Methods of modifying flame retardancy of polycarbonates

Abstract

A method including contacting one or more flame retardancy modifiers and a polycarbonate composition comprising one or more reactive polycarbonates having free hydroxyl and / or carboxyl groups in a polycarbonate solvent to form a modified polycarbonate that has flame resistance. The flame retardancy modifiers and the polycarbonate composition may be contacted in a polycarbonate solvent.

Description

METHODS OF MODIFYING FLAME RETARDANCY OF POLYCARBONATESFIELD[1] Disclosed are methods of chemically modifying polycarbonates so that the polycarbonates have improved flame retardancy.BACKGROUND[2] Polycarbonate and copolymers containing carbonate units are utilized in a variety of molded structures. Polycarbonates and copolymers containing carbonate units form molded structures that are rigid. The molded structures may be used for a variety of uses, including cases for electronics, automobile parts, medical devices, home appliances, loud-speakers, home furnishings and the like. Often, these products have certain target flame retardancy specifications that are met through the use of blended flame retardants. However, some applications of polycarbonate do not allow for these blended flame retardants.[3] After extended use, some of these products are disposed of due to being damaged or replaced by newer products. In some instances, the polycarbonate used with these products has degraded such that it is no longer re-useable in new products with the same quality as virgin polycarbonate.[4] Accordingly, what is needed are techniques to modify the flame retardancy of polycarbonates. What is needed are techniques to integrate modification of flame retardancy into techniques of recovering post-consumer polycarbonates.SUMMARY[5] The present application discloses a method including contacting one or more flame retardancy modifiers and a polycarbonate composition comprising one or more reactive polycarbonates having free hydroxyl and / or carboxyl groups in a polycarbonate solvent to form a modified polycarbonate that has flame resistance.[6] The modified polycarbonate may exhibit a flame resistance of V-1 or V-0 at a thickness of 1.6 mm or 1.0 mm, according to UL-94 vertical test. The modified polycarbonate may have the same flame resistance as or greater flame resistance than the polycarbonate composition. The method may include a step of before contacting the one of more flame retardancy modifiers and the polycarbonate composition, contacting the polycarbonate composition and one or more linking compounds to form the reactive polycarbonate. Themethod may include a step of before contacting the one of more flame retardancy modifiers and the polycarbonate composition, modifying a reactive group of the reactive polycarbonate from a first reactive group to a second reactive group, wherein the first reactive group comprises a hydroxyl and / or carboxyl group. The method may include a step of after contacting the one of more flame retardancy modifiers and the polycarbonate composition, contacting the modified polycarbonate and one or more end capping, chain extending, or branching agents to form an end capped, extended, and / or branched polycarbonate. The method may include a step of hydroxylating a precursor composition comprising one or more waste or virgin polycarbonates to form the polycarbonate composition comprising the one or more reactive polycarbonates that comprise a hydroxyl or carboxyl group. The step of hydroxylating the precursor composition may include oxidizing the one or more waste or virgin polycarbonates to form the one or more reactive polycarbonates. The step of hydroxylating the precursor composition may include exposing the one or more waste or virgin polycarbonates to ultraviolet light such that the one or more reactive polycarbonates are formed. The step of hydroxylating the precursor composition may include conducting hydrolysis on the one or more waste or virgin polycarbonates to form the one or more reactive polycarbonates. The one or more flame retardancy modifiers may include one or more functional groups configured to end cap, chain extend, branch, and / or crosslink with the hydroxyl group, carboxyl group, or both on the one or more hydroxylated polycarbonates. The one or more flame retardancy modifiers may include one or more functional groups configured to reactive with one or more operative groups of the linking compound. The linking compound may include one or more operative groups configured to react with the reactive group of the reactive polycarbonate and / or with the flame retardancy modifier. The one or more flame retardancy modifiers may include two or more functional groups that are configured to chain extend and / or branch with the hydroxyl group, carboxyl group, or both on the one or more hydroxylated polycarbonates. The one or more reactive, operative, or functional groups may include one or more nucleophilic and / or electrophilic groups. The at least one of the one or more reactive groups of the reactive polycarbonate may be different than at least one of the one or more operative groups of the linking compound. The one or more operative groups of the linking compound may be different than at least one of the one or more functional groups of the one or more flame retardancy modifiers. The one or more nucleophilic groups may include carboxylic acids, unsaturated aromatic acids, sulfonic acids, phosphorous based acids, boronic acids, or any combination thereof. The one or more electrophilic groups may include one or more of a epoxide, anhydride, imide, ester, acyl halide, acyl nitrile, aldehyde, ketone, isocyanate, isothiocyanate, phosphorous halides, silyl halide, orany combination thereof. The polycarbonate composition may include greater than 0 weight percent of waste polycarbonate, based on the total weight of the polycarbonate composition. The polycarbonate composition may include greater than 50 weight percent waste polycarbonate, based on the total weight of the polycarbonate composition. The method may include separating the modified polycarbonate and the polycarbonate solvent to yield the modified polycarbonate in a solid form. The method may include contacting the modified polycarbonate in the solid form with one or more flame retardants to form a product composition having a flame retardancy that is greater than a flame retardancy of the modified polycarbonate. The one or more flame retardants may be detached from and / or blended with the modified polycarbonate in the product composition. The modified polycarbonate may be free of flame retardants. The polycarbonate solvent may be configured to dissolve the one or more reactive, modified, virgin, and / or waste polycarbonates. The polycarbonate solvent may include one or more of methylene chloride, chloroform, tetra hydrofuran (THF), 2-methyl tetrahydrofuran, N- methyl-2-pyrrolidone, or a combination thereof. The modified polycarbonate may have a weight or number average molecular weight that is at least 5 percent greater than a weight or number average molecular weight of the hydroxylated polycarbonate. Before contacting the flame retardancy modifier and the polycarbonate composition, he polycarbonate composition may have greater than 0 percent to about 10 weight percent hydroxyl or carboxyl groups, based on the total weight of the polycarbonate composition.[7] Disclosed are compositions which include one or more polycarbonate backbones comprising residues of one or more polycarbonate oligomers or polymers; and one or more residues of a flame retardancy modifier each connected with the one or more polycarbonate oligomers or polymers at a residue of a hydroxyl or carboxyl group, the one or more flame retardancy modifiers comprising a residue of a phosphorous compound including phosphoric compounds, phosphonic compounds, and phosphinic compounds, a benzoxazine, a cyanophenyl compound, a benzonitrile, a silyl compound, a siloxane compound, or any combination thereof, or any other structure that imparts flame retardancy.[8] The composition may include a linking compound configured to end cap, chain extend, or branch the one or more the flame retardancy modifiers and the one or more polycarbonate oligomers or polymers. The composition may include one or more end capping, chain extending, or branching agents connected with the polycarbonate backbone and not contain one or more of the flame retardancy modifiers. The one or more residues of the flame retardancy modifier may connect with at least two different polycarbonate oligomers or polymers. The composition may include one or more flame retardants that are detached fromand blended with the combination of the one or more polycarbonate oligomers or polymers and the one or more flame retardancy modifiers. The one or more flame retardants may be configured to improve the flame retardancy of the composition. The composition may be essentially free of flame retardants. The composition may have a flame retardancy of V-0 or V-1 or more at a thickness of 1 .6 mm or 1 .0 mm, according to UL-94 vertical test. The one or more flame retardancy modifiers may be configured to end cap, chain extend, branch, and / or crosslink the one or more polycarbonate oligomers or polymers. The one or more polycarbonate oligomers or polymers may include residues of virgin and / or waste polycarbonate. The one or more polycarbonate oligomers or polymers may include at least 10 percent or more waste polycarbonate.[9] The present techniques allow for modification of a reactive polycarbonate to form modified polycarbonates that have desirable flame retardancy. The flame retardancy modifiers provide a dual advantage of removing hydroxyl and / or carboxyl groups on the reactive polycarbonates, which can be waste polycarbonates having hydroxyl and / or carboxyl groups formed from natural degradation, and imparting flame retardancy, and is some cases without blending flame retardants into the composition. Additionally, the flame retardancy modifiers can be used, alone or in combination with linking compounds or functional compounds, to end cap, chain extend, branch, and / or crosslink the polycarbonate to form modified polycarbonates with desirable molecular weights and imparted flame resistance.DETAILED DESCRIPTION

[0010] The present techniques allow for modification of the reactive groups of a reactive polycarbonate to form modified polycarbonates that have flame retardancy. By reacting the flame retardancy modifiers with one or more carboxyl and / or hydroxyl groups, the flame retardancy modifiers provide a dual advantage or removing hydroxyl and / or carboxyl groups on the reactive polycarbonates and imparting flame retardancy, without blending flame retardants into the composition.

[0011] Modified polycarbonates refer to polycarbonates that include residues of flame resistance modifiers that impart flame resistance into the polymer. Reactive polycarbonates include at least one reactive group as described herein. The modified or reactive polycarbonates may be comprised of virgin polycarbonate, waste polycarbonate, or any combination thereof. Modified polycarbonate as described here include at least a residue of a flame retardancy modifier. The term repaired refers to adjusting the molecular weight of the waste or reactive polycarbonate to a modified polycarbonate with a different molecular weight orwith a reduced number of carboxyl and / or hydroxyl end groups. A recovery solution includes at least polycarbonate solvent and at least one polycarbonate compound. Waste polycarbonate refers to polycarbonate located in waste feedstocks. Modified polycarbonate refers to polycarbonate recovered from waste feedstocks and contacted with one or more functional groups as described herein. Virgin polycarbonate refers to polycarbonate made by one or more techniques that react one or more diols and carbonic acids to form polycarbonate. Functional compounds as used herein end-cap, chain extend, or branch one or more polycarbonate chains without binding to or with the one or more linking compounds and / or flame retardancy modifiers. Linking compound as used herein end cap, chain extend, and / or branch the polycarbonate chains in combination with the flame retardancy modifier.

[0012] Waste feedstocks include at least some waste polycarbonate. Waste feedstocks include waste polycarbonate and at least one other waste non-polycarbonate compound, such as a metal compound. Waste feedstocks contain from about 10 weight percent to less than 100 weight percent waste polycarbonate. Non-polycarbonate compounds include one or more of metals, non-polycarbonate polymers, battery electrolytes, small organic compounds, oligomeric compounds, or any combination thereof. Non-polycarbonate compounds may include one or more compounds commonly mixed or blended with polycarbonate, including non-polycarbonate containing polymer, (such as styrenics, polystyrene, styrene acrylonitrile, acrylonitrile butadiene, butadiene elastomers, high impact polystyrene, polymethylmethacrylate), flame retardants, UV stabilizers, fillers, antioxidants, other additives, other polymers, or any other non-polycarbonate compound. Examples of waste feedstocks may include any non-polycarbonate material in any waste containing polycarbonates, such as cases for electronics, plastic waste, toys, packages, conveyors, trays, automobile parts, medical devices, home appliances, loud-speakers, home furnishings, any other electronic device including non-polycarbonate polymers, metals, printed circuit boards, batteries, magnets, or any combination thereof. A portion of the non- polycarbonate compounds in the waste feedstock may be removed through one or more pretreatment steps before contacting the waste feedstock and a polycarbonate solvent so some of the non-polycarbonate compounds are not undesirably dissolved in the polycarbonate solvent.

