CN1222541A - Polycarbonate Molding Composition - Google Patents

Abstract

Improvement of the droplet suppression performance of molded polycarbonate resin articles in the Underwriters Laboratories UL-94 test by selecting the particle size of the fluorinated polyolefin and the SAN component in the resin blend used to prepare the molded articles.

Description

Polycarbonate Molding Composition

This invention relates to thermoplastic blends of aromatic carbonate polymers and styrene-acrylonitrile copolymers.

Aromatic carbonate polymers, such as polycarbonate, have become major industrial thermoplastics due to their excellent physical properties. In addition, physical properties can sometimes be improved by blending with other thermoplastics, although the choice of type and amount of thermoplastic added is often critical.

For example, blends of polycarbonate and styrene-acrylonitrile copolymer (SAN) significantly improve flow properties for molding purposes; see, for example, US Pat. No. 5,106,907.

Polytetrafluoroethylene (PTFE) resins are also additives to polycarbonate molding compositions, especially if the composition is used in molded articles such as instrument housings requiring flame retardancy and drip retardancy; see for example US Patents 3,294,871 and 5,102,696. Typically, polytetrafluoroethylene (PTFE) is added to polycarbonate molding blends to prevent dripping of the molded article in the event of a fire. Certain applications require special ratings in the Underwriters Laboratory UL-94 test, like V-0 at 1.00mm. For example, this requirement is necessary in electrical applications such as enclosures and converters. If materials produce droplets in the UL-94 test, they cannot be used in these applications.

US Patent Application Serial No. 08/606,027, filed October 6, 1995, describes a polymer blend in which various derivatives of tetrafluoroethylene are polymer or copolymer encapsulated. These blends have been found to be useful as additives to increase the fire resistance of polymer compositions.

We have now found that tight control of the particle size of these encapsulated PTFE particles is the key to obtaining the required UL-94 properties in polycarbonate articles. Particle size has an important effect on the behavior of PTFE in flames.

Controlling the particle size of PTFE alone cannot completely determine the effect of anti-dropping agent. It is also necessary to control the average diameter of the agglomerates of encapsulated particles. Conventional shear, which occurs during the usual processing steps commonly used, stretches the polymer chains, producing the required anti-dripping properties.

Control of particle size and agglomerate size enables the production of products with the required anti-dripping properties when produced with conventional equipment.

We do not want to be bound by a theory of operation, but we hypothesize that during extrusion the encapsulated PTFE agglomerates are broken up and the PTFE particles are stretched such that a thermodynamically unfavorable situation for the PTFE molecules occurs. When burning, the material relaxes into an optimal configuration and shrinks away from the flame. A feature of this approach is the control of agglomerate and particle size in such a way that shear stress in the extruder can affect the molecular structure. If the pellets are too small, the forces in the extruder cannot stretch the chains. When the agglomerate and particle sizes are within limits, the molecules are stretched as described above and the PTFE acts on fire.

The present invention includes thermoplastic molding compositions comprising:

Aromatic thermoplastic polycarbonate resins;

Particles of fluorinated polyolefin resin in drip-inhibiting proportions wholly or partially encapsulated by thermoplastic copolymer into agglomerates, the average particle diameter of said fluorinated polyolefin resin is about 0.1 to 4 μm; said The average diameter of the agglomerates is from 30 to 70 μm, preferably from 35 to 65 μm and more preferably from 40 to 65 μm.

The molding compositions of the present invention are useful for molded articles having improved properties in the UL-94 drop test.

Aromatic carbonate polymers useful in the compositions of the present invention include polycarbonates and copolycarbonates. Polycarbonates and copolycarbonates are well known resins and are commercially available. Methods of preparing polycarbonates by interfacial polymerization are also well known; see, for example, the detailed descriptions provided in U.S. Patent Nos. 3,028,365; 3,334,154; 3,275,601; 3,915,926; The production of polycarbonates by the melt process is likewise known as a plant exists in Japan and another plant is being built in Spain.

Typically, the method of interfacial polymerization involves the reaction of dihydric phenols with carbonyl halides (precursors of carbonates). The method of melt polymerization involves the reaction of dihydric phenols with diaryl carbonates.

