Compositions containing sugar-based bisphenols and methods of manufacture and use thereof

Abstract

Provided are sugar-based bisphenol A (BPA) analog monomers, methods for preparing these BPA analogs, and use of these BPA analogs to manufacture corresponding polymers. Also provided are methods of manufacture of a polymer by subjecting aliphatic sugar diol monomers to polycondensation in the presence of a carbonylation agent and / or a diacid and / or a diester.

Description

Compositions Containing Sugar-based Bisphenols and Methods of Manufacture and Use Thereof Government Support

[0001] This invention was made with government support under grant numbers CHE-2003771 and CHE-2404191 awarded by the United States National Science Foundation. The government has certain rights in the invention. Technical Field

[0002] The disclosure relates to synthesis of sugar-based monomers derived from renewable and sustainable carbohydrates and naturally available aromatic phenolic aldehydes as an alternative for bisphenol A (BPA). The disclosure also relates to manufacture of polycarbonates and other macromolecular polymer materials using these BPA analogs. The disclosure also relates to manufacture of polymer materials using sugar-based diols. Background

[0003] BPA has been identified to cause adverse health effects in human beings, in particular for pregnant women and children, by releasing BPA from consumer products. There are some alternatives available for BPA, such as BPF (4,4’-methylenediphenol), BPS (bis-(4- hydroxyphenyl)sulfone), and BPAF (2,2-bis(4-hydroxyphenyl)hexafluoropropane), however, they have not been found to be safer than BPA and are not derived from sustainable sources. BPA alternatives from renewable resources (such as bisguaiacol F (from vanillyl alcohol and guaiacol obtained from lignin), isosorbide and its stereo- and regioisomers obtained from carbohydrates, and furan derivatives, such as furanic diols and furanic diphenols) have shown promising potential. However, synthesizing these BPA alternatives from their corresponding raw materials requires multi-step sequences including dehydration, isomerization, esterification, oxidation, or hydrogenation reactions, which involve either the destruction or removal of functional groups. Summary

[0004] Provided here are systems and methods to address these shortcomings of the art and provide other additional or alternative advantages. The disclosure herein provides one or more embodiments of BPA analogs from renewable sources and methods of preparation of these analogs and their corresponding polymers.

[0005] In certain embodiments, the starting materials for the sugar-based BPA analog monomers can be one or more of a mannopyranoside starting material (such as methyl α-D-mannopyranoside), xylose (such as D-(+)-xylose), or another carbohydrate natural product starting material having appropriate regio- and stereochemistry of two sets of hydroxyl group pairs to allow for installation of two naturally-sourced phenolic aldehydes or phenolic ketones via acetal or ketal formation, respectively. Embodiments include natural sugar-based bisphenol A (BPA) analog compositions containing one or more of a mannopyranoside or a xylofuranoside or a diglycerol. The mannopyranoside can be one or more of methyl 2,3:4,6-bis-O-(4’-hydroxybenzylidene) or methyl 2,3:4,6-bis-O-(vanillylidene)-α-D-mannopyranoside. The xylofuranoside can be one or more of 1,2:3,5-bis(4-hydroxybenzylidene)-D-(+)-xylose or 1,2:3,5-bis(vanillylidene)-D-(+)- xylose. In certain embodiments, the BPA analog monomers can be one or more of a mannopyranoside-derived bisphenolic monomer, or a xylose-derived bisphenolic monomer obtained by the bis- acetalization of mannose- and xylose-based sugars using naturally-sourced aromatic phenolic aldehydes (such as, vanillin, syringaldehyde, 4-hydroxybenzaldehyde, coniferaldehyde, etc.). For example, in certain embodiments, monomers from mannose or xylose are subjected to reactions with syringaldehyde as the phenolic aldehyde. In certain embodiments, the diglycerol can be one or more of bis(4-hydroxybenzylidene) diglycerol or bis(vanillylidene) diglycerol.

[0006] Embodiments include methods of manufacture of a polymer from natural sugar-based compositions. The polymer can be a polycarbonate, an epoxy resin, a polysulfone, a polyetherimide, a polyarylate, a polyurethane, or a polyester. One such method includes the step of subjecting one or more of a mannopyranoside- or a xylofuranoside- or a diglycerol-based BPA analog monomer to a melt condensation in the presence of a carbonylation agent. In certain embodiments, the method also includes mixing an aliphatic diol with the one or more of a mannopyranoside- or a xylofuranoside-based BPA analog monomer during the melt condensation. Embodiments of the aliphatic diol include sugar-based diols. The aliphatic diol can be a 1,4-butane diol or 1,3-propane diol. The aliphatic sugar-based diol can be methyl 4,6-O-laurylidene-D- glucopyranoside. In certain embodiments, the method also includes mixing a cyclic aliphatic diol with the one or more of a mannopyranoside- or a xylofuranoside-based BPA analog monomer during the melt condensation. In certain embodiments, the carbonylation agent can be diphenyl carbonate or dimethyl carbonate or phosgene or an analog thereof.

[0007] Embodiments include a polymer containing one or more natural sugar-based monomers described herein. The polymer can be a polycarbonate, an epoxy resin, a polysulfone, apolyetherimide, a polyarylate, a polyurethane, or a polyester. The monomer can be a bis-arylidene mannose and the polymer be poly(bis-arylidene mannose carbonate). The monomer can be a bis- arylidene mannose and the polymer be poly(bis-arylidene mannose-co-diol carbonate). The monomer can be a bis-arylidene xylose and the polymer be poly(bis-arylidene xylose carbonate). The monomer can be a bis-arylidene xylose and the polymer be poly(bis-arylidene xylose-co-diol carbonate). The monomer can be a bis-arylide diglycerol and the polymer be poly(bis-arylidene diglycerol carbonate). The monomer can be a bis-arylidene diglycerol and the polymer be poly(bis- arylidene diglycerol-co-diol carbonate).

[0008] Embodiments include methods of manufacture of a polymer from natural sugar-based monomers by subjecting these monomers to an interfacial polycondensation in the presence of an aliphatic or an aromatic diacid chloride. One such method includes subjecting mannose-based bisphenol A analog monomer to an interfacial polycondensation in the presence of an aliphatic or an aromatic diacid chloride. natural sugar-based bisphenol A (BPA) analog composition comprising one or more of a mannopyranoside or a xylofuranoside or a diglycerol

[0009] Embodiments include methods of manufacture of a polymer from natural sugar-based monomers by subjecting these monomers to a solution polycondensation in the presence of a sugar-based diol, an aliphatic diisocyanate, or an aromatic diisocyanate, or combinations thereof. An embodiment of the method of manufacture of a polymer includes subjecting mannose-based bisphenol A analog monomer to a solution polycondensation in the presence of a sugar-based diol, an aliphatic diisocyanate, or an aromatic diisocyanate, or combinations thereof. The sugar-based diol can be one or more of galactose, fructose, mannose, glucose, xylose, or a hexose. In certain embodiments, the aliphatic diisocyanate can be hexamethylene diisocyanate.

[0010] Another embodiment of the method of manufacture of a polymer includes subjecting aliphatic sugar diol monomers to polycondensation in the presence of a diacid and / or a diester. The sugar-based diol can be one or more of galactose, fructose, mannose, glucose, xylose, or a hexose. Also provided herein are galactose and fructose diol monomers and methods of making their polymers and copolymers. In certain embodiments, these galactose monomers can be ketal- protected galactose diol monomers that are subject to melt-phase synthesis of poly(galactose carbonate)s using diphenyl carbonate. Certain embodiments include copolymerization of the galactose diol monomers with aliphatic diols to produce poly(galactose diol-co-aliphatic diol carbonate)s.

[0011] In certain embodiments, the fructofuranoside diol monomers are used to produce poly(fructose carbonate)s. In certain embodiments, poly(fructose diol-co-aliphatic diol carbonate)s are produced from fructofuranoside diol monomer and aliphatic diols. An example of an aliphatic diol for use here is 1,4-butane diol.

[0012] Embodiments also include use of these sugar-derived bisphenolic monomers to produce a variety of types of polymers, including but not limited to polycarbonates, polyepoxides, polysulfones, polyetherimides, polyarylates, polyurethanes, and polyesters. These polymers can be used in the manufacture of epoxy resins, phenoplast resins, flame retardants, thermoplastics, and thermoset plastics. Brief Description of the Drawings

[0013] The patent or application file contains at least one drawing executed in color. Copies of this patent or patent application publication with color drawing(s) will be provided by the Office upon request and payment of the necessary fee.

[0014] Embodiments will be readily understood by the following detailed description in conjunction with the accompanying drawings. Embodiments are illustrated by way of example and not by way of limitation in the accompanying drawings.

[0015] FIG. 1 is a representation of BPA and the manufacture of the corresponding polycarbonate (left panel) and sugar-based BPA analogs and their corresponding polycarbonates (right panel).

[0016] FIG. 2A is a representation of the formation of the mannose- and xylose-derived bisphenolic monomers by acetalization of mannose or xylose, respectively, with naturally sourced phenolic aldehydes and their step-growth polymerization for the synthesis of sugar-based polymers from the sugar-based bisphenol A analogs as a substitute for the synthesis of bisphenol A-based polymers.

[0017] FIG. 2B is a representation of the conversion of the mannose- and xylose-derived bisphenolic monomers into various types of polymer structures.

[0018] FIG. 3 includes1H NMR spectra of poly(bis-arylidene xylose carbonate)s—(a) poly(1,2:3,5-bis(4-hydroxybenzylidene)-D-(+)-xylose) and (b) poly(1,2:3,5-bis(vanillylidene)-D- (+)-xylose).

[0019] FIG.4 includes FT-IR spectra (left) and DSC scans (right) of poly(bis-arylidene xylose carbonate)s—(a) poly(1,2:3,5-bis(4-hydroxybenzylidene)-D-(+)-xylose) and (b) poly(1,2:3,5-bis(vanillylidene)-D-(+)-xylose).

[0020] FIG. 5 shows the1H NMR spectrum of poly(methyl 2,3:4,6-bis-O-(4- hydroxybenzylidene)-α-D-mannopyranoside-co-methyl 4,6-O-laurylidene-D-glucopyranoside).

[0021] FIG.6 shows the1H NMR spectra of poly(1,2:3,5-bis(vanillylidene)-D-(+)-xylose)-co- 1,4-butane diol) synthesized at (a) 110 °C and (b) 140 °C.

[0022] FIG. 7 shows a representation of the formation of acetal-protected cyclic glucose- or ketal-protected cyclic galactose- or fructose-based sugar-derived diols for their use as monomers for copolymerizations with the sugar-based bisphenol A analogs or copolymerizations with aliphatic diols or copolymerizations with other typical bifunctional monomers and includes a table displaying several examples of structures.

[0023] FIG. 8 shows the1H NMR spectra of galactose-based polycarbonates derived from various ketal protected galactopyranoside diol monomers with or without aliphatic diol comonomers.

[0024] FIG.9 shows the FT-IR spectra of galactose-based polycarbonates derived from various ketal protected galactopyranoside diol monomers with or without aliphatic diol comonomers. Detailed Description

[0025] BPA is a non-renewable petroleum-based industrial chemical used for the synthesis of bisphenol A polycarbonates (BPA-PC) through an interfacial polycondensation process using phosgene (FIG.1, left panel). Despite extensive application of BPA-PC in many plastic materials due to its excellent properties such as high impact resistance, high tensile strength, transparency, hydrolytic stability, and electrical insulation, BPA-PC does undergo hydrolytic breakdown to release BPA, which has been identified to have adverse effects on human health. Although efforts continue academically and industrially to replace BPA in BPA-PC, including by substantial companies (e.g., Mitsubishi Chemical’s DURABIOTMpolycarbonates from isosorbide and comonomers), an even greater problem to be solved is that BPA is overlooked in its presence as a primary chemical component in the vast amounts of epoxy resins used in coatings, adhesives, etc., polyurethanes found in mattresses and other foam products, and other industrial plastic materials. Therefore, there is substantial need for the development of safe, alternative bisphenolic compounds that may replace BPA broadly.

[0026] Sugars are highly naturally abundant and relatively inexpensive, making them apromising sustainable alternative to petroleum-based feedstocks. Embodiments here include compositions that contain natural aldehydes with phenolic groups, which may be combined with sugars having appropriate regio- and stereochemical presentation of diol functionalities to install two phenolic sites through the formation of two acetals and afford sugar-based bisphenol A analogs. Additionally, aldehydes and ketones sourced from renewable natural sources can be utilized for the synthesis of protected sugar diol monomers. The functionality of these cyclic sugar monomers offers the flexibility to tailor the backbone structure and associated physicochemical properties of their corresponding polymers, making them an attractive choice for the synthesis of next-generation sustainable materials.

[0027] Provided herein are compositions of BPA analogs from renewable sources and methods of preparation of the compositions and their corresponding polycarbonates and other polymer materials types. In certain embodiments, the starting materials for the BPA analog monomers can be one or more of a mannopyranoside starting material (such as methyl α-D-mannopyranoside) or a natural product starting material (such as D-(+)-xylose). In certain embodiments, the BPA analog monomers can be one or more of a mannopyranoside monomer (such as 2,3:4,6-bis-O-(4’- hydroxybenzylidene)methyl-α-D-mannopyranoside), or a xylose monomer (such as 1,2:3,5-bis-O- (4-hydroxybenzylidene) D-(+)-xylose or 1,2:3,5-bis-O-(vanillylidene) D-(+)-xylose). In certain embodiments, the diol monomer used for copolymerization with the sugar-based BPA analog monomers can be aliphatic diols such as the aliphatic diol: 1,4-butane diol or 1,3-propane diol or other common diol monomers (e.g., ethylene glycol, 1,5-pentanediol, or cyclohexanedimethanol and sugar-derived aliphatic diols from glucose, galactose and fructose (such as illustrated in FIG. 7, including methyl 4,6-O-benzylidene-D-glucopyranoside, methyl 4,6-O-cinnamylidene-D- glucopyranoside, methyl 4,6-O-laurylidene-D-glucopyranoside, or other glucose-based diol monomers; analogous galactose- or xylose-based diol monomers; or regiochemically- and stereochemically-diverse galactose- or fructose-based diol monomers). One such method of manufacture includes a melt polycondensation process with diphenyl carbonate (DPC) as a carbonylation agent. Certain embodiments can include the use of phosgene or other common phosgene analogs (e.g., 1,1-carbonyldiimidazole, bis(pentafluorophenyl) carbonate, bis(4- nitrophenyl) carbonate, or dimethyl carbonate) as a carbonylation agent. In certain embodiments, sugar-based BPA analogs were also copolymerized with other aliphatic diols under melt conditions, resulting in corresponding copolymers with different physicochemical properties. TheBPA analog monomers were derived from renewable resources, such as sugars and naturally available, renewable aromatic aldehydes. Certain embodiments can include other types of polymers, such as polycarbonates, polyepoxides, polysulfones, polyetherimides, polyarylates, polyurethanes, and polyesters. These polymers can be used in the manufacture of epoxy resins, phenoplast resins, flame retardants, thermoplastics, and thermoset plastics.

[0028] Other methods of manufacture can include other types of polycondensation methods, such as solution polycondensation for preparing polyurethane or polyether or interfacial polycondensation for preparing polyester.

[0029] BPA can be described as having two segments in its structure: (1) a 3-carbon aliphatic spacer segment in the middle, and (2) two phenolic segments attached to the aliphatic segment (FIG.1, left panel). Methods disclosed here include substitution of the 3-carbon aliphatic segment with a sugar moiety, which has hydroxyl groups with the required regio- and stereochemical configurations to connect two phenolic moieties through acetal linkages (FIG.1, right panel, FIG. 2A and FIG.2B).

[0030] An embodiment of the method is disclosed in FIG.2A, which includes the step-growth polymerization of sugar-based BPA analog monomers for the synthesis of sugar-based BPA analog polycarbonates with a wide range of thermal properties. A further embodiment of the method is also disclosed in FIG. 2A, which includes a diol monomer for copolymerization with the sugar-based BPA analog monomers. A further embodiment of the method is also disclosed in FIG. 2A, which includes an acetal or ketal protected sugar derived aliphatic diol monomer for copolymerization with the sugar-based BPA analog monomers. Embodiments can also include a combination of the diol monomer and the acetal or ketal protected sugar derived aliphatic diol monomer for copolymerization.

[0031] In an embodiment, methyl α-D-mannopyranoside and D-(+)-xylose were chosen to replace the 3-carbon aliphatic spacer segment of BPA, where the 2,3-diol (cis) and 4,6-diol (trans) groups in mannopyranoside, and the 1,2-diol (cis) and 3,5-diol (cis) groups in xylose, regio- and stereochemically favor the 5-membered and 6-membered bis acetal linkages with phenolic aldehydes, such as 4-hydroxybenzaldehyde and vanillin, to give mannose-based and xylose-based BPA analogs (FIG. 2A). In an example, these sugar-based analogs were subjected to melt polycondensation using carbonylation agents, in the presence or absence of aliphatic diols, to give the corresponding sugar-based polycarbonates with varying physicochemical properties. Thesesugar-based BPA analogs can be used as a substitute for several polymers produced from BPA, such as polycarbonates, epoxy resins, polysulfones, polyetherimides, polyesters, polyurethanes, polyarylates, etc. (FIG. 2B). These polymers can be used in the manufacture of epoxy resins, phenoplast resins, flame retardants, thermoplastics, and thermoset plastics.

[0032] The starting compounds used in the examples were obtained commercially or synthesized and are summarized in Table 1.

[0033] Table 1. Starting Compounds.

[0034] Preparation of bisphenol A analogs

[0035] Example bisphenolic sugar-based monomers were prepared according to the following general scheme (Scheme 1) and are summarized in Table 2. Commercially obtained sugar derivatives and aromatic aldehydes were used as starting materials. Sugar-based bisphenol analogs are synthesized for the first time and obtained in a single step through bis-acetalization of commercially-available sugar derivatives using naturally derived phenolic aldehydes or their dimethyl acetals. Functionalities on the sugar moiety are preserved during the reaction and carried over to the product. Various bisphenol A analogs with a range of physicochemical properties can be prepared by altering the regiochemistry, stereochemistry and substituents of the sugars and by selecting different renewably sourced phenolic aldehydes.

