23SHPP0043-WO-PCT (SS230161PCT) FLAME RETARDANT POLYCARBONATE COMPOSITIONS CROSS-REFERENCE TO RELATED APPLICATION This application claims priority to and the benefit of European Patent Application No. 24159440.7, filed on February 23, 2024, the contents of which are incorporated by reference herein in their entirety. BACKGROUND [0001] This disclosure relates to polycarbonate compositions, and in particular to flame- retardant polycarbonate compositions, methods of manufacture, and uses thereof in thin-wall articles. [0002] Polycarbonates have utility as materials for a wide range of applications, from automotive parts to electric and electronic appliances. Because of their wide use, particularly in electronic applications, it is desirable for the polycarbonate compositions to have flame retardancy. Such properties may be particularly difficult to achieve in thin-wall applications. In addition, more stringent regulations are being put in place to reduce or eliminate the presence of halogens, in particular fluorine, in the final products. [0003] There accordingly remains a need in the art for flame-retardant polycarbonate compositions suitable for thin-wall applications. It would be a further advantage if the compositions were essentially fluorine-free and may achieve a bright white color. SUMMARY [0004] The above-described and other deficiencies of the art are met by a polycarbonate composition including: a linear homopolycarbonate; a branched polycarbonate; a non- fluorinated flame retardant including an organophosphorus flame retardant including a phosphorus-nitrogen bond, a poly(carbonate-siloxane) including greater than 10 wt% to less than or equal to 30 wt% siloxane repeating units, based on the total weight of the poly(carbonate-siloxane), a colorant composition including greater than 4 wt% of titanium dioxide; and optionally, an additive composition; wherein the linear homopolycarbonate, the branched polycarbonate, the non-fluorinated flame retardant, the poly(carbonate-siloxane), the colorant composition, and the optional additive composition total 100 wt%; optionally wherein the composition is essentially fluorine-free; and wherein a sample of the composition has a UL- 94 flammability test rating of V-0 at a thickness of 1.5 mm or thinner. [0005] In another aspect, a method of manufacture includes combining the above- described components to form a polycarbonate composition.
23SHPP0043-WO-PCT (SS230161PCT) [0006] In yet another aspect, an article includes the above-described polycarbonate composition. [0007] In still another aspect, a method of manufacture of an article includes molding, extruding, or shaping the above-described polycarbonate composition into an article. [0008] The above described and other features are exemplified by the following detailed description, examples, and claims. DETAILED DESCRIPTION [0009] Polycarbonates are thermoplastic resins with many desirable properties but are inherently flammable. Current design trends are focused on thinner designs for purposes of slimness, weight reduction, and size reduction of the overall final product, as well as to for the purpose of more complex designs. However, polycarbonates tend to drip when exposed to a flame, and this behavior worsens as the wall thickness decreases. The UL 94 flammability test includes both short flame out times and no dripping of flaming particles as requirements for a V- 0 or V-1 flammability test rating. Conventional low halogen compositions often incorporate fluorine-based anti-drip agents (e.g., TSAN) in order to achieve a UL 94 flammability rating of V0 or V-1. [0010] Other conventional approaches to reduce dripping and improve the flammability test performance include increasing the molecular weight of the resin and/or adding fillers, thus decreasing the flow of the composition. However, decreasing the flow undesirably makes processing difficult. Another conventional approach to minimize or eliminate dripping is to incorporate a branched polycarbonate with reactive end groups that crosslink when the flame is applied during flammability testing. The crosslinking of the resin may decrease the flow of the composition during flammability testing without adversely affecting processing conditions, while decreasing and/or inhibiting formation of drips. However, when branched polycarbonates with reactive end groups are used, a fluorinated flame retardant is still needed in order to achieve a UL 94 V-0 flammability test rating in thin-walled samples. [0011] Given that more stringent regulations are being put in place to reduce or eliminate the addition of halogenated materials, for example, perfluoroalkyl and polyfluoroalkyl substances (PFAS), to the compositions used to make final products, there is a need in the art for polycarbonate compositions that may achieve a V-0 flammability test rating for thin-walled molded articles, thin films, or the like, while also minimizing, preferably eliminating, the addition of PFAS into the polycarbonate compositions used to make the thin-walled molded articles, thin films or the like.
23SHPP0043-WO-PCT (SS230161PCT) [0012] The inventors hereof have discovered that a non-fluorinated flame retardant including an organophosphorus flame retardant including a phosphorus-nitrogen bond and a poly(carbonate-siloxane) including 10-30 wt% siloxane repeating units, based on the total weight of the poly(carbonate-siloxane) may 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 (e.g., TSAN) and fluorinated flame retardants such as Rimar salt may be omitted in the present polycarbonate compositions, thus eliminating added fluorine while providing improved flammability. Advantageously, the polycarbonate compositions may have a UL-94 flammability test rating of V-0 at a thickness of 3.0 mm or thinner (i.e., 2.5 mm, 2.0 mm, or 1.5 mm) and be considered “essentially fluorine-free”. [0013] As used herein, the phrase “essentially fluorine-free” can mean that the amount of fluorine present in the composition from any source (e.g., present in a component used to manufacture the thermoplastic composition, or introduced by contamination, for example cross- contamination during manufacture), is 1500 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. 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 20 ppm (20 mg/kg). Thus, the amount fluorine (from any source) present in the composition is bounded by this detection limit, and may be less than 20 ppm, such that the amount of fluorine in the compositions can be less than 20 ppm to 1500 ppm, less than 20 ppm to 1200 ppm, less than 20 ppm to 1000 ppm, less than 20 ppm to 500 ppm, less than 20 ppm to 400 ppm, less than 20 ppm to 380 ppm, less than 20 ppm to 300 ppm, less than 20 ppm to 200 ppm, less than 20 ppm to 100 ppm, less than 20 ppm to 50 ppm, or less than 20 ppm, each as determined in accordance with ASTM D7359-23. [0014] In some aspects, the amount of calculated intentionally added fluorine present in the composition is 1500 ppm or less, less than 1000 ppm, less than 500 ppm, less than 100 ppm, or less than 50 ppm. “Calculated intentionally added fluorine” refers to the amount of fluorine that is known to be present in the components used to manufacture the compositions and is exclusive of fluorine present as a result of, for example cross-contamination or other manufacturing procedures. For example, if 0.5 wt% encapsulated polytetrafluoroethylene, (e.g., TSAN, which is 50 wt% PTFE and PTFE estimated to have 76 wt% fluorine content), the amount of calculated intentionally added fluorine would equal 1900 ppm. In some aspects, the polycarbonate compositions of the present disclosure may have zero intentionally added fluorine.
