WO2024252357A1 - Compositions ignifuges de polycarbonate - Google Patents

Compositions ignifuges de polycarbonate Download PDF

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WO2024252357A1
WO2024252357A1 PCT/IB2024/055603 IB2024055603W WO2024252357A1 WO 2024252357 A1 WO2024252357 A1 WO 2024252357A1 IB 2024055603 W IB2024055603 W IB 2024055603W WO 2024252357 A1 WO2024252357 A1 WO 2024252357A1
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polycarbonate
group
alkyl
polycarbonate composition
composition
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Mark Adrianus Johannes van der Mee
Robert Dirk Van De Grampel
Bart VANDORMAEL
Peter Vollenberg
JR. Frederick C. PREHN
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SHPP Global Technologies BV
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SHPP Global Technologies BV
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • 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
    • C08G64/04—Aromatic polycarbonates
    • C08G64/06—Aromatic polycarbonates not containing aliphatic unsaturation

Definitions

  • This disclosure relates to polycarbonate compositions, and in particular to flame- retardant polycarbonate compositions, methods of manufacture, and uses thereof in thin-wall articles.
  • Polycarbonates are useful in the manufacture of articles and components for a wide range of applications, from automotive parts to electronic appliances. Because of their broad use, particularly in electronics, it is desirable to provide polycarbonate compositions with excellent physical, optical, and thermal properties in an adequate processing window. Such properties may be particularly difficult to achieve in thin-wall applications.
  • a polycarbonate composition including: polycarbonate; a polycarbonate including repeating units derived from a monomer including a pendant ester group; a non-halogenated flame retardant, optionally, a poly(carbonate-siloxane) present in an amount effective to provide 4 wt% or less of siloxane repeating units, based on the total weight of the composition, and optionally, an additive composition, wherein a sample of the composition has a UL-94 flame test rating of V-0 at a thickness of 1.5 mm or thinner.
  • a method of manufacture includes combining the above- described components to form a polycarbonate composition.
  • an article includes the above-described polycarbonate composition.
  • a method of manufacture of an article includes molding, extruding, or shaping the above-described polycarbonate composition into an article.
  • 23SHPP0022-WO-PCT (SS230150PCT) DETAILED DESCRIPTION Polycarbonates are thermoplastic resins with many desirable properties, but are inherently flammable. Current design trends are focused on thinner designs for purposes of slimness, weight reduction, and size reduction of the overall final product, as well as to for the purpose of more complex designs.
  • the UL 94 flammability test includes both short flame out times and no dripping of flaming particles as requirements for a V- 0 or V-1 flame test rating.
  • Conventional compositions often incorporate fluorine-based anti-drip agents either alone or in combination with a non-halogenated flame retardant in order to pass the UL94 flame test.
  • halogenated materials for example, per fluoroalkyl and polyfluoroalkyl substances (PFAS)
  • PFAS per fluoroalkyl and polyfluoroalkyl substances
  • polycarbonate compositions including: a polycarbonate, a polycarbonate comprising repeating units derived from a monomer comprising a pendant ester group; and optionally a poly(carbonate-siloxane); in combination with a non-halogenated flame retardant may provide the desired flame retardance while eliminating the need for halogenated additives, such as fluorinated flame retardants and anti-drip agents.
  • fluorinated anti-drip agents may be omitted in the present polycarbonate compositions, thus eliminating added fluorine while providing improved flammability.
  • the polycarbonate compositions may have a UL-94 flame test rating of V-0 at a thickness of 1.5 mm or thinner and be considered “essentially fluorine-free.”
  • the phrase “essentially fluorine-free” means that the amount of calculated intentionally added fluorine present in the composition is 1500 ppm or less, less than 1000 ppm, less than 500 ppm, less than 100 ppm, or less than 50 ppm.
  • TSAN polytetrafluoroethylene
  • the amount of calculated intentionally added fluorine would equal 1900 ppm.
  • the polycarbonate compositions of the present disclosure may have zero intentionally added fluorine.
  • the polycarbonate compositions may have a UL-94 flame test rating of V-0 at a thickness of 1.5 mm or thinner and be considered “essentially halogen-free” per IEC 61249-2-21 or UL 746H.
  • the phrase “essentially halogen-free” is as 23SHPP0022-WO-PCT (SS230150PCT) defined by IEC 61249-2-21 or UL 746H.
  • a composition should include 900 parts per million (ppm) or less of each of chlorine and bromine and also include 1500 ppm or less of total bromine, chlorine, and fluorine content.
  • a composition should include 900 ppm or less of each of chlorine, bromine, and fluorine and 1500 ppm or less of the total chlorine, bromine, and fluorine content.
  • the bromine, chlorine, and fluorine content in ppm may be calculated from the composition or measured by elemental analysis techniques.
  • non-halogenated flame retardants may include or exclude halogens, but commonly employed anti-drip agents include PTFE-encapsulated styrene-acrylonitrile copolymers (e.g., TSAN) and thus include fluorine.
  • Non-halogenated flame retardants that are not brominated, chlorinated, or fluorinated have been used in conventional polycarbonate compositions, but an anti-drip agent is usually present in combination with the non-halogenated flame retardant, causing the halogen content of the composition to exceed the 1500 ppm total halogen limit per IEC 61249-2-21 and UL 746H.
  • non-halogenated flame retardants that include or exclude halogens may be used in polycarbonate compositions so that the compositions may be considered “essentially halogen-free” per IEC 61249-2-21 or UL 746H.
  • the polycarbonate compositions include a polycarbonate composition including a polycarbonate, a polycarbonate including repeating units derived from a monomer including a pendant ester group, and optionally a poly(carbonate-siloxane) in an amount effective to provide 4 wt% or less siloxane; and a non-halogenated flame retardant.
  • the individual components of the polycarbonate compositions are described in detail below.
  • Polycarbonate as used herein means a polymer having repeating structural carbonate units of formula (1) in which at least 60 percent of the total number of R 1 groups contain aromatic moieties and the balance thereof are aliphatic, alicyclic, or aromatic.
  • each R 1 is a C 6-30 aromatic 23SHPP0022-WO-PCT (SS230150PCT) group, that is, contains at least one aromatic moiety.
  • R 1 may be derived from an aromatic dihydroxy compound of the formula HO-R 1 -OH, in particular of formula (2) HO–A 1 –Y 1 –A 2 –OH (2) wherein each of A 1 and A 2 is a monocyclic divalent aromatic group and Y 1 is a single bond or a bridging group having one or more atoms that separate A 1 from A 2 . In an aspect, one atom separates A 1 from A 2 .
  • each R 1 may be derived from a bisphenol of formula (3) wherein R a and R b are each independently a halogen, C1-12 alkoxy, or C1-12 alkyl, and p and q are each independently integers of 0 to 4.
  • X a is a bridging group connecting the two hydroxy-substituted aromatic groups, where the bridging group and the hydroxy substituent of each C6 arylene group are disposed ortho, meta, or para (preferably para) to each other on the C6 arylene group.
  • the bridging group X a is single bond, - O-, -S-, -S(O)-, -S(O)2-, -C(O)-, or a C1-60 organic group.
  • the organic bridging group may be cyclic or acyclic, aromatic or non-aromatic, and may further include heteroatoms such as halogens, oxygen, nitrogen, sulfur, silicon, or phosphorus.
  • the C1-60 organic group may be disposed such that the C 6 arylene groups connected thereto are each connected to a common alkylidene carbon or to different carbons of the C 1-60 organic bridging group.
  • p and q is each 1
  • R a and R b are each a C 1-3 alkyl group, preferably methyl, disposed meta to the hydroxy group on each arylene group.
  • R h is independently a halogen atom, C1-10 hydrocarbyl group such as a C1-10 alkyl, a halogen-substituted C1-10 alkyl, a C6-10 aryl, or a halogen-substituted C6-10 aryl, and n is 0 to 4.
  • the halogen is usually bromine.
  • dihydroxy compounds include the following: 4,4'-dihydroxybiphenyl, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, bis(4-hydroxyphenyl)methane, bis(4-hydroxyphenyl)diphenylmethane, bis(4-hydroxyphenyl)-1- naphthylmethane, 1,2-bis(4-hydroxyphenyl)ethane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 23SHPP0022-WO-PCT (SS230150PCT) 2-(4-hydroxyphenyl)-2-(3-hydroxyphenyl)propane, bis(4-hydroxyphenyl)phenylmethane, 2,2- bis(4-hydroxy-3-bromophenyl)propane, 1,1-bis (hydroxyphenyl)cyclopentane, 1,1-bis(4- hydroxyphenyl)cyclohexane, 1,
  • the polycarbonates may have an intrinsic viscosity, as determined in chloroform at 25°C, of 0.3 to 1.5 deciliters per gram (dl/gm), preferably 0.45 to 1.0 dl/gm.
  • the polycarbonates may have a weight average molecular weight (Mw) of 10,000 to 200,000 g/mol, preferably 20,000 to 100,000 g/mol, as measured by gel permeation chromatography (GPC), using a crosslinked styrene-divinylbenzene column using polystyrene standards and calculated for polycarbonate.
