WO2025026752A2

WO2025026752A2 - Methods of modifying polycarbonates with siloxanes

Info

Publication number: WO2025026752A2
Application number: PCT/EP2024/070380
Authority: WO
Inventors: Abidin Balan; Chiel Mertens; Pascal Lakeman
Original assignee: Trinseo Europe Gmbh
Priority date: 2023-07-31
Filing date: 2024-07-18
Publication date: 2025-02-06

Abstract

The present application discloses a method including contacting one or more reactive polycarbonates having free hydroxyl and/or carboxyl groups with one or more reactive siloxane compounds terminated by one or more acetoxy, methoxy, ethoxy, halide, hydrogen atoms in a solvent system to form one or more siloxane modified polycarbonates in a recovery solution, and the one or more reactive polycarbonates comprise one or more waste polycarbonates.

Description

METHODS OF MODIFYING POLYCARBONATES WITH SILOXANES

FIELD

[1] Disclosed are methods of chemically modifying recycled polycarbonates so that the polycarbonates have improved molecular weight, flame retardancy, and/or reduced hydroxyl and/or carboxyl groups in the polymer composition.

BACKGROUND

[2] Polycarbonate and copolymers containing carbonate units are utilized in a variety of molded structures. 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. Over time, the polycarbonates and copolymers thereof can become degraded. Degraded polycarbonates tend to accumulate in waste feedstocks. Because the degradation of the polycarbonates and copolymers thereof introduces undesirable side effects, such as introduction of undesirable derivative monomers and reduced properties from a loss of molecular weight, steps need to be taken to uptake and recycle the polycarbonates .

[3] Accordingly, what is needed are techniques to modify the recycled polycarbonates such that the polycarbonates have properties that are useable in new consumer products.

SUMMARY

[4] The present application discloses a method including contacting one or more reactive polycarbonates having free hydroxyl and/or carboxyl groups with one or more reactive siloxane compounds terminated by one or more acetoxy, methoxy, ethoxy, halide, or hydrogen atoms in a solvent system to form one or more siloxane modified polycarbonates in a recovery solution, and the one or more reactive polycarbonates comprise one or more waste polycarbonates.

[5] The one or more reactive polycarbonates may comprise the one or more waste polycarbonates in an amount of about 5 weight percent to about 95 weight percent, based on the total amount of reactive polycarbonates. The free hydroxyl and/or carboxyl groups may be positioned at one or more terminal ends of the reactive polycarbonate. The free hydroxyl and/or carboxyl groups may be positioned along a backbone of the reactive polycarbonate. The siloxane modified polycarbonates may have a number and/or weight average molecular weight that is at least 5 percent larger than a number and/or weight average molecular weight of the reactive polycarbonates incorporated into the siloxane modified polycarbonate. The method may further include contacting the solvent system and one or more waste feedstocks comprising the one or more waste polycarbonates and one or more non-polycarbonate compounds to form the recovery solution; and separating at least some of the one or more nonpolycarbonate compounds from the recovery solution. The method may further include contacting one or more precursor siloxane compounds with water to form the one or more reactive siloxane compounds in the recovery solution; and contacting the recovery solution with one or more polycarbonate solvents to form the solvent system comprising the water and the one or more polycarbonate solvents in the recovery solution. The method may further include contacting the one or more reactive polycarbonates with one or more allyl halides to form one or more vinyl ether terminated polycarbonates configured to react with the hydrogen atom of the one or more reactive siloxane compounds and form the one or more siloxane modified polycarbonates. The one or more allyl halides may be terminated by an alkene and a halide and comprises between one and one hundred carbon atoms between the halide and the carbon at the alkene. The method may include contacting one or more scavengers with the recovery solution to scavenge for acids formed from contacting the one or more reactive polycarbonates and the one or more reactive siloxane compounds. The reactive polycarbonate and the reactive siloxane compound may be contacted in the presence of a catalyst configured to facilitate formation of the siloxane modified polycarbonate. The solvent system may comprise at least a polycarbonate solvent configured to dissolve the one or more reactive polycarbonates and optionally may further include water. The one or more reactive siloxane compounds may comprise between one and one hundred units of siloxane connected in a chain that is terminated by at least one hydrogen acetoxy, methoxy, ethoxy, halide group, or any combination thereof.

[6] The present disclosure provides for a polymerizable composition including one or more reactive polycarbonates having free hydroxyl and/or carboxyl groups along the backbone and/or at one or more terminal ends of the one or more reactive polycarbonates, wherein the one or more reactive polycarbonates comprise one or more waste polycarbonates. The polymerizable composition includes a solvent system comprising one or more polycarbonate solvents and/or water. The polymerizable composition includes one or more siloxane modifiers, which include at least one of one or more reactive siloxane compounds terminated by at least one hydrogen and one or more allyl halides; one or more reactive siloxane compounds terminated by at least one acetoxy, methoxy, ethoxy, halide, or any combination thereof; or one or more precursor siloxane compounds configured to form the reactive siloxane compounds terminated by at least one halide in water. The one or more reactive polycarbonates and the siloxane modifier are react-able in the solvent system to form one or more siloxane modified polycarbonates.

[7] The present disclosure provides for a polymer composition including one or more one or more siloxane modified polycarbonates. The siloxane modified polycarbonates include one or more polycarbonate segments one or more siloxane segments connected with the one or more polycarbonate segments at oxygen atoms along the backbone and at a terminal end of the one or more polycarbonate segments. At least some of the one or more siloxane segments connect two or more polycarbonate segments.

[8] The one or more polycarbonate segments may include at least about 5 to 100 weight percent or more of residues of waste polycarbonate, based on the total amount of the siloxane modified polycarbonate. Each of the one or more siloxane segments may comprise between two and one hundred repeating units of siloxane. The polymer composition may be essentially free of hydroxyl and/or carboxyl containing compounds.

[9] The present techniques allow for modification of reactive polycarbonates by reactive siloxane compounds to form siloxane modified polycarbonates that have properties, such as improved molecular weight, flame retardancy, and/or reduced hydroxyl and/or carboxyl groups in the polymer composition. The reactive siloxane compounds are advantageous in recovery solutions containing recycled polycarbonates in that the formation and use of such reactive siloxane compounds is possible directly in the recycle solutions so that reactive siloxane compounds are formable and recycled polycarbonates can be repaired in the same step. Addition of the reactive siloxane compounds can be used to both modify properties of the reactive polycarbonates and to optionally remove smaller hydroxyl containing compounds, such as bisphenol A.

