White polycarbonate compositions

Abstract

White polycarbonate compositions having a low added fluorine content while also achieving a V-0 flame test rating at 1.5 mm or less include: a homopolycarbonate having a weight average molecular weight of 25,000 grams per mole or more, 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 3-20 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 gel permeation chromatography using polystyrene standards and calculated for polycarbonate; a flame retardant; a colorant composition comprising titanium dioxide; and optionally, an additive composition; wherein the polycarbonate composition comprises 1200 ppm or less of added fluorine to the total composition.

Description

WHITE POLYCARBONATE COMPOSITIONSCROSS-REFERENCE TO RELATED APPLICATIONThis application claims priority to and the benefit of EP 23199549.9, 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 white 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 and consumer goods. Because of their broad use including consumer goods, it is desirable to provide polycarbonate compositions with excellent chemical resistance, robust flame retardance and impact resistance, as well as achieving a white color in the finished articles. Such properties can be particularly difficult to achieve in thin-wall applications when a significant amount of titanium dioxide is present. In addition, more stringent regulations are under consideration 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 white polycarbonate compositions with enhanced chemical, impact resistance, and flame retardance 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: a homopolycarbonate having a weight average molecular weight of 25,000 grams per mole or more, using polystyrene standards and calculated for polycarbonate; and a poly(carbonate-siloxane) having a siloxane content of 30 to 70 wt% present in an amount effective to provide 3 to 20 wt% siloxane repeating units based on the total weight of the composition, and a weight average molecular weight of 26,000 to 50,000 grams per mole, as determined by gel permeation chromatography using polystyrene standards and calculated for polycarbonate; a flame retardant; a colorant composition comprising titanium dioxide; and optionally, an additive composition; wherein the polycarbonate composition comprises 1200 ppm or less of added fluorine to the total composition, and wherein a sample of thepolycarbonate 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 a method for forming the article 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

[0009] Colored articles are often desirable for customers and end-use applications, requiring the addition of colorants to polycarbonate compositions. Examples are bright whites, based on white pigments that with increasing concentration give lighter colors and higher light blocking ability, making them suitable for (electronic) housings. High loadings of white pigment, for example titanium dioxide, can adversely affect other desirable properties such as chemical resistance, flame retardancy, impact resistance, and processability.

[0010] Furthermore, 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-based anti-drip 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 under consideration, for example, in Europe, 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.

[0011] The inventors hereof have discovered that polycarbonate compositions can achieve the desired combination of color, chemical resistance, flame retardance, and impactresistance by including: a homopolycarbonate having a weight average molecular weight (Mw) of 25,000 g / mol or more, a polycarbonate siloxane) including 30-70 wt% siloxane repeating units present in an amount effective to provide 3-20 wt% siloxane repeating units, based on the total composition, and a flame retardant, 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. 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, less than 1000 ppm, less than 500 ppm, less than 100 ppm, or less than 50 ppm, or less than 20 ppm. For example, if 0.1 wt% encapsulated polytetrafluoroethylene, (e.g., TSAN, which is about 50 wt% PTFE and PTFE estimated to have about 76 wt% fluorine content), the amount of calculated intentionally added fluorine would equal 380 ppm. Further, the polycarbonate compositions can have zero intentionally added fluorine.

[0012] 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, or 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, less than 20-300 ppm, less than 20-200 ppm, 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.

[0013] 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., , e.g, at 1.5 mm or at 1.2 mm, and be considered “essentially halogen-free” per IEC 61249-2-21 or UL 746H. As used herein, thephrase “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.

[0014] “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 to 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.

[0015] 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 to 4. The halogen is usually bromine.

[0016] 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.

[0017] 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 15,000-40,000 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 mg per ml, and are eluted at a flow rate of 1.5 ml per minute. 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., 13different polystyrene standards ranging 1,000 to 200,000 g / mol), and calculating the molecular weight for polycarbonate.

[0018] The polycarbonate compositions can include a homopolycarbonate (wherein each R1in the polymer is the same). In an aspect, the homopolycarbonate in the polycarbonate composition is derived from a bisphenol of formula (2), preferably bisphenol A, in which each of A1and A2is p-phenylene and Y1is isopropylidene in formula (2).

[0019] The polycarbonate compositions include a homopolycarbonate (wherein each R1in the polymer is the same). The homopolycarbonate can have an Mwof 25,000 g / mol or more, for example 25,000-100,000 g / mol, or 25,000-75,000 g / mol, or 25,000-40,000 g / mol, or 25, GOO- 38, 000 g / mol, or 29,000-45,000 g / mol. Molecular weight can be determined by gel permeation chromatography (GPC), using polystyrene standards and calculated for polycarbonate. GPC samples are prepared at a concentration of 1 milligram per milliliter (mg / mL) and are eluted at a flow rate of 1.5 ml per minute. 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 and calculating the molecular weight for polycarbonate.