Although the reaction conditions of the preparation process may vary, some preferred interfacial methods generally involve dissolving or dispersing the diphenol reactant in caustic, adding the resulting mixture to a suitable water-immiscible solvent medium, and The reactants are contacted with a carbonate precursor such as phosgene in the presence of a catalyst and under controlled pH conditions. The most commonly used water immiscible solvents include methylene chloride, 1,2-dichloroethane, chlorobenzene, toluene, etc.

The catalyst used accelerates the rate of polymerization of the dihydric phenol reactant with the carbonate precursor. Representative catalysts include, but are not limited to, tertiary amines such as triethylamine, quaternary phosphonium compounds, quaternary ammonium compounds, and the like. A preferred method of preparing polycarbonate resins involves phosgenation. The temperature at which the phosgenation reaction is carried out can vary from below 0°C to above 100°C. The phosgenation reaction is preferably carried out at room temperature (25°C) to 50°C. Since the reaction is exothermic, the rate of phosgene addition can be used to control the reaction temperature. The amount of phosgene required generally depends on the amount of dihydric phenol.

其中A为含1至约15个碳原子的二价烃基；含1至约15个碳原子的取代二价烃基且取代基如卤素；-S-；-SS-；-S(O)-；-S(O)₂-；-O-或-C-；每个X独立地选自氢、卤素和单价烃基如1至约8个碳原子的烷基、6-18个碳原子的芳基、7至约14个碳原子的芳烷基、7至约14个碳原子的烷芳基、1至约8个碳原子的烷氧基或6至18个碳原子的芳氧基；m为0或1,n为0至4的整数。The dihydric phenols used are known, the reactive groups being two phenolic hydroxyl groups. Some dihydric phenols are represented by the following general formula:

wherein A is a divalent hydrocarbon group containing 1 to about 15 carbon atoms; a substituted divalent hydrocarbon group containing 1 to about 15 carbon atoms and substituents such as halogen; -S-; -SS-; -S(O)-; -S(O) ₂ -; -O- or -C-; each X is independently selected from hydrogen, halogen, and monovalent hydrocarbon groups such as alkyl groups of 1 to about 8 carbon atoms, aryl groups of 6-18 carbon atoms , an aralkyl group of 7 to about 14 carbon atoms, an alkaryl group of 7 to about 14 carbon atoms, an alkoxy group of 1 to about 8 carbon atoms, or an aryloxy group of 6 to 18 carbon atoms; m is 0 or 1, n is an integer from 0 to 4.

Some typical examples of dihydric phenols used are diphenols such as bis(4-hydroxy-phenyl)methane, 2,2-bis(4-hydroxyphenyl)propane (also known as bisphenol A), 2,2-bis( 4-Hydroxy-3,5-dibromophenyl)propane; dihydric phenol ethers such as bis(4-hydroxyphenyl)ether, bis(3,5-dichloro-4-hydroxyphenyl)ether; Benzene such as p,p'-dihydroxybiphenyl, 3,3'-dichloro-4,4'-dihydroxybiphenyl; dihydroxyaryl sulfones such as bis(4-hydroxyphenyl)sulfone, bis(3, 5-Dimethyl-4-hydroxyphenyl) sulfone, dihydroxybenzenes such as resorcinol, hydroquinone, halogen and alkyl substituted dihydroxybenzenes such as 1,4-dihydroxy-2,5-di Chlorobenzene, 1,4-dihydroxy-3-methylbenzene; and dihydroxydiphenylsulfides and sulfoxides such as bis(4-hydroxyphenyl)sulfide, bis(4-hydroxyphenyl)sulfoxide and Bis(3,5-dibromo-4-hydroxyphenyl)sulfoxide. A variety of more dihydric phenols exist and are disclosed in US Patent Nos. 2,999,835; 3,028,365 and 3,153,008; all incorporated herein by reference. Of course, two or more different dihydric phenols or combinations of dihydric phenols and diols can also be used.

The carbonate precursor may be a carbonyl halide, a diaryl carbonate or a bishaloformate. Carbonyl halides include carbonyl bromide, carbonyl chloride and mixtures thereof. Bishaloformates include bishaloformates of dihydric phenols such as 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3,5-dichlorophenyl ) bishaloformates of propane, hydroquinone, etc., or bishaloformates of diols such as ethylene glycol, etc. While all of the aforementioned carbonate precursors are useful, phosgene, also known as phosgene, is preferred for the interfacial approach. Diphenyl carbonate is preferably used in the melt process.

