CROSS REFERENCE TO RELATED APPLICATIONS

This application claims the benefit of U.S. Application No. 62/894044, filed on August 30, 2019, which is incorporated herein by reference in its entirety.

BACKGROUND

[0001] This disclosure relates to polycarbonate compositions, and in particular to polycarbonate compositions, methods of manufacture, and uses thereof.

[0002] Polycarbonates are useful in the manufacture of articles and components for a wide range of applications, from automotive parts to electronic appliances.

[0003] There accordingly remains a need in the art for flame retardant polycarbonate compositions having high heat resistance. It would be a further advantage if the compositions had improved flammability ratings at very low thicknesses. It would be a further advantage if the compositions contain ultra-low halogen content.

BRIEF DESCRIPTION

[0004] A flame retardant polycarbonate composition comprising: 60.0-99.9 weight percent of a poly(carbonate-bisphenol phthalate ester) comprising 1-50 weight percent of aromatic carbonate units and 50-99 weight percent of bisphenol phthalate ester units, each based on the sum of the weight of the carbonate units and the bisphenol phthalate ester units;

0.1-0.5 weight percent of a Ci-i ₆ alkyl sulfonate salt flame retardant; 0-30.0 weight percent of a homopolycarbonate; optionally, 0.01-1.0 weight percent of an anti-drip agent; optionally, 0.1-5.0 weight percent of an additive composition, wherein the amount of the poly(carbonate-bisphenol phthalate ester), the sulfonate salt flame retardant, the homopolycarbonate, the optional anti-drip agent, and the optional additive composition is based on the total weight of the flame retardant composition, which sums to 100 weight percent; and wherein a molded sample of the flame retardant polycarbonate composition has a flame- out time (5-bar FOT) of 250 seconds or less at a 1.0 millimeter thickness with zero dripping when measured in accordance with UL 94 standards, a flame-out time (5-bar FOT) of 250 seconds or less at a 0.8 millimeter thickness with zero dripping when measured in accordance with UL 94 standards, a UL 94 rating of V0 at a thickness of 1.0 millimeter, a UL 94 rating of V0 at a thickness of 0.8 millimeter, or a combination thereof; and a heat deformation temperature of at least 145°C measured according to the ISO-75 standard with a 5.5 Joule hammer on 4 millimeter-thick bars and a load of 1.8 megapascals, a Vicat softening temperature of at least 160°C as measured according to the ISO-306 standard at a load of 50 newtons and a speed of 120°C per hour on 4 millimeter bars, or a combination thereof.

[0005] In another aspect, a method of manufacture comprises combining the above- described components to form a flame retardant composition.

[0006] In yet another aspect, an article comprises the above-described flame retardant polycarbonate composition.

[0007] In still another aspect, a method of manufacture of an article comprises molding, extruding, or shaping the above-described flame retardant polycarbonate composition into an article.

[0008] The above described and other features are exemplified by the following drawings, detailed description, examples, and claims.

DETAILED DESCRIPTION

[0009] There is a need for thin-walled articles made from flame retardant polycarbonate compositions having high heat resistance, while maintaining other properties such as impact and heat resistance. In particular, compositions for thin-walled compositions are needed having a heat deformation temperature (HDT) of at least 145 °C, a Vicat softening temperature of at least 160°C, and a flame-out time (5-bar FOT) of 250 seconds or less at a 1.0 millimeter thickness with zero dripping when measured in accordance with UL 94 standards, a flame-out time (5-bar FOT) of 250 seconds or less at a 0.8 millimeter thickness with zero dripping when measured in accordance with UL 94 standards, a UL-94 flammability rating of V0 at 1.0 mm, a UL-94 flammability rating of V0 at 0.8 mm, or a combination thereof. In addition, there is an increasing demand for more environmentally friendly polycarbonate compositions with ultra-low halogen content (ULH). Some commercially available chlorine-free and bromine-free polycarbonate compositions that include flame retardants such as Rimar salt or poly(tetrafluoroethylene) have good heat resistance and impact properties; but do not possess adequate flammability ratings at low thicknesses, less than 1 millimeter (mm), for example. Other commercially available polycarbonate compositions that include chlorine-free and bromine-free flame retardants possess good flammability ratings at low thicknesses, but these materials have insufficient heat resistance for some high heat applications. For example, it is known that phosphonate or phosphazene flame retardants may decrease the heat resistance of polycarbonate compositions.

[0010] Surprisingly and unexpectedly, the inventors hereof have discovered flame retardant polycarbonate compositions having high heat resistance, improved flammability performance, and good impact properties. These compositions comprise a poly(carbonate- bisphenol phthalate ester) and a C _M6 alkyl sulfonate salt flame retardant.

[0011] A molded sample of the flame retardant polycarbonate composition may have, for example, a flame-out time (5-bar FOT) of 250 seconds or less at a 1.0 millimeter thickness with zero dripping when measured in accordance with UL 94 standards, a flame-out time (5-bar FOT) of 250 seconds or less at a 0.8 millimeter thickness with zero dripping when measured in accordance with UL 94 standards, UL 94 rating of V0 at a thickness of 1.0 millimeter, a UL 94 rating of V0 at a thickness of 0.8 millimeter, or a combination thereof. In addition, a molded sample of the flame retardant polycarbonate composition may have, for example, a heat deformation temperature of at least 145°C measured according to the ISO-75 standard with a 5.5 Joule hammer on 4 millimeter-thick bars and a load of 1.8 megapascals, a Vicat softening temperature of at least 160°C as measured according to the ISO-306 standard at a load of 50 newtons and a speed of 120°C per hour on 4 millimeter bars, or a combination thereof.

[0012] The individual components of the flame retardant compositions are described in further detail below.

