Compounds with perfluoroaryl groups that can facilitate post-synthetic functionalization

Abstract

To provide chemical compounds including perfluoroaryl groups that can facilitate post-synthesis functionalization.SOLUTION: A cyclic monomer comprises: one or more carbonate groups; a central chain of covalently bonded atoms that form a primary structure of the cyclic monomer, where the central chain is covalently bonded to the one or more carbonate groups; and side chains formed by covalently bonding one or more functional groups to the central chain, where the one or more functional groups include a perfluoroaryl group and a methylene group bonded to the perfluoroaryl group, where the perfluoroaryl group is bonded to the central chain at least via the methylene group.SELECTED DRAWING: None

Description

[Technical field]

[0001] The embodiments relate to one or more compounds that include perfluoroaryl groups, and more particularly to one or more compounds that include perfluoroaryl groups that can be functionalized after synthesis of the one or more compounds. Summary of the Invention

[0002] The following provides a summary to provide a basic understanding of one or more embodiments of the present invention. This summary is not intended to identify key or critical elements or to detail any scope of specific embodiments or any scope of claims. Its sole purpose is to present concepts in a simplified form as a prelude to the more detailed description presented later. In one or more embodiments described herein, methods and / or compositions related to compounds having perfluoroaryl groups are described.

[0003] According to one embodiment, a compound is provided. The compound may include a molecular backbone. The compound may also include a pendent functional group attached to the molecular backbone. The pendent functional group may include a perfluoroaryl group and a methylene group.

[0004] According to another embodiment, a polymer is provided. The polymer may include a molecular backbone that includes a polycarbonate structure. The polymer may also include pendant functional groups covalently attached to the molecular backbone. The pendant functional groups may include perfluoroaryl groups and methylene groups.

[0005] According to another embodiment, a polymer is provided. The polymer may include a molecular backbone that includes a polyurethane structure. The polymer may also include pendant functional groups covalently attached to the molecular backbone. The pendant functional groups may include perfluoroaryl groups and methylene groups.

[0006] According to one embodiment, a method is provided. The method can include functionalizing a compound by covalently attaching a trimethylsilyl-protected thiol to a pendant functional group of the compound in the presence of a catalyst. The pendant functional group can include a perfluoroaryl group and a methylene group.

[0007] According to one embodiment, a method is provided. The method can include functionalizing a compound by covalently attaching a trimethylsilyl-protected thiol to a perfluoro pendant functional group of the compound. The compound can include a molecular backbone. And, the molecular backbone can include a pendant perfluoroaryl group attached to an electron-withdrawing structure. [Brief description of the drawings]

[0008] [Figure 1] FIG. 1 depicts a diagram of exemplary, non-limiting chemical structures that may characterize one or more monomers according to one or more embodiments described herein. [Diagram 2] FIG. 1 shows a diagram of an exemplary, non-limiting chemical formation scheme that can facilitate the production of one or more monomers according to one or more embodiments described herein. [Diagram 3] FIG. 1 depicts a diagram of exemplary, non-limiting chemical structures that may characterize one or more polymers according to one or more embodiments described herein. [Figure 4] FIG. 1 shows an exemplary, non-limiting polymerization scheme that can facilitate the production of one or more polymers according to one or more embodiments described herein. [Diagram 5] FIG. 1 shows an exemplary, non-limiting representation of a chart that can represent structural characteristics of one or more polymers according to one or more embodiments described herein. [Figure 6] FIG. 1 shows exemplary, non-limiting graphical illustrations that can represent structural characteristics of one or more polymers according to one or more embodiments described herein. [Figure 7] FIG. 1 shows an exemplary, non-limiting polymerization scheme that can facilitate the production of one or more polymers according to one or more embodiments described herein. [Figure 8] 1 shows a flow diagram of an exemplary, non-limiting method that can facilitate post-synthetic functionalization of one or more compounds according to one or more embodiments described herein. [Figure 9] FIG. 1 shows a diagram of an exemplary, non-limiting functionalization scheme that can facilitate post-synthetic functionalization of one or more compounds according to one or more embodiments described herein. [Figure 10] FIG. 1 shows exemplary, non-limiting graphical illustrations that can represent structural characteristics of one or more polymers according to one or more embodiments described herein. [Figure 11] FIG. 1 shows a diagram of an exemplary, non-limiting functionalization scheme that can facilitate post-synthetic functionalization of one or more compounds according to one or more embodiments described herein. [Figure 12] FIG. 1 shows a diagram of an exemplary, non-limiting functionalization scheme that can facilitate post-synthetic functionalization of one or more compounds according to one or more embodiments described herein. [Figure 13] FIG. 1 shows a diagram of exemplary, non-limiting compounds that may be produced by post-synthetic functionalization of one or more compounds according to one or more embodiments described herein. [Figure 14] 1 shows a flow diagram of an exemplary, non-limiting method that can facilitate surface functionalization of one or more compounds according to one or more embodiments described herein. [Figure 15] FIG. 1 shows a flow diagram of an exemplary, non-limiting surface functionalization scheme that can facilitate post-synthetic functionalization of one or more compounds according to one or more embodiments described herein. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0009] The following detailed description is merely illustrative and is not intended to limit the embodiments or the application and / or uses of the embodiments, nor is there any intention to be bound by any express or implied information presented in the preceding "Background" or "Summary" sections, or in the "Description of the Preferred Embodiments" section.

[0010] One or more embodiments will now be described with reference to the drawings, wherein like reference 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 one or more embodiments. However, it will be apparent that in various instances, one or more embodiments may be practiced without these specific details.

[0011] Post-synthesis modification of polycarbonates can be important for the development of functional materials for therapeutic applications. By appropriate selection of pendant functional groups, polycarbonates can be readily diversified into a myriad of biomedical applications, ranging from injectable hydrogels for therapeutic delivery to highly potent antimicrobial polymers. Unfortunately, not all functional groups are compatible with the ring-opening polymerization process used to prepare polycarbonates. Furthermore, de novo monomer synthesis can be synthetically cumbersome and difficult to scale up. Thus, one or more handles for further functionalization of polycarbonate scaffolds have been utilized to enable the incorporation of a broader and more diverse range of functional groups into the polycarbonate platform. These handles have been widely utilized to incorporate additional functional groups in a synthetically convergent manner, facilitating a wide variety of biomedical applications.

[0012] However, in some cases, long reaction times, high temperatures, or the use of stoichiometric amounts of base are required to achieve a high degree of functionalization of the polycarbonate backbone. Although these conditions are effective, they can compromise backbone integrity and broaden the molecular weight distribution, especially when more basic reagents are used. In addition, some examples of post-synthetic modifications of polycarbonates include the use of azide-alkyne click chemistry. Although effective, the use of hazardous azide reagents and the problem of residual copper retained in the polymer matrix make this approach less desirable for the preparation of materials for therapeutic applications.

