WO2016016851A1 - Melt polymerized polycarbonate - Google Patents

Abstract

In an embodiment, a process of preparing a thermoplastic composition can comprise: feeding a thermoplastic resin to an extruder, wherein the thermoplastic resin comprises a melt polycarbonate and an impact modifier; adding a quencher composition to the polycarbonate; and mixing the quencher composition with the polycarbonate for a period of time of greater than or equal to 5 seconds prior to the addition to the polycarbonate of any reactive additive, wherein the reactive additive has a reactive OH group or reactive ester group; directing a fluoro-resin, a flame retardant, or a combination comprising one or both of the foregoing to the extruder; extruding the thermoplastic resin to form the thermoplastic composition.

Description

MELT POLYMERIZED POLYCARBONATE

TECHNICAL FIELD

[0001] This application relates to melt polymerized polycarbonate compositions and processes for making the same.

BRIEF SUMMARY

[0002] Disclosed herein are processes for preparing a thermoplastic composition, and compositions prepared thereby.

[0003] In an embodiment, a process of preparing a thermoplastic composition can comprise: feeding a thermoplastic resin to an extruder, wherein the thermoplastic resin comprises a melt polymerized polycarbonate and an impact modifier; adding a quencher composition to the polymerized polycarbonate; and mixing the quencher composition with the polymerized polycarbonate for a period of time of greater than or equal to 5 seconds prior to the addition to the polycarbonate of any reactive additive, wherein the reactive additive has a reactive OH group or reactive ester group; directing a fluoro-resin, a flame retardant, or a combination comprising one or both of the foregoing to the extruder; extruding the thermoplastic resin to form the thermoplastic composition.

DETAILED DESCRIPTION

[0004] The Applicants developed a method of preparing a thermoplastic composition comprising a thermoplastic resin and a fluoro-resin, a flame retardant, a phosphoric acid ester, or a combination comprising one or more of the foregoing. The thermoplastic resin can comprise an impact modifier. The thermoplastic composition can comprise 100 parts by weight of the thermoplastic resin, 0 to 5 parts by weight, specifically, 0.01 to 5 parts by weight of the fluoro-resin based on 100 parts by weight of the thermoplastic resin, 0 to 39 parts by weight, specifically, 0.1 to 39 parts by weight of the flame retardant based on 100 parts by weight of the thermoplastic resin, and 0 to 3 parts by weight, specifically, 0.02 to 3 parts by weight of the phosphoric acid ester based on 100 parts by weight of the

thermoplastic resin.

[0005] The thermoplastic resin can comprise a vinyl polymer (for example, derived from an aromatic vinyl monomer (such as styrene, alpha- methylstyrene), acrylonitrile, etc.), a polyorganosilioxane, a polyalkylacrylate, a polyolefin, a polyamide, a polyphenylene ether, a polyoxymethylene, a polycarbonate, or a combination comprising one or more of the foregoing. The thermoplastic resin can comprise polystyrene, polyisoprene, polychloroprene, polyacrylonitrile, polyethylene, polypropylene, poly(ethyl acrylate), poly(methyl acrylate), poly(methyl methacrylate), poly(butyl acrylate), polybutadiene, copolymers comprising two or more of the foregoing (for example, polybutadiene-polystyrene, polybutadiene- polyacrylonitrile, and polyethylene-polypropylene), or a combination comprising one or more of the foregoing. The thermoplastic resin can comprise a polymer derived from maleic anhydride, beta-unsaturated carboxylic acid, N-phenylmaleimide, N-methylmaleimide, N- cyclohexylmaleimide, glycidyl methacrylate, or a combination comprising one or more of the foregoing.

[0006] The thermoplastic resin can comprise 10 to 100 parts by weight, specifically, 10 to 90 parts by weight of the polycarbonate based on the total weight of the thermoplastic resin. The thermoplastic resin can comprise 10 to 90 parts by weight of the impact modifier based on the total weight of the thermoplastic resin.

[0007] "Polycarbonate" as used herein means a polymer having repeating structural carbonate units of formula ( 1)

O R¹— O— C— O (i) HO-A -Y -A^OH (2) in which at least 60 percent of the total number of R¹ groups contain aromatic moieties and the balance thereof are aliphatic, alicyclic, or aromatic. Each R¹ can be a C₆-3o aromatic group, that is, contains at least one aromatic moiety. R¹ can be derived from an aromatic dihydroxy compound of the formula HO-R^OH, in particular of formula (2); wherein each of

A 1 and A2 is a monocyclic divalent aromatic group and Y 1 is a single bond or a bridging group having one or more atoms that separate A 1 from A2. One atom can separate A 1 from

A 2. Specifically, each R 1 can be derived from a bis henol of formula (3)

wherein R^a and R^b are each independently a halogen, Ci_i₂ alkoxy, or CM₂ alkyl; and p and q are each independently integers of 0 to 4. It will be understood that when p or q is less than 4, the valence of each carbon of the ring is filled by hydrogen. Also in formula (3), X^a is a bridging group connecting the two hydroxy-substituted aromatic groups, where the bridging group and the hydroxy substituent of each C₆ arylene group are disposed ortho, meta, or para (specifically para) to each other on the C₆ arylene group. The bridging group X^a can be a single bond, -0-, -S-, -S(O)-, -S(0)₂-, -C(O)-, or a CM_S organic group. The CM_S organic bridging group can be cyclic or acyclic, aromatic or non-aromatic, and can further comprise heteroatoms such as halogens, oxygen, nitrogen, sulfur, silicon, or phosphorous. The CM_S organic group can be disposed such that the C₆ arylene groups connected thereto are each connected to a common alkylidene carbon or to different carbons of the C_1-18 organic bridging group. Each p and q can be 1, and R^a and R^b can each be a Ci_₃ alkyl group, specifically methyl, disposed meta to the hydroxy group on each arylene group.

[0008] X^a can be a substituted or unsubstituted C_3-18 cycloalkylidene, a C_1-25 alkylidene of formula -C(R^c)(R^d)- wherein R^c and R^d are each independently hydrogen, C_1-12 alkyl, C_1-12 cycloalkyl, C₇_i₂ arylalkyl, C_1-12 heteroalkyl, or cyclic C₇_i₂ heteroarylalkyl, or a group of the formula -C(=R^e)- wherein R^e is a divalent C_1-12 hydrocarbon group. Groups of this type include methylene, cyclohexylmethylene, ethylidene, neopentylidene, and isopropylidene, as well as 2-[2.2.1]-bicycloheptylidene, cyclohexylidene, cyclopentylidene, cyclododecylidene, and adamantylidene.

[0009] X^a can be a CM_S alkylene, a C_3-18 cycloalkylene, a fused C_6-18 cycloalkylene, or a group of the formula -B 1 -G-B2 - wherein B 1 and B2 are the same or different C_1-6 alkylene and G is a C₃_i₂ cycloalkylidene or a C₆-i6 arylene. For example, X^a can be a substituted C₃_i₈ cycloalkylidene of formula 4)

wherein R^r, R^p, R^q, and R^£ are each independently hydrogen, halogen, oxygen, or C_1-12 hydrocarbon groups; Q is a direct bond, a carbon, or a divalent oxygen, sulfur, or -N(Z)- where Z is hydrogen, halogen, hydroxy, C_1-12 alkyl, C_1-12 alkoxy, 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, with the proviso that at least two of R^r, R^p, R^q, and R^£ taken together are a fused cycloaliphatic, aromatic, or heteroaromatic ring. It will be understood that where the fused ring is aromatic, the ring as shown in formula (4) will have an unsaturated carbon-carbon linkage where the ring is fused. When k is one and i is 0, the ring as shown in formula (4) contains 4 carbon atoms, when k is 2, the ring as shown in formula (4) contains 5 carbon atoms, and when k is 3, the ring contains 6 carbon atoms. Two adjacent groups (e.g., R^q and R^£ taken together) can form an aromatic group, and R^q and R^£ taken together can form one aromatic group and R^r and R^p taken together can form a second aromatic group. When R^q and R^£ taken together form an aromatic group, R^p can be a double- bonded oxygen atom, i.e., a ketone. [0010] Bisphenols wherein X^a is a cycloalkylidene of formula (4) can be used in the manufacture of polycarbonates containing phthalimidine carbonate units of formula (la)

wherein R^a, R^b, p, and q are as in formula (3), R³ is each independently a C_1-6 alkyl, j is 0 to 4, and R₄ is hydrogen, Ci_₆ alkyl, or a substituted or unsubstituted phenyl, for example a phenyl substituted with up to five Ci_₆ alkyls. For example, the phthalimidine carbonate units are of formula (lb); wherein R⁵ is hydrogen, phenyl optionally substituted with up to five 5 Ci-6 alkyls, or C_1-4 alkyl. In formula (lb), R⁵ can be hydrogen, methyl, or phenyl, specifically phenyl. Carbonate units (lb) wherein R⁵ is phenyl can be derived from 2-phenyl-3,3'-bis(4- hydroxy phenyl)phthalimidine (also known as 3,3-bis(4-hydroxyphenyl)-2-phenylisoindolin- 1-one, or N-phenyl phenolphthalein bisphenol ("PPPBP")).

[0011] Other bisphenol carbonate repeating units of this type are the isatin carbonate units of formula (lc) and (Id)

wherein R^a and R^b are each independently C_1-12 alkyl, p and q are each independently 0 to 4, and R¹ is C_1-12 alkyl, phenyl, optionally substituted with 1 to 5 Ci_io alkyl, or benzyl optionally substituted with 1 to 5 Ci_io alkyl. Each R^a and R^b can be methyl, p and q can each independently be 0 or 1, and R¹ is Ci_₄ alkyl or phenyl.

[0012] Other examples of bisphenol carbonate units derived from bisphenols (3) wherein X^a is a substituted or unsubstituted C_3-18 cycloalkylidene (4) include the

cyclohexylidene-bridged, alkyl-substituted bisphenol of formula (le)

wherein R^a and R^b are each independently C_1-12 alkyl, R^g is C_1-12 alkyl, p and q are each independently 0 to 4, and t is 0 to 10. At least one of each of R^a and R^b can be disposed meta to the cyclohexylidene bridging group. Each R^a and R^b can independently be Ci_₄ alkyl, R^g is Ci_₄ alkyl, p and q are each 0 or 1, and t is 0 to 5. R^a, R^b, and R^g can each be methyl, p and q can each be 0 or 1, and t can be 0 or 3, specifically 0.

[0013] Examples of other bisphenol carbonate units derived from bisphenol (3) wherein X^a is a substituted or unsubstituted C₃_i8 cycloalkylidene include adamantyl units of formula If) and fluorenyl units of formula (lg)

to 4. At least one of each of R^a and R^b can be disposed meta to the cycloalkylidene bridging group. R^a and R^b can each be independently C_1-3 alkyl, and p and q can be each 0 or 1;

specifically, R^a, R^b can each be methyl, p and q are each 0 or 1, and when p and q are 1, the methyl group can be disposed meta to the cycloalkylidene bridging group. Carbonates containing units (la) to (lg) are useful for making polycarbonates with high glass transition temperatures (Tg) and high heat distortion temperatures.

[0014] Other useful dihydroxy compounds of the formula HO-R^OH include aromatic dihydroxy compounds of formula (6)

(6)

wherein each R is independently a halogen atom, CM_O hydrocarbyl group such as a Ci_io alkyl, a halogen-substituted Ci_io alkyl, a C₆-io aryl, or a halogen-substituted C₆-io aryl, and n is 0 to 4. The halogen is usually bromine.

[0015] 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)-l-phenylethane, 2-(4-hydroxyphenyl)-2-(3-hydroxyphenyl)propane, bis(4- hydroxyphenyl)phenylmethane, 2,2-bis(4-hydroxy-3-bromophenyl)propane, 1,1 -bis

(hydroxyphenyl)cyclopentane, 1 , 1 -bis(4-hydroxyphenyl)cyclohexane, 1 , 1 -bis(4- hydroxyphenyl)isobutene, l,l-bis(4-hydroxyphenyl)cyclododecane, trans-2,3-bis(4- hydroxyphenyl)-2-butene, 2,2-bis(4-hydroxyphenyl)adamantane, alpha, alpha' -bis(4- hydroxyphenyl)toluene, bis(4-hydroxyphenyl)acetonitrile, 2,2-bis(3-methyl-4- hydroxyphenyl)propane, 2,2-bis(3-ethyl-4-hydroxyphenyl)propane, 2,2-bis(3-n-propyl-4- hydroxyphenyl)propane, 2,2-bis(3-isopropyl-4-hydroxyphenyl)propane, 2,2-bis(3-sec-butyl- 4-hydroxyphenyl)propane, 2,2-bis(3 -t-butyl-4-hydroxyphenyl)propane, 2,2-bis(3 -cyclohexyl-

4- hydroxyphenyl)propane, 2,2-bis(3-allyl-4-hydroxyphenyl)propane, 2,2-bis(3-methoxy-4- hydroxyphenyl)propane, 2,2-bis(4-hydroxyphenyl)hexafluoropropane, l,l-dichloro-2,2- bis(4-hydroxyphenyl)ethylene, l,l-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, l,6-bis(4-hydroxyphenyl)-l,6-hexanedione, ethylene glycol bis(4-hydroxyphenyl)ether, bis(4-hydroxyphenyl)ether, bis(4-hydroxyphenyl)sulfide, bis(4- hydroxyphenyl) sulfoxide, bis(4-hydroxyphenyl)sulfone, 9,9-bis(4-hydroxyphenyl)fluorine, 2,7-dihydroxypyrene, 6,6'-dihydroxy-3,3,3',3'- tetramethylspiro(bis)indane ("spirobiindane bisphenol"), 3,3-bis(4-hydroxyphenyl)phthalimide, 2,6-dihydroxydibenzo-p-dioxin, 2,6- dihydroxythianthrene, 2,7-dihydroxyphenoxathin, 2,7-dihydroxy-9, 10-dimethylphenazine, 3,6-dihydroxydibenzofuran, 3,6-dihydroxydibenzothiophene, and 2,7-dihydroxycarbazole, resorcinol, substituted resorcinol compounds such as 5-methyl resorcinol, 5-ethyl resorcinol,

5- propyl resorcinol, 5-butyl resorcinol, 5-t-butyl resorcinol, 5-phenyl resorcinol, 5-cumyl resorcinol, 2,4,5, 6-tetrafluoro resorcinol, 2,4,5, 6-tetrabromo resorcinol, or the like; catechol; hydroquinone; substituted hydroquinones such as 2-methyl hydroquinone, 2-ethyl hydroquinone, 2-propyl hydroquinone, 2-butyl hydroquinone, 2-t-butyl hydroquinone, 2- phenyl hydroquinone, 2-cumyl hydroquinone, 2,3,5,6-tetramethyl hydroquinone, 2,3,5,6- tetra-t-butyl hydroquinone, 2,3,5,6-tetrafluoro hydroquinone, 2,3,5, 6-tetrabromo

hydroquinone, or the like, or combinations comprising at least one of the foregoing dihydroxy compounds.