[0036] Scheme 1: General synthesis of sugar-based bisphenol A analogs

[0037] Table 2. Mannose- and xylose-based bisphenol A analog monomers prepared for utilization in polymerizations. Yield Entry Sugar derivative Aromatic aldehyde Bisphenol A analog monomer (%)

[0038] Preparation of mannopyranoside BPA analog monomers

[0039] Examples of mannopyranoside-based BPA analog monomers were prepared according to the following schemes (Schemes 2 and 3). Commercially obtained mannopyranoside starting materials were used.

[0040] Scheme 2: Synthesis of methyl 2,3:4,6-bis-O-(4’-hydroxybenzylidene)-α-D- mannopyranoside (BHBM):

[0041] To a solution of 4-hydroxybenzaldehyde (2.76 g, 22.6 mmol) in anhydrous dimethylformamide (DMF) (ca.10 mL) under N2was added methyl α-D-mannopyranoside (2.00 g, 10.3 mmol) and trimethyl orthoformate (2.50 mL, 2.40 g, 22.6 mmol), followed by the addition of p-toluenesulfonic acid monohydrate (PTSA·H2O) (26 mg, 0.14 mmol) to obtain a colorlesssolution. The reaction flask was equipped with a Dean Stark apparatus and a circulating condenser. The reaction mixture was heated in an oil bath at 120 °C under N2as the methyl formate and methanol byproducts (bp = 36 °C and 65 °C, respectively) were collected in the Dean Stark apparatus (analyzed and confirmed by1H NMR and FT-IR) and the conversion was monitored by TLC. The color of the reaction mixture changed to pale yellow in ~ 1 h and the reaction was allowed to stir for 4 h before being cooled to room temperature and quenched by addition of 5 mL of saturated KHCO3solution (aq.). The solution was concentrated in vacuo and the resulting residue was dissolved in 50 mL of dichloromethane (DCM) and washed with water (40 mL × 2) and brine (10 mL). The organic layer was dried over anhydrous Na2SO4, filtered, concentrated, and purified by column chromatography using ethyl acetate / hexanes (1:1 to 2:1) to give BHBM as an inseparable mixture of diastereomers as a colorless solid (2.90 g, 71% yield, with a diastereoisomeric ratio (dr) of ~ 3:1).

[0042] The structure of the product was confirmed by the analysis of various spectroscopic, and spectrometric techniques. For instance, HRMS analysis showed that observed mass agreed with the expected mass of the product. Further, for the major isomer, singlets at 9.57 and 9.52 ppm, 6.09 and 5.59 ppm, and 4.98 ppm in the1H NMR spectrum confirmed the presence of protons assigned to two phenolic, two benzylic acetals and one aliphatic acetal groups, respectively, in the product.13C NMR signals at 158 ppm and 98-105 ppm also strongly supported the presence of phenolic and acetal carbons in the product. FT-IR stretching frequency absorbances at 3380 cm-1 and 1674-1519 also confirmed the presence of phenolic hydroxyl and aromatic carbon-carbon bonds in the product. Thus, all the data combined confirmed the composition and structure of the product. For all examples below, unless otherwise noted, NMR spectra were obtained for isolated reaction products before separation of isomers, and the shifts for the major isomer are reported. As a demonstrative example of isolated regioisomers, the IPGa isomers were separated, and NMR spectra were obtained for both individual isomers.

[0043] 1H NMR of major isomer (400 MHz, DMSO-d6) δ 9.57 (s, 1H), 9.52 (s, 1H), 7.27 – 7.19 (m, 4H), 6.78 – 6.70 (m, 4H), 6.09 (s, 1H), 5.59 (s, 1H), 4.98 (s, 1H), 4.50 (dd, J = 8.2, 5.4 Hz, 1H), 4.28-4.19 (m, 1H), 4.10 (d, J = 5.4 Hz, 1H), 3.88 (dd, J = 9.8, 8.3 Hz, 1H), 3.79 – 3.69 (m, 1H), 3.59 (tt, J = 10.0, 4.9 Hz, 1H), 3.33 (s, 3H).1H NMR of major isomer (400 MHz, DMSO- d6) δ 9.65 (s, 1H), 9.51 (s, 1H), 7.31 (d, J = 8.5 Hz, 2H), 7.27 – 7.19 (m, 2H), 6.80 (d, J = 8.5 Hz, 2H), 6.78 – 6.70 (m, 2H), 5.78 (s, 1H), 5.56 (s, 1H), 5.06 (s, 1H), 4.26-4.19 (m, 3H), 3.79 – 3.69(m, 2H), 3.59 (tt, J = 10.0, 4.9 Hz, 1H), 3.35 (s, 3H).13C NMR of mixture of diastereomers (101 MHz, DMSO-d6) δ 158.67, 158.38, 158.00, 129.22, 128.68, 128.51, 128.48, 128.14, 127.79, 127.17, 115.25, 115.14, 114.87, 114.84, 103.81, 102.50, 101.34, 98.27, 98.06, 80.25, 79.36, 77.70, 75.90, 75.20, 73.38, 68.01, 60.29, 59.94, 54.72, 54.68 ppm. FT-IR (ATR) 3382, 3198, 3179, 2915, 1674, 1608, 1519, 1457, 1387, 1316, 1295, 1219, 1165, 1094, 833 cm-1. HRMS (ESI+) m / z: [M+H]+Calculated for C21H22O8H+403.1387; found 403.1387.

[0044] Scheme 3: Synthesis of methyl 2,3:4,6-bis-O-(vanillylidene)-α-D-mannopyranoside (BVM):To a solution of methyl α-D-mannopyranoside (1.01 g, 5.15 mmol) in anhydrous acetonitrile (MeCN) (ca. 15 mL) under N2was added vanillylidene dimethyl acetal (2.24 g, 11.0 mmol) and (1S)-(+)-10-camphorsulfonic acid (CSA) (12 mg, 0.05 mmol) to obtain a pinkish solution with partially insoluble D-(+)-xylose. The reaction flask was equipped with a circulating condenser and heated in an oil bath at 70 °C under N2for 16 h to obtain a dark colored, homogeneous solution. The reaction mixture was cooled to room temperature and quenched by addition of 3 mL of saturated NaHCO3solution (aq.). The mixture was concentrated in vacuo and the resulting residue was dissolved in 50 mL of ethyl acetate and washed with water (2 × 50 mL) and brine (10 mL). The organic layer was dried over anhydrous Na2SO4, filtered, concentrated, and purified by column chromatography using ethyl acetate / DCM (0.5:9.5 – 1:9) to give BVM as an inseparable mixture of diastereomers as a pale white solid (1.01 g, 42% yield, dr = 2:1).1H NMR of major isomer (500 MHz, CDCl3) δ 7.10 – 6.85 (m, 6H), 5.91 (s, 1H), 5.80 – 5.64 (m, 2H), 5.45 (s, 1H), 5.08, (s, 1H), 4.45 (dd, J = 7.5, 6.1 Hz, 1H), 4.36 – 4.24 (m, 1H), 4.16 – 4.07 (m, 1H), 3.94-3.84 (m, 6H), 3.83-3.68 (m, 3H), 3.43 (s, 3H).1H NMR of minor isomer (500 MHz, CDCl3) δ 7.10 – 6.83 (m, 6H), 6.22 (s, 1H), 5.80 – 5.64 (m, 2H), 5.57 (s, 1H), 5.01 (s, 1H), 4.63 (dd, J = 7.8, 5.4 Hz,), 4.36 – 4.24 (m, 2H), 3.94-3.84 (m, 6H), 3.83-3.68 (m, 3H), 3.41 (s, 3H).13C NMR of mixture of diastereomers (126 MHz, CDCl3) δ 146.63, 146.49, 146.46, 146.44, 146.36, 146.32, 130.54, 129.43, 129.35, 129.06, 119.84, 119.79, 119.75, 119.40, 114.38, 114.35, 114.20, 114.17, 113.98,113.95, 109.02, 108.99, 108.67, 108.64, 108.60, 108.47, 108.44, 104.05, 102.98, 102.11, 101.93, 98.91, 98.73, 80.58, 78.24, 75.56, 75.29, 74.02, 68.88, 60.37, 60.28, 55.95, 55.93, 55.18, 55.12. FT-IR (ATR) 35385-3231, 2937, 2910, 2841, 1608, 1517, 1463, 1435, 1411, 1371, 1271, 1238, 1190, 1161, 1141, 1124, 1083, 1028, 1001, 974, 914, 860, 817, 777, 763, 734, 702, 663, 636 cm-1. HRMS (ESI+) m / z: [M+H]+Calculated for C23H26O10H+463.1599; found 463.1585.

[0045] Preparation of xylose-based BPA analog monomers

[0046] Example xylose-based monomers were prepared according to the following schemes (Schemes 4 and 5). Commercially obtained D-(+)-xylose starting material was used.

[0047] Scheme 4: Synthesis of 1,2:3,5-bis(4-hydroxybenzylidene)-D-(+)-xylose (BHBX)

[0048] To a solution of 4-hydroxybenzaldehyde (2.67 g, 22.0 mmol) in anhydrous DMF (ca. 10 mL) under N2 was added D-(+)-xylose (1.54 g, 10.0 mmol) and trimethyl orthoformate (2.40 mL, 2.33 g, 22.0 mmol), followed by the addition of PTSA·H2O (19.0 mg, 0.10 mmol) to obtain a colorless solution. The reaction flask was equipped with a Dean Stark apparatus and a circulating condenser. The reaction mixture was heated in an oil bath at 120 °C under N2as the methyl formate and methanol byproducts (bp = 36 °C and 65 °C, respectively) were collected in the Dean Stark apparatus (analyzed and confirmed by1H NMR and FT-IR) and the conversion was monitored by TLC. The color of the reaction mixture changed to dark pinkish brown in ~ 1.5 h and the reaction was allowed to stir for 3 h before being cooled to room temperature and quenched by addition of 5 mL of saturated KHCO3solution (aq.). The solution was concentrated in vacuo and the resulting residue was dissolved in 50 mL of DCM and washed with water (40 mL × 2) and brine (10 mL). The organic layer was dried over anhydrous Na2SO4, filtered, concentrated, and purified by column chromatography using ethyl acetate / hexanes (1:1 to 2:1) to give BHBX as an inseparable mixture of diastereomers as a pale orange solid (0.46 g, 13% yield, dr ~ 3:2).1H NMR (400 MHz, CDCl3)1H NMR of major isomer (500 MHz, DMSO-d6) δ 9.00 (s, 1H), 8.88 (s, 1H), 7.28 – 7.13 (m, 4H), 6.81 – 6.70 (m, 4H), 6.13 (d, J = 3.6 Hz, 1H), 5.96 (s, 1H), 5.36 (s, 1H), 4.66 (d, J = 3.7 Hz, 1H), 4.53 (d, J = 2.2 Hz, 1H), 4.35 (dd, J = 13.3, 3.9 Hz, 1H), 4.16 – 4.06 (m, 2H).1H NMR of minor isomer (500 MHz, DMSO-d6) δ 9.01 (s, 1H), 8.88 (s, 1H), 7.28 – 7.13 (m, 4H), 6.81 – 6.70 (m, 4H), 6.07 (d, J = 4.0 Hz, 1H), 5.75 (s, 1H), 5.34 (s, 1H), 4.58 (d, J = 4.0 Hz, 1H), 4.45 (d,J = 2.2 Hz, 1H), 4.35 (dd, J = 13.3, 3.9 Hz, 1H), 4.16 – 4.06 (m, 2H).13C NMR of mixture of diastereomers (126 MHz, DMSO-CDCl3) δ 158.22, 158.15, 157.49, 157.47, 128.07, 128.05, 127.34, 127.32, 126.81, 126.26, 114.86, 114.84, 114.60, 105.49, 104.87, 104.82, 104.13, 98.87, 98.80, 84.00, 83.93, 78.22, 78.18, 74.40, 71.98, 66.09, 65.92, 59.67. FT-IR (ATR) 3339, 2877, 1677, 1605, 1521, 1448, 1377, 1207, 1163, 11367, 1061, 995, 828, 790 cm-1. HRMS (ESI+) m / z: [M+H]+Calculated for C19H18O7H+359.1125; found 359.1118.

[0049] Scheme 5: Synthesis of 1,2:3,5-bis(vanillylidene)-D-(+)-xylose (BVX)

[0050] To a solution of D-(+)-xylose (0.76 g, 5.0 mmol) in anhydrous MeCN (ca.8 mL) under N2was added vanillylidene dimethyl acetal (2.24 g, 11.0 mmol) and (1S)-(+)-10-camphorsulfonic acid (8 mg, 0.03 mmol) to obtain a pinkish solution with partially insoluble D-(+)-xylose. The reaction flask was equipped with a circulating condenser and heated in an oil bath at 70 °C under N2for 16 h to obtain a dark colored, homogeneous solution. The reaction mixture was cooled to room temperature and quenched by addition of 3 mL of saturated KHCO3solution (aq.). The mixture was concentrated in vacuo and the resulting residue was dissolved in 50 mL of ethyl acetate and washed with water (2 × 40 mL) and brine (10 mL). The organic layer was dried over anhydrous Na2SO4, filtered, concentrated, and purified by column chromatography using ethyl acetate / hexanes (1:1 to 2:1) to give BVX as an inseparable mixture of diastereomers as a pale- yellow solid (1.20 g, 58% yield, dr ~ 3:2).1H NMR of major isomer (400 MHz, CDCl3) δ 7.00 – 6.79 (m, 6H), 6.18 (d, J = 3.6 Hz, 1H), 5.99 (s, 1H), 5.64 (s, 1H), 5.60 (s, 1H), 5.37 (s, 1H), 4.70 (d, J = 3.6 Hz, 1H), 4.54 (d, J = 2.1 Hz, 1H), 4.45 (d, J = 2.4 Hz 1H), 4.14-4.00 (m, 2H), 3.86-3.82 (m, 6H).1H NMR of minor isomer (400 MHz, CDCl3) δ 7.00 – 6.79 (m, 6H), 6.13 (d, J = 4.0 Hz, 1H), 5.79 (s, 1H), 5.64 (s, 1H), 5.60 (s, 1H), 5.34 (s, 1H), 4.62 (d, J = 4.0 Hz, 1H), 4.42 – 4.38 (m, 2H), 4.14-4.00 (m, 2H), 3.87-3.79 (m, 6H).13C NMR of mixture of diastereomers (101 MHz, CDCl3) δ 146.92, 146.88, 146.61, 146.48, 146.41, 129.55, 129.53, 128.55, 128.18, 120.08, 119.73, 119.58, 114.31, 114.12, 114.01, 108.62, 108.37, 108.35, 108.31, 105.96, 105.60, 104.60, 99.53, 99.47, 84.65, 84.50, 78.94, 75.01, 72.58, 66.80, 66.65, 55.98, 55.94. FT-IR (ATR) 3523, 3429, 2934, 1608, 1516, 1464, 14311, 1405, 1370, 1266, 1238, 1191, 1165, 1115, 1073, 1014, 986, 955,854, 823, 804, 729 cm-1. HRMS (ESI+) m / z: [M+H]+Calculated for C21H22O9H+419.1337; found 419.1323.

[0051] Preparation of diglycerol-based BPA analog monomers

[0052] Example diglycerol-based monomers were prepared according to the following schemes (Schemes 6 and 7). Commercially obtained diglycerol starting material was used.

[0053] Scheme 6: Synthesis of bis(4-hydroxybenzylidene) diglycerol (BHBDG):To a solution of mixed isomers of 80% diglycerol (3.80 g, 22.8 mmol) in anhydrous MeCN (ca. 60 mL) under N2was added 4-hydroxybenzaldehyde dimethyl acetal (8.94 g, 45.1 mmol) and (1S)- (+)-10-camphorsulfonic acid (40 mg, 0.18 mmol). The reaction flask was equipped with a circulating condenser and heated in an oil bath at 70 °C under N2for 16 h to obtain a dark colored, homogeneous solution. The reaction mixture was cooled to room temperature and quenched by addition of 5 mL of saturated KHCO3solution (aq.). The mixture was concentrated in vacuo and the resulting residue was dissolved in 100 mL of ethyl acetate and washed with water (60 mL × 2) and brine (20 mL). The organic layer was dried over anhydrous Na2SO4, filtered, concentrated, and purified by column chromatography using ethyl acetate / DCM (3:7) to give BHBDG as an inseparable mixture of diastereomers as a pale-white solid (0.65 g, 18% yield).1H NMR of mixture of diastereomers (400 MHz, CDCl3) δ 7.37 – 7.27 (m, 4H), 6.83 – 6.65 (m, 4H), 5.89 – 5.82 (m, 1H), 5.77 – 5.71 (m, 1H), 5.52 – 5.25 (m, 2H), 4.49 – 4.33 (m, 2H), 4.17 – 4.02 (m, 2H), 4.00 – 3.79 (m, 2H), 3.77 – 3.57 (m, 4H).13C NMR of mixture of diastereomers (126 MHz, CDCl3- DMSO) δ 157.26, 157.08, 156.63, 156.61, 128.43, 127.89, 127.53, 127.12, 127.09, 127.06, 126.89, 126.88, 126.83, 126.80, 126.76, 126.36, 126.33, 126.27, 126.24, 126.21, 113.96, 113.80, 113.70, 103.04, 102.41, 100.18, 99.83, 75.78, 75.49, 70.93, 70.74, 66.10, 65.99, 62.03, 61.69, 61.12, 59.45. FT-IR (ATR) 3637-3004, 2922, 2877, 1672, 1600, 1583, 1516, 1452, 1284, 1217, 1109, 1035, 927, 835, 786, 665, 602, 555 cm-1. HRMS (ESI+) m / z: [M+H]+Calculated for C20H22O7H+375.1438; found 375.1431.