[0020] In an aspect, the homopolycarbonate is a bisphenol A homopolycarbonate. The bisphenol A homopolycarbonate has repeating structural carbonate units of the formula (1).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 be included during polymerization to provide end groups, for example monocyclic phenols such as phenol, p-cyanophenol, and Ci- 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 mono-chloroformates 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% (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.

[0021] In an aspect, more than one homopolycarbonate can be present. For example, the homopolycarbonate can comprise a first homopolycarbonate having a first Mw, and a second homopolycarbonate having a second Mw, wherein the first and second Mws are not the same. Thus, the homopolycarbonate can be a homopolycarbonate composition including one or more homopolycarbonates wherein each of the one or more homopolycarbonates can be the same chemical composition, for example, each can be a bisphenol A homopolycarbonate, but each can have a different Mw, provided that at least one of the homopolycarbonates has an Mwof 25,000 g / mol or more. In an aspect, the of the first homopolycarbonate is less than 25,000 g / mol and the of the second homopolycarbonate is greater than or equal to 25,000 g / mol.

[0022] For example, the homopolycarbonate can comprise a first homopolycarbonate having an Mwof 19,000-25,000 g / mol, or 20,000-23,000 g / mol, and a second homopolycarbonate having an Mwof 29,000-32,000 g / mol, or 30,000-31,000 g / mol, each as determined by GPC using polystyrene standards and calculated for polycarbonate.

[0023] In an aspect, the composition can optionally comprises a homopolycarbonate having an Mwthat is less than 25,000 g / mol, or a homopolycarbonate having an Mwof 18, GOO- 24, 000 g / mol, or 20,000-22,000 g / mol, and a homopolycarbonate having an Mwof 29, GOO- 32, 000 g / mol, or 30,000-31,000 g / mol, each as determined by GPC using polystyrene standards and calculated for polycarbonate, provided that a weight average of the Mwof the two (or more) polycarbonates is 25,000 g / mol or more, or 26,000 g / mol or more, or 27,000 mole / g or more, for example for example more than 25,000-50,000 g / mol, or 26,000-40,000 g / mol, or 26,000-38,000 g / mol, or 28,000-45,000 g / mol.. For example, when present, the bisphenol A homopolycarbonate having an Mwthat is less than 25,000 g / mol can be present in a weight ratio of bisphenol A homopolycarbonate having an Mwof 25,000 g / mol or more to bisphenol A homopolycarbonate having a molecular weight of less than 25,000 g / mol of greater than 1:1, or 2:1 to 10:1, or 3:1 to 10:1.

[0024] In an aspect, the combined Mwweight of all homopolycarbonates present in the composition is greater than or equal to 25,000 g / mol. Stated another way, when a homopolycarbonate having an Mwthat is less than 25,000 g / mol is present in the composition, itcan be present in an amount such that the average of the of all homopolycarbonates present in the composition is greater than or equal to 25,000 g / mol.

[0025] The homopolycarbonate can be present in the composition in an amount of 80 to 95 wt%, based on the total weight of the composition. Within this range, the homopolycarbonate can be present in an amount of, for example, 80 to 90 wt%, 80 to 87 wt%, or 80 to 85 wt%, , each based on the total weight of the composition.

[0026] 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-i4 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.

[0027] The value of E in formula (10) can vary widely depending on the type and relative amount of each component in the polycarbonate composition, the desired properties of the composition, and like considerations. Generally, E has an average value of 2-1,000, or 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 polycarbonatesiloxane) 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.

[0028] 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.

[0029] 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.

[0030] 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 ismethyl, 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 formulaor 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.

[0031] 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.

[0032] 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, or 5-85, or 10-70, or 15-65, or 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.

[0033] Poly(carbonate-siloxane)s can have an Mwof 2,000-100,000 g / mol, or 5,000- 50,000 g / mol 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 polystyrenestandards 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 35,000-42,000 grams per mole, or 37,000-41,000, determined as described herein.

[0034] 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), or 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.

[0035] 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 to 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).

[0036] The poly(carbonate-siloxane) copolymers can comprise 50-99 wt% of carbonate units and 1-50 wt% siloxane units. Within this range, the poly(carbonate-siloxane) copolymer can comprise 70-98 wt%, or 75-97 wt% of carbonate units and 2-30 wt%, or 3-25 wt% siloxane units.

[0037] In addition to the polycarbonate siloxane) having 30-70 wt% siloxane repeating units, the polycarbonate compositions can include an additional poly(carbonate-siloxane) copolymer having greater than 70-99 wt% of carbonate units and 1 to less than 30 wt% siloxane units. Within this range, the additional poly(carbonate-siloxane) copolymer can have 15-25 wt% siloxane repeating units. The polycarbonate compositions can include an additional poly(carbonate-siloxane) copolymer having 10 wt% or less siloxane repeating units, based on the total weight of the poly(carbonate-siloxane). Within this range, the poly(carbonate-siloxane) copolymer can have 4-8 wt% siloxane repeating units. The polycarbonate compositions can include two or more of the foregoing.