High molecular weight thermoplastic randomly branched polycarbonates are also within the scope of this invention. These randomly branched polycarbonates are prepared by co-reacting polyfunctional organic compounds with the aforementioned dihydric phenols and carbonate precursors. Polyfunctional organic compounds useful for making branched polycarbonates are set forth in US Patent Nos. 3,635,895 and 4,001,184, incorporated herein by reference. These polyfunctional compounds are generally aromatic and contain at least three functional groups which are carboxyl, carboxylic anhydride, phenol, haloformyl or mixtures thereof. Some non-limiting examples of these polyfunctional aromatic compounds include 1,1,1-tris(4-hydroxyphenyl)ethane, trimellitic anhydride, trimellitic acid, trimellitic acid trichloride, 4-chloroformyl o Phthalic anhydride, pyromellitic acid, pyromellitic dianhydride, mellitic hexacarboxylic acid, mellitic anhydride, trimesic acid, benzophenone tetracarboxylic acid, benzophenone tetracarboxylic anhydride, etc. Preferred polyfunctional aromatic compounds are 1,1,1-tris(4-hydroxyphenyl)ethane, trimellitic anhydride or trimellitic acid or their haloformyl derivatives. Blends of linear polycarbonates and branched polycarbonates are also included herein.

The polycarbonate resin used in the method of the present invention can have a lower weight average molecular weight or a higher weight average molecular weight ( _Mw ). Lower _Mw resins are generally end-capped polycarbonates.

So-called "capped" polycarbonates are prepared by the process described above for the production of aromatic carbonate polymers, wherein the reaction mixture includes small amounts of molecular weight regulators or chain terminators to provide terminal or terminal groups in the carbonate polymers. , thereby controlling the molecular weight of polycarbonate.

Molecular weight modifiers, ie chain terminators, are typically added to the reactants before or during contacting the reactants with the carbonate precursor. Useful molecular weight modifiers include, but are not limited to, monohydric phenols such as phenol, chroman-I, p-tert-butylphenol, and the like. The preferred polycarbonate component in the compositions of the present invention is p-cumylphenol capped.

Other compounds are also known as chain terminators for carbonate polymers. For example, U.S. Patent 3,085,992 discloses alkanolamines as chain terminators; U.S. Patent 3,399,172 teaches imides as chain terminators; U.S. Patent 3,275,601 discloses aniline and Methylaniline; US Patent 4,011,184 discloses primary and secondary amines as molecular weight regulators for polycarbonates. In addition, US Patent No. 3,028,365 discloses that aromatic amines and other monofunctional compounds can be used to control or adjust the molecular weight of polycarbonates to form aryl carbamate end groups. Aromatic polycarbonates containing urethane end groups are disclosed in US Patent 4,111,910. These polycarbonates are prepared with terminating amounts of ammonia, ammonium compounds, cycloalkyl, aliphatic or aralkyl primary amines and cycloalkyl, alkyl or aralkyl secondary amines.

其中D为聚合反应中使用的二羟酚的二价芳基。羧酸酯单元的结构式例如：Aromatic carbonate polymers suitable for use in the compositions of the present invention include polyester-carbonates, also known as copolyester-polycarbonates, i.e. containing, in addition to cyclic polycarbonate chain units of formula (IIa), Resins with repeating or cyclic carboxylate units. The structural formula of the polycarbonate chain unit is:

where D is the divalent aryl group of the dihydric phenol used in the polymerization reaction. The structural formula of the carboxylate unit is for example:

-[-OC(O)-R ¹ -C(O)-OD-]- (IIb) wherein D is as defined above and R ¹ is as defined below.

Copolyester-polycarbonate resins can also be prepared by interfacial polymerization techniques, which are well known to those skilled in the art; see, for example, US Patents 3,169,121 and 4,487,896.

Typically copolyester-polycarbonate resins are prepared as described above for polycarbonate homopolymers but by adding the dicarboxylic acid (ester precursor) in a water-immiscible solvent.

