Flame retardant polycarbonate compositions

Abstract

Polycarbonate compositions having a low added fluorine content while also achieving a V-0 flame test rating at 1.5 mm include: a homopolycarbonate composition having one or more homopolycarbonates, wherein an average of the weight average molecular weight of the homopolycarbonate composition is 25,000 g / mol or more, a poly(carbonate-siloxane) having a siloxane content of 30-70 wt% present in an amount effective to provide 4.5-14 wt% siloxane repeating units based on the total weight of the composition, and having a weight average molecular weight of 26,000-50,000 grams per mole,; and having less than 1 wt% of a poly(carbonate-siloxane) with a siloxane content of less than 30 wt%; 0.01-1.0 wt% of a flame retardant comprising an aromatic sulfonate inorganic salt, an aromatic sulfone sulfonate inorganic salt, or a combination thereof.

Description

FLAME RETARDANT POLYCARBONATE COMPOSITIONSCROSS-REFERENCE TO RELATED APPLICATIONThis application claims priority to and the benefit of EP 23199544.0, filed in the European Patent Office on September 25, 2023, the entire contents of which are incorporated herein by reference.BACKGROUND

[0001] This disclosure relates to polycarbonate compositions, and in particular to flame retardant polycarbonate compositions, methods of manufacture, and uses thereof in thin-wall articles.

[0002] Polycarbonates are useful in the manufacture of articles and components for a wide range of applications, from automotive parts to electronic and electrical appliances. Because of their broad use, particularly in electronics, it is desirable to provide polycarbonate compositions with excellent physical, optical, and thermal properties in an adequate processing window. Such properties can be particularly difficult to achieve in thin-wall applications. In addition, more stringent regulations are being put in place to reduce or eliminate the presence of halogens, in particular fluorine, in the final products.

[0003] There accordingly remains a need in the art for flame retardant polycarbonate compositions suitable for thin-wall applications. It would be a further advantage if the compositions were essentially fluorine-free.SUMMARY

[0004] The above-described and other deficiencies of the art are met by a polycarbonate composition comprising: 80-92 wt% of a homopolycarbonate composition comprising one or more homopolycarbonates, wherein an average of the weight average molecular weight of the homopolycarbonates is 25,000 grams per mole or more, as determined by gel permeation chromatography using polystyrene standards and calculated for polycarbonate; 5-20 wt% of a poly(carbonate-siloxane) having a siloxane content of 30-70 wt% present in an amount effective to provide 4 -14 wt% siloxane repeating units based on the total weight of the composition, and having a weight average molecular weight of 26,000-50,000 grams per mole, as determined by gel permeation chromatography using polystyrene standards and calculated for polycarbonate; and having less than 1 wt% of a poly(carbonate-siloxane) having a siloxane content of less than 30 wt%; 0.01-1.0 wt% of a flame retardant comprising an aromatic sulfonate inorganic salt, anaromatic sulfone sulfonate inorganic salt, or a combination thereof; optionally, an additive composition; optionally, 5-20 wt% of glass fibers; wherein the polycarbonate composition comprises 1200 ppm or less of added fluorine to the total composition, and wherein a sample of the polycarbonate composition exhibits a UL-94 rating of V-0 at a thickness of 1.5 millimeters or less.

[0005] Another aspect is a method of making the polycarbonate composition, the method comprising melt-mixing the components of the composition, and, optionally, extruding the composition.

[0006] Another aspect is an article comprising the polycarbonate composition.

[0007] Another aspect is method for forming the article, the method comprising molding, casting, or extruding the composition to provide the article.

[0008] The above described and other features are exemplified by the following detailed description.DETAILED DESCRIPTION

[0001] Polycarbonates are thermoplastic resins with many desirable properties, but are inherently flammable. Current design trends are focused on thinner designs for purposes of slimness, weight reduction, and size reduction of the overall final product, as well as to for the purpose of more complex designs. However, polycarbonates tend to drip when exposed to a flame, and this behavior worsens as the wall thickness decreases. The UL 94 flammability test includes both short flame out times and no dripping of flaming particles as requirements for a V- 0 or V-l flame test rating. Conventional compositions often incorporate fluorine-containing antidrip agents either alone or in combination with a non-halogenated flame retardant in order to pass the UL94 flame test. Given that more stringent regulations are being put in place to reduce or eliminate the intentional addition of halogenated materials, for example, perfluoroalkyl and polyfluoroalkyl substances (PFAS), to compositions used to make final products, there is a need in the art for polycarbonate compositions that can achieve a V-0 or V-l flame test rating for thin-walled molded samples and / or thin films, while also minimizing and / or eliminating the intentional addition of PFAS into the polycarbonate compositions used to make the molded samples and / or thin films.

[0002] The inventors hereof have discovered that polycarbonate compositions can achieve the desired combination of flame retardance by including: a homopolycarbonate composition having a weight average molecular weight of greater than or equal to 25,000 grams per mole, a polycarbonate siloxane) including 30-70 wt% siloxane repeating units present in anamount effective to provide 3.5-14 wt%, or 4-4 wt% of siloxane repeating units, based on the total composition, and a flame retardant including a salt of an aromatic sulfonate, a salt of an aromatic sulfone sulfonate, or a combination thereof, wherein the polycarbonate composition includes 1200 ppm or less fluorine, and wherein a sample of the polycarbonate composition exhibits a UL-94 rating of V-0 at a thickness of 1.5 mm, or less. This combination can provide the desired flame retardance while eliminating the need for halogenated additives, such as fluorinated flame retardants and anti-drip agents. Surprisingly, unlike conventional compositions, fluorinated anti-drip agents can be omitted in the present polycarbonate compositions, thus eliminating added fluorine while providing improved flame test performance. Advantageously, the polycarbonate compositions can have a UL-94 flame test rating of V-0 at a thickness of 1.5 mm or thinner, e.g., at 1.5 mm or at 1.2 mm, and be considered “essentially fluorine-free.” As used herein, the phrase “essentially fluorine-free” means that the amount of calculated intentionally added fluorine present in the composition is 1200 ppm or less, 1000 ppm or less, 500 ppm or less, or 400 ppm or less, or 300 ppm or less, or 200 ppm or less, or 100 ppm or less, or 50 ppm or less, or 20 ppm or less. For example, if 0.1 wt% encapsulated polytetrafluoroethylene is intentionally added to a composition, (e.g., TSAN, which is 50 wt% PTFE, where PTFE is estimated to have 76 wt% fluorine content), the amount of calculated intentionally added fluorine would be 380 ppm. In a preferred aspect the amount of calculated intentionally added fluorine is 380 ppm or less, or 300 ppm or less or 200 ppm or less, or 100 ppm or less, or 50 ppm or less, or 20 ppm or less. Further, the polycarbonate compositions of the present disclosure can have zero intentionally added fluorine.

[0003] In a still further aspect, the amount of fluorine (from any source) present in the composition can be 1200 ppm or less, 1000 ppm or less, 500 ppm or less, or 400 ppm or less, or 380 ppm or less, or 300 ppm or less, or 200 ppm or less, or 100 ppm or less, or 50 ppm or less, or 20 ppm or less. It is to be understood that the present lowest detection limits of fluorine as determined in accordance with ASTM D7359-23 in the compositions is less than 20 ppm (20 mg / kg). Thus, the amount fluorine (from any source) present in the composition is bounded by this detection limit, and is less than 20 ppm, such that the amount of fluorine in the compositions is less than 20-1200 ppm, less than 20-1000 ppm, less than 20-500 ppm, less than 20-400 ppm, less than 20-380 ppm or less than 20-300 ppm, or less than 20-200 ppm,, or less than 20-100 ppm, or less than 20-50 ppm, or less than 20 ppm, each as determined in accordance with ASTM D7359-23.

[0004] In some aspects, the polycarbonate compositions can have a UL-94 flame test rating of V-0 at a thickness of 1.5 mm or thinner, e.g., 1.5 or 1.2 mm, and be considered“essentially halogen-free” per IEC 61249-2-21 or UL 746H. As used herein, the phrase “essentially halogen-free” is as defined by IEC 61249-2-21 or UL 746H. According to International Electrochemical Commission, Restriction Use of Halogen (IEC 61249-2-21), a composition should include 900 parts per million (ppm) or less of each of chlorine and bromine and also include 1500 ppm or less of total bromine, chlorine, and fluorine content. According to UL 746H, a composition should include 900 ppm or less of each of chlorine, bromine, and fluorine and 1500 ppm or less of the total chlorine, bromine, and fluorine content. The bromine, chlorine, and fluorine content in ppm can be calculated from the composition or measured by elemental analysis techniques. Conventional non-halogenated flame retardants can include or exclude halogens, but commonly employed anti-drip agents include PTFE or PTFE- encapsulated styrene-acrylonitrile copolymers (e.g., TSAN) and thus include fluorine. Nonhalogenated flame retardants that are not brominated, chlorinated, or fluorinated have been used in conventional polycarbonate compositions, but an anti-drip agent is usually present in combination with the non-halogenated flame retardant, causing the halogen content of the composition to exceed the 1500 ppm total halogen limit per IEC 61249-2-21 and UL 746H. Similarly, when non-halogenated flame retardants that are not brominated or chlorinated, but are fluorinated are used in combination with a fluorinated anti-drip agent, then the halogen content of the composition due to the presence of fluorine exceeds the 1500 ppm total halogen limit per IEC 61249-2-21 or UL 746H. Therefore, it would be a particular advantage if conventional antidrip agents could be minimized or eliminated, so that the anti-drip agent does not contribute halogen content to the total halogen content of the compositions. Accordingly, a variety of non- halogenated flame retardants that include or exclude halogens can be used in polycarbonate compositions so that the compositions can be considered “essentially halogen-free” per IEC 61249-2-21 or UL 746H.