[0013] One or more as used herein means that at least one, or more than one, of the recited components may be used as disclosed. Hydrocarbyl as used herein refers to a group containing one or more carbon atom backbones and hydrogen atoms, which may optionally contain one or more heteroatoms. Where the hydrocarbyl group contains heteroatoms, the heteroatoms may form one or more functional groups well known to one skilled in the art. Hydrocarbyl groups maycontain cycloaliphatic, aliphatic, aromatic or any combination of such segments. The aliphatic segments can be straight or branched. The aliphatic and cycloaliphatic segments may include one or more double and / or triple bonds. Included hydrocarbyl groups are alkyl, alkenyl, alkynyl, aryl, cycloalkyl, cycloalkenyl, alkaryl and aralkyl groups. Cycloaliphatic groups may contain both cyclic portions and noncyclic portions. Hydrocarbylene means a hydrocarbyl group or any of the described subsets having more than one valence, such as alkylene, alkenylene, alkynylene, arylene, cycloalkylene, cycloalkenylene, alkarylene and aralkylene. Valence as used herein means a covalent bond between a hydrocarbyl or hydrocarbylene group and another group such as a carbonyl, oxygen, nitrogen or sulfur containing group or atom, or the referenced base compound. As used herein percent by weight or parts by weight refer to, or are based on, the weight of the compositions unless otherwise specified. Tg is the temperature or temperature range at which a polymeric material shows an abrupt change in its physical properties, including, for example, mechanical strength. Tg can be determined by differential scanning calorimetry (DSC). Post-industrial as used herein refers to a source of a material that originates during the manufacture of a good or product. Post-consumer as used herein refers to a source of material that originates after the end consumer has used the material in a consumer good or product.

[0014] Hydroxyl and / or carboxyl containing compounds as used herein means a compound including at least one hydroxyl or carboxyl group bound to a carbon atom and having a molecular weight of about 500 g / mol or less, about 2000 g / mol or less, or about 3000 g / mol or less. The hydroxyl and / or carboxyl containing compound may be a residue of polycarbonate and have a molecular weight as described herein. Polycarbonate oligomers, as described herein, may be distinguished from hydroxyl and / or carboxyl containing compounds by having a number or weight average molecular weight of 1000 g / mol or more, 3000 g / mol or more, or 5000 g / mol or more. The hydroxyl and / or carboxyl containing compound may include more than one repeating unit or derivative thereof that is a residue of polycarbonate. A repeating unit of the hydroxyl and / or carboxyl containing compound may be those repeating units described in relation to polycarbonates discussed herein that is terminated by at least one hydroxyl or carboxyl group. The hydroxyl and / or carboxyl containing compound may include one or more bisphenol-A compounds or derivatives thereof. The hydroxyl and / or carboxyl containing compound may be separated from the recovery solution by any technique described herein such as by contacting a solvent with the recovery solution to extract the hydroxyl and / or carboxyl containing compound, using an absorbent or adsorbent to remove the hydroxyl and / or carboxyl containing compound, an additive that precipitates the hydroxyl and / or carboxylcontaining compound, applying a charge to the compound to remove the hydroxyl and / or carboxyl containing compound, filtering the hydroxyl and / or carboxyl containing compound, or any other separation technique described herein. After one or more separation steps of the recovery solution to remove the hydroxyl and / or carboxyl containing compounds, the polycarbonate solution may be essentially free of hydroxyl and / or carboxyl containing compounds. Essentially free of hydroxyl and / or carboxyl containing compounds may be about 150 ppm or less of the Hydroxyl and / or carboxyl containing compounds, about 100 ppm or less, or about 50 ppm or less. Essentially free of hydroxyl and / or carboxyl containing compounds may be about 25 ppm or less, 10 ppm or less, or an amount that is not detectable using conventionally known methods. Hydroxyl and / or carboxyl containing compounds may be reduced in the recovery solutions and / or polymeric compositions described herein by a weight percent using functional compounds, linking compounds, flame retardancy modifiers, and / or separation techniques to remove hydroxyl and / or carboxyl groups. Hydroxyl and / or carboxyl containing compounds may be reduced by about 10 percent or more, about 30 percent or more, or about 50 percent or more. Hydroxyl and / or carboxyl containing compounds may be reduced by about 70 percent or more, about 90 percent or more, or about 95 percent or more. Hydroxyl and / or carboxyl containing compounds may be determined by any technique known to the skilled artisan. As an example, free phenolic species (including bisphenol-a, phenol, and tertbutylphenol) may be detected using a HPLC equipped with a standard C18 column and fluorescence detector with excitation wavelength of 310 nm and emission monitoring at 275 nm. Quantification may be completed by making use of external standards of BPA and phenol. The sample preparation may include dissolving 1 g of the PC sample in 5 mL dichloromethane, followed by the addition of 20 mL acetonitrile under continuous shaking. 2 mL of the supernatant that is filtered over a 0.45 pm syringe filter before it is analyzed using HPLC.

[0015] Polycarbonate as used herein means a polymer containing carbonate units. Such polymers may be homopolymers consisting essentially of carbonate monomer units or copolymers containing one or more other monomer units (co-monomer units) and carbonate units. Such copolymers may be block copolymers containing two or more blocks of different monomer units or may be random copolymers with the different monomer units randomly located along the polymer backbone. The other monomer units may comprise any monomer units that do not negatively impact the inherent properties of polycarbonates, for instance heat resistance, impact resistance, moldability, flexural modulus, bending strength, haze and transparency, where required for the intended use. Among exemplary comonomer units are ester units, polysiloxane units, and the like. The amount of carbonate monomer units incopolycarbonates is selected such that the resulting polymer retains the desirable properties of polycarbonates, as disclosed herein. The copolycarbonates may contain greater than 50 mole percent carbonate monomer units, about 75 mole percent or greater carbonate monomer units, about 80 mole percent or greater carbonate monomer units or about 85 mole percent or greater carbonate monomer units. The copolycarbonates may contain about 99 mole percent or less carbonate monomer units, about 97 mole percent or less carbonate monomer units or about 95 mole percent or less carbonate monomer units. The copoly-carbonates may contain about 1 mole percent or greater co-monomer monomer units, about 3 mole percent or greater comonomer monomer units or about 5 mole percent or greater co-monomer monomer units. The copolycarbonates may contain less than 50 mole percent co-monomer monomer units, about 25 mole percent or less co-monomer monomer units, about 20 mole percent or less co-monomer monomer units or about 15 mole percent or less co-monomer monomer units. The polycarbonate units may contain aromatic units in the backbone of the polymer. Polycarbonates used herein may include any amount of virgin and / or waste polycarbonate as desired to achieve desirable flame retardancy, molecular weight, and / or other desired properties. For example, the present compositions and polymers may include about 10 percent or more, about 30 percent or more or about 50 percent or more virgin or waste polycarbonate. The present compositions and polymers may include about 100 percent or less, about 80 percent or less, or about 60 percent or less virgin or waste polycarbonate.

[0016] The production of polycarbonates is affected, for example, by the reaction of diphenols with carbonic acid halides, preferably phosgene, and / or with aromatic dicarboxylic acid dihalides, preferably benzenedicarboxylic acid dihalides, by the phase boundary method, optionally with the use of chain terminators, e.g., monophenols, and optionally with the use of trifunctional branching agents or branching agents with a functionality higher than three, for example triphenols or tetraphenols. Diphenols useful to produce the aromatic polycarbonates and / or aromatic polyester carbonates may correspond to formula Iwherein A denotes a single bond, a C 1-5 alkylene, a C 2-5 alkylidene, a C 5-6 cycloalkylidene, -O-, -SO-, -CO-, -S-, -SO2-, or a C 6-12 arylene, on to which other aromatic rings, which optionally contain hetero atoms, can be condensed, or a radical of formula II or III:IIwherein B in each case is independently hydrogen, a C 1-12 alkyl, preferably methyl, or a halogen, preferably chlorine and / or bromine; x in each case is mutually independently 0, 1 , or 2; p is 0 or 1 ;Rcand Rdare mutually independent of each other and are individually selectable for each X1and are hydrogen or a C i_6alkyl, preferably hydrogen, methyl or ethyl;X1denotes carbon; and m denotes an integer from 4 to 7, preferably 4 or 5, with the proviso that Rcand Rdsimultaneously denote an alkyl on at least one X1atom.

[0017] Exemplary diphenols are hydroquinone, resorcinol, dihydroxybiphenyls, bis (hydroxyphenyl)-C 1.5 alkanes, bis(hydroxyphenyl)-C 5-6 cycloalkanes, bis(hydroxyl-phenyl) ethers, bis(hydroxyphenyl)sulfoxides, bis(hydroxyphenyl)ketones, bis(hydroxyl-phenyl) sulfones and 4,4”-bis(hydroxyphenyl)diisopropylbenzenes, as well as derivatives thereof which have brominated and / or chlorinated nuclei. Diphenols which are particularly preferred are 4,4'- dihydroxybiphenyl, bisphenol A, 2,4-bis(4-hydroxyphenyl)-2-methyl-butane, 1 ,1-bis (4- hydroxyphenyl)-cyclohexane, 1 ,1-bis(4-hydroxyphenyl)-3,3,5-trimethyl-cyclohexane, 4,4- dihydroxydiphenyl sulfide and 4,4-dihydroxydiphenyl sulfone, as well as di- and tetra-brominated or chlorinated derivatives thereof, such as 2,2-bis(3-chloro-4-hydroxy-phenyl)propane, 2,2-bis-(3,5-dichloro-4-hydroxyphenyl)propane or 2,2-bis(3,5-dibromo-4-hydroxyphenyl)propane. 2, 2- bis-(4-hydroxyphenyl) propane (bisphenol A) is particularly preferred. The diphenols can be used individually or as arbitrary mixtures. The diphenols are known in the literature or can be obtained by methods known in the literature. Apart from bisphenol A homopolycarbonates, exemplary polycarbonates include copolycarbonates of bisphenol A with up to 15 mole percent, with respect to the molar sums of the diphenols, of other diphenols which are disclosed, such as 2,2-bis(3,5-dibromo-4-hydroxyphenyl)-propane.

[0018] To cap, branch, or chain extend the polycarbonates used in the present disclosure, one or more functional compounds are used. Functional compounds may include one or more chain extenders, chain terminators, branching agents, or a combination of both. Functional compounds as used herein end-cap, chain extend, or branch one or more polycarbonate chains without binding to or with the one or more linking compounds and / or flame retardancy modifiers. Functional compounds may be added to the recovery solution one at one time, individually over one or more periods of time, or in series to branch and / or chain extend and subsequently chain terminate and achieve desirable molecular weights and associated properties. The one or more functional compounds may be added to the recovery solution in an amount sufficient to reduce the amount of hydroxyl groups to the desired level, chain extend and / or branch the polycarbonates. The one or more functional compounds may be added to the recovery solution in an amount of about 0.01 weight percent or more, about 0.1 weight percent or more, or about 0.5 weight percent or more, based on the total weight of the waste polycarbonate in the recovery solution. The one or more functional compounds may be added to the recovery solution in an amount of about 10 weight percent or less, about 5 weight percent or less, or about 1 weight percent or less, based on the total weight of the waste polycarbonate in the recovery solution.

[0019] The chain terminator may be configured to react with at least one free hydroxyl and / or carboxyl group of one or more waste and / or modified polycarbonates to chain terminate, non-polycarbonate compounds to remove free hydroxyl and / or carboxyl groups, or both. The chain terminators described herein may be configured to bind with one or more hydroxyl or carboxyl groups in the recovery solution so that the free hydroxyl and / or carboxyl groups do not cleave one or more polycarbonate polymers. The chain terminators may include one or more groups that are reactable with the one or more hydroxyl or carboxyl groups in a condensation reaction. The chain terminators may be used to chain terminate the one or more waste and / or modified polycarbonates. The chain terminators may be used to bind with one or more nonpolycarbonate compounds so that free hydroxyl and / or carboxyl groups non-polycarbonatecompounds (e.g., carboxyl and / or hydroxyl containing compound) are removed from the recovery solution and / or to prevent the polycarbonate chains from being cleaved by undesired interactions by the hydroxyl and / or carboxyl groups. The chain terminator may be any compound that reacts with the hydroxyl and or carboxyl groups which do not negatively impact the usefulness of the resulting polycarbonates. Exemplary chain terminators may include one or more isocyanates, amines, esters, epoxides, anhydrides, carboxylic acids, or any combination thereof.

