a dye, a chain extender (e.g., a diglycidyl ether of bisphenol-A, triglycidyl isocyanurate, 3,4-epoxycyclohexanemethyl-3,4-epoxycyclohexanecarboxylate in combination with sodium stearate, JONCRYL ADR available from BASF, and the like, or a combination thereof) or a combination thereof.
  • the total amount of the additives (other than any toughening agent, impact modifier, filler, or reinforcing agents) can be 0.01 to 5 wt%, based on the total weight of the composition.
  • compositions can optionally exclude any polymer components not specifically defined herein.
  • the composition can exclude polyamides, poly(phenylene ether)s, poly(etherimide)s, or polyolefins (e.g., poly(ethylene), poly(propylene), and copolymers thereof).
  • the composition can exclude a triazine compound, or a salt thereof.
  • the composition can advantageously exhibit one or more desired properties.
  • the composition can have a shear melt viscosity of less than 200 Pa-s, as determined according to IS06721 using a shear rate of 100 s 1 at 250°C.
  • the composition can have a shear melt viscosity of 30 to 100 Pa-s as determined according to IS06721 using a shear rate of 1 s 1 at 250°C.
  • the composition can have a damping function value as determined using a combination of stress relaxation measurements and IS06721.
  • the stress relaxation measurements can be carried out at 250°C using a 25 mm cone and plate geometry with a cone angle of 0.1 radians and strain amplitudes from 1 to 50 % strain.
  • the composite can be manufactured by contacting the thermoplastic composition with the fibrous material to provide the composite.
  • the fibrous material can be contacted with the composition where the composition is in the form of a melt.
  • the fibrous material can be contacted with an aqueous slurry comprising the
  • thermoplastic material in particulate form When the composition is provided in particulate form in an aqueous slurry, the thermoplastic composition can first be ground into a powder having an average particle size of 15 to 80 micrometers, for example 15 to 40 micrometers, or 15 to 25 micrometers.
  • powder particles having a particle size close to fiber dimensions enable a more controlled concentration of particles to the fibers.
  • amorphous polymers cannot be
  • thermoplastic composition can be provided in particulate form wherein the particles have an average particle size of 200 to 400 micrometers, or 200 to 300 micrometers, or 200 to 250 micrometers, which is believed to enable good spreading of the powder and limit static electricity effects.
  • the fibrous material can be contacted with the thermoplastic composition, wherein in the thermoplastic composition is in the form of a thin film.
  • the fibrous material and the thin film of the thermoplastic composition can be contacted under heat, pressure, or both.
  • the thin film of the thermoplastic composition can be prepared by extrusion of the thermoplastic composition, and can have a thickness of 20 to 300 micrometers, or 20 to 100 micrometers.
  • the composite can have a thickness of 10 to 300 micrometers, or 15 to 300 micrometers, or, 50 to 300 micrometers, or 50 to 200 micrometers.
  • the composite can also have a fiber volume fraction (FVF) of 30 to 65 volume percent, preferably 45 to 60 volume percent.
  • the composite can also have a fiber weight fraction (FWF) of 30 to 85 wt%, or 50 to 85 wt%. FVF and FWF can be determined as described in the working examples below.
  • the composite of the present disclosure can also be useful for forming laminates which include at least two layers, preferably at least three layers of the above-described composite.
  • Each layer of the laminate can be the same or different in terms of the fibrous material and the thermoplastic composition.
  • Each layer of the laminate can have the same or different thickness.
  • Each layer can have the same or different FVF.
  • each layer of the laminate can have the same or different orientation.
  • the laminate preferably includes three layers of the composite, and the three superimposed layers of the composite are defined relative to each other than two outer layers of fiber composite material and at least one inner layer of fiber composite material.
  • the inner layers can be fibrous composites oriented substantially equally and their orientation can be rotated relative to the outer layers of fiber composite material by 30° to 90°.
  • At least some of the layers can have the same orientation and at least another part of the layers can be rotated by 30° to 90°, and the outer layers for this purpose are present in a 0° orientation.