[0013] One approach to post-synthetic modification is aromatic nucleophilic substitution (S N Ar). N The Ar reaction has the advantage of being compatible with a range of functional groups and nucleophiles, depending on the reaction conditions utilized. N Standard reaction conditions for Ar typically require excess base, high temperatures, long reaction times, and generate stoichiometric salt by-products that may need to be removed in a subsequent purification step. N The typical conditions for Ar may not be compatible with the more sensitive polycarbonate backbone.

[0014] Various embodiments described herein are capable of reacting with catalyst S under mild reaction conditions. NOne or more conditions may be considered that allow for the realization of Ar. For example, one or more compounds (e.g., monomers or polymers or both), schemes, or methods described herein, or combinations thereof, may consider the use of perfluoroaryls in combination with thiols ("SuFex reactions"). SuFex reactions can be utilized for a number of different applications, including peptide stapling and post-synthetic modification of polymers. To overcome the essential need for a stoichiometric base, the catalytic conditions of one or more SuFex reactions described herein may rely on the use of trimethylsilyl-protected thiols. The modifications provided by one or more SuFex reactions described herein may be suitable for generating new condensation polymers that exhibit dramatic increases in reactivity and can be easily purified since the major by-product is gas. Thus, one or more embodiments described herein may include post-synthetic functionalization of polycarbonate scaffolds with minimal backbone degradation while providing a high degree of control over polymer functionalization.

[0015] 1 shows an exemplary, non-limiting diagram of a chemical formula 100 that can characterize one or more cyclic monomers that can be used to make one or more perfluoroaryl polycarbonates. Repeated descriptions of similar elements used in other embodiments described herein are omitted for the sake of brevity.

[0016] As shown in FIG. 1, one or more cyclic monomers that may be characterized by chemical formula 100 may include one or more carbonate groups. The one or more carbonate groups may be covalently attached to a molecular backbone 102. "M" shown in FIG. 1 may represent the molecular backbone 102. The molecular backbone 102 may be a central chain of covalently bonded atoms that form the primary structure of one or more cyclic monomers that may be characterized by chemical formula 100. In various embodiments described herein, one or more cyclic monomers that may be characterized by chemical formula 100 may include side chains formed by attaching one or more functional groups to the molecular backbone 102.

[0017] The molecular backbone 102 may include multiple covalently bonded atoms. The multiple atoms may be linked in any desired configuration, including but not limited to, a chain or a ring, or combinations thereof. The molecular backbone 102 may include one or more chemical structures, including but not limited to, alkyl structures, aryl structures, alkenyl structures, aldehyde structures, ester structures, carboxyl structures, carbonyl structures, amine structures, amide structures, phosphide structures, phosphine structures, combinations thereof, or the like, or all of the above. One skilled in the art will recognize that the number of atoms that may comprise the molecular backbone 102 may vary depending on the desired functional groups of the cyclic monomer(s).

[0018] The one or more cyclic monomers that may be characterized by the chemical formula 100 may also include one or more pendant functional groups 104. As shown in FIG. 1, "R" may represent one or more pendant functional groups 104. The one or more pendant functional groups 104 may be covalently attached to the molecular backbone 102. Additionally, the one or more pendant functional groups 104 may include one or more perfluoroaryl groups or one or more methylene groups or both. For example, the one or more methylene groups may function to link the one or more perfluoroaryl groups to the molecular backbone 102. The one or more perfluoroaryl groups may include one or more aryls having various numbers of ring members ranging from four or more ring members to ten or fewer ring members. For example, the one or more pendant functional groups 104 may be perfluorobenzyl groups.

[0019] FIG. 2 shows a diagram of an exemplary, non-limiting compound formation scheme 200 that can facilitate the production of one or more cyclic monomers (e.g., cyclic carbonate monomer 202) that can be characterized by chemical formula 100. Repeated descriptions of similar elements used in other embodiments described herein are omitted for brevity. Although one or more specific monomer reactants (e.g., monomer reactant 204), perfluoroaryl alcohols, solvents, or catalysts, or combinations thereof, are depicted, additional embodiments of compound formation scheme 200 are also envisioned. For example, the main mechanism of compound formation scheme 200 can be applied to other monomer reactants (e.g., carbonate monomers), perfluoroaryl alcohols, solvents, or catalysts, or combinations thereof, in accordance with various features described herein.

[0020] As shown in FIG. 2, a compound formation scheme 200 can depict that one or more monomer reactants (e.g., monomer reactant 204) can be reacted with one or more perfluoroaryl alcohols to form one or more cyclic monomers (e.g., cyclic carbonate monomer 202), which can be characterized by chemical formula 100. The one or more monomer reactants can be cyclic carbonates. Additionally, the one or more monomer reactants can include a perfluoroaryl group directly bonded to a molecular backbone. For example, monomer reactant 204 includes a perfluorophenyl group directly bonded to its molecular backbone. The one or more perfluoroaryl alcohols can include a perfluoroaryl group covalently bonded to one or more hydroxyl groups. For example, the perfluoroaryl alcohol can be pentafluorobenzyl alcohol, as shown in FIG. 2.

[0021] The one or more monomer reactants (e.g., one or more monomer reactants 204) and one or more perfluoroaryl alcohols (e.g., one or more pentafluorobenzyl alcohols) can be dissolved in a solvent in the presence of a catalyst. The solvent can be an organic solvent, such as tetrahydrofuran (THF). Further, the catalyst can be an organic catalyst, such as tetra-n-butylammonium fluoride (TBAF). For example, the catalyst can be present in a molar percentage ranging from 5 molar percent to 20 molar percent. Further, the reaction of compound formation scheme 200 can be accelerated by stirring the one or more monomer reactants (e.g., one or more monomer reactants 204), the one or more perfluoroaryl alcohols (e.g., one or more pentafluorobenzyl alcohols), the solvent, or the catalyst, or a combination thereof, at a temperature of at least 10 degrees Celsius (° C.) and not more than 150° C. for a period ranging from 2 minutes to 48 hours.

[0022] For example, cyclic carbonate monomer 202 can be formed according to compound formation scheme 200 under the following exemplary conditions. A 250 milliliter (mL) round bottom flask can be equipped with a magnetic stir bar and charged with 6.5 grams of monomer reactant 204 at 19.9 millimoles (mmol), 4.5 grams of pentafluorobenzyl alcohol at 22.7 mmol, and 30 mL of THF. Additionally, 2.0 mL of TBAF at 2 mmol and / or 1 mole per liter (M) can be added. The reaction mixture can be stirred at room temperature (RT) for 24 hours. The solvent can then be removed using a rotary evaporator, and the crude residue can be purified by column chromatography to obtain the desired product as a white solid. Cyclic carbonate monomer 202 can be further purified by recrystallization from an ethyl acetate-hexane mixture.