BREIF DESCRIPTION OF THE DRAWING

[10] Figure 1 is GPC analysis of the material after heating it up to 300 °C.

DETAILED DESCRIPTION

[11] The present techniques allow for modification of the reactive groups of a reactive polycarbonate to form siloxane modified polycarbonates that have flame retardancy, improved molecular weight, and/or other improved polymeric properties. By reacting the reactive siloxane compounds with one or more carboxyl and/or hydroxyl groups, the reactive siloxane compounds provide a dual advantage or removing hydroxyl and/or carboxyl groups on the reactive polycarbonates and improving polymeric properties of the waste polycarbonate.

[12] Siloxane modified polycarbonates refer to polycarbonates that include residues of reactive siloxane compounds. Reactive polycarbonates include at least one reactive group as described herein. The siloxane modified or reactive polycarbonates may be comprised of virgin polycarbonate, waste polycarbonate, or any combination thereof. Siloxane modified polycarbonate as described herein include at least a residue of a reactive siloxane compound and a reactive polycarbonate. The term repaired refers to adjusting the molecular weight of the waste or reactive polycarbonate to a siloxane modified polycarbonate with a different molecular weight or with a reduced number of carboxyl and/or hydroxyl end groups. A recovery solution includes at least a solvent system and at least one polycarbonate compound. A solvent system comprises one or more solvents that may be miscible or immiscible. Waste polycarbonate refers to polycarbonate located in waste feedstocks. 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 with or without reacting with one or more reactive siloxane compounds.

[13] 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.

[14] 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 may contain 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.

[15] 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 carboxyl containing 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, reactive and/or precursor siloxane compounds, 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.

[16] 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 in copolycarbonates 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.

[17] 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 I

7

SUBSTITUTE SHEET (RULE 26)

wherein 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:

II

SUBSTITUTE SHEET (RULE 26)

wherein 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 ;

R^c and R^d are mutually independent of each other and are individually selectable for each X¹ and are hydrogen or a C i_₆ alkyl, preferably hydrogen, methyl or ethyl;

X¹ denotes carbon; and m denotes an integer from 4 to 7, preferably 4 or 5, with the proviso that R^c and R^d simultaneously denote an alkyl on at least one X¹ atom.

[18] 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.

[19] To cap, branch, or chain extend the polycarbonates used in the present disclosure, one or more functional compounds may be used in combination with the one or more reactive siloxane compounds. 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 and/or precursor and/or reactive siloxane compound. 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.

[20] 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 siloxane 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 siloxane modified polycarbonates. The chain terminators may be used to bind with one or more non-polycarbonate compounds so that free hydroxyl and/or carboxyl groups nonpolycarbonate compounds (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.

[21] 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.

[22] 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. [23] 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.

[24] The solvent system may comprise one or more solvents or only one solvent, such as the polycarbonate solvent. The solvent system may include two solvents present in concentrations that are miscible. The solvent system may include two or more solvents that are present in amounts such that part of the solvent system includes some water dissolved in the one or more polycarbonate solvents and some water that is phase separated from the polycarbonate solvents. Miscible amounts of two solvents may be impacted or changed based on temperature or pressure applied to the recovery solution. The solvent system may include polycarbonate and water in an amount that is miscible, such as about 0.6 weight percent or less, about 0.4 weight percent or less, about 0.2 weight percent or less, or about 0.1 weight percent, based on the total weight of the solvent system or recovery solution. In some examples, the water may be present in the solvent system in an amount that is in excess of a miscible amount of water in the polycarbonate solvent. Where water is involved in one or more reactions described herein, such as with precursor siloxane compounds that form reactive siloxane compounds, water may react within the polycarbonate solvent and excess water may dissolve into the polycarbonate solvent as the reaction occurs. One or more separation steps may be used to remove undesirable amounts of water or essentially all (e.g., until the solvent system has 0.1 or less, 0.01 or less, or 0.001 or less water in the solvent system) of the water. Water can be removed from the solvent system before or after dissolution of the reactive polycarbonates. Instead of water, the solvent system may include one or more other polar protic solvents configured to adjust the miscibility of components in the recovery solution or to participate in one or more reactions, such as during formation of the siloxane modified polycarbonates or reactive siloxane compounds. Examples of other polar protic solvents may include methanol, ethanol, n- or iso-propanol, n- or tert-butanol, acetic acid, ammonia, formic acid, or any combination thereof.

[25] 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 siloxane 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.

[26] The present disclosure provides for techniques to modify reactive polycarbonate polymers and oligomers with reactive siloxane compounds to formulate polymers with imparted flame resistance, larger molecular weights, fewer hydroxyl and/or carboxyl groups, and/or reduced hydroxyl and/or carboxyl groups in the polymer composition. By integrating the siloxane compounds within the polycarbonate chains, siloxane units can be added within and/or along the backbone of the polycarbonate such that one or more properties of the siloxane modified polycarbonate. Additionally, to simplify steps in the recovery of waste polycarbonate, reactive siloxane compounds can be formed in situ and/or using the same solvent systems as those used to dissolve the waste polycarbonate such that separate and processing steps can be reduced. Using these techniques, the siloxane modified polycarbonates can additionally be combined with techniques to integrate chain extenders and branching agents to achieve polycarbonates with desirable flame resistance, reduced hydroxyl and/or carboxyl groups in the polymer composition and increased molecular weight.

[27] Waste polycarbonates (e.g., reactive polycarbonate) include reactive groups that are formed from degradation of virgin polycarbonate over time. The reactive siloxane compounds disclosed herein can be easily contacted with the reactive groups of the waste polycarbonates and integrated into existing waste polycarbonates to improve molecular weight and adjust properties of the polycarbonates.

