Anti-drip polycarbonate composition

Abstract

The polycarbonate composition comprises a linear homopolycarbonate and an optional styrene-containing copolymer; a poly (carbonate-siloxane) comprising from about 10 wt% to less than about 30 wt% siloxane present in an amount effective to provide from about 1 to about 6 wt% siloxane based on the total weight of the composition; an ultra-high molecular weight polydimethylsiloxane present in an amount effective to provide from greater than about 0.3 to less than about 0.9 wt% siloxane based on the total weight of the composition; a flame retardant; and optionally, an additive composition. Molded samples of the polycarbonate composition have a UL94 burn test rating or V-0 at a thickness of 1.5 mm, exhibit anti-drip properties, and may be substantially halogen free, i.e., the polycarbonate composition includes about 900 parts per million (ppm) of each of chlorine, bromine, and optionally fluorine, and further includes a total chlorine, bromine, and fluorine content of about 1500 ppm or less.

Description

Technical Field

[0001] The present disclosure relates to polycarbonate compositions, and more particularly, to drip resistant polycarbonate compositions, methods of making, and uses thereof. Background Art

[0002] Polycarbonates are useful in making articles and components for a wide range of applications, from automotive parts to electronic appliances. Due to their widespread use, it is desirable to provide polycarbonates that are flame retardant when molded into articles.

[0003] Therefore, there remains a need in the art for polycarbonate compositions that are flame retardant. It would be a further advantage if the composition were substantially halogen free. Summary of the invention

[0004] The above and other deficiencies in the art are met by a polycarbonate composition comprising: a linear homopolycarbonate and an optional styrene-containing copolymer; a poly(carbonate-siloxane) comprising from about 10 wt % to less than about 30 wt % siloxane, present in an amount effective to provide a siloxane content of from about 1 wt % to about 6 wt %, based on the total weight of the polycarbonate composition; an ultra-high molecular weight polydimethylsiloxane, present in an amount effective to provide a siloxane content of from greater than about 0.3 wt % to less than about 0.9 wt %, based on the total weight of the composition, wherein the polydimethylsiloxane has a weight average molecular weight of at least 100,000 grams / mole as determined by gel permeation chromatography against polystyrene standards; a flame retardant; and optionally, an additive composition, wherein the linear homopolycarbonate, the optional styrene-containing copolymer, the poly(carbonate-siloxane), the ultra-high molecular weight polydimethylsiloxane, the flame retardant, and the optional additive composition total 100 wt %.

[0005] In another aspect, a method of making includes combining the above components to form a polycarbonate composition.

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

[0007] In yet another aspect, a method of making an article comprises molding, extruding, or forming 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] Due to the miniaturization and market trend of electronic components, flame retardant products substantially free of halogen are needed. As used herein, the phrase "substantially free of halogen" is defined by IEC 61249-2-21 or UL 746H. According to the International Electrochemical Commission, halogen restrictions are used (IEC 61249-2-21), and the composition should include each of 900ppm (ppm) below chlorine and bromine, and also include the total bromine, chlorine and fluorine content below 1500ppm. According to UL 746H, the composition should include each of 900ppm below chlorine, bromine and fluorine and the total chlorine, bromine and fluorine content below 1500ppm. Bromine, chlorine and fluorine content (in ppm) can be calculated by the composition or measured by elemental analysis technology. Conventional flame retardants may or may not include halogen, but the anti-dripping agent commonly used includes PTFE-encapsulated styrene-acrylonitrile copolymer (for example, TSAN) and therefore includes fluorine. Flame retardants that are not brominated, chlorinated, or fluorinated have been used in conventional polycarbonate compositions, but anti-drip agents are often present in combination with the flame retardants so that the halogen content of the composition exceeds the 1500ppm total halogen limit according to IEC 61249-2-21 and UL 746H. Similarly, when a non-brominated or chlorinated but fluorinated flame retardant is used in combination with a fluorinated anti-drip agent, the halogen content of the composition exceeds the 1500ppm total halogen limit according to IEC 61249-2-21 or UL 746H due to the presence of fluorine. Therefore, it would be particularly advantageous if the anti-drip agent is non-fluorinated so that the anti-drip agent does not contribute to the total halogen content of the composition. When a non-fluorinated anti-drip agent is used, a variety of flame retardants that may or may not include halogens may be used in combination with the non-fluorinated anti-drip agent so that the composition may be considered to be "substantially halogen-free" according to IEC 61249-2-21 or UL 746H.

[0010] The present inventors have found that polycarbonate compositions comprising linear homopolycarbonate and optionally a copolymer comprising styrene, a flame retardant, a poly(carbonate-siloxane) and an ultra-high molecular weight polydimethylsiloxane can provide anti-drip performance without compromising flame retardancy, e.g., a UL-94 burn test rating. Advantageously, at a thickness of 1.5 mm or 2.9 mm, the polycarbonate composition can have a UL-94 burn test rating of V-0, no dripping, and is considered to be "substantially halogen-free" according to IEC 61249-2-21 or UL 746H. A further advantage is that the V-0 burn test rating and anti-drip performance are not achieved at the expense of the aesthetic quality of the molded sample of the polycarbonate composition. In fact, the polycarbonate composition can include a colorant to provide a colored article, such as, for example, a white or black article.

[0011] As used herein, "polycarbonate" refers to a polymer having repeating structural carbonate units of formula (1):

[0012]

[0013] Among them, R 1 At least 60% of the total number of groups contain aromatic moieties, and the remainder are aliphatic, alicyclic, or aromatic. 1 It is C 6-30 An aromatic group, ie, containing at least one aromatic moiety. 1 Can be derived from the formula HO-R 1 -OH, especially an aromatic dihydroxy compound of formula (2):

[0014] HO-A 1 -Y 1 -A 2 -OH(2)

[0015] Among them, A 1 and A 2 Each is a monocyclic divalent aromatic group, and Y 1 is a single bond or has A 1 With A 2 In one aspect, one atom separates A 1 With A 2 Preferably, each R 1 It can be derived from bisphenols of formula (3):

[0016]

[0017] Among them, R a and R b are independently halogen, C 1-12 Alkoxy, or C 1-12 alkyl, and p and q are each independently an integer from 0 to 4. It should be understood that when p or q is less than 4, the valence of each carbon of the ring is filled with hydrogen. a is a bridging group connecting two hydroxy-substituted aromatic groups, wherein the bridging group and the hydroxy substituent of each C6 arylene group are arranged ortho, meta, or para (preferably para) to each other on the C6 arylene group. a is a single bond, -O-, -S-, -S(O)-, -S(O)2-, -C(O)-, or C 1-60 Organic groups. The organic bridging group may be cyclic or acyclic, aromatic or non-aromatic, and may further contain heteroatoms such as halogens, oxygen, nitrogen, sulfur, silicon, or phosphorus. 1-60The organic group is such that the C6 arylene groups attached thereto are each attached to a common alkylidene carbon or to a C 1-60 In one aspect, p and q are each 1, and R a and R b Each is C 1-3 An alkyl group, preferably a methyl group, is disposed meta to the hydroxy group on each arylene group.

[0018] In one aspect, X a It is C 3-18 Cycloalkylidene, formula -C(R c )(R d )-C 1-25 Alkylene, where R c and R d are independently hydrogen, C 1-12 Alkyl, C 1-12 Cycloalkyl, C 7-12 Aralkyl, C 1-12 Heteroalkyl, or cyclic C 7-12 heteroarylalkyl, or having the formula -C(=R e )-, wherein R e It is a two-price C 1-12 Hydrocarbyl. These types of groups include methylene, cyclohexylmethylene, ethylidene, neopentylidene, and isopropylidene, as well as 2-[2.2.1]-bicycloheptylidene, cyclohexylidene, 3,3-dimethyl-5-methylcyclohexylidene, cyclopentylidene, cyclododecylidene, and adamantylidene.

[0019] On the other hand, X a It is C 1-18 Alkylene, C 3-18 Cycloalkylene, fused C 6-18 Cycloalkylene, or formula -J 1 -GJ 2 - group, where J 1 and J 2 Is the same or different C 1-6 Alkylene, and G is C 3-12 Cycloalkylidene or C 6-16 Arylene.

[0020] For example, X a It can be a substituted C of formula (4) 3-18 Cycloalkylidene:

[0021]

[0022] Among them, R r , R p , R q , and R tare independently hydrogen, halogen, oxygen, or C 1-12 Hydrocarbyl; Q is a direct bond, carbon, or divalent oxygen, sulfur, or -N(Z)-, wherein Z is hydrogen, halogen, hydroxyl, C 1-12 Alkyl, C 1-12 Alkoxy, C 6-12 Aryl, or C 1-12 acyl; r is 0 to 2, t is 1 or 2, q is 0 or 1, and k is 0 to 3, provided that R r , R p , R q , and R t At least two of the fused rings together are fused alicyclic, aromatic, or heteroaromatic rings. It should be understood that when the fused ring is aromatic, the ring shown in formula (4) will have unsaturated carbon-carbon bonds, wherein the ring is fused. When k is 1 and q is 0, the ring shown in formula (4) contains 4 carbon atoms, when k is 2, the ring shown in formula (4) contains 5 carbon atoms, and when k is 3, the ring contains 6 carbon atoms. In one aspect, two adjacent groups (e.g., R q and R t together) form an aromatic group, and on the other hand, R q and R t together form an aromatic group and R r and R p Together they form a second aromatic group. q and R t When they form an aromatic group, R p It may be a double-bonded oxygen atom, ie, a ketone, or Q may be -N(Z)-, wherein Z is phenyl.

[0023] Bisphenol, of which X a is a cycloalkylidene group of formula (4), which can be used to prepare a polycarbonate comprising a phthalimide carbonate unit of formula (1a):

[0024]

[0025] Among them, R a , R b , p and q are as in formula (3), R 3 Each is independently C 1-6 alkyl, j is 0 to 4, and R4 is hydrogen, C 1-6 Alkyl, or substituted or unsubstituted phenyl, for example with up to 5 C 1-6 Alkyl substituted phenyl. For example, the phthalide carbonate unit has formula (1b):

[0026]

[0027] Among them, R 5is hydrogen, optionally replaced by up to five C 1-6 Alkyl or C 1-4 In one aspect of formula (1b), R 5 is hydrogen, methyl, or phenyl, preferably phenyl. Carbonate units (1b) wherein R 5 The phenyl group may be derived from 2-phenyl-3,3'-bis(4-hydroxyphenyl)phthalimide (also known as 3,3-bis(4-hydroxyphenyl)-2-phenylisoindolin-1-one, or N-phenylphenolphthalein bisphenol).