[0023] FIG. 3 shows an illustration of exemplary non-limiting chemical structures that can characterize a polymer having perfluoroaryl groups according to one or more embodiments described herein. Repeated descriptions of similar elements used in other embodiments described herein are omitted for brevity. Chemical formula 300 can characterize one or more polycarbonate polymers having one or more perfluoroaryl groups. Chemical formula 302 can characterize one or more polyurethane polymers having one or more perfluoroaryl groups. As shown in FIG. 3, "n" can represent an integer between 2 and 1000. The one or more polymers that can be characterized by chemical formula 300 and / or chemical formula 302 can be homopolymers or copolymers, such as, for example, but not limited to, alternating copolymers, random copolymers, block copolymers (e.g., diblock copolymers or triblock copolymers or both) or the like or all of the above.

[0024] As shown in Figure 3, the one or more polymers that may be characterized by formula 300 may include multiple carbonate groups covalently bonded to a molecular backbone 102 (e.g., represented in Figure 3 as "M"). Additionally, the one or more polycarbonates that may be characterized by formula 300 may include one or more pendant functional groups 104 (e.g., represented as "R"). As described with reference to Figure 1, the one or more pendant functional groups 104 may include perfluoroaryl and methylene groups. For example, the one or more pendant functional groups 104 may be perfluorobenzyl groups.

[0025] The one or more pendant functional groups 104 can be attached to the molecular backbone 102 by one or more linking groups 306. The one or more linking groups 306 can include alkyl and / or aryl structures. For example, the one or more linking groups 306 can include, but are not limited to, carboxyl groups, carbonyl groups, ester groups, ether groups, ketone groups, amine groups, phosphine groups, urea groups, carbonate groups, alkenyl groups, hydroxyl groups, combinations thereof, or the like.

[0026] Additionally, one or more polycarbonate polymers that may be characterized by formula 300 may include one or more functional groups 308 covalently attached to the molecular backbone 102 (e.g., via one or more carbonate groups). 1 " may represent one or more functional groups 308. The one or more functional groups 308 may include alkyl and / or aryl structures. For example, the one or more functional groups 308 may include, but are not limited to, a carboxyl group, a carbonyl group, an ester group, an ether group, a ketone group, an amine group, a phosphine group, a urea group, a carbonate group, an alkenyl group, a hydroxyl group, combinations thereof, or the like. For example, the functional group 308 may be an mPEG-2 carboxylate, an aryl group ... 5K , mPEG 10K or benzyl alcohol or a combination thereof.

[0027] As shown in FIG. 3, the one or more polymers that may be characterized by the chemical formula 302 may include a plurality of urethane groups. The plurality of urethane groups may be covalently bonded to the molecular backbone 102 (e.g., represented by "M" in FIG. 3). Additionally, the one or more polyurethane polymers that may be characterized by the chemical formula 302 may include one or more pendant functional groups 104 (e.g., represented by "R" in FIG. 3). As described with reference to FIG. 1, the one or more pendant functional groups 104 may include perfluoroaryl groups and methylene groups. For example, the one or more pendant functional groups 104 may be perfluorobenzyl groups. The one or more pendant functional groups 104 may be bonded to one or more amine groups of one or more urethane structures (e.g., as shown in FIG. 3).

[0028] FIG. 4 illustrates a diagram of an exemplary, non-limiting polymerization scheme 400 that can facilitate the production of one or more polycarbonate polymers (e.g., first polycarbonate 402, second polycarbonate 404, or third polycarbonate 406, or combinations thereof) that can be characterized by formula 300, according to embodiments described herein. Repeated descriptions of similar elements used in other embodiments described herein are omitted for brevity. As shown in FIG. 4, "n" can represent an integer between 2 and 1000, inclusive; "Me" can represent a methyl group. Although one or more specific reactants (e.g., cyclic carbonate monomer 202) are depicted, additional embodiments of polymerization scheme 400 are also envisioned. For example, the main mechanism of polymerization scheme 400 can be applied to other reactants (e.g., monomers that can be characterized by formula 100), according to various features described herein.

[0029] Polymerization scheme 400 can facilitate the production of homopolymers (e.g., first polycarbonate 402) or copolymers (e.g., diblock polymers such as second polycarbonate 404 or triblock polymers such as third polycarbonate 406 or both). Polymerization scheme 400 polymerizes a cyclic monomer (e.g., cyclic carbonate monomer 202), which may be characterized by formula 100, with an initiator in the presence of a catalyst to form a polycarbonate (e.g., first polycarbonate 402, second polycarbonate 404, or third polycarbonate 406 or combinations thereof), which may be characterized by formula 300. For example, polymerization scheme 400 can include ring-opening polymerization (ROP) of one or more cyclic monomers (e.g., cyclic carbonate monomers 202), which may be characterized by formula 100, with one or more initiators to form polymers or copolymers, or both, and can include functional groups 308 (e.g., “R 1 " may be derived from one or more initiators. Additionally, polymerization scheme 400 may facilitate polymerization of one or more cyclic monomers that may be characterized by formula 100 (e.g., cyclic carbonate monomer 202) with additional cyclic monomers, such as cyclic carbonate monomers not characterized by formula 100 (e.g., benzyl carbonate monomers), to form one or more copolymers (e.g., a diblock copolymer, second polycarbonate 404).

[0030] The one or more initiators may be microinitiators. Additionally, the one or more initiators may be block polymers and may include a water-soluble block. For example, the one or more initiators may include poly(ethylene glycol) (PEG) having various molecular weights. For example, the one or more initiators may include PEG (mPEG) having a molecular weight ranging from 4,800 grams per mole (g / mol) to 5,500 g / mol. 5K In another example, the one or more initiators may include PEG having a molecular weight in the range of 9,500 g / mol to 10,500 g / mol (mPEG). 10K). Additionally, the one or more initiators may include functional groups, such as hydroxy groups, to facilitate polymerization. Additionally, the catalyst may be an organic catalyst, such as, but not limited to, 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU); trifluoromethanesulfonic acid (TfOH); potassium salt of TU (TU-A). For example, the catalyst may be present in a mole percent ranging from 5 mole percent to 20 mole percent.

