Co 2-based aromatic polycarbonates and methods of making same

Abstract

Aromatic polycarbonate materials derived from direct copolymerization of CO2 and multifunctional aromatic epoxides in the presence of a catalyst. Such polycarbonates are derived free of Bisphenol A (BPA) and phosgene, but possess similar or improved properties over conventional aromatic BPA-based polycarbonates.

Description

[0001]CO2-BASED AROMATIC POLYCARBONATES AND METHODS OF MAKING SAME FIELD OF THE INVENTION The present disclosure relates generally to aromatic polycarbonate materials and a method for its synthesis. More specifically, the present disclosure relates to a polycarbonate derived from direct copolymerization of CO2and multifunctional aromatic epoxides in the presence of a catalyst. Such polycarbonates are derived free of Bisphenol A (BPA) and phosgene, but possess similar or improved properties over conventional aromatic BPA-based polycarbonates. BACKGROUND Aromatic Bisphenol A-based polycarbonates are some of the most widely used engineering grade thermoplastic materials because of their desirable impact resistance, transparency, heat and electricity resistance, thermal deformation resistance, dimensional stability, and durability. In this aspect, polycarbonate-based materials are widely employed in a variety of lifestyle applications ranging from automobiles (headlamp lenses, sunroofs, dashboard components), electric and electronic appliances (smartphones, TVs, wires, cables, portable computing devices, gaming systems), construction materials (skylights, windows, protective barriers), office equipment, sheets, resin for the optical disks of music or data and image storage (such as CDs and DVDs), food and beverage contact reusable containers, medical devices, glazing and films, ID cards, and sports safety equipment. As a result of these diverse applications, the global demand for polycarbonate materials reached over 5 MMT in 2023. The polycarbonate market is expected to increase by about 3 percent annually. As such, demand for polycarbonate materials is anticipated to reach almost 7 MMT over the next decade. However, most of the engineering thermoplastic aromatic polycarbonate currently used in a variety of sectors is produced using a conventional phosgene (also known as carbonyl chloride)- based method. Briefly, this polycarbonate is obtained from polymerization of 2,2-bis (4- hydroxyphenyl) propane (bisphenol A (BPA)) with phosgene (or diphenylcarbonate, which is also commonly derived from dimethylcarbonate or phosgene). The reaction product further requires a purification step to eliminate the presence of chlorinated impurities. The drawbacks of its preparation—such as the use of large quantities of highly toxic phosgene and carcinogenic solvent 4919-6390-8455.1 “CO2-Based Aromatic Polycarbonates and Methods of Making...” Attorney Docket No.302737-401005 methylene chloride—and the requirement of treating up to 100 metric ton of wastewater per ton of polycarbonate—are well known. Since the discovery in 1969 of the catalytic copolymerization of CO2 with epoxide monomer to produce polycarbonate, interest in production of CO2-based polycarbonate has risen exponentially; however, the efforts are mostly limited to aliphatic and alicyclic polycarbonates. Although CO2-derived aliphatic and alicyclic polycarbonates are suitable for biomedical applications, their low heat resistance and susceptibility to hydrolysis make it challenging to use them to replace BPA phosgene–based aromatic polycarbonates. For example, polypropylene carbonate, which is one of the most investigated CO2-derived polycarbonates, has a Tg of 37°C, which is much lower than the Tgof BPA phosgene–derived aromatic polycarbonate (150°C). Of the few examples of CO2-based aromatic polycarbonates reported with properties comparable to BPA-phosgene polycarbonates, these are made with monomers such as indene oxide and 1,4-dihydronapthalene oxide, which are not commercially available, challenging to handle, and impractical for the purpose of scaling up and reducing the carbon footprint. In addition, some of these polymers are amorphous in nature, and, as such, it is challenging to achieve a molecular weight comparable to the BPA phosgene–based commercially available polycarbonates. Moreover, all CO2-based synthesis methods reported in the literature require maintaining oxygen- and moisture-free environments for production of high-quality polycarbonates, which make the protocols challenging to scale up. Given the size of the BPA phosgene–based polycarbonate global market and lack of viable and / or scalable non-BPA polycarbonate solutions, there exists a need for CO2-derived aromatic polycarbonates that can replace BPA phosgene-based polycarbonates. There also exists a need to develop a scalable synthesis protocol for such CO2-derived aromatic polycarbonates that uses multifunctional aromatic monomers and an air-stable catalyst system. Indeed, it would be advantageous to have CO2-derived aromatic polycarbonates made from air-stable chemical feedstock so as to recycle CO2 and reduce the carbon footprint. The present disclosure satisfies such needs. SUMMARY The present disclosure relates to a method of producing aromatic polycarbonate including: 2 4919-6390-8455.1 “CO2-Based Aromatic Polycarbonates and Methods of Making...” Attorney Docket No.302737-401005 providing at least one multifunctional epoxide including an aromatic core and at least two epoxy groups; providing a catalyst system including a complex of a metal and salen or a linear dicarboxylic acid; mixing the multifunctional epoxide and catalyst system to form a mixture; transferring the mixture to a reactor having at least one gas inlet and a base temperature and a base pressure; feeding CO2 through the gas inlet, wherein the CO2 is at the base pressure; and increasing the base pressure to a first pressure and the base temperature to a reaction temperature for a first period of time sufficient to copolymerize the CO2and multifunctional epoxide and form the aromatic polycarbonate. In some embodiments, the metal is a transition metal. In other embodiments, the dicarboxylic acid includes C1-C10 dicarboxylic acids, or combinations thereof. In still other embodiments, the first pressure ranges from about 40 bar to about 150 bar. In yet other embodiments, the reaction temperature ranges from about 30°C to about 90°C. In some aspects, the aromatic core includes at least one disubstituted benzene. In other aspects, the aromatic core includes at least two disubstituted benzenes. In some embodiments, each disubstituted benzene includes a phenyl group, phenyldiamine, or oxyaniline. In other embodiments, the aromatic polycarbonate further includes cyclic carbonate. In still other embodiments, the aromatic polycarbonate has a glass temperature ranging from about 125°C to about 200°C and an average molecular weight of about 1 kg / mol to about 50 kg / mol. The catalyst system may include a mixture of complex of a metal and salen and at least one homogeneous amine-based organo-catalyst. In some aspects, the amine-based organo-catalyst is selected from the group consisting of bis(triphenylphosphoranylidene)ammonium chloride (PPNCl), 1-Methylimidazol (MeIm), 4-dimethylaminopyridine (DMAP), or combinations thereof. In other aspects, the complex of metal and salen includes a (salen) Cr-Cl catalyst or a (salen) Co- Cl catalyst. In other aspects, the step of providing at least one multifunctional epoxide includes providing the at least one multifunctional epoxide in an amount of more than about 50 mol percent with the remainder aliphatic epoxide. The present disclosure also relates to a method of producing an aromatic polycarbonate including: 3 4919-6390-8455.1 “CO2-Based Aromatic Polycarbonates and Methods of Making...” Attorney Docket No.302737-401005 providing a multifunctional epoxide including an aromatic core and at least two epoxy groups, wherein the aromatic core includes at least one para-disubstituted benzene; providing a catalyst system including a metal salen complex; mixing the multifunctional epoxide and catalyst system to form a homogenous mixture; transferring the homogenous mixture to a reactor having at least one gas inlet and a base temperature and a base pressure; feeding CO2through the gas inlet, wherein the CO2is at the base pressure; and increasing the base pressure to a first pressure and the base temperature to a reaction temperature for a period of time sufficient to copolymerize the CO2 and multifunctional epoxide and form the aromatic polycarbonate. In some embodiments, the metal salen complex includes a (salen) Cr-Cl catalyst or a (salen) Co-Cl catalyst. In other embodiments, the para-disubstituted benzene includes a phenyl group, phenyldiamine, or oxyaniline. In still other embodiments, the