Patent ID: 12227615

DETAILED DESCRIPTION

The following detailed description is merely illustrative and is not intended to limit embodiments and/or application or uses of embodiments. Furthermore, there is no intention to be bound by any expressed or implied information presented in the preceding Background or Summary sections, or in the Detailed Description section.

One or more embodiments are now described with reference to the drawings, wherein like referenced numerals are used to refer to like elements throughout. In the following description, for purposes of explanation, numerous specific details are set forth in order to provide a more thorough understanding of the one or more embodiments. It is evident, however, in various cases, that the one or more embodiments can be practiced without these specific details.

Numerous chemical process industries retain batch processing as their primary method of manufacture. For example, products traditionally manufactured by batch processing can include polycarbonate platforms that serve as the foundation for many modern-day applications such as therapeutic delivery and macromolecular therapeutics. However, batch processing can be time-consuming, require the design of manufacturing stages that can be difficult to reproduce, can necessitate adverse safety conditions (e.g., due to the transportation of chemicals and/or storage of volatile chemicals), can require a large labor force, and/or can be difficult to automate.

Various embodiments described herein can regard forming one or more functionalized cyclic carbonate monomers that can synthesize one or more polycarbonate polymers via one or more ROPs. Further, the cyclic carbonate monomers can be functionalized with one or more aryl halide compounds that can facilitate post polymerization modification of the one or more polycarbonate polymers. One or more embodiments can leverage the uniquely enabling aspects of continuous-flow synthesis and a class of highly active ring-opening polymerization catalysts to rapidly access the polycarbonate platforms. In addition, one or more embodiments can employ trimethylsilyl functional thiols as nucleophiles in a post polymerization scheme that can enable polymer modification of the polycarbonates without significantly altering the flow rate of the continuous-flow synthesis.

As used herein, the term “flow reactor” can refer to a device in which one or more chemical reactions can take place within one or more channels (e.g., microfluidic channels). For example, a flow reactor can facilitate continuous flow production, as opposed to batch production. One or more streams of chemical reactants can flow (e.g., continuously) through the one or more channels of the flow reactor, wherein one or more chemical reactions (e.g., polymerizations, protonations, and/or deprotonations) involving the chemical reactants can occur within the one or more channels as the one or more streams flow.

FIG.1illustrates a diagram of example, non-limiting first cyclic carbonate chemical structure102, second cyclic carbonate chemical structure104, and third cyclic carbonate chemical structure106that can characterize one or more functionalized cyclic carbonate monomers in accordance with one or more embodiments described herein. Repetitive description of like elements employed in other embodiments described herein is omitted for sake of brevity. “R1” can represent a first functional group comprising a hydrogen atom or an alkyl group having greater than or equal to one carbon atom and less than or equal to 3 carbon atoms. Example alkyl groups that can be represented by “R1” can include, but are not limited: a methyl group, an ethyl group, a propyl group, etc., and/or the like.

Also shown inFIG.1, the first cyclic carbonate chemical structure102can comprise one or more aryl halide groups (e.g., represented by “A”) can be covalently bonded to a first carbonate molecular backbone via one or more linkage groups (e.g., represented by “L”). In various embodiments, the one or more linkage groups (e.g., represented by “L”) can comprise: an alkyl chain having greater than or equal to one carbon atom and less than or equal to 20 carbon atoms; and/or aryl rings. Further, the one or linkage groups (e.g., represented by “L”) can comprise one or more end groups that include, for example, heteroatoms such as an oxygen or nitrogen atom bonded to the one or more aryl halide groups (e.g., represented by “A”) and/or carbonate molecular backbone. Additionally, the second cyclic carbonate chemical structure104can comprise the one or more aryl halide groups (e.g., represented by “A”) directly bonded to an oxygen atom of a second carbonate molecular backbone. Moreover, the third cyclic carbonate chemical structure106can comprise the one or more aryl halide groups (e.g., represented by “A”) directly bonded to a nitrogen atom of a third carbonate molecular backbone.

One or more example aryl halide structures108are also shown inFIG.1, wherein the “*” can delineate a connection to the one or more linkage groups (e.g., represented by “L”) or respective carbonate molecular backbones. Further, “X” can represent a halide (e.g., a fluorine atom, a chloride atom, a bromine atom, or an iodine atom). In one or more embodiments, “X” can represent a fluorine atom. Further, “Y” can represent an oxygen atom, —NH—, or a sulfur atom. Additionally, “n” can represent an integer greater than or equal to 1 and less than or equal to 8. One of ordinary skill in the art will recognize that the position of the one or more halides on the aryl ring can vary.

In various embodiments described herein, the aryl halide group (e.g., represented by “A”) can facilitate a post polymerization modification to one or more polycarbonate platforms formed from the functionalized cyclic carbonate monomers characterized the first cyclic carbonate chemical structure102, the second cyclic carbonate chemical structure104, and/or the third cyclic carbonate chemical structure106. For example, the one or more aryl halide groups can activate one or more nucleophilic aromatic substitutions to facilitate a post polymerization modification. For instance, the one or more aryl halide groups (e.g., represented by “A”), and their delineated position within the first cyclic carbonate chemical structure102, second cyclic carbonate chemical structure104, and/or third cyclic carbonate chemical structure106, can facilitate one or more: ketone-activated nucleophilic aromatic substitutions, imidazole-activated nucleophilic aromatic substitutions, quinoxaline-activated nucleophilic aromatic substitutions, ester-activated nucleophilic aromatic substitutions, amide-activated nucleophilic aromatic substitutions, and/or sulfonyl-activated nucleophilic aromatic substitutions. In various embodiments, one or more of the halides (e.g., represented by “X”) of the aryl halide groups (e.g., represented by “A”) can be activated towards displacement by the one or more nucleophilic aromatic substitutions during the post polymerization modifications described herein.

FIG.2illustrates a flow diagram of an example, non-limiting method200that can facilitate forming the one or more functionalized cyclic carbonate monomers characterized the first cyclic carbonate chemical structure102in accordance with one or more embodiments described herein. Repetitive description of like elements employed in other embodiments described herein is omitted for sake of brevity.

At202, the method200can comprise reacting, via a flow reactor, one or more linkage chemical compounds with one or more aryl halide compounds to form a first intermediate compound, wherein the one or more linkage chemical compounds can comprise greater than or equal to 1 carbon atom and less than or equal to 20 carbon atoms. Further, the one or more linkage chemical compounds can comprise at least one end group selected from the group consisting of: a halide, a hydroxyl group, an amino group, a combination thereof, and/or the like. In one or more embodiments, the one or more linkage chemical compounds can comprise one or more aryl rings.

At204, the method200can comprise forming a second intermediate chemical compound by reacting, via the flow reactor, the first intermediate compound with a molecular backbone characterized by the following structure:

“R1” can represent a hydrogen atom or a first functional group comprising an alkyl group having greater than or equal to one carbon atom and less than or equal to 3 carbon atoms. For example, the first intermediate compound can be reacted with dimethylolpropionic acid (“DMPA”) at202.

At206, the method200can comprise reacting, via the flow reactor, the second intermediate compound with one or more carbonyl equivalents to form a cyclic carbonate monomer functionalized with an aryl halide group. Example carbonyl equivalents can include, but are not limited to: triphosgene, bis-pentafluorophenyl carbonate, N,N-carbonyldiimidazole, methyl chloroformate, ethyl chloroformate, diphenyl carbonate, diethyl carbonate, dimethyl carbonate, N,N′-Disuccinimidyl carbonate, a combination thereof, and/or the like. For example, the cyclic carbonate monomer formed at206can be characterized by the first cyclic carbonate chemical structure102. For instance, the molecular backbone of the cyclic carbonate monomer can be derived from the chemical compound at204. Also, the one or more linkage groups (e.g., represented by “L”) can be derived from the one or more linkage chemical compounds at202, and the aryl halide group (e.g., represented by “A”) can be derived from the one or more alky halide compounds at202.

FIG.3illustrates a flow diagram of an example, non-limiting method300that can facilitate forming the one or more functionalized cyclic carbonate monomers characterized the first cyclic carbonate chemical structure102, the second cyclic carbonate chemical structure104, and/or the third cyclic carbonate chemical structure106in accordance with one or more embodiments described herein. Repetitive description of like elements employed in other embodiments described herein is omitted for sake of brevity.

At302, the method300can comprise forming an intermediate chemical compound by reacting, via the flow reactor, an aryl halide compound with a molecular backbone characterized by one of the following structures:

“R1” can represent a hydrogen atom or a first functional group comprising an alkyl group having greater than or equal to one carbon atom and less than or equal to 3 carbon atoms. For example, the first intermediate compound can be reacted with DMPA at302.

At304, the method300can comprise reacting, via the flow reactor, the intermediate compound with one or more carbonyl equivalents to form a cyclic carbonate monomer functionalized with an aryl halide group. Example carbonyl equivalents can include, but are not limited to: triphosgene, bis-pentafluorophenyl carbonate, N,N-carbonyldiimidazole, methyl chloroformate, ethyl chloroformate, diphenyl carbonate, diethyl carbonate, dimethyl carbonate, N,N′-Disuccinimidyl carbonate, a combination thereof, and/or the like. For example, the cyclic carbonate monomer formed at304can be characterized by the first cyclic carbonate chemical structure102, the second cyclic carbonate chemical structure104, and/or the third cyclic carbonate chemical structure106. With regards to cyclic carbonate monomers formed at304and characterized by first cyclic carbonate chemical structure102, the one or more linkage groups (e.g., represented by “L”) can be derived from the one or more alky halide compounds at302.

FIG.4Aillustrates a diagram of example, non-limiting chemical structures that can characterize one or more linkage chemical compounds that can be employed to synthesis the one or more functionalized cyclic carbonate monomers characterized by the first cyclic carbonate chemical structure102in accordance with one or more embodiments described herein. Repetitive description of like elements employed in other embodiments described herein is omitted for sake of brevity.

As shown inFIG.4A, chemical structure402can characterize a first type of linkage chemical compound comprising the one or more alkyl groups and/or aryl rings (e.g., represented by “L”), and two halide end groups (e.g., wherein the halides are presented by “X”). For example, the halide end groups (e.g., represented by “X”) can be positioned at opposite ends of the one or more alkyl groups and/or aryl rings (e.g., represented by “L”). Chemical structure404can characterize a second type of linkage chemical compound comprising one or more alkyl groups and/or aryl rings (e.g., represented by “L”), a first end group comprising an amino group, and a second end group comprising a hydroxyl group. For example, the amino group and the hydroxyl group can be positioned at opposite ends of the one or more alkyl groups and/or aryl rings (e.g., represented by “L”). Chemical structure406can characterize a third type of linkage chemical compound comprising one or more alkyl groups and/or aryl rings (e.g., represented by “L”), a first end group comprising a hydroxyl group, and a second end group comprising a halide (e.g., represented by “X”). Further, example linkage chemical compounds408of each chemical structure402,404, and406are shown inFIG.4A.

