WO2017203480A1 - High heat, high impact polycarbonate compositions and articles made therefrom - Google Patents

Abstract

An article includes a polycarbonate composition comprising up to 60 wt% of a bisphenol A homopolycarbonate; 7-25 wt% of a poly(carbonate-siloxane); 10-70 wt% of a polycarbonate copolymer having a glass transition temperature of 170°C or higher; 0.05-1.5 wt% of a flame retardant salt; 5-15 wt% of glass fibers; 0-0.2 wt% of an anti-drip agent; optionally, up to 10 wt% of an additive composition; wherein a molded sample of the polycarbonate composition has a Vicat B120 softening temperature of at least 150°C, an Izod notched impact strength of 10 kJ/m² or greater, measured at 23 °C, a flame test rating, when measured according to UL-94 at 0.8 millimeters thickness, of V2, and a probability of first time pass for V2 greater than 0.7.

Description

HIGH HEAT, HIGH IMPACT POLYCARBONATE COMPOSITIONS AND

ARTICLES MADE THEREFROM

BACKGROUND

[0001] This disclosure is directed to articles comprising polycarbonate compositions, specifically polycarbonate compositions comprising a polycarbonate homopolymer, a high heat polycarbonate copolymer, a poly(carbonate-siloxane), a flame retardant salt, and glass fibers, their method of manufacture, and the polycarbonate compositions thereof.

[0002] Materials used for electrical applications require high heat resistance, high impact strength, and good flammability properties. The market is also moving towards articles having thin walls for purposes of weight and size reduction, for example. Polycarbonates have been used in the manufacture of articles and components for a wide range of applications, from automotive parts to electronic appliances. Polycarbonates generally have low heat resistance but good impact strength.

[0003] There is a need for polycarbonate compositions that have high heat resistance, good impact strength, and good flammability properties.

SUMMARY

[0004] An article comprising a component, wherein the component comprises a polycarbonate composition comprising up to 60 weight percent (wt%) of a bisphenol A homopolycarbonate having a weight average molecular weight from 15,000-40,000 grams/mole measured via gel permeation chromatography using bisphenol A homopolycarbonate standards; 7-25 wt% of a poly(carbonate-siloxane); 10-70 wt% of a high heat polycarbonate copolymer having a glass transition temperature of 170°C or higher; 0.05-1.5 wt% of a flame retardant salt; 5-15 wt% of glass fibers; 0-0.2 wt% of an anti-drip agent; optionally, up to 10 wt% of an additive composition; wherein a molded sample of the polycarbonate composition has a Vicat B 120 softening temperature of at least 150°C when measured according to ISO 306, an Izod notched impact strength of greater than or equal to 10 kilojoules per square meter measured at 23°C according to ISO 180/1 A, a flame test rating, when measured according to UL-94 at 0.8 millimeters thickness, of V2, and a probability of first time pass for V2 greater than 0.7; wherein each amount is based on the total weight of the polycarbonate composition, which sums to 100 wt%, is provided. [0005] A polycarbonate composition, comprising up to 60 wt% of a bisphenol A homopolycarbonate having a weight average molecular weight from 15,000-40,000 grams/mole measured via gel permeation chromatography using bisphenol A homopolycarbonate standards; 7-25 wt% of a poly(carbonate-siloxane); 10-70 wt% of a high heat polycarbonate copolymer having a glass transition temperature of 170°C or higher; 0.05-1.5 wt% of a flame retardant salt; 5-15 wt% of glass fibers; 0-0.2 wt% of an anti-drip agent; optionally, up to 10 wt% of an additive composition, is provided.

[0006] A method for manufacture of a polycarbonate composition comprising melt- mixing the components of the provided polycarbonate composition, is provided.

[0007] The above described and other features are exemplified by the following detailed description, examples, and claims.

DETAILED DESCRIPTION

[0008] Provided is a polycarbonate composition having high heat resistance, high impact strength, and good flammability properties. The polycarbonate composition comprises a polycarbonate homopolymer, a high heat polycarbonate copolymer, a poly(carbonate-siloxane), a flame retardant salt, and glass fibers. The polycarbonate composition can be used to prepare articles, including thin walled articles. The polycarbonate composition provides a combination of the desired heat resistance, impact strength, and flammability properties. A molded sample of the polycarbonate composition has a Vicat B 120 softening temperature of at least 150°C, preferably from 155-165°C when measured according to ISO 306, an Izod notched impact strength of greater than or equal to 10 kilojoules per square meter, preferably 15-25 kilojoules per square meter, measured at 23°C according to ISO 180/1 A, and a flame test rating, when measured according to UL-94 at 0.8 millimeters thickness, of V2. A molded sample of the polycarbonate composition can also have a probability of first time pass for V2 greater than 0.8.

[0009] The polycarbonate composition comprises a bisphenol A homopolycarbonate. The polycarbonate composition further comprises a high heat polycarbonate copolymer having a glass transition temperature of 170°C or higher. The high heat polycarbonate copolymer can comprise carbonate units derived from bisphenol A and a high heat aromatic dihydroxy compound, preferably a phthalimidine carbonate unit, or a poly(phthalate-carbonate), preferably comprising ester units derived from bisphenol A and terephthalic, isophthalic, or phthalic acid, or a combination comprising at least one of the foregoing diacids, and carbonate units derived from bisphenol A. The polycarbonate composition further comprises a poly(carbonate- siloxane), also referred to in the art as a polycarbonate-poly siloxane copolymer. [0010] "Polycarbonate" as used herein means a polymer or copolymer having repeating structural carbonate units of formula (1)

wherein at least 60 percent of the total number of R¹ groups are aromatic, or each R¹ contains at least one C₆-30 aromatic group. Specifically, each R¹ can be derived from a dihydroxy compound such as an aromatic dihydroxy compound of formula (2) or a bisphenol of formula (3).

In formula (2), each R is independently a halogen atom, for example bromine, a Ci-io hydrocarbyl group such as a Ci-io alkyl, a halogen-substituted Ci-io alkyl, a C₆-io aryl, or a halogen-substituted C6-io aryl, and n is 0-4.

[0011] In formula (3), R^a and R^b are each independently a halogen, Ci-12 alkoxy, or Ci-12 alkyl, and p and q are each independently integers of 0-4, such that when p or q is less than 4, the valence of each carbon of the ring is filled by hydrogen. In an embodiment, p and q is each 0, or p and q is each 1, and R^a and R^b are each a C1-3 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 Ce arylene group are disposed ortho, meta, or para (specifically para) to each other on the Ce arylene group, for example, a single bond, -0-, -S-, -S(O)-, -S(0)₂-, -C(O)-, or a Ci-is 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. For example, X^a can be a substituted or unsubstituted C3-18 cycloalkylidene; a Ci-25 alkylidene of the formula - C(R^c)(R^d) - wherein R^c and R^d are each independently hydrogen, Ci-12 alkyl, Ci-12 cycloalkyl, C7-12 arylalkyl, Ci-12 heteroalkyl, or cyclic C7-12 heteroarylalkyl; or a group of the formula - C(=R^e)- wherein R^e is a divalent Ci-12 hydrocarbon group.