multifunctional epoxide is selected from the group consisting of 4,4’-Methylenebis(N,N-diglycidylaniline), Bis[4- (glycidyloxy)phenyl]methane, N,N-Diglycidyl-4-glycidyloxyaniline, Tris-(4- hydroxyphenyl)methane triglycidyl ether, 4,4'-Methylenebis(N-(2,3-epoxypropyl)-N- methylaniline, N,N,N’,N’-Tetraglycidyl-4,4’-diamino-3,3,’-dimethyldiphenylmethane, N,N,N’,N’-Tetraglycidyl-4,4’-diamino-3,3,’-diethyldiphenylmethane, N,N,N’,N’-Tetrakis(2- oxiranylmethyl)-1,4-benzenediamine, N,N,N’,N’-Tetrakis(2,3-epoxypropyl)-m-xylene-α,α’- diamine, N1,N1,N5,N5-Tetrakis(2-oxiranylmethyl)-1,5-naphthalenediamine, N-[3-(2- Oxiranylmethoxy)phenyl]-N-(2-oxiranylmethyl)-2-oxiranemethanamine, N-[2-(2- Oxiranylmethoxy)phenyl]-N-(2-oxiranylmethyl)-2-oxiranemethanamine, N-[2-Methyl-4- (oxiranylmethoxy)phenyl]-N-(oxiranylmethyl)oxiranemethanamine, 2,2’,2”-tris- [ethylidynetris(4,1-phenyleneoxymethylene), 2,2’,2”-tris-[propylidynetris(4,1- phenyleneoxymethylene) or combinations thereof. In yet other embodiments, the aromatic polycarbonate has a glass temperature ranging from about 150°C to about 200°C. In other embodiments, the aromatic polycarbonate has an average molecular weight of about 18 kg / mol to about 50 kg / mol. In some aspects, the first pressure ranges from about 40 bar to about 120 bar. In other aspects, the reaction temperature ranges from about 30°C to about 90°C. In other aspects, the aromatic polycarbonate has a thermal decomposition temperature of about 400°C or greater. 4 4919-6390-8455.1 “CO2-Based Aromatic Polycarbonates and Methods of Making...” Attorney Docket No.302737-401005 The present disclosure also relates to an aromatic polycarbonate including the reaction product of at least one multifunctional epoxide including an aromatic core and at least two epoxy groups and CO2, wherein the aromatic polycarbonate has a glass temperature of about 100°C or higher and an average molecular weight of about 1 kg / mol to about 50 kg / mol. In some embodiments, the aromatic core includes at least one disubstituted benzene. In other embodiments, the aromatic core includes at least two disubstituted benzenes. Each disubstituted benzene may include a phenyl group, phenyldiamine, or oxyaniline. In some aspects, the aromatic polycarbonate further includes cyclic carbonate. In other aspects, the aromatic polycarbonate has a glass temperature ranging from about 125°C to about 200°C. In still other aspects, the glass temperature ranges from about 150°C to about 200°C. In yet other aspects, the aromatic polycarbonate has an average molecular weight of about 18 kg / mol to about 50 kg / mol. For example, the average molecular weight may range from about 20 kg / mol to about 45 kg / mol. In some embodiments, the aromatic polycarbonate has a thermal decomposition temperature of about 400°C or greater (under an air atmosphere at a heating rate of 5-20°C / min). In other embodiments, the thermal decomposition temperature is about 510°C or more (under an air atmosphere at a heating rate of 5-20°C / min). In still other embodiments, the thermal decomposition temperature ranges from about 400°C to about 700°C. In yet other embodiments, the reaction product is produced from at least one multifunctional epoxide including an aromatic core, at least two epoxy groups, CO2, and aliphatic epoxides. BRIEF DESCRIPTION OF THE DRAWINGS Further features and advantages of the invention can be ascertained from the following detailed description that is provided in connection with the drawings described below: FIG. 1 is a graphical illustration of the characterization of a reaction mixture formed according to the present invention (Example 1) using Fourier Transform Infrared (FTIR) spectroscopy; and FIG. 2 is a graphical illustration of the characterization of a reaction mixture formed according to the present invention (Example 1) using thermogravimetric analysis (TGA). FIG. 3 is a graphical illustration of the characterization of a reaction mixture formed according to the present invention (Example 2) using Fourier Transform Infrared (FTIR) spectroscopy. 5 4919-6390-8455.1 “CO2-Based Aromatic Polycarbonates and Methods of Making...” Attorney Docket No.302737-401005 FIG. 4 is a graphical illustration of the impact of temperature on polymerization of a reaction mixture according to the present invention (Example 3). FIG. 5 is a graphical illustration of the impact of catalyst loading on polymerization of a reaction mixture formed according to the present invention (Example 4). FIG.6 is a graphical illustration of the FTIR characterization of a reaction mixture formed according to the present invention (Example 5). FIG.7 is a graphical illustration of the1H-NMR of a reaction mixture formed according to the present invention (Example 5). FIG. 8 is a graphical illustration of the13C-NMR of a reaction mixture formed according to the present invention (Example 5). FIG. 9 is a graphical illustration of the thermal stability of a reaction mixture formed according to the present invention (Example 5) using thermogravimetric analysis (TGA). FIG. 10 is a graphical illustration of the thermal stability of a reaction mixture formed according to the present invention (Example 5) using differential scanning calorimetry (DSC). FIG.11 is a graphical illustration of the molecular weight distribution of a reaction mixture formed according to the present invention (Example 5) using gel permeation chromatography (GPC). FIG. 12 is a graphical illustration of the FTIR characterization of a powdered form of product mixture formed according to the present invention (Example 6). FIG. 13 is a graphical illustration of the1H-NMR of a reaction mixture formed according to the present invention (Example 6). FIG. 14 is a graphical illustration of the13C-NMR of a reaction mixture formed according to the present invention (Example 6). FIG. 15 is a graphical illustration of the thermal stability of a reaction mixture formed according to the present invention (Example 6) using thermogravimetric analysis (TGA). FIG. 16 is a graphical illustration of the thermal stability of a reaction mixture formed according to the present invention (Example 6) using differential scanning calorimetry (DSC). FIG.17 is a graphical illustration of the molecular weight distribution of a reaction mixture formed according to the present invention (Example 6) using gel permeation chromatography (GPC). 6 4919-6390-8455.1 “CO2-Based Aromatic Polycarbonates and Methods of Making...” Attorney Docket No.302737-401005 DETAILED DESCRIPTION The present disclosure relates to CO2-derived aromatic polycarbonates and methods of producing the CO2-derived aromatic polycarbonates. More specifically, the present disclosure relates to conversion of anthropogenic CO2, i.e., carbon emissions associated with human activities such as burning of fossil fuels, deforestation, land use changes, livestock, and fertilization, into thermoplastic aromatic polycarbonate. As will be described in more detail below, in the presence of a catalyst system, direct copolymerization of CO2 with multifunctional epoxide monomers having an aromatic core produces aromatic polycarbonate with properties similar to or better than BPA phosgene–based polycarbonate. In some embodiments, the aromatic polycarbonates of the present disclosure are produced using feedstock free from BPA. CO2 Source The anthropogenic CO2emissions for use in the method of the present disclosure can be captured either from a concentrated point source or directly from air. In some embodiments, the CO2 used to derive aromatic polycarbonates in accordance with the present disclosure is captured through treatment of the combustion process effluent by absorption using non-aqueous amine- based solvent compositions. Suitable ways to capture CO2 for use in accordance with the present disclosure include, but are not limited to amine-based solvent scrubbing. In addition, carbon capture from a flue gas stream may be accomplished using the system described in U.S. Patent No. 11,612,854 and 11,691,105, the entire disclosures of which are incorporated by reference herein. In this aspect, a system for the removal of CO2 from a gas stream may include a rotating packed bed (RPB) arranged on a rotatable shaft. In other aspects, the system for the removal of CO2 from a gas stream may include a conventional packed column absorber. Other carbon capture methods suitable for use in accordance with the present disclosure involve reboiler-based, reboiler-free, and reboiler-assisted influent gas streams, absorbers, and solvent systems, and are described in U.S. Patent No. 10,065,148, the entire disclosure of which is incorporated by reference herein. In other embodiments, the CO2 is captured from the air. One such way to capture CO2 from the air for use with the present disclosure is described in U.S. Patent No. 