KR102368000B1 - Melt polymerized polycarbonate - Google Patents

Abstract

In one embodiment, a method of preparing a thermoplastic composition comprises: feeding a thermoplastic resin comprising molten polycarbonate and an impact modifier to an extruder; adding a quencher composition to the polycarbonate; and after mixing the quencher composition with the polycarbonate for at least 5 seconds, adding any reactive additive having reactive OH groups or reactive ester groups to the polycarbonate; conveying a fluoro-resin, a flame retardant, or a combination comprising one or both of the above to the extruder; It may include extruding the thermoplastic resin to form a thermoplastic composition.

Description

Melt polymerized polycarbonate {MELT POLYMERIZED POLYCARBONATE}

The present application relates to a melt polymerized polycarbonate composition and a method for making the same.

Disclosed herein are methods of making thermoplastic compositions and compositions made thereby.

In one embodiment, a method of making a thermoplastic composition may include the following steps: feeding a thermoplastic resin comprising melt polymerized polycarbonate and an impact modifier to an extruder; adding a quencher composition to the polymerized polycarbonate; and mixing the quencher composition with the polymerized polycarbonate for at least 5 seconds, then adding any reactive additive having reactive OH groups or reactive ester groups to the polycarbonate; transferring a fluoro-resin, a flame retardant, or a combination comprising one or both of the above to an extruder; Extruding the thermoplastic resin to form the thermoplastic composition.

Applicants have developed a method of making 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 may include an impact modifier. The thermoplastic composition comprises 100 parts by weight of a thermoplastic resin, 0 to 5 parts by weight based on 100 parts by weight of the thermoplastic resin, specifically 0.01 to 5 parts by weight of the fluoro-resin, 0 to 39 parts by weight based on 100 parts by weight of the thermoplastic resin, specifically 0.1 to 39 parts by weight of the flame retardant, 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.

Thermoplastic resins include vinyl polymers (e.g., derived from aromatic vinyl monomers (such as styrene, alpha-methylstyrene), acrylonitrile, etc.), polyorganosiloxanes, polyalkylacrylates, polyolefins, polyamides, polyphenylene ethers , polyoxymethylene, polycarbonate, or combinations comprising at least one of the foregoing. Thermoplastic resins include 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 (e.g., polybutadiene-polystyrene, polybutadiene-polyacrylonitrile and polyethylene-polypropylene), or combinations comprising one or more of the foregoing. . The thermoplastic resin is 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. may contain polymers.

The thermoplastic resin may include 10 to 100 parts by weight, specifically, 10 to 90 parts by weight of polycarbonate based on the total weight of the thermoplastic resin. The thermoplastic resin may include 10 to 90 parts by weight of an impact modifier based on the total weight of the thermoplastic resin.

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

wherein at least 60 percent of the total number of R ¹ groups contain aromatic moieties, the remainder being aliphatic, cycloaliphatic or aromatic. Each R ¹ may be a C _6-30 aromatic group, ie contains at least one aromatic moiety. R ¹ may be derived from an aromatic dihydroxy compound of the formula HO-R ¹ -OH, in particular of the formula (2) above; wherein each of A ¹ and A ² is a monocyclic divalent aromatic group and Y ¹ is a single bond or a linking group having one or more atoms separating A ¹ from A ² . One atom can separate A ¹ from A ² . Specifically, each R ¹ may be derived from a bisphenol of formula (3):

wherein R ^a and R ^b are each independently halogen, C _1-12 alkoxy or C _1-12 alkyl; p and q are each independently an integer from 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 occupied by hydrogen. Further, in formula (3), X ^a is a linking group linking two hydroxy-substituted aromatic groups, wherein the linking group and the hydroxy substituent of each C ₆ arylene group are relative to each other on the C ₆ arylene group Positioned as ortho, meta or para (specifically para). The linking group X ^a can be a single bond, -O-, -S-, -S(O)-, -S(O) ₂ -, -C(O)- or a C _1-18 organic group. The C _1-18 organic linking group may be cyclic or acyclic, aromatic or non _- aromatic and may further comprise heteroatoms such as halogen, oxygen, nitrogen, sulfur, silicon or phosphorus. The C _1-18 organic group may be positioned such that the C ₆ arylene group attached _{thereto is each linked to a different carbon or a common alkylidene carbon of the C 1-18 organic} linking group. Each of p and q may be 1, and R ^a and R ^b may each be a C _1-3 alkyl group positioned meta to the hydroxy group on the respective arylene group, specifically methyl.

X ^a is substituted or unsubstituted C _3-18 cycloalkylidene, C _1-25 alkylidene of the formula -C(R ^c )(R ^d )-, wherein R ^c and R ^d are each independently hydrogen, C _1-12 alkyl, C _1-12 cycloalkyl, C _7-12 arylalkyl, C _1-12 heteroalkyl or cyclic C _7-12 heteroarylalkyl), or a group of formula —C(=R ^e )— (wherein R ^e is a divalent C _1-12 hydrocarbon group). Groups of this type are methylene, cyclohexylmethylene, ethylidene, neopentylidene and isopropylidene, as well as 2-[2.2.1]-bicycloheptylidene, cyclohexylidene, cyclopentylidene, cyclodode silidene and adamantylidene.

X ^a is C _1-18 alkylene, C _3-18 cycloalkylene, fused C _6-18 cycloalkylene, or a group of formula —B ¹ -GB ² —, wherein B ¹ and B ² are the same or or different C _1-6 alkylene, and G is C _3-12 cycloalkylidene or C _6-16 arylene). For example, X ^a can be a substituted C _3-18 cycloalkylidene of formula (4):

wherein R ^r , R ^p , R ^q and R ^t are each independently hydrogen, halogen, oxygen or a C _1-12 hydrocarbon group; Q is a direct bond, carbon, or divalent oxygen, sulfur, or -N(Z)-, wherein Z is hydrogen, halogen, hydroxy, C _1-12 alkyl, C _1-12 alkoxy or C _1-12 acyl is); r is 0-2, t is 1 or 2, q is 0 or 1, and k is 0-3, provided that at least two of R ^r , R ^p , R ^q and R ^t are taken together and are fused cyclo form an aliphatic, aromatic or heteroaromatic ring. It will be understood that when the fused ring is aromatic, the ring as shown in formula (4) will have an unsaturated carbon-carbon linkage where the rings are fused. When k is 1 and i is 0, the ring as shown in formula (4) contains 4 carbon atoms, and when k is 2, the ring as shown in formula (4) contains 5 carbons atom, and when k is 3, the ring contains 6 carbon atoms. Two adjacent groups (eg, R ^q and R ^t taken together) can form an aromatic group, R ^q and R ^t can be taken together to form one aromatic group, and R ^r and R ^p can be taken together A second aromatic group may be formed. When R ^q and R ^t are taken together to form an aromatic group, R ^p may be a double-bonded oxygen atom, ie, a ketone.

Bisphenols wherein X ^a is a cycloalkylidene of formula (4) can be used for the preparation of polycarbonates containing phthalimidine carbonate units of formula (1a):

In the above formula, R ^a , R ^b , p and q are the same as in Formula (3), R ³ is each independently C _1-6 alkyl, j is 0 to 4, R ₄ is hydrogen, C _1-6 alkyl, or substituted or unsubstituted phenyl, for example phenyl substituted with up to 5 C _1-6 alkyl. For example, a phthalimidine carbonate unit has the above formula (1b); wherein R ⁵ is hydrogen, phenyl optionally substituted with up to 5 C _1-6 alkyl or C _1-4 alkyl. In formula (1b), R ⁵ may be hydrogen, methyl or phenyl, specifically phenyl. The carbonate unit (1b) in which R ⁵ is phenyl is 2-phenyl-3,3'-bis(4-hydroxy phenyl)phthalimidine (also 3,3-bis(4-hydroxyphenyl)-2-phenyl is soindolin-1-one, or N-phenyl phenolphthalein bisphenol (known as “PPPPP”)).

Another bisphenol carbonate repeat unit of this type is the isatin carbonate unit of the formulas (1c) and (1d):

wherein R ^a and R ^b are each independently C _1-12 alkyl, p and q are each independently 0 to 4, R ⁱ is C _1-12 alkyl, 1 to 5 C _1-10 alkyl optionally substituted phenyl, or benzyl optionally substituted with 1 to 5 C _1-10 alkyl. Each of R ^a and R ^b can be methyl, p and q can each independently be 0 or 1, and R ⁱ is C _1-4 alkyl or phenyl.

Another example of a bisphenol carbonate unit derived from bisphenol (3) wherein X ^a is substituted or unsubstituted C _3-18 cycloalkylidene (4) is a cyclohexylidene-linked, alkyl-substituted Contains bisphenols:

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 0-4, and t is 0-10. At least one of each of R ^a and R ^b may be meta to the cyclohexylidene linking group. each R ^a and R ^b can independently be C _1-4 alkyl, R ^g is C _1-4 alkyl, p and q are each 0 or 1, and t is 0-5. R ^a , R ^b and R ^g may each be methyl, p and q may each be 0 or 1, and t may be 0 to 3, specifically 0.

Examples of other bisphenol carbonate units derived from bisphenol (3) wherein X ^a is substituted or unsubstituted C _3-18 cycloalkylidene include an adamantyl unit of the following formula (1f) and a fluorenyl of the following formula (1g) Units include:

wherein R ^a and R ^b are each independently C _1-12 alkyl, and p and q are each independently 1 to 4. At least one of each of R ^a and R ^b may be meta to the cycloalkylidene linking group. R ^a and R ^b may each independently be C _1-3 alkyl, and p and q may each be 0 or 1; Specifically, R ^a , R ^b may each be methyl, p and q are each 0 or 1, and when p and q are 1, the methyl group may be meta to the cycloalkylidene linking group. The carbonates containing units (1a) to (1g) are useful for preparing polycarbonates with high glass transition temperature (Tg) and high heat deflection temperature.

Other useful dihydroxy compounds of the formula HO-R ¹ -OH include aromatic dihydroxy compounds of the formula (6):

wherein each R ^h is independently a halogen atom, a C _1-10 hydrocarbyl group such as C _1-10 alkyl, halogen-substituted C _1-10 alkyl, C _6-10 aryl, or halogen-substituted C _6-10 aryl, and n is 0 to 4. Halogen is typically bromine.

Some illustrative examples of specific dihydroxy compounds include: 4,4'-dihydroxybiphenyl, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, bis(4-hydroxy Roxyphenyl)methane, bis(4-hydroxyphenyl)diphenylmethane, bis(4-hydroxyphenyl)-1-naphthylmethane, 1,2-bis(4-hydroxyphenyl)ethane, 1,1- Bis(4-hydroxyphenyl)-1-phenylethane, 2-(4-hydroxyphenyl)-2-(3-hydroxyphenyl)propane, bis(4-hydroxyphenyl)phenylmethane, 2,2- Bis(4-hydroxy-3-bromophenyl)propane, 1,1-bis(hydroxyphenyl)cyclopentane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4 -Hydroxyphenyl)isobutene, 1,1-bis(4-hydroxyphenyl)cyclododecane, trans-2,3-bis(4-hydroxyphenyl)-2-butene, 2,2-bis(4 -Hydroxyphenyl)adamantane, alpha, alpha'-bis(4-hydroxyphenyl)toluene, bis(4-hydroxyphenyl)acetonitrile, 2,2-bis(3-methyl-4-hydroxyphenyl ) propane, 2,2-bis (3-ethyl-4-hydroxyphenyl) propane, 2,2-bis (3-n-propyl-4-hydroxyphenyl) propane, 2,2-bis (3-iso propyl-4-hydroxyphenyl)propane, 2,2-bis(3-sec-butyl-4-hydroxyphenyl)propane, 2,2-bis(3-t-butyl-4-hydroxyphenyl)propane, 2,2-bis(3-cyclohexyl-4-hydroxyphenyl)propane, 2,2-bis(3-allyl-4-hydroxyphenyl)propane, 2,2-bis(3-methoxy-4- Hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) hexafluoropropane, 1,1-dichloro-2,2-bis (4-hydroxyphenyl) ethylene, 1,1-dibromo -2,2-bis(4-hydroxyphenyl)ethylene, 1,1-dichloro-2,2-bis(5-phenoxy-4-hydroxyphenyl)ethylene, 4,4'-dihydroxybenzophenone , 3,3-bis(4-hydroxyphenyl)-2-butanone, 1,6-bis(4-hydroxyphenyl)-1,6-hexanedione, ethylene glycol bis(4-hydroxyphenyl)ether , bis(4-hydroxyphenyl)ether, bis(4-hydroxyphenyl)sulfide, bis(4-hydroxyphenyl)sulfoxide, bis(4-hydroxyphenyl)sulfone, 9,9-bis(4 -hydroxyphenyl) fluorine, 2 ,7-dihydroxypyrene, 6,6'-dihydroxy-3,3,3',3'-tetramethylspiro(bis)indane ("spirobindane bisphenol"), 3,3-bis(4 -Hydroxyphenyl) phthalimide, 2,6-dihydroxydibenzo-p-dioxine, 2,6-dihydroxythianthrene, 2,7-dihydroxyphenoxatin, 2,7-dihydr hydroxy-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 and 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, etc., or the above dihydro A combination comprising at least one of the hydroxy compounds.