  • the inner layers can have the same orientation and their orientation is rotated relative to the outer layers of fiber composite material by 30° to 90°.
  • the layers of the laminate can have the same or different fiber volume content (FVF).
  • the fiber volume content of the outer layers of the laminate is at most 50 volume percent based on the volume of the outer layers of fiber composite material.
  • the laminate can have a thickness of 40 micrometers to 5 millimeters, or 100 micrometers to 5 millimeters, or 0.5 to 5 millimeters, or 0.5 to 1.1 millimeters.
  • the laminate comprising the composite as described herein can have one or more advantageous properties.
  • the laminate can have a flammability rating of V2 or better, as determined according to UL 94 at a thickness of 1.0 millimeter.
  • the laminate can exhibit not more than a minor surface change detected by visual inspection following exposure to sunscreen at 65 °C, 90% relative humidity under 0.5% strain.
  • the properties of the laminates are further described in the working examples below.
  • the composites as described herein can also exhibit desirable dielectric properties.
  • the composites can have a dielectric constant (Dk) of 3 to 5, as determined at 1.1 or 5 GHz.
  • the composites can also have a dissipation factor (Df) of less than 0.05, preferably less than 0.02, as determined at 1.1 or 5 GHz.
  • a composite comprising: at least one layer of a fibrous material comprising glass fibers, carbon fibers, ceramic fibers, polymeric fibers, or a combination thereof, more preferably wherein the fibrous material is a continuous fibrous material, a unidirectional fibrous material, a woven fibrous material, non-crimp material, a knitted fibrous material, a nonwoven fibrous material, or a combination thereof; and a thermoplastic matrix comprising a thermoplastic composition comprising, based on the total weight of the thermoplastic composition: 30 to 90 wt%, preferably 35 to 88 wt%, more preferably 35 to 70 wt%, even more preferably 37 to 56 wt% of a polyester that comprises poly(butylene terephthalate), polyethylene terephthalate), glycol-modified polyethylene terephthalate), glycol-modified poly(cyclohexylene dimethylene terephthalate), spiro- glycol-modified poly(
  • a laminate comprising at least two layers of the foregoing composite, preferably wherein the laminate has one or more of: a flammability rating of V2 or better, as determined according to UL 94 at a thickness of 1.0 millimeter; not more than a minor surface change detected by visual inspection following exposure to sunscreen at 65°C, 90% relative humidity under 0.5% strain; and a thickness of 0.5 to 5 millimeters, preferably 0.5 to 1.1 millimeters.
  • a composite comprising: at least one layer of a fibrous material, preferably wherein the fibrous material comprises glass fibers, carbon fibers, ceramic fibers, polymeric fibers, or a combination thereof; and a thermoplastic matrix comprising a thermoplastic composition comprising, based on the total weight of the thermoplastic composition: 35 to 88 wt%, more preferably 35 to 70 wt%, of a polyester that comprises poly(butylene terephthalate), polyethylene terephthalate), glycol-modified polyethylene terephthalate), glycol-modified poly(cyclohexylene dimethylene terephthalate), spiro-glycol-modified poly(ethylene terephthalate), poly(cyclohexylene dimethylene terephthalate), poly(trimethylene terephthalate), glycol-modified poly(butylene
  • a phosphorus-containing flame retardant that comprises a phosphinate, a phosphate ester, a phosphazene, a polyphosphonate, or a combination thereof; preferably 5 to 25 wt% of a polycarbonate homopolymer, a polycarbonate-polysiloxane copolymer, a
  • copolycarbonate or a combination thereof; 1 to 10 wt% of an impact modifier, butadiene-styrene; and 5 to 20 wt% of a flame retardant synergist; one or more of an additive such as an antioxidant, a UV stabilizer, a transesterification stabilizer, a mold release agent, an antistat agent, a nucleant, a pigment, a dye, a chain extender, or a combination thereof; wherein the fibrous material is embedded in the thermoplastic matrix; wherein the composite has a thickness of 10 to 300 micrometers; wherein the composite has a fiber volume fraction of 30 to 65%, a fiber weight fraction of 30 to 85%; or both.