10,239,017, the entire disclosure of which is incorporated by reference herein. More specifically, the CO2may be 7 4919-6390-8455.1 “CO2-Based Aromatic Polycarbonates and Methods of Making...” Attorney Docket No.302737-401005 captured by directing CO2laden air through a sorbent structure that binds CO2and removes CO2from the sorbent structure (and thereby effectively regenerating the sorbent structure) by using process heat to heat the sorbent structure. Multifunctional Aromatic Epoxides As briefly discussed above, aromatic epoxide functional monomers, i.e., multifunctional epoxides having an aromatic core, can be copolymerized with CO2to synthesize aromatic polycarbonate. Suitable aromatic epoxide functional monomers for use in accordance with the present disclosure have two or more epoxide functionalities. Without being bound by any particular theory, the use of aromatic epoxide functional monomers with two or more epoxide functionalities allows for the propagation of two to four polymer chains per monomer molecule, which, in turn, increases the crosslinking density of the overall polymeric product. In some embodiments, the aromatic epoxide functional monomers have three or more epoxide functionalities. In this aspect, the aromatic epoxide functional monomers may have between 3 and 5 epoxide functionalities. In other embodiments, the aromatic epoxide functional monomers have more than four epoxide functionalities. In still other embodiments, the aromatic epoxide functional monomers have more than five epoxide functionalities. The aromatic epoxide functional monomers include at least one disubstituted benzene. In some embodiments, the aromatic epoxide functional monomers include at least two disubstituted benzenes. In other embodiments, the multifunctional aromatic epoxides include at least three disubstituted benzenes. In some aspects, the disubstituted benzenes are para-substituted (1,4). In other aspects, the disubstituted benzenes are phenyl groups. In yet other aspects, the disubstituted benzenes are phenyldiamines. In still other aspects, the disubstituted benzenes are oxyanilines. In some respects, the disubstituted benzenes may contain glycidyl ether functionality. For example, the aromatic epoxide functional monomers suitable for use in accordance with the present disclosure may include multifunctional aromatic glycidyl ether-based monomers. Without being bound by any particular theory, it is contemplated that multifunctional aromatic glycidyl ether monomers that have structural similarity to bisphenol A diglycidyl ether may be reactive with CO2in the presence of a catalyst and produce polycarbonates having properties similar to 8 4919-6390-8455.1 “CO2-Based Aromatic Polycarbonates and Methods of Making...” Attorney Docket No.302737-401005 BOA phosgene-based polycarbonates. In this aspect, examples of suitable multifunctional aromatic glycidyl ether monomers include the following: Bis[4-(glycidyloxy)phenyl]methane Additional examples of suitable multifunctional aromatic glycidyl ether-based monomers include the following: N,N-Diglycidyl-4-glycidyloxyaniline In another embodiment, the aromatic epoxide functional monomer may be a terminal epoxide. In some aspects, suitable terminal epoxides include, but are not limited to, the following: 4,4’-Methylenebis(N,N-diglycidylaniline) Other suitable aromatic epoxide functional monomers for use in accordance with the present disclosure include, but are not limited to, the following: 9 4919-6390-8455.1 “CO2-Based Aromatic Polycarbonates and Methods of Making...” Attorney Docket No.302737-401005 4,4'-Methylenebis(N-(2,3-epoxypropyl)-N- 10 4919-6390-8455.1 “CO2-Based Aromatic Polycarbonates and Methods of Making...” Attorney Docket No.302737-401005 N-[3-(2-Oxiranylmethoxy)phenyl]-N-(2- -2-oxiranemethanamine N- 11 4919-6390-8455.1 “CO2-Based Aromatic Polycarbonates and Methods of Making...” Attorney Docket No.302737-401005 Combinations of any of the above aromatic epoxide functional monomers are also contemplated. For example, in some aspects, a mixture of any of the above aromatic epoxide functional monomers may be used. In this regard, a mixture may include monomers with the same of differing numbers of epoxide functionalities. By way of a nonlimiting example, a suitable mixture of monomers for use in accordance with the present disclosure includes may include a first mol percent of a first aromatic epoxide functional monomer and a second mol percent of a second aromatic epoxide functional monomer. In this aspect, the first aromatic epoxide functional monomer may include a first number of epoxides and the second aromatic epoxide functional monomer may include a second number of epoxides. The first and second numbers of epoxides may be the same or different. Similarly, the first and second mol percents may be the same, substantially the same, or different. The aromatic epoxide functional monomer(s) may also be included in a monomeric system along with aliphatic epoxides (with one or more epoxides). For example, the aromatic epoxide functional monomer(s) may be included in a monomeric system as the majority component (e.g., at least 50 mol percent) with the remainder aliphatic epoxide. Polymerization Selective Catalyst System Since CO2 is relatively inert, a catalyst system may be employed to promote the reaction between the multifunctional aromatic epoxides and CO2. In this regard, the catalyst system suitable for use in accordance with the present disclosure may be any catalyst system capable of copolymerizing CO2with the multifunctional aromatic monomers discussed in the previous section. Suitable catalysts include homogenous catalyst systems and heterogeneous catalyst systems having high selectivity and activity toward the polymerization of the multifunctional aromatic monomers. In some aspects, the catalyst system has a selectivity of about 80 percent or higher. In other aspects, the catalyst system has a selectivity of about 90 percent or higher. In still other aspects, the catalyst system has a selectivity of about 92 percent or higher. In some embodiments, the catalyst system is a metal salen-based homogenous catalyst. As would be readily understood by those of ordinary skill in the art, salen refers to a tetradentate C2- symmetric ligand synthesized from salicylaldehyde (sal) and ethylenediamine (en). Without being bound by any particular theory, a metal salen-based catalyst has novel selectivity and activity 12 4919-6390-8455.1 “CO2-Based Aromatic Polycarbonates and Methods of Making...” Attorney Docket No.302737-401005 toward the polymerization of multifunctional aromatic monomers. In this aspect, the homogenous catalyst may be a complex formed from a metal cation and a ligand derived from N,N’- Bis(salicylidene)ethylenediamine (salen). The metal cation may be a transition metal. In some aspects, the metal cation may be titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, scandium, or combinations thereof. In other aspects, the metal cation may be chromium, cobalt, manganese, or combinations thereof. For example, a suitable metal salen-based catalyst for use in accordance with the present disclosure is (salen) Cr-Cl catalyst, the structure of which is shown below: Another suitable example of a catalyst for use in accordance with the present disclosure is (salen) Co-X catalyst, the structure of which is shown below: where X may be any suitable nucleophile. For example, X may be N3, Br, Cl, I, OAc, HCO3, BF4, PF6, OH, H, HSO4, and combinations thereof. Yet another suitable catalyst includes (salen) Mn- Cl catalyst or N,N'-bis(3,5-di-tert-butylsalicylidene)-1,2-cyclohexane-diaminomanganese(III) chloride, the structure of which is shown below: 13 4919-6390-8455.1 “CO2-Based Aromatic Polycarbonates and Methods of Making...” Attorney Docket No.302737-401005 In other may amine-based organo-catalysts. Nonlimiting examples of homogeneous amine-based organo-catalysts that may be used as the catalyst system are as follows: Bis(triphenylphosphoranylidene)ammonium chloride (PPNCl) 1-Methylimidazol (MeIm) 4-Dimethylaminopyridine (DMAP) Other amine-based organo-catalysts suitable for use as the catalyst system in accordance with the present disclosure are disclosed in Catal. Sci. Technol., 2017,7, 2651-2684, the entire disclosure of which is incorporated by reference herein. In other embodiments, the catalyst system is a combination of a metal salen-based catalyst and an amine-based organo-catalyst. For example, the catalyst system may be a (salen) Cr-Cl catalyst along with any of the amine-based organo-catalysts above. In some aspects, the catalyst system may include (salen) Cr-Cl catalyst and PPNC1. In other aspects, the catalyst system may 14 4919-6390-8455.1 “CO2-Based Aromatic Polycarbonates and Methods of Making...” Attorney Docket No.302737-401005 include (salen) Cr-Cl catalyst and DMAP. In still other aspects, the catalyst system may be a (salen) Co-Cl catalyst along with any of the amine-based organo-catalysts above. For example, the catalyst system may include (salen) Co-Cl catalyst and PPNC1. In other aspects, the catalyst system may include (salen) Co-Cl catalyst and DMAP. As briefly discussed above, heterogenous catalyst systems may also be used in accordance with the present disclosure. Without being bound by any particular theory, heterogenous catalysts may be easily separated from the product mixture and, thus, are desirable for use with the present disclosure. In some embodiments, the heterogenous catalyst is a metal dicarboxylate-based heterogenous catalyst. The metal may be a transition metal such as zinc, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, scandium, or combinations thereof. In some aspects, the metal dicarboxylate-based heterogenous catalyst may include a linear dicarboxylic acid such as glutaric acid, succinic acid, adipic acid, or combinations thereof. In some aspects, the linear dicarboxylic acid is a C1-C15 linear dicarboxylic acid. In other aspects, the linear dicarboxylic acid is a C1-C10 linear dicarboxylic acid. In one embodiment, the metal dicarboxylate-based heterogenous catalyst may be a metal glutarate. For example, the heterogenous catalyst may be zinc glutarate. The catalyst systems described herein allow for incorporation of CO2into the multifunctional aromatic epoxides discussed herein with a turnover frequency (i.e., number of molecules reacted / number of sites x time (TOF)) ranging from 1 hr-1 to 2500 hr-1. For example, the TOF may range from 10 hr-1 to 2000 hr-1. In some embodiments, the TOF may range from 1000 hr-1 to 2000 hr-1. In other embodiments, the TOF may range from 100 hr-1 to 900 hr-1. In some aspects, the TOF is greater than 200 hr-1. In other aspects, the TOF is greater than 210 hr- 1. In still other aspects, the TOF is greater than 220 hr-1. The catalyst systems described herein may be mixed with a solvent. As would be understood by those of ordinary skill in the art, the solvent selection depends on a variety of factors including, but not limited to the catalyst, the solubility of the reaction mixture, and ease of purification, among other factors. In some aspects, dichloromethane (DCM) may be added to any of the above catalysts to form a solution. In other aspects, organic solvents such as DMF, THF, toluene, and acetonitrile are suitable for use (depending on the solubility of the monomers). 15 4919-6390-8455.1 “CO2-Based Aromatic Polycarbonates and Methods of Making...” Attorney Docket No.302737-401005 However, it is preferred that the solvent is not a halogenated organic solvent. In this aspect, the process described herein is preferably free of any halogenated organic solvents. Moreover, the process described herein requires less solvent than conventional processes. Polymerization Conditions In an effort to optimize the polymerization yield, the direct copolymerization of the multifunctional aromatic epoxides with CO2is conducted in a pressure-controlled polymerization reactor at a desired range of polymerization temperatures. In this regard, if the selected catalyst system enables both reaction pathways, lower temperatures and appropriate CO2 pressures are preferred to avoid formation of cyclic carbonate. However, in some aspects, the aromatic polycarbonate formed in accordance with the present disclosure is a mixture of aromatic polycarbonate and cyclic carbonate. In some embodiments, the aromatic polycarbonate includes about 1 percent to about 50 percent cyclic carbonate end-groups with the remainder aromatic polycarbonate. In other embodiments, the aromatic polycarbonate includes about 1 percent to about 45 percent cyclic carbonate end-groups with the remainder aromatic polycarbonate. In yet other embodiments, the aromatic polycarbonate includes about 1 percent to about 40 percent cyclic carbonate end-groups with the remainder aromatic polycarbonate. In still other embodiments, the aromatic polycarbonate includes about 1 percent to about 35 percent cyclic carbonate end-groups with the remainder aromatic polycarbonate. In some embodiments, the CO2pressure ranges from about 1 bar to about 200 bar. In other embodiments, the CO2 pressure ranges from about 5 bar to about 150 bar. In still other embodiments, the CO2 pressure ranges from about 20 bar to about 140 bar. In yet other embodiments, the CO2pressure ranges from about 10 bar to about 130 bar. In yet other embodiments, the CO2 pressure ranges from about 0 bar to about 160 bar. In some embodiments, the polymerization temperature ranges from about 25°C to about 100°C. In other embodiments, the polymerization temperature ranges from about 25°C to about 75°C. In still other embodiments, the polymerization temperature ranges from about 50°C to about 90°C. In yet other embodiments, the polymerization temperature ranges from about 45°C to about 65°C. In yet other embodiments, the polymerization temperature ranges from about 55°C to about 90°C. 16 4919-6390-8455.1 “CO2-Based Aromatic Polycarbonates and Methods of Making...” Attorney Docket No.302737-401005 The reaction time may range from about 5 hours to about 50 hours. In some embodiments, the reaction time may range from about 10 hours to about 45 hours. In other embodiments, the reaction time may range from about 15 hours to about 40 hours. The molar ratio of the carbon dioxide incorporated into the polymer is about 1 to about 80 mol percent. In some embodiments, the carbon dioxide incorporated into the polymer is about 10 to about 80 mol percent. In other embodiments, the carbon dioxide incorporated into the polymer is about 20 to about 80 mol percent. In still other embodiments, the carbon dioxide incorporated into the polymer is about 50 to about 75 mol percent. Without being bound by any particular theory, the mixture of the multifunctional aromatic epoxides with varying epoxide functionalities in the monomeric feed may be used to tune the rigidity and / or the crosslinking density of the polymer backbone and, as such, ultimately customize the polycarbonate. In some embodiments, the molar ratio of the multifunctional aromatic epoxide with varying number of epoxide functionality ranges from 5 percent to about 50 percent. In other embodiments, the molar ratio of the multifunctional aromatic epoxide ranges from 15 percent to about 25 percent. In still other embodiments, the molar ratio of the multifunctional aromatic epoxide ranges from 10 percent to about 30 percent. The molar ratio of the catalyst to monomer ranges from about 0.01 mol percent to about 5 mol percent. In some embodiments, the molar ratio of the catalyst is about 0.1 mol percent to about 1 mol percent. Polycarbonate Properties The aromatic polycarbonates of the present disclosure may have average molecular weights ranging from about 1 kg / mol to about 50 kg / mol. In some embodiments, the CO2-derived aromatic polycarbonates of the present disclosure have a molecular weight of about 18 kg / mole or greater. In other embodiments, the molecular weight of the CO2-derived aromatic polycarbonates of the present disclosure is about 18 kg / mole to about 50 kg / mole. In yet other embodiments, the molecular weight of the CO2-derived aromatic polycarbonates of the present disclosure is about 20 kg / mole to about 45 kg / mole. In still other embodiments, the molecular weight of the CO2-derived aromatic polycarbonates of the present disclosure is about 22 kg / mole to about 40 kg / mole. 17 4919-6390-8455.1 “CO2-Based Aromatic Polycarbonates and Methods of Making...” Attorney Docket No.302737-401005 Without being bound by any particular theory, the high crosslinking density of the CO2- derived aromatic polycarbonates made in accordance with the present disclosure combined with the bulky and rigid aromatic core of the multifunctional aromatic epoxides restrict chain mobility within the polymer backbone to raise the Tg and impart significant robustness, thermal stability, and mechanical strength to the aromatic polycarbonate material. In this aspect, the CO2-derived aromatic polycarbonates of the present disclosure have a Tg of about 125°C or higher. In some embodiments, the Tg of the CO2-derived aromatic polycarbonates is about 125°C to about 200°C. In some aspects, the Tg of the aromatic polycarbonates of the present disclosure is about 150°C or more. In other embodiments, the Tg of the CO2-derived aromatic polycarbonates is about 150°C to about 200°C. In still other embodiments, the Tg of the CO2-derived aromatic polycarbonates is about 150°C to about 175°C. The CO2-derived aromatic polycarbonates of the present disclosure have a thermal decomposition temperature of about 400°C or greater (under an air atmosphere at a heating rate