[28] The reactive polycarbonate may include one or more reactive groups (e.g., carboxyl, hydroxyl, and/or phenol groups) configured to react with the acetoxy, methoxy, ethoxy, halide, and/or hydrogen groups of the reactive siloxane compound. Where the reactive polycarbonate is a recycled and unmodified polycarbonate polymer and/or oligomer, the reactive polycarbonate may include one or more hydroxyl, phenol, or carboxyl groups at terminal ends or along the backbone that have formed from natural degradation of the polymer over time. Natural degradation may occur from exposure to extreme temperature and/or sunlight (i.e., UV radiation). Before contacting the reactive siloxane compound with the reactive polycarbonate, the reactive polycarbonates or virgin polycarbonates described herein may be modified such that free hydroxyl, phenol, and/or carboxyl groups are introduced into the polymer at terminal ends and/or along the backbone so that the polycarbonate is react-able with the acetoxy, methoxy, ethoxy, halide, and/or hydrogen groups of the reactive siloxane compounds. 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, phenol, 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. The reactive polycarbonate may contain any amount of hydroxyl and/or carboxyl groups at terminal ends or along the backbone and the reactive siloxane compound may bind with the hydroxyl and/or carboxyl groups such that free hydroxyl and/or carboxyl groups are reduced or eliminated in the modified siloxane compound. Additionally, reactive polycarbonate in compositions may include an undesirable amount of hydroxyl and/or carboxyl containing compounds, which may be reduced through introduction of the separation steps and/or the reactive siloxane compounds described herein.

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

[30] Siloxane modifiers as used herein are configured to integrate siloxane units within and/or along the backbone of the siloxane modified polycarbonate. Siloxane modifiers may be any siloxane compound comprising repeating units of siloxane that includes at least one acetoxy, methoxy, ethoxy, halide, and/or hydrogen groups configured to react with a hydroxyl, carboxyl, and/or phenol group of the reactive polycarbonate. The siloxane modifiers may comprise, for example, between one and 100 siloxane units. The siloxane modifiers may include precursor and/or reactive siloxane compounds. The siloxane modifiers may be contacted with the reactive polycarbonates before or after the reactive polycarbonates are dissolved in the solvent systems. The siloxane modifiers may be configured to react in the solvent system to form multi-unit siloxanes. [31] The precursor siloxane compound may function as a basis for the reactive siloxane compound. The precursor siloxane compound may comprise a silicon or silane group substituted by at least one halide, acetoxy, ethoxy, and/or methoxy groups, and optionally one or more hydrogen and/or alkyl groups. The precursor siloxane comprising at least one halide, acetoxy, ethoxy, and/or methoxy groups may be configured to react with one or more water molecules dissolved in the solvent system to form the reactive siloxane compound having one or more terminal halide, acetoxy, ethoxy, and/or methoxy groups. The precursor siloxane compound may have a structure according to the follow formula:

Where at least one R^a comprises a hydrogen, methoxy, acetoxy, and/or halide groups and each R^a may independently include a halide, methoxy, ethoxy, acetoxy, hydrogen or straight or branched alkyl, aryl, alkyl-aryl, aryl-alkyl, heteroalkyl, or heteroaryl group, or any combination thereof.

[32] After reacting with the water molecules, one or more acids may be produced as a byproduct in the formation of the reactive siloxane compounds or siloxane modified polycarbonate. The one or more acids may be removed from the solvent system before, during, or after contacting the reactive polycarbonates with the solvent system by one or more scavengers as described herein. The precursor siloxane compound may be configured to introduce siloxane units along or within the backbone of the reactive polycarbonate such that a siloxane modified polycarbonate is formed with increased molecular weight relative to the reactive polycarbonates. The precursor siloxane may include any number of halide, acetoxy, ethoxy, and/or methoxy groups configured to reactive with one or more free hydroxyl , carboxyl, and/or phenol groups of the reactive polycarbonate. The precursor siloxane compound may include monomethoxysilane, dimethoxysilane, trimethoxysilane, and/or tetramethoxysilane. The precursor siloxane compound may include monoethoxysilane, diethoxysilane, triethoxysilane, and/or tetraethoxysilane. The precursor compound may include a monoacetoxysilane, diacetoxysilane, triacetoxysilane, and/or tetraacetoxysilane. The precursor siloxane compound may include a monohalosilane, a dihalosilane, a trihalosilane, and/or a tetrahalosilane. The precursor siloxane compound may be contacted with the solvent system before, during, or after the reactive polycarbonates are dissolved in the solvent system. The precursor siloxane compound may be dissolvable in the polycarbonate solvent or may be immiscible with the polycarbonate solvent. The precursor siloxane compound may be added to the solvent system in any amount sufficient to integrate siloxane units into the reactive polycarbonate. In some examples, the precursor siloxane compound may directly connect with reactive polycarbonate before formation of the reactive siloxane compound. Some of the precursor siloxane compound may react with water to form longer chained reactive siloxane compound and some of the precursor siloxane compounds may react with the reactive polycarbonates to end cap, chain extend, cross-link, or branch the reactive polycarbonates and form siloxane modified polycarbonates. The precursor siloxane compound may be added to the solvent system in an amount of about 0.1 weight percent or more, about 1 weight percent or more, or about 3 weight percent or more, based on the total weight of the solvent system. The precursor siloxane compound may be added to the solvent system in an amount of about 10 weight percent or less, about 8 weight percent or less, or 5 weight percent or less.