23SHPP0043-WO-PCT (SS230161PCT) [0015] In some aspects, the polycarbonate compositions may have a UL-94 flammability test rating of V-0 at a thickness of 3.0 mm or thinner and be considered “essentially halogen- free” per IEC 61249-2-21 or UL 746H. As used herein, the phrase “essentially halogen-free” is as defined by IEC 61249-2-21 or UL 746H. According to International Electrochemical Commission, Restriction Use of Halogen (IEC 61249-2-21), an “essentially halogen-free” composition includes 900 parts per million (ppm) or less of each of chlorine and bromine and also includes 1500 ppm or less of total bromine, chlorine, and fluorine content. According to UL 746H, an “essentially halogen-free” composition includes 900 ppm or less of each of chlorine, bromine, and fluorine and 1500 ppm or less of the total chlorine, bromine, and fluorine content. Each of the added (i.e., intentionally added) bromine, chlorine, and fluorine content may be calculated from the known bromine, chlorine, and fluorine content of the components used to manufacture the thermoplastic compositions or measured by known elemental analysis techniques. Alternatively, the bromine, chlorine, and fluorine content from any source may be measured using known elemental analysis techniques, for example determined in accordance with ASTM D7359-23. [0016] Conventional flame retardants may 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. Non-fluorinated 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-fluorinated 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 flame retardants that are not brominated or chlorinated, but are fluorinated flame retardants 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 anti-drip 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-fluorinated flame retardants that include or exclude halogens may be used in polycarbonate compositions so that the compositions may be considered “essentially halogen-free” per IEC 61249-2-21 or UL 746H. [0017] In addition to minimizing or eliminating intentionally added fluorine from fluorinated additives, the present polycarbonate compositions provide the desired flammability test rating in the presence of a high amount of a colorant composition including titanium dioxide This is advantageous because high loadings of titanium dioxide produce bright white
23SHPP0043-WO-PCT (SS230161PCT) compositions, which are commercially desirable. When a color other than bright white is desired, other colorants or white pigments may be present, which provides added color freedom, allowing for a variety of colors. [0018] The polycarbonate compositions include a linear homopolycarbonate, a branched polycarbonate, a poly(carbonate-siloxane) including greater than 10 wt% to less than or equal to 30 wt% siloxane repeating units, based on the total weight of the poly(carbonate-siloxane), a non-fluorinated flame retardant including an organophosphorus flame retardant including a phosphorus-nitrogen bond (e.g., a phosphazene), and a colorant composition including greater than 4 wt% of titanium dioxide. The individual components of the polycarbonate compositions are described in detail below. [0019] The polycarbonate compositions include a linear homopolycarbonate and a branched polycarbonate. “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 R1 groups contain aromatic moieties and the balance thereof are aliphatic, alicyclic, or aromatic. In an aspect, each R1 is a C6-30 aromatic group, that is, contains at least one aromatic moiety. R1 may be derived from an aromatic dihydroxy compound of the formula HO-R1-OH, in particular of formula (2) HO–A1–Y1–A2–OH (2) wherein each of A1 and A2 is a monocyclic divalent aromatic group and Y1 is a single bond or a bridging group having one or more atoms that separate A1 from A2. In an aspect, one atom separates A1 from A2. Preferably, each R1 may be derived from a bisphenol of formula (3)
wherein Ra and Rb are 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), Xa is a bridging group connecting the two hydroxy-substituted aromatic groups, where the bridging group and the hydroxy substituent of each C6 arylene group are disposed ortho, meta, or para (preferably para) to each other on the C6 arylene group. In an aspect, the bridging group Xa is single bond, - O-, -S-, -S(O)-, -S(O)2-, -C(O)-, or a C1-60 organic group. The organic bridging group may be cyclic or acyclic, aromatic or non-aromatic, and may further include heteroatoms such as
23SHPP0043-WO-PCT (SS230161PCT) halogens, oxygen, nitrogen, sulfur, silicon, or phosphorus. The C1-60 organic group may be disposed such that the C6 arylene groups connected thereto are each connected to a common alkylidene carbon or to different carbons of the C1-60 organic bridging group. In an aspect, p and q is each 1, and Ra and Rb are each a C1-3 alkyl group, preferably methyl, disposed meta to the hydroxy group on each arylene group. [0020] Other useful dihydroxy compounds of the formula HO-R1-OH include aromatic dihydroxy compounds of formula (6)
wherein each Rh is independently a halogen atom, C1-10 hydrocarbyl group such as a C1-10 alkyl, a halogen-substituted C1-10 alkyl, a C6-10 aryl, or a halogen-substituted C6-10 aryl, and n is 0 to 4. The halogen is usually bromine. [0021] 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, 1,1-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)-1,6-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-
23SHPP0043-WO-PCT (SS230161PCT) dihydroxyphenoxathin, 2,7-dihydroxy-9,10-dimethylphenazine, 3,6-dihydroxydibenzofuran, 3,6-dihydroxydibenzothiophene, and 2,7-dihydroxycarbazole, resorcinol, substituted resorcinol compounds such as 5-methyl resorcinol, 5-ethyl resorcinol, 5-propyl resorcinol, 5-butyl resorcinol, 5-t-butyl resorcinol, 5-phenyl resorcinol, 5-cumyl resorcinol, 2,4,5,6-tetrafluoro resorcinol, 2,4,5,6-tetrabromo resorcinol, or the like; catechol; hydroquinone; substituted hydroquinones such as 2-methyl hydroquinone, 2-ethyl hydroquinone, 2-propyl hydroquinone, 2-butyl hydroquinone, 2-t-butyl hydroquinone, 2-phenyl hydroquinone, 2-cumyl hydroquinone, 2,3,5,6-tetramethyl hydroquinone, 2,3,5,6-tetra-t-butyl hydroquinone, 2,3,5,6-tetrafluoro hydroquinone, 2,3,5,6-tetrabromo hydroquinone, or the like, or a combination thereof. [0022] The linear homopolycarbonate may be present, for example, from 10 to 90 wt%, based on the total weight of the polycarbonate composition. Within that range the linear homopolycarbonate may be present from at least 20 wt%, at least 30 wt%, or at least 40 wt% of the total composition, up to and including 65 wt%, up to and including 70 wt%, up to and including 75 wt%, up to and including 80 wt%, or up to and including 85 wt% of the total composition. The linear homopolycarbonate may be present in a range including any of the foregoing limits. [0023] In addition to the linear homopolycarbonate, the polycarbonate compositions include a branched polycarbonate. As used herein, the term “branched” refers to a polymer having statistically more than two end groups or to a polymer including moieties derived from a branching agent. Branched polycarbonates may 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 (1,3,5-tris((p- hydroxyphenyl)isopropyl)benzene), tris-phenol PA (4(4(1,1-bis(p-hydroxyphenyl)-ethyl) alpha, alpha-dimethyl benzyl)phenol), 4-chloroformyl phthalic anhydride, trimesic acid, and benzophenone tetracarboxylic acid. [0024] 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 may become very high upon addition of the branching agent, and to avoid excess viscosity during polymerization, an increased amount of a chain stopper agent may be used, relative to the amount used when the particular branching agent is not
23SHPP0043-WO-PCT (SS230161PCT) present. The amount of chain stopper used is generally above 5 mole percent and less than 20 mole percent compared to the bisphenol monomer. [0025] Such branching agents include aromatic triacyl halides, for example triacyl chlorides of formula (20)
wherein Z is a halogen, C1-3 alkyl, C1-3 alkoxy, C7-12 arylalkylene, C7-12 alkylarylene, or nitro, and z is 0 to 3; a tri-substituted phenol of formula (21)
wherein T is a 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 to 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. [0026] 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 R1 groups in formula (1), the amount of chain stopper, e.g., cyanophenol or para-cumylphenol, and the desired molecular weight of the polycarbonate. In general, the amount of branching agent is effective to provide 0.1 to 10 branching units per 100 R1 units, preferably 0.5 to 8 branching units per 100 R1 units,
23SHPP0043-WO-PCT (SS230161PCT) and more preferably 0.75 to 5 branching units per 100 R1 units. For branching agents having formula (20), the branching agent is present in an amount to provide 0.1 to 10 triester branching units per 100 R1 units, preferably 0.5 to 8, and more preferably 0.75 to 5 triester branching units per 100 R1 units. For branching agents having formula (21), the branching agent is present in an amount effective to provide 0.1 to 10 triphenyl carbonate branching units per 100 R1 units, preferably 0.5 to 8, and more preferably 2.5 to 3.5 triphenylcarbonate units per 100 R1 units. In some aspects, a combination of two or more branching agents may be used. Alternatively, the branching agents may be added at a level of 0.05 to 2.0 wt%. [0027] The branched polycarbonate may be present from 5 wt% to 20 wt% of the total polycarbonate composition. Within this range, the branched polycarbonate may be present from 5 wt% to 15 wt%, 7 wt% to 15 wt% or 7 wt% to 12 wt% of the total polycarbonate composition. [0028] The branched polycarbonate may be present in the polycarbonate compositions in an amount effective to provide 2.0 to 4.5 mol% of branched carbonate repeating units to the total composition, based on the total moles of carbonate repeating units in the polycarbonate composition. Within that range, the branched polycarbonate may be present in an amount effective to provide, for example, at least 2.2 mol%, at least 2.4 mol%, at least 2.5 mol%, at least 2.6 mol%, at least 2.8 mol%, at least 3.0 mol%, at least 3.2 mol%, not more than 4.0 mol%, not more than 4.2 mol%, or not more than 4.4 mol% of branched carbonate repeating units, based on the total moles of carbonate repeating units in the polycarbonate composition. The branched polycarbonate may be present in an amount effective to provide branched carbonate repeating units in a range including any of the foregoing limits. [0029] In an aspect, the polycarbonate is a branched polycarbonate including units as described above; greater than or equal to 3 mol%, based on the total moles of the carbonate repeating units, of moieties derived from a branching agent; and end-capping groups derived from an end-capping agent having a pKa between 8.3 and 11. The branching agent may include trimellitic trichloride, 1,1,1-tris(4-hydroxyphenyl)ethane, or a combination of trimellitic trichloride and 1,1,1-tris(4-hydroxyphenyl)ethane, and the end-capping agent may be 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. [0030] The polycarbonates may have an intrinsic viscosity, as determined in chloroform at 25°C, of 0.3 to 1.5 deciliters per gram (dl/gm), preferably 0.45 to 1.0 dl/gm. The polycarbonates may have a weight average molecular weight (Mw) of 10,000 to 200,000 g/mol,