[0031] To facilitate polymerization (e.g., ROP), polymerization scheme 400 may include dissolving one or more cyclic monomers (e.g., cyclic carbonate monomer 202), one or more initiators and / or catalysts in a solvent. The solvent may be an organic solvent such as 1-(3,5-bis(trifluoromethyl)-phenyl)-3-cyclohexyl-2-thiourea (TU). Additionally, polymerization of polymerization scheme 400 may be facilitated by stirring one or more cyclic monomers (e.g., cyclic carbonate monomer 202), one or more initiators, catalyst and / or solvent at a temperature of 10 degrees Celsius (° C.) to 150° C. for a period ranging from 2 minutes to 48 hours.

[0032] For example, a first polycarbonate 402 can be formed according to polymerization scheme 400 under the following exemplary conditions: In a nitrogen-filled glove box, 0.10 mmol of hydroxyl mPEG is added to a 20 mL scintillation vial equipped with a magnetic stir bar. 5K500 mg; 340 mg of 1.0 mmol of cyclic carbonate monomer 202; 18.7 mg of 0.05 mmol of TU; and 1.0 mL of CHCl. ​​The reaction mixture can be stirred at RT until all solids are dissolved. Additionally, 7.5 μL of 0.05 mmol of DBU can be added to initiate the polymerization. After stirring at RT for 15 min, the vial can be removed from the glove box and quenched using excess benzoic acid. The polymer can be precipitated twice from 40 mL of diethyl ether to obtain the desired material as a white solid. Additionally, the polymer can be further purified by dialysis against 1:1 acetonitrile:isopropyl alcohol.

[0033] 5 shows an exemplary, non-limiting diagram of a chart 500 that may represent the polymerization conditions of various polymerizations according to polymerization scheme 400 and / or the structural properties of various polycarbonates (which may be characterized, for example, by formula 300) that may be formed as a result of said polymerization conditions. Repeated descriptions of similar elements used in other embodiments described herein are omitted for the sake of brevity.

[0034] A first column 502 of the chart 500 can represent the polycarbonate sample being evaluated. A second column 504 of the chart 500 can represent the initiator utilized in the present polymerization. A third column 506 of the chart 500 can represent the catalyst utilized in the subject polymerization. A fourth column 508 of the chart 500 can represent the ratio ([I]:[M]) of the initiator ([I]) to the cyclic monomer ([M]). For the sixth polycarbonate sample or the seventh polycarbonate sample or both, the fourth column 508 can represent the ratio ([I]:[M]:[M2]) of the initiator ([I]) to the first cyclic monomer ([M1]) (e.g., cyclic carbonate monomer 202) to the second cyclic monomer ([M2]) (e.g., 5-methyl-5-benzyloxycarbonyl-1,3-dioxane-2-one). A fifth column 510 of the chart 500 can represent the duration of the subject polymerization. A sixth column 512 of the chart 500 can represent the percentage of cyclic monomer that was converted to polycarbonate. The conversion percentage in the sixth column 512 can be calculated using proton nuclear magnetic resonance (H 1 A seventh column 514 of the chart 500 can represent the degree of polymerization (Dp) of the subject polymerizations. An eighth column 516 of the chart 500 can represent the number average molecular weight (M) of the subject polycarbonate samples analyzed by nuclear magnetic resonance (NMR). n ) can be expressed in g / mole. The ninth column 518 of the chart 500 shows the M of the subject polycarbonate samples analyzed by gel permeation chromatography (GPC). n The tenth column 520 of the chart 500 can represent the molecular weight distribution / dispersity (D) of the subject polycarbonate samples. As can be seen from the chart 500, the M n Analysis of the percentage conversion can indicate the high level of control over the polymerization reaction and resultant molecular weight promoted by polymerization scheme 400.

[0035] 6 shows an exemplary, non-limiting graphical representation that may represent various structural characteristics of polycarbonate samples shown in chart 500. Repeated descriptions of similar elements used in other embodiments described herein are omitted for the sake of brevity. Graph 600 shows the relationship between the conversion of cyclic monomer (e.g., cyclic carbonate monomer 202) and M n and polydispersity index (PDI) can be plotted. Graph 600 can consider a polymerization performed according to polymerization scheme 400, in which benzyl alcohol can be used as the initiator, TU can be used as the solvent, and 5 mol % DBU can be used as the catalyst.

[0036] FIG. 7 shows a diagram of an exemplary, non-limiting compound formation scheme 700 that can facilitate the production of one or more polyurethane polymers (e.g., first polyurethane 702), which can be characterized by chemical formula 302. Repeated descriptions of similar elements used in other embodiments described herein are omitted for brevity. Although one or more specific reactants (e.g., urethane reactant 704) and / or isocyanates are depicted, additional embodiments of polymerization scheme 700 are also envisioned. For example, the primary mechanism of polymerization scheme 700 can be applied to other reactants (e.g., urethane monomers containing pendant functional groups 104) and / or isocyanates, in accordance with various features described herein. As shown in FIG. 7, "n" can represent an integer between 2 and 1000 inclusive.

[0037] The polymerization scheme 700 may include polymerizing one or more urethane monomers including pendant functional groups 104 (e.g., urethane reactant 704) with one or more isocyanates (e.g., first isocyanate 706) to form one or more polyurethane polymers (e.g., first polyurethane 702), which may be characterized by formula 302. The one or more polyurethane polymers produced by the polymerization scheme 700 may be copolymers (e.g., alternating, random, or block copolymers, or combinations thereof). The one or more isocyanates (e.g., first isocyanate 706) may include alkyl or aryl structures or both. Additionally, the one or more isocyanates may be diisocyanates. Polymerization of one or more urethane monomers (e.g., urethane reactant 704) with one or more isocyanates (e.g., first isocyanate 706) can form a polyurethane polymer (e.g., first polyurethane 702) that includes one or more carbamate groups (e.g., as shown in FIG. 7).

[0038] The polymerization of polymerization scheme 700 can be facilitated by dissolving one or more urethane monomers (e.g., urethane reactant 704), one or more isocyanates (e.g., first isocyanate 706) and / or a catalyst in a solvent to form a mixture. The catalyst can be an organic catalyst such as DBU (e.g., a catalyst system including a molar percent of DBU of 1 percent to 25 percent). The solvent can be an organic solvent such as TU, dichloromethane, combinations thereof, or the like, or all of the above. Additionally, the mixture can be stirred at a temperature of 10° C. to 150° C. (e.g., room temperature (RT)) for a period of 5 minutes to 48 hours (e.g., 18 hours). For example, polymerization scheme 700 can be used to produce a urethane having a number average molecular weight (M) of 60,413 g / mol. n ), and a weight average molecular weight (M w ), and a polydispersity index (PDI) of 1.52.