[33] The reactive siloxane compound functions to integrate siloxane units into the reactive polycarbonate to form the siloxane modified polycarbonate. The reactive siloxane may be configured to bind with the reactive polycarbonate at one or more locations on the reactive polycarbonate, optionally in the presence of a catalyst appropriate to form siloxane modified polycarbonates. Reactive locations include free carboxyl, hydroxyl, phenol, and/or alkene groups either along the backbone of the polycarbonate or at terminals ends of the polycarbonate. The reactive siloxane compounds may include any groups configured to react and bind with the reactive polycarbonates at reactive locations. Examples of groups configured to react at or bind with reactive locations may include methoxy, ethoxy, acetoxy, halides, and/or hydrogen groups. The reactive siloxane compounds may include any number of halides methoxy, ethoxy, acetoxy, and/or hydrogen groups configured to react at or bind with reactive locations of the reactive polycarbonate. The reactive siloxane compounds may include a number of methoxy, ethoxy, acetoxy, halides, and/or hydrogen groups configured to end cap, chain extend, branch, and/or cross-link the reactive polycarbonate such that desirable molecular weights of the siloxane modified polycarbonates are achieved. The reactive siloxane compounds may include methoxy, acetoxy, ethoxy, halides, and/or hydrogen groups. at different terminal ends, on different silicon atoms, or on the same silicon atoms. The reactive siloxane compounds may include one or more, two or more, three or more, four or more, five or more, or a plurality of methoxy, acetoxy, ethoxy, halides, and/or hydrogen groups, configured to end cap, chain extend, branch, and/or cross-link the reactive polycarbonate. The reactive siloxane compounds may include any number of siloxane units sufficient to introduce molecular weight increase, imparted flame resistance, reduced hydroxyl and/or carboxyl groups in the polymer composition, or any combination thereof. The reactive siloxane compound may include 1 or more, 10 or more, or 20 or more siloxane units. The reactive siloxane compound may include 100 or less, 70 or less, or 50 or less siloxane units. The reactive siloxane compound may be added to the solvent system in any amount sufficient to increase molecular weight of the reactive polycarbonate and/or to remove or bind with carboxyl and/or hydroxyl containing compounds in the recovery solution. The reactive siloxane compound may be added to the solvent system in an amount of about 0.1 weight percent or more, about 1 weight percent or more, or about 3 weight percent or more, based on the total weight of the solvent system. The reactive siloxane compound may be added to the solvent system in an amount of about 10 weight percent or less, about 8 weight percent or less, or 5 weight percent or less. The reactive siloxane compound may additionally or separately reduce the amount of hydroxyl containing compounds in the recovery solution. The reactive siloxane compound may be used to bind polycarbonate polymers and/or oligomers together and/or bind with hydroxyl containing compounds so that the final polycarbonate composition contains less free hydroxyl and/or carboxyl groups.

[34] The reactive siloxane compound may have a structure according to the following formula:

where m is an integer from 1 to 100, at least one R^a comprises a methoxy, ethoxy, acetoxy, halides, and/or hydrogen groups., and where each R^a may independently include a methoxy, acetoxy, ethoxy, halides, hydrogen, .or straight or branched alkyl, aryl, alkyl-aryl, aryl-alkyl, heteroalkyl, or heteroaryl group, or any combination thereof.

[35] The allyl halide may be configured to react with a hydroxyl and/or phenol group of the polycarbonate to form an acid and a vinyl ether terminated polycarbonate. Where the siloxane compound is terminated by or includes at least one hydrogen atom, the siloxane compound may be configured to react with the vinyl group of the vinyl ether terminated polycarbonate such that a siloxane modified polycarbonate is formed, optionally in the presence of an appropriate catalyst. The siloxane units of the siloxane modified polycarbonate may connect with the polycarbonate units through one or more alkyl, aryl, alkyl-aryl, or arylalkyl groups therebetween that are residues of the allyl halide. The allyl halide may be added to the solvent system in an amount sufficient to chain extend, end cap, and/or branch the reactive polycarbonates. The allyl halide may be added in a weight percent of about 0.1 weight percent or more, about 0.5 weight percent or more, or about 1 weight percent or more, based on the total weight solvent system. The allyl halide may be added in a weight percent of about 5 weight percent or less, about 3 weight percent or less, or about 2 weight percent or less, based on the total weight solvent system. The allyl halide may be added to the solvent system in a molar ratio relative to the reactive siloxane compounds such that desired molecular weight increases occur. The allyl halide and reactive siloxane compounds may be contacted in the solvent system in a molar ratio of about 4:1 or more, about 3:1 or more, or about 2:1 or more. The allyl halide and reactive siloxane compounds may be contacted in the solvent system in a molar ratio of about 1 :1 or less, about 1 :2 or less, or about 1 :4 or less. The allyl halide may have any structure that connects an alkene and a halide. The allyl halide may have any structure that is terminated by a halide at one end and an alkene at another end. The allyl halide may include one or more straight or branched alkyl, aryl, alkylaryl, arylalkyl groups, or any combination thereof between the alkene and the halide. The allyl halide may have a structure according to the following formula:

Where Ha is any halide, where R^b is one or more straight or branched alkyl, aryl, alkylaryl, arylalkyl groups, or any combination, and where x is an integer from 1 to 10.

[36] The vinyl ether terminated polycarbonates may have a structure according to the following formula:

Where R^b is one or more straight or branched alkyl, aryl, alkylaryl, arylalkyl groups, or any combination, where x is an integer from 1 to 10, and where PC is a residue of a reactive polycarbonate.

[37] After contacting the vinyl ether terminated polycarbonates and the reactive siloxane compounds, the siloxane modified polycarbonate may have a structure according to the following formula:

[38] Where R^b is one or more straight or branched alkyl, aryl, alkylaryl, arylalkyl groups, or any combination, where x is an integer from 1 to 10, where m is an integer from 1 to 100, at least one R^a is a hydrogen or halide atom, where each R^a may independently include a halide, hydrogen or straight or branched alkyl, aryl, alkyl-aryl, aryl-alkyl, heteroalkyl, or heteroaryl group, or any combination thereof, and where PC is a residue of a reactive polycarbonate.

[39] After formation of the reactive siloxane compound or siloxane modified polycarbonates, one or more acids may be produced as a side product of the reaction. Acids as described herein may comprise any acid compound including a halide, methoxy, ethoxy, and/or acetoxy group, such as a halide acid or acetic acid. Halide acids may include hydrochloric acid, hydrobromic acid, hydrofluoric acid, or any combination thereof. The acids formed herein may be removed through any separation step known to the skilled artisan before, during, or after addition of the reactive polycarbonates or formation of the siloxane modified polycarbonates.

