Patent Description:
Polycarbonates are useful in the manufacture of articles and components for a wide range of applications, from automotive parts to electronic appliances. Because of their broad use, particularly in electronic components such as chargers, it is desirable to provide polycarbonates with improved flame retardance. <CIT> discloses polycarbonate compositions comprising high-heat copolycarbonate, bisphenol A homopolycarbonate, poly(carbonatesiloxane), and a sulfonate flame retardant.

There accordingly remains a need in the art for impact resistant high-heat polycarbonate compositions that have improved flame retardance. It would be a further advantage if the compositions had improved low-temperature impact resistance.

The above-described and other deficiencies of the art are met by a polycarbonate composition comprising: a high-heat copolycarbonate derived from a high-heat bisphenol monomer and optionally a low heat bisphenol A monomer, wherein the high-heat bisphenol monomer is a monomer where the corresponding homopolycarbonate of the monomer has a glass transition temperature of <NUM> or higher as determined per ASTM D3418 with a <NUM> per minute heating rate; a poly(carbonate-siloxane) having <NUM>-<NUM> wt% siloxane content, based on the total weight of the poly(carbonate-siloxane); a homopolycarbonate; a flame retardant, wherein the flame retardant is not a phosphorous-containing flame retardant; and optionally, an additive composition, wherein a molded sample having a thickness of <NUM> millimeters has a notched Izod Impact of at least <NUM> joules per meter at -<NUM> according to ASTM D <NUM>.

In another aspect, a method of manufacture comprises combining the above-described components to form a polycarbonate composition.

In yet another aspect, an article comprises the above-described polycarbonate composition.

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

The inventors hereof have discovered a polycarbonate composition having a combination of low-temperature impact resistance, thermal resistance, and flame retardance. The polycarbonate compositions include a high-heat copolycarbonate derived from a high-heat bisphenol monomer and optionally a low heat bisphenol A monomer; a poly(carbonate-siloxane) having <NUM>-<NUM> wt% siloxane content, based on the total weight of the poly(carbonate-siloxane); a homopolycarbonate; a flame retardant, wherein the flame retardant is not a phosphorous-containing flame retardant; and optionally, an additive composition. Surprisingly and unexpectedly, although the siloxane content based on the total weight of the composition was the same, superior low-temperature impact performance was observed for compositions that include poly(carbonate-siloxane) having <NUM>-<NUM> wt% siloxane content as compared with compositions that include poly(carbonate-siloxane)s with lower siloxane content (e.g., less than <NUM> wt% siloxane). Advantageously, for polycarbonate compositions wherein the high-heat polycarbonate was derived from <NUM>-phenyl-<NUM>,<NUM>'-bis(<NUM>-hydroxyphenyl) phthalimidine can provide the desired combination of properties, for example, a UL-<NUM> flame test rating of V0 at a thickness of <NUM> millimeter (mm) and superior thermal and low-temperature impact properties, as compared to a compositions wherein the high-heat polycarbonate was derived from <NUM>,<NUM>-bis(<NUM>-hydroxyphenyl)-<NUM>,<NUM>,<NUM>-trimethyl-cyclohexane.

The individual components of the polycarbonate compositions are described in further detail below.

"Polycarbonate" as used herein means a polymer having repeating structural carbonate units of formula (<NUM>)
<CHM>
in which at least <NUM> percent of the total number of R<NUM> groups contain aromatic moieties and the balance thereof are aliphatic, alicyclic, or aromatic. In an aspect, each R<NUM> is a C<NUM>-<NUM> aromatic group, that is, contains at least one aromatic moiety. R<NUM> can be derived from an aromatic dihydroxy compound of the formula HO-R<NUM>-OH, in particular of formula (<NUM>).

wherein each of A<NUM> and A<NUM> is a monocyclic divalent aromatic group and Y<NUM> is a single bond or a bridging group having one or more atoms that separate A<NUM> from A<NUM>. In an aspect, one atom separates A<NUM> from A<NUM>. Preferably, each R<NUM> can be derived from a bisphenol of formula (<NUM>)
<CHM>
wherein Ra and Rb are each independently a halogen, C<NUM>-<NUM> alkoxy, or C<NUM>-<NUM> alkyl, and p and q are each independently integers of <NUM> to <NUM>. It will be understood that when p or q is less than <NUM>, the valence of each carbon of the ring is filled by hydrogen. Also in formula (<NUM>), Xa is a bridging group connecting the two hydroxy-substituted aromatic groups, where the bridging group and the hydroxy substituent of each C<NUM> arylene group are disposed ortho, meta, or para (preferably para) to each other on the C<NUM> arylene group. In an aspect, the bridging group Xa is single bond, - O-, -S-, -S(O)-, -S(O)<NUM>-, -C(O)-, or a C<NUM>-<NUM> organic group. The organic bridging group can be cyclic or acyclic, aromatic or non-aromatic, and can further comprise heteroatoms such as halogens, oxygen, nitrogen, sulfur, silicon, or phosphorous. The <NUM>-<NUM> organic group can be disposed such that the C<NUM> arylene groups connected thereto are each connected to a common alkylidene carbon or to different carbons of the C<NUM>-<NUM> organic bridging group. In an aspect, p and q is each <NUM>, and Ra and Rb are each a C<NUM>-<NUM> alkyl group, preferably methyl, disposed meta to the hydroxy group on each arylene group.