23SHPP0043-WO-PCT (SS230161PCT) preferably 20,000 to 100,000 g/mol, as measured by gel permeation chromatography (GPC), using a crosslinked styrene-divinylbenzene column using polystyrene standards and calculated for polycarbonate. GPC samples are prepared at a concentration of 1 mg per ml and are eluted at a flow rate of 1.5 ml per minute. When a single linear homopolycarbonate is used, the linear homopolycarbonate may have a weight average molecular weight of at least 25,000 g/mole, or 25,000-40,000 g/mole, preferably 25,000-35,000 g/mole, or 25,000-27,000 g/mole, each as determined by gel permeation chromatography using polystyrene standards and calculated for polycarbonate. When two or more linear homopolycarbonates are used, then the two or more linear homopolycarbonates may have an average weight average molecular weight of at least 25,000 g/mole, or 25,000-40,000 g/mole, preferably 25,000-35,000 g/mole, or 25,000-27,000 g/mole, each as determined by gel permeation chromatography using polystyrene standards and calculated for polycarbonate. The branched polycarbonate may have a weight average molecular weight of at least 25,000 g/mole, or 25,000-40,000 g/mole, preferably 25,000-35,000 g/mole, each as determined by gel permeation chromatography using polystyrene standards and calculated for polycarbonate. 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. [0031] The polycarbonate compositions may include a linear homopolycarbonate (wherein each R1 in the polymer is the same) and/or a branched polycarbonate. In an aspect, the linear homopolycarbonate and/or the branched polycarbonate in the polycarbonate composition is derived from a bisphenol of formula (2), preferably bisphenol A, in which each of A1 and A2 is p-phenylene and Y1 is isopropylidene in formula (2). [0032] In some aspects, the linear homopolycarbonate is a bisphenol A homopolycarbonate and/or the branched polycarbonate is derived from a bisphenol A homopolycarbonate. Bisphenol A homopolycarbonates may have: a melt flow rate of 3-150, per 10 min at 300 ºC and a 1.2 kg load and a Mw of at least 25,000 g/mole to 40,000, g/mole, or at least 25,000 g/mole to 35,000, each as measured as described above. In some aspects, the composition includes a linear bisphenol A homopolycarbonate or a branched polycarbonate derived from a bisphenol A homopolycarbonate. In some aspects, the composition includes a linear bisphenol A homopolycarbonate or a combination of two or more linear bisphenol A homopolycarbonates. When a single linear bisphenol A homopolycarbonate is used, the linear bisphenol A homopolycarbonate may have a weight average molecular weight of at least 25,000 g/mole, or 25,000-40,000 g/mole, preferably 25,000-35,000 g/mole, or 25,000-27,000 g/mole, each as determined by gel permeation chromatography using polystyrene standards and
23SHPP0043-WO-PCT (SS230161PCT) calculated for polycarbonate. When two or more linear bisphenol A homopolycarbonates are used, then the two or more linear bisphenol A homopolycarbonates may have an average weight average molecular weight of at least 25,000 g/mole, or 25,000-40,000 g/mole, preferably 25,000-35,000 g/mole, or 25,000-27,000 g/mole, each as determined by gel permeation chromatography using polystyrene standards and calculated for polycarbonate. [0033] “Polycarbonates” include homopolycarbonates (wherein each R1 in the polymer is the same) and copolymers including different R1 moieties in the carbonate (“copolycarbonates”), and copolymers including carbonate units and other types of polymer units, such as ester units or siloxane units. [0034] The polycarbonate compositions include one or more poly(carbonate-siloxane)s, also referred to in the art as polycarbonate-polysiloxane copolymers. The polysiloxane blocks include repeating diorganosiloxane units as in formula (10)
wherein each R is independently a C1-13 monovalent organic group. For example, R may be a C1- 13 alkyl, C1-13 alkoxy, C2-13 alkenyl, C2-13 alkenyloxy, C3-6 cycloalkyl, C3-6 cycloalkoxy, C6-14 aryl, C6-10 aryloxy, C7-13 arylalkylene, C7-13 arylalkylenoxy, C7-13 alkylarylene, or C7-13 alkylaryleneoxy. The foregoing groups may be fully or partially halogenated with fluorine, chlorine, bromine, or 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 may be used in the same copolymer. [0035] The value of E in formula (10) may vary widely depending on the type and relative amount of each component in the polycarbonate composition, the desired properties of the composition, and like considerations. Generally, E has an average value of 2 to 1,000, preferably 2 to 500, 2 to 200, or 2 to 125, 5 to 80, or 10 to 70. In an aspect, E has an average value of 10 to 80 or 10 to 40, and in still another aspect, E has an average value of 40 to 80, or 40 to 70. Where E is of a lower value, e.g., less than 40, it may be desirable to use a relatively larger amount of the poly(carbonate-siloxane) copolymer. Conversely, where E is of a higher value, e.g., greater than 40, a relatively lower amount of the poly(carbonate-siloxane) copolymer may be used. A combination of a first and a second (or more) poly(carbonate-siloxane) copolymers may be used, wherein the average value of E of the first copolymer is less than the average value of E of the second copolymer. [0036] In an aspect, the polysiloxane blocks are of formula (11)
23SHPP0043-WO-PCT (SS230161PCT)
wherein E and R is each as defined if formula (10); each R may be the same or different and is as defined above; and Ar may be the same or different and is a substituted or unsubstituted C6-30 arylene, wherein the bonds are directly connected to an aromatic moiety. Ar groups in formula (11) may be derived from a C6-30 dihydroxyarylene compound, for example a dihydroxyarylene compound of formula (3) or (6). Dihydroxyarylene compounds are 1,1-bis(4-hydroxyphenyl) methane, 1,1-bis(4-hydroxyphenyl) ethane, 2,2-bis(4-hydroxyphenyl) propane, 2,2-bis(4- hydroxyphenyl) butane, 2,2-bis(4-hydroxyphenyl) octane, 1,1-bis(4-hydroxyphenyl) propane, 1,1-bis(4-hydroxyphenyl) n-butane, 2,2-bis(4-hydroxy-1-methylphenyl) propane, 1,1-bis(4- hydroxyphenyl) cyclohexane, bis(4-hydroxyphenyl sulfide), and 1,1-bis(4-hydroxy-t- butylphenyl) propane. [0037] In another aspect, polysiloxane blocks are of formula (13)
wherein R and E are as described above, and each R5 is 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. R6 in formula (14) is a divalent C2-8 aliphatic group. Each M in formula (14) may be the same or different, and may 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, C6-10 aryl, C6-10 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. [0038] 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; R6 is a dimethylene, trimethylene or tetramethylene; and R is a C1-8 alkyl, haloalkyl such as trifluoropropyl, cyanoalkyl, or aryl such as phenyl, chlorophenyl or tolyl. In another aspect, R is
23SHPP0043-WO-PCT (SS230161PCT) methyl, or a combination of methyl and trifluoropropyl, or a combination of methyl and phenyl. In still another aspect, R is methyl, M is methoxy, n is one, and R6 is a divalent C1-3 aliphatic group. Specific polysiloxane blocks are of the formula
or a combination thereof, wherein E has an average value of 2 to 200, 2 to 125, 5 to 125, 5 to 100, 5 to 50, 20 to 80, or 5 to 20. [0039] Blocks of formula (14) may be derived from the corresponding dihydroxy polysiloxane, which in turn may be prepared effecting a platinum-catalyzed addition between the siloxane hydride and an aliphatically unsaturated monohydric phenol such as eugenol, 2- alkylphenol, 4-allyl-2-methylphenol, 4-allyl-2-phenylphenol, 4-allyl-2-bromophenol, 4-allyl-2-t- butoxyphenol, 4-phenyl-2-phenylphenol, 2-methyl-4-propylphenol, 2-allyl-4,6-dimethylphenol, 2-allyl-4-bromo-6-methylphenol, 2-allyl-6-methoxy-4-methylphenol and 2-allyl-4,6- dimethylphenol. The poly(carbonate-siloxane) copolymers may then be manufactured, for example, by the synthetic procedure of European Patent Application Publication No.0524731 A1 of Hoover, page 5, Preparation 2. [0040] Transparent poly(carbonate-siloxane) copolymers include carbonate units (1) derived from bisphenol A, and repeating siloxane units (14a), (14b), (14c), or a combination thereof (preferably of formula 14a), wherein E has an average value of 4 to 50, 4 to 15, preferably 5 to 15, more preferably 6 to 15, and still more preferably 7 to 10. The transparent copolymers may be manufactured using one or both of the tube reactor processes described in U.S. Patent Application No.2004/0039145A1 or the process described in U.S. Patent No. 6,723,864 may be used to synthesize the poly(carbonate-siloxane) copolymers. [0041] The poly(carbonate-siloxane) copolymers may include 30 to 99 wt% of carbonate units and 1 to 70 wt% siloxane units. In the disclosed polycarbonate compositions, the poly(carbonate-siloxane) copolymer includes 70 wt% to less than 90 wt%, more preferably 75 wt% to 85 wt% of carbonate units and greater than 10 wt% to less than or equal to 30 wt%, more preferably greater than or equal to 15 wt% to 25 wt% siloxane units, each based on the total weight of the poly(carbonate-siloxane).