[0020] Chain terminators may include one or more phenolic compounds. Phenolic compounds may include phenol, p-chlorophenol, p-tert-butylphenol, 4-(1 ,3-dimethyl-butyl)- phenol and 2,4,6-tribromophenol; long chain alkyl phenols, such as monoalkylphenols or dialkylphenols which contain a total of 8 to 20 carbon atoms in their alkyl substituents, exemplary are 3,5-di-tert-butyl-phenol, p-iso-octylphenol, p-tert-octylphenol, p-dodecylphenol, 2- (3,5-dimethylheptyl)-phenol and 4-(3,5-dimethylheptyl)-phenol.

[0021] Branching agents used in this disclosure may be any compound capable of separately reacting with three or more carboxyl and / or hydroxyl groups on the same or separate polycarbonate compounds. The branching agents may have a functionality of three or more, four or more, five or more, or six or more. The functionality is a measure of the ability to bind with individual hydroxyl and / or carboxyl groups. The branching agents may react with three or more, four or more, five or more, or a plurality of hydroxyl and / or carboxyl groups. The polycarbonates can be branched, for example by the incorporation of about 0.05 to about 2.0 mole percent, with respect to the sum of the branching agents used, of trifunctional compounds or of compounds with a functionality higher than three, for example those which contain three or more phenolic groups. Branched polycarbonates useful for the compositions disclosed can be prepared by known techniques, for example several methods are disclosed in USP 3,028,365; 4,529,791 ; and 4,677,162; which are hereby incorporated by reference in their entirety. Exemplary branching agents include tri- or multi-functional carboxylic acid chlorides, such as trimesic acid trichloride, cyanuric acid trichloride, 3,3'-,4,4'-benzophenone tetracarboxylic acid tetra chloride, 1 ,4,5,8-naphthalene-tetracarboxylic acid tetrachloride or pyromellitic acid tetra chloride, in amounts of about 0.01 to about 1.0 mole percent (with respect to the dicarboxylic acid dichlorides used) or tri- or multi-functional phenols such as phloroglucinol, 4,6-dimethyl- 2,4,6-tris(4-hydroxyphenyl)-2-heptene, 4,4-dimethyl-2,4,6-tris (4-hydroxy phenyl) heptane, 1 ,3,5- tris(4-hydroxyphenyl)-benzene, 1 ,1 ,1-tris(4-hydroxy phenyl)ethane, tris(4-hydroxyphenyl)- phenyl-methane, 2,2-bis[4,4-bis(4-hydroxyphenyl) cyclohexyl]propane, 2,4-bis[1-(4- hydroxyphenyl)-1-methyl-ethyl]phenol, tetrakis(4-hydroxy phenyl)-methane, 2,6-bis(2-hydroxy-5-methyl-benzyl)-4-methyl-phenol, 2-(4-hydroxyphenyl) -2-(2,4-dihydroxyphenyl)propane, or tetrakis(4-[1-(4-hydroxyphenyl)-1-methylethyl]-phen-oxy)-methane in amounts of about 0.01 to about 1.0 mole percent with respect to the diphenols used. Phenolic branching agents can be placed in the reaction vessel with the diphenols. Acid chloride branching agents can be introduced together with the acid chlorides.

[0022] The chain extenders may include any compound having sufficient groups to bind two separate polycarbonate chains together. The chain extenders may be configured to react with two separate carboxyl and / or hydroxyl groups so that polycarbonate is chain extend or to remove free carboxyl and / or hydroxyl groups in the recovery solution. The chain extenders may comprise at least two groups sufficient to separately react with two different polycarbonate chains and / or free hydroxyl and / or carboxyl groups. The chain extenders may be used to bind with one or more non-polycarbonate compounds so that free hydroxyl and / or carboxyl groups are removed from the recovery solution and / or to prevent the polycarbonate chains from being cleaved by undesired interactions by the hydroxyl and / or carboxyl groups. A combination of chain extenders may be used to bind polycarbonates having different end groups. Examples of chain extenders may include two or more functions groups including isocyanates, amines, esters, epoxides, anhydrides, carboxylic acids, or any combination thereof.

[0023] The polycarbonate solvent functions to dissolve solid polycarbonate from a waste feedstock. The polycarbonate solvent may dissolve one or more waste polycarbonates from the waste feedstock without dissolving one or more other non-polycarbonate polymers and other materials that negatively impact the use of the recovered polycarbonates present in the waste stream. Polycarbonate solvents may have a boiling point sufficient to be heated to a temperature that will not break the chains of the polycarbonate. The polycarbonate solvent may have a boiling point of about 25 °C or more, 40 about °C or more, or about 60 °C or more. The polycarbonate solvent may have a boiling point of about 160 °C or less, about 120 °C or less, or about 80 °C or less. The polycarbonate solvent may be any solvent that preferentially dissolves polycarbonates with respect to other polymers and materials present in the waste stream that could negatively impact the use of the recovered polymers. The polycarbonate solvent may be a polar aprotic solvent. The polycarbonate solvent may comprise at least one halogen atom. The polycarbonate solvent may be free of one or more reactable protons. The polycarbonate solvent may be free of one or more carboxyl and / or hydroxyl groups. The polycarbonate solvent may not be capable of reacting with one or more carboxyl and / or hydroxyl groups. The polycarbonate solvent may be immiscible with a polar protic solvent, such as water, so that the polycarbonate solvent can be used in a devolatilization process to recover the polycarbonate solvent and,separately, the modified polycarbonate in a solid form. The polycarbonate solvent may comprise one or more of trichloromethane, dichloromethane, chlorobenzene, dichlorobenzene, tetrahydrofuran, 2-methyl tetra hydrofuran, N-methyl-2-pyrrolidone, dimethylformamide, 1 ,4- dioxane, methyl ethyl ketone, ethyl acetate:ethanol (3:1 , binary solvent), dimethyl sulfoxide, or any combination thereof.

[0024] The present disclosure provides for techniques to modify reactive polycarbonate polymers and oligomers to formulate polymers with imparted flame resistance. By integrating the flame retardancy modifiers within the polycarbonate chains, functional groups on the flame retardancy modifier and / or resultant functional groups formed from reaction between the flame retardancy modifier and the reactive polycarbonate polymers and / or oligomers allow for avoidance of or reduction of traditional blended flame retardants in the compositions. Using these techniques, the modified polycarbonates can additionally be combined with techniques to integrate chain extenders and branching agents to achieve polycarbonates with desirable flame resistance and molecular weight.

[0025] Waste polycarbonates (e.g., reactive polycarbonate) include reactive groups that are formed from degradation of virgin polycarbonate over time. The flame retardancy modifiers disclosed herein can be easily contacted with the reactive groups of the waste polycarbonates and integrated into existing waste polycarbonates to impart flame resistance and form modified polycarbonates. Before, during, or after the use of the flame retardancy modifiers, the waste polycarbonates can simultaneously be modified using the disclosed flame retardancy modifiers, linking compounds, and / or flame retardancy modifiers to form modified polycarbonates with the desired flame resistance and molecular weight, which are derived from waste polycarbonate streams.

[0026] The reactive polycarbonate may include one or more reactive groups configured to react with the functional group of the flame retardancy modifier and / or the operative group of the linking compound. Where the reactive polycarbonate is a recycled and unmodified polycarbonate polymer and / or oligomer, the reactive polycarbonate may include one or more hydroxyl or carboxyl groups that have formed from natural degradation of the polymer over time. Before contacting the linking compound or flame retardancy modifiers with the polycarbonate compound, the reactive polycarbonates or virgin polycarbonates described herein may be modified such that free hydroxyl or carboxyl groups are introduced into the polymer so that the polycarbonate is react-able with the operative and / or functional groups of the linking compound and / or flame retardancy modifiers. The virgin or reactive polycarbonates may be modified to introduce reactive groups that are nucleophilic and / or electrophilic groups configured to reactwith appropriate electrophilic and / or nucleophilic groups of the functional compounds, flame retardancy modifier, and / or linking compound. The virgin or reactive polycarbonate may be modified to change a reactive group from a first reactive group to a second reactive group so that a desired linkage can occur between the reactive group and the flame retardancy modifier, functional compound, and / or linking compound. For example, the waste or virgin polycarbonate may be hydroxylated by any means sufficient to form the reactive polycarbonate that comprises one or more hydroxyl and / or carboxyl groups. Hydroxylation of the virgin and / or reactive polycarbonates may be conducted by oxidizing the polycarbonate, by exposing the polycarbonate to ultraviolet light to degrade the polycarbonate, and / or by conducting hydrolysis on the one or more virgin and / or waste polycarbonates.

[0027] By modulating the reactive group of the reactive polycarbonate, the linking compound, flame retardancy modifier, or a desired functional compound can be linked to the polycarbonate in a desired sequence such that flame retardancy is imparted, molecular weight is controlled, and / or hydroxyl and carboxyl groups are removed from the reactive polycarbonate. The linking compound and the reactive polycarbonate may first be contacted to form a bond having a chain sequence of linking compound-reactive polycarbonate, and the flame retardancy modifier may subsequently be contacted with the linking compound-reactive polycarbonate to form a modified polycarbonate having a chain sequence of flame retardancy modifier-linking compound-reactive polycarbonate. The flame retardancy modifier and the linking compound may be contacted to form a bond having a chain sequence of flame retardancy modifier-linking compound, and the linking compound may be subsequently contacted with the flame retardancy modifier-reactive polycarbonate to form a chain polycarbonate having a reaction sequence of flame retardancy modifier-linking compound-reactive polycarbonate. In either the case of a modified polycarbonate having a chain sequence of flame retardancy modifier-linking compound-reactive polycarbonate or a modified polycarbonate having a chain sequence of flame retardancy modifier-linking compound-reactive polycarbonate, the modified polycarbonate may subsequently be contacted with a functional group, additional reactive polycarbonate, additional linking compounds, additional flame retardancy modifiers, or any combination thereof such that desired flame retardancy is imparted within chains of the polymer, desired molecular weight is achieved, and / or hydroxyl and / or carboxyl groups are removed from the reactive polycarbonate to form the modified polycarbonate. At any of the free reactive groups of the reactive polycarbonate, a functional compound may be added to end cap or bind two or more polycarbonate chains together.

[0028] The linking compound as described herein may function to end cap, chain extend, and / or branch the reactive polycarbonate by reacting with the flame retardancy modifier, the reactive polycarbonate, or both. The linking compound may include one or more operative groups that are configured to react with the one or more functional groups of the flame retardancy modifier and / or the reactive groups of the reactive polycarbonate. The operative groups may be nucleophilic and / or electrophilic depending on the desired linkage and / or sequence of linkages between the flame retardancy modifier and the reactive polycarbonates. The linking compound may include two or more, three or more, four or more, five or more, or a plurality of operative groups such that desired chain extending or branching and / or linkage to flame retardancy modifiers is achieved along chains of the polycarbonate. The linking compound may include operative groups that are configured to react first with either the reactive polycarbonate or the flame retardancy modifier and subsequently react with other of the reactive polycarbonate or the flame retardancy modifier.