[40] The present disclosure provides for a polymer composition including siloxane modified polycarbonates, as described herein. Specifically, the residues of the reactive siloxane compounds may connect with polycarbonate units at oxygen atoms along the backbone or at the terminal ends of the polycarbonate segments. After formation of the siloxane modified polycarbonate, siloxane modified polycarbonate may be removed from the recovery solution through separation steps described herein to remove polycarbonates from the recovery solution or other liquids. The siloxane modified polycarbonates and/or polymer composition may be essentially free (i.e., containing 1 weight percent or less, 0.1 weight percent or less, or 0.01 weight percent or less) of the solvent system and/or hydroxyl and/or carboxyl containing compounds. The siloxane modified polycarbonates may contain one or more polycarbonate segments connected by residues of a reactive siloxane compounds such that a siloxanepolycarbonate copolymer is formed. The siloxane modified polycarbonates may be branched or unbranched siloxane-polycarbonate copolymers of repeating siloxane units and polycarbonate segments. The amount of branching may be derived from the reactive siloxane compound having three or more methoxy, ethoxy, acetoxy, halides, and/or hydrogen groups, that connect three different polycarbonate segments. In other examples, the amount of branching may be derived from the reactive polycarbonate having at least three hydroxyl and/or carboxyl groups configured to bind with the reactive siloxane group. The polycarbonate segments may be based on residues of waste polycarbonate polymer or oligomers with any number of repeating units of polycarbonate. For the siloxane blocks, the siloxane modified polycarbonates may include any number of siloxane units in each block. Each siloxane block may include one or more, four or more, or ten or more siloxane units. Each siloxane block may include one hundred or less, seventy five or less, or fifty or less siloxane units.

[41] The present application provides for polymerizable compositions that include any number of the components described herein that are present in waste feedstocks or used in the formation of the siloxane modified polycarbonates. For example, polymerizable compositions may include one or more acids, siloxane modifiers (e.g., reactive and/or precursor siloxane compounds), reactive and/or virgin polycarbonate, catalysts configured to form siloxane modified polycarbonates, solvent systems, non-polycarbonate compounds, waste feedstocks, or any combination thereof. The one or more reactive polycarbonates and the siloxane modifier are react-able in the solvent system of the polymerizable composition to form one or more siloxane modified polycarbonates.

[42] The polycarbonate or polymerizable compositions may contain waste polycarbonate, polycarbonate segments, or residues thereof in any amount sufficient to achieve desirable assemblies of recycled components. For example, the polycarbonate or polymerizable compositions may include about 5 percent or more, about 15 percent or more, or about 25 percent or more of waste polycarbonate, polycarbonate segments, or residues thereof. The polycarbonate or polymerizable compositions may include about 100 percent or less, about 80 percent or less or about 50 percent or less of waste polycarbonate, polycarbonate segments, or residues thereof.

[43] In downstream process uses, the siloxane modified polycarbonate may be contacted with one or more compounds desirable to make a downstream product or composition. The siloxane 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, styrene acrylonitrile, acrylonitrile butadiene, styrene, high impact polystyrene, polymethylmethacrylate, polyolefins or any combination thereof. The siloxane 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.

[44] The polycarbonate solvent, precursor and/or reactive siloxane compound, 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.

[45] 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.

[46] 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.

[47] Before, during, or after contacting the polycarbonate solvent, solvent system, 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 and/or precursor and/or reactive siloxane compound 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 and/or precursor and/or reactive siloxane compound 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 and/or precursor and/or reactive siloxane compound.

[48] 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 and/or precursor and/or reactive siloxane compound. 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 solvent system or 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 and/or precursor and/or reactive siloxane compound 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.

[49] 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. The agitation may be applied for any period of time or with any force sufficient to move reactive polycarbonate and/or precursor and/or reactive siloxane compound 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 and/or precursor and/or reactive siloxane 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.

[50] 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 and/or precursor and/or reactive siloxane compound 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.

[51] 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 reactive polycarbonates 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.

[52] The polycarbonate solvent, the reactive polycarbonate, precursor and/or reactive siloxane compound and/or the waste feedstock may be contacted for any period of time sufficient to dissolve and/or mix the reactive polycarbonate and/or precursor and/or reactive siloxane compound 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, and/or precursor and/or reactive siloxane compound 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.

[53] The recovery solution may be subjected to one or more separation steps configured to remove compounds that may have a negative impact on reactions within the recovery solution or compounds leftover in the recovery solution after dissolution of the reactive polycarbonate. The recovery solution may be contacted with one or more scavengers that are configured to precipitate or make inert one or more non-polycarbonate compounds or acids that were dissolved from the waste feedstock into the polycarbonate solvent or a byproduct of formation of the siloxane modified polycarbonate or reactive siloxane compounds. The recovery solution may be contacted with scavengers such as adsorption or absorption material configured to bind with an acid. Examples may include one or more of activated carbon, clays, zeolites, polymeric adsorbent or absorbents, caustic washes, buffers, 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 acid, hydroxyl, carboxyl, other non- polycarbonate compounds susceptible to cleaving polycarbonate chains or undesirable in polycarbonate compositions, 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 hydroxides, isocyanates, amines, esters, epoxides, anhydrides, carboxylic acids, or any combination thereof. After reacting or binding with one or more non-polycarbonate compounds or acids in the recovery solution, the scavengers, adsorption, and/or absorption compounds may be removed as liquids or solids as described herein.

[54] If the non-polycarbonate compounds or acids 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 siloxane modified polycarbonate s are removed.

[55] 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 reactive siloxane compounds. The one or more reactive siloxane compounds may include one or more functional groups, such as methoxy, ethoxy, acetoxy, halides, and/or hydrogen groups, that are configured to react with one or more reactive groups (i.e., hydroxyl, carboxyl, and/or phenol groups) of the reactive polycarbonate. The reactive siloxane compounds include any functional group as discussed herein that impart flame resistance to the polycarbonate after the reactive siloxane compounds binds to the polycarbonate chain and forms the siloxane modified polycarbonate. The reactive siloxane compounds may be added in an amount sufficient to achieve a desirable flame resistance in the siloxane 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 reactive siloxane compounds added or the reactive siloxane compounds or combination thereof present in the siloxane 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.

[56] Before or after contacting the reactive polycarbonate and reactive siloxane compounds, the recovery solution may be contacted with one or more functional compounds configured to adjust the molecular weight of the reactive and/or siloxane modified polycarbonate. The one or more functional compounds and/or precursor and/or reactive siloxane compound may chain terminate, chain extend, or branch the reactive and/or siloxane modified polycarbonate to have increased molecular weight and/or properties and reduced hydroxyl and/or carboxyl groups. The one or more functional compounds and/or precursor and/or reactive siloxane compounds may increase the number and/or weight average molecular weight of the polycarbonate. 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 precursor and/or reactive siloxane compound. 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 siloxane 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 siloxane 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 siloxane 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 siloxane 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 siloxane 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 and/or precursor and/or reactive siloxane compound to the recovery solution, the siloxane 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 siloxane modified polycarbonate may be greater or less than the melt flow rate of the waste polycarbonate due to having a modified molecular weight from addition of the one or more functional compounds. The melt flow rate of the siloxane 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 siloxane modified polycarbonate may be about 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.