[0039] In one or more embodiments, the urethane reactant 704 that can be utilized according to the polymerization scheme 700 can be prepared under the following exemplary conditions and / or similar conditions. A 250 mL round bottom flask equipped with a magnetic stir bar can be charged with 1.45 mL of 15 mmol of diethanolamine; 2.9 grams of 21 mmol of potassium carbonate; and 40 mL of acetonitrile. Additionally, 2.26 mL of 15 mmol of pentafluorobenzyl bromide can be added and the reaction mixture can be stirred at RT for 36 hours. The reaction mixture can be filtered and concentrated using a rotary evaporator. The crude residue can be filtered through a silica gel plug eluting with 10% acetone in hexane.

[0040] A first polyurethane 702 can be formed according to polymerization scheme 700 under the following exemplary conditions and / or similar conditions. In a nitrogen-filled glovebox, a 20 mL scintillation vial can be charged with 285 milligrams (mg) of 1.0 mmol of one or more urethane monomers containing one or more pendant functional groups 104 (e.g., urethane reactant 704); 209 microliters (μL) of 1.0 mmol of isopherone diisocyanate; and 1 mL of dichloromethane. Also, 3 μL of 0.02 mmol of DBU can be added and the reaction mixture can be stirred at RT for 18 hours. The reaction mixture can then be removed from the glovebox and the polymer precipitated twice from hexane to yield an off-white solid. This material can be further purified by dialysis against 1:1 acetonitrile:isopropyl alcohol to yield a pale yellow film.

[0041] 8 illustrates a flow diagram of an exemplary, non-limiting method 800 that can facilitate post-synthesis functionalization of one or more compounds according to one or more embodiments described herein. Repeated descriptions of similar elements used in other embodiments described herein are omitted for brevity. For example, method 800 can be utilized to functionalize a monomer that can include one or more pendant functional groups 104. In another example, method 800 can be utilized to functionalize a polycarbonate that can be characterized by chemical formula 300. In another example, method 800 can be utilized to functionalize a polyurethane that can be characterized by chemical formula 302.

[0042] At 802, the method 800 may include dissolving a compound (e.g., characterized by formula 300 and / or 302) and one or more trimethylsilyl protected thiols in a solvent to form a mixture. The compound may include one or more monomers or one or more polymers (e.g., characterized by formula 300 and / or 302) that may include one or more pendant functional groups 104 (e.g., perfluorobenzyl groups). For example, the compound may include a first polycarbonate 402, a second polycarbonate 404, a third polycarbonate 406, a first polyurethane 702, combinations thereof, or the like, or all of the above. The one or more pendant functional groups 104 containing compound may function as a means to facilitate functionalization via the method 800.

[0043] The one or more trimethylsilyl-protected thiols may include functional groups that may include alkyl structures, aryl structures, carboxyl groups, carbonyl groups, amine groups, amide groups, ether groups, ester groups, ketone groups, hydroxyl groups, alkenyl groups, aldehyde groups, alkene groups, combinations thereof, or the like, or all of the above. For example, the one or more trimethylsilyl-protected thiols may be trimethylsilyl-protected dodecanethiol. The solvent may be an organic solvent. Exemplary solvents may include, but are not limited to, dimethylformamide (DMF), N-methyl-2-pyrrolidone (NMP), combinations thereof, or the like, or all of the above.

[0044] In one or more embodiments, the mixture in 802 may be uncatalyzed. However, when the mixture is uncatalyzed, the functionalization achieved by method 800 may depend on the synthesis method of the compound. For example, when the compound is prepared via acid-catalyzed ROP (e.g., the first polycarbonate sample shown in chart 500), method 800 may achieve little conversion of the pendant functional group 104 of the compound. In another example, when the compound is prepared via base-catalyzed polymerization conditions (e.g., the second polycarbonate sample shown in chart 500), method 800 may achieve high reactivity between the compound and one or more trimethylsilyl-protected thiols, thereby resulting in a high percentage of conversion. In various embodiments, a catalyst may be added to mixture 802 to facilitate functionalization via method 800. The catalyst may be a basic salt, such as, but not limited to, a DBU-based salt and / or a potassium benzoate salt.

[0045] At 804, the method 800 can include stirring the mixture for a period of time of at least 2 minutes and at most 48 hours at a temperature of at least 10° C. and at most 150° C. For example, at 804, the method 800 can include stirring the mixture at RT for 5 minutes.

[0046] At 806, the method 800 may include functionalizing the compound by covalently attaching one or more trimethylsilyl-protected thiols to one or more pendant functional groups 104 of the compound in the presence of a catalyst. For example, the compound may be characterized by chemical formula 300. In another example, the compound (including, for example, a polymer or monomer) may be characterized by chemical formula 302. In another example, the compound may include a molecular backbone attached to one or more pendant functional groups 104, the molecular backbone may include one or more carbonate structures, one or more urethane structures, one or more amide structures, one or more ester structures, one or more ether structures, one or more acrylate structures, or one or more styrene structures, or combinations thereof. The catalyst may result from the addition to the mixture at 802 or from the synthesis reaction that produced the compound, or both. The functionalization at 806 may produce mono- or multi-substituted products, or both. As used herein, "mono-substitution" can refer to the substitution of a single fluoride on the subject pendant functional group 104. For example, the mono-substitution product produced in 806 can include a pendant functional group 104 covalently bonded to a single trimethylsilyl-protected thiol. As used herein, "poly-substitution" can refer to the substitution of multiple fluorides on the subject pendant functional group 104. For example, the poly-substitution product produced in 806 can include a pendant functional group 104 covalently bonded to multiple trimethylsilyl-protected thiols. Also, as used herein, "di-substitution" can refer to the substitution of two fluorides on the subject pendant functional group 104. Additionally, as used herein, "tri-substitution" can refer to the substitution of three fluorides on the subject pendant functional group 104.

[0047] As shown in Table 1 below, the amount of catalyst in the mixture at 802 (e.g., resulting from catalyst addition or residual catalyst from the synthesis reaction or both) can affect the functionalization at 806. For example, in Table 2, a compound prepared via acid-catalyzed ROP (e.g., the first polycarbonate sample shown in Chart 500) can be considered, where DBU and / or benzoate catalyst are added to the mixture at various mole percentages (mol%) at 802. As noted above, without the addition of DBU and / or benzoate catalyst, the compound evaluated by Table 1 would show little to no functionalization at 806. However, even with small amounts of DBU and / or benzoate catalyst (e.g., 0.5 mol%), the compound can be effectively functionalized at 806.

[0048] Additionally, the amount of catalyst in the mixture at 802 (e.g., resulting from catalyst addition or residual catalyst from the synthesis reaction or both) can affect the number of mono- or multi-substituted products or both produced by functionalization at 806. In Table 1, "I" can represent mono- or multi-substituted products, or "II" can represent multi-substituted products, or both.