The polycarbonates in the polycarbonate compositions include a homopolycarbonate (wherein each R<NUM> in the polymer is the same), a high-heat polycarbonate, and a poly(carbonate-siloxane). In an aspect, he homopolycarbonate in the polycarbonate composition is derived from a bisphenol of formula (<NUM>), preferably bisphenol A, in which each of A<NUM> and A<NUM> is p-phenylene and Y<NUM> is isopropylidene in formula (<NUM>). The homopolycarbonate may have an intrinsic viscosity, as determined in chloroform at <NUM>, of <NUM>-<NUM> deciliters per gram (dl/gm), preferably <NUM>-<NUM> dl/gm. The homopolycarbonate may have a weight average molecular weight (Mw) of <NUM>,<NUM>-<NUM>,<NUM> grams per mol (g/mol), preferably <NUM>,<NUM>-<NUM>,<NUM>/mol, as measured by gel permeation chromatography (GPC), using a crosslinked styrenedivinylbenzene column and polystyrene standards calculated for polycarbonate. GPC samples are prepared at a concentration of <NUM> per ml and are eluted at a flow rate of <NUM> per minute. As used herein, "using polystyrene standards and calculated for polycarbonate" refers to measurement of the retention time by GPC, fitting the retention time value to a curve for polystyrene and calculating the molecular weight for polycarbonate. In some aspects, the homopolycarbonate is a bisphenol A homopolycarbonate having an Mw of <NUM>,<NUM>-<NUM>,<NUM> grams/mole, preferably <NUM>,<NUM>-<NUM>,<NUM>/mol; or a bisphenol A homopolycarbonate having a weight average molecular weight of <NUM>,<NUM>-<NUM>,<NUM>/mol, preferably <NUM>,<NUM>-<NUM>,<NUM>/mol; or a combination thereof, each as measured as described above.

The homopolycarbonate may be present, for example, from <NUM>-<NUM> wt%, <NUM>-<NUM> wt%, <NUM>-<NUM> wt%, <NUM>-<NUM> wt%, <NUM>-<NUM> wt%, or <NUM>-<NUM> wt% each based on the total weight of the composition.

The polycarbonate compositions include a high-heat polycarbonate, which as used herein means a polycarbonate having a glass transition temperature (Tg) of <NUM> or higher, determined per ASTM D3418 with a <NUM>/min heating rate. The high-heat polycarbonate includes a high-heat carbonate group, optionally together with a low heat carbonate group. A combination of different high-heat groups or low heat groups can be used.

The low heat carbonate group can be derived from bisphenols of formula (<NUM>) as described above wherein Xa is a C<NUM>-<NUM> bridging group.

The low heat bisphenol group can be of formula (<NUM>)
<CHM>
wherein Ra and Rb are each independently a halogen, C<NUM>-<NUM> alkoxy, or C<NUM>-<NUM> alkyl, c is <NUM> to <NUM>, and p and q are each independently integers of <NUM> or <NUM>. In an aspect, p and q is each <NUM>, or p and q is each <NUM> and Ra and Rb are each a methyl, disposed meta to the hydroxy group on each arylene group. Xa in formula (<NUM>) is a bridging group connecting the two hydroxy-substituted aromatic groups, where the bridging group and the hydroxy substituent of each C<NUM> arylene group are disposed ortho, meta, or para (preferably para) to each other on the C<NUM> arylene group, for example, a single bond, -O-, -S-, -S(O)-, -S(O)<NUM>-, -C(O)-, or a C<NUM>-<NUM> organic group, which can be cyclic or acyclic, aromatic or non-aromatic, and can further comprise heteroatoms such as halogens, oxygen, nitrogen, sulfur, silicon, or phosphorous. For example, Xa can be a C<NUM>-<NUM> cycloalkylidene, a C<NUM>-<NUM> alkylidene of the formula -C(Rc)(Rd) - wherein Rc and Rd are each independently hydrogen, C<NUM>-<NUM> alkyl, or a group of the formula -C(=Re)- wherein Re is a divalent C<NUM>-<NUM> hydrocarbon group. Some illustrative examples of dihydroxy compounds that can be used in the manufacture of the low heat monomer units are described, for example, in <CIT>, <CIT>, and <CIT>.

In an aspect, the low heat monomer is bisphenol A, which provides the low heat group of formula (3a).

The high-heat bisphenol group is derived from a high-heat bisphenol monomer having at least <NUM> carbon atoms. As used herein, a high-heat bisphenol monomer is a monomer where the corresponding homopolycarbonate of the monomer has a glass transition temperature (Tg) of <NUM> or higher.