[57] After adding the functional compounds and/or precursor and/or reactive siloxane compound 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 and/or precursor and/or reactive siloxane compound 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 and/or precursor and/or reactive siloxane compound 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 and/or precursor and/or reactive siloxane compound 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 and/or precursor and/or reactive siloxane compound and configured to react with hydroxyl and/or carboxyl groups.

[58] After forming the siloxane modified polycarbonates, the recovery solution may be subjected to a step of recovering and/or separating the polycarbonate solvent and/or siloxane modified polycarbonate s. The polycarbonate solvent and the siloxane 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 siloxane modified polycarbonate at the same time so that the siloxane 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 siloxane modified polycarbonate and the polycarbonate solvent. Compounds that remain after removing the polycarbonate solvent and siloxane 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 siloxane modified polycarbonate from the polycarbonate solvent in a form that is free or essentially free of impurities or that may be subjected 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.

[59] 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.

[60] Before contacting the waste feedstock (including one or more reactive polycarbonates) and the one or more polycarbonate solvents or solvent systems, the waste feedstock may be subjected to one or more pretreatment steps to separate one or more nonpolycarbonate 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.

[61] 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 and/or precursor and/or reactive siloxane compounds may be conducted in a second chamber, and recovering and/or separating the polycarbonate solvent and siloxane modified polycarbonate may be conducted in a third chamber. Performing the above steps in a series of chambers may mitigate side reactions while functional or reactive/precursor siloxane 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, siloxane modified polycarbonate or a combination thereof from chamber to chamber as appropriate.

[62] 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, siloxane 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 nonpolycarbonate 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. [63] The disclosed compositions of siloxane 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 siloxane 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 EMBODIMENTS

Embodiment 1 . A method, comprising: a. contacting one or more reactive polycarbonates having free hydroxyl and/or carboxyl groups with one or more reactive siloxane compounds terminated by one or more methoxy, ethoxy, acetoxy, halides, and/or hydrogen groups in a solvent system to form one or more siloxane modified polycarbonates in a recovery solution, wherein the one or more reactive polycarbonates comprise one or more waste polycarbonates.

Embodiment 2. The method of embodiment 1 , wherein the one or more reactive polycarbonates comprise the one or more waste polycarbonates in an amount of about 5 weight percent to about 95 weight percent, based on the total amount of reactive polycarbonates.

Embodiment s. The method of embodiment 1 or 2, wherein the free hydroxyl and/or carboxyl groups are positioned at one or more terminal ends of the reactive polycarbonate.

Embodiment 4. The method of embodiment 3, wherein the free hydroxyl and/or carboxyl groups are positioned along a backbone of the reactive polycarbonate.

Embodiment 5. The method of any one of the preceding embodiments, wherein the siloxane modified polycarbonates have a number and/or weight average molecular weight that is at least 5 percent larger than a number and/or weight average molecular weight of the reactive polycarbonates incorporated into the siloxane modified polycarbonate.

Embodiment 6. The method of any one of the preceding embodiments, further comprising: a. contacting the solvent system and one or more waste feedstocks comprising the one or more waste polycarbonates and one or more non-polycarbonate compounds to form the recovery solution; and b. separating at least some of the one or more non-polycarbonate compounds from the recovery solution.

Embodiment 7. The method of any one of the preceding embodiments, further comprising: a. contacting one or more precursor siloxane compounds with water to form the one or more reactive siloxane compounds in the recovery solution; and b. contacting the recovery solution with one or more polycarbonate solvents to form the solvent system comprising the water and the one or more polycarbonate solvents in the recovery solution.

Embodiment 8. The method of any one of the preceding embodiments, further comprising: a. contacting the one or more reactive polycarbonates with one or more allyl halides to form one or more vinyl ether terminated polycarbonates configured to react with the hydrogen atom of the one or more reactive siloxane compounds and form the one or more siloxane modified polycarbonates.

Embodiment 9. The method of embodiment any one of the preceding embodiments, wherein the one or more allyl halides is terminated by an alkene and a halide and comprises between one and one hundred carbon atoms between the halide and the carbon at the alkene.

Embodiment 10. The method of any one of the preceding embodiments, further comprising: a. applying agitation to the recovery solution to intermix the solvent system as the one or more reactive siloxane compounds or siloxane modified polycarbonates are formed.

Embodiment 11. The method of any one of the preceding embodiments, further comprising: a. contacting one or more scavengers with the recovery solution to scavenge for acids formed from contacting the one or more reactive polycarbonates and the one or more reactive siloxane compounds.

Embodiment 12. The method of any one of the preceding embodiments, wherein the one or more scavengers comprise a caustic wash, an adsorbent, or any combination thereof.

Embodiment 13. The method of any one of the preceding embodiments, wherein the reactive polycarbonate and the reactive siloxane compound are contacted in the presence of a catalyst configured to facilitate formation of the siloxane modified polycarbonate.

Embodiment 14. The method of any one of the preceding embodiments, further comprising: a. separating essentially all of the water from the recovery solution and solvent system. Embodiment 15. The method of any one of the preceding embodiments, wherein the step of separating the one or more non-polycarbonate compounds or the water from the recovery solution comprises filtering, decanting, centrifugation, extracting, or any combination thereof.

Embodiment 16. The method of any one of the preceding embodiments, wherein the solvent system comprises at least a polycarbonate solvent configured to dissolve the one or more reactive polycarbonates.

Embodiment 17. The method of any one of the preceding embodiments, wherein the solvent system further comprises water.

Embodiment 18. The method of any one of the preceding embodiments, wherein the siloxane modified polycarbonate comprises one or more branched siloxanepolycarbonate copolymers.

Embodiment 19. The method of any one of the preceding embodiments, wherein the one or more reactive siloxane compounds comprises between one and one hundred units of siloxane connected in a chain that is terminated by at least one methoxy, ethoxy, acetoxy, halides, and/or hydrogen groups.