[0016] Specific examples of bisphenol compounds of formula (3) include l,l-bis(4- hydroxyphenyl) methane, l,l-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, l,l-bis(4-hydroxyphenyl) propane, l,l-bis(4-hydroxyphenyl) n- butane, 2,2-bis(4-hydroxy-2-methylphenyl) propane, l,l-bis(4-hydroxy-t-butylphenyl) propane, 3,3-bis(4-hydroxyphenyl) phthalimidine, 2-phenyl-3,3-bis(4-hydroxyphenyl) phthalimidine (PPPBP), and l,l-bis(4-hydroxy-3-methylphenyl)cyclohexane (DMBPC). Combinations comprising at least one of the foregoing dihydroxy compounds can also be used. The polycarbonate can be a linear homopolymer derived from bisphenol A, in which each of A 1 and A2 is p-phenylene and Y 1 is isopropylidene in formula (3).

[0017] The polycarbonate herein is prepared via the melt polymerization of a bisphenol and a carbonate precursor. Exemplary carbonate precursors include a carbonyl halide such as carbonyl bromide or carbonyl chloride (phosgene) a bishaloformate of a dihydroxy compound (e.g., the bischloro formate of bisphenol A, hydroquinone ethylene glycol, neopentyl glycol, or the like), and diaryl carbonates. Combinations comprising at least one of the foregoing types of carbonate precursors can also be used. The diaryl carbonate ester can be diphenyl carbonate, or an activated diphenyl carbonate having electron-withdrawing substituents on each aryl, such as bis(4-nitrophenyl)carbonate, bis(2- chlorophenyl)carbonate, bis(4-chlorophenyl)carbonate, bis(methyl salicyl)carbonate, bis(4- methylcarboxylphenyl) carbonate, bis(2-acetylphenyl) carboxylate, bis(4-acetylphenyl) carboxylate, or a combination comprising at least one of the foregoing.

[0018] In the melt polymerization process, the polycarbonate can be prepared by co- reacting, in a molten state, a dihydroxy reactant and a carbonate precursor in the presence of a transesterification catalyst. The reaction can be carried out in typical polymerization equipment, such as a continuously stirred reactor (CSTR), plug flow reactor, wire wetting fall polymerizers, free fall polymerizers, horizontal polymerizers, wiped film polymerizers, BANBURY mixers, single or twin screw extruders, or a combination comprising one or more of the foregoing. Volatile monohydric phenol is removed from the molten reactants by distillation and the polymer is isolated as a molten residue. Melt polymerization can be conducted as a batch process or as a continuous process. In either case, the melt

polymerization conditions used can comprise two or more distinct reaction stages. For example, the polymerization can comprise a first reaction stage (also referred to as an oligomerization stage) in which the starting dihydroxy aromatic compound and diaryl carbonate are converted into an oligomeric polycarbonate and a second reaction stage (also referred to a polymerization stage) wherein the oligomeric polycarbonate formed in the first reaction stage is converted to high molecular weight polycarbonate. The oligomerization stage can comprise 1 or more, specifically, 2 or more, more specifically, 2 to 4

oligomerization units (for example, 2 to 4 CSTR). The polymerization stage can comprise 1 or more, specifically, 2 or more, more specifically, 2 polymerization units (for example 2 horizontal or wire wetting fall polymerizers). The oligomerization unit is herein defined as a reaction unit that results in polycarbonates oligomers with a number average molecular weight of less than or equal to 8,000 Daltons (Da) and a polymerization unit is herein defined as a reaction unit that produces polycarbonate with a number average molecular weight of greater than 8,000 Da. It is noted that while less than or equal to 8,000 Da is used here to define a molecular weight achieved in the first stage, one skilled in the art readily understands that said molecular weight is used to define an oligomerization stage, where the oligomer molecular weight could be greater than 8,000 Da. A "staged" polymerization reaction condition can be used in continuous polymerization systems, wherein the starting monomers are oligomerized in a first reaction vessel and the oligomeric polycarbonate formed therein is continuously transferred to one or more downstream reactors in which the oligomeric polycarbonate is converted to high molecular weight polycarbonate. Typically, in the oligomerization stage the oligomeric polycarbonate produced has a number average molecular weight of 1,000 to 7,500 Da. In one or more subsequent polymerization stages the number average molecular weight (Mn) of the polycarbonate can be increased, e.g., to 8,000 and 25,000 Da (using polycarbonate standard), specifically, 13,000 to 18,000 Da.

[0019] Typically, solvents are not used in the process, and the reactants dihydroxy aromatic compound and the diaryl carbonate are in a molten state. The reaction temperature can be 100 to 350 degrees Celsius (°C), specifically, 180 to 310°C. The pressure can be at atmospheric pressure, supra- atmospheric pressure, or a range of pressures from atmospheric pressure to 15 torr in the initial stages of the reaction, and at a reduced pressure at later stages, for example 0.2 to 15 torr. Likewise, the polymerization can occur in a series of polymerization vessels that can have increasing temperature and vacuum. For example, an oligomerization stage can occur at a temperature of 100 to 260°C, specifically, 140 to 240°C and a polymerization stage can occur at a temperature of 240 to 350°C, specifically 280 to 300°C or 240 to 270°C, where the temperature in the polymerization stage is greater than the temperature in the oligomerization stage. The reaction time from the initial oligomerization unit to the final polymerization unit is generally 0.1 to 15 hours. As used herein, "final polymerization" is intended to mean a where the Mw does not increase by greater than 10 wt%, preferably doesn't increase by greater than or equal to 5 wt% thereafter)

[0020] After a final polymerization vessel (also referred to as a final polymerization unit), the polymer can be introduced to a reactor, extruded, subjected to filtration in a melt filter, or a combination comprising one or more of the foregoing. It is noted that the melt filter can be located before or after the extruder. For example, the melt polymerization process for the manufacture of a polycarbonate composition can comprise: melt polymerizing a dihydroxy reactant and a carbonate compound to produce a molten reaction product; quenching the molten reaction product; filtering the molten reaction product in a melt filter upstream of any extruders; optionally, introducing an additive to form a mixture; and extruding the mixture to form the polycarbonate composition. Likewise, the melt polymerization process for the manufacture of a polycarbonate composition can comprise: melt polymerizing a dihydroxy reactant and a carbonate compound to produce a molten reaction product; introducing a quencher composition and optionally an additive for form a mixture; and extruding the mixture to form the polycarbonate composition.

[0021] The polycarbonate can have one or more of the following endgroups of - (107).

wherein R is a Ci_io straight or branched alkyl group, for example, C₈H₁₇, C₁₂H₂₅, and C₁₈H₃₇. These endgroups can be derived from a polymerization monomer or from an endcapping agent (for example, p-t-butyl phenol, dicumyl phenol, and p-cumyl phenol) that is added during or after the polymerization. The endcapping ratio in percent (%EC) is determined by the following equation:

/ppmOH + Mn\

%EC = 100 - [ ^-—Γ Γ^—

V 340,000 wherein ppm OH is the amount of hydroxyl end groups in ppm and Mn is the number averaged molecular weight based on polycarbonate standards in Daltons. The ppm OH can be determined by Fourier Transform Infrared Spectroscopy (FTIR), for example, on a Perkin Elmer FTIR Spectrum One Device by dissolving 0.5 grams (g) of the polycarbonate sample in 25 milliliters (mL) of dried chloroform, measuring the absorbance at a wavelength of 3,584 inverse centimeters (cm ¹) using a univariable calibration, and normalizing the absorbance by dividing the absorbance by the absorbance at 2,779 cm^"1

[0022] The polycarbonate can have a weight average molecular weight of less than or equal to 23,000 g/mol, specifically, 5,000 to 23,000 g/mol as determined by gel permeation chromatography (GPC) based on polystyrene standards. The polycarbonate can have a weight average molecular weight of 1,000 to 300,000 g/mol, specifically, 5,000 to 100,000 g/mol, more specifically, 12,000 to 80,000 g/mol as determined by GPC based on polystyrene standards.

[0023] The polycarbonate can be, for example, a bisphenol A polycarbonate with a weight average molecular weight of 21800 Daltons with a melt flow of 24 to 32 g/10 min (ASTM D1238-04, 300°C, 2.16 kg).

[0024] The polycarbonate can have a melt flow of 4 to 40 g/10 min, for example, 4.5 to 15 g/10 min or 15 to 35 g/10 min as determined by ASTM D1238-04 at 300°C, 1.5 kg. The polycarbonate can have a melt flow of 5 to 15 g/10 min as determined by ASTM D1238- 04 at 250°C, 1.5 kg. Melt flow rate and melt volume rate is measured at 300 degrees Celsius (°C)/1.2 kilogram (kg) according to ASTM D1238-04 or ISO 1133.

[0025] Catalysts used in the melt transesterification polymerization production of polycarbonates can include alpha and/or beta catalysts. Beta catalysts are typically volatile and degrade at elevated temperatures. Beta catalysts can therefore be used at early low- temperature polymerization stages. Alpha catalysts are typically more thermally stable and less volatile than beta catalysts.

[0026] The alpha catalyst (also referred to an alkali catalyst) can comprise a source of alkali and/or alkaline earth ions. The sources of these ions include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide, as well as alkaline earth hydroxides such as magnesium hydroxide and calcium hydroxide. Other possible sources of alkali and alkaline earth metal ions include the corresponding salts of carboxylic acids (such as sodium acetate) and derivatives of ethylene diamine tetra acetic acid (EDTA) (such as EDTA tetra sodium salt, and EDTA magnesium disodium salt). The alpha catalyst can comprise alkali or alkaline earth metal salts of carbonate, such as CS2CO3, NaHC0₃, and Na₂C0₃, and the like, non-volatile inorganic acid such as NaH₂P0₃, NaH₂P0₄, Na₂HP0₃, KH₂P0₄, CsH₂P0₄, Cs₂HP0₄, and the like, or mixed salts of phosphoric acid, such as NaKHP0₄, CsNaHP0₄, CsKHP0₄, and the like.

[0027] Possible beta catalysts (also referred to as a quaternary catalyst) can comprise a quaternary ammonium compound, a quaternary phosphonium compound, or a combination comprising at least one of the foregoing. The quaternary ammonium compound can be a compound of the structure (R⁴)₄N⁺X^~, wherein each R⁴ is the same or different, and is a Ci_₂o alkyl, a C₄_₂o cycloalkyl, or a C₄_₂o aryl; and X^" is an organic or inorganic anion, for example a hydroxide, halide, carboxylate, sulfonate, sulfate, formate, carbonate, or bicarbonate.

Examples of organic quaternary ammonium compounds include tetramethyl ammonium hydroxide, tetrabutyl ammonium hydroxide, tetramethyl ammonium acetate, tetramethyl ammonium formate, tetrabutyl ammonium acetate, and combinations comprising at least one of the foregoing. Tetramethyl ammonium hydroxide is often used. The quaternary phosphonium compound can be a compound of the structure (R⁵)₄P⁺X^~, wherein each R⁵ is the same or different, and is a Ci_₂o alkyl, a C₄_₂o cycloalkyl, or a C₄_₂o aryl; and X^" is an organic or inorganic anion, for example a hydroxide, phenoxide, halide, carboxylate such as acetate or formate, sulfonate, sulfate, formate, carbonate, or bicarbonate. Where X^" is a polyvalent anion such as carbonate or sulfate, it is understood that the positive and negative charges in the quaternary ammonium and phosphonium structures are properly balanced. For example, where R 20 to R 23 are each methyls and X^" is carbonate, it is understood that

X^" represents 2(C0₃ -^"2 ). Examples of organic quaternary phosphonium compounds include tetramethyl phosphonium hydroxide, tetramethyl phosphonium acetate, tetramethyl phosphonium formate, tetrabutyl phosphonium hydroxide, tetrabutyl phosphonium acetate (TBPA), tetraphenyl phosphonium acetate (TPPA), tetraphenyl phosphonium phenoxide, and combinations comprising at least one of the foregoing.

[0028] The amount of alpha and beta catalyst used can be based upon the total number of moles of dihydroxy compound used in the polymerization reaction. When referring to the ratio of beta catalyst, for example, a phosphonium salt, to all dihydroxy compounds used in the polymerization reaction, it is convenient to refer to moles of catalyst per mole of the dihydroxy compound, meaning the number of moles of catalyst divided by the sum of the moles of each individual dihydroxy compound present in the reaction mixture.

The transesterification catalyst can be used in an amount sufficient to provide 1 x 10 -^"8 to 1 x 10^"5, specifically, 1 x 10^"7 to 8 x 10^"6, more specifically, 3 x 10^"7 to 2 x 10^"6 moles of catalyst per mole of aromatic dihydroxy compound used. The alpha catalyst can be used in an amount sufficient to provide 1 x 10 -^"2 to 1 x 10 -^"8 moles, specifically, 1 x 10 -^"4 to 1 x 10 -^"7 moles of metal per mole of the dihydroxy compound used. The amount of beta catalyst (e.g., organic ammonium or phosphonium salts) can be 1 x 10 -2 " to 1 x 10 -5 , specifically 1 x 10 -3 " to 1 x 10^"4 moles per total mole of the dihydroxy compound in the reaction mixture. Quenching of the transesterification catalysts and any reactive catalyst residues with an acidic compound after polymerization is completed can also be useful in some melt polymerization processes. Removal of catalyst residues and/or quenching agent and other volatile residues from the melt polymerization reaction after polymerization can also be useful in some melt polymerization processes.

[0029] The polymerization process can comprise a section of parallel polymerization, where parallel polymerization refers to the splitting of a polymerized polycarbonate stream into two or more streams that may or may not experience the same polymerization conditions thereafter (i.e. they can attain different molecular weights, have different additives added thereto, etc.). For example, polycarbonate can be prepared in a first portion of the

polymerization process; a stream comprising polymerized polycarbonate can be split into two or more streams and directed to 2 or more parallel operating lines. For example, a process can comprise polymerizing polycarbonate in a series of oligomerization units; a stream exiting the oligomerization stage can be split into two streams: A and B, where stream A is directed to polymerization unit A and stream B is directed to polymerization unit B.