[0028] Other bisphenol carbonate repeating units of this type are isatin carbonate units of formula (1c) and (1d):

[0029]

[0030] Among them, R a and R b are independently halogen, C 1-12 Alkoxy, or C 1-12 alkyl, p and q are each independently 0 to 4, and R i It is C 1-12 Alkyl, optionally with 1 to 5 C 1-10 alkyl-substituted phenyl, or optionally substituted with 1 to 5 C 1-10 In one aspect, R a and R b are each methyl, p and q are each independently 0 or 1, and R i It is C 1-4 Alkyl or phenyl.

[0031] Other embodiments of bisphenol carbonate units derived from bisphenol (3) wherein X a is substituted or unsubstituted C 3-18 Cycloalkylidene, including cyclohexylidene-bridged bisphenols of formula (1e):

[0032]

[0033] Among them, R a and R b Each is independently C 1-12 Alkyl, R g It is C 1-12 alkyl, p and q are each independently 0 to 4, and t is 0 to 10. In one specific aspect, each R a and R b In one aspect, at least one of R a and R b Each is independently C 1-4 Alkyl, Rg It is C 1-4 alkyl, p and q are each 0 or 1, and t is 0 to 5. In another specific aspect, R a , R b and R g Each is methyl, p and q are each 0 or 1, and t is 0 or 3, preferably 0. In yet another aspect, p and q are each 0, each R g is methyl, and t is 3, such that X a It is 3,3-dimethyl-5-methylcyclohexylidene.

[0034] Embodiments of other bisphenol carbonate units derived from bisphenol (3) wherein X a is substituted or unsubstituted C 3-18 Cycloalkylidene groups, including adamantyl units of formula (1f) and fluorenyl units of formula (1g)

[0035]

[0036] Among them, R a and R b Each is independently C 1-12 alkyl, and p and q are each independently 1 to 4. In one specific aspect, each R a and R b In one aspect, at least one of R a and R b Each is independently C 1-3 alkyl, and p and q are each 0 or 1; preferably, R a , R b Each is a methyl group, p and q are each 0 or 1, and when p and q are 1, the methyl group is arranged at the meta position of the cycloalkylidene bridging group. The carbonate containing units (1a) to (1g) can be used to produce a polycarbonate having a high glass transition temperature (Tg) and a high heat deformation temperature.

[0037] Formula HO-R 1 Other useful dihydroxy compounds of -OH include aromatic dihydroxy compounds of formula (6):

[0038]

[0039] Among them, each R h are independently halogen atoms, C 1-10 Hydrocarbon such as C 1-10 Alkyl, halogen substituted C 1-10 Alkyl, C 6-10 Aryl or halogen substituted C 6-10 Aryl, and n is 0 to 4. Halogen is typically bromine.

[0040] 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)isobutylene, 1,1-bis(4-hydroxyphenyl) Cyclododecane, trans-2,3-bis(4-hydroxyphenyl)-2-butene, 2,2-bis(4-hydroxyphenyl)adamantane, α,α'-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-tert-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) fluoride, 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-dihydroxyphenothiophene, 2,7-dihydroxy-9,10-dimethylphenazine, 3,6-dihydroxydibenzofuran, 3,6-dihydroxydibenzothiophene, and 2,7-dihydroxycarbazole, resorcinol, substituted resorcinol compounds such as 5-methylresorcinol, 5-ethylresorcinol, 5-propylresorcinol, 5-butylresorcinol, 5-tert-butylresorcinol, 5-phenylresorcinol, 5-cumylresorcinol, 2,4,5,6-tetrafluororesorcinol, 2,4,5,6-tetrabromoresorcinol, etc.; catechol; hydroquinone; substituted hydroquinones such as 2-methylhydroquinone, 2-ethylhydroquinone, 2-propylhydroquinone, 2-butylhydroquinone, 2-tert-butylhydroquinone, 2-phenylhydroquinone, 2-cumylhydroquinone, 2,3,5,6-tetramethylhydroquinone, 2,3,5,6-tetra-tert-butylhydroquinone, 2,3,5,6-tetrafluorohydroquinone, 2,3,5,6-tetrabromohydroquinone, etc., or combinations thereof.

[0041] Specific examples of the bisphenol compound of formula (3) include 1,1-bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl)propane (hereinafter "bisphenol A" or "BPA"), 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)octane, 1,1-bis(4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)n-butane, 2,2-bis(4-hydroxy-2-methylphenyl)propane, 1,1-bis(4-hydroxy-tert-butylphenyl)propane, 3,3-bis(4-hydroxyphenyl)phthalimide, 2-phenyl-3,3-bis(4-hydroxyphenyl)phthalimide (PPPBP), and 1,1-bis(4-hydroxy-3-methylphenyl)cyclohexane (DMBPC). Combinations may also be used. In one specific aspect, the polycarbonate is a linear homopolymer derived from bisphenol A, wherein each A in formula (3) 1 and A 2 is p-phenylene and Y 1 It is isopropylidene.

[0042] The polycarbonate composition may include bisphenol A polycarbonate homopolymer, also referred to as bisphenol A homopolycarbonate. Bisphenol A polycarbonate homopolymer has a repeating structural carbonate unit of formula (1).

[0043]

[0044] Polycarbonates can be prepared by known methods such as interfacial polymerization and melt polymerization, which are known and described, for example, in WO 2013 / 175448 A1 and WO 2014 / 072923 A1. End-capping agents (also called chain terminators or chain stoppers) can be included during polymerization to provide end groups, for example, monocyclic phenols such as phenol, p-cyanophenol and C 1-22Alkyl substituted phenols such as p-cumylphenol, resorcinol monobenzoate, and p-butylphenol and tert-butylphenol, monoethers of dihydric phenols such as p-methoxyphenol, monoesters of dihydric phenols such as resorcinol monobenzoate, functionalized chlorides of aliphatic monocarboxylic acids such as acryloyl chloride and methacryloyl chloride, and monochloroformates such as phenyl chloroformate, alkyl substituted phenyl chloroformate, p-cumylphenyl chloroformate, and toluene chloroformate. Combinations of different end groups may be used. Branched polycarbonate blocks can be prepared by adding a branching agent during the polymerization process, such as trimellitic acid, trimellitic anhydride, trimellitic acid chloride, tri-p-hydroxyphenylethane, isatin-bisphenol, trisphenol TC (1,3,5-tris((p-hydroxyphenyl)isopropyl)benzene), trisphenol PA (4(4(1,1-bis(p-hydroxyphenyl)-ethyl)α,α-dimethylbenzyl)phenol), 4-chloroformylphthalic anhydride, trimesic acid, and benzophenonetetracarboxylic acid. The branching agent can be added at a level of 0.05 to 4.0 weight percent (wt%), for example, 0.05 to 2.0 wt%. Combinations including linear polycarbonates and branched polycarbonates can be used.

[0045] The polycarbonate may have an intrinsic viscosity of 0.3 to 1.5 deciliters per gram (dl / gm), preferably 0.45 to 1.0 dl / gm, measured in chloroform at 25°C. The polycarbonate may have a weight average molecular weight (Mw) of 10,000 to 200,000 grams per mole (g / mol), preferably 20,000 to 100,000 g / mol, measured by gel permeation chromatography (GPC) using a crosslinked styrene-divinylbenzene column, according to polystyrene standards and calculated for polycarbonate. GPC samples are prepared at a concentration of 1 mg / ml and eluted at a flow rate of 1.5 ml / min. The linear homopolycarbonate may include a bisphenol A polycarbonate homopolymer. The linear bisphenol A polycarbonate homopolymer may have a weight average molecular weight of 15,000 to 25,000 g / mol, preferably 17,000 to 25,000 g / mol, as determined by GPC according to polystyrene standards and calculated for polycarbonate. The linear bisphenol A polycarbonate homopolymer may have a weight average molecular weight of 26,000 to 40,000 g / mol, preferably 27,000 to 35,000 g / mol, as determined by GPC according to polystyrene standards and calculated for polycarbonate.

[0046] In one aspect, there may be more than one linear homopolycarbonate. For example, the linear homopolycarbonate may include a bisphenol A homopolycarbonate having a weight average molecular weight of 15,000 to 25,000 g / mol, or 17,000 to 23,000 g / mol, or 18,000 to 22,000 g / mol, and a bisphenol A homopolycarbonate having a weight average molecular weight of 26,000 to 40,000 g / mol, or 26,000 to 35,000 g / mol, each measured by GPC according to a polystyrene standard and calculated for polycarbonate. The weight ratio of the linear homopolycarbonates relative to each other is 10:1 to 1:10, preferably 5:1 to 1:5, more preferably 3:1 to 1:3, or 2:1 to 1:2.

[0047] In addition to linear homopolycarbonates, polycarbonate compositions can include styrene-containing copolymers in combination with linear homopolycarbonates. The styrene-containing copolymer comprises an elastomeric phase comprising (i) butadiene and having a Tg of less than about 10°C, and (ii) a rigid polymer phase having a Tg greater than about 15°C and comprising a copolymer of a monovinyl aromatic monomer, the monovinyl aromatic monomer comprising styrene and an unsaturated nitrile such as acrylonitrile. The styrene-containing copolymer can include a monovinyl aromatic monomer other than styrene. Such styrene-containing copolymers can be prepared by first providing an elastomeric polymer and then polymerizing the constituent monomers of the rigid phase in the presence of an elastomer to obtain a grafted copolymer. The grafting can be connected to the elastomeric core as a grafted branch or as a shell. The shell can simply physically encapsulate the core, or the shell can be partially or substantially completely grafted to the core.

[0048] Polybutadiene homopolymers may be used as the elastomeric phase. Alternatively, the styrene copolymer-containing elastomeric phase comprises butadiene copolymerized with up to about 25 wt% of another conjugated diene monomer of formula (8):

[0049]

[0050] Among them, each X b are independently C1-C5 alkyl groups. Examples of conjugated diene monomers that can be used are isoprene, 1,3-heptadiene, methyl-1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3-pentadiene; 1,3- and 2,4-hexadiene, and the like, and mixtures comprising at least one of the foregoing conjugated diene monomers. A specific conjugated diene is isoprene.