[0005] “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 R1groups contain aromatic moieties and the balance thereof are aliphatic, alicyclic, or aromatic. In an aspect, each R1is a Ce-30 aromatic group, that is, contains at least one aromatic moiety. R1can be derived from an aromatic dihydroxy compound of the formula HO-R -OH, in particular of formula (2)HO-A^-A TH (2)wherein each of A1and A2is a monocyclic divalent aromatic group and Y1is a single bond or a bridging group having one or more atoms that separate A1from A2. In an aspect, one atom separates A1from A2. Preferably, each R1can be derived from a bisphenol of formula (3)wherein Raand Rbare each independently a halogen, C1-12 alkoxy, or C1-12 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 (3), Xais 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 (preferably para) to each other on the Ce arylene group. In an aspect, the bridging group Xais single bond, - O-, -S-, -S(O)-, -S(O)2-, -C(O)-, or a C1-60 organic group. The organic bridging group can be cyclic or acyclic, aromatic or non-aromatic, and can further include heteroatoms such as halogens, oxygen, nitrogen, sulfur, silicon, or phosphorous. The Ci-eo organic group can be disposed such that the Ce arylene groups connected thereto are each connected to a common alkylidene carbon or to different carbons of the Ci-eo organic bridging group. In an aspect, p and q is each 1, and Raand Rbare each a C1-3 alkyl group, preferably methyl, disposed meta to the hydroxy group on each arylene group.

[0006] Other useful dihydroxy compounds of the formula HO-R1-OH include aromatic dihydroxy compounds of formula (6)wherein each Rbis independently a halogen atom, C1-10 hydrocarbyl group such as a C1-10 alkyl, a halogen-substituted C1-10 alkyl, a Ce-io aryl, or a halogen-substituted Ce-io aryl, and n is 0-4. The halogen is usually bromine.

[0007] Some illustrative examples of specific dihydroxy compounds include the following: 4,4'-dihydroxybiphenyl, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, bis(4-hydroxyphenyl)methane, bis(4-hydroxyphenyl)diphenylmethane, bis(4-hydroxyphenyl)- 1 - naphthylmethane, 1 ,2-bis(4-hydroxyphenyl)ethane, 1 , 1 -bis(4-hydroxyphenyl)- 1 -phenylethane, 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,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-dihydroxy dibenzofuran,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.

[0008] The polycarbonate compositions include a homopolycarbonate (wherein each R1in the polymer is the same). In an aspect, the homopolycarbonate is a bisphenol A homopolycarbonate (also referred to as BPA carbonate) having repeating structural carbonate units of the formula (la).

[0009] Homopolycarbonates, e.g., bisphenol A homopolycarbonates 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, from bisphenol A ((2,2-bis(4-hydroxyphenyl)propane, or BPA). An endcapping agent can beincluded during polymerization to provide end groups, for example monocyclic phenols such as phenol, p-cy anophenol, and C1-22 alkyl-substituted phenols such as p-cumyl-phenol, resorcinol monobenzoate, and p-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 methacryloyl chloride, and monochloroformates such as phenyl chloroformate, alkyl-substituted phenyl chloroformates, p-cumyl phenyl chloroformate, and toluene chloroformate. Phenol and para-cumylphenol are specifically mentioned. Combinations of different endcapping agents 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 (l,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 0.05-4.0 wt%, for example, 0.05-2.0 wt%. Combinations comprising linear polycarbonates and branched polycarbonates can be used. In an aspect, the bisphenol A homopolycarbonate can be a linear bisphenol A homopolycarbonate, optionally endcapped with phenol or para-cumylphenol.

[0010] The polycarbonates can have an intrinsic viscosity, as determined in chloroform at 25 °C, of 0.3-1.5 deciliters per gram (dl / gm), preferably 0.45-1.0 dl / gm. The polycarbonates can have a weight average molecular weight (Mw) of 10,000-50,000 grams per mole (g / mol), preferably 15,000-40,000 g / mol, more preferably 20,000-40,000 g / mol, as measured by gel permeation chromatography (GPC), using a crosslinked styrene-divinylbenzene column using polystyrene standards and calculated for polycarbonate. GPC samples are prepared at a concentration of 1 milligram per milliliter (mg / ml) in dichloromethane with toluene as a flow marker, and are eluted at a flow rate of 1.5 ml per minute with detection at 254 nanometers. As used herein, “using polystyrene standards and calculated for polycarbonate” refers to measurement of the retention time by GPC, fitting the retention time value to a curve for polystyrene (using, e.g., 13 different polystyrene standards ranging 1,000 to 200,000 g / mol), and calculating the molecular weight for polycarbonate.

[0011] The homopolycarbonate can be a composition including one or more homopolycarbonates. In an aspect, each of the one or more homopolycarbonates can be the same chemical composition, for example, each can be a bisphenol A homopolycarbonate of formula (la), but each can have a different Mw, provided that the calculated average of the Mwof the homopolycarbonates present is greater than 25,000 g / mol or more, for example 25,000-50,000g / mol, or 25,000-40,000 g / mol, or 25,000-38,000 g / mol, or 29,000-45,000 g / mol. The calculated average of the Mwof the homopolycarbonates, e.g., bisphenol A homopolycarbonates, is determined based on the weight fraction of each of the homopolycarbonates in the homopolycarbonate composition wherein Mwis determined as described above.

[0012] In an aspect, the homopolycarbonate composition includes one or more homopolycarbonate having an Mwof 29,000-32,000 grams per mole, preferably 30,000-31,000 grams per mole, and one or more homopolycarbonates having an Mwof 19,000 to less than 25,000 grams per mole, preferably 20,000-23,000 grams per mole, each as determined by GPC using polystyrene standards and calculated for polycarbonate; or a combination thereof. In this aspect, the average Mwof the all homopolycarbonates present in the composition is 25,000 g / mol or more. Stated another way, when a homopolycarbonate having a weight average molecular weight that is less than 25,000 g / mol is present in the composition, it can be present in an amount such that the average Mwof all homopolycarbonates present in the homopolycarbonate composition is 25,000 g / mol or more.

[0013] The homopolycarbonate composition can be present in the composition in an amount of 80-92 wt%, based on the total weight of the composition. Within this range, the homopolycarbonate can be present in an amount of, for example, 80-90 wt%, 80-87 wt%, or SO- 85 wt%, each based on the total weight of the composition.

[0014] In addition to the homopolycarbonate, the composition further comprises a poly(carbonate-siloxane), also referred to in the art as a polycarbonate-poly siloxane copolymer. The poly(carbonate-siloxane) includes 30-70 wt% siloxane repeating units. The polysiloxane blocks include repeating diorganosiloxane units as in formula (10)wherein each R is independently a C1-13 monovalent organic group. For example, R can be a Ci- 13 alkyl, Ci-13 alkoxy, C2-13 alkenyl, C2-13 alkenyloxy, C3-6 cycloalkyl, C3-6 cycloalkoxy, Ce-14 aryl, Ce-io aryloxy, C7-13 arylalkylene, C7-13 arylalkylenoxy, C7-13 alkylarylene, or C7-13 alkylaryleneoxy. The foregoing groups can be fully or partially halogenated with fluorine, chlorine, bromine, iodine, or a combination thereof. In an aspect, 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.

[0015] 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 composition, and like considerations. Generally, E has an average value of 2-1,000, preferably 2-500, 2-200, or 2-125, 5-80, or 10-70. In an aspect, E has an average value of 10-80 or 10-40, and in still another aspect, 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. 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.

[0016] In an aspect, the polysiloxane blocks are of formula (11)wherein E and R is each as defined if formula (10); each R can be the same or different, and is as defined above; and Ar can be the same or different, and is a substituted or unsubstituted Ce-30 arylene, wherein the bonds are directly connected to an aromatic moiety. Ar groups in formula (11) can be derived from a Ce-30 dihydroxy arylene compound, for example a dihydroxy arylene compound of formula (3) or (6). Dihydroxy arylene 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, 1, l-bis(4- hydroxyphenyl) cyclohexane, bis(4-hydroxyphenyl sulfide), and l,l-bis(4-hydroxy-t- butylphenyl) propane.

[0017] In another aspect, polysiloxane blocks are of formula (13)wherein R and E are as described above, and each R5is independently a divalent C1-30 organic group, and wherein the polymerized polysiloxane unit is the reaction residue of its corresponding dihydroxy compound. In a specific aspect, the polysiloxane blocks are of formula (14):wherein R and E are as defined above. R6in formula (14) is a divalent C2-8 aliphatic group. Each M in formula (14) can be the same or different, and can be a halogen, cyano, nitro, C1-8 alkylthio, C1-8 alkyl, C1-8 alkoxy, C2-8 alkenyl, C2-8 alkenyloxy, C3-8 cycloalkyl, C3-8 cycloalkoxy, Ce-io aryl, Ce-io aryloxy, C7-12 aralkyl, C7-12 aralkoxy, C7-12 alkylaryl, or C7-12 alkylaryloxy, wherein each n is independently 0, 1, 2, 3, or 4.