Likewise, a process can comprise polymerizing polycarbonate in a series of oligomerization units followed by polymerizing in a series of polymerization units; a stream exiting the polymerization stage can be split into two streams: A and B, where stream A is directed to extruder A and stream B is directed to extruder B. Likewise, a process can comprise polymerizing polycarbonate in a series of oligomerization units followed by polymerizing in a series of two polymerization units; a stream exiting the first polymerization unit can be split into two streams: A and B, where stream A is directed to second polymerization unit A and stream B is directed to second polymerization unit B. In any of the aforementioned scenarios, a quencher composition can be added to one or both of streams A and B, where the quencher composition can be the same or different. One skilled in the art can readily envision other embodiments comprising more than 2 parallel streams and embodiments where the streams are split at different locations. [0030] A quencher composition can be added at one or more locations in the present melt preparation of the polycarbonate to reduce the activity of the catalyst. The quencher composition comprises a quenching agent (also referred to herein as a quencher). For example, the quenching agent can comprise a sulfonic acid ester such as an alkyl sulfonic ester of the formula R1SO3R2 wherein Ri is hydrogen, C1-C12 alkyl, C₆-Ci8 aryl, or C7-C19 alkylaryl, and R₂ is C1-C12 alkyl, C₆-Ci8 aryl, or C7-C19 alkylaryl. Examples of alkyl sulfonic esters include benzenesulfonate, p-toluenesulfonate, methylbenzene sulfonate, ethylbenzene sulfonate, n-butyl benzenesulfonate, octyl benzenesulfonate and phenyl benzenesulfonate, methyl p-toluenesulfonate, ethyl p-toluenesulfonate, n-butyl p-toluene sulfonate, octyl p- toluenesulfonate and phenyl p- toluenesulfonate. The sulfonic acid ester can comprise alkyl tosylates such as n-butyl tosylate. The sulfonic acid ester can be present in the quencher composition in an amount of 0.1 to 10 volume percent (vol%), specifically, 0.1 to 5 vol%, more specifically, 0.5 to 2 vol% based on the total volume of the quencher composition.

[0031] The quenching agent can comprise boric acid esters (e.g., B(OCH₃)3,

B(OCH₂CH3)3, and Β(( ₆Η₆)₃), zinc borate, boron phosphate, aluminum stearate, aluminum silicate, zirconium carbonate, zirconium C1-C12 alkoxides, zirconium hydroxycarboxylates, gallium phosphide, gallium antimonide, germanium oxide, C1-C32 organogermanium compounds, C₄-C3₂ tetraorganotin tin compound, C6-C32 hexaorganotin compound (e.g., [(C₆H₆0)Sn(CH₂CH₂CH₂CH₃)2]₂0), Sb₂0₃, antimony oxide, Q-C32 alkylantimony, bismuth oxide, C1-C12 alkylbismuth, zinc acetate, zinc stearate, Ci-C₃₂ alkoxytitanium, and titanium oxide, phosphoric acid, phosphorous acid, hypophosphorous acid, pyrophosphoric acid, polyphosphoric acid, boric acid, hydrochloric acid, hydrobromic acid, sulfuric acid, sulfurous acid, adipic acid, azelaic acid, dodecanoic acid, L-ascorbic acid, aspartic acid, benzoic acid, formic acid, acetic acid, citric acid, glutamic acid, salicylic acid, nicotinic acid, fumaric acid, maleic acid, oxalic acid, benzenesulfinic acid, C1-C12 dialkyl sulfates (e.g., dimethyl sulfate and dibutyl sulfate), sulfonic acid phosphonium salts of the formula (R^aS0₃ ^~)(PR^b ₄)⁺ wherein R^a is hydrogen, C1-C12 alkyl, C₆-Ci8 aryl, or C7-C19 alkylaryl, and each R^b is independently hydrogen, C1-C12 alkyl or C₆-Ci8 aryl, sulfonic acid derivatives of the formula A¹-^¹- SC^X¹)™ wherein A¹ is a Ci-C₄o hydrocarbon group having a valence of m, Y¹ is a single bond or an oxygen atom, X¹ is a secondary or tertiary alkyl group of the formula - CR¹⁵R¹⁶R¹⁷, a metal cation of one equivalent, an ammonium cation (e.g., NR^b ₃ ⁺ wherein each R^b is independently hydrogen, C1-C12 alkyl or C₆-Ci8 aryl), or a phosphonium (e.g., PR^b ₄ ⁺ wherein each R^b is independently hydrogen, C1-C12 alkyl or C₆-Ci8 aryl) wherein R¹⁵ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R is a hydrogen atom, a phenyl group or an alky group having 1 to 5 carbon atoms, and 17

R is the same as or different from R¹⁵ and has the same definition as R¹⁵, provided that two of R¹⁵, R¹⁶, and R¹⁷ cannot be hydrogen atoms, and m is an integer of 1 to 4, provided that when Y¹ is a single bond, all of X¹ in an amount of m cannot be metal cations of one equivalent, a compound of the formula

is a secondary, tertiary or quaternary ammonium cation or a secondary (e.g., tertiary or quaternary phosphonium cation, and Y¹ is a single bond or an oxygen atom, a compound of the formula A³-(⁺X³)_n- (R-Y¹-S0₃ ^~ )_n wherein A³ is a Ci-C₄o hydrocarbon group having a valence of n, ⁺X³ is a secondary, tertiary or quaternary ammonium cation (e.g., NR^b ₃ ⁺ wherein each R^b is independently hydrogen, C₁-C₁₂ alkyl or C₆-Ci₈ aryl), or a secondary, tertiary or quaternary phosphonium cation (e.g., PR^b ₄ ⁺ wherein each R^b is independently hydrogen, C₁-C₁₂ alkyl or C₆-Ci₈ aryl), R is a monovalent Ci-C₄o hydrocarbon group, n is an integer of 2 to 4, and Y¹ is a single bond or an oxygen atom, a compound of the formula A⁵-Ad¹-A⁴-(Ad²-A⁵)_t wherein A⁵ is a monovalent or divalent Ci-C₄o hydrocarbon group, A⁴ is a divalent Ci-C₄o hydrocarbon group, each of Ad 1 and Ad 2 is independently an acid anhydride group selected from -SO₂-O- SO₂-, -SO₂-O-CO- and -CO-O-SO₂-, and £ is 0 or 1, provided that when I is O, -(Ad²-A⁵)_t is a hydrogen atom or a bond between A⁴ and A⁵, in which A⁵ is a divalent hydrocarbon group or a single bond, aminosulfonic esters having the formula R_aR_bN-A-S0₃R_c, wherein R_a and R are each independently hydrogen, C₁-C₁₂ alkyl, C6-C₂₂ aryl, C₇-C₁9 alkylaryl or R_a and R , either singly or in combination, form an aromatic or non-aromatic heterocyclic compound with N (e.g., pyrrolyl, pyridinyl, pyrimidyl, pyrazinyl, carbazolyl, quinolinyl, imidazoyl, piperazinyl, oxazolyl, thiazolyl, pyrazolyl, pyrrolinyl, indolyl, purinyl, pyrrolydinyl, or the like), R_c is hydrogen, and A is C₁-C₁₂ alkyl, C₆-Ci₈ aryl, or C₁₇-C₁9 alkylaryl (e.g., compounds such as N-(2-hydroxyethyl) piperazine-N'-3-propanesulfonic acid, 1,4,- piperazinebis (ethanesulfonic acid), and 5-dimethylamino-l-napthalenesulfonic acid), ammonium sulfonic esters of the formula R_aR_bR_cN⁺— A— S0₃ ^", wherein R_a, R_b, are each independently hydrogen, C₁-C₁₂ alkyl, C₁-C₁₂ aryl, C₇-C₁9 alkylaryl, or R_a and R_b, either singly or in combination, form an aromatic or non-aromatic heterocyclic compound with N (e.g., pyrrolyl, pyridinyl, pyrimidyl, pyrazinyl, carbazolyl, quinolinyl, imidazoyl, piperazinyl, oxazolyl, thiazolyl, pyrazolyl, pyrrolinyl, indolyl, purinyl, pyrrolydinyl, or the like), R_c is a hydrogen, and A is C₁-C₁₂ alkyl, C₆-Ci₈ aryl, or C₇-C₁9 alkylaryl, sulfonated polystyrene, methyl acrylate-sulfonated styrene copolymer, and combinations comprising at least one of the foregoing.

[0032] The quencher composition can be added in a solid or a liquid form. When in the liquid form, the quencher composition can be added, for example, via an addition system. The addition system can comprise a first drum; a buffer drum; a dosing pump; a filter; an injector, or a combination comprising one or more of the foregoing, where one or both of the first drum and the buffer drum can comprise an agitator and/or a heating system. For example, the quencher and a liquid carrier can be added to the first drum and then added to a buffer drum. From the buffer drum, the liquid quencher composition can be injected to the polymerization system via an injector located in one or more of a polymerization unit, a reactor, a transfer line, a mixer, and an extruder. The pumping of the quencher composition to a dosing pump can be controlled by a main distribution loop, where the addition of the quencher composition can be monitored with a flow meter, either continuously or

intermittently. The pumping can further comprise a controller for automated monitoring of the flow meter and adjustment of the amount of the quencher composition to the

polymerization unit. The liquid quencher composition can be added to the polymerized polycarbonate at a pressure of greater than or equal to 1 bar, specifically, greater than or equal to 2 bars, specifically, greater than or equal to 3 bars, more specifically, 3 to 100 bar. The liquid quencher composition can likewise be added by spraying the liquid onto a solid polycarbonate substrate. The liquid quencher composition can be filtered before it is added to the polymerization system. The quencher composition can be mixed with the polymerized polycarbonate for a period of time of greater than or equal to 5 seconds prior to the addition to the polymerized polycarbonate of any additives having a reactive OH group or reactive ester group.

[0033] The thermoplastic resin can comprise a polysiloxane, for example, a polysiloxane-polycarbonate copolymer, also referred to as a poly(siloxane-carbonate). The polydiorganosiloxane (also referred to herein as "polysiloxane") can comprise repeating diorganosiloxane units as in formula (10)

wherein each R is independently a C_1-13 monovalent organic group. For example, R can be a Ci-Ci₃ alkyl, CrC₁₃ alkoxy, C₂-Ci₃ alkenyl, C₂-Ci₃ alkenyloxy, C₃-C₆ cycloalkyl, C₃-C₆ cycloalkoxy, C₆-Ci₄ aryl, C₆-Cio aryloxy, C₇-Ci₃ arylalkyl, C₇-Ci₃ aralkoxy, C₇-Ci₃ alkylaryl, or C₇-Ci₃ alkylaryloxy. The foregoing groups can be fully or partially halogenated with fluorine, chlorine, bromine, or iodine, or a combination thereof. Where a transparent polysiloxane-polycarbonate is desired, R can be unsubstituted by halogen. Combinations of the foregoing R groups can be used in the same copolymer.

[0034] The value of E in formula (10) can vary widely depending on the type and relative amount of each component in the thermoplastic composition, the desired properties of the composition, and like considerations. E can have an average value of 2 to 1,000, specifically, 2 to 500, 2 to 200, or 2 to 125, 5 to 80, or 10 to 70. E can have an average value of 10 to 80 or 10 to 40. E can have an average value of 40 to 80, or 40 to 70. Where E is of a lower value, e.g., less than 40, it can be desirable to use a relatively larger amount of the polycarbonate -polysiloxane copolymer. Conversely, where E is of a higher value, e.g., greater than 40, a relatively lower amount of the polycarbonate-polysiloxane copolymer can be used.

[0035] A combination of a first and a second (or more) polysiloxane can be used, for example, the polysiloxane can comprise a first copolymer and a second copolymer, wherein the average value of E of the first copolymer is less than the average value of E of the second copolymer.

[0036] The polydiorganosiloxane blocks can have the formula (11)

wherein E is as defined above; each R can be the same or different, and is as defined above; and Ar can be the same or different, and is a substituted or unsubstituted C₆-C₃o arylene, wherein the bonds are directly connected to an aromatic moiety. Ar groups in formula (11) can be derived from a C₆-C₃o dihydroxyarylene compound, for example, a dihydroxyarylene compound of formula (3) or (6) above. Dihydroxyarylene compounds are l,l-bis(4- hydroxyphenyl) methane, l,l-bis(4-hydroxyphenyl) ethane, 2,2-bis(4-hydroxyphenyl) propane, 2,2-bis(4-hydroxyphenyl) butane, 2,2-bis(4-hydroxyphenyl) octane, l,l-bis(4- hydroxyphenyl) propane, l,l-bis(4-hydroxyphenyl) n-butane, 2,2-bis(4-hydroxy-l- methylphenyl) propane, l,l-bis(4-hydroxyphenyl) cyclohexane, bis(4-hydroxyphenyl sulfide), and l,l-bis(4-hydroxy-t-butyrphenyl) propane. Combinations comprising at least one of the foregoing dihydroxy compounds can also be used.

0037] Polydiorganosiloxane blocks can be of formula (13)

wherein R and E are as described above, and each R⁵ is independently a divalent C₁-C30 organic group, and wherein the polymerized polysiloxane unit is the reaction residue of its corresponding dihydroxy compound. The polydiorganosiloxane blocks can be of formula (14); wherein R and E are as defined above. R⁶ in formula (14) is a divalent C₂-C8 aliphatic. Each M in formula (14) can be the same or different, and can be a halogen, cyano, nitro, Q- Cg alkylthio, Q-Cg alkyl, Q-Cg alkoxy, C₂-Cg alkenyl, C₂-Cg alkenyloxy, C₃-Cg cycloalkyl, C₃-Cg cycloalkoxy, C₆-Cio aryl, C₆-Cio aryloxy, C7-C12 aralkyl, C7-C12 aralkoxy, C7-C12 alkylaryl, or C₇-C₁₂ alkylaryloxy, wherein each n is independently 0, 1, 2, 3, or 4.