[0054] Scheme 7: Synthesis of bis(vanillylidene) diglycerol (BVDG):

[0055] To a solution of mixed isomers of 80% diglycerol (1.54 g, 9.30 mmol) in anhydrous MeCN (ca. 30 mL) under N2 was added vanillylidene dimethyl acetal (4.60 g, 23.2 mmol) and (1S)-(+)-10-camphorsulfonic acid (21.5 mg, 0.09 mmol). The reaction flask was equipped with a circulating condenser and heated in an oil bath at 70 °C under N2 for 16 h to obtain a dark colored, homogeneous solution. The reaction mixture was cooled to room temperature and quenched by addition of 5 mL of saturated KHCO3 solution (aq.). The mixture was concentrated in vacuo and the resulting residue was dissolved in 75 mL of ethyl acetate and washed with water (50 mL × 2) and brine (20 mL). The organic layer was dried over anhydrous Na2SO4, filtered, concentrated, and purified by column chromatography using ethyl acetate / DCM (3:7) to give BVDG as an inseparable mixture of diastereomers as a pale-yellow gummy liquid (0.60 g, 15% yield).1H NMR of mixture of diastereomers (400 MHz, CDCl3) δ 7.06 – 6.85 (m, 6H), 5.87 (br, 1H), 5.78 (br, 1H), 5.76 (br, 2H), 4.42 – 4.30 (m, 2H), 4.23 (dd, J = 8.3, 6.7 Hz, 1H), 4.08 (ddd, J = 8.0, 7.3, 0.7 Hz, 1H), 4.04 – 3.95 (m, 1H), 3.90 (br, 3H), 3.89 (br, 3H), 3.85 – 3.76 (m, 3H), 3.71 (tt, J = 11.8, 5.6 Hz, 2H).13C NMR of mixture of diastereomers (101 MHz, CDCl3) δ 146.73, 146.56, 129.45, 128.81, 120.09, 119.95, 114.20, 114.09, 108.64, 108.52, 104.35, 103.79, 76.45, 66.76, 66.68, 63.29, 62.77, 55.90. FT-IR (ATR) 3618-3075, 2937, 2881, 1672, 1604, 1516, 1462, 1435, 1402, 1371, 1269, 1240, 1188, 1064, 1028, 962, 856, 812, 777, 759, 713, 630, 599, 555 cm-1. HRMS (ESI+) m / z: [M+H]+Calculated for C22H26O9H+435.1650; found 435.1655.

[0056] Preparation of bisphenol A analog epoxide monomers Example bisphenolic sugar-based epoxide monomers were prepared according to the following general scheme (Scheme 8) and are summarized in Table 3. Bisphenolic sugar-based compounds as described above were used as starting materials. In certain embodiments with epoxy systems, the installation of the epoxides by reaction with epichlorohydrin leads to oligomerizations. These oligomers then contain hydroxyl side chains that may be used in formation of epoxy resins by reaction with multi-functional electrophiles, such as bi-functional isocyanates.

[0057] Scheme 8: General synthesis of sugar-based bisphenol A analog epoxide monomers

[0058] Table 3. Mannose- and xylose-based bisphenol A analog epoxide monomers prepared for utilization in polymerizations. henol A analogBisphenol A anaYield Entry Bisplog epoxide

[0059] Preparation of mannopyranoside BPA analog epoxide monomers

[0060] Examples of mannopyranoside-based BPA analog epoxide monomers were prepared according to the following schemes (Schemes 9 and 10). Mannopyranoside-based BPA analogs as described above were used as starting materials.

[0061] Scheme 9: Synthesis of methyl 2,3:4,6-bis-O-(4’-glycidylbenzylidene)-α-D- mannopyranoside

[0062] To a solution of methyl 2,3:4,6-bis-O-(4’-hydroxybenzylidene)-α-D-mannopyranoside(1.02 g, 2.53 mmol) in 10 mL of epichlorohydrin (ECH) was slowly added powdered potassium hydroxide (KOH) (420 mg, 7.48 mmol), followed by tetrabutylammonium bromide (TBAB) (161mg, 0.50 mmol). The resulting reaction mixture was stirred at room temperature for 14 h, diluted with water, and extracted with ethyl acetate (2 × 25 mL). The combined organic layers were washed with water (25 mL), dried over anhydrous Na2SO4, filtered, concentrated, and the residue was purified by silica gel chromatography (dichloromethane / ethyl acetate (EA) = 9 / 1) to give methyl 2,3:4,6-bis-O-(4’-glycidylbenzylidene)-α-D-mannopyranoside as an inseparable mixture of diastereomers as pale white solid (0.80 g, 64% yield, dr = 3:1)1H NMR of major diastereomer (500 MHz, CDCl3) δ 7.49 – 7.35 (m, 4H), 6.98 – 6.86 (m, 4H), 6.23 (s, 1H), 5.59 (s, 1H), 4.99 (s, 1H), 4.60 (dd, J = 7.9, 5.4 Hz, 1H), 4.37 – 4.17 (m, 3H), 4.13 (d, J = 5.4 Hz, 1H), 4.02 – 3.92 (m, 2H), 3.90 – 3.68 (m, 3H), 3.40 (s, 3H), 3.34 (br, 2H), 2.94 – 2.86 (m, 2H), 2.77 – 2.72 (m, 2H).1H NMR of minor diastereomer (500 MHz, CDCl3) δ 7.49 – 7.35 (m, 4H), 6.98 – 6.86 (m, 4H), 5.91 (s, 1H), 5.49 (s, 1H), 5.06 (s, 1H), 4.43 (dd, J = 7.6, 6.2 Hz, 1H), 4.37 – 4.17 (m, 4H), 4.02 – 3.92 (m, 2H), 3.90 – 3.68 (m, 3H), 3.40 (s, 3H), 3.34 (br, 2H), 2.94 – 2.86 (m, 2H), 2.77 – 2.72 (m, 2H).13C NMR of mixture of diastereomers (126 MHz, CDCl3) δ 159.43, 159.18, 159.06, 159.00, 131.44, 130.39, 130.29, 129.78, 128.09, 127.70, 127.66, 127.56, 114.59, 114.50, 114.33, 114.29, 104.02, 102.87, 101.84, 101.62, 98.91, 98.76, 80.64, 78.29, 75.58, 75.27, 74.05, 68.89, 68.81, 68.77, 60.31, 55.18, 55.11, 50.05, 44.71, 44.68. FT-IR (ATR) 3064, 2995, 2912, 2875, 2833, 1614, 1516, 1452, 1317, 1302, 1247, 1222, 1170, 1126, 1078, 1037, 1-12, 997, 970, 916, 893, 862, 827, 810, 754, 723, 657, 644, 624, 594 cm-1. HRMS (ESI+) m / z: [M+H]+Calculated for C27H30O10H+515.1912; found 515.1910.

[0063] Scheme 10: Synthesis of methyl 2,3:4,6-bis-O-(4’-glycidylvanillylidene)-α-D- mannopyranoside

[0064] To a solution of methyl 2,3:4,6-bis-O-(vanillylidene)-α-D-mannopyranoside (0.505 g,1.07 mmol) in 8 mL of epichlorohydrin was slowly added powdered KOH (180 mg, 3.21 mmol), followed by tetrabutylammonium bromide (70 mg, 0.21 mmol). The resulting reaction mixture was stirred at room temperature 14 h, diluted with water, and extracted with ethyl acetate (2 × 20mL). The combined organic layers were washed with water (25 mL), dried over anhydrous Na2SO4, filtered, concentrated, and the residue was purified by silica gel chromatography (dichloromethane / ethyl acetate (EA) = 9 / 1) to give methyl 2,3:4,6-bis-O-(4’- glycidylvanillylidene)-α-D-mannopyranoside as an inseparable mixture of diastereomers as a white solid (0.40 g, 65% yield, dr = 2:1).of major isomer (500 MHz, CDCl3) δ 7.12 – 6.84 (m, 6H), 5.92 (s, 1H), 5.45 (s, 1H), 5.07 (s, 1H), 4.45 (dd, J = 7.5, 6.2 Hz, 1H), 4.37 – 4.10 (m, 4H), 4.08-3.99 (m, 2H), 3.88 – 3.86 (m, 6H), 3.84 – 3.76 (m, 1H), 3.71 (ddd, J = 10.2, 9.0, 1.6 Hz, 2H), 3.42 (s, 3H), 3.39 – 3.32 (m, 2H), 2.93 – 2.84 (m, 2H), 2.71-2.75 (m, 2H).1H NMR of minor isomer (500 MHz, CDCl3) δ 7.12 – 6.84 (m, 6H), 6.22 (s, 1H), 5.57 (s, 1H), 5.00 (s, 1H), δ 4.62 (dd, J = 7.7, 5.4 Hz, 1H), 4.37 – 4.18 (m, 4H), 4.14 (d, J = 5.4 Hz, 1H), 4.08-3.99 (m, 2H), 3.88 – 3.86 (m, 6H), 3.84 – 3.76 (m, 2H), 3.40 (s, 3H), 3.39 – 3.32 (m, 2H), 2.93 – 2.84 (m, 2H), 2.71-2.75 (m, 2H).13C NMR of mixture of diastereomers (126 MHz, CDCl3) δ 149.61, 149.53, 149.46, 148.86, 148.67, 148.60, 148.55, 132.19, 131.05, 130.97, 130.76, 119.07, 118.99, 118.61, 113.85, 113.70, 113.63, 110.21, 109.90, 109.85, 109.63, 103.83, 102.78, 101.89, 101.72, 98.84, 98.65, 80.53, 78.23, 77.36, 75.52, 75.29, 74.01, 70.23, 68.85, 60.27, 60.22, 55.96, 55.93, 55.16, 55.09, 50.10, 50.05, 44.90, 44.84. FT-IR (ATR) 3070, 3008, 2924, 2846, 1735, 1612, 1512, 1442, 1396, 1303, 1242, 1172, 1141, 1080, 1026, 918, 825, 624, 509, 439 cm-1. HRMS (ESI+) m / z: [M+H]+Calculated for C29H34O12H+575.2123; found 575.2113.

[0065] Preparation of xylose-based BPA analog epoxide monomers

[0066] An example of a xylose-based BPA analog epoxide monomer was prepared according to the following scheme (Scheme 11). A xylose-based BPA analog as described above was used as the starting material.

[0067] Scheme 11: Synthesis of 1,2:3,5-bis(4’-glycidylbenzylidene)-D-xylose

[0068] To a solution of 1,2:3,5-bis(4’-hydroxybenzylidene) D-xylose (0.72 g, 2.0 mmol) in 6 mL of epichlorohydrin was slowly added powdered KOH (326 mg, 6.01 mmol), followed by tetrabutylammonium bromide (130 mg, 0.40 mmol). The resulting reaction mixture was stirred at room temperature 14 h, diluted with water, and extracted with ethyl acetate (2 × 25 mL). The combined organic layers were washed with water (25 mL), dried over anhydrous Na2SO4, filtered,concentrated, and the residue was purified by silica gel chromatography (dichloromethane / ethyl acetate (EA) = 9 / 1) to give 1,2:3,5-bis(4’-glycidylbenzylidene)-D-xylose as an inseparable mixture of diastereomers as a fluffy white solid (0.56 g, 60% yield, dr ~ 3:2).1H NMR of major diastereomer (500 MHz, CDCl3) δ 7.47 – 7.34 (m, 4H), 6.97 – 6.87 (m, 4H), 6.23 (d, J = 3.6 Hz, 1H), 6.08 (s, 1H), 5.45 (s, 1H), 4.74 (d, J = 3.6 Hz, 1H), 4.59 (d, J = 2.2 Hz, 1H), 4.47 (d, J = 12.5Hz, 1H), 4.26-4.18 (m, 2H), 4.18 – 4.10 (m, 2H), 3.96 (ddt, J = 11.0, 5.6, 1.7 Hz, 2H), 3.37 – 3.31 (m, 2H), 2.93 – 2.87 (m, 2H), 2.71 – 2.75 (m, 2H).1H NMR of minor diastereomer (500 MHz, CDCl3) δ 7.47 – 7.34 (m, 4H), 6.97 – 6.87 (m, 4H), 6.18 (d, J = 3.9 Hz, 1H), 5.87 (s, 1H), 5.42 (s, 1H), 4.67 (d, J = 4.0 Hz, 1H), 4.50 (d, J = 2.2 Hz, 1H), 4.47 (d, J = 12.5Hz, 1H), 4.26-4.18 (m, 2H), 4.18 – 4.10 (m, 2H), 3.96 (ddt, J = 11.0, 5.6, 1.7 Hz, 2H), 3.37 – 3.31 (m, 2H), 2.93 – 2.87 (m, 2H), 2.71 – 2.75 (m, 2H).13C NMR of mixture of diastereomers (126 MHz, CDCl3) δ 159.61, 159.57, 159.10, 130.52, 129.60, 129.13, 127.87, 127.49, 114.58, 114.38, 105.78, 105.67, 105.63, 104.46, 99.22, 99.16, 84.72, 84.53, 78.88, 78.84, 74.94, 72.55, 68.81, 68.78, 66.75, 66.59, 50.03, 50.01, 44.67, 44.65. FT-IR (ATR) 3062, 2993, 2931, 2831, 1735, 1597, 1519, 1465, 1411, 1381, 1257, 1234, 1165, 1134, 1080, 1026, 909, 856, 802, 648, 439 cm-1. HRMS (ESI+) m / z: [M+H]+Calculated for C25H26O9H+471.1650; found 471.1645.

[0069] Preparation of non-phenolic sugar-based diol monomers

[0070] Example non-phenolic sugar-based monomers were prepared according to the following general schemes (Schemes 12, 19, and 25) and are summarized in Tables 4-6. Commercially obtained sugar derivatives and ketones were used as starting materials.

[0071] Preparation of galactopyranoside diol monomers

[0072] Example galactopyranoside monomers were prepared according to the following general scheme (Scheme 12) and are summarized in Table 4. Commercially obtained galactopyranoside starting materials were used.

[0073] Scheme 12: General synthesis of ketal-protected galactose diol monomers

[0074] Table 4. Non-phenolic galactose-based monomers prepared for utilization inpolymerizations. Major (3,4-ketal) Minor (4,6-ketal) Ratio of Yield Entry

[0075] Scheme 13: Synthesis of methyl isopropylidene-α-D-galactopyranoside (IPGa)

[0076] The procedure for the synthesis of methyl isopropylidene-α-D-galactopyranoside is modified from the procedure reported in the literature. To a solution of methyl α-D- galactopyranoside (2.01 g, 10.4 mmol) in MeCN (ca. 15 mL) under N2was added 2,2- dimethoxypropane (1.38 g, 13.3 mmol) and (1S)-(+)-10-camphorsulfonic acid (12 mg, 0.05 mmol). The reaction was heated in an oil bath at 70 °C under N2for 5 h, cooled to room temperature, and quenched by adding 2 mL of saturated NaHCO3solution (aq). After 5 minutes of stirring, the reaction mixture was concentrated in vacuo and the residue was dissolved in 50 mL of ethyl acetate and washed twice with brine (2×30 mL). The ethyl acetate layer was collected and dried over Na2SO4, filtered, and concentrated to a volume of 5-8 mL of ethyl acetate before precipitation into 80 mL of hexanes. The precipitate was centrifuged and dried to obtain the product as a colorless solid (1.05 g, 43% yield, ratio of 3,4:4,6 ketal = 87:13). It is also demonstrated that diastereomeric mixture can be separated by flash column chromatography using ethyl acetate / hexanes in ratios from 60:40 to 80:20 to obtain the 3,4-ketal in 37% yield (890 mg) and 4,6-ketal in 6% yield (140 mg).1H NMR of 3,4-ketal (400 MHz, CDCl3) δ 4.80 (d, J = 3.8 Hz, 1H), 4.28 – 4.19 (m, 2H), 4.05 (ddd, J = 6.3, 4.3, 1.9 Hz, 1H), 3.94 (ddd, J = 12.0, 6.3, 3.4 Hz, 1H), 3.86 – 3.75 (m, 2H), 3.46 (s, 3H), 2.31 (d, J = 6.8 Hz, 1H), 2.22 (dd, J = 9.4, 3.4 Hz, 1H), 1.51 (s, 3H), 1.35 (s, 3H).13C NMR of 3,4-ketal (101 MHz, CDCl3) δ 109.89, 98.60, 76.32, 74.03, 69.57, 68.01, 62.84, 55.59, 27.74, 25.96.1H NMR of 4,6-ketal (500 MHz, DMSO-d6) δ 4.59 (d, J = 3.0 Hz, 1H), 4.53 (d, J = 6.4 Hz, 1H), 4.40 (d, J = 5.8 Hz, 1H), 4.09 – 4.02 (m, 1H), 3.99 (dd, J = 12.8, 2.2 Hz, 1H), 3.65 – 3.55 (m, 3H), 3.38 (d, J = 2.1 Hz, 1H), 3.26 (s, 3H), 1.36 (s, 3H), 1.27(s, 3H).13C NMR of 4,6-ketal (126 MHz, DMSO-d6) δ 100.61, 97.56, 68.96, 67.87, 67.61, 62.10, 62.06, 54.71, 29.40, 18.58. FT-IR (ATR) 3411, 2933, 2860, 1635, 1450, 1357, 1270, 1193, 1151, 1028, 925, 848, 787, 725, 647 cm-1. HRMS (ESI+) m / z: [M+H]+Calculated for C10H18O6H+235.1176; found 235.1177.

[0077] Scheme 14: Synthesis of methyl cyclohexylidene-α-D-galactopyranoside (CHGa)

[0078] To a solution of methyl α-D-galactopyranoside (1.0 g, 5.2 mmol) in MeCN (ca. 8 mL) under N2was added 1,1-dimethoxycyclohexane (0.95 g, 6.8 mmol) and (1S)-(+)-10- camphorsulfonic acid (6 mg, 0.03 mmol). The reaction was heated in an oil bath at 60 °C under N2for 15 min, cooled to room temperature, and quenched by adding 1 mL of saturated NaHCO3solution (aq). After 5 minutes of stirring, the reaction mixture was concentrated in vacuo and the residue was dissolved 25 mL of ethyl acetate and washed twice with brine (2×15 mL). The ethyl acetate layer was collected and dried over Na2SO4, filtered, and concentrated to a volume of 4 mL of ethyl acetate and dispersed in 50 mL of hexanes. The foamy precipitate obtained was centrifuged and residual solvent was removed in vacuo to obtain a colorless gooey product (0.48 g, 34% yield, ratio of 3,4:4,6 ketal = 81:19).1H NMR of 3,4-ketal (400 MHz, CDCl3) δ 4.79 (d, J = 3.8 Hz, 1H), 4.27 – 4.19 (m, 2H), 4.04 (ddd, J = 6.1, 4.1, 1.9 Hz, 1H), 4.01 – 3.93 (m, 1H), 3.89 – 3.82 (m, 1H), 3.82 – 3.76 (m, 1H), 3.45 (s, 3H), 2.42 – 2.30 (m, 2H), 1.74 – 1.64 (m, 4H), 1.65 – 1.45 (m, 4H), 1.40 (tt, J = 8.0, 3.3 Hz, 1H).13C NMR of 3,4-ketal (101 MHz, CDCl3) δ 110.56, 98.75, 76.06, 73.77, 70.02, 67.93, 62.96, 55.59, 37.53, 35.20, 24.94, 24.06, 23.71. FT-IR (ATR) 3379, 2931, 1638, 1450, 1357, 1277, 1149, 1026, 925, 848, 786, 732, 648, 609 cm-1. HRMS (ESI+) m / z: [M+H]+Calculated for C13H22O6H+275.1489; found 275.1486.