In general, any of the dicarboxylic acids commonly used in the preparation of linear polyesters can be utilized to prepare the copolycarbonate resins. In general, usable dicarboxylic acids include aliphatic dicarboxylic acids, aromatic dicarboxylic acids, and aliphatic-aromatic dicarboxylic acids. These acids are well known and disclosed, for example, in US Patent No. 3,169,121, which is incorporated herein by reference. Representatives of such aromatic dicarboxylic acids are represented by the following general formula:

HOOC-R ¹ -COOH (Ⅲ) where R ¹ represents aryl such as phenylene, naphthylene, biphenylene, substituted phenylene, etc.; divalent aliphatic-aromatic hydrocarbon groups such as arane or alkaryl ; or two or more aromatic groups linked by a non-aromatic bond of the formula:

其中j为含0至4(包括首尾数)的正整数；每一R³独立选自烷基，优选低级烷基(1至约6个碳原子)。-E-wherein E is a divalent alkylene or alkylidene group (alkylene RCH=). E can also be composed of two or more alkylene or alkylidene groups, non-alkylene or alkylidene groups such as aromatic bonds, tertiary hydrogen bonds, ether bonds, carbonyl bonds, silicon-containing bonds, or sulfur-containing bonds such as sulfur Ether, sulfoxide, sulfone, etc. are connected. In addition, E can be a cycloaliphatic group (such as cyclopentyl, cyclohexyl) containing five to seven (inclusive) carbon atoms, or a cycloalkylidene group containing five to seven (inclusive) carbon atoms, Such as cyclohexa fork. E can also be a carbon-free sulfur-containing bond, such as thioether, sulfoxide, or sulfone; an ether bond; a carbonyl group; a direct bond; a tertiary nitrogen group; Other groups that E can represent will be known to those skilled in the art. For the purposes of the present invention, aromatic dicarboxylic acids are preferred. Thus, in the preferred aromatic difunctional carboxylic acids of formula (III), ^R1 is aryl such as phenylene, biphenylene, naphthylene, or substituted phenylene. Some non-limiting examples of aromatic dicarboxylic acids useful in preparing the poly(ester-carbonate) or polyarylate resins of the present invention include phthalic acid, isophthalic acid, terephthalic acid, homophthalic dicarboxylic acid, acid, ortho, meta, terephthalic acid, and polynuclear aromatic acids such as diphenyl dicarboxylic acid, and isomeric naphthalene dicarboxylic acid. The aromatic compound may be substituted with a Y group. Y can be an inorganic atom such as chlorine, bromine, fluorine, etc.; an organic group such as a nitro group; an organic group such as an alkyl group; or an oxygen-containing group such as an alkoxy group. is inert and unaffected by it. Particularly useful aromatic dicarboxylic acids are represented by the general formula:

Wherein j is a positive integer containing 0 to 4 (inclusive); each R ³ is independently selected from alkyl, preferably lower alkyl (1 to about 6 carbon atoms).

Mixtures of these dicarboxylic acids may also be used. Accordingly, the term dicarboxylic acid as used herein should be understood to include mixtures of two or more dicarboxylic acids.

Most preferred aromatic dicarboxylic acids are isophthalic acid, terephthalic acid, and mixtures thereof. Particularly useful difunctional carboxylic acids include mixtures of isophthalic acid and terephthalic acid wherein the weight ratio of terephthalic acid to isophthalic acid ranges from about 10:1 to about 0.2:9.8.

It is possible and sometimes even preferred to use reactive derivatives of said acids rather than the dicarboxylic acids themselves. Illustrative of these reactive derivatives are acid halides. Preferred acid halides are diacid chlorides and diacid bromides. So, for example, instead of using isophthalic acid, terephthalic acid or mixtures thereof, it is possible to use isophthaloyl dichloride, terephthaloyl dichloride and mixtures thereof.

The proportions of the reactants used to prepare the copolycarbonate resin will vary according to the intended use of the blend of the invention comprising the product resin. Useful ratios are known to those skilled in the art, as described in the US patents referred to above. Typically, the amount of ester linkages can be from about 5 to about 90 mole percent, relative to carbonate linkages. For example, complete reaction of 5 moles of bisphenol A with 4 moles of isophthaloyl chloride and 1 mole of phosgene will yield a copolycarbonate with 80 mole percent ester linkages.

Preferred polycarbonates for use in the present invention are those derived from bisphenol A and phosgene having an intrinsic viscosity of from about 0.3 to about 1.5 dl/g and a porosity of from 0.00 to 2.0 ml as measured in methylene chloride at 25°C /gm range.