In various embodiments, the one or more linkage groups (e.g., represented by “L”) can be derived from the one or more linkage chemical compounds characterized by chemical structure402,404, or406. For example, the one or more alkyl groups and/or aryl rings of the one or more linkage chemical compounds (e.g., represented by “L”) can be the one or more alkyl groups and/or aryl rings comprised within the one or more linkage groups (e.g., represented by “L”). Further, a first of the end groups of the linkage chemical compound (e.g., a halide, a hydroxyl group, or an amino group) can facilitate a bond with the one or more aryl halide groups. Additionally, a second of the end groups of the linkage chemical compound (e.g., a halide, a hydroxyl group, or an amino group) can facilitate a bond with the carbonate molecular backbone.

FIG.4Billustrates a diagram of example, non-limiting chemical structures that can characterize one or more aryl halide compounds that can be employed to synthesis the one or more functionalized cyclic carbonate monomers characterized by the first cyclic carbonate chemical structure102, the second cyclic carbonate chemical structure104, and/or the third cyclic carbonate chemical structure106in accordance with one or more embodiments described herein. Repetitive description of like elements employed in other embodiments described herein is omitted for sake of brevity.

As shown inFIG.4B, chemical structure410can characterize a first type of aryl halide compound, chemical structure412can characterize a second type of aryl halide compound, chemical structure414can characterize a third type of aryl halide compound, chemical structure416can characterize a fourth type of aryl halide compound, chemical structure418can characterize a fifth type of aryl halide compound, chemical structure420can characterize a fifth type of aryl halide compound, and/or chemical structure422can characterize a sixth type of aryl halide compound. Moreover, example aryl halide compounds424of each chemical structure410,412,414,416,418,420, and422are shown inFIG.4B.

In various embodiments, “R” can represent a functional group that can facilitate a covalent bonding between the one or more aryl halide groups (e.g., delineated as “A” inFIG.1) of the aryl halide compounds and the one or more linkage groups (e.g., represented by “L” inFIG.1) derived from the one or more linkage chemical compounds exemplified inFIG.4A. In one or more embodiments, the functional group (e.g., represented by “R”) can facilitate a covalent bonding between the one or more aryl halide groups (e.g., delineated by “A” inFIG.1) of the aryl halide compounds and the respective carbonate molecular backbone. Example functional groups that can be “R” can include, but are not limited to: a halide, a hydroxyl group, a carboxyl group, an acyl chloride group, and alkyl group, a combination thereof (e.g., CH2Br, CH2Cl), and/or the like. As described herein, “X” can represent a halide atom. In various embodiments, during synthesis of the one or more functionalized cyclic carbonate monomers characterized by the first cyclic carbonate chemical structure102, the aryl halide group's bond to functional group “R” can be replaced with a bond to the alkyl group and/or aryl ring of the one or more linkage chemical compounds (e.g., a direct bond, or a bond facilitated by a hydroxyl or amino end group of the linkage chemical compound). Further, an opposite end of the linkage chemical compound's alkyl group can be bonded to the carbonate molecular backbone (e.g., a direct bond, or a bond facilitated by a hydroxyl or amino end group of the linkage chemical compound); thereby linking the aryl halide group to the carbonate molecular backbone. In various embodiments, during synthesis of the one or more functionalized cyclic carbonate monomers characterized by the first cyclic carbonate chemical structure102, the second cyclic carbonate chemical structure104, and/or the third cyclic carbonate chemical structure106, the aryl halide group's bond to functional group “R” can be replaced with a bond to the respective carbonate molecular backbone.

FIG.5illustrates a diagram of example, non-limiting synthesis schemes that can be employed to form one or more functionalized cyclic carbonate monomers characterized by the first cyclic carbonate chemical structure102, the second cyclic carbonate chemical structure104, and/or the third cyclic carbonate chemical structure106in accordance with one or more embodiments described herein. Repetitive description of like elements employed in other embodiments described herein is omitted for sake of brevity. For example, synthesis schemes500and502can be employed to form one or more functionalized cyclic carbonate monomers characterized by the first cyclic carbonate chemical structure102. Synthesis scheme504can be employed to form one or more functionalized cyclic carbonate monomers characterized by the second cyclic carbonate chemical structure104. Synthesis scheme506can be employed to form one or more functionalized cyclic carbonate monomers characterized by the third cyclic carbonate chemical structure106. In various embodiments, synthesis scheme500can include the various features of method200, and synthesis schemes502,504, and/or506can include the various features of method300.

At a first stage of synthesis scheme500, one or more linkage chemical compounds can be reacted with one or more aryl halide chemical compounds to form a first intermediate chemical compound508. For example, the one or more linkage chemical compounds can be characterized by chemical structure402,404, or406. Also, the one or more aryl halide chemical compounds can be characterized by chemical structure410,412,414,416,418,420, or422. In various embodiments, the one or more linkage chemical compounds and/or aryl halide chemical compounds can be reacted via one or more alkylation reaction conditions and/or coupling reaction conditions. As used herein, the term “alkylation reaction conditions” can refer to chemical reaction conditions in which the described reactants are reacted in the presence of a base (e.g., 1.2-1.8 equivalents of base), a solvent, and a temperature greater than or equal to 60 degrees Celsius (° C.) and less than or equal to 80° C. Example bases that can be employed in the alkylation procedure can include, but are not limited to: triethylamine (“Et3N”), diisopropylethylamine, potassium carbonate, potassium phosphate, sodium hydroxide, potassium hydroxide, a combination thereof, and/or the like. Example solvents that can be employed in the alkylation procedure can include, but are not limited to: dimethylformamide (“DMF”), dimethylacetamide (“DMA”), acetonitrile, dimethyl sulfoxide (“DMSO”), tetrahydrofuran (“THF”), THF:Water, a combination thereof, and/or the like. As used herein, the term “coupling reaction conditions” can refer to chemical reaction conditions in which the described reactants are reacted in the presence of a coupling reagent (e.g., 1.1 equivalents), 4-N, N-dimethylaminopyridine (e.g., 1.1 equivalents), a solvent, and a temperature greater than or equal to 0° C. and less than or equal to 22° C. Example coupling reagents that can be employed in the coupling reaction conditions can include, but are not limited to: 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide, diisopropylcarbodiimide, dicyclohexyldicarbodiimide, a combination thereof, and/or the like. Example solvents that can be employed in the coupling reaction conditions can include, but are not limited to: chloroform, dichloromethane, THF, acetonitrile, a combination thereof, and/or the like. For instance,FIG.5depicts an embodiment of the first stage of synthesis scheme500in which the one or more linkage chemical compounds and aryl halide chemical compounds are react in the presence of one or more alkylation reaction conditions. At a second stage of synthesis scheme500, the intermediate chemical compound can be reacted with a first molecular backbone monomers characterized by chemical structure510to form a second intermediate chemical compound characterized by chemical structure512. In various embodiments, the second stage of synthesis scheme500can be facilitated by the one or more alkylation reaction condition or coupling reaction conditions. For instance,FIG.5depicts an embodiment of the second stage of synthesis scheme500in which the one or more first intermediate chemical compounds508and first molecular backbone monomers characterized by chemical structure510are reacted in the presence of one or more alkylation reaction conditions. At a third stage of the synthesis scheme500, the second intermediate chemical compound can be reacted with one or more carbonyl equivalent compounds513to form a functionalized cyclic carbonate monomer that can be characterized by the first cyclic carbonate chemical structure102. Example carbonyl equivalent compounds513can include, but are not limited to: triphosgene, bis-pentafluorophenyl carbonate, N,N-carbonyldiimidazole, methyl chloroformate, ethyl chloroformate, diphenyl carbonate, diethyl carbonate, dimethyl carbonate, N,N′-Disuccinimidyl carbonate, a combination thereof, and/or the like. In various embodiments, the third stage of synthesis scheme500can be facilitated by one or more carbonate reaction conditions. As used herein, the term “carbonate reaction conditions” can refer to one or more to chemical reaction conditions in which the described reactants are reacted in the presence of a base (e.g., 1.2 to 4 equivalents of base), a solvent, and a temperature greater than or equal to −78° C. and less than or equal to 75° C. Example bases that can be employed in the one or more carbonate reaction conditions can include, but are not limited to: Et3N, diisopropyl ethylamine, a combination thereof, and/or the like. Example solvents that can be employed in the one or more carbonate reaction conditions can include, but are not limited to: dichloromethane, chloroform, acetonitrile, MeCN, a combination thereof, and/or the like.

At a first stage of synthesis scheme502, the one or more molecular backbone monomers characterized by chemical structure510can be reacted with one or more aryl halide chemical compounds to form a functionalized monomer compound characterized by chemical structure512. For example, the one or more aryl halide chemical compounds can be characterized by chemical structure410,412,414,416,418,420, or422. In various embodiments, the first stage of synthesis scheme502can be facilitated by alkylation reaction conditions or coupling reaction conditions. For instance,FIG.5depicts an embodiment in which the one or more molecular backbone monomers characterized by chemical structure510and aryl halide chemical compounds characterized by chemical structure410,412,414,416,418,420, or422can be reacted together in the presence of alkylation reaction conditions. At a second stage of the synthesis scheme502, the intermediate chemical compound can be reacted with one or more carbonyl equivalent compounds to form a functionalized cyclic carbonate monomer that can be characterized by first cyclic carbonate chemical structure102. In various embodiments, the second stage of synthesis scheme502can be facilitated by one or more carbonate reaction conditions.

At a first stage of synthesis scheme504, one or more molecular backbone monomers characterized by chemical structure514can be reacted with one or more aryl halide chemical compounds to form a functionalized monomer compound characterized by chemical structure516. For example, the one or more aryl halide chemical compounds can be characterized by chemical structure410,412,414,416,418,420, or422. In various embodiments, the first stage of synthesis scheme504can be facilitated by alkylation reaction conditions or coupling reaction conditions. For instance,FIG.5depicts an embodiment in which the one or more molecular backbone monomers characterized by chemical structure514and aryl halide chemical compounds characterized by chemical structure410,412,414,416,418,420, or422can be reacted together in the presence of alkylation reaction conditions. At a second stage of the synthesis scheme504, the intermediate chemical compound can be reacted with one or more carbonyl equivalent compounds513to form a functionalized cyclic carbonate monomer that can be characterized by the third cyclic carbonate chemical structure106. In various embodiments, the second stage of synthesis scheme504can be facilitated by one or more carbonate reaction conditions.

At a first stage of synthesis scheme506, one or more molecular backbone monomers characterized by chemical structure518can be reacted with one or more aryl halide chemical compounds to form an intermediate chemical compound characterized by chemical structure520. For example, the one or more aryl halide chemical compounds can be characterized by chemical structure410,412,414,416,418,420, or422. In various embodiments, the first stage of synthesis scheme506can be facilitated by alkylation reaction conditions or coupling reaction conditions. For instance,FIG.5depicts an embodiment in which the one or more molecular backbone monomers characterized by chemical structure518and aryl halide chemical compounds characterized by chemical structure410,412,414,416,418,420, or422can be reacted together in the presence of alkylation reaction conditions. At a second stage of the synthesis scheme506, the intermediate chemical compound can be reacted with one or more carbonyl equivalent compounds513to form a functionalized cyclic carbonate monomer that can be characterized by the second cyclic carbonate chemical structure104. In various embodiments, the second stage of synthesis scheme506can be facilitated by one or more carbonate reaction conditions.