[0029] The flame retardancy modifiers include one or more functional groups that are configured to react with the operative groups of the one or more linking compounds and / or the reactive groups of the polycarbonate compound to form the modified polycarbonate. Modified polycarbonates as disclosed herein may include at least some residues of flame retardant modifiers bound to the polycarbonate polymer. The flame retardancy modifier may include any number of functional groups sufficient to form a polymer of a desired structure with imparted flame resistance. The flame retardancy modifiers may include at least one functional group such that the residue of the flame retardancy modifier may both impart flame resistance to the polycarbonate and end cap the polycarbonate. The flame retardancy modifier may include two or more functional groups such that the flame retardancy modifier functions to both impart flame resistance and to chain extend or branch the polycarbonate by being capable of forming bonds with more than one separate reactive polycarbonate. Flame retardancy modifiers may be used in combination with or separately from linking compounds to end cap or bind two or more polycarbonate chains together. Examples of flame retardancy modifiers configured to react with the reactive polycarbonate may include one or more of phosphorous compounds, unsaturated hydrocarbons, amine compounds, functionalized cyanophenyl compounds, a silyl compounds, a siloxane compounds, and / or any other flame retardancy modifier described herein including one or more electrophilic or nucleophilic groups configured to react with reactive or operative groups and impart flame resistance. Some amine compounds may include benzoxazines. Phosphorous compounds may include one or more halogenated phosphates, phosphonics, and / or phosphinics. Examples of halogenated phosphates, phosphonics, and / or phosphinics mayinclude one or more of methylphosphonic dichloride, phenyl dichlorophosphate, dimethylphosphinic chloride, diphenylphosphinic chloride, diphenyl phosphoryl chloride, phosphoryl chloride, or any combination thereof. Other phosphorous compounds may include one or more phosphonates that are not halogenated, such as dimethyl methylphosphate, diphenyl methylphosphonate, or another mono, di, or tri-substituted phoshponate. Unsaturated carbons may include chlorides bound to an alkene or alkyne group, such as a propargyl halide. In any of the above flame retardancy modifiers, where the halide is a leaving group due to the reaction that forms an acid, acid may be removed during formation or after formation of the modified polycarbonate by a scavenger configured to bind with or remove the acid from the solution.

[0030] After contacting the operative group of the linking compound or the reactive group of the reactive polymer, the resultant functional group may impart flame retardancy to the polycarbonate polymers while being integrated with the polymer chains. Resultant functional groups may include any functional group configured to impart flame resistance to the modified polycarbonate. Resultant functional groups may be residues of the one or more functional groups of the flame resistance modifier and one or more of the reactive groups of the reactive polycarbonate and / or operative groups of the linking compound as described herein such that the flame resistance is imparted on the polycarbonate polymer. The resultant functional groups may bond together one or more polycarbonate chains and / or one or more residues of linking compounds and / or flame resistance modifiers. Resultant functional groups that impart flame resistance may include any functional group configured to scavenge for free radicals. The resultant functional groups may be free of halogens. Examples of flame retardancy modifiers that are incorporated into the modified polycarbonate may include one or more of benzoxazines, phenyl phosphates, phenyl phosphorous, benzonitrile, silyl compound, siloxane compound, and / or cyanophenyl groups. As an example, the flame retardancy modifier may have the following structure when bound to one or more polycarbonate chains, where the below “PC” comprises at least one polycarbonate chain:

[0031] The one or more linking compounds, reactive polycarbonates, and / or flame resistance modifiers containing one or more operative, reactive, and / or functional groups may include any nucleophilic group that reacts with an electrophilic group under the conditions described herein. Nucleophilic group as used herein is a group which donates an electron pair to make a covalent bond. Exemplary nucleophilic groups include carboxylic acid, unsaturated aromatic acids, sulfonic acids, phosphorous based acids, boronic acids, alcohol, phenol, amine, aniline, imidazole, tetrazole, thiol, boronic acid, glycol, hydrazine and hydroxyl amine groups. The one or more linking compounds, reactive polycarbonates, and / or flame resistance modifiers containing one or more operative, reactive, and / or functional groups may include any electrophilic group that reacts with a nucleophilic group under the conditions described herein. Electrophilic group as used herein is a group which receives an electron pair to form a covalent bond. Exemplary electrophilic groups include epoxide, anhydride, imide, ester, acyl halide, acyl nitrile, aldehyde, ketone, isocyanate silyl halide, halosiloxane, alkoxysiloxane, and isothiocyanate groups. The linking compounds, reactive polycarbonates, and / or flame resistance modifiers containing one or more containing nucleophilic groups or electrophilic groups in an amount of about 0 percent by weight of the polymer or polymerizable composition or greater, about 0.1 percent by weight or greater about 1.0 percent by weight or greater or about 2.0 percent by weight or greater. The polymer or polymerizable composition disclosed herein may contain one or more unsaturated compounds containing nucleophilic groups or electrophilic groups in an amount of about 10 percent by weight of the polymer or polymerizable composition or less, about 5.0 percent by weight or less, or about 2.0 percent by weight or less.

[0032] In downstream process uses, the modified polycarbonate may be contacted with one or more compounds desirable to make a downstream product or composition. The modified polycarbonate may be mixed or blended with one or more other polymers or virgin polycarbonate to achieve desirable properties. Other polymers may include polystyrene, styreneacrylonitrile, acrylonitrile butadiene, styrene, high impact polystyrene, polymethylmethacrylate, polyolefins or any combination thereof. The modified polycarbonate may be mixed or blended with one or more additives sufficient to achieve desirable properties using known techniques of blending additives with polymeric compositions. The additives may include one or more of fillers, flame retardants, pigments, UV stabilizers, antioxidants, mold release agents, dyes, or any combination thereof.

[0033] The flame retardants are different than the flame retardancy modifiers described herein. The compositions may contain one or more non-halogenated flame retardants commonly used in polycarbonate compositions. Non-halogenated means that there are no halogen atoms contained in the flame retardant. The use of non-halogenated flame retardants means that no halogens are released during combustion of the compositions containing non- halogenated flame retardants. The flame retardant may be any flame retardant known for use in polycarbonate-based compositions which provide flame retardant properties, and which do not negatively impact the impact, heat resistance, flexural modulus, bending strength, haze and transparency of the composition. Flame retardants may be used in a sufficient amount to meet the flame retardancy requirements for the final use and in an amount that does not deleteriously impact the properties of articles prepared from the compositions. Exemplary flame retardants include phosphorous containing compounds, such as oligomeric phosphates, poly(block- phosphonato-esters), and / or a poly(block-phosphonato-carbonates) see USP 7,645,850 which is incorporated in its entirety. Exemplary oligomeric phosphates include bisphenol-A bis(diphenyl phosphate) (BAPP). Exemplary additional fire retardants include 1 , 3- phenylenetetrakis (2, 6-dimethylphenyl) ester (Daihachi PX-200).

[0034] The one or more non-halogenated flame retardants may be one or more phospha zenes. Any one or more phosphazenes which enhances fire retardancy may be used. The phosphazenes may comprise more than one phosphazene unit. A phosphazene is an organic compound having a -P=N- structure. The phosphazene may be a linear structure containing one or more phosphazene units or a cyclic structure containing structure containing one or more phosphazene units. The phosphorous atoms on the phosphazene structure may have bonded thereto one or more hydrocarbyloxy structures. The hydro-carbyloxy groups may be alkoxy, aryloxy, alkyl substituted aryloxy, alkoxy substituted aryloxy or halo substituted aryloxy. The hydrocarbyloxy groups may be aryloxy or alkyl substituted aryloxy. The hydrocarbyloxy groups may be phenoxyoxy or alkyl substituted phenoxy. The alkyl groups may be C -MO alkyl, C 1.3 alkyl or methyl or ethyl. The cyclic phosphazene compounds may contain 1 or more phosphazene units or 3 or more phosphazene units. The cyclic phosphazene compounds may contain 25 orless phosphazene units, 10 or less phosphazene units or 5 or less phosphazene units. The linear phosphazene compounds may contain 1 or more phosphazene units, 3 or more phosphazene units, 5 or more phosphazene units or 6 or more phosphazene units. The linear phosphazene compounds may contain 10,000 or less phosphazene units, 1 ,000 or less phosphazene units, 100 or less phosphazene units, or 25 or less phosphazene units. Exemplary cyclic phosphazenes include phenoxy cyclotriphosphazene, octaphenoxy cyclotetraphosphazene, and decaphenoxy cyclopentaphosphazene. Cyclic phosphazenes may be obtained by allowing ammonium chloride and phosphorus pentachloride to react at 120 to 130°C to obtain a mixture containing cyclic and straight chain chlorophosphazenes, extracting cyclic chlorophosphazenes such as hexachloro cyclotriphosphazene, octachloro cyclotetraphosphazene, and decachloro cyclopentaphosphazene, and then substituting it with a phenoxy group. Exemplary linear phosphazenes include compounds obtained by subjecting hexachloro cyclotriphosphazene, obtained by the above-described method, to ring-opening polymerization at 220 to 250°C, and then substituting thus obtained chainlike dichlorophosphazene having a degree of polymerization of 3 to 10,000 (or as described before) with phenoxy groups. The phosphazene compounds may be crosslinked. The phosphazene compounds may be crosslinked by a bisphenol compound such as a 4,4'-diphenylene group, such as a 4,4'-sulfonyldiphenylene (bisphenol S residue), 2,2-(4,4'-diphenylene), isopropylidene group, 4,4'-oxydiphenylene group, and 4,4'-thiodiphenylene group. The phenylene group content of the crosslinked phenoxyphosphazene compound is generally 50 to 99.9 weight percent or 70 to 90 weight percent. The crosslinked phenoxyphosphazene compound may not have any free hydroxyl groups in the molecule.

[0035] The one or more non-halogenated flame retardants may be present in an amount of about 0.1 percent by weight or greater based on the weight of the composition containing polycarbonates and / or copolymers containing carbonate units, about 1 percent by weight or greater or about 5 percent by weight or greater. The one or more flame retardants may be present in an amount of about 30 percent by weight or less based on the weight of the composition, about 20 percent by weight or less or about 10 percent by weight or less.

[0036] The halogenated flame retardant is any halogenated flame retardant known for use in polycarbonate based compositions which provide flame retardant properties and which do not negatively impact the impact, heat resistance and environmental stress crack resistance properties of the composition. Preferably the halogenated flame retardant allows the compositions of the invention to achieve the level of properties listed hereinbefore. Preferred classes of flame retardants are brominated flame retardants. Exemplary flame retardantsinclude brominated polycarbonates, such as tetrabromobisphenol A polycarbonate oligomer, polybromophenyl ether, brominated BPA polyepoxide, brominated imides, halogenated polyacrylates, such as poly(haloaryl acrylate), poly(haloaryl methacrylate), brominated polystyrenes such as polydibromostyrene and polytribromostyrene, decabromobiphenyl ethane, tetrabromobiphenyl, brominated alpha, omega-alkylene-bis- phthalimides, such as, N,N'-ethylene-bis-tetrabromophthalimide, oligomeric brominated carbonates, especially carbonates derived from tetrabromobisphenol A, which, if desired, are end-capped with phenoxy radicals, or with brominated phenoxy radicals, or brominated epoxy resins. Mixtures of halogenated flame retardants may be utilized in the compositions of the invention. Exemplary preferred halogenated flame retardants include brominated polyacrylates, brominated polystyrenes and tetrabromobisphenol A polycarbonate oligomers. The halogenated flame retardant may be utilized in a sufficient amount to reduce the flammability of the composition of the invention and to maintain impact the impact, heat resistance and environmental stress crack resistance properties of the composition. Preferably the amount of the halogenated flame retardant allows the compositions of the invention to achieve the level of properties listed hereinbefore. The one or more halogenated flame retardants are present in an amount of about 0.1 percent by weight or greater based on the weight of the composition of the invention, more preferably about 1 percent by weight or greater and most preferably about 5 percent by weight or greater. Preferably the one or more halogenated flame retardants are present in an amount of about 30 percent by weight or less based on the weight of the composition of the invention and more preferably about 20 percent by weight or less.