[0049] [Table 1]

[0050] As shown in Table 1, the ratio of mono- to poly-substituted products can be determined by fluorine nuclear magnetic resonance (F NMR). Additionally, DBU·PhCO2H can represent the salt of DBU and benzoic acid. As shown in Table 1, increasing the presence of catalyst can directly increase the number of substitutions (e.g., the number of poly-substituted products) achieved by functionalization with 806.

[0051] FIG. 9 illustrates an exemplary, non-limiting diagram of a functionalization scheme that can facilitate functionalization of one or more polycarbonates (e.g., which may be characterized by chemical formula 300) according to one or more embodiments (e.g., method 800) described herein. Repeated descriptions of similar elements used in other embodiments described herein are omitted for brevity. Although one or more specific reactants (e.g., first polycarbonate 402) are depicted, additional embodiments of the functionalization scheme depicted in FIG. 9 are also envisioned. For example, the main mechanism of the functionalization scheme depicted in FIG. 9 can be applied to other reactants (e.g., other polycarbonates that may be characterized by chemical formula 300) according to various features described herein. As shown in FIG. 9, "n" can represent an integer between 2 and 1000 inclusive.

[0052] In each of the functionalization schemes of FIG. 9, one or more polycarbonates, one or more trimethylsilyl-protected thiols, or a catalyst, or a combination thereof, which may be characterized by formula 300, may be dissolved in a solvent to form a mixture. The catalyst may be an organic catalyst and may include a basic salt, such as a DBU-based salt. The solvent may be organic or polar or both. Exemplary solvents include, but are not limited to, DMF, NMP, combinations thereof, or the like, or all of the above. To facilitate functionalization, the mixture may be stirred at a temperature of 10° C. to 150° C. (e.g., RT) for a period of 2 minutes to 48 hours (e.g., 5 minutes).

[0053] The first functionalization scheme 900 includes the addition of one or more second functional groups 902 (e.g., “R 29 represents the functionalization of a polycarbonate, which may be characterized by formula 300 (e.g., first polycarbonate 402) with one or more trimethylsilyl-protected thiols (represented in FIG. 9 as "TMSS"), which may include a thiol, a thiol group ...

[0054] The second functionalization scheme 906 includes adding one or more second functional groups 902 (e.g., “R 2 9 represents the functionalization of a polycarbonate, which may be characterized by formula 300 (e.g., first polycarbonate 402) with one or more trimethylsilyl-protected thiols (represented in FIG. 9 as "TMSS"), which may include a trimethylsilyl-protected thiol (represented in FIG. 9 as "TMSS") to form a disubstituted product (e.g., fifth polycarbonate 908). Second functional groups 902 may include alkyl structures, aryl structures, carboxyl groups, carbonyl groups, amine groups, amide groups, ether groups, ester groups, ketone groups, hydroxyl groups, alkenyl groups, aldehyde groups, alkene groups, combinations thereof, or the like, or all of the above. For example, one or more second functional groups 902 may be undecane, and thus one or more trimethylsilyl-protected thiols may be trimethylsilyl-protected dodecanethiols.

[0055] The third functionalization scheme 910 comprises the addition of one or more second functional groups 902 (e.g., “R 29 represents the functionalization of a polycarbonate, which may be characterized by formula 300 (e.g., first polycarbonate 402) with one or more trimethylsilyl-protected thiols (represented in FIG. 9 as "TMSS"), which may include a thiol group, ...

[0056] The fourth functionalization scheme 914 involves the addition of one or more second functional groups 902 (e.g., “R 2 9 represents the functionalization of a polycarbonate, which may be characterized by formula 300 (e.g., first polycarbonate 402) with one or more trimethylsilyl-protected thiols (represented in FIG. 9 as "TMSS"), which may include a trimethylsilyl-protected thiol (represented in FIG. 9 as "TMSS"), to form a tri-substituted product (e.g., seventh polycarbonate 916). Second functional group 902 may include alkyl structures, aryl structures, carboxyl groups, carbonyl groups, amine groups, amide groups, ether groups, ester groups, ketone groups, hydroxyl groups, alkenyl groups, aldehyde groups, alkene groups, combinations thereof, or the like, or all of the above. For example, one or more of second functional groups 902 may be undecane, and thus one or more trimethylsilyl-protected thiols may be trimethylsilyl-protected dodecanethiols.

[0057] For example, the functionalized polycarbonate may be functionalized according to the functionalization scheme and / or method 800 shown in FIG. 9 under the following exemplary conditions or similar conditions or both. In a nitrogen-filled glovebox, an 8 mL vial equipped with a magnetic stir bar can be charged with 25 mg of 0.024 mmol of the first polycarbonate 402; 0.25 mL of NMP; or 5 μL of a 13.2 mg / mL stock solution in NMP and 1 mol% catalyst loading per perfluoroaryl unit of DBU·PhCO2H, or both. The reaction mixture can be stirred until the solids are dissolved. 17 mg of 0.062 mmol of trimethylsilyl-protected dodecanethiol can be added, and the reaction mixture can be stirred for 5 minutes at RT. The vial can be removed from the glovebox, and an aliquot of the reaction mixture can be analyzed by F NMR to determine the conversion. A sample was collected, and the crude material was purified by dialysis (1:1 acetonitrile:isopropyl alcohol).

[0058] 10 shows an exemplary, non-limiting diagram 1000 that can represent the structural characteristics of various polycarbonates functionalized according to one or more embodiments described herein (e.g., method 800 and / or one or more functionalization schemes shown in FIG. 9). Repeated descriptions of similar elements used in other embodiments described herein are omitted for brevity. Graph 1000 can show the F NMR spectrum of a first polycarbonate 402.

[0059] FIG. 11 illustrates a diagram of an exemplary, non-limiting functionalization scheme 1100 that can facilitate functionalization of one or more polyurethanes (e.g., which may be characterized by formula 302) according to one or more embodiments (e.g., method 800) described herein. Repeated descriptions of similar elements used in other embodiments described herein are omitted for brevity. Although one or more specific reactants (e.g., first polyurethane 702) are depicted, additional embodiments of functionalization scheme 1100 are also envisioned. For example, the main mechanism of functionalization scheme 1100 can be applied to other reactants (e.g., other polyurethanes that may be characterized by formula 302) according to various features described herein. As shown in FIG. 11, "n" can represent an integer between 2 and 1000 inclusive.

[0060] The functionalization scheme 1100 includes adding one or more second functional groups 902 (e.g., “R 2 11 depicts the functionalization of one or more polyurethanes, which may be characterized by formula 302 (e.g., first polyurethane 702) with one or more trimethylsilyl protected thiols (represented in FIG. 11 as "TMSS"), which may include a thiol group, such as methylsilyl, ...