[0013] “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. In an aspect, each R ¹ is a C6-30 aromatic group, that is, contains at least one aromatic moiety. R ¹ may be derived from an aromatic dihydroxy compound of the formula HO-R'-OH, in particular of the formula

HO-A^Y^-OH 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 . Specifically, each R ¹ may be derived from a bisphenol of formula (2) wherein 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. It will be understood that when p or q is less than 4, the valence of each carbon of the ring is filled by hydrogen. Also in formula (2), X ^a is a C1-60 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. In an aspect, the bridging group X ^a is single bond, -0-, -S-, -S(O)-, -S(0) ₂ -, -C(O)-, or a C1-60 organic group. The C1-60 organic bridging group may be cyclic or acyclic, aromatic or non-aromatic, and may further comprise heteroatoms such as halogens, oxygen, nitrogen, sulfur, silicon, or phosphorus. The C1-60 organic group may be disposed such that the Ce arylene groups connected thereto are each connected to a common alkylidene carbon or to different carbons of the C1-60 organic bridging group. In an aspect, 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.

[0014] In an aspect, X ^a is a C3-18 cycloalkylidene, a Ci-25 alkylidene of 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. Groups of these types include methylene, cyclohexylmethylidene, ethylidene, neopentylidene, and isopropylidene, as well as 2- [2.2. l]-bicycloheptylidene, cyclohexylidene, 3,3-dimethyl-5-methylcyclohexylidene, cyclopentylidene, cyclododecylidene, and adamantylidene.

[0015] In another aspect, X ^a is a C1-18 alkylene, a C3-18 cycloalkylene, a fused C6-18 cycloalkylene, or a group of the formula -J'-G-J ² - wherein J ¹ and J ² are the same or different Ci- ₆ alkylene and G is a C3-12 cycloalkylidene or a C6-16 arylene.

[0016] For example, X ^a may be a substituted C3-18 cycloalkylidene of formula (4) wherein R ^r , R ^p , R ^q , and R ^l are each independently hydrogen, halogen, oxygen, or Ci-12 hydrocarbon groups; Q is a direct bond, a carbon, or a divalent oxygen, sulfur, or -N(Z)- where Z is hydrogen, halogen, hydroxy, Ci-12 alkyl, Ci-12 alkoxy, Ce-n aryl, or Ci-12 acyl; r is 0 to 2, t is 1 or 2, q is 0 or 1, and k is 0 to 3, with the proviso that at least two of R ^r , R ^p , R ^q , and R ^l taken together are a fused cycloaliphatic, aromatic, or heteroaromatic ring. It will be understood that where the fused ring is aromatic, the ring as shown in formula (4) will have an unsaturated carbon-carbon linkage where the ring is fused. When k is one and q is 0, the ring as shown in formula (4) contains 4 carbon atoms, when k is 2, the ring as shown in formula (4) contains 5 carbon atoms, and when k is 3, the ring contains 6 carbon atoms. In an aspect, two adjacent groups (e.g., R ^q and R ^l taken together) form an aromatic group, and in another aspect, R ^q and R ^l taken together form one aromatic group and R ^r and R ^p taken together form a second aromatic group. When R ^q and R ¹ taken together form an aromatic group, R ^p may be a double-bonded oxygen atom, i.e., a ketone, or Q may be -N(Z)- wherein Z is phenyl.

[0017] Bisphenols wherein X ^a is a cycloalkylidene of formula (4) may be used in the manufacture of polycarbonates containing phthalimidine carbonate units of formula (la) wherein R ^a , R ^b , p, and q are as in formula (3), R ³ is each independently a Ci- ₆ alkyl, j is 0 to 4, and R4 is hydrogen, Ci- ₆ alkyl, or a substituted or unsubstituted phenyl, for example a phenyl substituted with up to five Ci- ₆ alkyls. For example, the phthalimidine carbonate units are of formula (lb) wherein R ⁵ is hydrogen, phenyl optionally substituted with up to five 5 Ci- ₆ alkyls, or C1 alkyl. In an aspect in formula (lb), R ⁵ is hydrogen, methyl, or phenyl, preferably phenyl. Carbonate units (lb) wherein R ⁵ is phenyl may be derived from 2-phenyl-3,3’-bis(4-hydroxy phenyl)phthalimidine (also known as 3,3-bis(4-hydroxyphenyl)-2-phenylisoindolin-l-one, or bi phenyl phenolphthalein bisphenol (“PPPBP”)).

[0018] Other bisphenol carbonate repeating units of this type are the isatin carbonate units of formula (lc) and (Id) wherein R ^a and R ^b are each independently a halogen, Ci-12 alkoxy, or Ci-12 alkyl, p and q are each independently 0 to 4, and R ¹ is Ci-12 alkyl, phenyl optionally substituted with 1 to 5 Ci-10 alkyl, or benzyl optionally substituted with 1 to 5 Ci-10 alkyl. In an aspect, R ^a and R ^b are each methyl, p and q are each independently 0 or 1, and R ¹ is CM alkyl or phenyl. [0019] Other examples of bisphenol carbonate units derived from of bisphenols (3) wherein X ^a is a substituted or unsubstituted C3-18 cycloalkylidene include the cyclohexylidene- bridged bisphenol of formula (le) wherein R ^a and R ^b are each independently Ci-12 alkyl, R ^g is Ci-12 alkyl, p and q are each independently 0 to 4, and t is 0 to 10. In a specific aspect, at least one of each of R ^a and R ^b are disposed meta to the cyclohexylidene bridging group. In an aspect, R ^a and R ^b are each independently C1-4 alkyl, R ^g is C alkyl, p and q are each 0 or 1, and t is 0 to 5. In another specific aspect, R ^a , R ^b , and R ^g are each methyl, p and q are each 0 or 1, and t is 0 or 3, preferably 0. In still another aspect, p and q are each 0, each R ^g is methyl, and t is 3, such that X ^a is 3,3- dimethyl-5-methyl cyclohexylidene.

[0020] Examples of other bisphenol carbonate units derived from bisphenol (3) wherein X ^a is a substituted or unsubstituted C3-18 cycloalkylidene include adamantyl units of formula (If) and fluorenyl units of formula (lg) wherein R ^a and R ^b are each independently Ci-12 alkyl, and p and q are each independently 1 to 4. In a specific aspect, at least one of each of R ^a and R ^b are disposed meta to the cycloalkylidene bridging group. In an aspect, R ^a and R ^b are each independently C1-3 alkyl, and p and q are each 0 or 1; preferably, R ^a , R ^b are each methyl, p and q are each 0 or 1, and when p and q are 1, the methyl group is disposed meta to the cycloalkylidene bridging group. Carbonates containing units (la) to (lg) are useful for making polycarbonates with high glass transition temperatures (Tg) and high heat distortion temperatures.