[0037] The composition disclosed herein may further comprise a fluorinated antidrip agent. Antidrip means to reduce the tendency of the composition to form burning drips in the event of a fire. Fluorinated polyolefins known in the art as antidrip agents may be used in the compositions disclosed. Exemplary fluorinated polyolefins are described in EP-A 0 640 655. They are marketed under the brand name Teflon® 30N by DuPont

[0038] The compositions disclosed herein may include one or more charring salts of a perflourohydrocarbyl sulfur compounds or aromatic sulfur compounds. The one or more salts of a perflourohydrocarbyl sulfur compounds may be one or more salts of perflouroalkane sulfur compounds. Any salts of perflourohydrocarbyl sulfur compounds or aromatic sulfur compounds that improve the fire retardancy of disclosed compositions may be used. The one or more salts of a perflourohydrocarbyl sulfur compounds or aromatic sulfur compounds may include one or more an alkali metal salt, an alkaline earth metal salt or both. For example, the one or moresalts of a perflourohydrocarbyl sulfur containing compounds or aromatic sulfur compounds may include a potassium salt, a sodium salt, a magnesium salt, a calcium salt, or any combination thereof. The one or more salts of perflourohydrocarbyl sulfur containing compounds or aromatic sulfur compounds may include or consist essentially of one or more potassium salts. The one or more salts of a perflourohydrocarbyl sulfur containing compounds or aromatic sulfur compounds are salts including one or more sulfur atoms. The one or more salts of perflourohydrocarbyl sulfur containing compounds or aromatic sulfur compounds may be a sulfonate. The sulfur- containing salt (e.g., the sulfonate) may include one or more carbon containing groups. The number of carbon atoms in the sulfur-containing salt may be about 15 or less, about 13 or less, about 7 or less, or about 5 or less. The number of carbon atoms in the sulfur- containing salt may be 1 or more, 2 or more, 3 or more, or 4 or more. The carbon containing group may be acyclic or aromatic. The carbon containing group may include one or more halogen atoms (e.g., a fluorine, a chlorine, a bromine, or any combination thereof). By way of example, the carbon containing group may include a fluoroalkane having one or more fluorine atoms (e.g., a perfluoroalkane, such as a perfluorobutane, a perfluorohexane, a perfluoropentane, a perfluoroheptane, a perfluoropropane, or a perfluorooctane). The sulfur- containing salt may include or consist substantially of one or more potassium perfluoroalkanesulfonates, such as potassium perfluorobutanesulfonate, sodium p- toluenesulfonate or potassium diphenylsulfone sulfonate. The perflourohydrocarbyl salts or aromatic sulfur compounds may be present in an amount of about 0.05 percent by weight or greater of the polycarbonate or carbonate containing polymer containing composition or about percent by weight or greater or about 0.1 percent by weight or greater. The perflourohydrocarbyl metal salts or aromatic sulfur compounds may be present in an amount of about 2.0 percent by weight or less of the polycarbonate or carbonate containing polymer containing composition, about 1.0 percent by weight or less, less than 0.5 percent by weight, about 0.4 percent by weight or less or about 0.25 percent by weight or less.

[0039] The composition containing one or more polycarbonates and / or copolymers containing carbonate units may contain antioxidants. The antioxidants may be present in sufficient amount to prevent oxidation of the compositions and structures formed. Exemplary antioxidant additives include, for example, organophosphites such as tris(nonyl phenyl)phosphite, tris(2,4-di-t-butylphenyl)phosphite (e.g., “IRGAFOS 168” or “1-168”), bis(2,4- di-t-butylphenyl)pentaerythritol diphosphite, distearyl pentaerythritol diphosphite or the like; alkylated monophenols or polyphenols; alkylated reaction products of polyphenols with dienes, such as tetrakis[methylene(3,5-di-tert-butyl-4-hydroxyhydrocinnamate)]methane, or the like;butylated reaction products of para-cresol or dicyclopentadiene; alkylated hydroquinones; hydroxylated thiodiphenyl ethers; alkylidene-bisphenols; benzyl compounds; esters of beta-(3,5- di-tert-butyl-4-hydroxyphenyl)-propionic acid with monohydric or polyhydric alcohols; esters of beta-(5-tert-butyl-4-hydroxy-3-methylphenyl)-propionic acid with monohydric or polyhydric alcohols; esters of thioalkyl or thioaryl compounds such as distearylthiopropionate, dilaurylthiopropionate, ditridecylthiodipropionate, octadecyl-3-(3,5-di-tert-butyl-4-hydroxy phenyl)propionate, pentaerythrityl-tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate or the like; amides of beta-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionic acid or the like, or combinations comprising at least one of the foregoing antioxidants. Antioxidants may be used in amounts of 0.0001 to 1 weight percent of the composition containing one or more polycarbonates and / or copolymers containing carbonate units. The antioxidants may be present in an amount of about 200 ppm to 2000 ppm of the one or more polycarbonates and / or copolymers containing carbonate units.

[0040] The polycarbonate solvent, flame retardant modifier, flame retardants, linking compounds, the reactive polycarbonate, and / or the waste feedstock may be contacted using any technique or a combination of techniques such that the polycarbonate solvent dissolves the components in the recovery solution or the components are dispersed within the recovery solution such that desirable surface contact is achieved between the components.

[0041] The recovery solution may be contacted in any housing sufficient to contain fluids (e.g., liquids and / or gases). The recovery solution may be contacted in a sealed housing that is configured to contain fluids and gases so that the waste feedstock and / or reactive polycarbonate may be mixed with fluids and gases to achieve desirable dissolution levels of reactive polycarbonate and / or waste feedstock. The waste feedstock may be moved into a sealed housing through an access point and moved into contact with polycarbonate solvent such that minimal or no polycarbonate solvent is lost through the access point as the waste feedstock is moved into and out of the sealed housing.

[0042] The recovery solution may be formed and mixed in a housing that is configured to apply heating and cooling in a series of sections within the housing so that the housing can apply liquid and gaseous polycarbonate solvent in different locations. The housing may include bottom and middle sections that can each optionally be heated and a top section that is optionally cooled, where the waste feedstock and / or reactive polycarbonate may be moved into the housing at any section, and as heat is applied in the middle or bottom sections to volatilize polycarbonate solvent, the top section cools solvent so that the solvent does not escape through a top of the housing.

[0043] Before, during, or after contacting the polycarbonate solvent and the waste feedstock, heat and / or agitation may be applied to the recovery solution to improve dissolution time or mixing of the reactive polycarbonate, linking compound, and / or flame retardant modifier into the polycarbonate solvent. The heat and / or agitation may be applied in combination, separately, or in series to achieve desired concentration levels, saturation, dispersion, mixing and / or dissolution times of the reactive polycarbonate, linking compound, and / or flame retardant modifier in the polycarbonate solvent. The heat and / or agitation may separately or in combination provide techniques to control the physical state (e.g., gas, liquid, solid) of the polycarbonate solvent, reactive polycarbonate, linking compound, and / or flame retardant modifier.

[0044] The housing may be equipped with any instrument sufficient to apply heating and / or cooling to control the physical state of the polycarbonate solvent and improve dissolution and mixing of the reactive polycarbonate, linking compound, and / or flame retardant modifier. Instruments that apply heating and / or cooling though any means sufficient to adjust the temperature of the recovery solution may be useable. The housing may be equipped with one or more, two or more, three or more, or a plurality of heating and / or cooling instruments to manipulate the temperatures of the recovery solution. The instruments for heating and cooling may be in the same section or may be positioned in separate locations and / or sections so that the state of the recovery solution is controlled and / or the polycarbonate solvent is prevented from escaping the housing. Agitation may be applied to polycarbonate solvent in a liquid state and separately in a gaseous state. Any type of agitation may be supplied which enhances the dissolution of reactive polycarbonate, linking compound, and / or flame retardant modifier into the polycarbonate solvent. The housing may be equipped with multiple instruments configured to apply agitation in a single state. The housing may be equipped with a sonication device (i.e. , for applying ultrasonic waves) and a stirring device so that two or more techniques can be used to improve agitation and, subsequently, dissolution of the waste polycarbonate into the polycarbonate solvent is improved. Examples of agitators may include sonicators, impellers, magnetic stirrers, vortexers, rockers, shakers, or any combination thereof.

[0045] The agitation may function to move dissolved waste polycarbonate molecules in a direction away from the waste feedstock so additional waste polycarbonate may be dissolved into the polycarbonate solvent and the entire recovery solution reaches a desired total concentration or saturation in less time. Agitation may be used on the polycarbonate solvent around the waste feedstock and / or reactive polycarbonate to mix the polycarbonate solvent and reduce localized saturation of the polycarbonate at a location in the recovery solution. Theagitation may be applied for any period of time or with any force sufficient to move reactive polycarbonate, linking compound, and / or flame retardant modifier molecules within the polycarbonate solvent and achieve desired concentration or saturation within the recovery solution. Combinations of agitation may be used both to the polycarbonate solvent and the waste feedstock, reactive polycarbonate, flame retardancy modifier, and / or linking compound or container holding the waste feedstock such that polycarbonate molecules are moved in the polycarbonate solvent. The container holding the waste feedstock may be shook or rocked as ultrasonic waves are applied from an external sonication device, which provides for improved shifting of polycarbonate solvent around the waste feedstock. Examples of agitation may include cavitating, swirling, shaking, rocking, spinning, stirring, or any combination thereof.

[0046] The application of heat may function to raise the temperature of the polycarbonate solvent to the boiling point or below of the polycarbonate solvent so that the disclosed methods can achieve desired levels of concentration, saturation, mixing, and / or dissolution times of the reactive polycarbonate, linking compound, and / or flame retardant modifier in the polycarbonate solvent. The heat may be applied such that the polycarbonate solvent boils and a portion of the polycarbonate solvent transitions to a gaseous form. When the heat is applied to transition the polycarbonate solvent into a gaseous form, the vaporized polycarbonate solvent may be contained in a sealed housing or chamber above the recovery solution and / or waste feedstock as waste and / or reactive polycarbonate is dissolved into the polycarbonate solvent. The heat may be applied up to a boiling temperature of the polycarbonate solvent and without cleaving one or more polycarbonate chains. The heat may be applied to the polycarbonate solvent in a temperature of about 30 °C or more, about 40 °C or more, or about 50 °C or more. The heat may be applied to the polycarbonate solvent in a temperature of about 160 °C or less, about 120 °C or less, or about 80 °C or less.

[0047] After contacting the polycarbonate solvent and the waste feedstock to form the recovery solution, the waste feedstock may be removed from the recovery solution once a desirable concentration of waste and / or reactive polycarbonate is achieved in the recovery solution. The waste feedstock may be removed by any means sufficient to separate a solid from a liquid. The waste feedstock may be raised out of the liquid recovery solution by an appropriate container. The waste feedstock may be raised out of the recovery solution, subsequently washed by a vapor phase polycarbonate solvent, and removed from the housing containing the recovery solution. The waste and / or reactive polycarbonates may have any desirable concentration in the polycarbonate solvent such that the waste polycarbonate can be repaired by one or more functional compounds in subsequent steps. The waste and / or reactivepolycarbonates may have a concentration in the polycarbonate solvent that is equal to or less than a saturation level at or just below the boiling point of the polycarbonate solvent. The waste and / or reactive polycarbonates may have a concentration in the polycarbonate solvent of about 1 weight percent or more, about 5 weight percent or more or about 10 weight percent or more. The waste polycarbonate may have a concentration in the polycarbonate solvent of about 50 weight percent or less, about 30 weight percent or less, or about 20 weight percent or less.