[0061] The one or more second functional groups 902 can include alkyl structures, aryl structures, carboxyl groups, carbonyl groups, amine groups, amide groups, ether groups, ester groups, ketone groups, hydroxyl groups, alkenyl groups, aldehyde groups, alkene groups, combinations thereof, or the like, or all of the above. For example, the one or more second functional groups 902 can be undecane, and thus the one or more trimethylsilyl-protected thiols can be trimethylsilyl-protected dodecanethiols.

[0062] To facilitate functionalization, one or more polyurethanes, one or more trimethylsilyl protected thiols, or a catalyst, or a combination thereof, which may be characterized by formula 302, may be dissolved in a solvent to form a mixture. The catalyst may be an organic catalyst and may include a basic salt, such as a salt of DBU or sodium dodecanoate or both. The solvent may be organic or polar or both. Exemplary solvents include, but are not limited to, DMF, NMP, combinations thereof, or the like, or all of the above. To facilitate functionalization, the mixture may be stirred at a temperature of 10° C. to 150° C. (e.g., RT) for a period of 2 minutes to 48 hours (e.g., 5 minutes).

[0063] For example, the second polyurethane 1102 can be produced according to the functionalization scheme 1100 and method 800 under the following exemplary conditions. On the benchtop, an 8 mL vial equipped with a magnetic stir bar can be charged with 50 mg of the first polyurethane 702 with 0.120 mmol of perfluorobenzyl groups; 5.4 mg of sodium dodecanoate with a catalyst loading of 20 mol% per perfluorobenzyl group; and 0.050 mL of DMF. The reaction mixture can be stirred until all solids are dissolved. Also, 40 mg of trimethylsilyl-protected dodecanethiol with 0.144 mmol, 1.2 equivalents per perfluorobenzyl unit, can be added, and the reaction mixture can be stirred at RT for 5 minutes. An aliquot can be removed and analyzed by F NMR to determine the conversion (e.g., >95%). The remainder of the reaction mixture can be purified by dialysis (e.g., 20% water in MeOH, with two solvent changes in 24 hours).

[0064] 12 shows a diagram of an exemplary, non-limiting functionalization scheme 1200 that may facilitate functionalization of one or more compounds, which may be polymers and / or monomers (e.g., may include one or more pendant functional groups 104), according to one or more embodiments (e.g., method 800) described herein. Repeated descriptions of similar elements used in other embodiments described herein are omitted for brevity. Although one or more specific reactants (e.g., monomeric reactant 1202) are depicted, additional embodiments of functionalization scheme 1200 are also envisioned. For example, the main mechanism of functionalization scheme 1200 may be applied to other reactants (e.g., other monomers including pendant functional groups 104), according to various features described herein. Reactants that can be functionalized according to functionalization scheme 1200 can include monomers and / or polymers that can include a molecular backbone attached to one or more pendant functional groups 104, where the molecular backbone can include one or more carbonate structures, one or more urethane structures, one or more amide structures, one or more ester structures, one or more ether structures, one or more acrylate structures, or one or more styrene structures, or combinations thereof.

[0065] The functionalization scheme 1200 includes adding one or more second functional groups 902 (e.g., “R 2 12 depicts the functionalization of one or more monomers that may include one or more pendant functional groups 104 (e.g., monomer reactant 1202) with one or more trimethylsilyl-protected thiols (represented in FIG. 12 as "TMSS"), which may include one or more pendant functional groups 104 (e.g., monomer reactant 1202) to form a functionalized monomer (e.g., first functionalized monomer 1204). Functionalization scheme 1200 can produce mono-substituted functionalized monomers (e.g., first functionalized monomer 1204) and / or multi-substituted functionalized monomers.

[0066] The one or more second functional groups 902 can include alkyl structures, aryl structures, carboxyl groups, carbonyl groups, amine groups, amide groups, ether groups, ester groups, ketone groups, hydroxyl groups, alkenyl groups, aldehyde groups, alkene groups, combinations thereof, or the like, or all of the above. For example, the one or more second functional groups 902 can be undecane, and thus the one or more trimethylsilyl-protected thiols can be trimethylsilyl-protected dodecanethiols.

[0067] To facilitate functionalization, one or more monomer reactants, which may include one or more pendant functional groups 104 (e.g., monomer reactant 1202), one or more trimethylsilyl protected thiols, or a catalyst, or a combination thereof, may be dissolved in a solvent to form a mixture. The solvent may be organic or polar or both. Exemplary solvents include, but are not limited to, DMF, NMP, combinations thereof, or the like. To facilitate functionalization, the mixture may be stirred at a temperature of 10° C. to 150° C. (e.g., RT) for a period of 2 minutes to 48 hours (e.g., 5 minutes).

[0068] Table 2, shown below, pertains to the functionalization of monomer reactant 1202 according to functionalization scheme 1200 with various catalysts.

[0069] [Table 2]

[0070] Additionally, experiments utilizing pyridinium p-toluenesulfonate as a catalyst yielded zero conversion. In various embodiments, the catalysts in Table 2 are also applicable to method 800, the functionalization scheme of Figure 9, or functionalization scheme 1200, or combinations thereof.

[0071] FIG. 13 shows a diagram of exemplary non-limiting functionalized polycarbonates that can be produced according to the method 800 and / or the functionalization scheme shown in FIG. 9. Repeated descriptions of similar elements used in other embodiments described herein are omitted for brevity. For example, the eighth polycarbonate 1302 can be an embodiment of the fourth polycarbonate 904. Also, the ninth polycarbonate 1304 can be produced from the second polycarbonate 404 according to the method 800 and / or the functionalization scheme shown in FIG. 9. Furthermore, the tenth polycarbonate 1306 can be produced from the third polycarbonate 406 according to the method 800 and / or the functionalization scheme shown in FIG. 9. It is evident from the examples shown in FIG. 13 that the functionalization described herein (see, e.g., method 800, functionalization scheme or functionalization scheme 1100 of FIG. 9, or a combination thereof) can be carried out on polymers (e.g., homopolymers) or copolymers (e.g., alternating, random or block copolymers or a combination thereof) or both.

[0072] 14 shows a flow diagram of an exemplary, non-limiting method 1400 that can facilitate surface functionalization of one or more compounds according to one or more embodiments described herein. Repeated descriptions of similar elements used in other embodiments described herein are omitted for brevity. In various embodiments, method 1400 can be utilized to functionalize perfluoroaryl coated surfaces.

[0073] At 1402, the method 1400 can include contacting a compound with one or more trimethylsilyl-protected thiols to form a composition. The compound can include one or more monomers or one or more polymers (e.g., homopolymers, alternating copolymers, random copolymers, or block copolymers, or combinations thereof), or both. For example, the compound can be located on a surface of an article, and the contacting can include dispersing (e.g., spraying or coating, or both) the one or more trimethylsilyl-protected thiols onto the surface covered with the compound.