  • an additive such as an antioxidant, a UV stabilizer, a transesterification stabilizer, a mold release agent, an antistat agent, a nucleant, a pigment, a dye, a chain extender, or a combination thereof
  • the fibrous material is embedded in the thermoplastic matrix
  • the composite has
  • a laminate comprising at least two layers of the foregoing composite, wherein the laminate has one or more of: a flammability rating of V2 or better, as determined according to UL 94 at a thickness of 1.0 millimeter; not more than a minor surface change detected by visual inspection following exposure to sunscreen at 65°C, 90% relative humidity under 0.5% strain; and a thickness of 0.5 to 5 millimeters, preferably 0.5 to 1.1 millimeters.
  • a composite comprising: at least one layer of a fibrous material comprising glass fibers, carbon fibers, ceramic fibers, polymeric fibers, or a combination thereof, wherein the fibrous material is a continuous fibrous material, a unidirectional fibrous material, a woven fibrous material, non-crimp material, a knitted fibrous material, a nonwoven fibrous material, or a combination thereof; and a thermoplastic matrix comprising a thermoplastic composition comprising, based on the total weight of the thermoplastic composition: 35 to 70 wt%, even more preferably 37 to 56 wt% of a poly(butylene terephthalate), polyethylene terephthalate), or a combination thereof; a flame retardant, which can be 15 to 35 wt%, preferably 20 to 30 wt% of a phosphinate, or 5 to 30 wt%, preferably 20 to 30 wt% of a phosphate ester, or 3 to 10 w
  • a laminate comprising at least two layers of the foregoing composite, preferably wherein the laminate has one or more of: a flammability rating of V2 or better, as determined according to UL 94 at a thickness of 1.0 millimeter; not more than a minor surface change detected by visual inspection following exposure to sunscreen at 65°C, 90% relative humidity under 0.5% strain; and a thickness of 0.5 to 1.1 millimeters.
  • the formulations were dry blended and extruded in a 25 mm Werner & Pfleiderer ZSK co-rotating twin screw extruder with a vacuum vented mixing screw, using a screw speed of 160 rpm.
  • the temperature profile for compounding starting from feed zone to die zone was 40-70-l70-230-240-245-245-245°C.
  • the desired torque was maintained during the extrusion by changing the throughput rate to achieve optimum mixing.
  • the extrudate was cooled through a water bath prior to pelletization.
  • the pellets were dried for 4 hours at 80°C in a forced air-circulating oven prior to injection molding.
  • Test specimens were injection molded on a 110 Ton Engel injection molding machine as per ISO test protocols.
  • the temperature profile for injection molding starting from feed zone to nozzle was 40-100-230-230-245-235 °C.
  • Tensile properties of the injection molded specimens were evaluated as per ISO 527 and notched Izod impact testing was performed in accordance with ISO 180. Flame testing was performed with 1.0 mm thickness flame bars in accordance with UL-94. Vicat was measured as per ISO 306 at a heating rate of 120° C/hr at 50 Newton (N).
  • the melt volume flow rate (MVR) of the pellets was determined according ISO 1133 at a specific load and temperature.
  • the melt viscosity (MV) of the polymers was determined according IS06721 at various shear rates (l/s, s 1 ) and temperatures.
  • DMA tensile modulus in Table 6 was measured using a Dynamic Mechanical Analyzer (DMA) run in tensile mode. DMA can be according to ASTM D5279.
  • the polymer was also evaluated for its chemical resistance to sunscreen, by applying 1 milliliter of the sunscreen in the center of a tensile bar. Subsequently the tensile bars were exposed to 65 °C, 90% relative humidity (RH) under 0.5% strain. Through visual assessment one could differentiate the following classifications: [1]: Sample is unaffected; [2] Sample shows some minor surface change;
  • Table 2 below shows various composition including PBT, and the properties associated with these compositions. As can be seen from Table 2, it was surprisingly found that by increasing the content of the phosphate ester flame retardant from 8.5 wt% to 25.5 wt%, the mechanical properties, ESCR, and heat properties were affected. Thus, an optimal loading of flame retardant is essential to balance these properties for use in composite structures.