[0079] Scheme 15: Synthesis of methyl heptylidene-α-D-galactopyranoside (HGa)

[0080] To a solution of methyl α-D-galactopyranoside (2.01 g, 10.3 mmol) in MeCN (ca. 15 mL) under N2was added 2,2-dimethoxyheptane (5.01 g, 30.9 mmol) and (1S)-(+)-10- camphorsulfonic acid (12 mg, 0.05 mmol). The reaction was heated in an oil bath at 70 °C under N2for 2.5 h after which the reaction mixture becomes homogeneous and was cooled to room temperature and quenched by addition of 1 mL of saturated NaHCO3solution (aq). After 5 minutes of stirring, the reaction mixture was concentrated in vacuo and the residue was dissolved 50 mL of ethyl acetate and washed twice with brine (2×30 mL). The ethyl acetate layer was collected and dried over Na2SO4, filtered, and concentrated to a volume of 10 mL of ethyl acetate and dispersed in 100 mL of hexanes. The foamy precipitate obtained was centrifuged and residual solvent was removed in vacuo to obtain a colorless viscous liquid (2.97 g, 86% yield, ratio of 3,4:4,6 ketal = 76:24).1H NMR of 3,4-ketal, 50 / 50 mixture of stereoisomers (400 MHz, CDCl3) δ 4.80 (d, J = 3.9 Hz, 0.5H), 4.78 (d, J = 3.9 Hz, 0.5H), 4.31-4.21 (m, 2H), 4.09 – 4.01 (m, 1H), 3.98-3.90 (m, 1H), 3.87 – 3.79 (br, 2H), 3.47 (s, 3H), 2.35 (br, 1H), 2.25 (br, 1H), 1.75 – 1.53 (m, 3H), 1.48 – 1.37 (m, 2H), 1.37 – 1.22 (m, 6H), 0.88 (t, J = 7.2 Hz, 3H).13C NMR of 3,4-ketal, 50 / 50 mixture of stereoisomers (101 MHz, CDCl3) δ 111.88, 111.44, 98.45, 98.30, 76.27, 75.67, 74.23, 73.56, 69.24, 68.17, 62.88, 55.53, 40.60, 39.27, 31.96, 25.27, 24.18, 23.91, 22.51, 13.96. FT-IR (ATR) 3417, 2931, 1712, 1450, 1373, 1149, 1049, 894, 786, 648, 601, 408 cm-1. HRMS (ESI+) m / z: [M+H]+Calculated for C14H26O6H+291.1801; found 291.1802.

[0081] Scheme 16: Synthesis of methyl undecylidene-α-D-galactopyranoside (UDGa)

[0082] To a solution of methyl α-D-galactopyranoside (1.03 g, 5.15 mmol) in MeCN (ca. 10 mL) under N2was added 2,2-dimethoxyundecane (2.20 g, 10.3 mmol) and (1S)-(+)-10-camphorsulfonic acid (12 mg, 0.05 mmol). The reaction was heated in an oil bath at 70 °C under N2for 2.5 h after which the reaction mixture becomes homogeneous and was cooled to room temperature and quenched by addition of 1 mL of saturated NaHCO3solution (aq). After 5 minutes of stirring, the reaction mixture was concentrated in vacuo and the residue was dissolved 50 mL of ethyl acetate and washed twice with brine (2×30 mL). The ethyl acetate layer was collected and dried over Na2SO4, filtered, concentrated and the residue was purified by column chromatography to obtain a colorless viscous liquid (1.20 g, 67% yield, ratio of 3,4:4,6 ketal = 77:23).1H NMR of 3,4-ketal, 50 / 50 mixture of stereoisomers (400 MHz, CDCl3) δ 4.80 (d, J = 3.9 Hz, 0.5H), 4.78 (d, J = 3.9 Hz, 0.5H), 4.31 – 4.18 (m, 2H), 4.08 – 4.00 (m, 1H), 3.94 (m, 1H), 3.84 (br, 2H), 3.46 (s, 3H), 2.38 (br, 1H), 2.26 (br, 1H), 1.74 – 1.54 (m, 3H), 1.48 – 1.36 (m, 2H), 1.25 (s, 14H), 0.87 (t, J = 6.9 Hz, 3H).13C NMR of 3,4-ketal, 50 / 50 mixture of stereoisomers (101 MHz, CDCl3) δ 111.87, 111.43, 98.46, 98.30, 76.27, 75.66, 74.22, 73.54, 69.41, 69.25, 68.16, 68.09, 62.87, 55.61, 55.52, 31.85, 29.52, 29.49, 29.28, 22.65, 14.08. FT-IR (ATR) 3425, 2924, 2854, 1458, 1373, 1198, 1150, 1058, 894, 786, 648, 601 cm-1. HRMS (ESI+) m / z: [M+H]+Calculated for C18H34O6H+347.2428; found 347.2427.

[0083] Scheme 17: Synthesis of methyl pentadecylidene-α-D-galactopyranoside (PDGa)

[0084] To a solution of methyl α-D-galactopyranoside (2.50 g, 12.9 mmol) in MeCN (ca. 26 mL) under N2was added 2,2-dimethoxypentadecane (7.07 g, 26.0 mmol) and (1S)-(+)-10- camphorsulfonic acid (30 mg, 0.13 mmol). The reaction was heated in an oil bath at 68 °C under N2for 3.5 h after which the reaction mixture becomes homogeneous and was cooled to room temperature and quenched by addition of 5 mL of saturated NaHCO3solution (aq). After 5 minutes of stirring, the reaction mixture was concentrated in vacuo and the residue was dissolved 60 mL of ethyl acetate and washed twice with brine (2×40 mL). The ethyl acetate layer was collected and dried over Na2SO4, filtered, concentrated, and the residue was purified by column chromatography to obtain a colorless viscous liquid (3.85 g, 74% yield, ratio of 3,4:4,6 ketal = 72:28).1H NMR of 3,4-ketal, 50 / 50 mixture of stereoisomers (400 MHz, CDCl3) δ 4.80 (d, J = 3.9 Hz, 0.5H), 4.78 (d,J = 3.9 Hz, 0.5H), 4.31 – 4.20 (m, 2H), 4.08 – 4.00 (m, 1H), 3.98 – 3.89 (m, 1H), 3.86 – 3.76 (m, 2H), 3.46 (s, 3H), 2.42 – 2.34 (m, 1H), 2.31 – 2.21 (m, 1H), 1.74 – 1.62 (m, 3H), 1.48 – 1.36 (m, 2H), 1.25 (m, 22H), 0.87 (t, J = 7.0 Hz, 3H).13C NMR of 3,4-ketal, 50 / 50 mixture of stereoisomers (101 MHz, CDCl3) δ 111.87, 111.43, 98.46, 98.30, 76.26, 75.66, 74.22, 73.54, 69.40, 69.24, 68.17, 68.09, 62.87, 55.61, 55.52, 40.69, 39.32, 31.90, 29.81, 29.66, 29.63, 29.57, 29.52, 29.33, 25.28, 24.52, 24.26, 23.38, 22.66, 14.10. FT-IR (ATR) 3425, 2924, 2854, 1458, 1373, 1190, 1153, 1058, 894, 787, 731, 645. HRMS (ESI+) m / z: [M+H]+Calculated for C22H42O6H+403.3054; found 403.3052.

[0085] Scheme 18: Synthesis of methyl (camphor ketylidene)-α-D-galactopyranoside (CKGa)

[0086] To a solution of methyl α-D-galactopyranoside (2.0 g, 10.3 mmol) in MeCN (ca. 20 mL) under N2was added dimethoxy camphor ketal (2.60 g, 13.4 mmol) and (1S)-(+)-10- camphorsulfonic acid (12 mg, 0.05 mmol). The reaction was heated in an oil bath at 68 °C under N2for 14 h and was cooled to room temperature, and quenched by addition of 5 mL of saturated NaHCO3solution (aq). After 5 minutes of stirring, the reaction mixture was concentrated in vacuo and the residue was dissolved 60 mL of ethyl acetate and washed twice with brine (2×40 mL). The ethyl acetate layer was collected and dried over Na2SO4, filtered, concentrated to a volume of ~15 mL, and dispersed in hexanes followed by cooling at -20 ℃ for 16h. The hexanes was decanted, and the residual solvent was removed in vacuo to obtain the product as a colorless solid (1.80 g, 53%, ratio of 3,4:4,6 ketal = 90:10).1H NMR of 3,4-ketal, complex mixture of stereoisomers (400 MHz, CDCl3) δ 4.81– 4.73 (m, 1H), 4.27 – 3.89 (m, 4H), 3.89 – 3.67 (m, 2H), 3.48 – 3.40 (m, 3H), 2.33 – 2.16 (m, 2H), 2.15 – 2.01 (m, 1H), 2.00 – 1.87 (m, 1H), 1.87 – 1.76 (m, 1H), 1.76 – 1.63 (m, 2H), 1.62-1.53 (m, 2H), 1.05 – 0.92 (m, 3H), 0.90 – 0.79 (m, 6H).13C NMR of 3,4-ketal, complex mixture of stereoisomers (101 MHz, CDCl3) δ 118.28, 118.05, 117.70, 99.27, 98.89, 98.61, 98.45, 76.40, 75.23, 73.61, 73.52, 72.27, 70.11, 69.54, 69.35, 69.03, 68.05, 67.90, 67.73,62.97, 55.58, 55.55, 55.50, 53.59, 53.52, 51.40, 48.59, 48.05, 47.88, 47.82, 46.40, 46.30, 45.20, 45.09, 45.04, 44.94, 44.81, 29.75, 29.62, 29.44, 28.44, 26.97, 26.86, 26.81, 26.71, 20.57, 20.51, 20.47, 20.37, 20.29, 20.16, 20.13, 11.32, 10.16, 9.75, 9.72. FT-IR (ATR) 3340, 2939, 2900, 1451, 1316, 1269, 1041, 972, 902, 786, 663, 447cm-1. HRMS (ESI+) m / z: [M+H]+Calculated for C17H28O6H+329.1959; found 329.1958.

[0087] Preparation of fructofuranoside diol monomers Example fructofuranoside monomers were prepared according to the following general scheme (Scheme 19) and are summarized in Table 5. Commercially obtained fructose starting materials were used.

[0088] Scheme 19: General synthesis of ketal-protected fructose diol monomers

[0089] Table 5. Non-phenolic fructose-based monomers prepared for utilization in polymerizations.6-membered Ratio of Yield Entry

[0090] Scheme 20: Synthesis of methyl isopropylidene-D-fructofuranoside (IPF)

[0091] D-fructose (finely powdered and dried overnight) (5.02 g, 27.8 mmol) was dissolved in 50 mL of anhydrous MeOH. To the solution was added 0.15 g of PTSA (polymer-bound, prewashed with methanol followed by acetone and oven dried), and the solution was stirred for 16 h at room temperature under argon.2,2-Dimethoxypropane (35 mL, 30.0 g, 288 mmol) was added, and the solution was stirred an additional 2h before being poured through a sintered funnel to remove the catalyst. The catalyst resin was washed with MeOH (2 × 25 mL), and the filtrate was concentrated in vacuo to afford a syrupy liquid, which was purified by column chromatography (hexanes / EtOAc= 7:3) to afford a clear pale-yellow syrup (2.02 g, 31% yield, ratio of cis:trans ketal = 93:7).1H NMR of cis ketal (400 MHz, CDCl3) δ 4.17 – 4.13 (m, 1H), 4.06 – 3.90 (m, 4H), 3.89 – 3.72 (m, 2H), 3.32 (s, 3H), 2.70 (d, J = 10.7 Hz, 1H), 2.47 (t, J = 5.8 Hz, 1H), 1.48 – 1.46 (s, 3H), 1.39 – 1.37 (s, 3H).13C NMR of cis ketal (101 MHz, CDCl3) δ 101.22, 98.74, 87.97, 79.39, 77.69, 62.81, 61.76, 48.75, 27.90, 19.13. FT-IR (ATR) 3394, 2939, 1450, 1381, 1211, 1157, 1087, 1018, 941, 856, 756, 702, 640, 586, 563 cm-1. HRMS (ESI+) m / z: [M+H]+Calculated for C10H18O6Na+257.0996; found 257.0991.

[0092] Scheme 21: Synthesis of methyl heptylidene-D-fructofuranoside (HF)

[0093] D-fructose (finely powdered and dried overnight) (4.01 g, 22.3 mmol) was dissolved in 40 mL of anhydrous MeOH. To the solution was added 0.12 g of PTSA (polymer-bound, prewashed with methanol followed by acetone and oven dried), and the solution was stirred for 5 h at room temperature under argon.2,2-Dimethoxyheptane (26.74 g, 166.6 mmol) was added, and the solution was stirred an additional 2h before being poured through a sintered funnel to remove the catalyst. The catalyst resin was washed with MeOH (2 × 25 mL), and the filtrate was concentrated in vacuo to afford a syrupy liquid, which was purified by column chromatography (hexanes / EtOAc= 7:3] to afford a clear pale-yellow syrup of an inseparable isomeric mixture (3.02 g, 46% yield, ratio of cis:trans ketal = 76:24).1H NMR of isomeric mixture (400 MHz, CDCl3) δ 4.30 – 3.64 (m, 7H), 3.36 (s, 1.5H), 3.32 (s, 0.5H), 2.81 – 2.56 (m, 1H), 2.50 – 2.29 (m, 1H), 1.83 – 1.73 (m, 1H), 1.64 – 1.53 (m, 1H), 1.49 – 1.18 (m, 9H), 0.96 – 0.81 (m, 3H). 13C NMR of the isomeric mixture (101 MHz, CDCl3) δ 111.28, 110.96, 101.27, 101.16, 100.66, 100.05, 97.94, 97.86, 88.10, 87.95, 79.24, 78.88, 76.68, 76.16, 75.77, 73.12, 72.24, 62.84, 61.66, 61.36, 60.50, 49.00, 48.76, 48.74, 41.06, 32.02, 31.98, 31.88, 31.34, 24.98, 24.24, 24.11, 23.75, 22.88, 22.55, 22.51, 17.12, 14.17, 13.97. FT-IR (ATR) 3425, 2939, 2870, 1458, 1381, 1308, 1256, 1213, 1084, 1026, 887, 732, 640, 609 cm-1. HRMS (ESI+) m / z: [M+H]+Calculated for C14H26O6Na+313.1622; found 313.1603.

[0094] Scheme 22: Synthesis of methyl undecylidene-D-fructofuranoside (UDF)

[0095] D-fructose (finely powdered and dried overnight) (2.01 g, 11.2 mmol) was dissolved in 16 mL of anhydrous MeOH. To the solution was added 0.060 g of PTSA (polymer-bound, prewashed with methanol followed by acetone and oven dried), and 2,2-dimethoxyundecane (18.8 g, 88.8 mmol). The reaction mixture was stirred for 5 h at room temperature under argon and aftermonitoring the conversion by TLC, the solution was poured through a sintered funnel to remove the catalyst. The catalyst resin was washed with MeOH (2 × 25 mL), and the filtrate was concentrated in vacuo to afford a syrupy liquid, which was purified by column chromatography (DCM / EtOAc= 7:3] to afford two separable isomers in 40% yield as a colorless viscous liquid (minor 0.130 g and major 1.25 g), ratio of cis:trans ketal = 90:10.1H NMR of trans ketal (400 MHz, CDCl3) δ 4.29 – 4.12 (m, 2H), 4.07 – 3.59 (m, 5H), 3.36 (s, 3H), 2.67 (d, J = 5.6 Hz, 1H), 2.35 (dd, J = 7.9, 5.0 Hz, 1H), 1.78 – 1.52 (m, 3H), 1.48 – 1.36 (m, 2H), 1.35 – 1.15 (m, 16H), 0.91 – 0.83 (m, 3H).13C NMR of trans ketal (101 MHz, CDCl3) δ 110.98, 97.84, 75.76, 72.56, 72.27, 63.39, 60.52, 49.03, 40.99, 31.86, 29.88, 29.53, 29.30, 24.46, 23.24, 22.66, 14.09. FT-IR (ATR) 3425, 2924, 2854, 1458, 1373, 1234, 1041, 871, 810, 717, 640 cm-1. HRMS (ESI+) m / z: [M+H]+Calculated for C18H34O6H+347.2428; found 347.2424.

[0096] 1H NMR of cis ketal (400 MHz, CDCl3) δ 4.20 – 4.10 (m, 1H), 4.09 – 3.64 (m, 6H), 3.36 and 3.32 (2s, 3H), 2.59 and 2.56 (2d, J = 12.0 Hz, 1H), 2.38 and 2.29 (2t, J = 4.0 Hz, 1H), 1.87 – 1.55 (m, 1H), 1.62 and 1.42 (2s, 3H), 1.40 – 1.15 (m, 15H), 0.92 – 0.78 (m, 3H).13C NMR of cis ketal (101 MHz, CDCl3) δ 101.27, 101.17, 100.67, 100.06, 88.19, 88.03, 79.20, 78.83, 77.75, 62.87, 61.67, 48.76, 41.14, 31.86, 29.84, 29.74, 29.56, 29.52, 29.28, 25.02, 23.24, 22.66, 17.11, 14.09. FT-IR (ATR) 3417, 2924, 2854, 1458, 1380, 1311, 1261, 1213, 1095, 1026, 887, 717, 640, 548 cm-1. HRMS (ESI+) m / z: [M+H]+Calculated for C18H34O6H+347.2428; found 347.2423.