[0038] 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 polycarbonate having less than 30 wt% siloxane repeating units, or less than 10 wt% siloxane repeating units. Preferably a poly(carbonate-siloxane) having less than 30 wt% siloxane repeating units or less than 10 wt% siloxane repeating units is excluded from the composition.

[0039] The poly(carbonate-siloxane) can be present in the composition in an amount of 5-20 wt%, based on the total weight of the composition. Within this range, the polycarbonate-siloxane) can be present in an amount of, for example, greater than 7-20 wt%, or 9-20 wt%, or 10-20 wt%, or 12-20 wt%, or 2-18 wt%, or 13-17 wt%, or 10-15 wt%, each based on the total weight of the composition.

[0040] The poly(carbonate-siloxane) can be present in an amount effective to provide 3- 20 wt%, 3.5-20 wt%, 4-20 wt%, 4.5-20 wt%, 3-15 wt%, or 3-10 wt% siloxane repeating units, based on the total composition.

[0041] 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.

[0042] 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, antistatic agents, 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 about 5 wt%, or in other aspects less than about 3 wt%, or in other aspects less than about 2 wt%. If present, the impurities do not significantly affect the properties of the compositions described herein.

[0043] 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.

[0044] 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.

[0045] 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.

[0046] 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-8 alkoxy or Ce-is aryloxy. Exemplary phasetransfer 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.

[0047] Alternatively, melt processes can be used to make the polycarbonates. Generally, 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°C-350°C, preferably 180°C-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 is generally 0.1 hours-10 hours.

[0048] Catalysts used in the melt transesterification polymerization production of polycarbonates can include alpha or beta catalysts. Beta catalysts are typically volatile anddegrade 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.

[0049] 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 NatEPCh. 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.

[0050] 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 and phosphonium structures are properly balanced. For example, where R4or R5are each methyl and X" is carbonate, it is understood that X" represents 1 / 2(CC>3’2). 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.

[0051] 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, or, 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, or 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.

[0052] 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.

[0053] 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. The molecular 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.

[0054] 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.

[0055] 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, or 0.5-8 branching units per 100 R1units, or 0.75-5 branching units per 100 R1units. For branching agents having formula (20), the branching agent is present in an amount-provide 0.1-10 triester branching units per 100 R1units, or 0.5-8, or 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, or 0.5-8, or 2.5-3.5 triphenylcarbonate units per 100 R1units. In some aspects, a combination of two or morebranching agents can be used. Alternatively, the branching agents can be added at a level of 0.05-2.0 wt%.

[0056] In an aspect, the polycarbonate is a branched polycarbonate including units as described above; greater than or equal to 0.2 to 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.

[0057] 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-substituted phenyl chloroformates, p-cumyl phenyl chloroformate, and toluene chloroformate. Combinations of different end groups can be used.

[0058] The polycarbonate compositions include a flame retardant. 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 brominated polycarbonate. Inorganic flame retardants can be used, for example salts of aromatic sulfonates such as sodiumbenzene sulfonate, sodium toluene sulfonate (NATS), and the like, salts of aromatic sulfone sulfonates such as potassium diphenylsulfone sulfonate (KSS), and the like; salts formed by reacting for example an alkali metal or alkaline earth metal (e.g., lithium, sodium, potassium, magnesium, calcium and barium salts) and an inorganic acid complex salt, for example, an oxoanion (e.g., alkali metal and alkaline-earth metal salts of carbonic acid, such as Na2CC>3, K2CO3, MgCCh, CaCCh, and BaCCh. KSS and NATS, alone or in combination with other flame retardants, are particularly useful. Exemplary amounts of an aromatic sulfone sulfonate salt can be 0.01-1.0 wt%, or 0.1-0.6 wt%, based on the total weight of the polycarbonate composition.

[0059] The polycarbonate compositions can include an organophosphorus flame retardant. In the aromatic organophosphorus compounds that have at least one organic aromatic group, 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 a bisphenol group (e.g., bisphenol A), a monoarylene group (e.g., a 1,3-phenylene or a 1,4-phenylene), or a combination including at least one of the foregoing.

[0060] 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).

[0061] The organophosphorus flame retardant can include an oxaphosphorinoxide of the Formula (23) below.