  • Pellets of the Table 2 compositions were cryogenically ground using a mill equipped with a 400 micrometer or 80 micrometer sieves to provide micronized powders having a D50 of 250 micrometers or 20 micrometers, respectively. Due to static effects, silica and antistatic agents were added to the powders in order to pass through the sieve.
  • the powder dimensions were characterized using a Mastersizer 2000 with Hydro 2000 MU liquid feeding system from Malvern to determine particle size distribution (PSD) in methanol with laser diffraction technology providing Dio, D50 and D90 data.
  • PSD particle size distribution
  • Micronized powders are described in Table 3. As shown in Table 3, micronized powders having a D50 of about 250 pm can easily be obtained through cryogenic grinding, as exemplified by CE2, Ex6 and Ex8. In contrast, when the target was to obtain a powder having a D50 in the range of 20 pm, only Ex5 achieved these dimensions upon the addition of silica and antistatic agents. It was observed that the cryogenic grinding of Ex7 was slower, yield was lower, and the overall particle size was larger than Ex5, which, without wishing to be bound by theory, is believed to be attributed to the ductile polycarbonate phase reducing the grindability of the composition.
  • Pellets of the Table 2 compositions were also converted to thin films using a film extruder having a 30 mm barrel, 3 zone screw (ratio 1 :4, L/D: 20), die width of 320 mm, and 100 pm gap. Films, having a thickness of 20-30 micrometers were obtained of CE3 and Ex 10 by using the film extrusion conditions as outlined in Table 4. However, Ex9 could not be extruded due to due to screw slippage (equipment limitations) or too high MVR of the polymer composition.
  • compositions of Exl-4 and Exl 1-16 were used to manufacture unidirectional (UD) tapes using a variety of fibers (e.g., glass, ceramic, carbon, and the like) using a direct melt impregnation method. Adjustment of the extruder’s throughput, temperature, line speed, die temperature, and fiber tension was made to enable production of tapes. Compositions and results are shown in Table 6.
  • the UD tapes were manufactured using the following commercial continuous fibers: HiperTex Glass, 2400 tex rovings, available from 3B; Nextel 610 ceramic oxide, 1111 tex rovings, available from 3M, and HR40 carbon fiber and approximately 600 tex rovings (12K), available from Mitsubishi.
  • micronized powders of Ex5 having a D50 of 32 micrometers were used to manufacture UD prepregs using an aqueous slurry process.
  • Thickness of the tapes was measured with a gauge at a minimum of three locations across the width of the tape.
  • the fiber volume fraction (FVF) was either estimated after determining the thickness, width, and weight of the tape.
  • the weight of 1 meter of tape was determined using a scale and the raw material densities.
  • the fiber weight fraction (FWF) was determined by burning the matrix off the fiber. The sample was weighed before and after burning. Impregnation quality, porosity, and fiber/composition distribution in the tape was evaluated by optical microscopy and image analysis.
  • Laminates can be made using any number of lamination processes including pressing in a hot press. FVF, FWF, UL94 flammability rating, ESCR, dimensions, mechanical properties, and dielectric performance of the laminates were evaluated. [0092] Flame retardancy of the laminates was determined according to Underwriter’s
  • the afterflame times tl and t2 for each individual specimen must have been less than or equal to 10 seconds; and the total afterflame time for all five specimens (tl plus t2 for all five specimens) must have been less than or equal to 50 seconds; and the second afterflame time plus the afterglow time for each individual specimen (t2 + 13) must have been less than or equal to 30 seconds; and no specimen can have flamed or glowed up to the holding clamp; and the cotton indicator cannot have been ignited by flaming particles or drops.