23SHPP0043-WO-PCT (SS230161PCT) [0042] The poly(carbonate-siloxane) copolymer including greater than 10 wt% to less than or equal to 30 wt% siloxane repeating units may be present in an amount effective to provide up to 10 wt% siloxane repeating units, based on the total polycarbonate composition. The poly(carbonate siloxane) including greater than 10 wt% to less than or equal to 30 wt% siloxane repeating units may be present in an amount effective to provide greater than or equal to 3 wt% to less than or equal to 10 wt% siloxane repeating units, based on the total composition. Within that range, the poly(carbonate siloxane) including greater than 10 wt% to less than or equal to 30 wt% siloxane repeating units may be present in an amount effective to provide at least 3.5 wt%, at least 4.0 wt%, or at least 4.5 wt% siloxane repeating units and less than or equal to 10 wt%, less than or equal to 8 wt%, or less than or equal to 6 wt% siloxane repeating units. The poly(carbonate siloxane) including greater than 10 wt% to less than or equal to 30 wt% siloxane repeating units may be present in an amount effective to provide siloxane repeating units in an amount within a range of any of the foregoing limits. [0043] Some poly(carbonate-siloxane) copolymers may have a siloxane content near the upper end of the 1-70 wt% range, for example, greater than 30 wt% to less than or equal to 70 wt% siloxane repeating units, based on the total weight of the poly(carbonate-siloxane). Within this range, such poly(carbonate-siloxane)s may have a siloxane content of 35 wt% to 70 wt%, or 35 wt% to 65 wt%, or 35 wt% to 55 wt%, or 35 wt% to 45 wt%, based on the total weight of the poly(carbonate siloxane) copolymer. Other poly(carbonate-siloxane) copolymers may have a siloxane content near the lower end of the 1-70 wt% range, for example, less than or equal to 10 wt% siloxane repeating units, based on the total weight of the poly(carbonate-siloxane). Within this range, such poly(carbonate-siloxane)s may have a siloxane content of 1-10 wt%, 2-8 wt%, or 4-8 wt%, each based on the total weight of the poly(carbonate siloxane) copolymer. [0044] Advantageously, the inventors have unexpectedly discovered (and as demonstrated in the Examples) that when the poly(carbonate siloxane) includes from greater than 10 wt% to less than or equal to 30 wt% siloxane repeating units, based on the total weight of the poly(carbonate-siloxane), then the polycarbonate compositions achieve a V-0 rating at a thickness of 1.5 mm. When a poly(carbonate-siloxane) copolymer including greater than 30 wt% to less than or equal to 70 wt% siloxane repeating units was used alone, the desired flame test rating was not achieved. In addition to the poly(carbonate siloxane) including from greater than 10 wt% to less than or equal to 30 wt% siloxane repeating units a poly(carbonate siloxane), additional poly(carbonate siloxanes) may be present, provided that a V-0 rating at 1.5 mm may be achieved.
23SHPP0043-WO-PCT (SS230161PCT) [0045] 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 formula
wherein x is 1 to 200, preferably 5 to 85, preferably 10 to 70, preferably 15 to 65, and more preferably 40 to 60; x is 1 to 500, or 10 to 200, and z is 1 to 1000, or 10 to 800. In an aspect, x is 1 to 200, y is 1 to 90 and z is 1 to 600, and in another aspect, x is 30 to 50, y is 10 to 30 and z is 45 to 600. The polysiloxane blocks may be randomly distributed or controlled distributed among the polycarbonate blocks. [0046] Poly(carbonate-siloxane)s may have a weight average molecular weight of 2,000 to 100,000 g/mol, preferably 5,000 to 50,000 g/mol as measured by gel permeation chromatography using a crosslinked styrene-divinyl benzene column, at a sample concentration of 1 milligram per milliliter, using polystyrene standards and calculated for polycarbonate. [0047] The poly(carbonate-siloxane)s may have a melt volume flow rate, measured at 300°C/2 kg, of 0.1 to 50 cubic centimeters per 10 minutes (cc/10 min), preferably 2 to 30 cc/10 min. Combinations of the poly(carbonate-siloxane)s of different flow properties may be used to achieve the overall desired flow property. [0048] The polycarbonates of the polycarbonate composition may include post- consumer recycled polycarbonate ("PCR-PC"). PCR-PC is derived or recycled from polycarbonate as described herein. PCR-PC may be recovered from a source after consumption. In addition, PCR-PC may 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 may be similar or even identical to the chemical composition of the corresponding original polycarbonate. In one example, the polycarbonate may be derived from an optical disc. In another example, the PCR- PC may 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. One possible difference between the original polycarbonate component used in the composition of the invention 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 may be present as impurities. Additional impurities may include
23SHPP0043-WO-PCT (SS230161PCT) 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 may 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. [0049] The polycarbonate composition may include post-consumer recycled polycarbonate in an amount up to 25 wt%, up to 20 wt%, up to 15 wt%, up to 10 wt%, or up to 5 wt%. [0050] The combination of the polymer components of the composition, in particular the linear homopolycarbonate, the branched polycarbonate, and the poly(carbonate siloxane) including from greater than 10 wt% to less than or equal to 30 wt% siloxane repeating units may have an average weight average molecular weight of at least 25,000 g/mole, or 25,000-40,000 g/mole, preferably 25,000-35,000 g/mole, or 25,000-27,000 g/mole, each as determined by gel permeation chromatography using polystyrene standards and calculated for polycarbonate. [0051] Polycarbonates may be manufactured by processes such as interfacial polymerization and melt polymerization, which are known, and are described, for example, in WO 2013/175448 A1 and WO 2014/072923 A1. An end-capping agent (also referred to as a chain stopper agent or chain terminating agent) may be included during polymerization to provide end groups, for example monocyclic phenols such as phenol, p-cyanophenol, 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, monoesters of diphenols such as resorcinol monobenzoate, functionalized chlorides of aliphatic monocarboxylic acids such as acryloyl chloride and methacryoyl chloride, and mono-chloroformates such as phenyl chloroformate, alkyl-substituted phenyl chloroformates, p-cumyl phenyl chloroformate, and toluene chloroformate. Combinations of different end groups may be used. As mentioned above, branched polycarbonate blocks may be prepared by adding a branching agent during polymerization. [0052] The polycarbonate compositions include a non-fluorinated flame retardant including an organophosphorus flame retardant including a phosphorus-nitrogen bond. In an exemplary aspect, the polycarbonate compositions avoid the use of fluorinated flame retardants such as Rimar salt. Halogenated flame retardants such as brominated polycarbonates may also be omitted from the polycarbonate compositions.
23SHPP0043-WO-PCT (SS230161PCT) [0053] The organophosphorus flame retardant including a phosphorus-nitrogen bond may be a phosphazene, phosphonitrilic chloride, phosphorus ester amide, phosphoric acid amide, phosphonic acid amide, phosphinic acid amide, or tris(aziridinyl) phosphine oxide. These flame-retardant additives are commercially available. In an aspect, the organophosphorus flame retardant containing a phosphorus-nitrogen bond is a phosphazene or cyclic phosphazene of the formulas
wherein w1 is 3 to 10,000; w2 is 3 to 25, or 3 to 7; and each Rw is independently a C1-12 alkyl, alkenyl, alkoxy, aryl, aryloxy, or polyoxyalkylene group. In the foregoing groups at least one hydrogen atom of these groups may be substituted with a group having an N, S, O, or F atom, or an amino group. For example, each Rw may be a substituted or unsubstituted phenoxy, an amino, or a polyoxyalkylene group. Any given Rw may further be a crosslink to another phosphazene group. Exemplary crosslinks include bisphenol groups, for example bisphenol A groups. Examples include phenoxy cyclotriphosphazene, octaphenoxy cyclotetraphosphazene decaphenoxy cyclopentaphosphazene, and the like. In an aspect, the phosphazene has a structure represented by the formula
[0054] 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. [0055] The polycarbonate compositions may include additional organophosphorus flame retardants other than an organophosphorus flame retardant containing a phosphorus-nitrogen bond, provided that the compositions may achieve a UL 94 V-0 flammability test rating at 1.5 mm. Additional organophosphorus flame retardants may include aromatic organophosphorus compounds that have at least one organic aromatic group, the aromatic group may be a substituted or unsubstituted C3-30 group containing one or more of a monocyclic or polycyclic aromatic moiety (which may optionally contain with up to three heteroatoms (N, O, P, S, or Si))
23SHPP0043-WO-PCT (SS230161PCT) and optionally further containing one or more nonaromatic moieties, for example alkyl, alkenyl, alkynyl, or cycloalkyl. The aromatic moiety of the aromatic group may be directly bonded to the phosphorus-containing group, or bonded via another moiety, for example an alkylene group. The aromatic moiety of the aromatic group may be directly bonded to the phosphorus-containing group, or bonded via another moiety, for example an alkylene group. 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. [0056] The phosphorus-containing group of the additional organophosphorus flame retardants may 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 phosphorus-containing groups may be the same or different, provided that at least one R is an aromatic group. A combination of different phosphorus-containing groups may be used. The aromatic group may be directly or indirectly bonded to the phosphorus, or to an oxygen of the phosphorus-containing group (i.e., an ester). [0057] The additional organophosphorus flame retardant may include an oxaphosphorinoxide of the Formula (23) below.