[0048] The polycarbonate solvent, the reactive polycarbonate, flame retardancy modifiers, linking compounds, and / or the waste feedstock may be contacted for any period of time sufficient to dissolve and / or mix the reactive polycarbonate, flame retardancy modifiers, and / or linking compounds in the polycarbonate solvent. The amount of time sufficient to dissolve the waste polycarbonate into the polycarbonate solvent at a desired concentration or to saturation may be dependent on the agitation and / or temperatures applied to the waste feedstocks and / or polycarbonate solvent. The polycarbonate solvent and the waste feedstock may be contact for a period of 10 min or more, about 60 min or more, or about 90 min or more. The polycarbonate solvent and the waste feedstock may be contact for a period of 6h or less, about 4h or less, or about 3h or less. More than one batch of waste feedstock, reactive polycarbonate, flame retardancy modifiers, and / or linking compounds may be contacted with and removed from the polycarbonate solvent until a desired concentration of waste polycarbonate is achieved in the recovery solution and / or a desired level of flame retardancy is imparted to the polycarbonate.

[0049] Before contacting the recovery solution (i.e., containing at least polycarbonate and polycarbonate solvent) and the one or more functional compounds, flame retardancy modifiers, and / or linking compounds, the recovery solution may be subjected to one or more separation steps. The recovery solution may be contacted with one or more adsorption or absorption materials or scavengers that are configured to precipitate or make inert one or more nonpolycarbonate compounds that were dissolved from the waste feedstock into the polycarbonate solvent. The recovery solution may be contacted with adsorption or absorption materials such as one or more of activated carbon, clays, zeolites, polymeric adsorbent or absorbents, or any combination thereof to remove non-polycarbonate compounds found in the waste feedstocks. Scavengers may include any functional groups sufficient to bind with free hydroxyl, carboxyl, other non-polycarbonate compounds susceptible to cleaving polycarbonate chains, or a combination thereof so that undesirable interactions with the functional groups and / or waste polycarbonates are mitigated or avoided. Examples of scavenger compounds may include one or more of isocyanates, amines, esters, epoxides, anhydrides, carboxylic acids, or any combination thereof. After reacting with one or more non-polycarbonate compounds in therecovery solution, the scavengers, adsorption, and / or absorption compounds may be removed as liquids or solids as described herein.

[0050] If the non-polycarbonate compounds from the waste feedstock are not precipitated with the scavenger, adsorption, and / or absorption materials, the non-polycarbonate compounds may be removed by one or more separation techniques configured to remove liquids from liquids, such as though solvent extraction, distillation, or any combination thereof. Solids may be present in the recovery solution due the above precipitation by the scavenger, adsorption, and / or absorption materials or by moving through the plurality of perforations in the perforated container. The recovery solution may have any solid non-polycarbonate compounds removed from the recovery solution before addition of the functional compounds to avoid undesired side reactions. The solids may be removed by any known techniques sufficient to separate a solid from a liquid. The solids may be removed from the recovery solution through filtration, decantation, precipitation, sedimentation, evaporation, centrifugation, solvent extraction, reverse osmosis, or any combination thereof. The solids may be filtered by using a filter having pores that are a width that is smaller than a width of the plurality of perforations. Liquids may be removed by any separation technique described herein. Some non-polycarbonate compounds that do not interfere with the polycarbonate compounds or functional compounds may remain in the recovery solution until the polycarbonate solvent and modified polycarbonate s are removed.

[0051] As discussed herein, once the reactive polycarbonate is dissolved in the polycarbonate solvent, the combination of the reactive polycarbonate and polycarbonate solvent is concurrently or subsequently contacted with one or more flame retardancy modifiers. The one or more flame retardancy modifiers may include one or more functional groups that are configured to react with one or more reactive groups of the reactive polycarbonate. The flame retardancy modifiers include any functional group as discussed herein that impart flame resistance to the polycarbonate after the flame retardancy modifier binds to the polycarbonate chain and forms the modified polycarbonate. The flame retardancy modifiers may be added in an amount sufficient to achieve a desirable flame resistance in the modified polycarbonate. Desired flame resistance may be the same or at least greater than reactive polycarbonates or virgin polycarbonate. The desired flame resistance may be achieved based on the amounts of flame retardancy modifiers added or the specific flame retardancy modifiers or combination thereof present in the modified polycarbonate. For example, the modified and / or reactive polycarbonate may have flame retardancy rating of a UL-94 vertical test at V-0 or more, V-1 or more, or V-2 or more at 3.0 mm, 1.6 mm, or 1 .0 mm.

[0052] Before or after contacting the reactive polycarbonate and flame retardancy modifier, the recovery solution may be contacted with one or more functional compounds and / or linking groups configured to adjust the molecular weight of the reactive and / or modified polycarbonate. The one or more functional and / or linking compounds may chain terminate, chain extend, or branch the reactive and / or modified polycarbonate to have increased molecular weight and / or properties and reduced hydroxyl and / or carboxyl groups. The one or more functional and / or linking compounds may increase the number and / or weight average molecular weight of the polycarbonate alone or in combination with the flame retardancy modifier. The weight and / or number average molecular weight may increase by a percentage relative to the number and / or weight average molecular weight of the waste and / or reactive polycarbonate before addition of the one or more functional and / or linking compounds. The percentage increase may be about 5 percent or more, 20 percent or more, or about 40 percent or more. The percentage increase may be about 100 percent or less, about 75 percent or less, or about 50 percent or less. The modified polycarbonate may have a number and / or weight average molecular weight that is larger than a number and / or weight average molecular weight of the waste and / or reactive polycarbonate. The weight average molecular weight of the modified polycarbonate may be about 10 kg / mol or larger, about 30 kg / mol or larger, or about 50 kg / mol or larger relative to the waste polycarbonate. The weight average molecular weight of the modified polycarbonate may be about 70 kg / mol or larger, about 90 kg or larger, or about 100 kg / mol or larger relative to the waste polycarbonate. The number average molecular weight of the modified polycarbonate may be about 3 kg / mol or larger, about 10 kg / mol or larger, or about 20 kg / mol or larger relative to the waste polycarbonate. The number average molecular weight of the modified polycarbonate may be about 30 kg / mol or larger, about 40 kg / mol or larger, or about 50 kg / mol or larger relative to the waste polycarbonate. The molecular weight in this disclosure is determined by gel permeation chromatography using narrow polystyrene standards (£> < 1 .2) and a broad range polycarbonate standard (£> > 1.5).After adding the one or more one or more functional compounds, linking compounds, and / or flame retardancy modifiers to the recovery solution, the modified polycarbonate may have a melt flow rate sufficient to be used in downstream processes with similar quality as virgin polycarbonate. The melt flow rate may be similar or substantially the same as virgin polycarbonate. The melt flow rate of the modified polycarbonate may be greater or less than the melt flow rate of the waste polycarbonate due to having an modified molecular weight from addition of the one or more functional compounds. The melt flow rate of the modified polycarbonate may be about 1 g / 10 min or more, about 5 g / 10min or more, or about 20 g / 10min or more. The melt flow rate of the modified polycarbonate may beabout 80 g / 10 min or less, about 60 g / 10min or less, or about 40 g / 10min or less. The melt flow rate is determined by measuring the grams passing through a standard die (2.095 x 8 mm) for 10 minutes (g / 10 min) as determined at 300°C under a load of 1 .2 kg according to the ISO 1133 standard.

[0053] After adding the functional compounds, linking compounds, and / or flame retardancy modifiers to the recovery solution, the hydroxyl and / or carboxyl groups may be present in a sufficiently low amount to reduce or avoid chain cleavage in the polycarbonates. After adding the functional compounds, linking compounds, and / or flame retardancy modifiers to the recovery solution, the functional compounds may react with hydroxyl and / or carboxyl groups such that the recovery solution is free or essentially free (e.g., 0.1 , 0.01 , or 0.01 weight percent or less present) of hydroxyl and / or carboxyl groups. The one or more functional compounds, linking compounds, and / or flame retardancy modifiers may reduce the amount of free hydroxyl and / or carboxyl groups by 50 mole percent or more, 70 mole percent or more or 90 mole percent or more. The one or more one or more functional compounds, linking compounds, and / or flame retardancy modifiers may reduce the amount of free hydroxyl and / or carboxyl groups by 95 mole percent or more 98 mole percent or more or 99 mole percent or more. The molar amount of hydroxyl and / or carboxyl groups present in the recovery solution may be reduced by the molar amount of groups in the functional compounds, linking compounds, and / or flame retardancy modifiers and configured to react with hydroxyl and / or carboxyl groups.

[0054] After forming the modified polycarbonate s, the recovery solution may be subjected to a step of recovering and / or separating the polycarbonate solvent and / or modified polycarbonate s. The polycarbonate solvent and the modified polycarbonate may be removed in a simultaneous fashion or separately in series. The recovery solution may be subjected to a process step that separates the polycarbonate solvent and the modified polycarbonate at the same time so that the modified polycarbonate can be used in downstream processes and the polycarbonate solvent is reusable to recover additional waste polycarbonate through a recycle pathway. The recovery solution may be subjected to any techniques sufficient to separate two components in a liquid state. The recovery solution may be subjected to one or more of devolatilization, centrifugation, filtration, distillation, or any combination thereof to separate the modified polycarbonate and the polycarbonate solvent. Compounds that remain after removing the polycarbonate solvent and modified polycarbonate may be disposed of or subjected to further separation steps to recover desirable compounds and recycle them. A non-solvent may be contacted with the with recovery solution to precipitate the modified polycarbonate from the polycarbonate solvent in a form that is free or essentially free of impurities or that may besubjected to further separation techniques. Non-solvents may include one or more compounds that are immiscible with polycarbonate solvent, such as water, aliphatic hydrocarbons, alcohols, acetonitrile, acetone, or any combination thereof.

[0055] The polycarbonate solvent may be recycled into a new and untreated waste feedstock to recover additional waste polycarbonate, begin the process again, and avoid undesirable disposal or loss of the polycarbonate solvent. The polycarbonate solvent may be separated from the recovery solution and moved back into a reservoir or the waste feedstock through one or more recycle pathways that extend between chambers. Before being recycled back into contact with the waste feedstock, the polycarbonate solvent may be subjected to one or more separation steps to remove undesired impurities. The polycarbonate solvent may be subjected to drying, centrifugation, filtration, distillation, or any combination thereof.

[0056] Before contacting the waste feedstock (including one or more reactive polycarbonates) and the one or more polycarbonate solvents, the waste feedstock may be subjected to one or more pretreatment steps to separate one or more non-polycarbonate compounds from the waste feedstock to recover desired compounds and / or to avoid undesirable reactions in the recovery feedstock. The waste feedstock may be subjected to any pretreatment step configured to remove one or more non-polycarbonate compounds or to prepare the waste feedstock for more efficient extraction of waste polycarbonate. The waste feedstock may be structurally altered to expose surface area of the components in the waste feedstock and / or prepare the waste feedstock for downstream processing steps, which may be conducted by shredding, grinding, pressing, dismantling, sorting, or any combination thereof. The waste feedstock may be treated to remove one or more non-polycarbonate compounds, such as inorganic compounds, non-polycarbonate polymers (e.g., polystyrene, styrene acrylonitrile resin, acrylonitrile butadiene styrene, high impact polystyrene, polymethylmethacrylate, other polymers commonly blended with polycarbonate, etc.), small organic molecules, or any combination thereof. The waste feedstock in the pretreatment step may be subjected to melting, magnetic field, density separation, freezing, agglomeration, washing, chemical removal of adhesives, selective dissolution of other polymers, drying, heating, cooling, or any combination thereof.

[0057] The above steps may be completed in the same chamber or in a series of chambers. Contacting the polycarbonate solvent and the waste feedstock may be conducted in a first chamber; contacting the recovery solution and one or more functional compounds, flame retardancy modifiers, and / or linking groups may be conducted in a second chamber, and recovering and / or separating the polycarbonate solvent and modified polycarbonate may beconducted in a third chamber. Performing the above steps in a series of chambers may mitigate side reactions while functional compounds are added or to more closely control separation steps. All of the steps may be conducted in the same chamber in a one pot style that recovers, adjusts / repairs / modifies, and removes polycarbonates in one location. One or more pathways may separate the chambers and move the recovery solution, waste feedstock, polycarbonate solvent, modified polycarbonate or a combination thereof from chamber to chamber as appropriate.