Specific examples of the bisphenol compound of formula (3) include 1,1-bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl) ) propane (hereinafter “bisphenol A” or “BPA”), 2,2-bis(4-hydroxyphenyl) butane, 2,2-bis(4-hydroxyphenyl) octane, 1,1-bis(4- Hydroxyphenyl) propane, 1,1-bis(4-hydroxyphenyl) n-butane, 2,2-bis(4-hydroxy-2-methylphenyl) propane, 1,1-bis(4-hydroxy- t-Butylphenyl) propane, 3,3-bis(4-hydroxyphenyl) phthalimidine, 2-phenyl-3,3-bis(4-hydroxyphenyl) phthalimidine (PPPBP) and 1,1- bis(4-hydroxy-3-methylphenyl)cyclohexane (DMBPC). Combinations comprising at least one of the above dihydroxy compounds may also be used. The polycarbonate may be a linear homopolymer derived from bisphenol A, wherein each of A ¹ and A ² in formula (3) is p-phenylene and Y ¹ is isopropylidene.

The polycarbonate herein is prepared via melt polymerization of a bisphenol and a carbonate precursor. Exemplary carbonate precursors include carbonyl halides such as carbonyl bromide or carbonyl chloride (phosgene), bishaloformates of dihydroxy compounds (e.g., bisphenol A, hydroquinone ethylene glycol, bischloroform of neopentyl glycol) mates, etc.), and diaryl carbonates. Combinations comprising at least one of the above types of carbonate precursors may also be used. Diaryl carbonate esters include diphenyl carbonate, or activated diphenyl carbonate with 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 at least one of the foregoing. may be a combination of

In a melt polymerization process, polycarbonate can be prepared by co-reacting a dihydroxy reactant and a carbonate precursor in the molten state in the presence of a transesterification catalyst. The reaction is carried out with typical polymerization equipment such as a continuous stirred reactor (CSTR), a plug flow reactor, a wire wetting fall polymerizer, a free fall polymerizer, a horizontal a polymerizer, a wiped film polymerizer, a BANBURY mixer, a single or twin screw extruder, or a combination comprising one or more of the foregoing. The volatile monohydric phenol is removed by distillation from the molten reactant and the polymer is isolated as a molten residue. Melt polymerization can be carried out as a batch process or as a continuous process. In either case, the melt polymerization conditions employed include at least two distinct reaction steps. For example, polymerization may include a first reaction step in which the starting dihydroxy aromatic compound and diaryl carbonate are converted to an oligomeric polycarbonate (also referred to as an oligomerization step), and the oligomeric polycarbonate formed in the first reaction step. may comprise a second reaction step (also referred to as polymerization step) in which polycarbonate is converted to high molecular weight polycarbonate. The oligomerization step may include one or more, specifically two or more, more specifically two to four oligomerization units (eg, two to four CSTRs). The polymerization step may include one or more, specifically two or more, more specifically two polymerization units (eg, two horizontal or wire wet drop polymerization reactors). An oligomerization unit is defined herein as a reaction unit that produces a polycarbonate oligomer having a number average molecular weight of 8,000 Daltons (Da) or less, and the polymerization unit is a reaction that produces a polycarbonate having a number average molecular weight greater than 8,000 Da herein. defined as a unit. Although 8,000 Da or less is used herein to define the molecular weight achieved in the first step, it is readily understood by those skilled in the art that this molecular weight is used to define an oligomerization step in which the oligomer molecular weight may be greater than 8,000 Da. pay attention to "Staged" polymerization reaction conditions may be used in a continuous polymerization system, wherein starting monomers are oligomerized in a first reaction vessel, wherein the oligomeric polycarbonate formed is continuously transferred to one or more downstream reactors, wherein the The oligomeric polycarbonate is converted to a high molecular weight polycarbonate. Typically, in the oligomerization step, the resulting oligomeric polycarbonate has a number average molecular weight of 1,000 to 7,500 Da. In one or more subsequent polymerization steps, the number average molecular weight (Mn) of the polycarbonate can be increased, for example, from 8,000 to 25,000 Da (using polycarbonate standards), specifically from 13,000 to 18,000 Da.

Typically, no solvent is used in the process and the reactants dihydroxy aromatic compound and diaryl carbonate are in the molten state. The reaction temperature may be 100 to 350 degrees Celsius (°C), specifically 180 to 310°C. The pressure may be atmospheric pressure, super-atmospheric pressure, or a pressure in the range of atmospheric to 15 torr for the initial stage of the reaction, and reduced pressure for later stages, for example from 0.2 to 15 torr. Similarly, polymerization may take place in a series of polymerization vessels that may have increasing temperature and vacuum. For example, the oligomerization step may occur at a temperature of 100 to 260°C, specifically 140 to 240°C, and the polymerization step may occur at a temperature of 240 to 350°C, specifically 280 to 300°C, or 240 to 270°C. wherein the temperature in the polymerization step is greater than the temperature in the oligomerization step. 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 when Mw does not increase by more than 10 wt%, preferably not by more than 5 wt% thereafter.

After the final polymerization vessel (also referred to as the final polymerization unit), the polymer may be introduced into the reactor, extruded, filtered in a melt filter, or a combination comprising one or more of the foregoing. Note that the melt filter may be positioned before or after the extruder. For example, a melt polymerization process for preparing a polycarbonate composition may include the following steps: melt polymerizing a dihydroxy reactant and a carbonate compound to produce a melt reaction product; quenching the molten reaction product; filtering the molten reaction product in a melt filter upstream of any extruder; optionally introducing an additive to form a mixture; and extruding the mixture to form a polycarbonate composition. Similarly, a melt polymerization process for preparing a polycarbonate composition may include the following steps: melt polymerizing a dihydroxy reactant and a carbonate compound to produce a melt reaction product; introducing a quencher composition and optionally additives to form a mixture; and extruding the mixture to form a polycarbonate composition.

The polycarbonate may have one or more of the end groups of formulas (100) to (107):

wherein R ^G is a C _1-10 linear or branched alkyl group, for example C ₈ H ₁₇ , C ₁₂ H ₂₅ and C ₁₈ H ₃₇ . These end groups can be derived from polymerization monomers or from end capping agents added during or after polymerization (eg, pt-butyl phenol, dicumyl phenol and p-cumyl phenol). The percent end-capping ratio (%EC) is determined by the equation:

where ppm OH is the amount of hydroxyl end groups in ppm, and Mn is the number average molecular weight based on a polycarbonate standard (Daltons). ppm OH was determined by Fourier Transform Infrared Spectroscopy (FTIR), for example on a Perkin Elmer FTIR Spectrum One Device, 0.5 in 25 milliliters (mL) of anhydrous chloroform. A sample of polycarbonate in grams (g) is dissolved and the absorbance at a wavelength of 3,584 centimeters (cm ^{- 1} ) is measured using a univariate calibration, and the absorbance is measured as the absorbance at 2,779 cm ^{- 1} It can be determined by normalizing the absorbance by dividing.

The polycarbonate may have a weight average molecular weight of 23,000 g/mol or less, specifically 5,000 to 23,000 g/mol, as determined by gel permeation chromatography (GPC) based on a polystyrene standard. The polycarbonate may 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.

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

The polycarbonate may have a melt flow rate of 4 to 40 g/10 min, such as 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. there is. The polycarbonate may have a melt flow rate 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 are measured at 300 degrees Celsius (° C.)/1.2 kilograms (kg) according to ASTM D1238-04 or ISO 1133.

Catalysts used to prepare the melt transesterification polymerization of polycarbonate may include alpha and/or beta catalysts. Beta catalysts are typically volatile and decompose at elevated temperatures. Thus, the beta catalyst can be used in the initial low temperature polymerization step. Alpha catalysts are typically more thermally stable and less volatile than beta catalysts.

Alpha catalysts (also referred to as alkali catalysts) may include a source of alkali and/or alkaline earth ions. 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 metal and alkaline earth metal ions include the corresponding salts of carboxylic acids (such as sodium acetate) and derivatives of ethylene diamine tetraacetic acid (EDTA) (such as EDTA tetrasodium salt, and EDTA magnesium disodium salt). . The alpha catalyst is an alkali metal or alkaline earth metal salt of a carbonate, such as Cs ₂ CO ₃ , NaHCO ₃ and Na ₂ CO ₃ , etc., non-volatile inorganic acids such as NaH ₂ PO ₃ , NaH ₂ PO ₄ , Na ₂ HPO ₃ , KH ₂ PO ₄ , CsH ₂ PO ₄ , Cs ₂ HPO ₄ , or the like, or a mixed salt of phosphoric acid, such as NaKHPO ₄ , CsNaHPO ₄ , CsKHPO ₄ , and the like.

Possible beta catalysts (also referred to as quaternary catalysts) may include quaternary ammonium compounds, quaternary phosphonium compounds, or combinations comprising at least one of the foregoing. The quaternary ammonium compound may be a compound of the formula (R ⁴ ) ₄ N ⁺ X ^- , wherein each R ⁴ is the same or different, C _1-20 alkyl, C _4-20 cycloalkyl or C _4-20 aryl; X ⁻ is an organic or inorganic anion, for example 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 may be a compound of the formula (R ⁵ ) ₄ P ⁺ X ^- , wherein each R ⁵ is the same or different, C _1-20 alkyl, C _4-20 cycloalkyl or C ₄ - ₂₀ aryl; X ⁻ is an organic or inorganic anion, for example hydroxide, phenoxide, halide, carboxylate, such as acetate or formate, sulfonate, sulfate, formate, carbonate or bicarbonate. It is understood that when X ⁻ is a polyvalent anion, such as carbonate or sulfate, the positive and negative charges in the quaternary ammonium and phosphonium structures are properly balanced. For example, when R ²⁰ to R ²³ are each methyl and X ^- is carbonate, it is understood that X ^- represents 2(CO ₃ ^-2 ). Examples of organic quaternary phosphonium compounds include tetramethyl phosphonium hydroxide, tetramethyl phosphonium acetate, tetramethyl phosphonium formate, tetrabutyl phosphonium hydroxide, tetrabutyl phosphonium acetate (TBPA), tetraphenyl phos phonium acetate (TPPA), tetraphenyl phosphonium phenoxide, and combinations comprising at least one of the foregoing.

The amount of alpha and beta catalyst used may be based on the total number of moles of dihydroxy compound used in the polymerization reaction. When referring to the ratio of the beta catalyst, for example the ratio of the phosphonium salt to all dihydroxy compounds used in the polymerization reaction, moles of catalyst per mole of dihydroxy compound (which is the number of moles of catalyst for each means dividing the sum of moles of individual dihydroxy compounds). The transesterification catalyst is 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 per mole of aromatic dihydroxy compound used. It may be used in an amount sufficient to provide 10 ^-6 moles of catalyst. The alpha catalyst may 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 dihydroxy compound used. there is. The amount of beta catalyst (eg organic ammonium or phosphonium salt) is 1 x 10 ^-2 to 1 x 10 ^-5 , specifically 1 x 10 ^-3 to 1 x per total moles of dihydroxy compound present in the reaction mixture. 10 ^-4 moles. Quenching the transesterification catalyst and any reactive catalyst residues with an acidic compound after polymerization is complete may also be useful in some melt polymerization processes. Removal of catalyst residues and/or quenching agents and other volatile residues from the melt polymerization reactants after polymerization may also be useful in some melt polymerization processes.