[0062] In Formula (23), the phosphorous atom and one oxygen atom are part of a cyclic structure, for example, a five or six membered ring and q is at least two. Each Ar is independently Ce-is aryl, preferably benzene, which is optionally substituted with a Ci-is hydrocarbyl group, or a Ci-ishydrocarbyloxy group (e.g., -O-hydrocarbyl). When n and p are each 0 and m is 1 (“mono-DOPO” type compounds), then R2is hydrogen, Ci-Cis alkyl, C3-10 cycloalkyl, (C1-6 alkyl)C3-io cycloalkyl, Ce-is aryl, (C1-6 alkyl)Ce-i8 aryl, C3-12 heteroaryl, or (C1-6 alkyl)C3 i2 heteroaryl. In the foregoing groups at least one hydrogen atom of these groups can be substituted with a group having an N, S, O, or F atom. As used herein, “(C1-6 alkyl)C3-io cycloalkyl” refers to a cycloalkyl group attached to an alkylene group, “(C1-6 alkyl)Ce-i8 aryl” refers to an aryl group attached to an alkylene group, and “(C1-6 alkyl)C3-i2 heteroaryl” refers to a heteroaryl group attached to an alkylene group. In any of the alkyl or cycloalkyl groups of R2, any carbon-carbon single bond is optionally replaced by a carbon-carbon double or triple bond, and any methylene is optionally replaced by O, S, S(=O), C(=O), P(=O), or NR10, wherein R10is hydrogen or C1-6 alkyl, and any methylene is optionally substituted with a group having an N, S, O, or F atom.

[0063] In Formula (23), when n and p are each 1 or more and m is 0 (“Di-DOPO” type compounds), then X is Ci-Cis alkylidene, C3-10 cycloalkylidene, Ce-is arylene, C3-12 heteroarylene, a group derived from Formula (3), or a group represented by -iJ-X’-L2-. The E1and L2linker groups are each independently a single bond, Ci-Cis alkylidene, or a C3-10 cycloalkylidene, where any carbon-carbon single bond is optionally replaced by a carbon-carbon double or triple bond, and any methylene is optionally replaced by O, S, S(=O), C(=O), P(=O), or NR10, wherein R10is hydrogen or C1-6 alkyl, and any methylene is optionally substituted with a group having an N, S, O, or F atom. X’ is Ci-Cis alkylidene, C3-10 cycloalkylidene, Ce-is arylene, C3-12 heteroarylene, or a group derived from Formula (3).

[0064] Specific examples of an oxaphosphorinoxide include 9,10-dihydro-9-oxo-10- phosphaphenanthrene-10-oxide (23a, “DOPO”), commercially available as from SANKO CO., ETD., 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”).wherein Ar1is C3-18 heteroaryl or Ce-is aryl, each instance of R3is independently hydrogen, C1-18 alkyl, C3-18 heteroaryl or Ce-is aryl, each instance of R1is independently C1-18 alkyl, C3-18 heteroaryl or Ce-is aryl, and any hydrogen atom on an aryl or heteroaryl ring can be optionally substituted with a C1-18 alkyl group. An exemplary Di-DOPO compound is HTP-6123G, commercially available from GUIZHOU YUANYI MINING GROUP CO.

[0066] In an aspect, the aromatic organophosphorus compound is a monomeric phosphate. Representative monomeric aromatic phosphates are of the formula (GO) iP=O. wherein each G is independently an alkyl, cycloalkyl, aryl, alkylarylene, or arylalkylene group having up to 30 carbon atoms, provided that at least one G is an aromatic group. Two of the G groups can be joined together to provide a cyclic group. In some aspects G corresponds to a monomer used to form the polycarbonate, e.g., resorcinol. Exemplary phosphates include phenyl bis(dodecyl) phosphate, phenyl bis(neopentyl) phosphate, phenyl bis(3,5,5'-trimethylhexyl) phosphate, ethyl diphenyl phosphate, 2-ethylhexyl di(p-tolyl) phosphate, bis(2-ethylhexyl) p- tolyl phosphate, tritolyl phosphate, bis(2-ethylhexyl) phenyl phosphate, tri(nonylphenyl) phosphate, bis(dodecyl) p-tolyl phosphate, dibutyl phenyl phosphate, 2-chloroethyl diphenyl phosphate, p-tolyl bis(2,5,5'-trimethylhexyl) phosphate, 2-ethylhexyl diphenyl phosphate, and the like. A specific aromatic phosphate is one in which each G is aromatic, for example, triphenyl phosphate, tricresyl phosphate, isopropylated triphenyl phosphate, and the like.

[0067] Di- or polyfunctional aromatic organophosphorus compounds are also useful, for example, compounds of the formulaswherein each G1is independently a C1-30 hydrocarbyl; each G2is independently a C1-30hydrocarbyl or hydrocarbyloxy; Xais as defined in formula (3) or formula (4); each X is independently a bromine or chlorine; m is 0-4, and n is 1-30. In a specific aspect, Xais a single bond, methylene, isopropylidene, or 3,3,5-trimethylcyclohexylidene.