  • GPC samples are prepared at a concentration of 1 mg per ml, and are eluted at a flow rate of 1.5 ml per minute.
  • the polycarbonate compositions may include a homopolycarbonate (wherein each R 1 in the polymer is the same).
  • the homopolycarbonate in the polycarbonate composition is derived from a bisphenol of formula (2), preferably bisphenol A, in which each of A 1 and A 2 is p-phenylene and Y 1 is isopropylidene in formula (2).
  • the polycarbonate may be a linear polycarbonate, a branched polycarbonate, or a combination thereof.
  • compositions having flame retardant properties such as a V0-V1 flame test rating (thus requiring zero burning drips) sometimes employ branched polycarbonates as anti-drip agents.
  • the branched polycarbonates exert an anti-drip effect by modifying the viscosity of the compositions. Therefore, the polycarbonate compositions may include low levels or branched polycarbonates. When present, branched polycarbonates are present in an amount effective to provide less than or equal to 0.04 mol% branching, based on the total moles of carbonate repeating units in the polycarbonate composition.
  • the branched polycarbonates are present in an amount effective to provide less than or equal to 0.025 mol%, less than or equal to 0.02 mol%, less than or equal to 0.015 mol%, less than or equal to 0.01 mol%, less than or equal to 0.005 mol%, or less than or equal to 0.001 mol% branching, based on the total moles of carbonate repeating units in the composition.
  • the polycarbonate compositions exclude branched polycarbonates.
  • the polycarbonate is a bisphenol A homopolycarbonate.
  • the bisphenol A homopolycarbonate may have: a melt flow rate of 3-150, per 10 min at 300 oC and a 1.2 kg load according to ASTM D1238-04 and a Mw of 15,000-40,000, g/mole, preferably 20,000-30,000 g/mole, more preferably 21,000 to 23,0000, each as measured as described above.
  • the polycarbonate includes a linear or branched bisphenol A homopolycarbonate.
  • the polycarbonate includes a linear bisphenol A polycarbonate homopolymer having a weight average molecular weight of 26,000 to 40,000 grams per mole, preferably 27,000 to 35,000 grams per mole, as determined by gel permeation chromatography using polystyrene standards and calculated for polycarbonate; or a linear bisphenol A polycarbonate homopolymer having a weight average molecular weight of 15,000 to 25,000 grams per mole, preferably 17,000 to 25,000 grams per mole, as determined by gel permeation chromatography using polystyrene standards and calculated for polycarbonate; or a combination thereof.
  • the polycarbonate of the polycarbonate composition may include post- consumer recycled polycarbonate ("PCR-PC").
  • PCR-PC is derived or recycled from polycarbonate as described herein.
  • PCR-PC may be recovered from a source after consumption.
  • PCR-PC may be recovered from post-consumer sources including, but not limited 23SHPP0022-WO-PCT (SS230150PCT) to, household appliance waste such as TV, air conditioner, washing machine, refrigerator, etc.
  • the recovered polycarbonate component may be similar or even identical to the chemical composition of the corresponding original polycarbonate.
  • the polycarbonate may be derived from an optical disc.
  • the PCR- PC may be derived from a plastic bottle, such as a plastic beverage bottle.
  • virgin polycarbonate polymers refer to polycarbonate polymers produced directly from petrochemical feedstocks, such as natural gas or crude oil, which have never been used or processed before.
  • impurities one or more additives conventionally used in the manufacture of impact modified thermoplastics may be present as impurities. Additional impurities may include processing residues such as lubricants, mold release agents, antistatic agents, stabilizers, light stabilizers, flame retardants, metals (e.g., iron, aluminum, and copper).
  • impurities may include polyurethane particles that cannot be completely removed during the recovery process.
  • the level of impurities in the PCR-PC is less than about 5 wt%, or in other aspects less than about 3 wt%, or in other aspects less than about 2 wt%. If present, the impurities do not significantly affect the properties of the compositions described herein.
  • the polycarbonate(s) may be present, for example, from 10-95 wt%, 20-90 wt%, 30-90 wt%, 40-90 wt%, 50-90 wt%, 60-90 wt%, 60-70 wt%, 20-60 wt%, 20-50 wt%, or 20-40 wt%, based on the total weight of the polycarbonate composition.
  • Polycarbonates include homopolycarbonates (wherein each R 1 in the polymer is the same) and copolymers including different R 1 moieties in the carbonate (“copolycarbonates”), and copolymers including carbonate units and other types of polymer units, such as ester units or siloxane units.
  • the polycarbonate compositions may include one or more poly(carbonate- siloxane)s, also referred to in the art as polycarbonate-polysiloxane copolymers.
  • the polysiloxane blocks include repeating diorganosiloxane units as in formula (10) wherein each R is independently a C 1-13 monovalent organic group.
  • R may be a C 1- 13 alkyl, C 1-13 alkoxy, C 2-13 alkenyl, C 2-13 alkenyloxy, C 3-6 cycloalkyl, C 3-6 cycloalkoxy, C 6-14 aryl, C 6-10 aryloxy, C 7-13 arylalkylene, C 7-13 arylalkylenoxy, C 7-13 alkylarylene, or C 7-13 23SHPP0022-WO-PCT (SS230150PCT) alkylaryleneoxy.
  • the foregoing groups may be fully or partially halogenated with fluorine, chlorine, bromine, or iodine, or a combination thereof.
  • R is unsubstituted by halogen. Combinations of the foregoing R groups may be used in the same copolymer.
  • the value of E in formula (10) may 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 2 to 1,000, preferably 2 to 500, 2 to 200, or 2 to 125, 5 to 80, or 10 to 70. In an aspect, E has an average value of 10 to 80 or 10 to 40, and in still another aspect, E has an average value of 40 to 80, or 40 to 70.
  • E is of a lower value, e.g., less than 40, it may be desirable to use a relatively larger amount of the poly(carbonate-siloxane) copolymer. Conversely, where E is of a higher value, e.g., greater than 40, a relatively lower amount of the poly(carbonate-siloxane) copolymer may be used.
  • a combination of a first and a second (or more) poly(carbonate-siloxane) copolymers may be used, wherein the average value of E of the first copolymer is less than the average value of E of the second copolymer.
  • the polysiloxane blocks are of formula (11) wherein E and R is each as defined if formula (10); each R may be the same or different, and is as defined above; and Ar may be the same or different, and is a substituted or unsubstituted C6-30 arylene, wherein the bonds are directly connected to an aromatic moiety.
  • Ar groups in formula (11) may be derived from a C6-30 dihydroxyarylene compound, for example a dihydroxyarylene compound of formula (3) or (6).
  • Dihydroxyarylene compounds are 1,1-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, 1,1-bis(4-hydroxyphenyl) propane, 1,1-bis(4-hydroxyphenyl) n-butane, 2,2-bis(4-hydroxy-1-methylphenyl) propane, 1,1-bis(4- hydroxyphenyl) cyclohexane, bis(4-hydroxyphenyl sulfide), and 1,1-bis(4-hydroxy-t- butylphenyl) propane.
  • polysiloxane blocks are of formula (13) 23SHPP0022-WO-PCT (SS230150PCT) wherein R and E are as described above, and each R 5 is independently a divalent C1-30 organic group, and wherein the polymerized polysiloxane unit is the reaction residue of its corresponding dihydroxy compound.
  • the polysiloxane blocks are of formula (14): wherein R and E are as defined above.
  • R 6 in formula (14) is a divalent C 2-8 aliphatic group.
  • Each M in formula (14) may be the same or different, and may be a halogen, cyano, nitro, C 1-8 alkylthio, C 1-8 alkyl, C 1-8 alkoxy, C 2-8 alkenyl, C 2-8 alkenyloxy, C 3-8 cycloalkyl, C 3-8 cycloalkoxy, C 6-10 aryl, C 6-10 aryloxy, C 7-12 aralkyl, C 7-12 aralkoxy, C 7-12 alkylaryl, or C 7-12 alkylaryloxy, wherein each n is independently 0, 1, 2, 3, or 4.
  • M is 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 is a dimethylene, trimethylene or tetramethylene; and
  • R is a C1-8 alkyl, haloalkyl such as trifluoropropyl, cyanoalkyl, or aryl such as phenyl, chlorophenyl or tolyl.
  • R is methyl, or a combination of methyl and trifluoropropyl, or a combination of methyl and phenyl.
  • R is methyl
  • M is methoxy
  • n is one
  • R 6 is a divalent C1-3 aliphatic group.
  • Specific polysiloxane blocks are of the formula or a combination thereof, wherein E has an average value of 2 to 200, 2 to 125, 5 to 125, 5 to 100, 5 to 50, 20 to 80, or 5 to 20.