  • the afterflame times tl and t2 for each individual specimen must have been less than or equal to 30 seconds; and the total afterflame time for all five specimens (tl plus t2 for all five specimens) must have been less than or equal to 250 seconds; and the second afterflame time plus the afterglow time for each individual specimen (t2 + t3) must have been less than or equal to 60 seconds; and no specimen can have flamed or glowed up to the holding clamp; and the cotton indicator cannot have been ignited by flaming particles or drops.
  • the afterflame times tl and t2 for each individual specimen must have been less than or equal to 30 seconds; and the total afterflame time for all five specimens (tl plus t2 for all five specimens) must have been less than or equal to 250 seconds; and the second afterflame time plus the afterglow time for each individual specimen (t2 + 13) must have been less than or equal to 60 seconds; and no specimen can have flamed or glowed up to the holding clamp; but the cotton indicator can have been ignited by flaming particles or drops.
  • Specimens not achieving a rating of V-2 were considered to have failed. Samples that bum all the way to the clamp are considered to have failed, and are given the rating“NR,” or non-rated.
  • Tensile properties of the laminates were measured according to ASTM D3039/D3039M- 17 test method.
  • Tensile strength and modulus of the fabric based laminates (Ex31-33) varied between 650-700 MPa and 30-32 GPa, respectively.
  • the tensile strength of the unidirectional 3B-Glass laminates (Ex34) varied between 900 and 950 MPa and 37-40 GPa respectively.
  • Flexural properties were measured according to ASTM D7264/D7264M-15 test methods.
  • the flexural strength of the roving based unidirectional laminates across the fiber direction varied between 800-950 and 35-45 GPa respectively (Ex34).
  • the flexural strength of the S-glass fabric laminates (Ex31-33) varied between 500-550 MPa and 25-28 GPa respectively (Ex34).
  • high glass transition additives can be used.
  • polyphosphonates having a Tg of l05°C, were evaluated.
  • the compositions exhibited a modulus of 2.6 to 2.8 GPa, whereas the composition of Ex 14 (using a phosphate ester flame retardant additive) exhibited a modulus of 0.56 GPa.
  • the Vicat values of the compositions of Table 8 were 89-l02°C, whereas the composition of Ex 14 had a Vicat value of 68.6°C.
  • all compositions of Table 8 exhibited low shear viscosities of less than 100 Pa.s, making them excellent candidates for preparing continuous fiber composites.
  • compositions of Ex35-4l have good mechanical properties, heat resistance and high P content. When exposed to the sunscreen ESCR test they showed softening of the surface. Without wishing to be bound by theory, each of these compositions includes a high
  • concentration e.g., 25-45 wt% of a polyphosphonate, which may be susceptible to the sunscreen, contributing to the observed softening.
  • Formulations of Table 8 were converted into thin films by using a double belt press.
  • the pellets of each experimental formulation were squeezed between two Teflon sheets into a film, having a 100 micrometer thickness using a double belt press under the following conditions: 240°C, 0.5 m/min, 10 N, 4 mm gap.
  • Ex 45 and Ex 46 resulted in a V0 ETL94 rating of the composite laminate having a thickness of 1.0 mm. Furthermore, it was found that the addition of 1 wt% of fumed silica in Ex 48 resulted in a VI of the 1 mm laminate, while its compositional benchmark Ex 47 failed the UL94 V rating test (VNOT due to flame out times exceeding 35 seconds for one specimen). It was surprisingly found that the addition of fumed silica effectively reduced the flame out time during the flame retardancy testing according UL94 V rating test protocol. This resulted in an increase of the p(FTP) VI from 0.04 to 0.79. The high loadings of the polyphosphonate polymer was observed to affect the ESCR performance, and to decrease modulus and failure strain of the composite laminate.
  • Table 10 shows compositions which include polyethylene terephthalate) (PET).