Embodiment 20. The method of any one of the preceding embodiments, wherein the one of more precursor siloxane compounds comprises at least two halide atoms at different terminal ends.

Embodiment 21. The method of any one of the preceding embodiments, wherein the one or more precursor siloxane compounds comprises a monohalosilane, a dihalosilane, a trihalosilane, and/or a tetrahalosilane.

Embodiment 22. A polymerizable composition, comprising: a. one or more reactive polycarbonates having free hydroxyl and/or carboxyl groups along the backbone and/or at one or more terminal ends of the one or more reactive polycarbonates, wherein the one or more reactive polycarbonates comprise one or more waste polycarbonates; b. a solvent system comprising one or more polycarbonate solvents and/or water; and c. one or more siloxane modifiers comprising at least one of: i. one or more reactive siloxane compounds terminated by at least one hydrogen and one or more allyl halides; ii. one or more reactive siloxane compounds terminated by at least one methoxy, acetoxy, ethoxy, and/or halides groups; or iii. one or more precursor siloxane compounds configured to form the reactive siloxane compounds terminated by at least one halide in water, wherein the one or more reactive polycarbonates and the siloxane modifier are react-able in the solvent system to form one or more siloxane modified polycarbonates.

Embodiment 23. The polymerizable composition of embodiment 22, further comprising: a. one or more hydroxyl and/or carboxyl containing compounds.

Embodiment 24. The polymerizable composition of embodiments 22-23 further comprising: a. one or more catalysts configured to facilitate formation of a siloxane modified polycarbonate.

Embodiment 25. The polymerizable composition of embodiments 22-24, wherein the reactive polycarbonates further comprise one or more virgin polycarbonates.

Embodiment 26. A polymer composition, comprising: a. one or more one or more siloxane modified polycarbonates, comprising: i. one or more polycarbonate segments; and ii. one or more siloxane segments connected with the one or more polycarbonate segments at oxygen atoms along the backbone and at a terminal end of the one or more polycarbonate segments, wherein at least some of the one or more siloxane segments connect two or more polycarbonate segments.

Embodiment 27. The polymer composition of embodiment 26, wherein the one or more siloxane modified polycarbonates comprises one or more branched siloxanepolycarbonate copolymers.

Embodiment 28. The polymer composition of embodiments 26-28, wherein the one or more polycarbonate segments comprise residues of waste polycarbonate.

Embodiment 29. The polymer composition of embodiments 26-29, wherein the one or more polycarbonate segments include at least about 5 to 100weight percent or more of residues of waste polycarbonate, based on the total amount of the siloxane modified polycarbonate.

Embodiment 30. The polymer composition of embodiments 26-30, wherein each of the one or more siloxane segments comprise between two and 100 repeating units of siloxane.

Embodiment 31. The polymer composition of embodiments 26-31 , wherein the polymer composition is essentially free of hydroxyl and/or carboxyl containing compounds. EXAMPLES

Example 1 :

[64] Degraded polycarbonate (see Table 1 , 10 g) is solubilized in 40 mL dichloromethane and 0.25 mL triethylamine is added, followed by the addition of 1 ,2- bis(chlorodimethylsilyl)ethane (180 mg). The reaction mixture is stirred at room temperature for 10 hours. Before the workup, a small sample is taken for analysis. The solution is washed with two times with 0.1 M HCI solution, and three times with demineralized water. After evaporation of the solvent, the siloxane modified polycarbonate is obtained.

[65] Table 1 : Molecular weight distribution measured by size-excluision chromatography of the degraded polycarbonate, and after the treatment with 1 ,2-bis(chlorodimethylsilyl)ethane.

Example 2:

[66] The material generated in Example 1 is heated to 300 °C in a melt flow rate apparatus and samples were taken after 0, 1 , 2, and 5 minutes. Analysis by GPC shows no significant decrease in molecular weight, confirming the high thermal stability.

[67] Figure 1 : GPC analysis of the material after heating it up to 300 °C.

[68] Table 2 illustrates the values at each minute of the GPC analysis.

Example 3:

Comparative example A

[69] PC-containing waste is solubilized in dichloromethane to obtain a 15 wt% solution. The insoluble parts is removed by coarse filtration with a 100 pm mesh filter cloth, followed by microfiltration with a 0.6 pm filter cartridge. After the removal of the solvent and drying of the recycled PC, the amount of free phenolic species are determined (Table 3). Phenolic species is determined by those techniques described in related to hydroxyl and/or carboxyl containing compounds described herein and is measured and represented by ppm, unless otherwise stated.

Example A

[70] PC-containing waste is olubilized in dichloromethane and filtered in a similar way as described in comparative example A. Then, 1 ,2-bis(chlorodimethylsilyl)ethane (0.28 wt%) is added together with triethylamine (0.27 wt%). After stirring the solution is stirred for 12 hours, the organic fraction is washed with a dilute hydrochloric acid solution 0.1 M) and water. The organic fraction is isolated, and the solvent is evaporated to obtain the polycarbonate. After drying, the free phenolic species are determined (Table 3). Phenolic species is determined by those techniques described in related to hydroxyl and/or carboxyl containing compounds described herein and is measured and represented by ppm, unless otherwise stated.

Example B

[71] PC-containing waste is solubilized in dichloromethane and filtered in a similar way as described in comparative example 3. Then, 1 ,3-Dichloro-1 ,1 ,3,3-tetramethyldisiloxane (0.27 wt%) is added together with triethylamine (0.27 wt%). After stirring the solution is stirred for 12 hours, the organic fraction is washed with a dilute hydrochloric acid solution 0.1 M) and water. The organic fraction is isolated, and the solvent was evaporated to obtain the polycarbonate. After drying, the free phenolic species are determined (Table 3). Phenolic species is determined by those techniques described in related to hydroxyl and/or carboxyl containing compounds described herein and is measured and represented by ppm, unless otherwise stated. Table 3

Claims

CLAIMS What is claimed is:

1. A method, comprising: a. contacting one or more reactive polycarbonates having free hydroxyl and/or carboxyl groups with one or more reactive siloxane compounds terminated by one or more acetoxy, methoxy, ethoxy, halide, or hydrogen atoms in a solvent system to form one or more siloxane modified polycarbonates in a recovery solution, wherein the one or more reactive polycarbonates comprise one or more waste polycarbonates.