Examples of such high-heat bisphenol groups include groups of formulas (<NUM>) to (<NUM>)
<CHM>
<CHM>
<CHM>
wherein Rc and Rd are each independently a C<NUM>-<NUM> alkyl, C<NUM>-<NUM> alkenyl, C<NUM>-<NUM> cycloalkyl, or C<NUM>-<NUM> alkoxy, each Rf is hydrogen or both Rf together are a carbonyl group, each R<NUM> is independently C<NUM>-<NUM> alkyl, R<NUM> is hydrogen, C<NUM>-<NUM> alkyl, or phenyl optionally substituted with <NUM> to <NUM> C<NUM>-<NUM> alkyl groups, R<NUM> is independently C<NUM>-<NUM> alkyl, or phenyl, preferably methyl, Xa is a C<NUM>-<NUM> polycyclic aryl, C<NUM>-<NUM> mono- or polycycloalkylene, C<NUM>-<NUM> mono- or polycycloalkylidene, - C(Rf)(Rg)- wherein Rf is hydrogen, C<NUM>-<NUM> alkyl, or C<NUM>-<NUM> aryl and Rg is C<NUM>-<NUM> alkyl, C<NUM>-<NUM> cycloalkyl, or C<NUM>-<NUM> aryl, or -(Qa)x-G-(Qb)y- group, wherein Qa and Qb are each independently a C<NUM>-<NUM> alkylene, G is a C<NUM>-<NUM> cycloalkylene, x is <NUM> or <NUM>, and y is <NUM> or <NUM>, and j, m, and n are each independently <NUM> to <NUM>. A combination of high-heat bisphenol groups can be used.

In an aspect, Rc and Rd are each independently a C<NUM>-<NUM> alkyl, or C<NUM>-<NUM> alkoxy, each R<NUM> is methyl, each R<NUM> is independently C<NUM>-<NUM> alkyl, R<NUM> is methyl, or phenyl, each R<NUM> is independently C<NUM>-<NUM> alkyl, or phenyl, preferably methyl, Xa is a C<NUM>-<NUM> polycyclic aryl, C<NUM>-<NUM> mono- or polycycloalkylene, C<NUM>-<NUM> mono- or polycycloalkylidene, -C(Rf)(Rg)- wherein Rf is hydrogen, C<NUM>-<NUM> alkyl, or C<NUM>-<NUM> aryl and Rg is C<NUM>-<NUM> alkyl, C<NUM>-<NUM> cycloalkyl, or C<NUM>-<NUM> aryl, or -(Q<NUM>)x-G-(Q<NUM>)y-group, wherein Q<NUM> and Q<NUM> are each independently a C<NUM>-<NUM> alkylene and G is a C<NUM>-<NUM> cycloalkylene, x is <NUM> or <NUM>, and y is <NUM> or <NUM>, and j, m, and n are each independently <NUM> or <NUM>.

Exemplary high-heat bisphenol groups include those of formulas (9a) and (10a) to (<NUM>)
<CHM>
<CHM>
<CHM>
<CHM>
wherein Rc and Rd are the same as defined for formulas (<NUM>) to (<NUM>), each R<NUM> is independently C<NUM>-<NUM> alkyl, m and n are each independently <NUM> to <NUM>, each R<NUM> is independently C<NUM>-<NUM> alkyl or hydrogen, R<NUM> is C<NUM>-<NUM> alkyl or phenyl optionally substituted with <NUM> to <NUM> C<NUM>-<NUM> alkyl groups, and g is <NUM> to <NUM>. In a specific aspect each bond of the bisphenol group is located para to the linking group that is Xa. In an aspect, Rc and Rd are each independently a C<NUM>-<NUM> alkyl, or C<NUM>-<NUM> alkoxy, each R<NUM> is methyl, x is <NUM> or <NUM>, y is <NUM>, and m and n are each independently <NUM> or <NUM>.

The high-heat bisphenol group is preferably of formula (9a-<NUM>) or (10a-<NUM>)
<CHM>
wherein R<NUM> is methyl or phenyl, each R<NUM> is methyl, and g is <NUM> to <NUM>. Preferably, the high-heat bisphenol group is derived from <NUM>-phenyl-<NUM>,<NUM>'-bis(<NUM>-hydroxyphenyl) phthalimidine (PPPBP) or from <NUM>,<NUM>-bis(<NUM>-hydroxyphenyl)-<NUM>,<NUM>,<NUM>-trimethyl-cyclohexane (BP-TMC). <CHM>
As discussed above, in compositions including a poly(carbonate-siloxane) having <NUM>-<NUM> wt% siloxane content, a homopolycarbonate, and the same flame retardants, polycarbonate compositions wherein the high-heat polycarbonate was derived from <NUM>-phenyl-<NUM>,<NUM>'-bis(<NUM>-hydroxyphenyl) phthalimidine provided the desired combination of properties, a UL-<NUM> flame test rating of V0 at a thickness of <NUM> millimeter (mm) and superior thermal and low-temperature impact properties, as compared to compositions wherein the high-heat polycarbonate was derived from <NUM>,<NUM>-bis(<NUM>-hydroxyphenyl)-<NUM>,<NUM>,<NUM>-trimethyl-cyclohexane. In some aspects, the high-heat polycarbonate is derived from N-phenyl phenolphthalein bisphenol, <NUM>,<NUM>'-(<NUM>-phenylethylidene)bisphenol, <NUM>,<NUM>'-(<NUM>,<NUM>-dimethyl-<NUM>,<NUM>-dihydro-<NUM>-indene-<NUM>,<NUM>-diyl)diphenol, <NUM>,<NUM>-bis(<NUM>-hydroxyphenyl)cyclododecane, <NUM>,<NUM>-dihydroxy-5a,10b-diphenyl-coumarano-<NUM>',<NUM>',<NUM>,<NUM>-coumarane, or a combination thereof, and optionally, <NUM>,<NUM>-bis(<NUM>-hydroxyphenyl)-<NUM>,<NUM>,<NUM>-trimethylcyclohexane. In certain aspects, the high-heat polycarbonate is derived from N-phenyl phenolphthalein bisphenol and <NUM>,<NUM>-bis(<NUM>-hydroxyphenyl)-<NUM>,<NUM>,<NUM>-trimethyl-cyclohexane. In a preferred aspect, the high-heat polycarbonate is derived from N-phenyl phenolphthalein bisphenol. The high-heat polycarbonate may include a single high-heat polycarbonate or a combination of high-heat polycarbonates. In some aspects, the high-heat polycarbonate includes a combination of a high-heat polycarbonate derived from N-phenyl phenolphthalein bisphenol and a high-heat polycarbonate derived from <NUM>,<NUM>-bis(<NUM>-hydroxyphenyl)-<NUM>,<NUM>,<NUM>-trimethyl-cyclohexane.