FIG.6illustrates a diagram of non-limiting example synthesis schemes that can exemplify formation of one or more functionalized cyclic carbonate monomers characterized by the first cyclic carbonate chemical structure102in accordance with one or more embodiments described herein. Repetitive description of like elements employed in other embodiments described herein is omitted for sake of brevity. In various embodiments, the one or more exemplary synthesis schemes depicted inFIG.6can exemplify the features of synthesis scheme500and method200.

As shown inFIG.6, synthesis scheme602can be employed to form functionalized cyclic carbonate monomer604. For example, a first stage of synthesis scheme602can form a first intermediate chemical compound508by reacting a linkage chemical compound characterized by chemical structure402with an aryl halide compound characterized by chemical structure414. In various embodiments, the first stage of synthesis scheme602can be facilitated by alkylation reaction conditions or coupling reaction conditions. At a second stage of synthesis scheme602, a second intermediate chemical compound (e.g., characterized by chemical structure512) can be formed by reacting the first intermediate chemical compound508with DMPA. In various embodiments, the second stage of synthesis scheme602can be facilitated by alkylation reaction conditions or coupling reaction conditions. Further, at a third stage of the synthesis scheme602the functionalized cyclic carbonate monomers characterized by the first cyclic carbonate chemical structure102can be achieve by reacting the second intermediate chemical compound (e.g., characterized by chemical structure512) with the carbonyl equivalent compound513triphosgene. In various embodiments, the third stage of synthesis scheme602can be facilitated by carbonate reaction conditions.

The resulting functionalized cyclic carbonate monomer604can comprise a linking group comprising a four carbon alkyl chain with an oxygen end group facilitating a bond with the aryl halide group, wherein the linking group couples the aryl halide group to the carbonate molecular backbone. As shown inFIG.6, an ester group can form as a result of the covalently bonding between the aryl halide group and the linkage group. Further, synthesis scheme602exemplifies that the functional group of the aryl halide compound can facilitate the bonding with the linkage chemical compound. For instance, in synthesis scheme502, the oxygen end group of the linkage group is derived from the hydroxyl functional group of the aryl halide compound. In various embodiments, the functionalized cyclic carbonate monomer604can comprise an ester group that is electron withdrawing and can facilitate activation of the halide (e.g., fluorine) towards displacement in one or more subsequent nucleophilic aromatic substitutions.

Also depicted inFIG.6, synthesis of the one or more functionalized cyclic carbonate monomers characterized by the first cyclic carbonate chemical structure102can further comprise one or more stages that modify the first intermediate chemical compound prior to formation of the second intermediate compound. For example, synthesis scheme606can be employed to form functionalized cyclic carbonate monomer608. A first intermediate chemical compound508can be formed at the first stage of synthesis scheme606by reacting a linkage chemical compound characterized by chemical structure404with an aryl halide compound characterized by chemical structure410. In various embodiments, the first stage of synthesis scheme606can be facilitated by alkylation reaction conditions or coupling reaction conditions. Further, the first intermediate chemical compound508can be modified at a second stage of synthesis scheme606to replace the non-bonded end group derived form the linkage chemical compound (e.g., the hydroxyl group) with a new functional group, such as a methane sulfonyl group (e.g., represented by “OMs”). For example, the first intermediate chemical compound can be reacted with one or more activating reagents607to facilitate the modification. Example activating reagents607can include, but are not limited to: p-tolylsulfonyl chloride (e.g., as depicted inFIG.6), methansulfonyl chloride, trifluoromethane sulfonic anhydride, trifluoroacetic anhydride, a combination thereof, and/or the like. In various embodiments, the second stage of synthesis scheme606can be facilitated by alkylation reaction conditions or coupling reaction conditions. Subsequently, the second intermediate chemical compound (e.g., characterized by chemical structure512) can be formed at a third stage of synthesis scheme606by reacting the modified first intermediate chemical compound609with DMPA. In various embodiments, the third stage of synthesis scheme606can be facilitated by alkylation reaction conditions or coupling reaction conditions. Further, at a fourth stage of the synthesis scheme606the functionalized cyclic carbonate monomer608characterized by the first cyclic carbonate chemical structure102can be achieved by reacting the second intermediate chemical compound (e.g., characterized by chemical structure512) with the carbonyl equivalent compound513triphosgene. In various embodiments, the fourth stage of the synthesis scheme606can be facilitated by the carbonate reaction conditions.

The resulting functionalized cyclic carbonate monomer608can comprise a linking group comprising a two carbon alkyl chain with a nitrogen end group facilitating a bond with the aryl halide group, wherein the linking group couples the aryl halide group to the carbonate molecular backbone. Further, synthesis scheme606exemplifies that the end group derived from the one or more linkage chemical compounds can facilitate the bonding with the aryl halide compound. For instance, in synthesis scheme606, the amino end group of the linkage group is derived from the amino end group of the linkage chemical compound. In various embodiments, the functionalized cyclic carbonate monomer608can comprise a sulfonyl group that is electron withdrawing and can facilitate activation of the halide (e.g., fluorine) towards displacement in one or more subsequent nucleophilic aromatic substitutions.

Synthesis scheme610can be employed to form functionalized cyclic carbonate monomer612. A first intermediate chemical compound508can be formed at the first stage of synthesis scheme610by reacting a linkage chemical compound characterized by chemical structure406with an aryl halide compound characterized by chemical structure414. In various embodiments, the first stage of synthesis scheme610can be facilitated by the alkylation reaction conditions or the coupling reaction conditions. Further, the first intermediate chemical compound508can be modified at a second stage of synthesis scheme610to replace the non-bonded end group derived form the linkage chemical compound (e.g., the hydroxyl group) with a new functional group. For example, the first intermediate chemical compound508can be reacted with activating reagent607tolylsulfonyl chloride to facilitate the modification. In various embodiments, the second stage of synthesis scheme610can be facilitated by the alkylation reaction conditions or the coupling reaction conditions. Subsequently, the second intermediate chemical compound (e.g., characterized by chemical structure512) can be formed at a third stage of synthesis scheme610by reacting the modified first intermediate chemical compound609with DMPA. In various embodiments, the third stage of synthesis scheme610can be facilitated by the alkylation reaction conditions or the coupling reaction conditions. Further, at a fourth stage of the synthesis scheme610the functionalized cyclic carbonate monomers characterized by the first cyclic carbonate chemical structure102can be achieve by reacting the second intermediate chemical compound (e.g., characterized by chemical structure512) with carbonyl equivalent compound513triphosgene. In various embodiments, fourth stage of synthesis scheme610can be facilitated by the carbonate reaction conditions.

The resulting functionalized cyclic carbonate monomer612can comprise a linking group comprising a two carbon alkyl chain with an oxygen end group facilitating a bond with the aryl halide group, wherein the linking group couples the aryl halide group to the molecular backbone. As shown inFIG.6, an ester group can form as a result of the covalently bonding between the aryl halide group and the linkage group. Further, synthesis scheme610exemplifies that the functional group of the aryl halide compound can facilitate the bonding with the linkage chemical compound. For instance, in synthesis scheme610, the oxygen end group of the linkage group is derived from the hydroxyl functional group of the aryl halide compound. In various embodiments, the functionalized cyclic carbonate monomer612can comprise an ester group that is electron withdrawing and can facilitate activation of the halide (e.g., fluorine) towards displacement in one or more subsequent nucleophilic aromatic substitutions.

Synthesis scheme614can be employed to form functionalized cyclic carbonate monomer616. A first intermediate chemical compound508can be formed at the first stage of synthesis scheme614by reacting a linkage chemical compound characterized by chemical structure404with an aryl halide compound characterized by chemical structure412. In various embodiments, the first stage of synthesis scheme614can be facilitated by alkylation reaction conditions or coupling reaction conditions. Further, the first intermediate chemical compound508can be modified at a second stage of synthesis scheme614to replace the non-bonded end group derived form the linkage chemical compound (e.g., the hydroxyl group) with a new functional group, such as methane sulfonyl group (e.g., represented by “OMs”). For example, the first intermediate chemical compound508can be reacted with activating reagent607tolylsulfonyl chloride to facilitate the modification. In various embodiments, the second stage of synthesis scheme614can be facilitated by alkylation reaction conditions or coupling reaction conditions. Subsequently, the second intermediate chemical compound (e.g., characterized by chemical structure512) can be formed at a third stage of synthesis scheme614by reacting the modified first intermediate chemical compound609with DMPA. In various embodiments, the third stage of synthesis scheme614can be facilitated by alkylation reaction conditions or coupling reaction conditions. Further, at a fourth stage of the synthesis scheme614the functionalized cyclic carbonate monomers characterized by the first cyclic carbonate chemical structure102can be achieve by reacting the second intermediate chemical compound (e.g., characterized by chemical structure512) with carbonyl equivalent compound513triphosgene. In various embodiments, fourth stage of synthesis scheme614can be facilitated by the carbonate reaction conditions.

The resulting functionalized cyclic carbonate monomer616can comprise a linking group comprising a two carbon alkyl chain with a nitrogen end group facilitating a bond with the aryl halide group, wherein the linking group couples the aryl halide group to the molecular backbone. Further, synthesis scheme614exemplifies that the end group derived from the one or more linkage chemical compounds can facilitate the bonding with the aryl halide compound. For instance, in synthesis scheme614, the amino end group of the linkage group is derived from the amino end group of the linkage chemical compound. In various embodiments, the functionalized cyclic carbonate monomer616can comprise a sulfonyl group that is electron withdrawing and can facilitate activation of the halide (e.g., fluorine) towards displacement in one or more subsequent nucleophilic aromatic substitutions.

Synthesis scheme618can be employed to form functionalized cyclic carbonate monomer620. For example, a first stage of synthesis scheme618can form a first intermediate chemical compound508by reacting a linkage chemical compound characterized by chemical structure406with an aryl halide compound characterized by chemical structure416. In various embodiments, the first stage of synthesis scheme618can be facilitated by the alkylation reaction conditions or the coupling reaction conditions. At a second stage of synthesis scheme618, a second intermediate chemical compound (e.g., characterized by chemical structure512) can be formed by reacting the first intermediate chemical compound508with DMPA. In various embodiments, the second stage of synthesis scheme618can be facilitated by the alkylation reaction conditions or the coupling reaction conditions. Further, at a third stage of the synthesis scheme618the functionalized cyclic carbonate monomer620characterized by the first cyclic carbonate chemical structure102can be achieve by reacting the second intermediate chemical compound (e.g., characterized by chemical structure512) with the carbonyl equivalent compound513triphosgene. In various embodiments, fourth stage of synthesis scheme618can be facilitated by the carbonate reaction conditions.