[0068] Specific aromatic organophosphorus compounds are inclusive of acid esters of formula (9)wherein each R16is independently Ci-8 alkyl, C5-6 cycloalkyl, C6-20 aryl, or C7-12 arylalkylene, each optionally substituted by C1-12 alkyl, specifically by C M alkyl and X is a mono- or polynuclear aromatic Ce-30 moiety or a linear or branched C2-30 aliphatic radical, which can be OH- substituted and can contain up to 8 ether bonds, provided that at least one R16or X is an aromatic group; each n is independently 0 or 1 ; and q is from 0.5-30. In some aspects each R16is independently C1-4 alkyl, naphthyl, phenyl(C 1-4) alkylene, aryl groups optionally substituted by C1-4 alkyl; each X is a mono- or poly-nuclear aromatic Ce-30 moiety, each n is 1; and q is from 0.5-30. In some aspects each R16is aromatic, e.g., phenyl; each X is a mono- or poly-nuclear aromatic Ce-30 moiety, including a moiety derived from formula (2); n is one; and q is from 0.8- 15. In other aspects, each R16is phenyl; X is cresyl, xylenyl, propylphenyl, or butylphenyl, one of the following divalent groupsor a combination including one or more of the foregoing; n is 1; and q is from 1-5, or 1-2. In some aspects at least one R16or X corresponds to a monomer used to form the polycarbonate, e.g., bisphenol A, resorcinol, or the like. Aromatic organophosphorus compounds of this type include the bis(diphenyl) phosphate of hydroquinone, resorcinol bis(diphenyl phosphate) (RDP), and bisphenol A bis(diphenyl) phosphate (BPADP), and their oligomeric and polymeric counterparts.

[0069] The 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. These flame-retardant additives are commercially available. In an aspect, the organophosphorus flameretardant containing a phosphorous-nitrogen bond is a phosphazene or cyclic phosphazene of the formulaswherein wl is 3-10,000; w2 is 3-25, or 3-7; and each Rwis independently a C1-12 alkyl, alkenyl, alkoxy, aryl, aryloxy, or polyoxyalkylene group. In the foregoing groups at least one hydrogen atom of these groups can be substituted with a group having an N, S, O, or F atom, or an amino group. For example, each Rwcan be a substituted or unsubstituted phenoxy, an amino, or a polyoxyalkylene group. Any given Rwcan further be a crosslink to another phosphazene group. Exemplary crosslinks include bisphenol groups, for example bisphenol A groups. Examples include phenoxy cyclotriphosphazene, octaphenoxy cyclotetraphosphazene decaphenoxy cyclopentaphosphazene, and the like. In an aspect, the phosphazene has a structure represented by the formula

[0070] Commercially available phenoxyphosphazenes having the aforementioned structures are LY202 manufactured and distributed by Lanyin Chemical Co., Ltd, FP-110 manufactured and distributed by Fushimi Pharmaceutical Co., Ltd, and SPB-100 manufactured and distributed by Otsuka Chemical Co., Ltd.

[0071] When the flame retardant includes an 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 composition.

[0072] 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 weightof 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.

[0001] The polycarbonate composition includes a colorant composition including titanium dioxide. Other colorants such as pigment or dye additives can also be present. Useful pigments can include, for example, inorganic pigments such as metal oxides and mixed metal oxides such as zinc oxide, titanium dioxides, iron oxides, or the like; sulfides such as zinc sulfides, or the like; aluminates; sodium sulfo-silicates sulfates, chromates, or the like; carbon blacks; zinc ferrites; ultramarine blue; organic pigments such as azos, di-azos, quinacridones, perylenes, naphthalene tetracarboxylic acids, flavanthrones, isoindolinones, tetrachloroisoindolinones, anthraquinones, enthrones, dioxazines, phthalocyanines, and azo lakes; Pigment Red 101, Pigment Red 122, Pigment Red 149, Pigment Red 177, Pigment Red 179, Pigment Red 202, Pigment Violet 29, Pigment Blue 15, Pigment Blue 60, Pigment Green 7, Pigment Yellow 119, Pigment Yellow 147, Pigment Yellow 150, and Pigment Brown 24; or a combination thereof.