  • Blocks of formula (14) may be derived from the corresponding dihydroxy polysiloxane, which in turn may be prepared effecting a platinum-catalyzed addition between the siloxane hydride and an aliphatically unsaturated monohydric phenol such as eugenol, 2- alkylphenol, 4-allyl-2-methylphenol, 4-allyl-2-phenylphenol, 4-allyl-2-bromophenol, 4-allyl-2-t- butoxyphenol, 4-phenyl-2-phenylphenol, 2-methyl-4-propylphenol, 2-allyl-4,6-dimethylphenol, 2-allyl-4-bromo-6-methylphenol, 2-allyl-6-methoxy-4-methylphenol and 2-allyl-4,6- 23SHPP0022-WO-PCT (SS230150PCT) dimethylphenol.
  • an aliphatically unsaturated monohydric phenol such as eugenol, 2- alkylphenol, 4-allyl-2-methylphenol, 4-allyl-2-phenylphenol,
  • Transparent poly(carbonate-siloxane) copolymers include carbonate units (1) derived from bisphenol A, and repeating siloxane units (14a), (14b), (14c), or a combination thereof (preferably of formula 14a), wherein E has an average value of 4 to 50, 4 to 15, preferably 5 to 15, more preferably 6 to 15, and still more preferably 7 to 10.
  • the transparent copolymers may be manufactured using one or both of the tube reactor processes described in U.S.
  • Patent Application No.2004/0039145A1 or the process described in U.S. Patent No. 6,723,864 may be used to synthesize the poly(carbonate-siloxane) copolymers.
  • the poly(carbonate-siloxane) copolymers may include 50 to 99 wt% of carbonate units and 1 to 50 wt% siloxane units. Within this range, the poly(carbonate-siloxane) copolymer may include 70 to 98 wt%, more preferably 75 to 97 wt% of carbonate units and 2 to 30 wt%, more preferably 3 to 25 wt% siloxane units.
  • the poly(carbonate-siloxane) copolymers may include 50 to 99 wt% of carbonate units and 1 to 50 wt% siloxane units. Within this range, the poly(carbonate-siloxane) copolymer may include 70 to 98 wt%, more preferably 75 to 97 wt% of carbonate units and 2 to 45 wt%, more preferably 5 to 10 or 30 to 45 wt% siloxane units.
  • a blend is used, in particular a blend of a bisphenol A homopolycarbonate and a poly(carbonate-siloxane) block copolymer of bisphenol A blocks and eugenol capped polydimethylsiloxane blocks, of the formula wherein x is 1 to 200, preferably 5 to 85, preferably 10 to 70, preferably 15 to 65, and more preferably 40 to 60; x is 1 to 500, or 10 to 200, and z is 1 to 1000, or 10 to 800.
  • x is 1 to 200
  • y is 1 to 90 and z is 1 to 600
  • x is 30 to 50
  • y 10 to 30 and z is 45 to 600.
  • the polysiloxane blocks may be randomly distributed or controlled distributed among the polycarbonate blocks.
  • Poly(carbonate-siloxane)s may have a weight average molecular weight of 2,000 to 100,000 g/mol, preferably 5,000 to 50,000 g/mol as measured by gel permeation chromatography using a crosslinked styrene-divinyl benzene column, at a sample concentration of 1 milligram per milliliter, using polystyrene standards and calculated for polycarbonate.
  • the poly(carbonate-siloxane)s may have a melt volume flow rate, measured at 300°C/1.2 kg, of 0.1 to 50 cubic centimeters per 10 minutes (cc/10 min), preferably 2 to 30 cc/10 min, according to ASTM D1238-04. Combinations of the poly(carbonate-siloxane)s of different flow properties may be used to achieve the overall desired flow property.
  • One or more poly(carbonate-siloxane) copolymers may be included in the polycarbonate compositions.
  • the polycarbonate compositions may include a poly(carbonate- siloxane) copolymer having a siloxane repeating units of greater than 30 to 70 wt%, based on the total weight of the poly(carbonate-siloxane) copolymer. Within this range, the poly(carbonate- siloxane) may have a siloxane repeating units of 35 to 70 wt%, or 35 to 65 wt%.
  • siloxane repeating units” of a poly(carbonate-siloxane) refers to the content of siloxane units based on the total weight of the poly(carbonate-siloxane).
  • the polycarbonate compositions may include a poly(carbonate-siloxane) copolymer having a siloxane repeating units of greater than 10 to 30 wt%, based on the total weight of the poly(carbonate-siloxane). Within this range, the poly(carbonate-siloxane) copolymer may have a siloxane repeating units of 15 to 25 wt%.
  • the polycarbonate compositions may include a poly(carbonate-siloxane) copolymer having a siloxane repeating units of 10 wt% or less, based on the total weight of the poly(carbonate- siloxane).
  • the poly(carbonate-siloxane) copolymer may have a siloxane repeating units of 4 to 8 wt%.
  • the polycarbonate compositions may include two or more of the foregoing.
  • the poly(carbonate siloxane) copolymers may be present in an amount effective to provide 4 wt% or less, less than 2 wt%, less than 1 wt%, less than 0.5 wt%, or less than 0.1 wt% of siloxane repeating units, each based on the total composition.
  • the polycarbonate compositions exclude poly(carbonate siloxane)s.
  • the polycarbonate compositions include a polycarbonate including repeating units derived from a monomer including a pendant ester group.
  • the polycarbonate having pendant ester groups includes a repeating unit derived from a bisphenol and a repeating unit derived from a monomer including the pendant ester group.
  • the monomer including the pendant ester group has the structure of Formula (A) or Formula (B): 23SHPP0022-WO-PCT (SS230150PCT) [00038]
  • R is a linear or a branched C2-C15 alkyl group, preferably a branched C2- C15 alkyl group.
  • R is ethyl, isopropyl, sec-butyl, tert-butyl, or isopentyl, preferably ethyl or isopropyl, more preferably isopropyl.
  • the a polycarbonate including repeating units derived from a monomer including a pendant ester group may include repeating units derived from Formula (A), repeating units of Formula (B), or a combination thereof.
  • the pendant ester groups in the polycarbonate may be the same or different.
  • the polycarbonate may be derived from Formula (A), Formula (B), or a combination thereof and the pendant ester groups may be the same.
  • the polycarbonate may be derived from Formula (A), Formula (B), or a combination thereof and the pendant ester groups may be different.
  • the a polycarbonate including repeating units derived from a monomer including a pendant ester group may include bisphenol A repeating units.
  • the a polycarbonate including repeating units derived from a monomer including a pendant ester group may include bisphenol A repeating units and repeating units derived from a monomer of Formula (A), a monomer of Formula (B), or a combination thereof, wherein the pendant ester groups include ethyl esters, isopropyl esters, or a combination thereof.
  • the polycarbonate(s) including repeating units derived from a monomer including a pendant ester group may include a polysiloxane block as described above.
  • the polycarbonate including repeating units derived from a monomer including a pendant ester group may include 1-99 mol%, 1-90 mol%, 1-75 mol%, 1-60 mol%, 1- 50 mol%, 1-40 mol%, 1-30 mol%, 1-25 mol%, 1-20 mol%, 1-15 mol%, 1-10 mol%, or 1-5 mol% of ester repeating units, each based on the total moles of monomers in the polycarbonate.
  • the a polycarbonate including repeating units derived from a monomer including a pendant ester group may be present in the composition in an amount effective to provide 0.1-1 mol%, 0.2-0.9 mol%, or 0.4 to 0.8 mol% ester repeating units, each based on the total monomers in the composition.
  • 23SHPP0022-WO-PCT (SS230150PCT)
  • the polycarbonate including repeating units derived from a monomer including a pendant ester group may be oligomeric or polymeric, with a weight average molecular weight ranging from 1,000 to 150,000 g/mol, each measured by GPC using polystyrene standards and calculated for polycarbonate.
  • the polycarbonate including repeating units derived from a monomer including a pendant ester group may have a Mw of 5,000 to less than 26,000 g/mol, or 5,000-20,000 g/mol, 5,000-15,000 g/mol, or 10,000-15,000 g/mol. In some aspects, the polycarbonate including repeating units derived from a monomer including a pendant ester group may have a Mw of 26,000-50,000 g/mol or 26,000-45,000 g/mol. In some aspects, the polycarbonate including repeating units derived from a monomer including a pendant ester group may have a Mw of 50,000-150,000 g/mol, 75,000-150,000 g/mol, or 100,000-150,000 g/mol.
  • polystyrene standards and calculated for polycarbonate refers to measurement of the retention time by GPC, fitting the retention time value to a curve for polystyrene and calculating the molecular weight for polycarbonate.
  • Polycarbonates may be manufactured by processes such as interfacial polymerization and melt polymerization.
  • an exemplary process generally involves dissolving or dispersing a dihydroxy compound in aqueous NaOH or KOH, adding the resulting mixture to a water- immiscible solvent, and contacting the reactants with a carbonate precursor in the presence of a catalyst such as, for example, a tertiary amine or a phase transfer catalyst, under controlled pH conditions, e.g., 8 to 10.