[0012] Examples of bisphenol compounds include 4,4'-dihydroxybiphenyl, 1,6- dihydroxynaphthalene, 2,6-dihydroxynaphthalene, bis(4-hydroxyphenyl)methane, bis(4- hydroxyphenyl)diphenylmethane, bis(4-hydroxyphenyl)-l-naphthylmethane, l,2-bis(4- hydroxyphenyl)ethane, l ,l-bis(4-hydroxyphenyl)- l-phenylethane, 2-(4-hydroxyphenyl)-2-(3- hydroxyphenyl)propane, bis(4-hydroxyphenyl)phenylmethane, 2,2-bis(4-hydroxy-3- bromophenyl)propane, 1, 1 -bis (hydroxyphenyl)cyclopentane, l,l-bis(4- hydroxyphenyl)cyclohexane, 1 , 1 -bis(4-hydroxyphenyl)isobutene, 1 , 1 -bis(4- hydroxyphenyl)cyclododecane, trans-2,3-bis(4-hydroxyphenyl)-2-butene, 2,2-bis(4- hydroxyphenyl)adamantane, alpha,alpha'-bis(4-hydroxyphenyl)toluene, bis(4- hydroxyphenyl)acetonitrile, 2,2-bis(3-methyl-4-hydroxyphenyl)propane, 2,2-bis(3-ethyl-4- hydroxyphenyl)propane, 2,2-bis(3-n-propyl-4-hydroxyphenyl)propane, 2,2-bis(3-isopropyl-4- hydroxyphenyl)propane, 2,2-bis(3-sec-butyl-4-hydroxyphenyl)propane, 2,2-bis(3-t-butyl-4- hydroxyphenyl)propane, 2,2-bis(3-cyclohexyl-4-hydroxyphenyl)propane, 2,2-bis(3-allyl-4- hydroxyphenyl)propane, 2,2-bis(3-methoxy-4-hydroxyphenyl)propane, 2,2-bis(4- hydroxyphenyl)hexafluoropropane, 1 , 1 -dichloro-2,2-bis(4-hydroxyphenyl)ethylene, 1,1- dibromo-2,2-bis(4-hydroxyphenyl)ethylene, 1 , 1 -dichloro-2,2-bis(5-phenoxy-4- hydroxyphenyl)ethylene, 4,4'-dihydroxybenzophenone, 3,3-bis(4-hydroxyphenyl)-2-butanone, l,6-bis(4-hydroxyphenyl)-l,6-hexanedione, ethylene glycol bis(4-hydroxyphenyl)ether, bis(4- hydroxyphenyl)ether, bis(4-hydroxyphenyl)sulfide, bis(4-hydroxyphenyl) sulfoxide, bis(4- hydroxyphenyl)sulfone, 9,9-bis(4-hydroxyphenyl)fluorene, 2,7-dihydroxypyrene, 6,6'- dihydroxy-3,3,3',3'- tetramethylspiro(bis)indane ("spirobiindane bisphenol"), 3,3-bis(4- hydroxyphenyl)phthalimide, 2,6-dihydroxydibenzo-p-dioxin, 2,6-dihydroxythianthrene, 2,7- dihydroxyphenoxathin, 2,7-dihydroxy-9, 10-dimethylphenazine, 3,6-dihydroxydibenzofuran, 3,6-dihydroxydibenzothiophene, and 2,7-dihydroxycarbazole; resorcinol, substituted resorcinol compounds such as 5-methyl resorcinol, 5-ethyl resorcinol, 5-propyl resorcinol, 5-butyl resorcinol, 5-t-butyl resorcinol, 5-phenyl resorcinol, 5-cumyl resorcinol, 2,4,5, 6-tetrafluoro resorcinol, 2,4,5, 6-tetrabromo resorcinol, or the like; catechol; hydroquinone; substituted hydroquinones such as 2-methyl hydroquinone, 2-ethyl hydroquinone, 2-propyl hydroquinone, 2-butyl hydroquinone, 2-t-butyl hydroquinone, 2-phenyl hydroquinone, 2-cumyl hydroquinone, 2,3,5,6-tetramethyl hydroquinone, 2,3,5,6-tetra-t-butyl hydroquinone, 2,3, 5, 6-tetrafluoro hydroquinone, 2,3,5, 6-tetrabromo hydroquinone, or the like.

[0013] 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 l,l-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane

(isophorone bisphenol).

[0014] The polycarbonate homopolymers can have an intrinsic viscosity, as determined in chloroform at 25°C, of 0.3-1.5 deciliters per gram (dl/gm), specifically 0.45-1.0 dl/gm. The polycarbonates can have a weight average molecular weight of 10,000-50,000 grams per mole (g/mol), specifically 20,000-40,000 g/mol, as measured by gel permeation chromatography (GPC), using a crosslinked styrene-divinylbenzene column and calibrated to bisphenol A homopolycarbonate references. GPC samples are prepared at a concentration of 1 milligram (mg) per milliliter (ml), and are eluted at a flow rate of 1.5 ml per minute.

[0015] "Polycarbonates" includes homopolycarbonates (wherein each R¹ in the polymer is the same), copolymers comprising different R¹ moieties in the carbonate

("copolycarbonates"), and copolymers comprising carbonate units and other types of polymer units, such as ester units or siloxane units.

[0016] "Polycarbonate" as used herein also includes copolymers comprising carbonate units and ester units ("poly(ester-carbonate)s", also known as polyester-polycarbonates). The high heat polycarbonate copolymer can be a copolymer of bisphenol A and an ester. Such copolymers further contain, in addition to recurring carbonate units of formula (1), repeating units of formula (7)

O O

C— T— C— O— J O

wherein J is a divalent group derived from a dihydroxy compound (including a reactive derivative thereof), and can be, for example, a C2-10 alkylene, a C₆-20 cycloalkylene, a C₆-20 arylene, or a polyoxyalkylene in which the alkylene groups contain 2-6 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 C2-20 alkylene, a C₆-20 cycloalkylene, or a C₆-20 arylene. Copolyesters containing a combination of different T or J groups can be used. The polyester units can be branched or linear.

[0017] In an embodiment, J is a C2-30 alkylene group having a straight chain, branched chain, or cyclic (including polycyclic) structure, for example ethylene, n-propylene, i-proplyene, 1,4-butylene, 1,6-cyclohexylene, or 1,4-methylenecyclohexane. In another embodiment, J is derived from a bisphenol of formula (3), e.g., bisphenol A. In another embodiment, J is derived from an aromatic dihydroxy compound of formula (2), e.g., resorcinol.

[0018] Aromatic dicarboxylic acids that can be used to prepare the polyester units include isophthalic or terephthalic acid, l,2-di(p-carboxyphenyl)ethane, 4,4'-dicarboxydiphenyl ether, 4,4'-bisbenzoic acid, or a combination comprising at least one of the foregoing acids. Acids containing fused rings can also be present, such as in 1,4-, 1,5-, or 2,6- naphthalenedicarboxylic acids. Specific dicarboxylic acids include terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid, 1,4-cyclohexane dicarboxylic acid, or a combination comprising at least one of the foregoing acids. A specific dicarboxylic acid comprises a combination of isophthalic acid and terephthalic acid wherein the weight ratio of isophthalic acid to terephthalic acid is 91:9 to 2:98.

[0019] Specific ester units include ethylene terephthalate, n-propylene terephthalate, n- butylene terephthalate, 1,4-cyclohexanedimethylene terephthalate, and ester units derived from isophthalic acid, terephthalic acid, and resorcinol (ITR). The molar ratio of ester units to carbonate units in the copolymers can vary broadly, for example 1:99 to 99: 1, specifically 10:90 to 90: 10, more specifically 25:75 to 75:25, or 2:98 to 15:85, depending on the desired properties of the final polycarbonate composition.

[0020] In a specific embodiment, the polycarbonate copolymer is a poly(bisphenol A carbon

(8a) wherein y and x represent the weight percent of arylate-bisphenol A ester units and bisphenol A carbonate units, respectively. Generally, the units are present as blocks. In an embodiment, the weight percent of ester units to carbonate units x in the copolymers is 50:50 to 99: 1, or 55:45 to 90: 10, or 75:25 to 95:5. Specific poly(ester-carbonate)s are those including bisphenol A carbonate units and isophthalate-terephthalate-bisphenol A ester units, also commonly referred to as poly(phthalate-carbonate)s (PPC). PPCs can comprise a compound of formula (8a) comprising 15-25 wt% of carbonate units and 75-85 wt% of ester units having a molar ratio of isophthalate to terephthalate from 98:2 to 88: 12.

[0021] The polycarbonate copolymers comprising arylate ester units are generally prepared from polyester blocks. The polyester blocks can also be prepared by interfacial polymerization. Rather than utilizing the dicarboxylic acid or diol per se, the reactive derivatives of the acid or diol, such as the corresponding acid halides, in particular the acid dichlorides and the acid dibromides can be used. Thus, for example instead of using isophthalic acid, terephthalic acid, or a combination comprising at least one of the foregoing acids, isophthaloyl dichloride, terephthaloyl dichloride, or a combination comprising at least one of the foregoing dichlorides can be used. The polyesters can also be obtained by melt-process condensation as described above, by solution phase condensation, or by transesterification polymerization wherein, for example, a dialkyl ester such as dimethyl terephthalate can be transesterified with the dihydroxy reactant using acid catalysis, to generate the polyester blocks. Branched polyester blocks, in which a branching agent, for example, a glycol having three or more hydroxyl groups or a trifunctional or multifunctional carboxylic acid has been incorporated, can be used. Furthermore, it can be desirable to have various concentrations of acid and hydroxyl end groups on the polyester blocks, depending on the ultimate end use of the polycarbonate composition.