The polymerization process may comprise parallel polymerization sections, wherein the parallel polymerization processes the polymerized polycarbonate streams thereafter which may or may not experience the same polymerization conditions (i.e., they may obtain different molecular weights, or different additives may may be added thereto, etc.) refers to splitting into two or more streams. For example, polycarbonate may be prepared in a first portion of a polymerization process; The stream comprising polymerized polycarbonate may be split into two or more streams and sent to two or more parallel operating lines. For example, the process may include polymerizing polycarbonate in a series of oligomerization units; The stream exiting the oligomerization stage can be split into two streams A and B, where stream A is sent to polymerization unit A and stream B is sent to polymerization unit B. Similarly, the process may include polymerizing polycarbonate in a series of oligomerization units followed by polymerizing in a series of polymerization units; The stream exiting the polymerization stage can be split into two streams A and B, where stream A is sent to extruder A and stream B is sent to extruder B. Similarly, the process may comprise polymerizing polycarbonate in a series of oligomerization units followed by polymerizing in two series of polymerization units; The stream exiting the first polymerization unit can be split into two streams A and B, wherein stream A is sent to a second polymerization unit A and stream B is sent to a second polymerization unit B. In any of the aforementioned scenarios, a quencher composition may be added to one or both of streams A and B, wherein the quencher composition may be the same or different. A person skilled in the art can readily envision other implementations involving more than two parallel streams and implementations in which the streams are split at different locations.

The quencher composition may be added at one or more locations in the melt preparation of the polycarbonate of the present invention to reduce the activity of the catalyst. The quencher composition includes a quenching agent (also referred to herein as a quencher). For example, the quenching agent is a sulfonic acid ester, such as formula R ₁ SO ₃ R ₂ , wherein R ₁ is hydrogen, C ₁ -C ₁₂ alkyl, C ₆ -C ₁₈ aryl or C ₇ -C ₁₉ alkylaryl, R ₂ is C ₁ -C ₁₂ alkyl, C ₆ -C ₁₈ aryl or C ₇ -C ₁₉ alkylaryl) alkyl sulfonic acid esters. Examples of alkyl sulfonic acid 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 may include an alkyl tosylate, such as n-butyl tosylate. The sulfonic acid ester may 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.

The quenching agent is a boric acid ester (eg, B(OCH ₃ ) ₃ , B(OCH ₂ CH ₃ ) ₃ and B(OC ₆ H ₆ ) ₃ ), zinc borate, boron phosphate, aluminum stearate, aluminum silicate, zirconium. carbonate, zirconium C ₁ -C ₁₂ alkoxide, zirconium hydroxycarboxylate, gallium phosphide, gallium antimonide, germanium oxide, C ₁ -C ₃₂ organogermanium compound, C ₄ -C ₃₂ tetraorganotin tin compound, C ₆ -C ₃₂ hexaorganotin compounds (eg, [(C ₆ H ₆ O)Sn(CH ₂ CH ₂ CH ₂ CH ₃ ) ₂ ] ₂ O), Sb ₂ O ₃ , antimony oxide, C ₁ -C ₃₂ alkylantimony, bismuth oxide, C ₁ -C ₁₂ alkylbismuth, zinc acetate, zinc stearate, C ₁ -C ₃₂ alkoxytitanium, and titanium oxide, phosphoric acid, phosphorous acid, hypophosphoric 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 acid, oxalic acid, benzenesulfinic acid, C ₁ -C ₁₂ dialkyl sulfates (eg, dimethyl sulfate and dibutyl sulfate), formula (R ^a SO ₃ ^- )(PR ^b ₄ ) ⁺ where R ^a is hydrogen, C ₁ -C ₁₂ alkyl, C ₆ -C ₁₈ aryl or C ₇ -C ₁₉ alkylaryl, each R ^b is independently hydrogen, C ₁ -C ₁₂ alkyl or C ₆ -C ₁₈ aryl ) sulfonic acid phosphonium salt, formula A ¹ -(Y ¹ -SO ₃ X ¹ ) _m , wherein A ¹ is a C ₁ -C ₄₀ hydrocarbon group having a valency of m, Y ¹ is a single bond or an oxygen atom; , X ¹ is a secondary or tertiary alkyl group of the formula —CR ¹⁵ R ¹⁶ R ¹⁷ , a monovalent metal cation, an ammonium cation (eg, NR ^b ₃ ⁺ , wherein each R ^b is independently hydrogen, is C ₁ -C ₁₂ alkyl or C ₆ -C ₁₈ aryl) or phosphonium (eg, PR ^b ₄ ⁺ , wherein each R ^b is independently hydrogen, C ₁ -C ₁₂ alkyl or C ₆ - C ₁₈ aryl)), R ¹⁵ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R ¹⁶ is a hydrogen atom, a phenyl group or an alkyl group, which has 1 to 5 carbon atoms, and , R ¹⁷ is the same as or different from R ¹⁵ and has the same definition as R ¹⁵ , with the proviso that two of R ¹⁵ , R ¹⁶ and R ¹⁷ cannot be a hydrogen atom, and m is an integer from 1 to 4, provided that Y When ¹ is a single bond, a sulfonic acid derivative of the formula ⁺ X ² -A ² -Y ¹ -SO ₃ ^- , where all of the amounts of X ¹ in m cannot be monovalent metal cations), where A ² is a divalent hydrocarbon a group, ⁺ X ² is a secondary, tertiary or quaternary ammonium cation or a secondary (eg tertiary or quaternary) phosphonium cation, and Y ¹ is a single bond or an oxygen atom; A ³ -( ⁺ X ³ ) _n ㆍ(RY ¹ -SO ₃ ^- ) _n , where A ³ is a C ₁ -C ₄₀ hydrocarbon group having a valency of n, and ⁺ X ³ is secondary, tertiary or 4 a primary ammonium cation (eg, NR ^b ₃ ⁺ , wherein each R ^b is independently hydrogen, C ₁ -C ₁₂ alkyl or C ₆ -C ₁₈ aryl), or secondary, tertiary or quaternary a phosphonium cation (eg, PR ^b ₄ ⁺ , wherein each R ^b is independently hydrogen, C ₁ -C ₁₂ alkyl, or C ₆ -C ₁₈ aryl), and R is monovalent C ₁ -C ₄₀ is a hydrocarbon group, n is an integer from 2 to 4, and Y ¹ is a single bond or an oxygen atom, formula A ⁵ -Ad ¹ -A ⁴ -(Ad ² -A ⁵ ) ₁ wherein A ⁵ is a monovalent or divalent C ₁ -C ₄₀ hydrocarbon group, A ⁴ is a divalent C ₁ -C ₄₀ hydrocarbon group, each Ad ¹ and Ad ² are independently an acid anhydride group selected from -SO ₂ -O-SO ₂ -, -SO ₂ -O-CO- and -CO-O-SO ₂ -, l is 0 or 1, provided that when l is O, -(Ad ² -A ⁵ ) ₁ is a hydrogen atom or a bond between A ⁴ and A ⁵ , where A ⁵ is a divalent hydrocarbon group or a single bond), formula R _a R _b NA —SO ₃ R _c , wherein R _a and R _b are each independently hydrogen, C ₁ -C ₁₂ alkyl, C ₆ -C ₂₂ aryl, C ₇ -C ₁₉ alkylaryl, or R _a and R _b are alone or in combination with N an aromatic or non-aromatic heterocyclic compound (e.g., pyrrolyl, pyridinyl, pyrimidyl, pyrazinyl, carbazolyl, quinolinyl, imidazoyl, piperazinyl, oxazolyl, thiazolyl, pyrazolyl, pyrrolyl, indolyl, purinyl, pyrrolidinyl, etc.), R _c is hydrogen, A is C ₁ -C ₁₂ alkyl, C ₆ -C ₁₈ aryl or aminosulfonic acid esters (eg, N-(2-hydroxyethyl) piperazine-N′-3-propanesulfonic acid, 1,4,-piperazinebis (ethanesulfonic acid) having a C ₁₇ -C ₁₉ alkylaryl ) and compounds such as 5-dimethylamino-1-naphthalenesulfonic acid), formula R _a R _b R _c N ⁺ —A—SO ₃ ^— , wherein R _a , R _b are each independently hydrogen, C ₁ -C ₁₂ alkyl, C ₁ -C ₁₂ aryl, C ₇ -C ₁₉ alkylaryl, or R _a and R _b , alone or in combination, together with N an aromatic or non-aromatic heterocyclic compound (eg, pyrrolyl , pyridinyl, pyrimidyl, pyrazinyl, carbazolyl, quinolinyl, imidazoyl, piperazinyl, oxazolyl, thiazolyl, pyrazolyl, pyrrolyl, indolyl, purinyl, pyrrolidinyl, etc.) _{ammonium sulfonic acid esters} , _{sulfonated polystyrene} , methyl _acrylate- sulfonated styrene copolymers, and combinations comprising at least one of the foregoing.

The quencher composition may be added in solid or liquid form. When in liquid form, the quencher composition may be added, for example, via an addition system. The addition system comprises a first drum; buffer drum; dosing pumps; filter; injectors, or combinations comprising one or more of the foregoing, wherein one or both of the first drum and the buffer drum may include a stirrer and/or a heating system. For example, the quencher and liquid carrier may be added to the first drum and then added to the buffer drum. From the buffer drum, the liquid quencher composition may be injected into the polymerization system via an injector located in one or more of the polymerization unit, reactor, transfer line, mixer and extruder. The pumping of the quencher composition to the dosing pump may be controlled by a main dispensing loop, wherein the addition of the quencher composition may be continuously or intermittently monitored using a flow meter. The pumping may further comprise a controller for automated monitoring of the flow meter and adjustment of the amount of quencher composition to the polymerization unit. The liquid quencher composition may be added to the polymerized polycarbonate at a pressure of 1 bar or more, specifically 2 bar or more, specifically 3 bar or more, more specifically 3 to 100 bar. Similarly, the liquid quencher composition can be added by spraying the liquid onto a solid polycarbonate substrate. The liquid quencher composition may be filtered prior to being added to the polymerization system. After the quencher composition is mixed with the polymerized polycarbonate for at least 5 seconds, any additive having a reactive OH group or a reactive ester group may be added to the polymerized polycarbonate.

The thermoplastic resin may include a polysiloxane, such as a polysiloxane-polycarbonate copolymer (also referred to as poly(siloxane-carbonate)). Polydiorganosiloxanes (also referred to herein as “polysiloxanes”) may comprise repeating diorganosiloxane units as in formula (10):

wherein each R is independently a C _{1-13 monovalent} organic group. For example, R is C ₁ -C ₁₃ alkyl, C ₁ -C ₁₃ alkoxy, C ₂ -C ₁₃ alkenyl, C ₂ -C ₁₃ alkenyloxy, C ₃ -C ₆ cycloalkyl, C ₃ -C ₆ Cycloalkoxy, C ₆ -C ₁₄ aryl, C ₆ -C ₁₀ aryloxy, C ₇ -C ₁₃ arylalkyl, C ₇ -C ₁₃ aralkoxy, C ₇ -C ₁₃ alkylaryl or C ₇ -C ₁₃ alkylaryloxy can be The group may be fully or partially halogenated with fluorine, chlorine, bromine or iodine, or combinations thereof. When a transparent polysiloxane-polycarbonate is desired, R may be unsubstituted by halogen. Combinations of the above R groups can be used in the same copolymer.