M can be bromo or chloro, an alkyl such as methyl, ethyl, or propyl, an alkoxy such as methoxy, ethoxy, or propoxy, or an aryl such as phenyl, chlorophenyl, or tolyl; R⁶ can be a dimethylene, trimethylene or tetramethylene; and R can be a Ci_g alkyl, haloalkyl such as trifluoropropyl, cyanoalkyl, or aryl such as phenyl, chlorophenyl or tolyl. R can be methyl, or a combination of methyl and trifluoropropyl, or a combination of methyl and phenyl. R can be methyl, M can be methoxy, n can be one, R⁶ can be a divalent Ci-C₃ aliphatic group. S ecific ol dior anosiloxane blocks are of the formula

or a combination comprising at least one of the foregoing, 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. [0038] Blocks of formula (14) can be derived from the corresponding dihydroxy polydiorganosiloxane, which in turn can be prepared effecting a platinum-catalyzed addition between the siloxane hydride and an aliphatically unsaturated monohydric phenol such as eugenol, 2-alkylphenol, 4-allyl-2-methylphenol, 4-allyl-2-phenylphenol, 4-allyl-2- bromophenol, 4-allyl-2-t-butoxyphenol, 4-phenyl-2-phenylphenol, 2-methyl-4-propylphenol, 2-allyl-4,6-dimethylphenol, 2-allyl-4-bromo-6-methylphenol, 2-allyl-6-methoxy-4- methylphenol and 2-allyl-4,6-dimethylphenol. The polysiloxane-polycarbonate copolymers can then be manufactured, for example, by the synthetic procedure of European Patent Application Publication No. 0 524 731 Al of Hoover, page 5, Preparation 2.

[0039] Transparent polysiloxane-polycarbonate copolymers can comprise carbonate units (1) derived from bisphenol A, and repeating siloxane units (14a), (14b), (14c), or a combination comprising at least one of the foregoing (specifically of formula 14a), wherein E has an average value of 4 to 50, specifically, 4 to 15, specifically, 5 to 15, more specifically, 6 to 15, and still more specifically, 7 to 10.

[0040] The polyorganosiloxane-polycarbonate can comprise 50 to 99 wt% of carbonate units and 1 to 50 wt% siloxane units. Within this range, the polyorganosiloxane- polycarbonate copolymer can comprise 70 to 98 wt%, more specifically, 75 to 97 wt% of carbonate units and 2 to 30 wt%, more specifically, 3 to 25 wt% siloxane units.

[0041] Polyorganosiloxane-polycarbonates can have a weight average molecular weight of 2,000 to 100,000 Daltons, specifically, 5,000 to 50,000 Daltons as measured by gel permeation chromatography using a crosslinked styrene-divinyl benzene column, at a sample concentration of 1 milligram per milliliter, and as calibrated with polycarbonate standards.

[0042] The polyorganosiloxane-polycarbonate can have a melt volume flow rate, of 1 to 50 cubic centimeters per 10 minutes (cc/10 min), specifically, 2 to 30 cc/10 min as determined by ASTM D1238-04 measured at 300°C and 1.2 kg. Mixtures of

polyorganosiloxane-polycarbonates of different flow properties can be used to achieve the overall desired flow property.

[0043] The thermoplastic resin can comprise an impact modifier. The impact modifier can comprise an elastomer-modified graft copolymer comprising (i) an elastomeric (i.e., rubbery) polymer substrate having a Tg less than or equal to 10°C, more specifically, less than or equal to -10°C, or more specifically, -40 to -80°C, and (ii) a rigid polymeric superstate grafted to the elastomeric polymer substrate. The elastomer-modified graft copolymers can be prepared by first providing the elastomeric polymer, then polymerizing the constituent monomer(s) of the rigid phase in the presence of the elastomer to obtain the graft copolymer. The grafts can be attached as graft branches or as shells to an elastomer core. The shell can merely physically encapsulate the core, or the shell can be partially or essentially completely grafted to the core.

[0044] The elastomeric phase can be polymerized by mass, emulsion, suspension, solution or combined processes such as bulk-suspension, emulsion-bulk, bulk-solution or other techniques, using continuous, semi-batch, or batch processes. The elastomer substrate can have an average particle size of 0.001 to 25 micrometers (μιη), specifically, 0.01 to 15 μηι, more specifically, 0.1 to 8 μιη can be used for emulsion based polymerized rubber lattices. A particle size of 0.5 to 10 μιη, specifically, 0.6 to 1.5 μηι can be used for bulk polymerized rubber substrates. Particle size can be measured by simple light transmission methods or capillary hydrodynamic chromatography (CHDF). The elastomeric phase can be a particulate, moderately cross-linked conjugated butadiene or C₄_₆ alkyl acrylate rubber, and specifically has a gel content greater than 70%. Also useful are combinations of butadiene with styrene and/or C₄_₆ alkyl acrylate rubbers.

[0045] The impact modifier can be prepared by an emulsion polymerization process that is free of basic materials such as alkali metal salts of C₆-3o fatty acids, for example, sodium stearate, lithium stearate, sodium oleate, potassium oleate, and the like, alkali metal carbonates, amines such as dodecyl dimethyl amine, dodecyl amine, and the like, and ammonium salts of amines. Such materials are commonly used as surfactants in emulsion polymerization, and can catalyze transesterification and/or degradation of polycarbonates. Instead, ionic sulfate, sulfonate or phosphate surfactants can be used in preparing the impact modifiers, particularly the elastomeric substrate portion of the impact modifiers. Useful surfactants include, for example, Ci_₂2 alkyl or C7_₂5 alkylaryl sulfonates, Ci_₂₂ alkyl or C7_₂5 alkylaryl sulfates, Ci_₂₂ alkyl or C7-25 alkylaryl phosphates, substituted silicates, or a combination comprising at least one of the foregoing. A specific surfactant is a C_6-16, specifically a C_8-12 alkyl sulfonate.

[0046] The surfactant can comprise rosin acid chloride, a higher fatty acid salt, an alkyl sulfuric acid ester salt, an alkylbenzene sulfonate, an alkyl diphenyl ether disulfone acid chloride, a polyoxyethylene alkylphenyl ether sulfate, a nonionic emulsifiers (such as the anionic emulsifiers of dialkyl sulfosuccinate, polyoxyethylene alkyl ether, and

polyoxyethylene alkyl phenyl ether), a surfactant of the formula (140), or a combination comprising one or more of the foregoing.

wherein R^M is an allyl group, an acrylyl group, or 1-propenyl group; R is hydrogen, a -

SO₃R z group (wherein R z is hydrogen, an alkaline metal, an alkaline-earth metal, ammonium, or a C_1-4 hydroxyalkyl ammonium), a carboxylate denoted group of the formula

z z

-CH2COOR (wherein R is defined above), or a monoester phosphate salt of the formula - (P=0)(OR^z)₂ (wherein each R^z independently is defined above); R^N and R° are each independently hydrogen, an alkyl group, an alkenyl group, a CM_S aralkyl group, a C_1-18 alkyl group, an alkenyl group, or an aralkyl group; R^p is hydrogen or a propenyl group; R^Q is an alkylene group or substituted C_2-4 alkylene group; and v is an integer of 1 to 200.

[0047] The surfactant can comprise a surfactant of the formula (141) and/or (142), wherein R and v are defined above.

[0048] Materials for use as the elastomer phase include, for example, conjugated diene rubbers; copolymers of a conjugated diene with less than or equal to 50 wt% of a copolymerizable monomer; olefin rubbers such as ethylene propylene copolymers (EPR) or ethylene-propylene-diene monomer rubbers (EPDM); ethylene- vinyl acetate rubbers; silicone rubbers; elastomeric Ci_₈ alkyl (meth)acrylates; elastomeric copolymers of Ci_₈ alkyl (meth)acrylates with butadiene and/or styrene; or combinations comprising at least one of the foregoing elastomers.

[0049] Conjugated diene monomers for preparing the elastomer phase include those of formula (17)

wherein each X^b is independently hydrogen, C1-C5 alkyl, or the like. Examples of conjugated diene monomers that can be used are butadiene, isoprene, 1,3-heptadiene, methyl- 1,3- pentadiene, 2,3 -dimethyl- 1,3 -butadiene, 2-ethyl- 1,3 -pentadiene; 1,3- and 2,4-hexadienes, and the like, or a combination comprising at least one of the foregoing. Specific conjugated diene homopolymers include polybutadiene and polyisoprene.

[0050] Copolymers of a conjugated diene rubber can also be used, for example, those produced by aqueous radical emulsion polymerization of a conjugated diene and at least one monomer copolymerizable therewith. Monomers that are useful for copolymerization with the conjugated diene include monovinylaromatic monomers containing condensed aromatic ring structures, such as vinyl naphthalene, vinyl anthracene, and the like, or monomers of formula (18); wherein each X^c is independently hydrogen, Cm alkyl, C₃-12 cycloalkyl, C₆-i2 aryl, C7-12 aralkyl, C7-12 alkylaryl, Q-12 alkoxy, C₃-12 cycloalkoxy, C₆-i2 aryloxy, chloro, bromo, or hydroxy, and R is hydrogen, C1-5 alkyl, bromo, or chloro. Monovinylaromatic monomers that can be used include styrene, 3-methylstyrene, 3,5-diethylstyrene, 4-n- propylstyrene, alpha-methylstyrene, alpha-methyl vinyltoluene, alpha-chlorostyrene, alpha- bromostyrene, dichlorostyrene, dibromostyrene, tetra-chlorostyrene, and the like, and combinations comprising at least one of the foregoing compounds. Styrene and/or alpha- methylstyrene can be used as monomers copolymerizable with the conjugated diene monomer.

[0051] Other monomers that can be copolymerized with the conjugated diene are monovinylic monomers such as itaconic acid, acrylamide, N-substituted acrylamide or methacrylamide, maleic anhydride, maleimide, N-alkyl-, aryl-, or haloaryl-substituted maleimide, glycidyl (meth)acrylates, and monomers of the generic formula (19); wherein R is hydrogen, C1-5 alkyl, bromo, or chloro, and X^c is cyano, Q-12 alkoxycarbonyl, Q-12 aryloxycarbonyl, hydroxy carbonyl, or the like. Examples of monomers of formula (19) include acrylonitrile, methacrylonitrile, alpha-chloroacrylonitrile, beta-chloroacrylonitrile, alpha-bromoacrylonitrile, acrylic acid, methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, t-butyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, 2- ethylhexyl (meth)acrylate, and the like, and combinations comprising at least one of the foregoing monomers. Monomers such as n-butyl acrylate, ethyl acrylate, and 2-ethylhexyl acrylate are commonly used as monomers copolymerizable with the conjugated diene monomer. Combinations of the foregoing monovinyl monomers and monovinylaromatic monomers can also be used.

[0052] (Meth)acrylate monomers for use in the elastomeric phase can be cross-linked, particulate emulsion homopolymers or copolymers of C_1-8 alkyl (meth)acrylates, in particular C₄_6 alkyl acrylates, for example, n-butyl acrylate, t-butyl acrylate, n-propyl acrylate, isopropyl acrylate, 2-ethylhexyl acrylate, and the like, and combinations comprising at least one of the foregoing monomers. The Ci_₈ alkyl (meth)acrylate monomers can be polymerized in admixture with less than or equal to 15 wt% of comonomers of formulas (17), (18), or (19), based on the total monomer weight. Comonomers include but are not limited to butadiene, isoprene, styrene, methyl methacrylate, phenyl methacrylate, vinyl methyl ether or acrylonitrile, phenethylmethacrylate, N-cyclohexylacrylamide, and combinations comprising at least one of the foregoing comonomers. Less than or equal to 5 wt% of a polyfunctional crosslinking comonomer can be present, based on the total monomer weight. Such polyfunctional crosslinking comonomers can include, for example, divinylbenzene, alkylenediol di(meth)acrylates such as glycol bisacrylate, alkylenetriol tri(meth)acrylates, polyester di(meth)acrylates, bisacrylamides, triallyl cyanurate, triallyl isocyanurate, allyl (meth)acrylate, diallyl maleate, diallyl fumarate, diallyl adipate, triallyl esters of citric acid, triallyl esters of phosphoric acid, and the like, as well as combinations comprising at least one of the foregoing crosslinking agents.

[0053] The rigid phase of the elastomer-modified graft copolymer can be formed by graft polymerization of a combination comprising a monovinylaromatic monomer and optionally at least one comonomer in the presence of at least one elastomeric polymer substrates. The above-described monovinylaromatic monomers of formula (18) can be used in the rigid graft phase, including styrene, alpha-methyl styrene, halostyrenes such as dibromostyrene, vinyltoluene, vinylxylene, butylstyrene, para-hydroxystyrene,

methoxystyrene, or the like, or combinations comprising at least one of the foregoing monovinylaromatic monomers. Useful comonomers include, for example, the above- described monovinylic monomers and/or monomers of the general formula (17). R can be hydrogen or Ci-₂ alkyl, and X^c can be cyano or Cn₂ alkoxycarbonyl. Comonomers for use in the rigid phase include acrylonitrile, methacrylonitrile, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, and the like, and combinations comprising at least one of the foregoing comonomers. [0054] The relative ratio of monovinylaromatic monomer and comonomer in the rigid graft phase can vary widely depending on the type of elastomer substrate, type of

monovinylaromatic monomer(s), type of comonomer(s), and the desired properties of the impact modifier. The rigid phase can comprise less than or equal to 100 wt% of monovinyl aromatic monomer, specifically, 30 to 100 wt%, more specifically, 50 to 90 wt%

monovinylaromatic monomer, with the balance of the rigid phase being comonomer(s).

[0055] The elastomeric phase can comprise 5 to 95 wt% of the total graft copolymer, more specifically, 20 to 90 wt%, and even more specifically, 40 to 85 wt% of the elastomer- modified graft copolymer, the remainder being the rigid graft phase.

[0056] Depending on the amount of elastomer-modified polymer present, a separate matrix or continuous phase of ungrafted rigid polymer or copolymer can be simultaneously obtained along with the elastomer-modified graft copolymer. Typically, such impact modifiers comprise 40 to 95 wt% elastomer-modified graft copolymer and 5 to 65 wt% graft copolymer, based on the total weight of the impact modifier. For example, such impact modifiers comprise 50 to 85 wt%, specifically, 75 to 85 wt% rubber-modified graft copolymer, together with 15 to 50 wt%, specifically, 15 to 25 wt% graft copolymer, based on the total weight of the impact modifier.

[0057] The rigid phase can comprise a copolymer derived from acrylonitrile and a monomer of the formula 18, for example, styrene, where the rigid phase can account for 0.1 to 80 parts by weight of the impact modifier in an elastomeric phase, for example, derived from a butyl acrylate.

[0058] The aromatic vinyl copolymer can comprise "free" styrene-acrylonitrile copolymer (SAN), i.e., styrene-acrylonitrile copolymer that is not grafted onto another polymeric chain. The free styrene-acrylonitrile copolymer can have a molecular weight of 50,000 to 200,000 Daltons on a polystyrene standard molecular weight scale and can comprise various proportions of styrene to acrylonitrile. For example, free SAN can comprise 75 wt% styrene and 25 wt% acrylonitrile based on the total weight of the free SAN copolymer. Free SAN can be present by virtue of the addition of a grafted rubber impact modifier in the composition that contains free SAN, and/or free SAN can by present independent of other impact modifiers in the composition.