[0021] Other useful dihydroxy compounds of the formula HO-R^OH include aromatic dihydroxy compounds of formula (6) wherein each R ^h is independently a halogen atom, Ci-10 hydrocarbyl group such as a Ci-10 alkyl, a halogen-substituted Ci-10 alkyl, a C6-10 aryl, or a halogen-substituted C6-10 aryl, and n is 0 to 4. The halogen is usually bromine. [0022] Some illustrative examples of specific dihydroxy compounds include the following: 4,4'-dihydroxybiphenyl, 1,6-dihydroxynaphthalene, 2, 6-dihydro xynaphthalene, bis(4-hydroxyphenyl)methane, bis(4-hydroxyphenyl)diphenylmethane, bis(4-hydroxyphenyl)- 1- 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, l,l-dichloro-2,2-bis(5-phenoxy-4- hydroxyphenyl)ethylene, 4,4'-dihydroxybenzophenone, 3,3-bis(4-hydroxyphenyl)-2-butanone,

1.6-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)fluorine, 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, or a combination thereof.

[0023] Specific examples of bisphenol compounds of formula (3) include l,l-bis(4- hydroxyphenyl) methane, l,l-bis(4-hydroxyphenyl) ethane, 2,2-bis(4-hydroxyphenyl) propane (hereinafter “bisphenol A” or “BPA”), 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-2-methylphenyl) propane, l,l-bis(4-hydroxy-t-butylphenyl) propane, 3,3- bis(4-hydroxyphenyl) phthalimidine, 2-phenyl-3,3-bis(4-hydroxyphenyl) phthalimidine (PPPBP), and l,l-bis(4-hydroxy-3-methylphenyl)cyclohexane (DMBPC). A combination may also be used. In a specific aspect, the polycarbonate is a linear homopolymer derived from bisphenol A, in which each of A ¹ and A ² is p-phenylene and Y ¹ is isopropylidene in formula (3).

[0024] The polycarbonates may have, for example, 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, for example, a weight average molecular weight (Mw) of 10,000 to 200,000 Daltons, preferably 20,000 to 100,000 Daltons, as measured by gel permeation chromatography (GPC), using a crosslinked styrene-divinylbenzene column and calibrated to bisphenol A homopolycarbonate references. GPC samples are prepared at a concentration of 1 mg per ml, and are eluted at a flow rate of 1.5 ml per minute. In some aspects, the homopolycarbonate, when present, is a bisphenol A homopolycarbonate having an Mw of 18,000-35,000 grams/mole, preferably 20,000-25,000 g/mol; or a bisphenol A homopolycarbonate having a weight average molecular weight of 25,000-35,000 g/mol, preferably 27,000-32,000 g/mol; or a combination thereof, each as measured as described above.

[0025] “Polycarbonates” includes homopolycarbonates (wherein each R ¹ in the polymer is the same), copolymers comprising different R ¹ moieties in the carbonate (“copolycarbonates”), and copolymers comprising carbonate units and other types of polymer units, such as ester units.

[0026] A specific type of copolymer is a poly(ester-carbonate), also known as a polyester-polycarbonate. 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 - (7) wherein J is a divalent group derived from a dihydroxy compound (including a reactive derivative thereof), and may be, for example, a CMO alkylene, a C6-20 cycloalkylene, a C5-20 arylene, or a polyoxyalkylene in which the alkylene groups contain 2 to 6 carbon atoms, preferably 2, 3, or 4 carbon atoms; and T is a divalent group derived from a dicarboxylic acid (including a reactive derivative thereof), and may be, for example, a C2-20 alkylene, a C5-20 cycloalkylene, or a C6-20 arylene. Copolyesters containing a combination of different T or J groups may be used. The polyester units may be branched or linear.

[0027] In an aspect, 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, 1,4-cyclohexylene, or 1,4-methylenecyclohexane. In another aspect, J is derived from a bisphenol of formula (3), e.g., bisphenol A. In another aspect, J is derived from an aromatic dihydroxy compound of formula (6), e.g, resorcinol.

[0028] Aromatic dicarboxylic acids that may be used to prepare the polyester units include isophthalic or terephthalic acid, l,2-di(p-carboxyphenyl)ethane, 4, 4'-dicarboxy diphenyl ether, 4,4'-bisbenzoic acid, or a combination thereof. Acids containing fused rings may 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 thereof. 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.

[0029] 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 may vary broadly, for example 1:99 to 99:1, preferably 10:90 to 90:10, more preferably 25:75 to 75:25, or 2:98 to 15:85, depending on the desired properties of the final composition. 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 (carbonate-ester) s (PCE) poly(phthalate-carbonate)s (PPC) depending on the molar ratio of carbonate units and ester units.

[0030] In a specific aspect, the polycarbonate copolymer is a poly(bisphenol A carbonate)-co-(bisphenol A-phthalate-ester) of formula (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 aspect, the weight percent of ester units y 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. Copolymers of formula (8a) comprising 35 to 45 wt% of carbonate units and 55 to 65 wt% of ester units, wherein the ester units have a molar ratio of isophthalate to terephthalate of 45:55 to 55:45 are often referred to as poly(carbonate-ester)s (PCE).

Copolymers comprising 15 to 25 wt% of carbonate units and 75 to 85 wt% of ester units having a molar ratio of isophthalate to terephthalate from 98:2 to 88:12 are often referred to as poly(phthalate-carbonate)s (PPC). [0031] In another aspect, a specific polycarbonate copolymer is a poly(carbonate-co- monoarylate ester) that includes carbonate units (1) and repeating monoarylate ester units of formula (7b) wherein each R ^h is independently a halogen atom, a Ci-io hydrocarbyl such as a Ci-io alkyl group, a halogen-substituted Ci-io alkyl group, a C _6-i o aryl group, or a halogen-substituted C _6-i o aryl group, and n is 0 to 4. Preferably, each R ^h is independently a Ci-4 alkyl, and n is 0 to 3, 0 to 1, or 0. These poly(carbonate-co-monoarylate ester)s include units of formula (8b) wherein R ¹ is as defined in formula (1) and R ^h and n are as defined in formula (7b), and the mole ratio of carbonate units x to ester units z is from 99:1 to 1:99, or from 98:2 to 2:98, or from 90:10 to 10:90. In an aspect the mole ratio of x:z is from 50:50 to 99:1, or from 1:99 to 50:50.