[0022] The polycarbonate copolymers comprising arylate ester units can have a weight average molecular weight of 10,000-50,000 g/mol, specifically 15,000-35,000 g/mol, more specifically 20,000-30,000 g/mol. Molecular weight determinations are performed using GPC using a cross linked styrene-divinyl benzene column, at a sample concentration of 1 milligram per milliliter, and as calibrated with bisphenol A homopolycarbonate standards. Samples are eluted at a flow rate of 1.0 ml/min with methylene chloride as the eluent.

[0023] The high heat polycarbonate copolymer can be a copolymer of bisphenol- A and a so-called high heat monomer.

[0024] In a specific embodiment the high heat comonomer is a phthalimidine of formula

(15)

wherein each R¹⁰, R¹¹, R¹², and R¹³ are independently hydrogen, a Ci-20 alkylene, a Ci-20 substituted alkylene, a C₆-20 arylene, or a C₆-20 substituted arylene, and t is an integer from 0 to 4. In particular embodiments, the phthalimidine monomer is 2-phenyl-3,3-bis(4-hydroxyphenyl) phthali d below as formula (15a).

(15a)

[0025] The phthalimidine blocks can make up from 20-50 mole% of the copolymer, preferably from 25-40 mole%. The polycarbonate blocks can make up from 50-80 mole% of the copolymer, preferably from 60-85 mole%. It is specifically contemplated that the bisphenol- phthalimidine copolymer is a diblock copolymer. The bisphenol-phthalimidine copolymer may have a weight average molecular weight of from 15,000-30,000 g/mol.

[0026] The polysiloxane blocks in the poly(carbonate-siloxane) comprise repeating diorganosiloxane units as in formula (10)

wherein each R is independently a Ci-13 monovalent organic group. For example, R can be a Ci- Ci3 alkyl, C1-C13 alkoxy, C2-C13 alkenyl, C2-C13 alkenyloxy, C3-C6 cycloalkyl, C3-C6 cycloalkoxy, C₆-Ci₄ aryl, C₆-Cio aryloxy, C7-C13 arylalkyl, C7-C13 aralkoxy, C7-C13 alkylaryl, or C7-C13 alkylaryloxy. The foregoing groups can be fully or partially halogenated with fluorine, chlorine, bromine, or iodine, or a combination thereof. In an embodiment, where a transparent poly(carbonate-siloxane) is desired, R is unsubstituted by halogen. Combinations of the foregoing R groups can be used in the same copolymer.

[0027] The value of E in formula (10) can vary widely depending on the type and relative amount of each component in the polycarbonate composition, the desired properties of the polycarbonate composition, and like considerations. Generally, E has an average value of 2- 1,000, specifically 2-500, 2-200, or 2-125, 5-80, or 10-70. In an embodiment, E has an average value of 10-80 or 10-40, and in still another embodiment, E has an average value of 40-80, or 40-70. Where E is of a lower value, e.g., less than 40, it can 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 can be used.

[0028] A combination of a first and a second (or more) poly(carbonate-siloxane) copolymers can be used, wherein the average value of E of the first copolymer is less than the average value of E of the second copolymer.

0029] In an embodiment, the poly siloxane blocks are of formula (11)

wherein E is as defined above; each R can be the same or different, and is as defined above; and each Ar can be the same or different, and is a substituted or unsubstituted C6-C30 arylene, wherein the bonds are directly connected to an aromatic moiety. Ar groups in formula (11) can be derived from a C6-C30 dihydroxyarylene compound, for example a dihydroxyarylene compound of formula (3) above. Dihydroxyarylene compounds are l,l-bis(4-hydroxyphenyl) methane, l,l-bis(4-hydroxyphenyl) ethane, 2,2-bis(4-hydroxyphenyl) propane, 2,2-bis(4- hydroxyphenyl) butane, 2,2-bis(4-hydroxyphenyl) octane, l,l-bis(4-hydroxyphenyl) propane, l,l-bis(4-hydroxyphenyl) n-butane, 2,2-bis(4-hydroxy-l-methylphenyl) propane, l,l-bis(4- hydroxyphenyl) cyclohexane, bis(4-hydroxyphenyl sulfide), and l,l-bis(4-hydroxy-t- butylphenyl) propane. Combinations comprising at least one of the foregoing dihydroxy compounds can also be used.

0030] In another embodiment, polysiloxane blocks are of formula (13)

(13)

wherein R and E are as described above, and each R⁵ is independently a divalent C1-C30 organic group, and wherein the polymerized polysiloxane unit is the reaction residue of its

corresponding dihydroxy compound. In a specific embodiment, the polysiloxane blocks are of formula (14):

wherein R and E are as defined above. R⁶ in formula (14) is a divalent C₂-C₈ aliphatic. Each M in formula (14) can be the same or different, and can be a halogen, cyano, nitro, Ci-Cs alkylthio, Ci-Cs alkyl, Ci-Cs alkoxy, C₂-Cs alkenyl, C₂-Cs alkenyloxy, C3-C8 cycloalkyl, C3-C8 cycloalkoxy, C₆-Cio aryl, C₆-Cio aryloxy, C₇-Ci₂ aralkyl, C₇-Ci₂ aralkoxy, C₇-Ci₂ alkylaryl, or C₇-Ci₂ alkylaryloxy, wherein each n is independently 0, 1, 2, 3, or 4.

[0031] In an embodiment, 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; R⁶ is a dimethylene, trimethylene or tetramethylene; and R is a C_1-8 alkyl, haloalkyl such as trifluoropropyl, cyanoalkyl, or aryl such as phenyl, chlorophenyl or tolyl. In another embodiment, R is methyl, or a combination of methyl and trifluoropropyl, or a combination of methyl and phenyl. In still another embodiment, R is methyl, M is methoxy, n is one, R⁶ is a divalent C1-C3 aliphatic group. Specific polysiloxane blocks are of the formula

or a combination comprising at least one of the foregoing, wherein E has an average value of 2- 200, 2-125, 5-125, 5-100, 5-50, 20-80, or 5-20.

[0032] Blocks of formula (14) can be derived from the corresponding dihydroxy polysiloxane, which in turn can 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- dimethylphenol. The poly(carbonate-siloxane) copolymers can then be manufactured, for example, by the synthetic procedure of European Patent Application Publication No. 0 524 731 Al of Hoover, page 5, Preparation 2.

[0033] The poly(carbonate-siloxane) copolymers can comprise 50-99 wt% of carbonate units and 1-50 wt% siloxane units. Within this range, the poly(carbonate-siloxane) copolymer can comprise 70-90 wt%, more specifically 75-85 wt% of carbonate units and 10-30 wt%, more specifically 15-25 wt% siloxane units.

[0034] In an embodiment, 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 polydimethylsilioxane blocks, of the formula

wherein x is 1-200, specifically 5-85, specifically 10-70, specifically 15-65, and more specifically 40-60; x is 1-500, or 10-200, and z is 1-1000, or 10-800. In an embodiment, x is 1- 200, y is 1-90 and z is 1-600, and in another embodiment, x is 30-50, y is 10-30 and z is 45-600. The polysiloxane blocks can be randomly distributed or controlled distributed among the polycarbonate blocks.

[0035] The poly(carbonate-siloxane) copolymer can be manufactured by reaction of the corresponding dihydroxy polysiloxane with a carbonate source and a dihydroxy aromatic compound of formula (3), optionally in the presence of a phase transfer catalyst as described above. Conditions are similar to those useful in forming polycarbonates. Alternatively, the poly(carbonate-siloxane) copolymers can be prepared by co-reacting in a molten state, the dihydroxy monomers and a diaryl carbonate ester, such as diphenyl carbonate, in the presence of a transesterification catalyst as described above. Generally, the amount of dihydroxy

polysiloxane is selected so as to produce a copolymer comprising 1-60 mole percent of polysiloxane blocks relative to the moles of polycarbonate blocks, and more generally, 3-50 mole percent of polysiloxane blocks relative to the moles of polycarbonate blocks.

[0036] Poly(carbonate-siloxane)s can have a weight average molecular weight of 10,000-50,000 grams per mole (g/mol), specifically 25,000-35,000 g/mol as measured by gel permeation chromatography using a crosslinked styrene-divinyl benzene column, at a sample concentration of 1 milligram per milliliter (mg/mL), and as calibrated with bisphenol A homopolycarbonate standards.