The high-heat polycarbonates may be present, for example, from <NUM>-<NUM> wt%, <NUM>-<NUM> wt%, <NUM>-<NUM> wt%, or <NUM>-<NUM> wt%, each based on the total weight of the composition.

Polycarbonates can be manufactured by processes such as interfacial polymerization and melt polymerization, which are known, and are described, for example, in <CIT> and <CIT>. An end-capping agent (also referred to as a chain stopper agent or chain terminating agent) can be included during polymerization to provide end groups, for example monocyclic phenols such as phenol, p-cyanophenol, and C<NUM>-<NUM> alkyl-substituted phenols such as p-cumyl-phenol, resorcinol monobenzoate, and p-and tertiarybutyl phenol, monoethers of diphenols, such as p-methoxyphenol, monoesters of diphenols such as resorcinol monobenzoate, functionalized chlorides of aliphatic monocarboxylic acids such as acryloyl chloride and methacryoyl chloride, and mono-chloroformates such as phenyl chloroformate, alkyl-substituted phenyl chloroformates, p-cumyl phenyl chloroformate, and toluene chloroformate. Combinations of different end groups can be used. Branched polycarbonate blocks can be prepared by adding a branching agent during polymerization, for example trimellitic acid, trimellitic anhydride, trimellitic trichloride, tris-p-hydroxyphenylethane, isatin-bis-phenol, tris-phenol TC (<NUM>,<NUM>,<NUM>-tris((p-hydroxyphenyl)isopropyl)benzene), tris-phenol PA (<NUM>(<NUM>(<NUM>,<NUM>-bis(p-hydroxyphenyl)-ethyl) alpha, alpha-dimethyl benzyl)phenol), <NUM>-chloroformyl phthalic anhydride, trimesic acid, and benzophenone tetracarboxylic acid. The branching agents can be added at a level of <NUM> to <NUM> wt. Combinations comprising linear polycarbonates and branched polycarbonates can be used.

"Polycarbonates" includes homopolycarbonates (wherein each R<NUM> in the polymer is the same), copolymers comprising different R<NUM> moieties in the carbonate ("copolycarbonates"), and copolymers comprising carbonate units and other types of polymer units, such as ester units or siloxane units.

In addition to the homopolycarbonate and the high-heat polycarbonate, the polycarbonate compositions include a poly(carbonate-siloxane), also referred to in the art as a polycarbonate-polysiloxane copolymer. The polysiloxane blocks comprise repeating diorganosiloxane units as in formula (<NUM>)
<CHM>
wherein each R is independently a C<NUM>-<NUM> monovalent organic group. For example, R can be a C<NUM>-<NUM> alkyl, C<NUM>-<NUM> alkoxy, C<NUM>-<NUM> alkenyl, C<NUM>-<NUM> alkenyloxy, C<NUM>-<NUM> cycloalkyl, C<NUM>-<NUM> cycloalkoxy, C<NUM>-<NUM> aryl, C<NUM>-<NUM> aryloxy, C<NUM>-<NUM> arylalkylene, C<NUM>-<NUM> arylalkylenoxy, C<NUM>-<NUM> alkylarylene, or C<NUM>-<NUM> alkylaryleneoxy. The foregoing groups can 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 can be used in the same copolymer.