of 5-20°C / min). In some embodiments, the thermal decomposition temperature of the CO2-derived aromatic polycarbonates of the present disclosure is about 510°C or more. In other embodiments, the thermal decomposition temperature of the CO2-derived aromatic polycarbonates of the present disclosure is about 520°C or more. For example, the thermal decomposition temperature of the CO2-derived aromatic polycarbonates of the present disclosure may range from about 400°C to about 700°C. In some aspects, the thermal decomposition temperature of the CO2-derived aromatic polycarbonates of the present disclosure may range from about 500°C to about 600°C. In other aspects, the thermal decomposition temperature of the CO2-derived aromatic polycarbonates of the present disclosure may range from about 500°C to about 560°C. The CO2-derived aromatic polycarbonates of the present disclosure have other mechanical and chemical properties comparable to BPA-phosgene polycarbonate materials. In this regard, the aromatic polycarbonates of the present disclosure have a tensile strength of about 60 MPa to about 85 MPa. In some embodiments, the aromatic polycarbonates have a tensile strength of about 65 MPa to about 80 MPa. In other embodiments, the aromatic polycarbonates have a tensile strength of about 70 MPa to about 75 MPa. The tensile modulus of the aromatic polycarbonates of the present disclosure may range from about 0.5 GPa to about 2.4 GPa. In some embodiments, the aromatic polycarbonates of the present disclosure have a tensile modulus of about 515 MPa to about 550 MPa. In other 18 4919-6390-8455.1 “CO2-Based Aromatic Polycarbonates and Methods of Making...” Attorney Docket No.302737-401005 embodiments, the tensile modulus of the aromatic polycarbonates of the present disclosure may range from about 520 MPa to about 540 MPa. The tensile elongation at break of the aromatic polycarbonates of the present disclosure may range from about 6% to about 138%. In some embodiments, the aromatic polycarbonates of the present disclosure have a tensile elongation of about 10% to about 40%. In other embodiments, the tensile elongation of the aromatic polycarbonates of the present disclosure may range from about 60% to about 90%. The tensile elongation at yield of the aromatic polycarbonates of the present disclosure may range from about 6% to about 8%. The aromatic polycarbonates of the present disclosure have a flexural strength of about 36 MPa to about 110 MPa. In some embodiments, the aromatic polycarbonates have a flexural strength of about 40 MPa to about 60 MPa. In other embodiments, the aromatic polycarbonates have a flexural strength of about 70 MPa to about 100 MPa. The flexural modulus of the aromatic polycarbonates of the present disclosure may range from about 0.9 GPa to about 4.1 GPa. In some embodiments, the aromatic polycarbonates of the present disclosure have a flexural modulus of about 1 GPa to about 2 GPa. In other embodiments, the flexural modulus of the aromatic polycarbonates of the present disclosure may range from about 2 GPa to about 4 GPa. The thermal degradation temperature of the aromatic polycarbonates of the present disclosure may be above 400°C. In some embodiments, the aromatic polycarbonates of the present disclosure have a thermal degradation temperature of about 400°C to about 500°C. In other embodiments, the thermal degradation temperature of the aromatic polycarbonates of the present disclosure may range from about 450°C to about 500°C. The notched impact strength of the aromatic polycarbonates of the present disclosure may range from about 10 to about 90 kJ / m2. In some embodiments, the aromatic polycarbonates of the present disclosure have a notched impact strength of about 20 to about 50 kJ / m2. In other embodiments, the notched impact strength of the aromatic polycarbonates of the present disclosure may range from about 60 to about 90 kJ / m2. 19 4919-6390-8455.1 “CO2-Based Aromatic Polycarbonates and Methods of Making...” Attorney Docket No.302737-401005 EXAMPLES The following example does not limit the invention or the claimed subject matter. Rather, the examples are intended to further illustrate embodiments of the present disclosure. Example 1: Preparation of CO2-derived Aromatic Polycarbonate (using only a catalyst) In the presence of air-stable homogeneous salen (Cr)-Cl catalyst, N,N-diglycidyl-4- glycidyloxyaniline and CO2were polymerized in a Parr reactor equipped with a gauge (and using conditions favorable for scaling up (which do not involve use of an oxygen- / moisture-free environment). More specifically, 10 mg of (R,R)-N,N’-Bis(3,5-di-tert-butylsalicylidene-1,2- cyclohexanediaminochromium(III) chloride) was measured and transferred to a Teflon liner, followed by the addition of 1 mL of dichloromethane (DCM) after which 2.1 grams of N,N- diglycidyl-4-glycidyloxyaniline was added to form a homogeneous mixture. The Teflon liner containing the homogeneous mixture was transferred to the Parr reactor and sealed to make it airtight. CO2 gas was added to the Parr reactor through the gas inlet. Once the CO2 gas pressure reached 60 bar, the temperature in the Parr reactor was raised to 85°C and maintained for 40 hours. After 40 hours, the Parr reactor was cooled and depressurized to obtain a reaction mixture of a cyclic carbonate derivative of N,N-Diglycidyl-4-glycidyloxyaniline and aromatic polycarbonate. The reaction mixture was characterized using Fourier Transform Infrared (FTIR) spectroscopy and thermogravimetric analysis (TGA). As shown in FIG. 1, the reaction mixture included about 55 percent aromatic polycarbonates and about 45 percent cyclic carbonates (as demonstrated by the carbonyl stretching signal at 1742 cm-1 and 1786 cm-1. As shown in FIG.2, the thermal degradation of the aromatic polycarbonate is above 400°C, which is comparable with the BPA phosgene–based polycarbonates. Example 2: Preparation of CO2-derived Aromatic Polycarbonate (using a catalyst and a co- catalyst system) 10 mg of (R,R)-N,N’-Bis(3,5-di-tert-butylsalicylidene-1,2- cyclohexanediaminochromium(III) chloride) as a catalyst and 3 mg of 4-Dimethylaminopyridine (DMAP) as a co-catalyst were measured and transferred to a Teflon liner, followed by the addition of 1 mL of dichloromethane (DCM) after which 2.1 grams of N,N-Diglycidyl-4- 20 4919-6390-8455.1 “CO2-Based Aromatic Polycarbonates and Methods of Making...” Attorney Docket No.302737-401005 glycidyloxyaniline was added to form a homogeneous mixture. The Teflon liner containing the homogeneous mixture was transferred to the Parr reactor and sealed to make it airtight. CO2 gas was added to the Parr reactor through the gas inlet. Once the CO2 gas pressure reached 60 bar, the temperature in the Parr reactor was raised to 45°C and maintained for 24 hours. After 24 hours, the Parr reactor was cooled and depressurized to obtain a reaction mixture of a cyclic carbonate derivative of N,N-Diglycidyl-4-glycidyloxyaniline and aromatic polycarbonate. The reaction mixture was characterized using Fourier Transform Infrared (FTIR) spectroscopy. As shown in FIG. 3, the reaction mixture included about 75 percent aromatic polycarbonates and about 25 percent cyclic carbonates (as demonstrated by the carbonyl stretching signal at 1743 cm-1 and 1794 cm-1). Unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art of this disclosure. It will be further understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the specification and should not be interpreted in an idealized or overly formal sense unless expressly so defined herein. Well known functions or constructions may not be described in detail for brevity or clarity. Example 3: Impact of Temperature on Polymerization 10 mg of (R,R)-N,N’-Bis(3,5-di-tert-butylsalicylidene-1,2- cyclohexanediaminochromium(III) chloride was measured and transferred to a Teflon®liner, followed by the addition of 1 mL of dichloromethane (DCM) after which 2.1 grams of N,N- diglycidyl-4-glycidyloxyaniline was added to form a homogeneous mixture. The liner containing the homogeneous mixture was transferred to the Parr reactor and sealed to make it airtight. CO2gas was then added to the Parr reactor through the gas inlet. Once the CO2 gas pressure reached 60 bar, the temperature in the Parr reactor was raised to different temperatures (in the range of 40°C to 80°C for 24 hours. After 24 hours, the Parr reactor was cooled to room temperature and depressurized to obtain a reaction mixture of a cyclic carbonate derivative of N,N-Diglycidyl-4- glycidyloxyaniline and aromatic polycarbonate. As shown in Figure 4, the mixture of cyclic carbonate derivative of N,N-Diglycidyl-4- glycidyloxyaniline and aromatic polycarbonate was characterized using FTIR. Polycarbonate 21 4919-6390-8455.1 “CO2-Based Aromatic Polycarbonates and Methods of Making...” Attorney