  • a catalyst such as, for example, a tertiary amine or a phase transfer catalyst
  • the water-immiscible solvent may be, for example, methylene chloride, 1,2-dichloroethane, chlorobenzene, toluene, and the like.
  • Exemplary carbonate precursors include a carbonyl halide such as carbonyl bromide or carbonyl chloride (phosgene) a bishaloformate of a dihydroxy compound (e.g., the bischloroformate of bisphenol A, hydroquinone ethylene glycol, neopentyl glycol, or the like), and diaryl carbonates. A combination thereof may also be used.
  • a carbonyl halide such as carbonyl bromide or carbonyl chloride (phosgene)
  • phosgene carbonyl chloride
  • bishaloformate of a dihydroxy compound e.g., the bischloroformate of bisphenol A, hydroquinone ethylene glycol, neopentyl glycol, or the like
  • diaryl carbonates e.g., the bischloroformate of bisphenol A, hydroquinone ethylene glycol, neopentyl glycol, or the like
  • the diaryl carbonate ester may be diphenyl carbonate, or an activated diphenyl carbonate having electron-withdrawing substituents on each aryl, such as bis(4-nitrophenyl)carbonate, bis(2-chlorophenyl)carbonate, bis(4-chlorophenyl)carbonate, bis(methyl salicyl)carbonate, bis(4-methylcarboxylphenyl) carbonate, bis(2-acetylphenyl) carboxylate, bis(4-acetylphenyl) carboxylate, or a combination thereof.
  • an activated diphenyl carbonate having electron-withdrawing substituents on each aryl such as bis(4-nitrophenyl)carbonate, bis(2-chlorophenyl)carbonate, bis(4-chlorophenyl)carbonate, bis(methyl salicyl)carbonate, bis(4-methylcarboxylphenyl) carbonate, bis(2-acetylphenyl) carboxylate, bis(
  • phase transfer catalysts that may be used are 23SHPP0022-WO-PCT (SS230150PCT) catalysts of the formula (R 3 )4Q + X, wherein each R 3 is the same or different, and is a C1-10 alkyl; Q is a nitrogen or phosphorus atom; and X is a halogen atom or a C1-8 alkoxy or C6-18 aryloxy.
  • Exemplary phase transfer catalysts include (CH3(CH2)3)4NX, (CH3(CH2)3)4PX, CH3(CH3(CH2)2)3NX, wherein X is Cl-, Br-, a C1-8 alkoxy or a C6-18 aryloxy.
  • An effective amount of a phase transfer catalyst may be 0.1 to 10 wt%, or 0.5 to 2 wt%, each based on the weight of dihydroxy compound in the phosgenation mixture.
  • melt processes may be used to make the polycarbonates.
  • polycarbonates may be prepared by co-reacting, in a molten state, a dihydroxy reactant and a diaryl carbonate ester in the presence of a transesterification catalyst.
  • the reaction can be carried out in typical polymerization equipment, such as a continuously stirred reactor (CSTR), plug flow reactor, wire wetting fall polymerizers, free fall polymerizers, wiped film polymerizers, BANBURY mixers, single or twin screw extruders, or a combination of the foregoing. Volatile monohydric phenol is removed from the molten reactants by distillation and the polymer is isolated as a molten residue. Melt polymerization can be conducted as a batch process or as a continuous process.
  • the melt polymerization conditions used may include two or more distinct reaction stages, for example, a first reaction stage in which the starting dihydroxy aromatic compound and diaryl carbonate are converted into an oligomeric polycarbonate and a second reaction stage wherein the oligomeric polycarbonate formed in the first reaction stage is converted to high molecular weight polycarbonate.
  • Such "staged" polymerization reaction conditions are especially suitable for use in continuous polymerization systems wherein the starting monomers are oligomerized in a first reaction vessel and the oligomeric polycarbonate formed therein is continuously transferred to one or more downstream reactors in which the oligomeric polycarbonate is converted to high molecular weight polycarbonate.
  • the oligomeric polycarbonate produced has a number average molecular weight of 1,000 to 7,500 g/mol.
  • the number average molecular weight (Mn) of the polycarbonate is increased to between 8,000 and 25,000 g/mol (using polycarbonate standard).
  • solvents are not used in the process, and the reactants dihydroxy aromatic compound and the diaryl carbonate are in a molten state.
  • the reaction temperature may be 100 o C to 350 o C, preferably 180 o C to 310 o C.
  • the pressure can be at atmospheric pressure, supra- atmospheric pressure, or a range of pressures from atmospheric pressure to 15 torr in the initial stages of the reaction, and at a reduced pressure at later stages, for example 0.2 to 15 torr.
  • the reaction time is generally 0.1 hours to 10 hours.
  • 23SHPP0022-WO-PCT (SS230150PCT) Catalysts used in the melt transesterification polymerization production of polycarbonates may include alpha or beta catalysts. Beta catalysts are typically volatile and degrade at elevated temperatures. Beta catalysts are therefore preferred for use at early low- temperature polymerization stages. Alpha catalysts are typically more thermally stable and less volatile than beta catalysts.
  • the alpha catalyst may include a source of alkali or alkaline earth ions.
  • the sources of these ions include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide, as well as alkaline earth hydroxides such as magnesium hydroxide and calcium hydroxide.
  • alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide
  • alkaline earth hydroxides such as magnesium hydroxide and calcium hydroxide.
  • Other possible sources of alkali and alkaline earth metal ions include the corresponding salts of carboxylic acids (such as sodium acetate) and derivatives of ethylene diamine tetraacetic acid (EDTA) (such as EDTA tetrasodium salt, and EDTA magnesium disodium salt).
  • carboxylic acids such as sodium acetate
  • EDTA ethylene diamine tetraacetic acid
  • alpha transesterification catalysts include alkali or alkaline earth metal salts of carbonate, such as Cs 2 CO 3 , NaHCO 3 , and Na 2 CO 3 , and the like, non-volatile inorganic acid such as NaH 2 PO 3 , NaH 2 PO 4 , Na 2 HPO 3 , KH 2 PO 4 , CsH 2 PO 4 , Cs 2 HPO 4 , and the like, or mixed salts of phosphoric acid, such as NaKHPO 4 , CsNaHPO 4 , CsKHPO 4 , and the like. Combinations including at least one of any of the foregoing catalysts may be used.
  • Possible beta catalysts may include a quaternary ammonium compound, a quaternary phosphonium compound, or a combination thereof.
  • the quaternary ammonium compound may be a compound of the structure (R 4 )4N + X-, wherein each R 4 is the same or different, and is a C1-20 alkyl, a C4-20 cycloalkyl, or a C4-20 aryl; and X- is an organic or inorganic anion, for example a hydroxide, halide, carboxylate, sulfonate, sulfate, formate, carbonate, or bicarbonate.
  • organic quaternary ammonium compounds include tetramethyl ammonium hydroxide, tetrabutyl ammonium hydroxide, tetramethyl ammonium acetate, tetramethyl ammonium formate, tetrabutyl ammonium acetate, and combination thereof. Tetramethyl ammonium hydroxide is often used.
  • the quaternary phosphonium compound may be a compound of the structure (R 5 )4P + X-, wherein each R 5 is the same or different, and is a C1-20 alkyl, a C4-20 cycloalkyl, or a C4-20 aryl; and X- is an organic or inorganic anion, for example a hydroxide, phenoxide, halide, carboxylate such as acetate or formate, sulfonate, sulfate, formate, carbonate, or bicarbonate.
  • X- is a polyvalent anion such as carbonate or sulfate it is understood that the positive and negative charges in the quaternary ammonium and phosphonium structures are properly balanced.
  • organic quaternary phosphonium compounds include tetramethyl phosphonium hydroxide, tetramethyl phosphonium acetate, tetramethyl phosphonium formate, tetrabutyl phosphonium hydroxide, 23SHPP0022-WO-PCT (SS230150PCT) tetrabutyl phosphonium acetate (TBPA), tetraphenyl phosphonium acetate, tetraphenyl phosphonium phenoxide, and combination thereof.
  • TBPA is often used.
  • the amount of alpha and beta catalyst used may be based upon the total number of moles of dihydroxy compound used in the polymerization reaction.
  • beta catalyst for example, a phosphonium salt
  • the alpha catalyst may be used in an amount sufficient to provide 1 x 10 -2 to 1 x 10 -8 moles, preferably, 1 x 10 -4 to 1 x 10 -7 moles of metal per mole of the dihydroxy compounds used.
  • the amount of beta catalyst may be 1 x 10 -2 to 1 x 10 -5 , preferably 1 x 10 -3 to 1 x 10 -4 moles per total mole of the dihydroxy compounds in the reaction mixture. Quenching of the transesterification catalysts and any reactive catalysts residues with an acidic compound after polymerization is completed may also be useful in some melt polymerization processes. Removal of catalyst residues or quenching agent and other volatile residues from the melt polymerization reaction after polymerization is completed may also be useful in some melt polymerization processes. [00048] Branched polycarbonate blocks may be prepared by adding a branching agent during polymerization.