[0058] In Formula (23), the phosphorus atom and one oxygen atom are part of a cyclic structure, for example, a five or six membered ring and q is at least two. Each Ar is independently C6-18 aryl, preferably benzene, which is optionally substituted with a C1-18 hydrocarbyl group, or a C1-18 hydrocarbyloxy group (e.g., -O-hydrocarbyl). When n and p are each 0 and m is 1 (“mono-DOPO” type compounds), then R2 is hydrogen, C1-C18 alkyl, C3-10 cycloalkyl, (C1-6 alkyl)C3-10 cycloalkyl, C6-18 aryl, (C1-6 alkyl)C6-18 aryl, C3-12 heteroaryl, or (C1-6 alkyl)C3-12 heteroaryl. In the foregoing groups at least one hydrogen atom of these groups may be substituted with a group having an N, S, O, or F atom. As used herein, “(C1-6 alkyl)C3-10 cycloalkyl” refers to a cycloalkyl group attached to an alkylene group, “(C1-6 alkyl)C6-18 aryl” refers to an aryl group attached to an alkylene group, and “(C1-6 alkyl)C3-12 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 R10 is
23SHPP0043-WO-PCT (SS230161PCT) hydrogen or C1-6 alkyl, and any methylene is optionally substituted with a group having an N, S, O, or F atom. [0059] In Formula (23), when n and p are each 1 or more and m is 0 (“Di-DOPO” type compounds), then X is C1-C18 alkylidene, C3-10 cycloalkylidene, C6-18 arylene, C3-12 heteroarylene, a group derived from Formula (3), or a group represented by -L1-X’-L2-. The L1 and L2 linker groups are each independently a single bond, C1-C18 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 R10 is hydrogen or C1-6 alkyl, and any methylene is optionally substituted with a group having an N, S, O, or F atom. X’ is C1-C18 alkylidene, C3-10 cycloalkylidene, C6-18 arylene, C3-12 heteroarylene, or a group derived from Formula (3). [0060] Specific examples of an oxaphosphorinoxide include 9,10-dihydro-9-oxo-10- phosphaphenanthrene-10-oxide (23a, “DOPO”), commercially available as from SANKO CO., LTD., under the trade name Sanko-HCA, 3-(6-oxidodibenzo[c,e][1,2]oxaphosphinin-6- yl)propanamide (23b, “AAM-DOPO”), and 6-[(1-oxido-2,6,7-trioxa-1- phosphabicyclo[2.2.2.]oct-4-yl)methoxy-6-oxide (23c, “DOPO-PEPA”).
[0061] A specific formula for a Di-DOPO compound is Formula (24).
wherein Ar1 is C3-18 heteroaryl or C6-18 aryl, each instance of R3 is independently hydrogen, C1-18 alkyl, C3-18 heteroaryl or C6-18 aryl, each instance of R1 is independently C1-18 alkyl, C3-18 heteroaryl or C6-18 aryl, and any hydrogen atom on an aryl or heteroaryl ring may 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. [0062] In an aspect, the additional organophosphorus flame retardant is a monomeric phosphate. Representative monomeric aromatic phosphates are of the formula (GO)3P=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
23SHPP0043-WO-PCT (SS230161PCT) groups may be joined together to provide a cyclic group. In some aspects G corresponds to a monomer used to form the polycarbonate, e.g., resorcinol. Exemplary phosphates include phenyl bis(dodecyl) phosphate, phenyl bis(neopentyl) phosphate, phenyl bis(3,5,5'-trimethylhexyl) phosphate, ethyl diphenyl phosphate, 2-ethylhexyl di(p-tolyl) phosphate, bis(2-ethylhexyl) p- tolyl phosphate, tritolyl phosphate, bis(2-ethylhexyl) phenyl phosphate, tri(nonylphenyl) phosphate, bis(dodecyl) p-tolyl phosphate, dibutyl phenyl phosphate, 2-chloroethyl diphenyl phosphate, p-tolyl bis(2,5,5'-trimethylhexyl) phosphate, 2-ethylhexyl diphenyl phosphate, and the like. A specific aromatic phosphate is one in which each G is aromatic, for example, triphenyl phosphate, tricresyl phosphate, isopropylated triphenyl phosphate, and the like. [0063] Di- or polyfunctional aromatic organophosphorus compounds are also useful, for example, compounds of the formulas
wherein each G1 is independently a C1-30 hydrocarbyl; each G2 is independently a C1-30 hydrocarbyl or hydrocarbyloxy; Xa is as defined in formula (3) or formula (4); each X is independently a bromine or chlorine; m is 0 to 4, and n is 1 to 30. In a specific aspect, Xa is a single bond, methylene, isopropylidene, or 3,3,5-trimethylcyclohexylidene. [0064] Specific aromatic organophosphorus compounds are inclusive of acid esters of formula (9)
wherein each R16 is independently C1-8 alkyl, C5-6 cycloalkyl, C6-20 aryl, or C7-12 arylalkylene, each optionally substituted by C1-12 alkyl, specifically by C1-4 alkyl and X is a mono- or poly- nuclear aromatic C6-30 moiety or a linear or branched C2-30 aliphatic radical, which may be OH- substituted and may contain up to 8 ether bonds, provided that at least one R16 or X is an aromatic group; each n is independently 0 or 1; and q is from 0.5 to 30. In some aspects each R16 is independently C1-4 alkyl, naphthyl, phenyl(C1-4)alkylene, aryl groups optionally substituted by C1-4 alkyl; each X is a mono- or poly-nuclear aromatic C6-30 moiety, each n is 1; and q is from 0.5 to 30. In some aspects each R16 is aromatic, e.g., phenyl; each X is a mono- or poly-nuclear aromatic C6-30 moiety, including a moiety derived from formula (2); n is one; and q is from 0.8 to 15. In other aspects, each R16 is phenyl; X is cresyl, xylenyl, propylphenyl, or butylphenyl,
23SHPP0043-WO-PCT (SS230161PCT) one of the following divalent groups
, or a combination including one or more of the foregoing; n is 1; and q is from 1 to 5, or from 1 to 2. In some aspects at least one R16 or X corresponds to a monomer used to form the polycarbonate, e.g., bisphenol A, resorcinol, or the like. Aromatic organophosphorus compounds of this type include the bis(diphenyl) phosphate of hydroquinone, resorcinol bis(diphenyl phosphate) (RDP), and bisphenol A bis(diphenyl) phosphate (BPADP), and their oligomeric and polymeric counterparts. [0065] In addition to the organophosphorus flame retardant containing a phosphorus- nitrogen bond, inorganic non-fluorinated flame retardants may be used, for example salts of aromatic sulfonates such as sodium benzene sulfonate, sodium toluene sulfonate (NATS), and the like, salts of aromatic sulfone sulfonates such as potassium diphenylsulfone sulfonate (KSS), and the like; salts formed by reacting for example an alkali metal or alkaline earth metal (e.g., lithium, sodium, potassium, magnesium, calcium and barium salts) and an inorganic acid complex salt, for example, an oxo-anion (e.g., alkali metal and alkaline-earth metal salts of carbonic acid, such as Na2CO3, K2CO3, MgCO3, CaCO3, and BaCO3, KSS and NATS, alone or in combination with other non-fluorinated flame retardants, are particularly useful. Exemplary amounts of an aromatic sulfone sulfonate salt may be 0.01 to 1.0 wt%, or 0.1 to 0.6 wt%, based on the total weight of the polycarbonate composition. [0066] The non-fluorinated flame retardant may be present in an amount effective to provide at least 0.3 wt%, at least 0.4 wt%, at least 0.5 wt%, or at least 0.7 wt% phosphorus, less than or equal to 3 wt%, less than or equal to 2.5 wt%, less than or equal to 2.0 wt%, less than or equal to 1.5 wt%, less than or equal to 1.2 wt%, or less than or equal to 1.0 wt% phosphorus, each based on the total weight of the composition. The non-fluorinated flame retardant may be present in an amount effective to provide phosphorus in a range which includes any of the foregoing limits. [0067] The polycarbonate compositions minimize or eliminate conventional anti-drip agents, in particular fluorinated anti-drip agents. Anti-drip agents include, for example, a fibril forming or non-fibril forming fluoropolymer such as polytetrafluoroethylene (PTFE). The anti- drip agent may be encapsulated by a rigid copolymer, for example styrene–acrylonitrile copolymer (SAN). PTFE encapsulated in SAN is known as TSAN. TSAN includes 50 wt% PTFE and 50 wt% SAN, based on the total weight of the encapsulated fluoropolymer. The SAN
23SHPP0043-WO-PCT (SS230161PCT) may include, for example, 75 wt% styrene and 25 wt% acrylonitrile based on the total weight of the copolymer. In some aspects, the fluorinated anti-drip agent is present in an amount effective to provide 0.15 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 compositions include a colorant composition including greater than 4 wt%, or at least 4.5 wt% titanium dioxide. This is an advantage because when present at high loadings, titanium dioxide produces bright white compositions, which are commercially desirable. In some aspects, white pigments other than titanium dioxide may be present in addition to titanium dioxide, provided that the bright white color and a UL 94 V-0 flammability test rating at 1.5 mm are achieved. When a bright white color is not desired, other colorants may present in addition to titanium dioxide, such as, for example white pigments other than titanium dioxide, dyes, and non-white pigments. This provides added color freedom, allowing for a variety of tinted white colors. The colors of the samples of the polycarbonate compositions may be described using the CIE LAB color scale. Test methods used to determine the color properties of the compositions include ASTM 2244, ASTM E308, ASTM, E1164, ASTM E2194, DIN 5033, DIN5036, DIN6174, DIN6175-2, and ISO7724. When a color is expressed in CIELAB, the "L* value" describes the lightness-darkness property. If the L* value is 0, then the object is black. If the L* value is 100, then the object is white. [0002] The polycarbonate compositions may have a non-bright white color. The non- bright white color is expressed by L*, which is measured in reflectance mode using the CIELAB method in accordance with ASTM D2244 at an angle of 10° observer with the specular component included and using the CIE standard daylight illuminant D65. In some aspects, the non-white color capability L* is at least 90.0, and less than 97.0. In some aspects, the non-bright white color capability L* is at least 90.0, and less than 95.0. In the foregoing aspects, titanium dioxide is present in an amount of less than 5 wt%. [0003] The polycarbonate compositions may have a bright white color. The bright white color is expressed by L*, which is measured in reflectance mode using the CIELAB method in accordance with ASTM D2244 at an angle of 10° observer with the specular component included and using the CIE standard daylight illuminant D65. In some aspects, the bright white color capability L* is at least 95.0, preferably at least 97.0. In some aspects, the bright white color capability L* is greater than 97.0. In at least one aspect, the bright white color capability L* is greater than 98.0. In some aspects, the bright white color capability L* ranges from 95.0 to 99.0. In an even further aspect, the bright white color capability L* ranges from 97.0 to 99.0. In a yet further aspect, the bright white color capability L* ranges from 97.0 to 98.5.