The resulting functionalized cyclic carbonate monomer620can comprise a linking group comprising a two carbon alkyl chain with an oxygen end group facilitating a bond with the aryl halide group, wherein the linking group couples the aryl halide group to the molecular backbone. As shown inFIG.6, an ester group can form as a result of the covalently bonding between the aryl halide group and the linkage group. Further, synthesis scheme618exemplifies that the functional group of the aryl halide compound can facilitate the bonding with the linkage chemical compound. For instance, in synthesis scheme618, the oxygen end group of the linkage group is derived from the hydroxyl functional group of the aryl halide compound. In various embodiments, the functionalized cyclic carbonate monomer620can comprise an ester group that is electron withdrawing and can facilitate activation of the halide (e.g., fluorine) towards displacement in one or more subsequent nucleophilic aromatic substitutions.

Synthesis scheme622can be employed to form functionalized cyclic carbonate monomer624. A first intermediate chemical compound508can be formed at the first stage of synthesis scheme622by reacting a linkage chemical compound characterized by chemical structure404with an aryl halide compound characterized by chemical structure416. In various embodiments, the first stage of synthesis scheme622can be facilitated by alkylation reaction conditions or coupling reaction conditions. Further, the first intermediate chemical compound508can be modified at a second stage of synthesis scheme622to replace the non-bonded end group derived form the linkage chemical compound (e.g., the hydroxyl group) with a new functional group, such as methane sulfonyl group (e.g., represented by “OMs”). For example, the first intermediate chemical compound508can be reacted with activating reagent607tolylsulfonyl chloride to facilitate the modification. In various embodiments, the second stage of synthesis scheme622can be facilitated by alkylation reaction conditions or coupling reaction conditions. Subsequently, the second intermediate chemical compound (e.g., characterized by chemical structure512) can be formed at a third stage of synthesis scheme622by reacting the modified first intermediate chemical compound609with DMPA. In various embodiments, the third stage of synthesis scheme622can be facilitated by alkylation reaction conditions or coupling reaction conditions. Further, at a fourth stage of the synthesis scheme622the functionalized cyclic carbonate monomer624characterized by the first cyclic carbonate chemical structure102can be achieve by reacting the second intermediate chemical compound (e.g., characterized by chemical structure512) with the carbonyl equivalent compound513triphosgene. In various embodiments, fourth stage of synthesis scheme622can be facilitated by the carbonate reaction conditions.

The resulting functionalized cyclic carbonate monomer624can comprise a linking group comprising a two carbon alkyl chain with a nitrogen end group facilitating a bond with the aryl halide group, wherein the linking group couples the aryl halide group to the molecular backbone. Further, synthesis scheme622exemplifies that the end group derived from the one or more linkage chemical compounds can facilitate the bonding with the aryl halide compound. For instance, in synthesis scheme622, the amino end group of the linkage group is derived from the amino end group of the linkage chemical compound. In various embodiments, the functionalized cyclic carbonate monomer624can comprise an amino group that is electron withdrawing and can facilitate activation of the halide (e.g., fluorine) towards displacement in one or more subsequent nucleophilic aromatic substitutions.

Synthesis scheme626can be employed to form functionalized cyclic carbonate monomer628. A first intermediate chemical compound508can be formed at the first stage of synthesis scheme626by reacting a linkage chemical compound characterized by chemical structure404with an aryl halide compound characterized by chemical structure414. In various embodiments, the first stage of synthesis scheme626can be facilitated by alkylation reaction conditions or coupling reaction conditions. Further, the first intermediate chemical compound508can be modified at a second stage of synthesis scheme626to replace the non-bonded end group derived form the linkage chemical compound (e.g., the hydroxyl group) with a new functional group. For example, the first intermediate chemical compound508can be reacted with activating reagent607tolylsulfonyl chloride to facilitate the modification. In various embodiments, second stage of synthesis scheme626can be facilitated by alkylation reaction conditions or coupling reaction conditions. Subsequently, the second intermediate chemical compound (e.g., characterized by chemical structure512) can be formed at a third stage of synthesis scheme626by reacting the modified first intermediate chemical compound609with DMPA. In various embodiments, third stage of synthesis scheme626can be facilitated by alkylation reaction conditions or coupling reaction conditions. Further, at a fourth stage of the synthesis scheme626the functionalized cyclic carbonate monomers characterized by the first cyclic carbonate chemical structure102can be achieve by reacting the second intermediate chemical compound (e.g., characterized by chemical structure512) with the carbonyl equivalent compound513triphosgene. In various embodiments, fourth stage of synthesis scheme622can be facilitated by the carbonate reaction conditions.

The resulting functionalized cyclic carbonate monomer628can comprise a linking group comprising a two carbon alkyl chain with a nitrogen end group facilitating a bond with the aryl halide group, wherein the linking group couples the aryl halide group to the molecular backbone. Further, synthesis scheme626exemplifies that the end group derived from the one or more linkage chemical compounds can facilitate the bonding with the aryl halide compound. For instance, in synthesis scheme626, the amino end group of the linkage group is derived from the amino end group of the linkage chemical compound. In various embodiments, the functionalized cyclic carbonate monomer628can comprise an amino group that is electron withdrawing and can facilitate activation of the halide (e.g., fluorine) towards displacement in one or more subsequent nucleophilic aromatic substitutions.

FIG.7illustrates a diagram of an example, non-limiting synthesis scheme702that can exemplify formation of one or more functionalized cyclic carbonate monomers characterized by the first cyclic carbonate chemical structure102in accordance with one or more embodiments described herein. Repetitive description of like elements employed in other embodiments described herein is omitted for sake of brevity. In various embodiments, exemplary synthesis scheme702can exemplify the features of synthesis scheme502and method300.

Synthesis scheme702exemplifies that the one or more functionalized cyclic carbonate monomers characterized by the first cyclic carbonate chemical structure102can be formed without a linkage chemical compound. For example, the one or more aryl halide compounds can be directly reacted with a chemical compound characterized by chemical structure510, such as DMPA to form the functionalized monomer compound characterized by chemical structure512. At a first stage of the synthesis scheme702, an aryl halide compound characterized by chemical structure414can be reacted with DMPA to form a functionalized monomer compound (e.g., characterized by chemical structure512). As shown inFIG.7,nvarious embodiments, the first stage of synthesis scheme702can be facilitated by the alkylation reaction conditions. At a second stage of the synthesis scheme702, the functionalized monomer compound (e.g., characterized by chemical structure512) can be reacted with the carbonyl equivalent compound513triphosgene to achieve functionalized cyclic carbonate monomer704characterized by the first cyclic carbonate chemical structure102. As shown inFIG.7, n various embodiments the second stage of synthesis scheme702can be facilitated by the carbonate reaction conditions. The resulting functionalized cyclic carbonate monomer704can comprise a linkage group comprising one carbon atom, which can be derived from the functional group of the aryl halide compound. In various embodiments, the functionalized cyclic carbonate monomer704can comprise a ketone group that is electron withdrawing and can facilitate activation of the halide (e.g., fluorine) towards displacement in one or more subsequent nucleophilic aromatic substitutions.

FIG.8illustrates a diagram of example, non-limiting synthesis schemes800and802that can exemplify formation of one or more functionalized cyclic carbonate monomers characterized by the third cyclic carbonate chemical structure106in accordance with one or more embodiments described herein. Repetitive description of like elements employed in other embodiments described herein is omitted for sake of brevity. In various embodiments, exemplary synthesis schemes800and802can exemplify the features of synthesis scheme504and method300.

At a first stage of synthesis scheme800the one or more aryl halide compounds characterized by chemical structure414can be directly reacted with a chemical compound characterized by chemical structure514to form a functionalized monomer compound characterized by chemical structure516. As shown inFIG.8, in various embodiments the first stage of synthesis scheme800can be facilitated by the coupling reaction conditions. At a second stage of the synthesis scheme800, the functionalized monomer compound characterized by chemical structure514can be reacted with the carbonyl equivalent compound513triphosgene to achieve functionalized cyclic carbonate monomer804characterized by the third cyclic carbonate chemical structure106. In various embodiments, the second stage of synthesis scheme800can be facilitated by the carbonate reaction conditions. In various embodiments, the resulting functionalized cyclic carbonate monomer804can comprise an amino group that is electron withdrawing and can facilitate activation of the halide (e.g., fluorine) towards displacement in one or more subsequent nucleophilic aromatic substitutions.

At a first stage of synthesis scheme802the one or more aryl halide compounds characterized by chemical structure410can be directly reacted with a chemical compound characterized by chemical structure514to form a functionalized monomer compound characterized by chemical structure516. As shown inFIG.8, in various embodiments the first stage of synthesis scheme802can be facilitated by the alkylation reaction conditions. At a second stage of the synthesis scheme802, the functionalized monomer compound characterized by chemical structure514can be reacted with the carbonyl equivalent compound513triphosgene to achieve functionalized cyclic carbonate monomer806characterized by the third cyclic carbonate chemical structure106. In various embodiments, second stage of synthesis scheme802can be facilitated by the carbonate reaction conditions. In one or more embodiments, the resulting functionalized cyclic carbonate monomer806can comprise an sulfonyl group that is electron withdrawing and can facilitate activation of the halide (e.g., fluorine) towards displacement in one or more subsequent nucleophilic aromatic substitutions.

FIG.9illustrates a diagram of example, non-limiting synthesis scheme900that can exemplify formation of one or more functionalized cyclic carbonate monomers characterized by the second cyclic carbonate chemical structure104in accordance with one or more embodiments described herein. Repetitive description of like elements employed in other embodiments described herein is omitted for sake of brevity. In various embodiments, exemplary synthesis scheme900can exemplify the features of synthesis scheme506and method300.

At a first stage of synthesis scheme900the one or more aryl halide compounds characterized by chemical structure414can be directly reacted with a chemical compound characterized by chemical structure518to form the functionalized monomer compound characterized by chemical structure520. As shown inFIG.9, in various embodiments the first stage of synthesis scheme900can be facilitated by the coupling reaction conditions. At a second stage of the synthesis scheme900, the functionalized monomer compound characterized by chemical structure520can be reacted with the carbonyl equivalent compound513triphosgene to achieve functionalized cyclic carbonate monomer902characterized by the second cyclic carbonate chemical structure104. As shown inFIG.9, in various embodiments the second stage of synthesis scheme900can be facilitated by the carbonate reaction conditions. In one or more embodiments, the resulting functionalized cyclic carbonate monomer902can comprise an ester group that is electron withdrawing and can facilitate activation of the halide (e.g., fluorine) towards displacement in one or more subsequent nucleophilic aromatic substitutions.

FIG.10illustrates a diagram of an example, non-limiting flow reactor system1000that can facilitate synthesis of the one or more functionalized cyclic carbonate monomers characterized by the first cyclic carbonate chemical structure102, the second cyclic carbonate chemical structure104, and/or the third cyclic carbonate chemical structure106in accordance with one or more embodiments described herein. Repetitive description of like elements employed in other embodiments described herein is omitted for sake of brevity. For example,FIG.10depicts the flow reactor system1000employed to facilitate synthesis scheme500.