[0032] Preferably, the monoarylate ester unit (7b) is derived from the reaction of a combination of isophthalic and terephthalic diacids (or a reactive derivative thereof) with resorcinol (or a reactive derivative thereof) to provide isophthalate/terephthalate-resorcinol (“ITR” _{esjer un} it ) of formula (7c).

In an aspect, the ITR ester units are present in the polycarbonate copolymer in an amount greater than or equal to 95 mol%, preferably greater than or equal to 99 mol%, and still more preferably greater than or equal to 99.5 mol%, based on the total moles of ester units in the copolymer.

Such (isophthalate/terephthalate-resorcinol)-carbonate copolymers (“ITR-PC”) may possess many desired features, including toughness, transparency, and weatherability. ITR-PC copolymers may also have desirable thermal flow properties. In addition, ITR-PC copolymers may be readily manufactured on a commercial scale using interfacial polymerization techniques, which allow synthetic flexibility and composition specificity in the synthesis of the ITR-PC copolymers.

[0033] A specific example of a poly(carbonate-co-monoarylate ester) is a poly(bisphenol A carbonate-co-isophthalate-terephthalate -resorcinol ester) of formula (8c) wherein the mole ratio of x:z is or from 98:2 to 2:98, or from 90:10 to 10:90. In an aspect the mole ratio of x:z is from 50:50 to 99:1, or from 1:99 to 50:50. The ITR ester units may be present in the poly(bisphenol A carbonate-co-isophthalate-terephthalate-resorcinol ester) in an amount greater than or equal to 95 mol%, preferably greater than or equal to 99 mol%, and still more preferably greater than or equal to 99.5 mol%, based on the total moles of ester units in the copolymer. Other carbonate units, other ester units, or a combination thereof may be present, in a total amount of 1 to 20 mole%, based on the total moles of units in the copolymers, for example resorcinol carbonate units of formula (20) and bisphenol ester units of formula (7a): wherein, in the foregoing formulae, R ^h is each independently a CMO hydrocarbon group, n is 0 to 4, R ^a and R ^b are each independently a Ci-12 alkyl, p and q are each independently integers of 0 to 4, and X ^a is a single bond, -O-, -S-, -S(O)-, -S(0) ₂ -, -C(O)-, or a Ci-13 alkylidene of formula - C(R ^c )(R ^d ) - wherein R ^c and R ^d are each independently hydrogen or Ci-12 alkyl, or a group of the formula -C(=R ^e )- wherein R ^e is a divalent Ci-12 hydrocarbon group. The bisphenol ester units may be bisphenol A phthalate ester units of the formula

[0034] In an aspect, poly(bisphenol A carbonate-co-isophthalate-terephthalate -resorcinol ester) (8c) comprises 1 to 90 mol% of bisphenol A carbonate units, 10-99 mol% of isophthalic acid-terephthalic acid-resorcinol ester units, and optionally 1 to 60 mol% of resorcinol carbonate units, isophthalic acid-terephthalic acid-bisphenol A phthalate ester units, or a combination thereof. In another aspect, poly(bisphenol A carbonate-co-isophthalate-terephthalate-resorcinol ester) (8c) comprises 10 to 20 mol% of bisphenol A carbonate units, 20-98 mol% of isophthalic acid-terephthalic acid-resorcinol ester units, and optionally 1 to 60 mol% of resorcinol carbonate units, isophthalic acid-terephthalic acid-bisphenol A phthalate ester units, or a combination thereof. [0035] The polycarbonate copolymers comprising arylate ester units are generally prepared from polyester blocks. The polyester blocks may 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 may be used. Thus, for example instead of using isophthalic acid, terephthalic acid, or a combination thereof, isophthaloyl dichloride, terephthaloyl dichloride, or a combination thereof may be used. The polyesters may 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 may 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, may be used. Furthermore, it may be desirable to have various concentrations of acid and hydroxyl end groups on the polyester blocks, depending on the ultimate end use of the composition.

[0036] The polycarbonate copolymers comprising arylate ester units may have, for example, an M _w of 2,000 to 100,000 g/mol, preferably 3,000 to 75,000 g/mol, more preferably 4,000 to 50,000 g/mol, more preferably 5,000 to 35,000 g/mol, and still more preferably 17,000 to 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 polycarbonate standards. Samples are eluted at a flow rate of 1.0 ml/min with methylene chloride as the eluent.

[0037] The poly(carbonate -bisphenol phthalate ester)s may be present, for example, from 60-99.9 wt%, 60-98 wt%, 90-99.9 wt%, 95-99 wt% or 60-80 wt%, each based on the total weight of the composition.

[0038] The flame retardant polycarbonate composition includes Ci-i ₆ alkyl sulfonate salts such as potassium perfluorobutane sulfonate (Rimar salt), potassium perfluoroctane sulfonate, tetraethylammonium perfluorohexane sulfonate, or a combination thereof. The C _\-\ e alkyl sulfonate salt may be present, for example, from 0.1-0.5 wt%, 0.1-0.3 wt%, 0.2-0.5 wt% or 0.2-0.4 wt% of the flame retardant composition. In some aspects, potassium diphenylsulfone sulfonate, sodium benzene sulfonate, sodium toluene sulfonate, potassium diphenylsulfone sulfonate, or a combination thereof may be used in combination with C _\-\ e alkyl sulfonate salt flame retardants. Salts such as Na2C03, K2CO3, MgC03, CaC03, and BaC03, or fluoro-anion complexes such as L1 ₃ AIF ₆ , BaSiF6, KBF ₄ , K ₃ AIF ₆ , KAIF ₄ , K ₂ S1F ₆ , or Na ₃ AlF ₆ may also be used. [0039] The flame retardant polycarbonate composition may include an additional flame retardant different from the Ci-i ₆ alkyl sulfonate salt flame retardants. In some aspects, an organophosphorous compound may be included in combination with the C _\-\ e alkyl sulfonate salt flame retardants in the composition. When present, inorganic flame retardant salts other than Ci-16 alkyl sulfonate salts are present in amounts of 0.01 to 1 parts by weight, more preferably 0.02 to 1 parts by weight, based on 100 parts by weight of the total composition, excluding any filler.