[0058] Between each of the above process steps, each of the chambers within the housing may connect through pathways that are configured to move compounds, such as the recovery solution, waste feedstock, modified polycarbonate, and / or polycarbonate solvent between chambers. The pathways may include any equipment sufficient to move the compounds and / or provide additional processing. The pathways may include equipment to separate one or more of the solid compounds from the recovery solution, such as filters. The housing may include any number of pathways between the chambers. The housing may include one or more, two or more, three or more, four or more, or a plurality of pathways between the chambers. Each of the pathways may be configured to simply move compounds between chambers, recycle polycarbonate solvents after processing polycarbonates, separate non-polycarbonate and polycarbonate compounds, remove separated non-polycarbonate compounds out of the housing, move waste feedstocks into and out of the housing, or any combination thereof. The pathways or chambers may be equipped with equipment configured to monitor the concentrations or properties of the compounds present in the pathways or chambers. The pathways and / or chambers may be equipped with concentration sensors, number and / or weight average molecular weight sensors, impurity sensors, phase sensors for detecting solids, gases, or liquids, humidity sensors, temperature sensors, or any combination thereof.

[0059] The disclosed compositions of modified polycarbonates may be used to prepare structures comprising or containing them utilizing any known processes, such as extrusion, molding, thermoforming, and the like. The disclosed compositions of modified polycarbonate s may be molded using procedure known in the art. The polycarbonate compositions may be molded into useful shaped articles by a variety of means such as injection molding, overmolding, extrusion, rotational molding, blow molding and thermoforming to form various molded articles. Such articles may include thin-walled articles for consumer goods like cellphones, MP3 players, computers, laptops, cameras, video recorders, electronic tablets, hand receivers, kitchen appliances, electrical housings, etc., e.g. a smart meter housing, and the like; electrical connectors, and components of lighting fixtures, ornaments, home appliances,roofs, greenhouses, sun rooms, swimming pool enclosures, Light Emitting Diodes (LEDs) and light panels, extruded film and sheet articles; electrical parts, such as relays; and telecommunications parts such as parts for base station terminals. The present disclosure further contemplates additional fabrication operations on said articles, such as, but not limited to, molding, in-mold decoration, baking in a paint oven, lamination, and / or thermoforming. The compositions disclosed are heated to temperatures at which the composition flows, which may be above the glass transition temperatures of the polycarbonates in the composition. The glass transition temperature is determined using differential scanning calorimetry. Such temperatures may be greater than 155 °C, above 200 °C or greater, 250 °C or greater. Such temperatures may be 400 °C or less or 300 °C or less. The mold may be heated to facilitate processing such as to 60 °C or greater, 80 °C or greater or 100 °C or greater.ILLUSTRATIVE EMBODIMENTSEmbodiment 1 . A method, comprising: contacting one or more one or more flame retardancy modifiers and a polycarbonate composition comprising one or more reactive polycarbonates having free hydroxyl and / or carboxyl groups in a polycarbonate solvent to form a modified polycarbonate that has flame resistance.Embodiment 2. The method of embodiment 1 , wherein the modified polycarbonate has a flame resistance of V-1 or V-0 at a thickness of 1.6 mm or 1.0 mm, according to UL-94 vertical test.Embodiment 3. The method of embodiments 1 or 2, wherein the modified polycarbonate has a flame resistance of V-0 at a thickness of 1.6 mm or 1 .0 mm.Embodiment 4. The method of any one of the previous embodiments, wherein the modified polycarbonate has the same flame resistance as or greater flame resistance than the polycarbonate composition.Embodiment 5. The method of any one of the previous embodiments, further comprising: before contacting the one of more flame retardancy modifiers and the polycarbonate composition, contacting the polycarbonate composition and one or more linking compounds to form the reactive polycarbonate.Embodiment 6. The method of any one of the previous embodiments, further comprising: before contacting the one of more flame retardancy modifiers and the polycarbonate composition, modifying a reactive group of the reactive polycarbonate from a first reactive group to a second reactive group, wherein the first reactive group comprises a hydroxyl and / or carboxyl group.Embodiment 7. The method of any one of the previous embodiments, further comprising: after contacting the one of more flame retardancy modifiers and the polycarbonate composition, contacting the modified polycarbonate and one or more end capping, chain extending, or branching agents to form an end capped, extended, and / or branched polycarbonate.Embodiment 8. The method of any one of the previous embodiments, further comprising: a. hydroxylating a precursor composition comprising one or more waste or virgin polycarbonates to form the polycarbonate composition comprising the one or more reactive polycarbonates that comprise a hydroxyl or carboxyl group.Embodiment 9. The method of embodiment 8, wherein the step of hydroxylating the precursor composition comprises:a. oxidating the one or more waste or virgin polycarbonates to form the one or more reactive polycarbonates; b. exposing the one or more waste or virgin polycarbonates to ultraviolet light such that the one or more reactive polycarbonates are formed; or c. conducting hydrolysis on the one or more waste or virgin polycarbonates to form the one or more reactive polycarbonates.Embodiment 10. The method of any one of the previous embodiments, wherein the one or more flame retardancy modifiers comprises one or more functional groups configured to end cap, chain extend, branch, and / or crosslink with the hydroxyl group, carboxyl group, or both on the one or more hydroxylated polycarbonates, and / or wherein the one or more flame retardancy modifiers comprises one or more functional groups configured to reactive with one or more operative groups of the linking compound.Embodiment 11 . The method of any one of the previous embodiments, wherein the linking compound comprises one or more operative groups configured to react with the reactive group of the reactive polycarbonate and / or with the flame retardancy modifier.Embodiment 12. The method of embodiment 11 , wherein the one or more flame retardancy modifiers comprise two or more functional groups that are configured to chain extend and / or branch with the hydroxyl group, carboxyl group, or both on the one or more hydroxylated polycarbonates.Embodiment 13. The method of embodiments 11 or 12, wherein the one or more reactive, operative, or functional groups comprise one or more nucleophilic and / or electrophilic groups.Embodiment 14. The method of embodiment 13, wherein at least one of the one or more reactive groups of the reactive polycarbonate is different than at least one of the one or more operative groups of the linking compound.Embodiment 15. The method of embodiment 13, wherein at least one of the one or more operative groups of the linking compound is different than at least one of the one or more functional groups of the one or more flame retardancy modifiers.Embodiment 16. The method of any one of embodiments 13-15, wherein the one or more nucleophilic groups comprise carboxylic acids, unsaturated aromatic acids, sulfonic acids, phosphorous based acids, boronic acids, or any combination thereof.Embodiment 17. The method of any one of embodiments 13-15, wherein the one or more electrophilic groups comprise one or more of a epoxide, anhydride, imide, ester, acyl halide, acyl nitrile, aldehyde, ketone, isocyanate, isothiocyanate, phosphorous halides, silyl halide, or any combination thereof.Embodiment 18. The method of any one of the previous embodiments, wherein the polycarbonate composition comprises greater than 0 weight percent waste polycarbonate, based on the total weight of the polycarbonate composition.Embodiment 19. The method of any one of the previous embodiments, wherein the polycarbonate composition comprises greater than 50 weight percent waste polycarbonate, based on the total weight of the polycarbonate composition.Embodiment 20. The method of any one of the previous embodiments, wherein one or more the hydroxyl and / or carboxyl containing compounds comprise one or more bisphenol compounds.Embodiment 21 . The method of any one of the previous embodiments, further comprising: a. separating one or more bisphenol compounds and / or flame retardants from the polycarbonate composition before contacting the one or more flame retardancy modifiers and the polycarbonate composition.Embodiment 22. The method of embodiment 21 , the step of separating the one or more bisphenol compounds and / or flame retardants from the polycarbonate composition comprises: a. contacting the polycarbonate composition and one or more solvents configured to dissolve the one or more bisphenol compounds and / or s flame retardants to separate the one or more bisphenol compound and the polycarbonate composition; b. contacting the polycarbonate composition and one or more absorbents or adsorbents to separate the bisphenol compounds and / or flame retardants from the polycarbonate composition; c. contacting the polycarbonate composition and one or more additives configured to precipitate the bisphenol compound and / or flame retardants from the polycarbonate composition; d. contacting the polycarbonate composition and the flame retardancy modifier to precipitate the bisphenol compound and / or flame retardants from the polycarbonate composition; e. applying a charge to the polycarbonate composition to separate the bisphenol compounds and / or flame retardants from the polycarbonate composition. f. filtering the bisphenol compound and / or flame retardants from the polycarbonate composition.Embodiment 23. The method of any one of the previous embodiments, further comprising: a. separating the modified polycarbonate and the polycarbonate solvent to yield the modified polycarbonate in a solid form.Embodiment 24. The method of embodiment 23, wherein the step of separating the modified polycarbonate and the polycarbonate solvent comprises: a. contacting the polycarbonate composition and a devolatilization solvent configured to separate the modified polycarbonate from polycarbonate composition, the devolatilization solvent, and the polycarbonate solvent; and / or b. contacting the polycarbonate composition and an antisolvent configured to separate the modified polycarbonate from the polycarbonate composition and polycarbonate solvent.Embodiment 25. The method of any one of the previous embodiments, further comprising: a. contacting the modified polycarbonate in the solid form with one or more flame retardants to form a product composition having a flame retardancy that is greater than a flame retardancy of the modified polycarbonate.Embodiment 26. The method of embodiments 25 or 26, wherein the one or more flame retardants are detached from and / or blended with the modified polycarbonate in the product composition.Embodiment 27. The method of embodiments 1 to 24, wherein the modified polycarbonate is free of flame retardants.Embodiment 28. The method of any one of embodiments 25-28, wherein the one or more flame retardants comprises one or more anti-drip agents, charring agents, or a combination thereof.Embodiment 29. The method of any one of the previous embodiments, wherein the one or more flame retardants comprise one or more of halogenated and / or non-halogenated flame retardants.Embodiment 30. The method of any one of embodiments 25-29, wherein the one or more flame retardants include phosphorous-based flame retardants, sulfur-based flame retardants, nitrogen-based flame retardants, and / or inorganic flame retardants.Embodiment 31. The method of any one of the previous embodiments, wherein the polycarbonate solvent is configured to dissolve the one or more reactive, modified, virgin, and / or waste polycarbonates.Embodiment 32. The method of any one of the previous embodiments, wherein the polycarbonate solvent comprises a polar aprotic solvent.Embodiment 33. The method of any one of the previous embodiments, wherein the polycarbonate solvent comprises one or more of methylene chloride, chloroform,tetrahydrofuran (THF), 2-methyl tetra hydrofuran, N-methyl-2-pyrrolidone, or a combination thereof.Embodiment 34. The method of any one of the previous embodiments, wherein the modified polycarbonate has a weight or number average molecular weight that is at least 5 percent greater than a weight or number average molecular weight of the hydroxylated polycarbonate.Embodiment 35. The method of any one of the previous embodiments, wherein the polycarbonate composition comprises greater than 0 percent to about 10 weight percent hydroxyl or carboxyl groups, based on the total weight of the polycarbonate composition.Embodiment 36. A composition, comprising: a. a one or more polycarbonate backbones comprising residues of one or more polycarbonate oligomers or polymers; and b. one or more residues of a flame retardancy modifier each connected with the one or more polycarbonate oligomers or polymers at a residue of a hydroxyl or carboxyl group, the one or more flame retardancy modifiers comprising a residue of a phosphorous compound, a benzoxazine, a cyanophenyl compound, a benzonitrile, a silyl compound, a siloxane compound, an unsaturated hydrocarbon, or any combination thereof.Embodiment 37. The composition of embodiment 36, further comprising: a. a linking compound configured to end cap, chain extend, or branch the one or more the flame retardancy modifiers and the one or more polycarbonate oligomers or polymers.Embodiment 38. The composition of embodiment 36, further comprising: a. one or more end capping, chain extending, or branching agents connected with the polycarbonate backbone and free of connection with the flame retardancy modifier.Embodiment 39. The composition of embodiment 37, wherein the one or more residues of the flame retardancy modifier connects with at least two different polycarbonate oligomers or polymers.Embodiment 40. The composition of any one of embodiments 36-39, further comprising: one or more flame retardants that are detached from and blended with the combination of the one or more polycarbonate oligomers or polymers and the one or more flame retardancy modifiers.Embodiment 41. The composition of embodiment 40, wherein the one or more flame retardants are configured to improve the flame retardancy of the composition.Embodiment 42. The composition of embodiments 40 or 41 , wherein the one or more flame retardants comprises one or more anti-drip agents, charring agents, or a combination thereof.Embodiment 43. The composition of embodiments 36-42, wherein the composition is essentially free of flame retardants.Embodiment 44. The composition of any one of embodiments 36-43, wherein the composition of a flame retardancy of V-0 or V-1 or more at a thickness of 1.6 mm or 1.0 mm, according to UL-94 vertical test.Embodiment 45. The composition of embodiments 36-44, wherein the one or more flame retardancy modifiers are configured to end cap, chain extend, branch, and / or cross-link the one or more polycarbonate oligomers or polymers.Embodiment 46. The composition of embodiments 36-45, wherein the one or more polycarbonate oligomers or polymers comprise residues of virgin or waste polycarbonate.Embodiment 47. The composition of embodiments 36-46, wherein the one or more polycarbonate oligomers or polymers comprise at least 10 percent or more waste polycarbonate.