[0059] An example of an impact modifier is a methyl methacrylate-butadiene- styrene (MBS) impact modifier wherein the butadiene substrate is prepared using above-described sulfonates, sulfates, or phosphates as surfactants. [0060] The impact modifier can comprise ABS, MBS, methyl methacrylate- acrylonitrile-butadiene-styrene (MABS), acrylonitrile-ethylene-propylene-diene-styrene (AES), hydrogenated styrene butadiene (SEBS), or a combination comprising one or more of the foregoing. The impact modifier can comprise an acrylic polymer.

[0061] Another specific type of elastomer-modified impact modifier comprises structural units derived from at least one silicone rubber monomer, a branched acrylate rubber monomer having the formula H₂C=C(R^d)C(0)OCH₂CH₂R^e, wherein R^d is hydrogen or a Ci-8 linear or branched alkyl and R^e is a branched C₃_i₆ alkyl; a first graft link monomer; a polymerizable alkenyl-containing organic material; and a second graft link monomer. The silicone rubber monomer can comprise, for example, a cyclic siloxane, tetraalkoxysilane, trialkoxysilane, (acryloxy)alkoxysilane, (mercaptoalkyl)alkoxysilane, vinylalkoxysilane, or allylalkoxysilane, alone or in combination, e.g., decamethylcyclopentasiloxane,

dodecamethyl cyclohexasiloxane, trimethyltriphenylcyclotrisiloxane, tetramethyl tetraphenyl cyclotetrasiloxane, tetramethyltetravinylcyclotetrasiloxane, octaphenyl cyclotetrasiloxane, octamethylcyclotetrasiloxane and/or tetraethoxysilane.

[0062] Branched acrylate rubber monomers include iso-octyl acrylate, 6-methyloctyl acrylate, 7-methyloctyl acrylate, 6-methylheptyl acrylate, and the like, or a combination comprising at least one of the foregoing. The polymerizable alkenyl-containing organic material can be, for example, a monomer of formula (18) or (19), e.g., styrene, alpha- methylstyrene, acrylonitrile, methacrylonitrile, or an unbranched (meth) acrylate such as methyl methacrylate, 2-ethylhexyl methacrylate, methyl acrylate, ethyl acrylate, n-propyl acrylate, or the like, alone or in combination.

[0063] The first graft link monomer can be an (acryloxy)alkoxysilane, a vinyl alkoxysilane, a (mercaptoalkyl) alkoxysilane, or an allylalkoxysilane, alone or in

combination, e.g., (gamma-methacryloxypropyl)(dimethoxy)methylsilane and/or (3- mercaptopropyl) trimethoxysilane. The second graft link monomer is a polyethylenically unsaturated compound having at least one allyl group, such as allyl methacrylate, triallyl cyanurate, triallyl isocyanurate, and the like, or a combination comprising at least one of the foregoing.

[0064] The silicone- acrylate impact modifiers can be prepared by emulsion polymerization, wherein, for example, a silicone rubber monomer is reacted with a first graft link monomer at a temperature from 30 to 110°C to form a silicone rubber latex, in the presence of a surfactant such as dodecylbenzenesulfonic acid. Alternatively, a cyclic siloxane such as cyclooctamethyltetrasiloxane and a tetraethoxyorthosilicate can be reacted with a first graft link monomer such as (gamma-methacryloxypropyl)methyldimethoxysilane. A branched acrylate rubber monomer is then polymerized with the silicone rubber particles, optionally in presence of a cross linking monomer, such as allyl methacrylate, in the presence of a free radical generating polymerization catalyst such as benzoyl peroxide. This latex is then reacted with a polymerizable alkenyl-containing organic material and a second graft link monomer. The latex particles of the graft silicone-acrylate rubber hybrid can be separated from the aqueous phase through coagulation (by treatment with a coagulant) and dried to a fine powder to produce the silicone-acrylate rubber impact modifier. This method can be generally used for producing the silicone-acrylate impact modifier having a particle size of 100 nanometers to 2 micrometers.

[0065] Coagulants can include acids having a pK_a of less than 5.0, specifically, less than 3.0, more specifically, less than 2.0. Accordingly, the acid can be a mineral acid having a hydrogen atom that completely ionizes in water. The acid coagulant can be an oxoacid (also referred to as an oxyacid), typically a strong acid, for example, an acid that completely ionizes in water (at least the first hydrogen proton). Specifically, the pK_a of the strong acid can be less than 2.0. The strong acid can comprise, for example, hydrochloric acid (HC1), hydroiodic acid (HI), hydrobromic acid (HBr), hydrofluoric acid (HF), perchloric acid (HC10₄), nitric acid (HN0₃), nitrous acid (HN0₂), chromic acid (H₂Cr0₄), sulfuric acid (H₂S0₄), sulfurous acid (H₂S0₃), phosphoric acid (H₃P0₄), trifluoromethanesulfonic acid (CF₃S0₃H), alkylsulfonic acid (CH₃S0₃H), or a combination comprising one or more of the foregoing. Specifically, the strong acid can comprise a nitrogen-containing and/or sulfur- containing strong acid, for example, nitric acid (HN0₃), nitrous acid (HN0₂), sulfuric acid (H₂S0₄), sulfurous acid (H₂S0₃), or a combination comprising one or more of the foregoing. A mineral acid such as sulfuric acid can be used as a coagulant.

[0066] The impact modifier can be a high rubber graft (HRG) impact modifier.

[0067] The impact modifier can be free of the alkali metal salts of fatty acids, alkali metal carbonates and other basic materials.

[0068] When present, the impact modifier can be present in the thermoplastic composition in amounts of 5 to 10 percent by weight, based on the total weight of

thermoplastic resin. The impact modifier can have an average diameter of 0.05 to 3 micrometers, specifically, 0.05 to 2 micrometers, more specifically, 0.1 to 1.5 micrometers. [0069] The polycarbonate and the impact modifier (such as an impact modifier prepared by an emulsion process, specifically, an emulsion process utilizing an acidic coagulant) can be compounded in the presence of a buffer, where the term "buffer" or "buffering agent" refers to the compounds capable of forming a buffer in an aqueous solution, and the pH of the buffer will refer to the pH obtainable by using the buffering agents in distilled water. Thus, the term buffer can refer to a combination of phosphate salts present in a solid composition that is in residual form but which phosphate salts are compounds that are capable of forming a buffer in an aqueous solution. The buffer can comprise one or more of a metallic salt of phosphoric acid, where at least one of which can comprise a potassium cation. The buffer can comprise a weak acid and a conjugate base (in equilibrium) capable of providing a pH of 6.3 to 7.0, specifically, of 6.4 to 6.9 in distilled water.

[0070] During the compounding, the amount of phosphorus atoms from the metallic salts of phosphoric acid can be 0.02 and 0.16 moles per 10 pounds (mol/10 lbs) (0.004 to 0.035 moles per kilogram (mol/kg)), specifically, 0.022 to 0.12 mol/10 lbs (0.004 to 0.026 mol/kg), more specifically, 0.025 to 0.08 mol/10 lbs (0.005 to 0.018 mol/kg), based on the weight of the polycarbonate composition. For example, the buffering agent can be present in the composition such that the amount of phosphorus in the composition is 0.04 mol/ 10 lbs (0.009 mol/kg), based on the weight of the composition. The potassium cations can represent of at least 50 mole percent (mol%), specifically, at least 75 mol%, of the cations in the metallic phosphate salts in the composition. The metallic salts of phosphoric acid can have a weak acid form and a conjugate base form in a ratio that is capable of forming a buffer in distilled water having a pH of 6.3 to 7.0, specifically, 6.4 to 6.9, more specifically, 6.5 to 6.8.

[0071] The relative ratio of respective acid and base forms that comprise the buffer can be determined using the following Henderson-Has selbalch equation:

pH = pKa + log[Base Form (A-)]/[Acid Form (HA)].

[0072] The metallic salt of phosphoric acid used as a buffer can comprise a cation other than potassium. The cation other than potassium can comprise a post-transition metal such as an alkali metal, an alkaline earth metal, a transition metal, or a combination comprising one or more of the foregoing. The cation other than potassium can comprise aluminum, sodium, lithium, calcium, zinc, or a combination comprising one or more of the foregoing. The buffer can comprise a conjugate base form comprising potassium cation and a weak acid form comprising a different metallic cation. Alternatively, the buffer can comprise potassium cations in both the weak acid form and conjugate base form. Specifically, buffers can consist of weak acid and conjugate base pairs such as monopotassium phosphate/dipotassium phosphate, lithium phosphate monobasic/dipotassium phosphate, aluminum phosphate monobasic/dipotassium phosphate, monozinc

phosphate/dipotassium phosphate, or a combination comprising one or more of the foregoing.

[0073] A polymeric flow promoter can be present during the compounding. The polymeric flow promoter can readily blend with the elastomer-modified graft copolymer and increase its melt flow rate without adversely affecting the desired properties of the

composition. The polymeric flow promoter can comprise repeat units derived from monomers selected from the group consisting of methyl (meth)acrylate, styrene, acrylonitrile, alpha-methyl styrene, or a combination comprising one or more of the foregoing. For example, the polymeric flow promoter can comprise a styrene-acrylonitrile copolymer, poly(methyl methacrylate), polystyrene, a methyl methacrylate-styrene-acrylonitrile copolymer, a poly(alpha methyl styrene), or a combination comprising one or more of the foregoing. Specifically, the flow promoter can comprise a styrene-acrylonitrile copolymer.

[0074] The polymeric flow promoter can form a separate matrix or continuous phase. The polymeric flow promoter can comprise ungrafted rigid polymer or "graft copolymer" that is simultaneously obtained along with the impact modifier. For example, a polymeric flow promoter can be produced at the same time as the impact modifier by using excess monomers from the polymerization of the impact modifier. Alternatively, the polymeric flow promoter can be prepared or obtained independently and introduced to the elastomer-modified graft copolymer later, for example, during compounding of the elastomer-modified graft copolymer with the polycarbonate.

[0075] The ratio of the impact modifier to the polymeric flow promoter, if present, can be 3: 1 to 1:3, specifically, 2: 1 to 1:2, more specifically, 1.5: 1 to 1: 1.5. The impact modifier can be present in an amount of 40 to 95 wt%, specifically, 50 to 85 wt%, more specifically, 75 to 85 wt% and the polymeric flow promoter can be present in an amount of 5 to 65 wt%, specifically, 15 to 50 wt%, more specifically, 15 to 25 wt% based on the total weight of the impact modifier and the polymeric flow promoter.

[0076] The average residence time of the compounding step can be 20 to 30 seconds (sec). The temperature during compounding can be 200 to 300°C.

[0077] The compounding can comprise two distinct mixing steps: a premixing step and a melt mixing ("melt blending") step. In the premixing step, the dry ingredients can be mixed together to form a pre-mixture, for example, in a tumbler mixer, a ribbon blender or a high shear mixer. The melt mixing can comprise melting the pre-mixture and mixing again as a melt, for example, in a single screw extruder, a twin screw extruder, a Banbury mixer, or a two roll mill.

[0078] An additive can further be added at one or more locations in the present melt preparation of the polycarbonate. For example, the additive can be added upstream of a polymerization unit, directly into a polymerization unit (for example, at an inlet, in a side feeder, in an outlet, or a combination comprising one or more of the foregoing), downstream of a polymerization unit, in a reactor that is not polymerizing polycarbonate, upstream of an extruder, directly into an extruder (for example, at the throat of the extruder, in a side feeder, in an outlet, or a combination comprising one or more of the foregoing), downstream of an extruder, or a combination comprising one or more of the foregoing. The additive can be added during the compounding with the impact modifier. The additive can be added as part of the quencher composition or can be added separately. The additive can be added in a molten state or can be added after an extruded polycarbonate is re-melted. The additive can be filtered prior to being added into the polymerization unit.

[0079] The additive can comprise, for example, a flow modifier, a filler (e.g., glass, carbon, a mineral, or metal), a reinforcing agent (e.g., glass fibers), an antioxidant, a heat stabilizer, a light stabilizer, an ultraviolet (UV) agent (such as a UV light stabilizer and a UV absorbing additive), a plasticizer, a lubricant, a release agent (such as a mold release agent (such as glycerol monostearate, pentaerythritol stearate, glycerol tristearate, stearyl stearate, and the like)), an antistatic agent, an antifog agent, an antimicrobial agent, a colorant (e.g., a dye or pigment), a surface effect additive, a radiation stabilizer, a flame retardant, a fluoro- resin (e.g., a PTFE-encapsulated styrene-acrylonitrile copolymer (TSAN)), or a combination comprising one or more of the foregoing. For example, a combination of a heat stabilizer, mold release agent, and ultraviolet light stabilizer can be used. In general, the additives are used in the amounts generally known to be effective. For example, the total amount of the additive composition (other than any filler or reinforcing agent) can be 0.001 to 10.0 weight percent (wt%), or 0.01 to 5 wt%, each based on the total weight of the polymer in the polymerized composition.

[0080] Heat stabilizer additives include organophosphites (e.g. triphenyl phosphite, tris-(2,6-dimethylphenyl)phosphite, tris-(mixed mono-and di-nonylphenyl)phosphite or the like), phosphonates (e.g., dimethylbenzene phosphonate or the like), phosphates (e.g., trimethyl phosphate, or the like), or combinations comprising at least one of the foregoing heat stabilizers. The heat stabilizer can comprise tris(2,4-di-t-butylphenyl) phosphate available as IRGAPHOS™ 168. The heat stabilizer can comprise IRGAPHOS™ 205. Heat stabilizers are generally used in amounts of 0.01 to 5 wt%, based on the total weight of polymer in the composition.

[0081] The term "antistatic agent" refers to monomeric, oligomeric, or polymeric materials that can be processed into polymers and/or sprayed onto materials or articles to improve conductive properties and overall physical performance. Examples of monomeric antistatic agents include ethoxylated amines, primary, secondary and tertiary amines, ethoxylated alcohols, alkyl sulfates, alkylarylsulfates, alkylphosphates, alkylaminesulfates, alkyl sulfonate salts such as sodium stearyl sulfonate, sodium dodecylbenzenesulfonate or the like, quaternary ammonium salts, quaternary ammonium polymers, imidazoline derivatives, sorbitan esters, ethanolamides, betaines, or the like, or combinations comprising at least one of the foregoing monomeric antistatic agents.