[0097] Scheme 23: Synthesis of methyl pentadecylidene-D-fructofuranoside (PDF)

[0098] D-fructose (finely powdered and dried overnight) (2.02 g, 11.2 mmol) was dissolved in 16 mL of anhydrous MeOH. To the solution was added 0.060 g of PTSA (polymer-bound, prewashed with methanol followed by acetone and oven dried), and 2,2-dimethoxypentadecane (13.0 g, 55.5 mmol). The reaction mixture was stirred for 5 h at room temperature under argon and after monitoring the conversion by TLC, the solution was poured through a sintered funnel to remove the catalyst. The catalyst resin was washed with MeOH (2 × 25 mL), and the filtrate was concentrated in vacuo to afford a syrupy liquid, which was purified by column chromatography (DCM / EtOAc= 7:3] to afford two separable isomers in 34% yield as colorless viscous liquids(major 1.36 g and minor 0.15 g) ratio of cis:trans ketal = 90:10.1H NMR of cis ketal (400 MHz, CDCl3) δ 4.19 – 4.09 (m, 1H), 4.08 – 3.74 (m, 6H), 3.36 and 3.32 (2s, 3H), 2.61 and 2.58 (2d, J = 11.5 Hz, 1H), 2.41 and 2.32 (2t, J = 4.0 Hz, 1H), 1.83-1.53 (m, 2H), 1.50 – 1.14 (m, 25H), 0.91 – 0.83 (m, 3H).13C NMR of cis ketal (101 MHz, CDCl3) δ 101.27, 101.17, 100.66, 100.06, 88.15, 88.00, 79.22, 78.84, 77.75, 62.86, 61.66, 48.74, 41.13, 31.90, 29.85, 29.75, 29.67, 29.63, 29.57, 29.52, 29.34, 25.01, 23.25, 22.67, 17.11, 14.10. FT-IR (ATR) 3410, 2924, 2854, 1458, 1380, 1303, 1264, 1213, 1095, 1026, 887, 717, 648, 601 cm-1. HRMS (ESI+) m / z: [M+NH4]+Calculated for C22H42O6NH4+420.3320; found 420.3311.

[0099] 1H NMR of trans ketal (400 MHz, CDCl3) δ 4.23 – 4.11 (m, 2H), 3.93 – 3.54 (m, 5H), 3.43-3.31 (m, 3H), 2.68 and 2.64 (2d, J = 4.2 Hz, 1H), 2.27 (dd, J = 7.8, 4.9 Hz, 1H), 1.69 – 1.58 (m, 2H), 1.44 – 1.30 (m, 2H), 1.22 (m, 23H), 0.81 (t, J = 6.7 Hz, 3H).13C NMR of trans ketal (101 MHz, CDCl3) δ 110.99, 97.84, 75.76, 72.56, 72.26, 63.39, 60.53, 49.03, 41.00, 31.91, 29.89, 29.68, 29.65, 29.59, 29.55, 29.35, 24.47, 23.24, 22.68, 14.11. FT-IR (ATR) 3441, 2924, 2854, 1458, 1373, 1234, 1049, 871, 810, 717, 644 cm-1. HRMS (ESI+) m / z: [M+H]+Calculated for C22H42O6H+403.3054; found 403.3050.

[0100] Scheme 24: Synthesis of methyl (camphor ketylidene)-D-fructofuranoside (CKF)

[0101] D-fructose (finely powdered and dried overnight) (2.01 g, 11.2 mmol) was dissolved in 16 mL of anhydrous MeOH. To the solution was added 0.060 g of PTSA (polymer-bound, prewashed with methanol followed by acetone and oven dried), and dimethoxy camphor ketal (13.0 g, 55.5 mmol). The reaction mixture was stirred for 16 h at room temperature under argon and after monitoring the conversion by TLC, the solution was poured through a sintered funnel to remove the catalyst. The resin was washed with MeOH (2 × 25 mL), and the filtrate was concentrated in vacuo to afford a syrupy liquid, which was purified by column chromatography (DCM / EtOAc= 7:3] to afford two separable isomers in 42% yield (major 1.4 g as foamy solid; minor 150 mg as gum) ratio of cis:trans ketal = 93:7.1H NMR of cis ketal (400 MHz, CDCl3) δ 4.23-4.06 (m, 2H), 4.02 – 3.64 (m, 5H), 3.42 – 3.24 (m, 3H), 2.60 and 2.58 (2d, J = 11.5, 1H), 2.35– 2.21 (2t, J = 4.1 Hz), 1H), 2.22 – 2.01 (m, 2H), 1.92 (ddd, J = 13.0, 9.4, 3.8 Hz, 1H), 1.80 (q, J = 4.3 Hz, 1H), 1.71 (t, J = 12.7 Hz, 1H), 1.51 (dd, J = 13.0, 7.9 Hz, 1H), 1.35 – 1.22 (m, 1H), 1.12 (tdd, J = 11.7, 9.2, 4.8 Hz, 1H), 1.05 – 0.76 (m, 9H).13C NMR of cis ketal (101 MHz, CDCl3) δ 107.80, 107.60, 100.61, 88.79, 88.74, 80.47, 77.99, 77.81, 77.74, 62.90, 62.87, 60.39, 53.47, 53.43, 48.89, 48.73, 48.03, 47.93, 45.09, 36.14, 28.71, 26.99, 20.62, 20.59, 20.54, 14.19, 9.94, 9.71.FT- IR (ATR) 3410, 2939, 1733, 1450, 1369, 1319, 1049, 972, 905, 864, 655 cm-1. HRMS (ESI+) m / z: [M+H]+Calculated for C17H28O6H+329.1959; found 329.1940.

[0102] 1H NMR of trans ketal (400 MHz, CDCl3) δ 4.26 – 3.61 (m, 7H), 3.32 and 3.31 (2s, 3H), 2.59 and 2.56 (2d, J = 11.5 Hz, 1H), 2.35 and 2.20 (2t, J = 4.1 Hz, 1H), 1.97 – 1.67 (m, 3H), 1.61 – 1.32 (m, 2H), 1.25 (t, J = 7.2 Hz, 2H), 1.05 – 0.70 (m, 9H).13C NMR of trans ketal (101 MHz, CDCl3) δ 117.39, 97.63, 73.15, 72.45, 72.01, 63.45, 60.76, 51.33, 49.00, 48.00, 45.12, 44.83, 29.74, 26.98, 20.43, 20.31, 14.18, 9.64. FT-IR (ATR) 3433, 2939, 1737, 1450, 1377, 1313, 1257, 1202, 1110, 1041, 887, 779, 602 cm-1. HRMS (ESI+) m / z: [M+H]+Calculated for C17H28O6H+329.1959; found 329.1940.

[0103] Preparation of glucopyranoside and mannopyranoside diol monomers

[0104] Example glucopyranoside and mannopyranoside monomers were prepared according to the following general scheme (Scheme 25) and are summarized in Table 6. Commercially obtained glucose and mannose starting materials were used.

[0105] Scheme 25: Synthesis of ketal-protected glucopyranoside and mannopyranoside diol monomers

[0106] Table 6. Non-phenolic glucose- and mannose-based monomers prepared for utilization in polymerizations. Non-phenolic diol Ratio of Yield Entry Sugar derivative Ketal monomer 4,6:2,3 ketal (%)

[0107] Scheme 26: Synthesis of methyl 4,6-O-undecylidene-α-D-glucopyranoside

[0108] To a solution of methyl α-D-glucopyranoside (1.0 g, 5.2 mmol) in MeCN (ca. 10 mL) under N2was added 2,2-dimethoxyundecane (2.20 g, 10.3 mmol) and (1S)-(+)-10- camphorsulfonic acid (13 mg, 0.05 mmol). The reaction was heated in an oil bath at 68 °C under N2for 14 h and was then cooled to room temperature and quenched by addition of 5 mL of saturated NaHCO3solution (aq). After 5 minutes of stirring, the reaction mixture was concentrated in vacuo and the residue was dissolved in 30 mL of ethyl acetate and washed with brine (2×20 mL). The ethyl acetate layer was collected and dried over Na2SO4, filtered, concentrated, and purified by column chromatography (DCM / EtOAc= 7:3] to afford inseparable diastereomers as a colorless solid (1.07 g, 60% yield).1H NMR of diastereomeric mixture (400 MHz, CDCl3) δ 4.76 (d, J = 3.9 Hz, 1H), 3.86 (td, J = 10.8, 5.0 Hz, 1H), 3.79 – 3.68 (m, 2H), 3.65 – 3.45 (m, 3H), 3.43 (s, 3H), 2.63-2.57 (m, 1H), 2.22 (d, J = 8.2 Hz, 1H), 1.68 – 1.55 (m, 2H), 1.49 – 1.13 (m, 17H), 0.88 (t, J = 4.3 Hz, 3H).13C NMR of diastereomeric mixture (101 MHz, CDCl3) δ 101.57, 100.92, 99.70, 73.24, 73.00, 72.29, 63.40, 62.17, 55.49, 42.04, 31.87, 29.81, 29.60, 29.53, 29.31, 24.04, 22.96, 22.66, 17.80, 14.10. FT-IR (ATR) 3417, 2924, 2854, 1462, 1373, 1249, 1195, 1134, 1041,979, 902, 864, 740, 663, 578 cm-1. HRMS (ESI+) m / z: [M+H]+Calculated for C18H34O6H+347.2428; found 347.2423.

[0109] Scheme 27: Synthesis of methyl 4,6-O-pentadecylidene-α-D-glucopyranoside

[0110] To a solution of methyl α-D-glucopyranoside (2.50 g, 12.9 mmol) in MeCN (ca.26 mL) under N2was added 2,2-dimethoxypentadecane (7.07 g, 26.0 mmol) and (1S)-(+)-10- camphorsulfonic acid (30 mg, 0.13 mmol). The reaction was heated in an oil bath at 68 °C under N2for 14 h and was then cooled to room temperature and quenched by addition of 5 mL of saturated NaHCO3solution (aq). After 5 minutes of stirring, the reaction mixture was concentrated in vacuo and the residue was dissolved in 40 mL of ethyl acetate and washed with brine (2×30 mL). The ethyl acetate layer was collected and dried over Na2SO4, filtered, concentrated, and purified by column chromatography (DCM / EtOAc= 7:3] to afford inseparable diastereomers as a colorless solid (1.75 g, 34% yield).1H NMR of diastereomeric mixture (400 MHz, CDCl3) δ 4.76 (d, J = 3.9 Hz, 1H), 3.86 (tdd, J = 11.6, 5.0, 1.4 Hz, 1H), 3.80 – 3.69 (m, 2H), 3.67 – 3.44 (m, 3H), 3.43 (s, 3H), 2.61-2.57 (m, 1H), 2.22 (dd, J = 9.7, 1.4 Hz, 1H), 1.97-1.74 (m, 1H), 1.64 (dd, J = 10.4, 6.2 Hz, 1H), 1.45-1.36 (2s, 3H), 1.44-1.38 m, 1H), 1.50 – 1.16 (m, 21H), 0.92 – 0.83 (m, 3H).13C NMR of diastereomeric mixture (101 MHz, CDCl3) δ 101.58, 100.92, 99.70, 73.24, 73.00, 72.29, 63.41, 62.17, 55.49, 55.46, 31.92, 29.82, 29.64, 29.35, 26.26, 22.68, 17.79, 14.11. FT-IR (ATR) 3425, 2924, 2854, 1458, 1373, 1254, 1197, 1141, 1041, 979, 902, 864, 740, 663, 578 cm-1. HRMS (ESI+) m / z: [M+H]+Calculated for C22H42O6H+403.3054; found 403.3047.

[0111] Scheme 28: Synthesis of methyl 2,3-O-pentadecylidene-α-D-mannopyranoside

[0112] To a solution of methyl α-D-mannopyranoside (1.0 g, 5.2 mmol) in MeCN (ca.26 mL) under N2was added 2,2-dimethoxypentadecane (2.80 g, 10.3 mmol) and (1S)-(+)-10- camphorsulfonic acid (12 mg, 0.0.05 mmol). The reaction was heated in an oil bath at 68 °C under N2for 14 h and was then cooled to room temperature and quenched by addition of 5 mL of saturatedNaHCO3solution (aq). After 5 minutes of stirring, the reaction mixture was concentrated in vacuo and the residue was dissolved in 30 mL of ethyl acetate and washed with brine (2×20 mL). The ethyl acetate layer was collected and dried over Na2SO4, filtered, concentrated, and purified by column chromatography (DCM / EtOAc= 7:3] to afford separable diastereomers as a viscous liquid (0.34 g, 15% yield).1H NMR of 5-membered ketal isomer (a) (180 mg) (400 MHz, CDCl3) δ 4.90 (s, 1H), 4.20 – 4.00 (m, 2H), 3.91 – 3.77 (m, 2H), 3.72 (tdt, J = 8.6, 5.9, 3.0 Hz, 1H), 3.63 (dt, J = 8.8, 4.2 Hz, 1H), 3.34 (s, 3H), 2.49 (dd, J = 4.7, 1.4 Hz, 1H), 2.07 (dd, J = 7.0, 6.0 Hz, 1H), 1.76 – 1.66 (m, 2H), 1.47-1.36 (m, 2H), 1.35-1.15 (m, 23H), 0.87 (t, J = 6.7 Hz, 3H).13C NMR of 5- membered ketal isomer (a) (101 MHz, CDCl3) δ 111.37, 98.62, 77.75, 75.10, 69.80, 69.71, 62.71, 55.15, 41.08, 31.91, 29.86, 29.65, 29.59, 29.54, 29.35, 24.55, 23.46, 22.68, 14.11. FT-IR (ATR) 3433, 2924, 2846, 1458, 1375, 1252, 1195, 1136, 1087, 918, 873, 732, 431 cm-1. HRMS (ESI+) m / z: [M+H]+Calculated for C22H42O6H+403.3054; found 403.3047.

[0113] 1H NMR of 5-membered ketal isomer (b) (160 mg, colorless solid) (400 MHz, CDCl3) δ 4.90 (s, 1H), 4.19 – 4.08 (m, 2H), 3.91 – 3.80 (m, 2H), 3.76 (dddt, J = 9.2, 7.7, 4.3, 2.0 Hz, 1H), 3.62 (tq, J = 9.0, 4.6 Hz, 1H), 3.40 (s, 3H), 2.99 – 2.38 (m, 1H), 2.34 – 1.95 (m, 1H), 1.65-1.53 (m, 2H), 1.47 (s, 3H), 1.25 (m, 22H), 0.88 (t, J = 4.2 Hz, 3H).13C NMR of 5-membered ketal isomer (101 MHz, CDCl3) δ 111.63, 98.55, 78.17, 75.54, 69.77, 69.55, 55.12, 39.49, 31.91, 29.84, 29.67, 29.64, 29.54, 29.35, 25.51, 24.52, 22.68, 14.11. FT-IR (ATR) 3302, 2916, 2847, 1465, 1389, 1203, 1143, 1087, 1041, 972, 864, 824, 717, 483 cm-1. HRMS (ESI+) m / z: [M+H]+Calculated for C22H42O6H+403.3054; found 403.3051.

[0114] Preparation of bisphenol A analog polycarbonates

[0115] Example bisphenolic sugar-based polycarbonates (Table 7) were prepared according to the following general scheme (Scheme 29) and characterization data are summarized in Table 8. Commercially obtained dicarbonate comonomers were used as starting materials.

[0116] Scheme 29: General synthesis of poly(bis-arylidene bisphenolic sugar-based carbonate)s

[0117] Table 7. Summary of the bisphenol A analog polycarbonates produced.

[0118] Preparation of poly(bis-arylidene xylose carbonate)s

[0119] The xylose monomers as prepared according to Schemes 4 and 5 were used to prepare example polymers according to the following Scheme 30.

[0120] Scheme 30: Syntheses of poly(bis-arylidene xylose carbonate)s—(a) poly(1,2:3,5- bis(4-hydroxybenzylidene)-D-(+)-xylose) (PBHBX) and (b) poly(1,2:3,5-bis(vanillylidene)-D- (+)-xylose) (PBVX).General procedure for the melt-phase synthesis of poly(bis-arylidene xylose carbonate)s using diphenyl carbonate is provided herein. FIG. 3 contains1H NMR spectra of poly(bis-arylidene xylose carbonate)s—(a) poly(1,2:3,5-bis(4-hydroxybenzylidene)-D-(+)-xylose) and (b) poly(1,2:3,5-bis(vanillylidene)-D-(+)-xylose). FIG.4 contains FT-IR spectra (left) and DSC scans (right) of poly(bis-arylidene xylose carbonate)s—(a) poly(1,2:3,5-bis(4-hydroxybenzylidene)-D- (+)-xylose) and (b) poly(1,2:3,5-bis(vanillylidene)-D-(+)-xylose).

[0121] Step 1: Transcarbonylation: The bis-arylidene xylose-based BPA analog monomer (1 equiv.), diphenyl carbonate (1 equiv.), and lithium acetyl acetonate (1-10 mol%) were charged into a round bottom Schlenk flask. The flask was equipped with a condenser, placed under positive N2flow, and heated in an oil bath at 110 °C. The solid reactants melted and formed a homogeneous mixture within ca. 30-40 min, at which time the condensate byproduct phenol could be observed crystallizing in the condenser. The reaction was allowed to stir an additional 0.5-2 h under N2 flow (> 1mL / min) before proceeding to step 2. In the cases of copolymerization with a diol monomer, the stoichiometries were adjusted to maintain an overall 1 equiv. of BPA analog monomer + diol monomer to 1 equiv. of the carbonylation agent (as detailed below).

[0122] Step 2: Polycondensation: After 0.5-2 h of transcarbonylation, the reaction mixture was a viscous liquid. The condenser was replaced with a glass stopper, and the reaction was placed under vacuum for 12-14 h, reaching a stable pressure of ca.50 millitorr at completion. The reaction mixture was allowed to cool to room temperature and dissolved in minimal THF. The polymer products were isolated through precipitation into methanol, centrifugation, and removal of residual solvent in vacuo to give dull white solids with yields of 20-60%, based upon 95% monomer conversions.