Docket No.302737-401005 linkage is evident from the signature peak around 1743 cm-1and cyclic carbonate derivative was characterized by a vibrational signature around 1782 cm-1. It can be observed that, at a certain catalyst loading, use of higher temperature favors polycarbonate formation. As the temperature of the polymerization medium increases, the peak at 1743 cm-1becomes more prominent, which demonstrates that higher temperatures favor polycarbonate formation. Example 4: Impact of Catalyst Loading on Polymerization Different quantities (5 mg to 20 mg) of (R,R)-N,N’-Bis(3,5-di-tert-butylsalicylidene-1,2- cyclohexanediaminochromium(III) chloride) were measured and transferred to a Teflon®liner, followed by the addition of 1 mL of dichloromethane (DCM) after which 2.1 grams of N,N- diglycidyl-4-glycidyloxyaniline was added to form a homogeneous mixture. The liner containing the homogeneous mixture was transferred to the Parr reactor and sealed to make it airtight. CO2 gas was added to the Parr reactor through the gas inlet. Once the CO2 gas pressure reached 60 bar, the temperature in the Parr reactor was raised to 80 °C and maintained for 24 hours. After 24 hours, the Parr reactor was cooled to room temperature and depressurized to obtain a reaction mixture of a cyclic carbonate derivative of N,N-Diglycidyl-4-glycidyloxyaniline and aromatic polycarbonate. Figure 5 shows that polycarbonate formation favors polycarbonate formation—as is evident by the most intense polycarbonate signature peak at 1741 cm-1at highest (0.40 wt.%) catalyst loading. Example 5: Characterization of the Reaction Mixture of Cyclic Carbonate Derivative of N,N- Diglycidyl-4-glycidyloxyaniline and Aromatic Polycarbonate Mixture of cyclic carbonate derivative of N,N-Diglycidyl-4-glycidyloxyaniline and aromatic polycarbonate was prepared using optimum catalyst loading (0.40 wt.%) and optimum temperature of 80˚C as described in Examples 3 and 4. The product mixture obtained was a crosslinked solid mass that was crushed down to powdered form using mechanical force, which was then characterized using FTIR. As shown in Figure 6, the presence of cyclic carbonate and polycarbonate species identified using signature vibrational peaks. The estimate of the cyclic carbonate derivative as to polycarbonate product was estimated to 70:30 from the FTIR spectrum. 22 4919-6390-8455.1 “CO2-Based Aromatic Polycarbonates and Methods of Making...” Attorney Docket No.302737-401005 The powdered product was then dissolved in deuterated DMSO at 90˚C to analyze using1H-NMR (Figure 7) and13C-NMR (Figure 8). As can be seen from the proton NMR spectrum of the powdered product, epoxy functionality of the monomer (2-4 ppm) has been consumed due to coupling with CO2to form the mixture of cyclic carbonate derivative of N,N-Diglycidyl-4- glycidyloxyaniline and aromatic polycarbonate.13C-NMR spectrum of the powdered product shows presence of the carbonate linkage consolidating the results of FTIR analysis. The powdered product mixture was then analyzed for the thermal stability using TGA (Figure 9) and DSC (Figure 10). TGA analysis demonstrates that the product mixture is a multicomponent system (mixture of cyclic carbonate and polycarbonate), each component showing characteristic thermal decomposition behavior with the polycarbonate component being the most thermally stable and decomposing at around 325˚C. DSC analysis demonstrates that the glass transition temperature (Tg) of the polycarbonate component may be 65˚C. The lower-than- expected Tg of the polycarbonate can be attributed to the low molecular weight of the polycarbonate. As shown in Figure 11, the polycarbonate component has a broad molecular weight distribution indicated by the broad GPC peaks. Example 6: Synthesis of CO2-derived Polycarbonate using a Monomer with Four Epoxy Functionalities - 4,4’-Methylenebis(N,N-diglycidylaniline) 20 mg (R,R)-N,N’-Bis(3,5-di-tert-butylsalicylidene-1,2- cyclohexanediaminochromium(III) was measured and transferred to a Teflon®liner. Separately, 2.1 grams of 4,4’-Methylenebis(N,N-diglycidylaniline) was dissolved in 5 mL dichloromethane (DCM), which was then added to the catalyst in the liner to form a homogeneous mixture. The liner containing the homogeneous mixture was transferred to the Parr reactor and sealed to make it airtight. CO2gas was added to the Parr reactor through the gas inlet. Once the CO2 gas pressure reached 60 bar, the temperature in the Parr reactor was raised to 80 °C and maintained for 24 hours. After 24 hours, the Parr reactor was cooled to room temperature and depressurized to obtain a product mixture of a cyclic carbonate derivative of 4,4’- Methylenebis(N,N-diglycidylaniline) and aromatic polycarbonate. A methodology similar to what described in the preceding examples was adopted to characterize the product mixture of a cyclic carbonate derivative of 4,4’-Methylenebis(N,N- diglycidylaniline) and aromatic polycarbonate. Product mixture obtained as a solid crosslinked 23 4919-6390-8455.1 “CO2-Based Aromatic Polycarbonates and Methods of Making...” Attorney Docket No.302737-401005 mass was mechanically forced into the powder form, which was then analyzed using FTIR. Figure 12 shows that the reaction product exists as a mixture of cyclic carbonate derivative and the polycarbonate component and that the estimate of ratio of cyclic carbonate to polycarbonate in this case may be 85:15. In this aspect, i.e., where the monomer has four epoxy functionalities, even the small proportion of polycarbonates can yield crosslinked mass. This demonstrates the novelty of the chosen monomers and their ability to form mechanically strong polycarbonate material subject to higher yield of polycarbonates. Proton NMR (Figure 13) and carbon NMR (Figure 14) spectra show consumption of epoxide functionality via coupling with CO2and presence of the carbonate linkage respectively. TGA (Figure 15) shows that the thermal decomposition temperature of the polycarbonate component is around 350˚C, which demonstrates the thermal stability of the polycarbonate material prepared using monomer with four epoxide functionalities. DSC analysis (Figure 16) shows broad glass transition temperature range for the polycarbonate material in which higher molecular weight component demonstrating glass transition around 80˚C. This can also be confirmed by GPC analysis (Figure 17), which shows broad molecular weight distribution for polycarbonate component. The terms “about” and “approximately” shall generally mean an acceptable degree of error or variation for the quantity measured given the nature or precision of the measurements. Numerical quantities given in this description are approximate unless stated otherwise, meaning that the term “about” or “approximately” can be inferred when not expressly stated. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting. As used herein, the singular forms “a”, “an” and “the” are intended to include the plural forms as well (i.e., at least one of whatever the article modifies), unless the context clearly indicates otherwise. The terms “first,” “second,” and the like are used to describe various features or elements, but these features or elements should not be limited by these terms. These terms are only used to distinguish one feature or element from another feature or element. Thus, a first feature or element discussed below could be termed a second feature or element, and similarly, a second feature or element discussed below could be termed a first feature or element without departing from the 24 4919-6390-8455.1 “CO2-Based Aromatic Polycarbonates and Methods of Making...” Attorney Docket No.302737-401005 teachings of the disclosure. Likewise, terms like “top” and “bottom”; “front” and “back”; and “left” and “right” are used to distinguish certain features or elements from each other, but it is expressly contemplated that a top could be a bottom, and vice versa. The polycarbonates described and claimed herein are not to be limited in scope by the specific embodiments disclosed, since these embodiments are intended as illustrations of several aspects of the disclosure. Any equivalent embodiments are intended to be within the scope of this disclosure. Indeed, various modifications in addition to those described herein will become apparent to those skilled in the art from the foregoing description. Such modifications are also intended to fall within the scope of the appended claims. All patents and patent applications cited in the foregoing text are expressly incorporated herein by reference in their entirety. Any section headings herein are provided only for consistency with the suggestions of 37 C.F.R. § 1.77 or otherwise to provide organizational queues. These headings shall not limit or characterize the invention(s) set forth herein. 25 4919-6390-8455.1