[0051] The elastomeric butadiene phase may additionally be copolymerized with up to 25 wt%, preferably up to about 15 wt%, of another comonomer, such as a monovinyl aromatic monomer containing a condensed aromatic ring structure, such as vinyl naphthalene, vinyl anthracene, etc., or a monomer of formula (9):

[0052]

[0053] Among them, each X c are independently hydrogen, C1-C 12 Alkyl, C3-C 12 Cycloalkyl, C6-C 12 Aryl, C7-C 12 Aralkyl, C7-C 12 Alkyl, C1-C 12 Alkoxy, C3-C 12 Cycloalkoxy, C6-C 12 The invention relates to a monovinyl aromatic monomer copolymerizable with butadiene. The monomers of the present invention are aryloxy, chlorine, bromine, or hydroxyl, and R is hydrogen, C1-C5 alkyl, bromine, or chlorine. Examples of suitable monovinyl aromatic monomers copolymerizable with butadiene include styrene, 3-methylstyrene, 3,5-diethylstyrene, 4-n-propylstyrene, α-methylstyrene, α-methylvinyltoluene, α-chlorostyrene, α-bromostyrene, dichlorostyrene, dibromostyrene, tetrachlorostyrene, and the like, and combinations comprising at least one of the foregoing monovinyl aromatic monomers. In one aspect, butadiene is copolymerized with up to about 12 wt %, preferably about 1 wt % to about 10 wt % of styrene and / or α-methylstyrene.

[0054] Other monomers that can be copolymerized with butadiene are monovinyl monomers such as itaconic acid, acrylamide, N-substituted acrylamide or methacrylamide, maleic anhydride, maleimide, N-alkyl-, aryl-, or haloaryl-substituted maleimide, glycidyl (meth)acrylate, and monomers of the general formula (10):

[0055]

[0056] Wherein, R is hydrogen, C1-C5 alkyl, bromine or chlorine, and X c It is cyano, C1-C 12 Alkoxycarbonyl, C1-C 12Examples of the monomer of formula (10) include acrylonitrile, ethacrylonitrile, methacrylonitrile, α-chloroacrylonitrile, β-chloroacrylonitrile, α-bromoacrylonitrile, acrylic acid, methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, tert-butyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and the like, and a combination comprising at least one of the foregoing monomers. Monomers such as n-butyl acrylate, ethyl acrylate, and 2-ethylhexyl acrylate are generally used as monomers copolymerizable with butadiene.

[0057] The particle size of the butadiene phase is not limited, and can be, for example, about 0.01 to about 20 microns, preferably about 0.5 to about 10 microns, more preferably about 0.6 to about 1.5 microns, and can be used for a rubber matrix of bulk polymerization. The particle size can be measured by light transmission or capillary hydrodynamic chromatography (CHDF). The butadiene phase can provide about 5wt% to about 95wt% of the total weight of the styrene-containing copolymer, more preferably about 20wt% to about 90wt%, and even more preferably about 40wt% to about 85wt% of the styrene-containing copolymer, and the remainder is a rigid graft phase.

[0058] The rigid graft phase comprises a copolymer formed from a styrene monomer composition together with an unsaturated monomer comprising a nitrile group. As used herein, "styrene monomer" includes monomers of formula (9), wherein each X c Independently, it is hydrogen, C1-C4 alkyl, phenyl, C7-C9 aralkyl, C7-C9 alkaryl, C1-C4 alkoxy, phenoxy, chlorine, bromine, or hydroxyl, and R is hydrogen, C1-C2 alkyl, bromine, or chlorine. Specific examples are styrene, 3-methylstyrene, 3,5-diethylstyrene, 4-n-propylstyrene, α-methylstyrene, α-methylvinyltoluene, α-chlorostyrene, α-bromostyrene, dichlorostyrene, dibromostyrene, tetrachlorostyrene, etc. A combination comprising at least one of the above styrene monomers can be used.

[0059] As further used herein, unsaturated monomers comprising a nitrile group include monomers of formula (10) wherein R is hydrogen, C1-C5 alkyl, bromine, or chlorine, and X c Specific examples include acrylonitrile, ethacrylonitrile, methacrylonitrile, α-chloroacrylonitrile, β-chloroacrylonitrile, α-bromoacrylonitrile, and the like. A combination comprising at least one of the foregoing monomers may be used.

[0060] The rigid graft phase of the styrene-containing copolymer may further optionally contain other monomers copolymerizable therewith, including other monovinyl aromatic monomers and / or monovinyl monomers such as itaconic acid, acrylamide, N-substituted acrylamide or methacrylamide, maleic anhydride, maleimide, N-alkyl-, aryl-, or haloaryl-substituted maleimide, glycidyl (meth)acrylate, and monomers of formula (10). Specific comonomers include C1-C4 alkyl (meth)acrylates, such as methyl methacrylate.

[0061] The rigid copolymer phase typically comprises from about 10 to about 99 wt%, preferably from about 40 to about 95 wt%, more preferably from about 50 to about 90 wt% of styrenic monomers; from about 1 to about 90 wt%, preferably from about 10 to about 80 wt%, more preferably from about 10 to about 50 wt% of unsaturated monomers containing nitrile groups; and 0 to about 25 wt%, preferably 1 to about 15 wt% of other comonomers, each based on the total weight of the rigid copolymer phase.

[0062] The copolymer containing styrene can further comprise a separate matrix or continuous phase of an ungrafted rigid copolymer that can be obtained simultaneously with the copolymer containing styrene. Based on the gross weight of the copolymer containing styrene, the copolymer containing styrene can comprise an elastomer-modified graft copolymer of about 40 to about 95wt% and a rigid copolymer of about 5 to about 65wt%. In another aspect, based on the gross weight of the copolymer containing styrene, the copolymer containing styrene can comprise an elastomer-modified graft copolymer of about 50 to about 85wt%, more preferably about 75 to about 85wt%, together with about 15 to about 50wt%, more preferably about 15 to about 25wt% of a rigid copolymer.

[0063] A variety of bulk polymerization methods for styrene-containing copolymer resins are known. In a multi-zone plug flow bulk method, a series of polymerization vessels (or towers) connected continuously to each other provide multiple reaction zones. The elastomer butadiene can be dissolved in one or more monomers for forming a rigid phase, and the elastomer solution is fed to the reaction system. During the reaction, which can be thermally or chemically initiated, the elastomer is grafted with a rigid copolymer (e.g., SAN). A bulk copolymer (also referred to as a free copolymer, a matrix copolymer, or a non-grafted copolymer) is also formed in the continuous phase containing the dissolved rubber. As the polymerization continues, the domains of the free copolymer are formed in the continuous phase of the rubber / comonomer to provide a two-phase system. As the polymerization proceeds and more free copolymers are formed, the elastomer-modified copolymer begins to disperse itself as particles in the free copolymer and the free copolymer becomes a continuous phase (phase inversion). Some free copolymers are also usually enclosed in the elastomer-modified copolymer phase. After the phase inversion, additional heating can be used to complete the polymerization. Many modifications of this basic process have been described, for example, in U.S. Pat. No. 3,511,895, which describes a continuous bulk ABS process using a three-stage reactor system to provide controlled molecular weight distribution and microgel particle size. In the first reactor, the elastomer / monomer solution is charged to the reaction mixture under high agitation to uniformly precipitate discrete rubber particles throughout the reactor bulk before appreciable crosslinking can occur. The solids content of the first, second, and third reactors is carefully controlled so that the molecular weight falls within the desired range. U.S. Pat. No. 3,981,944 discloses extracting elastomer particles using styrene monomer to dissolve / disperse the elastomer particles before adding an unsaturated monomer including a nitrile group and any other comonomers. U.S. Pat. No. 5,414,045 discloses reacting a liquid feed composition comprising a styrene monomer composition, an unsaturated nitrile monomer composition, and an elastomeric butadiene polymer in a plug flow grafting reactor to a point prior to phase inversion, and reacting a first polymerization product therefrom (grafted elastomer) in a continuous stirred tank reactor to produce a phase-inverted second polymerization product, which can then be further reacted in a finishing reactor and then devolatilized to produce the desired final product.

[0064] The linear homopolycarbonate or the linear homopolycarbonate and the styrene-containing copolymer can be present in an amount of about 10 to about 99 wt %, based on the total weight of the polycarbonate composition. Within this range, the linear homopolycarbonate or the combination of the linear homopolycarbonate and the styrene-containing copolymer can be present in an amount of about 50 to about 99 wt %, or about 60 to about 95 wt %, or about 65 to about 95 wt %, or about 70 to about 95 wt %.

[0065] In addition to the linear homopolycarbonate or the combination of a linear homopolycarbonate and a styrene-containing copolymer, a poly(carbonate-siloxane) comprising a siloxane content of about 10 to less than about 30 wt % is present in the polycarbonate composition. As used herein, the "siloxane content" of the poly(carbonate-siloxane) refers to the content of siloxane units based on the total weight of the polycarbonate composition. Within this range, the poly(carbonate-siloxane) copolymer can have a siloxane content of about 15 wt % to about 25 wt %.

[0066] The polysiloxane block of the poly(carbonate-siloxane) comprises repeating diorganosiloxane units of formula (10)

[0067]

[0068] Where each R is independently C 1-13 A monovalent organic group. For example, R can be C 1-13 Alkyl, C 1-13 Alkoxy, C 2-13 C alkenyl, C 2-13 Alkenyloxy, C 3-6 Cycloalkyl, C 3-6 Cycloalkoxy, C 6-14 Aryl, C 6-10 Aryloxy, C 7-13 Arylalkylene, C 7-13 Arylalkyleneoxy, C 7-13 Alkyl arylene, or C 7-13 Alkyl aryleneoxy. The above groups can be completely or partially halogenated with fluorine, chlorine, bromine or iodine or a combination thereof. In one aspect, when transparent poly(carbonate-siloxane) is desired, R is not substituted by halogen. Combinations of the aforementioned R groups can be used in the same copolymer. The polysiloxane block of the poly(carbonate-siloxane) can be substantially free of or exclude hydride-functionalized siloxane repeating units. With reference to formula (10), the hydride-functionalized siloxane repeating unit has hydrogen at at least one position corresponding to R. Based on the gross weight of the poly(carbonate-siloxane), as used herein, "substantially free of hydride-functionalized siloxane repeating units" refers to hydride-functionalized siloxane repeating units of less than 1wt%, less than 0.1wt% or less than 0.01wt%.

[0069] The value of E in formula (10) can vary widely, depending on the type and relative amount of each component in the polycarbonate composition, the desired performance of the composition, etc. 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 one aspect, E has an average value of 10 to 80 or 10 to 40, and in another aspect, E has an average value of 40 to 80, or 40 to 70. When E has a lower value, such as less than 40, it is desirable to use a relatively large amount of poly (carbonate-siloxane) copolymers. On the contrary, when E has a higher value, such as greater than 40, a relatively low amount of poly (carbonate-siloxane) copolymers can be used. A combination of the first and 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.

[0070] In one aspect, the polysiloxane block has formula (11):

[0071]

[0072] wherein E and R are as defined in 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 substituted or unsubstituted C 6-30 Arylene, wherein the bond is directly attached to the aromatic moiety. The Ar group in formula (11) can be derived from C 6-30 Dihydroxyarylene compounds, for example dihydroxyarylene compounds 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-tert-butylphenyl)propane.