  • branching agents include polyfunctional organic compounds containing at least three functional groups selected from hydroxyl, carboxyl, carboxylic anhydride, haloformyl, and mixtures of the foregoing functional groups.
  • Specific examples include trimellitic acid, trimellitic anhydride, tris-phenol TC (1,3,5-tris((p- hydroxyphenyl)isopropyl)benzene), tris-phenol PA (4(4(1,1-bis(p-hydroxyphenyl)-ethyl) alpha, alpha-dimethyl benzyl)phenol), 4-chloroformyl phthalic anhydride, trimesic acid, and benzophenone tetracarboxylic acid.
  • Combinations including linear polycarbonates and branched polycarbonates may be used.
  • a particular type of branching agent is used to create branched polycarbonate materials. These branched polycarbonate materials have statistically more than two end groups.
  • the branching agent is added in an amount (relative to the bisphenol monomer) that is sufficient to achieve the desired branching content, that is, more than two end groups.
  • the molecular weight of the polymer may become very high upon addition of the branching agent, and to avoid excess viscosity during polymerization, an increased amount of a chain stopper agent may be used, relative to the amount used when the particular branching agent is not 23SHPP0022-WO-PCT (SS230150PCT) present.
  • Such branching agents include aromatic triacyl halides, for example triacyl chlorides of formula (20) wherein Z is a halogen, C1-3 alkyl, C1-3 alkoxy, C7-12 arylalkylene, C7-12 alkylarylene, or nitro, and z is 0 to 3; a tri-substituted phenol of formula (21) wherein T is a C 1-20 alkyl, C 1-20 alkoxy, C 7-12 arylalkyl, or C 7-12 alkylaryl, Y is a halogen, C 1-3 alkyl, C 1-3 alkoxy, C 7-12 arylalkyl, C 7-12 alkylaryl, or nitro, s is 0 to 4; or a compound of formula (22) (isatin-bis-phenol).
  • Z is a halogen, C1-3 alkyl, C1-3 alkoxy, C7-12 arylalkylene, C7-12 alkylarylene, or nitro
  • z is 0 to
  • branching agents examples include trimellitic trichloride (TMTC), tris-p-hydroxyphenylethane (THPE), and isatin-bis-phenol.
  • TMTC trimellitic trichloride
  • THPE tris-p-hydroxyphenylethane
  • isatin-bis-phenol examples include trimellitic trichloride (TMTC), tris-p-hydroxyphenylethane (THPE), and isatin-bis-phenol.
  • the amount of the branching agents used in the manufacture of the polymer will depend on a number of considerations, for example the type of R 1 groups, the amount of chain stopper, e.g., cyanophenol, and the desired molecular weight of the polycarbonate. In general, the amount of branching agent is effective to provide 0.1 to 10 branching units per 100 R 1 units, preferably 0.5 to 8 branching units per 100 R 1 units, and more preferably 0.75 to 5 branching units per 100 R 1 units.
  • the branching agent is present in an amount to provide 0.1 to 10 triester branching units per 100 R 1 units, preferably 0.5 to 8, and more preferably 0.75 to 5 triester branching units per 100 R 1 units.
  • the branching agent is present in an amount effective to provide 0.1 to 10 triphenyl carbonate branching units per 100 R 1 units, preferably 0.5 to 8, and more preferably 2.5 to 3.5 triphenylcarbonate units per 100 R 1 units.
  • a combination of two or more branching agents may be used.
  • the polycarbonate is a branched polycarbonate including units as described above; greater than or equal to 3 mole%, based on the total moles of the polycarbonate, of moieties derived from a branching agent; and end-capping groups derived from an end-capping agent having a pKa between 8.3 and 11.
  • the branching agent may include trimellitic trichloride, 1,1,1-tris(4-hydroxyphenyl)ethane or a combination of trimellitic trichloride and 1,1,1-tris(4-hydroxyphenyl)ethane, and the end-capping agent is phenol or a phenol containing a substituent of cyano group, aliphatic groups, olefinic groups, aromatic groups, halogens, ester groups, ether groups, or a combination thereof.
  • the end-capping agent is phenol, p-t-butylphenol, p-methoxyphenol, p-cyanophenol, p-cumylphenol, or a combination thereof.
  • An end-capping agent (also referred to as a chain stopper agent or chain terminating agent) may be included during polymerization to provide end groups.
  • the end- capping agent (and thus end groups) are selected based on the desired properties of the polycarbonates.
  • Exemplary end-capping agents are exemplified by monocyclic phenols such as phenol and C1-22 alkyl-substituted phenols such as p-cumyl-phenol, resorcinol monobenzoate, and p-and tertiary-butyl phenol, monoethers of diphenols, such as p-methoxyphenol, and alkyl- substituted phenols with branched chain alkyl substituents having 8 to 9 carbon atoms, 4- substituted-2-hydroxybenzophenones and their derivatives, aryl salicylates, monoesters of diphenols such as resorcinol monobenzoate, 2-(2-hydroxyaryl)-benzotriazoles and their derivatives, 2-(2-hydroxyaryl)-1,3,5-triazines and their derivatives, mono-carboxylic acid chlorides such as benzoyl chloride, C1-22 alkyl-substituted benzoyl chloride, toluoyl chlor
  • the polycarbonate compositions include a non-halogenated flame retardant.
  • the polycarbonate compositions avoid the use of fluorinated flame retardants such as Rimar salt and brominated flame retardants such a brominated polycarbonate 23SHPP0022-WO-PCT (SS230150PCT) copolymers.
  • Inorganic non-halogenated flame retardants may be used, for example salts of aromatic sulfonates such as sodium benzene sulfonate, sodium toluene sulfonate (NATS), and the like, salts of aromatic sulfone sulfonates such as potassium diphenylsulfone sulfonate (KSS), and the like; salts formed by reacting for example an alkali metal or alkaline earth metal (e.g., lithium, sodium, potassium, magnesium, calcium and barium salts) and an inorganic acid complex salt, for example, an oxo-anion (e.g., alkali metal and alkaline-earth metal salts of carbonic acid, such as Na2CO3, K2CO3, MgCO3, CaCO3, and BaCO3, KSS and NATS, alone or in combination with other non-halogenated flame retardants, are particularly useful.
  • an alkali metal or alkaline earth metal e.g., lithium, sodium
  • Exemplary amounts of an aromatic sulfone sulfonate salt may be 0.01 to 1.0 wt%, or 0.1 to 0.6 wt%, based on the total weight of the polycarbonate composition.
  • the polycarbonate compositions may include an organophosphorus flame retardant.
  • the aromatic group may be a substituted or unsubstituted C 3-30 group containing one or more of a monocyclic or polycyclic aromatic moiety (which may optionally contain with up to three heteroatoms (N, O, P, S, or Si)) and optionally further containing one or more nonaromatic moieties, for example alkyl, alkenyl, alkynyl, or cycloalkyl.
  • the aromatic moiety of the aromatic group may be directly bonded to the phosphorus-containing group, or bonded via another moiety, for example an alkylene group.
  • the aromatic moiety of the aromatic group may be directly bonded to the phosphorus-containing group, or bonded via another moiety, for example an alkylene group.
  • the aromatic group is the same as an aromatic group of the polycarbonate backbone, such as a bisphenol group (e.g., bisphenol A), a monoarylene group (e.g., a 1,3-phenylene or a 1,4-phenylene), or a combination including at least one of the foregoing.
  • a combination of different phosphorus-containing groups may be used.
  • the aromatic group may be directly or indirectly bonded to the phosphorus, or to an oxygen of the phosphorus-containing group (i.e., an ester).
  • the organophosphorus flame retardant may include an oxaphosphorinoxide of the Formula (23) below.
  • 23SHPP0022-WO-PCT SS230150PCT
  • the phosphorus atom and one oxygen atom are part of a cyclic structure, for example, a five or six membered ring and q is at least two.
  • Each Ar is independently C6-18 aryl, preferably benzene, which is optionally substituted with a C1-18 hydrocarbyl group, or a C1-18 hydrocarbyloxy group (e.g., -O-hydrocarbyl).
  • R 2 is hydrogen, C1-C18 alkyl, C3-10 cycloalkyl, (C1-6 alkyl)C3-10 cycloalkyl, C6-18 aryl, (C1-6 alkyl)C6-18 aryl, C3-12 heteroaryl, or (C1-6 alkyl)C3-12 heteroaryl.
  • R 2 is hydrogen, C1-C18 alkyl, C3-10 cycloalkyl, (C1-6 alkyl)C3-10 cycloalkyl, C6-18 aryl, (C1-6 alkyl)C6-18 aryl, C3-12 heteroaryl, or (C1-6 alkyl)C3-12 heteroaryl.
  • at least one hydrogen atom of these groups may be substituted with a group having an N, S, O, or F atom.
  • (C 1-6 alkyl)C 3-10 cycloalkyl refers to a cycloalkyl group attached to an alkylene group
  • (C1-6 alkyl)C6-18 aryl refers to an aryl group attached to an alkylene group
  • (C 1-6 alkyl)C 3-12 heteroaryl refers to a heteroaryl group attached to an alkylene group.