[0123] PBHBX: Yield: 60%, 1H NMR (400 MHz, CDCl3) δ 7.39 – 7.17 (m, 4H), 7.11-6.90(m, 4H), 6.61 (dd, J = 10.5, 6.1 Hz, 1H), 6.06 – 5.51 (m, 2H), 5.41 – 5.06 (m, 1H), 4.64 – 4.09 (m, 3H), 4.05 – 3.78 (m, 2H), 3.27 (ddd, J = 16.6, 8.4, 4.7 Hz, 1H).13C NMR (126 MHz, CDCl3) δ 158.45, 157.83, 151.60, 151.53, 151.37, 151.33, 151.12, 150.71, 135.47, 135.43, 134.92, 129.39, 127.66, 127.57, 127.34, 127.17, 120.79, 120.67, 120.65, 120.50, 115.30, 115.08, 105.55, 105.51, 105.33, 104.92, 103.71, 98.29, 98.24, 84.61, 84.37, 84.21, 78.55, 78.52, 74.63, 72.36, 66.46, 66.32. FT-IR(ATR) 2904, 1768, 1612, 1510, 1444, 1390, 1300, 1222, 1180, 1161, 1138, 1114, 1074, 1008, 918, 869, 817 cm-1. Tg= 63, 142 °C. TGA in N2: 30 - 250 °C, 5% mass loss; 251 - 445 °C, 55% mass loss. SEC (THF, PS standards): Mn= 2.5 kDa, Mw= 4.3 kDa, Mp= 2.4 kDa, Đ = 1.7.

[0124] PBVX: Yield: 20%,1H NMR (400 MHz, CDCl3) δ 7.46 – 7.35 (m, 1H), 7.32 – 7.19 (m, 4H), 7.19 – 6.87 (m, 5H), 6.28 – 6.17 (m, 1H), 6.16 – 6.10 (m, 1H), 6.08 – 5.92 (m, 1H), 5.68 (d, J = 16.1 Hz, 1H), 5.53 – 5.38 (m, 1H), 4.79 – 4.39 (m, 3H), 4.22 – 4.05 (m, 2H), 3.95 – 3.86 (m, 6H).13C NMR (126 MHz, CDCl3) δ 151.35, 151.32, 151.26, 151.21, 151.16, 151.04, 150.99, 150.82, 150.79, 150.75, 146.96, 146.91, 146.64, 146.51, 146.43, 140.96, 140.88, 140.83, 140.63, 140.61, 140.53, 136.64, 136.58, 136.26, 136.23, 136.19, 135.99, 129.59, 129.54, 129.50, 128.58, 128.21, 126.26, 126.21, 126.17, 122.27, 122.19, 122.04, 122.01, 121.95, 120.88, 120.83, 120.81, 120.62, 120.07, 119.71, 119.57, 118.77, 118.73, 118.64, 118.52, 114.32, 114.13, 114.02, 110.69, 110.58, 110.49, 110.45, 110.34, 108.68, 108.43, 108.39, 108.36, 106.00, 105.80, 105.71, 105.59, 105.19, 104.62, 104.04, 99.45, 98.71, 98.66, 84.79, 84.61, 84.49, 84.45, 78.94, 78.85, 74.93, 74.80, 72.55, 66.74, 66.58, 56.19, 56.16, 56.13, 56.11, 55.99, 55.95. FT-IR(ATR) 2966-2860, 1778, 1610, 1512, 1463, 1416, 1398, 1280, 1232, 1188, 1153, 1114, 1076, 995, 858, 821, 760 cm-1. Tg= 108 °C. TGA in N2: 30 - 240 °C, 5% mass loss; 241 - 440 °C, 70% mass loss. SEC (THF, PS standards): Mn= 1.3 kDa, Mw= 1.6 kDa, Mp= 1.7 kDa, Đ = 1.2.

[0125] Preparation of poly(bis-arylidene mannose-co-diol carbonate)

[0126] The mannose monomer as prepared according to Scheme 2 was used to prepare example polymers according to the following Scheme 31.

[0127] Scheme 31: Synthesis of poly(methyl 2,3:4,6-bis-O-(4’-hydroxybenzylidene)-α-D- mannopyranoside-co-methyl 4,6-O-laurylidene-D-glucopyranoside) (P(BHBM-co-LMG)).General procedure for the melt-phase synthesis of poly(bis-arylidene mannose diol-co-glucose diol carbonate)s using diphenyl carbonate is provided herein. FIG. 5 shows the1H NMR spectrum of poly(methyl 2,3:4,6-bis-O-(4’-hydroxybenzylidene)-α-D-mannopyranoside-co-methyl 4,6-O- laurylidene-D-glucopyranoside).

[0128] Step 1: Transcarbonylation: The bis(4-hydroxybenzylidene) mannose-based BPAanalog monomer (x equiv.), diol comonomer (1-x equiv.), and diphenyl carbonate (1 equiv.) were charged into a round bottom Schlenk flask. The flask was equipped with a condenser, placed under positive N2flow, and heated in an oil bath at 110 °C. The solid reactants took almost 5 h to melt and form a homogeneous mixture due to the high melting point of the mannose monomer and its poor miscibility with other comonomers. To the homogeneous melt was added lithium acetyl acetonate (1-10 mol%) at which time the condensate byproduct phenol could be observed beginning to crystallize in the condenser. The reaction was allowed to stir an additional 5 h under N2flow (> 1 mL / min) before proceeding to step 2.

[0129] Step 2: Polycondensation: After 5 h of transcarbonylation, the reaction mixture was a viscous liquid. The condenser was replaced with a glass stopper, and the reaction was placed under vacuum for 12-14 h, reaching a stable pressure of ca. 50 millitorr at completion. The reaction mixture was allowed to cool to room temperature and was dissolved in minimal THF. The polymer products were isolated through precipitation into methanol, centrifugation, and removal of residual solvent in vacuo to give a dull white solid with a yield of 58%, based upon 95% monomer conversions.

[0130] P(BHBM20-co-LMG80): Yield: 58%, 1H NMR (400 MHz, CDCl3) δ 7.56 – 7.25 (m, 1H), 7.16 – 6.99 (m, 1H), 5.51 – 4.16 (m, 4H), 4.07 (brs, 1H), 3.83 – 3.05 (m, 7H), 1.69 – 1.39 (m, 2H), 1.18 (d, J = 6.2 Hz, 18H), 0.81 (td, J = 6.9, 2.7 Hz, 3H).13C NMR (126 MHz, CDCl3) δ 153.65, 153.64, 151.55, 151.20, 129.35, 127.72, 120.81, 115.03, 102.90, 98.74, 97.22, 78.57,75.27, 73.78, 68.86, 68.28, 62.33, 60.24, 55.50, 55.19, 34.04, 31.92, 31.90, 29.63, 29.53, 29.36, 29.32, 24.07, 23.92, 22.67, 14.09. FT-IR(ATR) 2922, 2852, 1764, 1615, 1599, 1514, 1465, 1377, 1334, 1274, 1230, 1197, 1126, 1093, 1051, 975, 833, 783, 721, 686 cm-1. Tg= 70 and 130 °C. TGA in N2: 30 - 280 °C, 5% mass loss; 281 - 410 °C, 85% mass loss. SEC (THF, PS standards): Mn= 4.6 kDa, Mw= 5.8 kDa, Mp= 4.7 kDa, Đ = 1.3.

[0131] Preparation of poly(bis-arylidene xylose-co-diol carbonate)s

[0132] The xylose monomer as prepared according to Scheme 5 was used to prepare example copolymers according to the following Scheme 32.

[0133] Scheme 32: Synthesis of poly(1,2:3,5-bis(vanillylidene)-D-(+)-xylose)-co-1,4-butane diol) (P(BVX-co-BD)) at 110 °C and 140 °C.General procedure for the melt-phase synthesis of poly(bis-arylidene xylose-co-aliphatic diol carbonate)s using diphenyl carbonate is provided herein. FIG. 6 contains1H NMR spectra of poly(1,2:3,5-bis(vanillylidene)-D-(+)-xylose)-co-1,4-butane diol) synthesized at 110 °C (a) and 140 °C (b). By increasing the temperature of the polymerization, the molar mass of the obtained polymer increased, as confirmed by SEC analysis. Qualitatively, NMR signals broadened with an increase in the molar mass of the polymer.

[0134] Step 1: Transcarbonylation: The bis(vanillylidene) xylose-based BPA analog monomer (x equiv.), diol comonomer (1-x equiv.), diphenyl carbonate (1 equiv.), and lithium acetyl acetonate (1-10 mol%) were charged into a round bottom Schlenk flask. The flask was equipped with a condenser, placed under positive N2 flow, and heated in an oil bath at 110 °C or 140 °C. The solid reactants melted and formed a homogeneous mixture within ca. 30-40 min, at which time phenol could be observed crystallizing in the condenser. The reaction was allowed to stir an additional 0.5 h under N2 flow (> 1 mL / min) before proceeding to step 2.

[0135] Step 2: Polycondensation: After 0.5-2 h of transcarbonylation, the reaction mixturewas a viscous liquid. The condenser was replaced with a glass stopper, and the reaction was placed under vacuum for 12-14 h, reaching a stable pressure of ca.50 millitorr at completion. The reaction mixture was allowed to cool to room temperature and was dissolved in minimal THF. The polymer products were isolated through precipitation into methanol, centrifugation, and removal of residual solvent in vacuo to give dull white solids with yields of 88-95%, based upon 95% monomer conversions.

[0136] P(BVX20-co-BD80): Yield: 95%,1H NMR (400 MHz, CDCl3) δ 7.38 (t, J = 7.8 Hz, 1H), 7.20 – 6.91 (m, 6H), 6.31 – 5.78 (m, 2H), 5.47 (d, J = 15.5 Hz, 1H), 4.83 – 4.42 (m, 3H), 4.34 – 4.03 (m, 22H), 3.87 (s, 6H), 1.95 – 1.64 (m, 20H), 1.56 (s, 6H13C NMR (126 MHz, CDCl3) δ 155.17, 153.66, 153.06, 151.31, 151.11, 151.09, 140.96, 140.59, 136.40, 135.99, 129.46, 126.01, 122.34, 122.10, 121.01, 118.74, 118.61, 110.36, 105.72, 105.25, 98.72, 78.88, 68.18, 68.07, 67.27, 56.04, 56.02, 30.89, 25.14, 25.10. FT-IR(ATR) 2962, 2920, 1737, 1608, 1512, 1463, 1454, 1402, 1234, 1205, 1163, 1072, 1018, 927, 862, 821, 788 cm-1. Tg= 22 and 82 °C. TGA in N2: 30 - 267 °C, 5% mass loss; 268 - 420 °C, 75% mass loss. SEC (THF, PS standards): Mn= 8.2 kDa, Mw= 18.1 kDa, Mp= 8.1 kDa, Đ = 2.2.

[0137] Preparation of non-phenolic sugar-based polycarbonates

[0138] Example non-phenolic sugar-based polycarbonates were prepared according to the following general schemes (Schemes 33-36). Sugar-based diol monomers as prepared above and commercially obtained dicarbonate comonomers were used as starting materials.

[0139] Preparation of poly(galactose carbonate)s

[0140] The galactopyranoside diol monomers as prepared according to Schemes 13-18 were used to prepare example polymers according to the following general scheme (Scheme 33) and their characterization data are summarized in Table 9. Scheme 33: General synthesis of poly(galactose carbonate)s from galactopyranoside-based diol monomers

[0141] General procedure for the melt-phase synthesis of poly(galactose carbonate)s using diphenyl carbonate is provided herein. FIG. 8 shows the 1H NMR spectra of galactose-based polycarbonates derived from various ketal protected galactopyranoside diol monomers with or without aliphatic diol comonomers. FIG. 9 shows the FT-IR spectra of galactose-based polycarbonates derived from various ketal protected galactopyranoside diol monomers with or without aliphatic diol comonomers.

[0142] Step 1: Transcarbonylation: Ketal protected methyl -^-galactopyranoside diol monomer (1 equiv.), diphenyl carbonate (1 equiv.), and lithium acetyl acetonate (1-10 mol%) were charged into a round bottom Schlenk flask. The flask was equipped with a condenser, placed under positive N2flow, and heated in an oil bath at 110 °C. The solid reactants melted and formed a homogeneous solution within ca.15 min, at which time phenol could be observed crystallizing in the condenser. The reaction was allowed to stir an additional 2-3 h under N2flow (> 1 mL / min) before proceeding to step 2.

[0143] Step 2: Polycondensation: After 2-3 h of transcarbonylation, the reaction mixture was a viscous liquid. The condenser was replaced with a glass stopper, N2flow was stopped, and the reaction was placed under vacuum for 12-14 h, reaching a stable pressure of ca. 50 millitorr at completion. The reaction mixture was allowed to cool to room temperature and was dissolved in minimal THF. The polymer products were isolated through precipitation into methanol, centrifugation, and removal of residual solvent in vacuo to give dull white solids with yields of 35-95%, based upon quantitative monomer conversions.

[0144] PIPGa: Yield: 85%, 1H NMR (400 MHz, CDCl3) δ 4.89 (dd, J = 7.6, 3.5 Hz, 1H), 4.80 (m, 1H), 4.39 (m, 3H), 4.23 (s, 2H), 3.39 (m, 3H), 1.60 – 1.49 (m, 3H), 1.33 (d, J = 2.9 Hz, 3H).13C NMR (126 MHz, CDCl3) δ 154.88, 154.63, 154.31, 129.49, 129.45, 120.91, 110.16, 110.09, 97.03, 96.98, 75.30, 73.46, 73.35, 67.26, 67.04, 65.55, 65.49, 65.43, 55.69, 55.66, 55.63, 27.86,27.78, 26.38FT-IR(ATR) 3036 – 2829, 1749, 1446,1374, 1331, 1240, 1071, 1043, 994, 866, 781 cm-1. Tg= 134 °C. TGA in N2: 30 - 302 °C, 5% mass loss; 303 - 405 °C, 90% mass loss. SEC (THF, PS standards): Mn= 7.3 kDa, Mw= 10.8 kDa, Mp= 10.0 kDa, Đ = 1.5.

[0145] PCHGa: Yield: 71%,1H NMR (400 MHz, CDCl3) δ 4.88 (m, 1H), 4.78 (m, 1H), 4.59 – 4.30 (m, 3H), 4.30 – 4.14 (m, 2H), 3.40 (m, 3H), 1.89 – 1.09 (m, 10H).13C NMR (126 MHz, CDCl3) δ 154.95, 154.70, 154.35, 129.49, 120.90, 110.73, 97.06, 75.83, 73.00, 67.36, 67.12, 65.61, 55.74, 37.74, 35.49, 24.88, 23.91, 23.66. FT-IR(ATR) 3006 – 2803, 1749, 1446, 1373, 1334, 1242, 1096, 1042, 925, 843, 784 cm-1.. Tg= 136 °C. TGA in N2: 30 - 300 °C, 5% mass loss; 301 - 405 °C, 90% mass loss. SEC (THF, PS standards): Mn= 4.1 kDa, Mw= 6.1 kDa, Mp= 4.9 kDa, Đ = 1.5.

[0146] PHGa: Yield: 38%,1H NMR (400 MHz, CDCl3) δ 4.93 – 4.73 (m, 2H), 4.65 – 3.70 (m, 5H), 3.64 – 3.26 (m, 3H), 1.80 – 1.51 (m, 2H), 1.48 – 1.14 (m, 9H), 0.89 (m, 3H).13C NMR (126 MHz, CDCl3) δ 154.92, 154.67, 154.59, 154.23, 112.02, 111.84, 111.76, 96.96, 75.44, 73.52, 73.46, 73.36, 73.31, 73.03, 72.96, 67.31, 67.08, 65.56, 55.64, 31.93, 31.88, 31.85, 24.07, 22.49, 22.46, 13.94, 0.98. FT-IR(ATR) 3024 – 2792, 1749, 1452, 1377, 1332, 1242, 1153, 1071, 1043, 997, 884, 787 cm-1. Tg= 85 °C. TGA in N2: 30 - 285 °C, 5% mass loss; 286 - 407 °C, 90% mass loss. SEC (THF, PS standards): Mn= 6.8 kDa, Mw= 8.3 kDa, Mp= 6.8 kDa, Đ = 1.2.

[0147] PUDGa: Yield: 85%,1H NMR (400 MHz, CDCl3) δ 5.27 – 4.68 (m, 2H), 4.65 – 3.60 (m, 5H), 3.52 – 3.13 (m, 3H), 1.85 – 1.03 (m, 19H), 0.87 (t, J = 6.7 Hz, 3H).13C NMR (126 MHz, CDCl3) δ 154.93, 154.68, 154.58, 154.22, 153.44, 151.09, 129.46, 129.40, 120.90, 120.85, 112.01, 111.83, 111.75, 96.97, 75.44, 73.52, 73.03, 72.96, 67.33, 67.09, 65.56, 62.24, 61.95, 55.66, 55.50, 31.84, 29.79, 29.52, 29.49, 29.29, 29.26, 22.63, 14.06. FT-IR(ATR) 3029 – 2781, 1749, 1455, 1377, 1334, 1242, 1075, 1041, 1003, 889, 784 cm-1. Tg= 56 °C. TGA in N2: 30 - 275 °C, 5% mass loss; 276 - 406 °C, 90% mass loss. SEC (THF, PS standards): Mn= 4.8 kDa, Mw= 6.7 kDa, Mp= 5.9 kDa, Đ = 1.4.

[0148] PPDGa: Yield = 90%,1H NMR (400 MHz, CDCl3) δ 5.27 – 4.68 (m, 2H), 4.65 – 3.60 (m, 5H), 3.52 – 3.13 (m, 3H), 1.85 – 1.03 (m, 27H), 0.87 (t, J = 6.7 Hz, 3H).13C NMR (126 MHz, CDCl3) δ 154.94, 154.69, 154.59, 154.23, 153.45, 151.09, 129.46, 120.91, 112.01, 111.82, 96.98, 75.48, 73.53, 73.01, 67.32, 65.56, 62.24, 61.96, 55.67, 31.90, 29.82, 29.69, 29.67, 29.63, 29.56, 29.34, 22.66, 14.08. FT-IR(ATR) 3024 – 2785, 1751, 1455, 1111, 1051, 1002, 897, 786, 514 cm-1. Tg= 42 °C. TGA in N2: 30 - 277 °C, 5% mass loss; 278 - 401 °C, 90% mass loss. SEC (THF,PS standards): Mn= 7.8 kDa, Mw= 13.0 kDa, Mp= 12.1 kDa, Đ = 1.7.