[0082] Polymeric antistatic agents include certain polyesteramides, polyether- polyamide (polyetheramide) block copolymers, polyetheresteramide block copolymers, polyetheresters, or polyurethanes, each containing polyalkylene glycol moieties polyalkylene oxide units such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and the like. Such polymeric antistatic agents are commercially available, for example PELESTAT™ 6321 (Sanyo) or PEBAX™ MH1657 (Atofina), IRGASTAT™ P18 and P22 (Ciba-Geigy). Other polymeric materials that can be used as antistatic agents are inherently conducting polymers such as polyaniline (commercially available as PANIPOL^®EB from Panipol), polypyrrole and polythiophene (commercially available from Bayer), which retain some of their intrinsic conductivity after melt processing at elevated temperatures. In an embodiment, carbon fibers, carbon nanofibers, carbon nanotubes, carbon black, or a combination comprising at least one of the foregoing can be used in a polymer composition containing chemical antistatic agents to render the composition electrostatically dissipative.

[0083] Radiation stabilizers can also be present, specifically gamma-radiation stabilizers, gamma-radiation stabilizers include alkylene polyols such as ethylene glycol, propylene glycol, 1,3 -propanediol, 1,2-butanediol, 1,4-butanediol, meso-2,3-butanediol, 1,2- pentanediol, 2,3-pentanediol, 1,4-pentanediol, 1,4-hexandiol, and the like; cycloalkylene polyols such as 1,2-cyclopentanediol, 1,2-cyclohexanediol, and the like; branched alkylenepolyols such as 2,3-dimethyl-2,3-butanediol (pinacol), and the like, as well as alkoxy-substituted cyclic or acyclic alkanes. Unsaturated alkenols are also useful, examples of which include 4-methyl-4-penten-2-ol, 3 -methyl -pentene-3-ol, 2-methyl-4-penten-2-ol, 2,4-dimethyl-4-pene-2-ol, and 9-decen-l-ol, as well as tertiary alcohols that have at least one hydroxy substituted tertiary carbon, for example 2-methyl-2,4-pentanediol (hexylene glycol), 2-phenyl-2-butanol, 3-hydroxy-3-methyl-2-butanone, 2-phenyl-2-butanol, and the like, and cyclic tertiary alcohols such as 1 -hydroxy- 1-methyl-cyclohexane. Certain hydroxymethyl aromatic compounds that have hydroxy substitution on a saturated carbon attached to an unsaturated carbon in an aromatic ring can also be used. The hydroxy-substituted saturated carbon can be a methylol group (-CH₂OH) or it can be a member of a more complex hydrocarbon group such as -CR⁴HOH or -CR₂ ⁴OH wherein R⁴ is a complex or a simple hydrocarbon. Specific hydroxy methyl aromatic compounds include benzhydrol, 1,3- benzenedimethanol, benzyl alcohol, 4-benzyloxy benzyl alcohol and benzyl benzyl alcohol. 2-Methyl-2,4-pentanediol, polyethylene glycol, and polypropylene glycol are often used for gamma-radiation stabilization.

[0084] Colorants such as pigment and/or dye additives can also be present. Useful pigments can include, for example, inorganic pigments such as metal oxides and mixed metal oxides such as zinc oxide, titanium dioxides, iron oxides, or the like; sulfides such as zinc sulfides, or the like; aluminates; sodium sulfo- silicates sulfates, chromates, or the like; carbon blacks; zinc ferrites; ultramarine blue; organic pigments such as azos, di-azos, quinacridones, perylenes, naphthalene tetracarboxylic acids, flavanthrones, isoindolinones, enthrones, dioxazines, tetrachloroisoindolinones, anthraquinones, phthalocyanines, and azo lakes;

Pigment Red 101, Pigment Red 122, Pigment Red 149, Pigment Red 177, Pigment Red 179, Pigment Red 202, Pigment Violet 29, Pigment Blue 15, Pigment Blue 60, Pigment Green 7, Pigment Yellow 119, Pigment Yellow 147, Pigment Yellow 150, and Pigment Brown 24; or combinations comprising at least one of the foregoing pigments.

[0085] Dyes are generally organic materials and include coumarin dyes such as coumarin 460 (blue), coumarin 6 (green), nile red or the like; lanthanide complexes;

hydrocarbon and substituted hydrocarbon dyes; polycyclic aromatic hydrocarbon dyes;

scintillation dyes such as oxazole or oxadiazole dyes; aryl- or heteroaryl-substituted poly (C₂_ s) olefin dyes; carbocyanine dyes; indanthrone dyes; phthalocyanine dyes; oxazine dyes; carbostyryl dyes; napthalenetetracarboxylic acid dyes; porphyrin dyes; bis(styryl)biphenyl dyes; acridine dyes; anthraquinone dyes; cyanine dyes; methine dyes; arylmethane dyes; azo dyes; indigoid dyes, thioindigoid dyes, diazonium dyes; nitro dyes; quinone imine dyes; aminoketone dyes; tetrazolium dyes; thiazole dyes; perylene dyes, perinone dyes; bis- benzoxazolylthiophene (BBOT); triarylmethane dyes; xanthene dyes; thioxanthene dyes; naphthalimide dyes; lactone dyes; fluorophores such as anti-stokes shift dyes which absorb in the near infrared wavelength and emit in the visible wavelength, or the like; luminescent dyes such as 7-amino-4-methylcoumarin; 3-(2'-benzothiazolyl)-7-diethylaminocoumarin; 2-(4- biphenylyl)-5-(4-t-butylphenyl)-l,3,4-oxadiazole; 2,5-bis-(4-biphenylyl)-oxazole; 2,2'- dimethyl-p-quaterphenyl; 2,2-dimethyl-p-terphenyl; 2,5-diphenylfuran; 3,5,3"",5""-tetra-t- butyl-p-quinquephenyl; 2,5-diphenyloxazole; 4,4'-diphenylstilbene; 4-dicyanomethylene-2- methyl-6-(p-dimethylaminostyryl)-4H-pyran; l,l'-diethyl-2,2'-carbocyanine iodide; 3,3'- diethyl-4,4',5,5'-dibenzothiatricarbocyanine iodide; 7-dimethylamino-l-methyl-4-methoxy-8- azaquinolone-2; 7-dimethylamino-4-methyl quinolone-2; 2-(4-(4-dimethylaminophenyl)-l,3- butadienyl) - 3 -ethylbenzothiazolium perchlorate ; 3 -diethylamino-7 -diethylimino

phenoxazonium perchlorate; 2-(l-naphthyl)-5-phenyloxazole; 2,2'-p-phenylen-bis(5- phenyloxazole); rhodamine 700; rhodamine 800; pyrene, chrysene, rubrene, coronene, or the like; or combinations comprising at least one of the foregoing dyes.

[0086] Possible fillers or reinforcing agents include, for example, mica, clay, feldspar, quartz, quartzite, perlite, tripoli, diatomaceous earth, aluminum silicate (mullite), synthetic calcium silicate, fused silica, fumed silica, expanded graphite, sand, boron-nitride powder, boron- silicate powder, calcium sulfate, calcium carbonates (such as chalk, limestone, marble, and synthetic precipitated calcium carbonates) talc (including fibrous, modular, needle shaped, and lamellar talc), wollastonite, hollow or solid glass spheres, silicate spheres, cenospheres, aluminosilicate or (armospheres), kaolin, whiskers of silicon carbide, alumina, boron carbide, iron, nickel, or copper, continuous and chopped carbon fibers or glass fibers, molybdenum sulfide, zinc sulfide, barium titanate, barium ferrite, barium sulfate, heavy spar, Ti0₂, aluminum oxide, magnesium oxide, particulate or fibrous aluminum, bronze, zinc, copper, or nickel, glass flakes, flaked silicon carbide, flaked aluminum diboride, flaked aluminum, steel flakes, natural fillers such as wood flour, fibrous cellulose, cotton, sisal, jute, starch , lignin, ground nut shells, or rice grain husks, reinforcing organic fibrous fillers such as poly(ether ketone), polyimide, polybenzoxazole, poly(phenylene sulfide), polyesters, polyethylene, aromatic polyamides, aromatic polyimides, polyetherimides, poly(vinyl alcohol), and polytetrafluoroethylene, as well combinations comprising at least one of the foregoing fillers or reinforcing agents. The fillers and reinforcing agents can be coated with a layer of metallic material to facilitate conductivity, or surface treated with silanes to improve adhesion and dispersion with the polymer matrix. Fillers are used in amounts of 1 to 200 parts by weight, based on 100 parts by weight of based on 100 parts by weight of the total composition.

[0087] Antioxidant additives include organophosphites such as tris(nonyl

phenyl)phosphite, tris(2,4-di-t-butylphenyl)phosphite, bis(2,4-di-t-butylphenyl)

pentaerythritol diphosphite, distearyl pentaerythritol diphosphite; alkylated monophenols or polyphenols; alkylated reaction products of polyphenols with dienes, such as tetrakis

[methylene(3,5-di-tert-butyl-4-hydroxyhydrocinnamate)] methane; butylated reaction products of para-cresol or dicyclopentadiene; alkylated hydroquinones; hydroxylated thiodiphenyl ethers; alkylidene-bisphenols; benzyl compounds; esters of beta-(3,5-di-tert- butyl-4-hydroxyphenyl)-propionic acid with monohydric or polyhydric alcohols; esters of beta-(5-tert-butyl-4-hydroxy-3-methylphenyl)-propionic acid with monohydric or polyhydric alcohols; esters of thioalkyl or thioaryl compounds such as distearylthiopropionate, dilaurylthiopropionate, ditridecylthiodipropionate, octadecyl-3 -(3 ,5-di-tert-butyl-4- hydroxyphenyl)propionate, pentaerythrityl-tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate; amides of beta-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionic acid, or

combinations comprising at least one of the foregoing antioxidants. Antioxidants can be used in amounts of 0.01 to 0.1 parts by weight, based on 100 parts by weight of the total thermoplastic composition, excluding any filler.

[0088] UV absorbing additives include hydroxybenzophenones;

hydroxybenzotriazoles; hydroxybenzotriazines; cyanoacrylates; oxanilides; benzoxazinones; aryl salicylates; monoesters of diphenols such as resorcinol monobenzoate; 2-(2H- benzotriazol-2-yl)-4-(l,l,3,3-tetramethylbutyl)-phenol (CYASORB™ 5411); 2-hydroxy-4-n- octyloxybenzophenone (CYASORB™ 531); 2-[4,6-bis(2,4-dimethylphenyl)-l,3,5-triazin-2- yl]- 5-(octyloxy)-phenol (CYASORB™ 1164); 2,2'-(l,4- phenylene)bis(4H-3,l-benzoxazin- 4-one) (CYASORB™ UV- 3638); poly[(6-morphilino-s-triazine-2,4-diyl)[2,2,6,6- tetramethyl-4-piperidyl) imino] -hexamethylene[(2,2,6,6-tetramethyl-4-piperidyl)imino] , 2- hydroxy-4-octyloxybenzophenone (UVINUL™3008), 6-tert-butyl-2-(5-chloro-2H- benzotriazole-2-yl)-4-methylphenyl (UVINUL™3026), 2,4-di-tert-butyl-6-(5-chloro-2H- benzotriazole-2-yl)-phenol (UVINUL™3027), 2-(2H-benzotriazole-2-yl)-4,6-di-tert- pentylphenol (UVINUL™3028), 2-(2H-benzotriazole-2-yl)-4-(l,l,3,3-tetramethylbutyl)- phenol (UVINUL™3029), l,3-bis[(2'cyano-3',3'-diphenylacryloyl)oxy]-2,2-bis-{ [(2'-cyano- 3', 3 '-diphenylacryloyl)oxy] methyl} -propane (UVINUL™3030), 2-(2H-benzotriazole-2-yl)- 4-methylphenol (UVINUL™3033), 2-(2H-benzotriazole-2-yl)-4,6-bis( 1 -methyl- 1- phenyethyl)phenol (UVINUL^1M3034), ethyl-2-cyano-3,3-diphenylacrylate (UVINUL^1M 3035), (2-ethylhexyl)-2-cyano-3,3-diphenylacrylate (UVINUL™3039), N,N'-bisformyl- N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)hexamethylendiamine (UVINUL™ 4050H), bis- (2,2,6,6-tetramethyl-4-piperidyl)-sebacate (UVINUL™4077H), bis-(l,2,2,6,6-pentamethyl-4- piperdiyl)-sebacate + methyl-(l, 2,2,6, 6-pentamethyl-4-piperidyl)-sebacate (UVINUL™ 4092H) l,3-bis[(2-cyano-3,3-diphenylacryloyl)oxy]-2,2-bis[[(2-cyano-3,3-diphenylacryloyl) oxy]methyl]propane (UVINUL™ 3030); 2,2'-(l,4-phenylene) bis(4H-3,l-benzoxazin-4-one); 1 ,3 -bis [(2-cyano-3 ,3 -diphenylacryloyl)oxy] -2,2-bis [ [(2-cyano-3 ,3 -diphenylacryloyl) oxy]methyl]propane; TINUVIN™ 234; nano-size inorganic materials such as titanium oxide, cerium oxide, and zinc oxide, all with particle size less than or equal to 100 nanometers; or the like, or combinations comprising at least one of the foregoing UV absorbers. UV absorbers can be used in amounts of 0.01 to 1 part by weight, based on 100 parts by weight of the thermoplastic resin. UV absorbers that can be particularly useful with the polycarbonate compositions disclosed herein include 2-(2H-benzotriazol-2-yl)-4-(l,l,3,3-tetramethylbutyl)- phenol (e.g., CYASORB™ 5411 commercially available from Cytec Industries, Inc., Woodland Park, New Jersey) and 2,2'-(l,4- phenylene)bis(4H-3,l-benzoxazin-4-one) (e.g., CYASORB™ UV- 3638, commercially available from Cytec Industries, Inc., Woodland Park, New Jersey), and combinations comprising at least one of the foregoing. The UV stabilizers can be present in an amount of 0.01 to 1 wt%, specifically, 0.1 to 0.5 wt%, and or 0.15 to 0.4 wt%, based upon the total weight of the thermoplastic composition.