  • any carbon-carbon single bond is optionally replaced by a carbon-carbon double or triple bond
  • n and p are each 1 or more and m is 0 (“Di-DOPO” type compounds)
  • X is C1-C18 alkylidene, C3-10 cycloalkylidene, C6-18 arylene, C3-12 heteroarylene, a group derived from Formula (3), or a group represented by -L 1 -X’-L 2 -.
  • X’ is C1-C18 alkylidene, C3-10 cycloalkylidene, C6-18 arylene, C3-12 heteroarylene, or a group derived from Formula (3).
  • an oxaphosphorinoxide examples include 9,10-dihydro-9-oxo-10- phosphaphenanthrene-10-oxide (23a, “DOPO”), commercially available as from SANKO CO., LTD., under the trade name Sanko-HCA, 3-(6-oxidodibenzo[c,e][1,2]oxaphosphinin-6- yl)propanamide (23b, “AAM-DOPO”), and 6-[(1-oxido-2,6,7-trioxa-1- phosphabicyclo[2.2.2.]oct-4-yl)methoxy-6-oxide (23c, “DOPO-PEPA”).
  • a specific formula for a Di-DOPO compound is Formula (24). wherein Ar 1 is C 3-18 heteroaryl or C 6-18 aryl, each instance of R 3 is independently hydrogen, C 1-18 alkyl, C 3-18 heteroaryl or C 6-18 aryl, each instance of R 1 is independently C 1-18 alkyl, C 3-18 heteroaryl or C 6-18 aryl, and any hydrogen atom on an aryl or heteroaryl ring may be optionally substituted with a C 1-18 alkyl group.
  • An exemplary Di-DOPO compound is HTP-6123G, commercially available from GUIZHOU YUANYI MINING GROUP CO.
  • the aromatic organophosphorus compound is a monomeric phosphate.
  • G corresponds to a monomer used to form the polycarbonate, e.g., resorcinol.
  • Exemplary phosphates include 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, and the like.
  • 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 organophosphorus compounds are also useful, for example, compounds of the formulas wherein each G 1 is independently a C1-30 hydrocarbyl; each G 2 is independently a C1-30 23SHPP0022-WO-PCT (SS230150PCT) hydrocarbyl or hydrocarbyloxy; X a is as defined in formula (3) or formula (4); each X is independently a bromine or chlorine; m is 0 to 4, and n is 1 to 30.
  • X a is a single bond, methylene, isopropylidene, or 3,3,5-trimethylcyclohexylidene.
  • Specific aromatic organophosphorus compounds are inclusive of acid esters of formula (9) wherein each R 16 is independently C 1-8 alkyl, C 5-6 cycloalkyl, C 6-20 aryl, or C 7-12 arylalkylene, each optionally substituted by C 1-12 alkyl, specifically by C 1-4 alkyl and X is a mono- or poly- nuclear aromatic C 6-30 moiety or a linear or branched C 2-30 aliphatic radical, which may be OH- substituted and may contain up to 8 ether bonds, provided that at least one R 16 or X is an aromatic group; each n is independently 0 or 1; and q is from 0.5 to 30.
  • each R 16 is independently C 1-4 alkyl, naphthyl, phenyl(C 1-4 )alkylene, aryl groups optionally substituted by C 1-4 alkyl; each X is a mono- or poly-nuclear aromatic C 6-30 moiety, each n is 1; and q is from 0.5 to 30.
  • each R 16 is aromatic, e.g., phenyl; each X is a mono- or poly-nuclear aromatic C6-30 moiety, including a moiety derived from formula (2); n is one; and q is from 0.8 to 15.
  • each R 16 is phenyl; X is cresyl, xylenyl, propylphenyl, or butylphenyl, one of the following divalent groups , or a combination including one or more of the foregoing; n is 1; and q is from 1 to 5, or from 1 to 2.
  • at least one R 16 or X corresponds to a monomer used to form the polycarbonate, e.g., bisphenol A, resorcinol, or the like.
  • Aromatic organophosphorus compounds of this type include the bis(diphenyl) phosphate of hydroquinone, resorcinol bis(diphenyl phosphate) (RDP), and bisphenol A bis(diphenyl) phosphate (BPADP), and their oligomeric and polymeric counterparts.
  • the organophosphorus flame retardant containing a phosphorus-nitrogen bond may be a phosphazene, phosphonitrilic chloride, phosphorus ester amide, phosphoric acid amide, phosphonic acid amide, phosphinic acid amide, or tris(aziridinyl) phosphine oxide. These flame-retardant additives are commercially available.
  • the organophosphorus flame 23SHPP0022-WO-PCT (SS230150PCT) retardant containing a phosphorus-nitrogen bond is a phosphazene or cyclic phosphazene of the formulas wherein w1 is 3 to 10,000; w2 is 3 to 25, or 3 to 7; and each R w is independently a C1-12 alkyl, alkenyl, alkoxy, aryl, aryloxy, or polyoxyalkylene group.
  • at least one hydrogen atom of these groups may be substituted with a group having an N, S, O, or F atom, or an amino group.
  • each R w may be a substituted or unsubstituted phenoxy, an amino, or a polyoxyalkylene group. Any given R w may further be a crosslink to another phosphazene group.
  • Exemplary crosslinks include bisphenol groups, for example bisphenol A groups. Examples include phenoxy cyclotriphosphazene, octaphenoxy cyclotetraphosphazene decaphenoxy cyclopentaphosphazene, and the like.
  • the phosphazene has a structure represented by the formula [00066]
  • Commercially available phenoxyphosphazenes having the aforementioned structures are LY202 manufactured and distributed by Lanyin Chemical Co., Ltd, FP-110 manufactured and distributed by Fushimi Pharmaceutical Co., Ltd, and SPB-100 manufactured and distributed by Otsuka Chemical Co., Ltd.
  • a cyclic siloxane, which also acts as a flame retardant, may also be used. Cyclic siloxanes have the general formula [(R) 2 SiO] y wherein R is a monovalent hydrocarbon or fluorinated hydrocarbon having from 1 to 18 carbon atoms and y is a number from 3 to 12.
  • a useful cyclic siloxane is octaphenylcyclotetrasiloxane.
  • the polycarbonate composition excludes a cyclic siloxane.
  • the organophosphorus flame retardant may be present in an amount effective to provide 0.05-3 wt%, 0.05-2.5 wt%, 0.05-2.1wt%, or 0.05 to less than 2.1 wt%, 0.05-2.0 wt%, 0.05-1.8 wt%, 0.05-1.5 wt%, 0.05-1.0 wt%, 0.05-0.8 wt%, 0.05-0.6 wt%, or 0.05-0.5 wt% phosphorus, each based on the total weight of the composition.
  • the polycarbonate compositions minimize or eliminate conventional anti-drip agents, in particular fluorinated anti-drip agents.
  • Anti-drip agents include, for example, a fibril forming or non-fibril forming fluoropolymer such as polytetrafluoroethylene (PTFE).
  • the anti- drip agent can be encapsulated by a rigid copolymer, for example styrene–acrylonitrile copolymer (SAN).
  • SAN styrene–acrylonitrile copolymer
  • TSAN PTFE encapsulated in SAN is known as TSAN.
  • An TSAN comprises 50 wt% PTFE and 50 wt% SAN, based on the total weight of the encapsulated fluoropolymer.
  • the SAN can comprise, for example, 75 wt% styrene and 25 wt% acrylonitrile based on the total weight of the copolymer.
  • the fluorinated anti-drip agent is present in an amount effective to provide 0.15 wt% or less fluorine to the total composition.
  • a fluorinated anti-drip agent is excluded from the polycarbonate compositions.
  • the polycarbonate composition may 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 polycarbonate composition, in particular flame resistance, impact resistance and the melt volume rate.
  • additives may be mixed at a suitable time during the mixing of the components for forming the composition.
  • Additives include 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, and radiation stabilizers.
  • a combination of additives may be used, for example a combination of a heat stabilizer, mold release agent, and ultraviolet light stabilizer. In general, the additives are used in the amounts generally known to be effective.
  • the total amount of the additives may be 0.01-10 wt%, 0.01-5 wt%, 0.01-2 wt%, or 0.01-1 wt%, each based on the total weight of the polycarbonate composition.
  • the polycarbonate compositions include a polycarbonate composition including a bisphenol A homopolycarbonate and a polycarbonate including bisphenol A carbonate units and repeating units derived from a monomer including a pendant ester group, based on the total weight of the polycarbonate composition; and an organophosphorus flame retardant present in amount effective to provide 0.05-1.0 wt% phosphorus.
  • the polycarbonate compositions include a polycarbonate composition including a bisphenol A homopolycarbonate and a polycarbonate including bisphenol A carbonate units and repeating units derived from a monomer including a pendant ester group, based on the total weight of the polycarbonate composition; and an 23SHPP0022-WO-PCT (SS230150PCT) organophosphorus flame retardant present in amount effective to provide 0.05-3.0 wt%, or 0.05- 2.1wt%, or 0.05 to less than 2.1 wt% phosphorus.