  • a composite comprising: at least one layer of a fibrous material, preferably wherein the fibrous material comprises glass fibers, carbon fibers, ceramic fibers, polymeric fibers, or a combination thereof, more preferably wherein the fibrous material is a continuous fibrous material, a unidirectional fibrous material, a woven fibrous material, non-crimp material, a knitted fibrous material, a nonwoven fibrous material, or a combination thereof; and a thermoplastic matrix comprising a thermoplastic composition comprising, based on the total weight of the thermoplastic composition: 30 to 90 wt%, preferably 35 to 88 wt%, more preferably 35 to 70 wt%, even more preferably 37 to 56 wt% of a polyester; 5 to 50 wt%, preferably 10 to 50 wt%, more preferably 20 to 50 of a phosphorus -containing flame retardant; and optionally, one or more of: 3 to 30 wt%, preferably 5 to 25 wt
  • Aspect 2 The composite of aspect 1, wherein the polyester comprises poly(butylene terephthalate), poly(ethylene terephthalate), glycol-modified polyethylene terephthalate), glycol- modified poly(cyclohexylene dimethylene terephthalate), spiro-glycol-modified polyethylene terephthalate), poly(cyclohexylene dimethylene terephthalate), poly(trimethylene terephthalate), glycol- modified poly(butylene terephthalate), poly(butylene terephthalate) derived from recycled poly(ethylene terephthalate), or a combination thereof; preferably wherein the polyester is poly(butylene terephthalate), polyethylene terephthalate), or a combination thereof; more preferably wherein the polyester is a poly(butylene terephthalate).
  • Aspect 3 The composite of aspect 1 or 2, wherein the phosphorus-containing flame retardant is a phosphinate, a phosphate ester, a phosphazene, a polyphosphonate, or a combination thereof, preferably wherein the thermoplastic composition comprises: 15 to 35 wt%, preferably 20 to 30 wt% of the phosphinate; 5 to 30 wt%, preferably 20 to 30 wt% of the phosphate ester; 3 to 10 wt% of the phosphazene; or 15 to 50 wt%, preferably 25 to 45 wt% of the polyphosphonate.
  • the thermoplastic composition comprises: 15 to 35 wt%, preferably 20 to 30 wt% of the phosphinate; 5 to 30 wt%, preferably 20 to 30 wt% of the phosphate ester; 3 to 10 wt% of the phosphazene; or 15 to 50 wt%, preferably 25 to 45 wt% of
  • Aspect 4 The composite of any of aspects 1 to 3, wherein the polycarbonate is present in the thermoplastic composition, preferably wherein the polycarbonate comprises a polycarbonate homopolymer, a polycarbonate-polysiloxane copolymer, a copolycarbonate, or a combination thereof; more preferably wherein the polycarbonate comprises a homopolycarbonate comprising repeating units derived from bisphenol A, a copolycarbonate comprising repeating units derived from bisphenol A and siloxane units, a copolycarbonate comprising bisphenol A carbonate units and 2 -phenyl-3, 3’-bis(4- hydroxyphenyl) phthalimidine carbonate units, a copolycarbonate comprising bisphenol A carbonate units and sebacic acid-bisphenol A ester units, a poly(ester-carbonate-siloxane) comprising bisphenol A carbonate units, isophthalate-terephthalate-bisphenol A ester units, and siloxan
  • Aspect 5 The composite of any of aspects 1 to 4, wherein the impact modifier is present in the thermoplastic composition, preferably wherein the impact modifier is poly(ether-ester) copolymer, a styrene-acrylonitrile copolymer, an acrylonitrile -butadiene-styrene copolymer, or a combination thereof.
  • the impact modifier is poly(ether-ester) copolymer, a styrene-acrylonitrile copolymer, an acrylonitrile -butadiene-styrene copolymer, or a combination thereof.
  • Aspect 6 The composite of any of aspects 1 to 5, wherein the flame retardant synergist is present in the thermoplastic composition, preferably wherein the flame retardant synergist comprises melamine polyphosphate, melamine cyanurate, melamine pyrophosphate, a melamine phosphate, silica, clay, talcum, or a combination thereof, more preferably wherein the flame retardant synergist comprises melamine polyphosphate, melamine cyanurate, melamine pyrophosphate, a melamine phosphate, silica, or a combination thereof.