23SHPP0043-WO-PCT (SS230161PCT) [0068] The titanium dioxide may have an average particle size of 0.01 to 10 micrometers (µm), specifically 0.05 µm to 1 µm, and more particularly 0.1 µm to 0.6 µm. [0069] White pigments other than titanium dioxide may be present provided that the desired properties, for example, a UL 94 V-0 flammability test rating at 1.5 mm and bright white color capability L* of at least 95.0, preferably at least 97.0, are still achieved. Exemplary white pigments other than titanium dioxide may include zinc sulfide, tin oxide, aluminum oxide, zinc oxide, calcium sulfate, barium sulfate calcium carbonate (e.g., chalk), magnesium carbonate, antimony oxide, white lead (a basic lead carbonate), lithopone (a combination of barium sulfate and zinc sulfide), sodium silicate, aluminum silicate, silicon dioxide, mica, clay, talc, metal doped versions of the foregoing materials, and combinations including at least one of the foregoing materials. [0070] The titanium dioxide and white pigment other than titanium dioxide may include rutile or anatase titanium dioxide, or zinc sulfide, and coated versions thereof such as silanized titanium dioxide. A combination of different types of white pigment may be used. In certain aspects, the white pigments other than titanium dioxide are excluded. [0071] In addition to titanium dioxide and white pigments other than titanium dioxide, other colorants may be present. Colorants such as non-white pigments or dye additives may also be present. Useful pigments may 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. [0072] 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;
23SHPP0043-WO-PCT (SS230161PCT) 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)-1,3,4-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; 1,1'-diethyl-2,2'-carbocyanine iodide; 3,3'-diethyl-4,4',5,5'- dibenzothiatricarbocyanine iodide; 7-dimethylamino-1-methyl-4-methoxy-8-azaquinolone-2; 7- dimethylamino-4-methylquinolone-2; 2-(4-(4-dimethylaminophenyl)-1,3-butadienyl)-3- ethylbenzothiazolium perchlorate; 3-diethylamino-7-diethyliminophenoxazonium perchlorate; 2- (1-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. [0073] The polycarbonate compositions include a colorant composition including greater than 4 wt% of titanium dioxide, preferably at least 4.5 wt% titanium dioxide. Within this range, the titanium dioxide may be present in an amount up to 10 wt%, up to 8 wt%, up to 6.5 wt%, or up to 5.5 wt%. The desired upper limit is dependent on the application for the polycarbonate compositions. In particular, as the loading of titanium dioxide is increased, the impact resistance (e.g., low-temperature impact resistance) of a sample of the polycarbonate composition may be adversely affected and/or the flow could be reduced. The titanium dioxide may be present in a range including any of the foregoing limits. [0074] The polycarbonate compositions may include an additive composition including 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 may be mixed at a suitable time during the mixing of the components for forming the composition. Additives include antioxidants, heat stabilizers, light stabilizers, ultraviolet (UV) light stabilizers, plasticizers, lubricants, mold release agents, antistatic agents, surface effect additives, and radiation stabilizers. A combination of additives may be used, for example a combination of a heat stabilizer, mold release agent, and ultraviolet light stabilizer. In general, the additives are used in the amounts generally known to be effective.
23SHPP0043-WO-PCT (SS230161PCT) For example, the total amount of the additives may be 0.01-10 wt%, 0.01-5 wt%, 0.01-2 wt%, or 0.01-1 wt%, each based on the total weight of the polycarbonate composition. [0075] The polycarbonate compositions may 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 may occur resulting in bromine or chlorine levels typically on the parts per million by weight scale. With this understanding it may be readily appreciated that “ultra-low chlorine or bromine content” may be defined as having a bromine or chlorine content of less than or equal to 100 parts per million by weight (ppm), less than or equal to 75 ppm, or less than or equal to 50 ppm. 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 non-halogenated flame retardant it is based on the total weight of the non-halogenated 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 may 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] In some aspects, the polycarbonate compositions include the poly(carbonate- siloxane) in an amount effective to provide at least 3 wt%, preferably at least 4 wt% siloxane repeating units, based on the total weight of the polycarbonate composition, and the branched polycarbonate in an amount effective to provide 2.0 to 4.5 mol% of branched carbonate repeating units, based on the total moles of carbonate repeating units in the polycarbonate composition. [0078] In some aspects, the polycarbonate compositions include the poly(carbonate- siloxane) is present in an amount effective to provide at least 3 wt%, preferably at least 4 wt% siloxane repeating units, based on the total weight of the polycarbonate composition; and the branched polycarbonate in an amount effective to provide 2.0 to 4.5 mol% of branched carbonate repeating units to the total composition, based on the total moles of carbonate
23SHPP0043-WO-PCT (SS230161PCT) repeating units in the polycarbonate composition; and the polycarbonate composition includes 1500 ppm or less intentionally added fluorine. [0079] In some aspects, the polycarbonate compositions include the non-fluorinated flame retardant including an organophosphorus flame retardant including a phosphorus-nitrogen bond in an amount effective to provide 1 wt% or less phosphorus, based on the total weight of the polycarbonate composition; and the branched polycarbonate in an amount effective to provide 2.0 to 4.5 mol% of branched carbonate repeating units, based on the total moles of carbonate repeating units in the polycarbonate composition. [0080] In the foregoing aspects, the polycarbonate compositions may include the branched polycarbonate in an amount effective to provide 3.0 to 4.5 mol% of branched carbonate repeating units, based on the total moles of carbonate repeating units in the polycarbonate composition. [0081] In some aspects, the polycarbonate compositions include the non-fluorinated flame retardant including an organophosphorus flame retardant including a phosphorus-nitrogen bond in an amount effective to provide 1 wt% or less phosphorus, based on the total weight of the polycarbonate composition; and the branched polycarbonate in an amount effective to provide at least 3 mol% branching, based on the total moles of carbonate repeating units in the polycarbonate composition; and the polycarbonate composition includes 1500 ppm or less calculated intentionally added fluorine. [0082] In any of the foregoing aspects, the calculated added bromine and chlorine content of the polycarbonate composition are each about 900 ppm or less and the calculated total added halogen content of the polycarbonate composition is about 1500 ppm or less; or the calculated added bromine, chlorine, and fluorine content of the polycarbonate composition are each about 900 ppm or less and the calculated total added bromine, chlorine, and fluorine content of the polycarbonate composition is about 1500 ppm or less. [0083] In some aspects, polycarbonate composition excludes intentionally added fluorine. [0084] In some aspects, the polycarbonate compositions include: a linear homopolycarbonate; a branched polycarbonate present in an amount effective to provide at least 3 mol% branching, based on the total moles of carbonate repeating units in the polycarbonate composition; a non-fluorinated flame retardant including an organophosphorus flame retardant including a phosphorus-nitrogen bond present in an amount effective to provide 1 wt% or less phosphorus, based on the total weight of the polycarbonate composition, a poly(carbonate- siloxane) including greater than 10 to less than or equal to 30 wt% siloxane repeating units,