The value of E in formula (<NUM>) can vary widely depending on the type and relative amount of each component in the thermoplastic composition, the desired properties of the composition, and like considerations. Generally, E has an average value of <NUM> to <NUM>,<NUM>, preferably <NUM> to <NUM>, <NUM> to <NUM>, or <NUM> to <NUM>, <NUM> to <NUM>, or <NUM> to <NUM>. In an aspect, E has an average value of <NUM> to <NUM> or <NUM> to <NUM>, and in still another aspect, E has an average value of <NUM> to <NUM>, or <NUM> to <NUM>. Where E is of a lower value, e.g., less than <NUM>, it can be desirable to use a relatively larger amount of the poly(carbonate-siloxane) copolymer. Conversely, where E is of a higher value, e.g., greater than <NUM>, a relatively lower amount of the poly(carbonate-siloxane) copolymer can be used. A combination of a first and a second (or more) poly(carbonate-siloxane) copolymers can be used, wherein the average value of E of the first copolymer is less than the average value of E of the second copolymer.

In an aspect, the polysiloxane blocks are of formula (<NUM>)
<CHM>
wherein E and R are as defined if formula (<NUM>); each R can be the same or different, and is as defined above; and Ar can be the same or different, and is a substituted or unsubstituted C<NUM>-<NUM> arylene, wherein the bonds are directly connected to an aromatic moiety. Ar groups in formula (<NUM>) can be derived from a C<NUM>-<NUM> dihydroxyarylene compound, for example a dihydroxyarylene compound of formula (<NUM>) or (<NUM>). Dihydroxyarylene compounds are <NUM>,<NUM>-bis(<NUM>-hydroxyphenyl) methane, <NUM>,<NUM>-bis(<NUM>-hydroxyphenyl) ethane, <NUM>,<NUM>-bis(<NUM>-hydroxyphenyl) propane, <NUM>,<NUM>-bis(<NUM>-hydroxyphenyl) butane, <NUM>,<NUM>-bis(<NUM>-hydroxyphenyl) octane, <NUM>,<NUM>-bis(<NUM>-hydroxyphenyl) propane, <NUM>,<NUM>-bis(<NUM>-hydroxyphenyl) n-butane, <NUM>,<NUM>-bis(<NUM>-hydroxy-<NUM>-methylphenyl) propane, <NUM>,<NUM>-bis(<NUM>-hydroxyphenyl) cyclohexane, bis(<NUM>-hydroxyphenyl sulfide), and <NUM>,<NUM>-bis(<NUM>-hydroxy-t-butylphenyl) propane.

In another aspect, polysiloxane blocks are of formula (<NUM>)
<CHM>
wherein R and E are as described above, and each R<NUM> is independently a divalent C<NUM>-<NUM> 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 (<NUM>):
<CHM>
wherein R and E are as defined above. R<NUM> in formula (<NUM>) is a divalent C<NUM>-<NUM> aliphatic group. Each M in formula (<NUM>) can be the same or different, and can be a halogen, cyano, nitro, C<NUM>-<NUM> alkylthio, C<NUM>-<NUM> alkyl, C<NUM>-<NUM> alkoxy, C<NUM>-<NUM> alkenyl, C<NUM>-<NUM> alkenyloxy, C<NUM>-<NUM> cycloalkyl, C<NUM>-<NUM> cycloalkoxy, C<NUM>-<NUM> aryl, C<NUM>-<NUM> aryloxy, C<NUM>-<NUM> aralkyl, C<NUM>-<NUM> aralkoxy, C<NUM>-<NUM> alkylaryl, or C<NUM>-<NUM> alkylaryloxy, wherein each n is independently <NUM>, <NUM>, <NUM>, <NUM>, or <NUM>.

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; R<NUM> is a dimethylene, trimethylene or tetramethylene; and R is a C<NUM>-<NUM> alkyl, haloalkyl such as trifluoropropyl, cyanoalkyl, or aryl such as phenyl, chlorophenyl or tolyl. In another aspect, R is methyl, or a combination of methyl and trifluoropropyl, or a combination of methyl and phenyl. In still another aspect, R is methyl, M is methoxy, n is one, and R<NUM> is a divalent C<NUM>-<NUM> aliphatic group. Specific polysiloxane blocks are of the formula
<CHM>
<CHM>
or a combination thereof, wherein E has an average value of <NUM> to <NUM>, <NUM> to <NUM>, <NUM> to <NUM>, <NUM> to <NUM>, <NUM> to <NUM>, <NUM> to <NUM>, or <NUM> to <NUM>.

Blocks of formula (<NUM>) can be derived from the corresponding dihydroxy polysiloxane, which in turn can be prepared effecting a platinum-catalyzed addition between the siloxane hydride and an aliphatically unsaturated monohydric phenol such as eugenol, <NUM>-alkylphenol, <NUM>-allyl-<NUM>-methylphenol, <NUM>-allyl-<NUM>-phenylphenol, <NUM>-allyl-<NUM>-bromophenol, <NUM>-allyl-<NUM>-t-butoxyphenol, <NUM>-phenyl-<NUM>-phenylphenol, <NUM>-methyl-<NUM>-propylphenol, <NUM>-allyl-<NUM>,<NUM>-dimethylphenol, <NUM>-allyl-<NUM>-bromo-<NUM>-methylphenol, <NUM>-allyl-<NUM>-methoxy-<NUM>-methylphenol and <NUM>-allyl-<NUM>,<NUM>-dimethylphenol. The poly(carbonate-siloxane) copolymers can then be manufactured, for example, by the synthetic procedure of <CIT> of Hoover, page <NUM>, Preparation <NUM>.