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 other considerations. E may have an average value of from 2 to 1,000, specifically from 2 to 500, from 2 to 200, or from 2 to 125, from 5 to 80, or from 10 to 70. E may have an average value of from 10 to 80, or from 10 to 40. E may have an average value of 40 to 80, or 40 to 70. When E is a lower value, for example less than 40, it may be desirable to use a relatively larger amount of polycarbonate-polysiloxane copolymer. Conversely, when E is a higher value, for example greater than 40, a relatively lower amount of polycarbonate-polysiloxane copolymer may be used.

Combinations of first and second (or more) polysiloxanes may be used, for example the polysiloxane may 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.

The polydiorganosiloxane block may have the formula (11):

wherein E is as defined above; each R can be the same or different and is as defined above; Ar, which may be the same or different, is substituted or unsubstituted C ₆ -C ₃₀ arylene, wherein the bond is directly connected to the aromatic moiety. The Ar group in formula (11) may be derived from a C ₆ -C ₃₀ dihydroxyarylene compound, for example, a dihydroxyarylene compound of formula (3) or (6) above. The dihydroxyarylene compound is 1,1-bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) propane, 2 ,2-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)octane, 1,1-bis(4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyl) hydroxyphenyl) n-butane, 2,2-bis(4-hydroxy-1-methylphenyl) propane, 1,1-bis(4-hydroxyphenyl) cyclohexane, bis(4-hydroxyphenyl sulfide) and 1,1-bis(4-hydroxy-t-butylphenyl)propane. Combinations comprising at least one of the above dihydroxy compounds may also be used.

The polydiorganosiloxane block may have the formula (13):

wherein R and E are as described above, each R ⁵ is independently a divalent C ₁ -C ₃₀ organic group, and the polymerized polysiloxane unit is the reaction residue of its corresponding dihydroxy compound. The polydiorganosiloxane block may have the formula (14) above; wherein R and E are as defined above. In Formula (14), R ⁶ is a divalent C ₂ -C ₈ aliphatic. Each M in formula (14) can be the same or different, halogen, cyano, nitro, C ₁ -C ₈ alkylthio, C ₁ -C ₈ alkyl, C ₁ -C ₈ alkoxy, C ₂ -C ₈ alkenyl, C ₂ -C ₈ alkenyloxy, C ₃ -C ₈ cycloalkyl, C ₃ -C ₈ cycloalkoxy, C ₆ -C ₁₀ aryl, C ₆ -C ₁₀ aryloxy, C ₇ -C ₁₂ ar alkyl, C ₇ -C ₁₂ aralkoxy, C ₇ -C ₁₂ alkylaryl or C ₇ -C ₁₂ alkylaryloxy, wherein each n is independently 0, 1, 2, 3 or 4.

M may be bromo or chloro, alkyl such as methyl, ethyl or propyl, alkoxy such as methoxy, ethoxy or propoxy, or aryl such as phenyl, chlorophenyl or tolyl; R ⁶ may be dimethylene, trimethylene or tetramethylene; R can be C _1-8 alkyl, haloalkyl, such as trifluoropropyl, cyanoalkyl, or aryl, such as phenyl, chlorophenyl or tolyl. R may 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 1 and R ⁶ can be a divalent C ₁ -C ₃ aliphatic group. Specific polydiorganosiloxane blocks have the formula: or a combination comprising at least one of:

wherein E has an average value of from 2 to 200, from 2 to 125, from 5 to 125, from 5 to 100, from 5 to 50, from 20 to 80, or from 5 to 20.

The blocks of formula (14) can be derived from the corresponding dihydroxy polydiorganosiloxanes, which in turn are aliphatic unsaturated monohydric phenols 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, and siloxane It can be prepared by carrying out a platinum-catalyzed addition between the hydrides. The polysiloxane-polycarbonate copolymer can then be prepared, for example, by the synthetic procedure of EP 0 524 731 A1 (Hoover), page 5, Preparation 2, for example.

The transparent polysiloxane-polycarbonate copolymer comprises a carbonate unit (1) derived from bisphenol A, and a siloxane repeating unit (14a), (14b), (14c) or at least one of the above (specifically, a repeating unit 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, even more specifically 7 to 10).

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

Polyorganosiloxane-polycarbonate, measured by gel permeation chromatography at a sample concentration of 1 milligram per milliliter using a crosslinked styrene-divinyl benzene column, and calibrated with a polycarbonate standard from 2,000 to 100,000 daltons, specifically may have a weight average molecular weight of 5,000 to 50,000 Daltons.

The polyorganosiloxane-polycarbonate has a melt volume 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 It can have a flow rate. Mixtures of polyorganosiloxane-polycarbonates of different flow properties can be used to achieve the overall desired flow properties.

The thermoplastic resin may include an impact modifier. The impact modifier comprises (i) an elastomeric (i.e., rubber) polymer substrate having a Tg of 10°C or less, more specifically -10°C or less, or more specifically -40 to -80°C, (ii) the elastomeric polymer and an elastomer-modified graft copolymer comprising a rigid polymeric superstrate grafted to a substrate. Elastomer-modified graft copolymers can be prepared by first providing an elastomeric polymer and then polymerizing the constituent monomer(s) of the hard phase in the presence of the elastomer to obtain a graft copolymer. The graft may be attached as a graft branch or as a shell to an elastomeric core. The shell may merely physically encapsulate the core, or the shell may be partially or essentially completely grafted to the core.

The elastomeric phase may be polymerized by mass, emulsification, suspension, solution or combined processes such as bulk-suspension, emulsification-bulk, bulk-solution or other techniques using continuous, semi-batch or batch processes. The elastomeric substrate may have an average particle size of 0.001 to 25 micrometers (μm), specifically 0.01 to 15 μm, and more specifically 0.1 to 8 μm may be used in the emulsion based polymerized rubber lattice. A particle size of 0.5 to 10 μm, specifically 0.6 to 1.5 μm, may be used for the bulk polymerized rubber substrate. Particle size can be measured by a simple light transmission method or by capillary hydrodynamic chromatography (CHDF). The elastomeric phase may be particulate, suitably crosslinked conjugated butadiene or C _4-6 alkyl acrylate rubber, specifically having a gel content of greater than 70%. Combinations of butadiene with styrene and/or C _4-6 alkyl acrylate rubbers are also useful.

Impact modifiers can be prepared by emulsion polymerization processes, which include basic substances such as alkali metal salts of C _6-30 fatty acids, eg sodium stearate, lithium stearate, sodium oleate, potassium oleate, etc., alkali metals It does not contain carbonates, amines such as dodecyl dimethyl amine, dodecyl amine and the like, and ammonium salts of amines. These materials are commonly used as surfactants in emulsion polymerizations and can catalyze transesterification and/or degradation of polycarbonates. Instead, ionic sulfate, sulfonate or phosphate surfactants may be used in the preparation of the impact modifier, in particular the elastomeric substrate portion of the impact modifier. Useful surfactants are, for example, C _1-22 alkyl or C _7-25 alkylaryl sulfonates, C _1-22 alkyl or C _7-25 alkylaryl sulfates, C _1-22 alkyl or C _7-25 alkylaryl phosphates, substituted silicates, or combinations comprising at least one of the foregoing. A specific surfactant is a C _6-16 , specifically a C _8-12 alkyl sulfonate.

Surfactants include rosin acid chlorides, higher fatty acid salts, alkyl sulfuric ester salts, alkylbenzene sulfonates, alkyl diphenyl ether disulfonic acid chlorides, polyoxyethylene alkylphenyl ether sulfates, nonionic emulsifiers such as dialkyl sulfosucci nates, anionic emulsifiers of polyoxyethylene alkyl ethers and polyoxyethylene alkyl phenyl ethers), surfactants of formula (140), or combinations comprising at least one of the foregoing:

wherein R ^M is an allyl group, an acrylyl group or a 1-propenyl group; R ^S is hydrogen, -SO ₃ R ^Z group, wherein R ^Z is hydrogen, alkali metal, alkaline earth metal, ammonium or C _1-4 hydroxyalkyl ammonium, formula -CH ₂ COOR ^Z , wherein R ^Z is as defined above), or a monoester phosphate salt of the formula -(P=O)(OR ^Z ) _-2 , wherein each R ^Z is independently as defined above; R ^N and R ^O are each independently hydrogen, an alkyl group, an alkenyl group, a C _1-18 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 a substituted C _2-4 alkylene group; v is an integer from 1 to 200;

Surfactants may include surfactants of formulas (141) and/or (142):

wherein R ^Z and v are as defined above.

Materials for use as elastomeric phases include, for example, conjugated diene rubbers; a copolymer of a conjugated diene with 50 wt% or less of a copolymerizable monomer; olefin rubbers such as ethylene propylene copolymer (EPR) or ethylene-propylene-diene monomer rubber (EPDM); ethylene-vinyl acetate rubber; silicone rubber; elastomeric C _1-8 alkyl (meth)acrylates; elastomeric copolymers of C _1-8 alkyl (meth)acrylates with butadiene and/or styrene; or combinations comprising at least one of the above elastomers.

Conjugated diene monomers for preparing the elastomeric phase include those of formula (17):

wherein each X ^b is independently hydrogen, C ₁ -C ₅ alkyl, and the like. Examples of conjugated diene monomers that can be used include butadiene, isoprene, 1,3-heptadiene, methyl-1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3-pentadiene diene; 1,3- and 2,4-hexadiene, etc., or a combination comprising at least one of the foregoing. Specific conjugated diene homopolymers include polybutadiene and polyisoprene.

Copolymers of conjugated diene rubbers can also be used, for example copolymers prepared by aqueous radical emulsion polymerization of a conjugated diene and at least one monomer copolymerizable therewith. Monomers useful for copolymerization with a conjugated diene include monovinylaromatic monomers containing a condensed aromatic ring structure, such as vinyl naphthalene, vinyl anthracene, and the like, or formula (18) above, wherein each X ^c is independently hydrogen, C ₁ - ₁₂ alkyl, C ₃ - ₁₂ cycloalkyl, C ₆ - ₁₂ aryl, C ₇ - ₁₂ aralkyl, C ₇ - ₁₂ alkylaryl, C ₁ - ₁₂ alkoxy, C ₃ - ₁₂ cycloalkoxy, C ₆ - ₁₂ aryloxy, chloro, bromo or hydroxy, _{and R is hydrogen, C 1-5 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-bromo styrene, dichlorostyrene, dibromostyrene, tetra-chlorostyrene, and the like, and combinations comprising at least one of the above compounds. Styrene and/or alpha-methylstyrene may be used as monomers copolymerizable with the conjugated diene monomer.

Other monomers that can be copolymerized with the conjugated diene include monovinyl monomers such as itaconic acid, acrylamide, N-substituted acrylamide or methacrylamide, maleic anhydride, maleimide, N-alkyl-, aryl- or haloaryl- Substituted maleimide, glycidyl (meth)acrylate, and formula ( _{19) above, wherein R is hydrogen, C 1-5 alkyl} , bromo or chloro, X ^c is cyano, C _{1-12 alkoxy} carbonyl, C _{1-12 aryloxycarbonyl} , hydroxy carbonyl, etc.). 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 above 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 above monovinyl monomers and monovinylaromatic monomers may also be used.

(meth)acrylate monomers for use on the elastomer are C _1-8 alkyl (meth)acrylates, especially C _4-6 alkyl acrylates, for example n-butyl acrylate, t-butyl acrylate, n- propyl acrylate, isopropyl acrylate, 2-ethylhexyl acrylate, and the like and a combination comprising at least one of the above monomers may be a crosslinked particulate emulsified homopolymer or copolymer. The C _1-8 alkyl (meth)acrylate monomer may be polymerized in admixture with up to 15 wt % of the comonomer of formula (17), (18) or ( ₁₉ ), based on the total monomer weight. The comonomer comprises butadiene, isoprene, styrene, methyl methacrylate, phenyl methacrylate, vinyl methyl ether or acrylonitrile, phenethylmethacrylate, N-cyclohexylacrylamide, and at least one of the above comonomers including, but not limited to, combinations. Up to 5 wt % of the polyfunctional crosslinking comonomer may be present, based on the total monomer weight. Such polyfunctional crosslinking comonomers are, for example, divinylbenzene, alkylenediol di(meth)acrylates such as glycol bisacrylates, alkylenetriol tri(meth)acrylates, polyester di(meth)acrylates, Bisacrylamide, triallyl cyanurate, triallyl isocyanurate, allyl (meth)acrylate, diallyl maleate, diallyl fumarate, diallyl adipate, triallyl ester of citric acid, triallyl ester of phosphoric acid and the like, as well as combinations comprising at least one of the above crosslinking agents.