  • 23SHPP0022-WO-PCT SS230150PCT
  • the polycarbonate compositions include a polycarbonate composition including a bisphenol A homopolycarbonate and a polycarbonate including bisphenol A carbonate units and repeating units derived from a monomer including a pendant ester group, based on the total weight of the polycarbonate composition; and 0.01 to 1.0 wt% of an aromatic sulfone sulfonate, preferably potassium diphenylsulfone sulfonate.
  • the polycarbonate compositions may have ultra-low halogen content.
  • “ultra-low chlorine and/or bromine content” refers to materials produced without the intentional addition of chlorine or bromine or chlorine or bromine containing materials.
  • “ultra-low chlorine or bromine content” may be defined as having a bromine or chlorine content of less than or equal to 100 parts per million by weight (ppm), less than or equal to 75 ppm, or less than or equal to 50 ppm.
  • “ultra-low chlorine and bromine content” means a total bromine and chlorine content of less than or equal to 100 parts per million by weight, or less than or equal to 75 ppm, or less than or equal to 50 ppm.
  • the polycarbonate composition may have an ultra-low chlorine, bromine, or fluorine content.
  • “ultra-low chlorine, bromine, or fluorine content” is defined as having a bromine, chlorine, or fluorine content of less than or equal to 200 ppm, less than or equal to 100 ppm, less than or equal to 75 ppm, or less than or equal to 50 ppm, based on the total parts by weight of the composition.
  • the polycarbonate composition has a combined bromine, chlorine, and fluorine content of less than or equal to 100 ppm, less than or equal to 75 ppm, or less than or equal to 50 ppm, based on the total parts by weight of the composition.
  • the polycarbonate composition may have an ultra-low fluorine content.
  • ultra-low fluorine content is defined as having a fluorine content of less than or equal to 200 ppm, less than or equal to 100 ppm, less than or equal to 75 ppm, or less than or equal to 50 ppm, based on the total parts by weight of the composition.
  • the polycarbonate compositions may be manufactured by various methods. For example, powdered polycarbonates, non-halogenated flame retardant, and/or optional components are first blended, optionally with fillers in a HENSCHEL-Mixer high speed mixer. Other low shear processes, including but not limited to hand mixing, may also accomplish this blending. The blend is then fed into the throat of a twin-screw extruder via a hopper. Alternatively, at least one of the components may be incorporated into the composition by feeding directly into the extruder at the throat or downstream through a sidestuffer.
  • Additives may also be compounded into a masterbatch with a desired polymeric polymer and fed into the extruder.
  • the extruder is generally operated at a temperature higher than that necessary to cause the composition to flow.
  • the extrudate is immediately quenched in a water bath and pelletized.
  • the pellets so prepared may be one-fourth inch long or less as desired. Such pellets may be used for subsequent molding, shaping, or forming.
  • a sample of the polycarbonate composition may have a flame test rating of V-0, as measured according to UL-94 at a thickness of 1.5 millimeter or less, such as, for example, 1.2 millimeter, 1.0 millimeter, 0.8 millimeter, and 0.6 millimeter.
  • Shaped, formed, or molded articles including the polycarbonate compositions are also provided.
  • the polycarbonate compositions may be molded into useful shaped articles by a variety of methods, such as injection molding, extrusion, rotational molding, blow molding and thermoforming.
  • Some examples of articles include computer and business machine housings such as housings for monitors, handheld electronic device housings such as housings for cell phones, electrical connectors, and components of lighting fixtures, ornaments, home appliances, roofs, greenhouses, sun rooms, swimming pool enclosures, and the like.
  • the article is an extruded article, a molded article, pultruded article, a thermoformed article, a foamed article, a layer of a multi-layer article, a substrate for a coated article, or a substrate for a metallized article.
  • the polycarbonate compositions may be used for such applications as a molded housing and other devices such as electrical circuit housing.
  • Thin films including the polycarbonate compositions are also provided..
  • the thin films can be prepare
  • the thin film of the thermoplastic composition can be prepared by extrusion of the polycarbonate composition.
  • the thin films may have improved thermal resistance.
  • the thin films may be transparent.
  • PC-1 Linear amorphous bisphenol A polycarbonate (BPA) homopolymer produced by interfacial polymerization (Mw 29,000-31,000 g/mol, using polystyrene SABIC standards)
  • PC-2 Linear amorphous BPA homopolymer produced by interfacial polymerization SABIC (Mw 20,000-22,000, using polystyrene standards)
  • PC-4 4/96 mol% amorphous IDHB-BPA copolymer produced by interfacial SABIC polymerization, Mw 29,000-31,000 g/mol, using polystyrene standards
  • PC-5 4/96 mol% amorphous EDHB-BPA copolymer produced by interfacial SABIC polymerization, Mw 29,000-31,000 g/mol, using polystyrene standards
  • PC-7 Branched, cyanophenol end-capped bisphenol A homopolycarbonate produced SABIC via interfacial polymerization, containing 3 mol% 1,
  • a pre-formulation tank 7 L water, 23 L methylene chloride, 4200 g BPA, 40 mL TEA, 10 g sodium gluconate, and propan-2-yl 3,5- dihydroxybenzoate (IDHB) or ethyl 3,5-dihydroxybenzoate (EDHB) are added and well mixed.
  • IDHB propan-2-yl 3,5- dihydroxybenzoate
  • EDHB ethyl 3,5-dihydroxybenzoate
  • a 30% caustic solution is then added at a program-determined rate.
  • Parameters Unit Typical values Feed °C 40 Zone 1 Temp °C 200 Zone 2 Temp °C 240 Zone 3 Temp °C 260 Zone 4-9 Temp °C 280 Screw Speed Rpm 300 Throughput kg/hr ⁇ 24 Torque % Max. [00087] An Engel 45 molding machine was used to mold the test parts for standard physical property testing. The parameters are provided in Table 3. Table 3. Parameters Unit Conditions Drying Temperature °C 120 Drying Time Hrs 2 Hopper temperature °C 40 Nozzle Temperature °C 275 Rear - Zone 1 Temperature °C 260 Middle - Zone 2 Temperature °C 270 Front - Zone 3 Temperature °C 280 [00088] Sample preparation and testing methods are described in Table 4. Table 4.
  • a polycarbonate composition including: polycarbonate; a polycarbonate including repeating units derived from a monomer including a pendant ester group; a non-halogenated flame retardant, optionally, a poly(carbonate-siloxane) present in an amount effective to provide 4 wt% or less of siloxane repeating units, based on the total weight of the composition, and optionally, an additive composition, wherein a sample of the composition has a UL-94 flame test rating of V-0 at a thickness of 1.5 mm or thinner.
  • a polycarbonate composition comprises: a polycarbonate; a polycarbonate comprising repeating units derived from a monomer comprising a pendant ester group present in an amount effective to provide 0.1-1.0 mol% repeating units derived from a monomer having a pendant ester group, based on the total moles of based on the total moles of carbonate repeating units in the polycarbonate composition; a non-halogenated flame retardant, optionally, a poly(carbonate-siloxane) present in an amount effective to provide 4 wt% or less of siloxane repeating units, based on the total weight of the composition, and optionally, an additive composition, wherein the polycarbonate composition comprises less than or equal to 400 ppm repeating units derived from a branching agent, based on the total moles of carbonate repeating units in the polycarbonate composition, wherein the polycarbonate is different from the polycarbonate comprising repeating units derived from a monomer comprising a pendant ester group, wherein a sample
  • a polycarbonate composition comprises: a polycarbonate; a polycarbonate comprising repeating units derived from a monomer comprising a pendant ester group; a non-halogenated flame retardant, optionally, a poly(carbonate-siloxane) present in an amount effective to provide 4 wt% or less of siloxane repeating units, based on the total weight of the composition, and optionally, an additive composition, wherein the polycarbonate is different from the polycarbonate comprising repeating units derived from a monomer comprising a pendant ester group, wherein the polycarbonate composition comprises 200 ppm or less added fluorine content, wherein a sample of the composition has a UL-94 flame test rating of V-0 at a thickness of 1.5 mm or thinner, in accordance with the Underwriter’s Laboratory (UL) UL 94 standard.
  • UL Underwriter’s Laboratory
  • Aspect 2 The polycarbonate composition of any one of the preceding aspects, wherein: the calculated added bromine and chlorine content of the polycarbonate composition are each about 900 ppm or less and the calculated total added halogen content of the 23SHPP0022-WO-PCT (SS230150PCT) polycarbonate composition is about 1500 ppm or less; or the calculated added bromine, chlorine, and fluorine content of the polycarbonate composition are each about 900 ppm or less and the calculated total added bromine, chlorine, and fluorine content of the polycarbonate composition is about 1500 ppm or less. [00097] Aspect 3.