Claims

CLAIMSWhat is claimed is:

1. A method, comprising: contacting one or more one or more flame retardancy modifiers and a polycarbonate composition comprising one or more reactive polycarbonates having free hydroxyl and / or carboxyl groups in a polycarbonate solvent to form a modified polycarbonate that has flame resistance.

2. The method of claim 1 , wherein the modified polycarbonate has a flame resistance of V- 1 or V-0 at a thickness of 1 .6 mm or 1 .0 mm, according to UL-94 vertical test.

3. The method of claims 1 or 2, wherein the modified polycarbonate has a flame resistance of V-0 at a thickness of 1.6 mm or 1 .0 mm.

4. The method of any one of the previous claims, wherein the modified polycarbonate has the same flame resistance as or greater flame resistance than the polycarbonate composition.

5. The method of any one of the previous claims, further comprising: before contacting the one of more flame retardancy modifiers and the polycarbonate composition, contacting the polycarbonate composition and one or more linking compounds to form the reactive polycarbonate.

6. The method of any one of the previous claims, further comprising: before contacting the one of more flame retardancy modifiers and the polycarbonate composition, modifying a reactive group of the reactive polycarbonate from a first reactive group to a second reactive group, wherein the first reactive group comprises a hydroxyl and / or carboxyl group.

7. The method of any one of the previous claims, further comprising: after contacting the one of more flame retardancy modifiers and the polycarbonate composition, contacting the modified polycarbonate and one or more end capping, chain extending, or branching agents to form an end capped, extended, and / or branched polycarbonate.

8. The method of any one of the previous claims, further comprising: a. hydroxylating a precursor composition comprising one or more waste or virgin polycarbonates to form the polycarbonate composition comprising the one or more reactive polycarbonates that comprise a hydroxyl or carboxyl group.

9. The method of claim 8, wherein the step of hydroxylating the precursor composition comprises:a. oxidating the one or more waste or virgin polycarbonates to form the one or more reactive polycarbonates; b. exposing the one or more waste or virgin polycarbonates to ultraviolet light such that the one or more reactive polycarbonates are formed; or c. conducting hydrolysis on the one or more waste or virgin polycarbonates to form the one or more reactive polycarbonates.

10. The method of any one of the previous claims, wherein the one or more flame retardancy modifiers comprises one or more functional groups configured to end cap, chain extend, branch, and / or crosslink with the hydroxyl group, carboxyl group, or both on the one or more hydroxylated polycarbonates, and / or wherein the one or more flame retardancy modifiers comprises one or more functional groups configured to reactive with one or more operative groups of the linking compound.11 . The method of any one of the previous claims, wherein the linking compound comprises one or more operative groups configured to react with the reactive group of the reactive polycarbonate and / or with the flame retardancy modifier.

12. The method of claim 11 , wherein the one or more flame retardancy modifiers comprise two or more functional groups that are configured to chain extend and / or branch with the hydroxyl group, carboxyl group, or both on the one or more hydroxylated polycarbonates.

13. The method of claims 11 or 12, wherein the one or more reactive, operative, or functional groups comprise one or more nucleophilic and / or electrophilic groups.

14. The method of claim 13, wherein at least one of the one or more reactive groups of the reactive polycarbonate is different than at least one of the one or more operative groups of the linking compound.

15. The method of claim 13, wherein at least one of the one or more operative groups of the linking compound is different than at least one of the one or more functional groups of the one or more flame retardancy modifiers.

16. The method of any one of claims 13-15, wherein the one or more nucleophilic groups comprise carboxylic acids, unsaturated aromatic acids, sulfonic acids, phosphorous based acids, boronic acids, or any combination thereof.

17. The method of any one of claims 13-15, wherein the one or more electrophilic groups comprise one or more of a epoxide, anhydride, imide, ester, acyl halide, acyl nitrile, aldehyde, ketone, isocyanate, isothiocyanate, phosphorous halides, silyl halide, or any combination thereof.

18. The method of any one of the previous claims, wherein the polycarbonate composition comprises greater than 0 weight percent waste polycarbonate, based on the total weight of the polycarbonate composition.

19. The method of any one of the previous claims, wherein the polycarbonate composition comprises greater than 50 weight percent waste polycarbonate, based on the total weight of the polycarbonate composition.

20. The method of any one of the previous claims, wherein one or more the hydroxyl and / or carboxyl containing compounds comprise one or more bisphenol compounds.21 . The method of any one of the previous claims, further comprising: a. separating one or more bisphenol compounds and / or flame retardants from the polycarbonate composition before contacting the one or more flame retardancy modifiers and the polycarbonate composition.

22. The method of claim 21 , the step of separating the one or more bisphenol compounds and / or flame retardants from the polycarbonate composition comprises: a. contacting the polycarbonate composition and one or more solvents configured to dissolve the one or more bisphenol compounds and / or s flame retardants to separate the one or more bisphenol compound and the polycarbonate composition; b. contacting the polycarbonate composition and one or more absorbents or adsorbents to separate the bisphenol compounds and / or flame retardants from the polycarbonate composition; c. contacting the polycarbonate composition and one or more additives configured to precipitate the bisphenol compound and / or flame retardants from the polycarbonate composition; d. contacting the polycarbonate composition and the flame retardancy modifier to precipitate the bisphenol compound and / or flame retardants from the polycarbonate composition; e. applying a charge to the polycarbonate composition to separate the bisphenol compounds and / or flame retardants from the polycarbonate composition. f. filtering the bisphenol compound and / or flame retardants from the polycarbonate composition.

23. The method of any one of the previous claims, further comprising: a. separating the modified polycarbonate and the polycarbonate solvent to yield the modified polycarbonate in a solid form.

24. The method of claim 23, wherein the step of separating the modified polycarbonate and the polycarbonate solvent comprises: a. contacting the polycarbonate composition and a devolatilization solvent configured to separate the modified polycarbonate from polycarbonate composition, the devolatilization solvent, and the polycarbonate solvent; and / or b. contacting the polycarbonate composition and an antisolvent configured to separate the modified polycarbonate from the polycarbonate composition and polycarbonate solvent.

25. The method of any one of the previous claims, further comprising: a. contacting the modified polycarbonate in the solid form with one or more flame retardants to form a product composition having a flame retardancy that is greater than a flame retardancy of the modified polycarbonate.

26. The method of claims 25 or 26, wherein the one or more flame retardants are detached from and / or blended with the modified polycarbonate in the product composition.

27. The method of claims 1 to 24, wherein the modified polycarbonate is free of flame retardants.

28. The method of any one of claims 25-28, wherein the one or more flame retardants comprises one or more anti-drip agents, charring agents, or a combination thereof.

29. The method of any one of the previous claims, wherein the one or more flame retardants comprise one or more of halogenated and / or non-halogenated flame retardants.

30. The method of any one of claims 25-29, wherein the one or more flame retardants include phosphorous-based flame retardants, sulfur-based flame retardants, nitrogen-based flame retardants, and / or inorganic flame retardants.

31. The method of any one of the previous claims, wherein the polycarbonate solvent is configured to dissolve the one or more reactive, modified, virgin, and / or waste polycarbonates.

32. The method of any one of the previous claims, wherein the polycarbonate solvent comprises a polar aprotic solvent.

33. The method of any one of the previous claims, wherein the polycarbonate solvent comprises one or more of methylene chloride, chloroform, tetra hydrofuran (THF), 2-methyl tetrahydrofuran, N-methyl-2-pyrrolidone, or a combination thereof.

34. The method of any one of the previous claims, wherein the modified polycarbonate has a weight or number average molecular weight that is at least 5 percent greater than a weight or number average molecular weight of the hydroxylated polycarbonate.

35. The method of any one of the previous claims, wherein the polycarbonate composition comprises greater than 0 percent to about 10 weight percent hydroxyl or carboxyl groups, based on the total weight of the polycarbonate composition.

36. A composition, comprising: a. a one or more polycarbonate backbones comprising residues of one or more polycarbonate oligomers or polymers; and b. one or more residues of a flame retardancy modifier each connected with the one or more polycarbonate oligomers or polymers at a residue of a hydroxyl or carboxyl group, the one or more flame retardancy modifiers comprising a residue of a phosphorous compound, a benzoxazine, a cyanophenyl compound, a benzonitrile, a silyl compound, a siloxane compound, an unsaturated hydrocarbon, or any combination thereof.

37. The composition of claim 36, further comprising: a. a linking compound configured to end cap, chain extend, or branch the one or more the flame retardancy modifiers and the one or more polycarbonate oligomers or polymers.

38. The composition of claim 36, further comprising: a. one or more end capping, chain extending, or branching agents connected with the polycarbonate backbone and free of connection with the flame retardancy modifier.

39. The composition of claim 37, wherein the one or more residues of the flame retardancy modifier connects with at least two different polycarbonate oligomers or polymers.

40. The composition of any one of claims 36-39, further comprising: one or more flame retardants that are detached from and blended with the combination of the one or more polycarbonate oligomers or polymers and the one or more flame retardancy modifiers.41 . The composition of claim 40, wherein the one or more flame retardants are configured to improve the flame retardancy of the composition.

42. The composition of claims 40 or 41 , wherein the one or more flame retardants comprises one or more anti-drip agents, charring agents, or a combination thereof.

43. The composition of claims 36-42, wherein the composition is essentially free of flame retardants.

44. The composition of any one of claims 36-43, wherein the composition of a flame retardancy of V-0 or V-1 or more at a thickness of 1.6 mm or 1.0 mm, according to UL-94 vertical test.

45. The composition of claims 36-44, wherein the one or more flame retardancy modifiers are configured to end cap, chain extend, branch, and / or cross-link the one or more polycarbonate oligomers or polymers.

46. The composition of claims 36-45, wherein the one or more polycarbonate oligomers or polymers comprise residues of virgin or waste polycarbonate.

47. The composition of claims 36-46, wherein the one or more polycarbonate oligomers or polymers comprise at least 10 percent or more waste polycarbonate.

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