[0002] Dyes are generally organic materials and include coumarin dyes such as coumarin 460 (blue), coumarin 6 (green), nile red or the like; lanthanide complexes; hydrocarbon and substituted hydrocarbon dyes; polycyclic aromatic hydrocarbon dyes; scintillation dyes such as oxazole or oxadiazole dyes; aryl- or heteroaryl-substituted poly (C2-8) olefin dyes; carbocyanine dyes; indanthrone dyes; phthalocyanine dyes; oxazine dyes; carbostyryl dyes; napthalenetetracarboxylic acid dyes; porphyrin dyes; bis(styryl)biphenyl dyes; acridine dyes; anthraquinone dyes; cyanine dyes; methine dyes; arylmethane dyes; azo dyes; indigoid dyes, thioindigoid dyes, diazonium dyes; nitro dyes; quinone imine dyes; aminoketone dyes; tetrazolium dyes; thiazole dyes; perylene dyes, perinone dyes; bis-benzoxazolylthiophene (BBOT); triarylmethane dyes; xanthene dyes; thioxanthene dyes; naphthalimide dyes; lactone dyes; fluorophores such as anti-stokes shift dyes which absorb in the near infrared wavelength and emit in the visible wavelength, or the like; luminescent dyes such as 7-amino-4- methylcoumarin; 3-(2'-benzothiazolyl)-7-diethylaminocoumarin; 2-(4-biphenylyl)-5-(4-t- butylphenyl)-l,3,4-oxadiazole; 2,5-bis-(4-biphenylyl)-oxazole; 2,2'-dimethyl-p-quaterphenyl; 2,2-dimethyl-p-terphenyl; 3,5,3"",5""-tetra-t-butyl-p-quinquephenyl; 2,5-diphenylfuran; 2,5- diphenyloxazole; 4,4'-diphenylstilbene; 4-dicyanomethylene-2-methyl-6-(p- dimethylaminostyryl)-4H-pyran; l,r-diethyl-2,2'-carbocyanine iodide; 3,3'-diethyl-4,4',5,5'- dibenzothiatricarbocyanine iodide; 7-dimethylamino-l-methyl-4-methoxy-8-azaquinolone-2; 7- dimethylamino-4-methylquinolone-2; 2-(4-(4-dimethylaminophenyl)-l,3-butadienyl)-3-ethylbenzothiazolium perchlorate; 3-diethylamino-7-diethyliminophenoxazonium perchlorate; 2- (l-naphthyl)-5-phenyloxazole; 2,2'-p-phenylen-bis(5-phenyloxazole); rhodamine 700; rhodamine 800; pyrene, chrysene, rubrene, coronene, or the like; or a combination thereof.

[0003] The colorant composition including titanium dioxide can be present in an amount up to 10 wt%, up to 7 wt%, or up to 5 wt%. Within this range, the colorant composition including titanium dioxide can be present in an amount from 0.5-10 wt%, 1-10 wt%, 1-5 wt%, or 1-3 wt%, each based on the total composition. In a preferred aspect, the colorant composition is titanium dioxide, i.e., no other colorant is present, wherein the titanium dioxide is present in an amount of up to 10 wt%, up to 7 wt%, or up to 5 wt%. Within this range, when only titanium dioxide is present, the titanium dioxide can be present in amounts from 0.5-10 wt%, 1-10 wt%, 1-5 wt%, or 1-3 wt%, each based on the total composition.

[0004] 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.

[0073] The polycarbonate compositions can include a homopolycarbonate, preferably a bisphenol A homopolycarbonate having an Mwof 25,000 g / mol 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 3-14 wt%, preferably 4-10 wt% siloxane repeating units based on the total weight of the composition, and an Mwof 26,000-50,000 g / mol, as determined by GPC using polystyrene standards and calculated for polycarbonate; 0.5-10 wt% titanium dioxide; 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 totalcomposition, 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.

[0074] The polycarbonate compositions can include a homopolycarbonate, preferably a bisphenol A homopolycarbonate having an Mwof 25,000 g / mol 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 3-14 wt%, preferably 4-10 wt% siloxane repeating units based on the total weight of the composition, and an Mwof 26,000-50,000 g / mol, as determined by GPC using polystyrene standards and calculated for polycarbonate; 0.5-10 wt% titanium dioxide; 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.

[0075] 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.

[0076] 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.

[0077] 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.

[0078] The composition of the present disclose can advantageously exhibit one or more desirable properties. For example, it was surprisingly found that the composition can exhibit a low melt volume rate (MVR). For example, the polycarbonate composition can have a melt volume rate of less than or equal to 10 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. 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.

[0079] It was further unexpectedly 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.

[0080] The polycarbonate compositions have good chemical resistance. The polycarbonate compositions can have a tensile strength retention of 80% and higher and a tensile elongation retention of 65% and higher after exposure of an ASTM tensile bar for 168 hours toSANI-CLOTH HB at a temperature of 23°C under 0.5% or 1% strain compared to a nonexposed reference tested at the same temperature. The polycarbonate compositions also can have a tensile strength retention of 80% and higher and a tensile elongation retention of 65% and higher after exposure of an ASTM tensile bar for 168 hours to CAVICIDE at a temperature of 23°C under 0.5% or 1% strain compared to a non-exposed reference tested at the same temperature.