[0149] PCKGa: Yield: 67%, 1H NMR (400 MHz, CDCl3) δ 5.32 – 3.68 (m, 7H), 3.54 – 3.17 (m, 3H), 2.34 – 1.06 (m, 7H), 1.01 – 0.58 (m, 9H). 13C NMR (126 MHz, CDCl3) δ 154.95, 153.49, 151.12, 129.50, 126.11, 120.94, 120.89, 118.41, 118.03, 115.29, 96.97, 74.17, 72.98, 72.52, 70.48, 67.16, 65.45, 55.68, 53.55, 51.58, 51.51, 48.14, 47.96, 47.80, 45.18, 45.01, 29.40, 28.34, 27.00, 26.78, 20.38, 20.27, 20.18, 20.10, 9.55, 9.42. FT-IR(ATR) 2924, 1751, 1458, 1375, 1332, 1245, 1160, 1074, 1044, 1002, 887, 787, 732 cm-1. Tg = 160 °C. TGA in N2: 30 - 281 °C, 5% mass loss; 282 - 410 °C, 90% mass loss. SEC (THF, PS standards): Mn = 4.7 kDa, Mw = 7.2 kDa, Mp = 4.9 kDa, Đ = 1.7.

[0150] Preparation of poly(galactose diol-co-aliphatic diol carbonate)s

[0151] The galactopyranoside diol monomers as prepared according to Schemes 15 and 18 were used to prepare copolymers according to the following general scheme (Scheme 34) and their characterization data are summarized in Table 10.

[0152] Scheme 34: General synthesis of poly(galactose diol-co-aliphatic diol carbonate)s from galactopyranoside diol and aliphatic diol comonomersGeneral procedure for the melt-phase synthesis of poly(galactose diol-co-aliphatic diol carbonate)s using diphenyl carbonate is provided herein.

[0153] Step 1: Transcarbonylation: Ketal protected methyl -^-galactopyranoside diol monomer (x equiv.), aliphatic diol comonomer (1-x equiv.), diphenyl carbonate (1 equiv.), and lithium acetyl acetonate (1-10 mol%) were charged into a round bottom Schlenk flask. The flask was equipped with a condenser, placed under positive N2flow, and heated in an oil bath at 110 °C. The solid reactants melted and formed a homogeneous solution within ca. 15 min, at which time phenol could be observed crystallizing in the condenser. The reaction was allowed to stir an additional 2-3 h under N2flow (> 1 mL / min) before proceeding to step 2.

[0154] Step 2: Polycondensation: After 2-3 h of transcarbonylation, the reaction mixture was a viscous liquid. The condenser was replaced with a glass stopper, N2flow was stopped, and the reaction was placed under vacuum for 12-14 h, reaching a stable pressure of ca. 50 millitorr at completion. The reaction mixture was allowed to cool to room temperature and was dissolved in minimal THF. The polymer products were isolated through precipitation into methanol, centrifugation, and removal of residual solvent in vacuo to give dull white solids with yields of 35-95%, based upon quantitative monomer conversions.

[0155] P(HGa19-co-BD81): Yield: 69%,1H NMR (400 MHz, CDCl3) δ 4.88 (m, 1H), 4.82 – 4.68 (m, 1H), 4.45 – 4.29 (m, 2H), 4.16 (m, 19H), 3.51 – 3.35 (m, 3H), 1.77 (m, 18H), 1.65-1.50 (m, 2H), 1.50 – 1.19 (m, 8H), 0.88 (td, J = 7.0, 3.1 Hz, 3H).13C NMR (126 MHz, CDCl3) δ 155.23, 155.17, 155.08, 155.04, 154.71, 154.63, 112.04, 112.00, 111.86, 111.45, 97.88, 97.69, 96.97, 96.93, 75.08, 73.45, 73.33, 73.03, 72.94, 72.28, 68.69, 67.77, 67.70, 67.66, 67.53, 67.44, 67.26, 67.07, 66.80, 65.61, 62.26, 55.64, 55.41, 55.37, 54.70, 40.87, 39.65, 39.22, 31.97, 31.94, 31.87, 28.90, 25.51, 25.14, 25.05, 24.09, 24.02, 23.78, 23.30, 22.61, 22.54, 22.51, 22.48, 20.90, 13.98, 13.95. FT-IR(ATR) 2954, 1735, 1458, 1404, 1234, 1026, 925, 787, 466 cm-1. Tg= -10 °C. TGA in N2: 30 - 200 °C, 5% mass loss; 201 - 360 °C, 90% mass loss. SEC (THF, PS standards): M= 6.7 kDa, Mw= 8.8 kDa, Mp= 7.5 kDa, Đ = 1.3.

[0156] P(CKGa19-co-BD81): Yield: 94%,1H NMR (400 MHz, CDCl3) δ 4.86 (dd, J = 6.5, 3.5 Hz, 1H), 4.79 – 4.56 (m, 0H), 4.49 – 4.27 (m, 2H), 4.17 (q, J = 7.8 Hz, 21H), 3.38 (t, J = 2.9 Hz, 3H), 1.77 (h, J = 3.1 Hz, 19H), 1.64 – 1.07 (m, 4H), 0.99 – 0.67 (m, 9H).13C NMR (126 MHz, CDCl3) δ 155.14, 155.00, 154.70, 154.62, 153.62, 151.08, 129.43, 125.98, 120.98, 120.90, 118.52, 118.37, 118.00, 97.03, 96.96, 96.76, 74.14, 73.86, 72.93, 72.50, 72.31, 70.55, 68.03, 67.92, 67.70, 67.60, 67.49, 67.23, 67.19, 66.63, 65.53, 65.38, 55.62, 55.56, 53.51, 51.54, 51.49, 48.12, 47.92, 47.75, 45.14, 44.97, 29.35, 28.32, 26.98, 26.69, 25.57, 25.11, 25.05, 20.41, 20.35, 20.27, 20.22, 20.13, 20.08, 11.38, 10.27, 9.52, 9.37. FT-IR(ATR) 3044 – 2797, 1743, 1458, 1404, 1234, 1111, 1033, 979, 933, 786, 532 cm-1. Tg= 23 °C. TGA in N2: 30 - 253 °C, 5% mass loss; 254 - 365 °C, 90% mass loss. SEC (THF, PS standards): Mn= 21.8 kDa, Mw= 73.6 kDa, Mp= 24.3 kDa, Đ = 3.4.

[0157] Preparation of poly(fructose carbonate)s

[0158] The fructofuranoside diol monomers as prepared according to Schemes 20-24 were used to prepare example polymers according to the following general scheme (Scheme 35) andtheir characterization data are summarized in Table 11.

[0159] Scheme 35: General synthesis of poly(fructose carbonate)s from fructofuranoside diol monomersGeneral procedure for the melt-phase synthesis of poly(fructose carbonate)s using diphenyl carbonate is provided herein.

[0160] Step 1: Transcarbonylation: Ketal protected methyl fructofuranoside diol monomer (1 equiv.), diphenyl carbonate (1 equiv.), and lithium acetyl acetonate (1-10 mol%) were charged into a round bottom Schlenk flask. The flask was equipped with a condenser, placed under positive N2 flow, and heated in an oil bath at 110 °C. The solid reactants melted and formed a homogeneous solution within ca.15 min, at which time phenol could be observed crystallizing in the condenser. The reaction was allowed to stir an additional 2-3 h under N2 flow (> 1 mL / min) before proceeding to step 2.

[0161] Step 2: Polycondensation: After 2-3 h of transcarbonylation, the reaction mixture was a viscous liquid. The condenser was replaced with a glass stopper, N2flow was stopped, and the reaction was placed under vacuum for 12-14 h, reaching a stable pressure of ca. 50 millitorr at completion. The reaction mixture was allowed to cool to room temperature and was dissolved in minimal THF. The polymer products were isolated through precipitation into methanol, centrifugation, and removal of residual solvent in vacuo to give dull white solids with yields of 50-90%, based upon 95% monomer conversions.

[0162] PIPF: Yield: 76%, 1H NMR (400 MHz, CDCl3) δ 4.81 – 4.70 (m, 1H), 4.54 – 4.23 (m, 3H), 4.17 (q, J = 3.4 Hz, 1H), 3.99 – 3.84 (m, 2H), 3.38 – 3.23 (m, 3H), 1.41 (d, J = 20.1 Hz, 6H).13C NMR (126 MHz, CDCl3) δ 154.67, 154.64, 154.25, 154.22, 154.18, 153.72, 153.51, 151.14, 129.42, 129.39, 121.05, 102.25, 99.19, 99.11, 82.68, 82.32, 82.26, 80.67, 80.65, 78.68, 78.59, 78.44, 67.79, 62.05, 48.68, 48.64, 48.61, 27.07, 20.08, 19.94. FT-IR(ATR) 3026 – 2816, 1749, 1454, 1375, 1244, 1167, 1078, 1010, 855, 777 cm-1. = 115 °C. TGA in N2: 30 - 306 °C, 5%mass loss; 307 - 450 °C, 90% mass loss. SEC (THF, PS standards): Mn= 6.1 kDa, Mw= 8.1 kDa, Mp= 6.8 kDa, Đ = 1.3.

[0163] PHF: Yield: 74%,1H NMR (400 MHz, CDCl3) δ 4.81 – 3.65 (m, 7H), 3.45 – 3.06 (m, 3H), 1.57 (m, 11H), 0.89 (m, 3H).13C NMR (126 MHz, CDCl3) δ 154.24, 153.74, 129.41, 121.03, 101.09, 100.38, 82.51, 80.60, 78.37, 68.13, 62.00, 61.78, 48.65, 31.99, 31.95, 30.88, 22.54, 14.00, 13.97. FT-IR(ATR) 3032 – 2789, 1749, 1454, 1377, 1242, 1070, 998, 881, 779 cm-1. Tg= 76 °C. TGA in N2: 30 - 283 °C, 5% mass loss; 284 - 393 °C, 90% mass loss. SEC (THF, PS standards): Mn= 10.3 kDa, Mw= 17.5 kDa, Mp= 12.0 kDa, Đ = 1.7.

[0164] PUDF: Yield: 65%,1H NMR (400 MHz, CDCl3) δ 4.93 – 4.61 (m, 1H), 4.57 – 4.07 (m, 4H), 4.03 – 3.75 (m, 2H), 3.36 – 3.23 (m, 3H), 1.85 – 1.04 (m, 19H), 0.87 (t, J = 6.5 Hz, 3H).13C NMR (126 MHz, CDCl3) δ 154.60, 154.20, 153.70, 153.47, 129.45, 129.38, 129.35, 121.04, 102.00, 101.82, 101.02, 100.94, 100.38, 100.34, 82.81, 82.44, 80.57, 78.35, 78.19, 68.14, 67.86, 61.96, 61.76, 48.66, 48.62, 31.85, 31.82, 29.76, 29.52, 29.49, 29.27, 29.25, 22.62, 14.05. FT- IR(ATR) 3044 – 2789, 1749, 1453, 1373, 1242, 1111, 1072, 993, 906, 782, 728, 643 cm-1. Tg= 53 °C. TGA in N2: 30 - 290 °C, 5% mass loss; 291 - 438 °C, 90% mass loss. SEC (THF, PS standards): Mn= 5.1 kDa, Mw= 7.1 kDa, Mp= 6.5 kDa, Đ = 1.4.

[0165] PPDF: Yield:73%,1H NMR (400 MHz, CDCl3) δ 4.93 – 4.03 (m, 5H), 3.96 – 3.85 (m, 2H), 3.46 – 3.12 (m, 3H), 1.86 – 1.10 (m, 27H), 0.88 (t, J = 6.6 Hz, 3H).13C NMR (126 MHz, CDCl3) δ 154.22, 153.72, 129.47, 129.40, 129.37, 121.07, 102.02, 101.04, 100.96, 100.40, 82.86, 82.46, 80.65, 78.38, 78.21, 68.17, 67.89, 61.98, 61.78, 48.69, 48.64, 31.84, 29.77, 29.54, 29.52, 29.29, 29.27, 22.64, 14.07. FT-IR(ATR) 3021 – 2788, 1749, 1457, 1377, 1242, 1113, 1072, 993, 785, 721 cm-1. Tg= 36 °C. TGA in N2: 30 - 285 °C, 5% mass loss; 286 - 490 °C, 90% mass loss. SEC (THF, PS standards): Mn= 5.1 kDa, Mw= 8.1 kDa, Mp= 6.6 kDa, Đ = 1.6.

[0166] PCKF: Yield: 76%,1H NMR (400 MHz, CDCl3) δ 4.95 – 3.66 (m, 7H), 3.44 – 3.10 (m, 3H), 1.99 (dq, J = 42.6, 13.0 Hz, 2H), 1.74 (d, J = 34.8 Hz, 2H), 1.49 – 1.02 (m, 2H), 1.01 – 0.76 (m, 7H).13C NMR (126 MHz, CDCl3) δ 154.29, 153.71, 153.49, 151.25, 129.51, 129.44, 129.41, 121.09, 107.69, 107.61, 100.95, 82.86, 81.22, 79.30, 68.17, 63.33, 60.71, 53.57, 53.47, 48.83, 48.77, 48.68, 48.10, 47.90, 45.16, 45.09, 28.75, 27.11, 26.91, 20.79, 20.70, 20.62, 20.54, 10.06, 9.86. FT-IR(ATR) 3044 – 2801, 1749, 1448, 1383, 1240, 1117, 1068, 988, 897, 842, 782, 647 cm-1. Tg= 140 °C. TGA in N2: 30 - 331 °C, 5% mass loss; 332 - 430 °C, 90% mass loss. SEC (THF, PS standards): Mn= 3.2 kDa, Mw= 5.1 kDa, Mp= 3.2 kDa, Đ = 1.6.

[0167] Preparation of poly(fructose diol-co-aliphatic diol carbonate)s

[0168] The fructofuranoside diol monomer as prepared according to Scheme 24 was used to prepare an example copolymer according to the following scheme (Scheme 36) and its characterization data are summarized in Table 12.

[0169] Scheme 36: Synthesis of example poly(fructose diol-co-aliphatic diol carbonate)s from fructofuranoside diol monomer and 1,4-butane diol comonomerGeneral procedure for the melt-phase synthesis of poly(fructose diol-co-aliphatic diol carbonate)s using diphenyl carbonate is provided herein.

[0170] Step 1: Transcarbonylation: Ketal protected methyl -^-fructofuranoside diol monomer (x equiv.), aliphatic diol comonomer (1-x equiv.), diphenyl carbonate (1 equiv.), and lithium acetyl acetonate (1-10 mol%) were charged into a round bottom Schlenk flask. The flask was equipped with a condenser, placed under positive N2flow, and heated in an oil bath at 110 °C. The solid reactants melted and formed a homogeneous solution within ca. 15 min, at which time phenol could be observed crystallizing in the condenser. The reaction was allowed to stir an additional 2-3 h under N2flow (> 1 mL / min) before proceeding to step 2.

[0171] Step 2: Polycondensation: After 2-3 h of transcarbonylation, the reaction mixture was a viscous liquid. The condenser was replaced with a glass stopper, N2flow was stopped, and the reaction was placed under vacuum for 3-4 h, reaching a stable pressure of ca. 50 millitorr at completion. The reaction mixture was allowed to cool to room temperature and was dissolved in minimal THF. The polymer products were isolated through precipitation into methanol, centrifugation, and removal of residual solvent in vacuo to give dull white solids with yields of 84%, based upon quantitative monomer conversions.

[0172] P(CKF20-co-BD80): Yield: 84%, 1H NMR (500 MHz, CDCl3) δ 7.37 (t, J = 7.9 Hz, 0.66H), 7.23 (t, J = 7.4 Hz, 0.37H), 7.16 (d, J = 8.2 Hz, 0.61H), 4.82 – 4.57 (m, 1H), 4.44 (td, J = 11.8, 3.8 Hz, 1H), 4.38 – 4.23 (m, 3H), 4.22 – 4.03 (m, 18H), 4.02 – 3.92 (m, 1H), 3.84 (dd, J = 12.2, 6.2 Hz, 1H), 3.77 – 3.68 (m, 1H), 3.27 (t, J = 2.6 Hz, 3H), 2.11 – 1.81 (m, 4H), 1.76 (dq, J = 6.3, 3.3 Hz, 16H), 1.70 – 1.58 (m, 2H), 1.45 (dd, J = 12.8, 3.8 Hz, 1H), 1.27 (qd, J = 12.0, 4.9 Hz, 1H), 1.18 – 1.05 (m, 1H), 1.05 – 0.88 (m, 4H), 0.84 (t, J = 4.4 Hz, 5H). 13C NMR (126 MHz, CDCl3) δ 155.14, 154.94, 154.91, 154.40, 153.62, 151.09, 129.43, 129.42, 125.97, 120.98, 107.58, 107.51, 100.86, 100.83, 82.56, 82.44, 81.53, 81.31, 79.29, 68.03, 67.92, 67.83, 67.78, 67.67, 67.57, 67.42, 67.37, 67.23, 67.17, 63.33, 60.77, 53.53, 53.42, 48.77, 48.70, 48.65, 48.05, 47.85, 45.12, 45.05, 36.81, 36.56, 28.75, 28.70, 27.07, 26.89, 25.57, 25.11, 25.07, 25.03, 20.70, 20.65, 20.58, 20.51, 9.95, 9.78. FT-IR(ATR) 3033-2811, 1738, 1467, 1454, 1404, 1321, 1232, 1125, 1104, 1071, 1054, 1026, 931, 790 cm-1. Tg = 15 °C. TGA in N2: 30 - 283 °C, 5% mass loss; 284 - 371 °C, 90% mass loss. SEC (THF, PS standards): Mn= 4.4 kDa, M= 8.4 kDa, Mp= 7.0 kDa, Đ = 1.9.

[0173] Preparation of bisphenol A analog polyesters

[0174] The mannose-based bisphenol A analog monomer as prepared according to Scheme 2 was used to prepare an example bisphenolic sugar-based polyester according to the following scheme (Scheme 37) and characterization data are summarized in Table 13. A commercially obtained sebacoyl chloride comonomer was used.