Claims

“CO2-Based Aromatic Polycarbonates and Methods of Making...” Attorney Docket No.302737-401005 THE CLAIMS What is claimed is:

1. A method of producing aromatic polycarbonate comprising: providing at least one multifunctional epoxide comprising an aromatic core and at least two epoxy groups; providing a catalyst system comprising a complex of a metal and salen or a linear dicarboxylic acid; mixing the multifunctional epoxide and catalyst system to form a mixture; transferring the mixture to a reactor having at least one gas inlet and a base temperature and a base pressure; feeding CO2 through the gas inlet, wherein the CO2 is at the base pressure; and increasing the base pressure to a first pressure and the base temperature to a reaction temperature for a first period of time sufficient to copolymerize the CO2 and multifunctional epoxide and form the aromatic polycarbonate.

2. The method of claim 1, wherein the metal is a transition metal.

3. The method of claim 2, wherein the dicarboxylic acid comprises C1-C10 dicarboxylic acids, or combinations thereof.

4. The method of claim 1, wherein the first pressure ranges from about 40 bar to about 150 bar.

5. The method of claim 1, wherein the reaction temperature ranges from about 30°C to about 90°C.

6. The method of claim 1, wherein the aromatic core comprises at least one disubstituted benzene. 26 4919-6390-8455.1“CO2-Based Aromatic Polycarbonates and Methods of Making...” Attorney Docket No.302737-401005 7. The method of claim 6, wherein the aromatic core comprises at least two disubstituted benzenes.