  • the flame retardant synergist comprises melamine polyphosphate, melamine cyanurate, melamine pyrophosphate, a melamine phosphate, silica, or a combination thereof.
  • thermoplastic composition further comprises an additive, preferably wherein the additive is an antioxidant, a UV stabilizer, a transesterification stabilizer, a mold release agent, an antistat agent, a nucleant, a pigment, a dye, a chain extender, or a combination thereof.
  • the additive is an antioxidant, a UV stabilizer, a transesterification stabilizer, a mold release agent, an antistat agent, a nucleant, a pigment, a dye, a chain extender, or a combination thereof.
  • Aspect 8 The composite of any of aspects 1 to 7, wherein the composite has a thickness of 10 to 300 micrometers, preferably 15 to 300.
  • Aspect 9 The composite of any of aspects 1 to 8, wherein the composite has a fiber volume fraction of 30 to 65%, preferably 45 to 60%; a fiber weight fraction of 30 to 85%, preferably 50 to 85%; or both.
  • a laminate comprising at least two layers of the composite of any of aspects 1 to 9, preferably wherein the laminate has one or more of: a flammability rating of V2 or better, as determined according to UL 94 at a thickness of 1.0 millimeter; not more than a minor surface change detected by visual inspection following exposure to sunscreen at 65°C, 90% relative humidity under 0.5% strain; and a thickness of 0.5 to 5 millimeters, preferably 0.5 to 1.1 millimeters.
  • a thermoplastic composition comprising: 30 to 90 wt%, preferably 35 to 88 wt%, more preferably 35 to 70 wt%, even more preferably 37 to 56 wt% of a polyester; 15 to 50 wt%, preferably 25 to 45 wt% of a polyphosphonate; and optionally, one or more of 3 to 30 wt%, preferably 5 to 25 wt%, more preferably 10 to 25 wt% of a polycarbonate; 1 to 10 wt% of an impact modifier; and 5 to 20 wt% of a flame retardant synergist, preferably wherein the flame retardant synergist comprises silica; wherein wt% of each component is based on the total weight of the composition; and wherein the thermoplastic composition exhibits one or more of: a shear melt viscosity of less than 200 Pa.s, as determined according to IS06721 using a shear rate of 100 s 1 at 250°C; a shear melt viscosity of
  • Aspect 13 The thermoplastic composition of aspect 12, wherein the polycarbonate is present, preferably wherein the polycarbonate comprises a polycarbonate homopolymer, a polycarbonate - polysiloxane copolymer, a copolycarbonate, or a combination thereof; more preferably wherein the polycarbonate comprises a homopolycarbonate comprising repeating units derived from bisphenol A, a copolycarbonate comprising repeating units derived from bisphenol A and siloxane units, a
  • copolycarbonate comprising bisphenol A carbonate units and 2-phenyl-3,3’-bis(4-hydroxyphenyl) phthalimidine carbonate units
  • a copolycarbonate comprising bisphenol A carbonate units and sebacic acid-bisphenol A ester units
  • a poly(ester-carbonate-siloxane) comprising bisphenol A carbonate units, isophthalate-terephthalate-bisphenol A ester units, and siloxane units
  • a copolycarbonate comprising units derived from bisphenol A and l,l-bis(4-hydroxy-3-methylphenyl)cyclohexane, a (isophthalate- terephthalate-resorcinol)-carbonate copolyester, or a combination thereof.
  • Aspect 14 The thermoplastic composition of aspect 12 or 13, wherein the composition is in the form of a micronized powder, preferably wherein the micronized powder has an average diameter of 15 to 40 micrometers, preferably 15 to 20 micrometers, or 200 to 400 micrometers, preferably 200 to 250 micrometers.