The flow reactor system1000can comprise, for example, one or more inlets1004, one or more channels1006, one or more reactor loops1008, and/or one or more outlets1010. The one or more channels1006can extend from the one or more inlets1004to the one or more outlets1010. The one or more channels1006(e.g., microfluidic channels) can comprise, for example: tubes (e.g., microfluidic tubes), pipes, joiners (e.g., T-mixers), a combination thereof, and/or the like. Additionally, the one or more channels1006can be oriented into one or more reactor loops1008at one or more stages between the one or more inlets1004and/or the one or more outlets1010. The one or more reactor loops1008can influence the length of the flow reactor system1000and thereby the residence time of the one or more synthesis reactions. One of ordinary skill in the art will recognize that the number of loops comprising the reactor loops1008and/or the dimensions of the loops can vary depending on a desired flow rate, residence time, and/or turbulence. Further, while the reactor loops1008are depicted inFIG.10as characterized by circular shaped structures, the architecture of the reactor loops608is not so limited. For example, the one or more reactor loops1008can be characterized by elliptical and/or polygonal shaped structures.

FIG.10exemplifies the features of the flow reactor system1000with regards to synthesis scheme500. In accordance with synthesis scheme500, the one or more aryl halide compounds (e.g., characterized by chemical structure410,412,414,416,418,420, or422) can enter the one or more flow reactor system1000via one or more first inlets1004, while the one or more linkage chemical compounds (e.g., characterized by chemical structure402,404, or406) can enter the one or more flow reactor system1000via one or more second inlets1004. Further, one or more bases and/or solvents employed in the alkylation reaction conditions or coupling reaction conditions can also enter the flow reactor system1000via the first or second inlets1004to facilitate the first stage of synthesis scheme500within the flow reactor system1000. The one or more aryl halide compounds can meet and/or mix with the one or more linkage chemical compounds within the one or more channels1006; thereby forming a stream of chemical reactants. As the stream flows through the one or more channels1006, the first intermediate chemical compound508can be formed (e.g., as delineated by the dashed lines shown inFIG.10).

Additionally, the first intermediate chemical compound508can flow downstream through the one or more channels1006and mix with a chemical compound characterized by chemical structure510to form a second intermediate chemical compound characterized by chemical structure512. For example, the chemical compound characterized by chemical structure510can enter the flow reactor system1000via one or more third inlets1004. Further, one or more bases and/or solvents employed in the alkylation reaction conditions or coupling reaction conditions can also enter the flow reactor system1000via the third inlet1004to facilitate the second stage of synthesis scheme500within the flow reactor system1000. Further, an additional set of reactor loops1008can facilitate the formation reaction of the second intermediate chemical compound characterized by chemical structure512(e.g., as delineated by the dashed lines shown inFIG.10).

Additionally, the second intermediate chemical compound characterized by chemical structure512can flow downstream through the one or more channels1006and mix with the one or more carbonyl equivalent compounds513to facilitate a reaction that forms a functionalized cyclic carbonate monomer characterized by the first cyclic carbonate chemical structure102. For example, the one or more carbonyl equivalent compounds513can enter the flow reactor system1000via one or more fourth inlets1004. Further, one or more bases and/or solvents employed in the carbonate reaction conditions can also enter the flow reactor system1000via the fourth inlets1004to facilitate the third stage of synthesis scheme500within the flow reactor system1000. Moreover, an additional set of reactor loops1008can facilitate the formation reaction of the resulting functionalized cyclic carbonate monomer. As the stream flows through the one or more channels1006and/or the third set of reactor loops1008, the functionalized cyclic carbonate monomer characterized by the first cyclic carbonate chemical structure102can be formed (e.g., as delineated by the dashed lines shown inFIG.10). In one or more embodiments, a quenching solution1012can be further introduced into the flow reactor system1000via a fifth inlet1004to quench the chemical reaction that is facilitated by the carbonate reaction conditions and forms the functionalized cyclic monomer characterized by the first cyclic carbonate chemical structure102. For example, the quenching solution1012can comprise hydrochloric acid.

Further, the one or more synthesis reactions described herein to form the one or more functionalized cyclic carbonate monomers characterized by first cyclic carbonate chemical structure102can be performed within one or more embodiments of the flow reactor system1000, and/or can be characterized by residence times within the flow reactor system1000ranging from, for example, greater than or equal to 0.001 seconds (s) and less than or equal to 1800 s. Further, each of the respective inlets1004can be controlled independently of the other inlets1004. Therefore, respective chemicals can be introduced into the one or more flow reactors system1000at respective quantities, speeds, and/or pressures. Additionally, one of ordinary skill in the art will recognize that the flow reactor system1000can be expanded or contracted to facilitate the reaction conditions of the various synthesis reactions (e.g., the flow reactor system1000can be employed with additional or fewer reactor loops1008, inlets1004, and/or channels1006).

FIG.11illustrates a diagram of the example, non-limiting flow reactor system1000with regards to example synthesis scheme610in accordance with one or more embodiments described herein. Repetitive description of like elements employed in other embodiments described herein is omitted for sake of brevity.

In accordance with synthesis scheme610, the one or more aryl halide compounds (e.g., characterized by chemical structure414) can enter the one or more flow reactor system1000via one or more first inlets1004, while the one or more linkage chemical compounds (e.g., characterized by chemical structure406) can enter the one or more flow reactor system1000via one or more second inlets1004. Further, one or more bases (e.g., Et3N) and/or solvents (e.g., DMF) employed in the alkylation reaction conditions can also enter the flow reactor system1000via the first or second inlets1004to facilitate the first stage of synthesis scheme610within the flow reactor system1000. The one or more aryl halide compounds can meet and/or mix with the one or more linkage chemical compounds within the one or more channels1006; thereby forming a stream of chemical reactants. As the stream flows through the one or more channels1006, the first intermediate chemical compound508can be formed (e.g., as delineated by the dashed lines shown inFIG.11).

Additionally, the first intermediate chemical compound can flow downstream through the one or more channels1006and mix with the activating reagent607tolylsulfonyl chloride to facilitate a reaction that modifies the intermediate chemical compound508. For example, the activating reagent607can enter the flow reactor system1000via one or more third inlets1004. Further, one or more bases (e.g., Et3N) and/or solvents (e.g., DMF) employed in the alkylation reaction conditions can also enter the flow reactor system1000via the third inlet1004to facilitate the second stage of synthesis scheme610within the flow reactor system1000. Moreover, an additional set of reactor loops1008can facilitate the modification reaction of the intermediate chemical compound508. As the stream flows through the one or more channels1006and/or the second set of reactor loops1008, the modified first intermediate chemical compound609can be formed (e.g., as delineated by the dashed lines shown inFIG.10).

Additionally, the modified first intermediate chemical compound609can flow downstream through the one or more channels1006and mix with DMPA to facilitate a reaction that forms the second intermediate chemical compound characterized by chemical structure512. For example, the DMPA can enter the flow reactor system1000via one or more fourth inlets1004. Further, one or more bases (e.g., Et3N) and/or solvents (e.g., DMF) employed in the alkylation reaction conditions can also enter the flow reactor system1000via the fourth inlets1004to facilitate the third stage of synthesis scheme610within the flow reactor system1000. Further, an additional set of reactor loops1008can facilitate the formation of the second intermediate chemical compound characterized by chemical structure512. As the stream flows through the one or more channels1006and/or the third set of reactor loops1008, the second intermediate chemical compound characterized by chemical structure512can be formed (e.g., as delineated by the dashed lines shown inFIG.11).

Additionally, the second intermediate chemical compound can flow downstream through the one or more channels1006and mix with the carbonyl equivalent compound513triphosgene to facilitate a reaction that forms the functionalized cyclic carbonate monomer612. For example, the carbonyl equivalent compound513triphosgene can enter the flow reactor system1000via one or more fifth inlets1004. Further, one or more bases (e.g., Et3N) and/or solvents (e.g., MeCN) employed in the carbonate reaction conditions can also enter the flow reactor system1000via the fifth inlets1004to facilitate the fourth stage of synthesis scheme610within the flow reactor system1000As the stream flows through the one or more channels1006and/or the fourth set of reactor loops1008, the functionalized cyclic carbonate monomer612can be formed (e.g., as delineated by the dashed lines shown inFIG.11). In one or more embodiments, a quenching solution1012of hydrochloric acid can be further introduced into the flow reactor system1000via a fourth inlet1004to quench the chemical reaction that is facilitated by the carbonate reaction conditions and forms the functionalized cyclic carbonate monomer characterized by the third cyclic carbonate chemical structure106.

FIG.12illustrates a diagram of the example, non-limiting flow reactor system1000with regards to synthesis scheme504in accordance with one or more embodiments described herein. Repetitive description of like elements employed in other embodiments described herein is omitted for sake of brevity. In accordance with synthesis scheme504, one or more aryl halide compounds (e.g., characterized by chemical structure410,412,414,416,418,420, or422) can enter the one or more flow reactor system1000via one or more first inlets1004, while the one or more chemical compounds characterized by chemical structure514can enter the one or more flow reactor system1000via one or more second inlets1004. Further, one or more bases and/or solvents employed in the alkylation reaction conditions or coupling reaction conditions can also enter the flow reactor system1000via the first or second inlets1004to facilitate the first stage of synthesis scheme504within the flow reactor system1000. The one or more aryl halide compounds characterized by chemical structure410,412,414,416,418,420, or422can meet and/or mix with the one or more chemical compounds characterized by chemical structure514within the one or more channels1006; thereby forming a stream of chemical reactants. As the stream flows through the one or more channels1006, an intermediate chemical compound characterized by chemical structure516can be formed (e.g., as delineated by the dashed lines shown inFIG.12).

Additionally, the intermediate chemical compound characterized by chemical structure516can flow downstream through the one or more channels1006and mix with the one or more carbonyl equivalent compounds513to facilitate a reaction that forms a functionalized cyclic carbonate monomer characterized by the third cyclic carbonate chemical structure106. For example, the one or more carbonyl equivalent compounds513can enter the flow reactor system1000via one or more third inlets1004. Further, one or more bases and/or solvents employed in the carbonate reaction conditions can also enter the flow reactor system1000via the third inlet1004to facilitate the second stage of synthesis scheme504within the flow reactor system1000. As the stream flows through the one or more channels1006and/or the second set of reactor loops1008, the functionalized cyclic carbonate monomer characterized by the third cyclic carbonate chemical structure106can be formed (e.g., as delineated by the dashed lines shown inFIG.12). In one or more embodiments, the quenching solution1012can be further introduced into the flow reactor system1000via a fourth inlet1004to quench the chemical reaction that is facilitated by the carbonate reaction conditions and forms the functionalized cyclic monomer characterized by the third cyclic carbonate chemical structure106.

FIG.13illustrates a diagram of the example, non-limiting flow reactor system1000with regards to synthesis scheme506in accordance with one or more embodiments described herein. Repetitive description of like elements employed in other embodiments described herein is omitted for sake of brevity. In accordance with synthesis scheme506, one or more aryl halide compounds (e.g., characterized by chemical structure410,412,414,416,418,420, or422) can enter the one or more flow reactor system1000via one or more first inlets1004, while the one or more chemical compounds characterized by chemical structure518can enter the one or more flow reactor system1000via one or more second inlets1004. Further, one or more bases and/or solvents employed in the alkylation reaction conditions or coupling reaction conditions can also enter the flow reactor system1000via the first or second inlets1004to facilitate the first stage of synthesis scheme506within the flow reactor system1000The one or more aryl halide compounds characterized by chemical structure410,412,414,416,418,420, or422can meet and/or mix with the one or more chemical compounds characterized by chemical structure518within the one or more channels1006; thereby forming a stream of chemical reactants. As the stream flows through the one or more channels1006, an intermediate chemical compound characterized by chemical structure520can be formed (e.g., as delineated by the dashed lines shown inFIG.13).