8. The method of claim 7, wherein each disubstituted benzene comprises a phenyl group, phenyldiamine, or oxyaniline.

9. The method of claim 1, wherein the aromatic polycarbonate further comprises cyclic carbonate.

10. The method of claim 1, wherein the aromatic polycarbonate has a glass temperature ranging from about 125°C to about 200°C and an average molecular weight of about 1 kg / mol to about 50 kg / mol.

11. The method of claim 1, wherein the catalyst system comprises a mixture of complex of a metal and salen and at least one homogeneous amine-based organo-catalyst.

12. The method of claim 11, wherein the amine-based organo-catalyst is selected from the group consisting of bis(triphenylphosphoranylidene)ammonium chloride (PPNCl), 1-Methylimidazol (MeIm), 4-dimethylaminopyridine (DMAP), or combinations thereof.

13. The method of claim 1, wherein the complex of metal and salen comprises a (salen) Cr-Cl catalyst or a (salen) Co-Cl catalyst.

14. The method of claim 1, wherein the step of providing at least one multifunctional epoxide comprises providing the at least one multifunctional epoxide in an amount of more than about 50 mol percent with the remainder aliphatic epoxide. 27 4919-6390-8455.1“CO2-Based Aromatic Polycarbonates and Methods of Making...” Attorney Docket No.302737-401005 15. A method of producing an aromatic polycarbonate comprising: providing a multifunctional epoxide comprising an aromatic core and at least two epoxy groups, wherein the aromatic core comprises at least one para- disubstituted benzene; providing a catalyst system comprising a metal salen complex; mixing the multifunctional epoxide and catalyst system to form a homogenous mixture; transferring the homogenous mixture to a reactor having at least one gas inlet and a base temperature and a base pressure; feeding CO2through the gas inlet, wherein the CO2is at the base pressure; and increasing the base pressure to a first pressure and the base temperature to a reaction temperature for a period of time sufficient to copolymerize the CO2 and multifunctional epoxide and form the aromatic polycarbonate.

16. The method of claim 15, wherein the metal salen complex comprises a (salen) Cr- Cl catalyst or a (salen) Co-Cl catalyst.

17. The method of claim 15, wherein the para-disubstituted benzene comprises a phenyl group, phenyldiamine, or oxyaniline.

18. The method of claim 15, wherein the multifunctional epoxide is selected from the group consisting of 4,4’-Methylenebis(N,N-diglycidylaniline), Bis[4- (glycidyloxy)phenyl]methane, N,N-Diglycidyl-4-glycidyloxyaniline, Tris-(4- hydroxyphenyl)methane triglycidyl ether, 4,4'-Methylenebis(N-(2,3-epoxypropyl)- N-methylaniline, N,N,N’,N’-Tetraglycidyl-4,4’-diamino-3,3,’- dimethyldiphenylmethane, N,N,N’,N’-Tetraglycidyl-4,4’-diamino-3,3,’- diethyldiphenylmethane, N,N,N’,N’-Tetrakis(2-oxiranylmethyl)-1,4- benzenediamine, N,N,N’,N’-Tetrakis(2,3-epoxypropyl)-m-xylene-α,α’-diamine, N1,N1,N5,N5-Tetrakis(2-oxiranylmethyl)-1,5-naphthalenediamine, N-[3-(2- Oxiranylmethoxy)phenyl]-N-(2-oxiranylmethyl)-2-oxiranemethanamine, N-[2-(2- Oxiranylmethoxy)phenyl]-N-(2-oxiranylmethyl)-2-oxiranemethanamine, N-[2- 28 4919-6390-8455.1“CO2-Based Aromatic Polycarbonates and Methods of Making...” Attorney Docket No.302737-401005 Methyl-4-(oxiranylmethoxy)phenyl]-N-(oxiranylmethyl)oxiranemethanamine, 2,2’,2”-tris-[ethylidynetris(4,1-phenyleneoxymethylene), 2,2’,2”-tris- [propylidynetris(4,1-phenyleneoxymethylene) or combinations thereof.

19. The method of claim 15, wherein the aromatic polycarbonate has a glass temperature ranging from about 150°C to about 200°C.

20. The method of claim 15, wherein the aromatic polycarbonate has an average molecular weight of about 18 kg / mol to about 50 kg / mol.

21. The method of claim 15, wherein the first pressure ranges from about 40 bar to about 120 bar.

22. The method of claim 21, wherein the reaction temperature ranges from about 30°C to about 90°C.

23. The method of claim 21, wherein the aromatic polycarbonate has a thermal decomposition temperature of about 400°C or greater.

24. An aromatic polycarbonate comprising the reaction product of at least one multifunctional epoxide comprising an aromatic core and at least two epoxy groups and CO2, wherein the aromatic polycarbonate has a glass temperature of about 100°C or higher and an average molecular weight of about 1 kg / mol to about 50 kg / mol.

25. The aromatic polycarbonate of claim 24, wherein the aromatic core comprises at least one disubstituted benzene. 29 4919-6390-8455.1“CO2-Based Aromatic Polycarbonates and Methods of Making...” Attorney Docket No.302737-401005 26. The aromatic polycarbonate of claim 25, wherein the aromatic core comprises at least two disubstituted benzenes.

27. The aromatic polycarbonate of claim 26, wherein each disubstituted benzene comprises a phenyl group, phenyldiamine, or oxyaniline.

28. The aromatic polycarbonate of claim 24, wherein the aromatic polycarbonate further comprises cyclic carbonate.

29. The aromatic polycarbonate of claim 24, wherein the aromatic polycarbonate has a glass temperature ranging from about 125°C to about 200°C.

30. The aromatic polycarbonate of claim 29, wherein the glass temperature ranges from about 150°C to about 200°C.

31. The aromatic polycarbonate of claim 24, wherein the aromatic polycarbonate has an average molecular weight of about 18 kg / mol to about 50 kg / mol.

32. The aromatic polycarbonate of claim 31, wherein the average molecular weight is about 20 kg / mol to about 45 kg / mol.

33. The aromatic polycarbonate of claim 24, wherein the aromatic polycarbonate has a thermal decomposition temperature of about 400°C or greater (under an air atmosphere at a heating rate of 5-20°C / min).

34. The aromatic polycarbonate of claim 33, wherein the thermal decomposition temperature is about 510°C or more (under an air atmosphere at a heating rate of 5- 20°C / min). 30 4919-6390-8455.1“CO2-Based Aromatic Polycarbonates and Methods of Making...” Attorney Docket No.302737-401005 35. The aromatic polycarbonate of claim 33, wherein the thermal decomposition temperature ranges from about 400°C to about 700°C.

36. The aromatic polycarbonate of claim 24, the reaction product of at least one multifunctional epoxide comprising an aromatic core, at least two epoxy groups, CO2, and aliphatic epoxides. 31 4919-6390-8455.1

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