[0037] Poly(carbonate-siloxane)s can have a melt volume flow rate, measured at 300°C/1.2 kilogram (kg), of 1-50 cubic centimeters per 10 minutes (cc/10 min), specifically 2- 30 cc/10 min. Mixtures of poly(carbonate-siloxane)s of different flow properties can be used to achieve the overall desired flow property.

[0038] The polycarbonate homopolymer in the polycarbonate composition can be a linear polycarbonate homopolymer containing bisphenol A carbonate units (BPA-PC), commercially available under the trade name LEXAN from SABIC. The high heat

polycarbonate copolymer includes poly(aromatic ester-carbonate) s comprising bisphenol A carbonate units and isophthalate-terephthalate-bisphenol A ester units, also commonly referred to as or poly(phthalate-carbonate)s (PPC). A specific copolycarbonate that can be used in the polycarbonate composition comprises bisphenol A and bulky bisphenol carbonate units, i.e., derived from bisphenols containing at least 12 carbon atoms, for example 12-60 carbon atoms or 20-40 carbon atoms. Examples of such copolycarbonates 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). The poly(carbonate-siloxane) in the polycarbonate composition comprises repeating siloxane units (polycarbonate- siloxanes), for example those comprising bisphenol A carbonate units and siloxane units (e.g., blocks containing 5-200 dimethylsiloxane units), such as those commercially available under the trade name EXL from SABIC.

[0039] The polycarbonate composition also comprises glass fibers. The term "glass" here refers generally to a material, natural or synthetic, which contains silicon dioxide (S1O2) or silica as its main material. The glass can be E, A, C, ECR, R, S, D, or NE glasses, or the like. The glass fiber may take any shape, for example elongated fibers or "whiskers," or glass flakes. The glass fibers can be provided in the form of monofilament or multifilament fibers and can be used individually or in combination with other types of fiber, through, for example, co-weaving or core/sheath, side-by- side, orange-type or matrix and fibril constructions, or by other methods known to one skilled in the art of fiber manufacture. Co- woven structures include glass fiber- carbon fiber, carbon fiber-aromatic polyimide (aramid) fiber, and aromatic polyimide fiberglass fiber or the like. Fibrous fillers can be supplied in the form of, for example, rovings, woven fibrous reinforcements, such as 0-90 degree fabrics or the like; non-woven fibrous

reinforcements such as continuous strand mat, chopped strand mat, tissues, papers and felts or the like; or three-dimensional reinforcements such as braids. In an embodiment, the glass fiber is a non-bonding glass fiber commercially available from Owens Corning. In an embodiment, the polycarbonate composition does not contain bonding glass fibers, which are believed to lower the impact resistance of a composition.

[0040] The polycarbonate composition further includes a flame retardant salts, for example salts of C2-16 alkyl sulfonates such as potassium perfluorobutane sulfonate (Rimar salt), potassium perfluoroctane sulfonate, and tetraethylammonium perfluorohexane sulfonate, 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 and an inorganic acid complex salt, preferably an alkali metal or alkaline earth metal salt of carbonic acid or a fluoro-anion complex such as Li₃AlF₆, BaSiF6, KBF₄, K3AIF6, KA1F₄, K2S1F6, or Na₃AlF6. Rimar salt and KSS and NaTS, alone or in combination with other flame retardants, are particularly useful. Flame retardant salts are generally present in amounts of 0.1-1.5 wt%, preferably 0.5-1 wt% based on the total weight of the polycarbonate composition. Rimar salt and KSS and NaTS, alone or in combination with other flame retardants, are particularly useful. The C2-16 alkyl sulfonates salt is preferably present in the polycarbonate composition in a total amount of 0.1-1.0 wt%, based on the total weight of the polycarbonate composition. The aromatic sulfonate sulfonate salt is preferably present in the polycarbonate composition in a total amount of 0.2-0.7 wt%, based on the total weight of the polycarbonate composition.

[0041] The polycarbonate 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 polycarbonate composition, in particular heat resistance and impact properties. Such additives can be mixed at a suitable time during the mixing of the components for forming the polycarbonate composition. Additives include, fillers, reinforcing agents, antioxidants, heat stabilizers, light stabilizers, ultraviolet (UV) light stabilizers, plasticizers, lubricants, mold release agents, antistatic agents, colorants such as carbon black, and organic dyes, surface effect additives, radiation stabilizers, an anti-fog agent, an antimicrobial agent, and anti-drip agents. A combination of additives can be used, for example a colorant, a surface effect additive, a filler, a reinforcing agent, an antioxidant, a heat stabilizer, a light stabilizer, an ultraviolet light stabilizer, a plasticizer, a lubricant, a mold release agent, an antistatic agent, anti-fog agent, antimicrobial agent, a radiation stabilizer, or a combination comprising at least one of the foregoing. The additives are used in the amounts generally known to be effective. For example, the total amount of the additives can be up to 10 wt%, preferably 0.01-5 wt%, based on the total weight of the polycarbonate composition.

[0042] In an embodiment, the polycarbonate composition does not include titanium dioxide. In an embodiment, the additive composition is a heat stabilizer, a thermal stabilizer, an ultraviolet stabilizer, a release agent, or a combination comprising at least one of the foregoing.

[0043] Heat stabilizer additives include organophosphites (e.g. triphenyl phosphite, tris- (2,6-dimethylphenyl)phosphite, tris-(mixed mono-and di-nonylphenyl)phosphite or the like), phosphonates (e.g., dimethylbenzene phosphonate or the like), phosphates (e.g., trimethyl phosphate, or the like), or combinations comprising at least one of the foregoing heat stabilizers. The heat stabilizer can be tris(2,4-di-tert-butylphenyl) phosphate available as IRGAPHOS 168. Heat stabilizers are generally used in amounts of 0.01-5 wt%, based on the total weight of polycarbonate composition.

[0044] Antioxidant additives include organophosphites such as tris(nonyl

phenyl)phosphite, tris(2,4-di-tert-butylphenyl)phosphite, bis(2,4-di-t-butylphenyl)pentaerythritol diphosphite, distearyl pentaerythritol diphosphite; alkylated monophenols or polyphenols;

alkylated reaction products of polyphenols with dienes, such as tetrakis[methylene(3,5-di-tert- butyl-4-hydroxyhydrocinnamate)] methane; butylated reaction products of para-cresol or dicyclopentadiene; alkylated hydroquinones; hydroxylated thiodiphenyl ethers; alkylidene- bisphenols; benzyl compounds; esters of beta-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionic acid with monohydric or polyhydric alcohols; esters of beta-(5-tert-butyl-4-hydroxy-3- methylphenyl) -propionic acid with monohydric or polyhydric alcohols; esters of thioalkyl or thioaryl compounds such as distearylthiopropionate, dilaurylthiopropionate,

ditridecylthiodipropionate, octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, pentaerythrityl-tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate; amides of beta-(3,5-di- tert-butyl-4-hydroxyphenyl)-propionic acid, or combinations comprising at least one of the foregoing antioxidants. Antioxidants are typically used in amounts of 0.01-0.1 wt%, based on the total weight of the polycarbonate composition.

[0045] Anti-drip agents can also be used in the polycarbonate composition, 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). PTFE encapsulated in SAN is known as TSAN. A 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. Anti-drip agents can be used in amounts of 0-0.2 wt%, based on the total weight of the polycarbonate composition.