The hard phase of the elastomeric-modified graft copolymer may 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 substrate. The aforementioned monovinylaromatic monomers of formula (18) can be used on the rigid graft phase, including styrene, alpha-methyl styrene, halostyrene, such as dibromostyrene, vinyltoluene, vinylxylene, butylstyrene, para-hydro oxystyrene, methoxystyrene, and the like, or combinations comprising at least one of the above monovinylaromatic monomers. Useful comonomers include, for example, the monovinyl monomers described above and/or the monomers of formula (17). R can be hydrogen or C _1-2 alkyl, _and X ^c can be cyano or C _{1-12 alkoxycarbonyl} . Comonomers for use in the hard 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 comonomers.

The relative ratio of monovinylaromatic monomer and comonomer in the rigid graft phase can vary widely depending on the type of elastomeric substrate, the type of monovinylaromatic monomer(s), the type of comonomer(s) and the desired properties of the impact modifier. there is. The hard phase may comprise up to 100 wt % of monovinyl aromatic monomer, specifically 30-100 wt %, more specifically 50-90 wt % monovinylaromatic monomer, with the remainder of the hard phase being comonomer(s).

The elastomeric phase may comprise from 5 to 95 wt % of the total graft copolymer, more specifically from 20 to 90 wt % of the elastomer-modified graft copolymer, and even more specifically from 40 to 85 wt %, with the remainder being the rigid graft copolymer. it's a prize

Depending on the amount of elastomer-modified polymer present, separate matrices or continuous phases of ungrafted hard polymers or copolymers can be obtained simultaneously with the elastomer-modified graft copolymer. Typically, such impact modifiers comprise from 40 to 95 wt % of the elastomer-modified graft copolymer and from 5 to 65 wt % of the graft copolymer, based on the total weight of the impact modifier. For example, such impact modifiers may contain 50 to 85 wt %, specifically 75 to 85 wt %, based on the total weight of the impact modifier, together with 15 to 50 wt %, specifically 15 to 85 wt % of the rubber-modified graft copolymer. 25 wt % of the graft copolymer.

The hard phase may comprise a copolymer derived from acrylonitrile and a monomer of formula (18), for example styrene, wherein the hard phase comprises 0.1 to 80 of an impact modifier on the elastomer phase derived, for example, from butyl acrylate may occupy parts by weight.

The aromatic vinyl copolymer may comprise a “free” styrene-acrylonitrile copolymer (SAN), ie a styrene-acrylonitrile copolymer that is not grafted onto another polymer chain. The free styrene-acrylonitrile copolymer may have a molecular weight of 50,000 to 200,000 Daltons on a polystyrene standard molecular weight scale, and may include various ratios of styrene to acrylonitrile. For example, the free SAN may comprise 75 wt % styrene and 25 wt % acrylonitrile, based on the total weight of the free SAN copolymer. The free SAN may be present in a composition containing the free SAN by addition of a grafted rubber impact modifier, and/or the free SAN may be present independently of other impact modifiers in the composition.

One example of an impact modifier is methyl methacrylate-butadiene-styrene (MBS) impact modifier, wherein the butadiene substrate is prepared using the aforementioned sulfonates, sulfates or phosphates as surfactants.

The impact modifier is ABS, MBS, methyl methacrylate-acrylonitrile-butadiene-styrene (MABS), acrylonitrile-ethylene-propylene-diene-styrene (AES), hydrogenated styrene butadiene (SEBS), or one or more of the foregoing. Combinations comprising The impact modifier may include an acrylic polymer.

Another specific type of elastomer-modified impact modifier is at least one silicone rubber monomer, formula H ₂ C=C(R ^d )C(O)OCH ₂ CH ₂ R ^e , wherein R ^d is hydrogen or C ₁ - branched acrylate rubber monomers with ₈ linear or branched alkyl and R ^e is branched C _3-16 alkyl; a first graft linking monomer; polymerizable alkenyl-containing organic materials; and a structural unit derived from the second graft linking monomer. The silicone rubber monomer is, for example, cyclic siloxane, tetraalkoxysilane, trialkoxysilane, (acryloxy)alkoxysilane, (mercaptoalkyl)alkoxysilane, vinylalkoxysilane or allylalkoxysilane alone or in combination, for example decamethylcyclopentasiloxane, dodecamethyl cyclohexasiloxane, trimethyltriphenylcyclotrisiloxane, tetramethyl tetraphenyl cyclotetrasiloxane, tetramethyltetravinylcyclotetrasiloxane, octaphenyl cyclotetrasiloxane, octamethylcyclotetrasiloxane and / or tetraethoxysilane.

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

The first graft linking monomer, alone or in combination, is an (acryloxy)alkoxysilane, vinyl alkoxysilane, (mercaptoalkyl) alkoxysilane or allylalkoxysilane, for example (gamma-methacryloxypropyl)(dimethoxy) methylsilane and/or (3-mercaptopropyl) trimethoxysilane. The second graft linking 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.

The silicone-acrylate impact modifier may be prepared by emulsion polymerization, wherein, for example, a silicone rubber monomer is reacted with a first graft linking monomer in the presence of a surfactant such as dodecylbenzenesulfonic acid at a temperature of 30 to 110° C. to form silicone rubber latex. Alternatively, cyclic siloxanes such as cyclooctamethyltetrasiloxane and tetraethoxyorthosilicate can be reacted with a first graft linking monomer such as (gamma-methacryloxypropyl)methyldimethoxysilane. The branched acrylate rubber monomer is then polymerized with the silicone rubber particles, optionally in the presence of a crosslinking 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 linking monomer. The latex particles of the graft silicone-acrylate rubber hybrid can be separated from the aqueous phase through agglomeration (by treatment with a coagulant) and dried to a fine powder to produce a silicone-acrylate rubber impact modifier. This method can generally be used for the preparation of silicone-acrylate impact modifiers having a particle size of 100 nanometers to 2 micrometers.

The flocculant may comprise an acid having a pK _a of less than 5.0, specifically less than 3.0, more specifically less than 2.0. Thus, the acid can be an inorganic acid with hydrogen atoms that are fully ionized in water. The acid coagulant may be an oxoacid (also referred to as an oxyacid), typically a strong acid, eg, an acid (at least the first hydrogen proton) that is fully ionized in water. Specifically, the pK _a of the strong acid may be less than 2.0. Strong acids are, for example, hydrochloric acid (HCl), hydroiodic acid (HI), hydrobromic acid (HBr), hydrofluoric acid (HF), perchloric acid (HClO ₄ ), nitric acid (HNO ₃ ), nitrous acid (HNO ₂ ), Chromic acid (H ₂ CrO ₄ ), sulfuric acid (H ₂ SO ₄ ), sulfurous acid (H ₂ SO ₃ ), phosphoric acid (H ₃ PO ₄ ), trifluoromethanesulfonic acid (CF ₃ SO ₃ H), alkylsulfonic acid (CH ₃ ) SO ₃ H), or a combination comprising at least one of the above. Specifically, the strong acid is a nitrogen-containing and/or sulfur-containing strong acid, such as nitric acid (HNO ₃ ), nitrous acid (HNO ₂ ), sulfuric acid (H ₂ SO ₄ ), sulfurous acid (H ₂ SO ₃ ), or any of the foregoing. Combinations comprising one or more may be included. Inorganic acids such as sulfuric acid may be used as flocculants.

The impact modifier may be a high rubber graft (HRG) impact modifier.

Impact modifiers may be free of alkali metal salts of fatty acids, alkali metal carbonates and other basic substances.

When present, the impact modifier may be present in the thermoplastic composition in an amount of from 5 to 10 weight percent based on the total weight of the thermoplastic resin. The impact modifier may have an average diameter of from 0.05 to 3 micrometers, specifically from 0.05 to 2 micrometers, more specifically from 0.1 to 1.5 micrometers.

Polycarbonate and impact modifiers (e.g., impact modifiers prepared by an emulsification process, specifically an emulsification process using an acidic flocculant) may be combined in the presence of a buffer, wherein the term "buffer" or "buffer" refers to a buffer solution in an aqueous solution. It refers to compounds capable of forming, and the pH of the buffer will refer to the pH obtainable using the buffer in distilled water. Thus, the term buffer may refer to a combination of phosphate salts, compounds that are present in a solid composition in residual form but are capable of forming a buffer in aqueous solution. The buffer may include one or more metal salts of phosphoric acid, and at least one of them may include a potassium cation. The buffer may include a weak acid and a conjugate base (equilibrium state) capable of providing a pH of 6.3 to 7.0, specifically 6.4 to 6.9, in distilled water.

During compounding, the amount of phosphorus atoms from the metal salt of phosphoric acid is 0.02 to 0.16 moles per 10 pounds (mol/10 lbs) based on the weight of the polycarbonate composition (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). For example, a buffer may be present in the composition such that the amount of phosphorus in the composition by weight of the composition is 0.04 mol/10 lbs (0.009 mol/kg). The potassium cation may represent at least 50 mole percent (mol %) of the cations in the metal phosphate salt in the composition, specifically at least 75 mol %. The metal salt of phosphoric acid may have a ratio, weak acid form and conjugate base form 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.

The relative ratios of each acid and base form that make up the buffer can be determined using the following Henderson-Hasselbalch equation:

pH = pKa + log[base form (A-)]/[acid form (HA)].

The metal salt of phosphoric acid used as the buffer may contain a cation other than potassium. The cation other than potassium may 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 may include aluminum, sodium, lithium, calcium, zinc, or a combination comprising at least one of the foregoing. The buffer may contain a conjugate base form containing potassium cations and a weak acid form containing different metal cations. Alternatively, the buffer may contain potassium cations in both the weak acid form and the conjugate base form. Specifically, the buffer comprises a weak acid and a conjugated base pair, such as monopotassium phosphate/dipotassium phosphate, lithium phosphate monobasic/dipotassium phosphate, aluminum phosphate monobasic/dipotassium phosphate, monozinc phosphate/dipotassium phosphate, or one or more of the foregoing. It may be made of a combination comprising.

A polymeric flow promoter may be present during compounding. The polymeric flow promoter can be readily blended with the elastomer-modified graft copolymer and can increase its melt flow rate without adversely affecting the desired properties of the composition. The polymeric flow promoter may comprise repeat units derived from a monomer selected from the group consisting of methyl (meth)acrylate, styrene, acrylonitrile, alpha-methyl styrene, or combinations comprising one or more of the foregoing. For example, the polymeric flow promoter may be a styrene-acrylonitrile copolymer, poly(methyl methacrylate), polystyrene, methyl methacrylate-styrene-acrylonitrile copolymer, poly(alpha methyl styrene), or any of the foregoing. Combinations comprising one or more may be included. Specifically, the flow promoter may include a styrene-acrylonitrile copolymer.

Polymeric flow promoters can form separate matrices or continuous phases. Polymeric flow promoters may include ungrafted hard polymers or "graft copolymers", which are obtained simultaneously with the impact modifier. For example, a polymeric flow promoter can be prepared concurrently with the impact modifier using an excess of monomer from polymerization of the impact modifier. Alternatively, the polymeric flow promoter can be independently prepared or obtained and subsequently incorporated into the elastomer-modified graft copolymer, for example during compounding of the elastomeric-modified graft copolymer with polycarbonate.

The ratio of impact modifier to polymeric flow promoter (if present) may be from 3:1 to 1:3, specifically from 2:1 to 1:2, more specifically from 1.5:1 to 1:1.5. The impact modifier may 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 is 5 to 65 wt %, specifically 15 to 50 wt % , more specifically in an amount of 15 to 25 wt % (based on the total weight of the impact modifier and the polymeric flow promoter).