[0018] In an aspect, 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; R6is a dimethylene, trimethylene or tetramethylene; and R is a C1-8 alkyl, haloalkyl such as trifluoropropyl, cyanoalkyl, or aryl such as phenyl, chlorophenyl or tolyl. In another aspect, R is methyl, or a combination of methyl and trifluoropropyl, or a combination of methyl and phenyl. In still another aspect, R is methyl, M is methoxy, n is one, and R6is a divalent C1-3 aliphatic group. Specific polysiloxane blocks are of the formula( c), or a combination thereof, wherein E has an average value of 2-200, 2-125, 5-125, 5-100, 5-50, 20-80, or 5-20.

[0019] 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.

[0020] In an aspect, a blend is used, in particular a blend of a bisphenol A homopolycarbonate and a poly(carbonate-siloxane) block copolymer of bisphenol A blocks and eugenol capped polydimethylsiloxane blocks, of the formulawherein x is 1-200, preferably 5-85, preferably 10-70, preferably 15-65, and more preferably 40- 60; x is 1-500, or 10-200, and z is 1-1000, or 10-800. In an aspect, x is 1-200, y is 1-90 and z is 1-600, and in another aspect, 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.

[0021] Poly(carbonate-siloxane)s can have a weight average molecular weight of 2,000- 100,000 g / mol, preferably 5,000-50,000 g / mol, or 10,000-50,000 g / mol as measured by GPC using a crosslinked styrene-divinyl benzene column, at a sample concentration of 1 milligram per milliliter, in dichloromethane with a flow rate of 1.5 mg / ml, using polystyrene standards and calculated for polycarbonate. In these compositions, the weight of the poly(carbonate-siloxane)s is preferably 30,000-45,000 grams per mole, or 32,000-43,000 grams per mole, or 35, GOO- 42, 000 grams per mole, or 37,000-41,000, determined as described herein.

[0022] The poly(carbonate-siloxane)s can have a melt volume flow rate, measured at 300°C / 1.2 kg, of 0.1-50 cubic centimeters per 10 minutes (cc / 10 min), preferably 2-30 cc / 10 min. Combinations of the poly(carbonate-siloxane)s of different flow properties can be used to achieve the overall desired flow property.

[0023] One or more poly(carbonate-siloxane) copolymers can be included in the polycarbonate compositions. The polycarbonate compositions can include two or more poly(carbonate-siloxane) copolymers including 30-70 wt% siloxane repeating units, each based on the total weight of the poly(carbonate-siloxane) copolymer. Within this range, the poly(carbonate-siloxane) can include 35-70 wt%, or 35-65 wt% siloxane repeating units. As used herein, “siloxane repeating units” of a poly(carbonate-siloxane) refers to the content of siloxane units based on the total weight of the poly(carbonate-siloxane). .

[0024] Other than the polycarbonate siloxane) having 30-70 wt% siloxane repeating units, the polycarbonate compositions do not include, or have less than 1 wt%, of an additional poly(carbonate-siloxane) copolymer including greater than 70-99 wt% of carbonate units and 1- less than 30 wt% siloxane units. For example, less than 1 wt%, or none of a poly(carbonate- siloxane) copolymer including 10 wt% or less siloxane repeating units, or 15-25 wt% siloxane repeating units, based on the total weight of the poly(carbonate-siloxane) is [present. Inparticular, the composition can include less than 5 wt% or less than or equal to 1 wt%, or less than or equal to 0.1 wt% of a poly(carbonate-siloxane) including less than 30 wt% siloxane repeating units, or less than 10 wt% siloxane repeating units. Preferably a poly(carbonate- siloxane) including less than 30 wt% siloxane repeating units or less than 10 wt% siloxane repeating units is excluded from the composition.

[0025] The poly(carbonate-siloxane) can be present in the composition in an amount of 8-20 wt%, based on the total weight of the composition. Within this range, the poly(carbonate- siloxane) can be present in an amount of, for example, 2-20 wt.%, or 9-20 wt%, or 10-20 wt%, or 10-18 wt%, or 10-16 wt%, or 10-15 wt%, or 10-13 wt%, each based on the total weight of the composition.

[0026] The poly(carbonate-siloxane) can be present in an amount effective to provide 3.5-14 wt%, or 3.5-12 wt%, or 4.0-14 wt%, or 4.0-12 wt%, or 4.0-10 wt%, of siloxane repeating units, based on the total weight of the composition.

[0027] In an aspect, one or both of the homopolycarbonate and the poly(carbonate- siloxane) can be derived from post-consumer recycled or post-industrial recycled materials, provided that the post-consumer recycled or post-industrial recycled materials include very low levels of fluorine or are fluorine-free, such that the polycarbonate compositions include 1200 ppm or less added fluorine content. In an aspect, one or both of the homopolycarbonate and the poly(carbonate-siloxane) can be produced from at least one monomer derived from bio-based or plastic waste feedstock. ("PCR-PC"). PCR-PC is derived or recycled from polycarbonate as described herein. PCR-PC can be recovered from a source after consumption. In addition, PCR- PC can be recovered from post-consumer sources including, but not limited to, household appliance waste such as TV, air conditioner, washing machine, refrigerator, etc. Regardless of the source, the recovered polycarbonate component can be similar or even identical to the chemical composition of the corresponding original polycarbonate. In one example, the polycarbonate can be derived from an optical disc. In another example, the PCR-PC can be derived from a plastic bottle, such as a plastic beverage bottle. In contrast, virgin polycarbonate polymers refer to polycarbonate polymers produced directly from petrochemical feedstocks, such as natural gas or crude oil, which have never been used or processed before.

[0028] One possible difference between the original polycarbonate component used in the polycarbonate composition and the PCR-PC is the presence of at least one impurity that is not present in the original material. For example, one or more additives conventionally used in the manufacture of impact modified thermoplastics can be present as impurities. Additional impurities can include processing residues such as lubricants, mold release agents, antistaticagents, stabilizers, light stabilizers, flame retardants, metals (e.g., iron, aluminum, and copper). In addition, impurities can include polyurethane particles that cannot be completely removed during the recovery process. In some aspects, the level of impurities in the PCR-PC is less than 5 wt%, or in other aspects less than 3 wt%, or in other aspects less than 2 wt%. If present, the impurities do not significantly affect the properties of the compositions described herein.

[0029] As used herein, the fluorine provided by fluorinated materials such as fluorinated additives is referred to herein as “added fluorine.” The bromine and chlorine provided by brominated and chlorinated materials is referred to as “added bromine” and “added chlorine,” respectively. “Added fluorine,” “added bromine,” and “added chlorine” excludes any fluorine, bromine, or chlorine present as a contaminant in the components used in the manufacture of the polycarbonates, i.e., the monomers, endcapping agents, and the carbonate source, for example. Nonetheless, it can be advantageous to minimize or eliminate fluorine, bromine, and chlorine as contaminants from these sources. Accordingly, in an aspect, the monomers each have a fluorine, bromine, or chlorine contaminant content of less than 5 ppm each. In another aspect, the monomers each have a purity of at least 99.6%, at least 99.7%, or at least 99.8% as determined by HPLC and a contaminant fluorine, bromine, or chlorine contaminant content of less than 5 ppm each.

[0030] Polycarbonates can be manufactured by processes such as interfacial polymerization and melt polymerization. Although the reaction conditions for interfacial polymerization can vary, an exemplary process generally involves dissolving or dispersing a dihydroxy compound in aqueous NaOH or KOH, adding the resulting mixture to a water- immiscible solvent, and contacting the reactants with a carbonate precursor in the presence of a catalyst such as, for example, a tertiary amine or a phase transfer catalyst, under controlled pH conditions, e.g., 8-10. The water-immiscible solvent can be, for example, methylene chloride, 1 ,2-dichloroethane, chlorobenzene, toluene, and the like.

[0031] Exemplary carbonate precursors include a carbonyl halide such as carbonyl bromide or carbonyl chloride (phosgene) a bishaloformate of a dihydroxy compound (e.g., the bischloroformate of bisphenol A, hydroquinone ethylene glycol, neopentyl glycol, or the like), and diaryl carbonates. A combination thereof can also be used. The diaryl carbonate ester can be diphenyl carbonate, or an activated diphenyl carbonate having electron-withdrawing substituents on each aryl, such as bis(4-nitrophenyl)carbonate, bis(2-chlorophenyl)carbonate, bis(4- chlorophenyl)carbonate, bis(methyl salicyl)carbonate, bis(4-methylcarboxylphenyl) carbonate, bis(2-acetylphenyl) carboxylate, bis(4-acetylphenyl) carboxylate, or a combination thereof.