[0074] At 1404, the method 1400 can include treating the composition to promote functionalization of the compound. The treatment can include one or more thermal treatments or one or more chemical treatments or both. For example, the composition can be heated to a cure temperature (e.g., a temperature between 150° C. and 300° C.).

[0075] At 1406, the method 1400 may include functionalizing the compound by covalently attaching one or more trimethylsilyl-protected thiols to perfluoro pendant functional groups of the compound. The compound may include a molecular backbone that includes one or more pendant perfluoroaryl groups covalently attached to one or more electron-withdrawing structures. For example, the one or more pendant perfluoroaryl groups may be pendant perfluorophenyl groups. Functionalization at 1406 may produce mono- or poly-substituted products or both. The low surface energy of fluorine may allow for preferential orientation of the one or more perfluoroaryl groups away from the surface, making the compound more readily available for displacement by nucleophiles.

[0076] Unlike the pendant functional group 104, which may include compounds that may be characterized by formula 100, 300, or 302, or combinations thereof, which attach a perfluoroaryl group to the molecular backbone or linking group 306, or both, via a methylene group; the compound of method 1400 may include one or more pendant perfluoroaryl groups attached directly to the molecular backbone without one or more intermediate methylene groups. Additionally, one or more pendant perfluoroaryl groups may be directly attached to one or more electron-withdrawing structures. Examples of electron-withdrawing structures include, but are not limited to, amide structures or sulfonamide structures or both. Thus, one or more pendant perfluoroaryl groups may be electron-deficient.

[0077] At 1408, the method 1400 can optionally include removing by-products of the functionalization at 1406. For example, the surface can be rinsed or otherwise cleaned, or both, to remove salt by-products, thereby leaving the functionalized surface free of contaminants.

[0078] FIG. 15 shows a diagram of an exemplary, non-limiting functionalization scheme 1500 that can facilitate the functionalization of one or more compounds according to one or more embodiments (e.g., method 1400) described herein. Repeated descriptions of similar elements used in other embodiments described herein are omitted for brevity. Although one or more specific reactants (e.g., reactant 1502) are depicted, additional embodiments of functionalization scheme 1500 are also envisioned. For example, the main mechanism of functionalization scheme 1500 can be applied to other reactants (e.g., other compounds that include pendant perfluoroaryl groups attached to electron-withdrawing structures) according to various features described herein.

[0079] Functionalization scheme 1500 can facilitate the production of one or more functionalized compounds according to method 1400. For example, functionalization can include functionalizing one or more perfluoroaryl groups of one or more compounds with one or more trimethylsilylthiols (e.g., represented as "TMSS" in FIG. 15). One or more perfluoroaryl groups (e.g., perfluorophenyl groups) can be directly bonded to one or more electron-withdrawing structures (e.g., including amide and / or sulfonamide groups), thereby rendering one or more perfluoroaryl groups electron-deficient. One or more trimethylsilylthiols can be bonded to one or more second functional groups 902 (e.g., represented as "R 2 "). The second functional group 902 can include alkyl structures, aryl structures, carboxyl groups, carbonyl groups, amine groups, amide groups, ether groups, ester groups, ketone groups, hydroxyl groups, alkenyl groups, aldehyde groups, alkene groups, combinations thereof, or the like, or all of the above. For example, one or more of the second functional groups 902 can be undecane, and thus the one or more trimethylsilyl-protected thiols can be trimethylsilyl-protected dodecanethiols.

[0080] The functionalization represented by functionalization scheme 1500 may be uncatalyzed. Moreover, the functionalization may produce a mono-substituted functionalized compound (e.g., first functionalized compound 1504) or a multi-substituted functionalized compound (e.g., second functionalized compound 1506) or both. Moreover, the functionalization represented by functionalization scheme 1500 may be facilitated by a solvent (e.g., NMP); may be carried out at a temperature (e.g., RT) of 10° C. or more and 150° C. or less; and may include a reaction period of 2 minutes or more and 48 hours or less (e.g., 18 hours).

[0081] In addition, the term "or" is intended to mean an inclusive "or" rather than an exclusive "or". That is, unless otherwise stated or clear from the context, "X uses A or B" is intended to mean any of the natural inclusive sequences. That is, if X uses A; X uses B; or if X uses both A and B, then "X uses A or B" satisfies any of the above examples. Furthermore, the articles "a" and "an" used in this specification and the accompanying drawings should generally be understood to mean "one or more" unless otherwise stated or clear from the context that the singular form is intended. 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. Moreover, any aspect or design described herein as "example" and / or "exemplary" is not necessarily to be construed as preferred or advantageous over other aspects or designs, and is not meant to exclude equivalent exemplary structures and techniques known to those skilled in the art.

[0082] The above description includes only examples of systems, compositions, and methods. Of course, for purposes of describing the present disclosure, it is not possible to describe every conceivable combination of reagents, products, solvents, or articles, or combinations thereof, but one of ordinary skill in the art can recognize many additional combinations and permutations of the present disclosure. 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 as comprehensive as the term "comprising," as "comprising" is interpreted when used as a transitional term in the claims. The description of various embodiments has been presented for illustrative purposes, but is not intended to be exhaustive or limited to the disclosed embodiments. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope of the described embodiments. The terms used herein have been selected to best explain the principles of the embodiments, practical applications or technical improvements to the technology found in the market, or to enable other skilled in the art to understand the embodiments disclosed herein.

Claims

1. one carbonate group; a central chain covalently bonded to said one carbonate group, said central chain being a trivalent group derived from an alkyl structure and forming, together with said one carbonate group, a primary structure of a cyclic carbonate monomer; a side chain covalently bonded to the central chain, the side chain being composed of a linking group covalently bonded to the central chain and a functional group covalently bonded to the linking group, the linking group being a divalent group selected from the group consisting of a carbonyl group, an ester group, an ether group, an amine group, an amide group, a phosphine group, a urea group, and a carbonate group, the functional group being composed of a perfluoroaryl group and a methylene group bonded directly to the perfluoroaryl group, the methylene group being bonded directly to the linking group; A cyclic monomer consisting of

2. The cyclic monomer described in claim 1, wherein the central chain is a trivalent group derived from a butyl structure, and the linking group is an ester group.

3. The cyclic monomer of claim 1 or 2, wherein the perfluoroaryl group comprises an aryl having a number of ring members ranging from 4 or more ring members to 10 or less ring members.

4. The cyclic monomer according to any one of claims 1 to 3, wherein the perfluoroaryl group and the methylene group are perfluorobenzyl groups.

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