[0040] In the aromatic organophosphorous compounds that have at least one organic aromatic group, the aromatic group may be a substituted or unsubstituted C3-30 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 organophosphorous compound, or bonded via another moiety, for example an alkylene group. The aromatic moiety of the aromatic group may be directly bonded to the organophosphorous compound, or bonded via another moiety, for example an alkylene group. In an aspect 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 thereof.

[0041] The organophosphorous compound may be a phosphate (P(=0)(OR) ₃ ), phosphite (P(OR)3), phosphonate (RP(=0)(OR) ₂ ), phosphinate (R ₂ P(=0)(OR)), phosphine oxide (R ₃ P(=0)), or phosphine (R3P), wherein each R in the foregoing organophosphorous compounds may be the same or different, provided that at least one R is an aromatic group. A combination of different organophosphorous compounds may be used. The aromatic group may be directly or indirectly bonded to the phosphorus, or to an oxygen of the organophosphorous compound (i.e., an ester).

[0042] In an aspect the aromatic organophosphorous compound is a monomeric phosphate. Representative monomeric aromatic phosphates are of the formula (GO) ₃ P=0, wherein each G is independently an alkyl, cycloalkyl, aryl, alkylarylene, or arylalkylene group having up to 30 carbon atoms, provided that at least one G is an aromatic group. Two of the G groups may be joined together to provide a cyclic group. In some aspects 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.

[0043] Di- or polyfunctional aromatic organophosphorous compounds are also useful, for example, compounds of the formulas wherein each G ¹ is independently a Ci-30 hydrocarbyl; each G ² is independently a Ci-30 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. In a specific aspect, X ^a is a single bond, methylene, isopropylidene, or 3,3,5-trimethylcyclohexylidene.

[0044] Specific aromatic organophosphorous compounds are inclusive of acid esters of formula (9) wherein each R ¹⁶ is independently Ci-s alkyl, C5-6 cycloalkyl, C6-20 aryl, or C7-12 arylalkylene, each optionally substituted by Ci-12 alkyl, specifically by C1 alkyl and X is a mono- or poly nuclear aromatic C6-30 moiety or a linear or branched C2-30 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. In some aspects each R ¹⁶ is independently C1-4 alkyl, naphthyl, phenyl(Ci-4)alkylene, aryl groups optionally substituted by Ci-4 alkyl; each X is a mono- or poly-nuclear aromatic C6-30 moiety, each n is 1; and q is from 0.5 to 30. In some aspects 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. In other aspects, each R ¹⁶ is phenyl; X is cresyl, xylenyl, propylphenyl, or butylphenyl, one of the following divalent groups or a combination comprising one or more of the foregoing; n is 1; and q is from 1 to 5, or from 1 to 2. In some aspects 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 organophosphorous 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.

[0045] The organophosphorous compound 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. In an aspect, the organophosphorous compound containing a phosphorus-nitrogen bond is a phosphazene or cyclic phosphazene of the formulas wherein wl is 3 to 10,000; w2 is 3 to 25, or 3 to 7; and each R ^w is independently a Ci-12 alkyl, alkenyl, alkoxy, aryl, aryloxy, or polyoxyalkylene group. In the foregoing groups 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. For example, 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. In an aspect, the phosphazene has a structure represented by the formula

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.

[0046] Anti-drip agents may also be used in the composition, for example a fibril forming or non-fibril forming fluoropolymer such as polytetrafluoroethylene (PTFE). The anti drip agent may be encapsulated by a rigid copolymer, for example styrene-acrylonitrile copolymer (SAN). PTFE encapsulated in SAN is known as TSAN. TSAN comprises 50 wt% PTFE and 50 wt% SAN, based on the total weight of the encapsulated fluoropolymer. The SAN may comprise, for example, 75 wt% styrene and 25 wt% acrylonitrile based on the total weight of the copolymer. Anti-drip agents may be used in amounts of 0.01 to 1 wt%, 0.1 to 0.5 wt%, or 0.1 to 3 wt%, based on 100 wt% of the total composition, excluding any filler. In some aspects, the anti-drip agent is absent. When the anti-drip is absent, the composition may be essentially free of halogens including fluorine.

[0047] The flame retardant polycarbonate composition may further comprise an additive composition that 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 thermoplastic composition, in particular heat resistance, impact, and flame retardance. Combinations of additives may be used. The additive composition may include an impact modifier, flow modifier, particulate filler (e.g., a particulate polytetrafluoroethylene (PTFE), glass, carbon, mineral, or metal), antioxidant, heat stabilizer, light stabilizer, ultraviolet (UV) light stabilizer, UV absorbing additive, plasticizer, lubricant, release agent (such as a mold release agent), antistatic agent, anti-fog agent, antimicrobial agent, colorant (e.g., a dye or pigment), surface effect additive, radiation stabilizer, a flame retardant different from the Ci-i ₆ alkyl sulfonate salt, or a combination thereof. The additive composition may be present from 0.1-5 wt%, or 0.1-3 wt%, or 0.1-2 wt% of the flame retardant composition.