[0046] Possible fillers or reinforcing agents include, for example, silicates and silica powders such as aluminum silicate (mullite), synthetic calcium silicate, zirconium silicate, fused silica, crystalline silica graphite, natural silica sand, or the like; boron powders such as boron- nitride powder, boron- silicate powders, or the like; oxides such as T1O2, aluminum oxide, magnesium oxide, or the like; calcium sulfate (as its anhydride, dihydrate or trihydrate); calcium carbonates such as chalk, limestone, marble, synthetic precipitated calcium carbonates, or the like; talc, including fibrous, modular, needle shaped, lamellar talc, or the like; wollastonite; surface-treated wollastonite; kaolin, including hard kaolin, soft kaolin, calcined kaolin, kaolin comprising various coatings known in the art to facilitate compatibility with the polymer matrix, or the like; single crystal fibers or "whiskers" such as silicon carbide, alumina, boron carbide, iron, nickel, copper, or the like; fibers (including continuous and chopped fibers) such as asbestos, carbon fibers; sulfides such as molybdenum sulfide, zinc sulfide or the like; barium compounds such as barium titanate, barium ferrite, barium sulfate, heavy spar, or the like;

metals and metal oxides such as particulate or fibrous aluminum, bronze, zinc, copper and nickel or the like; flaked fillers such as flaked silicon carbide, aluminum diboride, aluminum flakes, steel flakes or the like; fibrous fillers, for example short inorganic fibers such as those derived from blends comprising at least one of aluminum silicates, aluminum oxides, magnesium oxides, and calcium sulfate hemihydrate or the like; natural fillers and reinforcements, such as wood flour obtained by pulverizing wood, fibrous products such as cellulose, cotton, sisal, jute, starch, cork flour, lignin, ground nut shells, corn, rice grain husks or the like; organic fillers such as polytetrafluoroethylene; reinforcing organic fibrous fillers formed from organic polymers capable of forming fibers such as poly(ether ketone), polyimide, polybenzoxazole,

poly(phenylene sulfide), polyesters, polyethylene, aromatic polyamides, aromatic polyimides, polyetherimides, polytetrafluoroethylene, acrylic polymers, poly(vinyl alcohol) or the like; as well as additional fillers and reinforcing agents such as mica, clay, feldspar, flue dust, fillite, quartz, quartzite, perlite, tripoli, diatomaceous earth, carbon black, or the like, or combinations comprising at least one of the foregoing fillers or reinforcing agents. The fillers and reinforcing agents can be coated with a layer of metallic material to facilitate conductivity, or surface treated with silanes to improve adhesion and dispersion with the polymer matrix.

[0047] The polycarbonates and the polycarbonate composition can be manufactured by processes such as interfacial polymerization and melt polymerization, which are known, and are described, for example, in WO 2013/175448 Al and WO 2014/072923 Al. An end-capping agent (also referred to as a chain stopper agent or chain terminating agent) can be included during polymerization to provide end groups, for example monocyclic phenols such as phenol, p-cyanophenol, and C1-C22 alkyl-substituted phenols such as p-cumyl-phenol, resorcinol monobenzoate, and p-and tertiary-butyl phenol, monoethers of diphenols, such as p- methoxyphenol, monoesters of diphenols such as resorcinol monobenzoate, functionalized chlorides of aliphatic monocarboxylic acids such as acryloyl chloride and methacryoyl chloride, and mono-chloroformates such as phenyl chloroformate, alkyl-substituted phenyl

chloroformates, p-cumyl phenyl chloroformate, and toluene chloroformate. Combinations of different end groups can be used. Branched polycarbonate blocks can be prepared by adding a branching agent during polymerization, for example trimellitic acid, trimellitic anhydride, trimellitic trichloride, tris-p-hydroxyphenylethane, isatin-bis-phenol, tris-phenol TC (1,3,5- tris((p-hydroxyphenyl)isopropyl)benzene), tris-phenol PA (4(4(1, l-bis(p-hydroxyphenyl)-ethyl) alpha, alpha-dimethyl benzyl)phenol), 4-chloroformyl phthalic anhydride, trimesic acid, and benzophenone tetracarboxylic acid. The branching agents can be added at a level of 0.05-2.0 wt. %. Combinations comprising linear polycarbonates and branched polycarbonates can be used.

[0048] In the manufacture of poly(ester-carbonate)s by interfacial polymerization, rather than using the dicarboxylic acid or diol directly, the reactive derivatives of the diacid or diol, such as the corresponding acid halides, in particular the acid dichlorides and the acid dibromides can be used. Thus, for example instead of using isophthalic acid, terephthalic acid, or a combination comprising at least one of the foregoing acids, isophthaloyl dichloride,

terephthaloyl dichloride, or a combination comprising at least one of the foregoing dichlorides can be used.

[0049] The polycarbonates and polycarbonate compositions can be formulated by various methods known in the art. For example, powdered polycarbonates, and other optional components are first blended, optionally with any fillers, in a high speed mixer or by hand mixing. The blend is then fed into the throat of a twin-screw extruder via a hopper. Alternatively, at least one of the components can be incorporated into the polycarbonate composition by feeding it directly into the extruder at the throat or downstream through a sidestuffer, or by being compounded into a masterbatch with a desired polymer and fed into the extruder. The extruder is generally operated at a temperature higher than that necessary to cause the polycarbonate composition to flow. The extrudate can be immediately quenched in a water bath and pelletized. The pellets so prepared can be one-fourth inch long or less as desired. Such pellets can be used for subsequent molding, shaping, or forming.

[0050] The article can be in the form of a component, which can be a molded housing. The component can be an electrical circuit housing. The component can be an electrical device component, a medical device component, or a housing component for an electrical device, a vehicle light, a cell phone, a computer, a docking station, a personal data assistant (PDA), a MP3 player, a global positioning satellite (GPS) module, a circuit breaker case, or the like.

[0051] Shaped, formed, or molded articles comprising the polycarbonate compositions are also provided. The polycarbonate compositions can be molded into useful shaped articles by a variety of methods, such as injection molding, extrusion, rotational molding, blow molding, and thermoforming. Some example of components 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 articles, polycarbonate compositions, and methods are further illustrated by the following non- limiting examples.

EXAMPLES

[0052] The following components are used in the examples. Unless specifically indicated otherwise, the amount of each component is in weight percent, based on the total weight of the polycarbonate composition.

Table 1.

Opaque poly(carbonate-siloxane) comprising 20 wt% dimethylsiloxane units, 80 wt% BPA units, Mw about 30,500 g/mol (determined via GPC using bisphenol A

PC-Si homopolycarbonate standards) SABIC

NB GF Non-bonding glass fiber Owens Corning

Rimar Potassium perfluorobutanesulfonate (flame retardant) Lanxess

KSS Potassium diphenylsulphon-3-sulphonate (flame retardant) Arichem LLC

PETS Pentaerythritol tetrastearate (mold release)

NaTS Sodium p-toluenesulfonate (flame retardant) Arichem LLC

TSAN SAN encapsulated PTFE (anti-drip agent) SABIC-IP

Phosphite Tris(2,4-di-tert-butylphenyl)phosphite (heat stabilizer/antioxidant) Ciba

Ti0₂ Titanium dioxide (coated) Kronos

Phosphazene Phosphazene flame retardant (bisphenoxy phosphazene) Otsuka

2-(2 hydroxy-5-t-octylphenyl) benzotriazole (ultraviolet light absorber)

UVA Hunan

[0053] All thermoplastic compositions except where indicated were compounded on a ZSK co-rotating twin screw extruder, vacuum port located near die face. The twin-screw extruder had sufficient distributive and dispersive mixing elements to produce good mixing between the polymer compositions. The compositions were subsequently molded on an ENGEL 45T, 75T, 80T, or 90T injection-molding machine. Compositions were compounded and molded at a temperature of 285-330°C, though it will be recognized by one skilled in the art that the method is not limited to these temperatures.

[0054] Physical measurements were made using the tests and test methods described in Table 2. Unless indicated otherwise, all tests are the tests in effect in the year 2016. Injection molded test specimens were molded in accordance with ISO test methods.

Table 2.

[0055] The ductility for samples is measured using the Izod notched impact test according to ISO 180, and the ductility is specifically not measured using the multiaxial impact (MAI) test of ISO 6603. This serves as a proxy for determining whether the material will shatter rather than bending or deforming. The two tests will result in different measurements for the same composition. The percent of samples tested with ductile break is reported. A result of 100% ductility means 100% of the samples tested had a ductile break, rather than shattering. Flammability tests were performed following the procedure of Underwriter's Laboratory Bulletin 94 entitled "Tests for Flammability of Plastic Materials, UL94." According to this procedure, materials may be classified as V-0, V-1, or V-2 on the basis of the test results obtained for samples of a given thickness. It is assumed that a material that meets a given standard at a given thickness can also meet the same standard at greater thicknesses (e.g. a material that obtains VO performance at 0.8 mm thickness can also obtain VO performance at 1.0 mm thickness, 1.5 mm, etc.). The samples are made according to the UL94 test procedure. Samples were burned in a vertical orientation after aging for 48 hours at 23 °C. At least 10 injection molded bars were burned for each UL test. The criteria for each of the flammability classifications tested are described below.