  • Aspect 15 The thermoplastic composition of aspect 12 or 13, wherein the composition is in the form of a film, preferably having a thickness of 200 to 300 micrometers, preferably 20 to 100 micrometers.
  • compositions, methods, and articles can alternatively comprise, consist of, or consist essentially of, any appropriate materials, steps, or components herein disclosed.
  • the compositions, methods, and articles can additionally, or alternatively, be formulated so as to be devoid, or substantially free, of any materials (or species), steps, or components, that are otherwise not necessary to the achievement of the function or objectives of the compositions, methods, and articles.
  • All ranges disclosed herein are inclusive of the endpoints, and the endpoints are independently combinable with each other.“Combinations” is inclusive of blends, mixtures, alloys, reaction products, and the like.
  • the terms“first,”“second,” and the like do not denote any order, quantity, or importance, but rather are used to distinguish one element from another.
  • test standards are the most recent standard in effect as of the filing date of this application, or, if priority is claimed, the filing date of the earliest priority application in which the test standard appears.
  • hydrocarbyl refers to a residue that contains only carbon and hydrogen.
  • the residue can be aliphatic or aromatic, straight-chain, cyclic, bicyclic, branched, saturated, or unsaturated. It can also contain combinations of aliphatic, aromatic, straight chain, cyclic, bicyclic, branched, saturated, and unsaturated hydrocarbon moieties.
  • the hydrocarbyl residue when described as substituted, it may, optionally, contain heteroatoms over and above the carbon and hydrogen members of the substituent residue.
  • the hydrocarbyl residue can also contain one or more carbonyl groups, amino groups, hydroxyl groups, or the like, or it can contain heteroatoms within the backbone of the hydrocarbyl residue.
  • alkyl means a branched or straight chain, unsaturated aliphatic hydrocarbon group, e.g., methyl, ethyl, n-propyl, i-propyl, n-butyl, s- butyl, t-butyl, n-pentyl, s-pentyl, and n- and s-hexyl.
  • Alkoxy means an alkyl group that is linked via an oxygen (i.e., alkyl-O-), for example methoxy, eth
  • Alkylene means a straight or branched chain, saturated, divalent aliphatic hydrocarbon group (e.g., methylene (-CH 2 -) or, propylene (-(CFh ⁇ -)).
  • Cycloalkylene means a divalent cyclic alkylene group, -C n Fh n-x , wherein x is the number of hydrogens replaced by cyclization(s).
  • Cycloalkenyl means a monovalent group having one or more rings and one or more carbon-carbon double bonds in the ring, wherein all ring members are carbon (e.g., cyclopentyl and cyclohexyl).
  • Aryl means an aromatic hydrocarbon group containing the specified number of carbon atoms, such as phenyl, tropone, indanyl, or naphthyl.“Arylene” means a divalent aryl group.
  • Alkylarylene means an arylene group substituted with an alkyl group.
  • Arylalkylene means an alkylene group substituted with an aryl group (e.g., benzyl).
  • halo means a group or compound including one more of a fluoro, chloro, bromo, or iodo substituent. A combination of different halo groups (e.g., bromo and fluoro), or only chloro groups can be present.

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Abstract

La présente invention concerne un composite qui comprend au moins une couche d'un matériau fibreux, et une matrice thermoplastique comprenant une composition thermoplastique. La composition thermoplastique comprend un polyester; un ignifuge contenant du phosphore; et éventuellement, un ou plusieurs éléments parmi : un polycarbonate, un modificateur d'impact, et un synergiste ignifuge, chaque composant étant présent dans la composition en une quantité particulière définie dans la description. Le matériau fibreux est incorporé dans la matrice thermoplastique. Les composites de l'invention permettent d'obtenir un équilibre souhaitable de propriétés comprenant une résistance chimique, une résistance à la chaleur, une performance mécanique et un retard de flamme.
PCT/IB2019/058742 2018-10-16 2019-10-14 Préimprégné composite renforcé par des fibres continues formé d'un polyester ignifuge WO2020079565A1 (fr)

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