[0048] There is considerable overlap among plasticizers, lubricants, and mold release agents, which include, for example, phthalic acid esters (e.g., octyl-4, 5-epoxy- hexahydrophthalate), tris-(octoxycarbonylethyl)isocyanurate, di- or polyfunctional aromatic phosphates (e.g., resorcinol tetraphenyl diphosphate (RDP), the bis(diphenyl) phosphate of hydroquinone and the bis(diphenyl) phosphate of bisphenol A); poly-alpha-olefins; epoxidized soybean oil; silicones, including silicone oils (e.g., poly(dimethyl diphenyl siloxanes); fatty acid esters (e.g., Ci-32alkyl stearyl esters, such as methyl stearate and stearyl stearate and esters of stearic acid such as pentaerythritol tetrastearate, glycerol tristearate (GTS), and the like), waxes (e.g., beeswax, montan wax, paraffin wax, or the like), or combinations comprising at least one of the foregoing plasticizers, lubricants, and mold release agents. These are generally used in amounts of 0.01-5 wt%, based on the total weight of total weight of the flame retardant polycarbonate composition, which sums to 100 wt%.

[0049] Antioxidant additives include organophosphites such as tris(nonyl phenyl)phosphite, tris(2,4-di-t-butylphenyl)phosphite, bis(2,4-di-t-butylphenyl)pentaerythritol diphosphite, distearyl pentaerythritol 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, pentaery thrityl-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 used in amounts of 0.01-0.2, or 0.01-0.1 parts by weight, based on the total weight of the flame retardant polycarbonate composition, which sums to 100 wt%.

[0050] The flame retardant polycarbonate composition may be essentially free of chlorine and bromine. “Essentially free of chlorine and bromine” refers to materials produced without the intentional addition of chlorine or bromine or chlorine or bromine containing materials. It is understood however that in facilities that process multiple products a certain amount of cross contamination may occur resulting in bromine or chlorine levels typically on the parts per million by weight scale. With this understanding it may be readily appreciated that “essentially free of bromine and chlorine” 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. In some aspects, “essentially free of bromine and chlorine” 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. When this definition is applied to the flame retardant it is based on the total weight of the flame retardant. When this definition is applied to the flame retardant polycarbonate composition it is based on the total parts by weight of the flame retardant polycarbonate composition.

[0051] In another aspect, in particular when the anti-drip agent is absent, the flame retardant composition may be essentially free of chlorine, bromine, and fluorine. “Essentially free of chlorine, bromine, and fluorine” is defined as having a bromine, chlorine, or 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. Preferably, the flame retardant 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.

[0052] The flame retardant polycarbonate compositions may be manufactured by various methods. For example, powdered polycarbonates, flame retardant, or other 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, for example the reinforcing filler, 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 extmdate 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.

[0053] A molded sample of the flame retardant polycarbonate composition may have, for example, a flame-out time (5-bar FOT) of 250 seconds or less at a 1.0 millimeter thickness with zero dripping when measured in accordance with UL 94 standards.

[0054] A molded sample of the flame retardant polycarbonate composition may have, for example, a flame-out time (5-bar FOT) of 250 seconds or less at a 0.8 millimeter thickness with zero dripping when measured in accordance with UL 94 standards.

[0055] A molded sample of the flame retardant polycarbonate composition may have, for example, a flame test rating of V0, as measured according to UL-94 at a thickness of 1.0 millimeter.

[0056] A molded sample of the flame retardant polycarbonate composition may have, for example, a flame test rating of V0, as measured according to UL-94 at a thickness of 0.8 millimeter.

[0057] A molded sample of the flame retardant polycarbonate composition may have, for example, a Vicat B 120 softening temperature of at least 160°C as measured according to the ISO 306 standard at a load of 50 newtons and a speed of 120°C per hour on 4 millimeter bars.

[0058] A molded sample of the flame retardant polycarbonate composition may have, for example, a heat deflection temperature a heat deformation temperature of at least 145°C measured according to the ISO-75 standard with a 5.5 Joule hammer on 4 millimeter- thick bars and a load of 1.8 megapascals.

[0059] Shaped, formed, or molded articles comprising 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. In an aspect, 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. In addition, the polycarbonate compositions may be used for such applications as an electrical, medical, or automotive molded housing.

[0060] This disclosure is further illustrated by the following examples, which are non limiting.

EXAMPLES

[0061] The following components are used in the examples. Unless specifically indicated otherwise, the amount of each component is in weight percent (wt%), based on the total weight of the composition.

[0062] The materials shown in Table 1 were used.

Table 1.

[0063] The testing samples were prepared as described below and the following test methods were used.

[0064] All powder additives were combined together with the polycarbonate powder(s), using a paint shaker, and fed through one feeder to an extruder. Extrusion for all combinations was performed on a 25 mm twin screw extruder, using a melt temperature of 270-320°C and 300 revolutions per minute (rpm), then pelleted. The pellets were dried for 4-6 hours at 135°C. Dried pellets were injection molded at temperatures of 270-320°C to form specimens for most of the tests below. [0065] Heat distortion temperatures were measured in accordance with the ISO-75 standard with a 5.5 J hammer, using the flat side of 4 mm-thick ISO bars and a load of 1.8 MPa (A/f).

[0066] Melt volume rates were measured in accordance with the ISO- 1133 standard at 300°C, using 1.2 kg of force for 300 seconds (s). The pellets were dried for 3 hours at 120°C before testing.

[0067] Vicat softening temperatures were measured on 4 mm-thick ISO bars in accordance with the ISO-306 standard at a load of 50 N and a speed of 120°C per hour (B 120).

[0068] ASTM Izod notched impact (“ASTM INI”) values were determined according to ASTM D256-2010 on a 3.2 mm-thick bar at room temperature.

[0069] ISO Izod notched impact (“ISO INI”) values were determined according to ISO 180/1A at room temperature using a 5.5 J hammer on a multi-purpose ISO 3167 type A sample having a thickness of 4 mm.

[0070] Flammability tests were performed at a thickness of 1.5 mm, 1.2 mm, 1.0 mm, and 0.8 mm in accordance with the Underwriter’s Laboratory (UL) UL 94 standard. In some cases, a second set of 5 bars was tested to give an indication of the robustness of the rating. In this report the following definitions are used as shown in Table 2. Total flame-out-times for all 5 bars (FOT = tl + t2) were determined. V-ratings were obtained for every set of 5 bars.

Table 2

Examples 1-9

[0071] The formulations and properties of Examples 1-9 are shown in Table 3.

Table 3.