[0081] 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 exposure of an ISO tensile bar for 72 hours to insect repellant or sunscreen at a temperature of 23°C under 1 % strain.

[0082] In an aspect, the polycarbonate compositions have a tensile strength retention of 80% and higher after exposure of an ASTM tensile bar for 168 hours to SANI-CLOTH AF3 at a temperature of 23°C under 0.5% or 1% strain compared to a non-exposed reference tested at the same temperature, and a tensile elongation retention of 65% and higher after exposure of an ASTM tensile bar for 168 hours to SANI-CLOTH AF3 at a temperature of 23°C under 0.5% or 1 % strain compared to a non-exposed reference tested at the same temperature.

[0083] In an aspect, the composition can also exhibit good flame retardancy. In an aspect of measuring flame retardance, the UL94 standard utilizes a rating of V0, VI , V2 or HB , wherein a rating of V0 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 V0 or VI. In an aspect, a molded sample of the polycarbonate composition is capable of achieving a UL-94 V0 or VI rating at a thickness of , e.g, at 1.5 mm or at 1.2 mm, or less, or a UL-94 rating of V0 at a thickness of less than or equal to 1.5 mm, , e.g, at 1.5 mm or at 1.2 mm.

[0084] 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.

[0085] 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.

[0086] This disclosure is further illustrated by the following examples, which are nonlimiting.EXAMPLES

[0087] The following components are used in the examples. Unless specifically indicated otherwise, the amount of each component recited herein is in wt%, based on the total weight of the composition, which totals 100 wt%.Table 1.

[0088] 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 2. Total flame-out-times for all bars (FOT = tl + 12) were determined.Table 2.Examples 1-6

[0089] Tables 2 and 3 below provide the compositions and properties for the following comparative examples and exemplified examples of the polycarbonate composition. Comparative examples are indicated with an asterisk.Table 2.Table 3.

[0090] Examples 1-3 demonstrate that the combination of a BPA polycarbonate and a polycarbonate siloxane) having 30-70 wt% siloxane content can provide V-0 flame test ratings in the absence of an anti-drip agent. Comparative Examples 4-6 demonstrate that when the polycarbonate siloxane) has a lower siloxane content (e.g., 20 wt% siloxane), Comparative Examples 4-6 failed to provide a V-0 flame test rating.

[0091] This disclosure further encompasses the following aspects.

[0092] Aspect 1. A polycarbonate composition comprising: a homopolycarbonate having a of 25,000 grams per mole or more, as determined by gel permeation chromatography 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 3-20 wt% siloxane repeating units based on the total weight of the composition, and an Mwof 26,000-50,000 grams per mole, as determined by gel permeation chromatography using polystyrene standards and calculated for polycarbonate; a flame retardant; a colorant composition comprising titanium dioxide; optionally, an additive composition; 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, or at 1.5 mm, or at 1.2 mm.

[0093] Aspect 2. The polycarbonate composition of Aspect 1 comprising 200 ppm or less, or 100 ppm or less of fluorine, based on the total composition, or less than 20-380 ppm, less than 20-300 ppm, less than 20-200 ppm, less than 20-100 ppm, less than 20-50 ppm, or less than 20 ppm.

[0094] Aspect 3. The polycarbonate composition of Aspect 2, wherein added fluorine is excluded.

[0095] 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 about 900 ppm or less and the calculated total added bromine, added chlorine, and added fluorine content of the polycarbonate composition is about 1500 ppm or less; or the calculated added bromine, added chlorine, and added fluorine content of the polycarbonate composition are each about 900 ppm or less and the calculated total added bromine, added chlorine, and added fluorine content of the polycarbonate composition is about 1500 ppm or less.

[0096] Aspect 5. The polycarbonate composition of any one of the preceding Aspects, wherein the homopolycarbonate has an Mwof 29,000-45,000 grams per mole, as determined by gel permeation chromatography using polystyrene standards and calculated for polycarbonate.

[0097] Aspect 6. The polycarbonate composition of any one of the preceding Aspects, wherein the homopolycarbonate comprises: a first homopolycarbonate having an Mwof 19, GOO- 25 ,000 grams per mole, or 20,000-23,000 grams per mole, as determined by gel permeation chromatography using polystyrene standards and calculated for polycarbonate; or a second homopolycarbonate having an Mwof 29,000-32,000 grams per mole, or 30,000-31,000 grams per mole, as determined by gel permeation chromatography using polystyrene standards and calculated for polycarbonate; or a combination thereof.

[0098] Aspect 7. The polycarbonate composition of any one of the preceding Aspects, wherein the polycarbonate composition comprises at least 5 wt% siloxane repeating units.

[0099] Aspect 8. The polycarbonate composition of any one of the preceding Aspects comprising 4-10 wt% siloxane repeating units and 1000 ppm or less, or 500 ppm or less of added fluorine, based on the total composition.