23SHPP0043-WO-PCT (SS230161PCT) preferably 15-25 wt% siloxane repeating units, based on the total weight of the poly(carbonate- siloxane), present in an amount effective to provide at least 3 wt%, preferably at least 4 wt% siloxane repeating units, based on the total weight of the polycarbonate composition; a colorant composition including at least 4.5 wt% of titanium dioxide; and optionally, an additive composition; wherein the linear homopolycarbonate, the branched polycarbonate, the non- fluorinated flame retardant, the poly(carbonate-siloxane), the colorant composition, and the optional additive composition total 100 wt%; wherein a sample of the composition has a UL-94 flammability test rating of V-0 at a thickness of 1.5 mm or thinner; and wherein a sample of the composition has a bright white color, characterized by an L* of at least 95.0, preferably at least 97.0, according to ASTM D2244. [0085] The polycarbonate compositions may be manufactured by various methods. For example, powdered polycarbonates, non-halogenated flame retardant, and/or optional components are first blended, optionally with fillers in a HENSCHEL-Mixer high speed mixer. Other low shear processes, including but not limited to hand mixing, may also accomplish this blending. The blend is then fed into the throat of a twin-screw extruder via a hopper. Alternatively, at least one of the components may be incorporated into the composition by feeding directly into the extruder at the throat or downstream through a sidestuffer. Additives may also be compounded into a masterbatch with a desired polymeric polymer and fed into the extruder. The extruder is generally operated at a temperature higher than that necessary to cause the composition to flow. The extrudate is immediately quenched in a water bath and pelletized. The pellets so prepared may be one-fourth inch long or less as desired. Such pellets may be used for subsequent molding, shaping, or forming. [0086] A sample of the polycarbonate composition may have a flammability test rating of V-0, as measured according to UL-94 at a thickness of 1.5 millimeter or less, such as 1.2 millimeter, 1.0 millimeter, 0.8 millimeter, and 0.6 millimeter. [0087] Shaped, formed, or molded articles including the polycarbonate compositions are also provided. The polycarbonate compositions may be molded into useful shaped articles by a variety of methods, such as injection molding, extrusion, rotational molding, blow molding and thermoforming. Some examples of articles include computer and business machine housings such as housings for monitors, handheld electronic device housings such as housings for cell phones, electrical connectors, and components of lighting fixtures, ornaments, home appliances, roofs, greenhouses, sun rooms, swimming pool enclosures, and the like. 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
23SHPP0043-WO-PCT (SS230161PCT) metallized article. In addition, the polycarbonate compositions may be used for such applications as a molded housing and other devices such as electrical circuit housing. [0088] Thin films including the polycarbonate compositions are also provided. The thin film of the polycarbonate composition may be prepared by extrusion of the polycarbonate composition. [0089] This disclosure is further illustrated by the following examples, which are non- limiting. EXAMPLES [0090] The following components are used in the examples. Unless specifically indicated otherwise, the amount of each component is in wt%, based on the total weight of the composition. [0091] The materials shown in Table 1 were used. Table 1. PC-1 Linear amorphous bisphenol A polycarbonate (BPA) homopolymer produced by interfacial polymerization (Mw 29,000-31,000 g/mol, using polystyrene standards and calculated for SABIC polycarbonate) PC-2 Linear amorphous BPA homopolymer produced by interfacial polymerization (Mw 20,000- SABIC 22,000, using polystyrene standards and calculated for polycarbonate) Br PC Branched, cyanophenol end-capped bisphenol A homopolycarbonate produced via SABIC interfacial polymerization, containing 3 mol% 1,1,1-tris(4-hydroxyphenyl)ethane (THPE) branching agent (Mw=29,000-31,000 g/mol, using polystyrene standards and calculated for polycarbonate) SiPC20 PDMS – bisphenol A copolycarbonate, 20 wt% siloxane, average PDMS block length of 45 SABIC units, Mw = 29,500 to 30,500 g/mol as determined by GPC using BPA polycarbonate standards, p-cumylphenol end-capped SiPC40 PDMS – bisphenol A copolycarbonate, 40 wt% siloxane, average PDMS block length of 45 SABIC units, Mw = 37,000 to 38,000 g/mol as determined by GPC using BPA polycarbonate standards, p-cumylphenol end-capped PPZ Phenoxy phosphazene, 13.94 wt% phosphorus Fushimi TiO2 Titanium dioxide CAS# 13463-67-7 KRONOS STAB Tris(2,6 di tert-butylphenyl)phosphite (IRGAFOS 168) BASF [0092] The testing samples were prepared as described below and the following test methods were used. [0093] Typical compounding procedures are described as follows: The various formulations were prepared by direct dry-blending of the raw materials and pre-blended and then extruded using a twin-screw extruder. The composition was melt-kneaded, extruded, cooled through a water bath, and pelletized. A typical extrusion profile is listed in Table 2. Table 2. Parameters Unit Typical values Feed °C 37 Zone 1 Temp °C 200 Zone 2 Temp °C 240 Zone 3 Temp °C 260
23SHPP0043-WO-PCT (SS230161PCT) Zone 4-9 Temp °C 276 Screw Speed Rpm 425 Throughput kg/hr 80 Torque % 70 [0094] An Engel 45 molding machine was used to mold the test parts for standard physical property testing. The parameters are provided in Table 3. Table 3. Parameters Unit Conditions Drying Temperature °C 120 Drying Time Hrs 3-4 Hopper temperature °C 100 Nozzle Temperature °C 290-310 Rear - Zone 1 Temperature °C 270-295 Middle - Zone 2 Temperature °C 280-305 Front - Zone 3 Temperature °C 295-315 [0095] Sample preparation and testing methods are described in Table 4. Table 4. Property Standard Conditions Specimen Type Flammability UL 94 Vertical Burning Flame Bar [0096] Flammability tests were performed on samples at a thickness of 1.5 mm, 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 5. Total flame-out-times for all 5 bars (FOT = t1 + t2) were determined. V-ratings were obtained for every set of 5 bars. Table 5. UL 94 Rating t1 and/or t2 5-bar FOT burning drips V-0 <10 <50 no V1 <30 <250 no V2 <30 <250 yes N.R. (no rating) >30 >250 Examples 1-8 [0097] Table 6 shows the compositions and properties for the following comparative examples and examples. Comparative examples are indicated with an asterisk. Table 6. Unit 1* 2* 3* 4* 5 6 7 8 PC-1 wt% 37.99 46.79 46.49 45.29 36.05 34.85 34.55 39.53 PC-2 wt% 30 20 20 20 20 20 20 20 Br-PC wt% 11 11 11 11 11 11 11 11 PC-Si-20 wt% 23.87 23.87 23.87 23.87 PC-Si-40 wt% 11.93 11.93 11.93 11.93 TiO2 wt% 5 5 6.5 6.5 5 5 6.5 6.5 STAB wt% 0.08 0.08 0.08 0.08 0.08 0.08 0.08 0.08 PPZ wt% 4 5.2 4 5.2 4 5.2 4 5.2 Total wt% 100 100 100 100 100 100 100 100
23SHPP0043-WO-PCT (SS230161PCT) Phosphorus wt% 0.56 0.73 0.56 0.73 0.56 0.73 0.56 0.73 Siloxane wt% 4.77 4.77 4.77 4.77 4.77 4.77 4.77 4.77 UL 94, 1.5 mm N.R. N.R. V-1 V-1 V-0 V-0 V-0 V-0 [0098] The compositions of Table 6 include a combination of BPA homopolycarbonates and a branched polycarbonate. Comparative Examples 1-4 include a poly(carbonate siloxane) including 40 wt% siloxane repeating units. Comparative Examples 1-2 include 5 wt% TiO2 and achieve a N.R. flammability test rating at 1.5 mm. Increasing the wt% of TiO2 from 5 wt% to 6.5 wt% resulted in an improvement on the flame test rating, when the flame retardant loading was increased from 4 to 5.2 wt% (compare Comparative Examples 3-4 with 1-2, respectively). Examples 5-8 include a poly(carbonate siloxane) including 20 wt% siloxane repeating units. When the amount of TiO2 was increased from 5 to 6.5 wt%, the flammability test rating at 1.5 mm thickness was not affected. All of the compositions of Table 6 include the same siloxane content. Comparison of Examples 5-8 with Comparative Examples 1-4 demonstrate that the presence of poly(carbonate siloxane) having 20 wt% maintains the desired V-0 flammability test rating at 1.5 mm and a loading of TiO2 exceeding 5 wt%, based on the total composition. [0099] This disclosure further encompasses the following aspects. [0100] Aspect 1. A polycarbonate composition comprising: a linear homopolycarbonate; a branched polycarbonate; a non-fluorinated flame retardant comprising an organophosphorus flame retardant comprising a phosphorus-nitrogen bond, a poly(carbonate-siloxane) comprising greater than 10 wt% to less than or equal to 30 wt% siloxane repeating units, based on the total weight of the poly(carbonate-siloxane), a colorant composition comprising greater than 4 wt% of titanium dioxide; and optionally, an additive composition; wherein the linear homopolycarbonate, the branched polycarbonate, the non-fluorinated flame retardant, the poly(carbonate-siloxane), the colorant composition, and the optional additive composition total 100 wt%; and wherein a sample of the composition has a UL-94 flammability test rating of V-0 at a thickness of 1.5 mm or thinner. Optionally in this aspect, the composition is essentially fluorine-free. [0101] Aspect 2. The polycarbonate composition of any one of the preceding aspects comprising 5-20 wt% of a branched polycarbonate, preferably wherein the branched polycarbonate includes bisphenol A carbonate units, more preferably wherein only bisphenol carbonate units are present in the branched polycarbonate. [0102] Aspect 2a. The polycarbonate composition of any one of the preceding aspects comprising 10-90
of the linear homopolycarbonate.