[0073] In another aspect, the polysiloxane block has formula (13):

[0074]

[0075] Where R and E are as described above, and each R 5 Independently divalent C 1-30 In one specific aspect, the polysiloxane block is of formula (14):

[0076]

[0077] Wherein, R and E are as defined above. 6 It is a two-price C 2-8 Each M in formula (14) may be the same or different and may be halogen, cyano, nitro, C 1-8 Alkylthio, C 1-8 Alkyl, C 1-8 Alkoxy, C 2-8 Alkenyl, C 2-8 Alkenyloxy, C 3-8 Cycloalkyl, C 3-8 Cycloalkoxy, C 6-10 Aryl, C 6-10 Aryloxy, C 7-12 Aralkyl, C 7-12 Aralkyloxy, C 7-12 Alkyl, or C 7-12 Alkaryloxy, wherein each n is independently 0, 1, 2, 3 or 4.

[0078] In one aspect, M is bromo or chloro, alkyl such as methyl, ethyl, or propyl, alkoxy such as methoxy, ethoxy, or propoxy, or aryl such as phenyl, chlorophenyl, or tolyl; R 6 is dimethylene, trimethylene or tetramethylene; and R is C 1-8 In one aspect, R is methyl, M is methoxy, n is 1, and R is 1. 6 It is a two-price C 1-3 Aliphatic group. The specific polysiloxane block is the following formula:

[0079]

[0080] 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.

[0081] The blocks of formula (14) can be derived from the corresponding dihydroxy polysiloxanes, which in turn can be prepared to effect a platinum-catalyzed addition between siloxane hydrides and aliphatically unsaturated monohydric phenols such as eugenol, 2-alkylphenols, 4-allyl-2-methylphenol, 4-allyl-2-phenylphenol, 4-allyl-2-bromophenol, 4-allyl-2-tert-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. Poly(carbonate-siloxane) copolymers can then be made, for example, by the synthetic procedure of Hoover's European Patent Application Publication No. 0524731A1, page 5, Preparation 2.

[0082] The transparent poly(carbonate-siloxane) copolymer comprises carbonate units (1) derived from bisphenol A, and repeating siloxane units (14a), (14b), (14c), or a combination thereof (preferably 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 copolymer can be made using one or both of the tubular reactor methods described in U.S. Patent Application No. 2004 / 0039145A1, or the poly(carbonate-siloxane) copolymer can be synthesized using the method described in U.S. Patent No. 6,723,864.

[0083] In one aspect, blends of the following formula are used, especially blends of bisphenol A homopolycarbonate and poly(carbonate-siloxane) block copolymers of bisphenol A blocks and eugenol-terminated polydimethylsiloxane blocks:

[0084]

[0085] 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 one 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 in the polycarbonate blocks.

[0086] In one aspect, the polycarbonate composition can include a poly(carbonate-siloxane) comprising a siloxane content of less than about 10 wt %, preferably less than about 6 wt %, and more preferably less than about 4 wt % of the polysiloxane, based on the total weight of the poly(carbonate-siloxane) copolymer. In some aspects, the polycarbonate composition can exclude a poly(carbonate-siloxane) comprising a siloxane content of less than 10 wt %.

[0087] The poly(carbonate-siloxane) can have a weight average molecular weight of 2,000 to 100,000 grams per mole (g / mol), preferably 5,000 to 50,000 g / mol, as measured by gel permeation chromatography using a crosslinked styrene-divinylbenzene column at a sample concentration of 1 mg / ml, as measured according to a polystyrene standard and calculated for polycarbonate. In some aspects, a poly(carbonate-siloxane) having a siloxane content of 30 to 70 wt% and a poly(carbonate-siloxane) having a siloxane content of 10 to less than 30 wt% can each have a weight average molecular weight of at least 25,000 g / mol, preferably 27,000 g / mol. Within this range, the poly(carbonate-siloxane) can have a weight average molecular weight of 25,000 g / mol to 100,000 g / mol. The poly(carbonate-siloxane) with a siloxane content of 30 to 70 wt% may preferably have a weight average molecular weight greater than 21,000 g / mol, more preferably greater than 25,000 g / mol. When the weight average molecular weight of the poly(carbonate-siloxane) with a siloxane content of 30 to 70 wt% is within these ranges, delamination of the molded sample can be avoided. The poly(carbonate-siloxane) with a siloxane content of 30 to 70 wt% may have a weight average molecular weight greater than 30,000 to less than 50,000 g / mol. When the weight average molecular weight of the poly(carbonate-siloxane) with a siloxane content of 30 to 70 wt% is within this range, processability and chemical resistance can be improved.

[0088] Poly(carbonate-siloxane)s having a siloxane content of 10 wt % to less than 30 wt % can have a weight average molecular weight of 25,000 g / mol to 40,000 g / mol, more preferably 27,000 g / mol to 32,000 g / mol, measured by gel permeation chromatography using a cross-linked styrene-divinylbenzene column at a sample concentration of 1 mg / ml against polystyrene standards and calculated for the polycarbonate.

[0089] In one aspect, the composition comprises less than or equal to about 5 wt %, or less than or equal to about 1 wt %, or less than or equal to about 0.1 wt % of a poly(carbonate-siloxane) comprising a siloxane content of less than about 10 wt %. Poly(carbonate-siloxane) comprising a siloxane content of less than about 10 wt % can be excluded from the composition. Preferably, poly(carbonate-siloxane) comprising a siloxane content of about 6 wt % can be excluded from the composition.

[0090] The poly(carbonate-siloxane) having a siloxane content of about 10 to less than about 30 wt % can be present in an amount effective to provide about 1 to about 6 wt %, or about 3 to about 6 wt % siloxane, based on the total weight of the polycarbonate composition.

[0091] The poly(carbonate-siloxane) can have a melt volume flow rate of 1 to 50 cubic centimeters per 10 minutes (cc / 10 min), preferably 2 to 30 cc / 10 min, measured at 300°C / 1.2 kg. Combinations of poly(carbonate-siloxane)s having different flow properties can be used to achieve the overall desired flow properties.

[0092] The polycarbonate composition includes ultra high molecular weight (UHMW) polydimethylsiloxane. In some aspects, one or more of the two methyl groups on each siloxane repeating unit can be substituted with other functional groups to affect compatibility within a given composition.

[0093] The number of repeating units in UHMW polydimethylsiloxane can be as high as several thousand, which accounts for a molecular weight of up to one million g / mol. According to the GPC method using a polystyrene standard, the UMHW polydimethylsiloxane can have a weight average molecular weight of at least 100,000 g / mol or at least 120,000 g / mol. The UMHW polydimethylsiloxane can be included in a carrier resin as a masterbatch (MB). The carrier resin is not particularly limited and can include any thermoplastic polymer as long as the thermoplastic polymer is compatible with the polycarbonate composition. In some aspects, the carrier resin is polycarbonate. UMHW polydimethylsiloxane as MB in polycarbonate (30wt%) is available as PEARLENE, MB01 from Momentive Performance Materials.

[0094] The UHMW polydimethylsiloxane is present in an amount effective to provide a siloxane content of greater than about 0.3 to less than about 0.9 wt%, or greater than about 0.3 to less than about 0.75 wt%, each based on the total weight of the polycarbonate composition. When the amount of UHMW polydimethylsiloxane exceeds an amount effective to provide a siloxane content of about 0.9 wt%, aesthetic issues such as gate blush and surface defects may occur.

[0095] The composition provided by the poly(carbonate-siloxane) having a siloxane content of about 10 wt% to less than about 30 wt% has a siloxane content that is greater than the siloxane content provided by the UHMW polydimethylsiloxane. The weight ratio of siloxane provided by the poly(carbonate-siloxane) having a siloxane content of about 10 wt% to less than about 30 wt% to siloxane provided by the UHMW polydimethylsiloxane can be greater than about 1:1, or at least about 2:1, or at least about 3:1, or at least about 4:1, or at least about 5:1.

[0096] The polycarbonate composition comprises a flame retardant. The flame retardant may include a halogenated flame retardant, provided that the halogen content of the composition is within the guidance range as set forth in IEC 61249-2-21 and / or UL 746H. According to both IEC 61249-2-21 and UL746H, the bromine and chlorine contents are each below 900ppm and the total bromine, chlorine and fluorine content of the polycarbonate composition is below 1500ppm. UL 746H has an additional requirement that the fluorine content of the composition is below 900ppm. These values ​​can be calculated or determined by elemental analysis techniques.

[0097] The halogenated flame retardants may include halogenated compounds and polymers of formula (20):

[0098]

[0099] Wherein, R is an alkylene, an alkylidene, or an alicyclic bond (e.g., methylene, ethylene, propylene, isopropylene, isopropylidene, butylene, isobutylene, pentylene, cyclohexylene, cyclopentylidene, etc.), selected from bonds of oxygen ether, carbonyl, amine, sulfur-containing bonds (e.g., thioether, sulfoxide, or sulfone), phosphorus-containing bonds, etc., or R may also be composed of two or more alkylene or alkylidene bonds connected by groups such as aromatic, amino, ether, carbonyl, thioether, sulfoxide, sulfone, phosphorus-containing bonds, etc.; Ar and Ar' may be wherein X is an aromatic radical which may be the same or different and which is monocyclic or polycyclic, such as phenylene, biphenylene, terphenylene, naphthylene, etc.; Y is an organic, inorganic or organometallic radical, such as a halogen (e.g., chlorine, bromine, iodine, or fluorine), an ether radical of the general formula OE, wherein E is a monovalent hydrocarbon radical similar to X, a monovalent hydrocarbon radical of the type represented by R, or other substituents (e.g., nitro, cyano, etc.), the substituents being substantially inert, provided that at least one and preferably two halogen atoms are present per aromatic nucleus; each X is the same or different and is a monovalent hydrocarbon group, such as an alkyl group (e.g., methyl, ethyl, propyl, isopropyl, butyl, decyl, etc.), an aryl group (e.g., phenyl, naphthyl, biphenyl, xylyl, tolyl, etc.), an arylalkylene group (e.g., benzyl, vinylphenyl, etc.), an alicyclic group (e.g., cyclopentyl, cyclohexyl, etc.), and a monovalent hydrocarbon group containing an inert substituent; the letter d represents a maximum of 1 to the same number of replaceable hydrogens substituted on the aromatic ring including Ar or Ar'. The letter e represents an integer from 0 to a maximum value equal to the number of replaceable hydrogens on R; the letters a, b and c represent integers including 0, provided that when b is not 0, neither a nor c can be 0, or either a or c but not both can be 0, or when b is 0, the aromatic group is attached by a direct carbon-carbon bond; the hydroxyl and Y substituents, Ar and Ar' on the aromatic group can vary in the ortho, meta or para position of the aromatic ring, and the groups can be in any possible geometric relationship to each other.