* Comparative Examples

[0072] Examples 1-5 show that the addition of Rimar salt to poly(carbonate-bisphenol phthalate ester) (PPC) compositions resulted in a UL 94 rating of VO at a thickness of 1.0 mm. Examples 2-3 having a Rimar loading of 0.1-0.2 wt% resulted in a UL 94 rating of V0 at a thickness of 0.8 mm. The anti-drip agent (TSAN) is absent for PPC compositions (Examples 1-2 and 4-5). The anti-drip agent is present in the composition of Example 3, which includes both PPC and a homopolycarbonate (PC), and resulted in a UL 94 rating of V0 at a thicknesses of 1.0 mm and 0.8 mm.

[0073] Comparative Examples 6-7 show that the replacement of Rimar salt with KSS in PPC samples at loadings of 0.15 wt% and 0.3 wt%, respectively, resulted in a loss of UL 94 ratings, resulting in V2 at thicknesses of 1.0 mm and 0.8 mm, compared to V0 at a thickness of 1.0 mm for Examples 2 to 5. As shown by Comparative Examples 8-9, the incorporation of Rimar salt in an alternative high heat copolycarbonate PPPBP-BPA wherein PPC was absent resulted in a molded sample with a UL 94 rating of V2 at a thickness of 1.5 mm. In addition, the flammability rating deteriorated for the thinner molded samples, i.e., a UL 94 rating of V2 at a thickness of E2 mm.

[0074] Excellent flame retardant properties were obtained when combining relatively high loadings of Rimar salt (0.1-0.4 wt%) in PPC (Examples 1 to 5), which is not achieved for similar flame retardants like KSS in PPC (Comparative Examples 6 and 7) or with similar Rimar salt loadings in other high heat resins like PPPBP-BPA (Comparative Examples 8 and 9).

[0075] This disclosure further encompasses the following aspects.

[0076] Aspect 1: A flame retardant polycarbonate composition comprising: 60.0-99.9 weight percent of a poly(carbonate-bisphenol phthalate ester) comprising 1-50 weight percent of aromatic carbonate units and 50-99 weight percent of bisphenol phthalate ester units, each based on the sum of the weight of the carbonate units and the bisphenol phthalate ester units; 0.1-0.5 weight percent of a C _\-\ e alkyl sulfonate salt flame retardant; 0-30.0 weight percent of a homopolycarbonate; optionally, 0.01-1.0 weight percent of an anti-drip agent; optionally, 0.1-5.0 weight percent of an additive composition, wherein the amount of the poly(carbonate-bisphenol phthalate ester), the sulfonate salt flame retardant, the homopolycarbonate, the optional anti-drip agent, and the optional additive composition is based on the total weight of the flame retardant composition, which sums to 100 weight percent; and wherein a molded sample of the flame retardant polycarbonate composition has a flame-out time (5-bar FOT) of 250 seconds or less at a 1.0 millimeter thickness with zero dripping when measured in accordance with UL 94 standards, a flame-out time (5-bar FOT) of 250 seconds or less at a 0.8 millimeter thickness with zero dripping when measured in accordance with UL 94 standards, a UL 94 rating of V0 at a thickness of 1.0 millimeter, a UL 94 rating of V0 at a thickness of 0.8 millimeter; or a combination thereof; and a heat deformation temperature of at least 145°C measured according to the ISO-75 standard with a 5.5 Joule hammer on 4 millimeter-thick bars and a load of 1.8 megapascals, a Vicat softening temperature of at least 160°C as measured according to the ISO- 306 standard at a load of 50 newtons and a speed of 120°C per hour on 4 millimeter bars, or a combination thereof.

[0077] Aspect 2: The flame retardant polycarbonate composition of aspect 1, comprising 60.0-99.8 weight percent, preferably 98-99.8 weight percent of the poly(carbonate-bisphenol phthalate ester; 0.1-0.3 weight percent of potassium perfluorobutane sulfonate as the sulfonate salt flame retardant; 0.1-3.0 weight percent, preferably 0.1-2.0 weight percent of the additive composition; and 0-25.0 weight percent of a bisphenol A homopolycarbonate as the homopolycarbonate.

[0078] Aspect 3: The flame retardant polycarbonate composition of aspect 1 or aspect 2, wherein a weight ratio of carbonate units to ester units is 10:90-45:55, and the ester units have a molar ratio of isophthalate to terephthalate from 98:2-88:12.

[0079] Aspect 4: The flame retardant polycarbonate composition of any one of the preceding aspects, wherein the poly(carbonate-bisphenol phthalate ester) has the formula wherein the weight ratio of carbonate units x to ester units y is 10:90-45:55, and the ester units have a molar ratio of isophthalate to terephthalate from 98:2-88:12.

[0080] Aspect 5: The flame retardant polycarbonate composition of any one of the preceding aspects, wherein the weight ratio of carbonate units x to ester units y is 75:25-85:15.

[0081] Aspect 6: The flame retardant polycarbonate composition of any one of the preceding aspects, wherein the Ci-i ₆ alkyl sulfonate flame retardant comprises potassium perfluorobutane sulfonate, potassium perfluoroctane sulfonate, tetraethylammonium perfluorohexane sulfonate, or a combination thereof, preferably potassium perfluorobutane sulfonate.

[0082] Aspect 7: The flame retardant polycarbonate composition of any one of the preceding aspects comprising 0.1-0.3 weight percent of the Ci-i ₆ alkyl sulfonate salt flame retardant.

[0083] Aspect 8: The flame retardant polycarbonate composition of any one of the preceding aspects, wherein the additive composition is present and comprises an impact modifier, a flow modifier, an antioxidant, a heat stabilizer, a light stabilizer, an ultraviolet light stabilizer, an ultraviolet absorbing additive, a plasticizer, a lubricant, a release agent, an antistatic agent, an anti-fog agent, an antimicrobial agent, a colorant, a surface effect additive, a radiation stabilizer, a flame retardant different from the Ci-i ₆ alkyl sulfonate salt flame retardant, or a combination thereof.