Transparent poly(carbonate-siloxane) copolymers comprise carbonate units (<NUM>) 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 <NUM> to <NUM>, <NUM> to <NUM>, preferably <NUM> to <NUM>, more preferably <NUM> to <NUM>, and still more preferably <NUM> to <NUM>. The transparent copolymers can be manufactured using one or both of the tube reactor processes described in <CIT> or the process described in <CIT> can be used to synthesize the poly(carbonate-siloxane) copolymers.

The polycarbonate compositions include a poly(carbonate-siloxane) having a siloxane content of <NUM> to <NUM> wt%, based on the total weight of the poly(carbonate-siloxane). Within this range, the poly(carbonate-siloxane) may have a siloxane content of greater than <NUM>-<NUM> wt%, <NUM>-<NUM> wt%, <NUM>-<NUM> wt%, <NUM>-<NUM> wt%, or <NUM>-<NUM> wt%.

The poly(carbonate-siloxane) having a siloxane content of <NUM> to <NUM> wt% may have a weight average molecular weight of <NUM>,<NUM>-<NUM>,<NUM>/mol. Within this range, the weight average molecular weight can be <NUM>,<NUM>-<NUM>,<NUM>/mol, or <NUM>,<NUM>-<NUM>,<NUM>/mol, or <NUM>,<NUM>-<NUM>,<NUM>/mol, or <NUM>,<NUM>-<NUM>,<NUM>/mol, or <NUM>,<NUM>-<NUM>,<NUM>/mol. In an aspect, the poly(carbonate-siloxane)may have a weight average molecular weight of <NUM>,<NUM>-<NUM>,<NUM>/mol, or <NUM>,<NUM>-<NUM>,<NUM>/mol, or <NUM>,<NUM>-<NUM>,<NUM>/mol. The weight average molecular weight may be measured by gel permeation chromatography using a crosslinked styrene-divinyl benzene column, at a sample concentration of <NUM> milligram per milliliter, using polystyrene standards and calculated for polycarbonate.

The poly(carbonate-siloxane) having a siloxane content of <NUM> to <NUM> wt% may be present in amount effective to provide <NUM>-<NUM> wt%, <NUM>-<NUM> wt%, <NUM>-<NUM> wt%, or <NUM>-<NUM> wt% siloxane, each based on the total weight of the composition.

In addition to the poly(carbonate-siloxane) comprising <NUM> to <NUM> wt% siloxane units, the compositions may include an auxiliary poly(carbonate-siloxane) copolymer comprising <NUM> to <NUM> wt%, more preferably <NUM> to <NUM> wt% of carbonate units and <NUM> to <NUM> wt%, more preferably <NUM> to <NUM> wt% siloxane units. In a preferred aspect, the auxiliary poly(carbonatesiloxane) comprises bisphenol A carbonate units and dimethylsiloxane units, for example blocks containing <NUM>-<NUM> dimethylsiloxane units, such as those commercially available under the trade name EXL from SABIC.

In an aspect, the auxiliary poly(carbonate-siloxane) copolymer comprises <NUM> wt% or less, preferably <NUM> wt% or less, and more preferably <NUM> wt% or less, of the polysiloxane based on the total weight of the auxiliary poly(carbonate-siloxane) copolymer, and are generally optically transparent and are commercially available under the name EXL-T from SABIC. In another aspect, the auxiliary poly(carbonate-siloxane) copolymer comprises <NUM> wt% or more, preferably <NUM> wt% or more, and more preferably <NUM> wt% or more, of the polysiloxane copolymer based on the total weight of the auxiliary poly(carbonate-siloxane) copolymer, are generally optically opaque and are commercially available under the trade name EXL-P from SABIC.

The auxiliary poly(carbonate-siloxane) may have a weight average molecular weight of <NUM>,<NUM>-<NUM>,<NUM>/mol, preferably <NUM>,<NUM>-<NUM>,<NUM>/mol, more preferably <NUM>,<NUM>-<NUM>,<NUM>/mol as measured by gel permeation chromatography using a crosslinked styrene-divinyl benzene column, at a sample concentration of <NUM> milligram per milliliter, using polystyrene standards and calculated for polycarbonate.

In an aspect, the composition comprises less than or equal to <NUM> wt% or less than or equal to <NUM> wt%, or less than or equal to <NUM> wt% of the auxiliary poly(carbonate-siloxane). Preferably the auxiliary poly(carbonate-siloxane) is excluded from the composition.

The poly(carbonate-siloxane)s may have a melt volume flow rate, measured at <NUM>/<NUM>, of <NUM> to <NUM> cubic centimeters per <NUM> minutes (cc/<NUM>), preferably <NUM> to <NUM> cc/<NUM>. Combinations of the poly(carbonate-siloxane)s of different flow properties can be used to achieve the overall desired flow property.