[0032] Among tertiary amines that can be used as catalysts in interfacial polymerization are aliphatic tertiary amines such as triethylamine and tributylamine, cycloaliphatic tertiary amines such as N,N-diethyl-cyclohexylamine, and aromatic tertiary amines such as N,N- dimethylaniline. Among the phase transfer catalysts that can be used are catalysts of the formula (R3)4Q+X, wherein each R3is the same or different, and is a Ci-io alkyl; Q is a nitrogen or phosphorus atom; and X is a halogen atom or a Ci-g alkoxy or Ce-is aryloxy. Exemplary phase transfer catalysts include (CH3(CH2)3)4NX, (CH3(CH2)3)4PX, (CH3(CH2)s)4NX, (CH3(CH2)6)4NX, (CH3(CH2)4)4NX, CH3(CH3(CH2)3)3NX, and CH3(CH3(CH2)2)3NX, wherein X is CT, Br", a Ci-g alkoxy or a Ce-is aryloxy. An effective amount of a phase transfer catalyst can be 0.1-10 wt%, or 0.5-2 wt%, each based on the weight of dihydroxy compound in the phosgenation mixture.

[0033] Alternatively, melt processes can be used to make the polycarbonates. In the melt polymerization process, polycarbonates can be prepared by co-reacting, in a molten state, a dihydroxy reactant and a diaryl carbonate ester in the presence of a transesterification catalyst. The reaction can be carried out in typical polymerization equipment, such as a continuously stirred reactor (CSTR), plug flow reactor, wire wetting fall polymerizers, free fall polymerizers, wiped film polymerizers, BANBURY mixers, single or twin-screw extruders, or a combination of the foregoing. Volatile monohydric phenol is removed from the molten reactants by distillation and the polymer is isolated as a molten residue. Melt polymerization can be conducted as a batch process or as a continuous process. In either case, the melt polymerization conditions used can include two or more distinct reaction stages, for example, a first reaction stage in which the starting dihydroxy aromatic compound and diaryl carbonate are converted into an oligomeric polycarbonate and a second reaction stage wherein the oligomeric polycarbonate formed in the first reaction stage is converted to high molecular weight polycarbonate. Such "staged" polymerization reaction conditions are especially suitable for use in continuous polymerization systems wherein the starting monomers are oligomerized in a first reaction vessel and the oligomeric polycarbonate formed therein is continuously transferred to one or more downstream reactors in which the oligomeric polycarbonate is converted to high molecular weight polycarbonate. Typically, in the oligomerization stage the oligomeric polycarbonate produced has a number average molecular weight of 1,000-7,500 g / mol. In one or more subsequent polymerization stages the number average molecular weight (Mn) of the polycarbonate is increased to between 8,000 and 25,000 g / mol (using polycarbonate standard). Typically, solvents are not used in the process, and the reactants dihydroxy aromatic compound and the diaryl carbonate are in a molten state. The reaction temperature can be 100-350°C,preferably 180-310°C. The pressure can be at atmospheric pressure, supra-atmospheric pressure, or a range of pressures from atmospheric pressure to 15 torr in the initial stages of the reaction, and at a reduced pressure at later stages, for example 0.2-15 torr. The reaction time can be 0.1 hours to 10 hours.

[0034] Catalysts used in the melt transesterification polymerization production of polycarbonates can include alpha or beta catalysts. Beta catalysts are typically volatile and degrade at elevated temperatures. Beta catalysts are therefore preferred for use at early low- temperature polymerization stages. Alpha catalysts are typically more thermally stable and less volatile than beta catalysts.

[0035] The alpha catalyst can include a source of alkali or alkaline earth ions. The sources of these ions include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide, as well as alkaline earth hydroxides such as magnesium hydroxide and calcium hydroxide. Other possible sources of alkali and alkaline earth metal ions include the corresponding salts of carboxylic acids (such as sodium acetate) and derivatives of ethylene diamine tetraacetic acid (EDTA) (such as EDTA tetrasodium salt, and EDTA magnesium disodium salt). Other alpha transesterification catalysts include alkali or alkaline earth metal salts of carbonate, such as CS2CO3, NaHCO s. and Na^COi. and the like, non-volatile inorganic acid such as NaH2PO3, NaH2PO4, Na2HPO3, KH2PO4, CSH2PO4, CS2HPO4, and the like, or mixed salts of phosphoric acid, such as NaKHPO4, CsNaHPO4, CsKHPO4, and the like. Combinations including at least one of any of the foregoing catalysts can be used.

[0036] Possible beta catalysts can include a quaternary ammonium compound, a quaternary phosphonium compound, or a combination thereof. The quaternary ammonium compound can be a compound of the structure (R4)4N+X", wherein each R4is the same or different, and is a C1-20 alkyl, a C4-20 cycloalkyl, or a C4-20 aryl; and X" is an organic or inorganic anion, for example a hydroxide, halide, carboxylate, sulfonate, sulfate, formate, carbonate, or bicarbonate. Examples of organic quaternary ammonium compounds include tetramethyl ammonium hydroxide, tetrabutyl ammonium hydroxide, tetramethyl ammonium acetate, tetramethyl ammonium formate, tetrabutyl ammonium acetate, and combination thereof. Tetramethyl ammonium hydroxide is often used. The quaternary phosphonium compound can be a compound of the structure (R5)4P+X", wherein each R5is the same or different, and is a C1-20 alkyl, a C4-20 cycloalkyl, or a C4-20 aryl; and X" is an organic or inorganic anion, for example a hydroxide, phenoxide, halide, carboxylate such as acetate or formate, sulfonate, sulfate, formate, carbonate, or bicarbonate. Where X" is a polyvalent anion such as carbonate or sulfate it is understood that the positive and negative charges in the quaternary ammonium andphosphonium structures are properly balanced. For example, where R4or R5are each methyl and X" is carbonate, it is understood that X" represents 1 / 2(CO32). Examples of organic quaternary phosphonium compounds include tetramethyl phosphonium hydroxide, tetramethyl phosphonium acetate, tetramethyl phosphonium formate, tetrabutyl phosphonium hydroxide, tetrabutyl phosphonium acetate (TBPA), tetraphenyl phosphonium acetate, tetraphenyl phosphonium phenoxide, and combination thereof. TBPA is often used.

[0037] The amount of alpha and beta catalyst used can be based upon the total number of moles of dihydroxy compound used in the polymerization reaction. When referring to the ratio of beta catalyst, for example, a phosphonium salt, to all dihydroxy compounds used in the polymerization reaction, it is convenient to refer to moles of phosphonium salt per mole of the dihydroxy compound, meaning the number of moles of phosphonium salt divided by the sum of the moles of each individual dihydroxy compound present in the reaction mixture. The alpha catalyst can be used in an amount sufficient to provide 1 x 10"2to 1 x 10"8moles, preferably, 1 x 10"4to 1 x 10"7moles of metal per mole of the dihydroxy compounds used. The amount of beta catalyst (e.g., organic ammonium or phosphonium salts) can be 1 x 10"2to 1 x 10"5, preferably 1 x 10"3to 1 x 10"4moles per total mole of the dihydroxy compounds in the reaction mixture. Quenching of the transesterification catalysts and any reactive catalysts residues with an acidic compound after polymerization is completed can also be useful in some melt polymerization processes. Removal of catalyst residues or quenching agent and other volatile residues from the melt polymerization reaction after polymerization is completed can also be useful in some melt polymerization processes.

[0038] Branched polycarbonate blocks can be prepared by adding a branching agent during polymerization. These branching agents include polyfunctional organic compounds containing at least three functional groups selected from hydroxyl, carboxyl, carboxylic anhydride, haloformyl, and mixtures of the foregoing functional groups. Specific examples include trimellitic acid, trimellitic anhydride, tris-phenol TC (l,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. Combinations including linear polycarbonates and branched polycarbonates can be used.

[0039] In some aspects, a particular type of branching agent is used to create branched polycarbonate materials. These branched polycarbonate materials have statistically more than two end groups. The branching agent is added in an amount (relative to the bisphenol monomer) that is sufficient to achieve the desired branching content, that is, more than two end groups. Themolecular weight of the polymer can become very high upon addition of the branching agent, and to avoid excess viscosity during polymerization, an increased amount of a chain stopper agent can be used, relative to the amount used when the particular branching agent is not present. The amount of chain stopper used is generally above 5 mol% and less than 20 mol% compared to the bisphenol monomer.

[0040] Such branching agents include aromatic triacyl halides, for example triacyl chlorides of formula (20)wherein Z is a halogen, C1-3 alkyl, C1-3 alkoxy, C7-12 arylalkylene, C7-12 alkylarylene, or nitro, and z is 0-3; a tri-substituted phenol of formula (21)wherein T is a C1-20 alkyl, C1-20 alkoxy, C7-12 arylalkyl, or C7-12 alkylaryl, Y is a halogen, C1-3 alkyl, C1-3 alkoxy, C7-12 arylalkyl, C7-12 alkylaryl, or nitro, s is 0-4; or a compound of formula (22) (isatin-bis-phenol).Examples of specific branching agents that are particularly effective in the compositions include trimellitic trichloride (TMTC), tris-p-hydroxyphenylethane (THPE), and isatin-bis-phenol.

[0041] The amount of the branching agents used in the manufacture of the polymer will depend on a number of considerations, for example the type of R1groups, the amount of chain stopper, e.g., cyanophenol, and the desired molecular weight of the polycarbonate. In general, the amount of branching agent is effective to provide 0.1-10 branching units per 100 R1units, preferably 0.5-8 branching units per 100 R1units, and more preferably 0.75-5 branching unitsper 100 R1units. For branching agents having formula (20), the branching agent is present in an amount to provide 0.1-10 triester branching units per 100 R1units, preferably 0.5-8, and more preferably 0.75-5 triester branching units per 100 R1units. For branching agents having formula (21), the branching agent is present in an amount effective to provide 0.1-10 triphenyl carbonate branching units per 100 R1units, preferably 0.5-8, and more preferably 2.5-3.5 triphenylcarbonate units per 100 R1units. In some aspects, a combination of two or more branching agents can be used. Alternatively, the branching agents can be added at a level of 0.05-2.0 wt%.