Additionally, the intermediate chemical compound characterized by chemical structure520can flow downstream through the one or more channels1006and mix with one or more carbonyl equivalent compounds513to facilitate a reaction that forms a functionalized cyclic carbonate monomer characterized by the second cyclic carbonate chemical structure104. For example, the one or more carbonyl equivalent compounds513can enter the flow reactor system1000via one or more third inlets1004. Further, one or more bases and/or solvents employed in the carbonate reaction conditions can also enter the flow reactor system1000via the third inlet1004to facilitate the second stage of synthesis scheme506within the flow reactor system1000. As the stream flows through the one or more channels1006and/or the second set of reactor loops1008, the functionalized cyclic carbonate monomer characterized by the second cyclic carbonate chemical structure104can be formed (e.g., as delineated by the dashed lines shown inFIG.13). In one or more embodiments, a quenching solution1012of hydrochloric acid can be further introduced into the flow reactor system1000via a fourth inlet1004to quench the chemical reaction that is facilitated by the carbonate reaction conditions and forms the functionalized cyclic carbonate monomer characterized by the second cyclic carbonate chemical structure104.

FIG.14illustrates a diagram of example, non-limiting first polycarbonate chemical structure1402, second polycarbonate chemical structure1404, and/or third polycarbonate chemical structure1406that can characterize one or more functionalized polycarbonate polymers in accordance with one or more embodiments described herein. Repetitive description of like elements employed in other embodiments described herein is omitted for sake of brevity. In various embodiments, the polycarbonate polymers characterized by the first polycarbonate chemical structure1402, the second polycarbonate chemical structure1404, and/or the third polycarbonate chemical structure1406can be polymerized from the one or more functionalized cyclic carbonate monomers characterized by the first cyclic carbonate chemical structure102, the second cyclic carbonate chemical structure104, the third cyclic carbonate chemical structure106.

As described herein, “R1” can represent the first functional group comprising an alkyl group having greater than or equal to one carbon atom and less than or equal to three carbon atoms. Example alkyl groups that can be represented by “R1” can include, but are not limited: a methyl group, an ethyl group, a propyl group, etc., and/or the like. Also, “R2” can represent a second functional group comprising one or more of the following groups: an alcohol group, an alkyl group having from 1 to 20 carbon atoms, a benylic alcohol, an allylic alcohol, a propargylic alcohol, a group derived from a macromonomer, a combination thereof, and/or the like.

Also shown inFIG.14, the first polycarbonate chemical structure1402can comprise one or more handle functional groups (e.g., represented by “A1”) can be covalently bonded to a molecular backbone of the polycarbonate via the one or more linkage groups (e.g., represented by “L”). As described herein, in various embodiments, the one or more linkage groups (e.g., represented by “L”) can comprise an alkyl chain having greater than or equal to one carbon atom and less than or equal to 20 carbon atoms. Further, the one or linkage groups (e.g., represented by “L”) can comprise one or more end groups that include, for example, an oxygen or nitrogen atom bonded to the one or more handle functional groups (e.g., represented by “A1”) and/or the polycarbonate molecular backbone. The second polycarbonate chemical structure1404can comprise the one or more handle functional groups (e.g., represented by “A1”) directly bonded to the polycarbonate molecular backbone. Similarly, the third polycarbonate chemical structure1406can comprise the one or more handle functional groups (e.g., represented by “A1”) directly bonded to the polycarbonate molecular backbone.

In one or more embodiments, the one or more handle functional groups (e.g., represented by “A1”) can be modified embodiments of the aryl halide groups depicted inFIG.1(e.g., represented by “A”) such that at least one halide atom is replaced with a further bond to the one or more third functional groups (e.g., represented by “R3”) via a sulfur atom. One or more example handle functional group structures1408are also shown inFIG.14, wherein the “*” can delineate a connection to the one or more linkage groups (e.g., represented by “L”), the polycarbonate molecular backbone, or a connection to one or more sulfur atoms (e.g., in accordance with the first polycarbonate chemical structure1402, the second polycarbonate chemical structure1404, and/or the third polycarbonate chemical structure1406). Further, “X” can represent a halide (e.g., a fluorine atom, a chloride atom, a bromine atom, or an iodine atom). In one or more embodiments, “X” can represent a fluorine atom. Further, “Y” can represent an oxygen atom, —NH—, or a sulfur atom. Additionally, “n” can represent an integer greater than or equal to 1 and less than or equal to 8, and “m” can represent an integer greater than or equal to 2 and less than or equal to 5,000. In various embodiments, “R3” can represent a third functional group comprising: an alkyl group, aromatic group, heteroaromatic group, pendent ether groups, thioether groups, alkyl halide groups, phosphonate groups, epoxide groups, sulfonate groups, urea groups, thiourea groups, guanidinium groups, carbamate groups, ester groups, and carbonate groups, a combination thereof, and/or the like.

FIG.15illustrates a flow diagram of an example, non-limiting method1500that can facilitate polymerizing a polycarbonate compound and modifying the polycarbonate compound post polymerization to achieve a polycarbonate polymer characterized by the first polycarbonate chemical structure1402, the second polycarbonate chemical structure1404, the third polycarbonate chemical structure1406in accordance with one or more embodiments described herein. Repetitive description of like elements employed in other embodiments described herein is omitted for sake of brevity.

At1502, the method1500can comprise performing, via a flow reactor (e.g., flow reactor system1000), one or more ROPs of one or more cyclic carbonate monomers to form one or more polycarbonate polymers, wherein the one or more cyclic carbonate monomers comprise one or more aryl halide groups. For example, the one or more cyclic carbonate monomers can be characterized by the first cyclic carbonate chemical structure102, the second cyclic carbonate chemical structure104, and/or the third cyclic carbonate chemical structure106. In various embodiments, the one or more ROPs at1502can be facilitated by one or more initiators and/or anionic catalysts. Example initiators than can be employed to facilitate the one or more ROPs can include, but are not limited to: a primary alcohol, an amine, a thiol, a carbanion, a combination thereof, and/or the like.

At1504, the method1500can comprise reacting the one or more polycarbonate polymers with one or more silyl protected thiols, wherein the silyl protected thiols comprise a target functional group that covalently bonds to the aryl halide group. One of ordinary skill in the art will recognize, that the silyl group of the silyl protected thiols can comprise alkyl chains of various lengths. For example, the silyl group can be a trimethylsilyl, a triethylsilyl, a triisopropylsilyl, etc., a combination thereof, and/or the like. Further, the aryl halide group can serve as a handle functional group that can facilitate post polymerization functionalization of the polycarbonate polymers with the one or more target functional groups of the silyl protected thiols. For instance, the modification reaction facilitated by the reacting at1504can be a nucleophilic aromatic substitution, wherein the aryl halide group of the polycarbonate polymer formed at1502can comprise one or more electron withdrawing groups that can activate the one or more halides to be displaced by the sulfur atom of the one or more TMSS compounds. In one or more embodiments, the reacting at1504can be performed via batch reaction chemistry. Alternatively, in one or more embodiments, the reacting at1504can be performed in a continuous flow reaction via the flow reactor (e.g., flow reactor system1000). For instance, the flow rate associated with the one or more ROPs at1502can be set to match the flow rate associated with the modification reaction at1504.

In one or more embodiments, the reacting at1504can be facilitated by one or more catalysts and/or solvents. Example catalysts that can facilitate the reacting at1504can include, but are not limited to: DBU, DBU·OBz, BzOK, BzONa, potassium acetate, potassium hexanoate, sodium acetate, a combination thereof, and/or the like. Example solvents that can facilitate the reacting at1504can include, but are not limited to: NMP, DMF, acetonitrile, DMSO, THF, ethyl acetate, ethylene carbonate, a combination thereof, and/or the like. In various embodiments, method1500can be performed at room temperature.

FIG.16illustrates a diagram of example, non-limiting polymerization scheme1602,1604, and1606that can characterize the synthesis of one or more polycarbonate polymers that can be characterized, respectively, by the first polycarbonate chemical structure1402, the second polycarbonate chemical structure1404, the third polycarbonate chemical structure1406in accordance with one or more embodiments described herein. Repetitive description of like elements employed in other embodiments described herein is omitted for sake of brevity. As shown inFIG.16, “m” can be an integer greater than or equal to 2 and less than or equal to 5000.

Polymerization scheme1602exemplifies that the one or more polycarbonate polymers characterized by the first polycarbonate chemical structure1402can be polymerized from the one or more cyclic carbonate monomers characterized by first cyclic carbonate chemical structure102. For example, a first stage of the polymerization scheme1602can comprise one or more ROPs that can form a polycarbonate platform chemical structure1608. In various embodiments, the one or more cyclic carbonate monomers characterized by first cyclic carbonate chemical structure102can be reacted with the one or more initiator compounds1609and/or anionic catalyst compounds1610described herein (e.g., with regards to method1500) to facilitate the one or more ROPs. For example, the one or more initiator compounds1609can include, but are not limited to: a primary alcohol, an amine, a thiol, a carbanion, a combination thereof, and/or the like. Additionally, in various embodiments the one or more anionic catalyst compounds1610(e.g., employed in the various polymerizations and/or methods described herein) can be the anionic catalysts disclosed in the inventor's U.S. patent application Ser. No. 16/028,989 and U.S. patent application Ser. No. 16/029,025, which are incorporated in their entirety herein by this reference. During the one or more ROPs; the first functional group (e.g., represented by “R1”) can be derived from the one or more cyclic carbonate monomers, and the second functional group (e.g., represented by “R2”) can be derived from the one or more initiator compounds1609. In various embodiments, the one or more initiator compounds1609and/or anionic catalyst compounds1610can be supplied with one or more solvents (e.g., THF), and the one or more ROPs can be performed at room temperature.

At a second stage of the polymerization scheme1602, the polycarbonate platform chemical structure1608can be further reacted with one or more silyl protected thiol compounds1611. The one or more silyl protected thiol can comprise one or more silyl groups comprising one or more alkyl chains. Example silyl groups can include, but are not limited to: trimethylsilyl, a triethylsilyl, a triisopropylsilyl, etc., a combination thereof, and/or the like. For example, the one or more silyl protected thiol compounds1611can be characterized by the following chemical structure:

Wherein “R3” represents a third functional group that can be the target for functionalization with the polycarbonate platform chemical structure1608. In various embodiments, the modification reaction performed at the second stage can be facilitated by one or more catalysts described herein (e.g., with regards to method1500) to facilitate one or more nucleophilic aromatic substitutions. Additionally, “R4”, “R5”, and/or “R6” can respectively represent functional groups that can comprise alkyl groups, such as methyl, ethyl groups, propyl groups, etc., a combination thereof, and/or the like. In one or more embodiments, the “R4”, “R5”, and/or “R6” can have the same chemical structure or different chemical structures. For instance, in various embodiments the silyl protected thiol compound1611can be a trimethylsilyl protect thiol (“TMSS”) compound. In various embodiments, the silyl protected thiol compound1611can covalently bond to the aryl halide group (e.g., represented by “A”) of the polycarbonate platform chemical structure1608, such that at least one halide of the aryl halide group is replaced by a covalent bonding with a sulfur atom of the silyl protected thiol compound1611; thereby, forming the handle functional group (e.g., represented by “A1”) and functionalizing the polycarbonate platform chemical structure1608with the one or more third functional groups (e.g., represented by “R3”) bonded to the sulfur atom and derived from the silyl protected thiol compound1611.