The polycarbonate compositions include a flame retardant, wherein the flame retardant is not a phosphorous-containing flame retardant. Inorganic flame retardants can be used, for example salts of C<NUM>-<NUM> alkyl sulfonate salts such as potassium perfluorobutane sulfonate (Rimar salt), potassium perfluoroctane sulfonate, tetraethylammonium perfluorohexane sulfonate, and potassium diphenylsulfone sulfonate; salts such as Na<NUM>CO<NUM>, K<NUM>CO<NUM>, MgCO<NUM>, CaCO<NUM>, and BaCO<NUM>, or fluoro-anion complexes such as Li<NUM>AlF<NUM>, BaSiF<NUM>, KBF<NUM>, K<NUM>AlF<NUM>, KAlF<NUM>, K<NUM>SiF<NUM>, or Na<NUM>AlF<NUM>. In some aspects, the flame retardant includes an alkyl sulfonate, an aromatic sulfonate, an aromatic sulfone sulfonate, or a combination thereof. The flame retardant may be present, for example, from <NUM>-<NUM> wt%, <NUM>-<NUM> wt%, or <NUM>-<NUM> wt%, each based on the total weight of the composition. In some aspects, the flame retardant is a combination of an alkyl sulfonate salt and an aromatic sulfone sulfonate. In such aspects, the weight ratio of the aromatic sulfone sulfonate to the alkyl sulfonate salt to may be <NUM>:<NUM>, <NUM>:<NUM> to <NUM>:<NUM>, <NUM>:<NUM> to <NUM>:<NUM>, <NUM>:<NUM> to <NUM>:<NUM>, <NUM>:<NUM> to <NUM>:<NUM>, or <NUM>:<NUM> to <NUM>:<NUM>.

In addition to the polycarbonate, the polycarbonate compositions can include various additives ordinarily incorporated into polymer compositions of this type, with the proviso that the additive(s) are selected so as to not significantly adversely affect the desired properties of the thermoplastic composition, in particular impact resistance, heat resistance, and flame test ratings. Such additives can be mixed at a suitable time during the mixing of the components for forming the composition. Additives include processing aids, fillers, reinforcing agents, antioxidants, heat stabilizers, light stabilizers, ultraviolet (UV) light stabilizers, plasticizers, lubricants, mold release agents, antistatic agents, colorants such as such as titanium dioxide, carbon black, and organic dyes, surface effect additives, radiation stabilizers, flame retardant different from the flame retardant that is not a phosphorous-containing flame retardant, hydrostabilizers, epoxy resins, and anti-drip agents. A combination of additives can be used, for example a combination of one or more of a hydrostabilizer, an epoxy resin, an anti-drip agent, a processing aid, a heat stabilizer, an ultraviolet light stabilizer, a colorant, an inorganic filler, preferably a clay. In general, the additives are used in the amounts generally known to be effective. For example, the total amount of the additives (other than any impact modifier, filler, or reinforcing agents) can be <NUM> to <NUM> wt%, or <NUM> to <NUM> wt%, based on the total weight of the polycarbonate composition.

When present, the additive composition may include an anti-drip agent, an epoxy resin, a UV stabilizer, a hydrostabilizer, or a combination thereof. Anti-drip agents may be present in the additive composition, for example a fibril forming or non-fibril forming fluoropolymer such as polytetrafluoroethylene (PTFE). The anti-drip agent can be encapsulated by a rigid copolymer, for example styrene-acrylonitrile copolymer (SAN). PTFE encapsulated in SAN is known as TSAN. TSAN comprises <NUM> wt% PTFE and <NUM> wt% SAN, based on the total weight of the encapsulated fluoropolymer. The SAN can comprise, for example, <NUM> wt% styrene and <NUM> wt% acrylonitrile based on the total weight of the copolymer. Anti-drip agents can be used in amounts of <NUM>-<NUM> wt%, based on the total weight of the composition.

In an aspect, the polycarbonate composition includes <NUM>-<NUM> wt% a high-heat copolycarbonate derived from N-phenyl phenolphthalein bisphenol and bisphenol A; <NUM>-<NUM> wt% of bisphenol A homopolycarbonate; <NUM>-<NUM> wt% of a combination of an alkyl sulfonate and an aromatic sulfone sulfonate; and optionally, <NUM>-<NUM> wt% of the additive composition; wherein the poly(carbonate-siloxane) is present in an amount effective to provide <NUM>-<NUM> wt%, preferably <NUM>-<NUM> wt%, more preferably <NUM>-<NUM> wt% siloxane, each based on the total weight of the composition.

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

A molded sample of the polycarbonate composition having a thickness of <NUM> millimeters may have a heat deflection temperature (HDT) of at least <NUM>, or <NUM> -<NUM>, or <NUM> -<NUM>, <NUM> -<NUM>, or <NUM> -<NUM> each determined according to ASTM D648 at <NUM> megapascals (MPa).

A molded sample of the polycarbonate composition having a thickness of <NUM> millimeters may have a heat deflection temperature (HDT) of at least <NUM>, or <NUM> -<NUM>, or <NUM>-<NUM>, <NUM>-<NUM>, or <NUM> -<NUM> each determined according to ASTM D648 at <NUM> MPa.