2. The method of claim 1 , wherein the one or more reactive polycarbonates comprise the one or more waste polycarbonates in an amount of about 5 weight percent to about 95 weight percent, based on the total amount of reactive polycarbonates.

3. The method of claim 1 or 2, wherein the free hydroxyl and/or carboxyl groups are positioned at one or more terminal ends of the reactive polycarbonate.

4. The method of claim 3, wherein the free hydroxyl and/or carboxyl groups are positioned along a backbone of the reactive polycarbonate.

5. The method of any one of the preceding claims, wherein the siloxane modified polycarbonates have a number and/or weight average molecular weight that is at least 5 percent larger than a number and/or weight average molecular weight of the reactive polycarbonates incorporated into the siloxane modified polycarbonate.

6. The method of any one of the preceding claims, further comprising: a. contacting the solvent system and one or more waste feedstocks comprising the one or more waste polycarbonates and one or more non-polycarbonate compounds to form the recovery solution; and b. separating at least some of the one or more non-polycarbonate compounds from the recovery solution.

7. The method of any one of the preceding claims, further comprising: a. contacting one or more precursor siloxane compounds with water to form the one or more reactive siloxane compounds in the recovery solution; and b. contacting the recovery solution with one or more polycarbonate solvents to form the solvent system comprising the water and the one or more polycarbonate solvents in the recovery solution.

8. The method of any one of the preceding claims, further comprising: a. contacting the one or more reactive polycarbonates with one or more allyl halides to form one or more vinyl ether terminated polycarbonates configured to react with the hydrogen atom of the one or more reactive siloxane compounds and form the one or more siloxane modified polycarbonates.

9. The method of claim any one of the preceding claims, wherein the one or more allyl halides is terminated by an alkene and a halide and comprises between one and one hundred carbon atoms between the halide and the carbon at the alkene.

10. The method of any one of the preceding claims, further comprising: a. applying agitation to the recovery solution to intermix the solvent system as the one or more reactive siloxane compounds or siloxane modified polycarbonates are formed.

11 . The method of any one of the preceding claims, further comprising: a. contacting one or more scavengers with the recovery solution to scavenge for acids formed from contacting the one or more reactive polycarbonates and the one or more reactive siloxane compounds.

12. The method of any one of the preceding claims, wherein the one or more scavengers comprise a caustic wash, an adsorbent, or any combination thereof.

13. The method of any one of the preceding claims, wherein the reactive polycarbonate and the reactive siloxane compound are contacted in the presence of a catalyst configured to facilitate formation of the siloxane modified polycarbonate.

14. The method of any one of the preceding claims, further comprising: a. separating essentially all of the water from the recovery solution and solvent system.

15. The method of any one of the preceding claims, wherein the step of separating the one or more non-polycarbonate compounds or the water from the recovery solution comprises filtering, decanting, centrifugation, extracting, or any combination thereof.

16. The method of any one of the preceding claims, wherein the solvent system comprises at least a polycarbonate solvent configured to dissolve the one or more reactive polycarbonates.

17. The method of any one of the preceding claims, wherein the solvent system further comprises water.

18. The method of any one of the preceding claims, wherein the siloxane modified polycarbonate comprises one or more branched siloxane-polycarbonate copolymers.

19. The method of any one of the preceding claims, wherein the one or more reactive siloxane compounds comprises between one and one hundred units of siloxane connected in a chain that is terminated by at least one methoxy, ethoxy, acetoxy, halides, and/or hydrogen groups.

20. The method of any one of the preceding claims, wherein the one of more precursor siloxane compounds comprises at least two halide atoms at different terminal ends.

21. The method of any one of the preceding claims, wherein the one or more precursor siloxane compounds comprises a monohalosilane, a dihalosilane, a trihalosilane, and/or a tetrahalosilane.

22. A polymerizable composition, comprising: a. one or more reactive polycarbonates having free hydroxyl and/or carboxyl groups along the backbone and/or at one or more terminal ends of the one or more reactive polycarbonates, wherein the one or more reactive polycarbonates comprise one or more waste polycarbonates; b. a solvent system comprising one or more polycarbonate solvents and/or water; and c. one or more siloxane modifiers comprising at least one of: i. one or more reactive siloxane compounds terminated by at least one hydrogen and one or more allyl halides; ii. one or more reactive siloxane compounds terminated by at least one acetoxy, methoxy, ethoxy, halide, or any combination thereof; or iii. one or more precursor siloxane compounds configured to form the reactive siloxane compounds terminated by at least one halide in water, wherein the one or more reactive polycarbonates and the siloxane modifier are react-able in the solvent system to form one or more siloxane modified polycarbonates.

23. The polymerizable composition of claim 22, further comprising: a. one or more hydroxyl and/or carboxyl containing compounds.

24. The polymerizable composition of claims 22-23 further comprising: a. one or more catalysts configured to facilitate formation of a siloxane modified polycarbonate.

25. The polymerizable composition of claims 22-24, wherein the reactive polycarbonates further comprise one or more virgin polycarbonates.

26. A polymer composition, comprising: a. one or more one or more siloxane modified polycarbonates, comprising: i. one or more polycarbonate segments; and ii. one or more siloxane segments connected with the one or more polycarbonate segments at oxygen atoms along the backbone and at a terminal end of the one or more polycarbonate segments, wherein at least some of the one or more siloxane segments connect two or more polycarbonate segments.

27. The polymer composition of claim 26, wherein the one or more siloxane modified polycarbonates comprises one or more branched siloxane-polycarbonate copolymers.

28. The polymer composition of claims 26-28, wherein the one or more polycarbonate segments comprise residues of waste polycarbonate.

29. The polymer composition of claims 26-29, wherein the one or more polycarbonate segments include at least about 5 to 100weight percent or more of residues of waste polycarbonate, based on the total amount of the siloxane modified polycarbonate.

30. The polymer composition of claims 26-30, wherein each of the one or more siloxane segments comprise between two and 100 repeating units of siloxane.

31. The polymer composition of claims 26-31 , wherein the polymer composition is essentially free of hydroxyl and/or carboxyl containing compounds.