The average residence time of the compounding step may be 20 to 30 seconds (sec). The temperature during compounding may be between 200 and 300°C.

Blending can include two separate mixing steps: a premixing step and a melt mixing (“melt blending”) step. In the premix step, the dry ingredients may be mixed together in, for example, a tumbler mixer, ribbon blender or high shear mixer to form a pre-mix. Melt mixing may include melting the pre-mixture and mixing it back as a melt in, for example, a single screw extruder, twin screw extruder, Banbury mixer or two roll mill.

Additives may further be added at one or more locations in the melt manufacture of the polycarbonate of the present invention. For example, the additive is added upstream of the polymerization unit, added directly to the polymerization unit (eg, at the inlet, at the side feeder, at the outlet, or in a combination comprising one or more of the foregoing), or added downstream, added to a reactor that does not polymerize the polycarbonate, added upstream of the extruder, or added directly to the extruder (e.g., at the extruder throat, at the side feeder, at the outlet, or one or more of the above ), added downstream of the extruder, or added in combinations comprising one or more of the above. Additives may be added during compounding with the impact modifier. The additives may be added as part of the quencher composition or may be added individually. Additives may be added in the molten state or may be added after the extruded polycarbonate has been remelted. Additives may be filtered prior to being added to the polymerization unit.

Additives can be, for example, rheology modifiers, fillers (eg glass, carbon, minerals or metals), reinforcing agents (eg glass fibers), antioxidants, heat stabilizers, light stabilizers, ultraviolet (UV) light. Agents (such as UV light stabilizers and UV absorbing additives), plasticizers, lubricants, mold release agents (such as mold release agents (such as glycerol monostearate, pentaerythritol stearate, glycerol tristearate, stearyl stearate, etc.)) , antistatic agents, antifog agents, antimicrobial agents, colorants (eg dyes or pigments), surface effect additives, radiation stabilizers, flame retardants, fluoro-resins (eg PTFE-encapsulated styrene- acrylonitrile copolymer (TSAN)), or a combination comprising one or more of the foregoing. For example, combinations of heat stabilizers, mold release agents and ultraviolet light stabilizers can be used. In general, additives are used in amounts generally known to be effective. For example, the total amount of additive composition (other than optional fillers or reinforcing agents) can be from 0.001 to 10.0 weight percent (wt %), or from 0.01 to 5 wt %, respectively, based on the total weight of polymer in the polymerized composition.

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

The term “antistatic agent” refers to a monomeric, oligomeric or polymeric material that can be engineered into a polymer and/or sprayed onto a material or article to improve its 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 ste aryl sulfonate, sodium dodecylbenzenesulfonate and the like, quaternary ammonium salts, quaternary ammonium polymers, imidazoline derivatives, sorbitan esters, ethanolamides, betaines, or combinations comprising at least one of the foregoing monomeric antistatic agents includes

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

A radiation stabilizer may also be present, specifically a gamma-radiation stabilizer. 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-hexanediol, 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 are 4-methyl-4-penten-2-ol, 3-methyl-penten-3-ol, 2-methyl-4-penten-2-ol, 2,4-dimethyl -4-penten-2-ol and 9-deken-1-ol, as well as tertiary alcohols having at least one hydroxy substituted tertiary carbon, such as 2-methyl-2,4-pentanediol (hexyl silane 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 having a hydroxy substituent on the saturated carbon attached to the unsaturated carbon in the aromatic ring may also be used. The hydroxy-substituted saturated carbon may be a methylol group (—CH ₂ OH), or it may be a more complex hydrocarbon group such as —CR ⁴ HOH or —CR ₂ ⁴ OH, where R ⁴ is complex or 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.

Colorants such as pigments and/or dye additives may also be present. Useful pigments include, for example, inorganic pigments such as metal oxides and mixed metal oxides such as zinc oxide, titanium dioxide, iron oxide, and the like; sulfides such as zinc sulfide and the like; aluminate; sodium sulfo-silicate, chromate, and the like; carbon black; zinc ferrite; ultramarine blue; organic pigments such as azo, di-azo, quinacridone, perylene, naphthalene tetracarboxylic acid, flavanthrone, isoindolinone, enthrone, dioxazine, tetrachloroisoindolinone, anthraquinone, phthalocyanine and azo lake; Pigment Red 101, Pigment Red 122, Pigment Red 149, Pigment Red 177, Pigment Red 179, Pigment Red 202, Pigment Violet 29, Pigment Blue 15, Pigment Blue 60, Pigment Green 7, Pigment Yellow 119, Pigment Yellow 147, Pigment Yellow 150 and Pigment Brown 24; or a combination comprising at least one of the above pigments.

Dyes are generally organic materials, and include coumarin dyes such as coumarin 460 (blue), coumarin 6 (green), nile red and the like; lanthanide complex; hydrocarbon and substituted hydrocarbon dyes; polycyclic aromatic hydrocarbon dyes; scintillation dyes such as oxazole or oxadiazole dyes; aryl- or heteroaryl-substituted poly (C _2-8 ) olefin dyes; carbocyanine dyes; indanthrone dyes; phthalocyanine dyes; oxazine dyes; carbostyryl dyes; naphthalenetetracarboxylic acid dyes; porphyrin dyes; bis(styryl)biphenyl dyes; acridine dyes; anthraquinone dyes; cyanine dyes; methine dye; 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 that absorb at near infrared wavelengths and emit at visible wavelengths; luminescent dyes such as 7-amino-4-methylcoumarin; 3-(2'-benzothiazolyl)-7-diethylaminocoumarin;2-(4-biphenylyl)-5-(4-t-butylphenyl)-1,3,4-oxadiazole;2,5-bis-(4-biphenylyl)-oxazole;2,2'-dimethyl-p-quaterphenyl;2,2-dimethyl-p-terphenyl;2,5-diphenylfuran;3,5,3″″,5″″-tetra-t-butyl-p-quinquiphenyl;2,5-diphenyloxazole;4,4'-diphenylstilbene;4-dicyanomethylene-2-methyl-6-(p-dimethylaminostyryl)-4H-pyran;1,1'-diethyl-2,2'-carbocyanineiodide;3,3'-diethyl-4,4',5,5'-dibenzothiatricarbocyanineiodide;7-dimethylamino-1-methyl-4-methoxy-8-azaquinolone-2; 7-dimethylamino-4-methyl quinolone-2; 2-(4-(4-dimethylaminophenyl)-1,3-butadienyl)-3-ethylbenzothiazolium perchlorate; 3-diethylamino-7-diethyliminophenoxazonium perchlorate; 2-(1-naphthyl)-5-phenyloxazole; 2,2′-p-phenylene-bis(5-phenyloxazole); rhodamine 700; rhodamine 800; pyrene, chrysene, rubrene, coronene, and the like; or a combination comprising at least one of the above dyes.

Possible fillers or reinforcing agents are, 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 carbonate (such as chalk, limestone, marble and synthetic precipitated calcium carbonate), talc (fibrous, modular, needle-like and lamellar talc), wollastonite, hollow or solid glass spheres, silicate spheres, cenospheres, aluminosilicates or (armospheres), kaolin, whiskers of silicon carbide , alumina, boron carbide, iron, nickel, or copper, continuous and chopped carbon or glass fibers, molybdenum sulfide, zinc sulfide, barium titanate, barium ferrite, barium sulfate, heavy spar , TiO ₂ , aluminum oxide, magnesium oxide, particulate or fibrous aluminum, bronze, zinc, copper, or nickel, glass flake, 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 shell or rice grain husk, reinforcing organic fibrous fillers such as poly( ether ketones), polyimides, polybenzoxazoles, poly(phenylene sulfide), polyesters, polyethylene, aromatic polyamides, aromatic polyimides, polyetherimides, poly(vinyl alcohol) and polytetrafluoroethylene, as well as combinations comprising at least one of the above fillers or reinforcing agents. Fillers and reinforcing agents may be coated with a layer of metallic material to promote conductivity or surface treated with a silane to improve adhesion and dispersibility with the polymer matrix. The filler is used in an amount of 1 to 200 parts by weight based on 100 parts by weight of the total composition.

Antioxidant additives include organophosphites such as tris(nonylphenyl)phosphite, tris(2,4-di-t-butylphenyl)phosphite, bis(2,4-di-t-butylphenyl)pentaerythritol diphosphite, distearyl pentaerythritol diphosphite; alkylated monophenols or polyphenols; alkylation reaction products of polyphenols with dienes, such as tetrakis [methylene(3,5-di-tert-butyl-4-hydroxyhydrocinnamate)] methane; butylation reaction products of para-cresol or dicyclopentadiene; alkylated hydroquinones; hydroxylated thiodiphenyl ether; alkylidene-bisphenol; 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; amide of beta-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionic acid, or a combination comprising at least one of the foregoing antioxidants. The antioxidant may be used in an amount of 0.01 to 0.1 parts by weight based on 100 parts by weight of the total thermoplastic composition excluding any fillers.

UV absorbing additives include hydroxybenzophenone; hydroxybenzotriazole; hydroxybenzotriazine; cyanoacrylate; oxanilide; benzoxazinone; aryl salicylate; monoesters of diphenols such as resorcinol monobenzoate; 2-(2H-Benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)-phenol (CYASORB ^™ 5411); 2-hydroxy-4-n-octyloxybenzophenone (Ciasolv ^™ 531); 2-[4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl]-5-(octyloxy)-phenol (Ciasolv ^™ 1164); 2,2′-(1,4-phenylene)bis(4H-3,1-benzoxazin-4-one) (Ciasolv ^™ UV-3638); Poly[(6-morpholino-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 ^TM 3008), 6-tert-butyl-2- (5-chloro -2H-Benzotriazol-2-yl)-4-methylphenyl (Uvinul ^TM 3026), 2,4-di-tert-butyl-6-(5-chloro-2H-benzotriazol-2-yl)- Phenol (Uvinul ^TM 3027), 2-(2H-benzotriazol-2-yl)-4,6-di-tert-pentylphenol (Uvinul ^TM 3028), 2-(2H-benzotriazole-2- yl)-4-(1,1,3,3-tetramethylbutyl)-phenol (Uvinul ^TM 3029), 1,3-bis[(2'cyano-3',3'-diphenylacryloyl )oxy]-2,2-bis-{[(2′-cyano-3′,3′-diphenylacryloyl)oxy]methyl}-propane (Uvinul ^™ 3030), 2-(2H-benzo Triazol-2-yl)-4-methylphenol (Uvinul ^™ 3033), 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol ( Uvinul ^™ 3034), ethyl-2-cyano-3,3-diphenylacrylate (Uvinul ^™ 3035), (2-ethylhexyl)-2-cyano-3,3-diphenylacrylate (Uvinul ^™ 3039), N,N'-bisformyl-N,N'-bis(2,2, 6,6-tetramethyl-4-piperidinyl)hexamethylenediamine (Uvinul ^™ 4050H), bis-(2,2,6,6-tetramethyl-4-piperidyl)-sebacate (Uvinul ^™ 4077H), bis-(1,2,2,6,6-pentamethyl-4 -piperidyl)-sebacate + methyl-(1,2,2,6,6-pentamethyl-4-piperidyl)-sebacate (Uvinul ^TM 4092H), 1,3-bis[(2-cyano-3,3-diphenylacryloyl)oxy]-2,2-bis[[(2-cyano-3,3-diphenylacryloyl) )oxy]methyl]propane (Uvinul ^™ 3030); 2,2′-(1,4-phenylene)bis(4H-3,1-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-sized inorganic materials such as titanium oxide, cerium oxide and zinc oxide, all of which have a particle size of 100 nanometers or less, or the like, or combinations comprising at least one of the above UV absorbers. The UV absorber may be used in an amount of 0.01 to 1 part by weight based on 100 parts by weight of the thermoplastic resin. UV absorbers that may be particularly useful in the polycarbonate compositions disclosed herein are 2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)-phenol (e.g. , Cytec Industries, Inc. (Cyasolv ^™ 5411) commercially available from Cytec Industries, Inc. (Woodland Park, New Jersey) and 2,2'-(1,4-phenylene)bis(4H-3) , 1-benzoxazin-4-one) (eg, Siasolv ^™ UV-3638 commercially available from Citec Industries, Inc. (Woodland Park, New Jersey)), and combinations comprising at least one of the foregoing. includes The UV stabilizer may 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 on the total weight of the thermoplastic composition.