[0042] In an aspect, the polycarbonate is a branched polycarbonate including units as described above; greater than or equal to 0.2-3.5 mole%, based on the total moles of the polycarbonate, of moieties derived from a branching agent; and end-capping groups derived from an end-capping agent having a pKa between 8.3 and 11. The branching agent can include trimellitic trichloride, l,l,l-tris(4-hydroxyphenyl)ethane or a combination of trimellitic trichloride and l,l,l-tris(4-hydroxyphenyl)ethane, and the end-capping agent is phenol or a phenol containing a substituent of cyano group, aliphatic groups, olefinic groups, aromatic groups, halogens, ester groups, ether groups, or a combination thereof. In a specific aspect, the end-capping agent is phenol, p-t-butylphenol, p-methoxyphenol, p-cyanophenol, p-cumylphenol, or a combination thereof.

[0043] 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. The endcapping agent (and thus end groups) are selected based on the desired properties of the polycarbonates. Exemplary end-capping agents are exemplified by monocyclic phenols such as phenol and C1-22 alkyl-substituted phenols such as p-cumyl-phenol, resorcinol monobenzoate, and p-and tertiary-butyl phenol, monoethers of diphenols, such as p-methoxyphenol, and alkylsubstituted phenols with branched chain alkyl substituents having 8-9 carbon atoms, 4- substituted-2-hydroxybenzophenones and their derivatives, aryl salicylates, monoesters of diphenols such as resorcinol monobenzoate, 2-(2-hydroxyaryl)-benzotriazoles and their derivatives, 2-(2-hydroxyaryl)-l,3,5-triazines and their derivatives, mono-carboxylic acid chlorides such as benzoyl chloride, C1-22 alkyl-substituted benzoyl chloride, toluoyl chloride, bromobenzoyl chloride, cinnamoyl chloride, and 4-nadimidobenzoyl chloride, polycyclic, mono-carboxylic acid chlorides such as trimellitic anhydride chloride, and naphthoyl chloride, functionalized chlorides of aliphatic monocarboxylic acids, such as acryloyl chloride and methacryoyl chloride, and mono-chloroformates such as phenyl chloroformate, alkyl-substitutedphenyl chloroformates, p-cumyl phenyl chloroformate, and toluene chloroformate. Combinations of different end groups can be used.

[0044] The polycarbonate compositions include a flame -retardant composition that is a salt as described below. In an exemplary aspect, the polycarbonate compositions avoid the use of fluorinated flame retardants such as Rimar (potassium perfluorobutane sulfonate) salt. In some aspects, the polycarbonate compositions avoid the use of halogenated flame retardants such as a brominated polycarbonate.

[0045] The flame-retardant compositions include inorganic salts of aromatic sulfonates such as sodium benzene sulfonate, sodium toluene sulfonate (NATS), and the like; inorganic salts of aromatic sulfone sulfonates such as potassium diphenylsulfone sulfonate (KSS), and the like; or a combination thereof. In addition, salts formed by reacting, for example, an alkali metal or alkaline earth metal (e.g., lithium, sodium, potassium, magnesium, calcium, or barium) and an inorganic acid complex salt, for example, an oxo-anion (e.g., alkali metal and alkaline-earth metal salts of carbonic acid, such as Na2C0a, K2CO3, MgCCh. CaCCh. and BaCCh. KSS and NATS, alone or in combination, are particularly useful. Exemplary amounts of an aromatic sulfonate inorganic salt, aromatic sulfone sulfonate inorganic salt, or combination thereof (e.g., KSS, NATS, or a combination thereof) can be 0.01-1.0 wt%, or 0.1-0.6 wt%, based on the total weight of the polycarbonate composition.

[0046] The polycarbonate compositions can optionally include an additional organophosphorus flame retardant. Organophosphorus flame retardants containing a phosphorous-nitrogen bond can be a linear phosphazene or cyclic phosphazene, phosphonitrilic chloride, phosphorous 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, an aromatic organophosphorus compounds include at least one organic aromatic group can be used, where the aromatic group can be a substituted or unsubstituted C3-30 group containing one or more of a monocyclic or polycyclic aromatic moiety (which can 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 can be directly bonded to the phosphorous-containing group, or bonded via another moiety, for example an alkylene group. The aromatic moiety of the aromatic group can be directly bonded to the phosphorous- containing group, 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 abisphenol group (e.g., bisphenol A), a monoarylene group (e.g., a 1,3-phenylene or a 1,4- phenylene), or a combination including at least one of the foregoing.

[0047] The phosphorous-containing group can be a phosphate (P(=O)(OR)3), phosphite (P(OR)3), phosphonate (RP(=O)(OR)2), phosphinate (R2P(=O)(OR)), phosphine oxide (R3P(=O)), or phosphine (R3P), wherein each R in the foregoing phosphorous-containing groups can be the same or different, provided that at least one R is an aromatic group. A combination of different phosphorous-containing groups can be used. The aromatic group can be directly or indirectly bonded to the phosphorous, or to an oxygen of the phosphorous-containing group (i.e., an ester).

[0048] The phosphorous-containing group can be a phosphate (P(=O)(OR)3), phosphite (P(OR)3), phosphonate (RP(=O)(OR)2), phosphinate (R2P(=O)(OR), including oxaphosphorinoxides), phosphine oxide (R3P(=O)), or phosphine (R3P), wherein each R in the foregoing phosphorous-containing groups can be the same or different, provided that at least one R is an aromatic group. A combination of different phosphorous-containing groups can be used. The aromatic group can be directly or indirectly bonded to the phosphorous, or to an oxygen of the phosphorous-containing group (i.e., an ester). Exemplary phosphates include phenyl bis(dodecyl) phosphate, phenyl bis(neopentyl) phosphate, phenyl bis(3,5,5'-trimethylhexyl) phosphate, ethyl diphenyl phosphate, 2-ethylhexyl di(p-tolyl) phosphate, bis(2-ethylhexyl) p- tolyl phosphate, tritolyl phosphate, bis(2-ethylhexyl) phenyl phosphate, tri(nonylphenyl) phosphate, bis(dodecyl) p-tolyl phosphate, dibutyl phenyl phosphate, 2-chloroethyl diphenyl phosphate, p-tolyl bis(2,5,5'-trimethylhexyl) phosphate, 2-ethylhexyl diphenyl phosphate, and the like. A specific aromatic phosphate is one in which each G is aromatic, for example, triphenyl phosphate, tricresyl phosphate, isopropylated triphenyl phosphate, and the like. Di- or polyfunctional aromatic organophosphorus compounds are also useful, for example, the bis(diphenyl) phosphate of hydroquinone, resorcinol bis(diphenyl phosphate) (RDP), and bisphenol A bis(diphenyl) phosphate (BPADP), and their oligomeric and polymeric counterparts. An organophosphorus flame retardant containing a phosphorous-nitrogen bond can be a phosphazene, phosphonitrilic chloride, phosphorous ester amide, phosphoric acid amide, phosphonic acid amide, phosphinic acid amide, or tris(aziridinyl) phosphine oxide. Examples include hexaphenoxy cyclotriphosphazene, octaphenoxy cyclotetraphosphazene decaphenoxy cyclopentaphosphazene, and the like. Commercially available phenoxyphosphazenes include 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. Specific examples of an oxaphosphorinoxide include 9,10-dihydro-9-oxo-10-phosphaphenanthrene-10-oxide (23a, “DOPO”), commercially available as from SANKO CO., LTD., under the trade name Sanko-HCA, 3-(6- oxidodibenzo[c,e][l,2]oxaphosphinin-6-yl)propanamide (23b, “AAM-DOPO”), and 6-[(l - oxido-2,6,7-trioxa-l-phosphabicyclo[2.2.2.]oct-4-yl)methoxy-6-oxide (23c, “DOPO-PEPA”). Specific examples of an oxaphosphorinoxide include 9,10-dihydro-9-oxo-10- phosphaphenanthrene-10-oxide (23a, “DOPO”), commercially available as from SANKO CO., LTD., under the trade name Sanko-HCA, 3-(6-oxidodibenzo[c,e][l,2]oxaphosphinin-6- yl)propanamide (23b, “AAM-DOPO”), and 6-[(l-oxido-2,6,7-trioxa-l- phosphabicyclo[2.2.2.]oct-4-yl)methoxy-6-oxide (23c, “DOPO-PEPA”). Another exemplary Di-DOPO compound is HTP-6123G, commercially available from GUIZHOU YUANYI MINING GROUP CO.

[0049] When the polycarbonate composition includes an additional organophosphorus flame retardant, the organophosphorus flame retardant can be present in an amount effective to provide 0.3-1.5 wt%, 0.4-1.5 wt%, 0.5-1.5 wt% phosphorous, each based on the total weight of the polycarbonate composition. However, in an aspect, no addition organophosphorus flame retardant is present.