[0084] Aspect 9: The flame retardant polycarbonate composition of aspect 8, wherein the flame retardant different from the Ci-i ₆ alkyl sulfonate salt flame retardant is an organophosphorous compound comprising a phosphazene, phosphate, phosphite, phosphonate, phosphinate, phosphine oxide, phosphine, or a combination thereof, preferably comprising an aromatic group.

[0085] Aspect 10: The flame retardant polycarbonate composition of any one of the preceding aspects, wherein the anti-drip agent is present, and a molded sample of the flame retardant polycarbonate composition has a UL 94 rating of V0 at a thickness of 1.0 millimeter, preferably at a thickness of 0.8 millimeter.

[0086] Aspect 11: The flame retardant polycarbonate composition of any one of the aspects 1-9, wherein the anti-drip agent is absent, and the composition has a bromine, chlorine, or 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, preferably 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.

[0087] Aspect 12: The flame retardant polycarbonate composition of any one of the preceding aspects comprising 60-99.8 weight percent of a poly(bisphenol A carbonate-bisphenol A phthalate ester) as the poly(carbonate-bisphenol phthalate ester), wherein the weight ratio of carbonate units to ester units is 10:90-45:55, and the ester units have a molar ratio of isophthalate to terephthalate from 98:2-88:12; 0.1-0.3 weight percent of potassium perfluorobutane sulfonate as the sulfonate salt flame retardant; 0.1-3.0 weight percent of the additive composition; 0-30 weight percent bisphenol A homopolycarbonate as the homopolycarbonate.

[0088] Aspect 13: The flame retardant polycarbonate composition of any one of the preceding aspects comprising 60-80 weight percent of a poly(bisphenol A carbonate-bisphenol A phthalate ester) as the poly(carbonate-bisphenol phthalate ester), wherein the weight ratio of carbonate units to ester units is 10:90-45:55, and the ester units have a molar ratio of isophthalate to terephthalate from 98:2-88:12; 0.1-0.3 weight percent of potassium perfluorobutane sulfonate as the sulfonate salt flame retardant; 0.1-0.5 weight percent of the anti-drip agent; 20-30 weight percent bisphenol A homopolycarbonate as the homopolycarbonate.

[0089] Aspect 14: An article comprising the flame retardant polycarbonate composition of any one of the preceding aspects.

[0090] Aspect 15: The article of aspect 14, wherein the article is an electrical component, preferably an electrical, medical, or automotive housing.

[0091] Aspect 16: A method for forming the article according to aspect 14 or aspect 15, comprising molding, casting, or extruding the composition to provide the article.

[0092] The compositions, methods, and articles may alternatively comprise, 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.

[0093] All ranges disclosed herein are inclusive of the endpoints, and the endpoints are independently combinable with each other (e.g., ranges of “up to 25 wt%, or, more specifically,

5 wt% to 20 wt%”, is inclusive of the endpoints and all intermediate values of the ranges of “5 wt% to 25 wt%,” etc.). “Combinations” is inclusive of blends, mixtures, alloys, reaction products, and the like. The terms “first,” “second,” and the like, do not denote any order, quantity, or importance, but rather are used to distinguish one element from another. The terms “a” and “an” and “the” do not denote a limitation of quantity and are to be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. “Or” means “and/or” unless clearly stated otherwise. Reference throughout the specification to “some aspects,” “an aspect,” and so forth, means that a particular element described in connection with the aspect is included in at least one aspect described herein, and may or may not be present in other aspects. In addition, it is to be understood that the described elements may be combined in any suitable manner in the various aspects. A “combination thereof’ is open and includes any combination comprising at least one of the listed components or properties optionally together with a like or equivalent component or property not listed.

[0094] 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.

[0095] 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. 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.

[0096] Compounds are described using standard nomenclature. For example, any position not substituted by any indicated group is understood to have its valency filled by a bond as indicated, or a hydrogen atom. A dash that is not between two letters or symbols is used to indicate a point of attachment for a substituent. For example, -CHO is attached through carbon of the carbonyl group.

[0097] The term "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. “Alkenyl” means a straight or branched chain, monovalent hydrocarbon group having at least one carbon-carbon double bond (e.g., ethenyl (-HC=CH2)). “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 (-CH2-) or, propylene (-(CH2)3- )). “Cycloalky lene” means a divalent cyclic alkylene group, -CiThn-x, wherein x is the number of hydrogens replaced by cyclization(s). “Cyclo alkenyl” means a monovalent group having one or more rings and one or more carbon-carbon double bonds in the ring, wherein all ring members are carbon (e.g., cyclopentyl and cyclohexyl). "Aryl" means an aromatic hydrocarbon group containing the specified number of carbon atoms, such as phenyl, tropone, indanyl, or naphthyl. “Arylene” means a divalent aryl group. “Alkylarylene” means an arylene group substituted with an alkyl group. “Arylalkylene” means an alkylene group substituted with an aryl group (e.g., benzyl). The prefix "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. The prefix “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. “Substituted” means that the compound or group is substituted with at least one (e.g., 1, 2, 3, or 4) substituents that may each independently be a C _1-9 alkoxy, a C _1-9 haloalkoxy, a nitro (-NO ₂ ), a cyano (-CN), a Ci- ₆ alkyl sulfonyl (-S(=0) ₂ -alkyl), a C _6-12 aryl sulfonyl (-S(=0) ₂ -aryl)a thiol (-SH), a thiocyano (-SCN), a tosyl (CH3C6H4SO2-), a C3-12 cycloalkyl, a C2-12 alkenyl, a C5-12 cycloalkenyl, a Ce-n aryl, a C7-13 arylalkylene, a C _4-12 heterocycloalkyl, and a C _3-12 heteroaryl instead of hydrogen, provided that the substituted atom’s normal valence is not exceeded. The number of carbon atoms indicated in a group is exclusive of any substituents. For example -CH ₂ CH ₂ CN is a C ₂ alkyl group substituted with a nitrile.

[0098] While particular aspects have been described, alternatives, modifications, variations, improvements, and substantial equivalents that are or may be presently unforeseen may arise to applicants or others skilled in the art. Accordingly, the appended claims as filed and as they may be amended are intended to embrace all such alternatives, modifications variations, improvements, and substantial equivalents.