Plasticizers, lubricants and/or mold release agents may also be used. Substances of this type overlap significantly, 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), bis(diphenyl) phosphate of hydroquinone and bis(diphenyl) phosphate of bisphenol A; poly-alpha-olefins; epoxidized soybean oil; silicone including silicone oil; esters such as fatty acid esters such as alkyl stearyl esters such as methyl stearate, stearyl stearate, pentaerythritol tetrastearate, and the like; combination of methyl stearate with hydrophilic and hydrophobic nonionic surfactants, including polyethylene glycol polymers, polypropylene glycol polymers, poly(ethylene glycol-co-propylene glycol) copolymers, or combinations comprising at least one of the foregoing glycol polymers; methyl stearate and polyethylene-polypropylene glycol copolymers, for example in a suitable solvent; waxes such as beeswax, montan wax, paraffin wax, and the like.

Plasticizers, lubricants and/or mold release agents may comprise compounds of formula (I):

wherein R ₁ , R ₂ and R ₃ may be the same or different hydrocarbon chains having 8 to 20 carbon atoms and 0 to 6 unsaturation, and R ₁ , R ₂ and R ₃ are each independently C ₈ - C ₂₀ alkyl, C ₈ -C ₂₀ haloalkyl, C ₈ -C ₂₀ polyhaloalkyl, C ₈ -C ₂₀ alkene and C ₈ -C ₂₀ alkoxy. R ₁ , R ₂ and R ₃ may each be independently selected from C ₁₇ H ₃₅ , or both R ₁ , R ₂ and R ₃ may be C ₁₇ H ₃₅ . The plasticizer, lubricant and/or mold release agent may include glycerol monostearate, glycerol monopalmitate, glycerol tristearate, glycerol tristearate, stearyl stearate, or combinations comprising one or more of the foregoing. One or more of the above may have an acid value of 2 to 20 mg KOH, which may be obtained by dissolving the partial ester by adding 100 ml of isopropanol to 2.5 g of the partial ester; adding phenolphthalein as an indicator to the resulting solution; titration of the resulting mixture with 0.1 mol/L potassium hydroxide standard solution to obtain the acid value (mg KOH). When the acid value is measured, if the partial ester is expected to have an acid value of 1 or less, the amount of the partial ester to which the measurement is applied is changed to 20 g; When the partial ester is expected to have an acid number of 1 to 4, the amount of the partial ester to which the measurement is applied is changed to 10 g; When the partial ester is expected to have an acid value of 15 or more, the amount of the partial ester to which the measurement is applied is changed to 0.5 g.

The plasticizer, lubricant and/or mold release agent may 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.

Useful flame retardants include organic compounds comprising phosphorus, bromine and/or chlorine. Non-brominated and non-chlorinated phosphorus-containing flame retardants, such as organic phosphates and organic compounds containing phosphorus-nitrogen bonds, may be preferred in certain applications for regulatory reasons.

Flame retardant aromatic phosphates are 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 do. di- or polyfunctional aromatic phosphorus-containing compounds such as resorcinol tetraphenyl diphosphate (RDP), bis(diphenyl) phosphate of hydroquinone and bis(diphenyl) phosphate of bisphenol A, respectively, and their oligomeric properties and polymeric counterparts are also useful. Flame retardant compounds containing phosphorus-nitrogen bonds include phosphonitrilic chloride, phosphorus ester amide, phosphoric acid amide, phosphoric acid amide, phosphinic acid amide and tris(aziridinyl)phosphine oxide. If a phosphorus-containing flame retardant is used, it is present in an amount of 0.1 to 30 pbw, specifically 1 to 20 pbw, based on 100 parts by weight (pbw) of the composition excluding any fillers.

Halogenated substances, such as bisphenols, can also be used as flame retardants, the following being representative: 2,2-bis-(3,5-dichlorophenyl)-propane; bis-(2-chlorophenyl)-methane; bis(2,6-dibromophenyl)-methane; 1,1-bis-(4-iodophenyl)-ethane; 1,2-Bis-(2,6-dichlorophenyl)-ethane; 1,1-bis-(2-chloro-4-iodophenyl)ethane; 1,1-bis-(2-chloro-4-methylphenyl)-ethane; 1,1-bis-(3,5-dichlorophenyl)-ethane; 2,2-bis-(3-phenyl-4-bromophenyl)-ethane; 2,6-bis-(4,6-dichloronaphthyl)-propane; 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, 1,3-dichloro-4-hydroxybenzene, and biphenyls such as 2,2'-dichlorobiphenyl, polybromide 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 bisphenol A and copolycarbonates of tetrabromobisphenol A and a carbonate precursor (eg, phosgene). Metal synergists such as antimony oxide, bismuth oxide, iron oxide, zinc oxide, tin oxide may also be used with flame retardants, from 0.5 to 20 pbw, specifically 1, based on 100 pbw of the composition to 15 pbw, more specifically 1 to 10 pbw.

When present, the halogen-containing flame retardant may 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 fillers.

Inorganic flame retardants, for example salts of C _1-16 alkyl sulfonate salts such as potassium perfluorobutane sulfonate (Rimar salt), potassium perfluorooctane sulfonate, tetraethylammonium perfluorohexane sulfonate and potassium diphenylsulfone sulfonate; salts such as Na ₂ CO ₃ , K ₂ CO ₃ , MgCO ₃ , CaCO ₃ and BaCO ₃ , or Li ₃ AlF ₆ , BaSiF ₆ , KBF ₄ , K ₃ AlF ₆ , KAlF ₄ , K ₂ SiF ₆ and/or Na Fluoro-anionic complexes such as ₃ AlF ₆ may also be used. If 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 fillers.

Flame retardants include nitrogen-containing organic compounds (such as melamine), silicon compounds, halogen-containing organic compounds, inorganic compounds (such as magnesium hydroxide and aluminum hydroxide), phosphorus compounds (such as phosphine, hypophosphoric acid, phosphoric acid, metaphosphoric acid, pi lyophosphoric acid and phosphoric anhydride), or combinations comprising at least one of the foregoing.

Flame retardants include halogen-containing compounds such as hexachloro pentadiene, hexabromo diphenyl, octabromo diphenyloxide, tribromophenoxymethane, decabromo diphenyl, decabromo diphenyloxide, octave lomo diphenyloxide, tetrabromo bisphenol A, tetrabromo phthalimide, hexabromo butene, hexabromo cyclododecane, or combinations comprising at least one of the foregoing.

The halogen-containing compound may have the structure of formula (200):

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

(wherein iv is an integer from 0 to 3)

The halogen-containing compound may have the structure of formula (210):

wherein iii and R ^H are as defined above, wherein the group R ^H may have the formula (212):

The halogen-containing compounds include phosphoric acid esters 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, tripropyl phosphate, tributyl phosphate, tripentyl phosphate, trihexyl phosphate, tricyclohexyl phosphate, triphenyl phosphate, tricresyl phosphate, triza ylenyl phosphate, dimethylethyl phosphate, methyl dibutyl phosphate, ethyl dipropyl phosphate, hydroxyphenyl diphenyl phosphate, or combinations comprising at least one of the foregoing.

The phosphoric acid ester may have the formula (230):

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

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

The flame retardant may include a silicon flame retardant, such as a flame retardant of the formula RSiO, wherein R may be a hydrocarbon group (eg, a methyl group, a propyl group, a phenyl group, a xylyl group, or an alkenyl group).

The thermoplastic composition may include 0.1 to 39 parts by weight, specifically 0.1 to 30 parts by weight, more specifically 1 to 25 parts by weight, and still more specifically 3 to 22 parts by weight of the flame retardant based on 100 parts by weight of the thermoplastic resin.

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

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

The fluoro-resin may have a fibril shape, and the fibrils may have an average diameter of 0.5 micrometers or less. The fibrils may be branched fibrils. The fluoro-resin may be present in an amount of 0.01 to 5 parts by weight, specifically 0.1 to 1 part by weight, based on 100 parts by weight of the thermoplastic resin.

The thermoplastic composition may be prepared by the steps of: feeding a thermoplastic resin to an extruder; conveying a fluoro-resin, a flame retardant, or a combination comprising one or both of the above to the extruder; and extruding the thermoplastic resin to form a thermoplastic composition. The extruder may be, for example, a single screw extruder, a twin screw extruder or a Banbury mixer. Extrusion may be performed at or above the melting temperature of the thermoplastic resin. The thermoplastic resin may be melt-kneaded prior to the addition of the fluoro-resin, and when melt-kneaded at a shear rate of 240 sec ^{- 1} , the melt viscosity measured by a capillary rheometer at the resin temperature is 3,000 to 12,000 poise, specifically 3,000 to 10,000 poise. Melt-kneading may occur at a temperature of 320° C. or less or 310° C. or less.

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

The quenched composition may be essentially free of chlorine and bromine. "Essentially free of chlorine and bromine" means a bromine and/or chlorine content of 100 parts per million (ppm) or less, 75 ppm or less, or 50 ppm or less, based on the total parts by weight of the composition, excluding any fillers. defined as having

The polymerization of the present invention may take place in the absence of a branching agent, ie the process of the present invention may not include a branching agent addition step. Examples of branching agents include polyfunctional organic compounds containing at least three functional groups selected from hydroxyl, carboxyl, carboxylic acid anhydride, haloformyl and mixtures of said functional groups. Such branching agents include aromatic triacyl halides, for example of formula (20), wherein Z is halogen, C _1-3 alkyl, C _1-3 alkoxy, C _7-12 arylalkylene, C _7-12 alkylarylene. or nitro, and z is 0 to 3); Formula (21), wherein T is C _1-20 alkyl, C _1-20 alkoxy, C _7-12 arylalkyl or C _7-12 alkylaryl, Y is halogen, C _1-3 alkyl, C _1-3 alkoxy, C _7-12 arylalkyl, C _7-12 alkylaryl or nitro, and s is 0 to 4).

Specific examples of branching agents include trimellitic acid, trimellitic anhydride, trimellitic acid trichloride, tris-p-hydroxyphenylethane, isatin-bis-phenol of formula (22), tris-phenol TC (1,3 ,5-tris((p-hydroxyphenyl)isopropyl)benzene), tris-phenol PA (4(4(1,1-bis(p-hydroxyphenyl)-ethyl) alpha, alpha-dimethyl benzyl)phenol ), 4-chloroformyl phthalic anhydride, trimesic acid and benzophenone tetracarboxylic acid.

The polycarbonate composition may have a light transmittance of greater than 90% as determined using a 3.2 mm thick sample using ASTM D1003-00, Procedure B using CIE standard illuminant C as a unidirectional view. Accordingly, when a quenched composition has such light transmittance, it is referred to herein as an “optical grade” composition.

Some embodiments of the methods disclosed herein are set forth below.

Embodiment 1: A method of making a thermoplastic composition, the method comprising: feeding a thermoplastic resin comprising molten polycarbonate, and an impact modifier to an extruder; adding a quencher composition to the molten polycarbonate; and after mixing the quencher composition with the molten polycarbonate for at least 5 seconds, adding any reactive additive having reactive OH groups or reactive ester groups to the molten polycarbonate; conveying a fluoro-resin, a flame retardant, or a combination comprising one or both of the above to the extruder; and extruding the thermoplastic resin to form a thermoplastic composition.

Embodiment 2: The method of Embodiment 1, further comprising pelletizing the polycarbonate prior to the feeding step.

Embodiment 3: The method of Embodiments 1 or 2, further comprising melting the polycarbonate prior to adding the quencher composition.