[0100] Aspect 9. The polycarbonate composition of any one of the preceding Aspects, wherein the poly(carbonate-siloxane) has an Mwof 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 grams per mole, as determined by gel permeation chromatography using polystyrene standards and calculated for polycarbonate.

[0101] Aspect 10. The polycarbonate composition of any one of the preceding Aspects, wherein the flame retardant is present and 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 having an Mwof less than 25,000 grams per mole, as determined by gel permeation chromatography using polystyrene standards and calculated for polycarbonate.

[0102] 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.

[0103] Aspect 12. The polycarbonate composition of Aspect 1, wherein the colorant composition is titanium dioxide.

[0104] 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.

[0105] Aspect 14. An article comprising the polycarbonate composition of any of Aspects 1-12.

[0106] Aspect 15. A method for forming the article according to Aspect 14, comprising molding, casting, or extruding the composition to provide the article.

[0107] 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 are otherwise not necessary to the achievement of the function or objectives of the compositions, methods, and articles.

[0108] 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 “5-25 wt%,” etc.). “Combinations” is inclusive of blends, mixtures, alloys, reaction products, and the like. The terms “first,” “second,” and the like, do not denote any order, quantity, or importance, but rather are used to distinguish one element from another. The terms “a” and “an” and “the” do not denote a limitation of quantity and are to be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. “Or” means “and / or” unless clearly stated otherwise. Reference throughout the specification to “some aspects,” “an aspect,” and so forth, means that a particular element described in connection with the aspect is included in at least one aspect described herein, and may or may not be present in other aspects. In addition, it is to be understood that the described elements may be combined in any suitable manner in the various aspects. A “combination thereof’ is open and includes any combination comprising at least one of the listed components or properties optionally together with a like or equivalent component or property not listed.

[0109] 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.

[0110] 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.

[0111] 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 bondas indicated, or a hydrogen atom. A dash that is not between two letters or symbols is used to indicate a point of attachment for a substituent. For example, -CHO is attached through carbon of the carbonyl group.

[0112] The term "alkyl" means a branched or straight chain, unsaturated aliphatic hydrocarbon group, e.g., methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, t-butyl, n-pentyl, s- pentyl, and n- and s-hexyl. “Alkenyl” means a straight or branched chain, monovalent hydrocarbon group having at least one carbon-carbon double bond (e.g., ethenyl (-HC=CH2)). “Alkoxy” means an alkyl group that is linked via an oxygen (i.e., alkyl-O-), for example methoxy, ethoxy, and sec-butyloxy groups. "Alkylene" means a straight or branched chain, saturated, divalent aliphatic hydrocarbon group (e.g., methylene (-CH2-) or, propylene (-(CH2)3- )). “Cycloalkylene” means a divalent cyclic alkylene group, -CnFfcn-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.

[0113] While particular aspects have been described, alternatives, modifications, variations, improvements, and substantial equivalents that are or may be presently unforeseen may arise to applicants or others skilled in the art. Accordingly, the appended claims as filed andas 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: a homopolycarbonate having a weight average molecular weight of 25,000 grams per mole or more, as determined by gel permeation chromatography 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 3-20 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 gel permeation chromatography using polystyrene standards and calculated for polycarbonate; a flame retardant; a colorant composition comprising titanium dioxide; optionally, an additive composition; 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 millimeters or less.

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

3. The polycarbonate composition of Claim 2, wherein added fluorine is excluded.

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 about 900 ppm or less and the calculated total added bromine, added chlorine, and added fluorine content of the polycarbonate composition is about 1500 ppm or less; or the calculated added bromine, added chlorine, and added fluorine content of the polycarbonate composition are each about 900 ppm or less and the calculated total added bromine, added chlorine, and added fluorine content of the polycarbonate composition is about 1500 ppm or less.

5. The polycarbonate composition of any one of the preceding claims, wherein the homopolycarbonate has a weight average molecular weight of 29,000-45,000 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 as determined by gel permeation chromatography using polystyrene standards and calculated for polycarbonate; or a second homopolycarbonate having a weight average molecular weight of 29, GOO- 32, 000 grams per mole, as determined by gel permeation chromatography using polystyrene standards and calculated for polycarbonate; or a combination thereof.

7. The polycarbonate composition of any one of the preceding claims, wherein the polycarbonate composition comprises at least 5 wt% 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 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, or 37,000-41,000 grams per mole, 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 the flame retardant is present and 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 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.

11. The polycarbonate composition of any one of the preceding claims, wherein the flame retardant comprises salts of aromatic sulfonates, salts of aromatic sulfone sulfonates, an organophosphorous compound, or a combination thereof.

12. The polycarbonate composition of Claim 1, wherein the colorant composition is titanium dioxide.

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.

Images