[0175] Scheme 37: Synthesis of poly(bis-arylidene mannose ester) from mannose-based bisphenol A analog monomer and sebacoyl chloride

[0176] To a solution of NaOH (100 mg, 2.5 mmol) in 7.5 mL of water was added methyl 2,3:4,6-bis-O-(4’-hydroxybenzylidene)-α-D-mannopyranoside (501 mg, 1.25 mmol) followed by the addition of tetrabutylammonium bromide (25 mg, phase transfer catalyst) to obtain a clear solution. To the resulting reaction mixture was added sebacoyl chloride (300 mg, 1.25 mmol) in 3.5 mL of chloroform and the mixture was stirred at room temperature for 2 h. After completion, the reaction mixture was transferred to a separation funnel and extracted with chloroform (2 × 25 mL). The combined organic layers were washed with water, dried over anhydrous Na2SO4, filtered,and residual solvent was removed in vacuo. The residue was dissolved in 5 mL of chloroform and precipitated into 60 mL of methanol. The precipitate was recovered by centrifugation to give the polyester as a white solid (0.51 g, 84% yield).1H NMR (500 MHz, CDCl3) δ 7.49 – 7.36 (m, 4H), 7.06 - 6.98 (m, 4H), 6.20 (s, 0.60H), 5.88 (s, 0.40H), 5.52 (d, J = 17.0 Hz, 0.60H), 5.43 (s, 0.40H), 4.99 (s, 0.40H), 4.92 (s, 0.60H), 4.51 (dd, J = 7.9, 5.4 Hz, 0.60H), 4.40 – 4.33 (m, 0.40H), 4.30 – 4.17 (m, 1H), 4.08 – 4.00 (m, 1H), 3.83 – 3.54 (m, 3H), 3.34 (s, 1H), 3.31 (s, 2H), 2.54 – 2.42 (m, 4H), 1.67 (p, J = 7.4 Hz, 4H), 1.39 – 1.22 (m, 8H).13C NMR (126 MHz, CDCl3) δ 171.98, 171.89, 171.44, 169.50, 155.43, 151.45, 151.25, 151.18, 136.11, 134.72, 134.62, 133.89, 131.12, 127.60, 127.46, 127.43, 127.33, 127.17, 122.29, 121.56, 121.47, 121.37, 121.29, 121.24, 103.43, 102.40, 101.34, 101.11, 98.72, 98.61, 80.40, 78.27, 77.50, 75.47, 75.21, 74.09, 68.81, 68.74, 60.26, 60.21, 55.15, 55.07, 34.28, 28.98, 28.95, 28.90, 24.78, 24.69. FT-IR(ATR) 2924, 2854, 1751, 1604, 1519, 1381, 1195, 1080, 1010, 918, 833, 732, 656 cm-1. Tg= 78 °C. TGA in N2: 30 - 310 °C, 5% mass loss; 311 - 480 °C, 70% mass loss. SEC (THF, PS standards): Mn= 6.8 kDa, Mw= 13.3 kDa, Mp= 9.9 kDa, Đ = 2.0.

[0177] Preparation of bisphenol A analog polyurethanes

[0178] The mannose-based bisphenol A analog monomer as prepared according to Scheme 2 and the galactose-based diol monomer as prepared according to Scheme 17 were used to prepare an example bisphenolic sugar-based polyurethane according to the following scheme (Scheme 38) and characterization data are summarized in Table 13. A commercially obtained hexamethylene diisocyanate comonomer was used.

[0179] Scheme 38: Synthesis of poly(bis-arylidene mannose-co-galactose diol urethane) from mannose-based bisphenol A analog monomer, galactose-based diol, and hexamethylene diisocyanate

[0180] To a solution of methyl 2,3:4,6-bis(4-hydroxybenzylidene)-α-D-mannopyranoside (807 mg, 2.00 mmol) in THF (25 mL) was added methyl pentadecylidene-α-D-galactopyranoside (808 mg, 2.00 mmol), followed by the addition of hexamethylene diisocyanate (706 mg, 0.68 mL, 4.20 mmol). Dibutyltin dilaurate (DBTDL) (25 mg, 0.04 mmol) in 1 mL of THF was then added as a catalyst. The resulting reaction mixture was stirred under reflux at 70 °C for 7 h under a nitrogen atmosphere. After polymerization was complete, the solvent was removed under reduced pressure using a rotary evaporator. The residue was dissolved in 10 mL of THF and precipitated into 120 mL of diethyl ether at room temperature. The precipitate was collected by centrifugation and residual solvent was removed in vacuo to yield the polyurethane product as a colorless solid (1.81 g, 80% yield).1H NMR (500 MHz, DMSO) δ 8.01 – 6.95 (m, 10H), 6.87 – 6.70 (m, 1H), 6.34 – 5.51 (m, 2H), 5.15 – 4.47 (m, 3H), 4.42 – 3.47 (m, 9H), 3.45 – 3.19 (m, 8H), 3.43 - 3.21 (m, , 9H), 1.69 – 1.31 (m, 14H), 1.22 (d, J = 10.8 Hz, 29H), 1.09 (t, J = 7.0 Hz, 4H), 0.85 (t, J = 6.7 Hz, 3H).13C NMR (126 MHz, DMSO) δ 158.47, 158.19, 158.07, 157.82, 155.94, 155.51, 155.44, 154.08, 151.98, 151.73, 151.49, 151.46, 135.17, 134.07, 133.24, 130.91, 128.98, 128.41, 128.25, 127.87, 127.83, 127.54, 127.37, 127.20, 126.97, 121.67, 121.53, 121.26, 115.04, 114.92, 114.65, 114.61, 110.56, 110.40, 102.87, 102.35, 101.73, 101.17, 100.44, 100.32, 99.59, 98.79, 98.13, 98.00, 97.85, 97.07, 79.97, 77.66, 75.96, 75.88, 75.80, 75.11, 75.00, 73.44, 73.21, 73.00, 72.75, 72.65, 71.13, 67.87, 66.98, 65.57, 64.88, 62.99, 60.11, 60.06, 60.01, 59.69, 54.68, 54.56, 54.52, 54.48, 31.29, 30.03, 29.99, 29.29, 29.22, 29.13, 29.07, 29.03, 28.96, 28.92, 28.70, 26.12, 26.07, 25.99, 25.91, 25.09, 23.99, 23.84, 22.06, 15.10, 15.07, 13.86. FT-IR(ATR) 3479-3147, 2924, 2854, 1713, 1504, 1465, 1373, 1211, 1080, 840, 640 cm-1. Tg= 83 °C. TGA in N2: 30 - 120 °C, 5% mass loss; 121 - 360 °C, 60% mass loss; 361 – 470 °C, 20% mass loss; SEC (THF, PS standards): Mn= 3.8 kDa,Mw= 8.2 kDa, Mp= 7.3 kDa, Đ = 2.2.

[0181] Determination of polymer properties

[0182] The polymers prepared according to the preceding schemes were tested to determine physical properties according to the methods below. For molar mass determination, polymer samples (recovered from precipitation) were dissolved in THF (containing a 1% toluene flow marker) at a concentration of ~7 mg / mL, filtered through a 0.2 μm PTFE filter, and subjected to size exclusion chromatography (SEC) to determine the number-average molar mass (Mn), weight- average molar mass (Mw), peak-average molar mass (Mp) and dispersity (Đ). For thermal degradation, 5% mass loss (T5d) was measured by thermogravimetric analysis (TGA). Glass transition temperatures (Tg) were measured by differential scanning calorimetry (DSC). All samples were characterized directly as obtained from precipitation.

[0183] Embodiments of the BPA analog polymers exhibit Mwvalues ranging from about 1 kilodaltons (kDa) to 20 kDa with the Polydispersity Index (PDI) ranging from about 1.2 and 2.2. The polymers are thermally stable up to temperatures of at least 240 °C and as high as 310 °C with Tgvalues ranging from 20 °C to 150 °C. Embodiments of these polymers are thermally stable with less than 5% mass loss up to temperatures of at least 240 °C and as high as 310 °C. Traditional BPA polycarbonates have Tgvalues of ca ranging from about 140 °C to 150 °C. Embodiments of the galactose and fructose based polymers described herein exhibit Mwvalues ranging from 5 kDa to 75 kDa with the PDI between 1.2 and 3.4. Embodiments of these polymers are thermally stable up to temperatures of at least 200 °C and as high as 330 °C with Tgvalues ranging from -10 °C to 160 °C. Embodiments of these polymers are thermally stable with less than 5% mass loss up to temperatures of at least 200 °C and as high as 330 °C.

[0184] Tgis an important parameter in polymer processing, as a 15-25 °C difference can have a significant impact on the molding process. The temperature at which a polymer undergoes a glass transition also impacts their useful applications – at room temperature or under reduced or elevated temperatures – as a polymer is more flexible below the Tgand more rigid above the Tg. For instance, silicone polymers have values that are typically -50 to -150 C, whereas polystyrene exhibits a Tgat ca. 100 C and BPA polycarbonates are typically glassy and rigid until a Tgof ca. 140 C.

[0185] Table 8. Summary of characterization data for bisphenol A analog polycarbonates.SEC Data Thermal DataPBHBX 60 2.5 4.3 2.4 1.7 252 146 PBVX 20 1.3 1.6 1.7 1.2 240 108 P(BHBM20-co-LMG80) 58 4.6 5.8 4.7 1.3 280 70, 136 P(BVX20-co-BD80) 88 2.5 3.5 2.9 1.4 270 22, 82 P(BVX20-co-BD80) 95 8.2 18.1 8.1 2.2 270 22, 82

[0186] Table 9. Summary of characterization data for poly(galactose carbonate)s. SEC Data Thermal Data(PIPGa) = Poly(isopropylidene galactose carbonate); (PCHGa) = Poly(cyclohexylidene galactose carbonate); (PHGa) = Poly(hepytlidene galactose carbonate); PUDGa = Poly(undecylidene galactose carbonate); PPDGa = Poly(pentadecylidene galactose carbonate); PCKGa = Poly(camphor ketylidene galactose carbonate).

[0187] Table 10: Summary of characterization data for poly(galactose diol-co-aliphatic diol carbonate)s.PolymerP(HGa19-co-BD81) 69 6.7 8.8 7.5 1.3 200 -10 P(CKGa19-co-BD81) 94 21.8 73.6 24.3 3.4 253 23 P(HGa-co-BD) = Poly(cyclohexylidene galactose-co-butane diol carbonate); P(CKGa-co-BD) = Poly(camphor ketylidene galactose-co-butane diol carbonate).

[0188] Table 11: Summary of characterization data for poly(fructose carbonate)s. SEC Data Thermal Data R1 and R2 of ketal PolymerPIPF 76 6.1 8.1 6.8 1.3 306 115 PHF 74 10.3 17.5 12.0 1.7 283 76 PUDF 65 5.1 7.1 6.5 1.4 290 44 PPDF 73 5.1 8.1 6.6 1.6 285 36 PCKF 76 3.2 5.1 4.2 1.6 331 140 PIPF = Poly(isopropylidene fructose carbonate); PHF = Poly(hexylidene fructose carbonate); PUDF = Poly(undecylidene fructose carbonate); PPDF = Poly(pentadecylidene fructose carbonate); PCKF = Poly(camphor ketylidene fructose carbonate).

[0189] Table 12: Summary of characterization data for poly(fructose diol-co-aliphatic diol carbonate). SEC Data Thermal Data PolymerYieldMn Mw Mp (%) (kDa) (kDa) (kDa) Ð ° Tg(°C) P(CKF20-co-BD80) 84 4.4 8.4 7.0 1.9 283 15 P(CKF-co-BD) = Poly(camphor ketylidene fructose-co-butane diol carbonate).

[0190] Table 13: Summary of characterization data for sugar-based polyester and polyurethane examples.P(BHBM-co-SC) = Poly(hydroxybenzylidene mannose-co-sebacoyl chloride ester); P(BHBM-co- PDGa-co-HDI) = Poly(hydroxybenzylidene mannose-co-pentadecylidene galactose-co- hexamethylene diisocyanate urethane).

[0191] The disclosure herein provides one or more embodiments of sugar-based monomers, methods for preparing these monomers for the synthesis of BPA analogs, and use of two or more of these BPA analogs to manufacture corresponding polymers. Embodiments include BPA analogs that are synthesized by preserving and leveraging the regio- and stereochemical diversity of the sugars and requiring one or a few synthetic steps.

[0192] Embodiments also include methods of manufacture of polycarbonates from the foregoing BPA analog monomers. One such method includes subjecting one or more of a mannopyranoside-, or a xylose-derived bisphenolic monomer to a melt condensation in the presence of a carbonylation agent. One such method of manufacture includes a melt polycondensation process with a diphenyl carbonate (DPC) as a carbonylation agent. Certain embodiments can include the use of phosgene or other common phosgene analogs (e.g., 1,1- carbonyldiimidazole, bis(pentafluorophenyl) carbonate, bis(4-nitrophenyl) carbonate, or dimethyl carbonate as a carbonylation agent.

[0193] In certain embodiments, an aliphatic diol is mixed with the one or more of a mannopyranoside-, or a xylose-derived bisphenolic monomer during the polymerization. In certain embodiments, the aliphatic diol is 1,4-butane diol or 1,3-propane diol or other common diol monomers (e.g., ethylene glycol, 1,5-pentanediol, or cyclohexanedimethanol). Embodiments can also include use of glucose and mannose and other sugars for preparation of similar diols that may have less ideal regio- and stereochemical relationships as compared to galactose and fructose. In certain embodiments, BPA analogs were also copolymerized with other sugar-derived aliphatic diols (such as illustrated in FIG. 7, including methyl 4,6-O-benzylidene-D-glucopyranoside,methyl 4,6-O-cinnamylidene-D-glucopyranoside, methyl 4,6-O-laurylidene-D-glucopyranoside, or other glucose-based diol monomers; analogous galactose- or fructose-based diol monomers; or regiochemically- and stereochemically-diverse galactose- or fructose-based diol monomers), resulting in corresponding copolymers with different physicochemical properties. Also disclosed herein is use of the BPA analogs in their non-polymer form, such as a compounding agent, a coating additive, or an antioxidant.

[0194] Other objects, features and advantages of the disclosure will become apparent from the foregoing figures, detailed description, and examples. It should be understood, however, that the figures, detailed description, and examples, while indicating specific embodiments of the disclosure, are given by way of illustration only and are not meant to be limiting. Additionally, it is contemplated that changes and modifications within the spirit and scope of the disclosure will become apparent to those skilled in the art from the detailed description. In further embodiments, features from specific embodiments may be combined with features from other embodiments. For example, features from one embodiment may be combined with features from any of the other embodiments. In further embodiments, additional features may be added to the specific embodiments described herein.

Claims

1. Claims What is claimed is:

1. A natural sugar-based bisphenol A (BPA) analog composition comprising one or more of a mannopyranoside or a xylofuranoside or a diglycerol.

2. The composition of claim 1, wherein the mannopyranoside is methyl 2,3:4,6-bis-O-(4’- hydroxybenzylidene) or methyl 2,3:4,6-bis-O-(vanillylidene)-α-D-mannopyranoside.

3. The composition of claim 1, wherein the xylofuranoside is 1,2:3,5-bis(4-hydroxybenzylidene)- D-(+)-xylose or 1,2:3,5-bis(vanillylidene)-D-(+)-xylose.

4. The composition of claim 1, wherein the diglycerol is bis(4-hydroxybenzylidene) diglycerol or bis(vanillylidene) diglycerol.

5. A method of manufacture of a polymer, the method comprising: subjecting one or more of a mannopyranoside- or a xylofuranoside- or a diglycerol- based BPA analog monomer to a melt condensation in the presence of a carbonylation agent.

6. The method of Claim 5, further comprising: mixing an aliphatic diol with the one or more of a mannopyranoside- or a xylofuranoside-based BPA analog monomer during the melt condensation.

7. The method of Claim 6, wherein the aliphatic diol is 1,4-butane diol or 1,3-propane diol.

8. The method of Claim 6, wherein the aliphatic diol is a sugar-based diol.

9. The method of Claim 8, wherein the aliphatic sugar-based diol is methyl 4,6-O-laurylidene-D- glucopyranoside.

10. The method of Claim 5, further comprising: mixing a cyclic aliphatic diol with the one or more of a mannopyranoside- or a xylofuranoside-based BPA analog monomer during the melt condensation.

11. The method of any one of Claims 5-10, wherein the carbonylation agent is diphenyl carbonate or dimethyl carbonate or phosgene or an analog thereof.

12. A polymer containing one or more monomers of Claim 1.

13. The polymer of Claim 12, wherein the polymer is one of a polycarbonate, an epoxy resin, a polysulfone, a polyetherimide, a polyarylate, a polyurethane, or a polyester.

14. The polymer of Claim 12, wherein the monomer is a bis-arylidene mannose and the polymer is poly(bis-arylidene mannose carbonate).

15. The polymer of Claim 12, wherein the monomer is a bis-arylidene mannose and the polymer is poly(bis-arylidene mannose-co-diol carbonate).

16. The polymer of Claim 12, wherein the monomer is a bis-arylidene xylose and the polymer is poly(bis-arylidene xylose carbonate).

17. The polymer of Claim 12, wherein the monomer is a bis-arylidene xylose and the polymer is poly(bis-arylidene xylose-co-diol carbonate).

18. The polymer of Claim 12, wherein the monomer is a bis-arylide diglycerol and the polymer is poly(bis-arylidene diglycerol carbonate).

19. The polymer of Claim 12, wherein the monomer is a bis-arylidene diglycerol and the polymer is poly(bis-arylidene diglycerol-co-diol carbonate).

20. A method of manufacture of a polymer, the method comprising: subjecting one or more monomers of Claim 1 to an interfacial polycondensation in the presence of an aliphatic or an aromatic diacid chloride.

21. A method of manufacture of a polymer, the method comprising: subjecting one or more monomers of Claim 1 to a solution polycondensation in the presence of a sugar-based diol, an aliphatic diisocyanate, or an aromatic diisocyanate, or combinations thereof.

22. The method of Claim 21, wherein the sugar-based diol can be one or more of galactose, fructose, mannose, glucose, xylose, or a hexose.

23. The method of Claim 21, wherein the aliphatic diisocyanate is hexamethylene diisocyanate.

24. A method of manufacture of a polymer, the method comprising: subjecting aliphatic sugar diol monomers to polycondensation in the presence of a diacid and / or a diester.

25. The method of Claim 24, wherein the sugar-based diol can be one or more of galactose, fructose, mannose, glucose, xylose, or a hexose.

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