Embodiment 4: A method for preparing a thermoplastic composition, comprising melt polymerization of a carbonate compound and a dihydroxy compound in the presence of a catalyst composition to form a molten polycarbonate in a molten state, wherein the catalyst composition comprises an alkali catalyst and a quaternary catalyst one or both of; the alkali catalyst comprises a source of one or both of alkali and alkaline earth ions; wherein the quaternary catalyst comprises one or both of a quaternary ammonium compound and a quaternary phosphonium compound; and supplying a thermoplastic resin comprising an impact modifier and molten polycarbonate in the molten state to an extruder; adding a quencher composition to the molten polycarbonate after the feeding step; and after mixing the quencher composition with the molten polycarbonate for at least 5 seconds, adding any reactive additive having reactive OH groups or reactive ester groups to the molten polycarbonate; conveying a fluoro-resin, a flame retardant, or a combination comprising one or both of the above to the extruder; and extruding the thermoplastic resin to form a thermoplastic composition.

Embodiment 5: The target molecular weight of Embodiment 4, wherein after final polymerization, a chain severing agent is added to the molten polycarbonate in the molten state to reduce the molecular weight of the molten polycarbonate, so that the molecular weight of the molten polycarbonate is lower than the molecular weight of the molten polycarbonate. A method further comprising the step of forming a modified polycarbonate having a.

Embodiment 6: The method of any of Embodiments 1-5, wherein the quencher composition comprises polycarbonate powder.

Embodiment 7: The method of any of Embodiments 1-5, wherein the quencher composition contains no carrier.

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

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

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

Embodiment 11: The method 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.

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

Embodiment 13: The method of any of Embodiments 1-12, wherein the thermoplastic resin comprises polyorganosiloxane, polyalkylacrylate, polyolefin, polyamide, polyphenylene ether, polyoxymethylene, or one or more of the foregoing. A method further comprising a combination.

Embodiment 14: The method according to any one of Embodiments 1 to 13, wherein the impact modifier is treated with the above formula (141) and/or (142) prior to the feeding step, wherein each R ^Z is independently hydrogen, alkali metal, alkali. and polymerizing in the presence of a surfactant of an earth metal, ammonium or C _1-4 hydroxyalkyl ammonium, and v is an integer from 1 to 200.

Embodiment 15: The thermoplastic resin of any of Embodiments 1-14; polyisoprene; polychloroprene; polyacrylonitrile; polyethylene; polypropylene; poly(ethyl acrylate); poly(methyl acrylate); poly(methyl methacrylate); poly(butyl acrylate); polybutadiene; polymers derived from maleic anhydride, beta-unsaturated carboxylic acid, N-phenylmaleimide, N-methylmaleimide, N-cyclohexylmaleimide, glycidyl methacrylate, or combinations comprising at least one of the foregoing; The method further comprising a copolymer comprising two or more of the foregoing, or a combination comprising one or more of the foregoing.

Embodiment 16: The fluoro-resin 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 at least one of the foregoing. how to do it.

Embodiment 17: The method of any of Embodiments 1-16, wherein the flame retardant comprises a halogen-containing compound of formula (200); wherein iii is an integer from 0 to 10, each R ^I is independently halogen, and each R ^H independently has the formula (201) or (202) above, wherein iv is an integer from 0 to 3 How can it be.

Embodiment 18: The method of any of Embodiments 1-17, wherein the flame retardant comprises a phosphoric acid ester that may have the formula (230); wherein the average vi is an integer from 1 to 10; each R ^L is independently a phenyl group, a tolyl group, a xylyl group, an alkyl group, a cycloalkyl group, or an alkylaryl group; each R ^M is independently a divalent group of formulas (231) to (234) above.

Embodiment 19: The method of any one of Embodiments 1 to 18, further comprising melt-kneading the thermoplastic resin prior to the fluoro-resin transferring step, wherein the melt ^- kneading at a shear rate of 240 sec ⁻¹ is performed using a capillary rheometer. The measured melt viscosity of the thermoplastic resin is 3,000 to 12,000 poise.

Embodiment 20: The method of any of Embodiments 1-19, wherein the quencher composition is added at a pressure of at least 2 bar.

Embodiment 21: The polycarbonate of any of Embodiments 1 to 3 and 6 to 20, wherein the polycarbonate is a molten polycarbonate and in the presence of a catalyst composition comprising an alpha catalyst and/or a beta catalyst a carbonate compound and a dihydroxy compound Melt polymerization of the method further comprising the step of forming the molten polycarbonate.

Embodiment 22: The modified polycarbonate of Embodiment 21, wherein, after final polymerization, a chain severing agent is added to the polycarbonate to reduce the molecular weight of the polycarbonate to form a modified polycarbonate having a desired molecular weight less than that of the polycarbonate. A method further comprising the step of:

Embodiment 23: The method of any of embodiments 1-22, wherein the polycarbonate has an endcapping ratio of at least 85%, specifically at least 90%, and more specifically at least 95%.

Embodiment 24: The method 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 molten polycarbonate.

Embodiment 25: The method of embodiment 24, wherein the freeze level is less than or equal to 500 ppm (by weight).

As used herein, when referring to "reactive" or "reactive group" (eg, having a reactive OH- group or a reactive ester group), the reactivity relates to a polycarbonate.

In general, the present invention may alternatively comprise, consist of, or consist essentially of any suitable ingredient disclosed herein. The present invention may be additionally or alternatively formulated to be substantially free or substantially free of any ingredient, substance, ingredient, adjuvant or species used in the preceding compositions or otherwise necessary for the function and/or achievement of the object of the present invention. can

All ranges disclosed herein are inclusive of endpoints, which endpoints are independently combinable with each other (eg, a range of “up to 25 wt %, or more specifically 5-20 wt %” means “5-25 wt %” " including the endpoints of the range and all intermediate values, etc.). “Combination” includes blends, mixtures, alloys, reaction products, and the like. Also, the terms "first," "second," etc. herein are used to distinguish one element from another, rather than indicating any order, amount, or importance. The singular forms and the term “above” herein do not denote a limitation of quantity, and are to be construed to include both the singular and the plural unless otherwise indicated herein or otherwise clearly contradicted by context. As used herein, the suffix "(s)" is intended to include both the singular and the plural of the term it modifies, and thus includes one or more of that term (e.g., film(s) means one or more including film). References throughout this specification to “one embodiment,” “another embodiment,” “an embodiment,” etc. refer to a particular element (eg, feature, structure, and/or characteristic) described in connection with that embodiment herein. included in at least one embodiment described, which may or may not be present in other embodiments. It is also to be understood that the described elements may be combined in any suitable manner in the various embodiments. Other than broader ranges, the disclosure of a narrower range or a more specific group is not a disclaimer of the broader range or larger group.

While specific embodiments have been described, alternatives, modifications, changes, improvements and substantial equivalents that are not or may not be anticipated at present may occur to the applicant or to one of ordinary skill in the art. Accordingly, the appended claims, as filed and as may be amended, are intended to cover all such alternatives, modifications, changes, improvements and substantial equivalents.

Claims (20)

A method of making a thermoplastic composition comprising:
feeding a thermoplastic resin comprising molten polycarbonate, and an impact modifier to an extruder;
adding a quencher composition to the molten polycarbonate; and
mixing the quencher composition with the molten polycarbonate for at least 5 seconds, and then adding a reactive additive having reactive OH groups or reactive ester groups to the molten polycarbonate;
conveying a fluoro-resin, a flame retardant, or a combination comprising one or both of the above to the extruder; and
Extruding the thermoplastic resin to form a thermoplastic composition
How to include. The method of claim 1 , further comprising pelletizing the molten polycarbonate prior to the feeding step. The method of claim 1 , further comprising melting the molten polycarbonate prior to adding the quencher composition. The method of claim 1 , further comprising polymerizing said impact modifier in the presence of a surfactant of formula (141) and/or (142) prior to said feeding step:

wherein each R ^Z is independently hydrogen, alkali metal, alkaline earth metal, ammonium or C _1-4 hydroxyalkyl ammonium, and v is an integer from 1 to 200. The method of claim 1 , wherein the fluoro-resin comprises a tetrafluoroethylene resin, a perfluoro alkoxy resin, an ethylene propylene fluoro resin, or a combination comprising at least one of the foregoing. The method of claim 1 , wherein the flame retardant comprises a halogen-containing compound of formula (200):

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

(wherein iv is an integer from 0 to 3) The method of claim 1 , wherein the flame retardant comprises a phosphoric acid ester which may have the formula (230):

wherein the average vi is an integer from 1 to 10; each R ^L is independently a phenyl group, a tolyl group, a xylyl group, an alkyl group, a cycloalkyl group, or an alkylaryl group; Each R ^M is independently a divalent group of the following formulas (231) to (234).

According to claim 1, further comprising the step of melt-kneading the thermoplastic resin before the fluoro-resin transfer step, wherein the melt viscosity of the thermoplastic resin measured with a capillary rheometer when melt-kneading at a shear rate of 240 sec ^{- 1} is 3,000 to 12,000 poise. The method of claim 1 , wherein the quencher composition is added at a pressure of at least 2 bar. A method of making a thermoplastic composition comprising:
melt polymerization of a carbonate compound and a dihydroxy compound in the presence of a catalyst composition to form a molten polycarbonate in a molten state, the catalyst composition comprising one or both of an alkali catalyst and a quaternary catalyst; the alkali catalyst comprises a source of one or both of alkali and alkaline earth ions; wherein the quaternary catalyst comprises one or both of a quaternary ammonium compound and a quaternary phosphonium compound; and
supplying a thermoplastic resin comprising an impact modifier and the molten polycarbonate in the molten state to an extruder;
after the feeding step, adding a quencher composition to the molten polycarbonate; and
mixing the quencher composition with the molten polycarbonate for at least 5 seconds, and then adding a reactive additive having reactive OH groups or reactive ester groups to the molten polycarbonate;
conveying a fluoro-resin, a flame retardant, or a combination comprising one or both of the above to the extruder; and
Extruding the thermoplastic resin to form a thermoplastic composition
How to include. 11. The modified poly of claim 10, wherein after final polymerization, a chain severing agent is added to the molten polycarbonate in the molten state to reduce the molecular weight of the molten polycarbonate to have a target molecular weight less than that of the molten polycarbonate. The method further comprising the step of forming a carbonate. 12. The method of any one of claims 1-11, wherein the quencher composition comprises polycarbonate powder. 12. The method according to any one of claims 1 to 11, wherein the quencher composition contains no carrier. 12. The method according to any one of claims 1 to 11, wherein the quencher composition comprises 1 to 10 ppm of a sulfonic acid ester based on 100 parts of the polycarbonate; and/or 1 to 10 ppm of phosphoric acid based on 100 parts of the polycarbonate. 12. The method of any one of claims 1-11, wherein said quencher composition comprises n-butyl tosylate. 12. The method according to any one of claims 1 to 11, wherein said thermoplastic composition comprises 0.01 to 5 parts by weight of said fluoro-resin, based on 100 parts by weight of said thermoplastic composition. 12. The method according to any one of claims 1 to 11, wherein said thermoplastic composition comprises 0.1 to 39 parts by weight of said flame retardant based on 100 parts by weight of said thermoplastic composition. 12. The method according to any one of claims 1 to 11, wherein the flame retardant comprises a phosphoric acid ester, wherein the phosphoric acid ester is present in an amount of 0.02 to 3 parts by weight based on 100 parts by weight of the thermoplastic composition. 12. The method of any one of claims 1 to 11, wherein the thermoplastic resin comprises polyorganosiloxane, polyalkylacrylate, polyolefin, polyamide, polyphenylene ether, polyoxymethylene, or a combination comprising at least one of the foregoing. A method that further comprises a. According to any one of claims 1 to 11, wherein the thermoplastic resin is polystyrene; polyisoprene; polychloroprene; polyacrylonitrile; polyethylene; polypropylene; poly(ethyl acrylate); poly(methyl acrylate); poly(methyl methacrylate); poly(butyl acrylate); polybutadiene; polymers derived from maleic anhydride, beta-unsaturated carboxylic acid, N-phenylmaleimide, N-methylmaleimide, N-cyclohexylmaleimide, glycidyl methacrylate, or combinations comprising at least one of the foregoing; The method further comprising a copolymer comprising two or more of the foregoing, or a combination comprising one or more of the foregoing.