[0050] The polycarbonate compositions minimize or eliminate conventional anti-drip agents, in particular fluorinated anti-drip agents. Anti-drip agents include, for example, a fibril forming or non-fibril forming fluoropolymer such as polytetrafluoroethylene (PTFE). The antidrip agent can 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 can comprise, for example, 75 wt% styrene and 25 wt% acrylonitrile based on the total weight of the copolymer. In some aspects, the fluorinated anti-drip agent is present in an amount effective to provide 0.12 wt% or less fluorine to the total composition. In some aspects, a fluorinated anti-drip agent is excluded from the polycarbonate compositions.

[0051] The polycarbonate compositions include glass fibers, which can be non-bonding glass fiber, bonding glass fiber, or a combination thereof.

[0052] A non-bonding glass fiber, also characterized as a non-binding glass fiber, can refer to a glass fiber filler that does not provide specific adhesion to a polymer resin to which it is added. That is, individual fibers of the glass fiber filler may not demonstrate an affinity towards the polymer matrix. Comparatively, bonding glass fiber provides specific adhesion with the specific polymer resin to which it is added. A bonding glass fiber filler can exhibit affinitytoward the polycarbonate resin matrix. This affinity can be attributed to the glass sizing, among a number of other forces.

[0053] In an aspect, the disclosed compositions comprise a non-bonding glass fiber selected from E-glass, S-glass, AR-glass, T-glass, D-glass, and R-glass. In a still further aspect, the non-bonding glass fiber can be selected from E-glass, S-glass, and combinations thereof. In one example, the non-bonding glass fiber is an E-glass or EC glass type.

[0054] The non-bonding glass fibers can be sized or unsized. Sized glass fibers are coated on their surfaces with a sizing composition selected for compatibility with the polycarbonate. The sizing composition facilitates wet-out and wet-through of the polycarbonate upon the fiber strands and assists in attaining desired physical properties in the polycarbonate composition. In various further aspects, the non-bonding glass fiber is sized with a coating agent. In a further aspect, the coating agent is present in an amount from 0.1 wt % to 5 wt % based on the weight of the glass fibers. In a still further aspect, the coating agent is present in an amount from 0.1 wt % to 2 wt % based on the weight of the glass fibers.

[0055] In preparing the glass fibers, a number of filaments can be formed simultaneously, sized with the coating agent, and then bundled into what is called a strand. Alternatively, the strand itself can be first formed of filaments and then sized. The amount of sizing employed is generally that amount which is sufficient to bind the glass filaments into a continuous strand and ranges from 0.1-5 wt %, 0. 1-2 wt % based on the weight of the glass fibers. Generally, this can be 1.0 wt % based on the weight of the glass filament.

[0056] In a further aspect, the non-bonding glass fiber can be continuous or chopped. In some examples, the glass fiber is chopped. Glass fibers in the form of chopped strands can have a length of 0.3 mm to 10 cm, specifically 0.5 mm to 5 cm, and more specifically 1.0 mm to 2.5 cm. In various further aspects, the glass fiber has a length from 0.2 mm to 20 mm. In a yet further aspect, the glass fiber has a length from 0.2 mm to 10 mm. In an even further aspect, the glass fiber has a length from 0.7 mm to 7 mm. In this area, where a thermoplastic resin is reinforced with glass fibers in a composite form, fibers having a length of 0.4 mm are generally referred to as long fibers, and shorter ones are referred to as short fibers. In a still further aspect, the glass fiber can have a length of 1 mm or longer. In yet a further aspect, the glass fiber can have a length of 2 mm or longer.

[0057] In an aspect, bonding glass fibers can outperform non-bonding glass fibers especially with respect to tensile strength, while modulus is also higher, without a significant drop in impact. Bonding glass fibers have a sizing onto the surface of the glass fibers to allow good coupling of the fibers to the thermoplastic matrix, and as such improve properties such asstrength and stiffness. For instance, this can be achieved with a silane coating, which chemically bonds with the resin.

[0058] The glass fibers can be included in any amount so as to not significantly adversely affect the desired properties of the polycarbonate composition, in particular flame resistance. In some aspects, the glass fibers can be present from 5-20 wt%, or from 5-15 wt%, or from 5-10 wt%, each based on the total weight of the polycarbonate composition.

[0059] 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 flame resistance, impact resistance and the melt volume rate. Such additives can be mixed at a suitable time during the mixing of the components for forming the composition. Additives include antioxidants, heat stabilizers, light stabilizers, ultraviolet (UV) light stabilizers, plasticizers, lubricants, mold release agents, antistatic agents, colorants such as such as titanium dioxide, carbon black, and organic dyes, surface effect additives, and radiation stabilizers. A combination of additives can be used, for example a combination of a heat stabilizer, mold release agent, and ultraviolet light stabilizer. In general, the additives are used in the amounts generally known to be effective. For example, the total amount of the additives (other than any impact modifier, filler, or reinforcing agents) can be 0.01-10 wt%, 0.01-5 wt%, 0.01-2 wt%, or 0.01-1 wt%, each based on the total weight of the polycarbonate composition.

[0060] The polycarbonate compositions can include a homopolycarbonate, preferably a bisphenol A homopolycarbonate having a weight average molecular weight of 25,000 grams per mole or more, as determined by GPC using polystyrene standards and calculated for polycarbonate; and a poly(carbonate-siloxane) having a siloxane content of 30-70 wt% present in an amount effective to provide 3.5-14 wt%, or 4-14 wt% siloxane repeating units based on the total weight of the composition, and a weight average molecular weight of 26,000-50,000 grams per mole, as determined by GPC using polystyrene standards and calculated for polycarbonate; a flame retardant comprising an aromatic sulfone sulfonate, preferably potassium diphenylsulfone sulfonate, wherein the polycarbonate composition comprises 1200 ppm or less of added fluorine, based on the total composition, and wherein a sample of the polycarbonate composition exhibits a UL-94 rating of V-0 at a thickness of 1.5 mm or less, e.g., at 1.5 mm or at 1.2 mm.

[0061] The polycarbonate compositions can include a homopolycarbonate, preferably a bisphenol A homopolycarbonate having a weight average molecular weight of 25,000 grams per mole or more, as determined by GPC using polystyrene standards and calculated for polycarbonate; and a poly(carbonate-siloxane) having a siloxane content of 30-70 wt% presentin an amount effective to provide 3.5-14 wt%, or 4-14 wt% siloxane repeating units based on the total weight of the composition, and a weight average molecular weight of 26,000-50,000 grams per mole, as determined by GPC using polystyrene standards and calculated for polycarbonate; a flame retardant comprising an organophosphorus compound, preferably a phosphazene, wherein the polycarbonate composition comprises 1200 ppm or less of added fluorine, based on the total composition, and wherein a sample of the polycarbonate composition exhibits a UL-94 rating of V-0 at a thickness of 1.5 mm or less, e.g., at 1.5 mm or at 1.2 mm. In this aspect, the homopolycarbonate can be a homopolycarbonate composition comprising one or more homopolycarbonates, preferably bisphenol A homopolycarbonates, wherein an average of the Mwof the homopolycarbonate composition is 25,000 grams per mole or more, as determined by GPC using polystyrene standards and calculated for polycarbonate. Still further in this aspect, the composition can include less than 1 wt% of a poly(carbonate-siloxane) having a siloxane content of less than 30 wt%.

[0062] The polycarbonate compositions can have ultra-low halogen content. As used herein, “ultra-low chlorine and / or bromine content” refers to materials produced without the intentional addition of chlorine or bromine or chlorine or bromine containing materials. It is understood however that in facilities that process multiple products a certain amount of cross contamination can occur resulting in bromine or chlorine levels typically on the parts per million by weight scale. With this understanding it can be readily appreciated that “ultra-low chlorine or bromine content” can 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, “ultra-low chlorine and bromine content” means a total bromine and chlorine content of less than or equal to 100 parts per million by weight, or less than or equal to 75 ppm, or less than or equal to 50 ppm. 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 polycarbonate composition it is based on the total parts by weight of the polycarbonate composition.

[0063] In another aspect, the polycarbonate composition can have an ultra-low chlorine, bromine, or fluorine content. As used herein, “ultra-low chlorine, bromine, or fluorine content” 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 polycarbonate composition has a combined bromine, chlorine, and fluorine content of less than or equal to 100 ppm, less than or equal to 75 ppm, or less than or equal to 50 ppm, based on the total parts by weight of the composition.

[0064] The polycarbonate composition can optionally exclude other components not specifically described herein. For example, the polycarbonate composition can exclude thermoplastic polymers other than the bisphenol A homopolycarbonate and the poly(carbonate- siloxane)s. For example the composition can minimize or exclude polyesters (e.g., a polyester can be present in an amount of 1 wt% or less, preferably wherein a polyester is excluded from the composition). The composition can optionally minimize or exclude a polycarbonate other than the bisphenol A homopolycarbonate and the poly(carbonate-siloxane), for example a polyester-carbonate or a bisphenol A copolycarbonate different from the poly(carbonate- siloxane). The polycarbonate composition can optionally minimize or exclude impact modifiers, for example silicone-based impact modifiers different from the poly(carbonate-siloxane) copolymer, methyl methacrylate-butadiene-styrene copolymers, acrylonitrile-butadiene, styrene copolymers, and the like, or a combination thereof. The composition can minimize or exclude halogenated flame retardants, for example brominated flame retardants, including brominated polycarbonate (e.g., a polycarbonate containing brominated carbonate includes units derived from 2,2',6,6'-tetrabromo-4,4'-isopropylidenediphenol (TBBPA) and carbonate units derived from at least one dihydroxy aromatic compound that is not TBBPA), brominated epoxies, and the like or combinations thereof.