A molded sample having a thickness of <NUM> millimeters has a notched Izod impact of at least <NUM> joules per meter (J/m), or from <NUM>-<NUM> J/m at -<NUM>; and may have a notched Izod impact of at least <NUM> J/m, at least <NUM> J/m, or from <NUM>-<NUM> J/m, or from <NUM>-<NUM> J/m at -<NUM>; or a combination thereof, each according to ASTM D256.

A molded sample of the polycarbonate composition may have a flame test rating of V0, as measured according to UL-<NUM> at a thickness of <NUM> millimeter, V0 at a thickness of <NUM>, V1 at a thickness of <NUM>, or a combination thereof.

Shaped, formed, or molded articles comprising the polycarbonate compositions are also provided. The polycarbonate compositions can be molded into useful shaped articles by a variety of methods, such as injection molding, extrusion, rotational molding, blow molding and thermoforming. Some example of 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 some aspects, the article is an extruded article, a molded article, pultruded article, a thermoformed article, a foamed article, a layer of a multi-layer article, a substrate for a coated article, or a substrate for a metallized article, preferably wherein the article is a molded article. In a preferred aspect, the article is an electrical connector, for example, a charger for a device.

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.

The materials shown in Table <NUM> were used.

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

Typical compounding procedures are described as follows: All raw materials are pre-blended and then extruded using a twin extruder. The composition was melt-kneaded, extruded, cooled through a water bath and pelletized. A typical extrusion profile is listed in Table <NUM>.

The extruded pellets were molded into testing specimens after drying the extruded pellets at <NUM> for <NUM> hours using injection molding.

Sample preparation and testing methods are described in Table <NUM>.

Flammability tests were performed on samples at thicknesses of <NUM> in accordance with the Underwriter's Laboratory (UL) UL <NUM> standard. In some cases, a second set of <NUM> 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 <NUM>. Total flame-out-times for all <NUM> bars (FOT = t1 + t2) were determined. V-ratings were obtained for every set of <NUM> bars.

Table <NUM> shows the compositions and properties for Comparative Examples <NUM>-<NUM> and Examples <NUM>-<NUM>.

As shown in Table <NUM>, incorporation of the poly(carbonate-siloxane) having <NUM> wt% siloxane content("PC-Si-<NUM>") resulted in improved low temperature impact resistance, as compared with compositions having the poly(carbonate-siloxane) having <NUM> wt% siloxane content ("PC-Si-<NUM>"), even though the siloxane content of the composition was the same (i.e., <NUM> wt%, compare Comparative Example <NUM> with Example <NUM>). As the loading of PC-Si-<NUM> is increased from <NUM> wt% to <NUM>%, the heat resistance (i.e., HDT) is maintained while the low-temperature impact performance is improved (compare Examples <NUM>-<NUM>). Formulations including PC-Si-<NUM> with poly(N-phenylphenolphthaleinylbisphenol, <NUM>,<NUM>-bis(<NUM>-hydro) carbonate -co-bisphenol A carbonate) ("HHPC-<NUM>") as the high-heat polycarbonate provided improved low-temperature impact resistance as compared to similar formulations with poly(bisphenol A carbonate-co-isophorone bisphenol carbonate) ("HHPC-<NUM>") as the high-heat polycarbonate (compare Examples <NUM>-<NUM> with Comparative Example <NUM>-<NUM>). Examples <NUM>-<NUM> and Comparative Examples <NUM>-<NUM>, wherein the loading of PC-Si-<NUM> is the same, show that compositions having the HHPC-<NUM> and HHPC-<NUM> result in similar heat deflection values, but the low-temperature impact performance of compositions having HHPC-<NUM> (Examples <NUM>-<NUM>) is improved as compared with compositions having HHPC-<NUM> (Comparative Examples <NUM>-<NUM>). The loading of flame retardants is the same for Comparative Examples <NUM>-<NUM> and Examples <NUM>-<NUM>. However, only those compositions having a combination of HHPC-<NUM> as the high-heat polycarbonate and PC-Si-<NUM> as the poly(carbonate-siloxane) provide the desired V0 UL94 rating at a <NUM> thickness. Example <NUM> shows that a V0 UL94 rating at a <NUM> thickness and V1 UL94 rating at a <NUM> thickness can be achieved for compositions having HHPC-<NUM> and carbon black.

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

If a term in the present application contradicts or conflicts with a term in a reference, the term from the present application takes precedence over the conflicting term from the reference.

Claim 1:
A polycarbonate composition comprising
a high-heat copolycarbonate derived from a high-heat bisphenol monomer and optionally a low heat bisphenol A monomer, wherein the high-heat bisphenol monomer is a monomer where the corresponding homopolycarbonate of the monomer has a glass transition temperature of <NUM> or higher as determined per ASTM D3418 with a <NUM> per minute heating rate;
a poly(carbonate-siloxane) having <NUM>-<NUM> wt% siloxane content, based on the total weight of the poly(carbonate-siloxane);
a homopolycarbonate;
a flame retardant, wherein the flame retardant is not a phosphorous-containing flame retardant; and
optionally, an additive composition,
wherein a molded sample having a thickness of <NUM> millimeters has a notched Izod Impact of at least <NUM> joules per meter at -<NUM> according to ASTM D256.