The fluorinated polyolefins useful in the present invention and their method of preparation are described inter alia in Billmeyer, Fred W., Jr., Textbook of Polymer Science, Interscience Publishers, New York, NY, 1966, p. 425 -427 pages; Monermoso, J.C., Rubber Chem.Tech., 34, 1521 (1961); Rudner, M.A., Fluorocarbons, Reinhold Publishing Corp., New York , New York, and in US Patent 4,663,991, incorporated herein by reference.

Preferred fluorinated polyolefins for use in the methods and compositions of the present invention are polytetrafluoroethylene (PTFE) resins, preferably in fibrillar form.

PTFE obtained from polymerization is a finely divided powder or fluff. When the finely divided, untreated polytetrafluoroethylene resin material with an average particle size of 0.1 to 0.2 microns, such as J.F.Lontz and W.B.Happoldt, Jr. in "Industrial and Engineering Chemistry" (Ind.andEng.Chem.) No. 44 Vol. 1800 (1952), the illustration of Figures 1 and 2 in the article "Teflon" Tetrafluoroethylene Resin Disperson, when sheared by friction in the hand, the particles tend to Substances that stick to each other and form cohesion. If the material is drawn and examined with a microscope at 50-100X, it shows fibers of various sizes. Examination with an electron microscope indicates that these fibers are bundles of smaller fibers, many of which are fibers of elementary particles bound by very small fibrils having a diameter of one-quarter to one-tenth the diameter of the particle or less composition. Polytetrafluoroethylene which, when rubbed against each other by mechanical shear, causes the particles to stick and draw into ultrafine fibrils is preferred for use in the practice of the present invention.

The effective amount of the fluoropolymer for suppressing dripping incorporated into the polycarbonate resin by the method of the present invention is from about 0.01 to about 5 parts by weight, preferably from about 0.015 to about 3 parts by weight, per 100 parts by weight of polycarbonate , more preferably from about 0.02 to about 2 parts, and still more preferably from about 0.02 to about 1 part.

The fluoropolymer is preferably used in its aqueous dispersion, the particles having a preferred average particle size (diameter) of 0.05 to 4 microns, more preferably 0.08 to 2 microns, and still more preferably 0.1 to 1 microns. The aqueous dispersion of fluoropolymer mixed with the aqueous dispersion of thermoplastic copolymer is spray dried, particles of fluoropolymer are usually encapsulated by the copolymer to form agglomerates.

According to the method of the present invention, the two components, namely the polycarbonate resin and the agglomerates of encapsulated fluoropolymer particles, are mixed together at room temperature and at a prescribed rate using conventional mixing equipment, such as the above-mentioned prior art device. Typically, the mixture of components can be blended by mixing in conventional mixing rolls, dough mixers, Banbury mixers, and the like. Representative of a known and useful apparatus for coating particulate material with a homogeneous liquid is described in U.S. Patent 3,716,020 (De Wit et al.), issued February 18, 1973 and incorporated herein by reference.

Styrene-acrylonitrile (SAN) copolymer, as the preferred polymer for encapsulating PTFE particles in any of the well-known copolymers that can be used for this purpose, can be used from about 68% to about 80%, preferably from about 70% to about 78%. It is prepared by copolymerizing styrene and from about 20% to about 32%, preferably from about 22% to about 30%, of acrylonitrile. The molecular weight of the SAN can vary over a wide range, generally from about 30,000 to about 600,000, but is not critical.

SAN is readily produced by known methods such as bulk, solution, suspension or emulsion polymerization.

Within the broader scope of the invention, the encapsulating copolymer component of an agglomerate of encapsulated PTFE particles may be present in a proportion of from about 40% to about 50% by weight of the agglomerate, at which level it provides good Processability, significant shear thinning of PTFE particles. More preferably the copolymer component is from about 45 to about 49% by weight, and even more preferably it does not exceed 49% by weight.

The particle size (average) of the SAN particles is advantageously in the range of 35 to 70 μm, preferably in the range of 40 to 65 μm.

The blends of the invention can be modified by the addition of additives known in the art of plastics compounding. Such additives may include fillers such as clay or talc, reinforcing agents such as glass fibers, impact modifiers, other resins, plasticizers, flow promoters and other processing aids, stabilizers, colorants, mold release agents, Burning agent, UV shielding agent, etc.