[0056] V0: In a sample placed so that its long axis is 180 degrees to the flame, the average period of flaming and/or smoldering after removing the igniting flame does not exceed ten seconds and none of the vertically placed samples produces drips of burning particles that ignite absorbent cotton, and no specimen burns up to the holding clamp after flame or after glow. V-1, V-2: In a sample placed so that its long axis is 180 degrees to the flame, the average period of flaming and/or smoldering after removing the igniting flame does not exceed thirty seconds and, for a V-1 rating, none of the vertically placed samples produces drips of burning particles that ignite absorbent cotton. The V2 standard is the same as V-1, except that flaming drips that ignite the cotton are permitted.

[0057] The data were also analyzed by calculation of the average flame out time, standard deviation of the flame out time, as the total number of drips, and using statistical methods, such as those set forth in U.S. Pat. No. 6,308,142 to convert that data to a prediction of the probability of first time pass, or "p(FTP)", that a particular sample formulation would achieve a V0, VI, or V2 "pass" rating in the conventional UL94 testing of 5 bars. Preferably, p(FTP) is as close to 1 as possible, for example, greater than or equal to about 0.70, or greater than or equal to about 0.80, or greater than or equal to about 0.90, for maximum flame-retardant performance in UL testing. These standards are more stringent than merely specifying compliance with the referenced V-0 or V- 1 test.

[0058] A composition (CEx. 1) was prepared using PC-1 and PC-Si alone, and with the addition of increasing amount of PPC (CEx. 2-6) or PPPBP/BPA (CEx. 7).

Component Units CEx. 1 CEx. 2 CEx. 3 CEx. 4 CEx. 5 CEx. 6 CEx. 7

PC-1 wt% 78.45 64.05 50.35 36.65 22.85 9.15 50.85

PPC wt% 14.4 28.1 41.8 55.6 69.3

PC-Si wt% 12 12 12 12 12 12 12

PPPBP/BPA wt% 27.6 NB GF wt% 9 9 9 9 9 9 9

TSAN wt% 0.5 0.5 0.5 0.5 0.5 0.5 0.5

Phosphite wt% 0.05 0.05 0.05 0.05 0.05 0.05 0.05

Properties

Vicat °C 144.3 148.7 155.1 156.6 162.3 163.8 161.7

INI Impact (23°C) (kJ/m²) 20.0 19.8 18.1 17.3 15.6 15.1 11.0

Ductility (23°C) (%) 100 100 100 100 40 60 0

Table 3.

[0059] The data show that the composition with PC-1 and PC-Si alone had good impact strength, but lower heat resistance than the compositions with PPC or PPPBP/BPA. Increasing amounts of PPC improved heat resistance, but adversely affected impact properties, as did addition of PPPBP/BPA.

[0060] The effect of PPC on flammability was tested.

Table 4.

[0061] These experiments show that an increase in the amount of PPC resulted in improved flammability performance (Ex. 10 vs. CEx. 8). In particular, a higher pFTP is seen. As in CEx. 2-6, impact properties decreased with increasing PPC concentration.

[0062] A series of examples were made using an intermediate amount of PPC to attain a combination of acceptable impact and improved flame retardance. Varying amounts of TSAN were added. (CEx. 11-14).

Table 5.

[0063] Increasing amounts of TSAN further resulted in decreased impact and surprisingly, pFTP decreases as well.

[0064] A series of experiments were performed using an increasing amount of Rimar salt. TSAN was included in all of these examples.

Table 6.

[0065] As shown in the results, an increase in the amount of Rimar salt improves the flammability resistance of the composition (Ex. 20 vs. CEx. 15). Impact properties are adversely affected, however, compared to the composition with no Rimar salt (CEx. 15)

[0066] A series of experiments were performed using KSS flame retardant instead of Rimar salt, optionally in combination with NaTS.

Table 7.

[0067] As shown in Table 7, the best pFTP results were obtained when NaTS was also present (Ex. 26).

[0068] A series of experiments was performed using phosphazene flame retardant.

Table 8.

[0069] Impact properties were generally good. Surprisingly, however, the use of phosphazene did not improve the pFTP.

[0070] A series of experiments was performed using Rimar salt, and increasing the amount of TSAN from 0.06-0.2 wt%.

[0071] With the increase of the Rimar loading pFTP increases and with that flammability robustness is higher. Lower loadings of TSAN have positive effect on flammability.

[0072] A series of experiments was performed adding NaTS to compositions optionally containing KSS and TSAN.

Table 10.

[0073] These results show that in the absence of KSS, adding NaTS gives better pFTP. A combination of KSS and NaTS further improves pFTP.

[0074] A set of Examples containing a high heat copolycarbonate instead of a poly(phthalate-carbonate), no TSAN, and either Rimar salt or KSS and NaTS were formulated and analyzed in Ex. 49-54.

Table 11.

[0075] As shown in Table 11, when Rimar salt alone was used, a good balance of heat/impact and flammability was seen (Ex. 49-51), even in the absence of TSAN. A good balance of impact and flame retardant properties was also achieved with a combination of KSS and NaTS, even in the absence of TSAN.

[0076] The compositions, methods, and articles can alternatively comprise, consist of, or consist essentially of, any appropriate components or steps herein disclosed. The compositions, methods, and articles can additionally, or alternatively, be formulated so as to be devoid, or substantially free, of any steps, components, materials, ingredients, adjuvants, or species that are otherwise not necessary to the achievement of the function or objectives of the compositions, methods, and articles.

[0077] This disclosure further encompasses the following embodiments.

[0078] Embodiment 1. An article, preferably a housing for an electrical component, comprising a polycarbonate composition, comprising

up to 60 weight percent of a bisphenol A homopolycarbonate having a weight average molecular weight from 15,000-40,000 grams/mole measured via gel permeation chromatography using bisphenol A homopolycarbonate standards; 7-25 weight percent of a poly(carbonate- siloxane); 10-70 weight percent of a polycarbonate copolymer having a glass transition temperature of 170°C or higher; 0.05-1.5 weight percent of a flame retardant salt; 5-15 weight percent of glass fibers; 0-0.2 weight percent of an anti-drip agent; optionally, up to 10 weight percent of an additive composition; wherein a molded sample of the polycarbonate composition has a Vicat B 120 softening temperature of at least 150°C, preferably from 155 to 165°C, measured according to ISO 306, an Izod notched impact strength of greater than or equal to 10 kilojoules per square meter measured at 23°C according to ISO 180/1 A, a flame test rating, when measured according to UL-94 at 0.8 millimeters (mm) thickness, of V2, and a probability of first time pass for V2 greater than 0.7; wherein each amount is based on the total weight of the polycarbonate composition, which sums to 100 weight percent.

[0079] Embodiment 2. The article of Embodiment 1, wherein the article is a molded housing.

[0080] Embodiment 3. The article of Embodiment 1 or 2, wherein the article is an electrical circuit housing.

[0081] Embodiment 4. The article of any one or more of the preceding Embodiments, wherein the article is a molded article, a thermoformed article, an extruded film, an extruded sheet, a foamed article, a layer of a multi-layer article, a substrate for a coated article, or a substrate for a metallized article.

[0082] Embodiment 5. The article of any one or more of the preceding Embodiments, wherein the polycarbonate composition comprises 8-55 weight percent of the

homopolycarbonate; 10-25 weight percent of the poly(carbonate-siloxane), wherein the polycarbonate composition comprises 2-4 weight percent of silicon; 20-50 weight percent of the high heat polycarbonate copolymer; 0.1-0.7 weight percent of the flame retardant salt.

[0083] Embodiment 6. The article of any one or more of the preceding Embodiments, wherein the polycarbonate composition comprises a bisphenol A homopolycarbonate; the high heat copolycarbonate comprises at least one of carbonate units derived from bisphenol A and a high heat aromatic dihydroxy compound, preferably a phthalimidine carbonate unit, or a poly(phthalate ester-carbonate), preferably comprising ester units derived from bisphenol A and terephthalic, isophthalic, or phthalic acid, or a combination comprising at least one of the foregoing diacids, and carbonate units derived from bisphenol A; the flame retardant salt is a C₂- 16 alkyl sulfonate, preferably potassium perfluoroctane sulfonate, potassium perfluoroctane sulfonate, or tetraethylammonium perfluorohexane sulfonate, a salt of an aromatic sulfonates preferably sodium benzene sulfonate or sodium toluene sulfonate, a salt of an aromatic sulfone sulfonate, preferably a potassium diphenylsulfone sulfonate, a salt formed by reacting for example an alkali metal or alkaline earth metal and an inorganic acid complex salt, preferably an alkali metal or alkaline earth metal salt of carbonic acid or a fluoro-anion complex such as Li₃AlF₆, BaSiF₆, KBF₄, K3AIF6, KA1F₄, K₂SiF₆, or Na₃AlF6; and the anti-drip agent is styrene- acrylonitrile-encapsulated poly(tetrafluoroethylene) copolymer.