[0100] Included within the scope of the above formula are the following representative bisphenols: 2,2-bis-(3,5-dichlorophenyl)-propane; bis-(2-chlorophenyl)-methane; bis-(2,6-dibromophenyl)-methane; 1,1-bis-(4-iodophenyl)-ethane; 1,2-bis-(2,6-dichlorophenyl)-ethane; 1,1-bis-(2-chloro-4-iodophenyl)-ethane; 1,1-bis-(2-chloro-4-methylphenyl)-ethane; 1,1-bis-(3,5-dichlorophenyl)-ethane; 2,2-bis-(3-phenyl-4-bromophenyl)-ethane ; 2,6-bis-(4,6-dichloronaphthyl)-propane; 2,2-bis-(2,6-dichlorophenyl)-pentane; 2,2-bis-(3,5-dibromophenyl)-hexane; bis-(4-chlorophenyl)-phenyl-methane; bis-(3,5-dichlorophenyl)-cyclohexylmethane; bis-(3-nitro-4-bromophenyl)-methane; bis-(4-hydroxy-2,6-dichloro-3-methoxyphenyl)-methane; and 2,2-bis-(3,5-dichloro-4-hydroxyphenyl)-propane; 2,2-bis-(3-bromo-4-hydroxyphenyl)-propane. Also included in the above structural formula are: 1,3-dichlorobenzene, 1,4-dibromobenzene, 1,3-dichloro-4-hydroxybenzene, and biphenyls such as 2,2'-dichlorobiphenyl, polybrominated 1,4-diphenoxybenzene, 2,4'-dibromobiphenyl, and 2,4'-dichlorobiphenyl and decabromodiphenyl ether.

[0101] Oligomeric and polymeric halogenated aromatic compounds are also useful, such as copolycarbonates of bisphenol A and tetrabromobisphenol A with carbonate precursors (eg, phosgene). Metal synergists, such as antimony oxide, may also be used with the flame retardants.

[0102] Inorganic flame retardants such as C 2-16 Salts of alkyl sulfonates such as potassium perfluorobutanesulfonate (Rimar salt), potassium perfluorooctanesulfonate and tetraethylammonium perfluorohexanesulfonate, salts of aromatic sulfonates such as sodium benzenesulfonate, sodium toluenesulfonate (NATS), etc., salts of aromatic sulfone sulfonates such as potassium diphenylsulfonesulfonate (KSS), etc.; salts formed by reaction, for example, alkali metal or alkaline earth metal (for example, lithium, sodium, potassium, magnesium, calcium and barium salts) and inorganic acid complex salts, for example, oxygen-anions (for example, alkali metal and alkaline earth metal salts of carbonate, such as Na2CO3, K2CO3, MgCO3, CaCO3, and BaCO3, or fluorine-anion complexes such as Li3AlF6, BaSiF6, KBF4, K3AlF6, KAlF4, K2SiF6, or Na3AlF6, etc.). Rimar salts and KSS and NATS, alone or in combination with other flame retardants, are particularly useful. Rimar salts and KSS and NATS, alone or in combination with other flame retardants, are particularly useful.

[0103] Di- or polyfunctional aromatic phosphorus-containing compounds are also useful, for example, compounds of formula (14):

[0104]

[0105] Among them, each G 2 is independently a hydrocarbyl or hydrocarbyloxy group having 1 to 30 carbon atoms, and n is 0 to 3.

[0106] Specific aromatic organophosphorus compounds have two or more phosphorus-containing groups and include acid esters of formula (15):

[0107]

[0108] Among them, R 16 , R 17 , R 18 , and R 19 Each is independently C 1-8 Alkyl, C 5-6 Cycloalkyl, C 6-20 Aryl, or C 7-12 Arylalkylene, each optionally substituted with C 1-12 Alkyl, preferably C 1-4 alkyl substituted, and X is a mononuclear or polynuclear aromatic C 6-30 Partial or linear or branched C 2-30 an aliphatic group which may be OH-substituted and may contain up to 8 ether bonds, provided that R 16 , R 17 , R 18 , R 19 In some aspects, at least one of R 16 , R 17 , R 18 , and R 19 Each is independently C 1-4 Alkyl, naphthyl, phenyl (C 1-4 ) alkylene, or optionally C 1-4 Alkyl substituted aryl groups. Specific aryl moieties are tolyl, phenyl, xylyl, propylphenyl, or butylphenyl. In some aspects, X in formula (15) is a mononuclear or polynuclear aromatic C derived from a diphenol. 6-30 In addition, in formula (15), n is each independently 0 or 1; in some aspects, n is equal to 1. Also in formula (15), q is 0.5 to 30, 0.8 to 15, 1 to 5, or 1 to 2. Preferably, X can be represented by the following divalent group (16) or a combination thereof.

[0109]

[0110] In these respects, R 16 , R 17 , R 18 , and R 19 Each of R may be aromatic, i.e., phenyl, n is 1, and p is 1-5, preferably 1-2. In some aspects, R 16 , R 17 , R 18 , R 19 At least one of , and X corresponds to a monomer used to form a polycarbonate, for example, bisphenol A or resorcinol. In another aspect, X is particularly derived from resorcinol, hydroquinone, bisphenol A, or diphenylphenol, and R 16 , R 17 , R 18 , R 19 is aromatic, preferably phenyl. A specific aromatic organophosphorus compound of this type is resorcinol bis(diphenyl phosphate), also known as RDP. Another specific class of aromatic organophosphorus compounds having two or more phosphorus-containing groups is the compound of formula (17)

[0111]

[0112] Among them, R 16 , R 17 , R 18 , R 19 , n and q are as defined for formula (19), and wherein Z is C 1-7 Alkylene, C 1-7 Alkylene, C 5-12 A specific aromatic organophosphorus compound of this type is bisphenol A bis(diphenyl phosphate), also known as BPADP, wherein R 16 , R 17 , R 18 , and R 19 Each is phenyl, each n is 1, and q is from 1 to 5, from 1 to 2, or 1.

[0113] Flame retardant compounds containing phosphorus-nitrogen bonds include phosphazenes, phosphazene chlorides, phosphorus ester amides, phosphoric acid amides, phosphonic acid amides, phosphinic acid amides, and tris(aziridinyl)phosphine oxide. Specific examples include phosphoramides of the formula:

[0114]

[0115] wherein each A moiety is a 2,6-dimethylphenyl moiety or a 2,4,6-trimethylphenyl moiety. These phosphoramides are piperazine-type phosphoramides.

[0116] Phosphazene (18) and cyclophosphazene (19)

[0117]

[0118] In particular, it is possible to use wherein w1 is 3 to 10,000 and w2 is 3 to 25, preferably 3 to 7, and each R w Independently C 1-12 Alkyl, alkenyl, alkoxy, aryl, aryloxy, or polyoxyalkylene groups. In the above groups, at least one hydrogen atom in these groups may be substituted by a group having N, S, O, or F atoms, or an amino group. For example, each R w It may be a substituted or unsubstituted phenoxy, amino, or polyoxyalkylene group. w There may further be a crosslink to another phosphazene group. Exemplary crosslinks include bisphenol groups, such as bisphenol A groups. Examples include phenoxycyclotriphosphazene, octaphenoxycyclotetraphosphazene, decaphenoxycyclopentaphosphazene, and the like. Combinations of different phosphazenes may be used. Many phosphazenes and their synthesis are described in HR Allcook, "Phosphorous-Nitrogen Compounds" Academic Press (1972). In aromatic organophosphorus compounds having at least one organic aromatic group, the aromatic group may be substituted or unsubstituted C 3-30 Group, the C 3-30 The group contains one or more monocyclic or polycyclic aromatic moieties (which may optionally contain up to three heteroatoms (N, O, P, S, or Si)) and optionally further contains one or more non-aromatic moieties, such as alkyl, alkenyl, alkynyl, or cycloalkyl. The aromatic portion of the aromatic group may be directly bonded to the phosphorus-containing group, or bonded via another portion (e.g., an alkylene group). The aromatic portion of the aromatic group may be directly bonded to the phosphorus-containing group, or bonded via another portion (e.g., an alkylene group). In one aspect, the aromatic group is the same as the aromatic group of the polycarbonate backbone, such as a bisphenol group (e.g., bisphenol A), a monoarylene group (e.g., 1,3-phenylene or 1,4-phenylene), or a combination comprising at least one of the foregoing.

[0119] The phosphorus-containing group can be a phosphate (P(=O)(OR)3), a phosphite (P(OR)3), a phosphonate (RP(=O)(OR)2), a phosphinate (R2P(=O)(OR)), a phosphine oxide (R3P(=O)), or a phosphine (R3P), wherein each R in the aforementioned phosphorus-containing group can be the same or different, provided that at least one R is an aromatic group. Combinations of different phosphorus-containing groups can be used. The aromatic group can be directly or indirectly bonded to the phosphorus, or bonded to the oxygen of the phosphorus-containing group (i.e., ester).

[0120] In one aspect, the aromatic organophosphorus compound is a monomeric phosphate. Representative monomeric aromatic phosphates have 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 G groups can be linked together to provide a cyclic group. In some aspects, G corresponds to a monomer for forming a polycarbonate, for example, resorcinol. Exemplary phosphates include phenyl didodecyl phosphate, phenyl di(neopentyl) phosphate, phenyl di(3,5,5'-trimethylhexyl) phosphate, ethyl diphenyl phosphate, 2-ethylhexyl di(p-tolyl) phosphate, di(2-ethylhexyl) p-tolyl phosphate, tricresyl phosphate, di(2-ethylhexyl) phenyl phosphate, tri(nonylphenyl) phosphate, didodecyl p-tolyl phosphate, dibutylphenyl phosphate, 2-chloroethyl diphenyl phosphate, p-tolyl di(2,5,5'-trimethylhexyl) phosphate, 2-ethylhexyl diphenyl phosphate, etc. Specific aromatic phosphates are those in which each G is aromatic, for example, triphenyl phosphate, tricresyl phosphate, isopropylated triphenyl phosphate, etc.

[0121] Di- or polyfunctional aromatic organophosphorus compounds are also useful, for example, compounds of the formula:

[0122]

[0123] Among them, each G 1 Independently C 1-30 Hydrocarbon; each G 2 Independently for C 1-30 Hydrocarbyl or alkoxy; X a is as defined in formula (3) or formula (4); each X is independently bromine or chloride; m is 0 to 4, and n is 1 to 30. In one specific aspect, X a It is a single bond, methylene, isopropylidene or 3,3,5-trimethylcyclohexylidene.