[0065] The composition of the present disclose can advantageously exhibit one or more desirable properties. For example, it was found that the composition can exhibit a relatively low melt volume rate (MVR). For example, the polycarbonate composition can have a melt volume rate of less than or equal to 25 cm3 / 10 minutes, as determined according to ISO1133 under a load of 2.16 kg at 300 °C with a dwell time of 300 seconds. Surprisingly, the polycarbonate composition can further exhibit a low melt viscosity (MV) indicating the material is well processable despite the relatively low MVR. For example, in an aspect, the polycarbonate composition can have a melt viscosity of less than 200 Pa-s, as determined according to ISO11443 at a shear rate of 5000 s’1.

[0066] It was discovered that using a high siloxane content poly(carbonate-siloxane) in combination with a homopolycarbonate having a particular molecular weight, good chemical resistance and aesthetic properties could also be obtained. It was further unexpectedly discovered that in the absence of an anti-drip agent, a flame test rating of V0 could be achieved.

[0067] The composition can have good chemical resistance. In an aspect, a molded sample of the polycarbonate composition can have a tensile strain at break of at least 50% of the tensile strain at break of a non-exposed reference tested at the same temperature after exposureof an ISO tensile bar for 72 hours to insect repellant or sunscreen at a temperature of 23°C under 1% strain.

[0068] In an aspect, the composition can also exhibit good flame retardancy. In an aspect of measuring flame retardance, the UL-94 standard utilizes a rating of VO, VI, V2 or HB, wherein a rating of VO is better than VI or V2 and is required for many applications at the actual part thickness. Using this standard, the polycarbonate compositions are formed into a molded article having a given thickness. The thinner the article, the more difficult it is to achieve a rating of VO or VI. In an aspect, a molded sample of the polycarbonate composition is capable of achieving a UL-94 VO or VI rating at a thickness of 1.5 mm or less, e.g, 1.5 mm or 1.2 mm, preferably a UL-94 rating of VO at a thickness of less than or equal to 1.5 mm, e.g, at 1.5 mm or at 1.2 mm.

[0069] The polycarbonate composition can be manufactured by various methods known in the art. For example, powdered polycarbonate homopolymer, poly(carbonate-siloxane) 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 composition by feeding it directly into the extruder at the throat and / or downstream through a side stuffer, 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 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.

[0070] Shaped, formed, or molded articles including 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 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, sunrooms, 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 can be used for such applications as a molded housing and other devices such as electrical circuit housing.

[0071] Thin films including the polycarbonate compositions are also provided. The thin film of the thermoplastic composition can be prepared by extrusion of the polycarbonate composition. The thin films can have improved thermal resistance. In some aspects, the thin films can be transparent.

[0072] This disclosure is further illustrated by the following examples, which are nonlimiting.EXAMPLES

[0073] The following components are used in the examples. Unless specifically indicated otherwise, the amount of each component disclosed herein is in wt%, based on the total weight of the composition, and which totals 100 wt%.Table 1.

[0074] Sample preparation and testing methods are described in Table 2.Table 2.

[0075] Flammability tests were performed on samples at a thickness of 1.5 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 3. Total flame-out-times for all bars (FOT = tl + 12) were determined.Table 3.Examples 1, 3, 5

[0076] Table 4 provides the compositions and properties for Comparative example 1 (asterisk) and Examples 3 and 5 of the polycarbonate compositions.Table 4.

[0077] As shown in Table 4, the Examples 3 and 5 with KSS exhibited unexpectedly high flame resistance without use of the fluorinated anti-drip agent, TSAN. Typically, TSAN is added as a component to flame retardant polycarbonate compositions to achieve both the low flame out time needed for V0 ratings as well as preventing burning drips. The Comparative Example 1 with TSAN and Examples 3 and 5 without TSAN all provided a UL-94 rating of V0 at a thickness of 1.5 mm. The melt volume flow rates (MVR) were also comparable. Both Examples 3 and 5, containing the PC-Si-1, are able to achieve the same flame-out times as Comparative Examples without the TSAN added.Examples 7-14

[0078] Table 5 provides the compositions and properties for Comparative examples (asterisk) and Examples of the polycarbonate compositions.Table 5.

[0079] The data in Table 5 demonstrates that the same effect as in Examples 3 and 5 is not achieved when a different polycarbonate siloxane) of lower siloxane content and molecular weight is used. In particular, Comparative Example 8-10 demonstrated burning drips for all samples and have significantly higher flame out times.Examples 15-28.

[0080] Table 6 provides the compositions and properties for Comparative examples (asterisk) and Examples.Table 6.aAverage Mwof the homopolycarbonate component

[0081] Table 6 shows that TSAN can provide a UL-94 rating of VO at a thickness of 1.5 mm independently of the amount of siloxane (2-6 wt.%) (Comparative Examples 15-17). Example 18 shows that a UL-94 rating of VO at a thickness of 1.5 mm can be achieved in the absence of TSAN with a siloxane content of 4 wt%. Comparative Examples 19-25 show that a minimum amount of siloxane is critical to achieve the FOT required to achieve a VO rating with no drips, as amounts of 0-2% do not achieve this flame retardant performance even when the average Mwof the homopolycarbonates in the composition is greater than 25,000 g / mol. Similarly, Comparative Examples 26-28 show that a UL-94 rating of V0 at a thickness of 1.5 mm cannot be achieved when the average Mwof the homopolycarbonates in the composition is less than 25,000 g / mol and the amount of siloxane units is 2 wt% or less.

[0082] Comparison of Comparative Example 12 with Examples 13-14 demonstrate that although the polycarbonate siloxane) and the siloxane content of the composition is the same, the average Mwof the BPA polycarbonate(s) affects the flame test performance. Comparative Example 12 has a BPA polycarbonate composition having an average Mwof less than 25,000 g / mol, whereas Examples 13-14 include a BPA polycarbonate composition having an average Mwof at least 25,000 g / mol.

[0083] This disclosure further encompasses the following aspects.

[0084] Aspect 1. A polycarbonate composition comprising: 80-92 wt%, or 80-90 wt% of a homopolycarbonate composition comprising one or more homopolycarbonates, wherein an average of the weight average molecular weight of the one or more homopolycarbonates is 25,000 grams per mole or more, as determined by gel permeation chromatography using polystyrene standards and calculated for polycarbonate; 8-20 wt%, or 10-20 wt% of a poly(carbonate-siloxane) having a siloxane content of 30-70 wt% present in an amount effective to provide 3.5-14 wt%, or 4-14 wt%, or 4.5-14 wt% of siloxane repeating units based on the total weight of the composition, and having a weight average molecular weight of 26,000- 50,000 grams per mole, as determined by gel permeation chromatography using polystyrene standards and calculated for polycarbonate; and having less than 1 wt% of a polycarbonatesiloxane) having a siloxane content of less than 30 wt%; 0.01-1.0 wt% of a flame retardant comprising an aromatic sulfonate inorganic salt, an aromatic sulfone sulfonate inorganic salt, or a combination thereof; optionally, an additive composition; optionally, 5-20 wt% of glass fibers;wherein the polycarbonate composition comprises 1200 ppm or less of added fluorine to the total composition, and wherein a sample of the polycarbonate composition exhibits a UL-94 rating of V-0 at a thickness of 1.5 mm or less, or at 1.5 mm, or at 1.2 mm.

[0085] Aspect 2. The polycarbonate composition of Aspect 1, comprising 380 ppm or less of fluorine, or 300 ppm or less of fluorine, 200 ppm or less of fluorine, or 100 ppm or less of fluorine, based on the total composition for example less than 20 to 380 ppm, or less than 20 to 300 ppm, or less than 20 to 200 ppm, or less than 20 to 100 ppm of fluorine each as determined in accordance with ASTM D7359-23.

[0086] Aspect 3. The polycarbonate composition of Aspect 2, wherein added fluorine is excluded, and an amount of fluorine present in the composition is below 20 ppm as determined in accordance with ASTM D7359-23.

[0087] Aspect 4. The polycarbonate composition of any one of the preceding Aspects, wherein: the calculated added bromine and added chlorine content of the polycarbonate composition are each 900 ppm or less and the calculated total added bromine, added chlorine, and added fluorine content of the polycarbonate composition is 1500 ppm or less; or the calculated added bromine, added chlorine, and added fluorine content of the polycarbonate composition are each 900 ppm or less and the calculated total added bromine, added chlorine, and added fluorine content of the polycarbonate composition is 1500 ppm or less.

[0088] Aspect 5. The polycarbonate composition of any one of the preceding Aspects, wherein the homopolycarbonate has a weight average molecular weight of 25,000-45,000 grams per mole, as determined by gel permeation chromatography using polystyrene standards and calculated for polycarbonate.

[0089] Aspect 6. The polycarbonate composition of any one of the preceding Aspects, wherein the homopolycarbonate comprises: a first homopolycarbonate having a weight average molecular weight of 19,000-25,000 grams per mole, preferably 20,000-23,000 grams per mole, as determined by gel permeation chromatography using polystyrene standards and calculated for polycarbonate; and a second homopolycarbonate having a weight average molecular weight of 29,000-32,000 grams per mole, preferably 30,000-31,000 grams per mole, as determined by gel permeation chromatography using polystyrene standards and calculated for polycarbonate; or a combination thereof.