[0084] Embodiment 7. The article of any one or more of the preceding Embodiments, wherein the high heat copolycarbonate comprises 20-30 weight percent of a high heat copolymer of bisphenol-A and phthalimidine.

[0085] Embodiment 8. The article of any one or more of the preceding Embodiments, wherein the high heat copolycarbonate comprises 40-60 weight percent of a high heat copolymer of a poly(phthalate ester-carbonate).

[0086] Embodiment 9. The article of any one or more of the preceding Embodiments, wherein the flame retardant salt is potassium perfluorobutane sulfonate, potassium

diphenylsulfone sulfonate, sodium toluene sulfonate, or a combination comprising at least one of the foregoing.

[0087] Embodiment 10. The article of any one or more of the preceding Embodiments, wherein the flame retardant salt comprises 0.1-1.0 weight percent of a C2-16 alkyl sulfonate.

[0088] Embodiment 11. The article of Embodiment 10, wherein the flame retardant salt is potassium perfluoroctane sulfonate, potassium perfluorobutane sulfonate,

tetraethylammonium perfluorohexane sulfonate, or a combination comprising at least one of the foregoing.

[0089] Embodiment 12. The article of any one or more of the preceding Embodiments, wherein the flame retardant salt comprises a total of 0.2-0.7 weight percent of a salt of an aromatic sulfone sulfonate.

[0090] Embodiment 13. The article of Embodiment 12, wherein the flame retardant salt is sodium benzene sulfonate, sodium toluene sulfonate , a potassium diphenylsulfone sulfonate, or a combination comprising at least one of the foregoing. [0091] Embodiment 14. The article of any one or more of the preceding Embodiments, wherein the flame retardant salt does not contain phosphorous.

[0092] Embodiment 15. The article of any one or more of the preceding Embodiments, wherein the polycarbonate composition does not contain an anti-drip agent.

[0093] Embodiment 16. The article of any one or more of the preceding Embodiments, wherein the polycarbonate composition does not contain an acrylonitrile-butadiene-styrene copolymer or a methyl methacrylate-butadiene-styrene copolymer.

[0094] Embodiment 17. The article of any one or more of the preceding Embodiments, comprising 45-55 weight percent of a polycarbonate having a molecular weight from 20,000- 25,000 grams/mole; 10-20 weight percent of a poly(carbonate-siloxane) copolymer containing 15-25 weight percent siloxane; 20-30 weight percent of a high heat copolymer of bisphenol-A and phthalimidine, or 40-60 weight percent of a high heat copolymer of a poly(phthalate ester- carbonate); 0.3-0.8 weight percent of potassium perfluorobutane sulfonate, potassium

diphenylsulfone sulfonate, sodium toluene sulfonate, or a combination comprising at least one of the foregoing; 8-12 weight percent of glass fibers; 0.01-1.0 weight percent of a phosphite heat stabilizer; less than 0.15 weight percent of an anti-drip agent; wherein a molded sample of the polycarbonate composition has a Vicat B50 softening temperature of at least 150°C, preferably from 155 to 165°C, measured according to ISO 306, an Izod notched impact strength of greater than or equal to 10 kilojoules per square meter, measured at 23°C according to ISO 180/1 A, and a flame test rating of at least V2, measured according to UL-94 at 0.8 millimeters thickness.

[0095] Embodiment 18. A method for forming the article of any one or more of the preceding Embodiments, comprising molding, casting, or extruding the article.

[0096] Embodiment 19. A polycarbonate composition, comprising up to 60 weight percent of a bisphenol A homopolycarbonate having a weight average molecular weight from 15,000-40,000 grams/mole measured via gel permeation chromatography using bisphenol A homopolycarbonate standards; 7-25 weight percent of a poly(carbonate- siloxane); 10-70 weight percent of a high heat polycarbonate copolymer having a glass transition temperature of 170°C or higher; 0.05-1.5 weight percent of a flame retardant salt; 5-15 weight percent of glass fibers; 0-0.2 weight percent of an anti-drip agent; optionally, up to 10 weight percent of an additive composition.

[0097] Embodiment 20. A method for the manufacture of the polycarbonate

composition of Embodiment 19, comprising melt- mixing the components of the polycarbonate composition. [0098] The singular forms "a," "an," and "the" include plural referents unless the context clearly dictates otherwise. "Or" means "and/or" unless clearly indicated otherwise by context. The modifier "about" used in connection with a quantity is inclusive of the stated value (e.g., "about 25-50 wt%" is a disclosure of "25-50 wt%") and has the meaning dictated by the context (e.g., includes the degree of error associated with measurement of the particular quantity). The endpoints of all ranges directed to the same component or property are inclusive and

independently combinable (e.g., ranges of "less than or equal to 25 wt%, or 5 wt% to 20 wt%," is inclusive of the endpoints and all intermediate values of the ranges of "5 wt% to 25 wt%," etc.). Disclosure of a narrower range or more specific group in addition to a broader range is not a disclaimer of the broader range or larger group.

[0099] The suffix "(s)" is intended to include both the singular and the plural of the term that it modifies, thereby including at least one of that term (e.g., the filler(s) includes at least one filler). "Optional" or "optionally" means that the subsequently described event or circumstance may or may not occur, and that the description includes instances where the event occurs and instances where it does not. 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 disclosure belongs. A "combination" is inclusive of blends, mixtures, alloys, reaction products, and the like. The terms "first," "second," and the like, "primary," "secondary," and the like, as used herein do not denote any order, quantity, or importance, but rather are used to distinguish one element from another.

[00100] As used herein, the term "hydrocarbyl" and "hydrocarbon" refers broadly to a substituent comprising carbon and hydrogen, optionally with 1-3 heteroatoms, for example, oxygen, nitrogen, halogen, silicon, sulfur, or a combination thereof; "alkyl" refers to a straight or branched chain, saturated monovalent hydrocarbon group; "alkylene" refers to a straight or branched chain, saturated, divalent hydrocarbon group; "alkylidene" refers to a straight or branched chain, saturated divalent hydrocarbon group, with both valences on a single common carbon atom; "alkenyl" refers to a straight or branched chain monovalent hydrocarbon group having at least two carbons joined by a carbon-carbon double bond; "cycloalkyl" refers to a non- aromatic monovalent monocyclic or multicylic hydrocarbon group having at least three carbon atoms, "cycloalkenyl" refers to a non-aromatic cyclic divalent hydrocarbon group having at least three carbon atoms, with at least one degree of unsaturation; "aryl" refers to an aromatic monovalent group containing only carbon in the aromatic ring or rings; "arylene" refers to an aromatic divalent group containing only carbon in the aromatic ring or rings; "alkylaryl" refers to an aryl group that has been substituted with an alkyl group as defined above, with 4- methylphenyl being an exemplary alkylaryl group; "arylalkyl" refers to an alkyl group that has been substituted with an aryl group as defined above, with benzyl being an exemplary arylalkyl group; "acyl" refers to an alkyl group as defined above with the indicated number of carbon atoms attached through a carbonyl carbon bridge (-C(=0)-); "alkoxy" refers to an alkyl group as defined above with the indicated number of carbon atoms attached through an oxygen bridge (- 0-); and "aryloxy" refers to an aryl group as defined above with the indicated number of carbon atoms attached through an oxygen bridge (-0-).