[0124] Specific aromatic organophosphorus compounds include acid esters of formula (9):

[0125]

[0126] Among them, each R 16 Independently C 1-8 Alkyl, C 5-6 Cycloalkyl, C 6-20 Aryl, or C 7-12 Arylalkylene, each optionally substituted by C 1-12 Alkyl, specifically C 1-4alkyl substituted, and X is a mononuclear or polynuclear aromatic C 6-30 Partial or linear or branched C 2-30 an aliphatic group which may be OH-substituted and may contain up to 8 ether bonds, provided that at least one R 16 or X is an aromatic group; each n is independently 0 or 1; and q is from 0.5 to 30. In some aspects, each R 16 Independently C 1-4 Alkyl, naphthyl, phenyl (C 1-4 ) alkylene, optionally C 1-4 Alkyl substituted aryl group; each X is a mononuclear or polynuclear aromatic C 6-30 part, each n is 1; and q is from 0.5 to 30. In some aspects, each R 16 is aromatic, such as phenyl; each X is a mononuclear or polynuclear aromatic C 6-30 moieties, including moieties derived from formula (2); n is 1; and q is from 0.8 to 15. In other aspects, each R 16 is phenyl; X is tolyl, xylyl, propylphenyl, or butylphenyl, one of the following divalent groups

[0127]

[0128] or a combination comprising one or more of the foregoing; n is 1; and q is 1 to 5, or 1 to 2. In some aspects, at least one R 16 Or X corresponds to the monomer used to form the polycarbonate, for example, bisphenol A, resorcinol, etc. Aromatic organophosphorus compounds of this type include bis(diphenyl)phosphate of hydroquinone, resorcinol bis(diphenyl phosphate) (RDP), and bisphenol A bis(diphenyl)phosphate (BPADP), as well as their oligomeric and polymeric counterparts.

[0129] The organophosphorus flame retardant containing a phosphorus-nitrogen bond can be a phosphazene, a phosphazene chloride, a phosphorus ester amide, a phosphoric acid amide, a phosphonic acid amide, a phosphinate amide, or a tris(aziridinyl)phosphine oxide. These flame retardant additives are commercially available. In one aspect, the organophosphorus flame retardant containing a phosphorus-nitrogen bond is a phosphazene or a cyclic phosphazene of the formula:

[0130]

[0131] wherein w1 is 3 to 10,000; w2 is 3 to 25, or 3 to 7; and each R w Independently C 1-12 Alkyl, alkenyl, alkoxy, aryl, aryloxy, or polyoxyalkylene groups. In the above groups, at least one hydrogen atom in these groups may be substituted by a group having N, S, O, or F atoms, or an amino group. For example, each Rw It may be a substituted or unsubstituted phenoxy, amino, or polyoxyalkylene group. w There may further be a crosslink to another phosphazene group. Exemplary crosslinks include bisphenol groups, such as bisphenol A groups. Examples include phenoxycyclotriphosphazene, octaphenoxycyclotetraphosphazene, decaphenoxycyclopentaphosphazene, and the like. In one aspect, the phosphazene has a structure represented by the formula:

[0132]

[0133] Commercially available phenoxyphosphazenes having the above structure are LY202 manufactured and sold by Lanyin Chemical Co., Ltd., FP-110 manufactured and sold by Fushimi Pharmaceutical Co., Ltd., and SPB-100 manufactured and sold by Otsuka Chemical Co., Ltd.

[0134] When present, the phosphorus-containing flame retardant is typically present in an amount effective to provide up to 5 wt% phosphorus, based on the gross weight of the composition. In addition, if halogenated, the phosphorus-containing flame retardant is typically present in an amount effective to provide about 900 ppm or less of each of bromine, chlorine, and optionally fluorine, and about 1500 ppm or less of a total halogen content (e.g., bromine, chlorine, and fluorine), based on the gross weight of the composition.

[0135] Additive compositions can be used, including one or more additives selected to achieve the desired performance, provided that additives are also selected to not significantly adversely affect the flame retardancy and anti-drip properties of the polycarbonate composition. During the mixing of the components used to form the composition, additive compositions or separate additives can be mixed at the appropriate time. Additives can be soluble or insoluble in polycarbonate. Additive compositions can include impact modifiers, flow modifiers, fillers (e.g., particles, polytetrafluoroethylene (PTFE), glass, carbon, minerals, or metals), reinforcing agents (e.g., glass fibers), antioxidants, heat stabilizers, light stabilizers, ultraviolet (UV) light stabilizers, UV absorbing additives, plasticizers, lubricants, mold release agents (e.g., mold release agents), antistatic agents, antifogging agents, biocides, colorants (e.g., dyes or pigments), surface effect additives, radiation stabilizers, or combinations thereof. In some respects, the additive composition may not include fillers, such as mineral fillers. For example, a combination of heat stabilizers, mold release agents, and ultraviolet light stabilizers can be used. Typically, additives are used in a commonly known effective amount. For example, the total amount of the additive composition (other than any impact modifier, filler, or reinforcing agent) can be 0.001 to 10.0 wt%, or 0.01 to 5 wt%, each based on the total weight of the polymer of the composition.

[0136] Colorants such as 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 dioxide, iron oxide, etc.; sulfides such as zinc sulfide, etc.; aluminates; sodium thiosilicate sulfate, chromates, etc.; carbon black; zinc ferrite; ultramarine; organic pigments such as azo, diazo, quinacridone, perylene, naphthalenetetracarboxylic acid, flavanone, isoindolinone, tetrachloroisoindolinone, anthraquinone, anthrone, dioxazine, phthalocyanine, 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 combinations thereof.

[0137] Polycarbonate compositions can be prepared by various methods. For example, in a HENSCHEL-Mixer high-speed mixer, powdered polycarbonate, flame retardant or other optional components are optionally first blended with fillers. Other low shear methods, including but not limited to manual mixing, can also achieve this blending. The blend is then fed to the throat of a twin-screw extruder through a hopper. Alternatively, at least one component can be incorporated into the composition by directly feeding the extruder through a side stuffer (sidestuffer) at the throat or downstream. Additives can also be mixed into a masterbatch with the desired polymer and fed to the extruder. The extruder is usually operated at a temperature higher than that necessary to cause the composition to flow. The extrudate is immediately quenched and granulated in a water bath. As required, the pellets prepared in this way can be a quarter inch long or less. Such pellets can be used for subsequent molding, shaping, or forming.

[0138] The flammability test is conducted in accordance with the procedures of Underwriter's Laboratory Bulletin 94 entitled "Tests for Flammability of Plastic Materials for Parts in Devices and Appliances" (ISBN 0-7629-0082-2), Fifth Edition, October 29, 1996, incorporating revisions up to and including December 12, 2003. Several ratings may be applied based on burning rate, extinguishing time, ability to resist dripping, and whether dripping burns. According to this procedure, materials may be classified as UL-94HB, V-0, V-1, V-2, 5VA, and / or 5VB.

[0139] Also provided are molded, formed or molded articles comprising polycarbonate compositions. The polycarbonate compositions can be molded into useful molded articles by a variety of methods, such as injection molding, extrusion, rotational molding, blow molding and thermoforming. Some embodiments of the articles include computer and business machine housings such as housings for monitors, handheld electronic device housings such as housings for cellular phones, electrical connectors, and components of lighting equipment, decorative objects, household appliances, roofs, greenhouses, sunrooms, swimming pool covers, etc. In some aspects, the polycarbonate compositions can be used for articles such as mobile phones, tablets, industrial housings, circuit protection, personal safety helmets, electric vehicle power supply equipment (EVSE) housings and connectors. In some aspects, the polycarbonate compositions can be used for applications such as industry, construction, and architecture, automotive exterior and interior, electrical and electronics, sports / leisure, personal accessories, mass transportation, health care and consumers. It is also suitable for defense, outdoor lawn and landscape, water management, fossils, electrical devices and displays, special vehicles, surgery, ophthalmology, railroad, home decoration, household appliances, electrical components and infrastructure, personal entertainment, healthcare, patient testing, automotive under the hood, commercial appliances, industrial material handling and aerospace, etc.

[0140] The polycarbonate compositions are further illustrated by the following non-limiting examples.

[0141] Example

[0142] The following components were used in the examples. Unless otherwise specifically stated, the amount of each component is in wt % based on the total weight of the composition.

[0143] The materials shown in Table 1 were used.

[0144] Table 1

[0145]

[0146]

[0147] The test samples were prepared as described below and the following test methods were used.

[0148] The typical compounding procedure is described as follows: Various formulations were prepared by direct dry blending of the raw materials and homogenized with a paint shaker prior to compounding. These formulations were compounded on a 26 mm Coperion ZSK co-rotating twin screw extruder. Typical extrusion profiles are listed in Table 2.

[0149] Table 2

[0150] parameter unit 25mm ZSK Feed temperature ℃ 177 Zone 1 Temperature ℃ 232 Zone 2-8 Temperature ℃ 266 Die temperature ℃ 271 Screw speed rpm 400 Throughput kg / h 70 Torque ％ 75-80

[0151] A Demag molding machine was used to mold test parts for standard physical property testing. (See Table 3 for parameters).

[0152] Table 3

[0153] parameter unit Pre-drying time h 4 Pre-drying temperature ℃ 120 Zone 1-3 Temperature ℃ 290 Nozzle temperature ℃ 290 Mold temperature ℃ 82 Screw speed rpm 100 Backpressure -bar 3.4 Injection time s 1-2 Approximate cycle time s 31-35

[0154] Sample preparation and test methods are described in Table 4. A description and table for the UL-94 flame test needs to be added.

[0155] Table 4

[0156]

[0157] The samples were tested for flammability at 1.5 mm, 1.0 mm, and 0.8 mm thicknesses according to the Underwriter's Laboratory (UL) UL 94 standard. In some cases, a second set of 5 bars was tested to give an indication of the robustness of the rating. This report uses the following definitions as shown in Table 5. The total flame out time (FOT) of all bars (FOT=t1+t2) was determined. For each set of 10 bars to obtain a V rating, 5 were conditioned at 23°C for 48 hours and 5 were conditioned at 70°C for 168 hours.

[0158] Table 5

[0159]

[0160] Examples 1-8

[0161] The compositions and properties of the following comparative examples and examples are shown in Table 6. Comparative examples are indicated by asterisks.