Production of the compositions of the present invention can be achieved by blending the components using any blending method known for blending thermoplastics, such as in a kneader such as a Banbury mixer, Weiner-Friedler blending machine, or in an extruder, or by blending by the mill method, all of which will provide the proper shear to achieve the desired flame retardant properties of the composition.

The compounded compositions of the present invention can be extruded and, if desired, chopped into pellets, pellets, etc. using standard techniques. Further processing of the compounded composition can be achieved by conventional molding or extrusion methods well known in the art.

The present invention will be better understood by reference to the following examples, which are provided by way of illustration rather than limitation, and illustrating the best mode contemplated for carrying out the invention.

The reported Insurance Laboratories UL-94 tests are as follows:

The resin was injection molded at about 300°C into bars of about 12.7 cm x 1.27 cm x 3.175 thickness. These test strips were used to carry out the test procedure stipulated in Underwriters' Laboratories, Inc., Bulletin UL-94, Buring Test for Classified Materials (Underwriters' Laboratories, Inc., Bulletin UL-94, Buring Test for Classified Materials). According to this test procedure, the tested material is rated as V-0, V-I or V-II based on the results of 5 samples. The standard for each V (vertical) classification according to UL-94 is briefly as follows: "V-0": After removing the ignition flame, the average time of flame and/or glow does not exceed 10 seconds, and none of the 5 samples drips Pyrotechnic particles that ignite absorbent cotton. The total flame/glow time after ignition of 5 samples does not exceed 50 seconds.

Examples 1-6

Molding compositions were produced by blending the components indicated in the table below in a Leistriz ZSK 36 extruder at 270-300°C and 300rpm. The blended and extruded materials were then pelletized, dried and injection molded at about 240°C to prepare test specimens. Physical property measurements were performed on injection molded samples at 1.0 mm using Underwriters Laboratories UL-94 test method.

Example 1 is not part of the invention but is provided for comparison purposes. The formulations and results are given in the table below. The polycarbonate resin was ^Lexan® 920 grade polycarbonate resin (General Electric Co. Pittsfield, Mass.) (Examples 1 and 2) or ^Lexan® 940 grade polycarbonate resin (Examples 3-6) of blends. The copolymer used to form agglomerates of PTFE particles is styrene acrylonitrile (SAN). These agglomerates were prepared by standard methods using PTFE from the manufacturers indicated in the table to produce agglomerates of the average size and weight ratio of PTFE/SAN as specified in the table.

All US patents and patent applications provided herein are expressly incorporated herein by reference. surface

PTFE Emulsion Source X Average Attached SAN M _w M _w /M _n PTFE/SAN Ratio Passed UL-94

and Particle Size Polymer Size (1.0mm)

(μm) (yes/no)

1. Hoechst: Uncontrolled 24 330,000 2.77 50.4/49.5 No

2. ICI: 0.2μ

Fluon GDI 64 137,000 2.51 51.7/48.3 Yes

3. ICIP:0.2

Fluon GDI 42 332,000 2.61 52.6/47.4 Yes

4. Hoechst: 0.1μ 41 359,000 1.99 54.7/45.3 Yes

5. Ausimont:0.24μ 40 326,000 2.61 51.2/48.8 Yes

6. Dupont:0.3μ 45 341,000 3.36 52.8/47.2 Yes

Claims (8)

1. thermoplastic composition, said composition comprises:

The thermoplastic aromatic polycarbonate resin;

Become the fluoropolymer resin particle of the inhibition molten drop ratio of agglomerate by the thermoplastic copolymer encapsulation to small part, described fluorinated polyolefin resin particle has the average particulate diameter in about 0.1 to 4 mu m range; Described agglomerate has the mean diameter of 30 to 70 μ m.

2. the composition of claim 1, wherein fluoropolymer is a fluorinated polyethylene.

3. the composition of claim 2, wherein fluorinated polyethylene is a tetrafluoroethylene.

4. the composition of claim 1, wherein the fluoropolymer consumption is for about 0.01 to about 5 weight parts in per 100 weight part polycarbonates.

5. the composition of claim 1, wherein thermoplastic copolymer is a styrene acrylonitrile copolymer.

6. the composition of claim 1, wherein thermoplastic copolymer is about 40 to about 50% of an agglomerate weight.

7. the composition of claim 1, wherein polycarbonate prepares with interfacial process.

8. the composition of claim 1, wherein polycarbonate prepares with melting method.