In various embodiments, polymerization scheme1602can be employed within a flow chemistry procedure (e.g., employed within one or more flow reactor systems1000). For example, introduction of the one or more silyl protected thiol compounds1611and/or solvents at the second stage of polymerization scheme1602into the stream of chemical reactants characterized by the polycarbonate platform chemical structure1608can quench the chemical reaction initiated at the first stage of polymerization scheme1602. Further, one or more byproducts of the quenching can further catalyze the modification reaction of the second stage of the polymerization scheme1602(e.g., catalyze the functionalization of the aryl halide group with the silyl protected thiol compound1611).

Polymerization scheme1604exemplifies that the one or more polycarbonate polymers characterized by the second polycarbonate chemical structure1404can be polymerized from the one or more cyclic carbonate monomers characterized by second cyclic carbonate chemical structure104. For example, a first stage of the polymerization scheme1604can comprise one or more ROPs that can form a second polycarbonate platform chemical structure1612. In various embodiments, the one or more cyclic carbonate monomers characterized by second cyclic carbonate chemical structure104can be reacted with the one or more initiator compounds1609and/or anionic catalyst compounds1610described herein (e.g., with regards to method1500) to facilitate the one or more ROPs. During the one or more ROPs; the first functional group (e.g., represented by “R1”) can be derived from the one or more cyclic carbonate monomers, and the second functional group (e.g., represented by “R2”) can be derived from the one or more initiator compounds1609. In various embodiments, the one or more initiator compounds1609and/or anionic catalyst compounds1610can be supplied with one or more solvents (e.g., THF), and the one or more ROPs can be performed at room temperature.

At a second stage of the polymerization scheme1604, the second polycarbonate platform chemical structure1612can be further reacted with the one or more silyl protected thiol compounds1611(e.g., TMSS). In various embodiments, the modification reaction performed at the second stage can be facilitated by one or more catalysts described herein (e.g., with regards to method1500) to facilitate one or more nucleophilic aromatic substitutions. In various embodiments, the silyl protected thiol compound1611can covalently bond to the aryl halide group (e.g., represented by “A”) of the second polycarbonate platform chemical structure1612, such that at least one halide of the aryl halide group is replaced by a covalent bonding with a sulfur atom of the silyl protected thiol compound1611; thereby, forming the handle functional group (e.g., represented by “A1”) and functionalizing the second polycarbonate platform chemical structure1612with the one or more third functional groups (e.g., represented by “R3”) bonded to the sulfur atom and derived from the silyl protected thiol compound1611.

In various embodiments, polymerization scheme1604can be employed within a flow chemistry procedure (e.g., employed within one or more flow reactor systems1000). For example, introduction of the one or more silyl protected thiol compounds1611and/or solvents at the second stage of polymerization scheme1604into the stream of chemical reactants characterized by the second polycarbonate platform chemical structure1612can quench the chemical reaction initiated at the first stage of polymerization scheme1604. Further, one or more byproducts of the quenching can further catalyze the modification reaction of the second stage of the polymerization scheme1604(e.g., catalyze the functionalization of the aryl halide group with the silyl protected thiol compound1611).

Polymerization scheme1606exemplifies that the one or more polycarbonate polymers characterized by the third polycarbonate chemical structure1406can be polymerized from the one or more cyclic carbonate monomers characterized by third cyclic carbonate chemical structure106. For example, a first stage of the polymerization scheme1606can comprise one or more ROPs that can form a third polycarbonate platform chemical structure1614. In various embodiments, the one or more cyclic carbonate monomers characterized by third cyclic carbonate chemical structure106can be reacted with the one or more initiator compounds1609and/or anionic catalyst compounds1610described herein (e.g., with regards to method1500) to facilitate the one or more ROPs. During the one or more ROPs; the first functional group (e.g., represented by “R1”) can be derived from the one or more cyclic carbonate monomers, and the second functional group (e.g., represented by “R2”) can be derived from the one or more initiator compounds1609. In various embodiments, the one or more initiator compounds1609and/or anionic catalyst compounds1610can be supplied with one or more solvents (e.g., THF), and the one or more ROPs can be performed at room temperature.

At a second stage of the polymerization scheme1606, the third polycarbonate platform chemical structure1614can be further reacted with one or more silyl protected thiol compounds1611. In various embodiments, the modification reaction performed at the second stage can be facilitated by one or more catalysts described herein (e.g., with regards to method1500) to facilitate one or more nucleophilic aromatic substitutions. In various embodiments, the silyl protected thiol compounds1611(e.g., TMSS) can covalently bond to the aryl halide group (e.g., represented by “A”) of the third polycarbonate platform chemical structure1614, such that at least one halide of the aryl halide group is replaced by a covalent bonding with a sulfur atom of the silyl protected thiol compound1611; thereby, forming the handle functional group (e.g., represented by “A1”) and functionalizing the third polycarbonate platform chemical structure1614with the one or more third functional groups (e.g., represented by “R3”) bonded to the sulfur atom and derived from the silyl protected thiol compound1611.

In various embodiments, polymerization scheme1606can be employed within a flow chemistry procedure (e.g., employed within one or more flow reactor systems1000). For example, introduction of the one or more silyl protected thiol compounds1611and/or solvents at the second stage of polymerization scheme1606into the stream of chemical reactants characterized by the third polycarbonate platform chemical structure1614can quench the chemical reaction initiated at the first stage of polymerization scheme1606. Further, one or more byproducts of the quenching can further catalyze the modification reaction of the second stage of the polymerization scheme1606(e.g., catalyze the functionalization of the aryl halide group with the silyl protected thiol compound1611).

FIG.17illustrates a diagram of non-limiting, example silyl protected thiol compounds1611that can be employed to modify one or more polycarbonate platforms1608,1612, and/or1614to achieve a polycarbonate polymer characterized by the first polycarbonate chemical structure1402, the second polycarbonate chemical structure1404, and/or the third polycarbonate chemical structure1406in accordance with one or more embodiments described herein. Repetitive description of like elements employed in other embodiments described herein is omitted for sake of brevity. For instance, example chemical compounds1702,1704,1706,1708,1710,1712,1714,1716,1718,1720,1722,1724,1726,1728,1730can be employed within the polymerization scheme1602,1604, and/or1606as the silyl protected thiol compound1611. As shown inFIG.17, the one or more example chemical compounds can comprise a trimethylsilyl group bonded to a sulfur atom, which can be bonded to the third functional group.FIG.17depicts example functional groups that can be comprised within the one or more silyl protected thiol compounds1611. One of ordinary skill in the art will recognize that functional groups outside of the examples depicted inFIG.17are also envisage in accordance with the various features described herein.

FIG.18illustrates a diagram of the example, non-limiting polymerization scheme1602employed via flow reactor system1000in accordance with one or more embodiments described herein. Repetitive description of like elements employed in other embodiments described herein is omitted for sake of brevity. For example, the flow reactor system1000can facilitate the polymerization scheme1602and/or the various features of method1500.

In accordance with example polymerization scheme1602, the one or more functionalized cyclic carbonate monomers characterized by first cyclic carbonate chemical structure102can enter the one or more flow reactor system1000via one or more first inlets1004, while the one or more initiator compounds609and/or anionic catalyst compounds610(e.g., in a solution with a solvent, such as THF) can enter the one or more flow reactor system1000via one or more second inlets1004. For example, the one or more initiator compounds609and/or anionic catalyst compounds610can be in accordance with the various features described herein with regards to method1500. The one or more functionalized cyclic carbonate monomers characterized by first cyclic carbonate chemical structure102can meet and/or mix with the one or more initiator compounds609and/or anionic catalyst compounds610within the one or more channels1006; thereby forming a stream of chemical reactants. As the stream flows through the one or more channels1006, a polycarbonate platform characterized by the polycarbonate platform chemical structure1608can be formed (e.g., as delineated by the dashed lines shown inFIG.18).

Additionally, the polycarbonate platform characterized by polycarbonate platform chemical structure1608can flow downstream through the one or more channels1006and mix with the one or more silyl protected thiol compounds1611and/or solvents (e.g., DMF) to facilitate a modification reaction that forms a functionalized polycarbonate polymer characterized by first polycarbonate chemical structure1402. For example, the silyl protected thiol compound1611can enter the flow reactor system1000via one or more third inlets1004(e.g., in a solution with a solvent, such as DMF). In various embodiments, the introduction of the silyl protected thiol compound1611and/or the solvent can quench the polymerization reaction and catalyze the subsequent post polymerization modification reaction in flow. Further, the modification reaction can be a post polymerization nucleophilic aromatic substitution reaction facilitated by an additional set of reactor loops1008. As the stream flows through the one or more channels1006and/or the second set of reactor loops1008, the functionalized polycarbonate polymer characterized by first polycarbonate chemical structure1402can be formed (e.g., as delineated by the dashed lines shown inFIG.18). In one or more embodiments, the quenching solution1012(e.g., hydrochloric acid) can be further introduced into the flow reactor system1000via a fourth inlet1004to quench the post polymerization modification reaction. In one or more embodiments, the one or more ROPs and/or modification reactions can be performed within the flow reactor system1000with a residence time that is greater than or equal to 1 and less than or equal to 1800 seconds (s).

WhileFIG.18depicts both the ROP reaction and the post polymerization modification reaction (e.g., nucleophilic aromatic substitution occurring in flow), the architecture of polymerization scheme1602is not so limited. For example, in one or more embodiments, the one or more ROPs can be performed in the flow reactor system1000(e.g., as shown inFIG.18), and the resulting polycarbonate platforms characterized by polycarbonate platform chemical structure1608can exit the flow reactor system1000and be employed in a batch reaction. For instance, the post polymerization nucleophilic aromatic substitution with the silyl protected thiol compound1611can be employed via a batch reaction process using one or more catalysts (e.g., DBU, DBU·OBz, BzOK, and/or BzONa).

FIG.19illustrates a diagram of the example, non-limiting polymerization scheme1604employed via flow reactor system1000in accordance with one or more embodiments described herein. Repetitive description of like elements employed in other embodiments described herein is omitted for sake of brevity. For example, the flow reactor system1000can facilitate the polymerization scheme1604and/or the various features of method1500.