[0162] Table 6

[0163]

[0164]

[0165] Table 6 shows compositions comprising BPA homopolycarbonate (PC-1, PC-2) with a combination of poly(carbonate-siloxane) comprising a higher siloxane content (i.e., 40 wt%) and a poly(carbonate-siloxane) comprising a lower siloxane content (i.e., 20 wt%), and a combination of flame retardants, which were used to prepare molded samples having a white color. TiO2 was selected as a colorant because it is a challenge to produce white molded samples with a UL-94 burn test rating of V-0 at 1.5 mm. Comparative Example 1 contains an anti-drip agent (TSAN), and the anti-drip agent is excluded from the remaining compositions in Table 6. Comparative Examples 1 and 2 show that the removal of the anti-drip agent results in an adverse effect on the UL-94 burn test rating (from V-1 to V-2), the number of drips (from no drips to 3 at 23°C and from no drips to 4 at 70°C, some of which ignited the cotton), and FOT (from 1 to 3). FOT is a measure of how many molded bars have a flame out time greater than 10 s. In Examples 3-8, there is no anti-drip agent. In contrast, UHMW polydimethylsiloxane is added. The combination of UHMW polydimethylsiloxane (1 wt%, 0.3 wt% loading of siloxane content based on the total weight of the composition) failed to improve the UL-94 flame test rating, the number of drops, or the FOT. When the UHMW polydimethylsiloxane was increased to 2 wt% and 3 wt%, the desired combination of a UL-94 flame test rating of V-0 at a thickness of 1.5 mm, no dripping at 23° C. or 70° C., and a FOT of 0 s was obtained (see Examples 5-8). Although Example 5 has a higher siloxane content than Comparative Examples 1-4, the presence of UHMW polydimethylsiloxane (at a loading of greater than 1 wt%, corresponding to a siloxane content greater than 0.3 wt% based on the total weight of the composition) rather than the total siloxane content (contributed by both UHMW polydimethylsiloxane and poly(carbonate-siloxane)) provides the desired combination of properties. Indeed, as demonstrated by comparing Example 2 and Examples 6 and 8, where no anti-drip agent is present, even when the siloxane content of the total composition is the same (i.e., 4.44 wt%), the desired combination of properties is not achieved when UHMW polydimethylsiloxane is absent. Example 7 shows that increasing the total siloxane content to 5.34 wt% also provides the desired combination of properties.

[0166] The present invention further encompasses the following aspects.

[0167] Aspect 1. A polycarbonate composition comprising a linear homopolycarbonate and an optional styrene-containing copolymer; a poly(carbonate-siloxane) comprising a siloxane content of about 10 wt % to less than about 30 wt % siloxane, present in an amount effective to provide a siloxane content of about 1 wt % to about 6 wt % based on the total weight of the poly(carbonate-siloxane); an ultra-high molecular weight polydimethylsiloxane, present in an amount effective to provide greater than about 0.3 wt % to less than about 0.9 wt % siloxane based on the total weight of the composition, wherein the weight average molecular weight of the polydimethylsiloxane is at least 100,000 grams / mole, as determined by gel permeation chromatography based on polystyrene standards; a flame retardant; and optionally, an additive composition, wherein the linear homopolycarbonate, the optional styrene-containing copolymer, the poly(carbonate-siloxane), the ultra-high molecular weight polydimethylsiloxane, the flame retardant, and the optional additive composition total 100 wt %.

[0168] Aspect 1a. The polycarbonate composition according to aspect 1, wherein the additive composition comprises up to about 10 wt%, or up to about 5 wt% of the polycarbonate composition.

[0169] Aspect 1b. The polycarbonate composition according to any of the preceding aspects, comprising about 60 to about 95 wt %, preferably about 65 to about 95 wt %, more preferably about 70 to about 95 wt % of the linear homopolycarbonate and the optional styrene-containing copolymer.

[0170] Aspect 1c. A polycarbonate composition according to any of the preceding aspects, wherein the additive composition comprises an impact modifier, a flow modifier, a filler, a reinforcing agent, an antioxidant, a heat stabilizer, a light stabilizer, a UV light stabilizer, a UV absorbing additive, a plasticizer, a lubricant, a mold release agent, an antistatic agent, an antifog agent, an antimicrobial agent, a colorant, a surface effect additive, a radiation stabilizer, or a combination thereof.

[0171] Aspect 1d. A polycarbonate composition according to any of the preceding aspects, wherein the additive composition comprises an impact modifier, a flow modifier, a reinforcing agent, an antioxidant, a heat stabilizer, a light stabilizer, a UV light stabilizer, a UV absorbing additive, a plasticizer, a lubricant, a mold release agent, an antistatic agent, an antifog agent, an antimicrobial agent, a colorant, a surface effect additive, a radiation stabilizer, or a combination thereof.

[0172] Aspect 1e. A polycarbonate composition according to any of the preceding aspects, wherein the additive composition comprises an impact modifier, a flow modifier, an antioxidant, a heat stabilizer, a light stabilizer, a UV light stabilizer, a UV absorbing additive, a plasticizer, a lubricant, a mold release agent, an antistatic agent, an antifog agent, an antimicrobial agent, a colorant, a surface effect additive, a radiation stabilizer, or a combination thereof.

[0173] Aspect 1f. A polycarbonate composition according to any of the preceding aspects, wherein the additive composition comprises a flow modifier, a reinforcing agent, an antioxidant, a heat stabilizer, a light stabilizer, a UV light stabilizer, a UV absorbing additive, a plasticizer, a lubricant, a mold release agent, an antistatic agent, an antifog agent, an antimicrobial agent, a colorant, a surface effect additive, a radiation stabilizer, or a combination thereof.

[0174] Aspect 2. A polycarbonate composition according to any of the preceding aspects, wherein the calculated weight percentages of the bromine and chlorine contents of the polycarbonate composition are each about 900 ppm or less and the calculated weight percentage of the total halogen content of the polycarbonate composition is about 1500 ppm or less; or the calculated weight percentages of the bromine, chlorine, and fluorine contents of the polycarbonate composition are each about 900 ppm or less and the calculated weight percentages of the total bromine, chlorine, and fluorine contents of the polycarbonate composition are about 1500 ppm or less.

[0175] Aspect 3. The polycarbonate composition according to aspect 1, wherein a molded sample comprising the polycarbonate composition exhibits a UL-94 rating of V-0 at a thickness of 1.5 mm or less.

[0176] Aspect 4. The polycarbonate composition according to any of the preceding aspects, wherein the poly(carbonate-siloxane) comprises repeating diorganosiloxane units of formula (10)

[0177]

[0178] Where each R is independently C 1-13 A monovalent organic group, preferably C 1-13 Alkyl, C 1-13 Alkoxy, C 2-13 Alkenyl, C 2-13 Alkenyloxy, C 3-6 Cycloalkyl, C 3-6 Cycloalkoxy, C 6-14 Aryl, C 6-10 Aryloxy, C 7-13 Arylalkylene, C 7-13 Arylalkyleneoxy, C 7-13 Alkyl arylene, or C 7-13 The alkylaryleneoxy groups are each optionally fully or partially halogenated with fluorine, chlorine, bromine, or iodine, or a combination thereof.

[0179] Aspect 5. A polycarbonate composition according to any of the preceding aspects, wherein the linear homopolycarbonate is a bisphenol A polycarbonate homopolymer, including a linear bisphenol A polycarbonate homopolymer having a weight average molecular weight of 15,000 to 25,000 g / mol, preferably 17,000 to 25,000 g / mol, as measured by gel permeation chromatography according to polystyrene standards and calculated for polycarbonate; or a linear bisphenol A polycarbonate homopolymer having a weight average molecular weight of 26,000 to 40,000 g / mol, preferably 27,000 to 35,000 g / mol, as measured by gel permeation chromatography according to polystyrene standards and calculated for polycarbonate; or a combination thereof.

[0180] Aspect 6. The polycarbonate composition according to any one of the preceding aspects, wherein the poly(carbonate siloxane) comprises bisphenol A carbonate repeating units and poly(dimethylsiloxane) repeating units.

[0181] Aspect 7. The polycarbonate composition according to any of the preceding aspects, wherein the poly(carbonate siloxane) has a siloxane content of about 15 to about 25 wt %, based on the total weight of the poly(carbonate siloxane).

[0182] Aspect 8. The polycarbonate composition according to any one of the preceding aspects, wherein the flame retardant comprises an alkyl sulfonate, an aromatic sulfonate, an organic phosphorus compound, or a combination thereof.

[0183] Aspect 9. The polycarbonate composition according to any of the preceding aspects, wherein the flame retardant is non-halogenated.

[0184] Aspect 10. A polycarbonate composition according to any of the preceding aspects, wherein a styrene-containing copolymer is present and comprises an elastomeric phase, the elastomeric phase comprising (i) butadiene and having a glass transition temperature of less than 10°C, and (ii) a rigid polymer phase, the rigid polymer phase having a glass transition temperature greater than 15°C and comprising a copolymer of a monovinyl aromatic monomer, the monovinyl aromatic monomer comprising styrene and an unsaturated nitrile.

[0185] Aspect 11. The polycarbonate composition according to any of the preceding aspects, wherein the composition does not include a halogenated anti-drip agent, preferably a fluorinated anti-drip agent.

[0186] Aspect 12. A polycarbonate composition according to any of the preceding aspects, comprising a linear homopolycarbonate and an optional styrene-containing copolymer; a poly(carbonate-siloxane) comprising a siloxane content of about 10 wt % to less than about 30 wt % siloxane, present in an amount effective to provide a siloxane content of about 1 wt % to about 6 wt % based on the total weight of the polycarbonate composition; an ultra-high molecular weight polydimethylsiloxane, present in an amount effective to provide greater than about 0.3 wt % to less than about 0.9 wt % siloxane based on the total weight of the composition, wherein the weight average molecular weight of the polydimethylsiloxane is at least 100,000 grams / mole, as determined by gel permeation chromatography based on polystyrene standards; and a flame retardant comprising an aromatic sulfonate; and an optional additive composition.

[0187] Aspect 12a. A polycarbonate composition according to aspect 12, wherein the styrene-containing copolymer is present and comprises styrene-butadiene-styrene (SBS), styrene-butadiene rubber (SBR), styrene-ethylene-butadiene-styrene (SEBS), acrylonitrile-butadiene-styrene (ABS), acrylonitrile-ethylene-propylene-diene-styrene (AES), styrene-isoprene-styrene (SIS), methyl methacrylate-butadiene-styrene (MBS), styrene-acrylonitrile (SAN), or a combination thereof, preferably acrylonitrile-butadiene-styrene (ABS).

[0188] Aspect 13. A method of making the polycarbonate composition of any of the preceding aspects, the method comprising melt mixing the components of the composition.

[0189] Aspect 14. The method according to aspect 13, further comprising molding, casting or extruding the composition to provide the article.