[0090] Aspect 7. The polycarbonate composition of any one of the preceding Aspects, wherein the polycarbonate composition comprises at least 4 wt% siloxane repeating units.

[0091] Aspect 8. The polycarbonate composition of any one of the preceding Aspects comprising 4-20 wt% siloxane repeating units and 1000 ppm or less, preferably 500 ppm or less of added fluorine, based on the total composition.

[0092] Aspect 9. The polycarbonate composition of any one of the preceding Aspects, wherein the poly(carbonate-siloxane) has a weight average molecular weight of 30,000-45,000 grams per mole, or 32,000-43,000 grams per mole, or 35,000-42,000 grams per mole, or 37, GOO- 41, 000 g / mol, each as determined by gel permeation chromatography using polystyrene standards and calculated for polycarbonate.

[0093] Aspect 10. The polycarbonate composition of any one of the preceding Aspects, wherein a molded sample of the composition has improved chemical resistance as compared to a reference composition, wherein the reference composition is the same as the polycarbonate composition, except the reference composition comprises a homopolycarbonate composition comprising one or more homopolycarbonates wherein an average of the weight average molecular weight of the one or more homopolycarbonates is 25,000 grams per mole or more, as determined by gel permeation chromatography using polystyrene standards and calculated for polycarbonate having a weight average molecular weight of less than 25,000 grams per mole, as determined by gel permeation chromatography using polystyrene standards and calculated for polycarbonate.

[0094] Aspect 11. The polycarbonate composition of any one of the preceding Aspects, wherein the flame retardant comprises salts of aromatic sulfonates, salts of aromatic sulfone sulfonates, an organophosphorus compound, or a combination thereof.

[0095] Aspect 12. The polycarbonate composition of Aspect 1, wherein the polycarbonate composition comprises glass fibers.

[0096] Aspect 13. A method of making the polycarbonate composition of any one of the preceding Aspects, the method comprising melt-mixing the components of the composition, and, optionally, extruding the composition.

[0097] Aspect 14. An article comprising the polycarbonate composition of any of Aspects 1 to 12.

[0098] Aspect 15. A method for forming the article according to Aspect 14, comprising molding, casting, or extruding the composition to provide the article.

[0099] The compositions, methods, and articles can alternatively comprise, consist of, or consist essentially of, any appropriate materials, steps, or components herein disclosed. The compositions, methods, and articles can additionally, or alternatively, be formulated so as to be devoid, or substantially free, of any materials (or species), steps, or components, that areotherwise not necessary to the achievement of the function or objectives of the compositions, methods, and articles.

[0100] 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, 5-20 wt%”, is inclusive of the endpoints and all intermediate values of the ranges of “-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 embodiments,” “an embodiment,” and so forth, means that a particular element described in connection with the embodiment is included in at least one embodiment described herein, and may or may not be present in other embodiments. In addition, it is to be understood that the described elements can be combined in any suitable manner in the various embodiments. 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.

[0101] 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.

[0102] 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.

[0103] 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 dashthat 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.

[0104] 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, monovalenthydrocarbon 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- )). “Cycloalkylene” means a divalent cyclic alkylene group, -Cnbhn-x. wherein x is the number of hydrogens replaced by cyclization(s). “Cycloalkenyl” means a monovalent group having one or more rings and one or more carbon-carbon double bonds in the ring, wherein all ring members are carbon (e.g., cyclopentyl and cyclohexyl). "Aryl" means an aromatic hydrocarbon group containing the specified number of carbon atoms, such as phenyl, tropone, indanyl, or naphthyl. “Arylene” means a divalent aryl group. “Alkylarylene” means an arylene group substituted with an alkyl group. “Arylalkylene” means an alkylene group substituted with an aryl group (e.g., benzyl). 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 can 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 can each independently be a C1-9 alkoxy, a C1-9 haloalkoxy, a nitro (-NO2), a cyano (-CN), a C1-6 alkyl sulfonyl (-S(=O)2-alkyl), a C6-12 aryl sulfonyl (-S(=O)2-aryl)a thiol (-SH), a thiocyano (-SCN), a tosyl (CH3C6H4SO2-), a C3-12 cycloalkyl, a C2-12 alkenyl, a C5-12 cycloalkenyl, a C6-12 aryl, a C7-13 arylalkylene, a C4-12 heterocycloalkyl, and a C3-12 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 -CH2CH2CN is a C2 alkyl group substituted with a nitrile.

[0105] While particular embodiments 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.

Claims

CLAIMSWhat is claimed is:

1. A polycarbonate composition comprising:80-92 wt% of a homopolycarbonate composition comprising one or more homopolycarbonates, wherein an average of the weight average molecular weight of the one or more homopolycarbonates is 25,000 grams per mole or more, as determined by gel permeation chromatography using polystyrene standards and calculated for polycarbonate;8-20 wt% of a poly(carbonate-siloxane) having a siloxane content of 30-70 wt% present in an amount effective to provide 3.5-14 wt% siloxane repeating units based on the total weight of the composition, and having a weight average molecular weight of 26,000-50,000 grams per mole, as determined by gel permeation chromatography using polystyrene standards and calculated for polycarbonate; and having less than 1 wt% of a poly(carbonate-siloxane) having a siloxane content of less than 30 wt%;0.01-1.0 wt% of a flame retardant comprising an aromatic sulfonate inorganic salt, an aromatic sulfone sulfonate inorganic salt, or a combination thereof; optionally, an additive composition; and optionally, 5-20 wt% of glass fibers; wherein the polycarbonate composition comprises 1200 ppm or less of added fluorine to the total composition, and wherein a sample of the polycarbonate composition exhibits a UL-94 rating of V-0 at a thickness of 1.5 millimeters or less.

2. The polycarbonate composition of claim 1 comprising 200 ppm or less of fluorine, or 100 ppm or less of fluorine, based on the total composition.

3. The polycarbonate composition of claim 2, wherein added fluorine is excluded, and an amount of fluorine present in the composition is below 20 ppm as determined in accordance with ASTM D7359-23.

4. The polycarbonate composition of any one of the preceding claims, wherein: the calculated added bromine and added chlorine content of the polycarbonate composition are each 900 ppm or less and the calculated total added bromine, added chlorine, and added fluorine content of the polycarbonate composition is 1500 ppm or less; orthe calculated added bromine, added chlorine, and added fluorine content of the polycarbonate composition are each 900 ppm or less and the calculated total added bromine, added chlorine, and added fluorine content of the polycarbonate composition is 1500 ppm or less.

5. The polycarbonate composition of any one of the preceding claims, wherein the average of the weight average molecular weights of the homopolycarbonates is 25,000-40,000 grams per mole, as determined by gel permeation chromatography using polystyrene standards and calculated for polycarbonate.

6. The polycarbonate composition of any one of the preceding claims, wherein the homopolycarbonate comprises: a first homopolycarbonate having a weight average molecular weight of 19,000-25,000 grams per mole, preferably 20,000-23,000 grams per mole, as determined by gel permeation chromatography using polystyrene standards and calculated for polycarbonate; and a second homopolycarbonate having a weight average molecular weight of 29, GOO- 32, 000 grams per mole, preferably 30,000-31,000 grams per mole, as determined by gel permeation chromatography using polystyrene standards and calculated for polycarbonate.

7. The polycarbonate composition of any one of the preceding claims, wherein the polycarbonate composition comprises at least 4 wt% of siloxane repeating units.

8. The polycarbonate composition of any one of the preceding claims comprising 4-10 wt% siloxane repeating units and 1000 ppm or less, preferably 500 ppm or less of added fluorine, based on the total composition.

9. The polycarbonate composition of any one of the preceding claims, wherein the poly(carbonate-siloxane) has a weight average molecular weight of 30,000-45,000 grams per mole, or 32,000-43,000 grams per mole, or 35,000-42,000 grams per mole, or 37,000-41,000 g / mol as determined by gel permeation chromatography using polystyrene standards and calculated for polycarbonate.

10. The polycarbonate composition of any one of the preceding claims, wherein a molded sample of the composition has improved chemical resistance as compared to a reference composition, wherein the reference composition is the same as the polycarbonate composition, except the reference composition comprises a homopolycarbonate composition comprising one or more homopolycarbonates, wherein an average of the weight average molecular weight of the homopolycarbonate composition is 25,000 grams per mole or more, as determined by gel permeation chromatography using polystyrene standards and calculated for polycarbonate.

11. The polycarbonate composition of any one of the preceding claims, wherein the flameretardant composition comprises sodium benzene sulfonate, sodium toluene sulfonate, potassium diphenylsulfone sulfonate, or a combination thereof, in an amount of 0.1-0.6 wt%, based on the total weight of the polycarbonate composition.

12. The polycarbonate composition of any one of the preceding claims, wherein the polycarbonate composition comprises the glass fibers.

13. A method of making the polycarbonate composition of any one of the preceding claims, the method comprising melt-mixing the components of the composition, and, optionally, extruding the composition.

14. An article comprising the polycarbonate composition of any of claims 1 to 12.

15. A method for forming the article according to claim 14, comprising molding, casting, or extruding the composition to provide the article.

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