23SHPP0043-WO-PCT (SS230161PCT) [0103] Aspect 2b. The polycarbonate composition of any one of the preceding aspects wherein the linear homopolycarbonate is a linear bisphenol A homopolycarbonate. [0104] Aspect 2c. The polycarbonate composition of any one of the preceding aspects, wherein the branched polycarbonate is derived from a bisphenol A homopolycarbonate. [0105] Aspect 2d. The polycarbonate composition of Aspect 3, wherein the linear homopolycarbonate is a linear bisphenol A homopolycarbonate. [0106] Aspect 3. The polycarbonate composition of any one of the preceding claims, wherein the composition is essentially fluorine-free. [0107] Aspect 4. The polycarbonate composition of any one of the preceding aspects, wherein a sample of the composition has a bright-white color, characterized by an L* of at least 95.0, preferably at least 97.0, according to ASTM D2244. [0108] Aspect 5. The polycarbonate composition of any one of the preceding aspects, wherein the poly(carbonate-siloxane) is present in an amount effective to provide at least 3 wt%, preferably at least 4 wt% siloxane repeating units, based on the total weight of the polycarbonate composition. [0109] Aspect 6. The polycarbonate composition of any one of the preceding aspects, wherein: the poly(carbonate-siloxane) is present in an amount effective to provide at least 3 wt%, preferably at least 4 wt% siloxane repeating units, based on the total weight of the polycarbonate composition, and the branched polycarbonate is present in an amount effective to provide 2.0 to 4.5 mol% of branched carbonate repeating units, based on the total moles of carbonate repeating units in the polycarbonate composition. [0110] Aspect 7. The polycarbonate composition of any one of the preceding aspects, wherein: the poly(carbonate-siloxane) is present in an amount effective to provide at least 3 wt%, preferably at least 4 wt% siloxane repeating units, based on the total weight of the polycarbonate composition; and the branched polycarbonate is present in an amount effective to provide 2.0 to 4.5 mol% of branched carbonate repeating units to the total composition, based on the total moles of carbonate repeating units in the polycarbonate composition; and the polycarbonate composition comprises 1500 ppm or less intentionally added fluorine, preferably wherein the composition is essentially fluorine-free. [0111] Aspect 8. The polycarbonate composition of any one of the preceding aspects, wherein: the non-fluorinated flame retardant comprising an organophosphorus flame retardant comprising a phosphorus-nitrogen bond is present in an amount effective to provide 1 wt% or less phosphorus, based on the total weight of the polycarbonate composition; and the branched polycarbonate is present in an amount effective to provide 2.0 to 4.5 mol% of branched
23SHPP0043-WO-PCT (SS230161PCT) carbonate repeating units, based on the total moles of carbonate repeating units in the polycarbonate composition. [0112] Aspect 8a. The polycarbonate composition of any one of Aspects 6-8, wherein the branched polycarbonate is present in an amount effective to provide 3.0 to 4.5 mol% of branched carbonate repeating units, based on the total moles of carbonate repeating units in the polycarbonate composition. [0113] Aspect 9. The polycarbonate composition of any one of the preceding aspects, wherein: the non-fluorinated flame retardant comprising an organophosphorus flame retardant comprising a phosphorus-nitrogen bond is present in an amount effective to provide 1 wt% or less phosphorus, based on the total weight of the polycarbonate composition; and the branched polycarbonate is present in an amount effective to provide at least 3 mol% branching, based on the total moles of carbonate repeating units in the polycarbonate composition; and the polycarbonate composition comprises 1500 ppm or less calculated intentionally added fluorine. [0114] Aspect 10. The polycarbonate composition of any one of the preceding aspects, wherein: the bromine and chlorine content of the polycarbonate composition are each about 900 ppm or less as determined in accordance with ASTM D7359-23 and the total halogen content of the polycarbonate composition is about 1500 ppm or less as determined in accordance with ASTM D7359-23; or the calculated added bromine and chlorine content of the polycarbonate composition are each about 900 ppm or less and the calculated total added halogen content of the polycarbonate composition is about 1500 ppm or less; or the calculated added bromine, chlorine, and fluorine content of the polycarbonate composition are each about 900 ppm or less and the calculated total added bromine, chlorine, and fluorine content of the polycarbonate composition is about 1500 ppm or less. [0115] Aspect 11. The polycarbonate composition of any one of the preceding aspects, wherein the polycarbonate composition excludes intentionally added fluorine. [0116] Aspect 12. The polycarbonate composition of any one of the preceding aspects, comprising: a linear homopolycarbonate; a branched polycarbonate present in an amount effective to provide at least 3 mol% branching, based on the total moles of carbonate repeating units in the polycarbonate composition; a non-fluorinated flame retardant comprising an organophosphorus flame retardant comprising a phosphorus-nitrogen bond present in an amount effective to provide 1 wt% or less phosphorus, based on the total weight of the polycarbonate composition, a poly(carbonate-siloxane) comprising greater than 10 to less than or equal to 30 wt% siloxane repeating units, preferably 15-25 wt% siloxane repeating units, based on the total weight of the poly(carbonate-siloxane), present in an amount effective to provide at least 3 wt%,
23SHPP0043-WO-PCT (SS230161PCT) preferably at least 4 wt% siloxane repeating units, based on the total weight of the polycarbonate composition; a colorant composition comprising at least 4.5 wt% of titanium dioxide; and optionally, an additive composition; wherein the linear homopolycarbonate, the branched polycarbonate, the non-fluorinated flame retardant, the poly(carbonate-siloxane), the colorant composition, and the optional additive composition total 100 wt%; wherein a sample of the composition has a UL-94 flammability test rating of V-0 at a thickness of 1.5 mm or thinner; and wherein a sample of the composition has a bright white color, characterized by an L* of at least 95.0, preferably at least 97.0, according to ASTM D2244. [0117] Aspect 12 a. The polycarbonate composition of any one of the preceding aspects comprising 5-20 wt% of a branched polycarbonate. [0118] Aspect 12b. The polycarbonate composition of any one of the preceding aspects comprising 10-90 wt% linear homopolycarbonate. [0119] Aspect 12c. The polycarbonate composition of any one of the preceding aspects wherein the linear homopolycarbonate is a linear bisphenol A homopolycarbonate. [0120] Aspect 12d. The polycarbonate composition of any one of the preceding aspects, wherein the branched polycarbonate is derived from a bisphenol A homopolycarbonate. [0121] Aspect 12e. The polycarbonate composition of any one of the preceding aspects, wherein the linear homopolycarbonate is a linear bisphenol A homopolycarbonate and the branched polycarbonate is derived from a bisphenol A homopolycarbonate. [0122] Aspect 13. A method of making the polycarbonate composition of any one of aspects 1 to 12, the method comprising melt-mixing the components of the composition, and, optionally, extruding the composition. [0123] Aspect 14. An article comprising the polycarbonate composition of any one of the preceding aspects. [0124] Aspect 15. A method for forming the article according to aspect 14, comprising molding, casting, or extruding the composition to provide the article. [0125] The compositions, methods, and articles may alternatively include, consist of, or consist essentially of, any appropriate materials, steps, or components herein disclosed. The compositions, methods, and articles may additionally, or alternatively, be formulated so as to be devoid, or substantially free, of any materials (or species), steps, or components, that are otherwise not necessary to the achievement of the function or objectives of the compositions, methods, and articles. [0126] 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,
23SHPP0043-WO-PCT (SS230161PCT) 5 wt% to 20 wt%”, is inclusive of the endpoints and all intermediate values of the ranges of “5 wt% to 25 wt%”, etc.). “Combinations” is inclusive of blends, mixtures, alloys, reaction products, and the like. The terms “first”, “second”, and the like, do not denote any order, quantity, or importance, but rather are used to distinguish one element from another. The terms “a” and “an” and “the” do not denote a limitation of quantity and are to be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. “Or” means “and/or” unless clearly stated otherwise. Reference throughout the specification to “some aspects”, “an aspect”, and so forth, means that a particular element described in connection with the aspect is included in at least one aspect described herein, and may or may not be present in other aspects. In addition, it is to be understood that the described elements may be combined in any suitable manner in the various aspects. A “combination thereof” is open and includes any combination including at least one of the listed components or properties optionally together with a like or equivalent component or property not listed [0127] 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. [0128] 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. [0129] Compounds are described using standard nomenclature. For example, any position not substituted by any indicated group is understood to have its valency filled by a bond as indicated, or a hydrogen atom. A dash ("-") that is not between two letters or symbols is used to indicate a point of attachment for a substituent. For example, -CHO is attached through carbon of the carbonyl group. [0130] 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-
23SHPP0043-WO-PCT (SS230161PCT) )). “Cycloalkylene” means a divalent cyclic alkylene group, -CnH2n-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 may be present. The prefix “hetero” means that the compound or group includes at least one ring member that is a heteroatom (e.g., 1, 2, or 3 heteroatom(s)), wherein the heteroatom(s) is each independently N, O, S, Si, or P. “Substituted” means that the compound or group is substituted with at least one (e.g., 1, 2, 3, or 4) substituents that 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. [0131] While particular embodiments have been described, alternatives, modifications, variations, improvements, and substantial equivalents that are or may be presently unforeseen may arise to applicants or others skilled in the art. Accordingly, the appended claims as filed and as they may be amended are intended to embrace all such alternatives, modifications variations, improvements, and substantial equivalents.