[00101] Unless otherwise indicated, each of the foregoing groups can be unsubstituted or substituted, provided that the substitution does not significantly adversely affect synthesis, stability, or use of the compound. The term "substituted" as used herein means that at least one hydrogen on the designated atom or group is replaced with another group, provided that the designated atom's normal valence is not exceeded. When the substituent is oxo (i.e., =0), then two hydrogens on the atom are replaced. Combinations of substituents or variables are permissible provided that the substitutions do not significantly adversely affect synthesis or use of the compound. Exemplary groups that can be present on a "substituted" position include, but are not limited to, cyano; hydroxyl; nitro; azido; alkanoyl (such as a C2-6 alkanoyl group such as acyl); carboxamido; Cl-6 or Cl-3 alkyl, cycloalkyl, alkenyl, and alkynyl (including groups having at least one unsaturated linkages and from 2-8, or 2-6 carbon atoms); Cl-6 or Cl-3 alkoxys; C6-10 aryloxy such as phenoxy; Cl-6 alkylthio; Cl-6 or Cl-3 alkylsulfinyl; Cl-6 or Cl-3 alkylsulfonyl; aminodi(Cl-6 or Cl-3)alkyl; C6-12 aryl having at least one aromatic rings (e.g., phenyl, biphenyl, naphthyl, or the like, each ring either substituted or unsubstituted aromatic); C7-19 arylalkyl having 1-3 separate or fused rings and from 6-18 ring carbon atoms; or arylalkoxy having 1-3 separate or fused rings and from 6-18 ring carbon atoms, with benzyloxy being an exemplary arylalkoxy.

[00102] All cited patents, patent applications, and other references are incorporated herein by reference in their entirety. However, if a term in the present application contradicts or conflicts with a term in the incorporated reference, the term from the present application takes precedence over the conflicting term from the incorporated reference.

[00103] While typical embodiments have been set forth for the purpose of illustration, the foregoing descriptions should not be deemed to be a limitation on the scope herein.

Accordingly, various modifications, adaptations, and alternatives can occur to one skilled in the art without departing from the spirit and scope herein.

Claims

CLAIMS: We claim:

1. An article comprising a polycarbonate composition, comprising

up to 60 weight percent of a bisphenol A homopolycarbonate having a weight average molecular weight from 15,000-40,000 grams/mole measured via gel permeation chromatography using bisphenol A homopolycarbonate standards;

7-25 weight percent of a poly(carbonate-siloxane);

10-70 weight percent of a polycarbonate copolymer having a glass transition temperature of 170°C or higher;

0.05-1.5 weight percent of a flame retardant salt;

5-15 weight percent of glass fibers;

0-0.2 weight percent of an anti-drip agent;

optionally, up to 10 weight percent of an additive composition;

wherein a molded sample of the polycarbonate composition has

a Vicat B 120 softening temperature of at least 150°C, measured according to ISO 306,

an Izod notched impact strength of greater than or equal to 10 kilojoules per square meter measured at 23 °C according to ISO 180/1 A,

a flame test rating, when measured according to UL-94 at 0.8 millimeters thickness, of V2, and

a probability of first time pass for V2 greater than 0.7;

wherein each amount is based on the total weight of the polycarbonate composition, which sums to 100 weight percent.

2. The article of claim 1, wherein the article is a molded housing.

3. The article of claim 1 or 2, wherein the article is an electrical circuit housing.

4. The article of any one or more of the preceding claims, wherein the article is a molded article, a thermoformed article, an extruded film, an extruded sheet, a foamed article, a layer of a multi-layer article, a substrate for a coated article, or a substrate for a metallized article.

5. The article of any one or more of the preceding claims, wherein the polycarbonate composition comprises

8-55 weight percent of the homopolycarbonate;

10-25 weight percent of the poly(carbonate-siloxane);

20-50 weight percent of the high heat polycarbonate copolymer;

0.1-0.7 weight percent of the flame retardant salt, wherein the polycarbonate composition comprises 2-4 weight percent of siloxane.

6. The article of any one or more of the preceding claims, wherein

the polycarbonate composition comprises a bisphenol A homopolycarbonate;

the high heat copolycarbonate comprises at least one of

carbonate units derived from bisphenol A and a high heat aromatic dihydroxy compound, preferably a phthalimidine carbonate unit, or

a poly(phthalate ester-carbonate), preferably comprising ester units derived from bisphenol A and terephthalic, isophthalic, or phthalic acid, or a combination comprising at least one of the foregoing diacids, and carbonate units derived from bisphenol A;

the flame retardant salt is

a C2-16 alkyl sulfonate, preferably potassium perfluoroctane sulfonate, potassium perfluoroctane sulfonate, or tetraethylammonium perfluorohexane sulfonate, a salt of an aromatic sulfonates preferably sodium benzene sulfonate or sodium toluene sulfonate,

a salt of an aromatic sulfone sulfonate, preferably a potassium diphenylsulfone sulfonate,

a salt formed by reacting for example an alkali metal or alkaline earth metal and an inorganic acid complex salt, preferably an alkali metal or alkaline earth metal salt of carbonic acid or a fluoro-anion complex such as L13AIF6, BaSiF₆, KBF₄, K₃A1F₆, KA1F₄, K₂SiF₆, or Na₃AlF₆; and

the anti-drip agent is styrene-acrylonitrile-encapsulated poly(tetrafluoroethylene) copolymer.

7. The article of any one or more of the preceding claims, wherein the high heat copolycarbonate comprises 20-30 weight percent of a high heat copolymer of bisphenol-A and phthalimidine.

8. The article of any one or more of the preceding claims, wherein the high heat copolycarbonate comprises 40-60 weight percent of a high heat copolymer of a poly(phthalate ester-carbonate).

9. The article of any one or more of the preceding claims, wherein the flame retardant salt is potassium perfluorobutane sulfonate, potassium diphenylsulfone sulfonate, sodium toluene sulfonate, or a combination comprising at least one of the foregoing.

10. The article of any one or more of the preceding claims, wherein the flame retardant salt comprises 0.1-1.0 weight percent of a C2-16 alkyl sulfonate.

11. The article of claim 10, wherein the flame retardant salt is potassium perfluoroctane sulfonate, potassium perfluorobutane sulfonate, tetraethylammonium perfluorohexane sulfonate, or a combination comprising at least one of the foregoing.

12. The article of any one or more of the preceding claims, wherein the flame retardant salt comprises a total of 0.2-0.7 weight percent of a salt of an aromatic sulfone sulfonate.

13. The article of claim 12, wherein the flame retardant salt is sodium benzene sulfonate, sodium toluene sulfonate, a potassium diphenylsulfone sulfonate, or a combination comprising at least one of the foregoing.

14. The article of any one or more of the preceding claims, wherein the flame retardant salt does not contain phosphorous.

15. The article of any one or more of the preceding claims, wherein the polycarbonate composition does not contain an anti-drip agent.

16. The article of any one or more of the preceding claims, wherein the polycarbonate composition does not contain an acrylonitrile-butadiene-styrene copolymer or a methyl methacrylate-butadiene-styrene copolymer.

17. The article of any one or more of the preceding claims, comprising

45-55 weight percent of a polycarbonate having a molecular weight from 20,000-25,000 grams/mole;

10-20 weight percent of a poly (carbonate- siloxane) copolymer containing 15-25 weight percent siloxane; 20-30 weight percent of a high heat copolymer of bisphenol-A and phthalimidine, or 40- 60 weight percent of a high heat copolymer of a poly(phthalate ester-carbonate);

0.3-0.8 weight percent of potassium perfluorobutane sulfonate, potassium

diphenylsulfone sulfonate, sodium toluene sulfonate, or a combination comprising at least one of the foregoing;

8-12 weight percent of glass fibers;

0.01-1.0 weight percent of a phosphite heat stabilizer;

less than 0.15 weight percent of an anti-drip agent;

wherein a molded sample of the polycarbonate composition has

a Vicat B50 softening temperature of at least 150°C, measured according to ISO 306, an Izod notched impact strength of greater than or equal to 10 kilojoules per square meter, measured at 23 °C according to ISO 180/1 A, and

a flame test rating of at least V2, measured according to UL-94 at 0.8 millimeters thickness.

18. A method for forming the article of any one or more of the preceding claims, comprising molding, casting, or extruding the article.

19. A polycarbonate composition, comprising

up to 60 weight percent of a bisphenol A homopolycarbonate having a weight average molecular weight from 15,000-40,000 grams/mole measured via gel permeation chromatography using bisphenol A homopolycarbonate standards;

7-25 weight percent of a poly(carbonate-siloxane);

10-70 weight percent of a high heat polycarbonate copolymer having a glass transition temperature of 170°C or higher;

0.05-1.5 weight percent of a flame retardant salt;

5-15 weight percent of glass fibers;

0-0.2 weight percent of an anti-drip agent;

optionally, up to 10 weight percent of an additive composition.

20. A method for the manufacture of the polycarbonate composition of claim 19, comprising melt-mixing the components of the polycarbonate composition.