[0089] Plasticizers, lubricants, and/or mold release agents can also be used. There is considerable overlap among these types of materials, for example, phthalic acid esters such as dioctyl-4,5-epoxy-hexahydrophthalate; tris-(octoxycarbonylethyl) isocyanurate; tristearin; di- or polyfunctional aromatic phosphates such as resorcinol tetraphenyl diphosphate (RDP), the bis(diphenyl) phosphate of hydroquinone and the bis(diphenyl) phosphate of bisphenol A; poly-alpha-olefins; epoxidized soybean oil; silicones, including silicone oils; esters, for example, fatty acid esters such as alkyl stearyl esters, e.g., methyl stearate, stearyl stearate, pentaerythritol tetrastearate, and the like; combinations of methyl stearate and hydrophilic and hydrophobic nonionic surfactants comprising polyethylene glycol polymers,

polypropylene glycol polymers, poly(ethylene glycol-co-propylene glycol) copolymers, or a combination comprising at least one of the foregoing glycol polymers, e.g., methyl stearate and polyethylene-polypropylene glycol copolymer in a suitable solvent; waxes such as beeswax, montan wax, paraffin wax, or the like. [0090] The plasticizers, lubricants, and/or mold release agent can comprise compound of formula (I)

wherein Ri, R₂, and R₃ can be the same or different hydrocarbon chains with 8 to 20 carbon atoms and 0 to 6 unsaturations, wherein Ri, R₂, and R₃ are each independently selected from C₈-C₂o alkyl, C₈-C₂o haloalkyl, C₈-C₂o polyhaloalkyl, C₈-C₂o alkene, and C₈-C₂o alkoxy. Ri, R₂, and R₃ can each independently be from Ci₇H₃5 or all Ri, R₂, and R₃ can be Ci₇H₃5. The plasticizers, lubricants, and/or mold release agent can comprise glycerol monostearate, glycerol monopalmitate, glycerol tristearate, glycerol tristearate, stearyl stearate, or a combination comprising one or more of the foregoing. One or more of the aforementioned can have an acid value of 2 to 20 mg KOH as determined by: adding 100 ml of isopropanol to 2.5 g of a partial ester to thereby dissolve the partial ester; phenolphthalein is added to the resultant solution as an indicator; titrating the resultant mixture using a 0.1 mol/L standard solution of potassium hydroxide to thereby obtain the acid value (mg KOH). In the measurement of the acid value, when it is expected that the partial ester has an acid value of 1 or less, the amount of the partial ester subjected to measurement is changed to 20 g; when it is expected that the partial ester has an acid value of from 1 to 4, the amount of the partial ester subjected to measurement is changed to 10 g; and when it is expected that the partial ester has an acid value of 15 or more, the amount of the partial ester subjected to

measurement is changed to 0.5 g.

[0091] The plasticizers, lubricants, and/or mold release agent can be present in an amount of 0.01 to 5 parts by weight, specifically, 0.01 to 0.1 parts by weight, based on 100 parts by weight of the thermoplastic resin.

[0092] Useful flame retardants include organic compounds that include phosphorus, bromine, and/or chlorine. Non-brominated and non-chlorinated phosphorus -containing flame retardants can be preferred in certain applications for regulatory reasons, for example organic phosphates and organic compounds containing phosphorus -nitrogen bonds.

[0093] Flame retardant aromatic phosphates include triphenyl phosphate, tricresyl phosphate, isopropylated triphenyl phosphate, phenyl bis(dodecyl) phosphate, phenyl bis(neopentyl) phosphate, phenyl bis(3,5,5'-trimethylhexyl) phosphate, ethyl diphenyl phosphate, 2-ethylhexyl di(p-tolyl) phosphate, bis(2-ethylhexyl) p-tolyl phosphate, tritolyl phosphate, bis(2-ethylhexyl) phenyl phosphate, tri(nonylphenyl) phosphate, bis(dodecyl) p- tolyl phosphate, dibutyl phenyl phosphate, 2-chloroethyl diphenyl phosphate, p-tolyl bis(2,5,5'-trimethylhexyl) phosphate, and 2-ethylhexyl diphenyl phosphate. Di- or polyfunctional aromatic phosphorus -containing compounds are also useful, for example resorcinol tetraphenyl diphosphate (RDP), the bis(diphenyl) phosphate of hydroquinone and the bis(diphenyl) phosphate of bisphenol A, respectively, and their oligomeric and polymeric counterparts. Flame retardant compounds containing phosphorus -nitrogen bonds include phosphonitrilic chloride, phosphorus ester amides, phosphoric acid amides, phosphonic acid amides, phosphinic acid amides, and tris(aziridinyl) phosphine oxide. When used, phosphorus-containing flame retardants are present in amounts of 0.1 to 30 parts by weight (pbw), specifically, 1 to 20 pbw, based on 100 pbw of the composition, excluding any filler.

[0094] Halogenated materials can also be used as flame retardants, for example bisphenols of which the following are representative: 2,2-bis-(3,5-dichlorophenyl)-propane; bis-(2-chlorophenyl)-methane; bis(2,6-dibromophenyl)-methane; l,l-bis-(4-iodophenyl)- ethane; l,2-bis-(2,6-dichlorophenyl)-ethane; l,l-bis-(2-chloro-4-iodophenyl)ethane; 1,1-bis- (2-chloro-4-methylphenyl)-ethane; l,l-bis-(3,5-dichlorophenyl)-ethane; 2,2-bis-(3-phenyl-4- bromophenyl) -ethane; 2,6-bis-(4,6-dichloronaphthyl)-propane; and 2,2-bis-(3,5-dichloro-4- hydroxyphenyl)-propane 2,2 bis-(3-bromo-4-hydroxyphenyl)-propane. Other halogenated materials include 1,3-dichlorobenzene, 1,4-dibromobenzene, l,3-dichloro-4-hydroxybenzene, and biphenyls such as 2,2'-dichlorobiphenyl, polybrominated 1,4-diphenoxybenzene, 2,4'- dibromobiphenyl, and 2,4'-dichlorobiphenyl as well as decabromo diphenyl oxide, as well as oligomeric and polymeric halogenated aromatic compounds, such as a copolycarbonate of bisphenol A and tetrabromobisphenol A and a carbonate precursor, e.g., phosgene. Metal synergists, e.g., antimony oxide, bismuth oxide, iron oxide, zinc oxide, tin oxide, can also be used with the flame retardant and can be present in an amount of 0.5 to 20 pbw, specifically, 1 to 15 pbw, more specifically, 1 to 10 pbw based on 100 pbw of the composition.

[0095] When present, halogen containing flame retardants can be present in an amount of 1 to 25 parts by weight, more specifically 2 to 20 parts by weight, based on 100 parts by weight of the total thermoplastic composition, excluding any filler.

[0096] Inorganic flame retardants can also be used, for example salts of C_1-16 alkyl sulfonate salts such as potassium perfluorobutane sulfonate (Rimar salt), potassium perfluoroctane sulfonate, tetraethylammonium perfluorohexane sulfonate, and potassium diphenylsulfone sulfonate; salts such as Na₂C0₃, K₂C0₃, MgC0₃, CaC0₃, and BaC0₃, or fluoro-anion complexes such as Li₃AlF₆, BaSiF₆, KBF₄, K₃A1F₆, KA1F₄, K₂SiF₆, and/or Na₃AlF₆. When present, inorganic flame retardant salts are present in amounts of 0.01 to 10 parts by weight, more specifically 0.02 to 1 parts by weight, based on 100 parts by weight of the total thermoplastic composition, excluding any filler.

[0097] The flame retardant can comprise a nitrogen containing organic compound (such as melamine), a silicon compound, a halogen comprising organic compound, an inorganic compound (such as magnesium hydroxide and aluminum hydroxide), a phosphorus compound (such as phosphine, hypophosphorous acid, phosphorous acid, metaphosphoric acid, pyrophoric acid, and a phosphoric anhydride), or a combination comprising one or more of the foregoing.

[0098] The flame retardant can comprise a halogen-containing compound, for example, hexachloro pentadiene, hexabromo diphenyl, octabromo diphenyloxide, tribromo phenoxymethane, decabromo diphenyl, decabromo diphenyloxide, octabromo diphenyloxide, tetrabromo bisphenol A, a tetrabromo phthalimide, a hexabromo butene, a hexabromo cyclododecane, or a combination comprising one or more of the foregoing.

-containing compound can have a structure of the formula (200).

wherein iii is an integer 0-10, each R I independently is a halogen, and each R H independently can have the formula (201 or (202).

wherein iv is an integer 0 to 3.

[0100] The halogen-containing compound can have a structure of a following formula

(210).

wherein iii and R are defined above, where the R group can have the formula (212).

[0101] The halogen-containing compound can comprise a phosphoric ester such as trischloroethyl phosphate, trisdichloropropyl phosphate, tris-chloropropyl phosphate, beta- chloropropyl phosphate, tris (tribromophenyl) phosphate, tris (dibromophenyl) phosphate, tris (tribromo neopentyl phosphate) phosphate, trimethyl phosphate, triethyl phosphate, tri propyl phosphate, tributyl phosphate, tripentyl phosphate, trihexyl phosphate, tricyclohexyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, dimethylethyl phosphate, methyl dibutyl phosphate, ethyl dipropyl phosphate, hydroxyphenyl diphenyl phosphate, or a combination comprising one or more of the foregoing.

[0102] The phosphoric ester can have the formula (230).

wherein the average vi is 1 to 10, specifically, 1 to 1.3, more specifically, 1 to 1.2; each R independently is a phenyl group, a tolyl group, a xylyl group, an alkyl group, a cycloalkyl group, or an alkylaryl group; and each R^M independently is a divalent group of the formulae (231) - (234), specifically, of the formulae (232) and (234).

For example, the phosphoric ester of the formula (230) can be bisphenol A tetraphenyl diphosphate, bisphenol A tetraxylyl diphosphate, bisphenol A tetra cresyl diphosphate, resorcinol diphosphate.

[0103] The flame retardant can comprise a silicon fire retardant, such as that of the formula: RSiO, wherein R can be an hydrocarbon group (such as a methyl group, a propyl group, phenyl group, a xylyl group, or an alkenyl group).

[0104] The thermoplastic composition can comprise 0.1 to 39 parts by weight, specifically, 0.1 to 30 parts by weight, more specifically, 1 to 25 parts by weight, even more specifically, 3 to 22 parts by weight of the flame retardant based on 100 parts by weight of the thermoplastic resin.

[0105] The thermoplastic composition can comprise a fluoro-resin. The fluoro-resin can comprise a tetrafluoroethylene (TFE) resin, a perfluoro alkoxy (PFA) resin, an ethylene propylene fluoro (FEP) resin, or a combination comprising one or more of the foregoing. The fluoro-resin can be encapsulated by a rigid copolymer, for example, styrene-acrylonitrile copolymer (SAN). Polytetrafluoroethylene (PTFE) encapsulated in SAN is known as TSAN. TSAN can comprise 50 wt% PTFE and 50 wt% SAN, based on the total weight of the encapsulated fluoropolymer. The SAN can comprise, for example, 75 wt% styrene and 25 wt% acrylonitrile based on the total weight of the copolymer.

[0106] The fluoro-resin can be prepared by suspension polymerization or an emulsion polymerization, for example, as described in a "fluororesin handbook" (Nikkan Kogyo Shimbun, 1990 annual publications). The fluoro-resin can be added as a dispersion, where the dispersion can be an aqueous dispersion manufactured by adding a surfactant to an emulsion polymerized fluoro-resin.

[0107] The fluoro-resin can be fibril in shape, wherein the fibrils can have an average diameter less than or equal to 0.5 micrometers. The fibrils can be branched fibrils. The fluoro-resin can be present in an amount of 0.01 to 5 parts by weight, specifically, 0.1 to 1 parts by weight of the fluoro-resin based on 100 parts by weight of the thermoplastic resin.

[0108] The thermoplastic composition can be prepared by feeding the thermoplastic resin to an extruder, directing a fluoro-resin, a flame retardant, or a combination comprising one or both of the foregoing to the extruder; and extruding the thermoplastic resin to form the thermoplastic composition. The extruder can be, for example, a single screw extruder, a twin screw extruder, or a Banbury mixer. The extruding can be performed at or above a melting temperature of the thermoplastic resin. The thermoplastic resin can be melt kneaded prior to the addition of the fluoro-resin and a melt viscosity as measured with the capillary rheometer at the resin temperature at the time of the melt kneading at a shear rate 240 sec^"1 can have a viscosity of 3,000 to 12,000 poise, specifically, 3,000 to 10,000 poise. The melt kneading can occur at a temperature of less than or equal to 320°C, or less than or equal to 310°C.

[0109] The extruded thermoplastic composition can then be molded, for example, by extrusion molding, compression molding, injection molding, or by gas assisted molding.

[0110] The quenched composition can be essentially free of chlorine and bromine. "Essentially free of chlorine and bromine" is defined as having a bromine and/or chlorine content of less than or equal to 100 parts per million by weight (ppm), less than or equal to 75 ppm, or less than or equal to 50 ppm, based on the total parts by weight of the composition, excluding any filler.

[0111] The present polymerization can occur in the absence of a branching agent or in other words, the present process can be free of a branching agent addition step. Examples of branching agents include polyfunctional organic compounds containing at least three functional groups selected from hydroxyl, carboxyl, carboxylic anhydride, haloformyl, and mixtures of the foregoing functional groups. Such branching agents include aromatic triacyl halides, for example triacyl chlorides of formula (20); wherein Z is a halogen, Ci_₃ alkyl, Ci_₃ alkoxy, C₇_i₂ arylalkylene, C₇_i₂ alkylarylene, or nitro, and z is 0 to 3; a tri-substituted phenol of formula (21); wherein T is a C_1-2o alkyl, Ci_₂o alkoxy, C_7-12 arylalkyl, or C_7-12 alkylaryl, Y is a halogen, C_1-3 alkyl, C_1-3 alkoxy, C_7-12 arylalkyl, C_7-12 alkylaryl, or nitro, s is 0 to 4.

[0112] Specific examples of branching agents include trimellitic acid, trimellitic anhydride, trimellitic trichloride, tris-p-hydroxyphenylethane, isatin-bis-phenol of formula (22), tris-phenol TC (l,3,5-tris((p-hydroxyphenyl)isopropyl)benzene), tris-phenol PA

(4(4(1, l-bis(p-hydroxyphenyl)-ethyl) alpha, alpha-dimethyl benzyl)phenol), 4-chloroformyl phthalic anhydride, trimesic acid, and benzophenone tetracarboxylic acid.

[0113] The polycarbonate composition can have a light transparency of greater than 90% as determined using 3.2 mm thick samples using ASTM D 1003-00, Procedure B using CIE standard illuminant C, with unidirectional viewing. Accordingly, when the quenched composition has such a light transparency, it is herein referred to as an "optical grade" composition.

[0114] Set forth below are some embodiments of the process disclosed herein. [0115] Embodiment 1: A process of preparing a thermoplastic composition, comprising: feeding a thermoplastic resin and an impact modifier to an extruder, wherein the thermoplastic resin comprises a melt polycarbonate; adding a quencher composition to the melt polycarbonate; and mixing the quencher composition with the melt polycarbonate for a period of time of greater than or equal to 5 sec prior to the addition to the melt polycarbonate of any reactive additive, wherein the reactive additive has a reactive OH group or reactive ester group; directing a fluoro-resin, a flame retardant, or a combination comprising one or both of the foregoing to the extruder; and extruding the thermoplastic resin to form the thermoplastic composition.