  • Aspect 3 wherein R is a linear C2- C15 alkyl group, preferably an ethyl group, or R is a branched C2-C15 alkyl group, preferably an isopropyl group.
  • Aspect 5 The polycarbonate composition of any one of the preceding aspects, wherein the polycarbonate including repeating units derived from a monomer including a pendant ester group is present in an amount effective to provide 0.1-5.0 mol% repeating units derived from the monomer comprising a pendant ester group, based on the total moles of the composition.
  • Aspect 6 Aspect 6.
  • non-halogenated flame retardant comprises an aromatic sulfonate, an aromatic sulfone sulfonate, an organophosphorus flame retardant, or a combination thereof.
  • Aspect 8 The polycarbonate composition of any one of the preceding aspects, wherein the non-halogenated flame retardant includes an organophosphorus flame retardant including: combination thereof, wherein each occurrence of G 1 is independently a C 1-30 hydrocarbyl; each occurrence of G 2 is independently a C 1-30 hydrocarbyl or hydrocarbyloxy; each X is independently a bromine or chlorine; m is 0 to 4, and n is 1 to 30; wherein R 16 , R 17 , R 18 , and R 19 are each independently C1-8 alkyl, C 5-6 cycloalkyl, C 6-20 aryl, or C 7-12 arylalkylene, each optionally substituted by C 1-12 alkyl, preferably by C 1-4 alkyl and X is a mono- or poly-nuclear aromatic C 6-30 moiety or a linear or branched C 2-30 aliphatic radical, each optionally OH-substituted and optionally including up to 8 ether bonds, provided
  • Aspect 9 The polycarbonate composition of any one of the preceding aspects, wherein the wherein the non-halogenated flame retardant includes an organophosphorus flame retardant including phosphonitrilic chloride, phosphorus ester amide, phosphoric acid amide, phosphonic acid amide, phosphinic acid amide, or tris(aziridinyl) phosphine oxide; or a phosphazene or cyclic phosphazene of the formulas wherein w1 is 3 to 10,000; w2 is 3 to 25, or 3 to 7; and each R w is independently a C1-12 alkyl, alkenyl, alkoxy, aryl, aryloxy, or polyoxyalkylene group, optionally wherein at least one hydrogen atom is replaced with an N, S, O, or F atom, or an amino group.
  • an organophosphorus flame retardant including phosphonitrilic chloride, phosphorus ester amide, phosphoric acid amide, phosphonic
  • Aspect 11 The polycarbonate composition of any one of the preceding aspects wherein the polycarbonate composition comprises 0.15 wt% or less of an anti-drip agent comprising fluorine, preferably wherein the polycarbonate composition excludes an anti-drip agent comprising fluorine.
  • 23SHPP0022-WO-PCT SS230150PCT
  • Aspect 12 The polycarbonate composition of any one of the preceding aspects wherein the polycarbonate composition comprises an organophosphorus flame retardant present in amount effective to provide 0.05-1.0 wt% phosphorus.
  • polycarbonate composition of any one of the preceding aspects wherein the polycarbonate composition comprises 0.01 to 1.0 wt% of an aromatic sulfone sulfonate, preferably potassium diphenylsulfone sulfonate.
  • an article including the polycarbonate composition of any one of the preceding aspects preferably wherein the article is a housing for monitors, a thin film, a housing for a handheld electronic device, preferably a housing for a cell phone or a personal health care device, a housing for a consumer electronic device, preferably a battery housing, a covers, or a display panel, a housing for an electrical component, preferably an electric vehicle charger, a smart meter cover, a smart meter box, or a lighting component; an electrical connector; a component of a lighting fixture; an ornament; a home appliance; a roof; a greenhouse enclosure, a sun room enclosure, and a swimming pool enclosure.
  • compositions, methods, and articles may alternatively include, consist of, or consist essentially of, any appropriate materials, steps, or components herein disclosed.
  • the compositions, methods, and articles may 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.
  • a “combination thereof” is open and includes any combination including at least one of the listed components or properties optionally together with a like or equivalent component or property not listed [000112] Unless specified to the contrary herein, all 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. [000113] Unless defined otherwise, technical and scientific terms used herein have the same meaning as is commonly understood by one of skill in the art to which this application belongs. All cited patents, patent applications, and other references are incorporated herein by reference in their entirety.
  • hydrocarbyl refers to a residue that contains only carbon and hydrogen unless it is specifically identified as “substituted hydrocarbyl”.
  • the hydrocarbyl residue may be aliphatic or aromatic, straight-chain, cyclic, bicyclic, branched, saturated, or unsaturated. It may also contain combinations of aliphatic, aromatic, straight chain, cyclic, bicyclic, branched, saturated, and unsaturated hydrocarbon moieties. When the hydrocarbyl residue is described as substituted, it may contain heteroatoms in addition to carbon and hydrogen.
  • 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, ethoxy, and sec-butyloxy groups.
  • Alkylene means a straight or branched chain, saturated, divalent aliphatic hydrocarbon group (e.g., methylene (-CH 2 -) or, propylene (-(CH 2 ) 3 - )).
  • Cycloalkylene means a divalent cyclic alkylene group, -C n H 2n-x , wherein x is the number of hydrogens replaced by cyclization(s).
  • Cycloalkenyl means a monovalent group having one or 23SHPP0022-WO-PCT (SS230150PCT) 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 may be present.
  • hetero means that the compound or group includes at least one ring member that is a heteroatom (e.g., 1, 2, or 3 heteroatom(s)), wherein the heteroatom(s) is each independently N, O, S, Si, or P.

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Abstract

L'invention concerne une composition de polycarbonate appropriée pour des applications à paroi mince comprenant : un polycarbonate; un polycarbonate comprenant des unités de répétition dérivées d'un monomère comprenant un groupe ester pendant; un retardateur de flamme non halogéné, éventuellement, un poly (carbonate-siloxane) présent en une quantité efficace pour fournir 4% en poids ou moins d'unités de répétition de siloxane, sur la base du poids total de la composition, et éventuellement, une composition d'additif dans laquelle un échantillon de la composition a une note de test de flamme UL-94 de V-0 à une épaisseur de 1,5 mm ou plus mince. De manière avantageuse, les compositions de polycarbonate peuvent réduire au minimum ou éliminer des sels ignifuges fluorés tels que le sel de Rimar et des agents anti-goutte fluorés tout en obtenant une performance de test de flamme améliorée.
PCT/IB2024/055603 2023-06-07 2024-06-07 Compositions ignifuges de polycarbonate Ceased WO2024252357A1 (fr)

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US202363471621P 2023-06-07 2023-06-07
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EP23182731.2 2023-06-30

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0524731A1 (fr) 1991-07-01 1993-01-27 General Electric Company Mélanges comprenant des copolymères blocs de polycarbonate-polysiloxane avec des polycarbonates ou des copolymères polyestercarbonates
US20040039145A1 (en) 2002-08-16 2004-02-26 General Electric Company Method of preparing transparent silicone-containing copolycarbonates
US6723864B2 (en) 2002-08-16 2004-04-20 General Electric Company Siloxane bischloroformates
US20130317145A1 (en) * 2012-05-24 2013-11-28 Sabic Innovative Plastics Ip B.V. Flame retardant polycarbonate compositions, methods of manufacture thereof and articles comprising the same
US10597530B2 (en) * 2015-07-09 2020-03-24 Sabic Global Technologies B.V. Polycarbonate compositions with improved flame retardance
EP3798265A1 (fr) * 2019-09-30 2021-03-31 SHPP Global Technologies B.V. Compositions de polycarbonate ignifuges remplies de verre et articles à paroi mince correspondants
WO2022130211A1 (fr) * 2020-12-15 2022-06-23 Shpp Global Technologies B.V. Compositions de polycarbonate ignifuges pour applications transparentes à paroi mince

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0524731A1 (fr) 1991-07-01 1993-01-27 General Electric Company Mélanges comprenant des copolymères blocs de polycarbonate-polysiloxane avec des polycarbonates ou des copolymères polyestercarbonates
US20040039145A1 (en) 2002-08-16 2004-02-26 General Electric Company Method of preparing transparent silicone-containing copolycarbonates
US6723864B2 (en) 2002-08-16 2004-04-20 General Electric Company Siloxane bischloroformates
US20130317145A1 (en) * 2012-05-24 2013-11-28 Sabic Innovative Plastics Ip B.V. Flame retardant polycarbonate compositions, methods of manufacture thereof and articles comprising the same
US10597530B2 (en) * 2015-07-09 2020-03-24 Sabic Global Technologies B.V. Polycarbonate compositions with improved flame retardance
EP3798265A1 (fr) * 2019-09-30 2021-03-31 SHPP Global Technologies B.V. Compositions de polycarbonate ignifuges remplies de verre et articles à paroi mince correspondants
WO2022130211A1 (fr) * 2020-12-15 2022-06-23 Shpp Global Technologies B.V. Compositions de polycarbonate ignifuges pour applications transparentes à paroi mince

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