[0190] Aspect 15. An article comprising the polycarbonate composition according to any of the preceding aspects.

[0191] Alternatively, the compositions, methods and articles may comprise, consist of or consist essentially of any suitable material, step or component disclosed herein. The compositions, methods and articles may additionally or alternatively be formulated so as to be free of or essentially free of any material (or species), step, or component that is otherwise not necessary for achieving the function or purpose of the compositions, methods and articles.

[0192] All ranges disclosed herein include the endpoints, and the endpoints are independently combinable with each other (e.g., a range of "up to 25 wt %, or more specifically, 5 wt % to 20 wt %" includes the endpoints and all intermediate values ​​of the range of "5 wt % to 25 wt %, etc.). Taking into account the measurement in question and the errors associated with the measurement of a particular quantity (i.e., the limitations of the measurement system), as used herein, "about" includes the stated value and means within an acceptable deviation range for the particular value as determined by one of ordinary skill in the art. For example, "about" can mean within one or more standard deviations, or within ±30%, 20%, 10%, 5%, 1%, 0.5%, 0.2%, or 0.1% of the stated value.

[0193] "Combination" includes blends, mixtures, alloys, reaction products, etc. The terms "first", "second", etc. do not represent any order, quantity or importance, but are used to distinguish one element from another. Unless otherwise indicated in this article or clearly contradictory to the context, the terms "one" and "an" and "the" do not represent the limitation of quantity, but are interpreted as covering the singular and plural. Unless otherwise clearly stated, "or" means "and / or". Throughout the specification, mentioning "some embodiments", "embodiments", etc. means that the specific elements described in conjunction with the embodiments are included in at least one embodiment described herein, and may or may not exist in other embodiments. In addition, it should be understood that the described elements can be combined in various embodiments in any suitable manner. "Their combination" is open and includes any combination, which includes at least one of the listed components or properties, optionally together with unlisted similar or equivalent components or properties.

[0194] Unless specified to the contrary herein, all test standards are the most current standards 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 standards appear.

[0195] Unless otherwise defined, technical and scientific terms used herein have the same meanings as those generally understood by those of ordinary 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 this application contradicts or conflicts with a term in a combined reference, the term from this application takes precedence over the conflicting term from the combined reference.

[0196] Compounds are described using standard nomenclature. For example, any position not substituted by any indicator group is understood to have its valency filled by a bond or hydrogen atom as indicated. A dash ("-") not between two letters or symbols is used to indicate the point of attachment of a substituent. For example, -CHO is connected through the carbon of a carbonyl group.

[0197] The term "alkyl" refers to a branched or straight chain, unsaturated aliphatic hydrocarbon group, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, sec-pentyl, and n-hexyl and sec-hexyl. "Alkenyl" refers to a straight or branched monovalent hydrocarbon group having at least one carbon-carbon double bond (for example, vinyl (-HC=CH2)). "Alkoxy" refers to an alkyl group connected via oxygen (i.e., alkyl-O-), such as methoxy, ethoxy and sec-butoxy. "Alkylene" refers to a straight or branched, saturated, divalent aliphatic hydrocarbon group (for example, methylene (-CH2-) or propylene (-CH2)3-)). "Cycloalkylene" refers to a divalent cyclic alkylene group, -C n H 2n-x , wherein x is the number of hydrogens replaced by cyclization. "Cycloalkenyl" refers to 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" refers to an aromatic hydrocarbon group containing a specified number of carbon atoms, such as phenyl, cycloheptatrienone, indanyl, or naphthyl. "Arylene" refers to a divalent aryl group. "Alkylidenearylene" refers to an arylidene group substituted by an alkyl group. "Arylalkylene" refers to an alkylene group substituted by an aryl group (e.g., benzyl). The prefix "halo" refers to a group or compound comprising one or more of fluorine, chlorine, bromine, or iodine substituents. There may be a combination of different halogen groups (e.g., bromine and fluorine) or only chlorine groups. The prefix "hetero" refers to a compound or group comprising at least one ring member of a heteroatom (e.g., 1, 2, or 3 heteroatoms), wherein the heteroatoms are 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, each of which may be independently C 1-9 Alkoxy, C 1-9 Haloalkoxy, nitro (-NO2), cyano (-CN), C 1-6 Alkylsulfonyl (-S(=O)2-alkyl), C 6-12 Arylsulfonyl (-S(=O)2-aryl)thiol (-SH), thiocyanato (-SCN), tosyl (CH3C6H4SO2-), C 3-12 Cycloalkyl, C 2-12 Alkenyl, C 5-12 Cycloalkenyl, C 6-12 Aryl, C 7-13 Arylalkylene, C 4-12 Heterocycloalkyl, and C 3-12 A heteroaryl group replaces a hydrogen provided that the normal valence of the substituted atom is not exceeded. The number of carbon atoms indicated in the group does not include any substituents. For example, -CH2CH2CN is a C2 alkyl group substituted with a nitrile.

[0198] Although specific embodiments have been described, the applicant or other persons skilled in the art may conceive of alternatives, modifications, variations, improvements, and substantial equivalents that are not currently foreseeable or may not be foreseeable. Therefore, the appended claims as filed and as they may be amended are intended to cover all such alternatives, modifications, variations, improvements, and substantial equivalents.

Claims

1. A polycarbonate composition comprising: Linear homopolycarbonates and optionally styrene-containing copolymers; a poly(carbonate-siloxane) comprising about 10 wt % to about 30 wt % of a siloxane, present in an amount effective to provide a siloxane content of about 1 wt % to about 6 wt % based on the total weight of the polycarbonate composition; an ultra-high molecular weight polydimethylsiloxane present in an amount effective to provide from greater than about 0.3 wt % to less than about 0.9 wt % siloxane based on the total weight of the composition, wherein the polydimethylsiloxane has a weight average molecular weight of at least 100,000 grams per mole as determined by gel permeation chromatography against polystyrene standards; and flame retardants; and Optionally, up to about 5 wt % of an additive composition, in, The linear homopolycarbonate, the optional styrene-containing copolymer, the poly(carbonate-siloxane), the ultra-high molecular weight polydimethylsiloxane, the flame retardant, and the optional additive composition total 100 wt%.

2. A polycarbonate composition comprising: about 65 to about 95 weight percent of a linear homopolycarbonate and optionally a styrene-containing copolymer; a poly(carbonate-siloxane) comprising a siloxane content of about 10 wt % to about 30 wt % siloxane, present in an amount effective to provide a siloxane content of about 1 wt % to about 6 wt % based on the total weight of the polycarbonate composition; an ultra-high molecular weight polydimethylsiloxane present in an amount effective to provide from greater than about 0.3 wt % to less than about 0.9 wt % siloxane based on the total weight of the composition, wherein the polydimethylsiloxane has a weight average molecular weight of at least 100,000 grams per mole as determined by gel permeation chromatography against polystyrene standards; and flame retardants; and Optionally, up to about 10 wt % of an additive composition, wherein the linear homopolycarbonate, the optional styrene-containing copolymer, the poly(carbonate-siloxane), the ultrahigh molecular weight polydimethylsiloxane, the flame retardant, and the optional additive composition total 100 wt %.

3. The polycarbonate composition according to claim 1, wherein The polycarbonate composition has a calculated weight percent bromine and chlorine content of about 900 ppm or less each, and a calculated weight percent total halogen content of the polycarbonate composition of about 1500 ppm or less; or The calculated weight percentages of bromine, chlorine, and fluorine contents of the polycarbonate composition are each about 900 ppm or less, and the calculated weight percentages of the total bromine, chlorine, and fluorine contents of the polycarbonate composition are about 1500 ppm or less.

4. The polycarbonate composition according to claim 1, wherein Molded samples comprising the polycarbonate composition exhibited a UL-94 rating of V-0 at a thickness of 1.5 mm or less.

5. The polycarbonate composition according to any one of the preceding claims, wherein The poly(carbonate-siloxane) comprises repeating diorganosiloxane units of formula (10) Where each R is independently C 1-13 A monovalent organic group, preferably C 1-13 Alkyl, C 1-13 Alkoxy, C 2-13 Alkenyl, C 2-13 Alkenyloxy, C 3-6 Cycloalkyl, C 3-6 Cycloalkoxy, C 6-14 Aryl, C 6-10 Aryloxy, C 7-13 Arylalkylene, C 7-13 Arylalkyleneoxy, C 7-13 Alkyl arylene, or C 7-13 The alkylaryleneoxy groups are each optionally fully or partially halogenated with fluorine, chlorine, bromine, or iodine, or a combination thereof.

6. The polycarbonate composition according to any one of the preceding claims, wherein The linear homopolycarbonate is a bisphenol A polycarbonate homopolymer, comprising: A linear bisphenol A polycarbonate homopolymer having a weight average molecular weight of 15,000 to 25,000 g / mol, preferably 17,000 to 25,000 g / mol, as determined by gel permeation chromatography against polystyrene standards and calculated for polycarbonate; or A linear bisphenol A polycarbonate homopolymer having a weight average molecular weight of 26,000 to 40,000 g / mol, preferably 27,000 to 35,000 g / mol, as determined by gel permeation chromatography based on polystyrene standards and calculated for polycarbonate; or A combination of them.

7. The polycarbonate composition according to any one of the preceding claims, wherein The poly(carbonate siloxane) comprises bisphenol A carbonate repeating units and poly(dimethylsiloxane) repeating units.

8. The polycarbonate composition according to any one of the preceding claims, wherein The poly(carbonate siloxane) has a siloxane content of about 15 wt % to about 25 wt % based on the total weight of the poly(carbonate siloxane).

9. The polycarbonate composition according to any one of the preceding claims, wherein The flame retardant comprises alkyl sulfonate, aromatic sulfonate, organic phosphorus compound or a combination thereof.

10. The polycarbonate composition according to any one of the preceding claims, wherein The flame retardant is not halogenated.

11. The polycarbonate composition according to any one of the preceding claims, wherein The styrene-containing copolymer is present and comprises an elastomeric phase comprising (i) butadiene and having a glass transition temperature of less than 10°C, and (ii) a rigid polymer phase having a glass transition temperature of greater than 15°C and comprising a copolymer of a monovinyl aromatic monomer containing styrene and an unsaturated nitrile.

12. The polycarbonate composition according to any one of the preceding claims, wherein The composition does not include a halogenated anti-drip agent, preferably a fluorinated anti-drip agent.

13. A method of making the polycarbonate composition of any preceding claim, the method comprising melt mixing the components of the composition.

14. The method of claim 13, further comprising molding, casting or extruding the composition to provide an article.

15. An article comprising the polycarbonate composition of any of the preceding claims.

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