[0116] Embodiment 2: The process of Embodiment 1, further comprising pelletizing the polycarbonate prior to feeding.

[0117] Embodiment 3: The process of any of Embodiments 1-2, further comprising melting the polycarbonate prior to adding the quencher composition.

[0118] Embodiment 4: A process of preparing a thermoplastic composition, comprising: melt polymerizing a carbonate compound and a dihydroxy compound in the presence of a catalyst composition to form the melt polycarbonate in a molten state, wherein the catalyst composition comprises one or both of an alkali catalyst and a quaternary catalyst; wherein the alkali catalyst comprises a source of one or both of alkali and alkaline earth ions; and wherein the quaternary catalyst comprises one or both of a quaternary ammonium compound and a quaternary phosphonium compound; and feeding an impact modifier and a thermoplastic resin comprising the melt polycarbonate in the molten state to an extruder; adding a quencher composition to the melt polycarbonate after the feeding; and mixing the quencher composition with the melt polycarbonate for a period of time of greater than or equal to 5 sec prior to the addition to the melt polycarbonate of any reactive additive, wherein the reactive additive has a reactive OH group or reactive ester group; directing a fluoro-resin, a flame retardant, or a combination comprising one or both of the foregoing to the extruder; and extruding the thermoplastic resin to form the thermoplastic composition.

[0119] Embodiment 5: The process of Embodiment 4, further comprising, after a final polymerization, adding a chain scission agent to the melt polycarbonate in the molten state to reduce a molecular weight of the melt polycarbonate to form a modified

polycarbonate having a desired molecular weight that is less than the molecular weight of the melt polycarbonate. [0120] Embodiment 6: The process of any of Embodiments 1-5, wherein the quencher composition comprises a polycarbonate powder.

[0121] Embodiment 7: The process of any of Embodiments 1-5, wherein the quencher composition is free of a carrier.

[0122] Embodiment 8: The process of any of Embodiments 1-7, wherein the quencher composition comprises 1 to 10 ppm of a sulfonic acid ester, based upon 100 parts of the polycarbonate; and/or 1 to 10 ppm phosphorous acid, based upon 100 parts of the polycarbonate.

[0123] Embodiment 9: The process of any of Embodiments 1-8, wherein the quencher composition comprises n-butyl tosylate.

[0124] Embodiment 10: The process of any of Embodiments 1-9, wherein the thermoplastic composition comprises 0.01 to 5 parts by weight of the fluoro-resin based on 100 parts by weight of the thermoplastic composition.

[0125] Embodiment 11: The process of any of Embodiments 1-10, wherein the thermoplastic composition comprises 0.1 to 39 parts by weight of a flame retardant based on 100 parts by weight of the thermoplastic composition.

[0126] Embodiment 12: The process of any of Embodiments 1-11, wherein the flame retardant comprises a phosphoric acid ester and wherein the phosphoric acid ester is present in an amount of 0.02 to 3 pbw of the based on 100 parts by weight of the thermoplastic composition.

[0127] Embodiment 13: The process of any of Embodiments 1-12, wherein thermoplastic resin further comprises a polyorganosilioxane, a polyalkylacrylate, a polyolefin, a polyamide, a polyphenylene ether, a polyoxymethylene, or a combination comprising one or more of the foregoing.

[0128] Embodiment 14: The process of any of Embodiments 1-13, further comprising: polymerizing the impact modifier prior to the feeding in the presence of a surfactant of the formula (141) and/or (142); wherein each R is independently hydrogen, an alkaline metal, an alkaline-earth metal, ammonium, or a Ci_₄ hydroxyalkyl ammonium and v is an integer of 1 to 200.

[0129] Embodiment 15: The process of any of Embodiments 1-14, wherein the thermoplastic resin further comprises polystyrene; polyisoprene; polychloroprene;

poly aery lonitrile; polyethylene; polypropylene; poly(ethyl acrylate); poly(methyl acrylate); poly(methyl methacrylate); poly(butyl acrylate); polybutadiene; a polymer derived from maleic anhydride, beta-unsaturated carboxylic acid, N-phenylmaleimide, N- methylmaleimide, N-cyclohexylmaleimide, glycidyl methacrylate, or a combination comprising one or more of the foregoing; copolymers comprising two or more of the foregoing, or a combination comprising one or more of the foregoing.

[0130] Embodiment 16: The process of any of Embodiments 1-15, wherein the fluoro-resin comprises a tetrafluoroethylene resin, a perfluoro alkoxy resin, an ethylene propylene fluoro resin, or a combination comprising one or more of the foregoing.

[0131] Embodiment 17: The process of any of Embodiments 1-16, wherein the flame retardant comprises a halogen-containing compound of the formula (200); wherein iii is an integer 0-10, each R I independently is a halogen, and each R H independently can have the formula (201) or (202); wherein iv is an integer 0 to 3.

[0132] Embodiment 18: The process of any of Embodiments 1-17, wherein the flame retardant comprises a phosphoric ester can have the formula (230); wherein the average vi is an integer of 1 to 10; each R^L independently is a phenyl group, a tolyl group, a xylyl group, an alkyl group, a cycloalkyl group, or an alkylaryl group; and each R^M independently is a divalent group of the formulae (231) - (234).

[0133] Embodiment 19: The process of any of Embodiments 1-18, further comprising melt kneading the thermoplastic resin prior to directing a fluoro-resin, wherein a melt viscosity of the thermoplastic resin as measured with the capillary rheometer at the time of the melt kneading at a shear rate 240 sec-1 is 3,000 to 12,000 poise.

[0134] Embodiment 20: The process of any of Embodiments 1-19, wherein the quencher composition is added at a pressure of greater than or equal to 2 bars.

[0135] Embodiment 21: The process of any of Embodiments 1-3 and 6-20, wherein the polycarbonate is melt polycarbonate, and further comprising forming the melt

polycarbonate by melt polymerizing a carbonate compound and dihydroxy compound in the presence of a catalyst composition, wherein the catalyst composition comprises an alpha catalyst and/or a beta catalyst

[0136] Embodiment 22: The process of Embodiment 21, further comprising, after a final polymerization, adding a chain scission agent to the polycarbonate to reduce a molecular weight of the polycarbonate to form a modified polycarbonate having a desired molecular weight that is less than the molecular weight of the polycarbonate. [0137] Embodiment 23: The process of any of Embodiments 1-22, wherein the polycarbonate has an endcapping ratio is greater than or equal to 85%, specifically, greater than or equal to 90%, more specifically, greater than or equal to 95%.

[0138] Embodiment 24: The process of any of Embodiments 1-23, wherein the polycarbonate has a Fries level of greater than 0 and less than 5,000 ppm by weight based on the total weight of the melt polycarbonate.

[0139] Embodiment 25: The process of Embodiment 24, wherein the Fries level is less than or equal to 500 ppm by weight.

[0140] As used herein, when referring to "reactive" or a "reactive group", e.g., having a reactive OH^" group or a reactive ester group, the reactivity is with respect to polycarbonate.

[0141] In general, the invention may alternately comprise, consist of, or consist essentially of, any appropriate components herein disclosed. The invention may additionally, or alternatively, be formulated so as to be devoid, or substantially free, of any components, materials, ingredients, adjuvants or species used in the prior art compositions or that are otherwise not necessary to the achievement of the function and/or objectives of the present invention.

[0142] All ranges disclosed herein are inclusive of the endpoints, and the endpoints are independently combinable with each other (e.g., ranges of "up to 25 wt%, or, more specifically, 5 to 20 wt%", is inclusive of the endpoints and all intermediate values of the ranges of "5 to 25 wt%," etc.). "Combination" is inclusive of blends, mixtures, alloys, reaction products, and the like. Furthermore, the terms "first," "second," and the like, herein do not denote any order, quantity, or importance, but rather are used to denote one element from another. The terms "a" and "an" and "the" herein do not denote a limitation of quantity, and are to be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. The suffix "(s)" as used herein is intended to include both the singular and the plural of the term that it modifies, thereby including one or more of that term (e.g., the film(s) includes one or more films). Reference throughout the specification to "one embodiment," "another embodiment," "an embodiment," and so forth, means that a particular element (e.g., feature, structure, and/or characteristic) described in connection with the embodiment is included in at least one embodiment described herein, and may or may not be present in other embodiments. In addition, it is to be understood that the described elements may be combined in any suitable manner in the various embodiments. Disclosure of a narrower range or more specific group in addition to a broader range is not a disclaimer of the broader range or larger group.

[0143] While particular embodiments have been described, alternatives,

modifications, variations, improvements, and substantial equivalents that are or may be presently unforeseen may arise to applicants or others skilled in the art. Accordingly, the appended claims as filed and as they may be amended are intended to embrace all such alternatives, modifications variations, improvements, and substantial equivalents.

[0144] I/we claim:

Claims

1. A process of preparing a thermoplastic composition, comprising:

feeding a thermoplastic resin and an impact modifier to an extruder, wherein the thermoplastic resin comprises a melt polycarbonate;

adding a quencher composition to the melt polycarbonate; and

mixing the quencher composition with the melt polycarbonate for a period of time of greater than or equal to 5 sec prior to the addition to the melt polycarbonate of any reactive additive, wherein the reactive additive has a reactive OH group or reactive ester group;

directing a fluoro-resin, a flame retardant, or a combination comprising one or both of the foregoing to the extruder; and

extruding the thermoplastic resin to form the thermoplastic composition.

2. The process of Claim 1, further comprising pelletizing the melt polycarbonate prior to feeding.

3. The process of Claim 1, further comprising melting the melt polycarbonate prior to adding the quencher composition.

4. The process of Claim 1, further comprising polymerizing the impact modifier prior to feeding in the presence of a surfactant of the formula (141) and/or (142):

wherein each R is independently hydrogen, an alkaline metal, an alkaline-earth metal, ammonium, or a Ci_₄ hydroxyalkyl ammonium and v is an integer of 1 to 200.

5. The process of Claim 1, wherein the fluoro-resin comprises a

tetrafluoroethylene resin, a perfluoro alkoxy resin, an ethylene propylene fluoro resin, or a combination comprising one or more of the foregoing.

6. The process of Claim 1, wherein the flame retardant comprises a halogen containing compound of the formula (200):

wherein iii is an integer 0-10, each R I independently is a halogen, and each R H independently can have the formula (201) or

wherein iv is an integer 0 to 3.

7. The process of Claim 1, wherein the flame retardant comprises a phosphoric ester can have the formula (230):

(230) wherein the average vi is an integer of 1 to 10; each R independently is a phenyl group, a tolyl group, a xylyl group, an alkyl group, a cycloalkyl group, or an alkylaryl group; and each

R independently is a divalent group of the formulae (231) - (234):

8. The process of Claim 1, further comprising melt kneading the thermoplastic resin prior to directing a fluoro-resin, wherein a melt viscosity of the thermoplastic resin as measured with the capillary rheometer at the time of the melt kneading at a shear rate 240 sec^"1 is 3,000 to 12,000 poise.

9. The process of Claim 1, wherein the quencher composition is added at a pressure of greater than or equal to 2 bars.

10. A process of preparing a thermoplastic composition, comprising:

melt polymerizing a carbonate compound and a dihydroxy compound in the presence of a catalyst composition to form the melt polycarbonate in a molten state, wherein the catalyst composition comprises one or both of an alkali catalyst and a quaternary catalyst; wherein the alkali catalyst comprises a source of one or both of alkali and alkaline earth ions; and wherein the quaternary catalyst comprises one or both of a quaternary ammonium compound and a quaternary phosphonium compound; and

feeding an impact modifier and a thermoplastic resin comprising the melt

polycarbonate in the molten state to an extruder;

adding a quencher composition to the melt polycarbonate after the feeding; and mixing the quencher composition with the melt polycarbonate for a period of time of greater than or equal to 5 sec prior to the addition to the melt polycarbonate of any reactive additive, wherein the reactive additive has a reactive OH group or reactive ester group;

directing a fluoro-resin, a flame retardant, or a combination comprising one or both of the foregoing to the extruder; and

extruding the thermoplastic resin to form the thermoplastic composition.

11. The process of Claim 10, further comprising, after a final polymerization, adding a chain scission agent to the melt polycarbonate in the molten state to reduce a molecular weight of the melt polycarbonate to form a modified polycarbonate having a desired molecular weight that is less than the molecular weight of the melt polycarbonate.

12. The process of any of Claims 1-11, wherein the quencher composition comprises a polycarbonate powder.

13. The process of any of Claims 1-11, wherein the quencher composition is free of a carrier.

14. The process of any of Claims 1-13, wherein the quencher composition comprises 1 to 10 ppm of a sulfonic acid ester, based upon 100 parts of the polycarbonate; and/or 1 to 10 ppm phosphorous acid, based upon 100 parts of the polycarbonate.

15. The process of any of Claims 1-14, wherein the quencher composition comprises n-butyl tosylate.

16. The process of any of Claims 1-15, wherein the thermoplastic composition comprises 0.01 to 5 parts by weight of the fluoro-resin based on 100 parts by weight of the thermoplastic composition.

17. The process of any of Claims 1-16, wherein the thermoplastic composition comprises 0.1 to 39 parts by weight of a flame retardant based on 100 parts by weight of the thermoplastic composition.

18. The process of any of Claims 1-17, wherein the flame retardant comprises a phosphoric acid ester and wherein the phosphoric acid ester is present in an amount of 0.02 to 3 parts by weight of the based on 100 parts by weight of the thermoplastic composition.

19. The process of any of Claims 1-18, wherein the thermoplastic resin further comprises a polyorganosilioxane, a polyalkylacrylate, a polyolefin, a polyamide, a polyphenylene ether, a polyoxymethylene, or a combination comprising one or more of the foregoing.

20. The process of any of Claims 1-19, wherein the thermoplastic resin further comprises polystyrene; polyisoprene; polychloroprene; poly aery lonitrile; polyethylene; polypropylene; poly(ethyl acrylate); poly(methyl acrylate); poly(methyl methacrylate);

poly(butyl acrylate); polybutadiene; a polymer derived from maleic anhydride, beta- unsaturated carboxylic acid, N-phenylmaleimide, N-methylmaleimide, N- cyclohexylmaleimide, glycidyl methacrylate, or a combination comprising one or more of the foregoing; copolymers comprising two or more of the foregoing, or a combination comprising one or more of the foregoing.