In accordance with example polymerization scheme1604, the one or more functionalized cyclic carbonate monomers characterized by second cyclic carbonate chemical structure104can enter the one or more flow reactor system1000via one or more first inlets1004, while the one or more initiator compounds609and/or anionic catalyst compounds610(e.g., in a solution with a solvent such as THF) can enter the one or more flow reactor system1000via one or more second inlets1004. For example, the one or more initiator compounds609and/or anionic catalyst compounds610can be in accordance with the various features described herein with regards to method1500. The one or more functionalized cyclic carbonate monomers characterized by second cyclic carbonate chemical structure104can meet and/or mix with the one or more initiator compounds609and/or anionic catalyst compounds610within the one or more channels1006; thereby forming a stream of chemical reactants. As the stream flows through the one or more channels1006, a polycarbonate platform characterized by the second polycarbonate platform chemical structure1612can be formed (e.g., as delineated by the dashed lines shown inFIG.19).

Additionally, the polycarbonate platform characterized by second polycarbonate platform chemical structure1612can flow downstream through the one or more channels1006and mix with the one or more silyl protected thiol compounds1611and/or solvent (e.g., DMF) to facilitate a reaction that forms a functionalized polycarbonate polymer characterized by second polycarbonate chemical structure1404. For example, the one or more silyl protected thiol compounds1611can enter the flow reactor system1000via one or more third inlets1004(e.g., in a solution with a solvent, such as DMF). In various embodiments, the introduction of the silyl protected thiol compound1611and/or the solvent can quench the polymerization reaction and catalyze the subsequent post polymerization modification reaction in flow. Further, the post polymerization modification reaction can be a nucleophilic aromatic substitution reaction, and can be facilitated by an additional set of reactor loops1008. As the stream flows through the one or more channels1006and/or the second set of reactor loops1008, the functionalized polycarbonate polymer characterized by second polycarbonate chemical structure1404can be formed (e.g., as delineated by the dashed lines shown inFIG.19). In one or more embodiments, the quenching solution1012(e.g., hydrochloric acid) can be further introduced into the flow reactor system1000via a fourth inlet1004to quench the post polymerization modification reaction. In one or more embodiments, the one or more ROPs and/or modification reactions can be performed within the flow reactor system1000with a residence time that is greater than or equal to 1 and less than or equal to 1800 s.

WhileFIG.19depicts both the ROP reaction and the post polymerization modification reaction (e.g., nucleophilic aromatic substitution occurring in flow), the architecture of polymerization scheme1604is not so limited. For example, in one or more embodiments, the one or more ROPs can be performed in the flow reactor system1000(e.g., as shown inFIG.19), and the resulting polycarbonate platforms characterized by second polycarbonate platform chemical structure1612can exit the flow reactor system1000and be employed in a batch reaction. For instance, the post polymerization nucleophilic aromatic substitution with the silyl protected thiol compound1611can be employed via a batch reaction process using one or more catalysts (e.g., DBU, DBUOBz, BzOK, and/or BzONa).

FIG.20illustrates a diagram of the example, non-limiting polymerization scheme1606employed via flow reactor system1000in accordance with one or more embodiments described herein. Repetitive description of like elements employed in other embodiments described herein is omitted for sake of brevity. For example, the flow reactor system1000can facilitate the polymerization scheme1606and/or the various features of method1500.

In accordance with example polymerization scheme1606, the one or more functionalized cyclic carbonate monomers characterized by third cyclic carbonate chemical structure106can enter the one or more flow reactor system1000via one or more first inlets1004, while the one or more initiator compounds1609and/or anionic catalyst compounds1610(e.g., in a solution with a solvent such as THF) can enter the one or more flow reactor system1000via one or more second inlets1004. For example, the one or more initiator compounds1609and/or anionic catalyst compounds1610can be in accordance with the various features described herein with regards to method1500. The one or more functionalized cyclic carbonate monomers characterized by third cyclic carbonate chemical structure106can meet and/or mix with the one or more initiator compounds1609and/or anionic catalyst compounds1610within the one or more channels1006; thereby forming a stream of chemical reactants. As the stream flows through the one or more channels1006, a polycarbonate platform characterized by the third polycarbonate platform chemical structure1614can be formed (e.g., as delineated by the dashed lines shown inFIG.20).

Additionally, the polycarbonate platform characterized by third polycarbonate platform chemical structure1614can flow downstream through the one or more channels1006and mix with the one or more silyl protected thiol compounds1611and/or solvents (e.g., DMF) to facilitate a reaction that forms a functionalized polycarbonate polymer characterized by third polycarbonate chemical structure1406. For example, the one or more silyl protected thiol compounds1611can enter the flow reactor system1000via one or more third inlets1004(e.g., in a solution with a solvent, such as DMF). In various embodiments, the introduction of the silyl protected thiol compound1611and/or the solvents can quench the polymerization reaction and catalyze the subsequent post polymerization modification reaction in flow. Further, the post polymerization modification reaction can be a nucleophilic aromatic substitution reaction, and can be facilitated by an additional set of reactor loops1008. As the stream flows through the one or more channels1006and/or the second set of reactor loops1008, the functionalized polycarbonate polymer characterized by the third polycarbonate chemical structure1406can be formed (e.g., as delineated by the dashed lines shown inFIG.20). In one or more embodiments, the quenching solution1012(e.g., hydrochloric acid) can be further introduced into the flow reactor system1000via a fourth inlet1004to quench the post polymerization modification reaction. In one or more embodiments, the one or more ROPs and/or modification reactions can be performed within the flow reactor system1000with a residence time that is greater than or equal to 1 and less than or equal to 1800 s.

WhileFIG.20depicts both the ROP reaction and the post polymerization modification reaction (e.g., nucleophilic aromatic substitution occurring in flow), the architecture of polymerization scheme1606is not so limited. For example, in one or more embodiments, the one or more ROPs can be performed in the flow reactor system1000(e.g., as shown inFIG.20), and the resulting polycarbonate platforms characterized by third polycarbonate platform chemical structure1614can exit the flow reactor system1000and be employed in a batch reaction. For instance, the post polymerization nucleophilic aromatic substitution with the silyl protected thiol compound1611can be employed via a batch reaction process using one or more catalysts (e.g., DBU, DBUOBz, BzOK, and/or BzONa).

FIG.21illustrates a diagram of a non-limiting example polymerization scheme2100that can be performed in accordance with the features of polymerizations scheme1602and/or facilitated by the flow reactor system1000in accordance with one or more embodiments described herein. Repetitive description of like elements employed in other embodiments described herein is omitted for sake of brevity. For example, the flow reactor system1000can facilitate the polymerization scheme2100and/or the various features of method1500.FIG.21depicts the flow reactor system1000employed to facilitate an exemplary polymerization scheme2100in accordance with polymerization scheme1602to achieve functionalized polycarbonate polymer2102(e.g., characterized by the first polycarbonate chemical structure1402). The exemplary polymerization scheme2100can comprise the ROP of the functionalized cyclic carbonate monomer612and a post polymerization modification with example chemical compound1702(e.g., an example silyl protected thiol compound1611) to achieve the example functionalized polycarbonate polymer2102.

In accordance with example polymerization scheme2100, the one or more functionalized cyclic carbonate monomers612(e.g., characterized by first cyclic carbonate chemical structure102) can enter the one or more flow reactor system1000via one or more first inlets1004, while potassium methoxide “KOMe” (e.g., an example initiator compound1609) and/or an anionic urea catalyst (e.g., an example anionic catalyst compound610) in a solution with the solvent THF can enter the one or more flow reactor system1000via one or more second inlets1004. The one or more functionalized cyclic carbonate monomers612can meet and/or mix with the one or more initiator compounds609(e.g., KOMe) and/or anionic catalyst compound610(e.g., a anionic urea compound, as shown inFIG.21) within the one or more channels1006; thereby forming a stream of chemical reactants. As the stream flows through the one or more channels1006, a polycarbonate platform characterized by the polycarbonate platform chemical structure1608can be formed (e.g., as delineated by the dashed lines shown inFIG.21).

Additionally, the polycarbonate platform can flow downstream through the one or more channels1006and mix with the silyl protected thiol compound1611(e.g., example chemical compound1702to facilitate a nucleophilic aromatic substitution reaction that forms the functionalized polycarbonate polymer2102. For example, the silyl protected thiol compound1611(e.g., example chemical compound1702) and/or the solvent (e.g., DMF) can enter the flow reactor system1000via one or more third inlets1004. In various embodiments, the introduction of the silyl protected thiol compound1611(e.g., example chemical compound1702) and/or the solvent (e.g., DMF) can quench the polymerization reaction and catalyze the subsequent post polymerization modification reaction in flow. Further, an additional set of reactor loops1008can facilitate the post polymerization reaction. As the stream flows through the one or more channels1006and/or the second set of reactor loops1008, the functionalized polycarbonate polymer2102(e.g., as delineated by the dashed lines shown inFIG.21). In one or more embodiments, the quenching solution1012(e.g., hydrochloric acid) can be further introduced into the flow reactor system1000via a fourth inlet1004to quench the post polymerization modification reaction.

WhileFIG.21depicts both the ROP reaction and the post polymerization modification reaction (e.g., nucleophilic aromatic substitution occurring in flow), the architecture of polymerization scheme2100is not so limited. For example, in one or more embodiments, the one or more ROPs can be performed in the flow reactor system1000(e.g., as shown inFIG.21), and the resulting polycarbonate platforms characterized by polycarbonate platform chemical structure1608can exit the flow reactor system1000and be employed in a batch reaction. For instance, the post polymerization nucleophilic aromatic substitution with the example silyl protected thiol compound1611(e.g., example chemical compound1702) can be employed via a batch reaction process using one or more catalysts (e.g., DBU, DBUOBz, BzOK, and/or BzONa).

In addition, the term “or” is intended to mean an inclusive “or” rather than an exclusive “or.” That is, unless specified otherwise, or clear from context, “X employs A or B” is intended to mean any of the natural inclusive permutations. That is, if X employs A; X employs B; or X employs both A and B, then “X employs A or B” is satisfied under any of the foregoing instances. Moreover, articles “a” and “an” as used in the subject specification and annexed drawings should generally be construed to mean “one or more” unless specified otherwise or clear from context to be directed to a singular form. As used herein, the terms “example” and/or “exemplary” are utilized to mean serving as an example, instance, or illustration. For the avoidance of doubt, the subject matter disclosed herein is not limited by such examples. In addition, any aspect or design described herein as an “example” and/or “exemplary” is not necessarily to be construed as preferred or advantageous over other aspects or designs, nor is it meant to preclude equivalent exemplary structures and techniques known to those of ordinary skill in the art.

It is, of course, not possible to describe every conceivable combination of components, products and/or methods for purposes of describing this disclosure, but one of ordinary skill in the art can recognize that many further combinations and permutations of this disclosure are possible. Furthermore, to the extent that the terms “includes,” “has,” “possesses,” and the like are used in the detailed description, claims, appendices and drawings such terms are intended to be inclusive in a manner similar to the term “comprising” as “comprising” is interpreted when employed as a transitional word in a claim. The descriptions of the various embodiments have been presented for purposes of illustration, but are not intended to be exhaustive or limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments. The terminology used herein was chosen to best explain the principles of the embodiments, the practical application or technical improvement over technologies found in the marketplace, or to enable others of ordinary skill in the art to understand the embodiments disclosed herein.